Corrosion

and its Control

 Corrosion
and its Control
Proceedings of International Conference on Corrosion
CORCON-97, Nehru Centre, Mumbai, India

3-6 December 1997

Editors
A.S. Khanna
M.K. Totlani
S.K. Singh

Volume II
ELSEVIER SCIENCE B.V.
Sara Burgerhartstraat 25
P.O. Box 211, 1000 AE Amsterdam, The Netherlands

ISBN: 0-444-82916-4

1998 Elsevier Science B.V. All rights reserved

No part of this publication may be reproduced, stored in a retrieval system or transmitted in any form or
by any means, electronic, mechanical, photocopying, recording or otherwise, without the prior written
permission of the publisher, Elsevier Science B.V., Copyright & Permissions Department, P.O. Box 521,
1000 AM Amsterdam, The Netherlands.

Special regulations for readers in the USA-This publication has been registered with the Copyright
Clearance Center Inc. (CCC), Salem, Massachusetts. Information can be obtained from the CCC about
conditions under which photocopies of parts of this publication may be made in the USA. All other
copyright questions, including photocopying outside of the USA, should be referred to the publisher.

No responsibility is assumed by the publisher for any injury and/or damage to persons or property as a
matter of products liability, negligence or otherwise, or from any use or operation of any methods,
products, instructions or ideas contained in the material herein.

Printed at Replika Press Private Limit~, India

Acknowledgements
Preface
 Contents

Acknowledgement v
Preface vii

Volume One
Part I-Plenary Talks 1-198
1. Corrosion Control in Nuclear Power Industry
Y.S.R. Prasad 1
2. High Temperature Corrosion Problems in Coal Based Power Plant and
Possible Solutions
John Stringer 13
3. Corrosion Performance of Materials in Coal-Fired Power Plants
K. Natesan 24
4. Metallic Materials for High Temperature Fuel Cell Application
W.J. Quadakkers, M. Hansel and T. Rieck 36
5. Epoxy-Coated Reinforcing Bars-An Effective Corrosion-Protection System for
Reinforced Concrete Structures
David P. Gustafson 46
6. Corrosion of Reinforcement in Concrete Structures in India
S.A. Reddi 58
7. Corrosion Distress in Concrete-Causes and Protection
L.K. Aggarwal and S.C. Chakarbarti 81
8. Mechanisms of Carburization and Metal Dusting Methods of Protection
H.J. Grabke 89
9. Waterwall Corrosion in Low-NOx Combustion Boilers
S. Kihara, K. Nakagawa and I. Kajigaya 99
to. Biocorrosion in Industrial Applications
K.A. Natarajan 107
11. Recent Developments in the Use of Non Destructive Testing Techniques for
Monitoring Industrial Corrosion
Baldev Raj and T. Jayakumar 117
12. Prediction and Assessment of Corrosion in Industrial Operations
R.D. Kane, M.S. Cayard and S. Srinivasan 128
13. Corrosion 'Health' Monitoring Systems for Reduced Maintenance/Repair and
Increased System Reliability
Vinod S. Agarwala 140
x Contents

14. Life Extension of Plant Components and Damage Assessment Techniques

R. Viswanathan 151
15. Thermal Barrier Coatings for Advanced Gas Turbines: Some Materials,
Processing and Evaluation Related Issues
Shrikant V. Joshi 163
16. The Design of Sulphidation Resistant Materials: State-of-the-Art and
Future Prospects
P.K. Datta, H.L. Du, D. Jenkinson, J.S. Burnell-Gray and KN. Strafford 176
17. Advances in Surface Engineering
A.S. Khanna 188

Part II-Invited Talks 199-442

18. High Temperature Corrosion of Boiler Tube Steels in Simulated
Coal-Fired Plant Atmospheres Containing Water Vapour
W.J. Quadakkers, M. Thiele, P.J. Ennis, H. Teichmann and W. Schwarz 199
19. Prevention of Hot Corrosion in Boiler Piping by Laser Cladding Technique
~~~~~ ~
20. Oxidation and Hot Corrosion Behavior of Some Land Based Gas Turbine Alloys
Vimal Desai and Ming Li 216
21. Corrosion Characteristics of HSLA Steels in Sea Water
D.D.N. Singh, A.K. Dey, Mahuya Dey and B.K Singh 227
22. Corrosion Fatigue Problems in Ferritic Steels and Austenitic Steels
H.S. Khatak 249
23. Corrosion Control by Grain Boundary Modification
Vivekanad Kain, P.K. De and S. Banerjee . 258
24. Recent Development in Extreme Value Analysis for Maximum
PIT Depth Estimation
Toshio Shibata and Masahiro Yamamoto 270
25. Predicting Corrosivity of C021H2S Production and Transmission Environments
S. Srinivasan and R.D. Kane 280
26. Atmospheric Corrosion of 18 Years Study
Inder Singh 291
27. Scaling Behaviour of Steels in Simulated Reheat Furnace Environments
H.J. V. Lee, B. Gleeson and D.J. Young 301
28. Implications of Oxidation on High Temperature Mechanical Behaviour of
Nickel and Nickel Base Superalloys
M.C. Pandey and D.V.V. Satyanarayana. 310
29. Microbiologically Influenced Corrosion in Nuclear Industry
K.V.K Nair 318
30. Corrosion Related Failures-A Few Case Studies
R.K Dayal 323
 Contents xi

31. Industrial Applications of Thermal Surface Treatment with Lasers ~

K. Wissenbach, A. Gasser and R. Poprawe 333
32. Excimer Laser Treatment for Modifying Mechanical Properties and
Corrosion Behaviour of Metals
Michel Autric, Gines Nicolas and Roland Streiff 347
33. Thermal Barrier Function and Damage of Plasma-Sprayed Coatings for
Corrosion Protection
Y. Mutoh, M. Ohki, J. Lira-Oliveres and M. Takahashi 357
34. Corrosion/Abrasion of Metal Matrix Composite Coatings
C. Subramanian, R.L. Deuis and G. Cavallaro 367
35. Studies on Interpenetrating Polymer Network Based Coatings for
Corrosion Protection
T. Anandaraj, P.S. Mohan, S.M. Krishnan and K. Balakrishnan 375
36. Corrosion Fatigue Life of Cathodically Protected Tubular
Joints of Offshore Structures
D.S. Ramachandra Murthy, P. Gandhi and G. Raghava 390
37. Corrosion of Weldments
T.P.S. Gill 398
38. Localized Corrosion Behavior of Austenitic Stainless Steel
Weldments and the Role of Nitrogen
V.S. Raja 409
39. Fracture Mechanics Studies of Hydrogen Embrittlement
R.C. Prasad 421
40. Stress Corrosion Cracking Mechanisms: Recent Trends
u.K. Chatterjee 432

Volume Two
Part III-Oral Papers 443-870
41. Cross Country Pipelines Corrosion and its Control
P.M. Fanse and R.C. Arora 443
42. Serviceability of 13CR Tubulars in Oil and Gas Production Environments
M.S. Cayard and R.D. Kane 451
43. Microbially Induced Localised Corrosion in a Crude Oil Pipe Line-
A Case Study
P.K. De 458
44. Failure Analysis of Subsea Water Injection Pipeline Role of Deposits
A.K. Samant, v.K. Sharma, S. Thomas and P.F. Anto 463
45. Specification and Delivery Testing of Duplex Stainless Steels
Pasi Kangas, Knut Tersmeden and Magnus Nystrom 470
xii Contents

46. Corrosion Monitoring Studies by Electrochemical Device in Non-Aqueous

Hydrocarbon Systems
A. Jayaraman and R. C. Saxena 477
47. Insitu Chlorine Generation for Controlling Biofouling of Offshore Structures
N. Palaniswamy, P.F. Anto, SVNSSS Rao and Ani! Bhardwaj 484
48. High Temperature Corrosion Behavior and Applications of Modern Superalloys
Larry D. Paul, Venkat R. Ishwar and George Y. Lai 493
49. Study of Hot Corrosion Behaviour of Superni 600 in Na2S04- V 205 Environments
S.N. Tiwari and Satya Prakash 503
50. Corrosion in Railway Wagons: An Unsolved Riddle
R.K. Upadhyay 513
51. A Study of Corrosion in a Cement Plant
A. Wright, B. Verity, P. Heggen and C. Subramanian 519
52. Atmospheric Corrosion of Steel by the Exposure Test Avoiding Rain
Masahiro Yamamoto, Kazuhiro Masuda, Hiroshi Kihira and Takashi Tsuzuki 527
53. CW Treatment Formulations for Open Re-Circulation
D.K.N. Kutty and A. Periaswami 533
54. Corrosion-Organic & Inorganic and it's Prevention/Control
Through Dehumidification
Rajnish Joshi and Prem Sagar 540
55. Corrosion Problems in Chemical Process Industry-An Experience
B. Gaur and B.S. Srinivasan 548
56. Sensitization Studies on 304H Austenitic Stainless Steel Using EPR Technique
K. Venugopal, T.R. Jayararnan and Y. Kalpana 559
57. Nitrogen Ion Implantation of Type 316 Stainless Steel to Improve
Intergranular and Pitting Corrosion Resistances
U. Karnachi Mudali, T. Sundararajan, K.G.M. Nair and R.K. Dayal 566
58. Effect of Alloying Elements on the Polarization Behaviour of Low Carbon Steels
K. Ravi, A. Bhattacharyya and K.B. Mishra 574
59. Structure-Electrochemical CO!Telations in Amorphous and Devitrified
Fe-Based Ferromagnetic Alloys
I. Chattoraj and A. Mitra 582
60. The Influence of Cr Addition on the Elevated Temperature Erosion of Ni
Manish Roy, K.K. Ray and G. Sundarajan 588
61. Corrosion Problems in Turbogenerators
R. Viswanathan 595
62. A Review of Intermetallic Precipitates and Their Influence on
Zircaloy Corrosion in Nuclear Reactors
E.A. Preble and K.L. Murty 609
63. Parametric Analysis for Characterisation of Acoustic Emission Sources During
Charging and Discharging of Hydrogen in Palladium
C.K. Mukhopadhyay, T. Jayakumar, R. Ramesh and Baldev Raj 615
 Contents xiii

64. Stainless Steel in Liquid Sodium Environment-Prediction of Expected

Behaviour and Comparison with Experiment
S. Rajendran Pillai, H.S. Khatak, N. Sivaibharasi and J.B. Gnanamoorthy 621
65. Non-Chromate Anodic Corrosion Inhibition with Desired Deposition
Control in Industrial Cooling Water Systems
K.S. Rajan and K. Venkatnath 627
66. Dithiobiurets: A Novel Class of Corrosion Inhibitors
M.A. Quraishi, Jaya Rawat and M. Ajmal 634
67. Kinetics of Carbon Steel Corrosion in Picolinic Acid, Ascorbic Acid and a
Typical Mixture of the Two Acids
Chintamani Das, H.S. Gadiyar and M.K. Totlani 640
68. Impedance Measurements and High Temperature Weldment Corrosion and its
Inhibition in 2.25Cr 1.0 Mo Low Alloy Steel Used in Power Plants
S. Natarajan and V. Sivan 652
69. New Oxazole Derivatives as Corrosion Inhibitors for ARMCO
Iron in 1M HCI Solution
A. Khazraji, S. Kertit, J. Aride, K. Bougrin and M. Soufiaoui 662
70. New Triazole Derivatives as Corrosion Inhibitors for a Carbon Steel in
2M H3P04 Solution
S. Kertit, K. Bekkouch, M. Elfarissi, A. Aouniti and B. Hammouti 672
71. In-Line Crack Detection in Oil and Gas Pipelines: Operational Experience with the
Ultrascan CD
H.H. Willems, a.A. Barbian, N.J. Uzelac and P.M. Evans 679
72. Corrosion Monitoring in Remote or Hostile Locations
Neil Dickie 691
73. A Non-Destructive Testing Technique for Monitoring Corrosion in a
Buried Pipeline
J.K. Ghosh, S. Muralidhar, S.D. Raut, S. Rajendran, Gyanendra Singh,
D. Venkatesh, T.K. Bhaumik' and M.S. Ramakumar 695
74. Sensitisation of AISI 317 Stainless Steel Pipeline Carrying Phosphoric Acid due to
Fire Damage: In-Situ Metallographic Study
R.i. Chaudhari and V. Balasubramanian 700
75. Corrosion Behaviour of Metals in Sodium Chloride Medium by Single Drop and
Thin Layer Techniques
A. Subramanian, P. Rajendran, M. Natesan, K. Balakrishnan and T. Vasudevan 712
76. Cost Effective Multi-Layer Coating Systems
J.D. Kellner and B.B. Patil 718
77. Effect of Secondary Phases on the Pitting Behaviour of Highly Alloyed and
Laser Surface Alloyed Austenitic Stainless Steels
K. Sridhar, A.S. Khanna and M.B. Deshmukh 727
78. Evaluation of Durability Characteristics of Epoxy Poly Urethane Painting System
Through QUV Apparatus
M.P. Varma, J.L. Khanna and V. Murlidharan 736
xiv Contents

79. High Temperature Resistant Slurry Based Coating for Steel

M.N. Singh and Inder Singh 742
80. Preventing Reinforcement Corrosion-Corrosion Resistant Rebars from SAIL
Vinod Kumar, V.K. Singh, P.K. Bhor, A.K. De, B.K. Panigrahi,
A Bhattacharya, A.K. Mukherjee, S.K. Chaudhuri and S.K. Jain 751
81. Monolithic Chemical Resistant Floor Covering Based on
Nonisocyanate Polyurethanes
Oleg L. Figovsky, Leonid D. Shapovalov and Nellv Blank 757
82. Remedial Measures for the Concrete Lining Inside the Head Race Tunnel of
Nathpa-Jhakri Project (H.P.) Against the Corrosive Action of Hot Water Spring
K. Venkatachalam, Murari Ratnam and S.B. Suri 764
83. Effect of Aggressive Chloride Environment on Corrosion Resistant
Reinforcing Steels Embedded in Concrete
N. Banerjee, D. Mukerjee, B. Bhattacharya and D.S. Ramachandra Murthy 776
84. Cases of Stress Corrosion Cracking in Power Plant Components
Pradeep Jain, A.K. Sinha, U.c. Bhakta and S.K. Sanyal 783
85. Stress Corrosion Cracking of Micro-Alloyed Steel in Various Environments
S.K. Sen and G. Kaur 793
86. Preventing Pollution in Zinc and Cadmium Plating-A Novel Approach
M.B. Sunthankar and S.D. Joshi 802
87. Development of Nonchromate Treated Tinplate having Excellent
Resistance to Yellow Staining and Smudging
Tomonari Ohga and Hironobu Miyazaki 809
88. Corrosion of Tinned Sheets during Transportation-A Case Study
Inder Singh and AN. Mukherjee 815
89. Corrosion Protection by SS-316 Coatings by different Thermal Spray Processes
Eklavya Calla and S.c. Modi 816
90. Corrosion Study of Microencapsulated Surrogate Waste Forms Using AC
Electrochemical Impedance Spectroscopy (EIS)
Krishna Narayanan, Raj Mehta, Regina Sucaldito and Indira Chatterjee 831

Part IV-Poster Papers 871-1292

91. Studies on Scale Inhibitors for Industrial Waters
A. Alice Arul Antony, G. Paruthimal Kalaignan, A Gopalan,
K. Balakrishnan and T. Vasudevan 871
92. Effect of Variation of External Stress on the Oxidation Behaviour of
9Cr-1Mo Steel at 973 K
S. Rajendran Pillai, N. Sivaibharasi, H.S. Khatak and J.B. Gnanamoorthy 878
93. Corrosion of Wagons-Due to Change in the Condition of Consignment
M.P. Varma, Anil Madan and D.C. Misra 885
 Contents xv

94. Role of Sulphate Reducing Bacteria on Corrosion Process-A New Mechanism

S. Maruthamuthu, C. Stella, C. Jeyaprabha, A Mani and NS. Rengaswamy 891

95. A Portable Field A.C. Impedance Meter

S. Syed Azim, H. V. Shanboge, H. U. Nayak, R.B. Suresh Babu,
A Selvaraj and P. Jayakrishnan 902
96. Evaluation of Pyridine and Picolines as Inhibitors for Corrosion of Mild Steel in
Agitated 5% Hydrochloric Acid at 50C by DC Polarisation and
Weight Loss Methods
M.J. Sanghvi, S.K. Shukla, A.N. Misra, M.R. Padh and G.N Mehta 909
97. Scale Morphology Characterization of 304 Stainless Steel and its
Influence on Pickling Behaviour
S. Jana, R.K. Aiyar and A. Ganguly 914
98. Microbiologically Influenced Corrosion of Stainless Steel Weldments
R.P. George, K.R. Sreekumari, P. Muraleedharan, H.S. Khatak,
J.B. Gnanamoorthy and K. V.K. Nair 924
99. Platinised-Iridium Coated Titanium Electrodes for Electrochemical Applications
U. Kamachi Mudali, V.R. Raju and R.K. Dayal 930
100. High Temperature Nitridation and Oxidation of Inconel-601
S. Dash, R. Krishnan, S. Rajagopalan and A.K. Tyagi 939
101. Failure Analysis of a Monel-400 Heat Exchanger Tube from a
Nuclear Power Plant
NG. Muralidharan, N. Raghu, K. V. Kasiviswanathan, T. Jayakumar and
Baldev Raj 946
102. Influence of Anions on the Performance of Thiosemicarbazide as an Inhibitor of
Corrosion and Hydrogen Permeation Through Mild Steel in Acidic Solutions
K. Madhavan, S. Muralidharan and S. Venkatakrishna lyer 952
103. Influence of Hydrodynamics on the Electrochemical Behaviour of Aluminium
Alloy Anode and Steel Cathode in 3% NaCl Solution Under Cathodic Protection
Condition-A Rotating Disc Electrode Study
S. Muralidharan, K.B. Sarangapani, V. Kapali, R. Vijay Anand,
K. Vidyasankar and S.NS. Arun Kumar 961
104. Gasometric Studies of Mg-2Zn-lMn Alloy in Aqueous Media
A. Antonyraj and C.O. Augustin 968
105. Studies on Aluminium and its Alloy as Galvanic Anodes in
Alkaline Zincate Solution
M. Paramasivam and S. Venkatakrishna lyer 974
106. Corrosion Problems in Petroleum Production Using Enhanced
Oil Recovery Techniques
P.K. Sagar, P. V.S. Bhanu Murty and Amit Khanra 984
107. Development and Characterization of Coatings on Interconnector (Cr-ODS) used in
SOFCs
K.M.N. Prasanna, AS. Khanna and W.J. Quadakkers 990
xvi Contents

108. Effect of Water Vapour on the Oxidation of FeCrAl- and NiCrAI-Base ODS Alloys
K.M.N. Prasanna, AS. Khanna and W.J. Quadakkers 997
109. Role of Moisture on the Oxidation of Metals in Fused Nitrates Melt
I.B. Singh 1004
110. Effect of pH and Hardness on the Scale Formation of Mild Steel in
Bicarbonate Ion Containing Water
I.B. Singh and B. Chakradhar 1009
111. Evaluation of SS 316 as the Container and Current Collector in
EDL/Super/Ultra Capacitors
Devicharan Chidambaram, P. V. Karthik, L. John Berchmans and V. Kapali 1013
112. Influence of Triazole Derivatives on the Inhibition of Corrosion of
Arsenical Aluminium Brass in 3.5% NaCl
L. John Berchmans, M.A Quraishi, V. Sivan and S. Venkatakrishna 1yer 1023
113. Influence of Some Dyes on Corrosion of Mild Steel in Sulphuric Acid Solution
R.S. Chaudhary and Santosh Sharma 1032
114. Corrosion Behaviour of Zinc Coated Steel (Arc Sprayed) in Chloride Solutions
C. Marikkannu, C. Jeyaprabha arid A. Madhavamayandi 1037
115. High Temperature Corrosion Behaviour of Ceramics after Excimer Laser Sealing
Gines Nicolas, Michel Autric and Roland Streiff 1047
I 16. Microbiologically Influenced Corrosion (MIC) and its Mitigation in Industrial
Open Recirculating Cooling Water Systems
G.S. Bhattacharyya 1052
117. Synergistic and Biocidal Effects of a Phosphonate-Metal lon-Biocide System on the
Inhibition of Corrosion of Mild Steel in Neutral Aqueous Environment
Susai Rajendran, B. V. Apparao and N. Palaniswamy 1061
118. Effect of the Addition of In3+, Sn2+ and Zn2+ Ions on the Electrochemical
Behavior of AI-Zn, AI-In and AI-Sn Binary Alloys in 3.5% NaCI
A. Venugopal and V.S. Raja 1067
119. Hydrogen Embrittlement Behavior of Three High Manganese Stainless Steels
V.S. Raja and A Devasenapathi 1074
120. Hydrogen Embrittlement Studies of API 5LX 52 Pipeline Steel
R.C. Prasad, H. Avinash, T.R. Reddy, Viju Cherian,
P.P. Anto and S.K Singh 1082
121. Application of Nuclear Methods in Corrosion and Wear Studies
KG. Prasad and AS. Khanna 1088
122. Weldment Corrosion in Dissimilar Material Incoloy 800 vs 2.25 Cr IMo
Used in Process and Power Plants
R. Vaideeswaran, S. Natarajan and V. Sivan 1093
123. Prevention of Crevice Corrosion of SS 304 in Condensers of Power Plants by
Sacrifical Cathodic Protection
Ashwini K. Sinha, U.C. Bhakta, S.D. Chowdhary,
AK Mitra and G. Gunasekaran 1103
 Contents xvii

124. Localized Corrosion Behaviour of Argon Ion Implanted Titanium Modified Type
3l6L Stainless Steel for Application as Orthopaedic Implant Device
T. Sundararajan, U. Kamachi Mudali, KG.M. Nair,
S. Rajeswari and M. Subbaiyan 1121
125. Triazoles as Corrosion Inhibitor for Brass in Sea Water Environment
1.H. Farooqi and M.A. Quraishi 1128

126. Integrity of Incoloy-825 Cladded Mild Steel in Sour Gas Service

AS. Khanna, AK Pattanaik, P.F. Anto and S.K Chugh 1134

127. Performance and Cost Evaluation of Some Glass Fibre Reinforced Polyesters and
Steels for Hopper Box used in Seed-Cum-Fertilizer Drill Agricultural Machine
Kavita Gidwani, A.K Singh, V.S. Muneshwar and AK Gupta 1143

128. Corrosion Behaviour of Magnesium Alloys in Chloride Medium

lnder Singh and A.K Bhattamishra 1149
129. Effect of Mixed Cations on Phosphate Coating of Steel
D.D.N Singh and Bijay Kumar Singh 1154

130. Passivation of Galvanized Surfaces to Improve their Corrosion Resistance

D.D.N. Singh, A.K. Dey and lsrar Khan 1167
131. Corrosion Behaviour of Rapidly Solidified Lead-Aluminium Alloys for
Battery Grids
T.B. Singh, K. Lal, R.K. Mohanty and C.S. Shivaramakrisnan 1182

132. A Direct Electroless Process for Ni-P Protective Coating on Aluminium

L.G. Bhatgadde and Sharlet Joseph 1188
133. Fouling and Under Deposit Corrosion in CW System-A Case Study
D.KN. Kutty and A Periaswami 1195

134. Prediction of Pitting Corrosion Tendency of Materials During Extended

Storage of Spent Nuclear Fuels
Vivekanand Kain, S.S. Shinde and P. Seetharamiah 1201
135. Approaches to ISO Certification-Paint Manufacturing Industry
Jyoti 1:.ata Pandey, T.B. Rao, Sandeep Singh and M.K. Banerjee 1208
136. Electrochemical Corrosion Behaviour of Carbon Steel in Morpholine and
Sodium Hydroxide
R. Ramakrishnan, S. Rangarajan, S. V. Narasimhan and P.K. Mathur 1219

137. Electrochemical Corrosion Studies on Copper, Carbon Steel and Monel-400 in

Steam Generator Cleaning Formulations
R. Latha, S. Rangarajan, S. V. Narasimhan, S. Rajeswari and M. Subbaiyan 1224

138. Possible Effects of Coal Chlorine on Furnace Wall Fireside Corrosion in

Utility Boilers
A.K. Mehta, C.J. 'Davis, P.J. James, L. W. Pinder and l.G. Wright 1231

139. The Effect of Dilution on Corrosion and Wear of Superalloy Weld Overlays
Ram N. Chattopadhyay 1246

140. Corrosion Behaviour of Cobalt Based Metallic Glasses

K. Vinita, S.N. Malhotra and A.N. Tiwari 1251
xviii Contents

141. Electrochemical Corrosion Studies of Propeller-Bronze in Binary Mixtures of

Acetonitrile and Water
Lal Bahadur and M.A. Emami 1257
142. Water Treatment and Corrosion Control in Oil Field Water Injection
Schemes of Upper Assam
B.P. Babu, Jolly Joseph, S.K. Sahota and H.e. Dhawan 1264
143. Effect of Addition of Admixture on Strength and Corrosion Behaviour of Concrete
A. Bhattacharyya, S.K. Ghosh, S. Srikanth and K.B. Mishra 1270
144. Quantification of the Criterion for Corrosion
Ramesh Chandra Bagadi, R. Ramesh Reddy and Basant K. Parida 1277
145. Development of In-Service Inspection Techniques for Monitoring Intergranular Stress
Corrosion Cracking in AISI 304 Core Shroud Welds of Boiling Water Reactors
A.K. Bandyopadhyay, M. Bandyopadhyay, P.P. Nanekar, R. Ramanathan,
B~K. Shah and P.G. Kulkarni 1287

Author Index 1293

 Part III

Oral Papers
PftJc.. Int. Conf. on Corrosion CONCORN '97
Dax:mbcr 3-6, Mumbai, India

Cross Country Pipelines Corrosion and its Control

P.M. Fanse and R.C. Arora
Gas Authority of India Limited,
Baroda 390 005, India
Steel that is buried in earth corrodes and the transmission
pipeline is therefore protected on the outside partly by
cathodic protecftion. A coating is described as a passive
corrosion protection while cathodic protection where a con-
stant current is delivered to the steel structure is de-
scribed as active corrosion protection.
The principle of cathodic protection of, for exarq.ple,pipe-
lines is to prevent the dissoluation of iron (anodic process)
from occuring on the outer surface of the pipeline. This is
done by reducing the pipeline's potential to the eqilibrium
potential. When the potential corresponds to or has a higher
value than the equilibrium potential, corrosion ceases. The
potential is reduced by supplying the metal with electrons,
or put it in another way, by sending current in the opposite
direction to the corrosion current. The protecting current
must be of atleast the same magnitude as the corrosion cur-
rent.
In normally aerated earth ar-dwater, steel can be effectively
prevented from corroding at potentials less than 850 mv in
relation to CU/CUS04 reference electrode.
In principle corrosion can be prevented by covering the
entire surface of the structure with a non-productive paint,
plastic or tape. However, it is extremely costly to ensure
that a coating covers completely. Some sort of damage must
always occur. If the conditions are corrosive, the damaged
areas become seriously corroded. The use of a good coating
combined with cathodic protection is often the cheapest
sol,ution.
MB'l'BODS OP' CATHODIC PROTECTION
Since it is the potential that decides the degree of protec-
tion, there are, in practice, two way of establishing catho-
dic protection.
1. The pipeline is made into a cathode in a galvanic cell
by connecting it to a base metal like Zn or Mg. The
base metal acts as the anode. During the forth coming
electro chemical reaction, the pipeline is protected at
the cost of the base metal. The anode is consumed and
the method is therefore called Cathodic Protection by
means of a sacrificial anode.
2. The pipeline is made into a cathode by applying a
direct current. The pipeline is connected to an anode
via a rectifier. It does not matter whhether his anode
is noble or base, because the direction of the current

443
 is determined by the rectifier. As the cell does not
function by itself, the method is called cathodic
Protection with impressed current.

GAIL has employed both the methods in order to protect the

pipeline. The first method, namely cathodic protection by
means o'f sacrificial anodes, formed the basis of temporary
cathodic protection system and this system will remain in
effect till the time our permanent cathodic protection system
i.e. cathodic protection with ipressed current comes into
force.
The following section briefly sketches salient features of
both the system of protection.
TEMPORARY CATHODIC PROTECTION
The purpose of providing temporary cathodic protection is to
protect the pipeline against the corrosion when it is buried
in the soil prior to the commissioning of the permanent
cathodic protection system. The temporary cathodic protec-
tion system works on the principle of sacrificial anode
system and will be disconnected thoroughly, once the perma-
nent cathodic protection system is commissioned.
SALIENT PBATlJRBS OP GALVANIC ANODE SYSTEM:
1. Continuous supply of energy is not required.
2. The anode material is consumed almost proportional to
the current generated. AS the pipeline system employs
an excellent quality of coat1ng, the anode consumption
is low.
3. The structure's potential varies with the H20 & 02
condition, the rate of flow etc. The potentional
difference and thus the current generated therefore
vary by same factor i.e. more current is generated when
there is more need for it. Sacrificial anodes are
thus self regulating.
General Description of Work:
The work involved the installation of a temporary cathodic
protection system for the HBJ trunk/branch pipelines exclud-
ing the piping within the associated plants and including
installation of zinc anodes at railway cased crossings and
permanent test stations wherever temporary and permanent test
stations coincided. Indian and International codes and
standards were followed for all works. Work also covered
statutory regulations and safety codes of all local authori-
ties. The material associated with temporary cathodic pro-
tection system had been stored properly to avoid damage and
measures were taken to ensure the anode backfill remained dry
prior to installation.

INSTALLATION PROCBDORB:

Prior to the installation of the temporary cathodic protec-

tion equipment, verification of the soil resistivity measure-
ment had been carried out at each anode location.

444
All electrical cable connections to the pipeline had been
make using the exothermic welding process. This process in-
volved igniting a mixture of powdered copper oxide and alu-
minium with a thermit welder. When properly ignited the best
created from the reaction permanently welds the conductor to
the steel pipeline.

(a) A patch of coating (measuring 65 rom ot 45 rom or a~ per

the mould size was removed from the top of the p1pe-
line.
(b) 40 rom of insulation was removed from the cable and a
, copper sleeve was crimped on the conductor.
(c) The cad-weld mould was carefully positioned on the
exposed area of the pipeline, the catridge of weld
metal was put into the mould and the weld metal charge
ignited with a flint gun by holding the mould firmly on
the pipeline.
(d) The slag was removed and proper connection between the
cable and the pipeline was ensured.
(e) The thermit weld connection was encapsulated with epoxy
or by other suitable means. The wire was strapped with
pipeline near the thermit cable connection.
(f) The encapsulation was checked by a 25 KV holiday detec-
tor.

A'detailed soil resistivity was carried out which formed the

basis of the selection of anodes. As a rough guideline, it
can be stated that Zn anodes we+e selected where soil resis-
tivity varied between 0-10 m. and Mg anodes were selected
where soil resistivity varied between 10-60 m. and Mg
ribbons were used where soil resistivity exceeded 60 m.

Each prepacked anode had been installed in a hole of nominal

200 rom dia. All anodes were installed at 10 m side of the
R.O.U Anode holes were made with a special auger tool.
After a straight auger hole was made, a non metallic casing
was provided. The non-matallic casing was inserted in each
auger hole to maintain the integrity of the hole unit the
anode was installed.
On completion of making the hole a single anode was lowered
into the hole with the help of a cotton strip to avoid the
damage of anode lead wire. The anode was lowered straight
into the whole and the casing was removed. Backfilling was
done with the soil removed during augering or with soft soil.
Tempering was done layer by layer by adding little quantity
of water. Backfilling was done tipto the top of the hole.

5
Anode lead wires were routed to the test station by making
0.5 M and 1.5 M deep trench for temporary and permanent
cabling.
Wherever two anodes were to be installed at one location the
anodes where kept 10 m. apart.
C) TEST STATION INSTALLATION:

The anode to pipeline connection for all the temporary anodes

was made via a test station containing a current measuring
shunt and an isolation link. Hoaever at some locations,
where temporary anode locations coincided with the locations
of future permanent test stations, been installed.
Temporary test stations have been installed at every 250 m
distance whereas permanent test stations are insalled at the
following locations.
(a) At both the sides of major water, road rail crossing
and at all cased crossing ..
(b) At all insulating joints

.(c) At the crossing of AC/DC electric traction system,

(d) At vulnerable locations with grounding cells and popu-

larisation cells (as required) .

(e) At measuring points for pipeline.

(f) At HT over head line crossings and selected locations

where HT over head line is in vicinity of the trunk
pipeline.
(g) In the vicinity of DC net the working or the grounding
system where interference problems are suspected.

(h) At valve locations.

(i) At crossing with the other pipelines.

(j) At any other location considered vulnerable.

(k) Within the battery limit of plants (as required).

Prior to commissioning, measurement of natural potential pipe

to soil potential, anode output current, pipe to soil poten-
tial at the mid point of two test stations were carried out:
E) COMMISSIONING:
Cathodic protection potential level is maintained in between
0.950 to 1.50 volt at each test station location. Anode
output current is maintained as per the design criteria. If
the output current of an anode exceeds its rated capacity
proper resistance is to the inserted in the circuit to con-
trol the excess current.

446
After proper commissioning, the temporary cathodic protection
system PSP and anode output current measurements are carried
out monthly until the permanent system is commissioned.
Consortium has to prepare as-built drawing and to keep the
upto date records of the system.

1. Anodes are supplied with Canister.

2. The anode material is hardly consumed at all if it is
noble. Base anode material such as scrap steel is
consumed and must be replaced.
3. When current is supplied from a rectifier, there is
some choice of voltage. Impressed current iljl
therefore
suitable for protecting long pipelines in earth with
just a few anodes.
4. C.P. system with impressed current are more complicated
,than systems with sacrificial anodes, partly because of
extens~ve cable works, installation of power source
,regulating system etc, and partly because of a risk of
the current affecting other neighbouring structures:
5. The system requires regular control to ensure against
both under protection and over protection. Under
protection can become a problem after a long period of
operation due to deterioration of and damage to the
coating. OVer protection is usually seen after the
running in, period when the current requirement falls.

1. Leakage of current from electrical system through the

earth:
(a) Currents absorbed by nejghbouring structures of the
cathodically protected pipelines.

(b) Currents absorbed by cathodically protected pipe-

lines.

Stray current or interference current is electric current

flowing through paths other than the intended circuit. In a
C.P. System the' protective current can leak out into the
earth in an area around the anode or pipeline. The size of
the area over which it leaks depends on the geometry of the
protected structure, the type and quality 'of the coating and

447
the anodes supplying the current. Part of a current can'be
'picked up' by a neighbouring structure and cause increased
corrosion of the neighbouring structure where it re-enters
the surrounding earth. The damage is known as stray current
corrosion.
Intereference' is defined as changes in the potential of
neighbouring structures caused by stray current from various
sources.
2. Ageing and corrosion of pipeline coating.
3. over and under protection of pipeline.
The most widely used power source for impressed current
system of protection of HBJ pipeline has been the installa-
tion of closed Cycle Vapour Turbogenerators (CCVTs)
The CCVT is based on the thermodynamic Rankine cycle princi-
ple. The Rankine cycle components, turbo alternator, con-
denser and the vapour generator are the core of the CCVT and
comprise a single, hermetically sealed system containing an
organic motive fluid.
The CCVT system operates as follows:
The gas fired burner heats the organic fluid contained in the
vapour generator. As the liquid vapourises, it flows up the
turbine vapour inlet tube to the turbine wheel. There it
produces rotational shaft power to drive the alternator. The
vapour then passes into the condenser, is cooled and convert-
ed back into the liquid state. The cooled liquid motive
fluid, flows in parallel paths ~o the vapour generator, cools
the alternator stator and supports the turbo alternator rotor
within the fluid bearings. The' cycle continues as long as
heat ~s applied to the vapour generator and removed by the
condens~r. When the heat to the vapour generator is in-
creased so is the rate of vapourisation and as a result there
is increased rotational velocity in the turbo alternator
rotor, increased alternator torqe and increased generation of
electricity. The converse happnes when the heat supply to
the vapour generator is decreased.
Because the entire motive fluid is hermatically sealed none
of the organic fluid is lost in the process. An additional
advantrage is that the working fluid is completely immune to
the climatic conditions outside the sealed system.
A small quantity of the natural gas flowing in the transmis-
sion network is diverted, reduced in pressure, pre-heated and
is ultimately used in the CCVT fuel burner. The fuel con-
sumption is approximately 8.1 m3/hr. The generated voltage
is controlled by a cathodic protection voltage control modu-
le, which in turn supplies the C.P. system. Arrangement has
been made to vary the DC output current so that it is possi-
ble to select and maintain the pipe to soil potential at
desired values. This shall be arranged through distinctly
independent Auto & Manual modes selectable from a selector
switch.

448
In the automatic mode, the output current will automatically
adjust to maintain a pre-selected pipe to soil potential.
This shall be accomplished by the electronic control module
and a set of three permanent reference electrodes. The
controller shall contain a comparator circuit that will
accept the reference electrode with the lowest potential
above a pre-selected value higher than the native potential
of steel.

The turbogenerator produces 3 phase AC power (48-56.5V AC)

which is rectified and filtered. The DC output (48v DC) is
regulated in accordance with varying load. The amount of gas
fuel supplied to the burner automatically controls the sys-
tems heat input. The system is thus fully protected against
the effects of overheating, short circuits, over and under
voltages. Personnel safety is enhanced and equipment life is
rated to 20 years.

In addition to the CCVTs each station will be equipped with

NiCkel-Cadmium Alkaline storage batteries so as to provide
back up power supply. The batteries use Nickel hydroxide as
the positive active material, cadmium as the negative active
material and caustic potash as the electrolyte. Normally the
system is used in the floating charge mode. That is, the
rectifier will supply the power to load while supplying a
current of small amount to the battery to compensate self
discharge.

When the rectifier stops the operation, the battery starts

witnout interruption to supply the power to load for the
required duration. When the rectifier restarts operation,
the battery will be given a recovery charge and then return
to normal floating charge mode.

The locations of C.P. stations along HBJ pipeline have been

chosen in such a way so as to coincide with the RR/IP sta-
tions, compressor stations and terminals. CCVTs have been
deployed at mostly the RR/IP statuions where electrical
supply is not available. At the compressor stations,
however, where reliable power supply is available, transform-
er rectifier units are being installed.

Each C.P. station shall also have an independent anode ground

bed which may"be of horizontal, vertical, semi deep or deep
well c.onstruction. The anodes are high silicon alloy con-
taining: silicon: 14.5% Mg : 0.75 Carbon: 0.95% Chromium:
4.50% & Fe remaining part.

Manual and computerised test stations shall be provided along

the trunkline ROW for monitoring the performance of the
cathodic protection system at intervals not to exceed ~OOO

449
metres. Test Stations are also installed near locations
considered vulnerable for C.P. system. The computerised test
stations shall monitor and store data 'locally for later re-
trieval to central monitoring and data analysis facility.
Each of these test stations shall contain a microprocessor
capable of automatic monitoring and storing various data for
a period of upto six months without any maintenance. Each
test station will be provided with rechargeable Nickel-
Cadmium batteries.
Besides acting as test points for monitoring the health of CP
system, the manual test stations have been modified at spe-
cific locations where the pipeline crosses ,HT lines, Railway
Roads and Rivers. Surge diovertors and grounding cells have
been provided at HT line crossings and at insulating joints
respectively. The connections to these have been made
through the manual test stations.
However, the river crossing sections of the pipeline will be
protected by galvanic anode system in addition to ICCP
system.
,At railway crossings, the carrier pipeline is protecteed with
a coated casing pipe. The carrier inside the casing is
protected by Zn ribbon anodes welded at 4 & 8 0' clock posi-
tions. The casing pipe is also protected by galvanic anode
system. For all cable connections, XLPE armoured cables of
suitable sizes have been used.
Electronic corrosion sensing probes utilizing the electrical
resistance (ER) technique Will be provided along the pipeline
at approximately 10 KM interval and at vulnerable locations,
to monitor corrosion activity.
In addition to protecting the external surface of the under-
ground metallic structures at Hazira Compressor station the
permanent CP system also provided. A computerised potential
logging survey of the entire pipeline has been carried out
after commissioning of the Permanent CP system to ensure
protection. Regular monitoring and maintenance has been
carried out for power source and CP installations all along
ROW as per ISO-9002 Quality standard.

450
451
This paper is intendCd to provide guidance on the serviceability limits for 13Cr tubulars in oil and gas
production. The parameters affecting the perfonnance of 13Cj:ulars in both sweet and sour service are
discussed and their respective implication to the overall integrity essed.

PARAMETERS AFFECTING 13Cr PERFORMANCE

The major parameters affecting the performance of 13Cr tubulars in oil and gas production include pH, cr,
temperature and the partial pressures of HzS and COz. Additional considerations reported in the literature
include the role of acetates, flow velocity effects and acidizing resistance [I]. However, the effects of these three
variables are beyond the scope of this paper.

System pH

The system pH simply provides a measure of the hydrogen ion availability in the solution. The lower the pH the
larger the amount of atomic hydrogen available to potentially enter the steel. With respect to BCr alloys, the
ingress of atomic hydrogen into the steel can lead to hydrogen embrittlement, which in the presence of HzS is
referred to as sulfide stress cracking (SSC). An SSC domain chart, developed by Kennani, Harrop, Truchon and
Crolet [2], now serves as a guideline for specifying materials requirements for carbon and low alloy steels in
HzS environments and has been adopted by the European Federation of Corrosion (EFC) [3]. This chart, shown
in Figure I, illustrates SSC domains as a function of solution pH and HzS partial pressure. Domain I indicates a
safe region where SSC is no expected to occur. Domain 2 is referred to as the transition region wherematerials
should be qualified under some test program. Domain 3,indicates a region where SSC would be expected to
occur and hence requires sour service materials.

SSC data on both conventional and modified 13Cr published in the literature [4-10] was complied and plotted as
pH versus HzS partial pressure. The data collected was all taken at 25 C and stressed from 80 to 100% of the
SMYS in brine solutions ranging from 30,000 to 60,000 ppm cr. These data are presented in Figure 2. The
EFC SSC domain guidelines are plotted on the figure for reference. Cracking occurred more readily at low pH
levels and at higher HzS partial pressures as expected. Some failures were noted in Domain 2, however no
failures were observed in Domain I. Another interesting point is the number of no fail results observed in
Domain 3. This relates to the quality and control of the BCr material which was tested. The large majority of
the no fail data in this domain was the modified BCr chemi.stry. Hence, the modified BCr steels do appear to
offer substantial benefit in the sour regime which makes up Domain 3.

System pH also plays a direct role on the corrosion rate of BCr steels in oil and gas production. While the
system pH is a function of the partial pressures ofHzS and COz, bicarbonate concentration, weak acids and
temperature, it in itself does provide a trend with respect to corrosion rate. Data from the literature [11-13]
combined with data collected at CLI International, Inc. up through November 1995 [14] was plotted. The data
set represents a range of conditions with r~ to HzS, COz, temperature and cr's. The data for conventional
and modified 13Cr are shown in Figures 3 and 4, respectively. The magnitude in the corrosion rate at low pH
values varies between the conventional and modified chemistries as expected. However, the two plots do indicate
that above a pH of approximately 4.2, the corrosion rates remain quite low.

Chlorides

The role of chlorides on the corrosion I cracking perfonnance of martensitic stainless steels simply relates to the
break down of the corrosion films which are normally protective to the material. Increased chlorides result in an
increased tendency for localized corrosion resulting from the local breakdown of the protective' film. Modified

452
453
-P4l Cayard M.S. and Kane R.D., Compilation of 13Cr Data Generated at CLI International, Inc. through
November 1995.
(15J Ueda M., Kushida T., Kondo K. and Kudo T., Corrosion Resistance of 13Cr-5Ni-2Mo Martensitic
Stainless Steel, CORROSION/92, paper no. 55, 1992, Houston, TX, USA, NACE International.
(16J Hashizume S., Masamura K. and Ishizawa Y. Corrosion Data on Laboratory Performance of Type 420
for OCTG, CORROSION/95, paper no. 77, 1995, Houston, TX, USA, NACE International.
(17] Veda M. and Ikeda A., Effect of Microstructure and Cr Content in Steel on CO] Corrosion,
CORROSION/96, paper no. 13, 1996, Houston, TX, USA, NACE International.
(18J Kane R.D., Abayarathna D. and Schofield MJ., Final Report: Safe Use Limits for Stainless Steels in
Production of Oil and Gas Containing H~ and CO], Joint Industry Project, 1995, Houston, TX, USA,
CLI International, Inc.

TABLE 1

CHEMICAL COMPOSITION OF L80 AND VARIOUS

MARTENSITIC STAINLESS STEELS

455
456
457
Pro<:. In!. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai. India

Microbially Induced Localised Corrosion in

A Crude Oil Pipe Line-A Case Study
P.K. De
Materials Science Division, Bhabha Atomic Research Center,
Trombay, Mumbai-400 085, India

ABSTRACT

This paper deals with the leakage in an undersea carbon steel pipe line of grade API 5 LX 52
in which raw crude oil an<;lnatural gas have been transported between the off-shore platforms at
Bombay High, North. Pitting type attack was confined to the low lying areas on the inside surface
of the pipe where water had accumulated. At some locations, long corrosion channels (upto about
600 mm in length) were noticed. Detailed investigations indicated that the pipe line had suffered from
under <;lepositlocalised corrosion attack caused by the presence of organic acids generated due to the
metabolic activities of micro organisms.

1. INTRODUCTION

In Bombay High, North, a 4 km long, 325 mm. dia. undersea seamless pipe line of grade API
5LX 52 steel has been in operation for several years. Through this pipe line raw crude oil is
transported as and when required from one off shore platform to another for processing. It is
protected externally by coal tar epoxy coating and by sacrificial anodes. It is further covered with
thick concrete as per the norms of undersea pipe line. In 1990, leaks were observed at several
regions. Inspection revealed that the pipe line at low lying areas had developed perforations at the
bottom segments between 5 to 7 o'clock positions: However, no leaks or holes were noticed at the
remaining segments of this pipe line. A small portion of about 1 m length obtained from the affected
area of the pipe, was subjected to detailed metallurgical examination to ascertain the likely cause of
premature failure.

2. VISUAL EXAMINATION

The affected pipe sample under reference had two elliptical holes within a distance of about
250 mm. These holes were located at the low lying areas, and at about 6 o'clock position. These
holes were of thin lip type, spreading along the longitudinal direction without any associated bulging
or any change in the dia. Besides these, the remaining surfce on the OD side was not corroded. Fig.
1 shows the appearance of the outside surface of the leaking pipe having two elliptical holes.

The inside surface of the damaged pipe was found to be covered With thick black wax. On
cleaning, no corrosion products/rust or wall thinning could be noticed at the wax covered upper
region. However, at the bottom segment of the pipe, close to the 6 o'clock position, shallow to deep
gauging type corrosion attack along the length of the line pipe was noticed on the ill surface.
Considerable reduction in the wall thickness had occurred at 6 0' clock position, forming a corrosion

458
459
Figs. 3 and 4 - Photographs of physical surface appearance of the cross section of the corroded
in the as polished condition showing intergranular attack.

4. MICROBIOLOGICAL ANALYSIS

A detailed metallurgical examination indicated that intense localised corrosion had occurred
due to the accumulation ofacids at the 6 o'clock position, particularly at low lying areas. Some
residual acids could be present after the well perforation operation or due to the in-situ generation
by the metabolic activities of micro organisms. The processing condition was checked from the
records and it was found that proper care was taken to neutralise the mineral acids used for well
maintenance/perforation. Therefore, detailed microbiological analyses of the produce water samples
collected from this pipe line and from the associated separator were carried out. The results are
summarised in Table 1.

460
 Table 1
Microbiological analyses of water samples collected from
ofT-shore crude oil pipe line (N lBHN) and BHN separater

Corrosion rate (nun/yr) of 5LX x 52 steel in 2% NaCI under identical condition of exposure
Was found to be 0.06 nun/yr

The produce water sample from the crude oil pipe line gave higher counts (82 x 103/ml) for
-=robic bacteria as compared to the separator water (47 x lQ3/ml). The aerobic heterotrophic bacteria
present in the produce water appeared to be of the gram positive spore former type. There were
twice as many anaerobic heterotrophs counts (9.1 x 103/ml) in the separator water sample as in the
water sample from the crude oil (4.5 x 103/ml). It may be mentioned here that several regions of the
pipe that handling produce water were affeCted at low lying areas forming holes similar to crude oil
pipe line.

The counts for the total sulphate reducers (SRB) also were higher (2.4 x 102/ml) in the
separator water sample than those in the water of the crude oil pipe line (1.3 x 102/ml). However,
die counts for spore forming desulfotomaculum orientics present in the sulphate reducers were not
measured. It is believed that under optimal anaerobic conditions in the area of stagnant flow in the
pipe line, the bacteria could germinate and produce organic acids with evolution of CO2. Although
110 bacterial analysis was conducted on the samples taken from the corroded pit, X-ray diffraction
.-lysis of the adhered deposit adjacent to the pit showed the exclusive presence of iron carbonate
(FeCo3)

5. CORROSION EXPERIMENTS

Some controlled corrosion experiments, such as anodic polarization, weight loss

measurements etc. were carried out in water samples collected from the crude oil pipe line in the
ICpCBtor water and in a 2% NaCI solution. The anodic polarization behaviour of the API 5LX 52
smJpIe material in the separator water showed a higher rate of increase in current density compared

461
to those corresponding to the water in crude oil and the 2% NaCI solution. After the anodic
polarization tests, samples were examined by optical microscopy. The samples exposed in the
separator water showed intense grain boundary attack, whereas the samples tested in the 2% NaCI
solution showed pitting without revealing grain boundaries. Similar results were obtained on samples
exposed in these three types of media for 12 days at 30C. The uniform corrosion rate was found to
be higher in the separator water than in the other two media.

6. DISCUSSIONS

The detailed metallurgical examination of the affected crude oil pipe line, the microbiological
analysis and the laboratory corrosion experiments clearly demonstrated that the produce water was
more corrosive than the other water (solution) of identical chemical composition (salinity). The
microbiological analysis confirmed the presence of heterotrophic bacteria of aerobic and anaerobic
thpes and a small amount of sulphate reducers (SRB) was also detected. The organic acid generated
by the metabolic activities of bacteria and the carbonic acid inherently present .in the low pH solution
at the stagnant area could result in isolated attack at the biofilm/deposit build up sites and possibly
at the surface imperfections.

The attack from the sulphate reducing bacteria (SRB) was at best secondary due to lack of
FeS in the pits. No microbiological analyses could be performed on the corrosion deposit and
therefore it was not possible to comment on which of the other two types of bacteria - anaerobic or
aerobic was primarily responsible for causing the localised attack. The aerobic bacteria were present
in large numbers and if these were attached to a biofilm colony, they would create anaerobic
conditions at the metal surface as they would use up the oxygen in the water. The metabolic activities
ofanearobic bacteria (sporformers) could produce organic acids, hydrogen and carbon dioxide and
these could be considered as plausible biological agents in the pitting process. The entire corrosive
action, however, was aggravated due to the occurance of stratified flow within the crude oil pipe
line.

7. CONCLUSIONS

a) The crude oil pipe line studied in the present investigation was affected primarily due
to the metabolic activities of microorganisms, although stratified flow and stagnancy
had aggravated the situation further.

b) The microbially induced organic acid under deposit attack in the crude oil pipe line
could best be controlled by a small (0.5 to 5ppm) doze ofbiosite.

8. ACKNOWLEDGEMENT

The author is grateful to Dr. C.K. Gupta, Director and Dr. S. Banerjee, Associate Diretor of
Materials Group, BARC, for their keen interest during the course of this investigation. The author
also wishes to thank Shri P.F. Anto, DGM (C&M), IEOT, ONGC for stimulating discussions and
suggestions during the progress of this investigation. Thanks are also due to Dr. S.P. Kale, Nuclear
Agrictural Division, BARC for his help in micro biological analyses.

462
 Failure Analysis of Subsea Water Injection
Pipeline Role of Deposits
A.K. Samant, V.K. Sharma, S. Thomas and P.F. Anto
Institute of Engineering and Ocean Technology,
Oil & Natural Gas Corporation Limited,
Panvel-410 221, New Mumbai, India

ABSTRACT

For enhanced recovery of oil, chemically treated sea water of desired quality is normally injected
in to well bore through pipe lines. One of the water injection pipe line of Western offshore of
India leaked due to rupture. Detailed failure investigation of this pipe line was carried out by
aoalysing the metallurgical environmental and operational aspects. Study revealed under deposit
conosion as major reason for failure of pipe line.

INTRODUCTION

A 5.48 Km long 14" diameter pipeline was commissioned in Western Offshore ofIndia during
1986 to deliver water of given quality to the injection well bore. The material of pipe line was
API 5LX-52 and wall thickness was 12.7 mm. Details are given in Table No.1. This pipeline has
ruptured after an operational life of nearly 10 years on 05-06-1995, Before rupture, the operating
2
pessureofthe line was 128 Kglcm The ruptured portion of this pipe line was recovered from
sea surface for detailed failure analysis (Figure - 1). Following studies have been carried out _

VISUAL EXAMINATION

The concrete coating was found to be intact except at location of rupture. Insignificant brownish
coloration was observed on the external surface of the pipeline after removal of concrete coating.
On the inner surface thick deposits were found mostly at 6 O'C position. Ruptured portion was
bmd, with significant wall thickness reduction and deep continuous channel, at 6 O'C
position. The wall thickness reduction was in the range of2.4 mm to 4.4 mm along the channel at
60'C clock position.

DEPOSIT ANALYSIS

Thick deposits from inner surface was scraped from different places & tested chemically. The

463
464
The pipeline steel exhibited finely dispersed carbides in the ferrite matrix. (Figure' - 2). The
microstructure of the cross section near the fracture surface showed elongation in ferrite grains as
a result of rupture. The examination revealed that, pipeline has a microstructure typical of low
carbon API 5LX 52 carbon steel. Inter granular / trans granular type of attack has also been
observed.

Tensile Testing :-

Tensile testing of the pipeline was carried out as per ASTM standard E 8M - 89 '. TIle yield and
tensile strengths of fractured pipe material came out to be 40.89 Kg/mm2 and 51.90 Kg/mm2
respectively. The values are within limits of API specification 5LX 52.

Hydl'ogcn Entrapment Evaluation Test :-

Two identical tensile testing specimens were prepared for hydrogen entrapment evaluation test to
tind out the possibility. of HIC (hydrogen induced cracking). One of the specimen was baked at
200"(' for 4 hours. Thl' sample was air cooled at the end of 4 hours. The samples were tensile
tested as per ASTM standard E 8M-89. Both the specimens showed approx. 40% elongation.
Thus hydrogen indljced cmcking is ruled out as the cause of failure in the present case.

CORROSION RATE MEASUREMENT

Grllvimetric Technique :-

Corrosion mte measurements by gravimetric studies had been carried out with the metal coupons
cut from the pipeline salJlplt~. The coupons were wet ground with 120 grit emery papers,
ultrasonically cleaned, rinsed with acetone and air dried. Then, the coupons were exposed to
injection water with varying concentration of oxygen under static and dynamic conditions

465
(Table - 2) These Studies confirmed higher corrosion rate with increasing concentration of
oxygen in dynamic conditions.

TABLE-2

CORROSION RATE STUmES ON PIPE LINE MATERIAL

MEDIUM : TREATED INJECTION WATER

TEST DURATION : 24 HOURS
MATERIAL : WATER INJECTION PIPE LINE PIECE
TEMPERATURE : 25C

Potentiodynamic Polarization Studies :-

For electrochemical polarisation studies, sample was immersed in treated injection water solution
for one hour so that the open circuit potential got stabilized. At the end of one hour, the sample
surface was scanned from -950 mV \V.r.t. Ecorr to -350 mV w.r.t. Ecorr. and Tafel plot obtained
(Figure - 3). All potentials were measured w.r.t. saturated calomel electrode (SCE). Graphite
electrodes were usep.as auxiliary electrode.

The Ecorr, lcorr and general corrosion rate of pipe material were found to be -590 m V: 16.89
mNcm2 and 7.5 mpy respectively. Thus, the corrosion rate of the pipeline material was found
slightly higher than the acceptable limits in normal condition.

MICROBIOLOGICAL STUIlIES

The treated water samples of pipeline was tested for presence of sulfate reducing bacteria (SRB)
and general aerobic bacteria (GAB) as per API RP - 38 procedure2 Simultaneously the analysis
rep0l1 of operators had also been examined. The results showed presence of both SRB and GAB
in water samples.

Analysis of corrosion product, collected from inner surface of pipe line piece also showed the
presence of iron sulphide, thereby confirming the activity of sulphate reducing bacteria (SRB).

466
Scanning electron microscopic studies also showed the presence of sulfate reducing bacteria in
the water samples after :malysing the biotilm developed on metal coupon surface (Figure 4) .For
this, metal coupon was exposed to water sample in anaerobic environment.

WATER INJECTION QUALITY

Various water quality parameters, like suspended solids, turbidity, dissolved oxygen, residual
sulphite, total iron~ sulphide etc. of this pipeline have been examined. The analysis revealed that
often concentration. of dissolved oxygen , suspended solids and iron counts were found more
than the specified limits. From this it is clear that water quality was not upto the mark and
parameters like suspended solids, dissolved oxygen, bacteria ctc, were more than the permissible
limits.

DISCUSSION

Examination of internal surface of failed pipe line piece showed lot of deposits on the inner
surface. At 6 O'C clock position, a straight continuous channel was found. The thickness
measurement showed wall thickness reduction from l4mm to less than 4.00 mm.

Material defects that can lead to premature failure of pipelines are microstructural anomalies,
variation in elemental composition, hardness and tensile strength. Various tests were carried out
to ascertain the ahove mentioned parameters of pipeline material. The tests confirmed the
material properties of the pipeline to be as per API standard 5LX grade 52. Thus, mat,erial defect
is ruled out as a cause of pipeline rupture.

467
Studies carried out by various workers 3,4 shows that insolublc suspended solids deposition in the
pipeline system accelerates corrosion rate due to bacterial activity and concentration cell
formation.

Under Deposit Corrosion :-

Deposit provides a hiding place for bacteria and also results in the formation of oxygen
concentration cells, which accelerate corrosion on metal surface below the deposit 5. Formation
of insoluble iron sulphide and ferric hydroxide can create water quality problem.

The activities of microbes in, around or under the deposit often result in the formation of organic
acids, inorganic acids, hydrogen sulphide, Carbon dioxide or other metabolic products. These
by-products when concentrated to high levels in and under the deposits, result in localised
corrosion. Sulphate reducing bacteria, which was present in the pipe line, perfonned their
metabolic activity 'and converted sulfate ions into hydrogen sulfide. The hydrogen sulfide
formed, reacted with metal and formed insoluble metallic sulfide.

Concentration Cell Fo."mation :-

Water quality data indicated that most of the time oxygen concentration was found more than the
specified limit of 20 ppb. Analysis of corrosion product also confirmed the presence of iron
oxide. From this it appears that oxygen was also one of the important factor which had
initiated/accelerated the corrosion in this pipe line. Oxygen concentration cells formed under and
near deposits accelerated internal corrosion of pipeline mostly at 6 O'C position.

Metal dissolution resulted in increase of positive charge (Fe++). At the same time migration
of chloride ions (negative charge) also occurred to increase in metal chloride concentration
beneath the deposits. The hydrolysis of metal chloride resulted in increased hydrogen ion
concentration which lowered the pH and led to faster corrosion of the metal. Sufficient
concentration of chloride was present in the water being pumped through this pipe line.

Effect Of Velocity :-

Low velocities proljl1ote deposition of solids and bacterial growth in the injection water line. A
minimum velocity of 1 m/s (3ft/s) is generally recommended 6. The flow velocity \n this pipe
line was less than 1.0 m/s most of the time. Simultaneously, due to non pigging of the pipe line
for long time, corrosion products and insoluble solid particles accumulated at the low lying area
within the pipeline. Because of this, Under deposits localised corrosion took place resulting in
thinning of pipeline. This low wall thickness caused rupture at an operating pressure of about
128 kg/cm2

468
 CONCLUSIONS

1) Visual inspection of the pipeline revealed significant intemal corrosion along 6 0' clock
position.
2) Various studies indicated pipe line material as per API 5LX-52 without any significant
metallurgical anomalies.
3) Under deposit corrosion and bacterial activity were found as major cause of failure of the
pipeline.
4) The reduced thickness due to internal under deposit corrosion caused split of pipeline at
2
an operatin[l pressure of about 128 kg/cm

REFERENCES

1. ASTM-E-8M-89, "Standard test methods jor tension testing of Metallic materials",

Sec. 3, Vol. 03.01, 1989, pp. 147-161
2. API. RP-38, " Recommended Practices", 3'd Edition, March 1982.
3. Agostini, R.A & Young, R.D., "Investigation of MIC in a West Texas Water Flood,"
Materials perfonnance, July 1994,
.4. Hanson, Dan. "Water line cleaning reduces corrosionfailures", Materials performance,
July 1994.
5. Pope, D.H. & Zintel, T.P., "Methods for investigating under deposit microbiologically
ir!/luencedcorrosion", Material Performance Nov. 1989, pp 46-51
6. Patton, C.C. ,"Corrosion control in water injection .!>ystem",Material performance,
Aug 1993, pp. 46-49.

ACKNOWLEDGEMENTS

The authors are thankful to Shri S.K. Singh,GGM & Head of mOT for his interest in the subject
and for giving permission for publication of this paper.

469
 Specification and Delivery Testing of
Duplex Stainless Steels
Pasi Kangas, Knut Tersmeden and Magnus Nystrom
AB Sandvik Steel,
SE-8l1 81 Sandviken, Sweden

ABSTRACT

Duplex stainless steels are becoming more and more frequently used in the industry. To ensure that mate-
rial that is purchased is of good quality, it is necessary to have a well worked out specification to the
manufacturer. The material properties of duplex stainless steels are dependent on many factors, such as
the basic chemical composition, manufacturing method and heat treatment. For a consistent quality it is
necessary to define measurable requirements that will ensure that the properties of the materials are ful-
filled. In this paper the properties of duplex stainless steels are reviewed. Various quality control tests for
these alloys are reviewed, and the applicability of these tests as well as requirements that should be met
for good performance are discussed.

It can be concluded that a lot of tests are possible for duplex stainless steels. Some of the tests are time
consuming and does not give much more information regarding the quality of a material compared to
other more easily performed tests. For new materials it is necessary to perform a wide range of tests to be
able to define the range of application and suitable requirements for delivery testing, whereas for already
established material where the properties of a good quality material is known, a limited and less time con-
suming test program is preferable. Some of th~ more time consuming tests should therefore be amended
or performed only as a prequalification test, "nd not as a repeated test of each new heat or order of a
certain grade.

Requirements for the duplex stainless steels SAF 2304, SAF 2205 and SAF 2507 are discussed, and
based on these requirements quality control programs to be used for these alloys are suggested.

INTRODUCTION

Duplex stainless steels are frequently used as materials of construction in the fertilizer and petrochemical
industry. To ensure a long and secure lifetime, a good quality material is essential. When a,duplex stain-
less steel is evaluated for its quality, various types of tests may be performed. The scope of this paper is
to present a test program that verifies a good quality material. Two levels of testing are suggested, one

470
more extended test program for new materials or as a qualification test for a mill, and one level with a
more limited amount of tests but sufficient to ensure that the material is of highest quality.

PROPERTIES OF DUPLEX STAINLESS STEEL

Chemical Composition and Standards

The nominal chemical composition of the duplex stainless steels SAF 2304, SAF 2205 and SAF 2507 are
shown in table I (1,2,3) Applicable standards are shown in table 2. The most widely spread system is
ASTMIASME's Unified Numbering System with applicable ASTMIASME specifications. For type 22Cr
duplex stainless steels (SAF 2205) there are two alternative UNS numbers. UNS S32205 is a narrowed
specification ofUNS S31803 which ensures improved corrosion properties.

Microstructure

A duplex stainless steel comprises of two phases, ferrite and austenite. The balance depends on the com-
position and the heat treatment. A high amoeat of ferrite will impair both the mechanical and the corro-
sion properties of the weld and HAZ. On the other hand a very low content will affect the resistance to
stress corrosion cracking in an negative way. Based on 30 years of manufacturing of modem duplex
stainless steels with good welding characteristics an optimal balance seems to be 40-45 vol-% ferrite and
the rest austenite. This is the target for the alloys in table 1.

Mechanical Properties

Owing to the very fine grained structure and the mixture offerrite and austenite, the mechanical strength
is very high. Table 4 shows the tensile and hardness properties for the duplex stainless steels SAF 2304,
SAF 2205 and SAF 2507. Minimum impact strength requirements are shown in table 5.

471
Corrosion

The duplex stainless steels have a high resistance to corrosion, especially in chloride containing environ-
ments. It is important to distinguish between material selection and testing of the selected material. For
selection of material for chloride containing environment special diagrams are available.

At the selection it is important to include a certain safety margin to allow for the effects in the fabrication
(mainly welding) but also from the typical variations in the process parameters. A small margin makes it
necessary to have a careful control of the material properties, which adds to the total costs. Testing of
material often means an accelerated test, with a 'rery severe environment to be able on shortest possible
time to classify a material as accepted or not accepted. The environments have often very little sirnilaritie!
with the actual service conditions.

472
Pitting corrosion

The pitting and crevice corrosion resistance is primarily determined by the content of chromium, molyb-
denum and nitrogen. The PRE formula (PRE = Pitting Resistance Equivalent = %Cr + 3,3x%Mo +
16x%N) is a common method to describe the resistance to pitting corrosion. The pitting resistance is
often tested by the modified ASTM G48A pitting test, which means immersion testing in 6% ferric chlo-
ride followed by weight loss determination and visual examination for pits. Acceptance criteria is that
there is no visual pitting at 20x magnification and that the maximum weight loss is 1,0 g/m2/24 h. The
minimum PRE values and maximum test temperatures in pitting corrosion and crevice corrosion testing
that should be met by the duplex grades are shown in table 6.

Table 6. Minimum PRE values, maximum test temperature in pitting corrosion test
according to the modified ASTM G48A (4) and maximum test temperature

Stress Corrosion Cracking

The resistance to stress corrosion cracking (SCe) in chloride environments and in environments contain-
ing hydrogen sulphide (H2S) is very good. Different test methods have been used over the years. Testing
in a modified ASTM G-36 solution, where 40% CaCh is used has been found to give best correlation

473
between test results and practical experience. Table 8 shows maximum allowed load without risk for SCC
in as test according to the modified ASTM G36 method (7), where 40% CaCh pH 6,5 at 100DC is used
as test media, and in a solution defined in the standard NACE TM 0177 (8). The SCC resistance depends
onthe basic composition and to a very little extent on the manufacturing process. Consequently there is
no need to test individual production lots for SCC properties. The manufacturer can provide basic test
results to verifY the properties. For selection of SCC resistant material special SCC diagrams are available

Table 8. Constant load testing of duplex stainless steels.

The table shows maximum allowed tensile (constant) load in percentage of actual tensile strength (Rm)
at lOODCwhen tested in 40% CaCh pH 6,5 at lOODCand in test according to NACE TM 0177.

Applications

The duplex stainless steels are used in a wide variety of applications. The materials possess good mecha-
nical strength, low thermal expansion and a high resistance to chloride induced corrosion. The alloys are
therefore very useful in applications such as heat exchangers in the process industry where cWorides are
present, in chemical and petrochemical plants and for oil and gas production.

DELIVERY TESTING OF DUPLEX STAINLESS STEELS

Once it is decided what mill will have the order, based on proven record and/or pre-qualification tests,
delivery testing and certification has to be done in order to ensure that the mill has a sustainable high
quality level. In ASTM A78'9 and 790 (9) standard specifications for seamless duplex stainless steels is
described. Some important requirements of this standard together with comments are listed below.

Chemical composition; Important in order to keep the balance between ferrite and austenite and to obtain
good PRE-values (Pitting Resistance Equivalent). Check the PRE-value, which is defined as:
PRE=%Cr+3,3%Mo+ 16%N. The following minimum PRE-values should be guaranteed to secure good
corrosion resistance; SAP 2304 ~ 24; duplex (SAP 2205) ~ 35; super duplex (SAP 2507) ~ 41. Limits for
chemical composition of various duplex grades are given in ASTM A789/790. For tubing often exposed
for the most severe conditions it is recommended to specifY a minimum PRE value to get best possible
corrosion resistance.

Tensile test; The tensile test is conducted in the axial direction of the tube and the report includes me-
chanical properties such as proof strength (RpO.2, Rp1.0), tensile strength (Rm) and elongation (A). In
addition, hardness tests are made. Typical guaranteed values are shown in Table 4. The tensile test gives
valuable information about the properties of the material. The hardness test is of lesser value as the
method is not really suited for tubes with a curved surface., specially for tubing with a small diameter.
The results tend to spread a lot and therefore it should not really be used as a rejection criteria.

474
Flattening test; This is basically a ductility test where a ring, cut from a pipe, is flattened to reveal any
inhomogeneities, cracks etc. in the material.

Hydrotest/Eddy current; In the hydrotest the pipe is filled with liquid and pressurised, thus any defects
penetrating the wall will be revealed. It is a simple method but will only detect pinhole defects through the
wall. Non-destructive electric tests like eddy current or ultra sonic testing can detect both external and
internal defects of the tube wall. The eddy current is an inductive test method which is a fast and reliable
method suited to replace the hydrostatic testing. For heat exchanger tubing and smaller pipe sizes eddy
current testing is nowadays the most frequently used method.

The above tests, combined with checks for good workmanship and not least a proper marking of the
pipes is usually enough to secure the quality of the delivered material.

SPECIAL DELIVERY TESTS FOR CERTAIN APPLICATIONS

When the tubing is used in certain applications, such as Oil&Gas applications, additional tests can be
made to further ensure the quality and performance of the material. Naturally, th~se tests add to the cost
of the pipe and the delivery time. In the following some examples of additional tests are shown together
with comments.

Microstructure; Ferrite content should be within the limits of table 1 to obtain a balance between good
corrosion resistance and mechanical properties. The ferrite content shall be determined by ferritescope
and/or by point counting according to ASTM E562 (10) or equivalent. Check for no substantial amounts
of inter metallic phases by way of micro-photographs at 400x magnification using a suitable etching tech-
mque.

Ultrasonic testing; A good method to detect small defects in the tube wall. The test method is slow and
the calibration is also time consuming making it more costly than eddy current. Thus it is only recommen-
ded for very demanding applications.

Corrosion, Pitting; Test according to the modified ASTM G48A method. This test serves as a good
evaluation of the corrosion properties. The Critical Pitting Temperature value (CPT) that should be
guaranteed for duplex stainless steels are: duplex (SAF 2205) ::2: 25C; super duplex (SAF 2507) ::2: 45C.

Intergranular corrosion; According to methods in ASTM A 262, see Table 7 above. Those tests are
made to guarantee that the material is not sensitised.

MILL QUALIFICATION TEST AND TEST OF NEW MATERIALS

When evaluating offers from different manufacturers, prior to purchase of piping, it is of course essential
to evaluate the overall capability of the manufacturer. A way to ensure the capability ofa manufacturer of
producing good quality material is of course to check its proven record of deliveries to relevant applica-
tions. If such a record is lacking, or judged not to be sufficient, pre-qualification testing may serve as a
substitute. In the following, additional tests to the ones described in the delivery test part are suggested
for inclusion in a mill pre-qualification test program;

475
Argon Oxygen Decarburization (ADD) method or equivalent; An important requirement that has to be
put on the manufacturer of the steel is that the steel melt shall be refined with AOD'or equivalent.

Stress corrosion cracking; in CaCI2-s01ution, modified ASTM G36 method.

Sulphide stress corrosion; Test according to NACE TM-OI77. Should only be used if the material is to
be used in a hydrogen sulphide (H2S) environment.

DISCUSSION

In this paper, material properties of duplex stainless steels have been presented together with suitable tes
methods and proposed pre-qualification and delivery testing program. Both manufacturer and customer
will benefit from reasonable and technically justified specifications and test programs. Valuable time and
money can be saved if the specification reflects the application and is focused on material properties,
rather than manufacturing routes. Furthermore, different mechanical tests and corrosion tests may overla
considerably and inclusion of a lot of test... in a specification may add only cost, not quality of informatiol
A good quality product is necessary to fully utilise the great potential of duplex stainless steels in variom
applications. Examples of easy ways to ensure such a good quality product are the PRE-value given by
the chemical composition and a microstructural check to avoid material with substantial amounts of in-
termetallic phases that may deteriorate the properties.

CONCLUSIONS

A good quality product is necessary to fully utilise the poten!ial of duplex stainless steels in various
applications.
Both manufacturer and customer will benefit from reasonable and technically justified specifications
and test programs.
A test program that secures the quality of duplex stainless steels has been suggested. For certain
applications a suggestion for an extended test program has been put forward, and for mills that have
never produced the alloys before, a suitable qualification test program is suggested.

REFERENCES

1. Sandvik data sheet S-1871-ENG, SAF 2304 September (1996).

2. Sandvik data sheet S-1874-ENG, SAF 2205 March (1997).
3. Sandvik data sheet S-1875-ENG, SAF 2507 February (1997).
4. ASTM Annual book of ASTM Standards, Volume 03.02, ASTM G48, (1997).
5. MTI Manual. Method MTI-2 for laboratory testing of wrought iron and nickel base alloys for
relative resistance to crevice corrosion in a standard ferric chloride solution.
6. ASTM Annual book of ASTM Standards Volume 01.03, ASTM A262-93a ..(1997).
7. P .Kangas, M. Nicholls, Chloride-induced stress corrosion cracking of duplex stainless steels.
Models, test methods and experience. Werkstoffe u. Corrosion 46, 354-365 (1995).
8. H.Eriksson, M.Nicholls, Testing and selection of duplex stainless steels for sour environments.
Sandvik R&D lecture S-33-44 ENG, April (1994).
9. ASTM Annual book of ASTM Standards Volume 01.01, ASTM A789, ASTM A790, (1997).
10. ASTM Annual Book of ASTM Standards Volume 03.01, ASTM E562, (1997).

476
 Corrosion Monitoring Studies by Electrochemical
Device in Non-Aqueous Hydrocarbon Systems
A. Jayaraman and R.C. Saxena
Indian Institute of Petroleum, Dehradun, India

ABSTRACT

Electrochemical technique is one among the few which provide reliable, accurate
and instantaneous corrosion rate data that can be used to judge the effectiveness of
suitable corrosion control measure. However, such techniques do not find applications in
the hydrocarbon industries because of high electrolytic resistance encountered in the non-
aqueous environment. An electrochemical probe which can be used to monitor corrosion
in hydrocarbon rich environment has already been reported in literature. Present studies
relate to the development of an electrochemical probe in the laboratory based on the
literature information The dielectric material needed to make the probe has been prepared
in the laboratory. Studies made with the probe containing phenol-formaldehyde resin as
the dielectric material indicated the necessity for chemical activation of the dielectric for
application in the hydrocarbon media. The probe has been used to monitor the corrosion
of carbon steel in sulpholane or N-methylpyrrolidone (NMP), which are used in extraction
units. Specific studies have also been carried out in order to find out the effectiveness of
corrosion inhibitors which are used in hydrocarbon rich media.

INTRODUCTION

Corrosion has always been one of the major problems in hydrocarbon industry[l].
Various corrosion control measures which include corrosion inhibitors are being used in
hydrocarbon industry [2-4]. Corrosion monitoring is invariably required to test and prove
operational reliability [5]. Electrochemical monitoring techniques are finding increased use
in corrosion research and engineering applications [6]. Although electrochemical
techniques have been limited to near ambient temperature aqueous corrosion studies in the
past, these techniques are now being used to high-temperature, high pressure aqueous
application as well as to the study of corrosion processes in non-aqueous environments
and aqueous environments oflow conductivity. Electrochemical technique is one among

477
the few which provide reliable, accurate and instantaneous corrosion rate data[7] that can
be used to judge the effectiveness of suitable corrosion control measure. Moreover, the
instantaneous monitoring by electrochemical technique can be used as control function for
the online monitoring of the health of the processing equipments. It has the added
advantage of discriminating various types of corrosion like uniform and localized
corrosion[5]. The advanced linear polarization system has recently become available as a
field tool. It will differentiate between types of corrosion and would be able to detect
under-deposit-corrosion as well[8]. However, such techniques do not find applications in
hydrocarbon industries because of high electrolytic resistance encountered in the non-
aqueous hydrocarbon environment. An electrochemical probe which can be used to
monitor corrosion in hydrocarbon rich environment, has already been reported in
literature[9,1O,]. The present studies relate to the development of an electrochemical
probe in the laboratory, based on the literature information. This electrochemical probe
has been used to measure instantaneous corrosion rates in non-aqueous hydrocarbon
media.

EXPERIMENTAL

Probe Design & Electrode Material

Corrosion being an electrochemical process, always requires electrodes in ionic

conduction path for monitoring purpose. During the selection of probe design, the probe
having three-electrode system was chosen. These three electrodes are separated using the
dielectric which embedded the three electrode system for proper configuration of
electrochemical probe. The material for these electrodes can be chosen from metals/alloys
of the hydrocarbon processing equipments for which corrosion monitoring is needed. For
present studies, mild steel is chosen as material of construction for electrodes.

Dielectric Material

The dielectric material required for separating three electrodes was prepared in the
laboratory. Initially, various adhesives and resins were studied for exploring a suitable
dielectric material. After extensive studies, phenol formaldehyde resin has been chosen as
the dielectric material which separates the electrodes in the probe. The criteria for
selection of phenol-formaldehyde resin as a dielectric material was its high ionic
conductivity(11]. In addition, it has got an excellent metal adhesion. The preparation. of
phenol-formaldehyde as dielectric material has been adopted from literature[12] with some
modifications such as three times reduction in quantity of sodium hydroxide which is used
as catalyst and increase in reflux time to 110-120 minutes. This reflux duration was found
to be very critical in the sense, at lower duration no polymerization occurs, whereas for a
larger duration the dielectric material solidifies in the reflux flask itself. The dielectric resin
when it is prepared is highly viscous and has to be filled immediately in the three electrode
configuration of probe. The electrode containing the dielectric resin was cured in an air
oven at temperature of 60-70C for a duration of 4 to 6 hours.

478
Corrosion Monitoring

For monitoring corrosion in non-aqueous media such as sulpholane and N-

methylpyrrolidone (NMP), The three electrode probe has been applied using centre
electrode as reference electrode and the ring electrode, surrounding the centre electrode as
the working electrode and the outer most ring electrode as auxiliary electrode.
For monitoring corrosion in hydrocarbon system viz. kerosene, the centre
electrode of the probe was used as working electrode. The concentric ring electrode which
is adjacent to the centre electrode was used as reference electrode and outer most ring
electrode as auxiliary electrode. Kerosene-distilled water mixture was continuously
stirrered with a mechanical stirring device at a rate of 1000 50 rpm, while the probe was
kept immersed for corrosion monitoring. The high speed of stirring in the hydrocarbon-
water system, enabled the uniform dispersion of water so that the dielectric material
became water wettable, hence the ionic conductance between the electrodes was possible.
The polarization of the working electrode in the corrosive media was carried out
using PARC, EG&G potentodynarnic scanning potentiostat model 362. Potential
logarithmic current curves were recorded at a scan rate of 5mv/sec, one hour after the
immersion in the corrosive system. The corrosion current values were obtained from linear
interpolation of cathodic and anodic potentiij.!-logarithmiccurrent curves, corresponding
to each experiment. The area of the working electrode was taken into consideration for
the current density calculations. The temperature of corrosive media during these
experiments was kept constant at 35 0.1 C, excepting for those experiments where the
effect of temperature on corrosion rates were determined.
In addition to above studies some specific studies have been carried out in order to
find the effectiveness of some organic corrosion inhibitors which are used in hydrocarbon
rich media such as naphtha. For evaluating the performance of these organic corrosion
inhibitors, naphtha-water system in the ratio of 98:2, acidified with hydrocWoric acid upto
a pH of 3.0, is maintained at 50C. For obtaining efficiencies of these corrosion inhibitors
the corrosion current densities were calculated by linear polarization resistance (LPR)
technique using electrochemical probe.

RESULTS AND DISCUSSION

Corrosion Monitoring in Sulpholane & N-Methylpyrrolidone

Corrosion problems have been reported in some petroleum refineries where

sulpholane in used for aromatic extraction unit[13]. Exploratory studies for corrosion
monitoring in sulpholane and NMP using electrochemical probe indicated that no chemical
activation of dielectric is needed for getting polarization data. The electric resistance
between working and reference electrodes of the probe in sulpholane at different
temperature are given in table - I.

479
480
Corrosion Monitoring in Kerosene

Attempt made to monitor corrosion in kerosene containing varying quantities of

distilled water without chemical activation of the dielectric material of the probe were not
successful. Among the total chemical etchants, used for chemical activation of the
dielectric surface of the probe, ION sodium hydroxide at 80 C for one hour caused
swelling and peeling up of dielectric material from the probe. But, chemical etching with 5
N sodium hydroxide - 7% hydrogen peroxide mixture for 15 minutes at ambient
temperature condition was found to be suitable in reducing the resistance of the dielectric
without causing any damage such as swelling and dislodging of the dielectric material.
Chemical activation of the dielectric surface of the probe resulted in reduction of its
electrical resistance by an order of magnitude.
Corrosion monitoring using the probe under aerated and deaerated conditions in
kerosene water mixture indicated five times reduction in corrosion current density under
deaerated condition. A typical polarization curve using the probe in kerosene water
mixture at 35 C (figure - 2) gave a corrosion rate of 0.3!!Ncm2 .

481
Corrosion Inhibition Monitoring in Hydrocarbon System

For monitoring corrosion inhibition in hydrocarbon system viz. naphtha, chemically

activated probe was exposed to naphtha-water system in the ratio of 98:2 acidified with
hydrochloric acid up to a pH 3.0, maintained at 50 C. Potentiallogarithrnic corrosion
current curves were recorded at a scan rate of 5mv/sec. one hour after the exposure in the
system for obtaining corrosion rate data for uninhibited system. Corrosion rate data were
obtained at identical conditions for naphtha containing various corrosion inhibitors in a
separate set of experiments. The corrosion inhibitor efficiencies, corresponding to various
corrosion inhibitors are given in table - 2.

Table-2: Inhibitor Efficiencies of Various Corrosion Inhibitors at 100 ppm in Naphtha-

Water (pH 3.0) System in the Ratio of98:2 Using Electrochemical Probe.

Inhibitors Efficiency, %
Prop argyl alcohol 70.5
Linoleic acid 80.2
I, 1-Diethyl prop argyl amine 90.8
I-Ethynyl cyclohexyl amine 97.1

While carrying out these inhibitor evaluation studies, it was observed that. an
increase in efficiency in a neutral medium may be achieved by prior acidification of
hydrocarbon phase containing an inhibitor[14].

SUMMARY

I. An electrochemical probe having three-electrode system separated by a dielectric

material has been developed in the laboratory.
2. The dielectric material, having high ionic conductivity and metal adhesion has been
prepared in the laboratory.
3. The probe embeded in the dielectric resin, was found to be useful without any further
chemical activation for monitoring corrosion in non-aqueous polar solvents like
sulpholane.
4. For monitoring corrosion in high resistance hydrocarbon-rich media, chemical
activation of the probe-surface is essential.
5. Chemical activation of probe-surface using sodium hydroxide - hydrogen peroxide at
ambient temperature conditions provided reproducible corrosion rate data for
hydrocarbon systems.

ACKNOWLEDGMENT

Authors wish to acknowledge the constant encouragement given by Dr. T.S.R.

Prasada Rao, Director, Indian Institute of Petroleum, Dehradun, during the course of
these studies and are thankful for his permission to present the studies at the conference

482
REFERENCES

1. Jayaraman, A, Neemla, KD., Saxena, R.e., Protection of Metals and Alloys in Oil
Refinery Processing Environment, Proc. International Conference on Energy,
Environment and Electrochemistry, Karaikudi, India, Feb. 1993.
2. Jayaraman, A, Saxena, R.e., Inhibitors in Hydrocarbon System, Paper No. 96221,
Corrosion /96, The NACE International Annual Conference and Exposition, USA,
Mar. 1996.
3. Neemla, KD., Saxena, R.C., Jayaraman, A, Studies on Corrosion Inhibitor for
Petroleum Pipelines, Proc. VIII Symposium on Lubricant-Additives and Petroleum
Speciality Products, lIT Mumbai, Feb. 1993.
4. Jayaraman, A, Neemla, KD., Saxena, R.e., The Control ofInternal Corrosion of
Petroleum Pipelines by Inhibitors, Corrosion Prevention & Control, Vol. 38, na. 5,
Oct. 1991. pp. 119-127.
5. Jayaraman, A, Saxena, R.e., Corrosion and its Control in Petroleum Refineries - a
review, Corrosion Prevention & Control, Vol. 42, no. 6, Dec. 1995. pp.123-131.
6. Scully, JR., Electrochemical Methods of Corrosion Testing, Metals Handbook Ninth
Edition, Vol. 13 Corrosion, ASM International, 1987. pp. 212-220.
7. Dawson, JL., Corrosion Monitoring Techniques, in Wanklyn J (ed.) Corrosion
Monitoring, Oyez Scientfic and Technical Services Ltd. England, 1982, pp. 15-27 ..
8. Murphy, C.J, Auxilliary Equipment Corrosion Focus of Refining Meeting, Oil & Gas
J, Vol. 92, no. 14, Apr. 4, 1994. pp. 62-66.
9. Jasinski, R.J, Efird, KD., Electrochemical Corrosion Measurements in Crude Oil,
Corrosion, Vol. 43, no. 8, Aug. 1987. pp. 476-478.
10. Jasinski, R.J., Efird, KD., Electrochemical Corrosion Probe for High Resistivity
Hydrocarbon/Water Mixtures, Corrosion, Vol. 44, no. 9, Sept. 1988. pp. 658-663.
11. Golding, B., Polymers and Resins, D. Van Nostrad Company Inc. USA, 1959. p. 119.
12. Vogel, AI., Practical Organic Chemistry, Longman, 1959. p. 1022.
13. Kumar Raj, Proc. Work Shop on Solvent Extraction Technologies Used in Petroleum
& Petrochemical Industries, Indian Institute of Petroleum, Dehradun, 1992.
14. Pospelov, M.v., Fokin, A.v., Corrosion Inhibitor Science and Technology Reviews,
in Raman, A, Labine;P., (eds.) NACE, Houston, USA 1993. p. 1-4-1.

483
 Insitu Chlorine Generation for Controlling
Biofouling of Offshore Structures
N. Palaniswamy\ P.F. Anto2, SVNSSS Rao2 and Anil Bhardwaj2
'Corrosion Science and Engineering Division,
Central Electrochemical Research Institute,
Karaikudi 630 006, Tamilnadu, India
21nstitute of Engineering and Ocean Technology,
ONGC Ltd., Panvel, Mumbai, India

ABSTRACT

Marine biofouling occurs where certain sedentary organisms ranging from simple
plants to animals attach themselves to underwater structures and affect their operation
and maintenance to varying degrees. Catt).odic protection is used to control the corosion
but at the same time it may also enhance the fouling load on structures. The creation of
interfacial alkalinity by cathodic protection favours the attachment of organisms. Removal
of fouling by normal cleaning methods is costly and time consuming. Commercially
available systems for controlling biofouling are copper based. In that process, copper is
dissolved and the toxic copper ions generated are utilized for controlling biofouling.

Insitu chlorine generation using electrochemical process is an emerging and

promising technique to control biofouling. Under a collaborative research programme
sponsored by the Institute of Engineering and Ocean Technology, ONGC, Panvel, CECRI
had evaluated the efficiency of insitu chlorine generation for controlling biofouling of
marine structures by carrying out model studies at Offshore Platform and Marine
Electrochemistry Centre(OPMEC), Tuticorin. The data generated through the study are
presented and discussed.

INTRODUCTION

Cathodic protection(CP), as the principal means of corrosion control for steel

structures under water in the offshore platforms, is well known and has been widely

484
used for many years. Equally well known is that cathodic protection can be applied by
using sacrificial anodes or alternatively by the impressed current method, or alternatively
again, by using a combination of both the methods in a manner generally known as
"Hybrid" system.

The fact that CP can accelerate macrofouling is yet to be appreciated fully. A role
for interfacial alkalinity in promoting calcareous skeletons of organisms was pointed out
by many research workers[1-4]. Hence, control of biofouling is necessary to minimize
the fouling load and the costly maintenance in a dynamic environment such as seawater.
The initial stage in the biofouling process is the attachment of bacteria and formation of
a slime layer with other microorganisms. These films are important for subsequent
attachment and developement of macrofouling growth. Therefore, it greatly increases
the structure load and enhances the microbial induced corrosion. Marine fouling occurs
when certain sedentary organisms, ranging from simple plants to animals, attach
themselves to underwater structures and affect their operation and maintenance to varying
degrees.

Several methods, such as manual cleaning, chlorination, electrolytic chlorination

and electrochemical protection systems have been employed for fouling control in closed
systems. The removal of biofouling from offshore platforms by normal manual cleaning
methods by employing divers is costly and time consuming.

Campbell[5] has demonstrated that the prevention of fouling induced corrosion

can be effected by chlorination of water. Goodman[6] has also reviewed the chemical
reactions of chlorination on materials in seawater. It was reported[7] that addition of
chlorine to seawater oxdises the bromide ions present in seawater to bromine and
consequently, the agent controlling the fouling is bromine rather than chlorine.

Cathodic protection is used to control corrosion, but at the same time it may also
enhance the fouling load on structures. The creation of interfacial alkalinity by CP favours
the attachment of organisms. Some of the products available in the market to avoid the
above problems are:

(i) A dual anode system is available from M/s.Jotun Cathodic Protection, USA which
is applicable to seawater storage tanks and associated pumping equipment and
pipelines. In this system, the entering seawater is treated electrolytically by means
of copper and aluminium or soft-iron anodes. As a result, a float is formed in
closely controlled quantities, and is carried throughout the system to effectively
prevent fouling and corrosion.

(ii) MIs. Wilson Walton of USA is another leading company in CP who is supplying
antifouling anodes based on copper and aluminium. Under the action of an
impressed current, the dissolution of these anodes leads to the formation of

485
 hydrated aluminium oxides and this is combined with the controlled release of
copper ions, which control/prevent fouling.

The above anodes can be used only in closed systems and cannot be used in
dynamic environment such as seawater.

(iii) Another system, called as "Scomet" in antifouling treatments, utilizes the ability of
copper alloy to impart resistance to marine fouling on a variety of substructure
materials. It has been established that this environmentally safe system is capable
of producing long-term, cost effective, fouling-free surfaces which require minimum
maintenance.

In the present investigation various types of anodes were evaluated in open

dynamic environment for their performance against corrosion and fouling control of marine
structures.

MATERIALS AND METHODS

The following experiments were planned and executed in order to evaluate various
types of anodes in open dynamic environment at OPMEC, Tuticorin.

1. Bare mild steel tube as control

2. Mild steel tube with aluminium alloy anode(Sacrificial)
3. Mild steel tube with aluminium and magnesium alloy anodes(Sacrificial- Dual
anodes)
4. Mild steel tube with aluminium alloy and TSI anodes(Hybrid)
5. Mild steel tube with cupronickel and aluminium anodes(biofouling)
6. Mild steel tube with TSI anode (biofouling)

The mild steel tubes used in these experiments were cylindrical type of 100 cm
length and 20 cm in dia. The specimens were fixed in wooden rafts as shown in Fig.1.
Anodes were fixed near to the mild steel tube in wooden rafts and electrical connections
were made for potential and current measurements. These rafts were immersed in natural
seawater at 2m depth from water level. The cathodes (MS tube) were polarised by
using the anodes described above. These studies were conducted over a period of 6
months. During the experimental period, a systematic monitoring of potential and current
flow has been carried out. Every 15 days the rafts were lifted up and the nature of
biofouling, species identification, thickness of fouling and extent of corrosion were
observed.

RESULTS AND DISCUSSION

The observations made during the exposure studies are given in Tables I & II.
The current density thus calculated are also given in Table I.

486
 It can be seen from Table I that the potential of mild steel immersed in natural
seawater is -670 mV Vs SCE. Mild steel has undergone severe corrosion and heavy
fouling. When mild steel was coupled with aluminium alloy anode, the protective potential
of mild steel shooted upto -900mV Vs SCE. Application of cathodic. protection with
aluminium anode also did not control biofouling.

The dual anode system Mg-A1 polarised the mild steel structure quickly to the
protective potential. There was also heavy fouling.

The hybrid system (impressed current/sacrificial) also elevated the structure

potential immediately to the protective potential. Further this system also resulted in
heavy biofouling. Fig 2.1 to 2.4 shows the fouling nature of specimens immersed in
seawater.

The cupronickel along with aluminium was used as a corrosion preventive as well
as a biofouling control system. But under dynamic wave action of sea water, the dissolved
copper and nickel did not adhere on to steel surface, so that their bicidal efficiency could
not be fully utilised.

Among the various systems evaluated the titanium anode generating chlorine
insitu was the best performer in corrosion protection as well as biofouling control as it
can be seen from Fig. 3&4. The structure showed a protective potential of -1100 to _
1300 mV Vs SCE. The anode showed a potential of +1300mV. At this potential, seawater
gets electrolysed and chlorine is generated at the anode.

The nacent chlorine produces hypochlorous acid which is unstable and forms
hypochlorite ions which are strong oxidants and toxic to marine organisms.

The generation of chlorine at +1300mV is a continuous electrochemical reaction.

It effectively prevents the attachment of marine organisms on steel structures submerged
in seawater.

Also the higher cathodic potential favours high alkalinity in the immediate vicinity
of the structure and facilitates calcareous deposites(Fig.5). Over steel surface the
calcareous deposite formation decreases the current consumption and it acts as a
protective barrier against natural sea water environment.

487
 So the insitu chlorine generation using Titanium anode is the most promising
system interms of corrosion as well as biofouling control.

CONCLUSION

1. Mild steel without CP undergoes severe fouling and corrosion.

2. As a sacrificial type dual anode system, AJ-Mganode induces rapid polarization

of the structure.

3. The full efficiency of cupronickel could not be realised.

4. Titanium anode exhibits superior performance interms of both corrosion protec-

tion and antifouling characteristics.

5. Insitu chlorine generation using Titanium anode is a viable field process for con-
trolling marine biofouling.

REFERENCES

1. Ashworth.V and Googan.C, Cathodic Protection, Ellis Horwood Limited, 1993.

2. Humble,R.A. Cathodic protection of steel in seawater with magnesium anodes,

Corrosion, VolA, 1948, P.358-370.

3. Laque.F.L , Marine corrosion: Caus13sand prevention, John wiley and sons,

Newyork, Toronto.

4. Wolfson.S.L, Hartt.W.H , Initial investigations of calcareous deposite formation

upon cathodic steel in seawater, Corrosion, Vo1.40. 1981, P. 78-76.

5. Campbell.I.M. and Seaie.N.K, Proc.Conf.on fouling and corrosion of metals in

seawater, Scottish Marine Biological Association, April-1982.

6. Goodman.P.D., Effect of chlorination on materials for sea water cooling systems

: a review of chemical reactions, Br.Corros.J., Vo1.No.22, 1987, P-56.

7. Oldfield, J.w and Todd.B, Desalination, Vol.38, 1981, p-233.

8. Gurrappa.l, Electrochemical prevention of corrosion and fouling - A review,

Corrosion prevention and fouling control, (VoI.43, No.2) 1996, P-48.

488
489
490
491
492
Proc. Int. Cont". on Corrosion CONCORN '97
December 3-6, Mumbai, India

High Temperature Corrosion Behavior and

Applications of Modern Superalloys
Larry D. Paull, Venkat R. Ishwarl and George Y. Lai2
IHaynes International, ]020 West Park Ave, Kokomo, IN 46904
2Welding Services, Inc. Atlanta, GA

Material properties are the key to success for many high temperature industrial processes. Chemical
resistance to the process environment (corrosion properties) along with structural and dimensional integrity
(mechanical properties) are required for materials of construction. This paper reviews several high
temperature industrial applications for modern superalloys. The demands placed on materials in each
application are reviewed. The properties of materials considered as candidates for construction of
equipment are also given. Matching material properties to the application is shown to be critical for
successful equipment operation.

Industrial heating, chemical processing, petroleum refining, and power generation applications are several
areas where modem superalloys are making significant contributions. The key corrosion properties in these
applications are resistance to oxidation, sulfidation, and molten salt attack (hot corrosion). Strength, creep,
and fatigue are the high temperature mechanical properties iliat must be considered. The proven success of
HAYNES HR-120, HR-160, 230, 556, 214, and 242 alloys in these applications are reviewed

INTRODUCTION

Today's high temperature processes can be demanding on materials of construction. These demands are
varied, depending on the specific application. When selecting a a material, one must consider mechanical
properties, physical properties, thermal stability, and environmental resistance. In addition, the material
must be able to be fabricated; welding, forming, and machining properties are also important. Table I
shows a few examples of material considerations for selected applications in the heat treatment, chemical
processing, petrochemical processing, and power generation industries. In order to achieve success, the
material selection process must include consideration of parameters like those shown in Table I, as well
any additional requirements.

Table 2 gives the chemical compositions of the materials considered in this paper. While most are nickel
base superalloys, we have also considered a few of the popular stainless steels for comparison purposes.

CORROSION BEHAVIOR

When metals are exposed to high temperature process environments, reactions can occur between the metal
and environment. Environmental attack can be generally classified into two categories: I) surface reactions
IJetween the metal and the environment, this results in a loss of metal thickness and the formation of a
surface scale and, 2) subsurface attack where a particular species in the environment diffuses into the
metal, this results in the formation of nonmetallic particles within the metal itself. Fi.gure I shows the
approach used to evaluate a material's resistance to an environment. When evaluating resistance to an

493
environment, it is essential to include an evaluation of internal attack, which results in a loss of mechanical
strength of the material and also can be a precursor of breakaway corrosion.

The type of reaction and the rate at which high temperature corrosionproceeds are primarily a function of
the environment, the material, and the temperature. Figure 2 shows the rates of attack for selected alloys in
flowing air at various temperatures. It should be noted that the exposure period for this test is one year;
longer exposure periods represent the alloy behavior better, since less extrapolation is required (1).
Oxidation rates initially become slower with time, as protective oxide scales are formed. This results in the
kinetics following a parabolic rate law for some period of time. After longer exposure periods, spalling
events or excessive internal attack can change the oxidation kinetics and breakaway oxidation may result.
Therefore, one must be careful when using short term oxidation data (i.e. less than 4000 hours).

The best oxidation resistant material is 214 alloy, which forms a protective scale containing Ah03 that is
very effective at slowing the rate of further oxidation. Rare earth additions, such as La, Zr, Y, and Ce,
have also been used, along with higher chromium concentrations, to enhance the oxidation resistance of
high temperature alloys; both 556 and 230 alloys are examples of these types of oxidation resistant
materials. It should be noted that 556 is not recommended for applications above IlOQ"C (2012F).

In atmospheres containing sulfur, alloys may be attacked by a process know as sulfidation. This is
analogous to oxidation. Figure 3 shows the sulfidation rates for selected alloys in a mildly sulfidizing
atmosphere. G.Y. Lai, et. al. studied the sulfidati~n behavior of several alloys (2). Their studies showed
that even in environments containing a low oxygen potential and high sulfur potential, alloys can form a
protective oxide scale that results in improved sulfidation resistance.

It is fairly well known that alloys with high nickel contents have generally poor sulfidation resistance (3).
At temperatures as low as 790C (1454F) nickel sulfides can become molten resulting in catastrophic
corrosion rates. Cobalt containing alloys are generally more resistant to sulfidation, HR-160 alloy and also
556 alloy are examples of these types of alloys. In the case ofHR-160 alloy, which has the best sulfidation
resistance among the alloys studied, a silicon rich chromium oxide scale was observed. In other alloys,
such as 800H alloy and 330 alloy, the higher rates of sulfidation attack are believed to be due to the rapid
growth of Fe-rich sulfides.

In atmospheres containing carbon, particularly in reducing environments, carburizatioo of an alloy can

occur. Species, such as ciL and CO, can effectively charge caIbon into an alloy. This results in
consumption of the alloy and loss of mechanical properties. Figure 4 shows die CaIbon absOrption of
selected alloys in a carburizing atmosphere.

Another common corrosive specie in many process environments is chlorine. There are numerous
compounds containing this element, usually as a chloride; HC1, NaCl, CH2Ch etc. Figure 5 shows the
corrosion rates of selected alloys in a chloride environment containing ZnCh. Generally, alloys with
higher nickel and cobalt contents perform better in chloride environments.

MECHANICAL PROPERTIES

A primary consideration in using superalloys in most applications is the load bearing capacity of the metal.
Designs use the yield strength of the material as a factor in determining the thickness of components. Table
3 shows the yield and ultimate tensile strengths for selected alloys. It can be seen that 230, 214, and 242
alloys have higher yield strengths than other materials; however, 214 alloy loses its strength advantage at
temperatures in excess of 900C (l652F), due to the dissolution of y' precipitates. In addition, HR-120
and 556 alloys have higher strengths than other iron base alloys.

494
 Another consideration in designing high temperature components is creep. Time dependent deformation of
materials (i.e. creep) causes sagging and warping of components and eventually leads to fracture. The
creep behavior of selected materials is shown in Figure 6. The creep properties here are presented as the
stress necessary to cause rupture in 1000 hours. It is clear from Figure 6, that creep properties must be
designed into a material, as there are a wide variance in creep properties among superalloys and other high
temperature alloys. Alloys 230 and 214 have the best resistance to creep, followed by alloys HR-120 and
556. Alloy 242 also has good creep properties, but due to its unique strengthening mechanism (long range
ordering), good mechanical properties are maintained only up to 7600e (I400F).

APPLICATION EXAMPLES

From the discussions presented earlier, it is evident that a systems approach for choosing the appropriate
material for a specific application is important. The material chosen should have the necessary resistance
to the specific environment(s) and the required mechanical and physical properties at the temperatures of
operation. In Table I is presented a broad categorization of different environmental, physical and
mechanical property requirements for a variety of high temperature industries.

In the heat treating industry, the common applications include heat treating baskets, retorts, muffles,
radiant tubes and wire mesh belts. HR-120 alloy is increasingly being used in these applications. In Figure
. 7 is shown an example ofHR-120 alloy corrugated boxes for carburizing. For applications that involve
temperatures above 10900e (2000F), 230 alloy is commonly being used. As mentioned earlier, 214 alloy
offers excellent oxidation resistance due to the formation of an adherent alumina scale. For the
manufacture of delicate chinaware, it is important that the material used to support the chinaware during
firing does not contaminate the chinaware. In Figure 8 is shown an example of a wire mesh belt of 214
alloy used in the manufacture of chinaware.

Many industrial environments are contaminated with sulfur, chlorine, and metals; HR-160 alloy has
provided excellent service in these dirty industrial environments. Figure 9 shows an example of a retort
made of HR-160 alloy used for removing lead zinc and cadmium from the exhaust from an electric arc
furnace. HR -160 alloy is also extremely resistant to reducing sulfur environments and has found
widespread use in this application.

In the high temperature chemical process industry, alloys such as HR-160, 556, HR-120 and 230 are
c:oounonly used depending upon the operating conditions. For calciners, where oxidation, suIfidation and
cb10ride resistance are important, HR -160, 556 and HR -120 alloys are commonly used. Vortex finders of
556 alloys are used in black liquor waste boilers. In a specific case, 556 alloy vortex finder replaced .
HASTELLOY@ X alloy due to premature failure of the X alloy. While the X alloy lasted only six months
in this service, the 556 alloy, even after one year of service, was still in good condition. The CQmbination
ofhigh strength and excellent sulfidation resistance of 556 alloy allowed this improved service. Heat
exchangers utilizing tubing of HR-160 alloy are increasingly being used in chemical plants to recover heat
from gases that are carburizing and suIfidizing. A specific example involves the use of HR -160 alloy heat
excbanger tubing operating at looooe (I 832F) in the presence of gases containing about 2%
hydrocarbons and 2% sulfur under reducing conditions. In this case, HR-160 alloy replaced 253 MA
which had prematurely failed; the HR -160 alloy tubing which has been in service for 5 years is expected to
last several more years. In the production of nitric acid, catalyst grid supports of230 alloy are used.
Figure 10 shows an example of 230 alloy nitric acid catalyst grid support; excellent strength and resistance
110 nitridation were important considerations in selecting 230 alloy.

495
In the power generation industry, such as flying and land base gas turbines, high temperature and fatigue
strength, and resistance to the hot combustion gases are important. In this industry, one of the premier
alloys used as combustor cans, transition ducts and hot gas housings is 230 alloy. Figure 11 shows an
example of a combustor can made of 230 alloy for a land base gas turbine. Honeycomb seals of 214 alloy
are commonly used in this industry due to the excellent oxidation resistance of this alloy. For nozzle casing
and turbine seals in sections of turbines, where the metal temperature is less than 700C (l300F), 242
alloy is finding increasing use. The low thermal expansion characteristics and excellent oxidation
resistance of 242 alloy make this alloy an excellent choice for these applications.

SUMMARY

The development of new and advanced high temperature processes are often limited by available materials.
To meet this demand, new superalloys have been developed and continue to be developed. Superalloys fill
a critical need when material strength and corrosion resistance are needed at elevated temperatures.
Matching the appropriate material to the application is essential for success in these applications. Material
selection can be a complex prOcess and may, at times, require testing the materials unqer actual field
conditions. In this paper, the environmental resistance characteristics and the mechanical properties of
several Ni-base, Co-base, and Fe-Ni-Cr superalloys are presented. Specific examples of the selection
criteria and use of some of these superalloys are discussed.

REFERENCES

1) M.A. Harper, J.E. Barnes, and G.Y. Lai, "Long-Term Oxidation Behavior of Selected High
Temperature Alloys", Paper 132, CORROSION/97, NACE, Houston, TX, 1997.

2) G.Y. Lai, IF. Norton, and F.G. Hodge, "The Corrosion Behavior of a New Sulfidation Resistant
Alloy in a Sulfidizing/Oxidizing/Carburizing Atmosphere", First International Conference on Heat
Resistant Materials, September 22-26, 1991, Wisconsin, USA.

3) G.Y. Lai, HiszhTemoerature Corrosion of Engineering Alloys. pp. 130-131, ASM, Metals Park,
OH, 1990 _

496
498
 Figure 1.
Schematic showing high
temperature corrosion attack.
It is important to consider the
internal penetration (caused
by diffusion) as well as metal
loss when evaluating high
temperature corrosion.

Figure 2.
High temperature oxidiation of
m
selected alloys still air at
temperature noted in figure.
Note that the exposure time is
one year (8760 hours).

Figure 3.
High temperature sulfidation of
selected alloys. The corrosion
was measured after 215 hours
exposure to an environment of
0.15%H2S + 5% CO2 +
1 % CO + 5% H2 + balance Ar.

499
 Figure 4..
High temperature carburization
(carbon absorption) of selected
alloys. Test conditions were 55
hour exposure in Ar + 5% H2 +
1% ClL at 982C (1800"F).

Figure 5.
High temperature chloride attack
of selected alloys. Test
conducted for 190 hours in a
mixture of 14% CO2 + 3.6 % O2
+ 0.25% S02 + balance N2
saturated with ZnCh (2.8 x 10-2
atmZnCh) at 538C (lOOOF).

Figure 6.
High temperature creep
properties of selected alloys.

500
501
Figure 11.
RAYNES 230 alloy gas turbine engine combustor.
502
Proc. Int. Cont on Corrosion CONCORN '97
December 3-6, Mumbai, India

Study of Hot Corrosion Behaviour of Superni 600

In Na2S04- V205 Environments
S.N. Tiwari and Satya Prakash
Metallurgical Engineering Department,
4niversity of Roorkee, Roorkee, India

ABSTRACT

In order to evaluate .high temperature Corrosion property

of Superni 600 (Inconel 600) in boiler and gas turbine
components, pure Na2S04 and Na2S04-V20S ,mixture were" coated on
the mirror polished specimens and then subjected to temperatures
700, 800, 900 and 1l000C under Cyclic Conditions. The Wt.change
plots were used to study corrosion kinetics and the scales formed
on the alloy surface were characterised using techniques:
Scanning Electron Microscopy (SEM), Energy Dispersive X-ray
Analysis (EDAX)iX-ray Diffractometry (XRD) and Electron
Microprobe Analysis (EPMA). Rapid rate of Wt. gam was observed
in the initial hours of the test and afterwards the rates
decreased. Industrial tests also behaved similarly. Maximum
rate of corrosion was observed in Na2S04-60% V20S and at 9000C.

INTROI>UCTION:

Hot Corrosion is a serious problem in energy generation

units like steam boilers and gas turbines(l). Vanadium, sodium
and sflfhur are common impurities 'present in low grade petroleum
fuels 2 Fe-, Ni-and Co-base super alloys are the commercial
alloys containing high Cr leading to a higher corrosion
resistance. Cr forms a protective oxide layer on the metal
surface and inhibits the onset of attack regfrdless of the hot
corrosion mechanism(3). Seiersten and Kofstad 4) studied Superni
600 under NaV03-V205 mixture and have found that the corrosion
rate increased w:rtliincrease in V~OS content. Bornstein and
(3) Goebel and Pettitb) .
DeCrescente ' have recommended var10US
fluxing mechanisms of the hot corrosion. Investigations have
been carried out on the hot corrosion of superalloys in various

503
environments at different tem~t1atures for various time periods
under loads or without loads Nickel base superalloys were
found to be superior than other alloys specially in Na2s04(7,S).
Pantony and Vasu (9) have explained the process of fire side
corrosi?n in boilers by dividing it in six stages, while
Kofstad 10) concluded that the corrosion process took place by
diffusion. Otero et.a!. (11) studied the IN 657 alloy in 60%
V -40% Na SO and have suggested that the corrosion occurs by
efe~trochemtcat process. Further investigation of hot corrosion
of Ni-base alloys in gas turbine and boiler atmosphere has been
carried out.
EXPERIMENTAL :

The alloy superni 600 was procured from Mishra Dhatu Nigam
Ltd., Hyderabad and had a chemical composition 10% Fe, 15.5% Cr,
0.6% Al., 0.5% Mo, 0.2% C, bal-Ni.'After polishing with 1200 grit
silicon carbide paper and wheel polishing with 1 p.m alumina
powder, the specimens were coated with Na2S04 and Na2so4-V205
mixture. They were subjected to hot corrosion at 700, SOO and
900C ,iA laboratory silicon carbide tube furnace and, also at
llQ-O()C,inthe actual boiler atmosphere at Bhilai Steel Plant,
B~~i ,under cyclic conditions. The Wt. gain values were
me.sured after each cycle for thermogravimetric studies and also
scales formed were characterised by X-ray diffractometry,
'scauni.c1'19
electron, microscopy, energy dispersive X-ray analysis
and "electron microprobe analysis.

RESULTS ANDDISCOSSION;
The weight gain values were plotted against the time
(expressed in no. of cycles) for the specimens of the alloy
(superni 600) corroded at different temperatures and are shown in
Fig. 1 and 2. The plot (Fig. 1) shows that thereis a rapid
increase in Wt. gain during the first two cycles and then the
rates decrease at all temperatures of test (700, SOO and 9000C).
In pure Na2so4 the total Wt. gain values were 0.21, 0.32 and 0.47
mg/cm2 at 700, SOO and 9000C respectively. These values show
tha~ the temperature has a significant effect on corrosion. The
values are very nominal indicating good corrosion resistance of
the alloy in Na2so4 environment at all temperatures. Similar
trend of Wt. change was observed with 15% V205-S5% Na2S04 coating
with the only difference that the values were higher than that
for pure Na2S04 This shows that the addition of V205 in the
salt mixture increases the corrosion rate.

504
 The values of total Wt. change of the specimens with
Na2S04-60% v20s coating were much 'higher (2.25, 2.85 and
11.s5mg/cm2) as compared to that for pure Na2So4 and Na2S04 - 15%
V20s Fr9m this observation, it can be inferreq that the
increase in V 205 content in the mixture increases the corrosion
rate. The corrosion process obeyed parabolic rate law during the
tests conducted at 11000c in boiler atmosphere. The overall
ranking of the alloys on Wt. change basis is 900 C> 8000c> 7000C~.
0

The various phases identified by XRD (Table-I, Fig. 3) in

the scales of specimens tested under pure Na2S04, environment
were Cr203, ~ -Fe203, Nicr204, NiO and CrS, while with Na2S04-ls%
V 00 Ni(VO) and
2 5 coating the additional phases FeV2 4' 3 2
(Cr,Fe)203 were also detected. The phases identified in
industrially tested specimens were Cr203, 04 Fe203, NiO, CrS,
FeV 204 and Ni (VO )2. Thus it can be inferred that the alloy
~ehaved very simi!arlY during laboratory and industrial tests.

The SEM photographs (Fig. 4,5) show that the nature of the
scales were fine grained at 700 and 8000c while it was porous,
and nonadherent at 9000C. The maximum rate of corrosion observe~
at 9000C in all atmospheres may be attributed to the molten state
of Na2so4 (m.p. 8840C) and NaV03 (m.p. 6l00c i as. sugges~ed bY
Shores and Luthra(12) that the presence of liquid phase is
regarded as necessary for hot corrision to occur.

A rapid increase in Wt. gains during the initial period

may be due to the direct contact of the corrosive species with
the alloy during which Cr might have formed Cr203 due to its
high affinity for oxygen and also due to its higher thermodynamic
stability as compared to other oxides(13). After the formation of
stable cr203 layer at the alloy/scale interface, the oxygen
diffusion becomes difficult, hence the corrosion rate decreased.
The oxidation of various elements present in the alloy also
occurred and hence the oxides have been identified byXRD and the
EDAX analysis 'indicated their presence in the scale. Some
sulphidation was also observed with Na2S04 coating as identified
as CrS by XRD.

With V20s addition to Na2S04, it was found that they might

have reacted together to form a liquid phase NaV03(m.p. 6l00C) as

505
506
508
509
follows:

Na2S04 + V20S -> NaV03(1) + S02+~02 (1)

..
The oxygen available from the above reaction might react with Cr
to form Cr203 due to its higher thermodynamic stability. The
fluxing of Cr203 with NaV03 might have taken place as suggested
by Seiersten and Kofstad(4) as follows: .
cr203 + 4NaV03(1) -> Na2Cr04 + V20S + 02 (2)

Later Na2Cr04 might have evaporated(14)# EPMA detected Na to be

absent.

In the case of Na2so4 - 60% V20S{lSmaximum corrosion

abserved may be due to the following reasons )
1. Molten salts act as the oxygen carrier,
2. Protective scale is destroyed and/or eliminated by molten
salts,
3. Melten salts provide rapid diffusion paths for the reactant
species.
Cracking of the scale consisting of coarse grained
heterogeneous mixture of oxides and spinels has been observed as
shown by the BSE image of EPMA (Fig. 6-9). Radhakrishnan
et.al. (16) have explained the high rate of oxidation by the
development of stresses in the thick layer of the scale causing
cracks and creating fissures that acted as channels from the
oxide/salt interface to the metal/oxide interface. The SEM
micrograph shows a crystalline structure at the surface of the
scale while a thick protective inner layer of cr203 is clearly
visible in EPMA X-ray map.

~he visual observation of the corroded specimens of the

alloy after exposure for 6 cycles (cycle of 24h. heating and 1 h.
cooling) at 11000C with Na2S04, Na2So4 - lS% V20S and Na2S04- 60%
V20S coatings in combustion gas atmosphere shows that the alioy
did not suffer severe corrosion. It can be inferred that the
alloy has good corrosion resistance in actual atmosphere as well
were it has to be used. The scales consist of oxides (cr203,
Fe203, NiO) and some suiphide (CrS) with Na2S04 coating. But
with Na SO - V20S mixture the spinel (Ni(V03), FeV
formatio~ his been revealed in the scales as ident~fted by tRd.
)
The X-ray maps of the cross section of the alloy reveal that the
top layer is rich in Fe203 while the inner layer is mainly cr203
Other elements are distributed intraces in both the ~ayers.

510
CONCLUSIONS:

Similar trend of Wt. change was observed in both

laboratory and industrial tests as follows :
Na S0 -60% V20S > Na2S04-lS% V20S > Pure Na2S04
2 4
The alloy has shown good corrosion resistance at all temperatures
and in all environments based on its lower Wt. gain values and
also the formation of thin compact protective layer of Cr203
occurred. The hot corrosion kinetics in industrial tests obeyed
parabolic rate law. The corrosion products were mostly oxides of
the various elements indicating that the oxidation played the
predominent role during the hot corrosion tests.

REFERENCES:

1. Prakash Satya and Tewari V .K., High Temp. Oxidation of

Metals and Alloys, QIP Short Term Course Prec., University
of Roorke, June 23 - July 7 (1992).
2. Hwang Y.S. and Rapp R.A., Corrosion Nace, 4S(11),
Nov.(1989),P. 933.
3. Rapp R.A. and Zhang Y.S., Jom, Dec.(1994), P. 47.

4. Seiersten M. and Kofstad P., High Temp. Techno!., 5(3),

Aug. (1987), P. 115.
5. Goebel J.A. and Pettit F.S., Met. Trans. 1, (1970), R 1943.

6. Swaminathan J, Raghavan S. and Ramakrishnan Iyer S.,

Trans. 11M, l46(3), June (1993), P. 175.

7. Levy M., Huie R., and Pettit F.S., Corrosion Nace, 45(8),
Aug. (1989), PP. 661-674.
8. Sidky P.S. and Hocking M.G. ,Corros. Sci., 21(5), (1987)
PP. 183-203. '
9. Pantony D.A. and Vasu K.1., J.Inorg.Chem. 30,(1968)1 PP.
423-432. '
10. Kofstad P., Microscopy of Oxidation, (Proc.Conf.), London,
U.K., March (1990), P~ 1-9.
11. Otero E, Pardo A, Hernaez Jpnd Perez F.J., Corros. Sci.,
30, (1990), P.677.

511
12. Shores D.A. and Luthra K.L. Proc.Conf. Corrosion-Erosion
Behaviour of Materials, K. Natesan (Ed.) (1980), P~ 86-102.
13. Saxena D., Effect of Zr and Y Addition on High Temp.
Sulphidation Behaviour of Fe-15Cf-4Al Alloy, Ph.D. Thesis,
University of Roorkee (1986).
14. Fryburg G.C., Kohl F.J. and Stearns C.A.,
J.Electrochem.Soc.,13(4), Dec. (1984), PP. 2985-2997.
15. Otero E. , Merina M.C. , Pardo A and Buitrago G ~,
Proc.Conf., Int. Conf. on Metallic'Corrosion, De~ (1987),
PP 3583-3591 .
16. Radhakrishnan V.M., Srinivasan R., and Das S., Proc.
Symp., SOLCEC, IGCAR, Kalpakkam, 22-24 Jan. (1997), P.C29.

512
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Corrosion in Railway Wagons:

An Unsolved Riddle
R.K. Upadhyay
Executive Director, Wagon Project, R.D.S.O. Lucknow, India

Abstract

While the old four wheeler coal wagons, used on Indian Railways, gave a s,!tisfactory life of
35 years, the new BOX and BOXN Wagons start having heavy corrosion damage within eight to ten
years. In the BOXN Wagons introduced in 1980s, the material was changed to Corten SteeL These
wagons showed heavy corrosion even earlier than BOX Wagons. Corten steel has been rejected by
wagons builders all over the world as it can not reportedly withstand combined action of abrasion,
corrosion and vibrations due to its weak and friable layer of corten oxide. This was also confirmed in
laboratory tests done in RDSO. But there is some contractictory evidence also. There is need to
develop better understanding of this problem.

Indian Railway has around 280791 wagons and carries around 405 million tons of originating
traffic to an average lead of 692 kms. The average codal life of wagon is 35 years. As long as the
4-wheeler wagons with 22.5 ton carrying capacity were in use, this codal life could be maintained.
With the arrival of the bogie wagons, like BOX wagons, in early 60s, heavy corrosion was noticed
within 10 years life. Most of the Box wagons had to be rebuilt or given repeated heavy corrosion
repair after 20 to 25 years of service. This had not become necessary with 4-wheeler wagons.

2. When the next generation BOXN wagons were introduced in early, 80's, an improved material
i.e. corten steel (0.3% copper, 0.4% Ni) was specified. Due to non-availability of corten steel in the
country, only 33% of the wagons could be made from Corten Steel.. However, it was found that the
corrosion sets in even earlier in these wagons. The age profile and corrosion location of 167 sample
wag~ns is given below:

513
 3. Further analysis showed that cases of corrosion repair to body are more numerous than floor
amongst wagons of similar vintage although floor .is subjected to greater abrasion but is well
supported. The average extent of corrosion damage to body sheets is about 5.0 sqm. (13%) and to
floor sheet around 9.0 sqm. (31 %) after 8-10 years of service. The nQmber of wagons needing body
repair after 8-10 years of service is higher but the extent of damage to the body (sides and end) is
limited. Maximum number of wagons were taken for floor repair at an average age life of 9 years
having extent of corrosion in two slabs namely (i) 3-5 sqm, (ii) above 18 sqm. Assuming the level of
utilisation to be uniform, the large difference could only be explained by the difference in commodities
these wagons were mostly carrying and the area in which they were operating. Some areas may be
having high sulphur coal or may be loading products like salts, fertilisers etc. Wagons operating in
coastal areas where the rainfall is heavy and the atmosphere has some degree of salinity, lend themselves
to corrosion rapidly. It could also be that wagons with less corrosion were of corten steel because the
wagons with very early corrosion were found to be of mild steel.

514
 The data show that corrosion damage to end panels is much less than the side panels among wagons
of similar age. This could be due to less sliding abrasion taking place on end panels during tippling.
The low corrosion life of modem wagons still could not be explained satisfactorily.

The matter was also referred to various World Railways and Wagon Builders. The South African
and Australian Railways as well as prominent wagons builders in USA confirmed that Corten Steel is
not suitable for coal wagons as the protective layer of corten oxide is very brittle and friable. Corten
steel, as wagon body construction material, was given up in these countries 15-20 years back.

4. To confirm this, tests were conducted in RDSO on samples of Mild Steel and Corten Steel for
checking the above. Two sets of steel samples were kept in brine chamber. In one set the scales were
brushed away after every 25 hours to simulate the abrasive action of loading and unloading. The loss
in weight due to corrosion was compared after 300 hours and the results are given below. The results
show that if scales are brushed away regularly, corten steel and mild steel become almost similar
otherwise corten steel has better corrosion resistance.

Without Brushing

Weight loss in Mild Steel after 260 hours =

.360 gm
Weight loss in Corten Steel after 260 hours = .180 gm

With wire Brushing after every 25 hours

Weight loss in mild steel after 300 hours = .840 gm

Weight loss in corten steel after 300 hours = .856 gm.

South African and Australian Railways had experimented with wagons made from 12%
chromium, 3CR12 steel and found that the life of the coal wagons had more than doubled. Since it is
only 15 years since they introduced those wagons, the exact expected life cannot be stated at
present.

515
 5. Based an South African findings, samples of 409M steel which also has 10.8% chromium were
checked in Research Designs & Standards Organisation Laboratory at Lucknow and the comparative
results are given below:

Resistance to Salt IRSM-41 409M

Resistance to Sulphur .0123 gm .002 gm
(Loss in mass per 1000 mm2) .071-.081 gm .047-.057 gm
RDSO/M&C Report No. K408.

Since 'the increased resistance of this steel to sulphur was not as high as for salt, the sulphur
content in Indian coal in the last 15 years was checked. It was found that the average sulphur content
of coal has not changed substantially in the last twen~y years and has remained around 0.5-0.7% in
the major coal fields.

6. The low corrosion life of BOX wagons could be due to introduction of mechanised hopper/payloader
loading and unloading by tipplers after 1960s. Due to heavy abrasive action the protective layer
continuously got rubbed off thus exposing fresh layer for sulphurous corrosion.

7. The earlier corrosion of BOXN wagon compared to BOX wagons could also be explained by the
fact that average wagon utilisation has almost doubled in last 15 years. Also the number of tipplers
and pay loaders had also increased by 57% in last fifteen years. Thus making mechanised loading and
unloading as the primary means of coal handling.

8. While the BOX and BOXN wagons are vertically rectangular wagons, there is yet another popular
wagon for carrying coal i.e. Hopper Wagon which has slant end pannel and bottom discharge doors.
It has been seen in India that the corrosion in this type of wagon is much lower than BOX/BOXN
wagons. Although in the end panel coal slides as much as in the side walls of BOX wagons yet little
corrosion is seen on inclined end panel. Similarly corten steel, which has been given up all over the
world, showed very good results in an experimental coal hopper wagon made in USA where half the
wagon was made of mild steel and other half of corten steel. The result's of this corrosion has ''lken
from the paper of Mr. BJ. Kelly are given below:

516
 Weight Losses of Hopper Car Sheets
(After 11 To 13.5 Years of Service)
(Average Weight Loss Per Year of Service in LBS)

Name of the Part Copper Steel Corten Steel Ratio

1. Side Slope Sheet 18.5 8.6 2.15

2. Cross Ridge Sheet 7.0 3.7 1.91
3. Inside Hopper Sheet 2.5 1.6 1.56
4. Outside Hopper Sheet 3.6 1.8 2.0
5. Centre Side Sheet 6.7 3.4 1.97
6. Intermediate Side Sheet 9.1 2.1 4.33
7. End Sheet 1.4 0.7 2.0

N.B: Extracted from the paper 'Corrosion of Rail Road Hopper Car Body Sheets' by 8.J.
Kelly.

9. From the above it may be seen that the advantage of the corten steel was maximum in Item 1
and Item 6 which are sliding surfaces and thus subjected to abrasion.

This again is a very surprising finding which is very contradictory to world opinion. An abstract of
letter from Mis Trinity Industry is reproduced below:

"Corten performs as claimed when used for stationary objects not subject to vibration or abrasion,
such as buildings, sculpture etc. When used in coal wagons an accelerated corrosion however occurs.
Due to abrasion of coal during repeated loading unloading combined with vibration and flexing of
wagon body and moisture, the surface layer is removed.

I have actually seen on a number of occasions, door sized sheets of rust complete with flanges and
bends, coming out of wagon upon opening. I have encountered door pans having as many as ten
distinguishable layers of corrosion."

10. Therefore, in spite of intensive research, the following points cannot be satisfactorily
eXplained:

(I) Why hopper wagons show less corrosion than BOXIBOXN wagons inspite of similar mechanised
loading and unloading by sliding?

517
 (2) Why the corrosion in similar wagons vary so drastically from wagon to wagon.

(3) If sulphur in coal is responsibly for early corrosion of BOX and BOXN wagon, the same should
have also corroded coal carrying 4 wheeler wagons.

(4) In wagons made in India. substantially difference in life is found in wagons made in various
years say for example wagons made in 1974 may be much superior to wagons made in 1979.

II. Since no satisfactory explanation could be found for the above points the matter is left for the
house to give its opinion.

518
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

A Study of Corrosion in a Cement ~Iant

A. Wright!, B. Verity2, P. Heggen3 and C. Subramanian!
lIan Wark Research Institute, Universityof South Australia, Levels, S.A. 5095, Australia
2Schoolof Chemical Technology, Universityof South Australia, Levels, S.A. 5095, Australia.
3AdelaideBrighton Cement Ltd, Birkennead,S.A. 5015, Australia
ABSTRACT

A study has been undertaken to investigate the corrosion problems in the steel ductwork and process
vessels of a cement plant in Australia. The equipment concerned is in two sections, 4A and 4B, each
comprising a raw mill, electrostatic precipitator (ESP) and stack. While severe corrosion has occurred
in one section (4B), there has been little or no corrosion in the other section (4A). One of the primary .
aims of the study was to identify the reasons for such a discrimination. The corrosive species involved
were determined by analysing the dusts and scales found inside the plant, using a Scanning Electron
Microscope with Energy Dispersive Spectroscopy (SEM-EDS) and X-Ray Diffraction (XRD), and
condensates collected from the plant, using Inductively Coupled Plasma Spectroscopy (ICPS), Ion
Chromatography (IC) and Atomic Absorption Spectroscopy (AAS).

It was found that HCl(g), originating from the chloride in the kiln feed, was the corrosive. gas that
attacked the internal surfaces, on condensation at 50.to 70.C. The HCl was converted to CaCh on the
wall. surfaces by the reaction of HCl and the major component of the kiln feed, CaC03. The CaCh
solution caused severe pitting of the internal surfaces. This was confirmed by the chloride levels found
on the internal surfaces and the ionic compOsition of the condensates collected. The corrosion products
formed (Fe304, y-FeOOH, a-FeOOH, ~-FeOOH and y-FeOOH) also suggested that the surface was
attacked by a salt solution by a mechanism similar to that of atmospheric attack by a salt solution.
Although there was no significant difference in the flue gas conditions and compositions between the
two sections, the severe corrosion in the B side was due to the differences in the design of the two
sections - higher temperature and greater dust loading in the 4A stack due to the addition of hot waste
gases from the clinker cooler.

1 INTRODUCTION
The Birkenhead Cement Plant in Adelaide (South Australia), owned and operated b.y Adelaide Brighton
Cement Ltd, produces cement and cement clinker for local and interstate markets. Prior to 1990.,the
plant consisted of a dry process plant (the 4A side) and a wet process plant. 1n a $120.million upgrade
in 1990.-91,the wet process kilns (of 600 tonne/day capacity) were shut down and the dry process kiln
upgraded from a standard dry rotary kiln to a precalcining type. A new half of the plant was
constructed (4B side), incorporating a calciner, second set of preheaters and a kiln feed manufacturing
facility to aid the old dry process plant (4A side). This upgrade increased the plant capacity from 1800
to 4200 tonnes/day and reduced the amount of fuel used in clinker production.

In the current configuration, the raw materials (limestone, shale and ironstone) are fed into two roller
mills that grind them to a 90.11msize fraction. The exhaust gases carry the kiln feed dust upwards into
the mill classifier where the coarse particles settle back down into the mill and the fine particles are

519
carried up into the electrostatic precipitator!>(ESPs). The gas temperature in the ESPs is maintained
below 150C by the cooling towers to ensure efficient collection of the feed. This powdered feed is
preheated and precalcined by the preheater exhaust gases before entering a kiln where it is sintered.
The output from the kiln (clinker) is cooled in a grate cooler from 1300 to 150C by spraying water
and blowing air through the clinker. The cold clinkeris stockpiled for shipment or milled into cement.
The ESP attached to the cooler takes up waste gases from the cooler for cleaning. Another source of
gases is from a bypass system used at the kiln entrance to maintain chloride levels below 1.0%. The
output from the ESPs is ducted into the stacks for final dispersion into the atmosphere.

The raw mills are regularly taken off-line for maintenance and this has the effect of increasing the
temperatures of the gases in the process. Occasionally the plant is shut down and the plant structure
then cools to ambient temperature. During the upgrade in 1990-91, the 4A mild steel stack was
replaced with a 3CR12 stainless steel stack. The apparent corrosion resistance of the3CR12 stainless
steel resulted in it being used in the construction of the kiln feed manufacturing facility and stack for
the 4B side (refer to Figure 1). Within 2 years of operation of the new 4B side, it was observed that the
feed manufacturing facility and the stack of the 4B side had suffered greater pitting corrosion than that
of the 4A side for the same period. The 4B stack and ESP were replaced in M:ay 1996. Thus the aims
of this corrosion study were to
determine the corrosive agents and mechanism of corrosion of 3CR12
determine why the 4B side suffered more-severe corrosion than the 4A side.

2 ANALYSIS

The different parts of the plant were analysed for gas conditions and compositions of the gases and
condensates. The flue gas conditions in the plant, relative humidity and flow were measured using
vane anemometer, manometer and relative humidity probe. Analysis of the gas composition was
conducted by an outside contractor and by using a TESTO 350 analysis unit to find HCl, HF, SOx,02,
NOx, CO and C02 contents [1]. The condensate compositions (anions and cations) were ass~ssed using
Inductively Coupled Plasma Spectroscopy (ICPS), Ion Chromatography (IC) and Atomic Absorption
Spectroscopy (AAS).

Samples (100 mm x 190 mm) were taken along the length of the 4B stack as it was replaced and also
from the duct work. Examinations of the pit structure, scale features and composition of these samples
were carried out using stereomicroscopy, optical microscopy and scanning electron microscopy with
energy dispersive x-ray spectroscopy (SEM-EDS). Samples of the scale and dust from. the internal
surfaces were also collected. These samples were dried and ground, and examined by SEM-EDS and
X-Ray Diffraction (XRD).

3 RESULTS

3.1 Condensate Analysis .

The internal wall temperatures of the stacks during normal operation were calculated (from the easured
external wall temperatures and the heat transfer coefficients of the steel) to be 70-100 C for the 4A
stack and 30-80 C for the 4B stack. It was found that there was generally condensation on the inside
walls of the 4B stack but not on the 4A stack, depending on the operating conditions. There were
condensates in hoth ESPs. Table 1 shows the pH and levels of major ions present in the condensates
collected at various locations in the plant. In general, the compositions of the condensates varied

521
widely, depending on where and when the samples were collected in the plant operation cycle (e.g.
immediately after a shutdown). The 4A ESP condensates collected over a number of weeks of normal
operation of the plant contained greater amounts of chloride than the condensate obtained from the 4B
stack (which decreased with time after a shutdown). The condensate taken from the base of the 4B
stack was collected during a shutdown when large amounts of salts that had built up on the stack waIls
were washed down to the base. The low pH and high chloride levels of this solution meant that it
would be very corrosive.

The presence of N03- and S042- were from the absorption of NOx and SOx by the condensate, forming
HN03 and H2S04. The levels of these anions were very low compared to those of chloride. The
dominant cation in all of the condensates collected from the stacks was Ca2+. The condensates
collected from the preheater exit contained very high chloride levels and low pH, with low
concentrations of Ca2+; the main cation present in these condensates was H+.

3.2 Gas Analysis

The levels of HF and S02/S03 in the plant (Table 2) could 'be considered to be too low for significant
corrosion. The 4B stack gases had significantly higher HCl readings than either the 4A stack or the 4B
ESP gases (38 compared to 12 and 10 ppm). The greatest levels of HCl were in the clinker cooler ESP
exit gases (61 ppm). The HCl originated from the volatilisation of salts present in the kiln feed which
then reacted with the flue gases inside the preheaters [2]. The water sprays used to cool the clinker
were another possible source of HC!.

The levels of moisture were significantly higher in the 4B stack compared to the 4A stack, indicating
that condensation was more likely in the former. The higher NOx levels measured in the 4A side were
due to the feeding of exhaust gases from the kiln burner into this side.

522
13 Flue Gas Conditions
There was negligible difference between the gas temperatures and moisture contents (the relative
bmnidities) of the main ESP's (Table 3). There was a lower exit gas flow (indicated by the pressure
change) from the 4A ESP than from the 4B ESP. Due to the clinker cooler and bypass ESP exit gases
feeding into the 4A stack, the 4A stack gas temperatures and flows were greater than the 4B stack and
therefore less condensation occurred in the 4A stack.

3.4 Ambient Conditions

The 4B ESP was more exposed to the prevailing winds than the 4A ESP (Table 4) as the latter was
wedged between two buildings and other structures and its only exposed side was heated by the kiln.
For the 4B ESP, the prevailing winds blew directly onto the ESP access doors which may have caused
ingress of air. The 4A stack was more exposed to the weather than the 4B stack which was sheltered
and heated by the precalciner and the preheaters in the adjacent tower.

3.5 MicroscopicAnalysis of 4B Stack Walls

The microscopic examination of the 4B stack walls revealed that th~ scale formed on the 3CRl2
substrate was cracked, porous and of non-uniform composition and surface coverage. The walls were
heavily pitted with wide and shallow pits, comprising smaller elliptical, deep and narrow, or sub
surface pits. The number of pits in the wall decreased towards the top of the stack, but the size of the
pits increased. The reinforcing plating (mild s'teel) exhibited similar features, but the scale was more
uniform in composition and larger pits had formed.

SEM-EDS examination of the cross sections of the 4B stack walls found that the scale contained either
Cr or Fe. Evidently, the levels of chromium in the metal were too low to cover the surface with
cbromia (Cr203). Thus, the next most active element (iron) was substituted in the scale. In all the

523
scales, CI was observed with Ca (from kiln feed dust that had reacted with condensates). The Si
measured was from dusts or the metal composition (1%). In the cracks of some scale samples,
chlorides'had built up as crystalline deposits, and these are characteristic of dew point corrosion by HCI
[3]. No other corrosive agents (I and S) could be detected.

Samples of the scale and dust taken along the length of the 4B stack were also ground into powders and
analysed by SEM-EDS. These analyses also indicated high levels of Fe ~nd Cr (from corrosion of the
3CR12) in addition to Al and Ca (from kiln feed dusts). There were higher Cllevels in the scale and
dust at the top and middle of the stack, e.g. at the top of the stack, the scale contained 4% Cl and this
decreased to 0.18% at the base.

There were high levels of CI in the scale and dust samples taken throughout the rest of the plant, with
the highest being in the dust found on the 4A ESP doors and 4B ESP exit structure (10%) where
condensation had trapped the salts. In the dust from the top of the 4A stack, the CI level was only 2%.
The levels of S throughout the plant were either lower than CI (0.29 - 0.26%) or unmeasurable.

3.6 XRD Analysis

The solid phases identified by XRD are listed in Table 5. The main corrosion product in the scales
examined was haematite (Fe203) with the more protective goethite (a-FeOOH) present if! smaller
quantities [4]. Other oxides that could protect the surface against further dew point corrosion such as
chromium oxides (Cr203 and Cr03) and lepidocrocite (y-FeOOH) [5] were not found to the same
extent. The presence of iron hydroxide (Fe(OHh), lepidocrocite and akaganetite (~-FeOOH), although
in small amounts, indicated that corrosion was probably from a chloride solution [6]. There were no
ferrous sulfates, consistent with the low sax levels and further.ruling out condensation of H2S04 as the
corrosion mechanism.

4 DISCUSSION
From the analyses reported above, it can be concluded that the levels of S02 and S03 were insufficient
to cause S02/S03 dew point corrosion. But there was a relationship between the corrosion observed
and the levels of HCI in the gases: the 4B stack and ESP suffered severe corrosion and had higher
levels of HCI in their flue gases. Hence, it is proposed that the mechanism of corrosion is HCI dew
point condensation, and that the different amounts of condensation on the two sides .of the plant account
for the different rates of corrosion observed.

524
525
 increased availability of 02(g). The lepidocrocite will subsequently be dehydrated to haematite; as
mentioned above.

There were no significant differences in the gas properties or consensate compositions in various parts
of the plant. Hence the differences in corrosion behaviour have been ascribed to physical differences in
the plant. The clinker cooler ESP and 4A stack did not suffer severe corrosion because their high gas
temperatures maintained their wall temperatures above the dew point for HCI. On the other hand, the
4B stack suffered severe corrosion because the flue gas temperature in it was just below the HCI dew
point.

5 CONCLUSIONS
I. The corrosion of the steel in the cement plant has been ascribed to dew point corrosion by HCI.
. The HCI is produced from the heating of the kiln feed in the kiln and clinker cooler.
2. When the HCI condenses with water on the plant walls, it reacts with CaC03 in the kiln feed dust
to produce a condensate which is an aqueous solution of CaCIz.
3. The major factor which caused the different corrosion rates in different parts of the plant was the
temperature of the gas. This led to different rates of, condensation and hence of dew point
corrosion by HCI.
.4. The temperature of the 4A stack is significantly higher than that of the 4B stack due to plant
design, hence the 4A stack is less susceptible to corrosion.
5. The temperatures in sections of the 4B ESP were lower than those in the 4A ESP because of more
complex ductwork, leading to slower gas flow and more opportunities for ingress of cold air from
outside, hence the 4B ESP suffered more severe corrosion
6. Irregular interruptions to the operating process cause a drying-wetting cycle which exacerbates
the corrosion.

REFERENCES
1. Lapans, D., AMDEL report on miscellaneous testing of stacks (1996).
2. Thurlow, G.G., An air cooled metal probe for the investigation of the corrosive nature of boiler flue
gases, J. Inst. Fuel, 25 (1952) 252 - 255.
3. Holmes, D.R. (ed.), Dewpoint Corrosion, First Edition, Ellis Horwood, Chischester (UK) (1985).
4. Stratmann, M. and Hoffmann, K., In situ Mossbauer spectroscopic study of reactions with rust
layers, Corrosion Science, 29 (1989) 1329 - 1352.
5. Misawa, T., Asami, K., Shimodaria, K. and Shimodaira, S., The mechanism of atmospheric rusting
and the protective amorphous rust on low alloy steel, Corrosion Science, 14 (1974) 279 - 289.
6. Refait, Rezel, D. and Genin, J.M.R., The corrosion products of iron specific to the chloride
containing aqueous media, Proc. Conf Progress in the Understanding and Prevention of Corrosion,
vol. 2 (1993) 1122 - 1128.
7. Stratmann, M. and Streckel, H., On the atmospheric corrosion of metals which are covered with thin
electrolytic layers, Corrosion Science, 30 (1990) 681 - 734.
8. Craig, B.D. (ed.), Handbook of corrosion data, ASM International (1989)
9. Masic, S., Gotic, M. and Popvic, S., X-ray diffraction and FTIR analysis of the rust formed. by
corrosion of steel in aqueous conditions, J. Materia/Science, 28 (1993) 5744-5752.
IO.ASM Metals Handbook, vol. 13 - Corrosion, 9th edition, (1987), 511.
I1.Evans, U.R. and Taylor, C.A. J., Mechanism of atmospheric rusting, Corrosion Science, 12 (1972)
227 - 246.
12. Jansen, P., Hansen, V. and Jensen, T., Corrosion experience with carbon steel in spray absorption
FGD plant, Werkstoffe und Korrosion, 43 (1992) 310 - 315.

526
 Atmospheric Corrosion of Steel by the
Exposure Test Avoiding Rain
Masahiro Yamamoto1, Kazuhiro Masuda1,
Hiroshi Kihira1 and Takashi Tsuzuki2
'Steel Research Laboratories Technical Development Bureau,
Nippon Steel Corporation,
20-1 Shintomi Futtsu Chiba 293 Japan
2Nagoya Works Nippon Steel Corporation,
5-3 Tokai cho ITokai Aichi 476 Japan

ABSTRACT
Weathering steel has been widely used in many structures for its good
corrosion resistl;lnce in unpainted usage. The reason is that a dense and tig~t rust
layer is formed on the surface of weathering steel during a long service life. It is,
however, known that such a protective rust layer can not be created in the case of
usage at the seaside area. Especially, corrosion of the inside of the structure was more
severe than of the outside. It is estimated that the difference is caused by the washing
effect of rain.
Sheltered exposure stands have, therefore, been utilized to clarify the effects of
rain. Mild steel and weathering steel samples were exposed at the six weathering sites
having various sea salt amounts in the atmosphere. The results of five years of
exposure tests show that the amounts of corrosion were higher in the case of
sheltered exposure tests than for ordinary exposure tests. Furthermore, the
difference of the amounts of corrosion in the two types of exposure tests increased, as
the amounts of chloride in the atmosphere increased. The samples corroded in the
sheltered exposure tests accumulated more chloride ions than those in the ordinary
exposure tests. The amounts of chloride ions on the samples at the sheltered exposure
tests were accumulated without the effect of washing by rain. This accumulation of
sea salt accelerates the corrosion rates in both mild steel and weathering steel. It is,
therefore, realized that the portion of the seaside structure where the washing effect
is not formed by rain is an extremely severe corrosion environme~t. Furthermore, it
is also found that the modified weathering steel has better corrosion resistance in
such a severe environment.
Key words: atmospheric corrosion, weathering steel, outdoor exposure test, sea salt

I. INTRODUCTION
Weathering steel has been widely used for various steel structures such as bridges, buildings and
so on. Especially, its unpainted usage is a favorite of many people because of the tasteful color of its
appearance. Corrosion resistance is also superior by means of a dense and tight rust layer, which is

527
formed on the surface of weathering steel during a long service life.
Several reports have been introduced about the structure of the protective rust formed on weath-
ering steel. Okada et al. reported that a protective rust layer was formed with two layersl). They
showed that the inner layer of protective rust was optically isotropic and consisted of amorphoLis or
very fine spinel-type iron oxide. Some introduced the enrichment of alloy elements and the nature of
the rust layers25). Their analyses were almost based upon the protective rust formed on weathering
steel in a mild environment.
Recently, it has been pointed out that the above mentioned protective rust of weathering steel is
not formed at a coastal area6). The authors examined several structures located near coastal areas,
which were made of weathering steel. Some were maintained using an organic coating because of
corrosion. Others showed good appearances having relatively small corrosion. A degree of corrosion
seemed related to the structures' distance from the seaside. And a specific point was that the largest
corroded parts were located at the inner side of the structure, where the wind blows through but the
rain does not come. As the corrosion of steel at ordinary temperatures requires water, it. seemed
unusual that the atmospheric corrosion of steel was inhibited by rain.
To clarify this evidence, the sheltered exposure stands were applied. In addition, some steels
were exposed at six weathering sites having various sea salt amounts in the atmosphere. The present
report shows the results of these exposure tests and the effects of rain for atmospheric corrosion of
weathering steel.
2.2 Exposure Test
The exposure test has been carried out at six sites near coastal areas, as listed in Table 2. Table.2
also shows the amounts of chloride in the atmosphere, measured by the dry gaze method through a
month and averaged for two years.
In order to clarify the effects of rain, the ordinary exposure test and the sheltered exposure test
were examined. The sheltered exposure test was carried out using a specially designed exposure stand,
as shown in Fig. I. This stand consists of a sample stand and an aluminum cover. The purpose of the
aluminum C"overisto prevent the samples from being wetted by rain. In addition, the cover enables the
wind to be admitted to the samples. The open part of the cover looks fOf\~ardto the sea.

3.RESULTS AND DISCUSSION

3.1. Difference in Exposure Test
Figures 2 and 3 show the difference in
corrosion depth in the exposure method.
Figure 2 is the result of exposure test at
Ginowan and Fig.3 at Muroran. These plots
show the results for mild steel (Steel A). At
each site, the corrosion depth of the sheltered
exposure test is greater than that for the
ordinary test. The difference between the two
methods is greater as the exposure period
increases. And it is also shown that the
difference between the two methods at
Ginowan is greater than at Muroran. The
amount of chloride in the atmosphere at
Ginowan is greater than at Muroran, as shown
in Table 2. This reason is estimated the
accumulation of sea salt.
The differences in the corrosion rates

529
for the exposure method is shown by Fig. 4. This plot is obtained by the corrosion of mild steel at six
exposure sites. The vertical axis indicates the corrosion rate that was obtained by the average corrosion
from the five years of exposure test. The horizontal axis. indicates the amount of chloride in the
atmosphere.
There exist linear relationships between the corrosion rate and the amount of chloride in the
atmosphere in both exposure methods, but the slopes of these relationships are different. The slope of
the sheltered exposure test is greater than that for the ordinary exposure test. Namely, the corrosion of
the sheltered exposure test is much severer as the amount of chloride in the atmosphere increases. It is
estimated that without the washing effect of the rain, the sheltered exposure test accumulates sea salt.
Figure 5 shows the relation between
the adsorbed chloride ions onto a painted
steel sheet and the amount of chloride in the
atmosphere. A painted steel sheet was
exposed for one year at each exposure site
and then cleaned by a gaze containing
distilled water. An Amount of the chloride
ions were analyzed by chemical analysis from
the solution in the gaze.
This figure has a good correspondence
to Fig. 4. Linear relationships exist between
the adsorbed chloride and the amount of
chloride in the atmosphere. The slope of the
sheltered exposure test is greater than that for
the ordinary exposure test. Therefore, the
reason why the larger corrosion rate was
obtained at the sheltered exposure test is
caused by the accumulation of sea salt
without the washing effect by rain.
These experimental results correspond to the evidence from an investigation of real steel struc-
tures, that the large corroded part is located at the inner side of the structure where wind blows through
but rain does not come. So, the sheltered exposure test is a better method than an ordinary exposure
te~t for evaluating corrosion at a coastal area.
32 Differellce in Steels
The difference in steels was examined at the six exposure sites. Figure 6 shows the trend of
corrosion depth for the ordinary exposure test and Fig. 7 shows the similar result for the sheltered
exposure test. Both data were obtained at Ginowan. In the ordinary exposure test, the corrosion depth
of mild steel A is greater than for the other two steels. Likewise, the trends of corrosion of weathering
steel B and modified weathering steel C are not so different. Besides, the corrosion depths of mild steel
A and weathering steel B are almost the same as for the sheltered exposure test. The modified
weathering steel C has a better corrosion performance in this environment. But the amount of
corrosion depth of steel C is much greater than the level of the unpainted usage in this area.

The similar results at Muroran are shown in Figs. 8 and 9. The difference for the three steels in
the ordinary exposure test was rather small. The corrosion depth in the sheltered exposure test was
smaller in the order of steel A, B and C. Modified weathering steel C also had a good corrosion
resistance in the sheltered exposure
test at Muroran
Figure to shows the chloride
contents in the rust layer. The chloride
contents were obtained from samples
exposed five years at Muroran. The
accumulated chloride contents in the
sheltered exposure test are much
higher than those of the ordinary
exposure test. The differences of the
accumulated chloride contents in the
steels are very small. Therefore, the
difference of the corrosion resistance
in steels is due to another reason.
Element distribution analysis by

531
EPMA indicates that the chloride distribution at the interface between substrate and rust layer is small
in steel C. The reason for the good corrosion resistance in modified weathering steel C is thought to
be that the chloride permeation through the rust layer was retarded by the effect of added elements of
~hissteel.

4.CONCLUSION
In order to clarify the effects of rain in atmospheric corrosion, the sheltered exposure test was
utilized. The results obtained after five years of exposure tests at six exposure sites near the seaside
areas are shown above. These results indicate that the corrosion in the sheltered exposure test is more
severe than that for the ordinary exposure test, and the difference between the two types of exposure
tests increases as the amount of chloride in the atmosphere increases. The reason is estimated that sea
salt is accumulated on the sample surface without the washing effect of rain, in the case of the
sheltered exposure test.
The difference in corrosion performances between mild steel and weathering steel in the shel-
tered exposure test for large amounts of chloride in the atmosphere, i.e., Ginowan, is rather small, as
shown in Fig. 6. It is regarded that unpainted weathering steel is difficult to use in coastal areas. The
results shown in Fig. 6 indicate the problem of this usage. It is because a protective rust layer is not
formed on the ordinary weathering steel when the accumulation of chloride ion occurs. Nevertheless,
the newly developed modified weathering steel has a good corrosion resistance in such a severe
environment. The reason is estimated that the chloride permeation through the rust layer retarded by
the effect of the added elements of this steel, such as Ni and Ca.

S.REFERENCES
1) H. Okada, Y Hosoi, K. Yukawa and H. Naito, Transactions of ASM, 62,278(1969)
2) I. Matsushima and T. Veno, Corrosion Science, 11, 129(1971)
3) J. T. Keiser, C. W. Brown and R. H. Heiderbach, Corrosion Science, 23, 251(1983)
4) H. Kihira, S. Itoand T. Murata, Corrosion, 45,347(1989)
5) M. Yamashita, H. Miyuki, H. Nagano, T. Misawa, Corrosion Engineering, 43, 43(1994)
6) A. Raman, ASTM STP 965, 16( 19.88)

532
 CW Treatment Formulations for
Open Re-Circulation
D.K.N. Kutty and A. Periaswami
National Thermal Power Corporation Ltd. NTPC-Jhanor,
. Bharuch, 392 215, India

SYNOPSIS:
Recirculating cooling water treatment programs are recommended by looking at water chemistry,
system characteristics and environmental limitations. System implementation and mOnitoring play an
important role in getting good result out of a treatment program. Formulations are generally mark~
as proprietary with numbers only identifying the chemicals. Properties of the chemicals, its active
components, mechanism of working, limitations etc. are not generally disclosed by the supplier. Often
past experience play an important role in deciding the treatment formulations unlike the boiler or other
general water treatment chemicals which are well defined. Today's well managedCW treatment
programs give high return on investment and ease on operation and maintenance. This paper is a
compilation of different aspects on the CW treatment to give useful tips to the user in its selection and
implementation.

INTRODUCTION:
Water according to its source varies in its ion contents like Ca, Mg, Na, SiCh, CI, S04, Hm, ccn etc.,
suspended solids and organic matter. High raw water cost, scarcity of quality water and the stricter
environmental regulations on disposal of water have forced industries to reuse and conserve water.
Water carrying systems often come across problems like corrosion, scale and fouling. In'a recirculated
cooling water, aeration through cooling tower and low make up with high COCincreases these
problems.

Methods to control scale are acidification, lime and base exchange softening, demineralization, use of
chelating chemicals and scale inhibitors. Corrosion can be controlled by application of protective
coatings, controlled CaC03 scaling, use of non-corrosive metals, operation at higher pH and use of
corrosion inhibitors. Algae, slime and foulant control can be achieved by coagulation, settling and
filtration, aeration, use ofbiocides, surface active agents and dispersants.

533
CHEMICAL TREATMENT PRACTICES:
Different treatment chemicals, their mechanism of working and limitations are given in Table 11.
Treatment program for cooling water usually comprises the active components for inhibition of scale,
corrosion and fouling. While the earlier treatment programs focused on low or neutral pH treatments
with corrosion inhibitors, present emphasis is to go in for high pH and cae using scale inhibitors and
highly effective dispersants to keep the sealant and the foulants in solution. The evolution of treatment
practices23 can be chronologically depicted as below.
1930 's : Inorganic polyphosphates (SlIMP) prevented scale but exposed metal surfaces to corrosion
and precipitated phosphate sludge on heat exchanger surfaces.
1940 's : Acid feed was begun to reduce scale with higher levels of polyphosphate for corrosion
control, but deposits and corrosion in high heat flux areas still occurred.
Early 1950:s : Chromate-phosphate combinations improved corrosion control, but greater acid was
required. Polyphosphate continued to contribute calcium scale.
Late 1950's: Zinc-chromate compounds (phosphate free) overcame corrosion. Acid feed was still
required to pre~ent precipitation of calcium carbonate and basic zinc salts.
Late 1960 's : Environmental limitations on blow-down of water containing chromates and
polyphosphates. Organo-phosphonates like HEDP, AMP etc. were developed.
1970 's : Polymeric deposit control agents (DCA) like tannin were used to minimize precipitation of
phosphate and zinc products in phosphate based treatment with zinc at higher pH.
1980 's : Regulation on disposal of zinc lead to low zinc programs with more effective DCA's like low
molecular weight poly-acrylates and poly-acrylamides in neutral and alkaline range.
1990 's : Emphasis on disposal of organic and inorganic phosphorous and conservation of water.
Evolution of stabilized phosphate, Alkaline molybdate and All organic programs. Use of more
powerful DCA's to operate at high IDS & TSS.

WORKING MECHANISM4 OF TREATMENT CHEMICALS:

Corrosion inhibitors work as a) Passivation (Oxide) film type, wherein thin (30-200 N) film, closely
adherent to metal gives excellent corrosion protection. e.g .. Chromates, nitrites, molybdates. b)
Precipitation film type comprising of 1) Chemicals forming insoluble salt with Ca ions etc. and gives
fairly good corrosion protection. e.g .. Polyphosphates, orthophosphates, phosphonates and zinc salts.
Bivalent metals like zinc enhances corrosion inhibition of polyphosphate by reducing the conversion
of polyphosphate to orthophosphate and making the relatively porous film formed with polyphosphate
compact. 2) Chemicals forming water insoluble salts with the protected metal ion. They are retatively
close, thin and give fairly good protection. e.g .. mercapto benzothiazole, tolytriazole. 3) Adsorption
film type. e.g .. amines, surfactants etc.

Scale inhibitors work by a) preventing the formation of crystal by making them soluble (sequestration)
b) prevention of growth of crystal (threshold inhibition) and c) Dispersion of crystal. Phosphonate is
quite effective in inhibiting CaC03 scale even at low doses. Maleic acid based homopolymer follows
next. For calcium phosphate inhibition, acryl acid-sui phonic acid-sulphonated styrene terpolymer is
best suited followed by maleic acid based co-polymer. Chemicals which have sufficient inhibition
effect of magnesium silicate have not been reported yet.

Polymeric dispersants control the thickness of calcium phosphate & phosphonates on n;tetal surface
and prevent precipitation of calcium phosphate and phosphonates in the recirculating water. They also

534
help in dispersing suspended solids, silts and slime. Dodecyl guanidine hydrochloride is a powerful
surfactant used as bio-dispersanf.

SELECTION OF TREATMENT PROGRAMS:

LI, RI or PI indicates the tendency of water towards CaC03 precipitation. Separately, each chemical
has limitations on water chemistry, system parameters etc. However, in combination, sometimes they
give synergistic effects in controlling the problems. Limitations of different chemicals in isolation
helps in identifying and analyzing the problems associated with a treatment.

Water Chemisty Limitations4,7:

a) Calcium Hardness : Calcium hardness in excess of 50 ppm is needed for most of the treatment
programs with phosphates. With Ca-hardness less than 50 ppm, Zn or molybdate program provide
good corrosion inhibition. At more than 1000 ppm Ca levels, alkaline and all organic programs may
present deposit problems and stabilized-phosphate program with neutral pH is the best fit. Corrosion
rate lJ,nd phosphate requirement decreases sharply with increasing the hardness from 50 to 150 ppm
CaC03. For polyphosphates a minimum Ca-hardness of 100 ppm is requirej:i but precipitates when
exceeds 500 ppm even with a phosphate level of 5 ppm at pH of 7 and above. '
b) pH & Alkalinity: Silica solubility increases with pH. Above 7.5 pH, water becomes less corrosive
in general, but copper salts precipitates in presence of certain biocides like methylene bis-thio-cyanate
and chlorine hydrolyses to the less active ions. Polyphosphate conversion to o-phosphate depends on
pH. At pH more than 8.0, zinc solubility is less than 0.5 ppm and doesnot work as cathodic inhibitor.
At pH of 7 a stabilized-phosphate or molybdate program would perform best. For systems with a
cycled alkalinity upto 500 ppm, all organic, alkaline-zinc and molybdate programs may not require
acid feed. Biocides based on organosulphur and quaternary ammonium compounds work in an
alkaline environment.
d) Iron: Ferric ion reduces the performance of polymeric dispersant. With total iron levels more than 4
ppm, stabilized phosphate program gives under deposit corrosion.
e) Silica: Silica often limits the COCo At more than 150 ppm, amorphous silica becomes problematic.
In general, magnesium silicate precipitates, if the product of concentrations of silica and magnesium
increases above 35000.
f) Phosphate: High Pho~phate levels which may occur while re-using sewage eftluents or with product
contamination are best handled with stabilized- phosphate program. Zinc or all - ,organic treatments
can handle 4-8 ppm of re-circulating ortho-phosphate. Saturation Index based on critical pH (pH,) can
be used in finding the calcium phosphate sludge deposition pH.
plL = (11.755 -log [CaB] - log [P04] - 2 log t ) / 0.65, and
SI = pH. - plL, SI < 0 indicates unsaturation condition of calcium phosphate.
g) Conductivitv : Conductivity causes increased corrosion. For all programs the maximum allowable
conductivity is 4000 uS/cm. Molybdate programs do not work at high conductivity.
h) Chlorine: By chlorine, amino methylene phosphonate dissociates to o-phosphate which can make
calcium phosphate sludge. At high chlorine levels, HEDP also dissociates to o-phosphate.
i) Organics : Organics grow quickly at a logarithmic rate and develop slime which act as a binder for
other inorganic materials like mud and clay and foul the system. SRB and other anaerobic organisms
cause MIC. Carbon, nitrogen and phosphorous containing compounds like oil & grease, amnionia and
glycols are good nutrients of organics.

535
 System Characteristics 4,7 :
a) Metallurgy: 1) Copper based (Yellow metal) : Organophosphonates are weak chelating agents and
attack steel or copper alloys. Zinc, polyphosphates and organophosphonates cannot protect copper
Withoutthe use ofbenzo triazole or toly triazole.
2) Stainless Steel: SS is less corro!iivethan mild steel under normal conditions. High chloride content
induces stress corrosion cracking on SS. Titanium alloys are best suited for such water.
3) Concrete: High sulphate content attacks concrete structure.
4) Galvanized Iron: pH less than 6.5 can result in the loss of protective zinc coating.
b) Temperature: Phosphate and carbonate precipitation increases with temperature. Temperature will
cause corrosion rate to double with every 25-50 OFrise upto 160 OF.Above 160 OF,effect of
temperature on corrosion is relatively less. Above 70C, magnesium silicate deposits within a very
short time even with magnesium hardness of 140 ppm if Si02 is more than 150 ppm.
c) Water Flow Rate: As the flow rate increases the corrosion rate increases and the scaling rate
decreases. Scaling rate at a flow rate of 0.6 mlsec is only about one fifth of that at a flow rate of 0.2
mls. Polyphosphates cause fouling and reduced protection in low velocity water (below 0.3 mlsec).
Films produced by polyphosphates are easily damaged when water flow is more than 5 mlsec.
d) Holding Time Index (HTI): HTI is a measure of how long it takes for half the water in a 'system to
be replaced. It increases with cae and is given by the relation, HTI = 0.693 x System volume/ blow
down. In all treatments, slug or one time dosing is done to take care of the hold up volume and only
maintenance dose is done to compensate the losses. Hence, when HTI is more than 2 days, most
treatments have to be modified as the degradation or hydrolysis of the product starts.

Environmental Limitations:
Use of chromate based treatments have been discontinued as the chromium in its +3 and +6 valencies
is a carcinogen. Being a heavy metal and pollutant use of zinc is also being limited. As per IS 2490
(Partl) - 1981, the discharge limit of Zn and dissolved phosphate to inland surface water is 5 ppm.
Limit for phenolic compo4fids us~d as biocides is 1 ppm as CJfsOH. Residual chlorine limit of 0.2-0.3
ppm has forced to find chlorine alternatives.

Product Catalogues :
Product catalogue should include complete data on material safety, performance, mechanism of its
working, active components and their checking, water chemistry and other limitations, start up
requirement and a complete trouble shooting guide comprising effect of upset conditions and
corrections thereof Laboratory results on carbonate, phosphate and sulphate inhibition properties,
corrosion studies and dispersant ability should be properly known for the products in use. It is
unfortunate that different lab methods are employed by the suppliers to report the properties of their
chemicals. Many suppliers market the products as proprietary and do not share the product details with
~ant engineers, which should be discouraged.

Cost:
Operation of the' system at higher cycles reduces the water requirement and the chemicals feed. Above
5 cae, the reduction in water requirement is generally marginal. Improving results and reducing costs
will require a good understanding of the system variability and the specific limitations of the treatment
program used and product control. Where system contamination and temperature variation are
expected to be less, zinc - polyphosphate - organophosphonate - polymer combine is highly cost

536
 effective followed by stabilized phosphate treatment. Requirement of acid varies according to pH and
alkalinity to be maintained in the CW system and should be considered in the treatment cost.
Theoretically, 0.83 ppm sulphuric acid will be required to reduce 1 ppm alkalinity.

PROGRAM IMPLEMENTATION:
Product Controls:
In a stabilized phosphate treatment, at low calcium and pH conditions, the precipitation chance of
phosphate is less. Hence a low dosage of polymeric stabilizer and a high dosage of phosphate can be
used for better control. At high cillcium and low pH levels, where calcium scale can occur, a high
dosage of polymer is required. Moderate amount of phosphate can be used. At high levels of calciUm
and pH, a high dosage of polymer and a low dosage of phosphate with a high dosage of phosphonate
should be used. A selected treatment program can be controlled either by changing the product dose
level according to the change in CW characteristics or by fixing the product dose level constant and
limiting the water characteristics. The second option gives consistent results, operational ease and
cost.

Performance Requirement: .
Performance requirement for the system and methods of monitoring should be clearly spelt out before
. selecting a product. Monthly report from supplier on the functioning of the system should be part of
the services. This will help in performance evaluation and in optimization of the chemicals.

On Line Monitoring:
Recommended Practices as given in NACE standards, RP 0189-95, TM 0286-94, TM 0374-74 et~. can
be used for monitoring biofouling, deposit and corrosion. In addition removable spool pieces can be
introduced for periodical examination of scale and corrosion in the system. Photographs of critical
equipments including CT can be taken periodically and preserved for comparison of the performance.
It will be advisable to use the program in small pilot cooling towers with identical water chemistry,
system characteristics etc. for 3-6 months to evaluate the effect ofa new formulation and to optimize
the dosage.

Laboratory Methods for evaluation of Treatment Chemicals 9.7 :

Scale Inhibition Test: Inhibition of calcium phosphate, zinc phosphate, calcium carbonate and
calcium sulphate can be studied in lab utilizing solutions respectively containing calcium ion and
o-phosphate, zinc and o-phosphate, calcium and carbonate and calcium and sulphate ions. Here, the
solutions are mixed together and kept at a particular temperature for the specified equilibrium time.
After the stabilization time, the o-phosphate or calcium as the case may be remaining in solution is
determined. High residual ion concentration indicates good inhibition.
Corrosion Inhibition Tests: Coupon studies with hard water containing high chlorides and sulphates
are used to find the corrosion inhibition of the given formulation. Here, water with total hardness,
alkalinity, chloride and sulphate of 400, 175, 300 and 250 ppm respectively at 45C is circulated
through glass columns of 55 mm dia and 450 mm height for the same. Corrators can be used for
knowing instantaneous corrosion.
Dispersing ability: Dispersing ability of a polymer can be found out by visual method using Kaolin
clay and the antifoulants. A small clear zone indicates good dispersion. Dispersion of iron hydroxide
can be found out by usingferric chloride solution.

537
Heat Exchanger Performance: Performance of heat exchangers can be monitored by the heat given up
by the process steam or water to the cooling water or through tile heat gained by the cooling water
from the process water/ steam. Heat exchange coefficient, VA = Q/(AxDiff.T), where, Q is the energy
gained by the cooling water or the heat lost by the process water, A is the area of the heat exchanger
surface. Reciprocal of the heat transfer coefficient is called the fouling resistance. This olJlllber
multiplied by one thousand gives the fouling factor. However, it may be noted that, fouling within an
actual heat exchanger is seldom uniform.
Microbiological Tests: TVC below one lakh with no more than one positive SRB per ml out of four
water samples show good microbiological control. Lab methods include total plate count, dip tabs,
relative population test and zone inhibition test.
Monitoring of cooling water for chemicall1arameterS' : Cooling water should be periodically checked
for the active components of the treatment chemicals, calcium, magnesium and silica. COC w.r.! Ca,
Mg, Na and Si02 should match in a good treatment chemical applied in a new system. Ortho, meta and
organic phosphate determinations, can be used in the product control for a phosphate based treatment.
pH, turbidity an.diron determinations will also be required for close monitoring of the treatment.

ACKNOWLEDGMENT:
The authors are thankful to Dr. Pradeep Jain, Manager. (R&D), NTPC, representatives from Mis
Nalco, Chembond, Aquapharm, Drewtreat and lEI Dearborn, for providing valuable reference
materials and interaction in finalizing this paper. They also thank the NTPC management for giving
permission topublish this paper.

REFERENCES:
1. Sheldon D Strass and Paul R Puckorius, Cooling Water treatment for control of scaling, fouling,
corrosion, Power, June 1984.
2. C.W.Schweitzer, How Phosphonates control scale and corrosion in cooling water systems,
Heating/Piping/Air Conditioning, May, 1971.
3. K.S.Rajan and Nandkumar D., New Boundaries in industrial Cooling water treatment, NACE
conference on Corrosion, 1996.
4. Kurita Handbook of Water Treatment.
5. Zahid Amjad, Jeff Pugh, John Zibrida, and Bob ZOOl,Polymer Performance in Cooling Water,
The influence of Process Variables, MP, January 97.
6. lW.McCoy, The Chemical Treatment of Cooling Water, Chemical Publishing Co.
7. James. R.Macdonald, Choosing the correct cooling water program, Chemical Engineering,
January, 1987.
8. J.R.Macdonald, The Importance of Control for a Successful Cooling Water Program.
9. D.J.Banerjee and V.C.Bhandhari, New Antifoulants for use in cooling water treatment,.
Corrosion & Maintenance, July-Sept, 1983.

538
Proc. Int. ConI'. on Corrosion CONCORN '97
December 3-6, Mumbai. India

Corrosion-Organic & Inorganic and it's Prevention I

Control Through Dehumidification
Rajnish Joshil and Prem Sagar2
IBry-Air (India) Pvt. Ltd,.20, Rajpur Road, Delhi-I 10 054, India
2Arctic India Sales 319-T.V. Tower, Inds Estate,
Worli, Mumbai-400 025, India

ABSTRACT
Moisture causes corrosion and corrosion causes waste.
The devastating efficts of corrosion are not unknown. Over the years the most commonly adopted practice for
corrosion prevention on metals has been use of anti-corrosion coatings. Though the need for anti-corrosive
coating cannot be refuted, the need for alternate methods to control/prevent corrosion should not be
underestimated.
Corrosion Problems Are Moisture Problems
Corrosion does not occur is dry air.
The basic problem arises from the fact that the invisible water vapour present in the air condenses, on any surface,
colder than the dew point temperature of the surrounding air mass.
Also, sudden changes in temperature, within the room effects the internal humidity environment and lead to
condensation on any surface. This subsequently leads to corrosion.
Corrosion Phenomenon
Inorganic Corrosion is defined as destruction of a metal or alloy by chemical or electro-chemical reaction with its
environment.
Higher humidities lead to higher condensation of water on the metal surfaces. This molecular thickness of the
layers of water, eventually permits ionic conduction, which accelerates the rate of corrosion.
Organic Corrosion: Organic corrosion manifest itself in form of mould, mildew and fungus. The spores l~e
dormant on materials, until suitable conditions of temperature arid humidity are achieved. Once germinated, the
mould prospers and the speed of growth is a function of temperature and humidity. The condensed moisture on
material acts as a medium conducive to the growth of bacteria.
Corrosion Begins at 35
Between 30-35% relative humidity the rate of corrosion, is dormant. The critical level is 45%, above which the
rate of corrosion accelerates.
A little water removal saves a lot of money
Humidity control or dehumidification provides the answer to controlling moisture in a warehouse or a storage area.
Not only does the controlled RH restrict rusting of iron and steel, but also protects other moisture sensitive
materials.
Ihis paper willfocus on the above aspects of the corrosion phenomenon and it's prevention through humidity
control.

540
INTRODUCTION
When Moisture is Torture!!!
Nrcrafts, automotive parts, ammunition, bearings, batteries, chemicals, card board boxes, documents, engines,
electronic components, leather items, maps, metal parts, assemblies, gearboxes, films, foods, medicines, precision
parts for watches, spares and sea vessels all need to be stored at the raw material, semi assembled or prior to
packing stage.
The one single, enemy of goods, in storage, to be contended with is 'Corrosion'. In fact, Corrosion costs the
country a phenomenal Rs. 7000 crores annually. It costs an organisation, a tremendous amount of vital resources,
towards the annual maintenance and replacement of corrded, thereby useless components and parts etc.

Types of Corrosion
Corrosion can be classified into two types; Inorganic and Organic.
Inorganic takes the form of rust on metal surface.
Organic corrosion manifests itself in the form of appearances of mold, mildew, fungus or any other bacterial
growth.
Corrosion problems are Moisture Problems
Corrosion does not occur in dry-air. It is the invisible water vapour in the air which is the cause of rusty bolts and
industrial foe of product quality and storage.
A certain amount of water vapour is always present in the air. This water vapour or moisture in the air is measured
in terms of relative humidity.
The basic problem arises from the fact that water varpour will condense, on any surface, colder than the dew point
temperature of the surrounding air mas~.
Thus common factor between unlike group of products as corroded machine parts, defective plastic goods, eratic
computer data and bad qualitYnewsprint is suprisingly - the root cause of all defects in these products - Moisture.
And that creates havoc in apparently dry airconditioned areas.
Also, sudden changes in temperature, within the room affect the internal humidity environment and lead to
condensation on any surface. This subsequently leads to corrosion.

Condensation Causes Corrosion And Corrosion Causes Waste

THE CORROSION PHENOMENON
Inorganic Corrosion: Co"osion is defined as destruction of a metal or alloy by chemical or electro chemical
reaction with its environment. In most instances, the reaction is electrochemical in nature: a flow of electricity
between certain areas of a metal surface through a solution capable of conducting an electric current. This
electrochemical reaction causes destructive alteration (eating away) of a metal at areas.
Though corrosion is a complex function of many factors, the three most important are -
- a voltage differential between pure and impure areas.
- physical conditions of temperature and humidity
- oxygen in the air.

541
Higher humidities may lead to higher condensation of water on the metal surfaces. The concentration of molecules
of water vapour increases with increasing RH. This molecular thickness of the layers of water eventually permits
ionic conduction which accelerates the rate of corrosion.
With iron or steel, the ferrous ion may react with hydroxyl ion in water to form ferrous hydroxide and with oxygen
to produce ferric hydroxide (rust).
Accelerating and Intensifying Factors
In pure air almost no iron corrosion occurs, at relative humidities even upto 99%. But with contaminants such as
sulphur dioxide or solid particles of charcoal present, corrosion could proceed at relative humidities of 45% or
above. However pure air is seldom encountered in practice.
Figure 1 shows the comparative rate of corrosion in relatively clean and polluted air. The critical humidity level
which is at 45%, is approximately same for clear and polluted air, however the rate of corrosion is faster where
surfaces are exposed to polluted air in combination with high relative humidity. Industrial pollutants like sulphur
dioxide enhance the corrosion rate.
Out of the three factors, oxygen in the air cannot be prevented from coming into contact with the metal surface
and very little can be done to control pure and impure air on the surface of the m:etal due to contamination.
However, the water coming into contact with the metal surface can be avoided by surface treatment but most
effectively by control of humidity in the environment.
The relative humidity must be controlled to a level where it not only prevents condensation but is reduced to a
critical level below which corrosion does not occur.
Organic Corrosion
This form of corrosion is most familiar as Mould Mildew Fungi
Mould, Mildew and Fungi are all different types of bacteria. Outdoor air is well endowed with this bacteria which
are small enough to be carried indoors and which will settle on materials. The spores lie dormant until suitable
conditions of temperature humidity are achieved. In general the spores will not germinate below 60% RH. The
actual temperature conditions for germination may vary widely between different types of moulds.
Once germinated the mould prospers and the speed of growth is a function of temperature and humidity. The
condensed moisture on material acts as a medium conducive to the growth of bacteria. Moreover at high
temperature the activity of the micro-organisms increases but a certain amount of activity occurs even at very low
temperatures.
Thus micro-organisms growth is injurious to material; as it not only results in decomposition but also mechanical
weakening of the products. In most cases bacterial growth can be arrested ifRH is maintained below 35%.

Many Faces of Corrosion

Examples of Inorganic Corrosion
Defence In defence, operational reliability and availability are the key words.
Corrosion is the prime enemy of equipment in storage, like tanks, ammunition,
aircrafts etc. The variety and number of items required toback-up a military,
airforce or naval unit is immense and while in storage, problems of operational
availability, reliability and downtime are confronted.
Marine ..... In the marine industry, rust spells doom. Machinery, spares, engines, boilers,
electrical and electronic systems aboard the ships or near off-shore facilities
require protection from corrosion.

542
Power Plants .... In the power industry, the power plant may need to be deactivated for
temporary lay up or extended cold standby or simply for storage of back-up
turbines. It is during such times, the entire plant needs a safeguard against
corrOSlOn.
Waterworks ..... Rust and mildew on the extensive piping galleries and control instrumentation
result in high maintenance costs.
Sandblasting .... During sandblasting operations, the blasted surface begins to rust immediately
after it is cleaned for painting, ,preventing proper paint adhesion.
Storage of parts ..... In the storage of precision parts, before assembly of small or big spare parts, or
a finished inventory, rust spells a rejection rate as high as 50%.

Examples of Organic Corrosion

Breweries and Distilleries .... Organic corrosion is an inherent problem in breweries and distilleries where
fungus growth on walls, hop storage, fermentation and yeast room is
unacceptable under stringent hygiene demands of the process.
Seed Storage .... Mold and fungus growth on seeds during storage makes them unfit for
consumption and germination.
Archival material .... Mould and mildew on stored maps, film negatives, books or paintings in
museums and libraries destroys their usefulness and reduces their longevity.
Chemical and Pharmaceuticals ... Fungus growth or organic compounds and medicinal substances renders them
useless.
What can be done about it?
The rate of corrosion attack or rusting is considerable above a certain relative humidity. But below the critical
humidity the rate of corrosion is negligible. The critical humidity in most cases is about 45%, in some cases even
lower. However, in practice, the relative humidity to be maintained for storage of steel components and machinery
should not exceed 35-40%%.
Figure 2 shows the rate of corrosion acCelerating above 45% RH.
Hence, it is imperative that the RH must be controlled.

Methods for Control of Itelative Humidity

In order to maintain a controlled environment in an enclosure at the desired RH level, supply air to the enclosure
has to be dry enough to offset the moisture ingress into the enclosure. The process of physically removing moisture
from the air is called dehumidification.
Lowering of RH can be accomplished in several ways, viz. :
a) Heating the air;
b) Application of vacuum
c) Refrigeration;
d) Chemical Dehumidification
Heating the air increases the temperature, and since RH is a function of temperature, apparently lowers the RH
without actually removing the moisture from the air. It is impractical to maintain such conditions, hence this
approach is not desirable and not followed. Futile attempts have been made to supplement such efforts by placing
bags of desiccant in the enclosure for static adsorption, but these are not effective without provision for
reactivation.

544
545
Vacuum systems essentially work on the principle of humidity denial rather than humidity control. The
environmental barrier and its very complex sealing, by virtue of its design, dictate a very heavy (a few tons)
approach, which makes site handling almost impracticable. The energy consumption for creating and maintaining
the vacuum is also very high. This approach, therefore, has been more or less abandoned the world over.
Refrigeration system of dehumidification does actually remove moisture, by condensing it, but has some inherent
limitations unless one makes major compromises in application needs.
The limitation are :
a) It is suitable for maintaining RH upto 45% or above;
b) It continues to pump heat into the enclosure, since the heat of compression is rejected continuously within
the enclosure;
c) High ambient temperature reduces the efficiency of the condensing system and requires high energy
consumption for RH control.
Chemical dehumidification emerges as the best choice for RH control. Chemical Dehumidification based on the
principle of physical adsorption reduces the moisture content and dewpoint of the air.
The principle behind chemicaVdesiccant dehumidification is that the desiccant is exposed to the moisture' laden air,
from where it is extracted by the desiccant and held.

Equipment Options for Adsorption-based Dehumidification

The size of the enclosure in which the RH is to be controlled, the supply air quantity and the degree of
dehumidification required vary from situation to situation. Therefore, it is necessary that a wide range of
equipment be available to meet the specific requirements of a given situation.
Adsorption-based dehumidification systems operate on the principle of an adsorbent bed rotating between two
sections; a 'process' section in which the supply air is dehumidified, and a 'reactivation' section in which the
adsorbed moisture is removed and the bed is regenerated for a fresh process cycle. The operating principle of an
adsorption based dehumidificati~n system is schematically shown in Figure 3.
A wide range of ratings and capacities are available to built from small to very large enclosures, such as storage
sheds, warehouses etc. Bry-Air India (BAI) offers several options to suit th~ user needs. viz. :
* Compact (80 to 500 CMH dry air)
* Portable
* MVB (Modular Vertical Bed, 850 to 85000 CMH dry air).
* Specially Engineered Systems (for large warehouses, hangars, etc.)

pres "'pap" cor "'pap.doc

546
 Corrosion Problems in Chemical Process Industry-
An Experience
B. Gaur and H.S. Srinivasan
Gharda Chemicals Ltd.,
Dombivli (E), 421 203,
Mumbai, India

ABSTRACT

Investigations were carried out on a fe~ components removed from

service in a chemicalprocess industry which include a reaction
vessel, a part of an autoclave in pilot plant and a big bolt
across the shaft in a reactor used to support the impellers. The
analyses involved the visual/microscopic examination of the
suffered component, characterization of the construction
material of the equipment and process ingredients for
corrosive species, scrutinizing the operating conditions, etc.
It is concluded that the presence of halides, viscosity and
stagnancy of the handled medium, preferential dissolution of
alloy constituent, higher concentration of reactants etc. might
have contributed to shortened life of the equipments.

INTRODUCTION

stainless steels (SS) find wider application in chemical process

industries as a construction material of various plant equipments
and instrumentation such as reaction vessel., storage tanks,
pumps, condensers or heat exchangers, pipelines, etc. Out of
different classes, the austenitic SS of AISI 300 series i.e.
SS-304, 316, etc. are conventionally employed because of their
good combination of corrosion resistance, mechanical properties,
weldability and availability, etc (1,2). Nowadays, the
increased load of production and demand of new products and
process technologies have resulted in an increase in the process
temperature, pressure and ingredient's concentration.
Accordingly, the corrosivity of process streams has also been
enhanced, tremendously. Consequently, the number of failure
cases of process equipments has also been enormousli increased
(3). Thus, in the current scenario, stainless steels no longer
remain "stainless". Present paper deals with the case studies
of a few plant components, removed from the service after
rejection in a pesticides manufacturing industry, because of
certain corrosion problems associated with them. These are
discussed. item wise in the forthcoming paragraphs:

548
The vessel was made of SS 304 having a wall thickness of around
7-8 mm and a capacity of 1000L as shown schematically in Fig.1.
During actual operation, the temperature and pressure were kept
unavoidably far below (around half, as a safety measure) than
their design counterparts. The reactor frequently handled a
mod~rately viscous and nonaqueous organic reaction mass of the
high molecular weight aliphatic hydrocarbon and cyclic alkanolic
compounds at a temperature of around 50C. According to the
information available in corrosion literature, SS 304 is expected
to withstand the corrosivity of medium species .without any
hassles for over a decade. In contrast, the bottom dish of the
reactor ruptured catastrophically after 15 months of its
commissioning. As a result, a big ( of the order of square foot)
portion of structure detached from the main body causing the
reactor out of use.

Visual Observations

The overall reduction in the thickness of reactor's wall was not

significant throughout the vessel and the .fracture took place at
a far removed distance from the circumferential weld, i.e., the
junction of middle and bottom shell. For convenience of
discussion, the reactor may be divided into three zones, i.e.,
top, middle and bottom as shown in the Fig.1.

The top and middle zone suffered from severe pitting corrosion.
The observed pits were of varying shape, size, density and
'orientations, e.g., shallow, deep, narrow etc. and scattered over
the entire surfaces. Here, it is important to note that the
narrow pits were very deep and dense. Some of them, especially
at the lower part of middle zone, found to be changing the
direction of propagation from horizontal to vertical after
certain degree of attack. In such situation, pit tends to grow
autocatalytically in the direction of gravity as the process is
favoured by creation and maintenance of stagnant pockets in metal
structure to retain the corrosives (4). As an understood fact,
the occluded regions tremendously accelerate the.corrosivity of
solutions resulting in the perforation of metal-walls due to
penetrat.ion by pitting attack or by stress corrosion cracking
(SCC) if any sort of load is present. In brief, it may be stated
that the middle and bottom zones of the reactor were also prone
to failure, after a short period.

Unlike to the observation on two vessel-zones described in last

paragraph, bottom zone didn't suffer much from pitting corrosion,
visually. On the other hand, general corrosion had additionally

549
occurred on its entire surface. However, a few hidden pits became
visible after the removal of dark brown coloured layer of
corrosion product. Besides, large number of cracks either in
underdeveloped or fully developed stage appeared on cleaning the
surface close to the fracture region. After 3-4 days of
cleaning, it was noted that the liquid was oozing out of the
fine cracks resulting in the formation of small droplets at the
cleaned surface. This implies that the corrodent might have
entered and trapped in the fine cracks during their expansion
in presence of exerted pressure (operating pressure as well as
weight of the reaction mass). The overall appearance of the mode
of cracking was that of a 'brittle fracture'.

Characterization and Discussion

In order to investigate the cause of failure, characterization

of stainless steel and the chemical mass was carried out.
Chemical mass was analysed for certain inorganic speci~s as well
as pH and the results are given in Table-1. At metallic end,SS
samples were drawn from the reactor-wall for detailed
characterization. The crack morphology and microstructure are
shown in Fig.2. The chemic?l composition and mechanical
measurement results are reported in Table-2.

In the case of sample derived from middle zone, the

microstructure (not shown), chemical composition and mechanical
properties (Table-2) meet the specifications of SS 304. Thus,
there ,is no any signal of cracking in this part of the vessel.
However, it could fail by aggressive pitting corrosion in near
future, as described previously. The identified environmental
parameters (Table 1) responsible,for severe localized corrosion
may include the acidic pH -2-3, moderate temperature, higher
content of chlorides, presence of metallic cations, e.g., ferric,
zinc, etc. Now, subsequent discussion will deal only with the
bottom zone where actual failure took place.

The chemical analysis of sample, drawn from the fractured

portion, fulfils the requirement of SS 304 except for the carbon
content. The morphology (Fig.2) of crack propagation, primarily
classifies this as a case of SCC, i.e., the multiple cracks
advance through metal in the branching mode outwards (Fig.2).
Further, an effort was made to measure a' few mechanical
properties of a piece taken from the failure region but couldn't
be accomplished. The simple reason was the insufficient strength
and ductility of the corrosion affected sample required for the
machining job. Thus, the material had completely lost its tensile
properties. Moreover, the local hardness was also enhanced
(Table-2) thereby indicating an increase in the brittleness of
metal. The cross sectional view of microstructure (Fig.2)
indicates that the cracks were developed at the base of pits
beneath a layer of corrosion products and propagated through the
reactor-wall towards the outer surface. In the microstructure,
the microdeformations are not apparent, therefore, present case

550
seems to be that of a 'brittle fracture'.

According to chemical composition data (Table-2), the bottom zone

(failure zone) alloy contains lower carbon than the middle one.
Thus, the former has certainly lower strength and hence inferior
see resistance in comparison to the latter. Further, it is
obvious from microstructure that the cracks don' t propagate
preferentially through the grain boundaries, therefore, the
possibility of intergranular stress corrosion cracking (IGSee)is
ruled out. Low content of carbon (0.02%) in the bottom material
also supports this view by minimizing the chances of chromium
carbide precipitation (5). As evident from the microstructure of
fracture zone (Fig. 2), present case belongs to the class of
transgranular see. The important factors attributed to cause this
disastrous failure may include the residual stresses and low
carbon content in alloy, geometrically highest load on the bottom
part of the reactor and the acidic pH -2-3, considerable amount
of chloride, presence of excess zinc, etc. in the handled
reaction mass. Analytical results for these factors are available
in Table-1 & 2 (except residual stress). The source of aggressive
species in the reaction mass are either impurities (including
water) in the technical grade chemicals or generation during the
reaction process whereas zinc might have come along with
reactants from any galvanized carbon steel pipeline. Most
surprising observation was that the localized corrosion was not
severe in the fracture zone while most of the scientists have
emphasized the need of a localized ~ites, i.e., pits, trenches,
fissures, crevices, etc. to initiate the see attack (6-8). As the
chemical mass was of tarry nature (specific gravity -1.3), the
possibi~ity of trapping of the corrodents beneath its layer may
not be ruled out, while, stainless steels always require some
oxidant to repair its deteriorated protective film. Moreover,
cracking mechanism might have also involved the deleterious role
of metallurgical and process heterog~neities such as active
dislocation interaction sites, inclusions, grain boundary
dissimilarities, residual stresses, thermal gradients,
nonuniform composition of the mass etc. which were not studied
in detail.

Suqqestions

To avoid such type of serious corrosion problems in future,

following actions will be beneficial:
a) .Before selecting a material of construction for a process
stream, evaluate its performance at lab scale in plant
simulated conditions.
b). elean .the reactors regularly especially those made of stain
less materials.
c) :Oon't leave the reaction vessels in constant contact of
stagnant, viscous and tarry chemicals for an indefinite
period.

551
2. Bolt of a Reactor's Shaft

History

The bolt (length 8" and dia 1.5") was indicated to be made of
55-304 and used across a reactor's agitating-shaft to sustain the
impellers . The capacity of reactor was 5000L and function
involved the nitration of a heavy aromatic hydrocarbon at ambient
temperature. After around one year of service, the impellers
suddenly slipped from the shaft and fell on the bottom of
reactor. The bolt was also l~'ing on the bottom of reactor in the
broken state and its pieces were taken out for the failure
analysis.

Observation and Analysis

This was noted from collected bolt-pieces that uniform corrosion

didn't take place to a considerabl~ extent and the bolt failed
because of cracking in the threaded part. Material was analysed
for its chemical composition and microstructure and corresponding
results are available in Table-3 and Fig.3, respectively. From
the composition data, it is evident that the material meets the
specification of 55 316 instead of 55 304. Though 55 316 performs
superior to 55 304 in number of aggressive envi'ronmentsbecause
of containing more nickel and molybdenum in addition, it has been
reported (9) susceptible to more corrosion attack in nitric' acid
environment ~ The reason is that the molybdenum in 55 316,
normally added to improve localized corrosion resistance (10),
promotes the formation of sigma phase that is less resistant to
nitric acid attack (9). It may be seen from the optical
microstructure of failed sample (Fig. 3) that grain boundaries are
broadened which gives the signal of preferential attack at these
regions. Although it is not possible to distinguish the
intermetallic phases by optical microscopy, however, it seems to
be a case of intergranular stress corrosion cracking (IG5CC).

5uQQestions

Component should be used only after verifying its specification.

It should never be assumed that a material having additional
alloying constituents or more cost performs always better.

3. stirrer Rod of an Autoclave

History

A 55 316 stirrer, in a 5 liter autoclave, failed after seven

months of the service. The design pressure of the system ,was 700
psi. At the time of failure, autoclave was handling an aqueous
mixture of alkali, sulphides, orgahics, etc. upto a temperature

552
of around 250C. During the course of reaction, ingredients
spilled out through the inlet tube of autoclave along with a
pressure drop in the gauge.

Observation and analvsis

After opening the vessel, it was found that the stirrer-rod and
inlet tube broke into two parts along with longitudinal cracks
extending throughout the length. The photograph of the upper part
of broken stirrer-rod is shown in Fig.4. Later on, the
characterization for chemical constituents and microstructure
were carried out and results are given in Table-4 and Fig.5,
respectively. The chemical analysis conforms the requirement
of SS 316. It may be seen from the microstructure of failed
component that the cracks don't properly exhibit any directional
pattern though exist in large number. Further, there is no any
signal of preferential attack at the grain boundaries. Therefore,
this is attributed to be a case of 'caustic cracking'. Literature
also supports this view since temperature of reaction was
sufficiently high (11,12).

Suaaestion

At high temperatures, only nickel based alloys should be employed

to handle the concentrated alkaline media.

REFERENCES

1. A. Garner, Pulp & Paper Canada 86(12), 1985, P T419

2. L.H. Laliberte and W.B.A. Sharp, Pulp & Paper Canada, 80(2),
1979, P T35 .
3. B.J. Moniz and W.I. Pollock, (Ed.), Process Industry
corrosion, NACE, 1984.
4. M.G. Fontana, Corrosion science and Engineering, McGraw
Hill, 1986.
5. J.R. Davis, (Ed). ASM Speciality Handbook-Stainless Steels,
ASM International, Ohio, 1994.
6. R.N. parkins, Materials Science & Engineering, A103, 1988,
143
7. R.C. Newman & R.P.M. Procter, Br. Corros.J, 25(4), 1990, 259
8. L.L. Shrier, R.A. Jarman and G.T. Bursten (Eds.), Corrosion
Vol. 2, Butterworths Heinemann Ltd, Oxford, 1994.
9. C.M. Schillmoller, Chemical Engg. World, Vol. XXX, No. 11,
1996, p5I.
10. G.N~ Kirby, Chemical Engg. Progress, Feb. 1995, p. 47
11. D.A. Jones, Principles & Prevention of Corrosion, 1996,
Prentice Hall International, London
12. C.M. SChillmoller, Chemical Engg. Progress, May 1996, p.48

553
Fig. 2. Crack morphology and optical microstructure of the
reactor's fractured part (cross-sectional view)
(a) Crack morphology (X 200),
(b) Microstructure (X 50), and
(c) Microstructure (X 250)

556.
557
Fig. 5. Crack morphology. and optical microstructure
of broken stirrer rod;
(a) Crack morphology (cross-sectional view; X 50),
(b) Microstructure (cross-sectional view, X 100), and
(c) Microstructure (longitudinal view, X 250)

558
 Sensitization Studies on 304H Austenitic Stainless Steel
Using EPR Technique.
K. Venugopal, T.R. Jayaraman and Y. Kalpana
Bharat Heavy Electricals Ltd., (R&D), Vikasnagar,
Hyderabad-500 093, India

ABSTRACf

Austenitic stainless steel of 304H variety which is used as boiler tubes in power plants is subjected to
senl3ri7Jltiondue to continuous exposure to high temperatures during operation. This resuhs in intergranular
fililure leading to costly shutdown of the power plants. At present there is no reliable technique to quantify
the degree of !81l3ri7Jltion(DOS) and therefore predict the likelihood of material failure. An electrochemical
technique known as Electrochemical Potentio Kinetic Reactivation (EPR) Technique has been established
to quantify the DOS in 304H austenitic stainless steel A specially designed double wall all glass cell was
fabricated along With electrodes for carrying out the electro-chemical measurements using a Princeton
Applied Research Model 270 Versastat. EPR measurements were carried out on 304H stainless steel tube
samples heat treated at 500C,550C,600C&7000C for different time durations and the degree of
sensitization quantified. The paper discusses the EPR technique and the experimental test resuhs.

1.0 INTRODUCfION

Austenitic stainless steel of 304H grade is used extensively in thermal power plants for super heaters,
girdling loops and feed water heat-exchanger tubes because of their excellent oxidation and corrosion
resistance properties. This stainless steel undergoes sensitization due to improper heat treatment, welding
and continued exposure to high temperature during operation. Sensitization leads to chromium carbide
precipitatioti along grain boundaries leading to brittle intergranular failures even in very mild environments.
The sudden fililures can lead to costly shut down of the power plants and necessitated the need for a rapid,
quantitative, non-destructive means of detecting sensitization. The usual technique for detecting
sensitization is described in ASTM Practice A 262 which is destructive, time consuming and does not
readily quantify the degree of sensitization (DOS). These deficiencies limit the detection of sensitization in
heat treated, welded and high teDlperature service exposed components. Therefore, it has become necessary
to look foraltemative tests to quantify the DOS in austenitic stainless steels which can be used on small
mmces as a quality control tool on shop floor or field constructed components which are exposed to highet
temperatures during fabrication or service. In this aspect, the electro-chemical approach for quantifYing

559
3.0 MATERIAL AND EXPERIMENTAL PROCEDURE

The material used far the present study is type 304H stainless steel pipe af IOmm wall thickness imparted
fram Sandvik Asea, Sweden. The campasitian (in wt%) is 0.05 C, 0.50 Si, 1.56 Mn, 18.4 Cr and 9.1 Ni.
Small samples were cut fram the pipe and heat-treated at 500C, 550C, 600C, 650C, 700C far different
time duratians af 0.5 to. 300 haurs and caaled in air. This was dane to. induce variaus degrees af
sensitizatian in the samples. After heat-treatment, cylinders af Ilmm diameter were machined and maunted
in teflan withaut crevices. Pravisian was made in the sample and Teflan far attaching a AlSI 304 screw
far electric cantact. Greater care was taken during experiments so that anly the sample is expased to. the
electralyte solutian.
EPR experiments were carried aut in a specially designed dauble walled all glass cell. The cell is made
dauble wall to. circulate water at a cantralled temperature using a thermastat so. that the electralyte in the
cell is kept at a canstant temperature af 30C 1C. The cell has pravisians far
a. angular sideways insertian af reference prabe tip, very clase tawards the centre af the immersed
circular test specjmens
b. insertian aftwa patallel spectragraphic grade graphite counter electrades
c. centralinsertian afTeflan encapsulated circular test specimens afarea 1.0sq.cm
d. gas purging tube that cauld reach the battam afthe cell
e. gas escape bubbler and
jacketing far water circulatian, thraugh a thermastat.
The electrachenncal cell which was fabricated is shawn in Fig.2.

The electrochemical palarizatian cantral afthe test cell was achieved using a Princetan Applied Research
Madel 270 VERSASTAT. This is a fully camputerised equipment that cauld functian in Galvanastatic or
Patentiastatic made as the case may be, driven by a very versatile carra sian saftware, incarparating
advanced versians af carra sian rate measurement techniques. In the present case, the cell prabes were
connected to. the equipment, and the experiments were carried aut by automatic parametric cantral achieved

561
The Teflon mounted samples are polished as per the normal meta110graphic polishing procedure using rough
300, 400,600 grit emery papers. Final polishing is done with lJ.lm diamond paste and fine alumina slurry
on a nylon'cloth to obtain a scratch free mirror surface. Test specimens are prepared within one hr of the
experiment to prevent any surface contamination.
1 litre of O.5M H2S04 + 0.0 1M KCNS solution is prepared from reagent grade chemicals and distilled water.
Around 500ml of the solution is used for each test. The temperature of the solution is maintained at 30 C
1C by circulating water in the double-wall cell using the thermostat. The solution is purged with high
purity nitrogen gas for about 2min before the test and continuously during experimentation.
The specimen is slowly immersed in the test solution taking care that only the specimen and part of Teflon
is exposed to the solution. The open circuit specimen potential i.e.the corrosion potential of the specimen
is noted after about 2min immersion in the test solution. If the rest potential does not lie in the range of -350
to -45OmV, then the specimen is cathodically charged at - 600mV for 2 to 5 min and the corrosion potential
is rechecked. Ifit still shows abnormal value, then the specimen has to be repolished. The specimen is then
polarized to a potentialof+200mVvs a saturated calomel electrode (SCE) for a period of2mts. After this,
the potential is decreased to its open circuit value, E corr, at a constant rate of 6v/hr. The potential(E) and
current(I) values are automatically plotted in E-logI format, using the plot mode. The specimen is then
removed from the cell, rinsed in water, dried and the surface is examined under optical microscope and
photographed. The grain size of the sample is measured at 100X. If the specimen is not sufficiently etched
after the test to reveal the microstructure, then it is electrolytically etched in 10% oxalic acid and the grain
size measured.
The specimen surface area is measured to the nearest O.lmm. The area under the reverse scan ofE vs log
I plot gives the integral charge value Q. This Q value is normalized to the grain boundary area for each
specimen using the relationship, flCoulombslcm2) = Q/GBA as described earlier. Pa is a direct measure
of DOS. All the heat-treated samples are tested as per the procedure outlined above and the values ofPa

562
From the figures it can be seen that for poorly sensitized sample, there is only a slight increase in current
density (I.) as the specimen potential is swept from the passive to active regions. This is due to the
negligible precipitation of chromium carbides along the grain boundaries. The I.values are extremely low
of the order ofless than O.5maJcm2 However, in the case of heavily sensitized samples especially at higher
temperatmes and longer durations, a very large increase in I.values were observed during the reactivation
scan. This is due to the high degree of chromium carbide precipitation along the grain boundaries. After
measuring the Q value from the curve, the DOS values are calculated based on equation (1) and the results
of all tests are shown in Fig.5 in terms of sensitization temperature, time and DOS values.
The results clearly indicate that with increase of time at constant temperature for samples heat-treated at
700C,650Cand600oC there is an increase in Pa value. At higher temperature or 700 C there is a
significant increase in Pa value even when samples are exposed to short durations of the order of 0.5 hrs.
At 600C there is a sharp increase in Pa value at 20 hours. At lower temperatures of 500C and 550 c,
there is no significant increase in P avalue even after an exposure time of 300 hrs indicating that the extent
of carbide precipitation is very less.
The examination of microstructures in optical microscope immediately after EPR testing was carried out.
The microstructures are indicative of the extent of grain boundary attack due to chromium carbide
precipitation during reverse scan. Microstructural examination after EPR testing of samples sensitized at
higher temperatures with DOS values> 20 C/cm2 showed extensive net work of grain boundary carbide~.
These samples are likely to fail by intergranular cracking as against the samples sensitized at low~r
temperatures where discrete carbides were seen. Typical microstructures are shown in Figure 6.

5.0 CONCLUSION

Based on the above studies the following observations are made.

1. The EPR technique is a sensitive tool in assessing quantitatively the degree of sensitization in 304H .
stainless steel.
2. The technique will be helpful in carrying out failure analysis investigations and ~ assessing the
microstructural degradation of aged 304H stainless steel after long term exposure in service which will be
useful in residual life assessment studies.
3. For use in industry, the EPR measurements has to be correlated with other parameters such as toughness
degradation and stress corrosion susceptibility.

6.0 ACKNOWLEDGEMENT

The authors thank Sri.KM.Chowdary and Sri.A.P.Rao for their valuable guidance during the course of
this investigation. The authors also thank the B.H.E.L. Management for giving permission to present this
paper.

564
7.0 REFERENCES

1. Clarke W.L., Romero V.M., Danko IC., Detection of Sensitization in Stainless Steel using
Electrochemical Techniques, NACE Corrosion Conference, Paper No. 180, California, 1977.
2. Clarke W.L., CowanR.L., Walker W.L., Comparative Methods for Measuring Degree of Sensitization
in Stainless Steel, ASTM STP 656, 1978, pp. 99-132.
3. Clarke W.L., The EPR Method for the Detection of Sensitization in Stainless Steels, NUREG/CR-I095,
GEAP-24888. Available from National Technical Information Service, Springfield, VA 22161.

565
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Nitrogen Ion Implantation of Type 316

Stainless Steel to Improve Intergranularand
Pitting Corrosion Resistances
u. Kamachi Mudali\ T. Sundararajan2, K.G.M. Nair and R.K. Dayall
IMetallurgy Division, ZMaterials Science Division,
Indira Gandhi Centre for Atomic Research,
Kalpakkam-603 102, India

ABSTRACT

Type 316 stainless steel (SS) specimens sensitised at 923 K for 0.5, 1, 10 and 100 h were ion
implanted using alSO keV accelerator at an energy of 70 keVin different doses of nitrogen between 1 x
1016 to 3 x H)7 ions/em. Electrochemical potentiokinetic reactivation (EPR) tests were carried out to
assess the degree of sensitisation and intergranular corrosion (IGC). Specimens implanted at 1 x 1016
ions/cmz showed less charge values whereas those implanted at 1 x l(}? ions/cm showed insignificant
charge values, compared to unimplanted specimens sensitised up to 10 h indicating an improvement in the
IGC resistance. Specimens sensitised for 100 h showed excellent improvement at 3 x 1017 ions/cmz with
insignificant charge value. SEM observation of the tested specimens showed the absence of grain boundary
attack in the implanted specimens in comparision with unimplanted specimens. Potentiodynamic anodic
polarisation ~tudies carried out in an acidic chloride medium indicated that the pitting resistance improved
with nitrogen ion implantation for solution annealed specimens. In the case of sensitised specimens, the
fully sensitised specimens aged beyond 0.5 h showed a clear improvement in the pitting resistance.

INTRODUCTION

Austenitic stainless steels are extensively used in chemical, power, fertiliser, oil, refinery and
petrochemical industries where good corrosion resistance combined with ~dequate mechanical properties
is required. However, the components made of austenitic stainless steels are prone to intergranular
corrosion (IGC) whenever they are heat treated or slowly cooled through the temperature regime 723 -
1023 K and subsequently used in an aqueous environment [1-4]. This is due to sensitisation, during which
chromium-rich (...{j5%) Mz3C6carbides are formed along the grain boundaries with sufficient chromium-
depleted (::;;9 %) zones adjacent to them. In the present work an attempt was made to modify the surface
of sensitised type 316 stainless steel by nitrogen ion implantation. It is well known that by ion implantation
surfaces can be suitably modified to a few hundred angstrom thickness in a controlled manner by

566
implanting elements which are beneficial for improving corrosion resistance. In liddition, ion implantation
by itself -creates a near-amorphous layer of high corrosion resistance on the surface of the materials.
However, the extent of corrosion resistance depends on the parameters like, energy, dose, vacuum pressure
et-c,during ion implantation [5-7]. Nitrogen addition to stainless steels have been reported [8-12] to
improve the resistance towards -pitting, crevice corrosion, intergranular corrosion, and stress corrosion
cracking in some media. In the preserit work an attempt is made to implant nitrogen ions into the surface
of sensitised type 316 SS to study the changes in the intergranular corrosion and pitting corrosion
resistances. The results of the present investigation are described in this paper.

EXPERIMENTAL
Materials

The chemical composition of type 316 SS used in the present study is shown in Table 1. Prior to
sensitising heat treatment specimens of 10 x 10 x 5 mm were solution annealed at 1323 K for 30 minllte:;
in a high-temperature high-vacuum furnace (GCA make, USA) at 10-6 mbar. Sensitisation heat treatment
was carried out in a muffle furnace at 873 K for 0.5, 1, 10 and 100 h, and these specimens were polished
up to 1 I-lmfinish prior to ion implantation.

Table 1 : Chemica/composition of type 316 SS

Ion Implantation

Nitrogen ion implantation of the sensitised specimens were carried out using a 150 keY particle
accelerator at an energy of 70 keY. Nitrogen ions of 1 x 1016and 1 x !017 ions/cm2 were implanted for all
conditions, and at 3 x 1017 ions/cm2 for specimen aged for 100 h only. The vacuum in the target chamber
was maintained below 1 x 10-6mbar, and the beam current was 2 1-lA.After ion implantation the specimens
were examined for the surface appearance, and were attached with a brass rod using conducting silver paste
for electrical contact.

IGC Studies

The sensitised specimens were electrolytically etched in 10% ammonium persulphate solution at
6 V for 90 s as per ASTM A262 practice A test [13]. The resultant microstructure was classified as step,
dual and ditch structures. The EPR tests were carried out on both sensitised and implanted specimens as
per the procedures laid down by Clarke et al [14] and they are as follows: electrolyte - 0.5 M H2S04 + 0.01
MNH4SCN, scan rate - 6 V/h, passivation potential and time - +200 mV(SCE) and 120 s, deaeration by
argon purging. According to this test, a sensitized material shows significant reaction peak current and
charge density values which can be correlated to the degree of sensitization. The higher the reactivation
peak current and charge density values, the higher is the susceptibility of the material to sensitization and

567
IGC. After the electrolytic etching and EPR tests the specimens were observed in an optical microscope
and scanning electron microscope (SEM).

Pitting Corrosion Studies

Pitting corrosion studies on the specimens were carried out by potentiodynamic anodic
polarisation method in a solution containing 0.5 M NaCI and 0.5 M H2S04 at room temperature. The
electrode potential was measured with respect to a saturated calomel electrode (SCE). The electrolyte
was continuously purged with argon gas to deaerate the solution, and the potential was anodically
scanned at a rate of 10 mV/min from -500 mV(SCE) to a potential till pitting occurred. The potential
at which there was a monotonic increase in the anodic current was termed as the critical pitting
potential, Epp above which stable pitting occurs. The details of the experimental procedures can be
found elsew)1ere [15-19]. After the tests, the specimens were observed in SEM/EDAX for the
morphology of pits.

RESULTS AND DISCUSSION

Intergranular Corrosion Resistance

The microstructure of the etched specimens showed that ditch structure was present for all
specimens except the specimen sensitised for 0.5 h which showed dual structure. Thus the specimens
aged beyond 0.5 h are prone to intergranular corrosion. Figures 1 (a) and (b) show the ageing ti~e
versus peak current density and charge density respectively, for the as-sensitised and ion implanted
specimens. It can be seen that both the parameters increased as the ageing period increased

irrespective of the nitrogen dose value. However, the specimens implanted at 1 x 1017 ions/crrt
showed no reactivation peak till 10 h, and less peak current density and charge values were noticed
at 100 h. SEM examination (Fig. 2 (a-d of the specimens showed that up to 10 hours of ageing no
grain boundary attack was visible for the specimens implanted at 1 X 1017 ions/crrt. However,
discontinuO!'s grain boundary attack was found for the implanted specimens sensitized for 100 h. The

568
specimens implanted at 1 X 1016 ions/cm2 showed severe grain boundary attack for all the specimens
except for the specimen aged for 0.5 hour. The improvement in the IGC resistance of the specimens
could be attributed to the following reasons : (i) the formation of a near-amorphous surface, (ii)
formation of nitrogen-enriched surface and (iii) combined protective oxide-nitride compounds at the
surface. The presence of nitrogen at the surface has been reported [8-12] to significantly improve the
passive film stability and localised corrosion resistance of austenitic stainless steels. The presence of
higher nitrogen content at the surface enhanced the passivability at the chromium-depleted zones at
higher doses, and thus IGC resistance was improved.

Figure 2 shows the SEM micregraphs of the EPR tested implanted specimens
a) 0.5 h /1x 1016 b) 100 h /1 X 1016 c) 10'h /1 x 1017 d) 100 h /1 X 1017

569
Pitting Corrosion Resistance

In comparision with the solution annealed specimen, the nitrogen ion implanted specimen (1
x 1017 ions/cm2) showed lesser criticalcurrent density and passivation current density, and higher
pitting potential as shown in Fig. 3. This implies that nitrogen ion implantation improves the pitting
corrosion resistance which could be attributed to the beneficial effects of nitrogen. However,
contradictory reports have been published on the role of nitrogen ion implantation on the pitting
corrosion resistance. Sabot et al [20] reported that nitrogen ion implantation at 2.5 X 1016 ions/cm2
significantly lowered the pitting resistance of type 304 SS in chloride medium, and they have
attributed the deterioration in localised corrosion resistance to the ferrites formed due to the migration
of cmomium at low doses, and to the formation of various nitrogen compounds at high doses.

In the case of sensitised specimens different results were observed in the present study. The
specimens aged for 0.5 hour showed significant
deterioration in localised corrosion behaviour with
lesser critical pitting potential (Fig. 4). However, the
critical current density and the passivation current
density were lower compared to those of as-sensitised
specimens. The specimens aged for I and 10 h showed
improved pitting resistance upon ion implantation at I
x 1017 ions fcrn. in comparision with as-sensitised
specimens (Fig. 5 (a&b. Also, the critical current
density and passivation current density values were
lower with increase in dose value in comparision with
as-sensitised specimens. For the specimens aged for
100 h, the critical current density was lower with
increase in dose value (Fig. 6). The passivation
tendency was also higher with increase in dose value
compared to as-sensitised specimen which did not
show any tendency for passivation. SEM observation
(Fig. 7 (a&b of the pitted specimens showed deep and grown pits for the as-sensitised specimens
whereas shallow and smaller pits were observed for the ion implanted specimens.

The deterioration in the pitting resistance of type 304 SS has been reported due to (i) the
formation of ferrite at grain boundaries due to the migration ofCr during ion implantation [21], and
(ii) the formation of various precipitates and the damage caused due to implantation [20]. In the case
of type 316BS, the presence of molybdenum significantly improved the pitting resistance [22]. The
combined effect of molybdenum and nitrogen has been reporte<.ito be very significant in improving
the pitting corrosion resistance [19]. During implantation it was reported [20] that an oxide layer, Ni
and Cr enriched zone followed by nitrogen enriched zone was present from the top of the surface
towards the bulk. In that case during the active dissolution the oxide layer and the Cr and Ni enriched
layers could have dissolved in the acidic chloride medium of pH ~ I compared to neutral chloride
medium which provided a spontaneous passivity. Thus during passivation the presence of a nitrogen-
enriched zone promoted a stable passive film in the present study. It is well known that nitrogen
improved the passive film stability and pitting corrosion resistance by anyone of the following ways
: (i) during pit growth, nitrogen dissolves at the pIt site to form ammonium ions, and thus increased
the pH inside the pit leading to an unfavourable condition for the growth of pits [23], (ii) the
dissolution of nitrogen at the pit site, and the subsequent formation of an inhibiting nitrate or nitrite
improved the repassivation tendency and the stability of the passive film [IS], and (iii) enrichment of
nitrogen during anodic dissolution and the blocking effect of nitrogen on the surface [24,25]. In the
present work due to the predominant effect of nitrogen over the ferrite zones led to an improvement
in the pitting corrosion resistance of solution annealed and sensitised specimens. Nair et al [21]
described that the migration of chromium to the grain boundary compensated the chromium depleted
zones developed during the sensitisation treatment. Thus there was a significant 'improvement in the

571
pitting resistance. However, in the case of specimens aged for 100 h, a higher dose of nitrogen, 3 x
1017 ionslcm2, was necessary for this purpose.

CONCLUSIONS

The following conclusions could be drawn from the results of the present investigation on the
intergranular and pitting corrosion resistances of type 316 SS with nitrogen ion implantation:

1. With increase in dose value, both reactivation peak and charge density values decreased
indicating an improvement in the IGC resistance. SEM observation showed severe grain
botindary attack for specimens implanted at 1 X 1016 ions/cm2, whereas for specimens implanted
at 1 X 1017 ions/cm2 no severe grain boundary attack was seen.

2. The pitting resistance of the ion implanted specimen increased as the dose value increased in
comparision with the solution annealed specimen in acidic chloride medium.

3. The sensitised specimens showed variation in the pitting resistance as the ageing period
increased. No improvement in pitting resistance was noticed for specimen.s aged for 0.5 h,
whereas a clear improvement was noticed for the specimens aged for 1 and 10 hat 1 x 1017
ionslcm2 SEM observation showed deep and grown pits for as-sensitised specimens compared
to shallow and smaller pits for the ion implanted specimens.

ACKNOWLEDGEMENTS

The authors thank Dr. V.S. Raghunathan, Head, Metallurgy Division, and Dr. Baldev Raj,
Director, Metallurgy and Materials Group for their keen interest in the above work.

REFERENCES

1. E.C. Bain, R.H. Aborn, and J.J.B. Rutherford, Trans. Am. Soc. Steel Treating, 1933, Vol. 21,
pp.481-509.
2. R.L.Cowan, II and C.S.Tedmon, Jr., Advances in Corrosion Science and Technology, Vol.3,
M.G.Fontana and R.W.Staehle, Eds., Plenum Press, New York, 1973~ pp.293-400.
3. V.Cihal, lntergranular Corrosion of Steels and Alloys, Elsevier Publishing, Amsterdam 1984.
4. S.M.Brummer, L.A.Charlot and D.G.Atteridge, Evaluation of Welded and Repair-welded
Stainless Steelfor Light Water Reactor (LWR) Service, Reports NUREG/CR 3918, PNL~5186,
USA, 1984.
5. V. Ashworth, W.A. Grant and R.P.M. Procter, Corr. Sci., Vol. 16, 1976, pp. 661-675.
6. V. Ashworth, D. Baxter, W.A. Grant and R.P.M. Procter, Corr. Sci., Vol. 16, 1976, pp. 775-786.
7. E.McCafferty, P.G.Moore, J.D.Ayers and G.K.Hubler, Corrosion of Metals Processed by
Directed Energy Beams, eds. C.R.Clayton and C.M.Preece, The Metallurgical Society of AIME,
New York, USA, 1982, p.1.

572
8. J.J.Eckenrod and C.W.Kowach, in Properties of Austenitic Stainless Steels and Their Weld
Metals (Influence of Slight Chemistry Variations), ASTM'STP 679, ASTM, Philadelphia, 1979,
pp.l7-41.
9. U.Karnachi Mudali, Studies on Pitting, Intergranular Corrosion and Passive Film in
Nitrogen-Bearing Austenitic Stainless Steels, Ph.D Thesis, University of Madras, India, March
1993.
10. T.A.Mozhi, K.Nishimoto, B.E.Wilde & W.AT.Clark, Corrosion, Vo1.42, 1986, p.197
11. U.Karnachi Mudali, RK.Dayal,J.B.Gnanarnoorthy and P. Rodriguez, Metallurgical
Transactions A, Vo1.27A, 1996, pp.2881-2887.
12. U.Karnachi Mudali, R.K.Dayal, J.B.Gnanarnoorthy and P. Rodriguez, Transactions of IIM, Vol.
50,1997, pp. 37-47.
13. Standard Recommended Practices for Detecting Susceptibility to Intergranular Attack in
Stainless Steels, ASTM A262 Practice A, Vol 03.02, American Society for Testing and
Materials, Philadelphia, USA, 1986, p.2.
14. W.L.Clarke, RL.Cowan and W.L.Walker, Intergranular Corrosion o/Stainless Alloys, ASTM
STP 656, American Society for Testing and Materials, Philadelphia, USA, 1978, p.99.
15. U.Karnachi Mudali, R.K.DaYal, T.P.S.Gill and J.B.Gnanarnoorthy, Werkstoffe und Korrosion,
Vo1.37, 1986, pp.637-643.
16. U.Karnachi Mudali, R.K.Dayal, T.P.S.Gill and J.B.Gnanarnoorthy, Corrosion, Vo1.46, 1990,
ppA54-460.
17. U.Karnachi Mudali, AK.Bhaduri and J.B.Gnanarnoorthy, Materials Science and Technology,
V01.42, 1990, ppA 75-481.
18. U.Karnachi Mudali, H.S.Khatak, RK.Dayal and J.B.Gnanarnoorthy, Journal of Materials
Engineering and Performance, V 01.2, .1993, pp.135-140.
19. U.Karnachi Mudali, R.K.Dayal, J.B.Gnanarnoorthy and P.Rodriguez, Materials Transactions
JIM, VoU7, 1996, pp.1568-1573.
20. R. Sabot, R. Devaux, AM. De Becdelievre and C. Duret-Thual, Corr. Sci. Vol. 33, 1992, pp.
1121-1134.
21. M.R. Nair, S. Venkatrarnan, D.C. Kothari and K.B. Lal, Nuc. Inst. and Meth. in Phy. Res., Vol.
B34, 1988, pp. 53-61.
22. K. Sugimoto and Y. Sawada, Corr. Sci., Vol. 17,1977, pp. 425-4~5.
23. C.R.Clayton and K.G.Martin, in Proceedings of The International Conference on High Nitrogen
Steels HNS 88, The Institute of Metals, Lille (France), 1988, pp.256-260.
24. R.C.Newman and T.Shahrabi, Corrosion Science, 27 (1987), pp.827-838.

573
Proc. In!. ConI'. on Corrosion CONCORN '97
December 3-6. Mumbai, India

Effect of Alloying Elements on the Polarization

Behaviour of Low Carbon Steels
K. Ravi, A. Bhattacharyya a:nd K.B. Mishra
Research and Development Centre for Iron & Steel,
Steel Authority of India Ltd, Ranchi-834 002, India

Abstract

Polarization studies on four laboratory made steels were conducted. These steels were (i) A
plain carbon steel, (ii) Plain carbon steel alloyed with CU,Cr and Ni, (ii.) Plain carbon
steel alloyed with CU,Cr, Ni and AI and (iv) Plain carbon steel alloyed with CU,Cr,Ni and Mo.
Potentiodynamic studies, corrosion rates by weight loss method, and metallography of the
steels were studied. It was observed that when the steel is alloyed with CU,Cr and Ni, the
corrosion' rate decreased by 55%. When the steel is alloyed with CU,Cr,Ni and Mo, the
corrosion rate further decreased by 85%. But when the steel is alloyed with 0.5% AI, ~Iong
with CU.Cr and Ni the corrosion rate had increased by 130% from 6.5 to 16.4 mpy. The best
corrosion rate was observed for the alloy containing Cu, Cr, Ni and Mo.

Introduction
Low carbon steels are widely used for car body manufacturing, construction industry,
and many other applications. The possibilities of application depends upon the corrosion
behaviour. In this respect, the necessity to characterize electrochemical properties is the first
step to a more extended study of the corrosion problem. The use of electrochemical tests
are attractive because they operate on the mechanism .of the corrosion process [1-2]. The
corrosion of metals in aqueous electrolytes occurs by an electrochemical mechanism.
Electrochemical techniques offer a clean way to accelerate th~ corrosion process. For
example, they can be used to increase or to control the oxidizing potential of an environment
and thereby reveal specific characteristics of a material, such as passivity, without adding
chemical oxidizing agents. The critical pa~ameters that can be used to evaluate anodic
polarization curves are (i) critical current density (lcr), (ii) primary passive potential (Epp), (iii)
secondary current density maximum (Isc)' (iv) secondary passive potential (Esc),and passive
potential range (Rpp). The critical current density is an indicator of how easily the passive
state of low corrosion rates may be achieved since a small Icr encourages spontaneous

574
passivation. Maxima in the passive region, such as Isc,are indicative of the unstable passive
films or some electrochemical event that could lead to high corrosion rates under given
environmental conditions. The length of the passive potential range (Rpp) is important
because it reflects the variety of environments in which low corrosion rates prevail.
Electrochemical techniques can be used to measure corrosion rates without removing the
specimen from the environment. The corrosion rate will be an average over the entire
specimen.
It is well known that certain elements such as copper, nickel, chromium, molybdenum
and others improve the corrosion resistance of the steels. Copper stabilizes the deleterious
element sulfur in the steel in the form of cuss and increases the corrosion resistance of the
steels [3]. Copper additions to pure iron did not exhibit benefit compared to sulfur containing
steels. Improved corrosion resistance of steels due to chromium on atmospheric corrosion is
described by Maxwell [4]. Additions to low carbon steels by progressively increasing amount
of chromium led to continuously decreasing corrosion rates. The most notable effect was
produced by the first 3% of chromium. Excess chromium may deteriorate the corrosion
resistance due to formation of carbides with incoherent interfaces with the matrix. Yashino
[5] reported that nickel upto 1% increased corrosion resistance of the steels in acidic
environment. In high carbon steels addition of nickel is not desirable. Such additions may
lead to formation of needle shaped pearlite resulting in decreased corrosion resistance.
Molybdenum increases the resistance of steel to atmospheric corrosion. It was observed that
0.5% molybdenum in low alloy steel reduces the corrosion index from 145 to 45 mpy [6].
Molybdenum was found to refine the ferrite grain size and reduce the tendency for formation
of banded structure. The optimum molybdenum conte,nt is in the range 0.3% to 0.5%.
Excess molybdenum suppresses the carbon diffusion by lowering the transformation
temperature and promoting the formation of bainite and martensite/austenite islands [7]. This
decreases the corrosion resistance of the steels. Alloying plain carbon structural steels with
aluminum was found to ir:lcreasethe resistance to stress corrosion cracking [8]. Vereschagin
et al [9] show,ed that aluminum content in the range 0.20% to 0.47% in 16GS type steel
improves the resistance to stress corrosion cracking at stre~s levels less than 25 kgf/mm2.
However, corrosion resistance was found to decrease in steels of type 10kh2GMYu, where
aluminum content in the steel was more than 1% [10]. The favourable effect of aluminum is
due to the fact that it permits a substantial reduction of the solubility of carbon in ferrite and
makes it easy to obtain a structure of ferrite with evenly distributed carbides as a
consequence of which the corrosion resistance is improved.
Present studies are aimed at evaluating low carbon steels with different alloying
elements for their corrosion resistance. As electrochemical techniques have gained wide
acceptance in comparing different alloys, this method is selected in the present studies. For
electrochemical testing the corroding sample must be in an electrolyte. Ammonium nitrate
can be used as electrolyte because in this environment steels not only exhibit active-passive
behaviour, but are also subject to such types of corrosion as crevice corrosion, pitting,
intergranular attack, and stress corrosion cracking.

Experimental Methods
Materials: All the steels were made in a 100 kg air induction furnace and were cast into
ingots. These ingots were hot rolled to 7 mm thick plates. The chemical composition of the

575
steels studied are given in Table 1. Steel 1 is a plain carbon steel without any alloying
elements. Steel 2 is alloyed with copper, chromium and nickel. Steel 3 is alloyed with 0.5%
aluminum along with copper, chromium and nickel. Steel 4 is alloyed with 0.3% molybdenum
along with copper, chromium and nickel. Samples were prepared from these steels for
polarization studies, weight loss measurements and metallography.

Table:1 Chemical composition of the steels (Wt%)

Polarization tests: Polarization tests were carried out with AMEL potentiostat (Model 549).
Experiments were carried out in 1N ammonium nitrate solution, prepared from reagent grade
salt and distilled water. A standard polarization cell supplied by EG&G Princeton Applied
Research Centre was used for conducting the experiments. Standard samples of 15.5 mm
diameter and 3 mm thickness were used. Tests were carried out from -500 mV (cathodic
region) to +1000 mV (anodic region) at a scan rate of 50 mV per minute. A standard calomel
electrode was used as reference electrode. All the samples were polished through 400 grit
SiC paper to provide an uniform cross section and a reproducible surface. After polishing,
each specimen was cleaned in acetone in ultrasonic cleaning tank before immersion in the
electrolyte. Polarization curves were plotted on semi-logarithmic graph.
Determination of corrosion rates by weight loss method: Samples were exposed
for different periods ranging from 40 to 200 hours to 1N ammonium nitrate solution.
Corrosion rates were determined as follows:
Corrosion rate, mils per year (mpy) = K x WI ATD
where K = constant = 345 x 106
W = weight loss in grams
A = area exposed in cm2
T = time of exposure in hours
D = density, gm/cm3 = 7.8

Metallography: Microstructures of the steels were studied under an optical microscope

after etching with 2% nital. Detailed examinations were carried out with Scanning AL.:ger
Microprobe, Model JAMP 7100, Jeol, Japan.

Results
Microstructures: The microstructures of the steels had exhibited mostly ferrite-pearlite
structures. Auger spectra for steel 4 on pearlite, ferrite and grain boundary area are given

576
Fig.1. Copper and molybdenum contents are more in ferrite than in pearlite. Presence of
sulfur is more in pearlite than in ferrite.
Polarization studies: Polarization curves of the steels are given in Fig.2. Steel 2 and 4
exhibited active-passive behaviour where as steels 1 and 3 did not exhibit passive
behaviour. Current densities observed in the anodic region at +500 mV are given in Table 2.
Highest current density of 125 mAlcm2 was observed for steel 1 i.e. for plain carbon steel.
Lowest current density of 0.02 mAlcm2 was observed for steel 4 which contains copper,
chromium, nickel and molybdenum. This shows that steel 4 is possessing the best corrosion
resistance among the steels. Addition of copper, chromium, nickel to a plain carbon steel
(steels 1&2) resulted in decrease in the corrosion current from 125 to 4 mAlcm2 But addition
of 0.5% aluminum to the plain carbon steel (steels 1&3) resulted only in a marginal decrease
in the current density from 125 to 110 mAlcm2. Addition of copper, chromium, nickel and
molybdenum to a plain carbon steel (steels 1&4) resulted in the lowest corrosion rate.

Corrosion rates by weight loss method: Corrosion rates of the steels determined by
weight loss method are given in Table 3. Corrosion rates for steels 2 and 4 were lower as
compared to steel 1 which is a plain carbon steel lNithout any alloying elements. But
corrosion rate was found to increase for steel 3 which contains 0.5% aluminum along with
copper, chromium and nickel. Lowest corrosion rate was observed for steel 4 which contains
molybdenum along with copper, chromium and nickel. The corrosion rate was lowered from
14.8 mpy for steel 1 to 0.95 mpy for steel 4 after 200 hours of exposure, a decrease by 15
times.

Table:3 Corrosion rates of the steels by weight loss method (mpy)

577
Discussion
The results obtained in the present investigations rank the different steels in order of
their corrosion resistance as follows:
1. Steel 4, which contains Cu, Cr, Ni and Mo
2. Steel 2, which contains Cu, Cr and Ni
3. Steel 1, which is a plain carbon steel
4. Steel 3, which contains Cu, Cr, Ni and AI
The corrosion resistance characteristics of steel 4 have been found to be much
superior to other steels. This is due to the direct effect of the composition of the steel.
Molybdenum improves the resistance of the steels to pitting, and it reduces the tendency for
the formation of banded structure [7]. Also, copper improves the corrosion resistance by
formation of' CU2S, thus stabilizing the deleterious element sulfur in the steel. Sulfur
decreases the corrosion resistance of the steel in aqueous solutions [11]. When the
corrosion resistance of steels 1 and 2 are compared, it is evident that addition of copper,
chromium and nickel improves the resistance of the steel. Additions of copper, chromium,
nickel and molybdenum to the low carbon steel exhibited the best corrosion resistance for
.steel 4. This is due to the combined effect of copper, chromium, nickel and molybdenum as
well. But, addition of 0.5% aluminum along with copper, chromium and nickel resulted in
decrease in the corrosion resistance. The corrosion rate had increased from 6.5 mpy for
steel 2 to 16.4 mpy for steel 3 after 200 hours of exposure. This shows that aluminum does
not form a stable film in the medium studied. Available literature cites that addition of
aluminum to carbon steels had not shown any consistent results. Vereschagin etal [9]
observed that aluminum in the range 0.20 to 0.47% improves stress corrosion resistance at
lower stress levels, less than 25 kgf/mm2 But Golovanenko etal [10] had observed that
addition of aluminum in the excess of 1% decreases ~he corrosion resistance of the carbon
steels. Most of the studies on the effect of aluminum in carbon steels were carried out in
quenched and tempered condition [8-10]. In the present studies due to the non stable
corrosion film formed in ammonium nitrate solution, corrosion resistance of the steel is not
improved. Its corrosion rate was found to be similar to that of steel 1, which is a plain carbon
steel. Hence, the addition of aluminum to the steel is not desirable in the medium studied.

Conclusions

1. Addition of copper, chromium and nickel leads to lowering of corrosion rate by 50%.
2. Addition of molybdenum to a steel containing copper, chromium and nickel further
decreases the corrosion rate by 85%.
3. Addition of aluminum leads to either decrease in the corrosion resistance or increase
in the corrosion resistance depending upon the heat treatment condition, composition
and stress factors.
4. Addition of aluminum to a steel containing copper, chromium and nickel vyas found to
decrease the corrosion resistance in the present studies. The corrosion resistance of
aluminum containing steel is same as that ot'plaincarbon steel.
5. The best corrosion resistance was observed for steel 4 containing copper, chromium,
ni,..l,ol <>nrl rnnl\lhrlonllrn

580
References:
1. Higuchi, S., J.lron and Steel Institute of Japan, Vol.79, No.8, 1993, pp.961
2. Cash, GA, Schweinsburg, D.P., Hope, GA, Flih, H.J., Corrosion Science,
Vol. 33, No.3, 1993, pp.113
3. Fyfe, D., Proc. 4th Int. Congress on Metallic Corrosion, NACE, 1972, pp.399
4. Maxwell, X., Korroziv Metal/ov, No.1, 1952 pp.24
5. Yashino, Y., Corrosion, Vol 38, 1982, pp.156
6. Atmospheric Corrosion of metals, E.C. Grece(eds.) NACE, Houston, Texas,
1992, pp.156
7. Liao, C.M., Lec, J.L., Corrosion, Vol.50, No.9, 1994, pp.695
8. Zapffe, C., Sims,S., TransAIME, Vol.149, 1941, pp.225
9. Vereschcagin, K.I., Rubenchik, Yh., Karpenko, G.V., Fiz.Khim. Mech. Mater, Vol.
5,1971, pp.15
10. Golovaneko, SA, Konnova, I.Yu., Sergeeva, T.K., Metal/oved. Term.Obrab.Met,
Vol.8, 1976, pp.30
11. Dahl, W., Stahl and Elsen, Vol 87, No.3, 1967, pp.125

581
Proc. lnt. ConI. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Structure-Electrochemical Correlations in Amorphous and

Devitritied Fe-Based Ferromagnetic Alloys
I. Chattoraj and A. Mitra
National Metallurgical Laboratory,
Jamshedpur-831 007, India

ABSTRACT
The electrochemical response of some Fe-based ferromagnetic alloys in a few common electrolytes are
discussed. Potentiodynamic studies on amorphous, stress relaxed (but amorphous) and cre:vitrified alloys are
reported. The influen~ of crystallinity and alloying elements on. the electrochemistry of the alloys are
discussed.

INTRODUcnON
The synergistic effects ofNb and Cu on the crystaIlisation ofFe-B-Si alloys led to a class ofnanocrystalline
alloys which had excellent magnetic properties (l). The cootrolled mmeaIing of Fe-B-Si-Nb-Cu is utilised to elCploit
the excellent magnetic properties of these alloys in the nanocrystalline State. The structural changes ocxmring 00
crystaIlisatioo have been studied for these nanocrystaIline alloys (2-7) which demoostrate multiple stages of
crystallisation. It was initially felt that the result of the primary crystaIlisatioo process was a body cattred albic a-Fe
phase, but there is' increasing evidence now that the primary product is an ordeced IX>.J phase having a stoichiornry
close to FemSho (4-7). 1ht1e is some evidence that a critical cmcentratioo of Si is required for the formation of the
~ phase (6).
While the magnetic properties, crystallisation kinetics and the stmcturaI changes of Fe-B-Si-Nb-Cu alloys
have been studied exttnsively, there is very little infonnation regarding the electrochemical bEhaviour of~ alloys.
Such studies would be important for the widesj:>noo commercial utilisation envisaged for these alloys, since most
applications would expose the alloys to nonna! atmospheric 'environments and resultant corrosioo. This investigation
reports how the process of crystaIlisation affects the electrochemical ptq)erties of sonie Fe-B-Si-Cu-Nb
ferromagnetic alloys. The relative influence of the various alloying elements on the electrochemistry of the amorphous
as well as devitrified states are examined. It is shown that the electrocben1ical response is significantly aItered by the
process of crystaIlisatioo.

EXPERIMENTAL PROCEDURES
In this investigation four Fe-Si-B-Nb-Cu alloys were examined for thei~electrochemical bEhaviour and
structural modifications, and these had the nominal compositions shown in Table I. These alloys were prepared by
melt-spinning technique and kindly provided by Dr. P. Duhaj of the Institute of Physics, Slovak Academy d Sciences.

582
 Additiooally two well known Fe-Si-B commercial alloys, 2605S2 and 2605SC were also studied electrochemically to
provide an idea of the relative corrosion resistance of the former group of alloys. All the alloys were amorphous in the
as-receiVed state and were in the form of ribbons 1 an wide and about 25J.1D1thick. The alloys were subjected to .
. resistivity scans from room temperature up to 750C, at a scan rate of 20C/minute, in vacuwn, to estimate the
transition temperatures. To introduce structural cbanges, the alloys were heated at a scan rate of 20C/minute in
vacuum up to specified temperatures, and then furnace cooled. In this fashion, for each alloy three c:Iifferentstructures
were obtained, namely: (i) amorphous as-received, (ii) scanned up to 470C producing st:ruc:t:ureIstressrelaxation in
amorphous matrix, (iii) scanned up to 600C - crystallised to differmt extents producing a primary crystalline phaSe
and amorphous grain boundary phase. Both electrochemical and X-ray diffiact:ion (XRD) studies were cooducted on
the four alloys heat treated as above. The XRD studies used a Co K-a radiation.

The electrochemical studies on the alloys in their amorphous states were conducted in 0.1 N HzS04 and in 3.5%
NaO solutions at ambient temperature (25 +/- 1 0c). The isothermally annealed alloys were studied in 0.1 N N~S04
solution. The electrolytes were prepared from double distilled water and reagt'I1tgrade chemicals. The electrochemical
be11aviourwas measured by potentiodynamic polarizations performed at a scan rate of 1 mVlseoond. A platinum rod
counter electrode and a saturated calomel refennce electrode (SCE) were used. The amorphous and heat treated
alloy ribbons were cleaned with aatone; no other polishing treatments were provided prior to the tests. The alloys, in
their amorphous condition, were also subjected to immersion in simulated sea-water.

RESULTS and DISCUSSIONS

Amorphous State

The electrochemical response of the four Fe-B-Si-Nb-Cu alloys and the two commercial alloys in the two
test solutions are tabulated in Table n below. h is evident that the commercial alloys, 2605S2 and 2605SC, which are
Fe-Si-B alloys and thus devoid of Nb and Cu, have much worse corrosion resistance as compared to the family of
four Fe-B-Si-Nb-Cu alloys. Among the latter group of alloys, alloys C and D are very corrosion resistant to 0.1 N
H2S04 , in which solution both are fOlDldto passivate on anodic polarization. Although all the four alloys fail to
passivate in 3.5% NaCI, alloys C and D are quite resistant to corrosion in this medium, thus suggesting very good

583
utility of these alloys in marine atmospheres as well as regular atmospheric conditions. As a general observatim, all
the four alloy of the Fe-B-Si-Nb-Cu family have very good to reasonable corrosion resistance. Of these, alloy A is
quite suscq:>tibleto salt water corrosim, and alloy B also has less corrOsion resistance than alloys C and D.

Further proof of the good salt water corrosion resistance of the alloys C and D are obtained after inunersion
testing, the results of which are presented in Table ill below. The inunersion tests were conducted for poly one
month, hence the actual values may differ slightly if conducted over a year.

From tableS I and II it may be concluded that in the amorphous state, the presence of Nb and Cu improves the
corrosion resistance. This is borne out by the far better corrosion resistance of the Fe-B-Si-Nb-Cu family of alloys as
compared to the Fe-Si-B alloys. Within the Fe-B-Si-Nb-Cu family, evidently the presence of B is detrimental to
corrosion resistance, as indicated by the greater corrosion rate of alloy A. Alloy B seems to suffer due to its lower Nb
content, this is further proof of the benefits ofNb.

584
Devitrified State

Structural evolution
The evolution of the crystalline phases was studied by resistivity measuremmts as shown in figure 1. Here, a
change in the slope of the resistivity scan indicate evolution of a phase. From the resistivity scans, two armealing
temperatures were chosen, namely, 470C and 600C, armealing at the former temperature produced stress relaxation
without inducing crystaIlisation, and armealing at the latter temperature produced the primary crystalline phase. The
phases produced by armealing are indicated in Table IV. The alloys B, C and D have the same primary crystalline
phase, FegoSi20> but alloy A has a-Fe (Si) phase on crystaIlisation. While FegoSi20 is a superlattice phase having a
DO:J structure, a-Fe (Si) is a b.c.c phase with Si in solid solution. It has been reported that a critical amount of Si is
essential for the formation of the superlattice phase and the low-Si containing alloy A is thus deprived of the
superlattice phase on crystaIlisation.
ElectrocMmical ret$ponse

The electrOchemical behaviours of the alloys are quite dependent on crystallinity or the lack of it; moreover, the
alloys from the same family of Fe-B-Si-Nb-Cu alloys behave differently after crystallization. The changes in
the electrochemical responses with the evolution of crystallinity in the alloys is tabulated in Table V

TABLE V
Electrochemical response of the alloys after annealing, in 0.1 N Nll2S04

In the as received amorphous state, while the alloys A and B showed active dissolution at anodic potentials, alloy C
and Dwere passive. On heating up to 470C, which brought about short range ordering and stress relaxation, alloys
C and D were spontaneously passive in the electrolyte while alloy B was Set11to passivate after an active-passive
transition. On scanning up to 6ooC, the different alloys would have crystallised to different degrees. Alloys B, C and
D passivated spontaneously while alloy A remained chemically active in spite of the crystallisation. Thus the
evolution of the electrochemical properties of the four alloys occurred in different fashions consequent to armealing.
While the electrochemical response. of alloy A was essmtially l.III3ffectedby crystallisation, alloy B transformed from
an electrochemically active state in the amorphous oondition to become passive progressively with armealing up to the
formation of the primary crystallisation product. Alloys C and D were passive in the mtire armealing ttmperature
domain. It was fOlDldthat evtn prior to crystallisation, the process of structural relaxation brought about by
armealing at 470C, caused significant decrease in the corrosion rates of all alloys. Amongst the alloys, the striking
difference on crystallisation is the absence of the superlattice phase in alloy A. This absence is also reflected in the
different resistivity scans (Fig. 1). Our results suggest that the presence of the superlattice phase is beneficial to

586
ACKNOWLEDGEMENTS

The authors are grateful to Dr. Povol Duhaj of the Institute of Physics, Slovak Academy of Sciences,
Bratislava, for kindly providing the alloys used in this study. The authorsadmowledge the DepartmEntof Science
and Tedmology, India, for providing financial assistance for this investigation. The authors thank Professor P.
Ramad1andraRao, Director, National Metallwgical Laboratory, for his pennission to publish this article.

REFERENCES

1. Yoshizawa Y., Ogwna S. and Yamauchi K.,J. Appl. Phys., v64, 1988, p6044.
2. Yoshizawa Y. and Yamauchi K.,Mat. Trans. Jap.lnrt. Met., v31, 1990, p307.
3. Garcia Del Muro M, Batlle x., Zquiak R. and PareJlada 1., hoc. 4th lnt. Workshop Noncryst. solids,
Madrid, eels.M. Vazquez and A Hernando, p572 (1994).
4. R. Yavari, ibid, p35.
5. Muller M., Mattern N. and D1gt'1l L., J. Mag. Mag. Mat., v112, 1992,p263.
6. Muller M., Mattern N. and D1gt'1l L, Z. MEtallkde.,v82, 1991, p895.
7. Yavari A.R., Fish G., Das S.K. and Davis LA, Mater. Sci. Engg., v A1811A182,1994, p1415.

587
Proc. In\. Cont'. on Corrosion CONCORN '97
December 3-6, Mumbai. India

The Influence of Cr Addition on the Elevated

Temperature Erosion of Ni
Manish Roy, K.K. Rayl and G. Sundarajan2
Defence Metallurgical Research Laboratory, P.O. Kanchanbagh, Hyderabad-500 058, India
IDepartment of Metallurgical and Materials Engineering,

Indian Institute of Technology, Kharagpur-72l 302, India

21nternational Advanced Research Centre for Powder Metallurgy and
New Materials, Balapur, Hyderabad-500 005, India

ABSTRACT'

The primary objective of the present work is to assess the effect of Cr addition to Ni on the
dependence of erosion rate on test condition and also to understand its influence on the nature of
interaction between erosion and oxidation. Towards tlJis purpose Ni and Ni-20Cr alloy are eroded at
five different temperatures for three different impact velocities under normal impact conditions. The
result shows that erosion rate increases with increase of temperature and impact velocity for both Ni
and Ni-20Cr alloy. However, the nature of interaction between erosion and oxidation for Ni differ
significantly from that of Ni-20Cr alloy.

1. INTRODUCTION

Solid particle erosion implies degradation of material due to impact of particles traveIling with
significant velocity. Solid particle erosion at elevated temperature is an important mechanism for
material damage under a variety of industrial conditions [1-2]. Though substantial amount of literature
on room temperature erosion of metaIlic materials have been documented [3-6], the work on elevated
temperature erosion is stilI in its initial stage [7-12 ]. Further, erosion at elevated temperature causes
material loss by erosion and oxidation. The nature of interaction between erosion and oxidation is
governed by the thickness, adhesion, pliability and toughness of the oxide scale. The nature of the oxide
scale and its adhesion with the substrate is, in turn, controlled by the composition of the substrate
material.

Thus, the primary aim of the present work is to assess the influence of Cr addition to Nion the
dependence of erosion rates on test conditions and its effect on the mechanisms of interaction between
erosion and oxidation.

588
 2. EXPERIMENTAL DETAILS

2.1. Material :- Commercial pure Ni and Ni-20Cr is taken as the test materials. The measured
compositions of both the material is given in Table 1 along with their hardness. As can be seen, from
Table 1 that the hardness of Ni-20Cr alloy is almost double the hardness of C.P. Ni.

2.2. E r 0 S ion
Testing: Solid particle
erosion of Ni and Ni-
20Cr alloy was carried
out using high
temperature high
velocity erosion rig for
normal impact, particle
feed rate of 2 gm/min,
at three different
impact velocities of 35
mis, 65 m/s and 105
m/s. A schematic
presentation of the rig
is provided in Fig.1.
The erosion rig consists
of a compressor, air
drying unit, air heating
system, fluidising
chamber, particle
feeding system, test
chamber and sample
holding devices.
Compressed and dried air from the compressor is heated in the air heating system and them allowed to
enter the fluidising chamber. The hot air along with the fluidised particles then impacts the sample held
at test temperature at an angle of 90 with respect to the impacting particles. The details of the system,
methods of controlling test conditions and description of calibration of impact velocity is given in a
separate publication [13].

The standard test procedure is as follows. A number of polished, cleaned and weighed test
specimens were exposed to the given eroding condition for different interval of times. Each sample was
then taken out of the test chamber, cooled, cleaned and weighed again to measure the weight loss. If
WI' WZ..... Wn are the weight loss of the samples ingms exposed for tl, tz..... 1ntime to WI' WZ..... wn
amount of erodent (in gms.) then dimensionless incremental erosion rate (.dE) is given by, (Wz-W) I
(WZ-wI), (WrWJ I (w3-wJ .... (Wn-Wn_l) I (wn-wn). This erosion rate is expressed as gm/gm and the
experiment was repeated until incremental erosion rates reached a constant steady state value. This
steady state value will henceforth be called erosion rate (E).

589
 2.3. Examination of Eroded Samples: In order to study the morphology of the eroded surface,
eroded samples were observed under SEM. To understand the material removal mechanism eroded
:samples were plated with electroless Ni and then sectioned across the surface. The section surfaces
were subsequently polished and examined in SEM.

3. RESULTS

3.1. The Erosion Rate: The variation of

erosion rates as a function of cumulative weight
of the impinging particles at normal impact and
at impact velocity of 105 m/s are shown in Fig.2.
All circleS belong to materials tested at 1073K
and all triangles belong to materials tested at
room temperature. Unfilled circles or unfilled
triangles represent Ni, whereas filled circles or
triangles represent Ni-2UCr. As will be
discussed subsequently that erosion at 1073K
for both the material takes place by one
mechanism and the erosion of both the material
at room temperature occurs by a different
material loss mechanism .. However, it can be
clearly seen from Fig.2 that for both the material
removal mechanisms and for both the material,
erosion rate increases from an initial low value
and then attains a constant value. This constant
value is the characteristic erosion' rate of the
material at the test temperature. Because of the
similarity of t~e nature of plots, other data
describing incremental erosion rate at different
impact velocities and at different test
temperature are not presented.

The variation of erosion rate under normal impact condition as a function of temperature for
commercially pure Ni and Ni-20Cr alloy is presented in Fig.3. The erosion rates are given for three
different impact velocities namely 35 mis, 65 mls and 105 m/s. It is clear from Fig.3 that the erosion
rate increases with increase of impact velocity and test temperature. The rate of increase per unit
increase of temperature increases as the impact velocity and test temperature is increased. Even for Ni-
20Cr alloy also erosion rate increases with increase of impact velocity and test temperature. It is to be
noted that addition of Cr does not alter the erosion rate at low temperature. However, Cr addition
results in lower erosion rate at higher temperature and at low impact velocities (65 and 35 m/s) and
higher erosion rate at elevated temperature and high impact velocity (105 m/s).

590
 3.2. Morphology of Eroded Surfaces: The SEM
micrograph showing the morphology of the eroded
surface of Ni is illustrated in FigA. All the micrograph
corresponds to normal impact and to the impact
velocity of 35 mls. FigAa represents surface eroded at
room temperature (i.e. at 298K). FigAb belongs to the
surface eroded at 600C (i.e. at 873K) and finally
FigAc is v.alid for surface eroded at 800C (i.e. at
1073K). It is clear from FigA that at room
temperature material is removed by forming lip and
then fracturing these lips. This mode of material loss is
designated as metal erosion. At 600C also formation
of lip and their subsequent fracture is responsible for
material removal (FigAb). However, there is
substantial amount oioxide scale that can be seen as
white patch in each lip. Thus, iduring this mode of
material removal material loss takes place from a
composite layer containing the metal and the oxide
.scale and this mode of material removal mechanism is
called oxidation affected erosion. Finally, as shown in
Fig.4c, there is regions where the said scale has spalled.
Hence, in this regime material removal is primarily by
spalling of oxide scale and this mode is called
oxidation controlled erosion. As the impact velocity is
increased from 35 mls
to 65 mls or to 105 mis,
this particular mode of
material removal could
not be seen and only
metal erosion and
oxidation affected
erosion was present.
Thus oxidation affected
erosion dominates at
800C when impacted
at 105 mls and 65 mls
and also at 600C
when impacted at 65
mls and 35 m/s. At 35
mls this regime is
present even at 400C.
In rest of the test
condition only metal
erosion can be seen.
Moreover, the

591
transition from metal erosion to oxidation affected erosion takes place at higher temperature as the
impact velocity is increased.

For Ni-20Cr
alloy, the SEM
micrograph for the
morphology of the
surfaces eroded at
normal impact and at
impact velocity of 35
mls are shown in Fig.5.
Fig.5a through Fig.5c
corresponds to surfaces
eroded at room
temperature (298C),
600C (873 OK) and
800C (1073 OK),
respectively. In
contrast to Ni, in Ni-
20Cr alloy main
'material removal
mechanism is
formation of lip and
their subsequent Fig.5 : SEM micrograph showing the eroded surfaces of Ni-20Cr alloy.
fracture i.e. metal'
erosion up to 600C at 35 mls impact velocity. However, as the test temperature is increased to 800C
keeping impact velocity constant, there appears substantial amount of oxide scale along the edges of
each lip indicating that material removal takes place from a composite layer containing the metal and
the oxide scale. Though the presence of oxide scale in lips or this oxidation affected erosion can be
noticed in Ni-20Cr alloy impacted at 65 mls at 800C, no such material removal mechanism was
prevalent at any temperature when the same alloy was impacted at 105 m/s.

4. DISCUSSION

As mentioned earlier there are three different mechanisms for material loss in C.P. Ni and two
different mechanisms in case of Ni-20Cr. For the mechanism of Fig.4a, Fig.5a and Fig.5b, either there
is no oxide scale or the oxide scale plays a negligible role leading to erosion mainly from metal
substrate. Such erosion is characterised by ductile erosion response, velocity exponent of around 2.5
and a flux rate independent erosion rate [14]. For mechanisms described in Fig.4b and Fig.5c, both the
metal substrate and the oxide scale is involved in metal loss. As the erosion takes place from the oxide
scale in addition to metal substrate, the erosion rate is higher than metal erosion. This oxidation
affected erosion exhibits ductile or brittle erosion response and velocity exponent between 2 and in
excess of 3 depending on the amount of oxide scale present in the eroding composite layer [15].
Erosion rate in this regime is dependent on flux rate [16]. Finally, the mechanism of Fig.4c known as
oxidation controlled erosion takes place by spalling of qxide scale even though the damage due to

592
 impact is partially absorbed by metallic substrate. As a result the rate of erosion is significantly higher
than the metal erosion or oxidation affected erosion. Further, erosion in this regime shows a week
velocity dependence, a brittle erosion response and a flux rate dependent erosion rate [17].

The erosion rates for each regimes at higher

temperature can be estimated by extrapolating the
erosion rate in erosion rate vs. temperature plot and is
presented in Fig.6. At impact velocity of 35 mIs, the
extrapolated erosion rate of metal erosion regime is
much lower than the measured erosion rate at 400C
and 600C for Ni and at 600C or 800C for Ni-Cr.
Similarly, the erosion rates of oxidation affected
erosion regime of Ni when extrapolated to 800C
shows lower erosion rate than measured erosion rate
which pertains to oxidation controlled erosion regime.
Similarly, lower erosion rates of extrapolated metal
erosion regime than measured erosion rate at
oxidation affected erosion controlled regime can be
noted for Ni at an impact velocity of 105 m/s.

Thus, addition of Cr totally eliminates the

oxidation controlled erosion under test conditions
mentioned in this work and shifts the transition from
metal erosion to oxidation affected erosion to higher
test temperature and lower impact velocities. It is also
to be stated that Cr addition results in equal or D'6 Extn l t d . t
'" . rig.: apo a e erosIOnra es of
margmally mcreased eroSIOnrate compared to NI for .. t h' h t tu
.. " .. vanous regimes a 19 er empera reo
a gIven matenal loss mechamsm SImilar to what IS
observed at room temperature [18]. However, at
elevated temperature and low impact velocities erosion rate of Ni-20Cr alloy is lower than C.P. Ni as
different material loss mechanism operates.

5. CONCLUSIONS

1. The erosion rate of Ni increases with increase of impact velocity and test temperature. Addition
of Cr does not alter the above trend with regard to influence of impact velocity and test
temperature.
2. The addition of Cr shifts the transition from metal erosion to oxidation affected erosion to
higher test temperature and lower impact velocity and removes the oxidation controlled erosion
beyond the experimental conditions of present work.
3. Cr addition results in equal or marginally higher erosion rate than the base C.P. Ni provided
same material removal mechanisms is operative.

593
 REFERENCES
1. I.G.Wright, Matis. Sci. and Engg., 88 (1987) 261.
2. J.Stringer and S.Drenier, Proc. Am. Power Conf., 43 (1981) 943.
3. G.P.Tilly, Wear, 23 (1973) 87.
4. K.WelIinger and H.Vetz, Wear, 1 (1957-58) 255.
5. Manish Roy, Y.Tirupataiah and G.Sundararajan, Mater. Sci. and Engg., A165 (1993) 51.
6. I.Finnie, J. Wolak and Y.Kabil, J. Mater., 2 (1967) 682.
7. I.G.Wright, V.Nagarajan and J.Stringer, Oxid. of Metals, 25 (1986) 175.
8. A.V.Levy, E.Slamovch and NJee, Wear, 110 (1986) 117.
9. Y.Shida and H.Fujikawa, Wear, 103 (1985) 281.
10. W.Tabakoff and B.V.R.Vittal, Wear, 86 (1983) 89.
11. N.Gat and W.Tabakoff, Wear, 50 (1978) 85.
12. A.V.Levy and Yong-Fa Man, Wear, 131 (1~89) 39.
13. Manish Roy and G.Sundararajan, DMRL Technical Report.
14. J.Zhou and S.Bahadur, Ed. A.V.Levy, Proc. of Int. Conf. on Corrosiotl-Erosion-Wear of
Materials at elevated temperature, Berkeley, California (1990) 13-1.
15. C.T.Kangs, F.S.Pettit and N.Birks, Metal!. Trans., 18A (1987) 1785.
16. A.V.Levy and Yong-Fa Man, Wear, 11((1986) 173.
17. G.Sundararajan, Wear, 145 (1991) 251.
18. Manish Roy, Y.Tirupataiah and G.Sundararajan, Mater. Sci. and Techn., 11 (1995) 791.

594
Proc. Int.. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Corrosion Problems in Thrbogenerators

R. Viswanathan
Electric Power Research Institute, 3412 Hillview Avenue.
Palo Alto, California 94304, USA

ABSTRACT

Corrosion-related problems are a major cause of turbogenerator unavailability. In addition

failure of rotating components has resulted in major accidents involving loss of life and
injury to plant personnel. Two major classes of corrosion problems include corrosion
fatigue of turbine shafts and blades and stress corrosion cracking of turbine disks and
generator retaining rings. Use of monoblock or partial-integral rotors, use of cleaner and
lower strength steels, shot peening and control of cycle chemistry have emerged as viable
options to control stress corrosion of disks. Replacement of 18Mn-5Cr steels with 18Mn-
18Cr steels is believed to have mitigated the SCC problems with respect to retaining rings.
This paper :will present an overview of industry experience with respect to these problems.

1.0. INTRODUCTION
Corrosion fatigue, stress corro,sion, and pitting of major turbogenerator components such
as blades, discs, rotors, bolts, expansion bellows, and retaining rings have been identified
to be major' causes of turbogenerator unavailability. Several catastrophic failures have also
occurred in turbine discs [1] and retaining rings resulting in deaths and injuries to plant
personnel [2]. The environments responsible for the failures have been identified to be
principally the impurities in the steam for the turbine components and condensed moisture
for the generator components. Impurities are picked up in the steam from a variety of
causes including condenser leaks, demineralizer breakdown, oxygen in-leakage, and water
treatment chemicals. As the steam expands through the turbine, the solubility of impurities
in the vapor phase decreases. If the concentration of the impurities in steam exceeds its
solubility, droplets of concentrated impurity content will precipitate and deposit.

Pigure 1 shows a rough estimate of the solubility of NaOH in dry steam in relation to the
pressure-temperature conditions in the turbine and the concentration of sodium in the steam
[3]. Shown on the P-T chart are typical expansion lines for fossil turbines reheated to
538C (lOOOF) and a nuclear turbine expanded along the saturation line for water and
reheated to about 260C (5000P). Highly concentrated NaOH precipitates over the pressure-
temperature regime below the impurity level where the expansion line crosses the NaOH
saturation curves. To avoid precipitation of concentrated NaOH solutions in the turbine, it
would be necessary to maintain the steam purity better than 1 ppb of sodium, which cannot
be maintained in turbines over the long periods of operation. Similar levels of purity would

595
be required to avoid precipitation of chlorides, sulfates, phosphates, and other impurities in
the steam. The result is deposition of a variety of corrosive salts, both solid and liquid,
throughout the turbine. Sodium and iron chlorides in the deposits on the last few rows
result in acid chloride conditions, which promote pitting in 12 Cr blading steels. Jonas [4]
found that the pH of the condensed liquids varies from basic to acidic as the specific
volume of the steam increases. Saturated acidic chloride deposits in the presence of
dissolved oxygen are particularly aggressive to turbine steels.

Figure 1. Caustic solubility pressure~temperature diagram

Typical locations where cracking problems have been encountered in turbine rotors of disc-
shaft construction are illustrated in Figure 2. Circumferential cracks have occurred in shafts
under discs, couplings, and shaft seals due to corrosion-assisted fatigue. Radical axial
cracks have occurred in discs at keyways and bore surfaces due to stress corrosion. Stress
corrosion cracks have occurred in the"web regions arid rim regions of discs. Cracking in
the blades is generally attributed to corrosion fatigue. In the case of generators, the main
corrosion problem has been the cracking of retaining rings due to exposure to moist
environments [5]. Direct exposure to water has also. led to failure of rings in some water-
cooled generators. In the present paper, the problems and remedies with respect to stress
corrosion of discs and retaining rings are reviewed.

2.0. STRESS CORROSION CRACKING OF TURBINE DISCS.

The low pressure rotors (LP rotors) of steam turbines in nuclear power stations and in
older fossil stations generally employ a shrunk-on disc-shaft construction. The discs are
among the highest stressed components of the plant and have shown a tendency for stress
corrosion cracking (SCC). Disc cracking has occurred in five locations [6]: in keyways and
bore surfaces of shrunk-on discs; on hub faces of shrunk-on discs; on web faces of both
shrunk-on and integral discs; and in the rim-attachment area of both integral and shrunk-on
discs. Crack locations and orientations are illustrated in Figure 3. The two major types of
cracks are keyway cracks and rim-blade attachment cracks.

596
FigUre 3. Schematic drawing showing typical locations and orientations of cracks in
various D.S.low-pressure rotor discs. This illustration is of a shrunk-on disc with a
semicircular keyway and an axial-entry fir-tree rim-attachment configuration. Discs of this
type have experienced cracking at all of the locations illustrated except at the central web in
the axial-radial orientation and on the web below the rim (location 3). Cracks at the latter
two locations have been found in integral discs.

597
 2.1 Keyway Cracking
The concern with keyway cracking started in 1969, when a low pressure steam turbine disc
burst during a normal startup test at the Hinkley Point nuclear power station in the United
Kingdom [1]. The disc, fabricated from forged CrMo low alloy steel and shrunk on to the
rotor, failed as a result of intergranular stress corrosion cracks emanating from the disc
keyway. The incident at Hinkley Point prompted utilities throughout the world to examine
their machines for disc cracks. These investigations revealed numerous cases of SCC in
shrunk-on turbine discs fabricated from CrMo, CrMoV, and NiCrMQV low alloy steels
[6]. Cracking was observed in both nuclear and fossil power stations: in some cases,
specific environmental contaminants' were implicated, but in other plants no specific
contribution ionic species were identified [7]. Subsequent laboratory tests confirmed that
these low alloy steels are susceptible to SCC in pure condensing steam and in pure water at
oxygen levels as low as 10 parts per billion [8] as well as in chloride- and caustic-
contaminated environments. The industry experience with respect to keyway cracking has
been reviewed and documented in several publications [6,9-12]. Cracking has been found.
in built-up rotors with shrunk-on discs, in monoblock rotors with integral discs. and in
rotors with integral and bolted-on discs. The operating time for rotors in which cracked
discs were found has ranged from a few months to over 20 years. Cracking has occurred ir
plants rated from about 100 to 1,000 MWe. Unlike foreign experience in which disc
cracking was confined until recently to nonreheat LP turbines, disc cracking in the United
States has occurred in both reheat and nonreheat LP turbines. Among nuclear plants,
cracking of discs has been found in pressurized water reactor plants as well as boiling
water reactor plants. Among fossil plants, there appears to be a relation between cracking
susceptibility and the boiler type. More incidents of disc cracking have been reported in
plants employing once-through boilers and all volatile treatment. than in those using drum
type boilers and phosphate-plus-hydroxide water treatment [6]. In both nuclear and fossil
machines, cFacking.has occurred in disc stages downstream of the saturation (Wilson line),
where condensed phases are expected to be present. One common factor stands out in all of
the reported cracking incidents. Cracking has occum;d only at or downstream of the
Wilson line where an aqueous phase will be present. In the majority of cases, cracking has
occurred in the discs at which the Wilson line occurs, although in some cases cracks also
have been found at the second disc downstream of the Wilson line.

In nuclear plants, the Wilson line occurs near the inlet of the LP turbine and sometimes
(e.g., when reheaters are not working properly) before the LP turbine inlet. This is because
inlet steam temperatures in nuclear LP turbines (about 177 to 220C or 350 to 425F) are
. substantially lower than LP inlet steam temperatures in fossil-fueled plants (typically 345 to
400C or 650 to 750F). Consequently, in nuclear plants disc cracks have occurred in the
first two or three discs downstream of the steam inlet. In contrast, the Wilson line in LP
rotors of fossil-fueled plants occurs at latter-stage discs. Cracking has generally been more
severe in rotors used in nuclear plants primarily because the disc temperatures at the
location of the Wilson line in nuclear plants (approximately 150 to 163C or 300 to 325F)
can be more than 55C (lOOOP)higher than disc temperatures at the Wilson line in fossil-
fueled plants. The range of temperatures at which SCC has' been reported in LP rotor discs
in U.S. nuclear plants is from about. 118 to 220C (245 to 425P.) T~e temperature at

59R
which most see occurred in LP discs in U.S. fossil-fueled plants is about 190F. In the
U.K., discs which developed stress corrosion cracks in fossil~fueled plants were reported
to operate at temperatures between about 60 and 1200e (140 and 250F.)

InU.K., the initial reaction in the wake of the Hinkley Point failure in 1969 was that the
problem is characteristic of non-reheat machines with high disc-bore stresses. Reheat
machines of up to 500 MW output, such as"those in fossil stations, were considered to.be
safe. Examinations of reheat turbine discs from fossil power stations after 1987 started to
reveal that these discs are not immune to see. This concern was highlighted in February
1989 when a disc burst at speed on the IP turbine of a 200 MW machine in UK after
140,000 hours of service [13]. Subsequent to this incident, several U.S. utilities were
alerted by the. turbine manufacturers regarding a potential problem of see in fossil reheat
turbine discs. Several affected utilities contacted EPRl for guidance. A workshop was
organized to gather and consolidate the pertinent industry experience [12].

The principal conclusions resulting from the workshop were that see has ijeen found in
LP stages of fossil turbines operating in excess of about 100,000 hr. Stages that were
subject to continuous exposure to wet steam, especially in turbines coupled to once-through
boilers, were more susceptible to see than other stages and turbines coupled to drum-type
boilers. Wetness during transient operation conditions is a contributing but not a dominant
factor. Utility decisions for run/replace were generally based on inspection and fracture
mechanics analysis. It was suggested that material sampling or nondestructive methods to
estimate the FAIT of discs could reduce uncertainties in the fracture mechanics analysis.
Th~ effective stress intensity of see cracks could be less than that calculated due to crack
branching leading to larger critical crack sizes than anticipated. It was found that wide
variations in crack growth rate could exist, and assuming the worst case crack growth rates
is one source of conservatism in the analysis. Although the various procedures for
assessing the integrity of discs are essentially similar and based on a fracture mechanics
approach, different degrees of conservatism produce divergent assessments. Scatter in
material properties, environmental effects and uncertainties in interpreting NDE results
account for these differences.

A variety of remedies including redesign to eliminate keyways, use of lower strength

levels, reduction of stresses and use of partial-integral and monoblock rotors have reduced
the incidence of keyway cracking. Over the last five years or so, industry concern has
shifted toward addressing cracking in rim-attachments of LP rotors, which has increased
dramatically over this period.

2.2. Rim Cracking

Two types of rim-attachment configurations-axial-entry fir tree and circumferential notch-
entry dovetail-are used in U.S. LP rotors in which rim-attachment cracking has occurred.
These configurations and the orientation of cracks are illustrated in Figure 4. In the axial-
entry fir tree configuration, cracks which propagate across the fir trees or "steeples" have
been arbitrarily designed "type f' cracks; cracks propagating into the disc in an axial-radial
plane have been designated "type IT" cracks. Type I cracks have sometimes been designated

599
as "steeple cracks." Similarly, type II cracks have sometimes been referred to as "rim
cracks." In this paper, "rim cracks" refers to both type I and type II cracks. Cracks
originating on the face of the rim below the attachment grooves (designated "type ill"
cracks herein) were also found in one plant.

Figure 4. Schematic drawing of rim-attachment configurations used in U.S. low-pressure

rotor in which cracking has been found. Locations and orientations of rim-attachment
cracking experienced in various rotors are illustrated.

The result of recent EPRI surveys has shown that 38% of the 109 nuclear units surveyed,
were rim-cracked. Cracking was reported in units with operating hours ranging from
33,000 hours to 140,000 hours. In GE turbines cracking was most severe in the L-2 and
L-3 rows where the temperatures are 104 to 127C (220-260F). No cracking was reported
in L-O and L-l rows of GE turbines. In Westinghouse turbines cracking was primarily in
the L-O through L-4 rows which have axial entry blade attachments with the temperatures
being 50 to 127C (120to 260F). Higher incidence of cracking were reported in machines
with longer last stage blade. In the case of fossil units, the number of units with rim-
attachment cracks by in-service year indicates that the largest fraction of units with rim
cracks went into service between 1966 and 1975 (i.e., approximately 100,000 to 200,000
operating hours). Compared with nuclear units, the apparently longer time required for
initiation of cracking in fossil units is related to steam conditions (wetness and temperature)
during operation, which are typically drier for fossil units. For GE turbines no rim cracking
was reported in sub-critical units; in super-critical units, cracking was reported to be most
severe in the L-l and L-2 rows; temperatures in these rows are approximately in the 70 to
93C (160 to 200F) range. Cracking in GE designs was also reported at various location

600
(pin holes, base radius, ledges) in the multi-finger pinned type of attachment used in the
L-O and L-l rows of four units (of 39 units in the survey) with 33.5-inch last stage blades.
For Westinghouse turbines rim cracking reported was most severe in the L-O and L-l rows;
temperatures in these rows are approximately in the 38 to 93e (100 to 160F) range. Most
of the reported cracking propagated across the steeples, with no radial cracking reported at
the base of the steeples.

In terms of remedies, U.S. nuclear utility operators reported the use of the following types
of mechanical repairs for rim-attachment cracking: (D flaw excavation, (ii) shot peening,
(iii) blade removal, (iv) use of steeVtitanium notch blocks, (v) pressure plates and (vi) long
shank buckets. Though weld repair of cracked rims has been successfully implemented for
fossil rotors, it has not yet been reported for U.S. nuclear rotors; however, weld repairs are
now being initiated for some foreign nuclear rotors. In addition to the mechanical repairs
listed for nuclear rotors, U.S. fossil utility operators reported that the repair of choice was a
3600weld repair of the rim; 21 of 49 fossil units with rim cracks were weld repaired. No
recurrence of rim cracking in weld repaired rotors was reported, with 20,000 to 40,000
successful operating hours. While some OEMs have reportedly adopted shot peening for
additional protection against stress corrosion, at least one OEM avoids peening both in
initial manufacturing and in repair. However, the process is increasingly employed in the
field by utilities in conjunction with the removal of cracks by grinding, generally as a
temporary measure until a more permanent repair or replacement can be implemented. No
performance data was available for the prevention of the recurrence of stress corrosion
cracking by shot peening in low alloy steels, albeit the benefit has been demonstrated for
other materials.

2.3. Factors Affecting see

The key variables affecting see have generally been recognized to be as follows.

Stress: Increasing stresses adversely affect crack initiation as well as crack propagation. A
summary of Siemens experience and R&D studies on LP rotor see is provided by W.
David et. al. [14]. Only one of 430 disks in Siemens/KWU nuclear turbines had see;
none occurred in the rim attachment region. Extensive see initiation testing was performed
on low-alloy LP turbine rotor and disk materials for various applied stress-to-yield strength
(RSCCI) ratios and environments (high purity water up to loooe (212F), condensing steam
at 203F and 30% NaOH solution at 100 to 2000e (212-392F). Results are summarized in
Figure 5. As shown, an improvement in the operating environment permits high stress
levels up to and above the yield strength level of the material. Even in a severely corrosive
environment, see initiation does not occur for stress levels below half the material yield
strength (0.5 RSCCI)' Siemens has concluded that the absence of stress corrosion cracking
in the 1970 vintage rotors in nuclear power plants is probably due to the high-purity water
condition in those plants, which permits operating stress levels up to 10% above yield
strength (1.1 RSCCI) without initiating cracking.

601
Figure 5. Effect of stress, yield strength and environment on crack initiation susceptibility

Effect of Steel Composition The 3% CrMo disks of the original Hinkley Point design
combined the adverse effects of high strength, high operating stress and low fracture
toughness. It has long been recognized that nickel additions increase fracture toughness and
lower FAIT, but it was thought that increased nickel concentration relative to chromium
would reduce the resistance to stress corrosion cracking. For this reason 2% CrNiMo steel
was selected by certain OEMs in preference to 2%-3.5% NiCrMoV used elsewhere. It is
now recognized that in addition to improved brittle fracture resistance, increased nickel
level provides greater resistance to SCC, although the effect of yield strength clearly
dominates both the initiation and propagation stages of cracking. The superior though-
thickness hardenability and toughness of 3% NiCrMoV have been cited as the.basis for
selecting this material for welded rotor construction. The effect of steel cleanliness on SCC
is controversial and has been reviewed elsewhere [9]. It is well accepted that .cleanliness
has no effect on cra~kgrowth. It seems to delay crack initiation but only at strength levels
and environmental conditions where pitting is the initiation mechanism. Cleanliness,
however, improves the K1C and has a beneficial effect.

Microstructure. For a given heat of 3CrMo steel heat treated to various strengths and
microstructures, crack growth rates in bainitic structures have been found to be faster than
in martensitic structures at the same strength level [15].

Material Strength Level. Crack growth rates in various environments have been found to
increase with increasing material yield strength for a variety of steel compositions [16-19].
Higher yield strengths are also known to reduce the K1SCC and the K1C of the steel.

Temper Embrittlement. Temper embritt1ement, which is related to the segregation of P, S,

Sn, and Sb to grain boundaries, may accelerate crack growth rates in some cases but not in
others. The determining factors appear to be the electrode potential of the steel and the

602
solution composition, not the presence of temper embrittlement per se [20]. Embrittlement
also results in a reduction of the K1c of the steel.

Temperature. Crack growth rates have been shown to increase with increasing temperature
in a variety of environments [21, 22, 23]. The combined effect of temperature and yield
strength is shown in Figure 6.

Figure 6. Effect of temperature and yield strength on average crack growth rate

Solution Composition. As indicated previously, a liquid phase mllst be present for SCC to
occur. While SCC of disk steels can occur in pure water [15,16, 17], several
investigations have shown the importance of solution composition in determining SCC
crack growth rates. Growth rates increase with increasing caustic concentration [16], and
both ionic (e.g., S04--, CI-, OH-, etc.) and gaseous (e . g., O2, CO2) impurities can crack
growth rates [16].

Electrode Potential. One study of the effect of potential and caustic concentration on the
SCC of a 3.5 NiCrMoV steel [24] has shown that the steel cracks over a wide range of
potentials in 40% NaOH at 100C (212F), but only over two narrower ranges in 20% or
10% NaOH. Other investigations have also shown cracking to occur in specific zones of
potential [25]. The potential of a disc surface depends on the material and its properties, the
solution composition, temperature, and other factors such as crevices, galvanic coupling,
and presence of surface contaminants.

2.0. STRESS CORROSION CRACKING OF RETAINING RINGS

The most significant corrosion problem in generators is the stress corrosion cracking of
retaining rings [2, 5]. Retaining rings are massive steel rings that are shrunk onto the
generator rotor to retain the circumferential conductor coils wound around the two ends of
the rotor (see Figure 7). The rings are currently made of an austenitic steel containing 18%
Mn and 5% Cr. Retaining rings are highly stressed and critical components of a generator

603
and several catastrophic incidents involving failure of these rings have occurred worldwide.
The stress required can arise from the residual stresses from cold fabrication and
machining, shrink fit assembly stresses, or operating stresses. The aggressive
environments causing cracking may include lubricating oils and fluids used during
machining, solvents and paints used for cleaning and dye penetrant inspection, condensed
moisture, salt water, and industrial air environments encountered during storage and
shipping, and moist hydrogen or water used for generator cooling. Residual stresses from
fabrication alone are sometimes sufficient to cause cracking of the rings as evidenced by
instances of ring cracking in storage. The causes of retaining ring failures, remedies,
inspection requirements, etc., have been reviewed in detail elsewhere [26].

Figure 7. Cut-away view of the end section of agenerator rotor

For machines with hydrogen-cooled rotors, the periods of highest risk are frequently
during storage and assembly, i.e., before the machine is closed. During this time, retaining
rings are exposed to the ambient plant environment, and their temperature may easily drop
below the dew point. Humidity may enter the machine in a number of ways during
operation: from imperfectly dried hydrogen; leakages from water-fed heat exchangers; in
the oil of the hydrogen seal circuits; or, in the case of direct water cooling of the rotor
coppers, from simple leakage. In general, however, the increased temperature of rings in
operation is enough to avoid condensation: it will more readily accumulate on the cold
surface of the water circuit. As a further precaution, the dew point should be correctly
monitored and maintained at an acceptable level.

Attention has to be paid to keep the generator rotor dry during manufacture, transportation,
storage, and periodical shutdown in consideration of the electrical insulation and to prevent
general rusting of the rotor. Additional attention should be paid to prevent water
condensation on the retaining ring surface. SeverilI methods are possible, but application of
each is determined by considering the climate of the site location, the shipping route, etc.

604
605
Despite the extreme susceptibility of 18 Mn-5 Cr steel to crack growth under stress
corrosion conditions, retaining rings made of this steel have served the industry well. The
reasons for this are twofold. First, initiation of pits I cracks is also a function of stress-it
can take many years to occur. Second, the propagation of cracks is a discontinuous
process, due to the fact that the exposure to moist environments occurs only intermittently.

In view ofthe extreme stress corrosion susceptibility of 18 Mn-5 Cr steel rings, .

manufacturers have recently developed an alternate steel containing 18% Mn and 18% Cr.
Extensive laboratory tests have shown the 18 Mn-18 Cr steel to be very resistant to stress
corrosion cracking. During the last decade numerous rings of this new steel have been
installed. Recently, there have been a few instances of cracking in this steel as well,
causing some concern to utilities. Details of these incidents are still relatively unknown.

SUMMARY
Stress corrosion cracking problems have been. widely encountered in steam turbine discs
and generator retaining rings. While a number of material and design oriented remedies
have been identified for application to future components, methods are needed to estimate
the remaining life of components currently in service. Crack initiation, growth and final
fracture of these components are affected hy a number of environmental and metallurgical
variables. Since machine specific information is often not available, deterministic fracture
mechanics analysis assuming worst case environmental scenarios and lower bound material
properties have led to pessimistic life prediction inconsistent with service experience. A
probabilistic code that takes into account the many uncertainties involved has been
deveJoped for generator retaining rings.

REFERENCES
1. D. Kalderon, "Steam Turbine Failure at Hinkley Point A", I. Mech. E., 186 (1972),
pp.341-377.
2. R Viswanathan, "Retaining Ring Failures", in Retaining Rings for Electric
Generators, ed. R Viswanathan, EPRI Report EL-3209, August 1983.
3. R.J. Lindinger and RM. Curran, "Corrosion Experience in Large Steam Turbines",
Power Engineering, Octoberl9, 1981, Vol. 85 (10), p. 76-80.
4. O. Jonas, "Transfer of Chemicals in Steam Power Systems", ASME76-JPGCPWR-
12, IEEE-ASME Joint Power Generation Conference, Buffalo, New York,
September 1976.
5. R Viswanathan, "Materials for Generator Retaining Rings", ASME Journal of Engg.
Materials and Technology, October 1981, Vol. 103, No.3. PIY. 267-275.
6. F.F Lyleet al., "Steam Turbine Disc Cracking Experience", Vols. 1-7, EPRI Report
NP-2429-LD, June 1982, Electric Power Research Institute, Palo Alto, California,
U.S.A.
7. J.H. Hodge and I.L. Mogford, "U.K. Experience of Stress Corrosion Experience in
Steam Turbine Discs".Proc.ofI. Mech. E Vol 193, No 11, pp. 93-109.
8. B.W. Roberts and P. Greenfield, "Stress Corrosion ~racking of Steam Turbine Disc
and Rotor Steels", Corrosion, Vol. 35 (1979), p. 402 ..

606
9. R Viswanathan et al., Stress Corrosion Cracking of Steam Turbine Rotors,
Corrosion, In Press.
10. D.A Rosario, C.H. Wells and G.J. Licina, "Low-Pressure Rotor Rim Attachment
Cracking Survey of Utility Experience", EPRI TR-167088, Electric Power Research
Inst., March 1997.
11. F. F Lyle, Jr., "Stress Corrosion Cracking in Low Pressure Steam Turbines - An
Overview", paper No 219, Corrosion 94, NACE.
12. Proceedings: Fossil Steam Turbine Disc Cracking Workshop, EPRl Report GS-
7250, April 1991.
13. J. L. Bolton, Recent Experience of Stress Corrosion Cracking in the LP Discs of
Fossil Fired Reheat Turbines, in EPRI, Report GS-7250, pp. 6-1--6-15, April 1991.
14. W. David, et al., "Disk-Type LP Turbine Rotor Experience," The Steam Turbine
Generator Today: Materials, Flow Path Design, Repair and Refurbishment, PWR-
Vol. 21, ASME, New York, 1993,83-92.
15. B.W. Roberts and P. Greenfield, "Stress Corrosion of Steam Turbine Disk and
Rotor Steels". Corrosion, Vol. 35, 1979, pp~ 402-409.
16. A McMinn and P.P. Lyle, Jr., "Properties of Turbine Disk Materials, Vol. 1: The
Influence of Material Properties and Environment on the Stress Corrosion
Susceptibility of Turbine Disk Steels". EPRI Report NP-3634, Project 1398-5, July
1984.
17. M.O. Speidel. Proceedings of the International Symposium on Environmental
Degradation of Materials in Nuclear Power Systems-Water Reactors. Houston:
National Association Corrosion Engineers, 1983, pp. 113-131.
18. E.D. Eason, E.E. Nelson, and S.D. Patterson,""Stress Corrosion Cracking in Steam
Turbine Disks: Analysis ofField and Laboratory Data". EPRI Report NP-4056,
Project No. 2408-1, May 1985.
19. M.O. Speidel and RM. Magdowski, "Clean Steels for Steam Turbine Rotors-Their
Stress Co~osion Cracking Resistance", Proceedings: The International Conference
on Advances in Materials Technology for Fossil Power Plants, Sponsored by Electric
Power Research Institute, Palo Alto, California, at1d ASM International, Metals Park,
Ohio, September 1987.
20. J.D. Atkinson, AD. Adams, M.AM. Kahn, and PJ. Worthington. Central
Electricity Research Laboratories Note No. RD/L.N 169/79, C.E.RL., Leatherhead,
Surrey, United Kingdom, September 17, 1979.
21. H.M. Hodge and LL. Mogford. Proceedings of the Institute of Mechanical
Engineers, Vol. 193, No. 11, 1979, p. 93.
22. F.F. Lyle, Jr. and H.C. Burghard, Jr., "Steam Turbine Disk Cracking Experience".
EPRI Report NP-2429, Project 1398-5, June 1982.
23. W.G. Clark, B.B. Seth and D.M. Shaffer, "Procedures for Estimating the
Probability of Steam Turbine Disk Rupture from Stress Corrosion Cracking".
ASMEIIEEE Power Generation Conference, St. Louis, Missouri, October 1981.
24. RS. Shalvoy, "The Effect of Potential and Caustic Concentration on Stress
Corrosion Cracking of NiCrMoV Steel at 100DDDC. Corrosion, Vol. 39, 1983, pp.
66-78.
25. J.F. Newman, 'The Corrosion Potential of a 3% CrMo Steel in Sodium Hydroxide
Solutions and its Relationship to Stress Corrosion Cracking". CERL Note No.

607
 RD/2/N 186n3, Central Electricity Research Laboratories, Leatherhead, Surrey,
United Kingdom, July 1973.
26. R. Viswanathan, F.A. Ammirato, L. Nottingham, and J. Stein, "Guidelines for
Evaluation of Generator Retaining Rings", EPRl Report, Electric Power Research
Institute, Palo Alto, California, U.S.A., April 1987.
27. M.O. Speidel, "Preventing Failure of Retaining Rings", in Retaining Rings for
Electric Generators, ed. R. Viswanathan, EPRI Report EL-3209, August 1983,
p. 1-1.
28. P.K. Nair, F.F. Lyle, J.E. Buckingham and H.G. Pennick, "Guidelines For
Predicting the Life of Steam Turbine Discs Exhibiting Stress Corrosion Cracking",
EPRI Report NP-6444, Vols. 1-2, July 1989 and DICE Code available from EPRl.

608
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

A Review of Intermetallic Precipitates and Their

Influence on Zircaloy Corrosion in Nuclear Reactors
E.A. Preble and K.L. Murty
North Carolina State University,
Raleigh NC 27695-7909, USA

Summary
. Intermetallic precipitates are present in many aerospace and nuclear grade alloys and strongly
influence their corrosion behaviors. The nuclear industry around the world uses zirconium alloys in the
form of thin-walled tubing to clad radioactive fuel in light and heavy water reactors. Typical lifetimes
for these fuel rods can be from 3 to 8 years depending on the reactor type and operatiIig cycle, and
corrosion is a life limiting factor of these fuel rods. In zirconium alloys, corrosion behavior is strongly
tied to solute content and intermetallic precipitate size distributions. To produce a corrosion resistant
alloy for service conditions it is of prime importance to have a thorough understanding of these
precipitates, including their morphology and behavior during reactor operation.
Many factors influence these precipitates during fabrication as well as service exposure. Heat
treatments, thermomechanical processing, and radiation exposure cause. changes in the morphology of
these particles. This paper summarizes current knowledge on the types of precipitates responsible for
corrosion resistance, formation of these precipitates, their influence on in-reactor performance .. In
particular, beta quenching parameters along with heat treatment schedules strongly influence the
distribution and morphology of the precipitates. Also of importance is the effect of alloy composition,
which changes the chemistry of the predominant types of precipitates. Zirconium precipitate research is
now of great interest in the nuclear industry because of the desire to increase the lifetimes of nuclear fuel
to both reduce cost and waste. The formation of intermetallic particles in zirconium alloys is complex to
model. While current knowledge is extensive, more research is needed to determine what the optimum
types of precipitates are and how they form.

Introduction
Zircaloy-2 and Zircaloy-4 are used for reactor intemals, particularly as fuel cladding, in boiling
water reactors (BWR's) and pressurized water reactors (PWR's) respectively. Several alloying elements
(Fe, Cr, Ni) are added in dilute quantities to nuclear grade sponge zirconium and several impurities (0,
'Si, C etc.) are controlled at certain levels to obtain the two Zircaloys. Two variables that have a strong
influence on Zircaloy corrosion behavior are intermetallic particles and solute content. Intermetallics
vary in structure, chemical composition, size distributions, and location in the grains and can be a rough

609
indicator of the content of the solute in the matrix of the material. These variables are influenced
strongly by the quench step performed early in the Zircaloy production process, and post-quench heat
treatment.

Beta Quenching
The quench process, commonly called beta
quenching since it is performed from the ~
phase of the material, has two variables that can
change the microstructure of Zircaloy
dramatically. Varied initial temperatures and
cooling rates of the beta quench create quite
differing results. Cooling rates varying from
high (>2000C/s) to low OYC/s) lead to
structures such as martensitic, Widmanstatten,
parallel plate, or lenticular. As cooling rates
increase, grain size decreases as is shown in
Figure I. Also, impurity elements such as
oxygen [I], silicon [2], and carbon [3,4] have
been known to affect the final structures, and th~
cooling rates and temperatures leading to
transitions between the structures, as will be
discussed later.
The location of solute elements in quenched materials is of prime importance to tailor final
microstruc~es [6]. Bangaru et ai. [7] demonstrated schematically (Figure 2) the results of variations in
cooling rate and the time of the quenching operation. Faster quenching (Process B) yielded smaller
particle sizes than did the traditional quench (Process A) which involved a slower transfer from high
temperature to the quenching media. Also, the effect of heat treatments on the matrix content of solute
can be seen by the addition of another beta quench (Process C) late in the processing. It is clear from
these results that solute content and"particle size can be manipulated during processing to obtain optimal
corrosion behavior in-service.

Precipitate Details
Due to the low solubilities of most of the alloying elements in zirconium, several types of
intermetallic precipitates form in Zircaloy-2 and Zircaloy-4. The most prevalent of these particles are
Zr(Fe,Cr)2 and ZriFe,Ni) in Zircaloy-2 and Zr(Fe,Cr)2 in Zircaloy-4. Transmission electron microscopy
examinations during processing have revealed several other particle types that are listed jn Table I. Most
are rare or metastable, and are not generally seen in great numbers in a typical final product. In general,
particles that contain more zirconium than alloying elements (i.e. ZriFe,Ni)) will be larger than particles
with more alloying elements than zirconium (i.e. Zr(Fe,Cr)2) because less solute diffusion is required for
the particle to grow. Higher cooling rates will shrink the size of particles, as mentioned earlier, and will
significantly affect the particles with more solute because of the reduced diffusion rates during faster
cooling [7]. The zirconium-iron particles (Zr2Fe, Zr3Fe etc.) form when there exists excess iron that
cannot be accommodated into an intermetallic such as Zr(Fe,Cr)2 [8].

610
Precipitate Growth
Growth of particles in a system with several solutes is. difficult to model. Particle size
distributions must differentiate between particle types, and the models themselves must often contend
with several competing mechanisms. Growth kinetics of iron and chromium particles in a Zr-I.4%Sn
matrix were studied in terms of the particle size distributions to determine the growth mechanism in
ZrSnFeCr alloys [8],

611
Influence of Solute and Precipitate on Corrosion Resistance
Unifotm and nodular corrosion are potentially life limiting problems with Zircaloy fuel rods in
light water reactors. Minimizing corrosion of fuel rods is essential for high burnup fuel to reduce fuel
cycle cost and waste volume. Corrosion mechanisms are reported to have "breakaway" ranges where
previously good-performing fuel may shift to higher corrosion rates. Characterization of solute and
precipitate effects on long term corrosion is therefore necessary in high burnup fuel designs. Uniform
corrosion is a black, protective oxide layer that forms on the waterside of the fuel cladding. Samples to
the left in Figure 5 show this type of corrosion. Uniform corrosion is seen in both BWRs and PWRs.

612
Out-of-reactor testing for uniform corrosion resistance is typically characterized in wateror steam tests
in the temperature range of 300C to 400C. Higher test temperatures yield faster results, but can cause
discrepancies in correlating to in-reactor performance [20]. Uniform corrosion resistance is shown to
correlate to material having large precipitates [18], but the real variable of influence was postulated to
be matrix solute content [6]. Since Zircaloy has low solubility limits for it's alloying elements [8],
large precipitates in standard Zircaloys are an indication of low solute content in materials processed in
a standard fashion [17, 22]. Table 2 summarizes the effects of alloying elements and impurities on
uniform corrosion.

Nodular corrosion is a localized, non-protective, white blisters up to 2.0 mm in diameter that

form on the waterside portion of the fuel cladding. The samples progressing to the right of Figure 5
show worsening nodular corrosion resistance. Nodular corrosion is seen in BWR environments. When
nodular corrosion is combined with certain operating conditions (particularly the presence of copper),
crud induced localized corrosion (CILC) can cause thin-walled tubing to be susceptible to wall
breaches at these corrosion locations [28]. Nodular corrosion susceptibility is characterized in short
(16-24 hour) 500C steam tests and has been shown to correlate well with in-reactor nodular
susceptibility [21,29]. Several researchers [6,7,30,31,32] have shown that high solute content is the key
to reducing nodular corrosion. In typical Zircaloy processing, fine particle distributions are an
indication of higher solute levels, and alloys with small particles have shown better nodular corrosion

613
resistance [7, 33]. Caution must be exercised when using particle distributions as the indicatOr for
corrosion resistance. Standard beta quenched Zircaloy that has low cumulative heat treatments will
typically have small particles and high solute levels in the matrix [15]. However, materials with varied
alloying element levels or non-standard processing steps may not follow this correlation (Table 2).
Development of optimized zirconium alloys is complex. While data on the effects of many variable is
extensive, there are many complex interactions in processing and in service that can cause minute
changes in material properties that can be detritDental to product reliability. Research studies should
focus on isolation of a particular variable to characterize it fully in relation to other parameters.

Acknowledgments
This work is funded by the United States National Science Foundation Grant #DMR-9632043.

References
1.O.T. Woo and K. Tangri, Journal of Nuclear Materials 79 (1979) 82-94.
2. D. Charquet and E. Alheritiere, ASTM STP 939, ASTM, Philadelphia, 1987, pp 284-291.
3. James R. Theaker, Ram Choubey, Gerry D. Moan, Syd A. Aldridge, Lynn Davis, Ronald A.lJraham, and Christopher
E. Coleman, ASTM STP 1245, ASTM, Philadelphia, 1994, pp 221-241.
4. G. Okvist and K. Kallstrom, Journal of Nuclear Materials 35 (1970) 316-321.
5. G. Maussner, E. Steinberg, and E. Tenckhoff, ASTM STP 939, ASTM, Philadelphia, 1987, pp 307-320.
6. B. Cheng and R.B. Adamson, ASTM STP 939, AS~, Philadelphia, 1987, pp 387-416.
7. N.V. Bangaru, R.A. Busch, and J.H. Schemel, ASTM STP 939, ASTM, Philadelphia, 1987, pp 341-~63.
8. D. Charquet, R. Hahn, E. Ortlieb, J.P. Gros, and J.F. Wadier, ASTM STP 1023, ASTM, Phil., 1989",pp 405-422.
9. D. Arias, T Palacios, and C. Turrillo, Letter to the Editors, Journal of Nuclear Materials 148 (1987), pp 227-229.
10.A.T. Motta, J.A. Faldowski, L.M. Howe, and P.R. Okamoto, ASTM STP 1295, ASTM, Philadelphia, 1996, pp 557-579.
11.E. Steinberg, H.G. Weidinger, and A. Schaa, ASTM STP 824, ASTM, Philadelphia, 1982, pp 106-122 ..
12.H. Anad~, K. Nomoto, and Y. Shida, ASTM STP 1245, ASTM, Philadelphia, 1994, pp 307-327.
13.J.J. Schemel, D. Charquet, J. Wadier, ASTM STP 1023, ASTM, Philadelphia, 1989, pp 141-152.
14.H.G. Weidinger, F. Garzarolli, C.M. Euken, and E.F. Baroch, ASTM STP 939, ASTM, Philadelphia, 1987, pp 364-386.
15.R.A. Graham, J.P. Tosdale, and P.T. Finden, ASTM STP 1023, ASTM, Philadelphia, 1989, pp 334-345.
16.J.-P. Mardon, D. Charquet, andJ. Senevat, ASTM STP 1245, ASTM, Philadelphia, 1994, pp 328-348.
17.T. Thorvaldsson, T. Andersson, A. Wi~son, and A. Wardle, ASTM STP 1023, ASTM, Philadelphia, 1989, pp 128-140.
18.B. Wadman and H.-a. Andren, ASTM STP 1023, ASTM, Philadelphia, 1989, pp 423-434.
19.P. Rudling, et aI., ASTM STP 1245, ASTM, Phil., 1994, pp 599-614.
20.F. Garzarolli, Y. Broy, R.A. Busch, ASTM STP 1295, ASTM, Philadelphia, 1996, pp 850-864.
21.B. Cheng, et aI., ASTM STP939, ASTM, Philadelphia, 1987, pp 257-283.
22.M. Harada, M. Kimpara, and K Abe, ASTM STP 1132, ASTM, Philadelphia, 1990, pp 368-391.
23.C.M. Eucken et aI., ASTM STP 1023, ASTM, Philadelphia, 1989, pp 113-127.
24.E.R. Bradley and A.-L. Nystrom, ASTM STP 1245, ASTM, Philadelphia, 1994, pp 483-498.
25.Y. Etoh, et. aI., ASTM STP 1295, ASTM, Philadelphia, 1996, pp 825-849.
26.F. Garzarolli, R. Schumann, and E. Steinberg, ASTM STP 1245, ASTM, Philadelphia, 1994, pp 709-723.
27.J.P.Mardon, G.Garner, P.Beslu, D.Charquet, J.Senevat, Proceedings of the American Nuclear Society 'International
Topical Meeting on Light Water Reactor Fuel Performance, March 2-6, 1997, Portland, Oregon.
28.M.a. Marlowe, J.S. Armijo, B. Cheng, R.B. Adamson, Proceedings of the American Nuclear Society International
Topical Meeting on Light Water Reactor Fuel Performance, April 21-24, 1985, Orlando, Florida.
29.J.H. Schemel, ASTM STP 939, ASTM, Philadelphia, 1987, pp 243-256.
30.P. Rudling, K.L. Vannesjo, G. Vesterlund, and A.R. Massih, ASTM STP 939, ASTM, Philadelphia, 1987, pp 292-306.
31. T. Kubo and M. Uno, ASTM STP I 132,ASTM, Philadelphia, 1990, pp 476-498.
32.K: Ogata, ASTM STP 1023, ASTM, Philadelphia, 1989, pp 346-359.
33. T. Andersson and T. Thorvaldsson, ASTM STP 939, ASTM, Philadelphia, 1987,pp 32-l-337.

614
Proc. Int. Conf. on Corrosion CONCORN '97
December)-6, Mumbai, India

Parametric Analysis for Characterisation of

Acoustic Emission Sources During Charging and
Discharging of Hydrogen in Palladium
C.K. Mukhopadhyay, T. Jayakumar, R. Ramesh1 and Baldev Raj
Metallurgy and Materials Group, Indira Gandhi Centre for Atomic Research,
Kalpakkam-603 102, India
ITransducers Group, Naval Research and Ocenographic Laboratory,
Cochin-682 004, India

ABSTRACT

Different parameters of the acoustic emission (AE) signals have been used to study the absorption and
desorption of hydrogen in palladium (Pd). The AE generated during charging has been attributed to the
breaking of oxide film due to surface activation and formation and evolution of hydrogen bubbles during
absorption. In the case of discharging cycle, the AE activity continuously decreases due to continued
decrease in the rate of desorption of hydrog~n form the specimen.

INTRODUCTION

Acoustic emission technique (AET) has potential for detection and monitoring of crack initiation
and growth in materials, components and structures [1], kinetics of deformation [2], diffusionless phase
transformation [3], leak detection [4], detection of stress corroSion cracking (SCC) and hydrogen
embrittlement (HE) phenomena [5] etc. Acoustic emission during absorption of hydrogen in a material
occurs due to several reasons, like, crack initiation and growth induced by hydrogen, evolution of hydrogen
gas bubbles during electrochemical charging of hydrogen, breakdown of oxide film present on the surface,
decohesion of second phase particles, plastic deformation etc. [6]. In this paper, the results obtained by
analysing various parameters of the AE signal generated during charging and discharging of hydrogen in
palladium have been used for studying the absorption and desorption processes of hydrogen. Pd has been
chosen for the present investigation because it is known to absorb / desorb hydrogen readily under ambient
conditions [7]."Different parameters of the AE signal like root mean square (RMS) voltage, counts, event
duration, event rise time etc. have been used to analyse the results.

EXPERIMENTAL

AE generated during charging and discharging of hydrogen in palladium by electrochemical method

were recorded. Pd specimen (12 x 8 x 0.3 mm3 ) was cathodically charged in an electrochemical cell
containing 0.1 M NaOH solution as electrolyte. Charging was done at a current density of 5 mNcm2 and

615
at ambient temperature (-298 K). The specimen was allowed to discharge hydrogen under a concentration
gradient in the same electrochemical cell. 'Diffusion current transient' (a measure of hydrogen
concentration) during discharging of hydrogen from the specimen was obtained using a zero resistance
ammeter, the output of which was fed to a strip chart recorder. AE generated during charging and
discharging cycles were recorded using an AE system (Model 204B) of MIs. AET Corporation, USA. A
piezoelectric transducer with a resonant frequency at 175 kHz, a preamplifier (60 dB gain) and a
compatible filter (125-250 kHz) were used to capture the AE signals. A total system gain of 86 dB and a
threshold of 0.7V were maintained throughout the experiment. The transducer was coupled to the specimen
using a stainless steel waveguide.

RESULTS AND DISCUSSION

Figures la-Ie show the variation in AE RMS voltage with time during charging and discharging
of hydrogen in Pd. The variation in counts showed similar results. It can be seen from Fig. I that during
charging AE activity gradually increases and saturates with time. It is seen that in the first charging cycle
(Fig.la), the AE activity shows peaks occurring at about 10 minutes and 30 minutes. The AE activity then
increases slowly with time and finally saturates after ~bout 90 minutes. The second charging cycle (Fig. Ib)
is characterized by a small but distinct peak in AE at about 2 minutes of charging time, followed by a
gradual increase in AE and saturation at about 60 minutes. The peak is shown in the inset, for clarity.
The third cycle (Fig. Ie) shows rapid increase in the AE activity and saturation at about 30 minutes. The
entire procedure was repeated after taking out the specimen from the electrolyte and exposing it to air for
a few hours. It showed similar results.

It is known that AE occurs due to cracking of surface oxide layer [8], evolution of gas in liquid
medium, micro-cracking induced by hydrogen embrittlement, plastic deformation etc. [6]. From Fig.l, it
can be understood that the major sources of AE could be the cracking of oxide film during activation and
the evolution of hydrogen gas bubbIes from the surface of the specimen (cathode). The peaks observed
at the initial stages of charging during first and second cycles could be attributed to the surface activation
process for hydrogen absorption, which res~lts in the cracking'of surface oxide layers present invariably
on metal surfaces exposed to air. This process is considered to be an important criterion to enhance the
rate of hydrogen absorption [9,10]. The activated surface of a metal can readily absorb hydrogen without
the inhibition period and with rapid kinetics. Even the unactivated surface can absorb a little amount of
hydrogen with very slow kinetics. This situation leads to lew AE activity in the beginning of the charging
cycle. The cracking of oxide film at the surface during activation is responsible for the increase in AE.
Once the specimen surface becomes completely active, the cracking process ceases, thus leading to the
reduction in AE. This results in the occurrence of peaks in RMS voltage (points A, B and D in Figs. I a&b).

During charging, AE signal is also generated due to the evolution of hydrogen bubbles. Hydrogen
gas produced at the specimen during charging is partly absorbed by it, releasing the rest as bubbles. With
decrease in the rate of hydrogen absorption with time, the gas bubbles evolving from the surface of the
specimen increases and hence the AE activity increases. When the specimen is saturated with hydrogen,
all the hydrogen generated at the cathode is liberated as gas bubbles at a constant rate, which leads to
saturation in the AE activity at longer durations of charging as shown in Figs. I a-I c (points C, E and F).

The variations in the AE RMS voltage recorded during the three discharging cycles are also shown

616
in Figs. I a-I c .. The desorption of hydrogen from the specimen is characterised by a steady. decrease in the
RMS voltage which reaches a minimum, indicating the complete desorption of hydrogen from the!
specimen. Therefore, the AE activity during discharge can be attributed to the formation and evolution
of hydrogen gas bubbles. Variations in the current generated in the electrochemical cell due to the diffusion
of hydrogen out of the specimen (cathode) are also shown in Figs. la-Ic. The diffusion current density
is a function of hydrogen concentration in the specimen at any instant [II] and also follows the same trend,
as the RMS voltage, indicating the continued desorption of hydrogen from the specimen. '

It can also be seen from Fig. I that the time required to saturate the hydrogen concentration (abOut
90,60 and 30 mins.) depends upon the number of charging-discharging cycle employed prior to current
cycle, without exposing the specimen to air. The improved kinetics of hydrogen absorption on repeated
cycles is due to the availability of increased active surface resulting from the previous cycles. This could
be ascertained from the absence of the initial peak corresponding to surface activation, during the third
cycle (Fig.lc).

In addition to the RMS voltage and counts, variations in other AE parameters during charging have
provided interesting results. AE generated during charging process was record~ using another AE system,
Model Spartan 2000 (Mis. Physical Acoustics Corpn., USA). The data on amplitude, duration and rise time
of the AE events was collected and analysed corresponding to (i) the activation process (cracking of oxide
film) during the early stages of charging (initial 20 minutes) and (ii) the evolution of hydrogen gas bubbles
at saturation (final 20 minutes) for the first charging cycle. Figure 2 shows the distribution of the events
with amplitude, event duration and event rise time during initial 20 mins. (Figs.2a~2c) and final 20 mins.
(Figs. 2d-2f) of charging process. In Table 1, values of these parameters in the two cases are also prestnted.
It could be seen from Fig.2 and Table I that the event duration and rise time corresponding to oxide layer
cracking are lower as compared to those corresponding to.evolution of hydrogen gas bubbles. Whereas
the amplitudes of the events lie in the range between 30 dB and 60 dB in both the cases. It can be inferred
from the event duration and rise time values that the oxide layer craCking is relatively a mo~ transient
phenomenon than the gas bubble formation and evolution process. Thus, the nature of the distribution of
the event duration and rise time values could be used to distinguish the AE signals occurring due to the
cracking of surface oxide layer from that due to the evolution of hydrogen bubbles, during charging
process.

CONCLUSION

Acoustic emission generated during charging and discharging of hydrogen in palladium has been
studied. The AE generated during charging has been attributed to the breaking of oxide film due to surface
activation and formatio~ and evolution of hydrogen bubbles during absorption. In discharging cycle, AE
activity continuously decreases due to .the continued decrease in the rate of desorption of hydrogen form
the specimen. While the RMS voltage and counts of the AE signal have provided information on the
kinetics of these process, analysis of other AE parameters has been carried out to distinguish these
processes. LoweF event duration and lower event rise time of the AE signal corresponding to the oxide
layer cracking as compared to those corresponding to the evolution of hydrogen gas bubbles has been
attributed to the fact that the oxide layer cracking is relatively a more transient phenomenon than gas
bubble formation and evolution process. These investigations suggest the usefulness of various AE
parameters, to evaluate the kinetics and to identify the different stages of hydrogen absorption during

617
charging and discharging of hydrogen in palladium.

ACKNOWLEDGMENTS

We are thankful to Dr. Placid Rodriguez, Director, Indira Gandhi Centre for Atomic Research,
Kalpakkam for constant encouragement and support. We also thank Mr. P. Kalyanasundaram, Head,
DPEND and Mr. S. Vaidhyanathan, DPEND for'useful discussions.

REFERENCES

1. Carpenter S.H., Corrosion monitoring in industrial plants using non-destructive testing and
electrochemical methods, ASTM STP 908, G.c. Moran and P. Labine (eds.), ASTM, Philadelpia,
1986, p.165.
2. Baldev Raj and Jayakumar T, in Acoustic Emission - Current practices and future directions, ASTM
STPlO77, W.Sachse (ed.), Philadelphia, 199Q, p218.
3. Mukhopadhyay C.K., Jayakumar T., Kasiviswanathan K.V. and Baldev Raj, J. Mater. Science, Vol.
30, 1995, p.4556.
4. Jayakumar T., Moorthy V. and Baldev Raj, Proc. National Symp. on Aging Management of Nuclear
Facilities, Bombay, India, 1994, p647.
5. Kh. G. Schmitt Thomas, Proc. First Int. Conf. on Current Solution to Hydrogen Problems in Steel,
Washington, 1982.
6. Yuyama S., Corrosion monitoring in industrial plants using non-destructive testing and
electrochemical methods, ASTM STP 908, G.C. Moran and P. Labine (eds.), ASTM, Philadelpia,
1986, p.43.
7. Frieske H. and Wicke E., Ber. Bunsenges. Phys. Chern., Vol.77, 1973,50.
8. Khanna A.S. , Jhll B.B. and Baldev Raj, Oxidation of Metals, Vo1.23, 1985, 159,
9. Buschow K.HJ., in Handbook on the Physics and Chemistry of Rare Earth, Vo1.6, K.A.
Gschneidner and L. Eyring (eds.), Elsevier Science Publishers, B.V. p.l, 1984.
lO. Yamaguchi M. andE. Akiba, in Materials Science and Technology, R.N.Cabn, P.Hassen and
EJ.Kramer (eds.), Vo1.3B, VCH, New York, p.333, 1994.
11. DeLuccia J.J. and Berman D.A., Electrochemical Corrosion Testing, ASTM STP 727, F.Mansfeld
and U.Bertocci (eds.): ASTM, Philadelphia, 1981, p.256.

TABLE 1. Comparison of amplitude, event duration and event rise time of AE events generated during
initial and final stages of hydrogen absorption
Fig. 1 Variations in AE RMS voltage with time
during charging and discharging
(a) First cycle (b) Second cycle & (c) Third cycle

619
620
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Stainless Steel in Liquid Sodium Environment-

Prediction of Expected Behaviour and
Comparison with Experiment
s. Rajendran PiIlai, H.S. Khatak, N. Sivaibharasi and
J.B. Gnanamoorthy
Metallurgy Division, Metallurgy and Materials Group,
Indira Gandhi Centre for Atomic Research,
Kalpakkam-603 102, India
Abstract
Different ternary compounds of transition metals are reported to be formed in the sodium
loops . The driving force for their generation is the thermodynamic stability, Based on
thermodynamic data in the literature assessment has been carried out to examine the possibility of
generation of each of the corrosion products. A simulated experiment was also carried out in a
sodium loop to examine the different corrosion products formed. Analysis of the exposed specimen
revealed the formation of compounds of chromium and iron on the surface. The formations of the
corrosion products have occurred only in the downstream region. The favourable thermodynamics
for the formation of corrosion products prevailed only in this region. It is also possible that these
corrosion products are formed at the high temperature zone and precipitated at these r~gions oflower
temperature.

1. Introduction

Fast breeder nuclear reactors employ austenitic stainless steel as structural material in the
primary system. This choice is based on the good nuclear properties of stainless steel coupled with
adequate compatibility with liquid sodium. However, liquid sodium can act as a medium for causing
corrosion and mass transfer when dissolved non-metals such as oxygen or carbon is present in
it[ 1,2]. Depending on the relative thermodynamic stabilities of the oxides of sodium or the oxides
of the constituents of steels, different corrosion products are formed. These corrosion products are
subsequently leached out of the surface of the stainless steel and get deposited at locations oflower
temperatures.

It has been evaluated from accurate thermodynamic measurement that the stability of sodium
oxide is comparable to the stabilities of the oxides of chromium and iron[3]. Hence, when adequate
oxygen content is present in sodium the ternary compounds of sodium-transition metal-oxygen are
formed which have marginally higher stability than the binary oxides mentioned above.
Understanding the thermodynamic data of these compounds are essential to unravel the corrosion
and leaching behaviour by sodium.

2. Theoretical
The formation of the ternary compound (NaM02) by the reaction between Na20 and M (a
constituent metal of the stainless steel) may be written as;

621
Thus from equations (2), (3) and (4), the free energy change associated with the formation ofNaM02
is calculated.
The threshold concentrations of oxygen necessary for the formation of the different ternary
compounds were evaluated. The expected chemical changes in the sodium-steel system were
comp:ued with those observed while carrying out experiments with flowing sodium in a stainless
steel loop.

3. Experimcntal
3.1 Description of the sodium loop
An experimental sodium loop was s;onstructed using stainless steel grade AISI 316 as the
structural material. The loop consisted of mainly two sections; viz. the experimental'section and the
purification section. In the experimental section different sample holders were located. There were
heaters and coole'rs between the different sample holders. By proper control of these heaters and
coolers it was possible to attain the desired temperature in the different test sections .
. The purification section consisted of a cold trap that precipitated the impurities present in
sodium. The total impurity content in the sodium was monitored with the help of a plugging
indicator. A more comprehensive details about the loop and the sample holder is reported in the
literature (5). .
Stainless steel plates were employed as the specimen and incorporated into the test sections.
Specimens were subjected to tnermal ageing in the same test cha'llbers for the sake of delineating
the effect of sodium exposure. The exposure conditions were;
Temperature (hot leg) :; 623, 723 and 823 K
Temperature (cold leg) = 623 and 583 K
Duration of exposure =: 16 000 hours

3.2 Materials
Rectangular plates of AISI type 316 SS were incorporated into the test section, The chemical
composition of the plate is given in Table 1.

622
623
oxide with steel constituents. The investigation reveale.d the absence of characteristic spectra of
sodium on the surface ofthe specimen. Thus, there is no direc,t indication about the formation 'ofthe
ternary compounds of sodium in the prevailing loop conditions. It is also possible that some of the
corrosion products were lost from the corroding surface either due to the high velocity of sodium or
during the process of cleaning.
The XPS spectra of oxygen on the specimen from the downstream region revealed a chemicai
shift (Fig. I). The spectra of iron and chromium have also revealed chemical shifts in the 2P 312
energy levels (Figs. 2 and 3). Coupled with the chemical shift observed in the case of oxygen, it is
concluded that the compounds containing Fe-O or Cr-O bonds are formed on the surface of the
specimen. The energy spectrum revealed that these compounds are different from the usual oxides
ofironand chromium. It was not possible to fully characterize these compounds because of the lack
of adequate spectral information in the literature. Conditions favourable for the generation of ternary
compounds ofiron and chromium have obviously prevailed in the cooler parts of the loop where ~he
potential of oxygen is expected to be very high.
Investigations were also targetted to explore the possibility of the formation of corrosion
products involving carbon. The XPS spectrum of carbon is given in Fig. 4. Here again there was a
chemical shin in the Is energy level in the case of the specimen from thc down-strcam region. Such
a shift is expected only when a chemical compound of carbon is formed. The most Iil<ely compound
to be formed in the prevailing carbon potential in the loop is M2)C6 (M=Cr, Fe, Mo and Ni)[12]. The
XPS spectra also revealed the plating of carbon on the surface of the specimen exposed at 623 K in
the up-stream position. The condition favourable for the precipitation of carbon prevailed onlY'in this
region.

5. Conclusioll
Stainless steel (AISI type 316) was exposed to flowing sodium in a loop at different
temperatures for a duration of 16 000 hours. The surfaces of the specimens were examined for the
generation of different forms of corrosion products. The generation of corrosion products of iron and
chromium (probably ternary compounds) was indicated. This observation was in tune \.vith
predictions based on the stability data of these compounds.
Generation of carbon compounds were noticed in the downstream region. The precipitation
of carbon was noticed in the low temperature region in the upstream position. Conditions favourable
for precipitation prevailed in this zone.

Reference
I. T. Suzuki, I. Muloh. T. Vagi and Y.lkcnaga:.I. Nllc!. Malel'. LW~II)!l()97
2. B.H. Kolster, J.V.D.Veer and L.Bos; Mater. Behaviour and Physical Chemistry in Liquid Metal
Systems, Ed. H.U.Borgstedt(Plenum, NY, 1982) p.37
3. JANAr Thermochcmicallables, 3 rd edn. (National Bureau of Standards, USA, 1985)
4. O.M.Sreedharan and J.B.Gnanamoorthy; J.Nucl. Mater. 89(1980) 113
5. S.Rajendran Pillai, H.S.Khatak, N.Sivaibharasi. A.K.tyagi, J.B.Gnanamoorthy, R.D.Kale,
K.Swaminathan, M.Rajan and K.K.Rajan; Trans lIM, Vol 50 No.1 (1997) 103
6. A.W Thorley, A. I31undell and J.A.Bradley, Maler. Bchaviour and Physical Chemistry in Liquid
Metal System, Ed. H.U.Borgstedt (Plenum, NY) p.5
7. M.G.Barker and D.J.Wood; J. Less Comm. Metals, 35(1974)315
8. S.Rajendran Pillai, H.S.Khatak and J.B.Gnanamoorthy; J.Nucl. Mater. 224(1995) 17

624
9. A.M.Azad, O.M.Sreedharan and lB.Gnanamoorthy; lNucl. Maler. 144(1987)94
10. B.J.Shaiu, P.C.S.Wu and P.Chiotti; l Nucl. Mater.; 67(1977)13
11. T. Gnanasekaran, K.H.Mahendran, K.V.G.Kutty and C.K.Mathews; l Nucl.
Mater. 165( 1989)21 0
12. S.Rajendran Pillai, R.Ranaganathan and c.K.Mathews, Bull. Electrochem. 6(6)(1990)672
626
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Non-Chromate Anodic Corrosion Inhibition with

Desired Deposition Control in Industrial
Cooling Water Systems
K.S. Rajan (Technical Manager) and Venkatnath K. (Product Manager)
Betz-Dearbom (India) Pvt Ltd.
5th Floor, Vaydudhooth Chambers,
15/16, Mahatma Gandhi Road, Bangalore-560 001, India
Introduction

Chromate based corrosion inhibition programs were industry

standard in Cooling water systems, till the time when
growing environmental concerns and increasingly stringent
chromate discharge regulations spurred the need for non-
chromate alternatives for corrosion inhibition in cooling water
systems.
This paper discusses the best available alternative to the
Chromate based anodic corrosion inhibition programs, viz.,
High-Phosphate Cooling Water treatment programs.
History

Pre- 1950 period saw High Chromate treatment corrosion

inhibition programs in the cooling water systems. However, it Environmental
was soon recognized that chromate, as a heavy metal, had Concerns necessiated
certain health and environmental hazards associated with oil the need for a non
Treatment programs employing chromate alone at 200-500
chromate treatment
ppm rapidly gave way to programs such as "Zinc Dianodic",
which incorporated zinc and phosphate to reduce the
programs.
chromate levels to 15-25ppm.

Environmental regulations to further limit the discharge of

chromate sparked further efforts to reduce or eliminate
chromate. (The most recent concern relating to chromate
involves chromate present in the cooling tower drift. When
inhaled, hexavalent chrome is a suspected carcinogen. Hence,
application of chromate has been on the decline in all the new
cooling towers.) Hence, phosphates have been used as
alternative to chromate as a corrosion inhibition. As shown in
the figure 1, the transition from chromate based treatment to
phosphate .treatment resulted a shift in the inhibition
mechanism dependence from" anodic" to "cathodic'

627
The Dianodic II concept (patented by BETZ Lab.s Inc. in
1979), revolutionized non-chromate treatment technology.
This made anodic corrosion inhibition possible with non-
chromate treatment technologies in industrial cooling systems.

Chromate Treatment

Uninhibited corrosion of mild steel is caused by a

electrochemical reaction.that causes metal loss by oxidation of
iron to ferrous state. Reduction of oxygen occurs at cathode
which results at localised high pH at the cathode -
approximately 1 or 2 pH units above the bulk water pH.
This electrochemical corrosion reaction can be stifled. by
anodic and/ or cathodic corrosion inhibitors. Anodic
inhibitors passivate the metal surface by forming a stable 1-
F~03 (gamma iron oxide ) film. Chromate, orthophosphate,
nitrite, molybdate, and silicates are typical anodic passivating
corrosion inhibitors. Of these, only chromates and phosphates
in low levels, have been used successfully and cost effectively, Chromate based
as anodic corrosion inhibitors. programs rely
predominantly on
Cathodic corrosion inhibitors rely on a barrier type of film on anodic corrosion
the cathodic sites by controlled. precipitation of natural and inhibition by forming
added. salts. Calcium carbonate, zinc and calcium phosphate,
a stable y- Fe203
zinc hydroxide and lignins are cathodic corrosion inhibitors.
passivating film.
Programs having high levels of chromate gave way to
environmentally more acceptable programs with chromate
along with zinc and. phosphate. These programs were
typically operated with 15-20 ppm of chromate, 1-2 ppm of
zinc and 5-10 ppm of phosphate. Chromate and phosphate
provided the anodic corrosion inhibition whereas the zinc's
cathodic inhibition bolstered. the corrosion protection.
However, as the chromate became unacceptable due to the
environmental concerns, early phosphate programs were
developed..

Non- Heavy Metal Programs

Environmental restrictions on discharge of heavy metals like

chromate and zinc, necessitated alternative environmentally
safe treatment approaches.

629
These, non-heavy metal based programs predominantly
operated at elevated. pH levels ( 7.5 to 8.5) and phosphate
acted both as anodic and cathodic inhibitor - with much
greater dependence on the cathodic reaction.

The figure 3 shows the conventional low phosphate treatment

approach. Anodic corrosion inhibition is by passive iron oxide
film. But, major reliance is on cathodic corrosion inhibition by
Initially, non;.chromate
controlled precipitation of calcium salts like calcium carbonate
and calcium phosphates. programs' excessive
reliance on cathodic
Annexure shows the comparison between conventional corrosion inhibition
chromate zinc phosphate programs and non-chromate resulted in additional
treatments. Early non-chromate treatment had severe fouting/deposit potential
limitations :

(a) pH sensitivity: If pH is high or the overfeed of inhibitor

resultS in fouling. A low pH or insufficient inhibitor will strip
the metal surface of the cathodic barrier film, leaving the
system unprotected.

(b) Slow recovery : When an over feed or under' feed

condition occurs, repassivation of the system is slower than
the chromate. Hence, these programs were considered
"unforgiving" ..

(c) Inferior corrosion control: Generally, conventional non-

chromate programs offered inferior corrosion control
compared to chromate treatments because of excessive
reliance on cathodic corrosion inhibition.

High-Pho,phate Programs

Early phosphate programs were limited by the ability of the

dispersants to keep the high levels of ortho phosphate in
solution. The advent of DIANODIC II type programs
revolutionized the concept of non-chromate treatment.
technology. This program uses relatively high levels of ortho-
phosphate to promote a protective passivatlng metal oxide
film on the metal surfaces. This program with high ortho
phosphate levels, uses more desirable anodic corrosion
inhibition properties of the ortho- phosphate ..

630
The breakthrough and key to this is the development of a
patented calcium ortho-phosphate precipitation inhibitor
which permits the use of sufficiently high levels of phosphate Development of Ca-
to force the anodic reaction to prevail. The figure below ortho-P04 scale
demonstrates the superiority of the patented acrylate based
inhibitors enabled
co-polYmers as compared to the commonly used phosphate
deposit control agents. The various deposit control agents sufficiently high levels
were evaluated at 2.2 pH units above the calcium phosphate of O-P04 required for
saturation pH. anodic corrosion
inhibition.

The corrosion inhibition mechanism of high phosphate

(DIANODIC n) treatment is 80 % anodic and 20 % cathodic.
Typically, the program uses 10 - 25 ppm of ortho-phosphate to
promote anodic passivation reaction at about a neutral pH
(6.8-7.2) .. In addition, polyphosphate bolsters the anodic
corrosion inhibition. A chlorine resistant copper corrpsion
inhibitor is also incorporated if copper metallurgy exists.

631
More detailed control ranges are developed for individual
systems, based on the water characteristics and system
operating conditions. Annexure gives a comparative
performance of high phosphate program (Dianodic IT) with
conventional low phosphate and chromate based programs.
The heat exchanger tube sections' photographs reveal that
there is no barrier/ precipitating film in the high phosphate
program unlike the conventidnal low phosphate programs.
The tube exposed to high phosphate program is similar to the
one exposed to chromate based program.

High phosphate treatment ( DIANODIC IT) has been

successfully applied world wide for more than a decade and
half with corrosion and deposit control results comparable to
chromate based treatments. This program offers the following
benefits : High phosphate
Non-heavy metal based and hence environmentally program (Dianodic-II),
friendly.
has been the most
Corrosion rates comparable to chromate systems.
Calcium concentrations from 17 - 1500 ppm as CaC03. forgiving non-chromate
Conductivity up to 15,000 mmhos. treatment technology.
Bulk water temperatures up to 75 deg. C
Heat exchanger skin temperatures up to 95 deg. C
Systems containing varied metallurgy.
Shell side velocities as low as 0.5 ft / sec.
System upset conditions with pH as low as 2.0 and as high
as 9.0
Overfeed conditions to 50 ppm of ortho-phosphate.

In addition, in situations where sour leaks r.educe chromate

and consequently result in loss in corrosion protection,
Dianodic II program's performance is superior even to
chromate systems. No capital equipment is required for
chromate removal. Since, no heavy metals are present, it also
eliminates the problems of heavy metal contaminated sludge
disposal problems.

High-phosphate ( Dianodic II ) programs provide anodic

corrosion inhibition and deposit control comparable to
chromate programs. They are cost effective and
environmentally acceptable.

632
References :

"BETZ Handbook of Industrial Water Conditioning", 9th

edition, 1991

"New water treabnent can whip heavy metals problem" -

Lawrence C. Hale & John A. Tedesco, Betz Laboratories
Inc., Trevose, Pa.

Questions & Answers - DIANODIC -IT Cooling Water

Treabnent, Betz Laboratories Inc., Trevose, Pa.

"High- Phosphate Cooling Water Treabnent Programs" -

William J. Beer & Joseph F. Ertel, Betz Laboratories Inc.

633
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Dithiobiurets: A Novel Class of

Corrosion Inhibitors
M.A. Quraishi, Jaya Rawat and M. Ajrnal
Corrosion Research Laboratory, Department of Applied Chemistry,
Faculty of Engineering & Technology,
Aligarh Muslim University, Aligarh-202 002, India

ABSTRACT
The inhibiting action of four substitute.d dithiobiurets on corrosion of mild steel in IN-5N HCI
and 20% H2S04 was evaluated by weight loss method, All the investigated compounds gave I.E. in the
range of 95-99% in IN-5N HCl.AC impedance and potentiodynaIrlic polarisation techniques were also
used to understand the mechanism of inhibition.
A comparative study of the inhibiting action of dithiobiuret, viz., PCDTB and commercial
inhibitor (CP) revealed that synthesized inhibitor PCDTB is a better inhibitor than commercial corrosion
inhibitor. The percentage metal loss in presence ofPCDTB was nearly 7 times less in H2S04 as compared
with commercial inhibitor. Hydrogen permeation studies also indicated the better performance of PCDTB
than commercial inhibitor in H2S04 solution.

INTRODUCTION
Organic compounds containing both Nand 8 atoms constitute a potential class of
corrosion inhibitors [1J.. Most of the commercial corrosion inhibiting formulations incl~de N
& 8 containing thiourea derivatives as essential ingredients, due to their high inhibition efficiency
and commercial viability, However, these compounds suffer from two drawbacks (i) They induce
"2 - pick-up by metals which leads to hydrogen embrittlement (ii) They are toxic [2]. ,
In view of the above mentioned defects there exist a need for developing new inhibitors
which can inhibit corrosion as well as 'permeation of hydrogen through metal in acid solutions.
In continuation of previous work on the development of Nand 8 containing corrosion
inhibitors [3-6], four substituted dithiobiurets have been synthesized in the present investigation
with a view to investigate their inhibiting action on corrosion of mild steel in HCI and H2804.

EXPERIMENTATION
Mild Steel strips of size 40mm x 20 mm x ,25 mm having composition C = 0.14%, Mn = 0.35%,
Si = 0.17%, S = 0.025%, P = 0,03% and remainder Fe, were used for weight loss measurements and
hydrogen permeation studies. Mild Steel coupons with and without scales of area 36 cm2 were used for
weight loss measurements in 20% H2S04,

634
 For potentiodynamic polarisation and electron impedance spectroscopic studies, MS strips with
an expose4 area of 1 cm2 wer~ used. Weight loss measurements were carried out as described elsewhere
17]. Potentiodynamic polarisation impedance and hydrogen permeation studies were carried out using
poteiltiostat EG &0 PARC (Model - 173), Impedance system 6310, with software M 398, and
Devanathan& Stachurskis cell respectively at a constant temperature of 35rC. A platinum foil and
saturated calomel electrode were used as auxiliary and reference electrode respectively [8].

RESULTS AND DISCUSSION

Weight loss measurements
Table I gives the values ofIE obtained from weight loss measurements for different concentrations
of dithiobiurets in IN, 3N and 5N HCI. It is found that all the compounds under study inhibit corrosion
of mild steel in HCI solutions. The IE increases with increase in inhibitor concentration and reaches to
maximum at optimum concentrations of 500, 700 and 1000. ppm in IN, 3N and 5N HCI respectivily.
The increase in acid concentration from INto 5N slightly decreased the IE of each inhibitor. The % IE
values for different dithiobiurets decreased in the order: PADTB > PTDTB > DPDTB > PCDTB .
. The better performance ofPADTB may be attributed to the presence of electron releasing CH30
- group while the lowest value ofIE for PCDTB among the studied compounds can be explained on the
basis of -I effect (electron withdrawing inductive effect) of chlorogroup which decreases the electron
availability on the reactive site and causes less absorption of the chloroderivative (PCDTB) on the
metal surface which leads to lesser inhibition.

Table-! Corrosion parameter for MS in HCI in absence and presence of Dithiobiurets (Derived
from weizht loss methd)

Table 2 gives the values of percentage metal loss during pickling of mild steel in 20% H2S04 at
9O2C for 45 and 600 seconds (10 minutes) in absence and presence ofPCDTB and commercial inhibitor
(CP). The percentage metal loss was found to be higher in case of commercial inhibitor as compared to
PCDTB during pickling operation.

635
The electrochemical corrosion parameters for MS in IN HCl containing optimum concentration of
dithiobiurets aregivenin Table3. The results of polarisation study indicate that all the compounds
under study, bring down corrosion current significantly in HCI solutions. It is also seen that these
compounds do not cause appreciable change in the values of Ecorr in IN and 5N HC!. In 3N HCI
these inhibitors shift Ecorr values to negative side. These observations suggest that studied
dithiobiurets are mixed inhibitors in IN and 5N HCI and predominantly cathodic in 3N HC!.

Impedance Studies
Various impedance parameters such as R, (Charge transfer resistance), Cdl (double layer
capacitance) and IE obtained from Nyquist plot in IN HCl in absence and presence of optimum
concentration of dithiobiurets are given in Table 3." The results of the impendance studiesare also
summearised in Fig. 3. The IE values calculated from R, values clearly show that all the tested compounds
are effective inhibitors. It is also found that Cdl values are decreased in inhibited solutions. The decrease
in Cd! values in presence of dithiobiurets show that they adsorb on the metal surface which results in
decrease in double layer capacitance.
Hydrogen Permeation Studies
A study of hydrogen permeation was underta~en with an objective to investigate the effect of
PCDTB on hydrogen permeation and to compare its effectiveness as HP inhibitor with commercial
corrosion inhibitor (CP) in acid solutions through mild steel. Hydrogen permeation current vs
time curves for MS in acid soultions in abs~nce and presence of inhibitors are shown in FigsA&
5.
The results demonstrate that the compound PCDTB reduces hydrogen permeation current
through MS in both the acid solutions. It is also seen"that the reduction of hydrogen permeation
current is more for PCDTB than commercial inhibitor in H2S04,

Mechanism of Inhibition
The inhibition of corrosion of MS in acidic solution containing dithiobiurets can be explained
by the adsorption mechanism. Since dithiobiurets contain N, S and benzene rings besides C & H atoms.
These compounds can adsorb on the metal surface through lone pair of electrons present 9n Nand S
atoms or 1t electrons of the benzene ring. In addition to this, these compounds can also adsorb as
protonated species. All the tested dithiobiurets follow Temkin's isotherm plot. This observation
further suports inhibition of corrosion by adsortion mechanism ...

CONCLUSIONS
The conclusions of the present study are as follows.
I. In weight loss experiments, the order of the inhibition effecency of Dithiobiurets in IN-5N HCI
was as follows PADTB > PTDTB > DPDTB > PCDTB
2. The inhibition efficiency ofPCDTB was more then that of commercial inhibitor during pickling
of mild steel in 20% H2S04 at 902C.
3. The Dithiobiurets \are mixed inhibitors in IN and 5N HCI and are predominantly calhodic in 3N
HCI. .

638
4. The presence of Dithiobiurets has resulted in the increase of Rt values and decrease in Cdl
va,lues.
5. PCDTB reduced hydrogen permeation current through MS in both HCI and H2S04 solutions.
The reduction of hydrogen permeation current is more for PCDTB than commercial inhibitor in
H2S04,

REFERENCES
1. Ayre J.A. Corrosion on Aspects of Reactor Decontamination and Corrosion of Reaction Materials,
International Atomic Agency, Wien, 1962, 'pp. 199-240.
2. Schmitt G., Application of Inhibitors for Acid Media British Corrosion, 1.,\bI. 19,no. 4, 1984,
pp. 165-176.
3. Quraishi M.A., Khan M.A.W., Ajmal M., Muralidharan S. and Iyer S.V.K., Influence of
substituted Benzothiazoles on Corrosion in Acid Solution, J. Appl. Electrochem., Vol. 26, 1996,
pp. 1253-1258.
4. Qurashi M.A., Khan M.A.W., Ajmal M., Muralidharan S. and Iyer S.V.K., Influence of
Heterocyclic Anils on Corrosion Inhibition and Hydrogen Permeation Through Mild Steel in
Acid Chloride Environment, Corrosion, Vol. .53, no. 6, 1997, pp. 475-480.
5. Quraishi M.A., Khan M.A.W., 'Ajmal M., Muralidharan S. and Iyer S.V.K., Influence of
Molecular Structure of Substituted Bezothizoles on Corrosion Through Mild Steel in Sulphuric
Acid, Br. Corros. J., Vol. 32, no.l, 1997, pp. 72-76.
6. Quraishi M.A., Mideen A.S. and Ajmal M., 1,2,4, 5-Tetrazospiro [5,5} undencane-3-thione-A
Novel Acid Corrosion Inhibitor for Mild Steel, Ind. J. Chern. TechnoL, Vol. 1,1994, pp. 329-332.
7. Mathur P.B. and'Varsudevan T., Raction Rate Studies For Corrosion of Metals in Acids-I, Iron
in Mineral Acids, Corrosion, Vol. 38, no. 3,1982, pp. 171-177.
8. Muralidharan S., Quraishi M.A. and Iyer S.V.K., The Effect of Molceular Structures on
Hydrogen Permeation and the Corrosion Inhibition of Mild' Steel in Acidic Solution, Corrosion
Science, Vol. 37, no. 11,1995, pp. 1739-1750.

639
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Kinetics of Carbon Steel Corrosion in Picolinic Acid,

Ascorbic Acid and a Typical Mixture of the Two Acids
Chintamani DasI, H.S. Gadiyar and M.K. Totianil
ISurface Engineering Section, Materials Processing Division,
Bhabha Atomic Research Centre, Mumbai-400 085, India
2Sat-Sang Co-operative Housing Soc., Vashi, New Bombay-400 701, India
ABSTRACT

. The paper reports the results of the corrosion of carbon steel in picolinic acid
and ascorbic acid and their mixture. The corr-osion rates have been calculated from the
data obtained from immersion testsfor acid concentration upto 100 mM at 90C under
deaeration. While the rate showed linear increase with acid concentration for picolinic
acid, it remained almost unchanged beyond 50 mM in ascorbic acid. The effect of
temperature on the rate of carbon steel dissolution has been studied in 35 mM picolinic
acid, 110 mM ascorbic acid and their mixture between 30 to 90C. The activation energy
for individual acid and the mixture has been determined from Arrhenius plots; values
were about 43 and 21 10. mol-1 for 35 mM picolinic acid and 10 mM ascorbic acid
respectively; Arrhenius constant almost 5000 times higher for the former than the latter.
Mixing of the two acids did not affect the activation energy and the Arrhenius constant
and therefore, the corrosion rates in plain 35 mM picolinic acid and with 10 mM
ascorbic acid were identical within the experimental error. The effect of solution
deaeration on the dissolution of carbon steel. in the mixture was insignificant both at
50 and 90C. Higher corrosion rates were recorded for samples subjected to intermittent
clean~ng .

INTRODUCTION

In power or chemical plants, the ferrous components such as heat exchangers,

boilers, reactors and pipings corrode and form surface scales. These precipitated deposits
adversely affect heat transfer and flow of coolants and may eyen cause tube failure due
to overheating. In addition, these deposits provide scope for localized attack due to
differential oxygen distribution, leading to pitting and even perforation of the vessels
and the tQbes. This situation can result in the premature failures of the tubes and the
plant shut-down. In nuclear reactors, the corrosion product films on primary heat transfer
system create additional problem of high radiation field which makes routine maintenance
difficult. The efficient operation of the system with minimum shut-downs and least
system contamination necessitates the periodic cleaning of the surface.

The development of a suitable cleaning method needs to have full information

on the type of scale to be removed. The nature and chemistry of the scales depends on

640
the factors such as operating temperature, pH, dissolved oxygen, the physical and chemical
properties of the environment and the materials of construction. For example, a protective
corrosion product layer of magnetite is formed in the boilers operating in alkaline
conditions and in Pressurised Heavy W aterReactors operating under the reducing
environment and pH 10, the carbon steel, which constitutes about 10% of the total
surface of the heat transfer system, develops adherent scales of magnetite (Fe304)'

The cleaning of scales can be achieved by either physical or chemical methods.

Physical techniques have the common disadvantage of theirinability to reach the bends
and crevices. The chemical methods are free from this problem and are thus most
effective in removing the scales. The earlier chemical methods used mineral acids such
as hydrochloric, sulfuric and phosphoric acid. These solutions are highly corrosive and
can cause localized attack on the structural materials. The recent trends has been to use
a mixture of weak organic acids that attacks the oxide and a chelating agent to keep the
dissolved cations of oxide in the solution and thus prevent their precipitation. Picolinic
acid is known to form stable complexes with Fe+2, Fe+3, Co+2 and Cr+3 [1]. The additional
advantage of picolinic acid that it can be easily regenerated [2].

The stability of magnetite scale is due to the presence of both ferrous and ferric
ions in its lattice. Therefore, its ease of dissolution can be improved to a large extent
by converting all ferrous to ferric by oxidation or all ferric to ferrous by redu~tion. It
has been a practice to employ a suitable reducing agent to convert the ferric to ferrous
ions which are then complexed by the chelating agent and retained in the solution. L-
ascorbic acid is known to reduce ferric ions very effectively [3,4]. During the detailed
studies on the effect of addition of different reducing agents to picolinic acid on the
dissolution of magnetite, Emmert and Wille found that the mixture of picolinic acid and
ascorbic acid gives the best result [5]; a typical mixture consists of 35 mM picolinic
acid and 10 mM ascorbic acid (L-ascorbic acid). One of the important criteria in choosing
the cleaning formulation is the low corrosion attack on the base metal. Since no data
is available in open literature on the corrosion behaviour of this mixture it is necessary
to generate the required information for their effective use. This paper reports on the
corrosion of carbon steel in picolinic acid and ascorbic acid and the effect of the
concentration of these acids and reaction temperature on the kinetics of dissolution.

EXPERIMENTAL

Carbon steel of composition (wt %): C: 0.3; Si: 0.1; P: 0.06; Mn: 0.05; and
balance iron, .in the solution annealed condition (925C for 30 mins and furnace
cooled) was used in this study. Samples of dimension 20 x 20 x 2.5 mm were polished
successively upto 600 grit emery paper, thoroughly degreased followed by rinsing with
flowing water and then distilled water and acetone, and dried. The specimens. were
weighed with an accuracy of 0.01 milligram. The corrosion tests were carried out in
closed flasks. The test solutions were prepared from double distilled water. The deaeration
of the test solution was carried out by bubbling argon gas for 1 hr. The ratio of the

641
volume oftest solution to specimen surface area was maintained .at20: 1. All in1I11ersion
tests were performed under static condition in a thermostatic water bath with a
temperature control of 1C. At the end of the exposure, the specimens were water
cleaned ultrasonically and washed thoroughly with distilled water. Since no surface
deposit was observed, these samples were dried and weighed. The corrosion rates were
determined for each of. the specimens from the weight loss data. The values reported
are the average of four readings; the standard variation was within :t .5%.

RESULTS AND DISCUSSION

Corrosion in individual acids

Picolinic acid and ascorbic acid

Concentration effect

Fig. I shows the variation of the corrosion rate of carbon steel with the.concentration
of picolinic acid and ascorbic acid at 90C. The corrosion rates given are obtain~d after
6 and 24 hr exposure in the deaerated solution of the respective acids; because of
relatively high degree of attack, corrosion tests in picolinic acid were of 6 hr duration.
It may be noted that the concentration ranges chosen for the acids are such that the
critical acid concentration (35 mM and 10 mM for picolinic acid and ascorbic acid
respectively), reported by Emmert et al [5], is included within the limit. It is seen that
while the corrosion rate exhibited almost linear increase with total acid concentration
of pj.colinic acid, the rate increases with ascorbilOacid concentration upto 50 mM and
thereafter, it remains practically constant.

The corrosion of carbon steel in both picolinic acid and ascorbic acid is initiated
by the hydrogen ions in the solution; the pH of picolinic acid used was between 3.02
to 3.82, while that of ascorbic acid was 2.65 to 3.75. The ferrous ion so generated in
the solution gets complexed with picolinate ions and .ascorbate ions. This facilitates the
formation of ferrous ions in the solution through more dissolution of carbon steel.
Simultaneously, the decomposition df the free picolinic acid and ascorbic acid, due to
the removal of their anions from the solution, results the increased formation of protons.
Thus the dissolution of steeUs accelerated by the complexation and therefore, the rate
of corrosion increase with the acid concentration. However, at temperatures above 20C
ascorbic acid undergoes decomposition to dehydroascorbic acid (C6H606). This has been
reported to get adsorbed onto the metal surface (iron) [6]. This adsorbed layer results
in:inhibition. It has also been reported that the presence of ferrous ion in the solution
promotes the formation of the dehydroascorbic acid. In the present study, as the
accumulation of ferrous ion increases, increased amount of dehydroascorbic acid is
formed in the solution. This, in turn, gets adsorbed on the steel surface thus retarding
the dissolution of steel in the ascorbic acid. This explains the observed saturation
tendency at higher ascorbic acid concentrations.

642
643
 In order to determine the kinetic parameters for dissolution of carbon steel, the
corrosion rate obtained for picolinic acid ascorbic acid (upto the concentration of 50
mM) acid were fitted to the Power law expression [7]:

where Kc is the. specific reaction rate and nc is the order of the reaction with respect
to concentration. Thus a log-log plot between the corrosion rate and acid concentration
should be linear with the slope equal to the order of reaction. The plots for ascorbic acid
and picolinic acid are presented in Fig. 2. The observed linearity of the plot for both
the acids justifies the application of the Power law The order of reaction are 0.67 and
1.0 for ascorbic acid and picolinic acid respectively.

Effect of Temperature

The effect of temperature on the corrosion of carbon steel, studied by recording

the weight loss as a function of time in deaerated solution of 35 mM picolinic acid,
10 mM ascorbic acid and the mixture of two at temperatures between 30 to 90C, is
shown in Fig. 3. These data are fitted to the kinetic equation

where Y is the weight loss, t is the reaction time in hours and K is the rate constant for
carbon steel dissolution. The value of n has been obtained from the slope of the log-
log plot between the weight loss and exposure time. The values at each temperature, the
average of these and the standard deviation have been given in Table 1.

Table 1. Values ofn at different terpperatures, for the dissolution of carbon steel in
different medium

Using the average value in kinetic equation (2), the rate constant (K) was calculated
for each data point at each temperature. Making use of the avarage values of K at each
temperature, the Arrhenius plots have been drawn for 35 mM picolinic acid, -10 mM

644
ascorbic acid and their mixture as shown in Fig. 4. The activation energy and the values
of Log A (A is the Arrhenius constant), determined from the slope and intercept of
these plots, are given in Table 2.

Table 2. Activation energy and the Log A factors for carbon steel corrosion in different
medium

The activation energy obtained in picolinic acid is close to the limit reported by
Schorr and Yaholma [8] for the dissolution of metals. This indicates that the rate
controlling step is not the hydrogen evolution reaction but the metal dissolution

In case of ascorbic acid, the activation energy is 21 KJ. mole-I. Activation energy
of similar magnitude has been reported for corrosion of iron even in a strong acid like
H2S04 by Alexander et al. [9]. Although the activation energi is higher for picolinic
acid compared to ascorbic acid, the corrosion rates are also higher for picolinic acid.
This can be explained by higher Arrhenius factor for the reaction between iron (major
component of carbon steels) and picolinic acid. The presence of the adsorbed film of
ascorbic acid on the carbon steel lowers the chance" of interaction between iron and
ascorbic acid solution by a factor of about 5000. In short, the fast reaction kinetics that
would have been possible with ascorbic acid due to its lower activation energy is
negated by the reduced interaction because of the presence of adsorbed film on the
carbon steel surface. On the other hand, picolinic acid being a powerful complexing
agent for iron does not provide any barrier film and hence results in higher value for
A and higher corrosion rates. The addition of the 10 mM ascorbic acid to 35 mM
pi~olinic acid did not affect the activation energy or the Arrhenius constant and hence
the corrosion rates of similar magnitude in 35 mM picolinic acid with and without
10m ascorbic acid for the same time of exposure.

Effect of Dissolved Oxygen

The effect of dissolved oxygen on the corrosion rate of carbon steel was studied in
the mixture containing 35 mM picolinic acid and 10 mM ascorbic acid at 50 and 90C;

647
Fig. 4. Arrhenius plots for carbon steel corrosion in 0 35 mM
picolinic acid and - 10 mM ascorbic acid

648
the data collected is compared with those in deaerated solution. The progress of the reaction
was followed by recording the weight change in the sample after removal from the solution
and thorough cleaning at different time intervals. The results are shown in Fig. 5.

No effect of de aeration was seen at 90C, while the oxygen removal resulted in
slight decease 10%) in the weight loss at 50C. It can, therefore, be concluded that
the effect of dissolved oxygen initially present in the solution has no significant on the
corrosion of carbon steel in the mixture of 35 mM picolinic acid and 10 mM ascorbic
acid. Since the test runs were carried out in a closed system and thus oxygen could not
have escaped, a significant difference was expected at higher temperature. However, the
trend is reverse. This could be attributed to the fact that ascorbic acid is an reducing
agent and gets converted to dehydroascorbic acid in presence of oxygen according to
the reaction

In other words, ascorbic acid can itself scavange the oxygen without a need for
deaeration by N2 or Ar gas bubbling.

Effect of Surface Cleaning

The effect of intermittent surface cleaning on the corrosion behaviour of carbon

steel without deaerationof the solution is shown in Fig. 6 at temperatures between 60
to 90C. At the end of each exposure, weight change was measured after cleaning the
specimen surfa,ce by light rubbing with a soft rubber. The same specimen was exposed
for subsequent period. In another set of experiments, the weight changes were recorded
without any surface cleaning. From the Fig. 6, it can be seen that the samples those
were subjected to surface cleaning between two exposures resulted in higher weight
losses compared to the undisturbed ones. This effe:ct was observed for all temperatures.
This indicated the existence of a thin odsorbed .surface film on the specimen which gets
removed during the physical cleaning process thereby exposing fresh surface to corrosive
attack.

CONCLUSION

The present investigation has shown that the dissolution of carbon steel both in picolinic
acid and ascorbic acid is promoted by the protons arising from tl)e dissociation of the
acid and accelerated by the complex formation between the ferrous ion and the
corresponding anion of the acid; the latter process explaining the increase in the dissolution
with increased acid concentration. The saturation behavior observed in ascorbic acid is
due to the formation of an adsorbed/corrosion product' layer on carbon steel. The rate
of dissolution increased more rapidly with c.oncentration in picolinic acid compared to
ascorbic acid due to better complexing property of the former despite higher activation .
energy in this medium. Higher value of Arrhenius constant in picolinic acid nullified

649
the effect of high activation energy and the net result was higher corrosion rate in
picolinic acid compared to ascorbic. acid. The addition of 10 mM ascorbic acid to
35 mm picolinic acid does not cause in any enhancement of carbon steel dissolution.
Thus the ascorbic acid, which is added t<;> picolinic acid to enha,nce the dissolution of
magnetite by reducing ferric ion of the oxide lattice to ferrous ion, does not alter the
corrosion property of the picolinic acid. Ascorbic acid consumed the dissolved oxygen
present in the solution with very little chtulge in acid concentration and hence no effect
of solution dearation on the carbon steel dissolution was observed. Application of
intermittant cleaning of the sample surface during the exposure caused more dissolution
of the base metal, thereby indicating the formation of some film on the surface of the
film when exposed to the mixture of 35 mM picolinic acid and 10 mM ascorbic acid.
Thus a mixture of 35 mM picolinic acid and 10 mM ascorbic acid can be used quite
effectively instead of plain 35 mM ascorbic acid without any additional corrosion pr()blem.

REFERENCES

1. D.O. PeKin, Stability constants of metal ion complexes, Suppl. 2, part B, Organic
Ligands, Pergamon Press, 1979.
2. L.D. Anstine, J.e. Blomgren and P.J. Pettit, Water chemistry of nuclear reactor
systems 2, BNES, London, p. 395, 1980.
3. M.D.S. Afonso, P.J. Morando, M.A. Blesa, S. Banwart and W. Stumm, J. Colloid.
Interface. Sci., 138 (1990) 74.
4. S.V. Murugari, A.L. Rufus, V.S. Sathyaseelan, T.V. Padmakumari, S.V. Narasimhan
and P.K. Mathur, Nucl. Energy. 34 (1995) April, 103.
5. H. Emmert and H. Wille, Private communication.
6. I. Sekine, Y. Nakahata and H. Tanabe, Corros. Sci.,. 28 (1988) 987.
7. P.B. Mathur and T. Vasudevan, Corrosion, 38, (1982) 171.
8. M. Schorr and J. Yahalom, Corros. Sci., 12 (1972) 867.
9. BJ. Alexander and R.T. Foley, Corrosion, 31 (1975) 148.

651
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Impedance Measurements and High Temperature

Weldment Corrosion and its Inhibition in 2.25Cr 1.0 Mo
Low Alloy Steel Used in Power Plants
s. Natarajan and V. Sivan
Department of Metallurgical Engineering, Regional Engineering College,
Tiruchirappalli, 620015, Tamil Nadu, India

ABSTRACT
SA 213 (2.25 Cr-1.0Mo) Low alloy steel has been extensively used in power plants. Boiler scale is
conventionally removed by acid cleaning. This paper deals with Impedance measurements at room
temperature on 2.25Cr-1.0Mo low alloy steel weldments in HCl acid medium (O.lM, 0.5M and
1.0M) prepared by manual metal arc welding (MMAW) and tungsten Inert Gas (TIG) welding
processes. Electrochemical measurements at 100C in terms of polarisation techniques were made and
corrosion current values have been calculated by Tafel Line Extrapolation (Tafel) and Linear
Polarisation Resistance (LPR) methods. Parent metal, reinforcement and root are chosen as regions of
exposure for the study after, all the test specimens are suitably stress relieved. The role of hexamine as
inhibitor at 100 ppm concentration has been studied in all measurements. The surface morphologies of
all regions ofweldments have been examined and compared using scanning electron microscopy (SEM)
to highlight the nature and extent of oxide/film formation. Impedance measurements at room
temperature have also been carried out. Impedance measurements at room temperature indicate that
MMAW is better for T 22 parent metal and reinforcement regions. In the case of root TIG welding
registers a very minimum corrosion current in the order of 10-5 to 10-6 mA/cm2 SEM examination
reveals intensive, porous, fine globules of Fe304 distribution.

INTRODUCTION
Fossil boilers experience corrrosion problems in both waterside and fireside of the tubing as well as
elsewhere ill the plants. Welding plays an essential role in construction of components such as reactor
vessels, pipe work, heat exchangers etc. Water used for steam raising often contains dissolved solid and
gaseous impurities. These can cause scaling and corrosion in the boiler plant. These scales are
normally removed by many methods and one of them is acid cleaning [l]. Apart from these some of
the inorganic salts may hydrolyse to produce acidity causing corrosion of the. boiler tubes. For
prevention of boiler corrosion, inhibition is effected using organic compounds such as hexamine [2].
This paper describes an experimental work carried out to evaluate and compare corrosion and its
inhibition in low alloy boiler steel T II (2.25 Cr-1.0 Mo) weldments prepared by MMAW and TIG
welding processes in HCl acid medium. In the present study, hexamine at 100 ppm concentration is
used. SEM analysis also is done on samples exposed at 100C.

652
EXPERIMENTAL
Low alloy boiler steel (T2212.25 Cr-I.O Mo) weldments were made by MMAW and TIG welding
processes. The chemical composition, mechanical properties, the welding conditions are given in
Tables I and II. These weldments were prepared in the tubular form and the studies have been
made using a small coupon of (4.5 x 1.5) cm2 parent metal, with reinformcement and root. Before
exposure to the corrosive medium all the test coupons were stress relieved at 700 - 750C.
Each test coupon after stress relieving was surface polished using conventional method (degreasing
polishing with emery papers of different grades, etc.) The unwanted regions were masked using teflon.
Areas of regions of exposure were noted. In the case of reinforcement and root, the areas of exposure
were weld zone and HAZ identified by macro etching. In all experiments, deaeration was done by
nitrogen gas purging for half an hour to enable only the hydrogen reduction to take place as the
cathodic reaction.

ELECTROCHEMICAL TECHNIQUES
All studies were made using model-362 scanning Potentiostat (Princeton Applied Research
Corporatio~, U.S.A}. Following techniques were adopted to find corrosion current (Icorr) values.

Tafel Extrapolation (Tafel)

Applications of potentials upto ISO mV from OCP were made forTafel plot and a plot of E Vs log I
was made in all the experiments and a slope was drawn which on extrapolation to Ecorr has given
respective Icorr.
Linear Polarisation Resistance (LPR)
The open circuit potential (OCP) in each case was observed after the system became stable at least for
IS minutes. Accordingly from OCP upto 20 m V potentials were applied in a discrete fashion in
increments of2 mV and the corresponding current was read. A plot of E Vs I was made. It was found
to be linear in almost all cases. The studies pertained to both cathodic and anodic regions in the
absence and presence of hexamine as inhibitor at 100 ppm concentration. From the above plot Rp was
calculated. Icorr values were determined using the formula:
Icorr = babd2.3 (ba + be) IIRp where Rp = ~E/~I (1)
ba and bc values were obtained from the Tafel extrpolation m~od as described above.Table III shows
Icorr at 100C.

Impedance Studies
The well polished electrode has been introduced into 200 ml of deaerated solution and allowed to attain
steady potential value. AC signals have been impressed'to the system with the frequencies ranging
from O.1 Hz to 100.0 KHz. The values of Rs, Rt and Cd}have been obtained from the plot of real part
(2') Vs imaginary part (2"). The above measurements were made using the instrument EG & G PARC
5208 - Two phase lock-in-analyser coupled with potentiostat/Galvanostat Model 273 (Impedance
measurement system). (1""-1114. ~:Y)
The Icorrosion has been obtained by substituting Rt into Stem-Geary equation
Icorr = ba bd2.303 (ba + bc) x IIRt (2)
In this technique, studies at room temperature condition only, have been made.

SEM Analysis
Studies on surface morphologies of SA 213 T 22 have been carried out for all three regions of MMAW
and TIG weldments exposed at 0.5 M HCI concentration at 100C using JEOL Scanning electron
microscope 35 CF. (Japan make).

653
654
6SS
656
RESULTS AND DISCUSSION

Micro Structural Features

Ealier work by Natarjan and Sivan, [3] on T 22 at room temperature reveals a decreasing trend in
corrosion rate for parent metal region with increase in acid concentration. Although this is an ususnal
observation in the case of any steel, the reason can be attrbuted to the presence and combined effect of
Cr and Mo in the alloy. Photo .micrographs (Fig. 1 to 3) show three different zone of T 22 TIG
weldment Fig.l indicates the microstructure of polygonal ferrite and bainite. The formation of bainite
is due to the presence of alloying elements. Fig.2 for TIG HAZ indicates acicular ferrite and carbides
and Fig.3 reveals columnar ferrite and carbides for TIG weld zone. Unlike carbon steels [4,5] T22
weldments get accelerated towards their corrosion behaviour in presence of hexamine in most of the
zones and in all acid concentrations.

Tafel and LPR techniques

.k VcUuesat 100C for T 22 weldments for Tafel and LPR techniques are given in Table III. At 100C
T 22 parent"metal has shown a remarkable increase in lcorr values which widely differ to the tune from
two to hundred times in comparison with room temperature condition. Exactly similar trends are
observed both for reinforcement and root regions.

Regarding the influence of welding process at high temperture for 0.1 M and 0.5 M HCI
coneentrations, TIG currents are lower than MMAW for reinforcement region. However it is difficult
to strike a compromise towards the selection of the best welding process from the observed values.

The Role of Hexamine

Inhibition currents under TIG welding process are less than MMAW values in root region while
inhibition cnrrerrts for TIG in reinforcement are more than the MMAW.

The role played by hexamine does not seem to be very much beneficial for T 22 material at high
temperature situation. About one fifth of the experimetns have experienced acceleration in corrosion
due to the presence of inhibitor. This could be probably attributed to the high temperature effect. It is
also to be noted that the percentage' inhibitor efficiency is considerably high in the case of TIG welding
process than in MMAW. Comparison of other welding processes for T I I material, a low alloy steel
(lCr-O.5Mo), indicates that the hexamine is unsuitable [6,7].

SEM Analysis :
Like SA 213 T 1I material [4,8] SEM photographs reveal finer structures in TIG welding process due
to high temperature effect. SEM photos (Fig.4. to 8) describe the various ways by which the film
distribution has occurred .. Intensive porous fine globules of Fe30 4 as clusters are seen in the case of
weld zone of root region.

Earlier reports (9-11) on SEM examination indicate that even afer the shortest exposure, the oxide
contains substantial porosity and numerous cracks. Some of the oxide also has become detached from
the base metal. On longer exposure, specimen has more oxide missing and the oxide generally has
greater porosity. The oxide is found to be composed of two magnetite layers, the inner one containing
Cr and Mo. in about the same volume ratio as the alloy and the outer one essentially pure Fe30 4'.
Reports on growth structure and breakdown of magnetite film in a high temperature agueous solution
have been very much available which reflect the similarities of observations made in this investigation.

657
658
659
Figs. 9 and 10. Some typical Nyquist plot for T 22/HCVHexamine

660
 Impedance Studies:
In all the measurements made at room temperature a typical Nyquist plot has been obtained in the
absence (Fig.9) and presence of inhibitor (Fig. 10). The parametts of impedance technique are provided
The presence of inhibitor shows almost higher Rs values in all acid concentrations for MMAW process
and hence correspondingly corrosion rate in respective cases is found to be less. In root regions the
resistance offered by the solution .at O.5M Hcl concentration in nil and hence Icorrosion values have
become extremely meagre. However there is a considerable corrosion in reinforcement region. There is
an abnormal behaviour at l.OM concentration in the case of parent metal under the influence of
6
inhibitor. (i.e.) the resistance offered by the solution is very high to the tune of 3.70 x 10 ohms. This
may be attributed to the relatively greater content of Cr and Mo in the material and also the remarkable
role played by the inhibitor. The Cd! values are comparatively lower under TIG welding condition in
the case of root region.
CONCLUSION
By and large Impedance technique represents minimum corrosion rate for all regions of
T 22 weldments.
It may be stated that TIG welding process appears beneficial for T 22 root region.
It is, however, difficult to strike a compromise towards the selection of the best welding
process for T 22 material from corrosion resistance view point.
Hexamine, the inhibitor, is not found useful.
SEM examination reveals intensive, porous fine globules of Fe304 as clusters in the
cas~ of weld zone of root regions.
ACKNOWLEDGEMENTS
The authors sincerely thank the authorities of Bharat Heavy Electricals Limited, Tiruchirappalli - 620
014, for the supply of materials. They are also thankful to the Principal, Regional Engineering College,
Tiruchirappalli -620 015, for his kind encouragement and permission to present and publish this paper.
REFERENCES
1. Corrosion Testing of Chemical Cleaning Solvents NACE publication 3M182, Materials Perfonnance ,
21 December, 1982, P 48.
2 .. Rajagopalan , K. S. Corrosion Maintenance, April- June 1978, p 83 .
3. Natarajan, S. and Sivan, v., Polarisation studies on low alloy boiler steel (T22) weldments in acid medium.
lBull. Electrochem 6(5) May 1990, pp 501-504.
4. Natarajan, S. and Sivan, v., Corrosion behaviour of boiler steel Weldments - Proc. National Welding
Seminar, Dec. 1989, New Delhi.
5. Natarajan,S.and Sivan,V.,High Temperature Weldment Corrosion In SA 210 Gr AlICarbon Steel Used in process
and Power Industries-Proc. International Conference on' Maintenance, Inspection, Corrosion Management &
Plant reliability, Baroda, Feb. 14 - 16, 1991.
6. Natarajan,S. and Sivan, V., Influence of MlG welding process on corrosion behaviour of SA 213 T 11 low alloy
steel used in power plants. Proc. National Conference on Corrosion and its Control, Mumbai, Feb. 1992.
7. Natllrajan, S. and Sivan, v., Influence of Induction Pressure Welding ProceSs on Corrosion and its Inhibition
in SA 213rr II (1.0Cr-O.5Mo) Low Alloy Steel Used in Power Plants. Paper accepted for presentation in
National Welding Seminar, NWS'97 to be held at Bangalore during Dec.ll-13, 1997.
8. Natarajan,S. and Sivan, V., Impedance Measurements and high temperature weldment corrosion and its
inhibition in lCr-O.5Mo Low Alloy Steel Used in Process and power industries. Paper accepted for
presentation in Seventh National Congress on Corrosion Control to be held at Hyderabad during Sep.17-19, 1997 .
. 9. Bignold,G.l, Garnsey.R. and Mann G.M.W. High temperature aqeuouscorrosion of iron. Development of
theories of equilibrium. Solution phase transport through a poroUfl oxide,corrosion science,1972, Vo1.12, P325.
10. Mann. G.M.W and Teare.P.W., The oxidation of iron-chromium alloys in ferrous chloride solution at 300C,
corrosion science 1972, Vo1.12, P.361.
II. AshfordJ.H., Garnsey.R. and Mann.G.M.W., corrosion of Mild Steel under heat transfer in high temperaure
aerated sodium chloride solutions, corrosion science, 1974, Vo1.14, p.515.

661
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India .

ABSTRACT

The inhibitory effects of new oxazole derivatives on the ARMCO iron corrosion behaviour in 1M HCI
are examined by weight-loss and electrochemical methods, Cathodic polarisation measurements are made
after I hour of immersion. The weight loss measurements have confirmed the electrochemical trend.
From comparison of results, it was found that 5-chloro 2-(3'-nitrophenyl) 1,3 benzoxazole (I) is the best
inhibitor and its inhibition efficiency reaches a maximum value of 91 % at 10-3 M. The effect of temperature
indicated that inhibition efficiency of (I) is temperature dependent in the range 30-900C.

INT~ODUCTION

Azole derivatives are usually reported in the literature reviews, for corrosion inhibitors in acid solutions
[1--4]. Recently in our laboratory study of Tetrazole derivatives has been addressed to hydrochloric acid
solution [5]. The literature has references to extensive studies on the effects of Benzimidazoles, Benzothiazoles
and some of their derivatives on the corrosion behaviour of various metals and on the mechanism of
inhibition action in aqueous media [6-8]. Papers on the effect of benzoxazole derivatives and on their
mechanism of inhibition are quite rare.
The aim of this researoh is to deepen the knowledge of the mechanism of action of various benzoxazole
derivatives recently synthesised [9], by correlating the inhibiting efficiencies with the structural properties
of their molecules.
The purpose of the present paper is to study, through the modification of the dissolution kinetics of the
metal, the inhibition mechanism of 5~chloro 2-(3'-nitrophenyl) 1,3 benzoxazole (I) and some of its
structure-related compounds, against corrosion of ARMCO iron in 1M HCI, in the temperature range
from 30 to 90C.

EXPERIMENTAL DATAILS

Inhibitors
The synthesis of some oxazole derivatives is often performed by condensation of ortho-substituted.
Aniline or its derivatives with carboxylic acids or their derivatives in undiluted HCI or H S0 acids
2 4
solution [10] in heat or in presence of Polyphosphoric acid [11] at 150C, indeed, 2500C.

662
 Problems posed by the manipulation of concentrated HCI and H2S04 acids, their reaction pollutant rejects and
encouraged by our recent [12] performance of arylimidazoles under Microwave irradiation, leads us to examine
.another possibility of cyclocondensation of ortho-substituted aniline with carboxylic acid.
The principle cQJlsistsof submitting the reactional mixture under micro-wave field to obtain the products I-VI
(schemel): The reaction is conducted in monomodereactor (Syntewave 402 Prolabo) particularly adapted to the
synthesis [9].
In a pyrex tube of 2ero diameter and 15cm height, 10 mmoles of 2-arninophenol derivatives 1 and 10 mmoles of
benzoic acid are mixed. Under mechanical steering, the mixture is activated under microwave irradiation
[300W, temperature 202-226C , time 10-12 mn] until fusion of the two reacts. The liquid obtained solidifies
after cooling to room temperature. Crude products were recristallised in Xylene (yield>90%).

Scheme 1

The inhibitors synthesised were:

I: 5-chlor02-(3'--nitrophenyl)1,3benzoxazole
yield 90%; melting point : 183-184 C; M+(mlz): 274(6.25%); 154(100%)
0: 5-chlor02-(3'-chlorophenyl) 1,3benzoxazole
yield 94%; melting point: 137-138 C ; M+(mlz): 263(9.38%) ; 154(100%)
01: 6-nitr02-(4'-nitrophenyl) 1,3benzoxazole
yield 92%; melting point :>260C ; M+(mlz): 285(6.79%) ; 287(100%)
IV: 5-chlor02-(3'-hydroxy4 '-methoxyphenyl)1,3benzoxazole
yield 87%; melting point: 147-148 C ; M+(mlz): 275(11.92%) ; 277(100%)
V: 5-nitro2-(3'-nitrophenyl) 1,3benzoxazole
yield 89%; melting point :>260C ; M+(mlz): 285(2.16%) ;165(100%)
VI: 6-nitr02-phenyll,3benzoxazole
yield 98%; melting point :>260C ; M+(mlz): 240(1.79%); 242(100%)

Mass loss and polarization measurements

The iron specimens used were cut from ARMCO-type iron . The weight loss was measured OIl sheets of
apparent surface area 00 cm2 in 100 ml of acid solution.
Prior to gravimetric measurements, the iron surfaces were polished with different emery papers up grade 1000,
washed thoroughly with doubly distilled water, dried with acetone and finally dried ill dry air.

663
The aggressive solution (lM HCl) were prepared by dilution of Analytical Grade 37% HCI with doubly
distilled water. All tests have been carried out at different temperatures in magnetically stirred and aerated
solutions. Benzoxazoles are dissolved in minimum of DMF (dimethylformamide) before the addition to
electrolyte solution. The literature reveals that the protection efficiency of certain organic compounds in DMF-
acid solution, decreases as the concentration of DMF increases[13]. Starting from this consideration, we have
tried to minimize the % of DMF in the solution and the value of 2% was the very adequate and gave the best
efficiency for all the compounds tested .
After some initial series of measurements carried out at 30C, further measurements have been performed at
higher temperature until 90C at the same concentration of 10-3M and in the immersion time range froml to 6
hours . During the 6h tests, the iron dissolution and corrosion rates were determined .

Electrochemical experiments were performed in a conventional three electrodes cylindrical glass cell with
platinum counter electrode and a saturated calomel electrode(SCE) as reference . The working electrode in the
form of disc, was cut from ARMCO iron, had geometric area of 1,0 cm2.
The polarization curves were recorded with an Arnel 550 potentiostat using an amel 567 linear sweep generator
at a scan rate of 20 mV/mn .Before recording the cathodic polarization curves, the iron electrode was polarized
at -800 mV/SCE for 30 mn. Solutions were de-aerated with nitrogen. The nitrogen bubbling was maintained in
the solution during the electrochimical measurements.

RESULTS

Gravimetric measurements
The corrosion of iron in molar hydrochloric acid solution containingl0-3M concentration of various
Benzoxazole derivatives was studied by weight-loss measurements. The corrosion rate of iron is determined by
the relation: .

664
665
666
 Table 1 collects the corrosion rate values and the inhibiting efficiency percentages calculated from weight loss
measurements. From these data, it is evident that the lowest corrosion rates, in the examined temperature range,
are measUred in the presence of product I . A linear relationship between the corrosion rate and temperature is
. shown up to 70C, whereas by further increasing the temperature to 90C, sudden increase in the corrosion rate
is found. Trend similar to that described, is verified also for III and V ,clearly showing a shift of the corrosion
rates at higher values passing from70 to 90C. In the case of the other additives(Il, IV, Vl),evident increase in
the corrosion rates is observed just at 60C.
By considering the variation of the %IE depending on the type of additive and On the temperature, it can be
noticed that the protective efficacy of I is the best in the whole range of temperatures tested, exceeds 80% just
at 40C and reaches 91% at 70C. On the contrary, in the presence of III and V , the highest inhibiting
performances are obtained between 50 and 70C. By examining the behaviour of the other derivatives (II, IV,
VI), the negative effect of increasing temperature on their protecting efficiencies is clearly evident.
An analysis of the dissolution kinetics of ARMCO iron in the various experimental conditions has been carried
out, with the aim of differentiating the dependence of the various inhibitors on their molecular structure, testing
time and temperature.
Figuresla, b, c, d, e and fpresent the kinetics of ARMCO iron dissolved(mg cm-2) in 1M HCl, during the 6-11
tests, in the presence of different inhibitors studied at 30, 40, 50,66, 70 and 90C.
At 30C(fig.la) the amount of dissolved iron non-linearly increases during the whole 6-h test, except for I which
shows linear relationship between iron corrosion rates and time. In addition to I , II and IV present the best
efficiency at this temperature.
By increasing the temperature to 40C(fig.lb), 50C(fig.lc), 60C(fig.ld), 70C(fig.le), 90C(fig.lf), it is
evident that I maintains both its linearity and good efficiency with time. From the same figures it is also possible
to demonstrate the improvements in the efficiency of III and V by increasing the temperature. Also the decrease
of the inhibiting effects ofIl, IV, and VI are clearly emphasized.
Figures 2a-f collects the changes of the corrosion rates of ARMCO iron(mg cm-2 h-l) in 1M HCl, in the
presence of the various inhibitors, as function of testing time and temperature.
From these figures it can be observe<;lthat I, ill, V are able to reduce after the first hours of the tests the
corrosion rate to its minimum values and to maintain this value during the remaining testing time(fig.2c-f).
In the presence of the other derivatives(ll, IV, VI) the time necessary to reach the minimum corrosion rate value
is clearly gr~r. Whereas in some cases, such as in presence of these last derivatives at 50, 60 and 70C, a
constant value of the corrosion rate is not reached even at the end of the Q-htests.
These differences in the behaviour of the various compounds can be attributed to different action me.clumi!m1$ of
the additives. Visual observations of the metal surfaces during the tests seem to confirm this assumption. In fAct,
in the presence of II, III, IV or VI the formation of macroscopic surface layers is observed, particularly evident
at higher temperatures tested. In the presence of I or V, the surface of the specimens remains bright during the 6-
h te$tS,perhaps allowing a mechanism of action based on the chemisorption of the molecules.
The analysis of the polarization curves recorded at the end of the I-h tests confirms the above mentioo.edresults.
As an example, fig.3 shows the cathodic polarization curves in absence and presence of 1O-3Mconceotratioo. of
I which presents the best efficiency among the all compounds tested.
In the case of electrochimical method, the inhibition efficiency (lE%) is defined as:

Where lcorr and I'corr are uninhibited and inhibited corrosion current density determined by extrapolatioo. of
cathodic Tafel lines to the corrosion potential.

667
The inhibition efficiency calculated by the electrochimical method is the same as which is calculated by the
gravimetric measurements and gives agreement as to the efficacy ofI as good inhibitor.
The shape of the curve recorded in presence ofI is similar to that of the corresponding curve in uninhibited 1M
HCI solution, but a shift towards lower current densities is emphasized. This behaviour should support an
action of the additive based on an adsorption process without changing the reaction mechanism.

668
To have more ideas about the mechanism of inhibition, we have dressed the Arrhenius plots for the corrosion
process from the study of the effect of temperature (fig. 4). The apparent activation energies for ARMCO iron
dissolution in 1M HCI in the presence of 10-3 M concentration of various inhibitors tested are determined by the
following Arrhenius relations: '
W = k exp(-EalRT) (4)

W' = k exp(-E'a/RT) (5)

Where Ea and E'a are the apparent a(;tivation corrosion energies, in the absence and presence of the inhibitor
respectively.

Table 2: Values of the apparent activation energy for the inhibitors tested at 1O-3M concentration in 1M HCI
solution.

From data in table 2 we can observe :

Increase of the apparent activatioo. corrosion energy in presence of II, IV and VI. The decrease of efficiency
with the temperature, can be explained with the fact that the augmentation of temperature leads to the reduction
of the inhibitor adsorption and then acceleration of the dissolution process[14].
On the contrary, in presence of I, III and V, decrease of the apparent activation corrosion energy is clearly
evident.
This resuk can be related to modification in iron dissolution mechanism interpreted by manyauthors[15 ,16] by
one of these two reasons: .
- formation of surface complex which the constitution kinetics might be patronised by temperature elevation.
- Or formation of protective layer at the metallic surface, formed by metal- inhibitor interaction, where
temperature is predominant factor.

DISCUSSION

The analysis of the resuks emphasizes that only I reaches 91 % inhibition efficiency and has the highest value in
the whole interval of temperature examined. While the protective effect of the other compounds(at70C for
example) increases in the order:
v>m>IV>IV>II>VI
Actually, inhibitory efficiency depends upon a combination of intramolecular steric and electrOnic activities.
Therefore, the molecular structure of the inhibitor assumes special significance. The electron density of the
atoms in functional groups constituting a reaction centers affect the strength of the adsorption b,ond. The latter
aspect is particularly important for aromatic and heterocyclic compounds, since the electron density at the
reaction centers can change ,considerably when various substituents are added.
The substitution of CI atom in position 5 of inhibitor I with N02 group decreases the inhibiting efficacy of the
parent compound. According to the electron-donating character, N02 is more electron-attractive than C~ so in
V the nitrogen and oxygen center atoms have their electron densities decreased and then the strEOgt:b of the
adsorption bond and also the reduction of the nitro groups caused by the evolved hydrogen in acid soluticn aids
the desorption of compound V [17]

669
Compound In has the same molecular size and the same functional groups as V, but it is less effective. This
may be due to the positions of N02 groups which lowers the charge density of the molecule in addition to the
facility of the reduction ofN02 group in acid medium.
The possibility of hydrogen bond formation allowed by the presence of the hydroxyl group in the ortho-position
of methoxy group of aryl of inhibitor IV leads to decrease the negative charge density, causing decrease of the
protection efficiency. The mesomeric character(+M) of the CI and its meta-position of aryl group of inhibitor n
may destroy, according to the electronegative orientation, the electron pairs on the molecular centers ( double
bond, oxygen and nitrogen) , this in turn leads to decrease the inhibitor adsotption and the protective efficiency
of n. In the other hand, compound VI has the least effective inhibitor in this series. this is due to nitro group
more easily reduced in acid medium and to its low molecular size. We can easily notice that the molecular size
influences meagrely the inhibition efficiency.

CONCLUSION

From this study, the following conclusions can be drawn:

1. The corrosion rate of ARMCO iron in 1M HCI is markedly decreased in the presence of I even at high
temperature.
2. The inhibiting efficiency of these benzoxazole derivatives shifts with the nature of the substituents and their
positions.
3. The increase in the temperature produces an increase in the inhibiting efficiency of I, III and V. This fact,
together with the reduction of the apparent activation energy, is prooffor chemisorption of these inhibitors.
4. The rise of temperature produces a decrease in the inhibiting efficiency of II, IV and VI. This indicates that
these compounds are physically adsorbed on iron surface.
S. The advantages of the examined organic compounds are that they were rarely subject of inhibition corrosion
studies (because of their synthesis difficuhies) and are now obtained in high yields and good purity in easy
conditions and shortened times as under microwaves.

ACKNOWLEDGEMEN'1'S:

The authors are very indebted to the TWAS (Trieste Italy) for its financial support.

REFERENCES

1. Chin, R. 1. , Nobe K. ,1. Eelectochem. Soc. vol. 1I8 , 1971, p.545.

2. Abdenaby B. A., Eltourhy A., Elgamal M., MahgoubF., Surf.Coat Technol. vo1.27,1986, p.325.
3. Tadros A. B., Abdenaby B. A., 1. Eelectochern. Chern. vol. 246 , 1988, p.433.
4. Zucchi F., Trabanelli G., Brunoro G., Corros. Sci. vol. 33, 1992, p. 1135.
5. Hammouti B. , Kertit S. , Applied Surface Science vol. 93, 1996, p. 59.
6. TatarChenko G. 0., Tyupalo N. F., Kuzub U. S., Sukhomlinov A. B., Gru B. A., Zashch. Met. vol.
28,1992, p. 842.
7. Zhou G., Feng Y, Wu Y, Notoya T., Ishikawa T., Bull. Chern. Soc. Jpn. vol. 66, no.6, 1993, p. 1813-16,
8. Kuznetsov Va. I., Podgomova L. P., Zashch. Met. vol. 29, 1993, p. 471.
9. Bougrin K., Loupy A., Soufioui M., Tetrahedron, 1997, submited.
10. a) Phillips M. A., 1. Chern. Soc., 1928, p. 2839. b)Wright 1. B., Chern. Rev., vol. 48, 1951, p. 397,
11. a)Heine D. w., Alheim R. 1., Leavitt 1. 1., J. Am. Chern. Soc., vol. 79, 1957, p. 427.
b) Thompson L. K., Ramaswamy B. S., Seymour E. A., Can. 1. Chern., vol. 55, 1977, p. 878.
12. Bouarin K., Soufiaoui M., Tetrahedron lett., vol. 36, 1995, p.3683.

670
13. EI-Anadouly B. E., Corros. Sc., vol. 34, no. 5, 1993, p. 779.
14. Gaddallal A., Badawy M. W., Reban H. H., Abouromia M. M., 1. Appl. Electrochem. vol. 19,1989,p.92I.
15.1. R. Rigss O. L., R. M. Hood Corr., 1967, p. 252.
16. Sanigol B., Srivanostova K., Br. Corr. 1., vol. 9, 1974, p. 103.
17. Mohamed A. K., Bekheit M. M., Fouda A. S., Bull. Soc. Chim. Fr. vol. 128, 1991, p. 33.

671
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6. Mumbai, India

New Triazole Derivatives as Corrosion Inhibitors for a

Carbon Steel in 2M H3P04 Solution
s. Kertitl, K. Bekkouch2, M. Elfarissi2, A. Aouuiti3 and B. Hammouti3
ILaboratoire de Physico-Chimie des Materiaux associe a I' AUPELF-FREF (LAF 502)
Ecole Normale Superieure de Takaddoum, B.P. 5118, Rabat, Morocco
2Laboratoire de Chimie du Solide Mineral, Faculte des Sciences, Oujda. Morocco
3Laboratoire de Chimie des Eaux et Corrosion, Faculte des Sciences, Oujda, Morocco

Abstract
The inhibitory effects of new triazole derivatives on the steel corrosion behaviour in 2M HJl>04
solution are examined by weight-loss and electrochemical polarisation methods. Cathodic and anodic
polarisation measurements are made after 1 hour of immersion. The weight-loss measurements have
confirmed the electrochemical trend. Both methods showed that the dissolution rate was dependent on
the chemical properties and concentration of the product. From comparison of results, it was found
that 2,5-di(chloromethyl)-3-benzyl-I,3,4-triazole (TAZC) is the best inhibitor and its inhibition
efficiency reaches a maximum value of 88% at IO-3M. Polarisation measurements indicated that TAZC
acts as mixed inhibitor by merely blocking the reaction sites without changing the mechanism of the
hydrogen evolution reaction. It was found that TAZC was adsorbed on steel surface according to a
Langmuir isotherm model. The effect of temperature indicated that inhibitIon efficiency of TAZC is
temperature dependent in t\1e range 25 - 50C.

Introduction
A number of investigation have been conducted on the inhibitory effect of heterocyclic
compounds containing nitrogen. Several tetrazole, triazole, pyrazole, thiazole and imidazoles
derivatives [1-7] have been studied. The inhibition results generally from the adsorption of the organic
compounds on the surface of the metal, leading thus to a barrier to the corrosive medium.
Good results obtained with azole compounds in the corrosion inhibition in acid media [1-7]
have incited to test other azole type-compounds. Our choice was made on new triazoles.
The aim of the present investigations is to study the inhibitory action of new triazole
derivatives on the corrosion of carbon steel in 2M H3P04 solution.
The triazole derivatives studied are: 2,5-di(hydroxymethyl)-I,3,4-triazole (TAZA), 2,5-
di(chloromethyl)-3-benzyl-I,3,4-triazole (TAZC), Bis [2,3-diaza 4-methyl 2,5-pyrazolyl methyl] -
I,3,4-triazole (TAZD) et I-amino Bis [2,3-diaza 4-methyl 2,5-pyrazolyl methyl] -I,3,4-triazole
(TAZE). The molecular structure of these triazoles are shown in Figure!.

* Correspondence and reprints

672
 As can be seen from figure 2, current-potential curves rise to parallel Tafel lines indicating that
the hydrogen evolution reaction is activation controlled and the addition oftriazoles tested do not
affect the mechanism of this process. The values of corrosion potential are not changed in presence of
triazoles ..
The addition of triazoles leads to a decrease in the cathodic current densities, witch was so
pronounced with TAZD and TAZC. There inhibition efficiencies were maximum (80 and 88 %,
respectively). The corrosion inhibition efficiency oftriazoles studied increase in the sequence:

TAZA (36%) < TAZE (73%) < TAZD (80%) < TAZC (88%)

The comparative study of corrosion inhibition of 10-3Mtriazoles derivativess indicates that

TAZC has a much more significant effect. This phenomena is offered by the presence of electron
donor groups such nitrogen atoms and aromatic ring in TAZC structure. The presence of CH:zCI
group has the major role in the adsorption of the triazole ring. We concluded that TAZC is the best
inhibitor.

Moreover, cathodic curves of steel in 2M H:J>04in the absence and presence ofTAZC and
TAZDat various concentrations demonstrate that the hydrogen evolution reaction is inhibited and the
inhibition power of the compound increases with its concentration. be obtained from the parallel Tafel
lines indicate that the mechanism of the hydrogen discharge reaction is not modifi~d in presence of
TAZC and TAZD (Table 1). From this study, we can concluded that:
-Icordecreases with increasing inhibitor concentrations,
-addition oftriazoles does not affect the values ofEca and be,
-E % increases with inhibitor concentration, reaching about 90 % at 10-3M ofTAZC.

In the anodic rang,e, the polarisation curves of steel in phosphoric acid without and with
triazole derivatives at 10--'M show the inhibitory action of the molecules for the higher potentials,
(figure 3). This fact means that the inhibition mode oftriazoles doesn't depend on electrode potential
and the TAZC predominates as a mixed-type inhibitor

Gravimetric measurements
The corrosion rates of steel obtained after 3 hours of immersion in 2M H:J>04at various
concentrations ofT AZC are given in Table 2. The inhibition efficiency is calculated by the relation:

Table 2: Influence of the addition of TAZC on the corrosion rate of steel in 2M H3P04.
Corresponded inhibition efficiency produced (t = 3h).

673
Experimental details
Electrochemical measurements were carried out in a conventional three-electrode electrolysis
cylindrical Pyrex glass cell. The working electrode, in the form of a disc cut from carbon steel
(Fe: 99,5 %, C: 0.5% d = 0.10 cm) sheet, had a geometric area of 1.0 cm2 A saturated calomel
electrode (SCE) and platinum electrode were used as reference and auxiliary electrode, respectively.
The temperature was thermostatically controlled.
The polarisation curves were recorded with a potentiostat type Arnel550 using a linear sweep
generator type Arnel 567 at a scan rate of20mV/min. Before recording the cathodic polarisation
curves, the steel electrode was polarised at -800 mV vs SCE for 10 min For anodic curves, the
potential electrode was swept from its corrosion potential maintained for 30 min to more positive
values.
The weight loss was measured on sheets of surface area of 5.0 cm2 in 100 ml of acid.
. Prior to electrochemical and gravimetric measurements, the steel samples were polished with
different emery paper up 1000 grade, washed thoroughly with bidistilled water and dried with acetone.
The aggressive solution (2M H~04) were prepared by dilution of Analytical Grade 85 %
Riedel de Haen with bidistilled water. All tests have been obtained at diff.erent temperatures in
magnetically stirred and deaerated solutions. The triazoles tested [8] as corrosi6n inhibitors are shown
in Fig.1.

Fig. 1. Molecular structure of triazole type-organic compounds studied.

Results and discussion

Electrochemical steady-state measurements
The cathodic and anodic polarisation curves of steel in 2M H~04 solution in the absence and
presence oftriazoles studied are represented in Figures 2 and 3, respectively.
Values of associated electrochemical parameters and corrosion inhibition efficiency (E%) are
given in Table 1. The inhibition efficiency is defined as :
E% = ( 1 - I'cor IIcor ).100 ( 1)

674
where Icor and I'cor are the uninhibited and inhibited corrosion current densities, determined by
extrapolation of cathodic Tafel lines to corrosion potential, respectively.

675
 We note that the corrosion rate decrease with TAZC concentration. E% attains 89.4 % at 10-3
M. This gravimetric measurements are in good agreement with electrochemical method.

Effect of temperature

Gravimetric measurements were taken at various temperatures (25 - 50C) in the absence and
presence ofTAZC at 1O~3M. Results obtained are shown in Table 3.

Table 3: Influence of temperature on the corrosion rate of steel in 2M IhP04 without and with
addition of TAZC at 10-3M.Corresponded inhibition efficiency produced at t = 1hour.'

We note that the corrosion rates of steel increase more .rapidlywith temperature in the absence
of TAZC. The inhibition efficiency of TAZC inhibitor decreases slightly with temperature.
Arrhenius curves (In W vs Iff) are ploted from the corrosion rates (Fig.4). The activation
energies are determined by the relation :

W = k exp ( - Ea I RT) (3)

W = k exp ( - E'a I RT) (4)

where Ea and E'a are the activation corrosion energies in the absence and presence ofTAZC,
respectively, Ea = 51.8 kl Imole et E'a = 64.8 kllmole.

Figure 4. Arrhenius straight lines calculated from corrosion rate of steel in 2M H3P04 (0)
and 2M H3P04 + 10-3 M ofTAZC (.).

676
Figure 5. Langmuir isotherme adsorption model of TAZC on the surface of steel in 2M H3P04
electrochemical measurements (x); gravimetric measurements ( 0 ).

This behaviour show that the TAZC is an efficient inhibitor in the range of temperature
studied. In the presence of inhibitor, the activation corrosion energy decrease. This reduction may be
attributed to the chemisorption of TAZC on the steel surface and the corrosion process corresponds to
a different mechanism of the steel dissolution in the presence of the inhibitor [9]

677
Conclusion
On the basis of results and discussions, the following conclusions can be drawn :
. * The addition of triazoles do not change the hydrogen reduction mechanism and the corrosion
inhibition efficiency of these molecules can be classified in the followirig order :

TAZA (36%) < TAZE (73%) < TAZD (80%) < TAZC (88%)

* Triazoles act as mixed-type inhibitors and E% attains a maximum at 10-3 M,

* The T AZC adsorbs on steel according to Langmuir isotherm,
* The inhibitory effect is the result of the interaction between the molecule and the metallic
surface that decease the active surface,
The inhibition efficiency of TAZC decrease roughly with increasing temperature and its
. addition leads to a increase of activation corrosion energy

Aknowledgments : Authors acknowledge the donating oftriazole compounds by Dr. Najimi Ouafae,
Laboratoire de Chimie organique - Physique, Universite Mohamed ler Oujda - Morocco. Our
acknowledgment for TWAS (Trieste) Italy for financial support.

References
1. Kertit S.; Hammouti B., Corrosion inhibition of iron in 1M HCI by I-phenyl-5-mercapto-l;2;3;4-
tetrazole, Applied Surface Science 93, 1996, pp. 59-66.
2. Kertit -S., Hammouti B., Aouniti A.et Brighli M., I-phenyl-5-mercapto-l;2;3;4-tetrazole comme
inhibiteur de corrosion du fer pur en milieu acide chlorhydrique, Moroccan Patent No 23409(1994).
3. Zucchi F., Trabanilli G., Fontasati M., Tetrazole derivatives as corrosion inhibitors for copper in
chloride solutions, Corrosion Science, Vo1.38, nO 1, 1996, pp 2019-2029
4. Aouinti A., Hammouti B., Brighli M., Kertit S., Berhili F., El-Kadiri S., Ramdani A.,
Inhibition of the acid corrosion with new pyrazole derivatives, Journal de Chimie Physique, 93
1996,pp. 1262~1280
5. Bastidas J.M., Otero E., A comparative study ofbenzotriazole and 2-amino-5-mercapto-l,3,4-
thiazole as corrosion inhibitors for copper in acid media, Materials and Corrosion, Vol. 47, 1996, pp.
333-337
6. Abd-EI-Nabey B.A., EI-Toukhy A., EI-Gamal M., Mahgoub F., 4-Amino-3-substitued-5-mercapto;-
1,2,4-triazolines as inhibitors. for the acid corrosion of steel, Surface and Coatings Technologie,
Vol. 27, 1986, pp, 325-334
7. Ateya B.G., EI Khair A., At Qasimi, Inhibition of the acid corrosion of iron with triphenyl
tetrazolium chloride, ~orrosion Science, Vol. 22, 1982, pp. 717-721
8. Najimi 0., Macrocycles tetraheterocycliques: synthese et complexation, These de l'Universite de
Montpellier IT, France, 1988.
9. Talati J.D., Ghandi D.K., N-heterocyclic compounds as corrosion inhibitors for aluminium-copper
alloy in hydrochloric acid, Corrosion Science, Vo1.23, 1983, 1315-1332

678
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

In-Line Crack Detection in Oil and Gas 'Pipelines:

Operational Experience with the Ultrascan CD
H.H. Willems" O.A. Barbian" N.I. Uzelac2 and P.M. Evans3_
IPipetronix GmbH, Lorenzstr. 10, 76297 Karlsruhe-Stutensee, GelJllany
2Pipetronix Ltd., 50A Caldari Rd., Concord, Ontario, UK 4N8, Canada
3Pipetronix Ltd., 839 5th Avenue S.W., Suite 200, Calgary, T2P 3C8, Alberta, Canada

ABSTRACT
Pipetronix has developed a new generation of intemal inspection device for the detection of
cracks in pipelines. Since its commercial introduction in October 1994 the tool, UltraScan CD
(Qrack Qetectionj, has successfulry inspected nearly 1,000 km of operating oil and gas pipelines.
The runs were followed by verification excavations at specific locations selected from the
collected data .. Comparison of the. findings with corr-esponding verifications from excavations
illustrate the sensitivity and reliability of the inspection method and the ability of the tool to
accurately discriminate between different types of defects. The performance has proved the
UltraScan CD to be a reliable intemal inspection device for the detection of cracks (SCC, fatigue
and other crack like defects) on pipelines. As a result, the German TOV (authorized by the
German Government to verify the compliance with Regulations covering the operation and
inspection of pipelines) has approved the use of UltraScan CD as a substitute for hydrostatic
pressure testing of pipelines.

INSPECTION TECHNIQUE
The new tool is based on the ultraSonic technique since only ultrasound allows for the in-line
detection of extemal 8S well as Intemal cracks with the necessary sensitivity and high resolution.
 The technique applied uses shear waves which are generated in the pipe wall by angular
transmission of the ultrasonic pulses through a liquid coupling medium (oil, water etc.). The
angle of incidence is adjusted such that a propagation angle of 45 is obtained in pipeline steel.
This technique has proven appropriate for crack inspection and it is established as one of the
standard techniques in ultrasonic testing [1].

Because fatigue cracks as well as SCC are generally oriented perpendicularly to the main
stress component, Le. the hoop stress in a. pipe, the ultrasonic pulses are injected in a
circumferential direction in order to obtain maximal acoustic response. A schematic
representation of the measuring principle is shown in Fig. 1.

The sensor carrier of the UltraScan CD is designed such that the complete pipe circumference
is uniformly scanned in both clockwise and counterclockwise directions using 480 sensors
distributed on 16 sensor skids (24"/26") for crack detection (Fig. 2). This arrangement provides
multiple coverage which ensures that relevant reflectors are detected by up to ten sensors.
Additionally, two sensors per skid serve to continually measure the actual wall thickness and to
detect girth welds. This information is used as an aid to locate defects as precisely as possible
with respect to the nearest girth weld. All sensors are mounted in a highly flexible JX)lyurethane
carrier, maintaining a constant distance from the pipeline wall at a defined angle of incidence.

TOOL CHARACTERISTICS
Important technical data relating to the UltraScan CD are listed in Table 1. The tool is
designed to d.etect longitudinally oriented cracks or crack-like defects at any location in the pipe
body wall. Particular emphasis is placed on the longitudinal weld zone that is recognized on-line
and all the information from the two sensors detecting it from both inspection sides is stored
completely. The tool provides full axial resolution, of approx. 3 mm, at inspection speeds up to 1
m/s. At higher speeds a change in the axial resolution is required, however, even at speeds up
to 2 m/s it is still better than approx. 6 mm.

680
 After an inspection run is completed, collected data are pre-processed taking advantage of built-
in detection redundancy, thus considerably reducing the amount of indications to be looked at by
the interpretation group. The evaluation of the data is then performed on personal computers
using advanced data visualization software. After completion of data interpretation a features list
is compiled in a condensed form, containing all relevant indications, Special features are fully
documented including colored images of the corresponding ultrasonic B- and C-scans along with
precise information on the location of any defects. The final report includes a features list, fully
documented features and a complete pipe tally with full information on each individual pipe joint
(distance, wall thickness, pipe length, location of longitudinal weld, etc.).

RESULTS
The UltraScan CD tool has to date successfully inspected nearly 1,000 km of 24" and 26" crude
oil as well as 56" gas transmission pipelines.

The sensitivity of the detection method has been tested. extensively. It has been found that the
UltraScan CD, designed to detect 2 mm deep and 30 mm long cracks, exceeds the design
specifications. A significant number of intemal and extemal notches with depths from 0.5 mm
upwards, located in the weld area and the base material, were reliably detected. Typically,
individual defects with a depth of 1 mm are detected by three to six sensors, in some cases by as
many as ten sensors all dependent upon depth and location of the defect [2].

681
Re'peatabilitv
In order to test repeatability, a 26" crude oil pipeline was inspected twice. Comparing the
recordings from the two runs, the repeatability of the tool could be analyzed based on realistic
conditions. A total of 80 notch-like indications have been compared with respect to length,
amplitude and circumferential position. The arbitrarily selected indications, with depths smaller
than 1 mm, were, as was verified by excavation, most probably mechanically produced grooves
and scratches. These reflectors were detected in both I1.lnsand the repeatability with regard to
the relevant parameters was very good as can be seen from the standard deviations given in
Table 2.

Another example demonstrating the repeatability of data from the tool is given in Fig. 3. It
shows the C-scans of the same location on a crude oil pipeline as recorded from two subsequent
inspection runs. On the C-scans, the longitudinal welds as well as indications from two inclusioo-
like reflectors can be matched with impressive exactitude. The amplitudes of these indications
are well below the design criteria. Nevertheless, even such minor reflectors are repeatedly
detected by the tool and properly classified du,ring subsequent off-line data evaluation.

682
Figure 4. Top: C-scan of a pipe joint from a 26" crude oil line indicating an external
notch-like defect. Bottom: Results of the verification excavation show a 160
mm long, 1.5 mm (18 % WT) deep groove.

Discrimination of defects
Many indications detected in operational pipelines exhibit crack-like characteristics. They
originate from scratches or grooves usually caused during manufacture or transportation of the
pipe. The depth of this type of defect is normally less than 1 mm, but because they act as stress
concentrators, such defects must be considered as a potential site for crack initiation. Compared
to real cracks, the signal patterns exhibit some specific differences, therefore, this type of
indication is classified as notch-like. Some of the more pronounced notch-like indications found
during inspection runs, have been verified by manual ultrasonic testing as well as by MPI
(Magnetic PartiCle Inspection). The results, with regard to defect type, length and position were
in full agreement with the interpretation of the data from the tool. An example is shown in Fig. 4,
showing a C-scan (Fig. 4a) and a MPI trace (Fig. 4b) of an external, approximately 1.5 mm deep,
groove located near the girth weld.

683
Stress Corrosion Cracks (SCC)
Stress corrosion cracking (SCC) is a phenomenon gaining more and more attention as the rate
of SCC-induced pipeline failures increases worldwide. In some cases failures have occurred,
especially in gas pipelines, after only a few years of operation. SCC is generated under the
influence of internal pressure and a corrosive environment, combined with a particular
microstructural susceptibility found in some pipeline steels. The mechanisms of SCC initiation
and growth are still not well known arid are the subject of ongoing research. SCC can occur in
various forms from small isolated cracks to large crack fields (colonies) containing hundreds of
cracks [3]. SCC are usually found in the base material on the external pipe surface and are, like
fatigue cracks, longitudinally orientated. It is because o"f this orientation that the UltraScan CD
tool is so readily able to detect it.

In September 1995, a 56" gas transmission line with individual section length of 110 km was
inspected with the UttraScan CD (24"/26" tool modified for 56" pipe). In order to facilitate
ultrasonic coupling, the tool was run in a slug of water (the performance of the tool has already
been proven in crude oil and diesel, but other liquids can also be used) [4,5]. The tool performed
very well and excellent data was obtained. A significant number of pipe joints containing SCC
were identified, and the indications were classified into four categories based on the amplitude
and the length of the cracks.

The SCC-colonies sometimes have lengths in excess of one meter and contain hundreds of
cracks, but in some pipe joints isolated single cracks are detected. In this specific pipeline, the
location of colonies is mostly associated with the location of longitudinal weld. The majority of
the colonies lie within a range of 20 em from longitudinal welds, as can be seen from the
distribution graph shown in Fig. 5. As most of the damaged pipe joints are made from half-pipes,
it is assumed that the obseivedcorrelation is related to the manufacture process. Residual
stresses, for example, may play an important role. However, severe SCC-damage is also found
independently from the location of the longitudinal weld (see Fig. 5).

684
 Figure 6 shows a C-scan of a pipe joint containing three SCC-colonies near the longitudinal
weld. In the C-scan image, the ultrasonic data from all sensors is projected on the pipe surface.
From the C-scan image the size and location of the colonies are easily recognized. More
detailed information is obtained from the B-scans showing the crack indications as recorded by
an individual sensor (Fig. 7). In the B-scan image, individual cracks can be resolved, and their
length as well as the distances between the cracks can be estimated. In most SCC colonies, the
length of the majority of the cracks is below 30 mm. The classification of the crack colony
depends in particular on those indications with the largest sizes and the highest amplitudes. In
order to classify SCC-colonies as precisely as possible, statistical analysis of crack indications
within the colony is performed. As a result, a distribution of indications with regard to amplitude
and length is obtained (Fig. 8). Defects can be classified either based on information from
selected sensors or from all the sensors detecting. in a particular crack field.

Figure 8. Distribution of crack indications in a SCC colony with regard to length and
amplitUde.

Verification Excavations and Hydrostatic Testina

So far, 41 excavations have been performed on oil and gas pipelines inspected with the
UltraScan CD and the findings of the inspection method have been verified. There have not
been any false calls to- date. The findings included cracks, crack-like defects like scratches and
grooves, weld defects and in particular SCC damage. Comparison with the results of
excavations showed that the sensitivity of the tool is sufficient to detect even cracks and crack-
like defects with depths below 1 mm.

To date, 32 excavations have been performed on locations where SCC damage was indicated
by the tool,and SCC with depths between 2 mm and 12 mm were found. The crack depths were
in good agreement with those estimated by the UltraScan CD inspection method.

The performance of the tool was further tested by performing hydrostatic tests on three sections
of the inspected gas transmission line. Two ruptures occurred at locations where critical SCC
were detected by the tool.

686
687
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Corrosion Monitoring in Remote or

Hostile Locations
Neil Dickie
Flight Refuelling Limited, U.K.

Abstract

Over recent years several pipeline operators have set in motion programmes to cut the cost of building,
operating and maintaining their infrastructure. With these initiatives, we began to see a change in the
requirements for inspection and health monitoring of facilities and equipment, and' hard pressed
inspection departments are today driven towards automation of their data collection techniques in order
to do more work with less people. This trend is becoming widespread and has' prompted several
operators in the UK to investigate new technology solutions that could provide a step change in their
inspection costs.

This paper will describe one small, but significant element that has progressed through these
investigations and into operational use, under the guidance ofBP engineering in SunbUly and BP Wytch
Farm in Dorset, where our proving trials have been conducted. There are two aspects of this project;

a) the measurement of corrosion in hot, hostile and inaccessible locations, both within
process plants and on remote pipelines;

b) collection of data from widely separated measurement points at a single location for
monitoring and assessment.

I Corrosion Instrumentation: The Ml

691
The instrument to achieve a) has been developed by Rightrax Limited who have developed a
remarkable form of ultrasound transducer that is a flexible film. The unit, known as MI
comprises an array of 14 PVDF (poly VmyliDene Fluoride) transducers that are deposited onto
a copolymer film. Also deposited are electrical tracks that link the transducers to a microchip.
This in turn provides a unique identity for the film and manages, temperature compensation and
self calibration oftbe unit. The unit is extremely simple to interface with, having a single coaxial
connector.

For installation, the unit is provided with a self adhesive layer and can be fitted on complex 3
dimensional curves with no difficulty. BP have trialled the instrument and some interesting
milestones were achieved:

Measurement tolerance O.Olmm

Max operational temperature 100C

This instrument is now permanently installed on de-salter vessels running continuously at 55

and are inside the insulation and cladding on these units.

Data CoUection: The DTS 2000

For data collection, BP Wytch Farm and British Gas at Lepe and Barton Stacey facilities have
supported the development of a communication system which uses the metal structure of the
pipeline as a transmission path for an electromagnetic signal. The technique has to co-exist with
the pipelines Cathodic Protection regime and sources of external electrical noise from power
cables, rQtating machinery, electrified railways and the weather environment.

These constraints are onerous and tend to influence the equipment design in different directions,
for example, to be compatible with the CP regime, the signal amplitude must be very small,
which conflicts with conventional techniques for improving signal to D<~iseratio by simply
turning up the power, and has led designers along the route of digital data processing to extract
very small signals from noise, and for example 200 nano-volt signals are routinely detected in
complex noise environments of several volts amplitude, a situation that appears to be common
at electrified railway crossings.

In addition, energy flows out of the pipeline in areas where its coatings are damaged, and
complex circuits exist, where sacrificial anodes are used to protect the pipe at river or estuary

692
 crosstngS.

By far, the major influence on the range of signal propagation and the data rate that can be
achieved is the quality of the pipe Coatings. Modern PE coatings typically facilitate tenfold
improvements in range and data rate when compared with older coat tar wrappings.

Over many months of theoretical analysis and field trials, these various constraints have been
merged into a single electronics module which employs a common suite of hardware that is set-
ul"for any particular site by editing a configuration software file. This allows best use of the EM
spectrum available on the pipeline, interfacing to different instruments and addressing of the unit.
These parameters can be modified remotely (after installation) via the data link, as the physical
environment around the pipeline changes over its lifetime.

3. Power Supplv

A final point in the data collection is providing a 15 year power supply for the instrument and
the communications module. This is less trivial than it may at first appear; when the favoured
solution for protecting equipment sited in hostile locations is to bury it along with the pipeline.
With no mains power available, solar panels or wind generators prohibited and batteries alone
unable to meet the life cycle, a novel solution was clearly necessary. It came with the realisation
that the pipeline was already a power transmission line, by virtue of the CP currents within it.

By electrically stepping up the CP potential inside the unit a modest long term power supply can
be created and used to re-charge a battery between measurement and data transmission cycles,
although in practise oyer the long term its main duty is.to counter the self discharge rate of the
battery and keep it in good condition.

4. Operational Use

As an overall system, the corrosion monitoring instruments, remote data collection and
communication systems came together for the first time at BP Wytch Farm in October 1995.
This was a technology demonstration under the CRINE programme, and has been followed by
orders for operational systems for several sites on the BP Cusiana oilfield in Colombia. Each
site has an array of 10 MI instruments, giving 140 wall thickness measurement points at each.
Temperature is also measured at 10 locations. The pipeline is deeply buried, and after
installation the DTS 2000 and Ml will be wrapped and coated before the ground level is

693
 reinstated over them .

. .

An interesting point here is that the stations on the pipeline are under remote control by a PC
which is networked into BPts world-wide satellite communications system. This means that an
engineer in any BP office around the world could access the measurement reports, and subject
to authorisation, can control, monitor or adjust the sites as required.

5. The Way Ahead

The DTS 2000 communications system is not a panacea for all problems of instrument
monitoring, but it does offer an economic solution when the locations are remote or hazardous.
Our work on the project has now expanded to provide interfaces for many different instruments
and it may be interesting to summarise the current duties performed by the system at a variety of
locations.

CP monitoring Co-ordinated instant-off measurements continuous monitoring

of CP levels.

Process Monitoring Pressure, temperature and flow instruments

Valve positions

Structural Strain and wall thickness measurement on sub-sea installations.

Hydrogen production monitors.

I hope this paper has proved interesting, and I will be pleased to demonstrate our equipment either in the
UK or on your own pipelines.

694
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

A Non-Destructive Testing Technique for Monitoring

Corrosion in a Buried Pipeline
J.K. Ghosh, S. Muralidhar, S.D. Raut, S. Rajendrant, Gyanendra Singht,
D. Venkatesht, T.K. Bhaumikl and M.S. Ramakumarl
Radiometallurgy Division, 'Division of Remote Handling and Robotics,
Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India

ABSTRACT

A very !;implemethod of monitoring the extent of corrosion a pipe has undergone is by measuring
it's wall-thickness. The technique adopted is entirely dependent on the location and environment in which
the pipe is situated. In this paper we describe a technique of measuring the wall-thickness of a pipe buried
underground, access to which is from a small pit, so that the only surface from which any measurement
can be done is the inside-surface. The pipe, which has an internal diameter of 500mm and a walt'
thickness of 9.75mm, has undergone nodular corrosion on it's inner wall-surface. The method adopted
for this purpose was to use an ultrasonic technique, with the ultrasonic probe mounted on a remote-
controlled vehicle. A special probe-holder for coupling the ultrasonic waves, from the probe to the pipe-
wall has been developed. A description of the remote-controlled vehicle is also given.

INTRODUCTION

A programme has been initiated to evaluate the integrity and safety of the various reactor
components of the Indian nuclear reactor CIRUS, now in operation for over three decades. A part of this
programme will be the in-service inspection of the buried portion of the main coolant pipeline. The aim
of the inspection is to ensure that the pipeline has not undergone wall-thinning of more than 1 percent
due to corrosion. This pipeline of this main coolant loop is made of Carbon-steel ( ASTM Grade-A-53,
Grade A ) material with diameters of piping sections ranging from 12.5mm to 500mm. Seventy percent
of this piping is 500mm ~nd is buried about 4m below the ground.

To carry out this in-service inspection an ultrasonic nondestructive technique and a remote
controlled mobile vehicle which will carry the ultrasonic probe assembly through the inside ofthe pipeline
has been developed. The details of the nondestructive technique and the remote controlled vehicle are
described in this paper.

695
WALL-THICKNESS MEASUREMENT TECHNIQUE

Wall-thickness measurement using ultrasonics is the most suitable method when only one surface
of a pipeline is accessible. Usually the wall-thickness measurement of a corroded pipe is difficult even
when the surface accessible is the outer-one. However, when measurements are to be made from the
inside-surface it becomes more difficult as this is the corroded surface and a method needs to be devised
for carrying the probe for measurement.
The access to the buried portion of the coolant pipeline is through a pit. A section of the pipe in
the pit will be removed so that access to either side of the pipe will be possible. Due to this, all the
coolant water will be drained from the pipe. Therefore, an ultrasonic water-bubbler technique has been
developed so that the ultrasound can be coupled to the wall of the pipe for measurements. In the bubbler
technique a thin stream of water is allowed to continuously flow around the probe and the surface which
is being tested, so that this water forms the coupling medium. In order to do this a special probe holder
was designed (Fig.!). In this design a unique method has been adopted to keep the water near the probe's
surface steady by using a membrane transparent to ultrasonic waves. The probe holder consists of a
housing that surrounds the probe and serves as water-jacket to form a column above the probe. The
opening of the houSing is covered with a thin polymer membrane so that the water from the surface of
the probe to the membrane remains static. The membrane is transparent to ultrasound and is only weakly
reflecting even at higher frequencies. A water feeder is provided.to allow a small flow of water into the
space between the membrane aIJ.dthe pipe's inner wall-surface, when the probe is attached to the pipe-
wall. The probe-holder is provided with a compliance to align it normal to the pipes surface. Since the
inner-surfaCe of the pipe is corroded and the probe cannot be moved smoothly continuously over it, an
attach-retract arrangement has been made so that measurements can be made at different points of the
pipe.

THE MOBILE VEmCLE

The mobile vehicle, shown in Fig 2. in a representative pipe, has been developed to carry the
ultrasonic probe to measure the wall-thickness of the pipe and to observe any wall-thinning due to
corrosion. The vehicle can be lowered through the small pit which provides the access to the pipeline.
After removing the segment of the pipeline the vehicle will be inserted into the pipeline. A length of
about ten metres on either side of this segment will be initially inspected. The mobile vehicle consists
mainly of three parts. These are the transporter, the control unit, and the data collection unit.

The Transporter

The transporter is a four wheeled vehicle driven by pneumatic motors, used as actuators, as these
are safe, compact and have a higher power to weight ratio for operation. It houses the probe positioning
head on which the probe holder is mounted. The probe holder can be attached to Of retracted from the
pipe surface. Sensors are mounted to know the linear position and orientation of.the probe in the pipeline.
Tubes are provided for carrying a pneumatic line, a water line and electrical cables to a location above
on the ground for remote operation.

The Control Unit

The control unit provides for coarse and fine movement control for linear travel along the length
of the pipe and for orienting the probe to any angle for circumferential inspection at a location. A simple
proximity sensor is used for reading the distance travelled along the length of the pipe while

696
pQtentiometric sensors are used for reading the orientation of the probe.

The Data Collection Unit

The data acquisition is done by transmitting a normal beam ultrasonic wave and receiving the
reflected backwall echoes from the outer surface. This is done by using a lOMHz normal beam probe.
The echoes are observed on a commercially available ultrasonic flaw detector (Krautkramer USIP-ll) and
are digitised and stored using an indigenously developed ultrasonic digitiser system. A provision to
automatically read out the pipe wall-thickness indicating the condition of the pipe wall at the location is
being made in the ultrasonic system.

RESULTS AND DISCUSSION

Reference standards have been made from a section of the actual pipe removed for studies. The
standard has been made by drilling flat bottom holes to varying depths ranging from O.lmm to O.5mm
on the outer surface to be inspected. A number of trials have been successfully taken on a representative
section of the pipeline and the ultrasonic technique was capable of detecting a wall-thickness variation of
10%. Fig 3 shows the signals obtained from a normallocatio~ and one from a location of wall thinning.
One of the problems faced during the trials has been the loss of the front surface echo sometimes due to
the irregular surface of the pipe. This loss of front surface echo was also observed to be due to the
collection of debris in the water column between the membrane and the surface of the pipe. This
collection induces a large scatter of the ultrasound and hence periodically the probe holder had to be
brought to the six o'clock position and the debris cleared. To reduce this uncertainty, a visual aid is being
added to enable remote visual inspection of the pipe's inner surface before measuring the wall-thickness.

CONCLUSIONS

Monitoring of a buried pipeline by the simple method of wall~thickness measurement is really

quite difficult .An ultrasonic inspection technique for doing this measurement on the buried portion of
the main coolant pipeiine of the reactor CIRUS has been developed. The pipeline inspection vehicle is
presently capable of moving only in the straight section of the pipe. Future development involves
improving the mobile vehicle to negotiate steps encountered at flanges joining sections of the pipe and
turn at bends.

ACKNOWLEDGEMENTS

The authors wish to acknowledge and expres~ their thanks to all their colleagues who have helped
during this work. \In p!,rticular they express their thanks to Shri K.N. Mahule for the discussions and
ideas for the development of the probe-holder. Thanks are also due to Shri D.S.C. Purushotham,
Associa~e Director Nuclear fuels group ~d Head, Radiometallurgy Division for his keen interest and
support in this work ..

697
699
Proc . .In!. Conf. on Corrosion CONCORN '97
DecemJ;ler 3-6, Mumbai, India

Sensitisation of AISI 317 Stainless Steel Pipeline Carrying'

Phosphoric Acid Due to Fire Damage:
In-Situ Metallographic Study
R.J. Chaudhariand v. Balasubramanian
Offshore Testing & Inspection Services (I) Pvt. Ltd.
W-147, MIDC Pawane, Thane Belapur Road,
Navi Mumbai 400 703, India

ABSTRACT

A 300 metre - long section of a pipeline of AISI 317 stainless

steel carrying phosphoric acid was damaged by fire that
originated elsewhere. It was felt that sensitisation of the fire -
damaged section of the pipeline might have occurred,
rendering it unfit for service. In - situ metallographic
examination. of the damaged section as well as the
undamaged area, and comparison of the two sets of results,
confirmed that sensitisation had indeed occurred in the
damaged area. It was recommended that the damaged
section of the pipeline be removed ana be replaced by a new
section of the same stainlesssteel. The in - situ metallographic
study in this case is an illustration of the use of this technique in
the field to take decisions, and the multidisciplinary nature of
the study which' was supported by ultrasonic thickness
measurement and ultrasonic flaw detection.

USEFULNESS OF IN - SITU METALLOGRAPHY

In -. situ Metallography is gaining increasing importance as a

.nondestructiv'e method of studying the microstructure of components and
installations that are suspected to have undergone corrosion and other

700
 forms of damage. The authors of this paper have .undertaken several
investigations of corrosion damage, fatigue damage and structural
changes such as sensitisation in field conditions using in' - situ
metallography. This method often enables investigators to reach
decisions on the spot regarding the advisability of replacing a
component or an installation (wholly or in part) without having to cut any
piece of the component / installation for study in the laboratory by
conventional metallographic techniques. The present paper describes an
event that led to fire damage in a stainless steel pipeline carrying
phosphoric acid. In - situ metallography was used to establish as to
whether sensitisation had occurred in the pipeline as a consequence of
the fire and whether, therefore, the affected section of the pipeline
. should be replaced.

CONFIGURATION OF PIPELINE AND ADJACENT INSTALLATIONS RELEVANT TO

THE INVESTIGATION

A pipeline made of AISI31.7(UNSS317oo)grade stainlesssteel.was used to

carry phosphoric acid from an unloading jetty in a port to a storage tank
about two and quarter Kilometres inland. The pipeline was constructed
from pipe sections that had been supplied in the solution treated
condition. The chemical composition of AISI317 stainlesssteel as supplied,
and other relevant data pertaining to the pipeline construction and
operation are shown in table 1.
A pian view of a part of the pipeline and a road rvnning parallel to it is
shown in fig. 1. The pipeline rested on concrete supports spaced at
regular intervals and was secured to the supports by ~teel Clamps. Some
of these support locations are indicated in fig. 1, numbered 1, 6, .... 47. The
length of the stretch of the pipeline located between supports 1 and 47
was approximately 300 metres, and this pipeline stretch was damaged by
the fire. Just beyond the support 1, the pipe took a bend, crossed under
the road, reemerged above the surface, took a bend again. and
extended in the original direction up to the acid storage tank. Two
conveyor belts, located close to and parallel to each other inside a
common housing, ran above the pipeline. One of the conveyor belts
carried sulphur and the other carried urea. The conveyor belts at thejefty
end were very close to the pipeline and they proceeded at an upward
angle above the pipeline till pipeline support 1. Thereafter the conveyor
belts continued in a straight line to the sulphur and urea storage godowns,
while the pipeline direction changed as described earlier.

701
Figure 2 shows the beginning of the pipeline near the jetty end. The
stainlesssteel pipeline discussed in the present paper is the third pipeline
away from the viewer. The conveyor housing isseen above the pipeline.

NATURE OF EVENTS THAT LED TO THE PRESENT STUDY

A fire broke out on the conveyor belts in December, 1996. The fire
started at the warehouse end of the sulphur conveyor arid spread along
its length in the direction of the jetty. The two belts, which were made of
thick rubber reinforced with thin steel mesh and which ran on mild steel
rollers covered with rubber, were completely burnt up to pipeline support
47, by the time the fire was put out.
Visual examination of the fire - damaged stretch of the pipeline indicated
the following:
aj The dense tape covering the external surface of the pipeline had
burnt away over most of the length of the fire - damaged stretch of the
pipeline. The pipe surface had turned red in most places and black
elsewhere.
bj Residues of burnt material lay in dense clusters along the damaged
stretch, on the pipeline itself and adjacent to it.
c) At many places the pipeline had bent. had come out of the concrete
supports and was lying on the ground ..
d) Rollersfrom the conveyors had fallen on the pipeline at several places
and had dented the surface.
Figure 3 shows a damaged section of the acid pipeline (on the right) that
hqs come out of its support and is lying on the ground.

PRELIMINARY INVESTIGATION : ULTRASONIC MEASUREMENT AND IN - SITU

MET ALLOGRAPHY

The purpose of initial ultrasonic measurements was to ascertain as to

whether ph.osphoric acid vapour formed during the fire, from the small
amount of the acid that was present in the pipeline, had caused corrosion
damage inside the pipeline such as significant reduction in wall thickness
or formation of cracks.
Wall thickness measurement using a D- Meter was carried out over the
most damaged stretch of the pipeline between support nos. 21 and 42.
Wall thickness in this stretch of the pipeline ranged between 4.2 mm and
4.5 mm, which was considered acceptable.

703
Crack detection measurement at the three most badly bent regions,
which lay between support nos. 31 and 40, was carried out with a
Microscan EX-10detector. Th~re were no detectable flaws.
Preliminary in - situ metallographic examination was carried out at certain
badly damaged locations, which were in the region of support nos. 28~31,
36 and 42. It was felt that if in - situ examination did not reveal sensitisation
at these locations, no sensitisation would have occurred at other, less
damaged regions of the pipeline.
FigLJre4 shows polishing in progress at one of the locations where in - situ
metallographic examination was carried out.
The results of preliminary in - situ metallographic examination indicated
that sensitisation had occurred at all the four locations examined.

DETAILED IN - SITU MHALLOGRAPHIC INVESTIGATION

The occurrence of sensitisation in the locations examined during the initial

investigation indicated the need to examine more areas. It was jointly
decided by the clients, the insurance company and the investigators that
selected locations should be examined that covered the entire damaged
stretch of the pipeline from support no; 1 to support no. 47, the latter
location being the least damaged. This part of the investigation was
carried ~ut under the supervision of a third party inspection agency. Table
2 indicates the locations examined in the detailed investigation and the
corresponding figure numbers in the present paper. The table also
includes two undamaged locations indicated by the letters "i" and "h",
which were towards the warehouse and jetty respectively. These two
were examined for comparison with the damaged locations.

704
 TABLE 2

RESULTS OF IN - SITU EXAMINATION OF FIVE DAMAGED AND Two

UNDAMAGED LOCATIONS

A comparison of the microphotographs obtained from the in - situ

metallographic replicas at damaged locations [Figs. 5 - 9] with
microphotographs of undamaged locations [Figs.10-11] clearly brings out
the differences between the two types of locations. The undamaged
regions show austenitic grains with annealing twins and no sensitisation.
The damaged regions' show sensitisation, namely precipitation of
chromium carbides along' the grain boundaries. The absence of
annealing twins in the damaged locations is a further indication that the
initial pipeline material, which was in the solution treated condition and
contained annealing twins, was reheated and cooled through the
sensitisation-temperature range. The annealing twins disappeared during
thissecond annealing process.

Conclusions

Ultrasonic wall thickness measurement and flaw detection measurement

over the most badly damaged stretches of the pipeline indicated wall

705
thickness values that were within acceptable limitsand revealed no flaws
within the detectable limits. On the basis of these measurements alone a
case could have been made out for retaining those stretches of the
pipeline in the fire affected zone that were still straight and for discarding
only those stretches of the pipeline that had been bent out of shape. In -
situ metallographic examination, however, showed that sensitisation had
occurred over the entire length of the pipeline that was in the fire-
affected zone, including the least damaged location near support noA7.
Phosphoric acid is known to cause intergranular corrosion in sensitised
austenitic stainless steel. It was therefore decided to replace the entire
stretch of the pipeline that had been affected by the fire, which was
approximately 300 metres long and which lay between support nos. 1
and 47, with new sections of pipe of the same steel which were available
with the clients in the as-received condition.

ACKNOWLEDGMENTS

The authors thank Mr. T. N. Murali of Mis Offshore Testing and Inspection
Services (India) Private Limited for hisactive participation in the work. They
also acknowledge with thanks the cooperation rendered and valuable
suggestions given by the clients, the insurance company and the
inspection agency. The authors are grateful to the management of
Mis Offshore Testingand Inspection Services (India) Private Limited for their
support in conducting the investigation and for permission to present this
paper.

706
707
 FIG. 2: Beginning of pipeline
near jetty end. Pipeline
discussed in present paper is
the third pipeline away from
the viewer. Conveyor housing
isab~)Vepipeline.

FIG. 3: Damaged section of

acid pipeline (on the right)
has come out of its support
and islying on the ground.

FIG.4: In - situ metallographic

investigation. Polishing in
progress.

708
 FIG. 5: Fire-Damaged region
near support no.l
(see Fig.l). Sensitisation
has occurred.

FIG. 6: Fire-Damaged region

near support nO.6.
Sensitisation has
occurred.

FIG. 7: Fire-Damaged region

near support no.13.
Sensitisation has
occurred.

709
 FIG. 8: Fire-Damaged region
near support no.21.
Sensitisation has
occurred.

FIG. 9: Fire-Damaged region

near support no.47.
Sensitisation has
occurred.

FIG. 10: Location "I" in Fig.l.

Undamaged region.
Material in as -
received condition.
No sensitisation.
Annealing twins are
present.

710
 FIG. 11: Location "h" in Fig.1.
Undamaged region.
Material in as-
received condition.
No sensitisation.
Annealing twins
are present.

711
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Corrosion Behaviour of Metals in Sodium Chloride

Medium by Single Drop and Thin Layer Techniques
A. Subramanian" P. Rajendran2, M. Natesan3,
K. Balakrishnanl and T. Vasudevanl
IDept. of Industrial Chemistry, Alagappa University, Karaikudi-630 om, Tamil Nadu, India
2Dept. of Applied Chemistry, Govt. College of Technology, Coimbatore, Tamil Nadu, India
3Central Electrochemical Research Institute, Karaikudi, Tamil Nadu, India

ABSTRACT

The corrosion behaviour of mild steel, zinc and copper has been studied potentiodynamically by
single drop and thin electrolyte layer techniques using three electrode cell and atmospheric corrosion monitor
(ACM) respectively in various concentrations of sodium chloride medium. The values of corrosion current
obtained from both the methods are presented. From the results it is observed t~,at the corrosion rates are
nearly the same for all the metals in both the methods. However, the rates differ in a few cases by about 20%.
Likewise, the other kinetic parameters such as b. & beare also comparable. The single drop method involves
a well defined area, easy operations and the results are highly reproducible. Hence it is suggested that for
characterizing the corrosion behaviour of metals, the single drop technique may be preferred.

INTRODUCTION

Electrochemical techniques are widely used to obtain the corrosion rate of metals exposed to the bulk
electrolyte. Electrolytes involved in atmospheric corrosion vary"in thickness from several mono layers of
water, to droplets of water. Several experimental approaches have been suggested [1,2]. One of the most
useful investigating methods is the use of single droplet method in atmospheric corrosion studies. Another
method that has been suggested is the thin layer technique [3] which uses a thin sheet of the electrolyte.

The present study apart from investigating the corrosion behaviour of some metals using these
techniques, will also bring out the unique features of these methods. In this study the atmospheric corrosion
behaviour of mild steel; zinc and copper are to be investigated with a single drop of different concentrations
of sodium chloride electrolyte by potentiodynarrlic polarization method. Corrosion rates and other kinetic
parameters of the corrosion process are reported and discussed.

EXPERIMENTAL METHODS

Single Drop Technique

Polarization measurements were carried out in a three electrode cell in the presence of single drop of
an electrolyte. An experimental cell consists of the sample (working electrode) masked with araldite to
expose 1 Cm', a platinum mesh (counter electrode) and a saturated calomel electrode (reference electrode)
with a filter paper disc separating each electrode. The working electrode was placed on a small jack and the
working area covered with a tightly fitted paper and a flat platinum mesh was fi~ed into the center. The

712
sample was then raised and kept in a place against the fitting. The second filter paper disc was then dropped
over the working area. The droplet of the electrolyte was introduced and the reference electrode was positioned
over the sample using the fitting as a holder. The experimental set-up is schematically shown in Fig.1. A
typical droplet size was 50 J.II.Due to short distance between the electrodes. the ohmic resistance in the cell
was relatively small even with electrolytes. The steady state polarization hat:!been carried out from -200 mV
to +200 mV at the open circuit potential. Tafel slopes (ba be)' corrosion potential (Ecorr) and corrosion current
(ICOIT) were obtained from the E v~ logi curve.

Thin Layer Technique

1ml of sodium chloride solution was applied onto a well polished atmospheric corrosion monitor
(ACM) to have a film of moisture on the surface and it is schematically shown in Fig.2. Polarization
measurements were carried out potentiodynamically at a sweep rate of 100 mV/min using potentiodyne -It
(Electrochemical Corrosion System). The potential of the electrode was measured with respect to a saturated.
calomel electrode at an ambient temperature ..

713
RESULTS AND DISCUSSION

Corrosion behaviour of Metals in Sodium chloride under single drop method

Table 1 gives the values of corrosion kinetic parameters studies, Tafel slopes (ba be) corrosion
current (ICOIT) and corrosion potential obtained from the potentiodynamic polarization of mild steel, zinc and
copper in contact with different concentrations of sodium chloride solutions.

Table - 1

This table clearly reveals that in the case of mild steel the corrosion potential is shifted towards
positive values Le. -520 to -498 mV as the concentration increases from 1% to 5%. This shift in potential
towards more positive values may be due to the depolarization chloride ions. Corrosion rate reached maximum
(394 jJAlcm2) and then decreases (328 jJAlcm2) as the concentration of sodium chloride solution is increased
from 3 to 5%. This is due to the lower oxygen sollJbility in 5% sodium ctiloride solution.

In the case of zinc the corrosion current increases from 9 to 82 jJAlCm2 as the concentration of
sodium chloride increases. The corrosion potential is shifted towards more positive values Le. from -1110 to
-1040 mV as the concentration is increased, due to the depolarization by chloride ions. The anodic Tafel
slope lies in the range of 52 to 58 mV and the cathodic Tafel slope lies in the range of 112 to 122 mY. The
increase in corrosion rate'with increase in the concentration of the sodium chloride may be attributed to the
formation of highly soluble zincate in the solution.

But in the case of copper it is observed that as the concentration of sodium chloride solution increases.
the corrosion current increases from 2 to 6 jJAlcm2. The corrosion potential as in the case of mild steel and
zinc is shifted towards more positive values from -230 mV to -190 mV except for 5% sodium chloride solution.
The anodic and cathodic Tafel slopes are found to be in the range of 48 to 56 mVand 112 to 128 mV
respectively. In the presence of the chloride ion the reaction proceeds through the formation of CuCI2 which
later gets hydrolyzed to Cup. This products forms a compact oxide film on the copper surface [4].

714
Corrosion Behaviour of Metals in Sodium chloride under Thin Layer Method

Table 2-4 give values of corrosion kinetic parameters such as Tafel slope (ba & be)' corrosion potential
(Ecorr) and corrosion current (Icorr) obtained by potentiodynamic polarization method for mild steel, zinc and
copper in contact with a thin layer of sodium chloride solution of different concentration and at different
exposure times. These tables also give the values of corrosion current (Icorr) obtained by liner polarization
method and by making use of Stern" Geary equation.

It can be seen from the Ta.ble" 2, Corrosion rate of mild steel increases with increase in the concentration
of sodium chloride solution and al/>owith exposure time. But in this case Ecorr shifts towards more negative
values, unlike that observed in the case of single drop techniques.

Table - 2

Corrosion kinetic parameters for mild steel in different Concentrations of NaCI solution
and at diff~rent exposure times using thin layer technique

It can be observed from table - 3 that the corrosion rate for zinc increases with increase in sodium
chloride concentration and also with exposure period. Ecorr values become more negative with increase in the
concentration of sodium chloride solution as obselEld in the case of mild steel.

715
716
 Ecorrvalues also shifts towards more negative values with increase in the concentration of sodium
chloride solution. The comparison of values of lcorrobtained by single drop method and thin layer method is
shown in Table - 5 clearly shows that the values of Icorr
. obtained by both methods are almost
, same. The -ve
shift of Ecorruniformly for all the metals in this technique can be attributed to the predominant oxygen -
reduction reaction rather than chloride depolarization reaction in the former case.

CONCLUSIONS

A measurement of the kinetic parameters for metals such as mild steel, zinc and copper by single
drop and thin layer techniques bring out the following main conclusions.

1. The corrosion rate obtained by the single drop method increases with increase in the concentration of
sodium chloride solution. Ecorr shifts towards more positive value in the presence of increasing
concentration of sodium chloride solution.

2. In thin layer method also lcorrincreases with increase in the concentration of sodium chloride
solution, but the Ecorrshifts towards more negative value unlike that observed in the single drop
technique.

3. The values of lcorrvalues obtained by the single drop method and thin layer method for different
metals in sodium chloride solution are almost same.

4. Single drop technicfue is preferable to thin layer technique because of the easy way of operation and
the greater reproducibility.

References

1. Stratmann, M; The Investigation of the Corrosion Properties of Metals covered with absorbed
electrolyte Layers - A New Experimental Technique, Corr, ScL VoI.27,.No.8, 1987, PP:869-872.

2. Yee, S., Stratmann M. and Oriani R.A., Application of a Kelvin micro probe to the corrQsion of metals
in Humid atmospheres - J. Electrochem. Soc" Vo1.138. No.1, January 1991, PP.55-60.

3. Brusic, V, Frankel, G.S. Perterson, T.A., and Huang S.M. Galvani Corrosion of Zinc/Steel under thin
layer electrolytes - Proc. 12th fnternational Corrosion Congress, Vo1.2, 1993, PP.687-699.
4. Mattson, E. Holin P. Copper and Alloys (Corrosion) ASTM, Vol. 435, 1968, PP.187-195.

717
Proc. Int. ConI. on Corrosion CONCORN '97
December 3-6; Mumbai, India

Cost Effective Multi-Layer Coating Systems

J.D. Kellner and B.B. Patil
Kendall Polyken Laboratory,
17 Hartwell Avenue, Lexington, MA 02173

Abstract
Two cost effective polyethylene based coating systems that can be applied using conventional
coating equipment and have excellent performance in a heavy duty maintainance environment are
presented in this paper. The first of the two sysytems is a hot applied plant coating which consists ofa
thermally activated primer layer and fused polyolefin outcrlayer. The heat of application. initiates a
reaction in the inrerfaciallayer resulting in a completely fused coating system. The second coating
system utilizes the outstanding performance of spray applied liquid epoxy primer and a
multifunctional polyolefin laminate. The lami'nate is applied in a solid state to .the preheated, epoxy
primed pipe and fused immediately by the residual heat in the pipe resulting in a monolithic coating
with strong chemical and mechanical bonds that maximize the performance properties of the coating
system.
The plant coating technique and equipment is described in petail for both the coating systems.
Details of the coating constructions, and results of extensive laboratory testing are presented.

Kevwords: pipeline, coating, 3-layer, 2-layer, liquid epoxy, polyethylene

Introduction

External corrosion of the pipeline is generally provided by the combination of two systems. A
"passive" protection is achieved by a tough, continuous, impervious external coating which protects
the pipe during storage, transportation and rough handling on he right of way. An "active" cathodic
protection supplements the external coating to minimize the corrosionin the event of holiday in the
coating. The earliest external protection coatings were based on coal tar enamels. The polynuclear
aromatics present in the coal tar are'resistant to alkali attack ana hence provided excellent corrosion
protection to the pipe. Because of the health related concerns and poor thermal and mechanical
properties coal tar based coatings did not see explosive growth and paved way for cold applied
polyethylene tapes.

718
 Cold applied tape coatings have been used to protect pipelines since the 1960s. When
properly specified for the pipe and soil conditions and properly applied, these coating systems have
worked well. The increased use of plant applied coatings has provided the opportunity to improve the
performance ofthe "tape" coating systems by the introduction of novel materials and processes. This
has been accomplished by the use of new heat activated primer and pressure sensitive adhesives and
through the use of epoxy primers and thermoplastic adhesives. These new materials and heat
activated application processes have revolutionized the old "tape" teGh.nology into modem more
effective coating systems. The two coatings we will discuss here are the SynergyTMand Vanguard
coating systems. The SynergyTMsystem uses a conventional rubber based primer and pressure
sensitive anti-corrosion innerwrap. The Vanguar'd system uses a liquid epoxy primer which can be
applied with conventional plural-component sprayers. Both systems use a specially engineered
outerwrap that is a multi-layered sheet designed to fuse at the application temperature. With a
reasonable source of pipe-heating, the spray unit already mentioned, and roll let-off stands, virtually
any fixed or portable pipe-coating plant can apply these new coating systems.
Polyethylene coatings using an epoxy primer and an adhesive tie coat have been used
extensively throughout the world. These coatings, known as "3-layer" or "2-layer" coatings. generally
have a fusion bonded epoxy primer and two layers of a polyethylene based material extruded over it.
The two layers consist of a thin layer of modified polyethylene for adhesion to the epoxy primer and a
thicker working layer of polyethylene on the outside.
A drawback of the 3-layer coatings is that they require application in a fusion-bonded coating
plant to which has been added expensive plastic extrusion equipment. The temperatures required for
epoxy fusion are high and the plastic extrusion rates are low, both of which limit the coating rates that
can be achieved". The new coatings shown schematically in Figure 1 overcome these limitations
without sacrificing the excellent performance of the 3-layer systems. In each case, the polyolefin
laminate composite is pre-formed in an extremely efficient and productive plastics converting factory
and delivered to the coating plant in rolls that are easily handled and stored. It is supplied in rolls of
the appropriate width and thickness for the pipe size and customer requirements. The laminate
outerlayer is spirally applied to the primed surface in half-lap fashion so that the final thickness is
twice that of the applied sheet. The sheets may be supplied in thikf!esses from 20 to 30 mils (.5 to
.75 mm). More than one laminate outerlayer is applied when the customer requires a thickness that
would not be met by a double thickness of a sheet flexible enough to be applied in the solid state.

Construction
SynergyTU
Figure Ia shows the various layers in the SynergyTMcoating. The primer layer is a heat
activated thermoplastic polymer dissolved in an organic solvent system that is applied at 75-100 11M
wet thickness. The function of the primer layer is to provide a thin continuous layer that bonds
directly to the pipe surface and ensures instantaneous bonding with the intermediate adhesive layer.
This results in high peel adhesion and good cathodic disbondment resistance in the coating system.
The primer also protects the pipeline steel against stress corrosion cracking with a proprietary SCC
inhibitor added to the primer formulation. This inhibitor has been shown to be effective in pipeline
primers for SCC prevention2. After the primer, a second layer is applied that is actually a three layer
composite of 0.64 mm. The first layer consists ofa pressure sensitive elastomeric adhesive laminated
to the second layer, a polyethylene backing. Finally, the outside or third layer is a.thermoplastic
polyolefin. The three layer laminate is prepared into roll form for application. The elastomeric
adhesive layer is designed to chemically bond during application with components in the primer layer

719
 to provide bonding between the pipe surface and the polyethylene top layer. The last wrap to be
applied is also a three layer laminate of 0.64 mm total thickness. It has a central high density
polyethylene core which is the source of the mechanical strength of this layer. One either side of this
. central core is a thin layer of thermoplastic adhesive. Each of the plastic layers are designed to fuse
together during the application process. The pressure sensitive adhesive supplies the adhesion to the
pipe.and the thermoplastic adhesives melt and fuse, completely sealing the overlaps and sealing the
two laminates together.

VanguardTM
Figure Ib shows the construction of the Vanguard coating. The first layer next to the pipe
is 75-100 J.lMofa two-part liquid epoxy spray-applied as a primer. The outer mechanical layer
consists of three parts: a tough high molecular weight, high density polyethylene which supplies the
bulk of the mechanical and barrier properties; a permanently bonded layer of modified polyolefin
designed to adhesively react with the epoxy primer; and a third permanently bonded polyolefin layer
designed to effect the complete fusion of the laminate into a monolithic coatin~ at temperatures low
enough to be economical and without affecting the integrity of the high density barrier layer. The next
section describes the application process.
Application

The SynergyTMand Vanguard multi-layer coating systems are specifically designed for plant
application using a minimum of equipment and labor in a continuous operation. The basic application
process consists of the following steps:
I. Cleaning of the pipe to remove surface contaminants.
2. Preheating the pipe to the appropriate preheat temperature. The recommended range for Vanguard
is 300-325F (1 50-163C) for 50 mils (1.27 mm) final thickness of coating. For a 100 mils (2.54 mm)
thick coating the recommended pipe temperature is 325-350F (163-177C). The recommended
range for Synergy is 200-220F (93-104C).
3. Shot blasting the pipe to an anchor pattern of 1.5-3 mils (37 - 75 microns) and to a SSPC-SP-6 or
NACE TM-01-70 #3 or Swedish Standard SA 2/2.5 TM-01-75 #3.
4. Application of the primer. Liquid epoxy primer for Vanguard at a thickness 00-4 mils (75-100
microns). Primer for Synergy is applied either by airless spray units or by a drip feed technique. In
drip feed, the primer is spread over the pipe surface with the aid of rubber scrapers or sock. The
primer is applied to a thickness of about 100 ,.IM wet.
5. After inspection of the pipe for surface irregularities, application of the polyethylene sheet
laminates. The layers are spirally wrapped on the pipe under tension (width decreased by 1-2%) using
a mechanical coating apparatus equipped with a constant tension breaking system. The tension
applied during application of the SynergyTManti-corrosion layer, produces a gasket effect and seals
the coating system at the spiral overlap3
6. Water quenching of the coated pipe over a distance of6 meters to avoid damage to the outer
coating surface during subsequent pipe handling ..
7. To insure high quality and precise coating application the coating rolls and primer are
manufactured at a state-of-the-art facility using modem techniques of production to achieve total
quality and zero defects. During the coating application process, key parameters are monitored
including pipe preheat temperature, temperature of the surface after priming, coating temperature and

720
line speeds. Only coated pipe that has a record of the correct parameters during application is
released. These application steps are schematically summarized in Figure 2.
To insure high quality and precise adherence to the coating application specification, the
following quality control measures have been instituted at each certified application plant.
1. Coating rolls and primer are manufactured at a modern ISO certified facility using state-of-
the-art computer technology to monitor each phase of production. Raw materials and finished
product are tested under strict quality' assurance guidelines to ensure a consistent and uniform coating
system.
2. During application, key parameters are monitored. These include pre-heat pipe
temperature, wrapping tension, oven temperature, coating temperature and line speeds. Each
application parameter value is recorded continuously with alarm limits for a permanent record. Only
properly applied coated pipe is released to the warehouse or customer.
The combination of the manufacturing quality standards, parametric release and non-
destructive testing guarantees the quality of the pipe coating and also the quality of the plant
applicator.
Presently, a small but growing group of coating plants have successfully applied these
multi-layer systems on a commercial basis. The~e plants have applied the coating system for several
gas and oil companies on projects requiring pipe ranging from 10 through 60 cms in diameter.

Patch and Repair and Girth Welds

.
Although rare, damage could occur to the coating during handling and transportation. The
toughness and thickness of the polyolefin layer in the new coatings should make these areas small and
infrequent. In case of Synergy TM the damaged areas can be repaired in the field using cold applied
tape system such as Polyken 934 anti-corrosionjointwrap used with Polyken 954 mechanical
protection layer. This cold applied tape system can also be used for the protection of the girth weld
joints. The other recommended systems for the girth weld protection are a DIN approved double
face coating system such as Polyken 943 or Polyken 942 anti-corrosion layer with a mechanical
protection layer (polyken 954 or 955) and a heat shrinkabie polyolefin based system that is supplied
as a wrap around sleeve with a heat fusible closure system to seal the sleeve overlap area. The sleeve
is overlapped onto the plant applied coating system and is fused with a torch. The fused joint coating
is thus permanently bonded to the plant coating system.
For Vanguard TM coating system the repair kit consists of a roll of polyolefin laminate and epoxy
primer provided in a twin pack. The damaged area is cleaned and coated with epoxy primer. The
adhesive side of the laminate is heated with a torch at low flame. As the adhesive layer becomes tacky
it is adhered to the pipe surface over the damaged area and compressed w.ith a hand held pressure
roller. The covered area is carefully heated with a torch and compressed with a roller to ensure that
the patch is completely fused.
A similar procedure may be followed for the coating' of the girth welds in the field. The primer
supplied in a disposable twin package pouch is sqeezed onto cleaned pipe surface and spread with a
brush. A length of polyolefin laminate is then applied in cigarette wrap fashion by wrapping around
tightly and held in place with a closure tape. The coating is then fused in place with a flame torch:
The overlap of the polyolefin laminate is fused to the upper surface of the line pipe coating. In this
way, the girth weld coating has the same anti-corrosioll quality as the coating used on the rest of the
pIpe.

721
 Laboratory Evaluation
Synergy TU
The performance characteristics of these fused multi-layer coating systems have been
measured in the laboratory and during field application. The characteristics that are critical for long
term in-ground corrosion protection are adhesion to the pipe, resistance to cathodic disbondment,
resistance to soil stress, low water absorption, and tough mechanical integrity enabling the coating
system to withstand the rigors of handling and transportation.
Standard ASTM test methods were used to evaluate the performance characteristics of the
SynergyTMfused multi-layer coating system. The test results listed in Table 1 are for production
coated pipe from certified applicators. The data show the coating system has high peel strength, low
water absorption, high resistance to cathodic disbondment, and tough mechanical properties.

Table 1 - 1.27mm and 2.54mm Systems

VanguardTU
Extensive testing of the Vanguard coating was performed in the laboratory using a battery
of standard pipeline coating evaluation tests in use in the USA 4 and abroad56. All samples used were
obtained from commercial production runs at qualified applicators' facilities. At least one of these

722
 facilities was a portable plant which was easily and quickly modified to apply the new system. The test
results.are averages of at least three samples and are typical of the performance of2 or 3-layer
systems.in these tests. Tests of shear strength, thermal and hydrolytic stability were modified tests
.which are described in previous publications2,7. The shear test is similar to the Aramco "Alyeska"
shear testS and a test protocol from Russia9. The results are given below in Table 2 for the 50 mil
(1.27 nun) coating consisting of two layers of25 mil (0.64 mm) outerwrap.

Table 2 -25 mil (1.27 mm) System .

723
 Peel forces are high even at elevated temperatures and after thermal aging at lOOCfor2,OOO
hours. Peel forces after aging in 95C water for 30.0. hours are higher than would be the case for bare
epoxy not coated with polyethylene. More important than peel force, from a coating functionality
point of view is the shear strength of the coating. The shear strength will determine the tendency ofa
coating to slide across the pipe surface under the action of soil moving across the pipe. This sliding of
thl;!pipe coating could result in wrinkling and coating failure 7. The shear strength is measured by a
technique that determines the rate of movement under the influence of a normal force and a shear
force. The rate of movement is so low, that no shear movement at all could be detected even after 48
hours of testing. These extremely low rates of shear movement assure that no soil stress effects will
be seen by the coating after burial even at elevated temperatures.
Impact strength is chiefly a function of coating thickness. And is given in units of average
energy that causes a detectable holiday at about 12kV. For a 1.27 mm system, the impact strength is
76 in-lb. Or 8.6 J.This is more than sufficient to resist damage from the normal mechanical stresses of
handling and transportation. The penetration resistance is high because of the absence of an
elastomeric adhesive which could cold flow under the influence of a steady pressure. This allows the
coating to withstand the localized pressure of contact with rocks after burial. T\1e tensile strength of
the high molecular weight polyethylene is higher than conventional polyethylenes. The coated pipe
can be bent to greater than the API specification for steel pipe without producing a holiday or
damaging the coating in any way. The water vapor transmission rate is very low as is typical of this
class of polyethylenes.
The dielectric strength and resistivity values are typical of polyethylene. The dielectric strength
is a function of the coating thickness and is high per unit coating thickness for this coating due to the
fact that an elastomeric adhesive, with a lower dielectric strength is absent. The cathodic disbonding
resistance is excellent dueto the effect of the epoxy primer and the polyethylene acting together. The
epoxy has excellent interface adhesion with steel, and the polyethylene is an excellent barrier to water
penetration to the epoxy layer.
Results for the 100 mil (2.54 mm) coating system consisting of 4 layers of outerwrap are given in
Table 3.

724
 Test protocols for the 100 mil (2.54 mm) coating system were taken from the DIN standard
(DIN 30 670) in common use in Europe and other parts of the world for 2- and 3- layer coatings.
This was done because it is common in European countries to use a larger coating thickness for the
same size pipe than is commonly used in the USA. Differences in the angle of peel and the rate of peel
.resulted in different values for the peel forces, although the same excellent aging results were
obtained. Since the shear strength depends on the shear adhesion at the steeVcoating interface, these
values were independent of sample coating thickness.

Conclusions

1. New hot applied plant coatings are now available with similar adhesive, mechanical and electrical
properties as the commonly used 3-layer ep~xy/polyethylene coating systems ..
2. The new coating systems are supplied from the manufacturer in roll form with the proper thickness
and width for the pipe size to be coated. The application process is simple, requiring only a primer
spray unit, a roll goods let-off stand and a preheat temperature of about 210F (100C) for SynergyTM
and 350F (177C) for Vanguard.
3. The peel adhesion, shear, and impact results observed for Vanguard coating system are similar
to epoxy based three layer systems published literature for 3 layer system6,IO
4. The advantage of the fused multi-layer coating systems is that they can be engineered to end-user
requirements and combine desired performance characteristics to meet the challenge of individual
pipeline or pipeline sections.
References

1. "3 Layer Epoxy-Polyolefin Pipe Coatings," NACE Corrosion88, St. Louis, March 21-25, 1988.

2. Kellner, 1. D., 1. M. Serra,- "Recent Developments in Polymer Pipeline Coatings", Corrosion91,

National Association of Corrosion Engineers, 1991, Paper #355

3. Dempster, W., W. Seager, "The Gasket Effect Principle"

. Corrosion91, National Association of Corrosion Engineers, 1991, Paper#354.

4. ASTM, American Association for Testing and Materials, 100 Barr Harbor Drive, West
Conshohocken, Pennsylvania, 19428.

725
5. DIN, Deutsches Institut fur Normung e.V. (German Institute for Standardization), Berlin,
Germany.

6. CSA, Canadian Standards Association, 178 Rexdale Boulevard, Rexdale, Toronto, Ontario,
Canada M9W 1RJ.

7. I.A Davis, F.R. Hammond, J.D. Kelln,er, H. Schonhom, J.M. Serra and H.L. Simons, "Interaction
Between Soil and Coatings on Buried Pipelines", Proceedings, Conference 26, Australasian Corrosion
Association, Adelaide, Australia, November, 1986.

8. Aramco Materials Specification No. 09-AMSS-96, "Alyeska Shear Rate Determination".

9. PolykenIVNIlST "Methods of Adhesive Compound Tests for Shear Resistance" by V.K. Skubin,
S.A Rijov and lG. Kitina, Moscow, 1989.

10. M.Alexander, AM.Glowach Ii". "Success and Failure of Multi-Layer EpoxylPolyethylene Coating
for Pipe. ", Proceedings ofBHRA Conference, Florence, Italy October 1995

726
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Effect of Secondary Phases on the Pitting Behaviour of

Highly Alloyed and Laser Surface Alloyed
Austenitic Stainless Steels
K. Sridhar!, A.S. Khanna2 and M.B. Deshmukh1
INaval Materials Research Laboratory, Naval Dockyard, Bombay-400 023, India
2Corrosion Science & Engineering, lIT, Bombay-400 076, India

ABSTRACT
Highly alloyed austenitic stainless steels containing high levels of molybdenum (:> 5wt%) are being used due
to their excellent localised corrosion resistance. However, due to their high molybdenum contents, they are
susceptible to formation of secOndary phases which degrade the corrosion and mechanical properties. In this
paper, the effect of microstructural features on the pitting behaviour of two highly alloyed experimentaI
austenitic stainless steels are studied. Also for comparison, the microstructural characteristics of
commercially available austenitic stainless steel Avesta 254 SMO and laser surface alloyed stainless steel
containing very high molybdenum contents are compared.

INTRODUCTION

Conventional austenitic stainless steel such as AISI type 304 SS are being used for seawater piping
applications due to their desirable mechanical properties and good weldability [l]. However, these stainless
steels suffer from pitting corrosion in sea water due to aggtessive nature of chloride ions. Even, the
improved version, viz., AISI Type 316 SS, which has about 2-3 wt.% Mo for improved pitting resistance
in chloride media, has very limited life in marine environments.

Increased addition of Mo to the extent of 6 wt.% with.minor additions of nitrogen increases the pitting
resistance of stainless steels. In this context, a new generation of highly alloyed austenitic stainless steels has
been developed, known as superaustenitics [2], These steels have very good Ioca\ised corrosion resistance and
high strength, however, they are susceptible to the formation of undesirable secondary phases, such as sigma
and chi (due to high molybdenum & chromium contents) which deteriorates both t:\;1e mechanical and corrosion
ptoperties [3]. Nitrogen helps in retarding the kinetics of precipitation of the secondary phases, but cannot
eliminate them. Also, controlled addition of nitrogen is mandatory, as excessive addition will lead to the
formation of undesirable chromium nitride. All this factOrs lead to expensive processing routes to minimise
the deleterious second phases for satisfactory performance. In this context, the microstructural features of two
experimentally alloyed austenitic stainless steels with high contents of molybdenum were studied for
identification of the phases present in the microstructure and their influence on pitting behaviour of these
alloys. Also, presented are the microstuctural features of comimercially available high alloyed austenitic
stainless steel Avesta 254 SMO and laser surface alloyed steel.

727
EXPE~ENTALPROCEDURE

The designation of two experimental alloys, a commercially available stainless steel and the laser surface alloy
chosen for determining the effect of secondary phases on the pitting behaviour are shown in Table 1. The
chemical composition of the experimental alloys SS Mo 5.4 and SS Mo 6.5 were determined by wet Chemical
Analysis. The composition of Avesta 254 SMO is that of reported in its trade literature and that ofLSA was
determined by SEM-EDAX analysis.

* assumed carbon content as that of base metal ** Not determined

or general microstructure, the alloys were etched in methanolic aqua regia. For revealing secondary phases,
the alloys were etched in modified Murakami's reagent (30 gms potassium hydroxide, 30gms potassium
ferricyanide, 100 ml distilled water) in boiling condition. Further identification of thesephases were done
by X-ray diffraction studies (XRD) in Rigaku diffractometer. The composition of these phases we're
determined by Electron Microprobe Analysis (EPMA) of CAMECA make. Potentiostatic tests were carried
out to carry out in order to elucidate the effect of secondary phases on the pitting behaviour of stainless steels.

RESULTS AND DISCUSSION

Two experimentally alloyed austenitic stainless steels with high levels of molybdenum viz., SS M05.4 & SS
Mo 6.5 and the commercially available highly alloyed austenitic stainless steel Avesta 254 SMO were
compared with the surface alloy LSA-4 which exhibited the highest pitting resistance. The chemical of the
alloys and their Cr eq / Ni eq are shown in Table 1.

For comparing the microstructures, the experimental alloys viz., SS Mo 5.4 and SS Mo 6.5 [which were
solutionised at 1150 0 C for 60 minutes and water quenched], Avesta 254 SMO and LSA-4 were etched in
methonalic aquaregia. The corresponding microstructures are shown in Fig 1 (a), (b), (c) and (d) respectively.
From the microstructure, it is evident that there exists second phase constituents in the austenitic matrix in
the case of experimental alloys and Avesta 254 SMO, whereas no secondary phases was found in LSA-4. In
order to delineate the secondary phases, all the samples were etched with modified Murakamis reagent (30gms
potassium hydroxide,30 gms potassium ferricyanide, 100 ml distilled water) in boiling condition. This
selective etching revealed the presence of sigma phase in the sample which appeared reddish brown under
the optical microscope. The microstructure thus obtained of SS Mo 5.4, SS Mo 6.5, Avesta 254 SMO and
LSA-4 are shown in Fig. 2(a), (b), (c) and (d) respectively. The volume fraction of these secondary phases are
shown in Table 2.

728
729
The composition of the experimental alloys were chosen such that the ratio of the chromium equivalents
(Creq =Cr+ MQ + 1.5 Si) to nickel equivalents ( Nieq = Ni + 30C +0.5 Mn) is always less than 1.35
(Creq/Nieq). This facilitated solidification to take place by primary austenite formation. In spite of these
precautionary measures to have a fully developed austenitic microstructure, the alloys formed secondary
phases due to high tendency of molybdenum for segregation. However the segregation is higher only for alloy
SS Mo 6.5 with molybdenum content of 6.5 wt %. Even the commercially available Avesta 254 SMO showed
the presence of few amounts of secondary phases in spite of its nitrogen content of 0.20 wt % to minimise the
secondary phase formation. The surface alloy LSA-4 in spite of its very high molybdenum contents of 11 wt
% was free from any secondary phases such as sigma and chi. This could be attributed very high
solidification and Coolingrates inherent in laser surface processing.

The energy dispersive X-ray analysis (EDAX) of these phases using JEOL- Scanning Electron Microscope of
alloy SS Mo 6.5 revealed the presence of higher percentage of chromium, manganese and lower nickel
than that of the austenitic matrix as revealed in Figure 3. The electron microprobe analysis (EPMA) was
conducted using CAMECA electron microprobe instrument to determine the composition variation
between the secondary phases and the matrix at randomly selected points. The electron beam was fixed
at a given point of interest and the intensities of chromium, nickel and molybdenum were obtained by
sequentially setting the spectrometer to the requisite position in order to yield maximum count rates. The
reference in~ities were obtained from pure metal standards of Fe, Cr, Ni and Mo under similar
conditions. The composition at different points of the secondary phases and the interface are given in Table 2.

The samples (1 cm2 size) were then subjected to X-ray diffraction (Rigaku X-ray diffractometer) using a
Cu-Ka target at a voltage of 25 kV for further identification of these phases. The diffraction peaks
corresponding to samples SS Mo 6.5 and SS Mo 5.4 were matched with JCPDS X-ray diffraction files of
expected phases in these alloys. It was found that XRD peak lines of sample SS Mo 6.5 corresponds to
sigma, chi and austenite while that ofSS Mo 5.4 to austenite only. This is due to the presence ofvery few
amounts of finer secondary phases (3.95%) in SS Mo 5.4 as the detectable limit in the instrument
employed is only five percent. Fig.4(a) and Fig 4(b) Shows the X- ray diffraction pattern of the abovesaid
samples.

730
Fig 4. X-ray diffiaction pattern ofSS Mo 5.4 (a) showing the presence of austenite phase and that
ofSS Mo 6.5 (b) indicating the presence of secondary phases.

731
732
Fig 5. Optical micrograph showing the pit formed adjacent to sigma in the interface region (a) and
scanning electron micrograph of the same at higher magnification (b).

Due to the enrichment of chromium and molybdenum in the melt retained between the austenite dendrites, the
last fraction can solidifies eutectically to ferrite and austenite or purely as ferrite. The
interdendritic ferrite has high chromium and moly~um contents and upon further cooling decomposes to
sigma or similar intermetallic phases. It is well known that such phases deteriorate the corrosion
properties. These chromium and molybdenum segregation is not completely dispersed by subsequent hot
rolling but Tllther it is smeared into sheets parallel to the rolling plane. Segregation can be adequately
dispersed only by high temperature annealing [4] . In the present study it was found that soaking at 1150
o C for 150 min followed by water quenching was found sufficient to render SS Mo 5.4 with
minimum secondary phases.

733
This pittIng index (or crevice corrosion index) known as "Wirksumme" is based on parametric
observations . This serves as a guideline for selecting stainless steels for seawater service. As
reported, a value of 38 or higher suggests that the material will have exCellentpitting corrosion resistance in
seawater [5]. The major drawback ill using parameters based on chromium and molybdenum contents is
that they totally ignore the effects of microstructural factors on the breakdown of passivity by pitting or
crevice corrosion.

It is evident from the EPMA data that the composition of alloying elements varies to a great extent at the
secondary phases and interface. Based on this, it is possible to calculate the pitting index of these
secondary phases, interface and the base metal thereby taking into account the microstructural
variations. The pitting index (P.I) value of the secondary phases viz., sigma is found to be very much higher
than the interface region or matrix due to its very high chromium and molybdenum contents. Since thC::
pitting index variation of 74 to 35 was observed between the secondary phases and the interface region
(austenite with reduced chromium and molybdenum), the interface region was found to be susceptible to
pitting and sigma remained nobler to the matrix .

Reported studies indicate that the thickness of the passive films in Cr-Ni steels was found to increase with
increasing molybdenum content of the steels [6]. Also the molybdenum content of the film increased almost
linearly with molybdenum content of the steels which facilitates the formation of Mo (VI)oxide. This
oxide present in passive films. promotes the ability of Cr(Ill) oxyhydroxide film for enhanced pitting
resistance since the stability of Mo(VI) oxide is very high in acid solutions with chloride [tij. Based on this,
it can be inferred that the passive films formed over the interface .region will be of lower thickness and
lower in molybdenum cOntent than the sigma phase and the base matrix. Consequently the formation of
Mo(VI)oxide is also minimised and hence the interface becomes more susceptible to pitting attack by
chloride ions. Sigma, being higher in chromium and molybdenum contents is expected to have a strong,
thick passive film with requisite amounts of Mo(VI)oxide in it and hence nobler to the interface which is
denuded of molybdenum and chromium.

CONCLUSIONS

In highly alloyed austenitic steels with molybdenum contents greater than 5 wt% and higher, brittle
intermetallic secondary phases such as sigma and chi were found to be precipitated .predominantly at
grain boundaries.

The interface region between the secondary phases and the austenite was found to be depleted of
chromium and molybdenum.

The interface region, denuded in chromium and molybdenum has been found to be the favourable sites for
initiation and propagation of pitting in natural seawater.

Laser surface alloying technique has been found to eliminate the formation of secondary phases even with
higher molybdenum contents due to rapid solidification.

734
REFERENCES

I. R.A. Walker," duplex and high alloy stainless steels - Corrosion resistance and weldability"
Materials Science and Technology, VolA, No.2,lan 1988, pp 78-84.

2. H.Brandis & H.Kiesheyer," Influence of chromium and molybdenum on chloride corrosion

of stainless steels in "Stainless steels '84 " , Institute of metals, 1981,pp.217-221.

3. E.Wallis,"Influence of molybdenum content of high alloy stainless steels and of the

precipitation of intermettallic phases on pitting resistance in chloride containing media",
Werkstoffe und Korrosion, Vol. 41, 1991, pp 155-162.

4. Ralph. M. Davison and lames D. Redmond," Practical Guide to using 6 Mo austenitic

stainless steel", Materials Preformance, Dec. 1988

.5. G.L.Swales and B.Todd," Nickel containing alloy piping for offshore, oil and gas
production", NiDi Technical Series, N 10083. Pub. Nickel Development Institute .

.6. K. Sugimoto and YSawada," The role of alloyed molybdenum additions to austenitic stainless
steels in the inhibition of pitting in acid chloride solutions.", Corr.Sci.Vo1.17,1977, ppA25-445.

735
Proc. In\. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Evaluation of Durability Characteristics of Epoxy Poly

Urethane Painting System Through QUV Apparatus
M.P. Varma!, J.L. Khanna2 and V. Murlidharan3
[Add!. Exec. Director Met. & Chern. Dte., R.D.S.O., Lucknow
2Ex. A.R.O. ,Chern.) Met. & Chern. Dte., R.D.S.O., Lucknow
3C.R.A. (Chern) Met. & Chern. Dte., R.D.S.O., Lucknow

Simulation of weather conditions in the laboratory for

studying the degradation of polymeric coatings has been
attracting the attention of the research workers in the field of
protective coatings. Whenever a new polymeric formulation is
developed, it is important to determine the durabili ty of new
material towards the vagaries of weather condi tions, the
conditions under which the degradation of polymeric coatings is
inevitable. This aspect assumes greater importance whenever
costly protective systems based on epoxy/poly-urethane resin
medium are to be implemented as a regular measure on a large
scale. To generate reliable weatherability data, a co-ordinated
exposure study was conducted in 2 phases with different colour
shades and this paper deals with the systems taken up for the
study & the results obtained and the 'conclusions drawn from the
study.

In the fast developing' field of paint technology,

numerous polymeric coatings are introduced in the market with
excellent properties which needs to be evaluated properly before
ascertaining the validity of the claims of the manufacturers of
the new products. In this context, the evaluation of durability
characteristics assemes greater significance as all the
polymeric coatings degrade in different levels under the
vagaries of weather conditions'. In order to predict the
behaviour of these polymeric coatings with confidence, it is
necessary to do thorough evaluation of the coatings material in
a laboratory equipment in which the weather conditions can be
simulated and which will provide reliable results that has a
reproducibility to a fair degree. Out of the several versions of

736
laboratory equipment available for this purpose, the QUV
Apparatus is said to be more stringent and less time consuming
for generating reliable data.

With today's accelerated weathering testers, it is

possible to generate reliable'weatherability data in' a matter
of days or weeks provided the mechanisms of outdoor weathering
and use a tester of proper design is ,understood properly. The
following three crucial concepts provide the key to successful
accelerated weathering in the Laboratory.
1) To simulate the effects of sunlight,the best approach is to
reproduce just the shortest of the UV wavelengths, the UV-B.
2) The proper way to simulate outdoor wetnessattack is with
hot condensation.
3) Accelerate the effects of UV and condensation by elevating
the test temperature.

The shortest wa~elengths in sunlight are the

ul traviolet, extending down to a wavelength of about 295
nanometers. Even though UV constitutes just 5 percent of the
sunlight falling on the earth, these short wavelengths are
responsible for virtually all the damage to polymers. For this
reason, the lamps in the QUV are designed to produce only UV.
This .is an exceptionally good way to reproduce the damaging
effects of sunlight.
The QUV has been succesful in simulating the effects
of sunlight while reproducing only the shortest wavelengths in
sunlight because of a sound principle: the shorter the
wavelength of light" the greater it's ability to cause
photochemical damage.The Quantum Theory states that light comes
in discrete particles called photons. Photons behave much like
tiny projectiles travelling at the speed of light.The size of a
photon is inversely proportional to wavelength-the shorter the
wavelength the bigger the photon. Photochemical reactions are
caused by a single photon colloiding with a single electron.If
the photon is big enough(i.e.,contain more energy than the
organic bond strength)the electron is knocked out of its orbit
and a reation occurs.For each type of chemical bond,there is a
critical threshold size of photon (and he!lce a threshold
wavelength) to cause a reaction.Light of any wavelength shorter
than the threshold wavelength can break the bond. Therefore,
even within the UV, the shorter wavelengths are more destructive
than the longer UV wavelengths. For laboratory weathering, the
UV-B wavelengths are the most important.

The destructive effects of UV exposure are accelerated

when temperature is increased. Any laboratory weathering test

737
must provide accurate control of UV exposure temperature, and it
must provide a means to elevate the temperature to produce
acceleration.

WHY CONDENSATION ?

The best way to simulate outdoor wetness attack on

organic material is with condensation. In addition, the
condensation exposure should be conducted at elevated
temperatures to provide acceleration. The old fashined methods
of water immersion, high humidity, fog, or spray do not
accurately reproduce typical outdoor conditions, nor do they
provide the elevated temperatures necessary for proper
acceleration.
The QUV simulates rain and dew by condensing liquid
water directly on the test specimen. Water in the bottom of the
test chamber is heated, filling the chamber with hot vapor and
creating 100 percent humidity at400C to 50oC. Because the test
samples are the actual side wall of the chamber, room air on
their back side cools the samples a few degreeds below the vapor
temperature. This cooling in turn causes condensation on the
front side. There are important reasons why QUV's method of
condensation is the best way to simulate natural wetness
exposure. Materials are wet from dew more frequently and for
longer dl.lrationsthan is commonly supposed. Further more, the
incidence of rain is such that it can account for only a small
fraction of these hours of wetness is dew, or condensation. In
order to condense dew, a material must be cooler than the
surrouding air. More specifically, it must be below the dewpoint
temperature of the air. High humidity can not cause liquid water
to condense unless there is a temperature difference.
Dew is saturated with oxygen. It is often the case that water
is not destructive in itself,but that water cause damage by
bringing oxygen in to intimate contact with the material and
thereby promoting oxidation. Any attempt" to simulate outdoor
wetness must ensure that the water is fully and reliably
saturated with oxygen.The only way to do this is with
condensation.
The fact that dew lies on materials for many hours at a
time is also of crucial significance. This allows the water to
penetrate deep within the material to ciause internal
oxidation.It also allows time for soluble additives to be
leached from the material.And i'n case of paint films,it gives
the water time to permeate through the coating and dissolves
soubles between the coating and the substrate.This creates an
osmotic cell,with the coating as the membrane. The pure condensed
dew is the dilute solution,and the water between the substrate
and coating is the concentrated solution.rhe resulting osmotic
pressure literally pumps water through the coating, causing
blistering and lifting of the coating.A proper simulation of
outdoor wetness must provide wet periods of several hours
duration, rather than a few minutes of spray followed by rapid
dry-off.rhe QUV's condensation cycles meets this requirement.

738
 Finally, the fact that materials spend such a large
proportion of their outdoor life wet puts a special burden on
accelerated tests.With .outdoor materials wet eight hours a
'day;it is virtually impossible to accelerate condensation damage
by increasing the number of hours of wetness. Some others means
must be used.The QUV accelerates by increasing the temperatures
of wetness to 400C to 500C. This preserves the essential
features of pure condensed dew,while providing a high degree of
acceleration.It is not uncommon to find that a 100C increase in
condensation temperature results in a doubling of the rate of
deterioration. It is now clear that tests that spray cool room -
temperature water on the sample are incapable of accelerating
outdoor wetness,a problem which is exacerbated by the fact that
these cold sprays also usually give much fewer daily hours of
wetness than is typical outdoors.To accelerate outdoor wetness,
both long periods of wetness and elevated temperatures are
needed.There is definitely a synergistic effect between UV and
condensation.Materials resistant to UV alone or to condensation
alone often fail when subjected to Uv and condensation in
combination. A weathering tester which produces both UV and
condensation can take advantage of the synergy between t~ese two
forces.

COLOUR SHADES EXPOSED - POST OFFICE RED & PALE CREAM SHADE
SIZE OF PANEL - 150 X 75 X 1.25 mm
PAINTING SCHEDULE - EPOXY ZINC PHOSPHATE PRIMER-1COAT
- EPOXY SURFACER - ONE COAT
- POLY URETHANE FINISH - TWO COATS
RECOMMENDED DFT - 140 MICRONS
CURING TIME - SEVEN DAYS OF'AIR DRYING
TEST CONDITIONS AS -QUV TEMPERATURE 50 + 10C .
PER ASTM G 53-93 CONDENSATION TEMPERATURE 45 + 10C
(TYPE A) QUV RADIATION SOURCE-UVB 313 LAMPS
LAMP OPERATION,INDICATOR-300-400mA
EXPOSURE CYCLE - 4 HOURS UV AND 4 HRS. CONDENSATION
NO.OF FIRMS - FOUR
PARTICIPATED

739
740
 The painted panels were prepared' by the respective firms
themselves . wide variations in the DFT could be observed as
indicated above against the normal DFT of 140-150 microns.
Panels in duplicate were exposed in the QUV Apparatus of all the
participating firms at their premises simultaneously with the
test commencing on the same date and concluding on the same
date. The data given above are representative values of minima
and maxima obtained during the evaluation of the exposed panels.
The results obtained indicates the following :
1) In case of pale cream shade, the colour change in case of
firm D was rated Fa which in turn has shown the highest
Delta E value, while in case of firms A,B & C, the colour
change was rated D9 having low Delta E value.
2) In case of post office red shade, the colour change in
case of Firm D was rated F7 which in turn has shown the
highest Delta E value while in case of firms A, B & C,
the colour change was rated D9, D9 & D7-8 and their Delta
E value also ~hows increasing trend in the same order.
3) The % gloss retention of firm D in case of pale cream and
post office red shade was lowest when compared with the
values of firms A, B & C.
4) In case of gulf red shade, the colour change in case of firm
E was rated F5 which in turn has shown the highest Delta E
value and lowest gloss retention. In general all the panels
exposed have shown fading except firm C which has shown
darkening (D9) yet the Delta E value was on par with firm
A & B. Delta E value increases with increase in fading and
colour change.
5) In case of oxford blue. shade, all the exposed panels except
firm C have shown fading and the Delta E value. increase
with the increase in fading and colour change.
6) In general, pale cream and post office red shades tend to'
darken, gulf red and oxford blue shade tend to fade.
7) The data obtained shows that it is possible to attain high
percentage of gloss retention if genuine pigments are used
in the paint formulation.
8) While spotting was observed in case of pale cream shade &
gulf red shade, micro blistering. was observed in oxford
blue shade.
9) The performance of the system of firm D in phase. I and
firms D & E in phase II is not considered satisfactory.

741
Prol;. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

High Temperature Resistant Slurry

Based Coating for Steel
M.N. Singh and Inder Singh
National Metallurgical Laboratory,
Jamshedpur-831007, India

ABSTRACT

The current teclmologies for high temperature protective coating based on composite systems, such as
complex oxides, silicide, aluminides, carbides and nitrides etc.are meant for high temperature service
'alloys,which are not easily removable from meal surface

In the present investigation, studies were made to provide a barrier type of protective coating over steel
surface. the coating consisted of metallic aluminum powder, asbestos powder, cobalt oxide, kaoline, Alz~
Tio, and ZrQ, and the binders. The binders, such as aluminium phosphate, sodium silicate, ethyl silicate,
modified sodium silicate and Ivory-400 were used.

It was aimed to produce a slurry based coating which would be strippable as. desired in subsequent
processing. The coating particulates were added in varying amo,unt varying from 1-10 % by weight of the
binder.

Mild steel sample of 50 mm x 2 mm were used for the test. The coating was applied over the steel
samples and dried for 24 hours in open air before the test. The coated and un-coated steel sampleS were
exposed at temperature of 500-800 C for 2-4 hours. After the over of desired period of exposure, the samples
were taken out, allowed to cool in air and pickled in inhibited acid for 5-10 minutes for the removal of the
scale. The loss in weight per unit surface was expressed as oxidation/scaling loss. The amount of protection
given by the coating was calculated as usual.

The modified silicate binder is found to be superior to both sodium silicate and ethyl silicate because it
has greater spreadability and better compatibility with respect to sodium silicate. Aluminium phosphate dOes
not provide good adherence to the substrate. Ivory-400 available in the market is also superior because of its
greater spreadability, stability and adhesion as compared to the Aluminium phosphate. The data are discussed
in detail.

742
INTRODUCTION

In industry, various types of stee1 articles Wldergo exposure at higher temperatures during which thick
oxide scales form on the surface. It is well known that high temperature oxidation is one of the most injurious
types of corrosion which contributes to the national economic loss, safety and conservation of metals and
alloys. Corrosion protection by high temperature coating is one of the known techniques adopted allover the
world. Now-a-days ceramic additives to the binder play an important role in the protection of steel at higher t
emperatures. The current technology for high temperature protective coating are based on composite systems
such as complex oxide, silicides, aluminides, carbides and nitrides which are used for high temperature service
alloys:9.
The need for protective coating based on refractory metal oxide has been perfected through imperical
development. Still considerable research is Wlderway to improve bond coats and properties of the ceramics2.
Protection to steel articles during short term high temperature exposures can be met with such coating systems
which are, no doubt,protective, but also removable by easy means. Phosphate, silicate and Ivory-4oo binders
could be preliminary choice because of easy availability and low cost. A number of high temperature resistant
coating particulates can be incorporated into these binders depending on their mutual cpmpatibility. It was
aimed to produce a slurry based coating which would be strippable as desired in subsequent processing.

The present study discusses the development of the corrosion resistant slurry based coating and its
behaviour at high temperature (800 C). The coating provided a barrier type of protective coat;ing over stee1
surfaces. For this purpose, metallic aluminium powder, asbestos powder, zinc oxide, Zr<h, Ti~ cobalt oxide
and kaoline were introduced into the binders, namely aluminum phosphate, silicates and Ivory-4oo ..

EXPERIMENTATION

Mild steel sample of 50 mm x 2 mm were cut from cold rolled sheet polished with "000" emery paper,
degreased by rubbing with MgO paste, washed with rurming water, dried and stored in a dessicator for 24
hours before use. Various types of particulate materials(-200 mesh size) were selected for incorporation into
the binders as mentioned earlier. The coating particulate were added in varying amount ( 1-10 % ) by weight
of the binder. The binders uSed were aluminum phosphate, sodium silicate, ethyl silicate, modified silicate and
Ivory-400.

The aluminium phosphate binder was prepared by treating aluminium sulphate with tri-basic sodium
phosphate. Commercial grade ethyl silicate and sodium silicate binders were also used, the latter having
silicate to alkali ration of 2.3:1. A modified silicate solution was prepared by mixing about 1-10 % absolute
alcohol to the sodium silicate solution. The coating particulates were 'mixed with the binder to from a slurry
which was applied over the steel. Each sample was weighed before and after applying the coating ..

Excessive swelling of the coating containing silicate binders was observed which was due to rapid
dehydration immediately after the samples were put inside the furnace .. This could be prevented by preliminary
treatment of the coated samples at 100-300 C. But this operation was fOWld to produce a coating which was
very difficult to remove after exposure to high temperature by acid pickling. So only air drying for 24 hours
was followed. The coated and Wlcoated steel samples were suspended inside the furnace at a temperature of
800 C for 2 to 4 hours for observing the performance of the coating. After the desired period of exposure of
samples at 800 C was over, the samples were taken out, allowed to coolin air and pickled in inhibited
hydrochloric acid for 5-10 minutes for the removal of the scale.

743
744
CONCLUSIONS

A formulation incorporating both aluminiwn powder and zinc oxide as particulates and aluminiwn
phosphate and sodiwn silicate as binder provides protection to steel to the extent of 35 % at a temperature of
8000 C for 4 hours.
1. Addition of metallic aluminiwn powder to binders imparts scaling resistance. This may be
due to better adhesion of aluminiwn oxide with metal surface in presence of binders.
2. Scaling resistance improves with the use of modified silicate as binder
3. The modified silicate binder is found to be superior to both sodiwn silicate and ethyl silicate
because it has greater spreadability and better compatibility with respect to sodiwn silicate .
Aluminiwn phosphate does not provide good adherence to the substrate. Ivory-400 binder is
superior to AlP04 but fails at temperature of above 7000

745
REFERENCES

1. Harrison, W.N.,Moore,O.G.,Richmand,T.C., "Ceramic coatings for high temperature

protection of steel", lRes. Nat. Bur. Std. Report., 1775. Marcl1,1947,pp. 293-307.

2. Stringer,J.,Vishwanathan, Proceedings of ASM, Materials Congress Materials Week,

Pittsburgh,PA, 93, Oct.,1993. pp. 17-21.

3. Strafford,KN.,Datta,P.K,Govani,C.G.,Coating and surface treatment for corrosion and wear

resistance.,Ellis Horward Limited, 1984.

4. Singhal,S.C.,High temperature protective coating conference proceedings, AIME,1982.

5. Lang,E., Coating for high temperature application., Applied Sc., Publishers, 1983.

6. Tolly, 'G., lApp. Chern.,1,86, 1951.

7. Holmes,O.R., Rahmat,A., Materials and coatings to resist high temperature corrosion,

.Applied Science Publication Limited, London, 1978.

8. Samsonov,G.V.,Epik,A.P., Coating for high temperature materials. Part. I

Bibeant,WA,Bark,E.S., Part- n
Lews,O.H. Part -m., H.H.Hanswer Plenum Press, 1966.

9. Vargin,V.v.,Teclmology of Enamels.
Maclaren and Sons Limited, London, 1965.

10. Singh. M.N.,Singh, Inder, Pandey,J.L., High temperature corrosion resistant coating on steel
for short term applications, Anti-Corrosion Methods and Materials, U.K, Vol. 44, No.
2, I997,pp.90-93.

11. Rhys-Jones, T.N.,Toriz,F.C., High Temperature Teclmology, Vol. 7, No. 2,1989, pp.73-81.

12. Taylor, R.,Brandon, lR., Morrell,P., Surface and Coating Teclmology, Vol. 50, No.
2,1994,pp.141-9.

13. Van DC Voorde,M.H., Hocking, M.G., Vasan tas race,VA, Comprehensive review on the
development of ceramic coatings for thermo-mechanical applications, High Temperature
Materials and Processes, Vol. 7,No. 2 & 3, '1986, pp. 107-21. .

746
to provide bonding between the pipe surface and the polyethylene top layer. The last wrap to be
applied is also a three layer laminate of 0.64 mm total thickness. It has a central high density
polyethylene core which is the source of the mechanical strength of this layer. One either side of this
central core is a thin layer of thermoplastic adhesive. Each of the plastic layers are designed to fuse
together during the application process. The pressure sensitive adhesive supplies the adhesion to the
pipe.and the thermoplastic adhesives melt and fuse, completely sealing the overlaps and sealing the
two laminates together.

VanguardTM
Figure Ib shows the construction of the Vanguard coating. The first layer next to the pipe
is 75-100 J.lMofa two-part liquid epoxy spray-applied as a primer. The outer mechanical layer
consists of three parts: a tough high molecular weight, high density polyethylene which supplies the
bulk of the mechanical and barrier properties; a permanently bonded layer of modified polyolefin
designed to adhesively react with the epoxy primer; and a third permanently bonded polyolefin layer
designed to effect the complete fusion of the laminate into a monolithic coatin~ at temperatures low
enough to be economical and without affecting the integrity of the high density barrier layer. The next
section describes the application process.
Application

The SynergyTMand Vanguard multi-layer coating systems are specifically designed for plant
application using a minimum of equipment and labor in a continuous operation. The basic application
process consists of the following steps:
I. Cleaning of the pipe to remove surface contaminants.
2. Preheating the pipe to the appropriate preheat temperature. The recommended range for Vanguard
is 300-325F (1 50-163C) for 50 mils (1.27 mm) final thickness of coating. For a 100 mils (2.54 mm)
thick coating the recommended pipe temperature is 325-350F (163-177C). The recommended
range for Synergy is 200-220F (93-104C).
3. Shot blasting the pipe to an anchor pattern of 1.5-3 mils (37 - 75 microns) and to a SSPC-SP-6 or
NACE TM-01-70 #3 or Swedish Standard SA 2/2.5 TM-01-75 #3.
4. Application of the primer. Liquid epoxy primer for Vanguard at a thickness 00-4 mils (75-100
microns). Primer for Synergy is applied either by airless spray units or by a drip feed technique. In
drip feed, the primer is spread over the pipe surface with the aid of rubber scrapers or sock. The
primer is applied to a thickness of about 100 I..IM wet.
5. After inspection of the pipe for surface irregularities, application of the polyethylene sheet
laminates. The layers are spirally wrapped on the pipe under tension (width decreased by 1-2%) using
a mechanical coating apparatus equipped with a constant tension breaking system. The tension
applied during application of the SynergyTManti-corrosion layer, produces a gasket effect and seals
the coating system at the spiral overlap3
6. Water quenching of the coated pipe over a distance of6 meters to avoid damage to the outer
coating surface during subsequent pipe handling ..
7. To insure high quality and precise coating application the coating rolls and primer are
manufactured at a state-of-the-art facility using modem techniques of production to achieve total
quality and zero defects. During the coating application process, key parameters are monitored
including pipe preheat temperature, temperature of the surface after priming, coating temperature and

720
line speeds. Only coated pipe that has a record of the correct parameters during application is
released. These application steps are schematically summarized in Figure 2.
To insure high quality and precise adherence to the coating application specification, the
following quality control measures have been instituted at each certified application plant.
1. Coating rolls and primer are manufactured at a modern ISO certified facility using state-of-
the-art computer technology to monitor each phase of production. Raw materials and finished
product are tested under strict quality' assurance guidelines to ensure a consistent and uniform coating
system.
2. During application, key parameters are monitored. These include pre-heat pipe
temperature, wrapping tension, oven temperature, coating temperature and line speeds. Each
application parameter value is recorded continuously with alarm limits for a permanent record. Only
properly applied coated pipe is released to the warehouse or customer.
The combination of the manufacturing quality standards, parametric release and non-
destructive testing guarantees the quality of the pipe coating and also the quality of the plant
applicator.
Presently, a small but growing group of coating plants have successfully applied these
multi-layer systems on a commercial basis. The~e plants have applied the coating system for several
gas and oil companies on projects requiring pipe ranging from 10 through 60 cms in diameter.

Patch and Repair and Girth Welds

.
Although rare, damage could occur to the coating during handling and transportation. The
toughness and thickness of the polyolefin layer in the new coatings should make these areas small and
infrequent. In case of Synergy TM the damaged areas can be repaired in the field using cold applied
tape system such as Polyken 934 anti-corrosionjointwrap used with Polyken 954 mechanical
protection layer. This cold applied tape system can also be used for the protection of the girth weld
joints. The other recommended systems for the girth weld protection are a DIN approved double
face coating system such as Polyken 943 or Polyken 942 anti-corrosion layer with a mechanical
protection layer (polyken 954 or 955) and a heat shrinkabie polyolefin based system that is supplied
as a wrap around sleeve with a heat fusible closure system to seal the sleeve overlap area. The sleeve
is overlapped onto the plant applied coating system and is fused with a torch. The fused joint coating
is thus permanently bonded to the plant coating system.
For Vanguard TM coating system the repair kit consists of a roll of polyolefin laminate and epoxy
primer provided in a twin pack. The damaged area is cleaned and coated with epoxy primer. The
adhesive side of the laminate is heated with a torch at low flame. As the adhesive layer becomes tacky
it is adhered to the pipe surface over the damaged area and compressed w.ith a hand held pressure
roller. The covered area is carefully heated with a torch and compressed with a roller to ensure that
the patch is completely fused.
A similar procedure may be followed for the coating' of the girth welds in the field. The primer
supplied in a disposable twin package pouch is sqeezed onto cleaned pipe surface and spread with a
brush. A length of polyolefin laminate is then applied in cigarette wrap fashion by wrapping around
tightly and held in place with a closure tape. The coating is then fused in place with a flame torch:
The overlap of the polyolefin laminate is fused to the upper surface of the line pipe coating. In this
way, the girth weld coating has the same anti-corrosioll quality as the coating used on the rest of the
pIpe.

721
 Laboratory Evaluation
Synergy TU
The performance characteristics of these fused multi-layer coating systems have been
measured in the laboratory and during field application. The characteristics that are critical for long
term in-ground corrosion protection are adhesion to the pipe, resistance to cathodic disbondment,
resistance to soil stress, low water absorption, and tough mechanical integrity enabling the coating
system to withstand the rigors of handling and transportation.
Standard ASTM test methods were used to evaluate the performance characteristics of the
SynergyTMfused multi-layer coating system. The test results listed in Table 1 are for production
coated pipe from certified applicators. The data show the coating system has high peel strength, low
water absorption, high resistance to cathodic disbondment, and tough mechanical properties.

Table 1 - 1.27mm and 2.54mm Systems

VanguardTU
Extensive testing of the Vanguard coating was performed in the laboratory using a battery
of standard pipeline coating evaluation tests in use in the USA 4 and abroad56. All samples used were
obtained from commercial production runs at qualified applicators' facilities. At least one of these

722
 facilities was a portable plant which was easily and quickly modified to apply the new system. The test
results.are averages of at least three samples and are typical of the performance of2 or 3-layer
systems.in these tests. Tests of shear strength, thermal and hydrolytic stability were modified tests
.which are described in previous publications2,7. The shear test is similar to the Aramco "Alyeska"
shear testS and a test protocol from Russia9. The results are given below in Table 2 for the 50 mil
(1.27 nun) coating consisting of two layers of25 mil (0.64 mm) outerwrap.

Table 2 -25 mil (1.27 mm) System .

 Peel forces are high even at elevated temperatures and after thermal aging at lOOCfor2,OOO
hours. Peel forces after aging in 95C water for 30.0. hours are higher than would be the case for bare
epoxy not coated with polyethylene. More important than peel force, from a coating functionality
point of view is the shear strength of the coating. The shear strength will determine the tendency ofa
coating to slide across the pipe surface under the action of soil moving across the pipe. This sliding of
thl;!pipe coating could result in wrinkling and coating failure 7. The shear strength is measured by a
technique that determines the rate of movement under the influence of a normal force and a shear
force. The rate of movement is so low, that no shear movement at all could be detected even after 48
hours of testing. These extremely low rates of shear movement assure that no soil stress effects will
be seen by the coating after burial even at elevated temperatures.
Impact strength is chiefly a function of coating thickness. And is given in units of average
energy that causes a detectable holiday at about 12kV. For a 1.27 mm system, the impact strength is
76 in-lb. Or 8.6 J.This is more than sufficient to resist damage from the normal mechanical stresses of
handling and transportation. The penetration resistance is high because of the absence of an
elastomeric adhesive which could cold flow under the influence of a steady pressure. This allows the
coating to withstand the localized pressure of contact with rocks after burial. T\1e tensile strength of
the high molecular weight polyethylene is higher than conventional polyethylenes. The coated pipe
can be bent to greater than the API specification for steel pipe without producing a holiday or
damaging the coating in any way. The water vapor transmission rate is very low as is typical of this
class of polyethylenes.
The dielectric strength and resistivity values are typical of polyethylene. The dielectric strength
is a function of the coating thickness and is high per unit coating thickness for this coating due to the
fact that an elastomeric adhesive, with a lower dielectric strength is absent. The cathodic disbonding
resistance is excellent dueto the effect of the epoxy primer and the polyethylene acting together. The
epoxy has excellent interface adhesion with steel, and the polyethylene is an excellent barrier to water
penetration to the epoxy layer.
Results for the 100 mil (2.54 mm) coating system consisting of 4 layers of outerwrap are given in
Table 3.

724
 Test protocols for the 100 mil (2.54 mm) coating system were taken from the DIN standard
(DIN 30 670) in common use in Europe and other parts of the world for 2- and 3- layer coatings.
This was done because it is common in European countries to use a larger coating thickness for the
same size pipe than is commonly used in the USA. Differences in the angle of peel and the rate of peel
.resulted in different values for the peel forces, although the same excellent aging results were
obtained. Since the shear strength depends on the shear adhesion at the steeVcoating interface, these
values were independent of sample coating thickness.

Conclusions

1. New hot applied plant coatings are now available with similar adhesive, mechanical and electrical
properties as the commonly used 3-layer ep~xy/polyethylene coating systems ..
2. The new coating systems are supplied from the manufacturer in roll form with the proper thickness
and width for the pipe size to be coated. The application process is simple, requiring only a primer
spray unit, a roll goods let-off stand and a preheat temperature of about 210F (100C) for SynergyTM
and 350F (177C) for Vanguard.
3. The peel adhesion, shear, and impact results observed for Vanguard coating system are similar
to epoxy based three layer systems published literature for 3 layer system6,IO
4. The advantage of the fused multi-layer coating systems is that they can be engineered to end-user
requirements and combine desired performance characteristics to meet the challenge of individual
pipeline or pipeline sections.
References

1. "3 Layer Epoxy-Polyolefin Pipe Coatings," NACE Corrosion88, St. Louis, March 21-25, 1988.

2. Kellner, 1. D., 1. M. Serra,- "Recent Developments in Polymer Pipeline Coatings", Corrosion91,

National Association of Corrosion Engineers, 1991, Paper #355

3. Dempster, W., W. Seager, "The Gasket Effect Principle"

. Corrosion91, National Association of Corrosion Engineers, 1991, Paper#354.

4. ASTM, American Association for Testing and Materials, 100 Barr Harbor Drive, West
Conshohocken, Pennsylvania, 19428.

725
5. DIN, Deutsches Institut fur Normung e.V. (German Institute for Standardization), Berlin,
Germany.

6. CSA, Canadian Standards Association, 178 Rexdale Boulevard, Rexdale, Toronto, Ontario,
Canada M9W 1RJ.

7. I.A Davis, F.R. Hammond, J.D. Kelln,er, H. Schonhom, J.M. Serra and H.L. Simons, "Interaction
Between Soil and Coatings on Buried Pipelines", Proceedings, Conference 26, Australasian Corrosion
Association, Adelaide, Australia, November, 1986.

8. Aramco Materials Specification No. 09-AMSS-96, "Alyeska Shear Rate Determination".

9. PolykenIVNIlST "Methods of Adhesive Compound Tests for Shear Resistance" by V.K. Skubin,
S.A Rijov and lG. Kitina, Moscow, 1989.

10. M.Alexander, AM.Glowach Ii". "Success and Failure of Multi-Layer EpoxylPolyethylene Coating
for Pipe. ", Proceedings ofBHRA Conference, Florence, Italy October 1995

726
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Effect of Secondary Phases on the Pitting Behaviour of

Highly Alloyed and Laser Surface Alloyed
Austenitic Stainless Steels
K. Sridhar!, A.S. Khanna2 and M.B. Deshmukh1
INaval Materials Research Laboratory, Naval Dockyard, Bombay-400 023, India
2Corrosion Science & Engineering, lIT, Bombay-400 076, India

ABSTRACT
Highly alloyed austenitic stainless steels containing high levels of molybdenum (:> 5wt%) are being used due
to their excellent localised corrosion resistance. However, due to their high molybdenum contents, they are
susceptible to formation of secOndary phases which degrade the corrosion and mechanical properties. In this
paper, the effect of microstructural features on the pitting behaviour of two highly alloyed experimentaI
austenitic stainless steels are studied. Also for comparison, the microstructural characteristics of
commercially available austenitic stainless steel Avesta 254 SMO and laser surface alloyed stainless steel
containing very high molybdenum contents are compared.

INTRODUCTION

Conventional austenitic stainless steel such as AISI type 304 SS are being used for seawater piping
applications due to their desirable mechanical properties and good weldability [l]. However, these stainless
steels suffer from pitting corrosion in sea water due to aggtessive nature of chloride ions. Even, the
improved version, viz., AISI Type 316 SS, which has about 2-3 wt.% Mo for improved pitting resistance
in chloride media, has very limited life in marine environments.

Increased addition of Mo to the extent of 6 wt.% with.minor additions of nitrogen increases the pitting
resistance of stainless steels. In this context, a new generation of highly alloyed austenitic stainless steels has
been developed, known as superaustenitics [2], These steels have very good Ioca\ised corrosion resistance and
high strength, however, they are susceptible to the formation of undesirable secondary phases, such as sigma
and chi (due to high molybdenum & chromium contents) which deteriorates both t:\;1e mechanical and corrosion
ptoperties [3]. Nitrogen helps in retarding the kinetics of precipitation of the secondary phases, but cannot
eliminate them. Also, controlled addition of nitrogen is mandatory, as excessive addition will lead to the
formation of undesirable chromium nitride. All this factOrs lead to expensive processing routes to minimise
the deleterious second phases for satisfactory performance. In this context, the microstructural features of two
experimentally alloyed austenitic stainless steels with high contents of molybdenum were studied for
identification of the phases present in the microstructure and their influence on pitting behaviour of these
alloys. Also, presented are the microstuctural features of comimercially available high alloyed austenitic

727
EXPE~ENTALPROCEDURE

The designation of two experimental alloys, a commercially available stainless steel and the laser surface alloy
chosen for determining the effect of secondary phases on the pitting behaviour are shown in Table 1. The
chemical composition of the experimental alloys SS Mo 5.4 and SS Mo 6.5 were determined by wet Chemical
Analysis. The composition of Avesta 254 SMO is that of reported in its trade literature and that ofLSA was
determined by SEM-EDAX analysis.

* assumed carbon content as that of base metal ** Not determined

or general microstructure, the alloys were etched in methanolic aqua regia. For revealing secondary phases,
the alloys were etched in modified Murakami's reagent (30 gms potassium hydroxide, 30gms potassium
ferricyanide, 100 ml distilled water) in boiling condition. Further identification of thesephases were done
by X-ray diffraction studies (XRD) in Rigaku diffractometer. The composition of these phases we're
determined by Electron Microprobe Analysis (EPMA) of CAMECA make. Potentiostatic tests were carried
out to carry out in order to elucidate the effect of secondary phases on the pitting behaviour of stainless steels.

RESULTS AND DISCUSSION

Two experimentally alloyed austenitic stainless steels with high levels of molybdenum viz., SS M05.4 & SS
Mo 6.5 and the commercially available highly alloyed austenitic stainless steel Avesta 254 SMO were
compared with the surface alloy LSA-4 which exhibited the highest pitting resistance. The chemical of the
alloys and their Cr eq / Ni eq are shown in Table 1.

For comparing the microstructures, the experimental alloys viz., SS Mo 5.4 and SS Mo 6.5 [which were
solutionised at 1150 0 C for 60 minutes and water quenched], Avesta 254 SMO and LSA-4 were etched in
methonalic aquaregia. The corresponding microstructures are shown in Fig 1 (a), (b), (c) and (d) respectively.
From the microstructure, it is evident that there exists second phase constituents in the austenitic matrix in
the case of experimental alloys and Avesta 254 SMO, whereas no secondary phases was found in LSA-4. In
order to delineate the secondary phases, all the samples were etched with modified Murakamis reagent (30gms
potassium hydroxide,30 gms potassium ferricyanide, 100 ml distilled water) in boiling condition. This
selective etching revealed the presence of sigma phase in the sample which appeared reddish brown under
the optical microscope. The microstructure thus obtained of SS Mo 5.4, SS Mo 6.5, Avesta 254 SMO and
LSA-4 are shown in Fig. 2(a), (b), (c) and (d) respectively. The volume fraction of these secondary phases are
shown in Table 2.

728
729
The composition of the experimental alloys were chosen such that the ratio of the chromium equivalents
(Creq =Cr+ MQ + 1.5 Si) to nickel equivalents ( Nieq = Ni + 30C +0.5 Mn) is always less than 1.35
(Creq/Nieq). This facilitated solidification to take place by primary austenite formation. In spite of these
precautionary measures to have a fully developed austenitic microstructure, the alloys formed secondary
phases due to high tendency of molybdenum for segregation. However the segregation is higher only for alloy
SS Mo 6.5 with molybdenum content of 6.5 wt %. Even the commercially available Avesta 254 SMO showed
the presence of few amounts of secondary phases in spite of its nitrogen content of 0.20 wt % to minimise the
secondary phase formation. The surface alloy LSA-4 in spite of its very high molybdenum contents of 11 wt
% was free from any secondary phases such as sigma and chi. This could be attributed very high
solidification and Coolingrates inherent in laser surface processing.

The energy dispersive X-ray analysis (EDAX) of these phases using JEOL- Scanning Electron Microscope of
alloy SS Mo 6.5 revealed the presence of higher percentage of chromium, manganese and lower nickel
than that of the austenitic matrix as revealed in Figure 3. The electron microprobe analysis (EPMA) was
conducted using CAMECA electron microprobe instrument to determine the composition variation
between the secondary phases and the matrix at randomly selected points. The electron beam was fixed
at a given point of interest and the intensities of chromium, nickel and molybdenum were obtained by
sequentially setting the spectrometer to the requisite position in order to yield maximum count rates. The
reference in~ities were obtained from pure metal standards of Fe, Cr, Ni and Mo under similar
conditions. The composition at different points of the secondary phases and the interface are given in Table 2.

The samples (1 cm2 size) were then subjected to X-ray diffraction (Rigaku X-ray diffractometer) using a
Cu-Ka target at a voltage of 25 kV for further identification of these phases. The diffraction peaks
corresponding to samples SS Mo 6.5 and SS Mo 5.4 were matched with JCPDS X-ray diffraction files of
expected phases in these alloys. It was found that XRD peak lines of sample SS Mo 6.5 corresponds to
sigma, chi and austenite while that ofSS Mo 5.4 to austenite only. This is due to the presence ofvery few
amounts of finer secondary phases (3.95%) in SS Mo 5.4 as the detectable limit in the instrument
employed is only five percent. Fig.4(a) and Fig 4(b) Shows the X- ray diffraction pattern of the abovesaid
samples.

730
Fig 3. SEM-EDAX analysis of the austenite matrix in SS Mo 5.4 (a) and that of secondary phase
(sigma) in SS Mo 6.5 (b).

Fig 4. X-ray diffiaction pattern ofSS Mo 5.4 (a) showing the presence of austenite phase and that
ofSS Mo 6.5 (b) indicating the presence of secondary phases.

731
In order to determine the effect of these secondary phases on the initiation of pitting sites, the samples of
SS Mo 6.5 were subjected to potentiostatic tests. A potential of + 950 mV vs SCE was applied to the
sample for a period of 600 seconds in sea water at room temperature. The samples were then cleaned and
observed under optical and scanning electron microscope. It was found that the pit initiated at the
interface between the secondary phases and the austenite i.e., the si~ phase remained unattacked which
indicated their noble nature in seawater. Fig 5 (a) shows the optical micrographs of the pitted samplt!
and the pit formed at the interface between the sigma phase and the austenitic matrix and Fig 5 (b) .shows
the scanning electron micrograph of the same at higher magnification with sigma phase on the left of the
photograph. The sample was cleaned and the chemical composition of alloying elements ~t the pit were
determined using EPMA and the results are shown in Table 4.

732
Fig 5. Optical micrograph showing the pit formed adjacent to sigma in the interface region (a) and
scanning electron micrograph of the same at higher magnification (b).

Due to the enrichment of chromium and molybdenum in the melt retained between the austenite dendrites, the
last fraction can solidifies eutectically to ferrite and austenite or purely as ferrite. The
interdendritic ferrite has high chromium and moly~um contents and upon further cooling decomposes to
sigma or similar intermetallic phases. It is well known that such phases deteriorate the corrosion
properties. These chromium and molybdenum segregation is not completely dispersed by subsequent hot
rolling but Tllther it is smeared into sheets parallel to the rolling plane. Segregation can be adequately
dispersed only by high temperature annealing [4] . In the present study it was found that soaking at 1150
o C for 150 min followed by water quenching was found sufficient to render SS Mo 5.4 with
minimum secondary phases.

733
This pittIng index (or crevice corrosion index) known as "Wirksumme" is based on parametric
observations . This serves as a guideline for selecting stainless steels for seawater service. As
reported, a value of 38 or higher suggests that the material will have exCellentpitting corrosion resistance in
seawater [5]. The major drawback ill using parameters based on chromium and molybdenum contents is
that they totally ignore the effects of microstructural factors on the breakdown of passivity by pitting or
crevice corrosion.

It is evident from the EPMA data that the composition of alloying elements varies to a great extent at the
secondary phases and interface. Based on this, it is possible to calculate the pitting index of these
secondary phases, interface and the base metal thereby taking into account the microstructural
variations. The pitting index (P.I) value of the secondary phases viz., sigma is found to be very much higher
than the interface region or matrix due to its very high chromium and molybdenum contents. Since thC::
pitting index variation of 74 to 35 was observed between the secondary phases and the interface region
(austenite with reduced chromium and molybdenum), the interface region was found to be susceptible to
pitting and sigma remained nobler to the matrix .

Reported studies indicate that the thickness of the passive films in Cr-Ni steels was found to increase with
increasing molybdenum content of the steels [6]. Also the molybdenum content of the film increased almost
linearly with molybdenum content of the steels which facilitates the formation of Mo (VI)oxide. This
oxide present in passive films. promotes the ability of Cr(Ill) oxyhydroxide film for enhanced pitting
resistance since the stability of Mo(VI) oxide is very high in acid solutions with chloride [tij. Based on this,
it can be inferred that the passive films formed over the interface .region will be of lower thickness and
lower in molybdenum cOntent than the sigma phase and the base matrix. Consequently the formation of
Mo(VI)oxide is also minimised and hence the interface becomes more susceptible to pitting attack by
chloride ions. Sigma, being higher in chromium and molybdenum contents is expected to have a strong,
thick passive film with requisite amounts of Mo(VI)oxide in it and hence nobler to the interface which is
denuded of molybdenum and chromium.

CONCLUSIONS

In highly alloyed austenitic steels with molybdenum contents greater than 5 wt% and higher, brittle
intermetallic secondary phases such as sigma and chi were found to be precipitated .predominantly at
grain boundaries.

The interface region between the secondary phases and the austenite was found to be depleted of
chromium and molybdenum.

The interface region, denuded in chromium and molybdenum has been found to be the favourable sites for
initiation and propagation of pitting in natural seawater.

Laser surface alloying technique has been found to eliminate the formation of secondary phases even with
higher molybdenum contents due to rapid solidification.

734
REFERENCES

I. R.A. Walker," duplex and high alloy stainless steels - Corrosion resistance and weldability"
Materials Science and Technology, VolA, No.2,lan 1988, pp 78-84.

2. H.Brandis & H.Kiesheyer," Influence of chromium and molybdenum on chloride corrosion

of stainless steels in "Stainless steels '84 " , Institute of metals, 1981,pp.217-221.

3. E.Wallis,"Influence of molybdenum content of high alloy stainless steels and of the

precipitation of intermettallic phases on pitting resistance in chloride containing media",
Werkstoffe und Korrosion, Vol. 41, 1991, pp 155-162.

4. Ralph. M. Davison and lames D. Redmond," Practical Guide to using 6 Mo austenitic

stainless steel", Materials Preformance, Dec. 1988

.5. G.L.Swales and B.Todd," Nickel containing alloy piping for offshore, oil and gas
production", NiDi Technical Series, N 10083. Pub. Nickel Development Institute .

.6. K. Sugimoto and YSawada," The role of alloyed molybdenum additions to austenitic stainless
steels in the inhibition of pitting in acid chloride solutions.", Corr.Sci.Vo1.17,1977, ppA25-445.

735
Proc. In\. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Evaluation of Durability Characteristics of Epoxy Poly

Urethane Painting System Through QUV Apparatus
M.P. Varma!, J.L. Khanna2 and V. Murlidharan3
[Add!. Exec. Director Met. & Chern. Dte., R.D.S.O., Lucknow
2Ex. A.R.O. ,Chern.) Met. & Chern. Dte., R.D.S.O., Lucknow
3C.R.A. (Chern) Met. & Chern. Dte., R.D.S.O., Lucknow

SYNOPSIS :

Simulation of weather conditions in the laboratory for

studying the degradation of polymeric coatings has been
attracting the attention of the research workers in the field of
protective coatings. Whenever a new polymeric formulation is
developed, it is important to determine the durabili ty of new
material towards the vagaries of weather condi tions, the
conditions under which the degradation of polymeric coatings is
inevitable. This aspect assumes greater importance whenever
costly protective systems based on epoxy/poly-urethane resin
medium are to be implemented as a regular measure on a large
scale. To generate reliable weatherability data, a co-ordinated
exposure study was conducted in 2 phases with different colour
shades and this paper deals with the systems taken up for the
study & the results obtained and the 'conclusions drawn from the
study.

INTRODUCTION :

In the fast developing' field of paint technology,

numerous polymeric coatings are introduced in the market with
excellent properties which needs to be evaluated properly before
ascertaining the validity of the claims of the manufacturers of
the new products. In this context, the evaluation of durability
characteristics assemes greater significance as all the
polymeric coatings degrade in different levels under the
vagaries of weather conditions'. In order to predict the
behaviour of these polymeric coatings with confidence, it is
necessary to do thorough evaluation of the coatings material in
a laboratory equipment in which the weather conditions can be
simulated and which will provide reliable results that has a
reproducibility to a fair degree. Out of the several versions of

736
laboratory equipment available for this purpose, the QUV
Apparatus is said to be more stringent and less time consuming
for generating reliable data.

With today's accelerated weathering testers, it is

possible to generate reliable' weatherability data in" a matter
of days or weeks provided the mechanisms of outdoor weathering
and use a tester of proper design is -understood properly. The
following three crucial concepts provide the key to successful
accelerated weathering in the Laboratory.
1) To simulate the effects of sunlight,the best approach is to
reproduce just the shortest of the UV wavelengths, the UV-B.
2) The proper way to simulate outdoor wetnessattack is with
hot condensation.
3) Accelerate the effects of UV and condensation by elevating
the test temperature.

The shortest wa~elengths in sunlight are the

ul traviolet, extending down to a wavelength of about 295
nanometers. Even though UV constitutes just 5 percent of the
sunlight falling on the earth, these short wavelengths are
responsible for virtually all the damage to polymers. For this
reason, the lamps in the QUV are designed to produce only UV.
This .is an exceptionally good way to reproduce the damaging
effects of sunlight.
The QUV has been succesful in simulating the effects
of sunlight while reproducing only the shortest wavelengths in
sunlight because of a sound principle: the shorter the
wavelength of light., the greater it's ability to cause
photochemical damage.The Quantum Theory states that light comes
in discrete particles called photons. Photons behave much like
tiny projectiles travelling at the speed of light.The size of a
photon is inversely proportional to wavelength-the shorter the
wavelength the bigger the photon. Photochemical reactions are
caused by a single photon colloiding with a single electron.If
the photon is big enough(i.e.,contain more energy than the
organic bond strength)the electron is knocked out of its orbit
and a reation occurs.For each type of chemical bond, there is a
critical threshold size of photon (and he!lce a threshold
wavelength) to cause a reaction.Light of any wavelength shorter
than the threshold wavelength can break the bond. Therefore,
even within the UV, the shorter wavelengths are more destructive
than the longer UV wavelengths. For laboratory weathering, the
UV-B wavelengths are the most important.

TEMPERATURE ACCELERATES DY :
The destructive effects of UV exposure are accelerated
when temperature is increased. Any laboratory weathering test

737
must provide accurate control of UV exposure temperature, and it
must provide a means to elevate the temperature to produce
acceleration.

WHY CONDENSATION ?

The best way to simulate outdoor wetness attack on

organic material is with condensation. In addition, the
condensation exposure should be conducted at elevated
temperatures to provide acceleration. The old fashined methods
of water immersion, high humidity, fog, or spray do not
accurately reproduce typical outdoor conditions, nor do they
provide the elevated temperatures necessary for proper
acceleration.
The QUV simulates rain and dew by condensing liquid
water directly on the test specimen. Water in the bottom of the
test chamber is heated, filling the chamber with hot vapor and
creating 100 percent humidity at400C to 50oC. Because the test
samples are the actual side wall of the chamber, room air on
their back side cools the samples a few degreeds below the vapor
temperature. This cooling in turn causes condensation on the
front side. There are important reasons why QUV's method of
condensation is the best way to simulate natural wetness
exposure. Materials are wet from dew more frequently and for
longer dl.lrationsthan is commonly supposed. Further more, the
incidence of rain is such that it can account for only a small
fraction of these hours of wetness is dew, or condensation. In
order to condense dew, a material must be cooler than the
surrouding air. More specifically, it must be below the dewpoint
temperature of the air. High humidity can not cause liquid water
to condense unless there is a temperature difference.
Dew is saturated with oxygen. It is often the case that water
is not destructive in itself,but that water cause damage by
bringing oxygen in to intimate contact with the material and
thereby promoting oxidation. Any attempt" to simulate outdoor
wetness must ensure that the water is fully and reliably
saturated with oxygen.The only way to do this is with
condensation.
The fact that dew lies on materials for many hours at a
time is also of crucial significance. This allows the water to
penetrate deep within the material to ciause internal
oxidation.It also allows time for soluble additives to be
leached from the material.And i'n case of paint films,it gives
the water time to permeate through the coating and dissolves
soubles between the coating and the substrate.This creates an
osmotic cell,with the coating as the membrane. The pure condensed
dew is the dilute solution,and the water between the substrate
and coating is the concentrated solution.rhe resulting osmotic
pressure literally pumps water through the coating, causing
blistering and lifting of the coating.A proper simulation of
outdoor wetness must provide wet periods of several hours
duration, rather than a few minutes of spray followed by rapid
dry-off.rhe QUV's condensation cycles meets this requirement.

738
TEMPERATURE ACCELARATES CONDENSATION:

Finally, the fact that materials spend such a large

proportion of their outdoor life wet puts a special burden on
accelerated tests.With .outdoor materials wet eight hours a
day;it is virtually impossible to accelerate condensation damage
by increasing the number of hours of wetness. Some others means
must be used.The QUV accelerates by increasing the temperatures
of wetness to 400e to 500e. This preserves the essential
features of pure condensed dew,while providing a high degree of
acceleration.It is not uncommon to find that a lOoe increase in
condensation temperature results in a doubling of the rate of
deterioration. It is now clear that tests that spray cool room -
temperature water on the sample are incapable of accelerating
outdoor wetness,a problem which is exacerbated by the fact that
these cold sprays also usually give much fewer daily hours of
wetness than is typical outdoors.To accelerate outdoor wetness,
both long periods of wetness and elevated temperatures are
needed.There is definitely a synergistic effect between UV and
condensation.Materials resistant to UV alone or to condensation
alone often fail when subjected to uv and condensation in
combination. A weathering tester which produces both UV and
condensation can take advantage of the synergy between t~ese two
forces.

739
740
CONCLUSIONS :

The painted panels were prepared' by the respective firms

themsel ves . wide variations in the DFT could be observed as
indicated above against the normal DFT of 140-150 microns.
Panels in duplicate were exposed in the QUV Apparatus of all the
participating firms at their premises simultaneously with the
test commencing on the same date and concluding on the same
date. The data given above are representative values of minima
and maxima obtained during the evaluation of the exposed panels.
The results obtained indicates the following :
1) In case of pale cream shade, the colour change in case of
firm D was rated Fa which in turn has shown the highest
Delta E value, while in case of firms A,B & C, the colour
change was rated D9 having low Delta E value.
2) In case of post office red shade, the colour change in
case of Firm D was rated F7 which in turn has shown the
highest Delta E value while in case of firms A, B & C,
the colour change was rated D9, D9 & D7-8 and their Delta
E value also ~hows increasing trend in the same order.
3) The % gloss retention of firm D in case of pale cream and
post office red shade was lowest when compared with the
values of firms A, B & C.
4) In case of gulf red shade, the colour change in case of firm
E was rated F5 which in turn has shown the highest Delta E
value and lowest gloss retention. In general all the panels
exposed have shown fading except firm C which has shown
darkening (D9) yet the Delta E value was on par with firm
A & B. Delta E value increases with increase in fading and
colour change.
5) In case of oxford blue. shade, all the exposed panels except
firm C have shown fading and the Delta E value. increase
with the increase in fading and colour change.
6) In general, pale cream and post office red shades tend to'
darken, gulf red and oxford blue shade tend to fade.
7) The data obtained shows that it is possible to attain high
percentage of gloss retention if genuine pigments are used
in the paint formulation.
8) While spotting was observed in case of pale cream shade &
gulf red shade, micro blistering. was observed in oxford
blue shade.
9) The performance of the system of firm D in phase. I and
firms D & E in phase II is not considered satisfactory.

741
Prol;. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

High Temperature Resistant Slurry

Based Coating for Steel
M.N. Singh and Inder Singh
National Metallurgical Laboratory,
Jamshedpur-831007, India

ABSTRACT

The current teclmologies for high temperature protective coating based on composite systems, such as
complex oxides, silicide, aluminides, carbides and nitrides etc.are meant for high temperature service
'alloys,which are not easily removable from meal surface

In the present investigation, studies were made to provide a barrier type of protective coating over steel
surface. the coating consisted of metallic aluminum powder, asbestos powder, cobalt oxide, kaoline, Alz~
Tio, and ZrQ, and the binders. The binders, such as aluminium phosphate, sodium silicate, ethyl silicate,
modified sodium silicate and Ivory-400 were used.

It was aimed to produce a slurry based coating which would be strippable as. desired in subsequent
processing. The coating particulates were added in varying amo,unt varying from 1-10 % by weight of the
binder.

Mild steel sample of 50 mm x 2 mm were used for the test. The coating was applied over the steel
samples and dried for 24 hours in open air before the test. The coated and un-coated steel sampleS were
exposed at temperature of 500-800 C for 2-4 hours. After the over of desired period of exposure, the samples
were taken out, allowed to cool in air and pickled in inhibited acid for 5-10 minutes for the removal of the
scale. The loss in weight per unit surface was expressed as oxidation/scaling loss. The amount of protection
given by the coating was calculated as usual.

The modified silicate binder is found to be superior to both sodium silicate and ethyl silicate because it
has greater spreadability and better compatibility with respect to sodium silicate. Aluminium phosphate dOes
not provide good adherence to the substrate. Ivory-400 available in the market is also superior because of its
greater spreadability, stability and adhesion as compared to the Aluminium phosphate. The data are discussed
in detail.

742
INTRODUCTION

In industry, various types of stee1 articles Wldergo exposure at higher temperatures during which thick
oxide scales form on the surface. It is well known that high temperature oxidation is one of the most injurious
types of corrosion which contributes to the national economic loss, safety and conservation of metals and
alloys. Corrosion protection by high temperature coating is one of the known techniques adopted allover the
world. Now-a-days ceramic additives to the binder play an important role in the protection of steel at higher t
emperatures. The current technology for high temperature protective coating are based on composite systems
such as complex oxide, silicides, aluminides, carbides and nitrides which are used for high temperature service
alloys:9.
The need for protective coating based on refractory metal oxide has been perfected through imperical
development. Still considerable research is Wlderway to improve bond coats and properties of the ceramics2.
Protection to steel articles during short term high temperature exposures can be met with such coating systems
which are, no doubt,protective, but also removable by easy means. Phosphate, silicate and Ivory-4oo binders
could be preliminary choice because of easy availability and low cost. A number of high temperature resistant
coating particulates can be incorporated into these binders depending on their mutual cpmpatibility. It was
aimed to produce a slurry based coating which would be strippable as desired in subsequent processing.

The present study discusses the development of the corrosion resistant slurry based coating and its
behaviour at high temperature (800 C). The coating provided a barrier type of protective coat;ing over stee1
surfaces. For this purpose, metallic aluminium powder, asbestos powder, zinc oxide, Zr<h, Ti~ cobalt oxide
and kaoline were introduced into the binders, namely aluminum phosphate, silicates and Ivory-4oo ..

EXPERIMENTATION

Mild steel sample of 50 mm x 2 mm were cut from cold rolled sheet polished with "000" emery paper,
degreased by rubbing with MgO paste, washed with rurming water, dried and stored in a dessicator for 24
hours before use. Various types of particulate materials(-200 mesh size) were selected for incorporation into
the binders as mentioned earlier. The coating particulate were added in varying amount ( 1-10 % ) by weight
of the binder. The binders uSed were aluminum phosphate, sodium silicate, ethyl silicate, modified silicate and
Ivory-400.

The aluminium phosphate binder was prepared by treating aluminium sulphate with tri-basic sodium
phosphate. Commercial grade ethyl silicate and sodium silicate binders were also used, the latter having
silicate to alkali ration of 2.3:1. A modified silicate solution was prepared by mixing about 1-10 % absolute
alcohol to the sodium silicate solution. The coating particulates were 'mixed with the binder to from a slurry
which was applied over the steel. Each sample was weighed before and after applying the coating ..

Excessive swelling of the coating containing silicate binders was observed which was due to rapid
dehydration immediately after the samples were put inside the furnace .. This could be prevented by preliminary
treatment of the coated samples at 100-300 C. But this operation was fOWld to produce a coating which was
very difficult to remove after exposure to high temperature by acid pickling. So only air drying for 24 hours
was followed. The coated and Wlcoated steel samples were suspended inside the furnace at a temperature of
800 C for 2 to 4 hours for observing the performance of the coating. After the desired period of exposure of
samples at 800 C was over, the samples were taken out, allowed to coolin air and pickled in inhibited
hydrochloric acid for 5-10 minutes for the removal of the scale.

743
744
CONCLUSIONS

A formulation incorporating both aluminiwn powder and zinc oxide as particulates and aluminiwn
phosphate and sodiwn silicate as binder provides protection to steel to the extent of 35 % at a temperature of
8000 C for 4 hours.
1. Addition of metallic aluminiwn powder to binders imparts scaling resistance. This may be
due to better adhesion of aluminiwn oxide with metal surface in presence of binders.
2. Scaling resistance improves with the use of modified silicate as binder
3. The modified silicate binder is found to be superior to both sodiwn silicate and ethyl silicate
because it has greater spreadability and better compatibility with respect to sodiwn silicate .
Aluminiwn phosphate does not provide good adherence to the substrate. Ivory-400 binder is
superior to AlP04 but fails at temperature of above 7000

745
REFERENCES

1. Harrison, W.N.,Moore,O.G.,Richmand,T.C., "Ceramic coatings for high temperature

protection of steel", lRes. Nat. Bur. Std. Report., 1775. Marcl1,1947,pp. 293-307.

2. Stringer,J.,Vishwanathan, Proceedings of ASM, Materials Congress Materials Week,

Pittsburgh,PA, 93, Oct.,1993. pp. 17-21.

3. Strafford,KN.,Datta,P.K,Govani,C.G.,Coating and surface treatment for corrosion and wear

resistance.,Ellis Horward Limited, 1984.

4. Singhal,S.C.,High temperature protective coating conference proceedings, AIME,1982.

5. Lang,E., Coating for high temperature application., Applied Sc., Publishers, 1983.

6. Tolly, 'G., lApp. Chern.,1,86, 1951.

7. Holmes,O.R., Rahmat,A., Materials and coatings to resist high temperature corrosion,

.Applied Science Publication Limited, London, 1978.

8. Samsonov,G.V.,Epik,A.P., Coating for high temperature materials. Part. I

Bibeant,WA,Bark,E.S., Part- n
Lews,O.H. Part -m., H.H.Hanswer Plenum Press, 1966.

9. Vargin,V.v.,Teclmology of Enamels.
Maclaren and Sons Limited, London, 1965.

10. Singh. M.N.,Singh, Inder, Pandey,J.L., High temperature corrosion resistant coating on steel
for short term applications, Anti-Corrosion Methods and Materials, U.K, Vol. 44, No.
2, I997,pp.90-93.

11. Rhys-Jones, T.N.,Toriz,F.C., High Temperature Teclmology, Vol. 7, No. 2,1989, pp.73-81.

12. Taylor, R.,Brandon, lR., Morrell,P., Surface and Coating Teclmology, Vol. 50, No.
2,1994,pp.141-9.

13. Van DC Voorde,M.H., Hocking, M.G., Vasan tas race,VA, Comprehensive review on the
development of ceramic coatings for thermo-mechanical applications, High Temperature
Materials and Processes, Vol. 7,No. 2 & 3, '1986, pp. 107-21. .

746
Fig. 1. Scaling loss of mild steel without coating

747
Fig. 2 Effect of amount of particulate in the sodium silicate binder
on the % protection

748
Fig. 3 Relation between % protecrtion and time of exposure of Aluminium + Zinc Oxide
coating in sodium silicate binder at 8000 C.

749
 Fig. 4 Effect of amQunt of coating particulates on % protection

ACKNOWLEDGMENT

The authors record their sincere thanks to Prof. P.Ramdumdra Rao, Director, NML, ]amshedur for
giving pennission to publish this paper.

750
 Preventing Reinforcement Corrosion-
Corrosion. Resistant Rebars from SAIL
Vinod Kumar" V.K. Singh" P.K. Bhor" A.K. De" B.K. Panigrahi"
A. Bhattacharya" A.K. Mukherjee2, S.K. Chaudhuri1 and S.K. Jain2
'R&D Centre for Iron & Steel, Steel Authority ofIndia Ltd., Ranchi, India
2Bhilai Steel Plant, Steel Authority of India Limited, Bhilai, India

Abstracts Work carried out .at Steel Authority of India Limited during the development of low
.alloy rebars having superior corrosion resistance as compared to ordinary rebars has been presented.
The rebars possess high yield strength (in excess of 415 MPa), good elongation, and bendability
achieved by water quenching the rebars immediately after finish rolling using Thermex or Thermo-
coil process. and are characteri;zed by the composite microstructure - a tempered martensite rim at the
surface and a ferrite + pearlite core. The rebars also exhibit good weldability due to low carbon

.
equivalent.

INTRODUCTION
The reinforcement bars used to strengthen the concrete structure are prevented from corrosion
by the formation of a thin and adherent passive oxide film in the high pH environment of
coricrete[l,2]. Thehigh pH (usually 12.5 to 13.5) is achieved by the formation of calcium hydroxide

during hydration of cement and is good enough to maintain and protect the oxide film for sufficiently
long time. However, presence of carbon dioxide and moisture in the environment form a weak
carbonic acid which react with the calcium hydroxide in the concrete mix and forms calci~
carbonate lowering the pH and in turn its passivating ability[3]. Passivity may be lost if pH fall dUll:
to carbonation to the region of 10.5 - 11.2. Calcium carbonate deposits in the pores of the paste and
since it occupies a greater volume than the hydroxide, the initial effect is to partially block the pores
and give a denser paste. However, if the reaction goes to completion, pore water pH is reduced to 8.3
and certain products of hydration in the paste notably basic silicates, basic aluminates and basic
ferrites become unstable and may begin to decompose. Steel no longer remains passive and with the
availability of oxygen and moisture is open to corrosionprocess[4]. However, it has been observed
that lowering of pH of the concrete cover due to carbonation is not beyond 0.5. inch. Therefore, if the
cover thickness is less, it may destroy the passive film[5].

In addition to this, a more serious problem arises with chloride ingress particularly in the
coastal regions since even in concrete with low permeability, chlorides in the marine environment or

751
sea water can penetrate at a much faster rates well beyond the usual depths of concrete cover within a
time shorter than the life time of the structure [4]. Pitting corrosion caused by the chlorides is most
harmful. The chloride ions are able to destroy locally the passivated film even in an uncarbonated
concrete cover. A very small anodic surface is then facing a larger cathodic surface still coated with
the passivating layer. These unfavorable surface conditions cause highly accelerated and deep
corrosion penetration into the steel. Chloride is used in an intermediate chemical reaction but at the
end is not consumed and acts as a permanent catalyst in the corrosion process. Furthermore, the
hydrochloric acid simultaneously formed reduces the pH value at the corrosion pit. If the steel
reinforcement are corroded by chloride penetration then no superficial remedial treatment is available
at present. The only possible solution is to replace the steel or rebuild it after demolishing the
element[ 4].

Chloride ions may come from the deliberate additions of calcium chloride in the cement as
accelerator or from the environment (presence of chloride ions in the marine! coastal regions or from
de-icing salts). T.he combined effect of carbonation and the presence of chloride can provide a very
corrosive environment for the embedded steel. The corrosion products thus formed are more
voluminous than the parent material[2], their formation and deposition on the bars results in
expansive pressure in the surrounding concrete leading to cracking of the concrete. Obviously, the
formation of such cracks accelerates further deterioration[ 6}

In recent ye~s, extensive work has been carried out to develop protection techniques to
prevent reinforcement corrosion. These include rebars with better corrosion resistance[7Jlike,
microalloyed rebars, dual phase steel rebars, stainless steel rebars, and low-alloy steel rebars. These
rebars do not require any special care during transportation, storage, fabrication, placement and even
construction. Moreover, it does not require any skilled labour, capital investment, design changes,
etc.

CORROSION RESISTANT REBARS FROM SAIL

SAIL has also developed low-alloy high strength rebars (yield strength in excess of 415 MPa)
having superior corrosion resistance[B.,9]compared to conventional rebars. These rebars are produced
using rapid water quenching systems; like Thermex or Thermo-coil process. Newly developed TMT
rebars offer following advantages:

Higher useful strength level due to distinct yield point,

high ductility, good bendability and superior weldability due to low carbon equivalent,
superior corrosion resistance,
savings in steel consumption,
indirect savings during transportation, fabrication, welding, etc. due to less material handling, and
higher yield and easier epoxy coating, whenever required due to less scale generation as
compared to con.vention cooling.

PRODUCTION ROUTE

Steel is made in 250' tons twin hearth furnace. Cu is added in the bath while o~her alloy
additions are made in the ladle. Ingot casting is carried out and the samples are collected while

752
teeming for chemical analysis. Ingots are reheated ata temperature of 1340 - 1350C for 2 hours and
are rolled into blooms and then into ~illets. Billets can also be produced through continuous casting.
The billets are reheated in pusher type reheating furnaces at a temperature of 1200IOC and are
further rolled into rebars. Finish rolling is carried out within a temperature range of 98020C. The
hot rolled rebars are immediately water quenched using Thermax (diameter : 12 - 40 mm) or
Thermo-coil (diameter: 8 & 10 mm) process followed by air cooling on the cooling bed / loop
conveyor.

PRODUCT CHARACTERISTICS

Chemistry
Specified chemical composition is given in Table 1. Addition of corrosion resistant alloying
elements, like Cr, Cu, Ni, etc. in these rebars improves the corrosion resistance by making the initial
iron oxide film more dense and adherent. Though, alloying additions improves corrosion resistance,
their amount is restricted due to cost of production and to keep the carbon equivaldnt low.

Microstructure

Typical macrostructure of a TMT rebar revealed a dark rim and bright core (Fig. I).
Microstructural observation made through optical metallography .revealed dark rim as tempered
martensite (Fig.2a) and bright core as ferrite + pearlite (Fig.2b), essentially responsible for a tough
structure. The formation of such a composite microstructure can be explained as follows. The
thermo-mechanical treatment comprises two stage cooling of the hot rolled rebars i.e. primary
cooling and secondary cooling. Primary cooling involves intense cooling'ofhot rolled rebars through
rapid water quenching provided immediately after last finish rolling stand. Primary cooling ensures
martensite transformation at and near the surface of rebar, while the core remains in the austenitic
temperature range. The depth of IT).artensiterim can be controlled by intensity of cooling (the
temperature below Ms) and residence time in the cooling pipe. The heat flux entrapped at the core
diffuses out during secondary cooling and tempers the outer martensitic rim (Fig.2a), while core
transforms to ferrite"pearlite structure (Fig.2b). The composite microstructure thus evolved is
responsible for high yield strength and elongation.

Mechanical Properties and Bond Strength

These rebars possess a unique combination of strength, ductility and bendability (Table 2)
which is significantly higher than the stipulated requirements of IS: 178(:1-1985.These' rebars also
meet the bond strength requirements as per IS: 1786-1985.

Corrosion Resistance
Corrosion resistance can be improved by alloying and / or by microstructural contro
these options have been incorporated in the production of SAIL TMT rebars to ensure good
corrosion resistance. As stated earlier, alloying additions improves corrosion resistance, their amount
is restricted due to cost of production and to keep the carbon equivalent low. Therefore, the extent of
improvement in corrosion resistance of the newly developed low alloy rebars can not be compared
with high alloy stainless steel rebars which cost 6-8 times higher than low alloy steel rebars.

753
 A number of corrosion tests have been carried out to study the corrosion behaviour of these
rebars vis-a.vis ordinary TMT rebars having no alloying elements. These include corrosion tests on
virgin rebars as well as on embedded rebars in concrete and in different environments like 3.5%
NaCi solution, cement-water suspension with and without chloride ions and in tap-water.

Corrosion Behaviour of Virgin Rebars

Immersion, salt spray and potentiodynamic tests were conducted in 3.5% NaCI solution to
assess the corrosion rate of the newly developed TMT bars with respect to ordinary TMT bars and
the same has been reported in the form of corrosion rate indices (CRI) as ratio of corrosion rate of
plain C-Mnand corrosion resistant rebars (Fig.3). A perusal of this figure revealed that CRI varted
between 1.45 to 2.12 showing superiority of newly developed rebars over the ordinary TMT rebars.

Time-potential measurement of newly developed rebars as well as ordinary rebars carried out
in cement-water suspension is shown in Fig.4. A perusal of this figure revealed that the potential of
corrosion resistant rebars initially decreased from about -160mV to -300mV and remained in the
range of -200m V to -260m V upto about 90 days, there after moved towards more positive values. In
the case of conventional rebars potential moved from -350m V to -450m V and stabilized in the range
of -300mV to -350mV (some values showing more positive potential than -300mV). The shift of
potential of about 100m V (even more in the later stage) in the case of corrosion resistant rebars
towards more positive side indicates its better passivity as compared to conventional rebars. In the
presence of chloride ions, potentials of both plain C-Mn TMT rebars as well as corrosion resistant
rebars have been shifted to more negative values due to a decrease in the pH value in the presence of
chloride ions. Though, the difference of potential between the two types of rebars narrowed down to
an average of about 50m Vto 60m V, corrosion resistant rebars still maintained less negative potential
showing its superiority over the plain C-Mn TMT rebars.

Corrosion Behaviour of Concrete-Embedded Rebars

Time-potential measurement of concrete-embedded rebars in tap water for about 60 days and
then in 3.5% NaCI solution revealed similar observation as in the case of virgin rebars. Though, the
potentials of both types ofrebars were in the passive range in tap water, the corrosion resistant rebars
showing substantially higher positive potential (even close to 0 mY). In the 3.5% NaCI solution also,
the corrosion resistant rebars indicated better passivation though the difference between the two types
of rebars narrowed down.

As seen above, all corrosion tests have indicat.ed superior corrosion resistance behaviour of
the newly developed TMT rebars as compared to the ordinary TMT rebars.

Weld ability Behaviour

The weldability of TMT rebars (8mm) was evaluated by shielded metal arc welding using
copper being electrode (TENSOTHERME-Cu). Single and double lap joints as well as double V -butt
joints were made at low heat input (1-2 kJ/mm) without pre-heat. Tensile tests were done on the both
welded and unwelded TMT rebars. Ultimate tensile strength of both butt-welded as well as lap-
welded TMT rebars were found to be more than the ultimate tensile strength values of un welded
TMT rebars (Table 3). In all the tests, fracture occurred in the base metal. Therefore, the newly
developed rebars Can be welded without loosing the strength ..

754
 CONCLUSIONS

Based on the above findings, following conclusions can be drawn :.

The microstructure of the rebar comprised of a rim of tempered martensite at the surface and
ferrite + pearlite in the core.
Newly developed rebars showed superior corrosion resistance as compared to oridnary TMT
rebars under different test conditions.
The ultimate tensile strength of the welded TMT rebars was higher than the unwelded TMT
rebars. Fracture occurred in the base metal.

REFERENCES

1. c.L. Page and KW.J. Treadway, Nature 297,109-114(1982).

2. P:K. Mehta, Concrete: Structure, Properties and Materials, Prentice Hall, Englewood Cliffs,
NJ, 153(1986) .
.3. 1. Solomon, M.F. Bird and B. Phang, Corrosion Science, 35(5-8), 1649-1660(1993).
4. P.C. Bhasin, Trans. of the SAEST, 23(2-3),101-107(1988).
5. H.KCook and W.J. McCoy, "Chloride Corrosion of Steel in Concrete", ASTM STP 629, 20-
29.
6. T. Uonoto and S. Mishra, ACI SP-I09, 127-146(1988).
7. Vinod Kumar, Corrosion Review, in press.
8. Vinod Kumar, Corrosion Prevention & Control, Oct., 135-139(l996).
9. Vinod Kumar, Project Report Nos. R&D 21:02:2452:01:95 and R&D 21:02:2635:01:97, R &
D Centre for Iron & Steel, SAIL, Ranchi ..
10. Vinod Kumar, P.P. Rao and A.K. Patwardhan, Materials Performance, 30(8), 72-74(1991).

755
Fig. I Macrostructure of a TMT rebar

756
Proc. Int. ConL on Corrosion CONCORN '97
December 3-6. Mumbai. India

Monolithic Chemical Resistant Floor Covering

Based on Non-Isocyanate Polyurethanes
Oleg L. Figovskyl, Leonid D. Shapovalov2 and Nellv Blank2
lEurothec, Ltd., Rockville, USA
2Chemonol Ltd., Nesher, Israel

Durability and chemical resistance of monolithic floor covering dep-

ends on properties of a.binder Polyurethane compounds allow to provide
long stability of monolithic covering and it's high crack stability. Existing
polyurethanes have good mechanical properties, but its hydrolytic stabyli-
ty isn't high and materials have a lot of pores, for producing polyurethanes
are used toxic isocyanates. Nonisocyanate polyurethane materials are fo-
rmed by the reaction between olygomeric cyclocarbonates and primary di-
and polyamines. Materials are without solvents. An intramolecular hydro-
gen bond is formed through the hydroxy group at the ~-carbon atom of
the polyurethane chain, that are extremely promising raising the hydrolytic
stability of heterochain polymers.
Materials haven't pores because the reaction of its formation haven't
sensed to the moisture of fillers or surfaces and the technology of its
synthesis is ea;;y and ecology safety.
The chemical resistance of materials containing intramolecular hydrogen
bonds is 1.5-2 times greater than that of materials of similar chemical stru-
cture without such bonds. Nonisocyanate Polyurethane Materials could be
applied for monolithic floor-covering. Tensile strength and deformation of
such materials keep place with standard isocyanate polyurethanes but che-
mical resistant is better because penetrability is 3-4 times less. Using of
aliphatic polycyclocarbonates (pCC) lead to reception of fle-xible and
crackstable monolithic coveri.ngs with low hardness. Using of aromatic
PCC lead to reception of monolithic floor covering with increased hard-
ness, durability. Modification by aliphatic PCC lead to improvement of
wearstability and elastic properties. M~:molithic coverings are very homo-
geneous, have extremely high wearstability and high chemical resistant
It is created the general conception of such materials and found out the
interconnection between structurai parameters and properties of the
materials It is created monolithic floor coverings with high chemical
properties, with high fire resistance and minimum absorption of the toxic
and radioactive contamination

757
Applications for polyurethane materials have increased significantly over other kinds
of thermosetting polymer materials. While their mechanical properties are sufficiently
utilized, conventional monolithic polyurethanes are porous and have poor hydrolytic
stability and insufficient permeability. The involvement of toxic components, such as
isocyanates, in their fabrication process rendering production extremely toxic and
dangerous.

Polyurethanes have an inherent weakness on account of their molecular composition.

Within their polymer structure are hydrolytic ally unstable bonds making the material
wlnerable to environmental degradation. By modifying the structure of the polymer,
a new and promising method of raising hydrolytic stability is introduced and readily
displayed in nonisocyanate polyurethane - a modified polyurethane material with
lower permeability, increased resistance properties and safe fabrication processes .

. Network nonisocyanate polyurethanes are formed from the reaction between

cyclocarbonate olygomers and primary amine olygomers [1, 2]. This reaction carbon
forms an intramolecular hydro'gen bond through the hydroxy group at the J}..carbon
atom of the polyurethane chain as illustrated below:

Quantum-mechanical calculation, IR and N1i1R spectroscopic investigations have

confirmed the stability of such a ring [3]. The blockage of carbonyl oxygen
considerably lowers the susceptibility of the whole urethane group to hydrolysis.
Moreover, materials containing intramolecular hydrogen bonds display chemical
resistance 1.5-2 times greater in comparison with materials of similar chemical
structure without such bonds.

Basic cyc10carbonate olygomers are formulated by bubbling the carbon dioxide

through epoxy liquid olygomers in the presence of a catalyst, and by interacting
olygomeric chlorinehydrine ethers with carbonates of alkaline metals or olygomeric
polyo1s with acid chloride of carbonic acid. The present investigation uses main
cyclocarbonate and primary amine olygomers, as shown below in figures 1-4.

Where one of the possible side reactions is the carbonization of amines in air, two
parallel reactions were studied: amine CO2 and amine cyclocarbonate. The cc:mstants
of their reaction velocities (Kl and K2) and relative reaction rates were
calculated with the parameters listed in table 1.

758
Table 1. Data o/the chemica/kinetic o/reaction between olygomers,
according Fig. 1-4

760
 Nonisocyanate polyurethanes have superior properties over conventional
polyurethanes. Their tensile strength and deformation are similar to those of
conventional isocyanate polyurethane materials, but display chemical resistance
properties 30-50% greater and have significantly reduced permeability: three to five
times less than conventional isocyanate polyurethane materials On account of their
unique molecular composure, unlike conventional polyurethanes that have a very
porous structure, nonisocyanate polyurethanes form into a material with practically no
pores, and that is why they are not sensitive to the moisture in surfaces or fillers
.upon formation. As a result, nonisocyanate polyurethane materials exhibit superior
resistance to qegradation, making them ideal for applicatiqns in crack resistant
composlte materials, chemically resistant coatings, sealants, glues, etc

Because nonisocyanate polyurethanes do n9t contam the highly toxic compound,

isocyanate, material synthesis can be carried Out in a safe and nontoxic manner
Furthermore, nonisocyanate polyurethanes can be easily produced with material
hardening usually occurring at normal temperature.

Table 2 lists the mechanical properties of nonisocyanate pol'fUIethanes for figures 1

and 2. Each material is composed or 150 weight parts (w. p) of quartz filler for 100
w.p. of the binder

Table 2. lltJechanical propertiesoffiIIed nonisocyanate polyurethanes

*crt- tensile strength, MFa

ep- elongation, %

Nonisocyanate polyurethanes have advantages over ~onventional polyurethanes that

can be efficiently utilized in applications such as nonporous sealants, glies and
coatings [2, 4].' Siloxane-p.olyurethane sealants, fabricated from siloxane
pent~cyclocarbonate olygomers, displayed the same high adhesion, elasticity and

761
Tae chemical resistance of noIrisocyanate polyurethanes can be increased by adding
inorganic powdered substances during the fabrication process [3]. The substances
selectively interact v.itb. water and aggressive medium (i.e., acids,aL"'<:alisand salts)
by forming a system. of high-strength hydrate complexes into durable inorganic
adhesive cements. As the substances interact with the medium, hydrate complexes
Ccrystalhydrates) form in the defects (i.e., micropores, microcracks) of the materiaL
This process acts to "repair" the defects of the material increasing its strength. As the
crystalhydrates are formed., the volume and the ,contact specific surface of an active
additive expand into the constant volume of the polymeric matri"'(. Due to the
increased specific surface of the active filler and formation of a material with viscous
features, the adhesion on the polymer-crystal boundazy becomes stronger. Figure 5
illustrates the effect of increasing chemic3..l resistance for nonisocyanate polyurethane
mastics for monolithic flooring.

Fig. 5 Data of chemical resistance of nonisocy(inate polyurethane'

762
The protective properties for water-dispersion nonisocyanate polyurethane coatings
can be increased by using the same type of additives used to increase properties in
conventional polyurethane water-dispersion coatings [5].

Network nonisocyanate polyurethane materials, which have been described above are
another by structure, and properties in comparison witli linear polyurethanes which
are prepared by reacting a moiar excess ofbis-carbonate of a bis-glycidil ether of
neopentyl glycol or 1,4-cyc1ochexanedimethanol with a polyoxyalkylendiamine. [6].

Conclusions

Nonisocyanate polyurethane is' a modi.fied polyurethane material with tower

permeability, increased resistance properties and safe fabrication pr~ceSses
when compared to conventional polyurethanes. Nonisocyanate polyurethane
network polymers are formed from the reaction between olygomeric
cyclocarbonat~ and primary amines. The function of both olygomers have a
significant impact on improving structural and appliCation properties of
nonisocyanate polyurethanes. As a result, nonisocyanate. polyufethanes can be
effectively utilized in manr industrial applications.

References:
1. Blank R, Figovsky O. Nonisocyanate Polyurethan~ Glues for Jointing'R.einforced
Plastics. II Proceedings of Intemational Adhesion Symposium.
Tokyo, Japan, 1994, pp. 87-88.
2. Shapovalov L., Blank N., Tartakovsky A. Nonisocyanate Polyurethane for
Protective Coatings. II Abstracts of the 2nd Conference of the Corrosion Forum-
NACE - Israel, Tel-Aviv, Israel, 1996, No. 1.1.3.
3. Figovsky O. Improving the Protective Properties of Nonmetallic Corrosion-
Resistant Materials and Coatingsll Journal of Mendeleev CheInical Society, N.Y.,
USA, 1988, Vol. 33, No.3, pp. 31-36.
4. Kreidlin 1., Figovsky 0., Rappoport L. Mastics for floorings based on
nonisocyanate polyurethanes. II Building materials, Moscow, USSR, 1977,
No.5, pp. 22-23. (Russian.). .
5. Figovsky 0., FiskinZ. Ways of increasing chemical resistance ofpolyiners. II
Proceedings of Seminar" New Chemical Materials & High Technologies. Tel-Aviv,
Israel, 1995, pp 11-17. '
6. Crawford W, Marquis E, KleinLiquification ofbiscarbonates ofbis-glicidil
ethers. US-patentN 5340889. 1994

763
Proc. Inl. ConI'. on Corrosion CONCORN '')7
Deeemher 3-6, Mumhai. India

M
Remedial Measures for the Concrete Lining Inside the
c Head Race Thnnel of Nathpa-Jhakri Project (H.P.)
Against the Corrosive Action of Hot Water Spring
Murari Ratnam, S.B. Suri and K. Venkatachalam
Central Soil & Materials Research Station,
Ministry of Water Resources,
New Delhi-I JO 016, India

ABSTRACT

For long it has been a well known fact that deterioration

mechanism aggressive water on concrete is due to important
parameters such as pH, Chlorides, Temperature, Sulphates,
Magnesium, Ammonium etc. in the water. Individual effect of each
one of the parameters on concrete is also well understood and
documented in literature. Contribution of external factor like wet-
dry cycles, hydraulic head etc. has been studied by many research
workers. Code and practices hitherto available have addressed
themselves to some combinations of the above factors, but not the
cumulative effect of all the parameters. An effort in this
direction has been made by J.J. Basson and B.J. Addis in their
approach paper published in the special ACI publication SP-131,
"Durability of Concrete", 1992. It takes into account all the
relevant factors and categorizes water into various classes.
Depending upon the class of water, suitable remedial measures for
ensuring durability of concrete have been suggested. Further, the
corrosion of reinforcement "has peen attributed to chloride ions.
This paper especially takes into account the high temperature
effect of chloride ions in water on concrete and the reinforcement.

The above approach has been applied in the upcoming 1500 MW

Nathpa Jhakri Project located in the state of Himachal Pradesh,
India. The 27.3 Km long Head Race Tunnel under construction is
facing the problem of hot water springs in a stretch of 2.1 Km
which is likely to affect the long term durability of concrete
lining. Temperature of spring water as high as 64C has been
recorded at some locations. In the ongoing exercise of assessing
the effect of aggressive spring water encountered in the tunnel,
the approach of the above mentioned authors has been found to be
handy and useful in suggesting appropriate remedial measures for
~oncrete in the problematic reach of the underground tunnel under
r:eference.

764
INTRODUCTION

It is a well known fact that a combination of chemical

parameters in water affect the long term durability of concrete.
The effect of these chemical parameters may lead to the
deterioration of concrete and thus bring down the useful life of
the structure. The chemical attack can be both on the concrete as
well as on the reinforcement. The effect of individual parameters
such as pH, chloride, sulphate, magnesium, ammonium, sulphides is
well understood and document'ed in literature. Some of the codes and
practices such as International Commission on Large Dams bulletin,
Langelier Index, French National Code etc. have attempted to
categorise the water in contact with the concrete taking into
consideration combination of two or three chemical parameters only.
These codes and practices do not take into account cumulative
effect of all the parameters, effect of high temperature and the
flow condition at the site. These codes and practices though useful
in categorising the degree of aggressivity are not in a position to
offer any solid remedial measures to overcome the problem.

An effort to overcome the limitations mentioned above was made

by J.J. Basson and B.J. Addis in t~eir appr9ach paper published in
the special ACI publication SP-131, "Durability of Concrete", 1992,
which takes into consideration cumulative effect of all parameters,
including effect of temperature, flow condition. Based on these,
the degree of aggressivity of water is arrived at. Suitable
remedial measures such as type of cementitious material, wlc ratio,
cement content, concrete cover for reinforcement and coatings are
suggested in this approach paper.

The utility of this approach paper was put to test for the
upcoming 1500 MW Nathpa Jhakri Power Project, H.P. where a 27.3 Km
long head race tunnel is under construction. In a brief stretch
(2.1 Km) of this 10.5 m dia tunnel, hot water was found seeping.
The inside of the tunnel is proposed to be lined with 60-70 cm
thick concrete. Due to this hot water seepage, long term durability
of concrete become a subject of immediate concern to the project
authorities. Suitable precautionary measures were required to be
suggested before undertaking the construction of the lining. The
approach paper of Basson and Addis was'used for suggesting remedial
measures. Based on the water quality studies conducted over a
period of time the possible type of attack on concrete could be
discerned. Suitable remedial measures were suggested based on the
recommendations made in this paper.

This paper brings out the usefulness of the approach in

understanding the corrosive attack of water on concrete.

CHEMICAL INVESTIGATION

Sampling point at regular intervals were selected during the

inspection of the tunnel. Water samples collected from these
location were chemically analysed as per the procedure given in
Table 1. In all, seven observations .were made. Derived parameters

765
such as Corrected Leaching Corrosion Index (CLCI), Corrected
Spa-llingCorrosion Index (CSCI), Corrected Overall Corrosion Index
(COCI) and Chloride Corrosion Sub-Index were calculated on the
basis of chemical data (Table 2) .

ASSESSING AGGRESSIVENESS

Aggressive Chemical Exposure

Concrete can be made which will perform satisfactorily when

766
exposed to various atmospheric conditions, to most waters and soils
containing chemicals, and to many other kinds of chemicals. There
are, however, some chemical environments under which the useful
life of even the best concrete will be reduced. Understanding
these conditions enables measures to be taken to prevent or reduce
deterioration. There are numerous factors which influence the
abi{ity of concrete to resist deterioration, some of which are
shown below.
Factors increasing Factors decreasing
deterioration deterioration

* Higher temperatures * Lower water-cement ratio

* Increased fluid * Proper cement type (in

velocity some circumstances)

* Poor consolidation of * Lower absorption

concrete
* Poor curing of concrete * Lower Permeability

* Alternate wetting pnd

drying

* Corrosion of reinfor-
cing steel

* Water Quality

Codes of Practice

Codes of practice for concrete work used in various parts of the

world deal with the question of aggressiveness of water to concrete
in some detail. There are different code & practices available for
assessing the effect of water on concrete, viz: BIS, USBR code,
French code, Langelier Index, etc. A study of these codes show
that:
* They generally consider. individual parameters such as
sulphate/chloride content in isolati9n and do not allow for
the continued effects.'of various ionic species. In some
practices limited combinations are used.

* They give widely divergent permissible limits of ionic

concentration.
* They are often based on water-treatment technology while
corrosion technology would be more appropriate.

These codes though useful for routine use, fail to address to

the problem of effect of high temperature on concrete. Normally,
the deteriorating effect of water on concrete is likely to increase
with temperature. J.J. Basson & B.J. Addis have done extensive
work in this field in their approach paper (SP 131) published by

767
ACI in 1992. " A holistic approach for corrosion of concrete in
aqueous environments using indices of aggressiveness", have
considered all relevant influencing parameters as a part of total
corrosive environments. They have come out with suitable indices
to quantify the aggressiveness and also used these indices to
select appropriate remedial measures for the circumstances for the
consideration.

The guidelines (taken from the approach paper) given below are
exhaustive and used primarily for assessing the corrosivity of
waters of natural origin (such as lakes, streams, subterranean
aquifers etc). The indices are not, therefore, applicable to
industrial effluents and wastes.

Fixing of acceptable limiting values

This requires an evaluation of which characteristics of the

water are significant in assessing its aggressiveness and what the
limiting values of such characteristics should be under "standard
conditions" which, for the purpose of this study are defined as
follows:

* A prevailing water temperature of 20C.

* Laminar flow conditions (ie gentle, non-turbulent flow, with
a velocity sufficient to ensure that the replenishment of
corrosive agents is not diffusion-rate limited) .
* All corrosive ions present in their least corrosive form.

Derivation of corrosion indices and correction factors

The method involves the derivation of a series of numerical

subinde~es, related to the aqueous parameters discussed previously,
that can be used to calculate a leaching corrosion index (LCI)i a
spalling corrosion index (SCI)i and an overall corrosion index
(OCI). These indices are used in turn to decide on any
anticorrosive measures needed to protect the concrete. These are
calculated using coefficients and formulas given in Table 3. The
following notation is used:

V = the value 9r result reported for the applicable analytical

determination or other required parameter
N = the number resulting from the calculation and indicating the
magnitude of the subindex.

It was arbitrarily decided that each subindex would be 1000 at

the normalized limiting value for the relevant corrodent
concentrations. Since the index apply to standard normal
conditions, they may be corrected to allow the environmental factor
of turbulent or stagnant conditions and temperature, as shown in
Table 3. (To distinguish between uncorrected and corrected indexes,
the later have been prefixed with a letter C. e.g. LCI becomes
CLCI, SCI becomes CSCI and OCI becomes COCI after correction) . Once
the indices have been calculated, they are used -to assess the
corrosivity of.the water by comparing their values with those shown

768
in Table 4.

Table 4

AGGRESSIVENESS OF WATER ACCORDING TO CALCULATED INDEX

Finally, recommended anticorrosive measures are determined by

following the procedure described below.

Thi's e"ssentially involves identifying the dominant mode of

attack (leaching or spalling), providing concrete of adequate
water-cement ratio and cement content, and type, and, if necessary,
providing further protection in the form of anticorrosive coatings.
In case dominant corrosive index is LCI or CLCI, then refer Table
5 und~r leaching, otherwise follow the recommendations under
spalling. Depending upon the class of water, refer to Table 6
and/or 7.-

Corrosion of steel in concrete

Reinforcing and prestressing steel in dense, impermeable

concrete are passivated by a thin surface film which forms in the
high pH of the pore water. This passivating layer can however be
disrupted by chloride ions. As it happens, the steel becomes
vulnerable to corrosion. The potential danger caused to steel
embedded in concrete in a.aqueous environment is a function of a
concentration of a chloride ions in the water. In line of the rest
of the Paper, ,normalised limiting values are calculated as per the
formula given below:

N, = C, X V,

Where, C,' = 0.2

The degree of aggressiveness of water is due to chloride ion attack

is decided based on Table, 8. Remedial measures are given in Table
9.

770
771
772
773
Based upon the Sub-index of the chloride ion recommended counter
measures are suggested in Table 9.

Table 9

Counter measures against chloride corrosion of embedded steel

INTERPRETATION AND REMEDIAL MEASURES

i) It is seen from the present study that there is a distinct

possibility of attack of seeping water on concrete at high
temperatures.

ii) Since the corrected leaching corrosion index values are

greater than Corrected spalling corrosion index values (see Table
2), it is expected" that leaching corrosion is a distinct
possibility ..

iii) Based on Table 5, all the locations fall in the class 3 or 4.

Chloride attack is possible at certain locations.

iv) Types of cements recommend=d:

a) Portlan~ slag cement conforming to IS 455 : 1989 with the slag

constituent not less than 50%.
or
b) Portland pozzolana cement with flyash content = 30%.
or
c) Ordinary portland cement incorporating 15% silica fume.

v) Minimum cementitious content: 420 Kg/M3

VI) Maximum water cement ratio (by wt.) = 0 ..

45

VII) Minimum concrete cover of 50mm throughout or as stipulated in

the design requirement, whichever is greater.

774
CONCLUSION

The approach Paper of Basson and Addis was useful in the following
way for this project:
(i) Classifying the degree of aggressivity of water at high
temperature.
(ii) Identifying the type of attack on concrete at high
temperature.
(iii) Clearcut remedial measures to overcome the problem.

ACKNOWLEDGEMENTS

The authors would like to place deep appreciation of the

technical help rendered by Shri Kachhal Prabhakar, Asstt. Research
Officer in the preparation of this Paper.

REFERENCES

1. American Concrete Institute, Manual of Concrete Practice, Part

I, 1992.
2. Orchard, D.F., " Concrete Technology" 4th Edition, Vol. 1,
Published by Applied Science Publishers Ltd., London, 1979.

3. Biczok, I. , " Concrete Corrosion Concrete Protection",

Published by House of Hungarian Academy of Sciences, Budapest,
1964.
4. Lea, F.M., "The Chemistry of Cement and Concrete", Published
by Edward Arnold (Publishers) Ltd., UK, 1980.

5. ",Durability of Concrete Construction", American Concrete

Institute Monograph, No.4, 1984.

7. "Corrosion of Steel in Concrete" edited by P.Schiessl, RILEM

Report by Chapman & Hall.
8. IS:456-1978, "Code of Practice for Plain & Reinforced
Concrete" .
9. "Exposureof Concrete in .Dams to Special Aggressive Agents",
ICOLD, 71, 1989.
10. "Manual of Concrete Practice", Part 3, American Concrete
Institute, USA, 1988.
lL IS: 12330-1988, "Specification for Sulphate Resisting Portland
Cement.
12. Holm Jens, Geikker Mette, "Durability of.concrete",G.M. Idorn
International Symposium, SP-131, American Concrete Institute,
Michigan, USA, 1992.

775
Proc. In!. C:onf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Effect of AggressiveCbloride Environment on

Corrosion Resistant Reinforcing Steels
Embedded in Concrete
N. Banerjee!, D. Mukerjee!, B. Bhattacharya2 and D.S. Ramachandra Murthy3
lR&D Centre for Iron and Steel, SAIL, Ranchi, India
2Indian Institute of Technology, New Delhi, India
3Structural Engineering Research Centre, Chennai, India

Abstract : High corrosion resistant (HCR) reinforcement bars, developed by Steel Authority of
India Limited (SAIL) through the thermomechanical treatment (TMT) route, have superior corrosion
resistance compared to conventional cold twisted and deformed (CTD) rebars. The corrosion
behaviour of the HCR- TMT and CTD rebars were evaluated in aggresive chloride environments in
concrete through short-term accelerated tests and long-term field exposure test. Galvanostatic results
conducted with admixed chloride and synthetic sea water environment, under short duration
laboratory tests, reveal superior corrosion resistance of HCR- TMT than CTD rebars. Long duration
(583 days) field tests in marine conditions also reveal a much lower corrosion rate for HCR-TMT
rebars than CTD rebars. Corrosion Resistance Index (CRIT) of 1.66 and 1.18 were achieved in
HCR- TMT rebars in admixed chloride and synthetic sea water environment respectively. In field
(marine exposure) tests HCR-TMT rebars exhibited a high CRITvalue of 1.91.

INTRODUCTION

The corrosion of steel embedded in concrete structures is crucial in determining the structural
integrity and durability of reinforced cement concrete (RCC) structures High corrosion resistant
(HCR) reinforcement bars, containing suitable alIoying elements such as copper, chromium and
nickel have been developed by Steel Authority of India Limited(SAIL), through the
thermomechanicalIy treated(TMT) route, to impart superior corrosion resistance compared to
conventional cold twisted and deformed (CTD) rebars [l].
Reduction of alkalinity of the concrete through carbonation and contamination by chlorides
induces corrosion of the reinforcement in RCC structures Chloride attack is known to aggravate
corrosion risk, if Cl"/(OH)" ratio is sufficiently high. The different sources of chloride affecting a
reinforced concrete structure are seawater, wind borne salt spray in coastal areas, aggregates used for
concrete and calcium chloride(CaCI2) added to concrete mixing water for accelerated setting.
Reinforcing steel embedded in concrete is surrounded by a highly alkaline pore solution, which
develops a protective layer that shields the surface from further corrosion[2,3]. However, this
protective film breaks down when chlorides reach the steel in sufficient concentration, even under
conditions of high alkalinity. Adsorption and oxide film theories have been ~uggested on the
mechanism of breakdown of the protective film in chloride environments[ 4]. The adsorption theory

776
proposes that chloride ions are adsorbed preferentially into the metal surface. These ions compete
with oxygen and hydroxyl ions fo~ adsorption at the surface. The chloride ions also have a faster rate
of reaction with the iron, resulting in the formation of complex solubles. These solubles lead to
pitting of the surface. The oxide film theory proposes that the chloride ions preferentially penetrate
the oxide film, and this leads to pitting.
In the present work systematic studies were carried out to assess the impact of aggressive chloride
environment on corrosion behaviour of HCR- TMT rebars vis-a-vis CTD rebars, embedded in
concrete, and both having minimum yield strength of 415 MPa.

EXPERIMENTAL

The corrosion behaviour of the two types of reinforcement bars, namely HCR- TMT and
CTD were studied through short-term accelerated tests carried in the laboratory, under two types of
aggressive environments: (a) cement containing 2% admixed anhydrous CaClz by mass and (b)
synthetic sea water. Galvanostatic measurements on reinforced concrete specim~ns were undertaken
in the laboratory. The long-term field exposure performance of the rebars was e~aluated by exposing
concrete prisms in sea water. In both the laboratory and field tests the process of corrosion was
accentuated by alternate wetting and drying. The short-term accelerated tests were done as they
would be likely indicators of the long-term performance of rebars under actual service condition.
The average compressive strengths of the concrete for laboratory and field tests were 29.2 MPa and
39 MPa respectively.

Chemical Composition

HCR- TMT and CTD rebars of 20mm diameter were used as reinforcements. The chemical
analyses of both the rebars are shown in Table-I. HCR- TMT grade of steel had small amounts of
Cu, Cr and Ni to enhance corrosion resistance of these rebars. Besides it had lower C and Mn
contents than CTD rebars The rebars free from mill scales and pits, were cleaned thoroughly and all
stains were removed with acetone before embedding them in concrete.

Short Term Accelerated Tests

Specimens for Galvanostatic Measurements

Rectangular beam samples of 500 mm in length and 200 mm x 100 mm in cross-section were
used for galvanostatic tests. Three beams each, for each of the two exposure environments pertaining
to each of the two different grades of steel were cast. The rebars of 600 mm length were placed with
a clear cover of 20 mm (Fig. I). The exposed portions of the steel rebars required for electrical
connections were coated with epoxy and covered with adhesive tapes. Epoxy was also applied on the

777
Alternatf! Wetting and Drying Cycle

Mter curing for 28 days, all the samples were exposed to cycles of alternate wetting and
drying; each cycle consisting of 3 days of wetting followe~ by 11 days of drying, in order to
accelerate the corrosion process. This process of wetting and drying was continued for 84 days
corresponding to 6 cycles of wetting and drying.

Concrete Expusure Environment

Two types of concrete samples were cast: (a) samples with 2% admixed anhydrous CaClz by
mass of cement added during casting and (b) samples without any admixed chloride. The free
chloride content of the concrete pore solution, for this amount of admixed CaClz, is sufficient to
initiate corrosion of rebars embedded in concrete even at the age of 1 day, provided that, moisture
and oxygen is available in the concrete at the rebar level in sufficient quantity to sustain corrosion
[5]. The beams with admixed CaClz were subjected to alternate wetting and drying in tap water, so
that the samples remain in partially saturated condition, enabling continuation of corrosion. The
second type of samples were exposed to alternate wetting and drying in synthetic sea water to
simulate marine environment. This process enhanced the ingress of chlorides as well as sulphates in
concrete.

Set Up fur Galvanostatic Measurement

The standard reference electrode used for the galvanostatic measurement was Cu/CuS04
electrode covered by ASTM C876-1991. The sample rebar was used as the working electrode.
Details of the arrangement with the procedure has been described elsewhere [6]. A multimeter of 0.1
mV sensitivity and an ammeter of 0.01 micro Amp sensitivity were used to measure the voltage and
current respectively. Simultaneous measurements of (a) half-cell potential and (b) corrosion current
density were taken based on the principle of linear polarisation technique. The corrosion rate of the
rebars were derived from the average steady state corrosion current density using the Faraday's Law.

Long Term Field Exposure Test

Long-term field exposure studies were undertaken on HCR- TMT and CTD rebars to measure

778
the corrosion in reinforcing steels in concrete prisms in aggressive seawater environment. The rate of
corrosion of steel in concrete was determined using the weight loss method, using the procedures
described in ASTM standard GI-1990.

Concrete Prism Specimen

Concrete prisms of 700 mm X ISO mm X ISO mm size were cast with rebars of 570 mm
length, placed at the centre (Fig.2). A clear cover of 65 mm for the bars was maintained on all sides
as required by Indian Standard IS:456-1978. The prisms were cured in water for 28 days and then
kept in the marine environment.

Exposure Environment and Duration

The concrete prisms were placed in the tidal range of the Chennai Port Trust area, such that
alternate wetting and drying of the samples was ensured with the change of seawater levels from low
tide to high tide. Four prisms each, of the two types of rebars,namely HCR-TMT and CTD, were
placed with steel stands and tied with plastic ropes to prevent dislodging. The prisms were taken out
after 583 days of exposure and the rebars were removed from the prisms and thoroughly cleaned and
weighed to calculate the weight loss on account of corrosion.

RESULTS AND DISCUSSION

Short Term Accelerated Tests

The galvanostatic measurements on the HCR- TMT and CTD embedded concrete specImens,
exposed to admixed chloride and marine environments, generated data on the half-cell potential,
corrosion current density and rate of corrosion.

Half-Cell Potentials and Corrosion Chance

The ranges and mean of the half-cell potential values obtained at the end of the sixth cycle of
alternate wetting and drying for HCR-TMT and CTDrebarsare shown in Table-2 for admixed
chloride and marine environments. As per ASTM C876-1991, the half-cell potential data can be
related to corrosion chances(Table-3).The half-cell potential data reveals that the chances of
corrosion for CTD rebars was 90% in both the severe exposure conditions, while it was only 10%
and 50% for HCR-TMT bars in admixed chloride and marine environments respectively.

779
Effect of Environment

Comparision of the data of the rebars in admixed chloride and simulated marine
environments, as shown in Table-2, reveal that the performance of HCR- TMT in terms of half-cell
potential values was better than that of the corresponding CTD rebars. The chance of corrosion for
HCR- TMT was 10% compared to 90% in the case of CTD rebars in admixed chloride environment.
Similarly, the half-cell potential values of CTD rebars exhibited a greater active state when
compared to HCR- TMT rebars in the simulated marine environment and the chance of corrosion for
CTD rebars was 90% while those for HCR- TMT rebars was 50%. This shows the advantage of
HCR- TMT rebars over CTD rebars in such environments. Moreover, with respect to corrosion risk,
HCR- TMT rebars have performed better in admixed chloride environment as compared to simulated
marine environment; the former being one of the most aggressive environment.

The corrosion resista~ce of HCR- TMT rebars is expected to be better than CTD rebars as the
former contains copper, chromium and nickel which are known to improve corrosion resistance [1,7].
Further, CTD rebars by virtue of higher surface torsional stresses, due to cold twisting, accentuates
corrosion [1,8].

Performance of Rebar in Terms of Corrosion Rate

The rate of corrosion in mils per year (lmil = 1/1000 inch) of the rebars was derived from
the average steady state corrosion current density using Faraday's Law.
Corrosion rate (mils/yr) = [W/(Pst x F)] X leoITx 12.416 ------ {I}
where, W = equivalent weight of steel (27.925 gms),'F = Faraday's constant (96487 coulombs),
Pst = density of steel (7.85 gms/cc) and leoIT= corrosion current density (nAlcm2)
The cGrrosion resistance of the rebars was expressed in terms of a corrosion resistance index,
which is a relative measure of the corrosion resistance of a steel rebar compared with a reference
material. Using CTD rebar as a reference, the corrosion resistance index(CRIT) of HCR-TMT rebar
would be the ratio of corrosion rate of CTD rebar to the corrosion rate of HCR- TMT rebar.
The performance of HCR- TMT rebars in terms of corrosion rate was better than that of the
CTD rebars in both the aggressive environments as shown in Table-4. In admixed chloride
environment, the corrosion rates for HCR-TMT and CTD rebars were 0.0303 mils/yr and 0.0503

780
mils/yr respectively; corrosion rate of HCR-TMT rebars being 39.8% lower than CTD rebars. For
simulated marine environment, the corrosion rates in HCR-TMT and CTD rebars were 0.0261
mils/yr and 0.0309 mils/yr respectiv~ly; corrosion rate of HCR-TMTrebars being 15.5% lower than
CTD rebars. The performance of HCR-TMT rebar was better than CTD rebar, as evident from the
CRlT values of 1.66 and 1.18 for admixed chloride and simulated marine environments respectively.

Long Term Field Exposure Tests

The corrosion rates were determined from the followil!g equation using the weight loss data:
. Corrosion rate (mils/yr) = (KxW) / (AxTxD) ------ {2}
where, K = Constant (3.45 x 106), T = exposure time ( hrs.), A = initial surface area of sample (cm2),
W = weight loss in gms and D = density of steel (7.85 gms/cc)

Tabfe-5 reflects the corrosion rates observed in HCR-TMT and CTD rebars in the field
exposure test. The corrosion rates, based on the average of 4 samples tested, for HCR-TMT and
CTD rebars were 0.34 mils/yr and 0.65 mils/yr respectively; the former having a corrosion rate
47.7% lower than the latter.The CRlT value for the long term field exposure test calculated for
HCR-TMT rebars was 1.91 which -reveals their better performance and corrosion resistance than
conventional CTD rebars.

The CTD rebars exhibited inferior corrosion b~haviour due to its higher carbon and manganese
contents as well as the presence of surface torsional stresses [1]. As explained earlier, the superior
performance of HCR-TMT rebars is also attributable to the presence of copper, chromium and
nickel which inhibits corrosion.
The superior corrosion resistance of HCR-TMT rebars over CTD rebars in accelerated tests
have also been confirmed by long-term field exposure tests in marine environment. However, the

781
CRh values for HCR-TMT rebars in long term-field exposure test (1.91) was slightly higher than
those (1.66 and 1.18) observed in short-term accelerated tests carried out in the laboratory.

CONCLUSIONS

Short-term accelerated tests with admixed chloride and simulated marine conditions, have
revealed the superior performance of HCR- TMT rebars embedded in concrete compared to
conventional CTD rebars. The corrosion rates for HCR- TMT rebars were lower than CTD rebars by
39.8% and 15.5% in admixed chloride and simulated marine conditions. CRlT values of 1.66 and
1.18 were obtained for HCR- TMT rebars in admixed chloride and simulated marine conditions
respectively. The corrosion risk was 90% for CTD rebars for both the aggressive environments. The
corrosion risk for HCR- TMT rebars was lower than CTD rebars. In fact, for admixed chloride
environment it was 10% and for simulated marine environment it was 50%.
Field exposure studies with marine exposure conducted on HCR- TMT and CTD rebars have
also shown lower con:osion rate fOf HCR-TMT rebars (47.7%). The HCR-TMT nibars were 1.91
times more corrosion resistant than CTD rebars after an exposure of 583 days. The long-term field
tests, under actual service conditions, have confirmed the superior performance of HCR- TMT rebars
over CTD rebars as indicated in short-term accelerated tests ..
The CTD rebars exhibited inferior corrosion resistance due to its higher carbon and
manganese contents, as well as the presence of surface torsional stresses. The presence of
copper, chromium and nickel in HCR- TMT rebars have helped in inhibiting corrosion.

ACKNOWLEDGEMENTS

The authors are grateful to the management of RDCIS, SAIL for their support,
encouragement and guidance during the various stages of the investigation. The requisite help
extended by Structural Engineering Research Centre, Chennai and Indian Institute of Technology,
New Delhi is gratefully acknowledged.

REFERENCES

I. Ray, A., et. aI., Microstructure and Properties of Thermomechanically Strengthened

Reinforcement Bars: A Comparative Assessment of PI~in-Carbon and Low-Alloy Steel Grades,
Journal of Materials Engineering and Performance, Vol. 6, no. 3,1997, pp.335-343.
2. Haussman, D.A., Steel Corrosion in Concrete, How Does it Occurs Material Protection, Vol. 6,
no. 11, 1967,p. 19.
3. Pourbaix, M., Atlas of Electrochemical Equilibria in Aqueous Solutions, Pergamom Press, 1966.
4. Foley R.T., Corrosion, Vol. 26, no. 2,1970, p.58.
5. Pullar-Strecker, P., Corrosion Damaged Concrete: As~essment and Repair,Construction Industry
Research and Information Association (CIRlA), Butterworths, 1987
6. Ahmed, S., Bhattacharya, B., A Simple Arrangement and Procedure for In-situ Measurement of
Corrosion Rate of Rebar Embedded in Concrete, Corrosion Science, Vo!..37, no. 5, pp.781-791.
7. Boyd, W.K., Fink,F.W.,Corrosion of Metals in Atmosphere, MCIC Report No. 74-23, Battelle
Colombus Laboratories, August 1974, pp.I-77.
8. Chawla,S.L., Gupta, R.K., Factors Influencing Corrosion and its Forms, Material Selection for
Corrosion Control, ASM International, 1993, pp. 29-63.

782
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Cases of Stress Corrosion Cracking in

Power Plant Components
Pradeep Jain, A.K. Sinha, V.C. Bhakta and S.K. Sanyal
Research and Development Centre,
National Thermal Power Corporation Limited,
A-SA, Sector-24, Noida-201 301, India

ABSTRACT

Many instances of stress corrosion cracking (SCe) have been observed in different components
in power plant like L.P. Heater tubes, condenser tubes and lacing wire of L.P. turbine etc. These
components are exposed to various environments which cause the SCC. Investigations have been carried
out of failed components in laboratory which indicated the reasons of failures. Remedial measures have
also been suggested to reduce the failures in power plant components. The present paper describes the
case histories of three failures in power plants ..

1. Investigation of L.P. heater tube which was made of Admiralty brass indicated that the main
cause of tube failure is sec. The environment consisted of ammonia in steam and was responsible for
SCC. It was suggested to replace the heater tubes by cupronickel 90:10 or .SS-304 grade which is more
resistance to SCC in this environment.

2.. Failure analysis of steam condenser tubes revealed the presence of SCC from the steam side in
Admiralty brass. Pitting corrosion and intergranular corrosion has also been observed in metallographic
examination. It was suggested to replace the condenser tubes by 90:10 Cupro Nickel alloy tubes.

3. Failure investigation of Lacing wire in low pressure turbine indicated the presence of impurities
like sodium and chloride in the deposit. SEM study revealed the failure due to SCC. It was suggested to
control the water/steam chemistry parameters of boiler.

783
PREAMBLE:

Thermal power plant is having different components of various alloys which are
susceptible to localised corrosion mainly due to the presence of high temperature, mechanical
stressess and corrosion atmosphere .. Many instances of stress corrosion cracking (SCC) have
been observed in different components like L.P. heater tubes, condenser tubes and lacing wire of
L.P. tube etc. This paper describes three case histories pertaining to failures of power plant
components due to S.C.c. '

CASE-I: TUBEFAILURESTUDYOFLOWPRESSUREHEATER

INTRODUCTION:

Low pressure heaters in some of the power stations were in operation for 6-7 years. The tube
material used in these heater was admiralty brass. Steam coming from the tapping of L.P.
turbine was at a temperature of 350 deg. C (approx.) and pressure about 6kg/cm2. Feed water
temperature inside the tubes was approx. 130 deg.C and pressure about 12 kg/cm2. Material of
tubes were admiralty brass having the size O.D. 16mm and thickness of the tube was 1.0 mm.
These heaters are vertical and tubes were U shaped. Frequent tube failure had been observed in
these heaters. This case history will deal with the detailed examination of these failed tubes and
their remedial action to prevent the further tube failure.

VISUAL OBSERVATION:

The outer surface of the unfailed portion of the tube was found to be very smooth and black in
colour but failed portion shows the erosion-corrosion sign as shown in the photographs No.1.
Circumferencial cracks had been observed on the surface L.P. heater tubes. The failed tubes were
opened at the different places by cutting longitudinally and inspected. No scale deposition had
been observed inside the tubes. The inner surface was showing brownish colour. Thinning of the
tube,had been observed at the failed portion as shown in photographs.

METALLOGRAPHIC EXAMINATION:

The LP heater tube sample was cut into pieces at different places and mounted. These mounted
samples were polished upto diamond grade and were investigated under the optical microscope.
Evidence of material cracking due to stress corrosion was observed at the point of failure. The
microstructure of the samples have been seen under the microscope after etching. The material
had suffered from dezincification as shown in the photograph no.2. The microstructure reveals
that the failure are mainly due to stress corrosion cracking (SCC).

784
SCANNING ELECTRON MICROSCOPE EXAMINATION:

SEM study of the failed tube has been carried by Scanning Electron Microscope of Cambridge
make. The study reveals the shoe shapped structure which is due to impingment attack on the
outer surface of the tube, as shown in micrograph no. 3.

CONCLUSION:

The study reveals that the tube failure of LP heater had occured due to combined effect of
erosion-corrosion from the inside of the tube. The stress corrosion cracking and dezincification
have been observed at the location of failure. Most of the tube failure had occured
circumferentially. The tube surface away from the failure was very smooth from the outside and
no corrosion sign have been observed. The tube material is not resistant to stress corrosion
cracking in the environment prevailing and failed.

RECOMMENDATIONS:

It is suggested to replace admiralty brass tube of LP heater by cupro-Nickel material grade

90: 10, which is more resistant to stress corrosion cracking. Alternatively austenitic stainless
steel (AISI-304) may be used.

785
 CASE-II: FAIL URE ANALYSIS OF CONDENSER TUBE

INTRODUCTION:

Steam condenser is used in power plant to condense the steam coming from L.P. turbine.
This is under the vacuum condition. The cooling water passes through the condenser tubes and
steam is at the outer surface of tubes. the condensed water temperature is around 50 deg.C on
the shell side whereas the cooling water inlet and outlet temperatures is around 30 and 40 deg.C.
respectively. The steam condenser was double pass, single shell, type number of tubes was
approx.10,000 having the O.D. 24mm and tube wall thickness was1.0 rom. and tube material
was admiralty brass. Cooling water used was river water, downstream of sewage treatment
plant, once through type. Failure of condenser tubes were observed after the service period of 15
years in these condenser. Investigation of the failure and its remedial action are given in detail in
this paper.

VISUAL OBSERVATION:

The failed tubes were cut into pieces and opened into two halves to examine the internal
and external surfaces of the.tube under stereo microscope. Visual observations indicated that the
tube failure had initiated from internal surface. This is shown in photograph No.4. Very little
deposit, mainly silt, on the internal surface and a thin layer of black oxide deposition on the outer
surface of consdenser tubes has been observed.

The thickness measurement of condenser tubes had been carried out after chemical
cleaning of these tubes. The thickness had reduced upto 0.5 - 0.6 mm at failed portion from
original thickness of 1.0 mm

METAUOGRAPHIC EXAMINATION:

The condenser tube sample was cut from failed as well as healthy portion and was
mounted and polished upto diamond grade. These samples were seen under the optical
microscope. The examination indicated the branched intergranular cracks originating from the
water side on all along the tube length. The nature of cracks is shown in photograph No.5.

SCANNING ELECTRON MICROSCOPICEXAMINATION:

Condenser tube sample was analysed by SEM after cleaning. Intergranular creacks were
observed on the internal surface of tube as shown in Photographs no. 6.

786
CHEMICAL ANALYSIS:

Chemical composition of condenser tube material was analysed by Atomic absorption

spectrophotometer. It showed the presence of Tin 1% and Arsenic 0.02% by weight which
indicated that the tube material is Arsenical grade admiralty brass. It is well within the
composition of standard arsenical admiralty brass.

ANALYSIS OF EXTERNAL & INTERNAL DEPOSITS FROM THE TUBE:

The deposit samples from external & internal side of the tube were examined through X.
Ray Diffraction. The diffractogram indicated that external deposit consists of mainly FeO(OH)
alongwith Fe203, Fe304. The internal deposit mainly consist of Cu20 alongwith Si02, Fe203,
CuO & CaC03.

DISCUSSIONS:

Admiralty brass with nominal composition of 71% Cu, 28% Zn, and 1% Sn containing
small amounts of either As, Sb or P (to. reduce dezincification of the base metal) have been
widely used in fresh water steam surface condensers' and heat exchangers, oil coolers, L.P.
heaters for the last several years. General performance has been satisfactory however, the tube
failures in condensers and heat exchangers due to pitting and intergranular corrosion have been
reported in cooling water containing sulphide, ammonia, nitrate and metallic ions of copper and
manganese. In the present case intergranular, corrosion pitting corrosion, SCC may be attributed
to ammonia, nitrate and sulphide, ions present in the cooling water system. these corrodents can
be generally expected from the raw water mixed with sewage water.

RECOMMENDATION:

It is suggested to replace all the condenser tubes by cupronickel (90: 10) as a permament
solution to the leakage problem because all the tube. supposedly have developed the cracks to
different depths at various points of time.

787
 CASE - III FAILURE ANALYSIS STUDY OF TURBINE LACING WIRE

INTRODUCTION:

Lacing wire is used in low pressure turbine to keep the blades intact and reduce the
mechanical vibration. These wire are made up of Martenstic stainless steel. After the operation
of about 8-10 years of these turbines, these wire failed and unit had to be stopped immediately.
The failure investigation of failed wire were conducted and are given in this paper.

METALLOGRAPHIC EXAMINATION:

Visual observations indicate the black and rough surface at the crack side. Brazing on
the lacing wire were also failed. the sample was cut and observed under stereo microscope.
Micro cracks were observed near the fracture surface. Marks of rubbing and identification were
also observed on the surface. Examination by SEM revealed that the failure is due to stress
corrosion cracking (SCC) as shown in photographno.7

SCANNING ELECTRON MICROSCOPIC EXAMINATION:

One sample was examined under scanning electron microscope. This revealed that the
failure is due to stress corrosion cracking (SCC). Photographs No.7 & 8 are enclosed for
reference. Cracks are all around the grain boundaries.

DISCUSSIONS:

The probable reason of failure is by Stress Corrosion Cracking which has been caused by
the presence of moisture, oxygen and il'!gress of impurities like chloride and sodium in steam
through condenser leakages.

788
789
790
791
792
Proc. lnt. ConI. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Stress Corrosion Cracking of Micro-Alloyed

Steel in Various Environments
S.K. Sen and G. Kaur
Research & Development Division,
Tata Steel, Jamshedpur

ABSTRACT

The effect of environment and strain rate on the stress corrosion cracking of
microalloyed high strength steel have been evaluated at 955C by using the Cortest
instrument: Test were conducted in hot nitrate, hydroxide, carbonate and bicarbonate
solution at a strain rate of 1.4xlO-8/sec.Sulphide stress corrosion tests were carried out at
ambient temperature in NACE solution. The results .show that the corrosion effect of
NILN03 is more severe in comparison to NaC03. Moreover, NaOH is less aggressive on
the steel than bicarbonate and carbonate solution. The time of failure of microalloyed
plates in various metal nitrate solutions increases in the following order : ammonium,
calcium and sodium. The present study also shows that these plates do not show any
cracks in 33% boiling nitrate solution when tested at 1.4xI0-8/sec strain rate.

The microscopic observation of failed s~ples in NILN03 and CaC03 solution

show intergranular cracks. Such failures were not observed either in air or NaN03, NaOH;

NaHC0J and Na2C03 solution.

793
 The load displacement curves of microalloyed steel in NACE solution indicate that
there is a substantial reduction of time for failure to occur. This is due to the inclusions
content in the steel which act as preferential sites for entrapment of hydrogen atoms.

INTRODUCTION

High strength microalloyed steel is increasingly being used in construction,

fabrication, pipe lines etc. because of their versatile mechanical properties and is replacing
plain carbon low strength steel. Some of the application called for are in mild to
aggressive corrosion environment under a stress field. Resistance to stress corrosion
cracking is a desirable property for the material and is of paramount importance. The
process of stress corrosion cracking involves a complex interaction of metallurgical,
chemical and mechanical parameters. Since these three factors corresponds to the three
conditions necessary to produce stress corrosion cracking, it is important that the role of
each factor must be considered to understand this phenomena. The other important factors
involved in stress corrosion cracking apart from stress and environment are time,
temperature and microstructure of a material. Addition of microalloying elements in
carbon steel changes the microstructure and hence increases the strength and toughness of
the steel. A considerable number of studies have been reported on the stress corrosion
cracking of mild steel in nitrate, hydroxide, and carbonate solution [1-6]. But very little
information is available on the stress corrosion behaviour of microalloyed steel.

The present study deals with stress corrosion cracking of microalloyed steel in
nitrate, hydroxide, carbonate bicarbonate and in NACE solution under different strain
rates.

EXPERIMENTAL PROCEDURE

Test Material: The material used in the present investigation was commercial grade
microalloyed steel plates of 12 mm thickness. The chemical composition and mechanical
properties at room temperature are given below.

794
Constant strain rate tensile specimen corresponding to ASTM A370 was machined and

used for testing. Details of the specimen dimension are given in Fig. 1.

Test media: The following are the media in which the testing were carried out.

i) Nitrate solution - The solutions considered to study the effect of nitrate

environment were NR.N03, Ca(N03)2 and NaN03. The concentration of the

solutions was 4N.

ii) Hydroxide solution - The corrosion media used was 33% NaOH solution.

iii) Carbonate and bicarbonate solution-A mixture of Na2(C03) + NaHC03 solution

was used for SCC testing.

iv) H2S saturated solution - Tests were carried out in 5% NaCI +0.5% CH3COOH
solution as per NACE specification 01-77. PH of the solution was maintained in

the range of 3 - 3.5.

Testing Procedure: The stress corrosion cracking (SCe) of the polished test samples
were performed within an inbuilt autoclave of a Cortest instrument. Necessary solution

was injected into the autoclave by a syringe. The load displacement curves were recorded

automatically on a fast response strip chart recorder. The heater in the autoclave was put

on to raise the solution temperature to the desired level.

795
796
chemistry, microstructure, strain rate, and temperature. Environment induced fracture
arises from complex environmental interaction within the steel. That is why normally crack
initiations start from the surface. It has been conceived that there are two theories for
stress corrosion crack propagation in nitrate solution. Firstly SCC may.be caused by the
reduction in bond strength at the' crack tip in the presence of nitrate compound. The
second is regarded as a selective electrochemical dissoMion process of metal at the crack
tip. Microphotograph of the present study confirms the second possibility.

Electron microscope studies on failed samples in nitrate solution indicates that

intergranular cracking is due to the dissolution of carbon and nitrogen rather than
precipitation of these elements at the grain boundaries. In agreement with .a number of
workers the present study confirmed that it is difficult to produce cracking in microalloyed
steel in 33% boiling pure NaOH solution. Accelerated caustic cracking occurs only in
impure NaOH solution.

The load displacement curve in Fig. 12 shows that microalloyed steel failed in
NAC~ solution only after 23 hours. The percentage elongation and reduction of area was
reduced from 22% in air to 7% and from 41% to 8% respectively iIiNACE solution.

Optical microscopy observation confirmed earlier reports that hydrogen sulphide

solution produce only one crack which lead to fracture of the steel, unlike in nitrate
solution.,where numerous cracks initiate but failures take place only by the propagation of
one of them. The mode of fracture inNACE solution was transgranular. The failure of
microalloyed steel possibly is due to high sulphur content as a consequence of which the
number and size of inclusions are

797
CONCLUSION

1. At a strain rate of and temperature of 95C, microalloyed steel is most

susceptible to stress corrosion cracking in NlLN03 solution.

2. Initiation and propagation of cracks occur at grain boundies of NlLN03 and

CaN03 in nitrate solution. Such failure was not observed in NaN03.

3. The time offailure of microalloyed plates in various nitrate solutions increases in

the following order: ammonia, calcium and sodium.

'4. NaQH is less aggressive on the steel than bicarbonate.

5. The inclusion size and number plays a major roll for resistance to sulphide stress
corrosion cracking. The sulphur content in the steel should be less than 0,005
percent to resist such cracking. The number of inclusion must be minimum and it
should be globular in form.

REFERENCES

1. Parkins R.N., Journal of Iron and Steel Inst. Oct. 1952, P 149 - 161.

2. Ells J., Corrosion - NACE Jan. 1973, P 37-43.

3. Parkins R.N., Corrosion ScL vol. 29, P 1019-1024.

4. Stiksma John and Bradford SA, Corrosion - NACE vol. 41, 1985, P 446-450.

5. DadivARobert,CorrosionFeb.1963,P451-551.

6. Jones H. Russell, Stress Corrosion Cracking, ASM International Publication 1992,

P41.

798
799
800
801
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Preventing Pollution in Zinc and Cadmium

Plating-A Novel Approach
M.B. Sunthankar and S.D. Joshi
IonEdge Corporation, Ft. Collins, CO 80524, USA

ABSTRACT

Electroplated zinc and cadmium coatings are widely used in the defense, aerospace and automobile industries for
corrosion protection of steels. Cadmium coatings are well suited for critical applications in maiine environments'
because these coatings provide a rare combination of properties such as superior corrosion tesistance as well as
high lubricity. However in recent years, the use of cadmium coatings has declined due to concerns over its
toxicity. In addition, electroplating is also under scrutiny since it generates large quantities of toxic solid and
liquid waste. To address these issues, a novel "Zero-Waste" Physical Vapor Deposition (Z-PVD) method has
been developed for zinc and cadmium. In this vacuum coating process, the parts are placed in a metal vapor-bath
and are coated simultaneously from all sides in a rapid coating cycle. Furthermore, the coating material is
deposited only on the parts and not wasted on fixtures and walls. These features have made the Z-PVD process
econontica1ly competitive with electroplating. This paper presents data to demonstrate the feasibility of fonning
zinc-cadmiuni alloys in the process and discusses overall accomplishments of the technology in production.

INTRODUCTION

Electroplating is known to use toxic liquids and generate large quantities of toxic solid and liquid waste. A study'
conducted by the U.S. Environmental Protection Agency (EPA) noted that electroplating eftluents are the single
largest source of contamination ofnatural water streams in the U.S. [1]. For the past two decades, considerable
research has been conducted to minimize hazardous waste in these operations. Yet, effective econontical solutions
have not been found. The quantity of material plated in electroplating shops is large compared to that of vacuum
coating facilities. Electroplating shops can plate 20,000 to 30,000 kilograms of steel fusteners and automotive
components daily [2]. Most of this plating is still conducted in cyanide baths. These shops discharge between
15,000 to 40,000 liters of eflluents per day [3]. In order to comply with the current EPA regulations, over
$650,000 worth of pollution control equipment and facilities is required [4]. In addition, the cost ofwaste-water
treatment is over $1,200 per day including the cost of 15 to 20 tons of sludge disposal per week [5]. In these
cases, the Z-PVD method would be an environmentally safe econontical alternative.

The conventional PVD techniques have not been able to compete well with electroplating in large scale production
economics. As a rule-of-thumb, the cost of conventional PVD is typically over an order of magnitude higher.
The PVD processes in general have long coating cycle-times, low throughput and are also substantially line-of-

802
sight in nature. On the other hand, in the novel Z-PVD method presented here, the substrates are immersed in a
vapor-bath analogous to that in electroplating. This results in simultaneous multidirectional uniform condensation
of vapors on all surfaces of the substrates. In addition, special features of the technology allow for vapor
condensation onlyon the substrates leaving the chamber walls clean. There are several materials such as zinc and
cadmium that are suitable for such a vapor-bath type process. This Z-PVD process is now in production at the
IonEdge facility.

THE VAPOR-BArn TECHNIQUE

In the basic cold-wall PVD utilizing vacuum evaporation, the source metal to be coated is heated in a crucible
until it is melted and vaporized. Several improvements in the apparatus as well as vaporization technique have
been incorporated within the last thirty years. Yet the basic line-of-sight nature of the deposition has not changed
substantially, and a significant portion of the vaporized material is still wasted due to condensation on extraneous
surfaces. On the other hand, the unique arrangement of the Z-PVD is shown in Fig. 1. The p~ to be plated are
placed on a 'rack ai1dthe. whole set up Is enclosed inside a barrel made of the zinc or cadmium source material.
When the wall material is vaporized, the source barrel behaves like a vapor-bath.

Zinc and cadmium metals sublime at temperatures well below their respective melting points of 4200 and 3210 C.
This allows for vaporization of wall liners without melting. These source liners can be heated using several
practical means such as ion bombardment or external thermal. heating. In order to prevent extraneous deposits,
the surfaces not meant for deposition are heated above the vaporization temPeratures. This is the principle of
zero-waste in the patented Z-PVD process.

A glow discharge apparatus that is shown in Fig. 2 was used to demonstrate the vapor-bath concept. In this
apparatus, a cadmium foil in the shape of a barrel is placed on the cathode. Several small parts to ~e coated are
placed at random inside the barrel. A glow discharge is generated at the argon pressure of about 100 milliTorr
and at the anode voltage of about 500 volts. When the energy of argon ions is sufficient, the cadmium foil
1aDperature begins to rise due to ion bombardment. After about a minute of heating time, cadmium starts to
vaporize and the parts placed inside the barrel get coated rapidly. In addition, most of the vapors are used for

803
coating resulting in a relatively high deposition rate. Deposition rates as high as 17 f.lIDI'minutehave been
measured for cadmium and even higher rates are feasible. The photograph in Fig. 3 shows cadmium plated
fasteners that were plated using the arrangement shown in the Fig. 2. These coatings were dense, uniform and
adherent around the parts. A washer as shown in the photograph indicated the feasibility of masking the
deposition when required, and another part indicated the feasibility of soldering directly to the cadmium coating.

804
As the research progressed, the following advantages of the Z-PVD became evident:
it is a relatively rapid and simple coating process
it has a short load-to-unload c~cle
it requires simple loading and unloading procedures
it eliminates complex turning and moving racks
it eliminates liquid waste and minimizes solid waste
it has high throughput per hour
it can coat small as well as large complex shaped parts

ZINC-CADMIUM ALLOY FORMA nON IN THE Z-PVD

The Z-PVD technique is also suitable for coating alloys. In order to demonstrate the feasibility of alloy coating, a
new experimental arrangement was used as shown in Fig. 2. The experiments were conducted in a separate 25 cm
diameter evacuated stainless steel vessel. The vacuum level maintained was of the order of about 5 x 10.5 Torr,
and no glow discharge was used. Two source foil sections, one of zinc and the other of cadmium with 99.5%
purity each, were utilized for the alloy formation. The source foil dimensions were 15 cm x 3.8 cm x 0.05 cm
thick each. Each foil section was placed on a ceramic heater and heated independently below its melting point
using temperature controllers. The experiments resulted in zinc-cadmium deposits of various compositions. In
order to quantify the effect of process parameters on the alloy composition, a process model was derived using the
fractional factorial statistical design method. The effect of two independent variables, zinc source temperature
and cadmium source temperature, was studied on the alloy composition.

Most electroplated zinc and cadmium coatings range in thickness from 5 I-1ffi to 15 J.LIl1 and are deposited on mild
steel. Consequently, experiments were carried out on mild steel substrates. The substrates were made from
commercial grade, 0.195 cm thick cold-rolled medium carbon steel. These were cut into 1.15 cm2 pieces and
polished on 600 grit sandpaper. Later, these were polished to a mirror finish using 0.3 J.LIl1 alumina slurry on a
polishing wheel. Finally, the substrates were ultrasonically rinsed in acetone and alcohol before mounting on the
rack. For the alloy formation purpose, the cadmium foil temperature was varied between 230 and 260 DC,and

805
zinc source temperature was varied between 300 and 340 C. lbickness measurements were made using the
gravimetric method, and chemical composition was determined by energy dispersive spectroscopic (EDS) x-ray
analysis under a Scanning Electron Microscope (SEM).

The computational analysis of the data resulted in a process model for the alloy composition as a function of
source foil temperature. The analysis showed that the content of zinc in the alloy, Zn % Y = 61.06 - 11.57 Xl +
28.94 X2 + 12.32 X1X2 ,where Xl and X2 are factors related to cadmium and zinc foil temperature respectrively.
The resultant conrour map has been presented in Fig. 5. Further analysis indicated that, within the experimental
space used for the setup, the zinc content in the alloy was nearly proportional ro the zinc foil temperature. lbis
indicated that the zinc foil was vaporizing at a significantly higher rate that that of the cadmium foil at the
temperatures used. In order to equalize the vaporization effect, a higher cadmium temperature range was
necessary. Nonetheless, zinc-cadmium alloys containing 7% to 97% zinc were deposited on steel substrates. lbis
demonstrated the feasibility of coating zinc-cadmium alloys of various compositions in the Z-PVD process.

The Z-PVD concept has been advanced further ro commercial production. A pilot apparatus has been in
operation in order to coat zinc and cadmium on industrial components. The apparatus consists of a 60 cm III x
75 cm long cylindrical outer main. chamber as shown in the photograph of Fig. 6. The vapor-bath is mounted
inside on a rack. The parts ro be coated are placed on a loading-rack such as the one shown in the phorograph of
Fig. 7. lbis rack is suspended in the vapor-bath. The typical coating cycle consists of two minutes of pump
down to fraction of a milliTorr, argon purge and ion bombardment, vaporization, nitrogen back-fil~ and unload.
Load and unload times are typically one minute each. The vaporization is about two to three minutes for a 8 ro
12 ~ cadmium coating. The load-ro-unload cycle time is less than 15 minutes.

806
1be complete process cycle has been automated using'PLC controllers for a production plating operation. After
nearly a year of daily production, it has been demonstrated that the vaporized material is coated only on the
substrates. Since there are no extraneous deposits, routine scraping or cleaning of the vapor-bath; chamber walls
and fixtures has not been necessary. Hundreds of runs and thousands of parts have been processed without waste.
Interestingly, the only waste generated has been that of gloves and cloth-wipes used in handling cadmium and
coated parts. However, even this waste is eliminated when zinc is used for coating.

THE PILOT PRODUCTION OPERATION

As shown in the process flow chart of Fig. 8, the pilot-line consists of only four process steps and one quality
control inspection as opposed to dozen or more process operations in electroplating. Furthermore, there is no need
fur a waste treatment facility. For a batch of parts, the start-to-finish process time in the five-step operation is
less than an hour. The operation minimizes the use of hazardous liquids, there is little solid waste, and the
operation is occqpationally safe.

807
 Incoming parts are degreased in an aqueous degreaser and dried in the air. Descaling is performed using dry-
blasting with 230 grit aluminum oxide media. Subsequently, the parts are coated with cadmium or zinc and then
treated in a bath of chromate conversion as required by most customers. The cadmium quality is measured
according to standard U.S. specification QQ-P-416 and U.S. military specification Mll..-C-8837. The Z-PVD
cadmium coatings have passed well over 4,000 hours of salt-fog tests according to ASTM B 117 specification.
The quality control inspection consists of thickness measurements using magnetic and eddy current methods,
and adhesion monitoring using tape-test on customer parts. Additional adhesion tests are performed on coated
test coupons using the bend test. A pull-test apparatus is used for quantitative determination of the adhesion.
All operations have been documented and consecutive processes have been setup to run a smooth production
operation. In addition, statistical process control (SPC) has been implemented to secure high quality of the
product.

CONCLUSION

The "zero-waste" dry plating (Z-PVD) is a robust, economical and environmentally safe method for coating zinc
and cadmium metals on steel. The vapor-bath concept of the Z-PVD has overcome several disadvantages of the
conventional PVD as described in this article. The coatings deposited in production have been thoroughly tested
for adhesion, corrosion and uniformity according to the U.S. industry standard QQ-P-416. The results indicate
that Z-PVD coatings are at least equal in performance to those of electroplated coatings. The coating uniformity
and cavity coverage studies show that the quality of the Z-PVD coatings is superior to electroplated counterparts.
The coating equipment has provided repeatable performance and acceptable thickness control from run-to-run
over a period of a year.

ACKNOWLEl>GMENTS

The zero-waste dry plating research conducted from the early phase to the pilot-line development has been funded
by the U.S. EPA under the Small Business Innovation Research (SBIR) program. Additional SBIR funding has
been provided by the National Science Foundation (NSF), Defense Advanced Research Projects Agency
(DARPA) and the Office of Naval Research (ONR). IonEdge also appreciates the Materials Laboratory and the
Engineering Research Center, Colorado State University (CSU) for providing research assistance and facilities
under a Collaborative Research Agreement. Special thanks to Dr. W. Sampath, Director, Materials Laboratory,
CSU, for valuable guidance and encouragement.

REFERENCES

1. Meredith, 1. W., et al, EPA Report # EPA-600/S2-81-064 and NTIS PB-81-109-92.

2. Meyer, W.T., SAB Tech. Paper Series, No. 860612, Int.Congress and Expo, Detroit, MI, Feb.24-28,1986, p 5.
3. Horelick., Plating and Surface Finishing, Vol. 69, No. 11, Nov. 1982, pp 30-33.
4. Poll, G. H., Cadmium Council Report on Reilly Plating, Gardner Publications, NY, NY, 1985, P 1-6.
5. Holmes, V. L., et al, AFESC Report, Aug. 1989, DTIC Publication No. AD-A215-633, pp 102-108.

808
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Development of Nonchromate Treated Tinplate having

Excellent Resistance to Yellow Staining and Smudging
Tomonari OHGA 1
, Hironobu MIYAZAKI2
ISurface Treatment Lab., Steel Research Laboratories, Nippon Steel Corporation,
20-1, Shintomi, Futtsu-shi, Chiba-ken 293, Japan
2Sheet & Coil Div., Yawata Works, Nippon Steel Corporation,
leI, Tobihata-cho, Tobata-ku, Kitakyushu-shi, Fukuoka-ken 801, Japan
ABSTRACT
The resistance of nonchromate treated tinplate for powdered milk cans to yellow staining and
smudging with the passage of time was studied. Anodic treatment in a sodium phosphate solution was
found to be effective as a nonchromate treatment, and the resistance. to smudging was found to be
improved by adding cathodic treatment as a pretreatment.
The O/Sn ratio of the tinplate with anodic treatment determined by using AES was higher than that
of tinplate with cathodic treatment and the P'e/O ratio of the tinplate with anodic treatment scarcely
increased with the passage of time.
In addition, the refractive index and thickness of the tin oxide film with anodic treatment measured
by ellipsometry scarcely changed after the passage of time, and the binding energy of Sn3d XPS spectra
of the tin oxide film with anodic treatment also hardly changed.
Keywords: tinplate, nonchromate treatment, yellow stain, smudging, AES, XPS, ellipsometry,
tin oxide film
1. INTRODUCTION
Generally, tinplate is subjected to reflow treatment after tinning and then to chromate treatment in a
sodium dichromate solution as che!11icaltreatment.
It is known well that tin surface oxidation produces stannous oxide (SnO) or stannic oxide (Sn02).
At high temperature, as when lacquer is baked, SnO mainly is formed, while Sn02 mainly is formed
during storage at room temperature 1)-3). If the thick tin oxide film is formed on the tinplate surface, the
whole surface is stained yellow 4) because of its interference color, and the commercial value of the
tinplate is lost. In addition, the b~ittle and thick tin oxide layer flakes off and fall.sinto the contents of
the cans as smudges that look like black powders.
Although chromate treatment is greatly effective in preventing the decrease in tinplate performance,
the tinplate for powdered milk cans carinot be chromate treated for hygienic reason~ and is required
nonchromate treatment.
There are many reports on the chromate treatment of tinplate 5) - 9J, but no report is to be found on
the technical study of the nonchromate treatment of tinplate, though there is one study on the general
idea of such treatment 10).
This paper clarifies the performances of the yellow staining and the smudging of tinplate with
anodic treatment in a sodium phosphate aqueous solution as nonchromate treatment and the various
surface characteristics of the tinplate that determine these performances are analyzed by AES, XPS and
ellipsometry.

2. EXPERIMENTAL
2.1 Samples

809 .
 In the laboratory, black plate with a temper 4 (HR30T : 61 3) and a thickness of 0.22 mm was
0
electrolytically cleaned in a 5 weight % sodium hydroxide solution at 70 e as pretreatment and then
electrolytically pickled in a 10weight % sulfuric acid solution at room temperature.
The black plate was tinned in a circulation cell at a flow rate of 2 rn/s using Ferrostan electrolyte.
The tin coating weight was 5.6 g/m2 Tinning was followed by reflow treatment.'
Then, three types of treatment were applied: one sample (No. A in Table 1) is prepared by 1C/dm2
anodic treatment after 1 C/dm2 cathodic treatment galvanostatically at 1 C/dm2 in a 30 g/dm3 sodium
0
phosphate (Na3P04 12HP) solution at a pH value of 2.5 at 50 e. And another sample (No. B in Table,
0

1) is prepared by 2 C/dm2 anodic treatment. Next, as a reference, one more sample (No. C in Table 1)
was prepared by 2 C/dm2 cathodic treatment. For oiling, the samples were immersed in a DOS (dioctyl
sebacate) solution in hexane to get a fixed amount of oiling. Three types of the post-treatment are
summarized in Table 1.

2.2 Evaluation of Performance Characteristics

2.2.1 Yellow staining
The samples were placed one over another and packed with filter paper., After kept them at a
temperature of 38 e and a relative humidity of 85 % for period of 15 days, one month, and' three
months, the degree of yellow stain was visually observed.
2.2.2 Smudging
After the passage of each duration mentioned above, the samples were placed one by one on a flat
steel plate. V-shaped magnet of 4kg total weight wrapped in Japanese paper was reciprocally passed
once over the same place of each sample, and the smudges attached to the Japanese paper were visually
observed.

2.3 Electrochemical Determination

2.3.1 Determination of the amount of tin oxide
The amount of tin oxide before and after the passage of time was determined by the amount <?f
electrolytic reduction charge in deaerated 0.001mol HBr.
2.3.2 Anodic polarization ch~racteristics of tinplate
The anodic polarization characteristics of tinplate were determined potentiostatic'scanning method
(10mV/s), using Nichia Seiki's CW-E2 potentiostat and with an SCE (saturated calomel electrode) as the
reference electrode. The anodic polarization characteristics of tinplate without pretreatment and
tinplate with I C/dm2 cathodic treatment in a sodium phosphate solution at 50 e as pretreatment were
determined in a sodium phosphate solution at 50 e. The measured area was 100mm2(10 X 10mm).

2.4 Surface Layer Analysis

2.4.1 Surface layer analysis by AES (Auger electron spectroscopy)
The O/Sn and Fe/O ratios in tin oxide film for as received samples and acceleration tested samples
were determined using Perkin Elmar's ESCNAES (550 special type). The samples were kept at a
temperature of 70(; and a relative humidity of 85 % for three days as acceleration test of tin oxidation.

810
2.4.2 Tin oxide film analysis by ellipsometry
The tin oxide films for as received samples and acceleration tested samples were analyzed by the
multi-incident angle method using Mizojiri Kogaku's ellipsometer.
2.4.3 ,Surface layer analysis by XPS (X-ray photoelectron spectroscopy)
The surfaces layer of as received samples and acceleration tested samples were analyzed by using
Shimadzu Seisakusho's ESCA 750.

3~ EXPERIMENTAL RESULTS
3.1 Pedonnance Characteristics and Evaluation Results
Figures 1 and 2 show the results of 'test of the yellow staining and smudging resistance of the
samples. The yellow stain of the sample with cathodic treatment progressed with the passage of time,
and its smudging resistance sharply decreased correspondingly.
On the other hand, the two samples with anodic treatment were scarcely stained yellow with the
passage' of time. The smudging resistance of the sample with cathodic pretreatment before anodic
treatment did not decrease at all, while that of the sample with anodic treatment somewhat decreased
after a long duration of three months.
Under the accelerating conditions (70 Cand .85 % for three days), almost the same results of
yellow staining and smudging resistance as above were obtained. '

From these results, it is cleared that the yellow stained sample has not exhibited good smudging
resistance. On the other hand, the sample that doesn't stain yellow has excellent smudging resistance.
The thick and brittle tin oxide film is considered to be the cause of the yellow stain and smudges.

3.2 Electrochemical Detennination Results

3.2.1 Results of the amount of tin oxide
Based on the above results of yellow staining
and smudging resistance, the amount of tin oxide
of samples A, B and C were determined. The
results were shown in Fig. 3.
The sample with cathodic treatment showed a
sharp increase in the amount of tin oxide with the
passage of time. However, the sample with
anodic treatment scarcely showed an increase in
tbe amount of tin oxide.

811
 These results indicate that the thick tin oxide film is considered to be the cause of yellow stain
because of its interference color, and the thick and brittle tin oxide film causes the smudge.
3.2.2 Anodic polarization characteristics of tinplate
. In order to clarify the effectiveness of cathodic pretreatment before anodic treatment, the anodic
polarization characteristics of the tinplate with and without the cathodic pretreatment were determined in
a sodium phosphate solution. Figure 4 shows the results. As seen from these results, current in the
passiVe state for cathodically treated tinplate is lower than that for tinplate without cathodic
pretreatment.

3.3 Surface Layer Analytical Results

3.3.1 Results of surface layer analysis
by AES
The a/Sn ratios for the as received
and the acceleration tested samples
subjected to the three types of treatment
were determined by AES. The results
are shown in Fig. 5. The a/Sn ratios
of the samples with anodic treatment
were initially higher than that of sample
with cathodic treatment, that is, over 1.5
and scarcely changed after the passage
of time. However, the a/Sn ratio of
the sample with cathodic treatment was
initially low.
Figure 6 shows the changes in Fe/a
ratios. While the Fe/a ratio of the
cathodically treated sample greatly
increased with the passage of time, those of the anodically treated samples did not increase noticeably.

3.3.2 Results of tin oxide film analysis by ellipsometry

. Table 2 shows the results of the refractive index and thickness of the tin oxide film by multi-
incident angle ellipsometry. All the test pieces just after they were produced showed a refractive index
of about 1.5 and.a thickness of about 601\. As time passed, however, the values of the cathodically
treated sample greatly increased to 3.0 and 1201\, while the values of the anodic~lly treated samples

812
scarcely changed.

3.3.3 Results of surface layer analysis by XPS

. Figure 7 shows the spectrum of tin analyzed by XPS both before and after storage. Initially, a
peak corresponding metallic tin was observed from the cathodically treated sample, while no such peak
was detected in the anodically treated samples.
Regarding tin oxide, the anodically treated samples and the cathodically treated sample initially
showed different binding energy, but later they all showed the same binding energy.

4. DISCUSSION
The reasons why anodic treatment in a sodium phosphate solution imparts good yellow staining and
smudging resistance to tinplate are considered below.
Figures 1, 2 and 3 suggest that it is important to prevent the in(;rease in the amount of tin oxide due
to the passage of time so as to secure the yellow staining and smudging resistance. The amount of tin
oxide in the surface layers of the anodically treated samples scarcely increased with the passage of time.
Furthermore, the sample with cathodic pretreatment and then anodic treatment was superior in
long-term smudging resistance as well compared to thesample without cathodic pretreatment.
Cathodic pretreatment performed greatly decreased the amount of t~noxide, which did not increase
with the passage of time. On the other hand, the initial amount of lin oxide in the surface layer of the
sample with anodic treatment was large and it slightly increased with the passage of time. The brittle
and thick tin oxide film causes the yellow stain and flake off as smudges. It is considered that the
difference in the absolute value of the amount of tin oxide between the samples with and without the
cathodic pretreatment was reflected in the difference in long-term smudging resistance.
The anodic polarization curves are shown in Fig. 4. The current in the passive state for
cathodically treated tinplate is lower than that for tinplate without cathodic pretreatment. The low
current in the passive state indicates that the measured surface is covered with the dense passive film.
These results are considered that the effectiveness of cathodic pretreatment was due to the fact that the

813
tin oxide film formed during reflow treatment was reduced firstly by cathodic treatment and then
changed into dense tin oxide film by the following anodic treatment, that has excellent smudging
resistance.
Regarding the yellow stain, the refractive index of the tin oxide film of the cathodically treated
sample increased with the passage of time, as seen from Table 2. This is presumably due to the
increase in iron content of the oxide film, ,as suggested by the AES analytical results shown in Fig. 6.
Cathodically treated tinplate becomes yellow stained with the passage of time due to the increase in the
thickness and the refractive index of the tin. oxide film because of its interference color.
The source of iron is the pinholes in. the tin coating layer. Anodic treatment is considered to
prevent the increase in iron content of the tin oxide film by changing the iron in the pinholes into iron
phosphate and thereby sealing the pinholes.
Furthermore, it is considered from Fig. 7 that the anodically treated sample and the cathodically
treated sample are different in quality of the initially formed tin oxide film. In the case of the
cathodically treated sample which becomes yellow stained, the tin oxide film which grows with the
passage of time is different in composition from the initially formed one.
Although the difference between the two kinds of tin oxide film is considered to result from the
difference between SnO and SnO:z, it was difficult Jo quantify the two kinds of tin oxide separately
because the binding energy of Sn2+was close to that of Sn4+11);

5. CONCLUSION
. Regarding the nonchromate treatment of tinplate, the following points were made clear:
1) Anodic treatment in a sodium phosphate solution imparts good yellow staining and smudging
resistance to tinplate. Also, cathodic pretreatment performed for anodic treatment improves the
smudging resistance.
2) The O/Sn ratio of tinplate with anodic treatment in a sodium phosphate solution determined by AES
is higher than that of tinplate with cathodic treatment. The Fe/O ratio of tinplate with anodic
.treatment determined likewise does not increase noticeably with the passage of time.
3) The refractive index and thickness of the film determined by ellipsometry donor change with the
passage of time, and also the binding energy of the tin oxide- determined by XPS does not change.

REFERENCES
1) "Tinplate and Tin-Free Steel", Toyo Kohan Co., Ud, p178, Agune, 1970.
2) T. Oyama, K. Matsuzaka and A Miyaji: Toyo Kohan, 15, p24, 1966.
3) T. Oyama, A Miyaji, T. Nemoto and K. Yamada: Toyo Kohan, 16, p56, 1969.
4) ''Tinplate and Tin-Free Steel", Toyo Kohan Co., Ud., p138, Agune, 1970.
5) Y. Takei, O.Yoshioka, H. Kawamura and T. Fujimoto: Tetsu-to-Hagane, 73, A139, 1989.
6) S. Maeda, Y. Komata and H. Asario: Tetsu-to-Hagane; 5, p539, 1978.
7) V. leroy, J.P. SerVais, L. Habraken, L. Renard and J. Lempereur ; Ist Int. Tinplate Conf., p399,
London, 1976.
8) J.P. Servais, J. Lempereur, L. Renard and V. Leroy: Br. Corros. J., 14, p126, 1979.
9) H. Kawamura, o. Yoshioka, Y. Takei and T. Fujimoto: Toyo Kohan, 28, pI, 1989.
to) Japanese Patent: No. 52-53739.
11) S. Maeda, T. Asai and T. Sawairi: 2nd Int. Tinplate Conf., p286, London, 1980.

814
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Corrosion of Tinned Sheets During Transportation-

A Case Study
Inder Singh and A.N. Mukherjee
National Metallurgical Laboratory,
Jamshedpur-831 007, India

ABSTRACT

At buyer's end complaints regarding black stains/spots on the tinned sheet transported by a Tin Sheet
Manufacturing Co. were received very frequently. The problem was investigated thoroughly. In general, the.
tinned sheets are stacked one above the other and in between Di-octyl-sebacate (DOS) ill applied which acts
as an inhibitor as well as the lubric3nt. Normally, 1000 sheets are stacked in a bundle, Strapped crosswise'and
then transported to different parts of the country. On examination of the whole system, it was observed that the
sheets were packed loosely, resulting in fretting corrosion due to uneven load on the sheets and the relative
movement of the sheets. Further, the DOD was found to be acidic in nature. No fault in electro-tinning process
was observed.
The potentiodynamic polarization studies on the untreated and treated sheets with DOS and DOS
containing stearic acid and sodium nitrite were also conducted in 3.5 % NaCI solution. The OCP was found to
be more negative in comparison to the treated sheets and the corrosion rate of the treated sheets was also on the
higher side: Photographs show that there is dissolusion of tine coating, associated with fret. The data are
discussed in deails. Recommendation for the solution of the problem are given.

INTRODUCTION

Complaints by the buyer at a distance place regarding the black stains/spots on the tinned sheets were
lodged with a Tin Sheets Manufacturing Co. very frequently. The problems which was referred to NMLfor its
investigation was studied thoroughly. The affected areas on the tinned sheets were cut for examination, study
and photographs

After tinning and normal processing the sheets are stacked one above the other and in between the
sheets Di-octyl sebacate (DOS) is applied which.acts as both inhibitor and lubricant. About 1000 sheets are
packed, strapped crosswise as shown in Fig,l.and then it is transported to different parts of the country. It was
reported that the black stains developed during transit. The same is not seen during storage at works.

815
OBSERVATIONS

On examining the whole system, it was observed that packing of treated tinned sheets with DOS was
not done properly and uniformly and the load distribution on the sheets was also not uniform. At some place,
the sheets were strapped too lightly and at other places too loosely. This had resulted in relative movement of
sheets during transit and friction amongst

EXPERIMENTATION

Affected areas of the tinned sheets were collected for examination and study at the lab. The affected
areas were examined using magnifying glass. Samples of DOS was also collected to know its alkalinity/
acidity. 24 gms of DOS which is insoluble in water was shaken with 100 ml of distilled water. The pH of the
resultant solution was taken using Toshniwal pH meter. The experiment was repeated thrice. The data are
set-forth in Table-2 Liquid chromatographic analysis of DOS was also carried out to confirm its molecular
structure. (Fig.2)..

Potentiodynamic polarization studies on the untreated and treated tinned sheets with DOS containing
stearic acid and NaN~ as inhibitor were conducted using PotentiosatiGaivanostat of PARC-273 in 3.5 %
NaCI solution at room temperature. One square centimeter area of the sample were exposed for polarization
test at a scan rate of 5 mY/Sec .. A saturated calomel electrode was used as a reference electrode and platinum
(oil as an auxiliary electrode. The results of the polarization studies are showri in Table-l and Figs 3-7.
Photographs of the affected areas was taken (Figs. 8-11).

RESULTS AND DISCUSSION

Liquid chromatograph curve and data indicate that the DOS which is being used is a perfect and
stable compounds (Fig.2). Table-l shows that OCP of treated tinned sheet.is more negative in comparison to
untreated tinned sheet., indicating high corrosion rate which is found experimentally (Figs.3-7). On
neutralization of DOS with mild alkali, the potential is found to be positive and the corrosion rate comes down
and equivalent to untreated tinned sheet.(0.12 mpy). On treatment of the tinned sheet.with DOS containing 0.2
% stearic acid, no doubt, the potential becomes positive (-469.78 mV), but the corrosion rate increases from
0.12 to 0.73 mpy. An attempt was also made to decrease the corrosion rate of tinned sheet. using DOS with
sodium nitrite, which is known to as a good passivator. Here, sodium nitrite does not inhibit the dissolution
of tin coating due to DOS, rather it increases the dissol~on rate from 0.12 to 0.29 mpy. Further, on
increasing the concentration of sodium nitrite from 0.2 to 0.5 %, the corrosion rate also increases from 0.21
to 0.55 mpyand OCP become more and more positive, indicating anodic polarization. This results in higher
dissolution of tin coating.

The micro-photographs at magnification of 80 indicate the dissolution of tin coating associated with
fret (Figs.8-11) The affected area appeared to have a good pattern with perforation. This substantiates that
there is dissolution of tin coating due to acidic nature of DOS and the pH of the DOS/distilled water mixture
was found to be acidic in nature (Table -2) The acidic nature of DOS what is being used by the conipany
contributes in the dissolution of the coating and substantiate the potentiodynamic data. The black spots
observed may be due to the oxidation oftin ions released during fretting,

816
CONCLUSIONS

1. The packing of sheet has loosely been stripped, resulting in abrasion/friction because of
relative movement of sheets in the package

2. DOS being acidic in nature which should have been neutral aggravates further the dissolution
of tin coating

3. Photographs indicating perforation substantiate the dissolution /abrasion of tin coating

4. Black spots observed on the sheets id due to the oxidation of tin during fretting/abrasion

RECOMMENDATIONS

1. It is recommended to pack tinned sheets securely and tightly such that here should not be any
relative movement during transportation

2. DOS should be neutralized with mild alkali before use.

ACKNOWLEDGMENT

The authors record their sincere thanks to Prof. P.Ramchandra Rao, Director, NML, Jamshedur for
giving permission to publish this paper.

817
818
819
820
821
Fig.7 Polarization curve of tinned sheet treated with DOS containing
0.5 % NaN02 in 3.5 % NaCI solution at room temperature'

822
823
824
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Corrosion Protection by SS-316 Coatings by

Different Thermal Spray Processes
Eklavya Calla and S.C. Modi
Metallizing Equipment Co. Pvt. Ltd.,
5th Chopasni Road, Jodhpur, 342 003, India

ABSTRACT

The corrosion protection ability of thermally sprayed stainless steel coatings in aggressive environments is
considerably limited as compared to bulk materials of same composition (I). The two main reasons for
the decrease in corrosion resistance are the porosity in the coatings and the ox.idation of elements
particularly chromium, during spraying process.
Stainless steel 316 coatings were prepared using different thermal spray prOCess, namely Air Plasma
Spray (APS), High Velocity Oxy Fuel system (HVOF), Flame Spray (FS), Arc Spray (AS) & by the
newly developed thermal spray system, HIJET 96 - a high velocity oxy fuel wire spray process wires. The
coatings produced were electrochemically evaluated in NaCI and in sulfuric acid solution. The structure
and composition of coatings were studied by optical microscopy & SEM. The porosity in the coatings
was measured and related to the corrosion resistance of the coatings. X-Ray diffraction studies for the
coating were also carried out.

Corrosion Protection by Thermal Spraying

Metallic/Non-metallic surfaces can be given corrosion protection by applying a suitable coating on them.
Thermal spray coatings protect the surface either cathodically or by providing a barrier to the entry of
corrosive medium to the substrate surface. linc & Aluminium are Anodic to steel & lience linc &
Aluminium coatings are widely used for the atmospheric corrosion. protection of the steel structures in
TV. Towers, steel structure of bridges etc. (4) eg.the TV. Tower in Mumbai is zinc sprayed for
corrosion protection. Thermal spraying offers the advantages of low operating cost & coatings can be
built upto thicknesses of <25 micron to >2mm. The Coatings for the above purpose are sealed to prevent
the entry of corrosive media through the pores. Corrosion protecton for periods of 30 to 40 years can be
achieved by spraying linc and/or Aluminium. Typical application of zinc spraying include. Railway
bridges, TV. transmission towers, Wind turbine towers, Hydro & Irrigation dam gates, LPG tanks &
cylinders, Liners of concrete tanks, Refrigerant coils, Large steel girders (5).

825
 A barrier coating provides the barrier between the substrate & the corrosive medium. Thermal spray
coatings can be used to provide such barrier coatings for specific corrosive environments. The coatings
generally given for such applications are the corrosion resistant metals & alloys, ceramics & plastics.
However the thermal spray coatings have proved incapable of protecting the substrate from corrosion in
aggressive environments. The coatings produced either by powder melting process (Plasma, Flame,
HVOF) or by wire melting process (Arc, Flame) have got certain inherent porosity. Moreover during the
spraying process phase changes in the sprayed material may occur, either due to the transformation at
high temperature or due to the interaction of sprayed particles with the spray gases & the ambient
atmosphere (6).
The. properties of thermal spray coatings are highly dependent upon the coating method used & the
parameters of spraying. The microstructure, porosity, hardness & bond strength of the coatings are
mainly controlled by the flame temperature & the velocity (Kinetic energy) of the molten particle (6).
The porosity in the thermal spray coating may be caused by improper melting of the sprayed material,
such porosity is usually> 0.5 microns in size. The pores of the size < 0.5microns in size are caused by
the solidification of individual lamellae which leaves a micropore between two lamellae. Moreover cracks
may also be present in the coating structure due to the residual stresses in the coatings (1), (6).
The interaction of the sprayed particles with the atmosphere leads to the formation of deleterious phases
like Oxides, Nitrides etc. The high temperature during the thermal spraying leads to the oxidation of the
sprayed particle. The temperature during plasma spraying are in the range of 14000C to 16000C &
during flame spray & arc spray are 3000C to 4500C. These temperatures are sufficient to oxidise most
of the metals & alloys. However the oxidation of the particles is somewhat retarded due to the velocity of
the particles which leads to low dwell time of the particles at higher temperatures (6).
Experiment

The aim of this study was to produce stainless steel coatings with various methods of thermal spraying to
obtain coatings with dissimilar microstructures i.e. with different porosities & levels of oxidation & to
find out the factors which affect the corrosion resistance of thermal sprayed coatings. Stainless steel 316
was chosen for the experiment.
Miller Thermal Powde~s AI-1082C was used for plasma spraying & powder flame spraying & AI-1082
powder was used for HVOF spraying (Table I) 1.6mm diameter wires were used for arc spraying &
flame spraying.
Plasma sprayed samples
were prepared using
SG 100 gun of Miller
Thermal (now Praxair) &
the HVOF samples were
prepared using Top gl,ln
of Miller Thermal using
Hydrogen as fuel.
Metallizing Equipment
Co.'s (MEC)
SPRAYJET -88 was used
to prepare the flame spray
samples & ARCJET -95
HV of MEC was used for

826
preparing the arc sprayed samples. The powder flame spray samples were prepared using MEC
POWDERJET -85.
SS-3l6 sprayed samples were also prepared by the MEC's newly developed gun HiJet-96. This is a wire
spraying gun in which the sprayed particles move at a supersonic speed. The thickness of coating for all
the samples was kept 250 microns. Plasma spraying was done using Ar as primary gas & Hydrogen as
secondary gas. Carrier gas was Argon. HVOF spraying was done using Hydrogen gas as fuel. The wire
flame spraying was done using Acetylene as the fuel gas while the HVOF wire spraying was done using
LPG as fuel gas. The arc spraying was done in the High Velocity (H.V.) mode & the current was kept at
50A & voltage at 32 volts. Table 2 gives the details of the samples prepared.

827
The corrosion resistance of the sample no. 2 in chloride environments was detennined by measuring the
breakdown potential of coatings in 3.5% NaCI solution at room temperature (2), (3).
The samples for the electrochemical evaluation of corrosion were mounted in such a way that only the
coated surface was in contact with the solution. A saturated calomel electrode was used as a reference
electrode thescan rate of potential was Imv/Sec.
The microstructure of the coatings was evaluated on SEM (Fig I) & the optical microscopy image
analysis system was used to measure th~ porosity of the coatings & the oxide content of the coatings.
Discussion and Results
The porosity & oxide content of different. coatings as
measured through optical microscopylImage Analysis
is given in table 3. The porosity content is the lowest
in the HVOF' sprayed sample (No.6). The high
velocity processes give very low levels of porosity
due to the high velocity at which the particles impinge
upon .the substrate or the previously deposited
coating.
The result of the electrochemical ~sts on the coatings
are given in Table 4. The polarization curves are given in Fig.3.
Fig.2 shpws the effect of % of chromium in steel on the
anodic polarization curves (1). The steels show low
Icorr with 'increasing % of chromium moreover the
potential range of the aotivearea also decreases with the
increase in chromium content. The sprayed coatings show
relatively high values of Icorr as compared to the bulk
AlSI-3l6.
All the coatings show the transition from the active to
passive region. The use of inert & reducing gases in
APS reduces the oxide content of the coating and the
maximum current density in active area however the
presence of an active peak in the coating indicates that
oxidation of chromium has occurred due to the mixing
of ambient air with the plasma gases.

828
FIG-3. Polarization curves for SS-316 in sulfuric acid (A, B,C, D, E)/ Polarization curves for SS-316
in 3.5% NaCl Soln (F).l (A) Sample I, (B) Sample 2, (C) Sample 3, (D) Sample 4, (E) Sample 5. (F)
Sample 2

The presence of large amount of oxygen and the air for atomising of molten droplets at the high
temperatures prevalent during spraying lead to substantial depletion of the chromium in the steel.
This leads to the decrease in the corrosion resistance of the coating as indicated by the high values of
Icorr & Ip when compared to bulk AISI-316. The high Ip values shown by the samples No.5 is
probably due to the high porosity of this coating. The corrosive media penetrates to the substrate due to
the interconnected porosity of the coating & thus high value ofIp is seen.

829
 The' sample NO.2 was also checked for corrosion resistance in 3.5% NaCI Soln. The potentiodynamic
curves in 3.5% NaCI soln at room temperatures showed no presence of a breakdown potential. This is
. due to the oxidation of the chromium in the coatings.
Conclusions
Although thermal spray coatings seem attractive for providing corrosion protection to various
substrates however they suffer from drawbacks like oxidation of coating species & porosity in the
coatings which renders it quite ineffective for corrosion protection uses in severe corrosive
environment. APS coatings appear very promising from the point of view of corrosion protection. The
high velocity processes are also promising as these coatings have very less porosity as compared to the
low velocity processes (Sprayjet-88, PowdeIjet-85). Moreover due to the high velocity of the particles.
the interaction time of the particles with atmosphere is very less which could result in lower oxide
content of the coatings. The parameters of spraying for the High Velocity processes should be optimised
to produce coatings with low levels of porosity alongwith low levels of oxides in the sprayed coating In
the case of HiJet-96 the replacement of atomising air with inert gas like Nitrogen or Argon might
result in lowering of the oxide content of the coatings considerably.
Potentiodynamic polarization measurements in sulfuric acid can be used for determination of the
quality of thermally sprayed stainless steel coatings. The corrosion resistance of thermal sprayed
coatings samples is considerably less as compared to the bulk AISI 316 stainless steel in dilute sulfuric
acid solutions.
The anodic polarization Curve for sample No. 6 & the X-ray diffraction phase analysis for all the
samples are ROt available at the time of sending this manuscript. These results will be incorporated into
the paper when they are received by us.

Acknowledgement
The authors want to thank Prof. AIS. Khanna of lIT, Powai, Mumbai for carrying out the Anodic
polarization test on our samples. Aknowledgement is due to Mr. Ashok Chandak of Mis Sreenath
Engineering Industries, ~agpur for preparing the HVOF coated samples for this experiment. The authors
want to thank Mr. N. Ravi ofIARC Hyderabad for carrying out the evaluations of the coated samples
References
(I) P. Siitonen, T. Konos, P.O. Kettunen in Proceedings ofthe 7th National Thermal Spray
conference Boston 1994.
(2) Corrosion Engineering' Mars G. Fontana McGrawHil1.
(3) ASM Metals Hand-Book Volume 13.
(4) Metallisation Application Bulletins & Data Sheets.
(5) Dr. K. Elaya Perumal, Seminar on Thermal Spraying Bangalore 1986.
(6) 'The Science & Engineering of Thermal Spray Coatings' by Lech Pawlowsky Publishers - Wiley

830
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

C'orrosion Study of Microencapsulated Surrogate Waste Forms

Using AC Electrochemical Impedance Spectroscopy (EIS)
Krishna Narayanan!, Raj Mehta2, Regina Sucaldito3 and Indira Chatterjee4
IGraduate Student in Metallurgical Engineering
2 Associate Professor of Chemical and Metallurgical Engineering
3Undergraduate Student in Biology
4Associate Professor of Electrical Engineering University of Nevada; Reno,
Reno, NV 89557 USA

ABSTRACT

The U. S. Department of Energy is interested in the stabilization, storage and monitoring of

the radioactive contaminated soils and sludges. In order to meet this objective, the
microencapsulation concept was used to convert the waste streams into an appropriate waste
form. The noninvasive Electrochemical Impedance Spectroscopy (EIS) was used to study the
corrosion behavior of the microencapsulated surrogate waste forms.

This paper presents the EIS test. results conducted using four different cement based
microencapsulated surrogate waste forms in three different lixiviants. The waste forms in the
form of "agglomerates" contained lead, zinc, cesium and a mixture of these metals. The
lixiviants were tap water, acetic acid, and dilute sulfuric acid .. The rate controlling steps and
time dependent characteristics were studied in an added dimension of frequency. T~e EIS data
was interpreted in the form of Nyquist and Bode plots. On the basis of the EIS data, a two-
layer model with Warburg impedance (TLMW) was fitted. This EIS data in the form of the
TLMW provided a qualitative and quantitative insight into the leaching process.

831
INTRODUCTION

The low level radioactive waste streams such as soils and sludges contaminated with heavy/toxic

metals and radionuclides need to be suitably transformed in an appropriate stable and durable

waste form fortheir storage in the DOE complex. These waste streams are analogous to the acid

mine tailings which have been successfully microencapsulated using binders such as cement, fly

ash, pozzolan and converted in the form of agglomerates which were strong and stable under

severe conditions [1,2]. The microencapsulation concept is therefore an attractive option for

stabilizing the radioactive soils and sludges as well. Figure I-a and l-b show the different steps

and the processes utilized in the microencapsulation scheme.

The success of microencapsulation is measured in-terms of the corrosion behavior of the

microencapsulated waste. The conventional measurement is done through the use of the

Environmental Protection Agency's (EPA) Toxicity Chemical Leaching Procedure (TCLP).

However, the TCLP method is an ex situ rather than an in situ procedure. It is also a very

cumbersome and expensive method. Literature search reveals that the use of AC

Electrochemical Impedance Spectroscopy (EIS) has been used to study the corrosion behavior of

pipelines and coatings [3,4,5,6] and the microencapsulated agglomerates [7].

On the basis of the arguments presented above, one can utilize the microencapsulation technique

as a means to prepare the waste form and the EIS method as a means to study the chemical

stability/corrosion behavior of these waste forms. Prior to using this concept on the real

radioactive waste streams, it was decided to use the surrogate waste stream. The "surrogate

waste stream" is defined as a mixture of uncontaminated soil spiked with ,different particulate

l;1eavymetals (Cs, Zn, Pb) as metal powders or salts. The "surrogate waste form" is referred to

the mixture of surrogate waste stream mixed with difterent binders (cement, fly ash etc.) in the

form of agglomerates or pellets prepared in a pelletizer.

832
ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY (EIS)

EIS has been used to investigate the dynamics of bound or mobile charge in the bulk or
interfacial regions of any kind of solid or liquid material: ionic, semi-conducting, mixed
electronic-ionic and even insulators. Results thus obtained may often be correlated with many
complex material variables: such as mass transport, rates of chemical reaction, corrosion and
dielectric properties, defects, microstructure, and compositional influences on the conductance of
solids. EIS is therefore useful as an empirical quality control procedure and at the same time can
contribute to the interpretation of fundamental electrochemical, electronic and electrolytic
corrosion processes.

In the EIS technique [8], the general approach is to apply an electrical stimulus to the electrodes
and observe the response. In a transient measurements a step function of voltage V(t) = V for 0

t>0; V(t) = 0 for t<O may be applied at t=Oto the system and the resulting time varying current
i(t) measured. The ratio V 0/ i(t), called indical impedance, measures the impedance resulting
from step function voltage perturbation at the interface. A second technique is to apply a signal
v(t) composed of random noise to the interface and measure the resulting current. The fourier
transform into the frequency domain from the time domain gives the impedance.

Another approach is to measure impedance directly in the frequency domain by applying a

single-frequency voltage to the interface and calculating the phase shift and amplitude, or real
and imaginary parts of the resulting current at the frequency. This is the most common and
standard technique and will be used in this experiment. The output is generally expressed as
Nyquist plot Bode plot or admittance plot. The Nyquist plot refers to the transfer function,
relating the real and imaginary part of the impedance and the Bode plot expresses frequency as a
function of impedance or phase angle in the logarithmic plane. These plots give valuable
information regarding the frequency response of the system. Using these plots, it is also
possible to represent the electrochemical cell as an electronic model. In other words, in this
experiment, the waste form immersed in aqueous medium is analogous to an electrical circuit

833
consisting of an array of resistors and capacitors. The parameters calculated and fitted at

different time intervals enlighten the kinetic changes the system undergo quantitatively. The

parameters when correlated with the physical process gives qualitative results.

EXPERIMENTAL MATERIALS AND PROCEDURE

The test materials used in this study were of two types viz., the microencapsulated surrogate

mixed waste forms and the lixiviants. The waste forms were prepared using the portland cement

and the fly ash with the composition as shown in Table I.

A conductive wire assembly was inserted into the stabilized waste form immediately after it's

preparation. This asSembly consisted of a conductive copper wire enclosed in a hollow glass rod.

The lower end of this wire was soldered to a 3-4 cm long platinum wire. The platinum wire in

turn was inserted into the waste form. After this insertion, the waste form/wire assembly was

cured. The electrochemical cell consisted of a reactor, Luggin probe, agglomerate/assembly as

working electrode, Hg/HgCI2 reference electrode and a graphite counter electrode. The cell was

filled with the appropriate lixiviant up to a level sufficient enough to immerse the waste form.

The Schlumberger SI 1260 impedance gain-phase analyzer in conjunction with the Schlumberger

SI 1286 ele'ctrochemical interface and a PC loaded with the Scribner Z-Plot and Z-View

windows version software was used in acquiring the data. The impedance data was collected in

the frequency range of as low as 0.3 Hz to as high as 1 MHz and the tests were performed

automatically in a batch mode. The data was collected for the time intervals t= 0, 3, 9 and 18

hours. The schematics ?f the experimental cell arid the schematics of the experimental set up

are shown in Figure 2 and 3 respectively.

834
 Table 1: Materials and conditions used in the EIS runs

Performance Criteria

The performance criteria used in evaluating the stability of the waste form was to measure the
charge transfer resistance of the waste form immersed in a lixiviant as a function of the waste
form-lixiviant contact time .. The charge transfer resistance is easily measured by the radius of the
arc on the x axis (Z' in the Nyquist plot). These discrete time measurements were made up to a
time period of 18 hrs chosen on the basis of TCLP (EPA Method 3) test time. The charge
transfer resistance is inversely proportional to the corrosion or metal dissolution rate and

835
therefore, higher charge transfer resistance equates to greater metal dissolution resistance offered

by the waste form to the surroundings. Ideally, one would like the waste form to be chemically

stable, which means that the metals should not dissolve in the surrounding aqueous media. This

condition, however, will only be identified by the EIS, as one of overload condition in principle.

However, the discretized overload measurements will guarantee the stability of the waste forms.

Any departure from the overload condition to a condition leading to the EIS measurement will

indicate the onset of metal dissolution. This measurement can then be used to study the

dissolution process and effect any changes that may be necessary for stabilization.

RESULTS AND DISCUSSION

The impedance data is generally interpreted in the form of three formats referred to as the

Nyquist plot, the Bode magnitude plot, and the Bode-angle plot In the Nyquist plot, the lower

frequency relates to the higher real Z' and the higher frequency relates to the lower Z'. This

complex plane impedance spectra mainly expresses two resistances. The first is the solution

resistance measured as the distance from origin to the high frequency point of the real

impedance. The second is the charge transfer resistance measure ideally as the diameter of the

arc. A smaller arc means less charge transfer resistance implying high corrosion or dissolution

of metal ions from the waste. In other words, the waste form is unstable. A large semi-circle arc

on the other hand is an indicator of greater chemical stability. The Bode-magnitude plot (log Izi

vs. Logro )can also yield solution and charge transfer resistance. At intermediate frequencies, the

break point of this curve should lie on a straight lirie with a slope of -1. Extrapolating this line to

log Izi axis at CdI = 1 yields the value of double layer capacitance (CdI)[ IZI = 1/CdI]. This result

can also be obtained from the Bode - angle plot by noting the frequency (ro 8max), where the phase

shift is maximum. From this frequency the capacitance can be calculated by ro 8max

= (1+Rt/RO)ll2/CRt. These Bode plots are sometimes considered useful over Nyquist plots

because they allow more effective extrapolation of data from high frequency. Also they can be

used when data scatter preclude adequate fitting of the Nyquist plot. However, it is seen that in

this study Nyquist plot is sufficiently informative.

836
Next, for a diffusion control, Warburg impedance has to be considered. This is generally in the

lower frequency range, usually indicated by the straight lines having an approximate slope of

forty five degrees to the normal. Quantitatively, when Z' is plotted against 1/sqrt(T), the slope is

termed as Warburg coefficient (F). The rate of diffusion is inversely proportional to F. In other

words, largerF amounts to the reduced rate of diffusion.

EIS of the Microencapsulated Zinc Waste Form

Figures 4-a and 4-b show the Nyquist and the Bode plots obtained in the tap water as the

leaching medium. The semicircle in the Nyquist plot clearly shows that the process is activation

controlled. The Warburg distortion in the low frequency shows the added diffusion control.

Upon examining the diffusion part of the spectra, the slope is seen to decrease from t=O to t=3

hours which means that the rate of diffusion slows down during this time period. However, there

is reversal in the value ofF from t=3 to t=9 hours indicating that rate of diffusion increases and

finally from t=9 to t= 18 Ius, the rate of diffusion again slows down. Therefore, during the test

period, the reversal in the diffusion rate is observed indicating the physical changes the

agglomerate is undergoing. The diffusion mechanism will also change due to precipitation and

dissolution reactions. It can be said that the charge transfer resistance (Rt) also follows a similar

pattern giving us an insight into the rate of metal dissolution i.e. the corrosion rate is inversely

proportional to Rt as per Steam-Geary equation. During the 18 hour period, we can see that the

Zinc dissolution is almost constant and the agglomerate is not stable.

Figures 4-c and 4-d show the Nyquist and the Bode plots obtained with sulfuric acid as the

leaching medium. Clearly, the Nyquist plot shows that the charge trans~er resistance increases

from t=O to t=3 hours, which is consistent with the decrease in diffusion rate. After three hours

the data. obtained is seen to be noisy and of high impedance. This electrode stability indicates

either the agglomerate has become stable due to the formation of some protective coating or all

the metal, the lixiviant was able to dissolve has leached out. From the corrosion behavior of the.

837
zinc waste form, it can be said that the latter is true.

Figures 4-e and 4-f show the Nyquist and the Bode plots obtained with the acetic acid as the
leachfug medium. Clearly, the charge transfer resistance consistently decreases from t=Oto t=18
.hours, which is consistent with the increase in the diffusion rate. Therefore, the corrosion rate
increases with time, for the period considered.

EIS of the Mi&:roeo&:apsulatedCesium Waste Form

Figures 5-a and 5-b show the Nyquist and the Bode plots obtained in the tap water as the
leachfug medium. The charge transfer resistance is way higher initially and indicates that the
waste form is quite stable. This is consistent with the highest crushing strength value obtained
for this waste. form. As time progresses, the arc gets smaller and smaller indicating the reduced
charge transfer resistance and reduced F, which consistently results in a higher rate of diffusion.
The extent to which the diffusion control distorts the low frequency depends on the relative
magnitudes of the charge transfer resistance, double layer capacitance and F. The process is seen
to be controlled less by activation control and to a greater extent by diffusion with time. It can be
predicted that the metal will dissolute soon and the agglomerate may not be stable for long.

Figures 5-c and 5-d show the Nyquist and the Bode plots obtained with sulfuric acid as the
leachfug medium. With, data of this type, the interpretation of exact Rt is difficult because the
extrapolation of the semicircle to real axis is not accurate. This can be better done by replotting
the data on a Z''ro against Z' or sqr. fu/ Y', where Y' is the real admittance. However, since
calculating the corrosion rate is not the aim,.the Nyquist plot will suffice here. It is seen that
relativel)' the Rt decreases with time and corrosion rate therefore increases. This indicates
instability of the waste form in the medium.

Figures 5-e and 5-f show the Nyquist and the Bode plots obtained with acetic acid as the leachfug
medium. The process is controlled by activation and diffusion control. Clearly, the charge

838
transfer resistance consistently decreases from t=9 to t= 18 hours, which is consistent with the

increase in the diffusion rate. Therefore the dissolution rate is increasing with time and in the

eighteen hour period not all the metal has leached out. The initial impedance values were very

noisy showing the stability of the agglomerate till about 9 hrs.

EIS of the Microencapsulated Lead Waste Form

Figures 6-a and 6-b show the Nyquist and the Bode plots obtained in the tap water as the

leaching medium. The agglomerate is seen stable initially, however, during the period 3-18

hours, the Rt has decreased consistently showing increased metal dissolution. Also the reduction

in F shows higher rate of diffusion.

Figures 6-c and 6-d show the Nyquist and the Bode plots obtained in the sulfuric ~cid as the

leaching medium. Though, stable initially, the metal dissolution is seen ~ 3 hours. In 9 hours

the slope of the diffusion spectra shows an increased control of diffusion from activation. In the

18th hour the Rt value is less and therefore the metal dissolution rate is high.

Figures 6-e and 6-f show the Nyquist and the Bode plots obtained in the acetic acid as the

leaching medium. Interestingly atthe very beginning and at the end, the data was quite noisy

indicating stability. It is expected that at the beginning, lead will solubilize and may form the

layer around the agglomerate resulting in .very high resistance. Similarly, at the end a similar

precipitation phenomenon might take place or all the possible dissolution should have occurred.

Clearly, the charge transfer resistance decreases from t=3 to t:=9 hours, which is consistent with

the increase in the diffusion rate leading to .solubilization of the lead which is v~ry much

expected. In acetic acid lead is highly unstable and therefore it can be said that all the possible

lead was dissolved between the 9th and the 18th hour.

839
EIS of the Microencapsulated Combined Waste Form

Figures 7-a and 7-b show the Nyquist and the Bode plots obtained in the tap water as the
leaching medium; Interestingly, the charge transfer resistance consistently increases and there is
consistent increase in F, which results in a lower rate of diffusion. This indicates that initially the
corrosion rate was very high and the metal dissolution rate had decreased substantially. This
effect could be from any of the metal constituent in the agglomerate or due to the combined
effect of two or more.

Figures 7-c and 7-d show the Nyquist and the Bode plots obtained in the sUlfuric acid as the
leaching medium. The impedance data lip to 9. hours was quite noisy and was of high
impedance. The ftrst data was obtained at 18 hours showing appreciable corrosion rate. Further
corrosion is expected to occur and the stability will be lost completely. But the time for
dissolution is seen higher than the tap water.

Equivalent Circuit Analysis

The impedance data obtained during the test runs was used in fttting an equivalent circuit. An
example of such analysis is presented in Figure 8 for the lead/acetic acid system. It is seen that a
TLMW (two-layer model with Warburg impedance) model such as described for a coated
electrode with diffusion contribution was found to be satisfactory. The value of the circuit
parameters are also listed in the table enclosed in the Figure 8. The pore resistance is seen to
decrease resulting in increased leaching. The values of double layer capacitance and coating
capacitance give a quantitative measure of the binder used for stabilization.

CONCLUSIONS

The following conclusions can be made from the this study:

840
1. For a given waste form, the stability and leaching mechanism was found to change
significantly depending upon the leaching medium.

2. EIS tests data on the stability of the waste forms in most cases was supporting and
consistent with their crushing strength and the chemical dissolution tests data [9].

3. The measurement of the charge transfer resistance and theWarburg coefficient at

different time intervals can give important insight into the kinds of precipitation and
dissolution reactions that are taking place in the vicinity of the waste form.

4. A TLMW (two-layer model with Warburg impedance) model was fitted to the
experimental data satisfactorily. The parameters give an insight into the physical changes
the electrode undergoes.

5. This procedure can be used effectively in conducting the in-situ testing for the long term
monitoring of the stored wasted forms.

ACKNOWLEDGEMENTS

The authors would like to acknowledge the fmancial support of this research from the U.S.
Department of Energy, Nevada Operations through the contract TIP NV06MW 14.

REFERENCES

1. X. SU;" Mitigation of Acid Mine Drainage by an agglomeration-Encapsulation Process,"

M.S. Thesis, Chemical and Metallurgical Engineering, University of Nevada, Reno, Dec.
. 1994.

841
2.. M. Misra, K. Yang, and R. K. Mehta," Application of Fly Ash in the Agglomeration of
Reactive Acid Mine Tailings," Journal of Hazardous Materials. 51 (1996);pp. 181-192.

3. F. Wei, I. Chatterjee and D. A. Jones, "Evaluation of Corrosion Degradation in Coated

Steel Using AC Impedance Spectroscopy,"Corrosion. Vol. 51,1995, pp. 97-104.

4. N. Murray and P.J. Moran," An EIS Study of the Corrosion Behavior of Polyethylene
Coating Holidays in Natural Soil Conditions," Corrosion Science. Vol. 45, No.ll, pp.
885-95, Nov. 1989.

5. J. N. Murray and P.J. Moran, Influence of Moisture on Corrosion of Pipeline Steel in Soils
Using In Situ Impedance Spectroscopy," Corrosion Science. Vol. 45, No.1, pp. 34-43,
Jan. 1989.

6. G. Thompson, K. M. Lawson and J.A. Beavers," Monitoring Cathodically Protected

Steel in Concrete Structures with Electrochemical Impedance" Techniques," Corrosion
Enli!:ineerinlZ~
VoL 44, No.8, pp. 581-88, Aug. 1988.

7. Misra, X. Su and I. Chatterjee," Application of Impedance Spectroscopy for the

Prediction of Reactivity of Acid Mine Tailings," Proceedings of the 1994 EPD Congress,
Ed. G. W. Warren, San Francisco, pp. 293-305, Warrendale, PA, Feb. 1994.

8. J. R. McDonald, Ed. Imoedance SoectroscODV.John Wiley & Sons, New York, 1987.

9. R. K. Mehta, I. Chatterjee, R. Sucaldito and K. Yang, "Mixed Waste Laboratory," Final

Report submitted to DOE-NV, Work Performed Under DOE/NV Contract TTP NV06MW
14/94, 56 pp.

842

Figure I-b: Schematics of the Processes Involved in the Microencapsulation Scheme

844
845
848
849
850
851
852
853
854
855
856
857
858
859
860
861
862
863
864
865
866
867
868
Figure 8 : Equivalent Circuit Analysis for the lead
waste form in acetic acid

869
 Part IV

Poster Papers
Proc. In!. Cont'. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Studies on Scale Inhibitors for Industrial Waters

A. Alice Arul Antony, G. Paruthimal Kalaignan, A. Gopalan,
K. Balakrishnan and T. Vasudevan
Alagappa University, Karaikudi, 630 003, India

ABSTRACT
This article deals with the evaluation of antiscaling efficiency of some of the modified polymer
systems under laboratory conditions. The modifications have been done in the polymer chain backbone of
conventional acrylate systems through the introduction of thib-end groups. The evaluating procedures
include both chemical and electrocherr.icai methods for inhibition ofCaCo3, CaSo4 and iron deposits. Thio-end
introduced polymers are found to be more efficient.

INTRODUCTION

In Industrial water treatment, the major emphasis is on preventing corrosion and deposit (scale)
formation. The scales generally consist of inorganic compounds like CaCo3, CaSo4, Ca(P04)2' CaF2, BaS04.
MgC03, Silica and Iron compounds, which are derived entirely from the ions ofthe system water. The encrustation
of mineral salts are formed by super-saturation of scale forming compounds in water. The type, nature and
extentof the scale is determined by many factors like increase in temperature, changes in alkalinity, concentration
of dissolved salts, high concentration of corrosion inhibitors, alternate weather e;onditions ate.,
One of the most accepted methods of avoiding such scale formation is by the addition of anijscalant
chemicals (or scale inhibitors). These scale inhibitors, when aaded in very small concentraticns to a normally
scaling water, delay or reduce or prevent the formation of adherent scale either by bringing morphological
changes of scale forming nuclei upon adsorption or by complexing with the ions responsible for scale formation
and keeping them in solution.
The depostion of CaC03 occurs due to the reaction between Calcium and dissolved CO2 / Bicarbonate
content. The scaling tel1dency is a function of pH, temperature and total dissolved solids. The nucleation and
growth of Calcium Sulfate from aqueous solutions are affected by various factors like temperature, pH and
impurity level. Polymers containing carboxyl groups such as Carboxy Methyl Cellulose, alignic acid,
polymethacrylic acid and Polyacrylicacid (PM) have been reported as scale inhibitors for gypsum scale. (1)
Iron arising from the corrosion products is not a persistent problem provided they are in dissolved form.
Precipitation will occur during industrial operation as carbonates or sulfides of iron. Iron (II) may be oxidised to
iron (III), which will get precipitated as ferric-hydroxide or hydrated form of ferric hydroxide. In most of the
cases, the presence of even a very small amount of iron (ous/ic) was found to decrease the antiscaling
efficiency of the polymers to a greater extent~2) Hence, besides the antiscaling efficiency ofthe polymers, the
ability to complex the metal ions like iron and manganese is therefore considered as an additional desired
property for water treating chemicals.

871
 Extensive work has been carried out and reported on the development and testing of antiscalants
(1-4). Both Inorganic and organic scale inhibitors have been widely studied. Polycarboxylates have been
reported for its enhanced dispersing capacity by the modification ofthe polymer backbone through the introduction
of different groups. (3)
In the present study the effect of introduction of sulfur groups in various forms to the backbone of some
of the conventional polymers on scale inhibition has been examined both by chemical and electrochemical
methods. The carbon-carbon double bond in acrylic acid and acrylamide can be made to react with other
functional groups which are capable of holding the cations in solution, preventing the precipitation of inorganic
salts. The sulfur groups intended to add as end in the polymer backbone include thiourea, thioglycollicacid and
thiodipropionicacid.
The modifications of polymer structure due to the introduction of the group are expected to have the
effects of enhanced water solubility, ability to avoid gelation and decreased molecular weight.

EXPERIMENTAL

Homopolymers and copolymers of acrylamide, acrylic acid and methacrylic acid were synthesised by
a method reported elsewhere (5). For introduction of thio groups as end in the polymer, conditions were so
monitored as mentioned in the earlier work(6).
The CaC03 and CaS04 inhibition tests were carried out as per NACE standards (7). Calcium and
bicarbonate containing brines were separately prepared and saturated with CO2, Test solutions were prepared
by mixing suitable amounts of brines to which specified concentration of polymers were added. Test solution
without the polymer was used as control. The Langlier Index calculated for the untreated test sample gave
positive value indicating the possible scaling tendency of the water and confirming its suitability as test solution
for the antiscaliilg chemicals. The test solutions were kept in a constant temperature water bath at 70 + 1c for
24 hours. After the test period the soluble calcium retained in solution was determined and the percentage
inhibition was calculated.
Similarly CaS04 inhibition efficiencies were calculated by mixing calcium and sulphate solutions keeping
the other operating conditions same.
To study the effect of ferrours ions on CaC03 scale solutions of ferrous sulphate and soidium bicarbonate
were prepared and mixed such that the ferrous ions concentration was 145 ppm. 5 ppm of polymer under
study, was added to the test solutions where pH was adjusted to 9.5. After allowing the solution to'stand for a
period of 24 hours, the solution was centrifuged to remove colloidal Fe(OH)3 and an aliquot amount of the
supernatant solution was tested for the ferrus iron retained in the solution by spectrophotometry.
The effect of ferrous ion on the inhibition of CaC03 scale was tested in presence of 5 ppm of ferrous
ions.
The formation of scale from typical scale-forming waters can be accelerated by cathodically polarising
the electrode(8). The formation of hydroxyl ions due to the reduction of oxygen increases the pH at the
immediate vicinity of the electrode causing rapid precipitation of scale forming substances at the interface. The
cathodic currents which is initially high on applying the potential decrease with time due to the coverage of the
electrode surface with the film, and finally attains a constant value.
The current-time measurements at constant potential were carried out using BAS 100A. The current
Vs time curves were recorded for various concentration of polymers with 350 ppm calcium concentration. The
intersection of the tangent drawn at the linear region with time axis, is taken as the scaling time ts, ie the time
when the electrode surface is almost fully covered by the scale formed.

RESULTS AND DISCUSSION

872
where, (Ca++)p = Concentration of Ca ions at the end of the test in solution contail)ing the polymer.
(Ca++)c == Concentration of Ca at the end of the test in polymer free solution and
(Ca++), = Total Ca concentration in solution before the test.
The inhibition efficiencies for CaC03 and CaS04 scale obtained for the various polymers are given in
terms of percentage efficiency in Table-1. Among the modified and conventional acrylate systems, (AA-AA)
and (MAA - AA) copolymers, with thio end groups are found to have enhanced' antiscaling efficiency. Thus the
inclusion of functional groups provides further possibility for hydrogen and chelate type bonding which are
suitable for binding the cations.

873
 The efficiencies of the polymers for inhibition of iion deposits were obtained spectrocolorimetrically.
The results shown in Figure -1 indicate the complexing (sequestering) ability of the p 11ymerswith ferrous ions,
as found out by spectrocalorimeter. Thio end polymers show better performance in all the cases of acrylic,
methacrylic and copolymer systems. Almost in all cases an optimum concentration of 180-200 ppm is required
to sequestrate the iron present in the solution (nearly 145 mg/1). For (MAA - AA) TGA polymer the threshold
level to keep tl1e available fe2> ions in solution is in the range of 120-140 ppm and therefore is found to be the
best ferrous sequestering polymer among the studied polyelectrolytes.

The effect of ferrous ion on the scaie inhibition efficiency of various polymers is shown in Figure-2. It
may be seen that the presence of ferrous ions siightly affects the CaC03 scale Inhibition in all the cases. Earlier
reports also reveal that the presence of ferrous/ferric ions in the feed water interferes with the antiscaling
efficiency of polyacrylates only slightly whereas the effidency of polyphosphonates to a greater extent.
Polymethacrylicocid show a marked decrease in the inhibition efficiency in presence of iron.

874
875
From Figure-4, it is seen that the scaling time increases with increasing amounts of polymer. In other words
the time required for the full coverage of the pt electrode with CaC03 is increased in presence of antiscaling
polymers. Also the residual current oberseved increases with increasing polymer addition (Figure - 5). The
residual current is a direct measure of the current when the oxygen reduction attains a steady state. Addition
of polymers inhibits the formation of scale giving ions to larger active areas for oxygen reduction.

876
CONCLUSION

Among the conventional systems, polymers with thio-end groups are found to have high antiscaling
efficiency. Thus inclusion of functional pendant groups provides sites suitable for binding the cations. The
ferrous sequestering ability is also found good, especially for (MMA - AA)TGA

The effect of iron on inhibiton of CaC03 deposition was very low except for polymethacrylic acid.

The current-time measurements also confirm the inhibition efficiency of the antiscaling chemicals as
shown by the scaling time and residual current.

ACKNOWLEDGEMENT

The authors are thankful to Tamil Nadu State Council for Science and Technology for providing the
grants for carrying out the project work.

One of the authors, Dr.K.Balakrishnan also thanks CSIR for providing funds under CSIR-Emeritus
Scientist Scheme.

REFERENCES

1. Zahid Amjad, Mat.Perf.,11, 52 (1989)

2. M.C.Cushner, W.C. Melchior and J.L. Przybylinaki, Ibid., 1,49 (1990)
3. S. Patel and AJ. Nicol, Ibid., 6, 41 (1996)
4. M. Lindahin, Edward W. Ekis Jr, Richard.J. mouche and Peter. A Nassos, Ibid., 6, 39 (1989)
5. L. Latha, A Gopalan, P. Manisankar, G. paruthimal kalaignan and S.S. Hariharan, J. Polymer, Mat.11 ,263
(1994)

6. S.Seetharaman, S.S. Hariharan, A Gopalan and N.R. Subbaratnam, Polymer Commun, 59(A), 395
(1989)

7. Test method "Laboratory screening tests to determine the ability of scale inhibitors and CaC03 from
solution". NACE, Houston, 1974.

8. C.Gabruelli, M.Keddim, H.Perrot, AKhalil, R. Rosset, M.Zidoune, J. App. EI.'Chem, 26, (1996)

877
Proc, Int, Conf. on Corrosion CONCORN '97
December 3-6. Mumbai. India

Effect of Variation of External Stress on the Oxidation

Behaviour of 9Cr-lMo Steel at 973 K
s. Rajendran Pillai, N. Sivaibharasi,
H.S. Khatak and J.B. Gnanamoorthy
Metallurgy 'Division, Metallurgy and Materials Group,
Indira Gandhi Centre for Atomic Research,
Kalpakkam, 603 102, India
Abstract
Specimens of 9Cr-1 Mo steels were subjected to external stresses in the range of 20 to 40
MPa. The behaviour of scale on oxidation was examined at a temperature of 973 K. The integrity
of the scale was recorded in-situ with the aid ofan acoustic.emissitm unit which responded to scale
cracking. Investigations revealed that the integrity of the scale was nearly intactduring oxida~ion at
the isothermal condition. However, it was affected during the cooling of the specimen due to
differential in the thermal expansion coefficients of the oxide and the alloy. Specimens were also
subjected to oxidation without the application of external stress in order to delineate the effect of
applying external stress. The durl/tions of experiment under each applied stress conditions were in
the range of25 to 140 hours. Post-oxidation examination of the scale was carried out using scanning
electron microscope. In the case of the specimens without external stress, spaUing was preceded by
buckling. Nearly the same behaviour was noticed when external stresses of 20 and 28 MPa were
applied. However, tl.ta stress of 40 MPa the scale showed wedge-type cracking prior to spalling.
Analysis by energy dispersive X-Ray spectrometry revealed the segregation of silicon and chromium
at the oxide ridges. Such segregations were more predominant in the case of the specimen subjected
to external stress.

1. Introduction
Most of the, metals and alloys form a layer of oxide when they are heated to elevated
temperatures. The growth of the oxide is associated with an increflse of volume because its density
is less than that of the parent metal or the alloy. Oxidation generally proceeds by the outward
diffusion of cations and hence is considered to occur in an unhindered fashion without the
development of stress. But recently Rapp and others [l,2] have proposed that even \vhen the
oxidation mechanism involves the outward diffusion of it cation, the interchange of cations occurs
with the vacancies in the oxide film. Such an interchange causes oxidation to occur within the scale
resulting in the generation of growlh stress. On the other hand, when lhe kinetics of oxiJalioll is
controlled by the diffusion of oxygen into the metal surface (through the interface of the oxide layer
that is already generated), the growth of oxide inevitably occurs under stress. In this case the
formation of fresh oxide occurs at the oxide-metal interface [3,4]. Thus unconstrained growth of the
scale occurs only in very rare cases when the metal atom density in the alloy and the oxide is the
same.
Oxidation does not a/Tcet the alloy if a thin impervious layer is formcd. Howcver. this is
seldom the case due to factors described above. The scale, in general, undergoes buckling and
cracking due to differentiai expansion. Such a loss in integrity of the scale is even more predominant
under non-isothermal conditions, especially during cooling of a component.
In a service environment the components are also subjected to stress introduced due to the
operating system. This external stress also affects the integrity of the scale because ox:des have very
878
low tensile fracture strain [5,6]. Relaxation in the stressed oXide occurs predominanOy through two
ro).ltes; viz. by creep oftbe oxide or its buckling and cracking. Thus, the integrity of the oxide scale
is influenced by growth stress, thermal stress and externally applied stress ..
Alloys of the type 9Cr~IMo steel and itsmodified varieties are favoured structural materials
for the steam generator systems owing to the superior resistance to wafer induced stress corrosion
cracking, when compared to the austenitic steels. Oxidation followed by spalling causes the
continuous reduction in the thickness of the components. Thus it is necessary to have adequate
knowledge about the oxidation and spalling behaviour of these alloys in order to gauge the design
life or provide adequate allowance in the design stage itself. Oxidation behaviour of 9Cr-1 Mo steel
was studied in this laboratory. However, the impact of external stress in influencing the external
stress was examined only recently [8]. This investigation is an extension to unravel the influence of
varying stress levels.

2. Experimental
2.1 Material
Commercially procured alloy of. 9Cr-l Mo ste~l in the mill-annealed condition was used in
the investigation. The chemical composition is given in Table I. This material was tempered by
heating at 1003 K in a furnace for I hour followed by cooling in' air. Tensile specimens (of size
3x2.8x15 rnm gauge length) are prepared from the heat-treated plate these specimens were polished
to a surface finish of I J.1m.
Table 1 Chemical composition of the material

2.2 System for oxidation under stress

The schematic of the system to study oxidation urider stress is given in Fig. 1. The system
comprised of a stainless steel shaft hung vertically from a rigid mild steel frame. The region of the
shaft coming in contact with the high temperature of the experiment was fahricated using highly
oxidation.resistant alloy. '1lIe shan design also facilitated free movement in all the directions. Tensile
specimen was mounted at the centre of the shaft using serrated connectors. These connectors were .
also fabricated using oxidation resistant alloy. There was an arrangement to apply the desired stress
on the specimen by adding weights at the bottom of the. shaft. The movement of the central shaft was
coupled to an extensometer so that the elongation of the specimen was recorded at periodic intervals.
The furnace was placed in the desired position by using a putley arrangement. A thermocouple was
attached to the specimen to enable the accurate measurement of the temperature. The temperature
of the furnace was controlled by a proportional controller.
The integrity of the oxide scale was monitored by an in-situ device. The wave guide of the
acoustic emission system was press-fitted to the tensile specimen. The acoustic emission activity
associated with the cracking of the scale was determined using this unit. The schematic of the sstem
for the retrieval of the acoustic activity is shown in Fig, 2. The acoustic wave was converted to
electrical signal using a transducer. The resulting electrical signal was anlplified and filtered (using
a band pass filer with frequency in the range of 125 to 2000 kHz). The cumulative ring down counts

879
were monitored using a millivolt recorder.

2.3 Oxidation without external stress

To aid in the resolution of the effect of the external stress on the behaviour of the scale.
experiments were also carried out without the application of stress using the same system. The
experimental temperature of 973 K was controlled with an acc~racy of 2 K. The durations chosen
for the experiments were 25, 47, 70, 97, 120, and 140 hours.

2.4 Oxidation u~der external stress

After assembling the tensile specimen, a stress of 40 MP A. was applied on it by adding
weights. The oxide scale was monitored in the same way as described above. In this case also the
durations of the experiments were same as mentioned above. The effect of variation in external stress
on the oxidation behaviour was studied by carrying out the experiments under different stress
conditions of28 and 20 MPA.

2.5 Morphological changes on the oxidized surface

The morphological changes that had occurred on the surface ofthe specimens were examined
using a scanning electron microscope.

2.6 Chemical transformation on the surface

TIle chemical transformation that had occurred on the surface was monitored using Energy
Dispersive X-Ray Spectr'ometry(EDS). The analyzing beam was scanned in a horizontal direction
from the central point to either sides. The concentrations of iron, chromium and silicon were
determined by measuring the intensity of the characteristic X-Ray spectra emitted by these elements.
The scan interval was 6 to 7 f..lm.The grain size of the material was in the range 000 to 40 f..lm.Thus
by scanning nearly 60 f..lmat least one grain boundary was encountered. These grain boundaries were
the regions of ridge formation and elemental segregation.

3. Results and discussion

Examination of the acoustic emission activity revealed that the integrity of the scale was not
affected during the process of oxidation. The mechanism of oxidation was the outward diffusion of
cation and hence the new oxide was formed in a relatively unconstrained way. However, when the
specimen was cooled, compressive stress was generated on the scale. This strcss was released by tht::
cracking and spallirig of the scale. This process caused the release of strain energy in the form of
acoustic waves. The ring down counts obtained (when no external stress was applied) was monitored
initially. Similarly, the ring down counts when 40, 28 and 20 MPa of external stresses were applied
were recorded. The threshold drop in temperature for the on-set of acoustic activity was monitored
and l!iven in Table 2.
The weight changes of the specimen were determined (a resultant effect of oxidation and spalling)
by weighing the specimens prior to and after the oxidation experimcnts. In general, the specimen
under external stress showed enhanced weight gain when compared to the unstressed specimen. The
increase in weight was marginally higher when the external stress was higher. This behaviour is
attributed to the release of growth stress due to tensile elongation of the specimen. On the other
hand, spallation (by buckling due to differential contraction while cooling) was maximum in the case
of the unstressed specimen. One of the unstressed specimens even exhibited a loss in weight.

880
 The tensile elongation ofthe-spectm-ensls plotted in Fig. 4. The data obtained for the 140
hours durations were plotted. Data for the other durations were nearly on the same line. The strain
rates in all the cases were below the threshold required fo~ the spalling of the scale during isothermal
condition. There were a well developed primary, secondary and tertiary stages of creep only at the
stress level of 40 MP A. There were only primary and secondary stages when the stresses were 28
and 20 MP A. Thus, there is a threshold stress in the region of 28 to 40 MPa that causes high rate
of creep rate and cracking of the oxide scale.
The typical SEM micrographs of the specimens after the oxidation are given in Fig. 5. There
were generation of wedge-type cracks on the oxide scale only at the highest stress of 40 MP A. For
the specimens without external stress and for those stressed under lower stresses buckling preceded
spalling.
The examination of an oxidized surface of the specimens revealed the segregation of silicon
and chromium on the oxide ridges. Such segregation was more predominant in the case of the
stressed specimens.

4. Conclusion
. Specimens of9Cr-IMo steels were subjected to oxidation (T=973 K) under two conditions;
viz. with rio ~xternal stress and under the influence 'of different external stresses. Investigation
revealed that,
(I) application of external stress contributes to release of growth stress .
. (ii) the specimen subjected to stress of 40 MP A developed wedge-type cracks. In all other cases
spalling was preceded by buckling
(iii) The specimen subjected to stress developed enhanced segregation of chromium and silieon on
the ridges ..

Acknowledgment , .
The lluthors wish 10 acknowledge Ihc help or M.Radhika inlhc SEM and EDS analyses.

Reference
I. A.Pieraggi and R. A. Rapp: Acta. Metal!. 36(1988)1281

881
2. AStrawbridge and R.ARapp; J. Electrochem. Soc. 140(1994)1905
3. C.Roy and B.Burgess; Oxid. Met. 2(1970)235
4. AT. Donaldson and H.E.Evans; J. Nucl. Mater; 99(1981)38
5. AG.Crouch and R.B.Dooley: Corros. Sci. 16(1976)341
6. lC.Grosskreutz: J. Electrochem. Soc. 116(1969)1232
7. R.K.Singh Raman, A.K. Tyagi, K. Krishnan and lB.Gnanamoorthy: Mater. Sci. Techno!.
10(1994)593
8. S.Rajendran Pillai, N.Sivaibharasi, H.S.Khatak and J.B. Gnanamoorthy; in; Proc.
Symp. Localized Corrosion and Environmental Cracking, IGCAR, Kalpakkam (India) (1997)
paper C-31
9. M.Schuetze; Werkstoffe und Korrosion; 38(1987)397
fig: 4 Tensile elongation of specimen due to external stress
883
Fig. 5 SEM micrograph (a) unstressed specimen (b) external stress of 40 Mpa indicating the
wedge-type crack

884
Proc. Int. ConL on Corrosion CONCORN '97
December 3-6, Mumbai, India

Corrosion of Wagons-Due to Change in the

Condition of Consignment
M.P. Varma, 1 Anil Madan2 and D.C. Misra3
lAddi. Exe. Director (Met. & Chern.), RDSO, Lucknow, India
2General Manager, Rites, New Delhi, India
3Group General Manager, Rites, New Delhi, India

ABSTRACT
:

Tunisia is one of the foremost phosphate mineral

producing country in the world. This mineral is exported
worldwide both after processing as a fertilizer/acid and as
beneficiated ore. The transport of this ore is undertaken by
the TUNISIANRAILWAYS wi th the fleet of 898 open bogie wagons.
These wagons with the codal life of 30 years are signs of
extensive damagedue to corrosion. The situation has reached a
stage where urgent attention is required to ensure that the
capacity of the TUNISIANRAILWAYS for transporting this ore is
not impaired due to immobilization of wagons. Therefore, the
TUNISIANRAILWAYS awarded a consul tancy contract to RITES for
the study of the repurcussions of transport of phosphate ore
and determination of solutions. This paper deals with the
methodology adopted by the authors, who worked as consultants
in the project in the study of the corrosion problems and the
remedial measures suggested by them to combat the same.

INTRODUCTION :

Tunisia is one of the foremost phosphate producing

countries in the world and the mining of this ore is an
important aspect in the economy of the country. The mineral is
beneficiated by water washing method in washing plants located
in four mining centres. About 70% of the ore is meant for
transformation into fertilizer and acid is transported from the
washing plants to the chemical plants in humid form. The
remaining 30% is dried after beneficiation for transportation
mainly to loading points for export. Thetransporation of the
ore both in humid and dry form is undertaken by TUNISIAN
RAILWAYS who are utilising a fleet of 898 open bogie wagons for
this purpose. The age of these wagons are between 2 years

885
(200 wagons) and 16 years (698 wagons). The codal life of these
wagons is 30 years but signs of extensive damage due to
corrosion is being evidenced. The situation has reached a point
where urgent attention is required to ensure that the capacity
of TUNISIAN RAILWAYS for carrying this important consignment is
not impaired by immobilisation of wagons on account of
corrosion. Therfore, a consultancy was awarded for studying the
repurcussions of transport of phosphate in humid form and to
recommend remedial measures for combating the same.

OBJECTIVE

The objective of the consultancy was to study the

incidence/impact of transport of phosphate ore in humid form
containing upto 20% water on the wagon fleet and to ascertain
the exact causes of corrosion and to recommend a feasible,
rational and effective technical solution to combat the problem
of corrosion.

INVESTIGATION :

The wagons used for the transport of phosphate ore

are of three types as indicated below :
RDA Wagon (Germany) 698 wagons introduced in 1979-80.
MFGT (Tunisia) 100 wagons introduced in 1992.
AFR Wagons (France) 100 wagons introduced in 1993.
The chemical analysis of the steel samples taken
from these wagons revealed that the steel used for cassie of
wagons are as follows :
RDA Wagons Copper bearing carbon steel with 0.65% Cr
MFGT Wagons Carbon steel
AFR Wagons Copper bearing carbon steel
The Mech. properties of these steels are as per UIC-843AC 52 .
The analysis of dry and humid phosphate ore revealed
that the humidity level of phosphate varies from 0.74% (Dry
Phosphate) and 15.26%. The chloride content was found to be
200 ppm from all washing station ..The water analysis revealed
that in all washing stations the water was near neutral with
salinity varying from 1.54 to 8.38 gm/lit. The chloride
contents varied from 300 mg/lit. to 2500 mg/lit.
Wagons used for the transport of phosphate ore were
examined at various locations including TUNISIAN RAILWAY
Workshops, loading and unloading points and yards. The
examinations revealed the following facts :
In the last two years the humide phosphate carried by each
wagon has increased by 2.54 times.
The moisture level in the humide phosphate transported is
of the order of 10 to 15 percent.
During loading by dumpers in washing stations the wagons
suffer heavy damage.
At loading stations tracks are embeded in phosphate and
thus maintenance is not possible.

886
 Wagon tipplers do not turn through full 180 deg. and
therefore, large quantities of phosphate ore is left
behind in the wagons.
Lack of proper shunting arrangment at certian unloading
points is also causing damage to wagons.
On account of corrosion about 40% of RDA wagons required
replacement of full end walls, all colonnes and over 70%
of the sidewalls.
Corosion has begun on AFR and MFGT Wagons also.

From the observations made during the inspection of

corroded wagons and the analytical investigations conducted as
mentioned above, it was clear that corrosion on the inteior of
wagons can not be attributed to atmospheric condition. In this
context, it is intersting to note that there is no significant
corrosion on the exteriors of wagons subjected to natural
environment. Thus the corrosion on the interior of the wagon is
primerly on account of the product carried and is a classical
example of wet corrosion which occurs when a liquid is present
usually as aquous solutions or electrolyte. This is because
the solubles salts present in water are stronglyionised and
readily make a strong electrolyte conducive for corrosion to
occur. This was further confirmed in the laboratory tests where
steel panels immersed in dry phosphate did not show any
significant corrosion for 9 days whereas panels in .humid
phosphate showed high rates of corrosion. The experience of
SNCFT Workshop indicates that corrosion has become a serious
problem only in the past 2-3 years during which the amount of
humid phosphate transported per wagon went up by 2.54 times
wi th a corresponding decrease in the transport of dry
phosphate.
The basic cause of pitting corrosion in wagons
carrying phosphate is the presence of water contaminated with
chloride ions. Pitting corrosion is autocatylitic in nature
i.e. the corrosion process within a pit produces conditions
which are both simulating and necessary for continued activity
of the pit;
The rate of corrosion for a moisture level of 15.25\
was observed to the 1.28 mg/sq.cm/day while for a dry phosphate
of 2% moisture level the rate was 0.30 mg/sq.cm/day, thus
proving that the rate of corrosion increases with the moisture
content in the phosphate ore.

Inspection of corroded wagons revealed thick layers

of rust on the side and end walls upto height of 30 cm from
the bottom of wagons. The pillars of most of the wagons were
totally corroded. It was also observed that corrosion
progresses from widely dispersed pit to pit in close proximity

887
and the pits are covered by a cap of corrosion product. The
examination of the wagons revealed that the form of corrosion
occuring is of the type encountered on steel exposed to water
~ith chloride as contaminent. Micrographic examination of
corroded panels revealed the pits under the rust layer in which
fissures could be seen. The analysis of the corrosion product
showed the presence of chloride ions.

REMEDIAL MEASURES:

Based on the above observations, all the 898 corroded

wagons were bifurcated into the following three groups :
Group-I : 200 AFR and MFGT Wagons on which there was no
significant damage to wagon caisse.
Group-II : 200 RDA wagon on which mostly the pillers only
were damaged due to corrosion.
Group-III : 498 RDA wagons on which extensive damage due
to corrosion was observed on side walls,end
walls and pillers.

Thus it can be seen from the above out of the three

types of wagons used for the transportation of humid phosphate
ore, the RDA wagons have undergone more damage due to corrosion
as they had been in service for more than 16 years when
compared to the other two types of wagons namely MFGT & AFR
wagons.
A search for solution was made by systematically
studying the various options and the following priorities were
considered -
1. Design changes.
2. Change in -the construction material.
3. Protective coatings.

DESIGN CHANGE :

The design of wagons used for the transport of

phosphate ore did not present any acute problems so long as the
ore was in dry form. With the switch over to transporation of
humid phosphate the scenario changed due to the change in the
environment due to which severe corrosion is experienced. Thus
it became inavitable to make design changes to mitigate the
problem of corrosion. The interior of the wagons have a large
number of sharp corners, edges and nooks. The humid phosphate
adheres to the nooks and corners and get accumulated there and
is retained even after the unloading operations. This
accumulated ore does not dry up even after several days and
therefore the moisture and chloride ions are always present in
the nooks and corners leading to the onset of corrosion.
The main feature which prevents complete unloading of
the humid phosphate ore is the box section at the top of each

888
side wall. Obviously, the ideal solution for ensuring complete
unloading is to make entire interior of the wagon surface into
a perfectly smooth and continuous surface. To achieve this, one
of the solution suggested was to reduce the large number of
right angles and corners inside the wagon by shifting the
pillar exterior to the wagon side wall, which will
substantially reduce the area of the wagon exposed to corrosive
environment. To achieve this, the side wall sheets of the
existing wagons would have to be moved inside the colonnes,
whose shape is to be altered to HAT or U section so that the
exterior of the side wall provides sufficient surface area to
the wall of the wagon tippler against which it is turned for
unloading and there will be minimum loss of the internal
volume. A wider angle between the side walls and the floor
would alleviate most of the problems arising due to the
presence of sharp corners. Hence it was proposed to provide a
curved sheet of radius 175 rom R and to change the top coping
sheet angle from 20 to 30. A demonstration of unloading
wagons provided with 175 rom radius at the bottom arranged by
TUNISIAN RAILWAYS confirmed that humid phosphate do not get
lodged at the corners.

CHANGE IN CONSTRUCTION MATERIAL :

Regarding changing the construction material, it was

observed that copper bearing steel, though superior to plain
carbon steel from the point of view of corrosion, do not in
reality perform better under stagnant condition of the
electrolyte coupled with abrasion. This is because the salt
residues and dampness in the ore inhibit the formation of a

889
protective oxide film. It is also a well known fact that in
case of mechanical abrasion and contact with aggresive aquous
electrolyte, the anti corrosive effect of copper additive
decreases. In view of the above low alloy high tensile
corrosion resistance corten steel to HSA 355Wl of ISO : 5952-
1983 was recormnended both for modification of the existing
wagons and also for rebuilding. Welding electrodes and welding
wire suitable for corten steel were also recormnended as per ISO
Standards.

PROTECTIVE COATINGS :

Considering the corrosive environment in the interior

of wagons, the protective coatings should meet the following
requirements :
Resistance to water, resistance to ionic passage, strong
adhesion, abrasion and ability to withstand alternate cycles of
wet and dry conditions. To meet the above requirements, it was
considered that only only high performance organic coatings
should be used. These are speciality projects designed to
resist varied range of corrosive conditions. From the range of
high performance coatings available, those that offer the
desired characteristics are high build epoxy coatings and poly
urethane coatings. Based on the above, the following painting
system was recormnended for adoption.

WAGON INTERIOR :
2 coats of high built epoxy self primer - 250 microns DFT
2 coats of aliphatic polyurethane enamel - 60 microns DFT
WAGON EXTERIOR :
1 coat of high build epoxy self primer - 40 microns DFT
1 coat of aliphatic polyurethane enamel .- 60 microns DFT

The surface preparation standard recormnended was

Sa 2.5 to ISO:8501-1.Recoating was advised once in 6-8 years
depending upon the condition of the paint coatings.

CONCLUSION :

The recormnendations made by the consultants by way

of design modifications, change in construction material and
protective coatings had been accepted in toto by TUNISIAN
RAILWAYS. In fact they had implemented these recormnendations
on 10 wagons during rehabilitation repairs and the results have
been very encouraging. It is envisaged that it would be
possible for TUNISIAN RAILWAYS to continue transportation of
phosphate ore with the existing feeds of wagons by implementing
the recormnendations of the consultants and thus the fear of
irmnobilisation of wagons due to corrosion will be a thing of
the past.

890
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Role of Sulphate Reducing Bacteria on

Corrosion Process-A New Mechanism
s. Maruthamuthu, c. Stella, c. Jeyaprabha,
A. Mani and N.S. Rengaswamy
Central Electrochemical Research Institute,
Karaikudi-630 006, India

Abstract

Sulphate-reducing bacteria (SRB) are the most studied microorganisms in biological corrosion.
However, there is a great deal of controversy over the mechanism of corrosion enhancement. Until
now, no specific mechanism ofSRB corrosion has been identified as associated with physiology of
SRB. In the present study postgate medium has been used to find the corrosion mechanism on mild
steel. Electrochemical and weight loss techniques have been employed to study the mechanism of
corrosion. Electrochemical study reveals that 'anodic depolarization' is offered by SRB. At the
same time, the bacteria enhances localized attack. The present study concludes that the bacteria
enhances activation control in the initial period and enhances diffusion control reaction in the later
period.

Introduction

Sulphate-reducing bacteria (SRB) related corrosion in industrial water systems, which is of vital
importance to many industries, is much less comprehensively understood. It has been well
documented. For example, that accumulation of mixed population biofilms containing SRB in
industrial water systems cause corrosion (1-2). Field observations are influenced by a variety of
environmental factors which obstruct the study of corrosion mechanisms. Hence, there is a need to
bridge the gap between mechanisms derived from studies in the laboratory and the reality of field
observations. The anaerobic corrosion of iron and steel where sulphate reducing bacteria play a
part was described by Volwolzogen Kuhr and Van der Vlugt<3)(1934). Besides, stimulation of
anodic reaction by bacterially produced sulphide has been suggested by many authors (4-6).

The previous authors proposed SRB mechanism by using culture-medium(7-9)where the same
medium was used as control (without bacteria). But the present authors feel that bacteria cannot
be separated from organic nutrients. There is no report available on the influence of SRB with
inorganic and organic nutrients on corrosion process. Besides it is an imagination that if an
environment has high quantity of organic or inorganic nutrients what is the role of bacteria on corrosion
process. Hence, in the present study experiments were carriedout in two independent systems by
using Postgate medium.

891
Materials and Methods

Experiments were conducted in mixed cultures of SRB. By using postgate medium B, two systems
were made: (I) postgate medium (PGM) (Inorganic constituents + Organic constituents + SRB) (2)
Inorganic constituents of post gate medium (IPGM). Two mls. ofSRB cultures were inoculated in
the above medium and the influence of above bacteria with nutrients was studied. The mild steel
specimens were immersed and removed periodically from the medium and subjected to vanous tests
in the period of 10,20,30,40,50 and 60 days. For reproducibility, a minimum of6 specimens were
used for weight loss technique triplicate experiments were conducted for each electrochemical
study.

Weight loss measurements

Surface of the test specimens was polished successively with 1/0 to 4/0 emery papers and
degreased with trichloroethylene. Specimens of lx4xO.2 cm size were immersed in 500 ml of the
test solution for a period of seven days. Loss in weight due to corrosion was calculated.

Electrochemical Measurements
1. Pot~ntial Measurements

Mirror polished specimens were immersed in the above systems and potentials Vs saturated calomel
electrode were measured by using multimeter Model HIL2208.

2. Polarization study

Polarization measurements were carried out potentiodynamically using Potentiostat (AR Model
173) in conjunction with Potentioscan generator and XV recorder (Rikadenky Model R206) employing
stationary electrodes. The electrode potential was fixed at 200 mV negative to OCP and allowed
to attain a steady state value. The steady state polarization was carried out from -200 mV to +200
mV from the OCP at a scan rate of 0.5 mY/sec. icolT values were obtained from the plot ofE Vs i
curve.

3. Impedance study

A three electrode cell assembly was used for impedance measurements. A mild steel test specimen
as the working electrode, a large platinum foil as counter electrode and saturated calomel
electrode as reference electrode respectively were used. AC impedance studies were carried out
using computer controlled EG&G PAR system model M6310 with software M 398.

Results
1. Weight loss measurement

The weight loss data are presented in figure 1. The weight of PGM was lower (0.4 mpy) in
presence ofSRB upto 20 days when compared to IOPGM (0.62 mpy). After 20 days, the corrosion
rate in PGM increases gradually and starts to decrease after 40 days of immersion. The corrosion

892
rate of mild steel was about 0.22 mpy in 60th day. In IOPGM the corrosion rate was observed to
lie in the range between 0.62 mpy and 0.42 mpy with time.

2. Electrochemical study
a. Potential Measurement

The OCP shifted to negative side in the initial period upto 10 days and then moved to positive side.
After 12th day OCP became more positive when compared to IOPGM system (Fig.2).

b. Polarization Measurement

The potentiodynamic polarization behaviour of steel in PGM and IOPGM are shown in charasteric
parameters are given in Tables 1&2 and Figures 3&4.

Postgate Medium (PGM)

The corrosion current was about 0.0006 mAlm2 in 1st day and the current was about 0.0005 mA!
m2 in 10th day. The current gradually increased from 20th day to 60th day. It indicates that SRB
improves the passivity upto 20 days.

Inorganic based postgate medium (IOPGM)

The corrosion current was 0.027 mAlcm2 in first day and gradually decreased with time upto 60
days. At 60th day, the corrosion current was about 0.0017 mAlcm2 It reveals that inorganic species
present in the system improves the passivity with time.

c. Impedance Studies
Post Gate Medium (PGM) (Fig.5&6; Table3)

The solution resistance values were about 750 ohmlcm2 upto 20 days and were drastically reduced
in later stages to about 50 ohmlcm2 It can be seen that Rctvalues lie in the range of 350 to 7000
ohm/cm2 over a period of 0 to 60 days. The Rctvalues were very least (about 350 ohm/cm2) in
40th day and highest (7000 ohm/cm2) in lOth day. It shows that bacteria and organic species improves
the passivity in the initial period. The capacitance values were also higher in 1st day and very least
in lOth and 20th day in presence ofSRB. But in later periods, the values were higher (about 10-7 to
10.8) when compared to initial periods. Surface coverage in presence of SRB system with an initial
value of 0.9754 (1st day) increased to 0.9999 at 10th day and 0.9396 atthe end of 20th day. The
value of surface coverage was drastically reduced at 30th day (0.5906) and gradually reduced
with time upto 60 days. It indicates that bacterial species fully covers in the initial period when
compared to later period.

Inorganic Post Gate Medium (IOPGM) (Fig 7-8; Table 4)

The solution resistance values were in the range between 50 and 250 ohm/cm2 over a period of 10th
day to 60th day. Rct values gradually increased from 420 ohm/cm2 in first day to 1950 ohm/cm2 at

893
the end of 40th day. At 50th day, it decreased to about 6200hmlcmz and increased in 60th day to
1800 ohmlcmz It shows that the corrosion rate is reduced by the presence of inorganic species. The
capacitance values were high in the initial period upto 10 days (10-3F/cmZ). But in later stages, the
values were about 1O7F/cmz.

Discussion

It is well known that SRB is strictly anaerobic with ability to carry out oxidation of substrates such
as lactate to CO and acetate, the latter can not be oxidized.further (10). This group possesses
z
mainly a respiratory type of metabolism with sulphate or other sulphur compounds as the terminal
electron acceptors, being reduced to HzS.

Previous studies had been carried out by using culture medium (7-8)and mechanisms have been
proposed on the basis of sulphide production. In the present study, postgate medium B was used for
mixed cultUre which was lactate based and the quantity was 3.5 gIlitre. The role of hydrogenase
activity in SRB-related corrosion of mild steel is uilclear. Hydrogenase-positive SRB can oxidize
the molecular hydrogen generated at the cathodic sites to facilitate cathodic depolarization (3,11-13).
In this mechanism, where the combination of adsorbed H atoms to produce Hz gas is considered to
be the rate-controlling step, bacteria effectively increase the hydrogen evolution rate and increase
the corrosion rate accordingly. The correlation between hydrogenase activity and corrosion rate
has been confirmed in a batch culture but shown to be very weak in semi-continuous and continuous
cultUre(J4,15).
Besides, stimulation of the anodic reaction by bacterially produced sulfide has been
suggested by some authors (4-6). However, the real impact ofSRB.with lactate/acetate in the medium
yet to thoroughly probed.

The present study, shows that the weight loss is very least upto 20 lys in presence of postgate
medium and gradually increased upto 40 days. In later stage, the weight loss is lower. The polarization
study has also revealed that the corrosion rate is gradually in increasing trend in postgate medium
but in inorganic nutrient system offers decreasing trend. These results indicate that organic nutrients
and SRB decrease corrosion when compared to inorganic nutrients in the initial period. Anodic
passivation was also observed in the initial period in PGM and it persisted' upto the end of20 days.
The subsequent higher corrosion current indicates that anodic depolarization' is offered by SRB
due to the depletion of organic nutrients. But the influence of cathodic reaction in organic system
is very least. In IOPGM system, cathodic reaction is altered (cathodic polarisation) with time. It
indicates that the absorbent species of calcium, magnesium and carbonates may act as cathodic
inhibitors.

The above may be explained considering the physiology of SRB, The conversion of acetate from
lactate may act as inhibitor in the initial period. Besides, heterotrophic bacteria may also produce
organic compounds which may act as inhibitors in the initial period. In later period, after 20th day
the dOlIlination of sulphide ions may disturb the inhibitive activity. At the same time, the
presence of anions in the medium may penetrate through the FeS film which enhances the pitting
corrosion. The reduction of corrosion rate in later period may be due to end product of acetate in

894
presence oflow chloride condition with calcium and magnesium. Ushirode et a1(6) has also reported
that sodium acetate and calcium magnesium acetate are marginally effective as corrosion inhibitors
for reinforced concrete.

Pitting attack beneath the tubercle was earlier reported by Hardy and Brown (17). On the other hand
pitting was not observed by Nielson's group (9) in alternating oxide and anoxic biofilm systems. But
in the present study, 30% of pitting was observed within seven days where sulphide film was not
observed on metal surface.

The high Rctvalues indicate that the high resistance is developed on mild steel by SRB upto 20
days which supports with the polarization and weight loss observations. After 1st day, the Cdl values
are least which indicate that the negatively charged SRB or acetate anions neutralize the cations and
reduces the charges on the metal surface. In inorganic system also, the same trend was observed but
it may be due to cheraical species. The surface coverage on postgate medium indicates that the
bacteria covers the whole area within 24 hrs and it persists vpto 20 days. In later stage, the
production ofH2S may disturb the film.

Besides EIS curves explain that SRB offers activation control in the initial period upto 20 days and
it controls diffusion by enhancement ofFeS in later periods. It also explains that H2S may be low
which may enhance diffusion control reaction (18). As can be seen in figure. 6, the diffusion
impedance is caused by the transport of1lggressive anions with the pores film of iron sulphide on
the metal surface. Hence, it also explains that the porous sulphide tilm favours localized pitting
corrosion in presence ofSRB.

Conclusions

1. SRB corrosion is due to anodic depolarization

2. SRB corrosion is due to the influence of both organic and inorganic nutrients present in the
system.
3. EIS explains that anodic reaction dominating in the initial period and cathollic reaction
dominates in the later period
4. Pitting had been observed on metal surfaces with;n seven days where sulphide film was not
observed on the metal surface.

Acknowledgements

The authors gratefully acknowledge the support of this work by Deptt. of Science & Technoloy,
New Delhi under grant No.GAP 01/97. In addition Dr.C.Stella would like to express her
gratitude to the CSIR, New Delhi for the award of Research Associateship.

895
References

I. Hamilton W A, Sulphate reducing bacterial and anaerobic corrosion. Ann. Rev. Microbiol39:
(1986) 195 - 217.
2. Pankhania I.P, Hydrogen metabolism in sulphate reducing bacteria and its role in anaerobic
corrosion, Biofouling I : (1988) 27-47
3. Vonwolzogen Kuhr C.AH, Vender Vulgt L.S, Graphication of cast iron as an electrochemical
process in anaerobics soil water 18 : (1934) 147- 165
4. Salvarezza RC, Videla H.A, Passivity breakdown of mild steel in seawater in the presence of
sulphate reducing bacteria, Corrosion 36, (1980) 500 - 554
5. Salvarezza, R.C. Videla H.A. Arvia AJ,The electrochemical behaviour of mildsteel in
phosphate borate sulphide solution, Corros. Sci. 23 (1983): 717-732.
6. Crolet J.L, From biology and corrosion to biocorrosion, Oceanol Acta 15. (1992) 87-94.
7. Lee W, Lewandowshi Z, Okabe S, Charackli S W.G. Avci R. corrosion of mild steel underneath
aerobic biofilm containing sulphate reducing bacteria part I : at low dissolved oxygen
concentration. Biofouling 7: (1993) 197-216
8. Lee W, Lewandowshi Z, Nielson P.H. Morrison M, Characklis W.G. Avei R, corrosion of mild
steel underneath aerobic biofilm containing sulphate reducing bacteria Part II: at high dissolved
oxygen concentration. Biofouling 7: (1993 b) 217-239.
9. Nielsen P H, Lee W.C. Lewandowsk Z, Morison M a!ld Characklis W, Corrosion of mild steel
in an alternating oxic and Anoxic biofilm system, Biofouling Vol.7, (1993) pp.267-284
10. Postgate J.R, The sulphate-reducing bacteria (Second Edition), Pub. by Cambridge University,
Cambridge, USA, (1984) P 1-200.
II. Cord-Ruwisch R, Widdel F, Corroding iron as hydrogen source for sulphate reducing in growing
cultures of sulphate reducing bacteria. Appl. Microbial Biotechnol 25 : (1986) 169-174.
12. Daumas S, Massiani Y, Crousier J, Microbial battery induced by sulphate reducing bacteria.
Corrs. Sci. 28: (1988) 1041 - 1050.
13. Bryant RD, Jansen W, Boivin J, Laishley EJ, Costerton J. W, Effect of hydrogenase and
mixed sulphate reducing bacterial populations on the corrosion of steel. Appl. Environ.
Microbiol57 : (1991) 2804 - 2809.
14. Mara DD, Williams D J A, The mechanism of sulphide corrosion by sulphate reducing bacteria.
Biodeterior. Mater. 2: (1972) 103-113
15. King RA Miller J.D .A, Wakerlay D S, Corrosion of mild steel in cultures of sulphate reducing
bacteria : Effect of changing the solution iron concentration during growth. Br. Corr. 1.8 :
(1973) 89-93
16. Vshirode. W.M, Hinatsu J.T, Foulkes F.R, Voltammetric behaviour of iron in cement part N :
Effect of acetate and urea additions. Journal of Applied Electrochemistry, 22 : (1992) 224-
229.
17. Hardy J.A, Bown J.L, The corrosion of mild steel by biogenic sulphide film exposed to air,
Corrosion 40: (1984) 650-654.
18. Sardisco J.B, and Pitts RE, Corrosion of iron in an H2S - CO2 - HP system. Mechanism of
sulphide film formation and kinetics of corrosion reaction Vol.21, No.8, (1965) 245 -253.

896
897
898
899
900
Proc. In!. Cont. on Corrosion CONCORN '97
December 3-6. Mumbai, India

A Portable Field A.C. Impedance Meter

s. Syed Azim, H.V. Shanboge, H.U. Nayak, R.H. Suresh Babu,
A. Selvaraj and P. Jayakrishnan
CECRI, Karaikndi-630 006, India

ABSTRACT

It is now well established that to characterize or to determine the corrosion resistance of any
organic coating (paint film) A.c. Impedance technique is the one which is widely used at present.
The conventional A.c. Impedance measurements involve, the use of potentiostats lock-in-amplifiers,
and to compute the data generated from these measurements, tailor made software on personal
computers is a must. This paper describes an attempt that has been made to design and to develop
a portable A.C. impedance meter with indigenous technology. The results obtained from this
instrument is compared with the conventional A.C. Impedance unit (imported PARC EG&G).
Epoxy paints of varying thickness were used to evaluate the usefullness of this instrument. The
paint films were subjected to 3% sodium chloride solution for a period of six months. Bode plots
were used to calculate Rp of the paint film.

INTRODUCTION

In predicting the expected service life of a painted substrate, the protective properties of paint
scheme are critical and important-parameter. Conventional methods such as salt-spray tests, cyclic
wetting and drying operations are rather time-consuming and are visually evaluated. For studying
the mechanism of corrosion prevention by organic coatings, the electrochemical approach is in
principle is the most acceptable means of research (I) since Corrosion itself is the result of a
number of complex electrochemical reactions.

Electrochemical impedance spectroscopy (EIS) has been in use for some time for predicting the life
of a painting scheme. Many authors hav~ used this tool for determining the life of a coating (2, 3) and
also used a.c. impedance to correlate various under film corrosion and phYSIcalproperties such as
adhesion failure to coating failure [4]. However all these conventional EIS methods are useful in
evaluating the behaviour of painted metal panels in laboratory stimulated cOl1ditions.Only in recent

902
times there is an attempt to develop a portable field impedance meters [5], which are capable
of measuring paint film rl(sistance in field conditions.
In this paper an attempt has been made to develop an indigenous fielda.c. impedance meter.
The results obtained namely paint film resistance from this instrument is compared with the
results got from an imported PARC EG & G unit using M 378 impedance software.

EXPERIMENTAl
(a) Field A.C. Impedance meter description

The schematic block diagram of the instrument is shown in Fig. I. This consists of a variable
frequency sine wave generator having an amplitude of + 10 mV (20 mV pack to peak). The
frequency can be varied in steps from 100 KHz to 10 Hz: The output of this sine wave generator
is fed to the buffer amplifier, output of which is applied to the metallic base of the painted!
coated specimen. The current due to the coating impedance is sensed though a current sensing
probe and fed to the current voltage (I to V) converter, to get an output voltage proportional
to the current through the painted specimen due to the impedance of the coating. This a.c.
output voltage is rectified using a precision full wave rectifier. The resultant d.c. voltage is
applied to a liquid crystal display with suitable scaling to display the irripedance of the paint
coating in ohms.

1. Preparation of painted panels

Cold rolled mild steel panels were used as substrate for the present study. The size of the panels
were 6" x 4". They were sand blasted to SA 2.5 standard. These panels were kept in a decicator
prior to paint application. Two commercial anticorrosive' paint scheme and one paint scheme
developed by CECRI were used for evaluation. The paint scheme details are given in Table 1.

S. No. Product Primer Undercoat Top coat Sealer coat OFT

name (microns)

1 COC Zinc ethyl High build Aliphatic - 250

Carboline silicate epoxy polyurethane
Limited,
India

2 -do- Epoxy - Aliphatic - 200

mastic polyurethane

3 CECRI, Epoxy zinc Epoxy MIO Epoxy Ti02 Aliphatic 350

Karaikudi phosphate polyurethane

903
These paints were applied using airspray on to the sand blasted mild steel panels. The sequence
of paint application is as follows. Primer, undercoat and topcoat in the case of two commercial
paints. Where as for CECRI painting scheme the sequence is primer, undercoat, topcoat and a
sealer coat. Triplicate specimens were prepared for each painting scheme. The painted panels
were allowed to cure at room temperature 30 + 2C for 7 days, after which the respective DFr
was measured using elecometer (Sheen, U.K. make).

Impedance measurement by conventional technique.

On to these painted panels glass tubes (LD 1 sq. cm) were fixed using m-seal compound. These
tubes were allowed to cure for another 7 days. 3% sodium chloride solution was prepered using
A.R. grade sodium chloride and triple distill water. This is poured in to the glass tubes. One
end of the mild steel panel was ground to expose the base metal. A platinum auxilury electrode
and a saturated calomel electrode were used to get a 3 electrode configuration.

The above test panels were used for measuring a.c. impedance through PARG E&G impedance
mea~uring unit. The frequency is varied from 100 KHz to 1 MHz and an a.~. amplitude of 20
mV is applied. The resultant impedance RP was calculated from Bode plots for various.frequencies.

Impedance measurements by developed unit

For measuring impedance response from the painted panels by the developed a.c. impedance
meter, one end of the (ground base) painted metal panel is connected to the meter probe and
the other end is connected to the impedance sensing probe. This probe has a large platinum
electrode embedded in a conducting sponge. (Resistance of the sponge approximately 100
ohms.) The frequency is varied from 100 KHz to 10 Hz in steps. The resultant current sensed
by the probe is converted by the meter in terms of coating impedance. For each frequency the
impedance is noted and a plot is made (Bode type) with respect to the impedance and log of
frequency applied from these graphs the paint film resistance is calculated. The sensing probe
was kept wet by means of three present sodium chloride solution throughout the measurements.

Results and. Discussions

Fig. 2a shows the plots drawn from the impedance measured by means of the developed
instrument and Rp obtained from E&G instrument. From the plots it is clear that the impedance
valve obtained from developed instrument agrees well with those obtained from the imported
impedance unit from 100 KHz to 10 Hz. After words the Rp values increases sharply in the case
of conventional impedance measurements, using imported impedance meter.

Fig. 2b and 2c shows the bode plots for commercial CDC carboline paint and the paint developed by

904
CECRI. In this case also there is close agreement of Rp values up to 10 Hz. These results also
indicate that developed instrument is also able to sense paint film resistance for different dry
film thickness, which also agrees well with the values obtained from conventional EIS measurement.
Figure 3 which clearly indicates that the developed meter can well be used to determine the
impedance of the paint film within a given set of frequency ranges.

CONCLUSION

From these set of datas we can conclude that the indegenously developed field A.C. impedance
meter can well be used to fmd out the paint film resistance on filed conditions. However the
above investigation is only a preliminary one. Efforts are on to make the instrument to continuously
apply frequencies from 100 KHz to 0.1 m Hz so that the equipment can be used to determine
the exact impedance i.e. paint film resistance in field conditions.

REFERENCE

I. F. Deflorian, L. Fedrizzi and P.L. Bonora "Impedance study of the corrosion protection
properties of fluropolymer coatings". Prog. Org. Coating Vol. 23 No. I, Oct. (1993),
p. 73-88.

2. Proc. 2nd Conf. Electrochem. Test methods (ETM-2) April (1984), p. 12-13.

3. T. Szauer, "Impedance measurements for the evaluation of protective non metallic coatings"
Prog. Org. Coating Vol. 10. (1982) p. 171-183.

4. E.P.M. Van Westing, G.M. Ferrai, F.M. Goonen and J.H.W. Dewit "In-situ determination
of the loss of adhesion barrier epoxy coatings using electrochemical impedance
spectroscopy". Prog. Org. Coating Vol. 23 No. I, Oct. (1993) p. 89-103.

5. C.H. Tasi et al "Determination of organic coating deterioration with EIS. Part IT-development
of a method for field testing of protective coatings. Corrosion (U.S.A) Vol. 49, No.9,
(1993) p. 729-37.

905
906
907
908
Proc. Int. Conf. 0.1 Corrosion CONCORN '97
December 3-6. Mumbai. India

Evaluation of Pyridine and Picolines as Inhibitors for

Corrosion of Mild Steel in Agitated 5 % Hydrochloric Acid
at 50C by DC Polarisation and Weight Loss Methods
M.J. Sanghvil, S.K. Shukla}, A.N. Misra!, M.R. Padh1 and G.N. Mehta2
lR&D Centre, Gujrat Alkalies and Chemicals Limited,
P 0 Petrochemicals-391 346, Dist Baroda, Gujrat State, India
2Asstt Prof of Chemistry, A S and Humanities Deptt., S V Regional College of
Engineering and Technology, Surat-395 007, Gujrat, India

ABSl'RACT :
Three mild steel-l 018 cylindrical electrodes of equal area were used in the
probe ofPotentiodyne Analyser, Cortest Instruments (Petrolite), USA and exposed in
agitated 5% HCI at 50C without and with 0.24, 0.50,0.75, I .00 ~Uld1.25% ofthc additives ..
Open circuit (corrosion) potentials were first recordcd aLlcr about halfrul hour WIdthe
pl'e-progrwnmed potentials were scanned fiom far cathodic to anodic sideds. The pot-.,.tials
WIdthe resultant currents were stored in the computerised Potcntiodyne WIj then Wla1YSed
first on the monitor for WIadequate reliability. The reliable data were then ofl:'loaded in the
tabular and graphical modes on the hard copiess. TIle polarisation resistance values from
the linear mode, and corrosion current density WIdthe Tafel constants from the logrithmic
mode, ofpolarisatious were obtained. The weight-loss data were also obtained by the
difference in the weights ofthe pre- and post-exposures ofthe mild steel-l a 18 working
electrodes of the polarisation studies. Percent inhibition efficiencves obtained by all the
three methods were in fair agreement and the additives have predominantly retarded the
rate of cathodic reduction ofWions because the values of cathodic Tafel constant in HCl
were changed remarkably. The increasing order of inhibition by the additives was
as -Pyridine < 2-Picoline < 4-Picoline < 3 Picoline. The probable mechanisms ofthc
corrosian and its inhibition by the additives are proposed.

JNTROCpcnON
Low cost, and desirable mechanical properties of mild steel (MS) make it a
material ofchoice in the industrial structures. MS is prone to corrosion in HCl frequently
used in acid cle<'Uling,in acidizing oil wclls and in descating (1). To cut colossal MS loss in
such .treatments effective inhibitors are used (2). Pyridinels (3-6) and Quinoline/s (7) arc
reported as the inhibitors. Higher electron density on N-atom/s render them to inhibit
corrosion (4). In this paper, Pyridine <'U1dP icolines are eval uated as inhibitors for MS-l 0 18
corroding in 5% HCI at 50C (agitated).

909
EXPERIMENTAL:
Aplication ofthree MS-l 018 cylindrical electrodes' probe ofthe computerised
Potentiodyne Analyser Model-IN 4300, Cortest Instruments (Petro lite) USA. based on the
softwares for the linear (low) and log (high) DC polarisations was given earlier (8). The
reference electrode (MS) was used simultaneously for the weight~loss (WL) data. The
procedural details ofpre-progammed polarisations were followed from the operation mannual.
At third hour of immersion, the values of Open circuit (corrosion) potential (OCP) were
o\)tained. TIle values of polaris ation ressistance (~) from the,lin~r (~,9) curves and those
of corrosion current density (iCOrT) from the log curves (10) were obtained; the later by
extrapolation ofthe Tafel regions of high cathodic and anodic curves using two cross-hairs
facility. From the slopes ofthese regions, the values of cathodic (be) and andic (b.> Tafel
constants
,
were obtrained. TIlese values of bc, ba and iCOlT were computed using Stem-Geary
equation (10) to obtain the values of constant B and~. TIle percent inhibition efficientcies
(1E%) were calulated from the ~ and WL data (8). The cOllunericial (GACL) 5% w/v
HCl and high purity Pyridine (LR) and 2-, 3- and 4- Picolines (E Merck) were used to
prepare 0.25, 0.50. 0.75, 1.00 and 1.25% solutions ,inthe acid using double distilled water.
RESULTS AND DISCUSSION:
The values ofOCP, icorr , --p
R , Band IE% are comprised in Table-I.

(a) Corrosion of MS : TIle table shows very low ( 5 mY) OCP values for MS due to
similar potentials of working and reference electrodes exposed into most conductive 5%
HClandcwmot be used to interpretcorrosionlinhibition. 'l11evalues ofbc' b. and were in
agreement with those reported(ll) for the Fe/acid systems. The corrosion was under mixed
control and both cr and OH- ions were involved in the anodic dissolution (12) and H- ions
2
mAlcm2)
reduction. The highest icarr(10.22 and lowest ~ (1.860hm.cm ) values confirmed
.the highest corrosion rate ofMS-l 0 18 in 5% HCI. It showed that cok)ssalloss of MS in the
.industrial application ofHCI need very serious attention to minimise it, preferably by use of
the inhibitors(2).
(I,) Effect of Pyridine and Picolines : The table also shows rise in ~ values when the
cone. raised from
I
0.25 to 1.25 % ofthe additives but _.
to different extents which proved that
the ,?orrosion ~as retarded differently; the gradual f;lIl in iCOrT values confimed the action.
The calculated (by B/ icorr ) ...
R-p- values .(10) were lower than the experimental ones due to
heavy polarisation which roughenned the MS surface and resulted into lower (IE%)
coverage (1~). TIle lE% obteined from the WL data were lower because average values of
the WL da~a upto three hours w~re taken whereas the IE% from the Rp were
instantaneous ( 13).
(c) Effect of rise in concentration of the additives: Lowest(0.25%) conc. did not inhibit
remarkably due to insufficient coverage and disturbance by hydrodynamic-and thermal
effects. From increase in b valueofblankHCl (-120 mY/decade) with rise in cone., it was

910
 ..
concluded that rate of~ ions reduction was retarded. The b value (68 mY/decade) did
not cl)ange remarkably because the rate of anodic dissolution was nqt so much retarded.
The highest rang ofIE% with rise in cone. of 3-Picoline confirmed that it was the best
inhibitor. An extent C?finhibition (IE%) by 2- and 4- Picolines was almost same but lower
than that of3-Picoline; of2-Picoline being lower than 4-Picoline. The inhibition exerted by
Pyridine was least. lit stagnant HCI the order of inhibition was reported (4) as Pyridine
< 3-Picoline < 2-Picoline::: 4-Picoline on the basis o(el~on density. Most effective conc.
ofaU the additives were 0.75 to 1.00% but at higher (IP5%) cone., there was no much rise
in the inhibition.
(d) Mechanisms proposed: Pyridine did not exert noteworthy and useful inhibition because
cr ions adsorbed (12) facilitated an electrostatic (poor) adsorption ofpyridinium cations (5)
possibly in vertical position ofthe MS surface (14) suffered the mechanical (stirring) and
thermal (SOGC) effects. In 2-Picoline, on N-atom electron density ..enriched by
electron-repelling methyl group in 2-position enhanced protanation (basicity) and the cations
were adsorbed due to favourable zero charge potential (14) and via CI- ions perpendicularly.
The prominent steric hinderance offered by methyl group made the inhibition difficult.
Though 2- and 4- Picolines acted as better inhibitors (4), in this study, at higher (SOC)
temp., higher conc. ofHCI (5%) and in agitated solutions, these two did not perform better
(than 3-Picoline) due to strong steric hindrance of methyl group. Lower steric hindrance
and basicity of3-Picoline resulted into the highest inhibition probably due to parallel adsorption
ofunprotonated complexed (with Fe++:)picoline molecules via 3d- pi-interaction (1 5) because
methrl group in3-position might have made 2-,4- and 6- positions richer with electrons
density and made the stronger bond and larger surface coverage (IE%).
C.ONCLUSIONS : Pyridine did not protect MS.:.IOI8 much but 2- and 4- Picolinium
catioris, due to electron-repelling methyl group, exerted better inhibition by vertical adsorption
via ci" ions; an extent of inhibition by 2-Picoline was lower due to higher steric hindrance.
The cprrosion at 50C was highly retarded by 3-Picoline, probably due to strong parallel
adso.ption ofunprotonated molecules by 3d-pi bond and least steric hindrance. With rise in
conc.: the inhibition gradually raised; the lowest 0.25% and the highest 1.25% being less
.important for the industrial applications. The lower IE% obtained by (B/i COlT ) high (log)
polarisation was due to rough enning of the MS surface, and stirring and higher temp. effects
on the molec~es adsorbed directly or via cr ions. The additives retatrded the rate of
cathodic reduction ofW ions.
ACKNOWLEDGEMENTS:
The authors thank the dynamic Management of MIS Gujarat Alkalies and
Chemicales Ltd for the funds, facilities and timely encouragement. Dr Mehta' also thank
Principal, Dr J C Vyas, S V Regional College ofEngg andTech, Surat for permitting to
work on the sponsored research project at the Rand 0 Centre of MIS GACL.

911
REFERENCES :
1 S H Sanad, A A Ismail and A A El Meligi~B Electrochemistry, 11( 1995)462.
2 J S Robinson, in 'Corrotion inhibitors; recent developments', N J Noyes Data Corpn
(1979), Park Ridge Chern Tech Review, 132, Based on Patents issued since 1976.
3 S J Zakvi and G N Mehta, JElectrochem Soc India, 36(1987)143.
4 R C Ayers and N Hackerman,J Electrochem. 110(1963)507.
5 L I Antropov, Corros Sci, 7(1967)667.
6 M H Desai and G N Mehta, B Electrochemistry, 13( 1997)49-52.
7 G N Mehta and T P Sastry, 2nd Int'l Symp Indus and Oriented Basic Electrochem',
(SAEST) Tech Sess VI, lIT, Mndms (1980)6.24 ...
8 M J Sanghvi, S K Shukla, A N Misra, M R Padh and G N Mohta, Sth Nal'l Cogr
Corros Control (NCCI, CECRI) Feb(199S) New Delhi.
9 D A Jones andNDGreene, Corrosion, 22(1966)198.
10 M Stem and AL Geary, J Electrochem Soc, 104(1957)56.
11 MPrazak, WerlstKorros, 25(1974)104.
12 N C Subramanyan, B S Sheshadri and S M Mayanna, J Electrochem Soc India,
42(1993)95.
13 M GFontana and R W Staehle,'Advances in Corrosion Science and Technology',
VoI6(1976) Plenum Press, New York, USA -
14 G Banerjee and S N Malhotra, B Electrochemistry, 6(1990)907; Corrosion
(1992)10-15.
15 EMAgres,AIAltsybeeva, V S Fedorov and S JLenin, ZhFizKhim, 50(1976)3152-5.

912
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6. Mumbai. India

Scale Morphology Characterization of 304 Stainless

Steel and its Influence on Pickling Behaviour
s. Jana, R.K. Aiyar and A. Ganguly
Mukand Ltd., Mumbai, India

ABSTRACT

Oxide scale morphology of steel affects the subsequent pickling characteristics to a significant extent. Therefore
the effect of various heat treatment conditions on the pickling behaviour of type 304 stainless steel wir~rods were
investigated. Heat treatment temperature and time were varied in the range of 1173 - 1348 K and 30- qo mins,
respectively for different heat treatment cycles. Morphology and composition of the oxide scales were
characterized by SEM and EDS studies. Oxidation kinetics in different annealing treatment in air cooling has also
been studied to have an idea about the metal loss as scale. Pickling efficiency has been found to depend not only
on the chemical nature of the oxide but also on the oxide morphology. EDS investigations revealed that the
efficiency of pickling depends on the chemical composition of the spinel structure of scale. Higher annealing
temperature showed a decreasing pickling efficiency due to the presence of Mn in spinel structure of the oxide.

INTRODUCTION

The descaling operation of the oxide scales formed on the wire rod surface during annealing is one of the most
important steps in producing stainless steel of austentic, ferritic, and martensitic grades. Two major constituents
of the scale are spinels and rhombohedral oxides. The spinel (M203) is capable of a wide variation in composition
as (Fe, Ni, Mn) and (Fe, Cr, Mn)203. The rhombohedral oxide (M203) also may have variable composition ovI'
the range (Fe, Cr, Mnh03. The spinel parameter is described simply as being closer to that ofF~03 or Cr203. It
has been observed that when Mn content is high or the Ni is low, the spinel parameter is high and vice versa [1,2] .

In general, the preferential oxidation of scale depends on the scaling rate and scale thickness. It has been observtJP
that Cr is higher in the more slowly scaling specimens but the outer most layer of all scales is lower in Cr
apparently due to the lower diffusivity and perhaps also due to higher volatility of Cr compound as compared to
Fe.
Croll and Wall [3] work recently showed in a comprehensive study on the oxidation of ternary Fe-Cr-Ni alloys Ilt
1273 K that the minimum chromium interface concentration required to maintain 'Cr203' scales is 14.

914
The oxide scales formed on 304 at 1323 K contain spinel constituents like FeCr20", NiF~O", and F~03. Since
Cr was rich in the oxide scale layer during annealing, chromic oxide (Fe, Crh03 might have been formed below
Cr-rich spinel oxide FeCr204. Fujikawa et. at and several investigators [4, 5, 6] also reported thatCr~~
precipitate on the oxide/metal interface during high temperature oxidation oftheF~20%Cr alloy.

The present paper was aimed to study the effect of oxide scale morphology and chemical composition of scale OIl
the subsequent pickling characteristics.

EXPERIMENTAL PROCEDURE
304 grade samples of 150 mm length, and 5.5 mm dia. were cut from the rolled coils and subjected to various heat
treatment cycles with temperatures ranging from 1173 - 1348 K. The quenching medium was either air or water
and the soaking period was also varied from 30 min. to 120 min. Rate constants from kinetic 'data have been
estimated to have an oxidation mechanism. Such estimated rate constant values are shown in Table 1. The scal,
thickness of different heat treatment specimens were recorded to correlate it ~th pickling behaviour. Th,
microhardness values of different phases present within the oxide scales at different temperatures and times wer,
also looked into to get an idea about the presence of different constituents within the oxide layer.

While a part of the sample was taken up for metallurgical studies, the other part was used for pickling behaviour
studies, wherein the oxide specimens were exposed to 20% H2S04 solution for 20 min., and beyond in thp
pretreatment stage. Subsequently, it dipped into the 15% HN03 + 5% HF solution for a post. treatment to studf
the descaling behaviour. Energy dispersive spectroscopic study was conducted to have an idea.about the chemical
composition of the scale p~es. Finally, attempts have been made for scale morphology correlation with pickling
bdlaviour ..

RESULTS & DISCUSSION

The summarised experimental data are provided in Table 2 and 3.. The change in rates of oxidation was
prominently observed at 1298 K and 1348 K, as can be seen from Fig. 1. At 1173 K, the oxidation rate was
found to behave linearly but at higher temperature, it followed a hyperbolic law. Fig. 2 clearly brings out the
trmds in quench and air cooled condition for soaking periods of 30 min. to 120 min. It has been found that the
thickness of the oxide scale is least in all cases except that of specimep which was water quenched from 1298 k
after soaking for 30 min.

The variable composition range of oxides is one of the most important factors while considering oxidation
RaCtion. The nature of the defect structure of an oxide which thickened by diffusion mechanism, determines the
oxidation rate. For an oxide layer growing on a metal, an. oxygen pressure gradient and a defect gradient exist
aaoss the oxide. The simplest rates expression is the linear equation, where the oxide f11m has no influence on the
ate of uptake of oxygen and directly prportional to time of exposure. If an oxide-is nonprotective, offering no
burier between the gas phase and metal surface, the linear law is expected to hold. Porous and cracked oxide are
fiJrmcd on a number of metals which show a strong tendency to oxidize at a linear rate. These metals generally
lave low or high volume ratio~of oxide to metal consumed. A low volume ratio suggest that the metal is always
aposed to the gas phase [3].

915
Scale thickness is another critical parameter which needs to be looked into. Fig. 2 clearly bring out the trends in
variations of scale thickness at different austenising temperatures in water quench and air cool condition for
soaking periods of 30 miD. and 120 min. The figure shows minimum scale thickness at 1323 K except heat
treated at 1273 K for 30 min. and subsequently water quench specimen. It is evident that the scale thickness is
directly proportional to temperature. However, at higher temperatures due to formation of Cr-rich oxide at. the
oxide/metal interface, crackes are formed in the scale layer which eventually lowered the scale thickness. At the
soaking time of 30 min. at 1273 K failed to yield larger scale thickness due to the lower oxidation rate at lower
time and temperature.

Moreau and Benard [7] hence presented a general classification of the different scale morphologies which may
occur on an alloy A-B based on experimental observations. According to them one of the most important mixed
oxides, that is, oxides in which the two alloying elements are associated. These oxides occur most frequently at
high temperatures and higher oxygen potentials. The simplest case to descn"be is the formation of oxide of one
element in the oxide of the other. The case concerns the formation of oxides which approach stoichiometric
composition. This reaction often gives rise to spinel oxide, like AB204, where A and B are two alloying element.

In optical microscopy, some distinct differences were observed between high and low temperature oxidized
samples. Two layers, having gray and bright colors were found to be present in low temperature oxidized
samples.

The variation of pickling time with austenitic temperatures as observed in Fig. 3 for water quench condition
lowered the pickling time at 1298 K and 1323 K. which had lower adherent scale thickness values. The same
trend was observed in air cool condition.

There were some distinct differences between high and low temperature oxidation while in ~ cooled mode it
showed only a dense phase with a few black spot in SEM study (Fig. 4). But at higher temperature (water quench
or air cool condition) a microstructure combination of in black, white & gray phases Was found ~ch is
presented in Fig. 5.

As per as surface finish is concerned, 1298 K with 30 min. soaking time got the best surface fmish with lesser
pickling time (35 min.). On the other hand, 1323 K with 90 min. and 120 miD. soaking periods followed by water
quench, decreased the pickling time to 31 min. and 21 min. (Table 2) respectively. Similar case was observed for
sample heat treated to 1273 K where pickling time was quite large albeit lower scale thickness value. The air
cooled specimen also did not indicate good surface quality with lower pickling time. But heat treatment at slightly
higher temperature does not have well pickling behaviour. Samples heat treated at 1348 Kfollowed by water
quenching revealed more rough surface with a few black spot as can be seen from Fig. 6.

Microhardness values were found to be varying extensively within the oxide scale layer (Table 4) and the pickling
behaviour was found to be vary with different microhardness values. It reveals that the scale having hardness 550
is the best for pickling and the scale with hardness in between 950-1100 VPN is cauases some problem in
pickling.

From the EDS (Energy Dispersive Spectroscopy) analysis, revealed a composition of different oxide phases which
can be correlated with pickling as well as with microhardness values. Various phases found in the scale formed at
different temperatures are:
1. At 1173 K. Cr-rich phase was found in inner layer and F~03 indicated value on the outer side.

916
The surface quality of wire rods after pickling was found to depend on the nature of the scale, its thickness and
with the pickling time. However, it has been noticed that for larger holding time, the scale thickness was found to
be decreased due to spailingof nonadherent scale due to crack formation within the scale. The pickling time was
also found to be depend on the morphology of the oxide layer. In spite of having a slightly thick scale in the
temperature ranges from 1298 K to 1323 K with different soaking periods, the specimens with the presence of
crack and porosity shows lower pickling time thereby enhancing the chemical contact with the oxide surface as
can be seen in Figs. 7 and 8. Hence, in the case of heat treatment at 1348 K the black oxide layer due to the
presence of Mn within the spinel structure enhances pickling time without achieving good surface fmish.

CONCLUSIONS

1. Samples heat treated at 1298 K with a soaking period of 30 min. and subsequently water quenched, having the
oxide composition, FeCr204, NiF~04, Ni metal and (FeCrh03 type FeCr203 type oxides and microhardness
values below 550 VPN, could be easily pickled with a good surface fmish.
2. Samples heat treated to 1348 K with a soaking period of 60 min. ~d above and subsequently water quenched
(microhardness value of 946 VPN) have an adverse effect on pickling due to the presence of Mn in spinel oxide
structure.
3. Pickling efficiency has been found to depend not only on the chemical nature of the oxide but also on its
morphology.

REFERENCE

l. Caplan, D., Cohen, M., Corrosion, Vol. 15, March 1959, pp. 57-62.
2. Bittel, J.T., Jodahl, J., Corrosion" Vol 25, no. 1, Jan. 1969, pp. 7-14.
3. Croll, J. E., and Wallwork, G. R., Oxide. Metal, Vol. 1, 1969, pp. 55.
4. Lee, Y.D. et.al., Proceedings of International Coriference on Stainless Steels, 1991, chiba ISU, pp. 957-
958.
5. Fujikawa, H. et. aI., Iron and Steels Inst. Japan, Vol. 70, 1994.
6. Fernando, L.A., Zannske, n.R., Met Trans., Vol. 19A, no. 4,1994, pp. 1083.
7. Moreau, J., Benard, J., Rev. Metal. (Paris), Vol. 59, 1962, pp. 161.

917
918
 TABLE 2. EFFECT OF VARIOUS HEAT TREATMENT ON SCALE FORMATION AND
PICKLING FOR AISI 304 GRADE STAINLESS STEEL.

Heating Soaking Heat Nature Micro Scale Piclding

Temp., Period, Treatment of Hardness, Thickness, Observations,
K. miD. Given Scale VPN micron min.
30 NAD 237,464 7-8 20+30:SBF
60 Water AD 946,464,297 5 - 7.5 20+33:SBF
90 Quenched AD 946,464,297 10 - 16.5 20+33:SBF
1273 120 LAD 724,464,527 21 25+28:SBF
I 30 NAD 527,464,201 23 30+35:SBF
60 Air Cooled AD 824,383 24 30+35:SBF, BRP
I 90 AD 946,206 27 30+35:SBF, BRP
120 LAD 383,642,572 30 30+35:SBF, BRP
30 NAD 232,473 12 20+15:SBF
60 Water NAD 964,532,1288 19 - 29 20+15:SBF, BRP
90 Quenched AD 841,303, 1288 15 - 22.5 20+30:SBF, BRP
1298 120 LAD 232,644,412 9.5 - 12 20+25:SBF, BRP
30 NAD 386,549,473 21.5 20+23:SBF
60 Air Cooled AD 766, 1145,514 14 - 29.5 20+30:SBF, BRP
90 AD 1288,642 19 _ 29.5 20+30:SBF, BRP
120 AD 549,386,644 20.5 - 22 20+35:SBF, BRP
30 NAD 493, 322, 407 II 20+20:SBF
60 Water AD 689,1097,873 10 20+35:SBF, BRP
90 Quenched AD 1097,946, 102 14 20+9:SBF, BRP
1323 120 LAD 1297, 946, 540 17 20+ 11:SBF, BRP
30 LAD 237,642,439. 15 20+35:BRP
60 Air Cooled AD 642,439 15 20+35:BRP
90 AD 572,724,648 14 20+30:BRP
120 NAD 420,724, 1288 18.5 20+12:SBF
30 LAD 464,642,447 11 25+30:SBF
60 Water AD 572,946,741 15 - 16.5 27+30:RS, BP
90 Quenched AD 572,946 25 - 35 25+30:RS, BP
1348 120 LAD 724,464,667 18 - 44 22+30:VRS, BP
30 . AD 824,440 12 - 20 30+35:SBF
60 Air Cooled AD 1288,946,835 28 - 24 30+32:SBf, BP
90 AD 946,537 19.5-25 27+30:RS,BP
120 AD 642, 420, 1097 15 - 35 30+30:RS, BP

lades.: AD - Adherent, NAD - Non-Adherent, LAD - Less Adherent, SBF - Smooth Bright Finish, RS-
Rough Surface, VRF - Very Rough Surface, BP - Black Patch, BRP - Bright Patch.

919
920
Fig. 3. Variation of pickling time of 304 stainless steel with
temperature at water quench and air cool heat treatment
conditions.

921
922
923
Proc. lnt. Conf. on Corrosion CONCORN '97
December 3-6. Mumbai, India

Microbiologically Influenced Corrosion of

Stainless Steel Weldments
R.P. GeorgeI, K.R. SreekumariI, P. MuraleedharanI, H.S. KhatakI,
J.B. Gnanamoorthyl and K.V.K. Nair2
'Metallurgy Division, Indira Gandhi Centre for Atomic Research,
Kalpakkam 603 102, India
2Marine Biology Programme, Water and Steam Chemistry Laboratory,
IGCAR Campus, Kalpakkam 603 102, India

ABSTRACT

Stainless steels (SS) of the basic 18 Cr - 8 Ni compositions are commonly used in nuclear power
plants especially in high purity environments. There are several reports ofMIC attack on SS when untreated
or potable water is used for hydrotesting. Investigations on the behaviour of SS components in
seawater-cooled plants by earlier workers have demonstrated that biofilm formed on SS can increase the
corrosion potential considerably leading to pitting of more anodic areas like welds and heat effected zones.
In the present study, an attempt was made to understand the role of microorganisms in the corrosion of SS
weldments in a fresh water reservoir. This reservoir water is used in the service water system of the Fast
Breeder Test Reactor at Kalpakkam. The monitoring of open circuit potential (OCP) of AISI Type 304 SS
with time in the raw reservoir water showed a steady positive shift ofOCP to about 200 mV in 30 days.
This positive shift of OCP was not observed in the sterile water. Rise in OCP was also observed on
specimens with pure algal biofilms, but not with bacterial biofilms in the dark conditions and in the pure
culture bacterial biofilms. Biofilm characterisation studies in the fresh water reservoir showed that
photosynthetic algal-dominated biofilms is developing in this environment. To understand the effect of this
algal-influenced ennoblement on the SS-welds, AISI Typ~ 304 SS frames with welded regions were also
exposed in the reservoir. Within one and a half year, weld started corroding and after five years heavily
corroded SS frames were withdrawn and total microbiological and metallurgical analysis were done.
Results are discussed in the light of available literature.

INTRODUCTION

Materials which rely on the presence of a stable oxide film for their corrosion resistance like
stainless steel (88) are particularly susceptible to pitting and crevice corrosion, should the film be damaged
or oxygen screened from the metal by the presence of a biofilm (I). There are several reports ofMIC attack
on S8 when untreated or potable water is used for hydrotesting (2). Investigations on the behaviour of 88
components in sea water cooled plants by earlier workers (3) demonstrated that biofilm formed on S8 can
increase the corrosion potential considerably leading to pitting of more anodic areas like welds and heat
affected zones. In this investigation using electrochemical, surface-analytical and metallographic
techniques, studies were done on the effect ofbiofilm formation on the electrochemical characterisation
of S8 base metal and weldments. Complete biofilm characterisation on 88 base metal and weldments were
also done to get a clear picture on the role of microorganisms on the degradation of welds.

924
EXPERIMENTAL

Biofilm Characterisation Studies

Perspex panels (15 cm X 10 cm X 0.5 cm and 7 cm X 3 cm X 0.5 cm) were suspended in an open
reservoir used for storing underground river water (Palar water) at a depth of 1.5 m and retrieved after 24,
72 and 120 h of immersion to study the sequential developmemt of biofilm. Two set of panels were used;
one set was exposed in the reservoir under the natural day and night conditions (normal) and the other set
was exposed in the reservoir under continuous dark conditions (dark) using a darkened chamber.
Parameters such as counts of diatoms, chlorophyIl content, total viable counts (TVC) of bacteria, biofilm
thickness and particulate organic carbon (POC) were determined (4),

Some predominant species of bacteria (Pseudomonas sp. and Desulfovibrio sp.) and algae
(Coelastrum sp. and Oscillatoria sp.) were isolated from the biofilms and cultured using specific culture
media. Biochemical tests were done to identify the species using'the methods available in literature (5).

Electrochemical Studies

The material used in this study was AISI Type 304 SS of the normal 18 Cr / 8 Ni composition
(Table I), Specimens of approximately lOX 10 mm, cut from 1.6 mm thick sheet were mounted in an
epoxy resin (araldite) after making provision for electrical connection. The mounted specimens were
polished up to diamond finish (2-3 ~m) and cleaned thoroughly before exposing them in various fresh water
environment.

The monitoring of open circuit potential (OCP) was carried out in raw reservoir water as well as
in sterile reservoir water. Sterile reservoir water was prepared by filtering the reservoir water successively
through 0.45 ~m and 0.22 ~m Millipore filters and exposing this water to UV light for one hour. Specimens
were exposed to these waters and the electrochemical potential of SS with respect to saturated calomel
electrode was monitored for a period of 30 days, This experiment was repeated 3-4 times to get consistent
results.

Specimens with the biofilms of Pseudomonas sp. (aerobic bacteria) and Desulfovibrio sp, (anerobic
bacteria) were developed by exposing in the pure culture of the respective bacteria 'for 24. hand 34 h.
Specimens with the biofilms ofCoelastrum microsporum (green alga) and Oscillatoria sancta (blue green
alga) were developed by exposing in the pure culture of green alga for 15 and 20 days and in the culture
of blue green alga for 8 and 13 days. OCP of these specimens were also noted after it reached equilibrium
in the open reservoir water.

Weld Exposure Studies

AISI Type 304 stainless steel frames (300 mm X 450 mm X 7 mm) with TIG welded joints were

925
exposed in the fresh water for 5 years. Frames were pickled and passivated and then degreased betore
exposure. These frames were suspended in the fresh water reservoir at a depth of 1.5 m from the surface.

RESULTS AND DISCUSSION

Biofilm Characterisation Studies

In the present study, development of biofilm was followed both in the 'normal' and 'dark'
conditions in a fresh water to differentiate the effect of photosynthesising organisms on biofilm
characteristics. The results showed clear differences between the biofilms developed in the two conditions.
Thickness of the biofilm was higher in the 'normal' environment compared to those in the 'dark'
environment (Table 2). The predominant colonisers in the 'dark' biofilm were bacteria. However, the high
values of POC and chlorophyll in the 'normal' biofilm confirmed the richness of the algal flora in this
condition.

Electrochemical Studies

The OCP of 304 SS in raw reservoir water showed a positive shift i.e., about 200 mV nobler to
the OCP of freshly polished SS specimen obtained in raw water soon after immersion. This small but
significant positive shift was consistently observed in many samples. However, for the specimens exposed
in the sterile reservoir water, the OCP did not show any positive shift at all.

An ennoblement of OCP generally increased the probability for localized corrosion. Studies by
Little et al. (6) and Motoda et al. (7) demonstrated an ennoblement by 200 mV for stainless steel in the
presence of photosynthetic diatoms. The biofilm on SS exposed in the normal day and night conditions in
the reservoir was also dominated by photosynthetic algae and here also OCP showed an increase of 200
mV above the initial OCP (-180 mV) on the 30th day of exposure in raw water. Algal photosynthesis can
increase the partial pressure of oxygen in the biofilm. Thermodynamically this increase in oxygen may shift
the reversible potential of the oxygen electrode in the positive direction (8).-

926
 To distinguish the roles of aerobic bacteria, anaerobic bacteria and photosynthetic algae in the
ennoblement, OCP of specimens with pure culture biofilm of above microorganisms were also noted. Algal
biofilms on SS showed higher OCP (-75 mV to -50 mV) compared to bacterial biofilms (-200 mV to -250
mV) revealing again a major role for the photosynthetic algae in the ennoblement.

Weld Exposure Studies

Earlier studies demonstrated that ennoblement of SS can lead to pitting of more anodic areas like
welds and heat affected zones (3). In the past few years, analysis of costly pitting failures from power
plants, chemical process plants and pulp and paper mills have indicated that stainless steel especially, welds
are preferentially attacked by microbes (9). Pitting can occur at the heat-affected zones (HAZ), at the fusion
line and in the base metal near weld (10).

In the present study AISI Type 304 SS frames welded at the joints exposed in the reservoir water
started corroding at few welds after one year. Frames were withdrawn after 5 years. Two welded regions
were heavily corroded. Biofilm characterisation at the welds and the base metal showed higher total
bacterial density, Pseudomonas sp., iron oxidizing bacteria and chlorophyll content (indicating algal
density) on the welded regions compared to the base metal (Table 4). EDAX analysis of the corrosion
products showed higher iron content in the corrosion deposits compared to the base metal. SEM photo of
the thick algal biofilm on the weld region is shown in the Fig. I.

Table 3. Results of the microbiological analysis of the AISI Type 304 SS welded frame.

927
 According to Shutz (II) oxidizing species like O2 can cause cathodic depolarization and
cathodically depolarized areas could initiate corrosion under anodic areas. Therefore on a biofilmed sample
dominated by algae, release of oxygen can cause ennoblement, whereas, smaller welded regions can
contribute to anodic areas. This larger cathodic and smaller anodic coupling can cause severe corrosion as
per the unfavourable cathode-anode ratio of Fontana and Greene (12).

In the present study algal dominated natural biofilm and pure algal biofilm caused ennoblement
ofSS samples and long term field exposure studies showed severly corroded weld joints in the SS frame.
Hence this study confirmed the hypothesis that biofilm formed on active-passive material can raise the
potential of the material leading to pitting of more anodic areas like welds.

CONCLUSIONS

I. Photosynthetic, algal dominated biofilm was found to develop in the normal day and night
exposures, whereas, bacterial-dominated biofilm alone was seen in the dark exposures.

2. The monitoring of OCP of Type 304 SS with time in the raw reservoir water showed a steady
positive shift of OCP to about 200 mV in 30 days. This positive shift was not observed in sterile water.

3. Among the pure culture biofilms, algal biofilms on SS showed higher OCP compared to bacterial
biofilms.

928
4. Welded sS frames exposed in the fresh water reservoir started corroding at the welds within one
year. BiofiIm charecterisation of these frames showed maximum density of microorganisms at the corroded
welds compared to the base metal.

REFERENCES

I. Dexter, S.C., Ducquette, DJ., Siebert, O.W. and Videla, A.H., Corrosion. Vol. 47, no. 4, 1991,
pp. 308-318.
2. Borenstein, S.W. and Lindsay, P.B., Mater. Perf .. March 1988.
3. Mollica, A. and Trevis, A., Proc. of 4th IntI. Con~. on Marine Corrosion and Foulin~. Antibes,
France, 1976, p.351.
4. APHA, Standard Methods for the Examination of Water and Waste Water. 14 ed., APHA, USA,
1989.
5. Buchanan, R.E. and Gibbons, N.E., (eds.)., Ber~ey's Manual of Determinative Bacteriolo~. 8th
ed., 1974.
6. Little, 8., Ray, P., Wagner, P., Leewandowski, Z., Lee, W.C., Charackilis, W.G. and Mansfeld,
F., Biofoulin~, Vol. 3,1991, pA5.
7. Motoda, S., Suzuki, Y., Shinohara, T. and Tsujikawa, S., Corrosion Science. Vol. 31, 1990, p. 515.
8. Carew, J.A. and Abdullah, A., Corrosion Science. Vol. 34, no. 2, 1993, p. 217.
9. Borenstein, S.W., Mater. Perf .. 1991, pp. 52-54.
10. Metals Hand Book, Corrosion, 13, 9th ed., materials Park, OH, ASM International, 1987, p.118.
I I. Schutz, R.W., Mater. Perf., 1991, p.58.
12. Fontana, M.G., Corrosion En~ineerin~. 3rd ed., Mcgraw Hill Co., New York, pp. 23-28.

ACKNOWLEDGEMENT

The authors gratefully acknowledge the support and encouragement from Dr. Placid Rodriguez,
Director, IGCAR during the course of investigation. They are also grateful to Dr. P.K. Mathur for providing
some facilities at the WSCL during the course of this experiment. They also acknowledge the assistance
from Mrs. M. Radhika for SEM studies and Mr.A.Varadarajanin for field studies. The first author
acknowledges the receipt of research associateship from the C.S.I.R.

929
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Platinised-Iridium Coated Titanium Electrodes for

Electrochemical Applications
U. Kamachi Mudali, V.R. Raju and R.K. Dayal
Aqueous Corrosion and Surface Studies Section, Metallurgy Division,
Indira Gandhi Centre for Atomic Research, Kalpakkam-603 102, India

ABSTRACT

Metallic coatings ofPt and Pt-Ir were prepared by thermochemical glazing process on titanium substrates
for application as electrodes in the electrolytic dissolution of spent nuclear fuels in a severe corrosive environment
containing boiling nitric acid, uranium and other redox ions. Titanium substrates with single layer of RuOz- TiOz,
applied with Pt and Pt-Ir chemical solutions, were heat treated in vaccum at different temperatures between 973
to 1473 K for I h. Electrochemical cathodic and anodic polarisation studies were carried out on these samples
in 1M HN03 at room temperature. Physical characterisation of these electrodes by SEM/EDAX, XRD and SIMS
indicated that adherent, smooth metallic coatings ofPt- Ti, Pt-Ir and other intermetallic compounds of Ti, Pt and
Ir were present on the surface. It was found that the specimens prepared at 1373 K showed better electrochemical
performance in comparision with Pt sheet electrodes. Significant changes in the open circuit potential (OCP) and
the polarisation behaviour of the electrodes prepared were noticed. Life assessment of these electrodes in a
simulated reprocessing boiling nitric acid (10 N) test solution containing uranium and other redox ions showed
excellent performance of the Pt-Ir layered electrode, prepared at 1373 K, in comparison with conventional
MOCTA electrodes.

INTRODUCTION

Electrochemical methods are one of the promising ways of dissolving and purifying the spent nuclear fuel
from the nuclear reactors compared to the conventional chemical methods. A number of electrochemical
processes [1-5] are currently employed world wide due to their simplicity, high efficiency and easy control over
the process including remote operation. They are : electrolytic dissolution and conditioning, electrolytic
partitioning and purification, electrolytic production of uranous ions, electrolytic destruction of organics, nitric
acid and radioactive wastes etc. All the above processes use nitric acid from dilute to concentrated, from room
temperature to boiling condition, and with the addition of redox systems in for improving the current efficiency.
The success and current efficiency of the electrochemical processes mainly depend on the durability or the
corrosion resistance of the electrodes, electrocatalytic activity or the low over voltage for the desired rate
determining electrochemical reaction, and high conductivity facilitating operation of the electrolytic cells at high

930
current densities. In addition, to avoid minimum interruption to the operation, or due to the risk in frequent
replacement or addition of new electrodes in a radioactive environment, longer life of the electrodes used are of
paramount importance while choosing an appropriate electrode for the electrochemical processes employed in
the reprocessing plants. Currently platinum metallic electrodes are being used in the above applications. However,
it has been reported [I] that platinum undergoes corrosion at high current densities of operation in nitric acid
medium at high temperatures. Moreover, platinum is expensive considering the cost involved in operating the
plant with many unit operations, and the failed platinum electrodes in a highly contaminated state could not be
refabricated for further use. All this necessitated the development of economical platinised electrodes with
corrosion resistant substrates providing high efficiency on par with platinum elecrodes for effective use in the
plant.

Platinised tantatum and titanium electodes were used in many electrochemical applications in the
reprocessing plants [6-8]. The details of preparation and performance evaluation of such electrodes are scarce in
the literature and in most cases they are available as patents. Hence there was a need to take up detailed
investigations to develop new electrodes and electrode coatings which can show improved performance in the
severe conditions encountered in the reprocessing plants. Mixed oxide coated titanium anodes (MOCTA) were
developed [9,10] for application as electrodes in the electrochemical processes employed for the dissolution and
the purification ofthe spent (U,Pu)C fuel ofthe fast breeder test reactor (FBTR). MOCT A belongs to the category
of dimensionally stable anodes (DSA) which are basically a mixture of oxides ofRu, Ti, Pt, Rh, Ir, Sn and Pd
coated over the surface ofTi, Ta, W, Cr, or Zr [11-14]. The MOCTA electrodes are titanium substrate coated with
Ru02+Ti02, with or without an overlay ofPt~. For the electrolytic dissolution of the ceramic (U,Pu)C fuels,
severe corrosive conditions are encountered with boiling nitric acid containing redox ions [5]. The presently used
composition of the MOCT A coating of RuO/fi02 with an overlay of Pt02 are found to operate only for durations
up to 230 h [9]. To increase the life of the electrode coatings, a new approach was made in the present work to
develop thermochemically metallic coatings with an intermittent MOCTA layer on Ti substrate. The electrodes
prepared were characterised by scanning electron microscopy (SEM) combined with energy dispersive x-ray
analysis (EDAX), x-ray diffraction (XRD), secondary ion mass spectrometry (SIMS). Electrochemical anodic
and cathodic polarisation behaviour of the electrodes was carried out in nitric acid medium, and the life
assessment of the electrode was carried out in a simulated reprocessing solution containing uranium and other
redox ions in boiling concentrated nitric acid medium. This paper describes the results of the present
investigation.

EXPERIMENTAL WORK

Commerc'ially pure (CP) grade titanium was used in the present investigation. Analytical grade chemicals
were employed for all purposes.

Preparation of Titanium Surface

The problem faced in obtaining good adhesion of the coating on titanium was mainly due to the presence
of the tough oxide film on the surface and its chemical composition which depends on the conditions of
formation. An adherent electrode coating over titanium can be obtained only if the oxide film is removed or is
replaced by another film that does not interfere with adhesion. Several procedures such as chemical etching in
acid solutions and electrolytic etching in different baths are usually followed for the preparation of titanium for
adherent deposition of metals.

Commercially pure titanium in mesh form was cut into the required shape with a lead for electrical
connection. These specimens were then sand blasted for mt;chanical roughening of the surface to improve the
adherence ofthe coating. Degreasing oftitanium was carried out to remove oil, grease and other foreign materials

931
potentiodynamic method in 1M HN03 medium at room temperature. Pure titanium Wasused as counter electrode,
and a saturated calomel electrode (SCE) was used as the reference electrode to measure the electrode potential.
A sweep rate of 0.166 mV/s was used for applying the potential from the open circuit potential (OCP).

Prior to the potential sweep, the electrodes were immersed in the electrolyte for an hour in order to
establish a steady state between the electrodes and the electrolyte. The potential observed between the electrode
specimen and reference electrode after this period was known as OCP. After noting the OCP, an external potential
was applied at the rate of 0.166 mV/s, and the corresponding current values were measured. For comparison
purpose, electrodes of platinum sheet and Pt electroplated on Ti were also tested under similar conditions.

Life Assessment of MOCT AG Coatings

Cylindrical electrodes of 45 mm diameter and 50 mm long were prepared for life assessment experiments.
Titanium was used as cathode and both titanium and MOCTAG were seperated using a polytetrafluoroethylene
disc. Simulated reprocessing solution containing uranium and other redox ions was prepared as per the
composition shown in Table 1. A DC voltage regulator was used to apply the cell potential to the electrodes
immersed in the boiling simulated reprocessing test solution. The cell potential and current were monitored
periodically while the electrolysis was continued. The cell voltage was maintained at 2 V at a current density of
12.8 mAlcm2 for the MOCTAG electrodes. The corresponding initial current for this potential was 1.4 A. Similar
test conditions were applied for the life assessment of MOCTA and modified MOCTA with Pt02 coating.

RESULTS AND DISCUSSION

Analysis of MOCTAG Coated Surface

Figure 1 (a) shows the typical cracked-mud morphology of the conventional MOCTA electrodes. The
presence of cracks, and the sharp edges of the oxide slabs facilitate efficient gas evolution during its use as
electrode in electrochemical processes. In comparision with this Fig. 1 (b) shows the smooth and compact Pt02
overlayer present in platinised MOCTA coating on titanium substrate. Figures 1 (c) and (d) show the general
appearance of the MOCTAG layer developed on the surface for both Pt and Pt-Ir compositions. In addition to the
general appearance seen in Figs.1 (c) and (d), significant changes in the morphology was noticed at the surface
in various locations. A well-developed and ordered structure was noticed for both Pt and Pt-Ir layered coatings.
Such a structure formation could be attributed to the smooth transformation of the coating solution into an ordered
metallic layer consisting of intermetallic Pt-Ti and Pt-Ir phases like Pt3 Ti, TiPtg, PtTi, PtIr, IrTi etc.[15, 16]. The
EDAX analysis of the specimens confirmed the significant presence ofPt and Pt-Ir on the surface in comparison
with the conventional MOCTA electrode specimens. SIMS analysis indicated the presence ofPt, Ru and Pt, Ru
and Ir on the surface for both type of electrodes. The distribution ofPt- and Ir- rich alloy phases was also noticed
during the analysis. The degradation of the MOCTAG surface was insignificant after anodic polarisation studies
in 1 N HN03, as shown in Figs. 2 (a) and (b).

Polarisation Behaviour of MOCTAG Electrodes

Figure 3 shows the variation of OCP with the type of coating present on the surface of titanium, in
comparision with Pt sheet. It can be noticed that the OCP values of the Pt and Pt-Ir layered Ti electrodes were
much active compared to those of Pt sheet and Pt-electroplated on Ti electrodes. Fig.4 (a) shows the anodic
polarization curves for conventional MOCTA, MOCTAG and Pt sheet electrodes. Significant changes in the
polarisation behaviour of the MOCT AG electrodes, depending on the heat treatment, can be noticed. It was
observed that the MOCTAG electrodes prepared at 1273, 1373 and 1473 K showed better polarisation behaviour
which was superior than MOCTA electrode, and tending towards the polarisation behaviour of Pt sheet electrode.

932
using organic solvents like acetone or trichloroethylene in boiling condition for. I0 minutes and then air dried.
The degreased surface was etched with 10% sodium hydroxide solution, and thoroughly washed with distilled
water. The final surface preparation of titanium mesh was done in a mixture of HF and HNO] solutions, and
finally washed with distilled water and air dried. The surface thus prepared has been reported to provide an
excellent configuration for the development of coatings with good adherence [14].

Coating Solution Preparation

The homogeneity and adherence of the coating also depends on the concentration and viscosity of the
coating solution. The solvents generally preferred for mixing the chloride salts of ruthenium or titanium were
hydrochloric acid and n-butly alcohol (n-butanol). It w.asfound that coating with n-butanol gives better adherence
than hydrochloric acid [14]. Hence, appropriate amount of RuCI] was dissolved in n-butanol to prepare 0.1 M
solution. This standard solution was mixed with appropriate mole percentage of tetra butly titanate to give a mole
ratio of 40:60 of Ru02 :TiQ, as this ratio is found to exhibit better dimensional stability over others for
electrochemical reactions occurring at potentials higher than chlorine evolution [14].

Application of Coating Solution and Thermochemical Treatment

The solution thus prepared was applied on the pretreated titanium substrate using a soft painting brush
in such a way that there was not an excess amount of solution on the surface to avoid the cloud formation and
discontinuous layers. Then the sample was allowed to dry at ambient temperature for about 10 minutes. Thereafter
it was heated at 623 K for 10 minutes in a muffle furnace to dry the coating solution applied over the surface.
After the application of a single layer of RuOlTi02 coating, solutions of chloroplatinic acid mixed with n-butanol
was applied over the dried surface with intermittent drying at 623 K for 10 minutes for a number of times in order
to produce the required thickness of coating. Similarly, solutions of chloroplatinic acid mixed with iridium
chloride and n-butanol was applied over the dried surface with intermittent drying at 623 K for.l 0 minutes for
a number of times in order to produce the required thickness of coating. Thermochemical treatment of these
coated Ti substrates were carried out in a high-temperature high-vacuum furnace, GCA make, USA, at 10-6bar,
at different temperatures viz. 973, 1173, 1273, 1373 and 1473 K in order to produce bright, glazed surfaces
containing Pt and Pt-Ir alloy. These "thermochemically glazed (MOCTAG)" electrodes would possess higher
electrocatalytic activity at the surface, with better adherence of the coating in comparison with the conventional
MOCT A electrodes coated with mixed oxides.

Physical Characterisation of MOCT AG Coatings

Specimens of lOx lOx 2 mm sizes with MOCTAG coatings were examined for the surface morphology
in a SEM coupled with EDAX. Also examination of the cross-section of the electrodes was carried out after
electroplating with Ni and mounting using epoxy resin. Ti Ka, Ru La and Lp, Pt La and Ma, and II' La and Ma
lines were analysed for the intensity of the above alloying elements present in the coating. X-ray diffraction was
performed on the specimens, using Cu Ka radiation in a Philiphs diffractometer, for the phases present. SIMS
analysis of the specimens were carried out using a CAMECA IMS-4F system using Cs+primary ion beam at 10
KV. The intensity profile of Ti, 0, Pt, Ru and II' was obtained with respect to time of sputtering.

Electrochemical Polarisation Studies

Anodic and cathodic polarisation studies were carried out to understand the electrocatalytic behaviour
of the MOCT AG electrodes prepared at different temperatures. The experiments were conducted by

933
Figure 4 (b) shows the anodic polarisation curves of MOCTA, in comparision with MOCTAGelectrodes prepared
at 973, 1173 and 1373 K, and tested at 323 K in I N HN03 In comparision'with MOCTA, the MOCTAG
electrodes showed better polarisation behaviour even at a lower current density (MOCTA - 100 J.1Ncm2,
MOCTAG (Pt) - 20 J.1Ncm2, MOCTAG(Pt/Ir) - 10 J.1A/cm2,whereas for Pt sheet it was 2 J.1A/cm2,the current
density at which stable polarisation was noticed). From the above results the performance of the MOCTAG,
particularly the one prepared at 1373 K, was found to be better than the conventional MOCTA electrodes.

Life Assessment of MOCTAG Electrodes

The results of the life assessment test showed that the MOCTA electrode worked satisfactorily up to 215
h at an operating current density of 6 mNcm2. Beyond this, the cell current decreased to negligible values
indicating that the electrode failed. The platinised MOCTA worked satisfactorily up to 230 h at an operating
current density of 8 mNcm2 This could be due to the high catalytic activity ofPt, and the fine grained oxide
structure present at the surface compared to cracked-mud morphology of MOCTA as shown in Fig. 1(a). In the
case of MOCTAG, the electrode continued to work up to 1050 h, and still the experiment is in progress at an
operating current density of 12.8 mNcm2 (Fig. 5). This indicated the superiority of the Pt-Ir metallic coating
developed by the thermochemical-glazing process in comparision with MOCTA and platinised MOCT A
electrodes. The high current density of MOCTAG could be attributed to the better conductivity and high
electrocatalytic activity of Pt, and the presence of intermetallic Pt, Ti and Ir alloy phases. The long life of this
electrode is due to the strong adhesion ofthe metallic coatings prepared at high temperature in coniparision with
the oxide coated electrodes developed at temperatures ~ 773 K.

CONCLUSIONS

The results of the present investigation suggested the following conclusions:

(i). Pt and Pt-Ir layered titanium electrodes prepared by thermochemical glazing process showed better
electrochemical properties during OCI>measurements and anodic polarisation studies; the electrode prepared
at 1373 K showed superior properties.
(ii). SEM/EDAX examination indicated better adhesion of the layer with Pt and Pt-Ir, and XRD analysis
confirmed the presence of intermetallic Pt-Ti and Pt-Ir alloy phases at the surface. SIMS analysis indicated
the distribution ofPt- and Ir- enriched phases on the surface.
(iii). Life assessment of the electrodes during electrolysis in a severe corrosive environment showed that these
electrodes possessed longer life compared to conventional platinised electrodes.

REFERENCES

1. Baumgartner, F., Schmieder, H., RadiochemicaActa, Vo1.25, 1978, p.191.

2. Hj. Matzke, Science of Advanced LMFBRfuels, North-Holland physics publishing company, Amsterdam,
1986, p.623.
3. Bray, L.A., Ryan, J.L., Actinide recovery from waste and low grade sources, J.D.Navrutil and
W.W.Schulz,(eds)., Harwood publishers, New York, 1982, p.129,.
4. Palamalai, A., Rajan, S.K., Chinnusamy, A., Sampath, M., Verghese, P.K., Ravi, T.N., Raman, V.R.,
Balasubramanian, G.R., Radiochemica Acta, Vo1.55, 1991, p.29.
5. Palamalai, A., 'Development of an electro-oxidative dissolution technique for repeocessing of fast breeder
reactor ceramic fuel materials', PhD thesis, Madras University, 1988..
6. Bray, L.A., Ryan, J.L., Wheelwright, E.J., Development of the CEPOD Process for Dissolving Plutonium
Oxide and Leaching Plutonium from Scrap or Wastes, Report No. PNL-5657 UC-70, Pacific Northwest

934
 Laboratory, Washington, November 1985.
7. He Jianyu, Zhang Qingxuan, Luo Longjun, Tian Baosheng, Application of Electro-Reduction and Oxidation
Technique in Reprocessing of Nuclear Fuels in China, RECOD-91, Sendai, Japan, 1991.
8. Schmieder, H., Goldacker, H., Galla, U., Heilgeist, M., Kluth, M., Petrich, G., Electroreduction for the
Plutonium separation in Pulsed Columns and Mixer Settlers and comparision with chemical separation,
Proceedings on Fuel Reprocessing and Waste Management, American Nuclear Society Topical Meeting,
Jackson, Wyoning, 1984.
9. Kamachi Mudali, U., Dayal, R.K., Gnanamoorthy, J.B., Nuclear Technology, Vol. 100, 1992, pp.395-401.
10. Kamachi Mudali, Dayal, R.K., Gnanamoorthy, J.B., Rajan, S.K., Palamalai, A., Proceedings of the
International Symposium on Thermochemistry and Chemical Processing, Kalpakkam, 1991, p.293.
11. Beer, H.B., British Patent, 964, 913.
12. Beer, H.B., Electrochemistry in Industry, P.19, U.Landu, E.Yeager and D.Kortan, (eds), Plenum press, New
York, 1982.
13. Trasatti, S., Electrodes of Conductive Metallic Oxides, Part A & B, Elsevier Scientific Publishing Company,
Amsterdam, 1980.
14. Kamachi Mudali, U., 'Development of Dimensionally Stable anodes for Chlor Alkali Industry', M.Tech
Thesis, lIT Bombay, 1984.
15. Beard, B.C., Ross, Jr., P., Journal of Electrochemical Society, Vol. 133, No.9, p.1839.
16. Massalski, A., Binary Alloy Phase Diagrams, Vol. 3, American Society for Metals, ASM, Philadelphia,
USA, 1980.

935
936
938
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6. Mumbai, India
HIGH TEMPERATURE NITRIDATION AND OXIDATION OF INCONEL-601

High Temperature Nitridation and

Oxidation of INCONEL-601
S. Dash, R. Krishnan, S. Rajagopalan and A.K. Tyagi
Materials Science Division,
Metallurgy and Materials Group,
Indira Gandhi Centre for Atomic Research,
Kalpakkam-603 102, India

Abstract
Gas phase nitridation and oxidation studies at high temperatures in inconel-601 have been carried
out. The resulting modified surface region was analysed using SIMS and GIXRD techniques. SIMS
investigations on nitrided samples showed two distinct stoichiometric layers of major elements Ni,
Fe, Cr and minor elements Cu, Si, lying below the thermodynamically stable nitride overlayer of
Ti. Surface segregation of manganese during nitridation is also noticed during SIMS
investigations. Similarly oxidation lead to the formation of surface oxide layer rich in Cr203' This
was succeeded by buried interfacial layers of Fe and Ni oxide. The depth resolved GIXRD was
used to identify various transition metal nitrides and oxides of these reacted surface zone. The
presence of passive overlayers is responsible for the hot corrosion resistance and also for the
appearance of two distinct stoichiometric layers.

Introduction
Inconel series of nickel base superalloys are routinely used for hot corrosion resistance
applications[l]. The solution hardenedinconel-600, having nickel, iron and chromium as major
constituents with manganese, silicon and copper as minor additives, is known for its excellent hot
corrosion resistance. It's 601 variant possesses superior mechanical strength at elevated
temperatures due to precipitation hardening with minor additives like Ti and AI: Also it has
enhanced chromium and' iron contents. Superior creep and fatigue resistance is derived from y'
precipitates of Ni3AI and Ni3 Ti present in y inconel matrix. This 601 alloy was exposed to moving
nitrogen and oxygen gas streams at 1000C and 800C respectively. The post exposed specimen
were analysed by Secondary Ion Mass Spectrometry (SIMS) [2-4]and Grazing Incidence X-Ray
Diffraction (GIXRD)[5] for depth resolved microchemical and structural characterisation of surface
and subsurface regions. Results obtained from these measurements are discussed in this paper.

939
Experimental
Precision cut (12 mm diameter and 2 mm thick), polished inconel-601 flat discs were
exposed to moving gas stream at 12733 K for various time durations ranging from I to 40 hours in
a specially built furnace. After nitridation / oxidation schedule, the samples were analysed by SIMS
and GIXRD. Secondary Ion Mass Spectrometry (Model: IMS 4f CAMECA, France) having 10 keY
Cs+ primary beam operating in the ~A current range was used in dynamic SIMS mode for depth
profiling. The intensities of quasi-molecular charge transfer ion species (CsXf, where X=Ni, Cr,
Fe, Mo, Si, Cu, AI, Ti, formed as collisional complexes in the gas phase, were measured for
elemental depth profiling of alloy constituents in the altered region. This procedure is quantitative
and eliminates matrix effect. The depth calibration was achieved by crater depth measurements
executed through surface profilometry. A Siemens 05000 Diffractometer with a grazing incidence
attachment was used to record the depth resolved XRD pattern of exposed specimen.
Results and Discussion
The CsX+ ion intensities of pristine as well as exposed inconel-601 sample are shown in
fig. I. These depth dependent concentration depletion profiles pertain to the onset and completion of
nitridation. The metal to non-metal MIX (X=N+ or 0+) ratios in the converted matrix with differing
density and stoichiometry reveal a two stage conversion. This is attributable to the existence of
thermodynamically varying non-metal chemical potential. gradients in the near surface region. Also
considerable surface segregation of Mo was noticed in the nitrided specimen having exposures upto
20 hours. Similarly oxygen exposure of these samples at 1073K and subsequent analysis by SIMS
revealed a stoichiom~ic CrzOJ formation at the top surface (fig.2). This is evident from the fixed
(CsCrt/(CsOf ratio~t the surface region (upto thickness "",I~m). For the 5 hour oxygen 'exposed
specimen the depth prdfiles indicated the presence of oxides of Mo, Fe, and Ni below cromia layer
in thicknesses varying from I ~m to 2 ~m. The bulk composition of the alloy is attained at a depth of
"'"2.5 ~m. GIXRD at 3 incident angle (which corresponds to probing depth of"", 0.5 ~m) was
carried out for nitrided specimen having different exposure durations. These GIXRD patterns are
shown in fig.3. In this case, a controlled oxidation along with nitridation was noticed. This could be
attributed to the finite oxygen partial pressure present as impurity in the commercial nitrogen gas.
This has been revealed from the oxide phases identified"in GIXRD studies. The diffraction pattern
of pristine inconel sample resembles that of pure nickel y phase. The presence of CrzOJ, AlzOJ and
FezOJ along with TiN have been identified in nitrided specimen. With the increase in the nitrogen
exposure duration, the y-phase diminishes and a completely modified overlayer is seen after 40 hr.
In case of oxidised specimen, the conversion layers are shallow as seen from the diffractogram
shown in figA. In the diffraction pattern recorded with the angle of incidence 8=1, in which the
depth probed amounts to roughly 0.2 ~m, complete conversion to oxides is noticed, AS the angle of
incidence (depth probed) increases, the ratio of diffraction intensities arising from bulk and surface
also increases. These oxide phases predominantly consisting of CrzOJ and A1z0J constitute a
coherent protective overlayer. By conducting sequential exposures with isotopically labelled oxygen
gases like 016 and 018, it will be possible to investigate mechanism of formation such subsurface
oxide layers which probably accrues from internal oxidation.

940
Conclusion
Inconel-601 is resistant to oxidation even at higher teq1peratures in oxygen stream due to the
formation of coherent overlayers of stable oxides like Cr203 and A1203. Followed by these, there is
buried oxide interface comprising of oxides of Ni, Fe and Mo. In contrast, nitridation at high
temperature leads to formation of TiN as a coherent overlayer. This is inferr~d from GIXRD
studies. Also surface segregation of Mo and other minor constituents resulting from nitridation was
found to be absent in oxygen exposed specimen.

References
[1] See, for example, Source Book on Materials for Elevated Temperature Applications, E. F. Bradley (ed.),
American Society for Metals, USA (1979).
[2] F. Degreve, N. A. Thorne and 1. M. Lang, 1. Mater. Sci. 23 (1988) 4181- 4208.
[3] A. Benninghoven, F. G. Rudenauer and H. W. Werner, Secondary Ion Mass Spectrometry, Wiely, New
York (1987).
[4] H. Ganser, Surf. Interface Anal. 24, (1996) 483.
[5] B. L. Ballard, X. Zhu, P. K. Predecki, D. Albin, A. Gabor, 1. Tuttle and R. Noufi, Adv. X-Ray Analysis,
38, P. K. Predecki, Plenum Press, New York (1995).

941
942
943
944
945
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6. Mumbai. India

Failure Analysis of a Monel-400 Heat Exchanger

Thbe from a Nuclear Power Plant
N.G. Muralidharan, N. Raghu, K.V. Kasiviswanathan,
T. Jayakumar and Raldev Raj
Metallurgy and Material Group,
Indira Gandhi Centre for Atomic Research,
Kalpakkam-603 102, India

ABSTRACT

Failure of a heat exchanger was reported in one of the nuclear power plants. The plant has eight boilers and
each boiler has eleven heat exchanger bundles. The Monel-400 heat exchanger bundles are of V-Tube
construction consisting of 192 tubes having 12 mm outer diameter and Imm wall thickness. The tube sheet
of the heat exchang~r is made of 65mm thick stainless steel with monel overlay on the outer face. The heat
exchanger tubes were fully expanded in the tube sheet and welded on to the outer face of the tube sheet
having the monel overlay. The tubes ide fluid is heavy water and the shell side fluid is feed water. The failure
in the form of a leak was noticed in the particular heat exchanger when routine inspection of the boiler feed
water was analyzed. The heat exchanger bundle was cutout of the boiler and the)eaky tube was identified
by conducting pressurization tests. The failure location was close to the tube sheet at the heavy water inlet
end where large amount of sludge deposit was noticed. Detailed failure investigation revealed extensive wall
thinning in the failed region. The failure was found to be intergranular in nature and leaching of nickel from
the grain boundary region was also observed. The cause of the failure was found to be 'underdeposit'
corrosion. Details of the failure investigation carried out are presented in the paper.

lntroduction

Failure of a heat exchanger (HX) bundle was reported in one of the nuclear power plants. The
concerned heat exchanger was in operation for the last twenty years. The plant has eight individual boilers
and each boiler consists of II heat exchanger bundles. The heat exchanger bundles are of V-tube construction
consisting of 192 tubes. The material of heat exchanger tubes is Monel-400, having..12.0mm outer diameter
and Imm wall thickness with 65mm thick tube sheets on either leg. The tube sheet is stainless steel with
Monel overlay on the outer face. The HX-tubes are fully expanded in the tube sheet and welded on the outer
face of the tube sheet having the Monel overlay.

The tube side fluid is heavy water with inlet temperature and pressure of about 558 K and 85 kglcm2
respectively. The shell side fluid is the boiler/ feed water at temperature and pressure of 533 K and 45 kglcm2

946
respectively. The failed heat exchanger was cut out of the boiler and the leaky tube was identified by
conducting pressurization tests. The failure location was near the tubesheet in the heavy water inlet (boiling
leg of HX) where large amount of sludge deposit was noticed.

Visual Inspection.

Visual inspection of the failed HX bundle revealed adherent sludge deposit upto approximately 25mm
in length from the tube sheet. Scaling was also seen on all the HX-tubes. The exact nature of the defect and
its location were not possible to be identified precisely due to interference from adjacent tubes, obstructing
a clear view. Hence leaky tube was trepanned fro~ the tubesheet. Figure I shows the photograph of the
trepanned portion with the failed tube in the center. The inside surface of the tube was clean and clear.
Steromicroscopy revealed deep pit marks and a through and through defect at the bottom of a pit as depicted
in Fig. 2. The size of the defect was O.5mm width and 3mm in length.

Chemical Analysis

Samples from the tube sheet deposits and the scales on the tube surface, when analyzed by Atomic
Absorption Spectroscopy (AAS) and Spectrophotometric methods, revealed that the deposit contains iron,
Dickel, copper, calcium, magnesium, zinc and silicon. The presence of these elements can be attributed to the
material transport phenomenon associated with erosion-corrosion of the boiler feed water circuit of the

947
reactor. X-ray powder diffraction analysis of the deposits revealed Fe304 as the major constituent and F~03'
NiO and CuO as the minor constituents.

Non-Destructive Testing

The cleaned tubes were subjected to dye-penetrant and radiographic examinations. Corrosion pits
and wall thinning were observed where it was covered by the sludge. To assess the extent of wall
thickness loss and to facilitate examination of the tube surface inside the tube sheet, the defective tube was
pulled out of the tube sheet after machining the weld. Figure 3 shows the positive print of the radiograph
at the defective location. Radiographic examination of the defective tube revealed extensive wall thinning
in the pitted region. It was seen that the wall thinning extended to about 20mm from the tube sheet
location of the tube. The adjacent tubes also showed evidence of wall thinning and presence of corrosion
pits.

Metallographic Examination

In-situ metallographic examination carried out close to the defective region revealed extensive
grain boundary attack. The microstructure on the cut section close to the defect revealed extensive wall
thinning due to intergranular attack. Figures 4 and 5 show the intergranular attack on the outer surface of
the tube taken away from the defective location and at the defective location respectively. Scanning
electron microscopic examination revealed extensive grain boundary attack and grain decohesion on the
outer side of the tube (Fig. 6). Energy dispersive X- ray analysis (EDAX) made on various locations
revealed the following:

1. The grain boundary area near the corrosion attacked region indicated nickel depletion, compared
to the matrix region and

2. The corrosion product was seen to contain predominantly Ni, Fe and Cu.

Typical EDAX pattern obtained on the corrosion product of the tube is given in Fig. 7. Figure 8
gives the microprobe analysis obtained at ~he crack region.

948
Results and Discussion

The sludge deposit was seen to be porous in nature and was adherent at certain locations. The tubes
were seen to have undergone corrosion attack under the sludge deposit. The extent of attack varied from
robe to tube and approximately 20-30% of the wall thickness loss was seen at various locations. However,

949
950
 severe attack was seen on the failed tube at one location which had resulted in the through wall opening.
The thfough wall opening was seen to be at the bottom of a large and shallow corrosion pit. Micro probe
. analysis confinned segregation of sulphur in this region. The final opening is attributed to rupture of thin
ligament that could not withstand the internal pressure. This region was obviously under the sludge
leading to accelerated corrosion. The corrosion attack was seen to be intergranular in nature indicating that
the failure initiated by grain boundary decohesion followed by progressing into a small pit and then further
growing into a larger pit.

Conclusion

Monel-400 is considered as an excellent heat exchanger tube material. Many such heat exchanger
are still in operation for a longer durations even in the same plant. However, Monel-400 is known to be
susceptible to intergranular attack [1], due to the absence of a protective chromium oxide layer. Pitting
attack in the creviCe regions and under deposits have been reported [2] under lake water exposure.
Accelerated corrosion attack due to oxygen generation under tailing conditions have also been reported,
but these are normally in the primary side of the heat exchanger tubes. Presence of copper/copper oxides
is also seen to enhance pitting corrosion attack [3].

From the morphology of the corrosion pits and general wall thinning seen on the tubes, it is clear
that only on~ tube failed by way of small through and through opening originating presumably from an
inclusion site. Accumulation of sludge near this inclusion site had aided under deposit corrosion. Hence
it is felt that there is no risk of sudden failure of a number of heat exchanger tubes at the same time. It is
JeCOmmended that the heat exchanger with balance tube bundles can be continued to be kept in operation.

AclmowledgmelJ,t

We are thankful to Dr. Placid Rodriguez, Director, IGCAR for constant support and
CIICOuragement. The authors are also thankful to Shri K. Hariharan, NP~IL, Shri P. Kalyanasundaram,
Head, DPEND, IGCAR, Dr. S.V. Narasimhan, WSCL, IGCAR and Dr. K.S. Krishna Rao, NPCIL, for
many useful discussions during the investigation.

References
1. Mc Intyre N.S. etal, The Corrosion of Steam Generator Surface under typical Secondary Coolant
Condition Effects of pH Excursion on the Alloy Surface Compositions, Corrosion Science, 37 (7),
July 1995.
it .
2. King PJ. and Dautovich D.P., Pitting Corrosion of Nuclear Steam 'Generator Materials, Nuclear
Technology, Vol. 55, Oct 1981.

3. Theus OJ. and Daniel PL., Corrosion in Steam Generating Systems, Conference on Corrosion in
Power Generating Equipments, Baden, Switzerland, 19-20Sept. '1983.

951
 Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Influence of Anions on the Performance of Thiosemicarbazide

as an Inhibitor of Corrosion and Hydrogen Permeation
Through Mild Steel in Acidic Solutions
K. MadhavanI,S. Muralidharan and S. Venkatakrishna Iyer
Radioelectrochemistry Laboratory, Central Electrochemical Research Institute,
Karaikudi-630 006, Tamilandu, India
IDepartment of Chemistry, Govt. Arts College, Karaikudi-630 003

ABS'l'RACT

The influence ofthiosemicarbazide on the inhibition of corrosion and

hydrogen permeation through mild steel in 1 M HCl and 0.5 M H SO has been
2 4
studied by weight loss determination, gasometric technique and other various
electrochemical techniques. The compound is found to be more inhibi ti ve
in H2S04 and it is found to function as a cathodic inhibitor in both the acids.
Thiosemicarbazide is found to enhance the permeation of hydrogen through mild
steel in both the acids. The adsorption of this compound on mercury is studied
using capillary electrometer. Its adsorption on the mild steel surface is
found to obey Tamkin's adsorption isotherm.

1 INTRQDOCTIQN

Thiosemicarbazide as an inhibitor for the corrosion of metals both in

acidic and alkaline media has been studied by several authors [ 1-5 ] " Acid
pickling process usually creates a condition favourable for hydrogen entry
into the metal leading to hydrogen ernbri ttlement . Organic compounds added
to pickling acids are expected to minimise the base metal attack and reduce
the hydrogen entry into the metal. Inhibitors which are effective in retarding
the corrosion of metals ned not necessarily decrease the hydrogen uptake.
Putilova [5] observed that thiourea and its derivatives enhance the hydrogen
entry into the metal surface, because of their partial decornposition to form
hydrogen sulphide which accelerates the diffusion of hydrogen through steel,

952
thereby inducing hydrogen embrittlement. So it is of interest to see whether
thiosemicarbazide which is a derivative of thiourea having an extra -NH group
behaves in a similar way in both the acids. In the present study the influence
of anions in the pickling media on the inhibition of corrosion and hydrogen
permeation through mild steel has been investigated usoing different non-electro-
chemical and electrochemical techniques. The results obtained are presented
and discussed.

2 EXPERIMBlI'l'AL DETAILS

Cylindrical mild steel specimens of the composition 0.07 wt% C, no Si,

0.034 wt% Mn, 0.08 wt% P, no S and the remainder Fe and of size 5 x 2 x 0.25
em were used for weight loss, gasometric and hydrogen permeation studies.
These strips were given fine mechanical polishing and then degreased with
trichloroethylene before use. For polarisai:ion studies an electrode of exposed
2
surface area 0.283 cm was fabricated by embedding it in Teflon and provided
with a screw type stem for the electrical contact was used. This :~lectrode
was polished using a sequence of emery papers and degreased. A.R.grade HCl
and H S0 were used for preparing solutions. Thiosemicarbazide (extra pure)
2 4
was procured from SISCO research laboratories, Bombay. Double distilied
water was used to prepare all solutions. Triply distilled water and A.R.grade
vacuum distilled mercury were used for electrocapillary measurements.

Weight loss ard gasometric studies were carried out as described earlier
[6] . Gal vanostatic polarisation were carried out as reported earlier [7]
at a constant temperature of 32 1C. A platinum foil was used as the auxili-
ary electrode and Hg!Hg2Cl/1M HCl and
Hg!Hg SO/O.5M H S04 were used as
2 2
reference electrodes. The electrocapillary behaviour of thiosemicarbazide
in both the acids were studied at 25 1C using a capillary electrometer
according to Devanathan and Peries [8]. Hydrogen permeation studies were
carried out using an adaptation of Devanathan and Stachurski's two compartment
cell [9].

3 RBSUL'!'S AND DlsaJSSION

Table 1 gives the values of inhibition efficiency for different concentrat-

ions of thiosemicarbazide in 1 M HCl and 0.5 M H S0 obtained from weight
2 4
loss and gasometric measurements. It is found from the table that the

953
inhibition efficiency increases with increase in the concentration of the
compound. Moreover it is found that the compound is IlIOre effective as an
inhibitor in 0.5 M H so than in 1 M HC!. The better performance of the
2 4
compound in H S0 can be explained as follows.
2 4
Chloride ions are strongly adsorbed and they occupy IlIOSt of the space
on the metal surface. So very little space is available for the organic
IlIOlecules to get adsorbed. But sulphate ions are adsorbed considerably
to a lesser extent, leaving IlIOre space for the organic molecules to get
adsorbed on the metal surface [10]. It leads to IlIOre coverage on the metal
surface by the organic IlIOlecules and thereby to IlIOreinhibition of corrosion.

The additional -NH group present in thiosemicarbazide is IlIOre basic

than - C - NH . In thiosemicarbazide lone pairs of electrons of thioamide
2
group are involved .in reasonance. But lone pairs of electrons of the -NH2
group are' available for protonation. So in acidic solutions, a proton adds
to the thiosemicarbazide IlIOlecule in the following way:

'!he above protonation reaction is IlIOre strongly favour~d than protonation

on sulphur atom because of the strong basic properties of the -N-NH group [11].
2
Inhibition of corrosion brought about by thiosemicarbazide ca,n be due
to the following interactions.

1 Interaction between the lone pairs of electrons of the sulphur

atom of the organic IlIOlecule and the positively charged metal surface
[12]
2 Interaction between the lone pairs of nitrogen atoms and the positi-
vely charged metal surfaces [13] and
3 Interaction between the protonated species formed i~ acidic solutions
and the negatively charged metal surface [11].

Tables 2 (a & b) give values of corrosion kinetic parameters such as

Tafel slopes (b and b ), corrosion current (I ), corrosion potential
a c curr
(E ) and inhibition efficiency obtained from gal vanostatic polarisation
corr
curves for mild steel in 1 M HCI and 0.5 M H S0 containing different
2 4

954
955
956
concentrations of thiosemicarbazide. It can be seen from these tables that
values of these parameters are quite similar to those reported earlier [ 7]
It can also been seen from these tables that an increase in the concentration
of thiosemicarbazide enhances the values of b
considerably in both the acids.
c
But the values of b are changed only to a very little extent. This observation
a
clearly brings out the fact that inhibition of corrosion of mild steel in
both the acids is under cathodic control. The compound inhibits the corrosion
by enhancing the cathodic overvoltage for proton discharge. Values of E
corr
are shifted to less negative values in the presence of different concentrations
of .the compound. This can be ascribed to the formation of a closely adherent
adsorbed film on the metal surface. The presence of increasing concentrations
of thiosemicarbazide brings down I values very effectively. Most of
corr
the values of inhibition efficiency obtained by weight loss measurements
and galvanostatic polarisation studies agree very well.

Electrocapillary curves for 1 M HCl and 0.5 M H S0 in the presence

2 4
of different Conceatrations of thiosemicarbazide clearly reveal~ the fact
that it adsorbs more from H So than from HCl. This compound performs more
2 4
effectively in B So , because of its greater adsorption on the surface of
2 4
mild steel from H S0 ,
2 4
Hydrogen permeation currents obtained for 1 M HCl and 0.5 M H so in
2 4
the absence and presence of thiosemicarbazide are given in Table 3. The
permeation current is found to be more for HCl because of the more aggressive
nature of chloride ions. It can also be seen from this table that the presence
of thiosemicarbazide in acidic solutions enhances the perme~tion current
in both the acids. This enhancement in permeation current can be attributed
to the decomposition of the compound on the mild steel surface [14]. In all
the mechanism suggested so far, invariably the product of decomposition of
thiourea and its derivatives is H S which is evolved on the metal surface.
2
Its formation can be detected by radiometric measurements, if labelled thiourea
(S35) or its derivative is used.

The whole process takes place in two stages. In the first stage, thiosemi-
carbazide molecules are adsorbed on the metal surface by virtue of the inter-
action of lone pairs electrons of sulphur and nitrogen atoms with the metal

957
surface. In the second stage the adsorbed thiosemicarbaz id:! molecules slowly
undergoes chemical changes. The molecule usua~ly decomposes with the formation
of H S by the action of hydrogen evolved on the metal. The reaction takes
2
place in the following way:

According to Gu Hough et al [ 15] the enhanced permeation of hydrogen

through the metal surface in acidic solutions in the presence of thiourea
and its derivatives can arise from il)creased surface adsorption energies of
the hydrogen atom caused by the adsorption of thiourea and its derivatives.
It may also be due to the increased concentration of surface hydrogen atom
due to the inhibition of the recombination step of hydrogen evolution. Trabanelli
and Zucchi [16] are of the view that the sulphur of hydrogen sulphide can
act as a negative catalyst for the recombination of atomic hydrogen into mole-
cular hydrogen .

A decrease in the enhancement of permeation current with increase in
the concentration of thiosemicarbazide can be due to increased adsorption
of the compound with increase in its concentration forming a barrier for the
permeation of ionised hydrogen.

Values of surface coverage (0) obtained from values of inhibition effi-

ciency in the absence and presence of thiosemicarbazide have been plotted
against log' C. A straight line relationship was obtained thereby showing
that the adsorption of this compound on th~ mild steel surface obeys Temkin's
adsorption isotherm.

4 CatCLUSI~

1 Thiosemicarbazide as been found to perform ""ell in both the acids

with better performance in H S0 .
2 4
2 The inhibition of corrosion of mild steel in both the acids by this
compound is under cathodic control.
3 The presence of thiosemicarbazide in both the acids is found to enhance
hydrogen permeation through mild steel surface.
4 The adsorption of the compound on the mild steel surface from both
the acids obey Temkin's. adsorption isotherm.

958
ACKNOWLEDGEMENT
One of the authors (S.M) wishes to thank Council of Scientific and Industrial
Research, New Delhi, for the award of Research Associateship.

5 REFERENCES
1 Mostafa, A.B., Kamal, KH.M., Abdel-Hamid, J.A., T~iosemicarba-
zide as an inhibitor for the corrosion of aluminium and zinc,
Indian Journal of Chemistry, Vol.15, No.11, November 1977,

pp. 1 1- 11 .
2 Fouda, A.S., Moussa, M.N., Taha, N.L, Elneana, A.I., The role of some
thiosemicarbazide derivatives in the corrosion inhibition of aluminium
in hydrochloric acid, Corrosion Science, Vol. 26, No.9, September 1986,
pp.719 - 726.
3 Khamis, E., Abdel-Nabey, B.A., Impedance studies of the effect of time
of immersion on the inhibition of acid corrosion of steel, Corrosion
Prevention and Control, Vol.37, No.1, October 1990, pp. 127-130.
4 Ateya, G. R., Adsorption of thiosemicarbazide on iron cathodes, Journal
of Electroanalytical Chemistry, Vol. 76, No.4, April 1977, pp.191 - 198.
5 putilova, I.N., Balezin, S.A., Barranik, V.P., Metallic corrosion inhibitors,
Ryback G. and Bishop, E (Eds), Pergamon Press, New York, 1960, pp.115-136.
6 Rengamani, S., Muralidharan, S., Ganesan, M., Venkatakrishna Iyer, S.,
Influence of anions on the performance of anisidines as inhibitors for
the corrosion of mild steel in acidic solutions, Indian Journal of Chemical
Technology, Vol.1, No.5, May 1994, pp. 168 - 174.
7 Muralidharan, S., Quraishi, M.A., Venkatakrishna Iyer, S., The effect
of molecular structure on hydrogen permeation and the inhibition of corrosion
of mild steel in acidic solutions, Corrosion Science, Vol.37, No.11,
November 1995, pp. 1739 - 50.
B Devanathan, M.A.V., Peries, P., The adsorption of potassium halides at
the mercury/water interface. Transaction of Faraday Society, Vol.50,
No.11, November 1954. pp. 1236 - 1243.

9 Devanathan, M.A.V., Stachurski, Z., The adsorption and diffusion of hydrogen

in palladium, proceedings of Royal Society (London), Vol.A270, No.10,
OCtober 1962, pp.90 - 102.

959
10 Subramanyan, N., Rangarajan, S.K., Balakrishnan, K., Venk::ltakrishna Iyer
S., Venkatesan, S., Snthyanandham, B., The influence of azoles and methyl
pyrid'~nes on the corrosion of mi l.d s ':eel in acids, Proceedigs of Third
European Symposium on corrosion inhibitors, A~nali.del. Universita di
Ferrara, Italy, NeoNseries, Supplement No.4, 1970. pp. 592 - 598.

11 walter, W., Voss, J., The chemistry of amides, Zabicky (Ed), IntersGience,
New York, 1970, pp. 187 - 190.

12 Devanath.;In, M.A.V., Tilak, B., The structure of thl,,! l;lectrical doubl.=

layer at the metal-solution interface, Chemical Reviews, Vol.65, No.4,
1965, pp, 635 - 684.

13 Lane T.J., Yama':Juchi, A, Quaghano, J.V., Ryan, J.A., Mizhushimll, A., Infra-
red absorption spectra of inorganic coordination complexes, Journ:'ll of
American Chemical Society, Vol. 81 , No.8, August 1959, pp. 3824 - 26.

14 Cavallaro, L., Felloni, L., Trabanelli, G., Pulidori, F., Potentiodynamic

measurements of polarisation curves on Armco iro:1 in acid medium in the
presence of thiourea dl=ri vati ves, Electrochimicd Acta, Vol. 8, No.6, June
1963 , pp. 5 21 - 5 28 .

15 Gu Hough, Zhow Zhongbai, Tao Yingachu, Yao Luaw, Diffusion of hydrogen

in metals - A study on the effect of thiourea and its derivatives on hydrogen
permeation rate in steel in HCI, Wahan Dauxe Xuebao, Ziran Kexuebaw, 1982,
Vol. 2, No.1,- January 1982, pp. 57 - 68 (Chinese).

16 Trabanelli, G., Zucchi, F., Organic sulphur compounds as corrosion inhi-

bitors, Reviews on corcosion and coatings, Vol.1, No.2, 1973, pp.97 -
129.

960
Proc. Int. Cont". on Corrosion CONCORN '97
December 3-6, Mumbai, India

Influence of Hydrodynamics on the Electrochemical

Behaviour of Aluminium Alloy Anode and Steel Cathode in
3% NaCI Solution Under Cathodic Protection
Condition-A Rotating DISC Electrode Study
s. Muralidharant, K.B. Sarangapanil, v. Kapalil, R. Vijay Anand2,
K. Vidyasankar2 and S.N.S. Arun Kumar2
lRadioelectrochemistry Lab., Electrodics & Electrocatalysis Division,
Central Electrochemical Research Institute, Karaikudi-630 006 Tamilnadu, India
2Centre for Education, CECRI, Karaikudi, India
ABSTRACT

Different hydrodynamic conditions prevailing in seawater in-

fluence very much the electrochemical characteristics of Al based
alloy sacrificial anode (AI-Zn-In alloy) and the steel cathode
during cathodic protection (C.p) of submerged structures. Different
hydrodynamic regions namely laminar, viscous and turbulent have
been simulated using the rotating disc electrode (ROE) technique
in 3% NaCI solution. Reynold's numbers corresponding tothese regions
were calculated for a rotating impeller disc type of electrode and
adopted throughout this study. The electrochemical characteristics
of the aluminium alloy anode and the steel cathode were determined
at all hydrodynamic regions by varying the rpm of the rotating disk
electrode. Data collected with the help of ROE are found to be use-
ful as cathodic protection engineering design parameters. Hence
it is strongly felt that in future the use of R.D.E. technique in
C.P. design studies may become a more reliable, less time consuming
and highly reproducible accelerated testing method.

1. INTRODUCTION
During cathodic protection (CP) of steel structures such as
oil drilling platforms, sheet piles made of steel, buoys and caison
gates in sea water using aluminium alloy sacrificial anodes, both
the anodes and cathodes are facing the same environment namely,
sea water containing about 3 to 3.5% NaCI (W/W) under different
hydrodynamic conditions. So a prior knowledge of the characteristics
of the anode and the cathode under actual CP conditions is a neces-
sity. But the corresponding data are totally lacking. Hence it was
decided to study systematically the same at ambient temperature

* CorresDond1n~
. author

961
by varying the hydrodynamics from laminar through viscous to turbu-
lent conditions, which were simulated in the laboratory using a
RDE set up [1]
.2. EXPERIMENTAL DETAILS
2.1. Materials
Previously cast AI-Zn-In (anode prepared as per Indian patent)
was used throughout this investigation [2]. Cylindrical specimen
of diameter 0.7 cm and length 1.8 cm was embedded in a Teflonjacket.
The disc electrode was connected to a cylindrical stainless steel
or brass rod which served as the lead as well as the shaft for
rotation. Similarly a cylindrical piece of steel was embedded inside
a Teflon jacket and was used as before as the RDE. These specimens
were given surface treatment as per procedures described else-
where [3,4]. NaCI solution was prepared in triply distilled water
using A.R. NaCl.
2.2. Open circuit potential (O.C.P.) and potentiodynamic polari-
sation .
The disc electrode was immersed in a solution of 3% NaCI taken
in a 125 ml spherical cell and was made the working electrode along
with a saturated calomel electrode (SCE) as the reference electrode.
The working electrode was made to rotate at different speeds as
mentioned above by connecting the rotating disc set up to a speed
controller (MSRX Speed Controller, Mis. Pine Instruments, U.S.A)
and corresponding steady state values of open circuit potentials
were measured at the end of 30 minutes in each case. The R.D.E.
set up was that of Mis. pine Instruments, U.S.A. The experiments
were repeated to get reproducible values of O.C.P. The temperature
was maintained constant at 321C.
After measuring the steady state OCP the anodic and cathodic
polarisation curves werf recorded with good reproducibility at a
sweep rate of 10 mV.sec-
2.3. Measurement of current delivered at different anodic potentials
at various rotating speeds
Measurement of current delivered at different potentials posi-
tive to O.C.P. at various rpm values were made using the above
polarisation curves at different hydrodynamic regions and all the
results were tabulated.

3. EXPERIMENTAL RESULTS
Table-l gives the details regarding the actual values of
Reynold I s numbers in different hydrodynamic regions including the
transition regions and the respective rpm values for the Teflon
embedded AI-Zn-In anode and steel cathode.

962
 Table-2 gives the values of O.C.P. and various corrosion kine-
tic parameters such as corrosion potential (Ecorr)'corrosion current
(i ), the anodic and cathodic exchange current density values
corr
(i and i ) for the anode at different rpm values in 3% NaCl
so~d~ion. o,c
Table-3 gives values of current output values at different
rpms indicating the current giving capacities of anode under the
tested experimental conditions.
Table-4 gives different kinetic parameters and also the pro-
tective currents of the steel cathode at dif ferent rpm values in
3% NaCl solution.

4. DISCUSSION
4.1. Justification for the choice of RDE technique in this study
It is well established that the kinetics of corrosion, anodic
dissolution and CP of immersed structures in sea water of both acti-
vation and in the RDE, the rate of mass transfer is uniform, inspite
of the fact that the linear velocity of points on the .surface in-
creases with their distance from the centre of rotation. The other
important property is that the rate of rotation around RDE is lami-
nar upto a rather high rotation rate. Further in hydrodynamics the
transition from laminar to turbulent flow is characterised by NRf
(Renold's number) which is a dimensionless number and is eqtlaElto

Where, V = Characteristic Velocity; 1 = Length; v = Kinematic Vis-

cosity (viscosity/density).
4.2. Potentiodynamic polarisation of Al-alloy in 3% NaCl solution
From the table-2 it is seen that as the rpm increases icorr also
increases. Since the corrosion of Al is under cathodic control and
more precisely under the control of diffusion of oxygen and since
oxygen diffusion is dependent on rpm, the above statement is, true.
The reason for the shift of Ecorr towards more positive values is
due to cathodic depolarisation reaction on the alloy with the rate
of supply of oxygen increasing with rpm increase.
4.3. Current delivery capacity of aluminium alloy at different
impressed potentials at different rpms in 3% NaCl
As rpm increases the current output values also increase at
all impressed potentials positive to OCP. At any such fixed poten-
tials positive to OCP the current output of the anode increases
with increasing rpm. But at any fixed rpm as the potential becomes

963
more and more negative, the increase in output current values were
found to increase due to the increase in driving potentials [poten-
tial of anode vs SCE - 0.77 V vs SCE the protective potential of
steel cathode]. At any potential the higher output of the anode
can also be explained as follows. As the current density for re-
quired for the CP increases with the rpm the anode also starts deli-
vering higher output of current without any prejudice to the anode
efficiency. This is called self healing property of anode. Thus
changes in hydrodynamics have a beneficial effect on the performance
of the anode.

4.4. Electrochemical parameters of steel cathode in 3% NaCl solution

From Table-4 it is clear that as rpm increases i increases

corr
and so also i pro t ec t"10n current (i.e. the current required to pola-
rise the cathode to -0.77 V vs SCE). The corrosion of steel is under
cathodic control (Le) 0 + 2 H0 + 4 e } 4 OH- is the rds. But
incidentally the reactiJhs rate is dependent on the rate of supply
of oxygen which is directly dependent on rpm. Hence more and more
current is required for the CP of steel that is rotating at higher
speeds due to the systematic increase of supply of oxygen. So to
say the same cathode (steel) requires the higher amount of CPo
Current in the turbulent region is more than in the viscous region
and the least in the laminar region.

But it is quite interesting to note that the Al-Zn-In anode

exhibits a characteristic self healing property by virtue of which
it is capable of giving more or less current required by the cathode
for complete protection depending on the increase or decrease of
i corr based on the hydrodynamic region in which CP is required.
Thus the increasing rpm value has opposite effects on the anode
and the cathode. The effect on cathode is the increase in current
required for CP and the effect on Al is better anode capacity.

5. CONCLUSIONS

1) This study establishes beyond doubt that RDE study of the Al-
Zn-In anode and the steel cathode in 3% NaCl is a useful tech-
nique to understand the role of hydrodynamics on the behaviour
of the anode and the cathode in saline media especially. during CPo

2) The RDE technique is a very compact technique capable of being

used under very well defined hydrodynamic conditions by fixing
the rpm values accurately and we can switch over from laminar
through viscous to turbulent regions smoothly and in a repro-
ducible manner.

3) Using the RDE, various corrosion kinetic parameters have been

calculated with appreciable reproducibility for the aluminium
alloy anode and the current required for the CP of the steel

964
 cathode in 3% NaCl solution at different rpms. The extra para-
meter namely current output values at fixed potentials for unit
area of the anode have also been calculated.
4) It is quite interesting to note that the total effect of changing
hydrodynamics on the anode and the cathode characteristics are
mutually opposing but they can be expected to tell upon the
design aspects of cathodic protection of steel structures in
seawater in a positive way.
5) The testing procedures for aluminium based sacrificial anodes
(under stationary and flow condition) that are being used at
present need to be critically analysed based on the above data
got from RDE studies.

ACKNOWLEDGEMENTS
Authors thank Director, CECRI for kind permission to present
this paper. One of the authors (S.M) thank CSIR, New Delhi for the
award of Research Associateship.

6. REFERENCES
1. Vijay Anand, R., Vidyasankar, K., Arun Kumar, S.N.S., B.Tech.
Dissertation, Madurai Kamaraj University, India, April 1995.
2. Kapali, V., Srinivasan, K.N., Venkatraman, B., Balakrishnan, K.,
Vasu, K.I., Indian Patent No. 370/DEL/88 dt. 28-04-1988.
3. Kapali, V., Venkatakrishna Iyer, S., Balaramachandran, V., Saran-
gapani, K.B., Ganesan, M., Anbukulanthainathan, M., Sheik Mideen,A
Studies on the best alkaline electrolyte for aluminium air batte-
ries, J. Power Sources, Vol. 39, 1992, pp.263-269.
4. Patnaik, R.S.M., Ganesh, S., Ashok, G., Ganesan, M., Kapali,V.,
Heat management in Aluminium Air batteries: Sources of Heat,
J. Power Sources, Vol. 50, 1994, pp.331-342.

965
966
966
967
Proc. Int. Conl'. on Corrosion CONCORN '97
December 3-6, Mum~ai, India

Gasometric Studies of Mg-2Zn-lMn Alloy in

Aqueous Media
A. Antonyraj and C.O. Augustin
Central Electrochemical Research Institute,
Karaikudi-630 006, India

ABSTRACT

Magnesiwn one of the lightest non-ferrous metals has gained great importance
bec&useof its passive potential and ability to form nwnerous alloys with Zn, MIl. Li and
rare earth metals. These alloys have excellent mechanical properties, corrosion resistance
and casting capabilities which make them.. suitable for applications in transportation,
battery, corrosion and metallurgy areas. The Mg-Zn-Mn ternary alloy is in demand where
improved mechanical characteristics and resistance to dissolution are required. TIle
addition of manganese to Mg-Zn alloy eliminate the detrimental effect of nobler impurities.
However in certain aggressive environment they are susceptible to corrosive attack
re$Ultinga premature f8ilure.

Electrocherr.ica! investigation of the alloy has not been carried out elaborately.
Hence an understanding of the corrosion characteristics of the alloy will help in designing
suitable schemes to enhance its applicatIon. A combined study of gasometry and
galvanostatic polarisation of the alloy in magnesiwn bromide, magnesiwn chloride, sodiwn
bromide and sodiwn chloride solutions at concentrations ranging from 0.1 M to 2.0 M is
undertaken and the hydrogen evolution rate, dissolution rate, difference effect, etc. are
calculated. These parameters are found to be dependent upon current density, nature and
concentration of the solutions. In magnesiwn salt solutions negative difference effect only
is observed whereas in sodiwn salt solutions both positive and negative difference effects
are observed. The reasons for the different behaviours and the higher hydrogen evolution
rate than predicted by Faraday are discussed in this presentation.

968
Iatroduetion :

Magnesium and its alloys posses many advantageous properties such as high
strength to weight ratio combined with low density, high dimensional accuracy, castability
and formability. Besides these beneficial behaviours other fi1ctorsalso mvour the use of
the Mg alloys especially ZM alloy in service areas[I,2]. Various investigations have been
carried out to understand the corrosion behaviour of Mg and its alloys in different aqueous
environment[3-5]. But the ZM21 alloy has not been subjected to serious electrochemical
study. Hence this work has been undertaken and this paper presents the outcome of a
novel study carried out by a combined set up consisting of gasometric measurement and
galvanostatic polarisation of Mg-2Zn-IMn (ZM) in aqueous solutions of NaCI, NaBr,
MgCh and MgBr2 at different concentrations upto 2.0 M. The dependency of hydrogen
evolution rate on the nature and concentration of the solution has been established. The
difference effect (A) which.is defined as the difference in hydrogen evolution rate from an
anode with and without polarisation under steady conditions, calculated from the
hydrogen evolution rate was also found to be related to the solution characteristics. A
negative difference effect (NDE) in magnesium media, both positive (PDE) and negative
difference effect in sodium media have been observed. Another worthwhile observation
made in this study is the transition current density denoted by the symbol 'i1" in sodium
solutions. The reasons for such unusual phenomena are also discusSed in this
communication.

Experimental Procedure :

The set up used for the measurement of hydrogen gas evolved from the anode
during self corrosion and from both electrodes during anodic polarisation is shown in
Fig.I. It consists of tiny buttons of the allQYwith an active area lcm2 as working electrode
and a higher size platinum sheet as the auxilIary electrode along with eudiometer
arrangement to collect the hydrogen gas. 2.0 M solutions were prepared by dissolving
G.R.grade NaCI, NaBr, MgCh and MgBr2 salts in triple distilled water and 0.1,0.25,0.5,
1.0 and 1.5 M solutions were obtained by further dilution.
150 Ill! or'the solution was taken into the cell, was magnetically stirred and the
temperature was kept at 29 1 C. The working electrode was connected to the positive
terminal and platinum to the negative terminal of the constant current generator. The
hydrogen liberated for 5 minutes was measured (V0). A 5 mA cm'2 current was passed and
at the end of 5 minutes the hydrogen was measured (VI). The VI measurements wete
repeated with higher currents upto 100 mA cm'2 in all other solutions and the difference
effect was calculated by the relationship,

Where 6.97 converts mA into mm3 of the hydrogen, I is the current density corresponding
to VI. The A values were plotted against current density values (Figs 2 & 3) from which
the Transition current density was evaluated (FiR;.4).

969
 Fig.l Gasometric set up.
1.Platinium electrode, 2. Working electrode, 3. Graduated burette, 4. Coloured
liquid, 5.Resevoir bulb, 6. Water from bath, 7. Water to bath, 8.Water jacket and
9. Reaction vessel.
Results and discussion :

The hydrogen evolution rate obtained during the self dissolution of the anode,
changes irregularly which is found to be higher in 0.1 M solution in a particular medium
and decreases to reach a minimum in 1.0 M concentration, then starts increasing again.
Thus the highest value 110 mm3 cm,2 min,l is obtained in 0.1 M NaCI solution and lowest
value 10 mm3 cm,2 min,l in 1.0 M MgBr2 solution. Similarly the hydrogen evolution rate
with passing fixed current (V I) is also found to be dependent upon medium which is
noticed to be higher in 0.1 M concentration for particular medium and decreases to a
minimum in 0.5 M and thereafter increases to a highest value in 2.0 M solution.
Accordingly the highest VI 1500 mm3 cm,2 min,l observed in 2.0 M NaCI as against a
lowest value of 20 recorded in 0.5 M NaBr, all other VI values fall in-between the two
extremes. The V I is observed to increase linearly with poIarisation and highest value is
noticed for 100 mA cm,2 current in all the solutions. At this current the V I is found to be
independent of concentration as all the VI are almost equal irrespective of concentration
but dependent only on current density and nature of solution. From. the values the
corrosiveness of the medium can be graded as NaCI > NaBr ~ MgBr2 > MgCh. Generally
the hydrogen evolution rate is found to be 2-3 times higher than predicted by Faraday's
law for divalent ion formation during magnesium dissolution. The excess hydrogen
formation may be due to subvalent ion generation and disintegration of tiny particles from
the anode particularly at high current density values. Both these causes and effects may

970
971
Conclusions:

1. The self corrosion of the alloy is observed to be high in.dilute solutions.

2. The hydrogen evolution rate is found to be dependent on medium and current density,
but independent of concentration at high current density.
3. Negative.difference effect only is shown by ZM alloy in magnesium salt solutions,
whereas positive and negative with a transition are exhtbited in sodium salt solutions.
4. This study has enabled the postulation of a new parameter Transition current density 'i

Acknowledgements:

The authors express their gratitude to Dr.Utpal Sen for his constant
encouragement. One of the author (A.A.) thanks the CoWlCilof Scientific and Industrial
Research, New Delhi for the award of Senior Research Fellowship.

References. :

1. PoJmear, I.J; Materials Sei. and Tech. VoLlO, No.1, 1994, pp 1-15..
2. Soba, G.O; Sivakesavam. 0 and Murty, K.L; Trans. Indian Inst. Met. VoL 41, No.4,
1994, pp 251-261.
3. Makar,G.L and Kruger, J; J.E1ectrochem.Soc., VoLl31, No.2, 1990,414-421.
4. Tunold, E; Holtan, H; Berg,M; Lasson, A and Rolf: Corros .Sci, VoL34, No.9~ 1993,
pp 1423-1440.
5. Nordlien, J.H; 000, S; Masuko, N and Nisaucioglu,K; J.Electrochem. Soc., VoL142,
No.10, 1995, pp 3320-3322.

973
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Studies on Aluminium and its Alloy as Galvanic

Anodes in Alkaline Zincate Solution
M. Paramasivam and S. Venkatakrishna Iyer
Central Electrochemical Research Institute,
Karaikudi-630 006, Tamil Nadu, India

ABSTRACT
Aluminium has received much attention as a possible galvanic
anode in primary alkaline batteries, since' if has attractive proper-
ties such as high energy density (2500 Ah Kg- ), high negative poten-
tial in alkaline media and abundance. But it has drawbacks like high
rate of self corrosion, and gassing. Self corrosion of aluminium
can be reduced by incorporating inhibitors, complexing agents and
addition agents in the electrolyte. Another method is to alloy alu-
minium with elements such as zinc, indium, gallium, thallium and
lead which has yielded a number of successful alloy compositions
in alkaline media. Since the corrosion rate of zinc is very low in
a highly alkaline solution, the corrosion of aluminium can be reduced
by modifying its surface with zinc, by forming a suitable conversion
coating over its surface. A suitable zincate coating has been found
to be very useful in reducing the self c.orrosionof dfffefent grades
of aluminium to a negli~ible level of 0.04-0.08 mg.cm- mm-; while
yielding high anode efflciency in alkaline media.
In the present study an alkaline zincate coating has been
formed on the binary and ternary alloys of 26S and 57S aluminium
and the electrochemical behaviour of these alloys in alkaline zincate
solution has been studied using different techniques such as weight
loss measurements, galvanostatic polarisation studies, anoqe effici-
ency measurement, impedance measurements and hydrogen permeation
studies. It is found that ternary alloys of both 26S and 57S alumi-
nium containing zinc and indium can serve as good galvanic anodes
in alkaline media.

INTRODUCTION
Eventhough aluminium possesses some advantages such as high
negative potential and high energy density in alkaline media, it

974
975
976
977
978
979
980
981
Permeation Current Measurement:
Values of permeation current for 26S and 57S aluminium and
their binary and ternary alloys in O.OlM NaOHclearly shows the fact
that the incorporation of zinc and indium in 26S and 57S leads to
a decrease in the permeation of hydrogen through aluminium. A com-
bined incorporation of both zinc and indium has more influence on
the. extent of hydrogen oermeated. So the initial corrosion of alu-
minium in alkali, before the formation of a zincate coating can be
controlled by the formation of an alloy, thereby improving its per-
formance as a galvanic anode. [Table-6).

A good galvanic anode should possess (1) minimum self corrosion

(2) less anodic polarization and (3) high anode efficiency. Based
on these requirements, both the ternary alloys of 26S and 57S alu-
minium can serve as good galvanic anodes in 4M NaOHcontaining 0.6M
ZnO.

CONCLUSION

It can be concluded that ternary alloys of 26S and 57S alu-

minium containin~ zinc and indium can perform as good galvanic anodes
in 4M NaOHcontaIning 0.6M ZnO.

REFERENCES

1. Saran~apani, K.B., Balaramachandran, V, Kapali, V, Venkata-

krishna Iyer, S., Studies on the utility of electrolytic grade
aluminium as galvanic anode in orimary alkaline batteries, Tran-
sanctions of SAEST, Vol. 22, No.6, June 1987, pp.1-4.

2. Bharathi, S., Ganesan, M., Sarangapani, K.B.,- Kapali, V., Ven-

katakrishna Iyer, S., Alloys of commercial aluminium as galvanic
anode in primary alkaline batteries, Bulletin of Electro-
chemistry, Vol. 5, No.1, Jan. 1989, pp.33-36.

3. Sheik Mideen, A., Ganesan, M., Anbukulandainathan, M., Saranga-

pani, K.B., Balaramachandran, V., Kapali, V., Venkatakrishna
Iyer, S., Development of new alloys of commercial aluminium
with zinc, indium, tin and bismuth as anodes for alkaline batte-
ries, Journal of Power Sources, Volo27, No.6, June 1989, pp.
235-240.

4. Sheik Mideen, A., Gartesan, M., Suresh, G., Anbukulandainathan~M.

Sarangapani, K.B., Balaramachandran, V., Kapali, V., Venkata-
krishna Iyer, S., Aluminium and its alloys as noade materials
in alkaline aluminium/air batteries, Indian Journal of Tech-
nology, Vol~ 31, No.1, Jan. 1993, pp.47-50.

5. 'Subramanyan, N., Yamuna, A.R., British Corrosion Journal, Vol.4,

No.1, Jan. 1969, pp.32-34.

982
 6. Kapali, V., Venkatakrishna Iyer, S., Subramanyan, N., Anodic
behaviour of aluminium and its alloys in the presence of inhi-
biting and complexing substances, British Corrosion Journal,
Vol. 14, No.2, Feb. 1969, pp.303-306.

7. Sarangapani, K.B., Balaramachandran, V., Kapali, V., Arghode,R.,

Venkatakrishna Iyer, S., Potdar, M.G., Aluminium as anode in
primary alkaline batteries - behaviour of 2S al~inium in alka-
line solution containing sodium citrate, potassium citrate and
calcium hydroxide, Surface Technology, Vol. 26, No.1, Jan. 1985,
pp.67-76.

8. Sarangapani, K.B., Balaramachandran, V., Ka1?ali, V., Venkata-

krishna Iyer, S., PO,tdar, M.G., Rajagopalan, K.S., Aluminium
as anodes in primary alkaline batteries - Influence of additives
on the corrosion and anodic behaviour of 2S aluminium in alka-
line citrate, Journal of Ap1?lied Electrochemistry, Vol.14, No.4,
July 1984, pp.475-480.

9. Zaromb, S., Investigations on the development of aluminium as

a galvanic anode in alkaline media, Proc. Symposium on "Power
Systems for Electric Vehicles", organised by U.S. Department
of Highways, Energy and Water, April 1967.

10. Paramasivam, M., Suresh, G., Muthuramalingam, B., Venkatakrishna

Iyer, S., kapali, V., Different commercial grades of aluminium
as galvanic anode in alkaline zincatesolution, Journal of
Applied Electrochemistry, Vol. 21, No.5, May 1991, pp.452-56.

11. Paramasivam, M., Venkatakrishna Iyer, S., Kapali, V., Effect

of zincate conversion coating as corrosion and anodic behaviour
of commercial aluminium in alkaline media, British Corrosion
Journal, Vol. 29, No.3, March 1994, pp.207-209.

12. Muralidharan, S., Phani, K.L.N., Pitchumani, S., Ravichandran,S.

Venkatakrishna Iyer, S., Journal of Electrochemical Society,
Vol. 142, No.5, May' 1995, p1?1478-83.

983
 Pro<:. In!. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Corrosion Problems in Petroleum Production Using

Enhanced Oil Recovery Techniques
P.K. Sagar, P.V.S. Bhanu Murty and Amit Khanra
Institute of Oil & Gas Production Technology,
ONGC, Panvel-41O 221, India

1.0 INTRODUCTION:
Primary petroleum recovery followed by pressure maintenance by water flooding still leaves
about fifty percent of the original oil in place. This remaining un,recovered oil represents potentially a
huge reservoir. Combination of many factors viz.: increased oil prices, increased oil consumption,
depletion of many big fields etc. have focussed oil industry's attention towards this residual heavy oil.
Enhanced oil recovery techniques are aimed at recovering this balance oil.
EOR methods involve production of crude oil from reservoirs through action taken to
increase primary reservoir drive via thermal method, chemical method & gas method. Steam injection
and Insitu combustion are the most popular thermal methods providing the greatest increment in oil
recovery. The most popular chemical method are micellar polymer injection & polymer injection
pushed by polymer and polymer augmented water flooding. Hydrocarbon gas and carbon dioxide
injection are the two most common gas methods.
EOR techniques like C02 Injection & In-Situ combustion produce one of the most corrosive
environment encountered by oil industry downhole equipment (most commonly made of carbon steels)
because of presence of corrodents like C02, H2S, Chlorides, Oxygen coupled with high temperatures
and high pressures.

2.0 FACTORS INFI.UENCING CORROSION:

2.1 Presence of Carbon dioxide:

As the major corrodent in Carbon dioxide Injection & In-situ combustion is C02, it would be
worthwhile to discuss factors influencing the C02 corrosion.

2.2 Partial pressure of Carbon dioxide:

The general rule of the thumb in sweet systems is:
PC02 < 7 psia: Less corrosive
PC02 >7 psia < 30 psia: Moderately corrosive
PC02 >30 psia: severely corrosive

984
 Whether or not corrosion in a C02 system is inherently controlled or uncontrolled depends
critically on factors governing the deposition & retention of protective iron carbonate (siderite) scales.
Conditions favoring the formation of protective iron carbonate scale are elevated temperature;
Increased pH & Lack ofturbulence.
2.3 Temperature:
Around 60 C, the corrosion product films change into more prot~ctive layers. The
protectiveness generally increases with increasing temperature. Within the temperature range of 60 to
130 C, the highest susceptibility for localized corrosion (pitting, Erosion-corrosion, Stress corrosion
cracking) is observed. On low alloy steels, the corrosion product layers are again composed of iron
carbonate incorporating Ca and Mg' carbonate if Ca and Mg ions are present in the medium. But in
contrast to scales formed below 60 C, they exhibit a higher crystallinity. Corrosion at temperatures
above 100 c also produces iron oxide. Chromium oxides are present in the scales of Cr. containing
steels.
The solubility and/or the permeability of the scales becomes rate determining due to their
increasing protectiveness. The solubility increases with increasing C02 Partial pressure and the
concentration of Ca and Mg ions in the solutions, but decreases with increasing temperature, pH, and
HC03- concentration. The temperature, the alkalinity, and the composition of the medium influence the
permeability of the corrosion product layers.

2.4 Velocity:
Increase in corrosion rate of carbon steel is observed as the fluid velocity increases from 0.4
mls to 4.2 mls. The fluid velocity has very little effect on corrosion rate of 13 % Cr. steel may be due
to the presence of corrosion layer having a greater resistance to erosion damage.

2.5 Chlorides:
Carbon steel C02 Corrosion is not directly affected by the chloride content of the brine, but
rather by its specific composition. No general conclusion can be drawn regarding this particular affect
with respect to carbon steels. While highly alloyed carbon steels are subject to higher corrosion rates at
increasing sodium chloride concentrations.

2.6 Hydrogen Sulfide:

At the vicinity of ambient temperature, H2S could accelerate corrosion reaction of C02
Corrosion. At the temperature between 60C and 100C this tendency seems to diminish. At 100C,
&hecorrosion rate in pure C02 Comes to be higher than that in the conditions with H2S.
Hydrogen sulfide in oil and gas production can be detrimental in two ways: it is an aggressive
piUing agent and it introduces cracking in many ways. It acts as a catalyst to promote adsorption by
steel of atomic hydrogen formed by the cathodic reduction of hydrogen ion. This accoUnts for its rol8
in promoting sulfide stress cracking of high strength steels. Temperatures above and below about 80
F tend to decrease hydrogen entry and retard embrittlement.
Martensitic alloys like 410 are more susceptible'to sulfide stress cracking than low grade alloys
lite 4130 through 4140 types used in steel API tubulars. SSC susceptibility is a strong function of yield
and tensile strength. In general steels below 80,000 to 90,000 psi tensile strength are relatively resistant
to cracking.

985
A Generally accepted rule for resistance of carbon and low alloy steels to SSC is to maintain hardness
below HRC 22. The acceptable hardness limits for many alloys to reduce the risk of SSC are described
in NACE specification MR-01-75.
The environment becomes still more complex when some of the above mentioned corrodents &
factors are present in various combinations in an EOR system.

3.0 METALLURGY OPTIONS:

3.1 9 Cr-l MO steel:

Corrosion of steel in presence of carbon dioxide is a function of both chromium and nickel content
& atleast 9% Cr. is necessary to gain good corrosion resistance. This steel is normally immune to
stress corrosion cracking in presence of chlorides like other nickel free low alloy steels (4130 and
4140). Tests conducted in autoclaves suggest that it can be 8sed in environments containing upto 100
atm partial pressure of C02 and at temperature upto 100 C. Corrosion resistance of this steel in
presence ofH2S is poor.

3.2 13-Cr Stainless Steel:

These steels can be used upto 100 atms C02 partial pressure and upto 150 C, with increasing
chlorides and temperature the corrosion rate increases. This martensitic grade is known to be
susceptible to cracking in sour water containing low partial pressures of H2S and generally are
specified for sweet wells or where minimum souring is expected. This steel is also generally immune
to chloride stress corrosion cracking.

3.3 Duplex Stainless steel:

These alloys have a two-phase structure approximately balanced with 50 % ferrite and 50 %
austenite. The duplex stainless steels generally have a composition of 22-25 % Cr., 5 % Ni, and 3 %
Mo. Sometimes nitrogen is added for enhanced pitting resistance. Generally with increasing chlorides
and temperature the corrosion rate increases for 13 Cr. but 22 Cr. (duplex) shows much better
resistance to corrosion. The increased alloy content of the duplex stainless steels improves weight loss
corrosion and pitting resistance for many down hole environments. The limitation of their usage is their
susceptibility to stress corrosion cracking at high temperature and their limited resistance to sulfide
stress cracking, when H2S is present in the produced fluid,
Experiments conducted in autoclaves have shown that 22Cr- duplex stainless steels can be used
in extremely corrosive downhole environments containing very high chlorid1f and very high partial
pressure of carbon dioxide (upto 1000 atms) and at t8mperatures upto 200 C while the 25 Cr. -
duplex can be used in similar environments upto 250 C .The limitation in usipg these steels is that
they can be used only upto 0.1 atmsofpartial pressures of hydrogen sulfide.

4.0 EOR TECNIQUES:

Methods like polymer flooding, hydrocarbon gas injection etc. do not pose much challenge to
present oilfield metallurgy and are not very corrosive. In-situ combustion and C02 injection present
one of the most corrosive environment encountered under downhole conditions posing unique
challenge to existing metallurgy for tubulars & other downhole equipment, therefore special emphasis
has been paid to the above two EOR methods.

986
987
4.2 In-situ combustion:
Also called fireflooding involves the introduction of heat in the reservoir through the injection
of air to, burn some of the oil in the place. Air is introduced through injection wells and burning may
take place spontaneously or heat source may be employed to start combustion. The flame front moves
through the reservoir and oil production takes place through production wells. Water may also be
alternated with air injection in wet insitu-combustion to transfer excess heat from the burned region.
During the burn, steam and other gases from combustion displace oil and connate water ahead of the
combustion front. 0
In the combustion zone, temperatures in the range of 600-1200 F can occur. The combination
of combustion gases; steam and temperature produce a severely corrosive environment composed of
oxygen, organic acids, carbon dioxide, sulfides and chlorides. This aggregate of corrodents can cause a
serious materials problem in the producing wells throughout the fireflood.
Some reservoirs are susceptible to spontaneous combustion when contacted with sufficient air.
In these wells, combustion occurs a short distance from the wellbore and then burns back into the
borehole. This can result in temperatures up to 1700 0 F and has resulted in failure of pipe in the hole
by creep or melting. Even stainless-steel liners have been reported to have melted following ignition .
. A Table reorganized from Table 7 & 8 of "State of the art review of fireflood Field projects"
by Chu is presented below:

Field experience has indicated that corrosion and erosion are the two most serious materials
problems. Mild steel has been reported to have weight losses of 73% in two months. Stainless steel is
also susceptible to rapid failure by chloride cracking, intergranular corrosion, and pitting attack. In
some fields, 316 SS and titanium have performed satisfactorily and are used for tubing and liners
opposite the production interval. Corrosion and erosion failures of casing, tubing chokes, valves, and
fittings have been reported at producing wells.
Care must be taken in selecting oxygen injection equipment since each alloy has an oxygen
threshold above which once ignited, combustion is sustained. Moreover, oxygen compatible pipe dope
and elastomeric seals must be selected. An aid to selecting materials for oxygen service has been
published by ASTM as standard G63.

988
5.0 CONCLUSION:
Steamflooding, Polymer flooding, C02 flooding, Fireflooding hydrocarbon gas injection etc.
are the most popular methods of enhanced oil recovery. Of these, fireflooding & C02 flooding present
one of the most corrosive environments encountered under downhole conditions. Selection of
appropriate material becomes very critical in these EOR techniques depending on the service life of the
plant and economics involved Literature survey confirms that conservative metallurgy like plastic
coated J-55 tubings etc are still being used inspite of recent advances in tubing metallurgy and easy
availability of highly corrosion tubings like 13 Cr, 22-25 Cr DSS & CRA's. Before selecting material
for downhole equipment it is very important to study the various factors influencing corrosion in the
down hole conditions and assess the corrosivity of the system. Obviously, choice of metallurgy is a
functional oftechno-economics in EOR Systems too.

6.0 REFERENCES:

1. Craig, Bruce. D." Practical oilfield metallurgy and corrosion, Second edition.", 1993.
2. Metals handbook, Ninth edition, "Volume-13, Corrosion", ASM International 1989.
3. Rice, P. W "Selecting metallic materials for downhole service ." World oil, Nov- 1989.
4. Schillmoller, C. M.; "Selection of corrosion resistant alloy tubulars for offshore applications";
OTC-6069, 1989.
5. Ikeda. A, Mukai. S, Ueda. M, "Corrosion behavior of9 to 25 % Cr. steel in wet 002 environment
."Corrosion/84 (Paper number-289).
6. Ikeda. A, Mukai. S, Ueda. M, C02 Behavior of Carbon & Cr steels ,Advances in C02 corrosion,
Vol. -1,NACE 1984.
7. Enhanced recovery of residual and heavy oils,second edition ,Noyes Data Corporation.
8. Martin R.L, Braga T.G, Corrosion control in enhanced oil recovery wells. SPE -15024.
9. Zawierucha. R, Henningson. C. J, Material performance in thermal enhanced oil recovery
environment Jcpt May-June 1965.
10. Chu Chieh, State of the art review offireflood field projects. SPEIDOE 9772.
11. Newton L.E.,McClay,R.A. Corrosion And operational problems,C02 Project, SACROC Unit SPE
6391.
12. Patterson, K.W. Downhole corrosion encountered in the C02 flood at SACROC unit, C02
corrosion in oil and gas production,selected papers,abstracts,and references NAGE 1984.
13. Collier, T.S. State of the art installation of C02 injection equipment: A case study, SPE 17294.
14. Chitwood,G.B,Coyle,W.R. Case history analysis: Material for completion equipment in C02
service SPE 27719.

989
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Development and Characterization of Coatings on

Interconnector (Cr-ODS) used in SOFCs
K.M.N. PrasannaI, A.S. Khannal and W.J. Quadakkers2
'Indian Institute of Technology, Bombay-400 076, India
2Forshungscentrum Juelich GmbH, D-52425, Juelich, Germany

Abstract

Oxidation behavior of aluminide coated Cr-ODS alloy having different coating

thicknesses was investigated at temperatures ranging from 800-950C in air. Coating
degradation due to rapid AI diffusion into the matrix resulting in Kirkendall porosity
was characteristic of all coated alloys. The microhardness of the alloy was
substantially increased due to AI diffusion. Pre-oxidation was found to be an
effective means of reducing rapid growth of AI coating into the substrate. The
aluminide coating modified with Co+Ni showed less tendency towards void
formation at the sites where the coating was adhered. Silicide coating did not show
any enhancement in the microhardness of the alloy or Kirkendall porosity as a result
of Si diffusion. From this study, it has been found that an effective silicide coating
for Cr-ODS alloy can be produced by selecting suitable coating parameters.

Introduction

Chromium based oxide dispersion strengthened alloy, protected by chromia and

having matching thermal expansion coefficient with other cell components, is
considered as the potential material for interconnectors [1] in SOFC. However, the
evaporation of chromia poses a serious problem in reducing the. cell efficiency. A
selective coating which forms stable oxide would reduce 70-800/0of the evaporation
and hence increases the cell performance. Therefore, various coatings based on
aluminide, modified aluminide and silicide coatings on Cr-ODS alloy were developed
by pack cementation. Their high temperature characteristics were also determined.

990
Experimental Details

The aluminide coated Cr-ODS alloy used in the present study were procured from
Plansee Metall, Austria and Diffusion Alloy Ltd, UK The aluminium rich CrsAls
intermetallic phase, based on Cr-Al phase diagram [2], was formed on Cr-ODS alloys
by pack cementation. The second part of the investigation was devoted to develop a
silicide coating and modified aluminide coating on Cr-ODS alloys. The 1000 grit
polished and ultrasonically cleaned specimens were silconized at 1050C for 15 h in
flowing argon with the objectofforming a surface coating ofCrSh phase on the basis
of Cr-Si phase diagram [3]. The Co- and Co+Ni -modified aluminide coatings were
produced after electroplating Co or Co+Ni on the alloy which were then aluminised by
pack cementation. About 10 l1mthickness of cobalt was applied on we specimen. The
same procedure was used for coating Co and Ni subsequently on the alloy for
producing Co+Ni-modified aluminide coating. Aluminization was carried out at
1000C for 5 h in flowing argon.

Results and Discussion

The Al-coated Cr-ODS alloys, received from Diffusion Alloys Ltd. and Plansee Metall,
showed a two phase coating, CrsAls in the outer zone with a granular morphology and
Cr-Al solid solution in the inner zone (Fig la and b). The yttria association in the outer
zone suggested that the coating was grown by inward diffusion of Al Microhardness
of the coating confirmed the above findings of coating composition as reported in the
case ofCr5WO.IY [4].

Fig 1 (a) Morphology (b) Cross section of aluminized Cr-ODS alloy after etching in
80ml ethanol + 15ml HcI + 5ml HN<n.

991
Morphological examination of scale formed at 950C by SEM/EDAX indicated an
exclusive alumina formation on specimen with maximum coating thickness whereas
other specimens with less thicknesses showed formation of Cr203 along with Ah03
(Fig 2 a and b).

Fig 2. Morphology of oxide formed after exposure at 950C (a) Coating with
. maximum thickness of 40Jllll (b) Coating with 15llm.

The Kirkendall porosity and cracks due to embrittlement of aluminide coated Cr-ODS
alloy exposed at 950C for 300 h (Fig 3a and b) could be attributed to the inward
diffusion of aluminium in the coating which is considered to be one of the degradation
modes of the coating [5l

Fig 3. Optical micrograph showing (a) Typical cracking (b) Void formation of
aluminized Cr-ODS alloy at 950C in air for 300h.

The EDAX depth profile analysis and microhardness value 0500-600 HV [4] directly

992
reflects the formation of AI-Cr solid solution deep into the matrix due to inward
diffusion of the coating.

The effect of reducing temperature on the the extensive formation of Kirkendall

porosity was studied at 875C and at 800C. The observation was similar to specimen
exposed at 950C. It Could be attributed to rapid diffusion of the surface coating into
the substrate and revealed that there is no beneficial effect produced by reducing the
temperature.

The aluminide coated substrates pre-oxidised in at 950C for 50 h and

subsequently subjected to oxidation at 950C in air for 1000 h (Fig 4a) showed a
reduced interdiffusion zone and void formation . It can be assumed that the major
portion of the AI was consumed in forming initial alumina layer by inward diffusion of
oxygen in the reduced atmosphere, thereby, the availability of AI in the surface coating
for inward diffusion in the later part of exposure was decreased. The substrates with
less thicknesses were totally free of voids but were undergone spallation and internal
oxidation after 1000 h of exposure (Fig 4b) which is indicative of insufficient AI in the
coating.

The internal oxides were found in the AI depleted zone. This suggests that the inward
diffusion of AI and hence the void formation- could be combated considerably by the
pre-oxidation treatment if the coating thickness was within a certain limit of 30 ~m to
35 ~m.

The aluminide coating developed on electroplated Co (Fig 5a) and Co+Ni (Fig 5b)
showed a very narrow interdiffusion zone on Co+Ni-modified aluminde coating. It
could be due to the effect of Ni on the surface which might form intermediate
intermetallic phases with AI in the initial stage. This would develop an AI gradient and

993
bring about the coating to grow by inward diffusion of AI.

The higher hardness in the inner zone of Co-modified coating than Cr-AI solid solution
could be attributed to the Co-association in the interdiffusion zone. However, Co or Ni
association was not observed in the interdiffusion zone of Co+Ni-modified aluminide
coating. The outer coating was determined to be CrsA4 along with slight amounts of
Co and Ni. This was supported by EDAX analysis and confirmed that Co-modified
coating grown by outward diffusion of Cr; while Co+Ni-modified coating grown by
inward diffusion of AI.

The void formation (Fig 5c) and microhardness values of Co-modified aluminide
coating after exposure suggests that the cobalt association would not have much
influence on inhibiting inward coating growth.

In the case of Co+Ni modified coating, the extent of void formation and coating
growth into the matrix was reduced considerably (Fig 5d).

Fig 5. Cross section showing modified aluminide coating on Cr-ODS alloy (a) as-
coated Co-modified coating, (b) as-coated Co+Ni-modified coating, (c) exposed
Co-modified coating at 950C in air and (d) exposed Co+Ni-modified coating at
950C in air.

994
These observations were found at the locations where the coating seemed to have
better adherence. Therefore, the association of Co and Ni together in the outer coating
of CrsM is beneficial in reducing the coating degradation.

The silicide coating developed at 1050C on Cr-ODS alloy indicated a single phase
consisting of CrSh (Fig 6a). This was confirmed by EDAX, XRD and microhardness
measurements. The hardness values did not show any embrittlement of the substrate
after exposure. The specimens were free of void formation (Fig 6b).

Fig 6. Optical micrograph showing cross section of as-coated and exposed silicide
coating at 950C in air for 300h ..

This suggests that there is no inward diffusion of Si into the matrix. These results
indicated a positive step in the direction of developing such silicide coating for Cr-
ODS alloy.

Conclusion

The pack aluminized Cr-ODS alloy revealed a characteristic observation of rapid

coating diffusion into the substrate resulting in extensive Kirkendall porosity and
embrittlement under different exposure conditions. Pre-oxidation treatment is found to
reduce extensive interdiffusion.Modified aluminide coating with Co+Ni is beneficial in
terms of reducing the diffusion of the coating into the substrate and void formation.
However, the poor adherence of electroplated Co and Ni on Cr-ODS alloy is an
inherent problem. The silicide coating offered the greatest benefit in preventing coating
diffusion into the matrix and hence embrittlement and void formation.

995
996
Proc. Int. ConI. on Corrosion CONCORN '97
December 3-6. Mumbai, India

Effect of Water Vapour on the Oxidation of

FeCrAl- and NiCrAI-Base ODS Alloys
K.M.N. Prasanna1, A.S. Khanna! and W.J. Quadakkers2
Ilndian Institute of Technology, Bombay, Bombay-76, India
2Porschungszentrum Juelich GmbH, D-52425, Juelich, Germany

997
produces outward growth of the scale [1]. However, an understanding of many of the
observed effects is still lacking. Therefore, in the present investigation, an attempt has
been made to elucidate a mechanism for the reduction in the oxidation rate in the presence
of water vapour.

Experimental Details

The alloys, MA6000 ( Ni-base ODS alloy containing Ti ), PM2000 ( Fe-base ODS alloy
containing Ti ) and PM3030 ( Ni-base alloy without Ti ) were subjected to oxidation tests
using SETARAM TG at 1000C. The tests were performed in Ar/(20%)02 and in
for SOh. The oxide scales were analyzed by XRD, optical and SEMI

Results

Oxidation kinetics

Figures 1 shows the kinetics of ODS alloys, MA6000, PM3030 and PM2000, at 1000C
in Ar/02 and in Ar/H2/H20 for 50 h.

998
A reduced oxidation rate in ArlHifhO environment was exhibited by all the alloys.
MA6000 and PM2000 did not show much difference in their oxidation rate in both the
atmospheres. However, PM3030 indicated a higher rate in Ar/02 which is three times
greater than that in ArlHiH20. It is surprising to note that the rate of oxidation of
PM3030 in ArIHiH20 was reduced to the value of PM2000, an alumina former, in
Ar/02.

Characterization of scale

The SEM analysis showed spallation and a porous oxide scale on MA6000 in Ar/02 (Fig
2a) which became slightly dense in the reduced atmosphere of ArlHiH20. There was
compositional difference between the porous outer layer, consisting of NitCr oxides and
spalled site rich in AI. The subsurface porosity was practically absent in ArIHiH20 (Fig
2b) as is evident from cross sections of the scale (Fig 2c and dt

999
The EDAX analysis showed that the scale composed mainly of Cr and Ti oxides in both
atmospheres. The only difference observed was that the specimen oxidised in reduced
atmosphere incorporated Y in the scale but not very significantly to explain the reduction
in the rate. P~OOO showed small granular oxide with needle shaped crystals in both
Ar/02 and Ar/HiH20 atmospheres (Fig 3a and b). It is ~vident from the cross sectional
analysis that a thin layer of oxide scale was formed in both the conditions (Fig 3c and d).

Fig 3. Morphology and cross section of oxide scale on PM2000at lOOOC after SOh, (a and
c) in Ar/02, (b and d) in Ar/H2/H20.

The oxide composition determined by EDAX was nearly the same under dry and moist
conditions, consisting mainly of aluminium. Needle shaped crystals, mainly composed of

1000
1001
Discussion

The observed reduction in the oxidation rate of MA6000, PM3030 and PM2000 in
ArIH~20 (Fig 1) relative to that in Ar/02 .could either be attributed to reduced partial
pressure of oxygen (_lO-lS bar) in the moist atmosphere or due to proton association in
.the oxide. The improved resistance can also be attributed to the micropegs formation in
Fe-base ODS alloy which would impart scale adherence and hence oxidation resistance.
This is in accordance with the reported results that the oxides formed in water vapour are
more adherent than those formed in air [2]. However, peg formation was not observed in
Ni-base alloys which was also showed a reduced oxidation rate in ArIH~20. The
difference in the morphology (Fig 2a) and composition between outer layer and spalled
site ofMA6000 in Ar/02 indicated that the outer layer was grown by outward diffusion of
cation. However, the difference in the rates in dry and wet conditions was significant
between the different alloys. Therefore, the observed reduction in the rate could not be
explained by the influence of reduced pOz or micropeg formation.

To explain the above mentioned anomalies, it is proposed that the oxide growth
mechanism is clmnged from predominant grain boundary diffusion to volume diffusion;
and. hence doping and further incorporation of proton in the oxide influence the growth
significantly. The equilibrium dissolution of interstitial protons in an oxide can be written
as fOllows,

It is possible that proton may, in principle, associate with interstitial oxide to form
interstitial hydroxide, OH;' [3]. The incorporation of proton helps in accelerating the
inward transport of oxygen by diffusing hydroxide ion which is faster than oxide ion . The
faster inward diffusion of oxygen thus occurred reduces the scale growth or transforms the
microstructure or even produces a change in the oxide composition [4]. It has been
reported that donor doping reduces and acceptor .doping increases proton concentration
[3]. Therefore, the insignificant reduction in: the oxidation rate of MA6000 in wet
condition, which incorporated Ti and Ni in chromia significantly, could be explained by a
resultant effect of donor doping ofTi and acceptor doping ofNi in Cr203. But in the case
of PM3030, the scaling resistance was increased significantly in ArIH2IH20 atmosphere.
There was even a compositional change of the scale from oxides ofNi and Cr in Ar/02 to
an AI enriched scale in ArIH2IH20. This could be due to the increase in the proton
concentration produced by acceptor doping of Cr203 by Ni in the 'transient stage. The
increase in hydroxide ion accelerated inward oxygen transport significantly and hence
established a protective scale composed mainly of a-alumina which is grown by inward
oxygen diffusion. The establishment of alumina is the reason for the observed greater
reduction in the oxidation rate of PM3030 in ArIH2IH20 which was almost equal to
alumina former, PM2000 in Ar/02. The doping effect of Si in PM3030 was practically
absent. This could be due to the insufficient amount of Si in the transient oxide to produce

1002
doping effect and therefore Ni which was predominant would control the doping and
oxidation process. PM2000 which exhibited a similar behaviour as MA6000 in both the
conditions could be attributed to the incorporation of Ti and Fe in alumina which
produced the same resultant effect of donor and acceptor doping as tbat produced on
MA6000. From these results, it was concluded that the growth mechanism of oxide is
changed from grain boundary diffusion to volume diffusion in the presence of water
vapour and hence the reduction in the rate depends on the incorporation of proton which
in turn depends on the doping of major oxide.

Conclusion

The better scaling resistance of Fe- and Ni-base ODS alloys in ArIH:zIH20 compared to
that in Ar/02 is due to doping effect. Volume diffusion has beCome predominant growth
mechanism in ArIH:zIH20. The acceptor doping of Cr203 by Ni increases the proton
incorporation which enhances the inward diffusion resulting in a reduction in the oxidation
rate. The addition of Ti decreases the proton incorporation and hence increases the
oxidation rate in a great extent.

References

1. T. Norby and P. Kofstad, Solid State Ionics, 20 (1986) 169.

2. M. Labaiz, I. Guillot, D. Petelot and G. Beranger, Abstract Bookl.et, 4th

International symposium on high temperature CORROSION and Protection of
Materials, Les Embiez. France, 20-24 May,(1996) 4.

3. T. Norby, Studies in Inorganic chemistry, 9, eds. Anderson.A.G and'. Johannesen.

Elsevier, Amsterdam. (1989) 101.

4. T. Norby, 3rd International symposium on high temperature ,corrosion and

protection of materials, ed. R. Streiff, Publ. Editions de Physique., Les Embiez.
France, 2,5-29May, (1992) 1.

1003
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Role of Moisture on the Oxidation of

Metals in Fused Nitrates Melt
I.B. Singh
Regional Research Laboratory,
Council of Scientific and Industrial Research,
Hoshangabad Road, Bhopal-462 026, India

Abstract

The electrochemical studies have been carriedout to understand the role of moisture on the
oxidation of metals in NaN03 - KN03 melt at 340 0C.It was found that presence of traces of
moisture in the melt increases the oxidation rate of iron significantly. Cyclic voltammetric study on
platinum surface. indicates the occurrence of well defined reduction peak due to alkali metal oxide
formation. The effects of moisture on the oxidation rate of iron and cathodic process on platinum
surfaces in NaN03 - KN03 melt have been investigated and discussed with available work related in
separate NaN03 and KN03 melts at 340C.

INfRODUCfION
Because of low eutectic temperature , high heat capacities , thermal stabilities and low
corrosiveness, alkali metal nitrites and nitrates are being used as heat transfer and storage media in
thermal power system. (1,2 ). They are also commonly used as heat treatment bath for metals and
alloys. Moisture is considered to be the main contaminant in fused salt because it affects the various
electrochemical reactions. In-situ identification and estimation of moisture in fused salt system is
very difficult. However, electroanalytical technique like poiarography and cyclicvoltammetry (3-4)
are used preferably for identification and quantification of moisture in the melt. A characteristic
"water wave " prior to nitrate ion reduction in nitrates melt is generany observed on many noble
metals surface (4-6). Recently, it has been reported (7) that presence of traces of moisture (10-4M)
in ( Na/K) N03 melt at 300C catalyses the nitrate ion reduction and increases the solubility of
alkali metal oxide. Besides, a number of studies have also been undsertaken to resolve the
electrochemistry of nitrate ion reduction (8-9).
The magnitute of increase of the oxidation rate of iron in presence of traces of moisture in
NaN03 and KN03 melt has been determined recently by author (10). Mixed NaN03 - KN03
eutetcic melt is commonly used for heat transfer and storage media due to their use upto wide range
of temperature (220 to 550C). The actual oxidation rate of iron, a metal of practical importance
was not estimated in earlier study. Thus, present investigation was carriedout to measure the
oxidation rate of iron and also to understand the role of moisture on oxidation reaction on iron and
platinum surface, respectively in dry and wet NaN03 - KN03 melts at 3400C. Due to fast oxidation
of iron electrode the platinum surface was used for cyclic voltammetric study to know the cathodic
process of the melt. To compare the result, investigations related to electrochemical studies of iron
and platinum in separate NaN03 and KN03 melts (7,10) have also been discussed.

1004
EXPERIMENfAL PROCEDURE
ARgrades NaN03 and KN03 salts were dried for nearly 12 hours in vaccum oven at 150 0e.
After drying ,50 grams of their equimolar mixture was kept at 2500C ( above the eutectic
temperature)for 6 hours in vacuum. During drying, oxygen free dried nitrogen gas was bubbled
continuosly upto three hours in the melt for removing traces of moisture present in the melt (3,6).
The moisture free NaN03 - KN03 melt is named as dried melt while moisture containing ( without
any drying) melt is named as wet melt.
The cross section of the rectangular pure iron ( Armco grade ) rod (area 0.16 cm2) and
platinum wire ( 0.01 cm2 )electrodes were exposed in the melt for polarisation and cyclic
voltammetric studies, respectively. The details of electrode preparation are available elsewere (10-
13 ). The whole electrochemical set-up was placed vertically in muffel furnace and temperature
was controlled by a variable transformer. The reference electrode was the pure silver wire immersed
in the melt of equimolar NaN03 - KN03 containing 0.07 M AgN03 in one end closed Pyrex glass
tube ( 5,7) . The details of electrochemical setup and reference electrode preparation are given in
other papers (7,10). A rectangular platinum foil ( 1cm2 ) was used as counter electrode. For
measuring the oxidation rate of iron, potentiodynamic polarisation curves were recorded upto
150mV from oxidation potential. To know the cathode process of melts, liner cyclic voltammetric
curves were recorded on platinum surfaces in the potential range of - 1.0 to - 2.5 V vs Ag/ Ag+ .
potentiodynamic polarisation and cyclic voltammetric curves were recorded by using PAR model
173 potentiostat , 175 programmer and Rikadenki 0363 x-y recorder. All the experiments were
carriedout at 340 2e.

RESULTS AND DISCUSSION

Oxidation of Iron
The steady oxidation potential ( Ecorr) measured for iron in dried and wet NaN03 - KN03
melt , is shown in Table 1. A rapid shift of Ecorr in positive potential region immediately after
immersion was noted in wet and dried melts. Presence of moisture increases Ecorrvalues distinctly in
positive region because -385 mY Ecorrwas observed in dried NaN03 - KN03 melt while -373 mY
Ecorrvalue was obtained in wet NaN03 - KN03 melt. Similar trends of decrease of Ecorrvalues was
also noticed in dried and wet NaN03 and KN03 melts at 3400(: (10).
The partial polarisation plots of iron in dried and wet NaN03 - KN03 melt at 3400C ( scan
rate 5 mV/sec ) are shown in Fig. 1. The oxidation rate (Icorr) of iron was obtained by Tafel
extrapolation , is given in Table 1. The measurement of nearly 28 % higher corrosion rate in wet
NaN03 - KN03 melt compared to their dried melt obviously confirm the increase of oxidation rate of
iron in presence of moisture. Influence of moisture on the oxidation rate of iron in NaN03 and
KN03 melts has been estimated in earlier study (0) and neary 45 % and 11 % higher oxidation rate
of iron measured in wet NaN03 and KN03 melts, respectively compared to their dried melt. Present
results suggest that a medium oxidation rate of iron occurs in NaN03 - KN03 melt compared to
NaN03 and KN03 melt.

Table 1 . Oxidation potential (Ecorr)and oxidation rate (Icorr) of iron and cathodic peak potentials
(Epc)and cathodic peak current (Ipc) on platinum in wet and dried NaNO" - KN03 melt at
340C.

1005
1006
1007
CONCLUSIONS
from the present study it may be concluded that traces of moisture in nitrates melt enhance
the nitrate ion reduction reaction and solubility of inhibitive alkali metal oxides in the melt. This
leads to an increase of oxidation of iron in moisture containing wet melt. Occurrence of lower
oxidation rate in dried nitrates melt is due to decrease of solubility of alkali metal oxides on the
electrode surface which reduces the nitrate ion reduction reaction significantly.

ACKNOWLEDGEMENf
The author is grateful to Director, Regional Research Laboratory, Bhopal -462026 , India for
his permission to publish this work.

REFERENCES
1. Sundermeyer, W.,Angew Chem,Vol. 77, 1965, P 241.
2. Reddy,T.B.,Electochem Techno ,Vol. 1 ,1963, P 325.
3. Swofford, H.S.and MeCornick, P.G.,Anal Chern ,Vol. p 37 ,1965, P 970
4. Swofford ,H.S.and Laitinen H.A.,J. Electrochem Soc, Vol.110 ,1963, P 810.
5. Zambonin, P.G., Electronal Chern Interfacial Electrochem ,Vol. 24, 1970, P 365.
6. Peleg M.,). Phys. Chern. Vol. 71 ,1967, P 868.
7. Singh I.B. , Sultan, S. and Balakrishnan ,K. Electrocnem. Acta ,Vol. 38, 1993, P 2611.
8. Bertlett, H.E,and Johnson, K.E.,f. Electrochem Soc, VoL64 , 1967 ,p 1149
9. Zambonin P.G.andJordanJ.,). Am. Chern; Soc VQl.91,1969, P 2225
10. Singh LB. , Corrosion Sci., Vol. 37 ,1995 , P 1981.
11. Singh I.B.,Venkatachari , G.and Balakrishnan, K, Corros. Sci, Vol. 36,1994, P 1777.
12. Singh I.B.,SultanS and Balakrishnan, K, Electochim Acta ,Vol. 40 ,1995, P1755.
13. Singh LB.,and Sen, U, Corrosion Sci., Vol.34 ,1993, P 1733.
14. Kanzaki , Y. and Takahashi, MJ, Electronal Chern. Interfacial Electrochem, Vol.58 ,1975, p
349.
15. Miles, M.H. and Fletcher,J.J.Electrochem Soc, Vol.127 ,1980, P 1761.
16. Hills, GJ and Power, P.O.,). Polarog. Soc, Vol. 139,1967, P 71.
17. Mazzochin G.A.,Bombi G.G and Sacchetto G.A.,J. Electrochem. Soc, Vol 21,1969, P 305.

1008
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Effect of pH and Hardness on the Scale Formation of

Mild Steel in Bicarbonate Ion Containing Water
I.B. Singh and B. Chakradhar
Regional Research Laboratory,
Council of Scientific & Industrial Research,
Hoshangabad Road, Bhopal-462026, India

Abstract
Seide formation on metals causes damage of equipment and decreases their efficiency
Surface Water is generally used for cooling of heat exchanger etc., contains a high level of
alkalinity and carbonate hardness which are responsible for scale formation. In present work, an
attempt has been made to see the effect of pH and Ca and Mg ions on the scale formation of mild
steel in 300 ppm bicarbonate ion containing sodium bicarbonate water solutions !1pto 120 hours of
immersion. Weight loss measured upto 120 hours of immersion attributes to a decrease of
corrosion rate with the increase of pH from 7 to 9. However, no significant decrease of corrosion
rate of mild steel was noticed even in presence of 700 ppm CaH and MgH ion at pH 9. Langlier
water saturation index has also been calculated and result is discussed in view of various factors
responsible for corrosion and scale formation.

INfRODUCfION

Corrosion , scale deposition and fauling pose a great problems (or the stability of various
components of cooling water system at industrial and power plants. Because of above problems ,
damage of equipment often happens and reduces the efficiency of energy generation. Seale,. a
dense coating consisting of inorganic materials and results from super saturation of water soluble
minerals ( 1-3). Seale interfere with heat transfers, thus reducing their efficiency. ~lcium
carbonate is the most common scale forming constituents of cooling water. The degree of scaling
depends primarily on concentration of calcium hardness and pH of water. The chemistry of scale
fomtation in presence of Ca and Mg bicarbonates is well established. However, the tendency of
scale formation in presence of alkali metal sodium bicarbonate was not studied earlier in detail. In
present investigation , therefore , an attempt has been made to see the scale formation in absence
and presence of Ca and Mg ions in sodium bicarbonate containing water at various pH.

EXPERIMENfAL PROCEDURE

Mild Steel ( C = O.I % ) specimens ( 5 cm x 2.5 cm x O.I cm ) were polished till the mirror
finish by various grades of emery papers and cleaned by acetone before immersing into the solution.
Bicarbonate containing solution was prepared by taking ARgrade NaHC03 in tripple

1009
 distilled water. Ca and Mg containing solutions were prepared by dissolving CaC03 and MgC03 in
dil H2S04. pH adjustme.nt was made by addition of ARgrade NaOH.
The immersion test for preweighed specimen was performed in 300 ppm containing
bicarbonate ion in pH range 7 to 9 in absence and presence of various concentration of Ca and Mg
like 325 pptn (225 ppm Ca++ and 100 ppm Mg ++ ),500 ppm (350 ppm Ca++ and 150 ppm Mg++)
and 700 ppm ( 500 ppm Ca++ and 200 ppm Mg ++). The immersion test was carried out in static
condition upto 120 hours of. duration. Afterwards they were suspended in solution containing 250
ml beaker with the help of glass hooks. The specimens were removed at different interval, rubbed
with wet cotton and finally cleaned with distilled water. They were then dried-and reweighed with
mettler balance. All the tests were performed at room temperature ( + 30C) in open condition.

RESULTSAND DISCUSSION

Fig.). Corrosion behaviour of mild steel in 300 ppm bicarbonate containing water upto 120
-- hours of exposure.

From the Figure 1 it is obvious that a higher corrosion rate is observed in the beginning .
Nearly two times higher corrosion rate was noted at pH 7 in comparison to pH 9. The corrosion
rate of mild steel decreases linearly with passage of immersion time. No visible scale formation was
noticed on specimens surface at any investigated pH even after 120 hours of immersion. Weight
loss data indicates that sodium bicarbonate is not helpful for scale formation. Decrease of corrosion
rate at pH 8 and 9 is mainly due to decrease of hydrogen ion concentration in the solution.

1010
fig. 3.Effect of Ca and Mg ions on the corrosion behaviour of mild steel in 300 ppm bicarbonate
water at pH 8.
As in case of bicarbonate ion , no visible scale formation was noticed on the specimen surface even in
presence of 700 ppm Ca and Mg at pH 8 and 9. In the beginning, higher weight loss was noticed.
If the effect of concentration of Ca and Mg on corrosion rate is compared one may find slight
decrease of corrosion rate in highly concentrated ( 700 ppm ) Ca and Mg containing solution.
Nearly 1.80 mpy corrosion rate was noted in 325 ppm Ca and Mg while 1.73mpy corrosion rate
was measured in 700 ppm Ca and Mg containing bicarbonate water at pH 9. Present results also
indicate that decrease of corrosion with pH is mainly due to reduction of hydrogen ion
concentration. It is well known that CaC03 is the main scale forming constituents in water.
Fonnation of CaC03 is mainly due to breakdown of soluble calcium bicarbonate, a naturally

1011
Fig. 4. Effectof Ca and Mg ions on the corrosion behaviour of mild steel in 300 ppm
bicarbonate water at pH 9.

occurring soluble salt. The degree of scale formation primarily depends on level of calcium
hardness and bicarbonate alkalinity in the system. The breakdown of calcium bicarbonate increases
with the increase of pH and rise of temperature ( 4 - 5). In the present investigation occurrence of
corrosion reactions instead of scale formation suggests the presence of sodium bicarbonate in
solution responsible for inhibition of scale formation on metal surfaces. Inclusion of sodium in the
scale may also increase the solubility of scale in case if it is formed.
Water saturation Langlier index was calculated for investigated solutions at various pH. A negative
Langlier index was found in 300 bicarbonate containing NazC03 solution at all the investigated pH
whereas a positive Langlier index was measured in Ca and Mg containing bicarbonate solution from
pH 7 to 9. Measurement of negative water saturation index in sodium bicarbonate water suggest its
corrosive nature which is in good agreement with the present result. Occurrence of positive index
predict the possibility of scale formation in Ca and Mg cOl'\taining water. In contrast, a slight
corrosion is mild steel is measured in present investigatiori even in presence of 700 ppm Ca and Mg
at pH 9.
From the present study, it may be concluded that presence of Ca and Mg ion in sodium bicarbonate
containing water is not helpful for scale formation. Bicarbonate ion in presence of sodium is only
assisting the corrosion reaction. Further electrochemical study is necessary to know the kinetics of
metal dissolution in presence of Ca and Mg ion in sodium bicarbonate containing water.

ACKNOWLEDGEMENf
Authors are grateful to the Director Regional Research Laboratory (CSIR) Bhopal for his
permission to publish this work.

REFERENCES
1. Handbook of industrial Water Conditioning, Betz Laboratories Inc. Trevose, Par 1980.
2. Principles of Industrial Water Treatment , Draw Chemicals Co., Boonton, NJ , 1977.
3. The Naloo Water handbook, McGraw - Hill Book Co, New York, 1997.
4. M. Brooke, The Calcium Carbonate Story, Corrosion 83 , Anaheim, Calif.
5. Sheldon D Strauss and Paul R. Puckorius , Cooling Water Treatment, a special report, Power
June 1984 p 8.1 - 8.24.

1012
Proc. In!. Cont". on Corrosion CONCORN '97
December 3-6, Mumbai, India

Evaluation of SS 316 as the Container and Current

Collector in EDL/Super/Ultra Capacitors
Devicharan Chidambaraml, P.V. Karthikl,
L. John Berchmans2 and V. KapaU2
'Students, Final Year, B. Tech (Chemical and Electrochemical Engineering)
Madurai Kamaraj University,
CECRI, Karaikudi-630 006, Tamil Nadu, India
2Central Electro-Chemical Research Institute, Karaikudi-630 006, Tamil Nadu, India

ABSTRACT

This paper deals with the systematic investigation aimed at selecting a suitable metallic
material to be used as the container and current collector of the electrodes in EDL / SUPER /
ULTRA capacitors. Since the electrolytes of such capacitors can vary from highly acidic to highly
alkaline, aqueous and non-aqueous solutions, the interference from the corrosion and anodic
behavior of prospective candidate metals or alloys may influence the characteristics of the
capacitors. The best solution under such circumstances will be the choice of the most suitable
material of construction and current collector completely free from the deleterious effects of
corrosion and anodic dissolution of the metallic materials.

In order to arrive at the best candidate metallic material for use in capacitors our first choice
is the stainless steel family and especially SS 316 having a high content of Molybdenum. The
general corrosion and anodic behavior, in particular of SS 316 have been studied intensely in
aqueous alkaline media such as KOH , NaOH, K2C03, Na2C03, and in their mixtures.

The CECRI capacitor electrolyte is based on aqueous 1.0 M potassium carbonate solution.
The corrosion rate in the 1.0 M solution based on potentiodynamic polarization and the actual
CDTOsion rate in long term experiments are found to be very low, most probably due to the
formation of a protective film, verified by anodic polarization, impedance measurements and optical
surface characterization techniques, wherever possible.

Our studies reveal that the overall kinetics of corrosion of SS 316 in 1.0 M K2CO, and other
alkaline solutions is found to be under anodic control. Hence the choice of SS 316 which shows a
tendency for the formation of a protective film in 1.0 M K2C03 solution, thereby leading to a very
low corrosion rate.

S corresponding author.

1013
1.1 INTRODUCTION

Electrical double layer / ultra / super capacitors are being developed [I] either to improve
the life of the existing batteries or to replace the same in computer memory circuits, electric
vehicles, power electronics, where high wattage pulses are required. The different components of
these capacitors are encased in a container which may be either metallic or non-metallic. Since the
electrolytes used in such capacitors vary from highly acidic to highly alkaline in nature, it is but
natural that they give rise to different forms of corrosion of the metall(c container and the current
collector, such as general corrosion, pitting, hydrogen embrittlement, stress corrosion cracking
including hydrogen induced cracking and anodic passivation. This paper deals with systematic
investigations carried out to understand the interference from general corrosion and anodic behavior
of prospective candidate metals or alloys in capacitor electrolyte solutions.

In order to arrive at the best candidate metallic material for use in capacitors as the current
collector as well as the container, SS 316 alloy having a high content of Molybdenum has been
chosen as a typical representative of the stainless steel family. Since SS 304 has already been studied
in KHC03 solution [2] and in NaOH solution [3]. General corrosion and active-passive transition
behavior of SS 316 have been studied systematically in KOH, NaOH, KZC03, NaZC03, and in their
mixtures using techniques such as potentiodynamic polarization, anodic passivation, impedance
measurements, weight loss measurements, and optical surface characterization. Special emphasis is
given to the SS 316 alloy / 1.0 M KZC03 aqueous solution system.

1.2 EXPERIMENTAL

1.2.1 Chemicals and solutions.

The chemicals used namely, sodium hydroxide, potassium hydroxide, sodium carbonate and
potassium carbonate, were all of analytical grade. All the test solutions used in the work are based
on molarity and prepared from the above chemicals and conductivity water.

1.2.2 Specimens

The study was made using austenitic stainless steel SS 316 ( AISr 316 ) with the following
composition: 68.08Fe - 18Cr - IONi - 2.75Mo - 0.80Mn - 0.30Si - 0.07C. All specimens were
mechanically polished to a mirror~ like finish using emery papers with decreasing grit size from I/O
to 4/0, and degreased using acetone, before the start of each measurement.

1.2.3 Techniques

a. Potentiodynamic polarization studies:

The potentiodynamic polarization studies were carried out with a three electrode
configuration, using a BAS 100 A (Bio Analytical Systems, U.S.A.). A platinum disc of large area
(10 cmz ) was used as counter electrode. A saturated calomel electrode ( SCE ) connected to the cell

1014
by a bridge with luggin capillary served as the reference electrode. The exposed surface area of the
AISI 316 working electrode was 1 cm2. At the beginning of each experiment the electrode was
cathodically polarized at -1500 m V in the test solution to remove any surface oxides. The working
electrode was left under OCP conditions for 25 minutes and the stabilized open circuit potential (

OCP ) value was noted. The measurement was carried out at ambient temperature ( 28 2 0q, to a
difference of300 mV on either direction of OCP, at a scan rate of 1 mV per second.

b. Anodic passivation studies :

Anodic passivation studies were also carried out using the same set up used for
potentiodynamic polarization. The measurements were done from 300 m V cathodic to OCP to
+3000 mY, at a scan rate of 10 mV per second. This was done using BAS 100 A. The reference
electrode used was SCE.

c. Impedance studies:

Impedance measurements were made using a three electrode configuration as described

previously. The measurements were carried out in the range of 100 mHz to 10KHz, using a EG &
G instrument (Princeton applied research, model 6310, M398 ).

d. Weight loss measurements.

Long term corrosion studies were done using two numbers of AISI 316 specimens, each of
area 14 cm2 immersed in 200 ml of the test solutions. The specimens were polished and de greased
as before and immersed in solution using glass hooks.

e. Optical characterization: X-ray Diffraction:

The surface of the AISI 316 specimens were analyzed by the x-ray Diffraction technique
before and after weight loss measurements, using JEOL JDX 8030 x-ray diffractometer. The
specimens from weight loss experiments were cleaned with conductivity water, dried and then
examined.

1.3 RESULTS

1.3.1 Potentiodynamic polarization curves.

Table (1) gives all the kinetic parameters pertaining to the corrosion of AISI 316 in various
concentrations ( 0.1 M, 0.5 M, 1.0 M) of the following electrolytes:
KOH, NaOH, K2C03, Na2C03, and their mixtures.

The order of anodic tafel slope ( ba) is as follows:

KOH ( 1.0 M) < NaOH (0.1 M) + Na2C03 (O.IM) < NaOH (0.5 M) +Na2C03 (0.5 M) <
Na2C03 (0.5) < K2C03 (0.5 M) < NaOH ( 0.1 M).

1015
1016
3) 1.0 M KOH, which is the least corrosive according to polarization studies, has the least critical
passivation current of 15.84 ).lA/cm2 for passivation.

4) The 1.0 M NaOH system, which is found to be the most corrosive according to polarization
studies, has the highest critical passivation current of 316 ).lA/cm2 for passivation.

5) The transpassive voltage is found to be very high and it ranges above 1.8 V.

1.3.3 Impedance measurements:

The following observations can be made:

1) The Icorr values in 1.0 M solutions, calculated from Stern-Geary equation [4,5] are :
KOH - 15.73871.JAJcm2, K2C03 - 51.5012 ).lA/cm2, KOH + K2C03 mixture - 24.9197 ).lA/cm2,
2
NaOH - 21.5553 ).lA/cm2, Na2C03 - 20.3015 ).lA/cm , NaOH + Na2C03 mixture - 12.2499 J.l.A/cm2.

2) The typical Warburg's impedance was not observed in any of the systems.

3) For all systems the curves indicated a diffusion layer of finite thickness, the only exception being
K2C03, where a diffusion layer of semi-infinite thickness was indicated.

1.3.4 Weight loss measurements.

Table (3) gives the results pertaining to weight loss measurements and the general observations are
as follows:

I) In general, weight loss measurements have indicated the corrosion rate to be less when compared
with electrochemical methods.

2) Corrosion rate varies from 0.053 x 10-9 g/cm2/s ( 1.0 M NaOH + 1.0 M Na2C03 mixture) to
0.2656 X 10-9 g/cm2/s ( 1.0 M KOH ).

3) The order of corrosion rate (in 1.0 M solutions) is:

NaOH + Na2C03 < Na2C03 < KOH + K2C03 < K2C03 < NaOH < KOH.

1.3.5 Optical characterization: X-ray diffraction:

The following inferences were made:

I) X-ray diffraction analysis shows the initiation of film formation.

2) The above observation is common for both hydroxide and carbonate systems.

1017
1.4 DISCUSSIONS:

1.4.1 Potentiodynamic polarization and weight loss:

Since the values ofba are greater than the corresponding be values, it can be said that the
overall kinetics of corrosion of AISI 316 is under anodic control. It is meant that the partial anodic
reaction, namely ionization of iron is :

is the overall rate determining step. But the reaction need not necessarily be under perfect activation
or diffusion control. Hence to understand the actual mechanism of corrosion, impedance
measurements were carried out and results have been dealt with separately.

Corrosion of AISI 316 in NaOH is reduced by the addition of Na2C03 . The synergistic
inhibition of corrosion of AISI 316 in NaOH and Na2C03 mixture is not observed in KOH and
K2CO, mixture. Perhaps this is associated with the dissociation constants of the sodium salts and
potassium salts and their mixtures.

From weight loss measurements carried out for a duration of one week, there is a definite
decrease in corrosion rate as compared to corrosion rates obtained from polarization curves. The
decrease is four to ten times. Most probably this can be attributed to the slow formation of a
protective film on the surface of corroding material. Yet the corrosion rate is of the order of 10-9
g/cm2/sec. This corrosion rate is expected to reduce further to a negligible value, thereby showing
the slow kinetics of protective film formation during immersion.

1.4.2 Anodic passivation studies and impedance and x-ray diffraction

With a view to know the tendency of the stainless steel in different electrolytes to exhibit
active-passive transition, anodic passivation studies were carried out. This was again confirmed by
impedance studies. From the anodic passivation curves, it was confirmed that none of the systems
under the present study are capable of showing spontaneous passivity. Further we could not obtain
the typical active-passive transition region, that is the active region followed by active-passive,
passive, transpassive regions. It was quite interesting to note that in all curves the typical active-
passive transition region was not pronounced, but all other regions were present. One definite
conclusion would be that the stainless steel in most of the electrolytes did not give rise to either
spontaneous passivation or the usually expected typical anodically induced passivation. Actually the
typical currents required for passivation were found to be higher than the respective corrosion
currents obtained by polarization studies.

From impedance measurements, two important data were obtained, the first one being the
determination of the relative corrosion rates of the different systems. It was found that KOH +
K2C03 mixture has the least corrosion followed by Na2C03 + NaOH mixture followed by KOH,
and Na2C03 individually followed by NaOH and then K2C03 . It may be noted that all the above
solutions were of 1.0 M concentrations.

1018
 For the sake of analysis the solutions studied were divided into two groups, one comprising
of sodium salts and the other consisting of potassium salts. Such a division was warranted as it
yielded the valuable information that the order of corrosion of stainless steel AISI 316 in sodium and
potassium salts separately as per impedance measurements, conform to corrosion rates obtained
from polarization data as well as long duration weight loss tests. The second information that could
be obtained from impedance studies was the proof for the existence or non-existence of passive film
on stainless steel in different systems. An analysis of the impedance diagrams obtained in the case of
different systems investigated in this paper help one to conclude that:

a) none of the systems gave the typical Warburg's impedance, thereby indicating the absence of
diffusion layer of infinite thickness.

b) however all the systems exhibited the presence of associated diffusion problems of one kind or
the other which is not of the Warburg's type.

The system namely 1.0 M K2C03 showed the probable diffusion of active species in a
diffusion layer of semi-infinite thickness, whereas all other systems exhibited a diffusion layer of
finite thickness [6]. In essence the impedance measurements bring out the fact that the there exists a
diffusion which may be semi infinite or finite and yet from this we can infer that some kind of film
formation is occurring which is not completely continuous and pore free.

This factor was confirmed by the x-ray diffraction studies, which indicated the absence of a
phase film. All that we could get from the x-ray diffraction was the presence of Fe, K, C, 0 and Fe,
K, 0, H on the surface of the specimens in the case of immersion in K2C03 and KOH solutions
respectively.

1.5 CONCLUSION:

Now, by combining the data obtained by various techniques it can be safely concluded that
the AISI 316 in different electrolyte solutions studied does not give rise to spontaneous passivity and
yet it's corrosion rate is only of the order of 10-9 to 10-10 gJcm2/s. On this basis AISI 316 can be
safely recommended as the material for fabrication of containers and current collectors for EDU
Super / ultra capacitors wherein K2C03, Na2C03, KOH, NaOH, or their mixtures are used as
electrolytes.

ACKNOWLEDGEMENTS:

Authors thank director, CECRI, for kind permission to present this paper. The help obtained
in impedance measurements from Dr.Venkatachari, G., and Dr. Muralidharan, S., CECRI, is also
acknowledged.

1019
1.6 REFERENCES:

1. Kapali, V., Muralidharan, S., Sarangapani, K.V., Balaramachandran, v., Venkatakrishna Iyer, S.,
Novel supercapacitors with carbon/Ni-NiO electrodes and an aqueous mixture of an organic
bicarbonate and inorganic carbonate as electrolyte, presented at the Third Indo-German seminar on
modern aspects of electrochemistry, at IISc, Bangalore, India, 28 September to I October, 1996.

2. Drowgowska, M., Menard, H., Lasia, H., Brossard, L., Impedance study of the passive film on the
stainless steel 304 in pH 8 carbonate solution, Journal of Applied Electrochemistry, vol.26, no. 11,
November 1996. pp. 1169-1177.

3. Chandrasekaran, V.R., and Radhakrishnan, T.P., Corrosion of stainless steel in strongly alkaline
solutions, Bulletin of Electrochemistry, vo1.10, no.6-7, June-July 1994. pp. 258-260.

4. Sluyters, M.H., and Sluyters-Rehbach, J.H., Electroanalytical chemistry, vol.4, (00) Bard, A.J.,
Dekker, 1970.

5. Stern, M., and Geary, A.L., Journal of the Electrochemical Society, vol.104, no.l,1957.pp.56-60

6. Claude Grabielli, technical report 004/83, Identification of electrochemical processes by

frequency response analysis, Solartron instuments, issue 2, August 1994. pp.14-16.

1020
TABLE 1: KINETIC PARAMETERS DERIVED FROM POLARIZATION STUDIES

1021
Table 2: DATA FROM ANODIC PASSIVATION EXPERIMENTS.

Table 3 : WEIGHT LOSS DATA

1022
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Influence of Triazole Derivatives on the

Inhibition of Corrosion of Arsenical
Aluminium Brass in 3.5 % NaCI
L. John Berchmanst, M.A. Quraishi2, V. Sivan3 and S. Venkatakrishna Iyer1
'Central Electrochemical Research Institute, Karaikudi-630 006, Tamilnadu, India
2Department of Applied Chemistry, Z.H. College of Engineering and Technology,
Aligarh Muslim University, Aligarh-202 002, U.P., India
3Department of Metallurgical Engineering, Regional Engineering College,
Tiruchirappalli-620 015, Tamilnadu, India

ABSTRACT

The influence of a few synthesised triazole derivatives on

the inhibition of corrosion of arsenical aluminium brass in 3.5%
NaCl has been investigated using weight loss measurements ana poten-
tiodynamic polarisation studies. Different corrosion kinetic para-
meters obtained reveals the fact that the inhibition of corrosion
of arsenical aluminium brass in 3.5% NaCl by these compounds is
under mixed control. The inferior performance of these compounds
at higher temperatures may be due to the desorption of these com-
pounds leading to a decrease in the inhibition efficiency. UV ref-
lectance studies, X-ray diffraction studies' and scanning electron
microscopic studies have been carried out to understand the mecha-
nism of corrosion inhibition and also morphological changes on the
surface of the alloy. The adsorption of these compounds on the metal
surface from 3.5% NaCl is found to obey Temkin I s adsorption iso-
therm .

INTRODUCTION

Copper and its alloys especially brasses have been extensively

used as material for the construction of tubes and pipes for trans-
water, and for fabricating condensers and heat exchangers
Aluminium brass is finding extensive use as the tube material
for condensers and heat exchangers having sea or brackish water
as the coolant [4-8]. Incorporation of phosphorus and/or arsenic
as the minor alloying additive is found to bring down the. occur-
rence of dealloying attack [9,10]. The greater resistance of alu-
minium brass may be attributed to the presence of an aluminium com-
pound, when has a passivating effect [1112]. A thorough literature

1023
survey reveals the fact that a variety of organic compounds ranging
from long chain aliphalic sulphides to benzene derivatives contain-
ing nitrogen or sulphur have been found to be effective as inhi-
bitors for the corrosion of copper in sodium chloride solution [13,
14]. Benzotriazole, benzimidazole and their derivatives have been
studied as inhibitors for the corrosion of copper and copper alloys
in chloride solutions [15,16]. In the present study the influence
of a few triazoles such as, 4-amino-S-mercapto-3-methyl-l,2,4 tria-
zole (AMMT), 4-amino-S-mercapto-3-ethyl-l,2,4 triazole (AMET) and
4-amino-S-mercapto-3-propyl-l,2,4 triazole (AMPT) has been investi-
gated using wei~ht loss and potentiodynamic polarisation studies.
UV spectral stud1es, scanning electron microscopic studies and X-ray
diffraction studies have also been carried out to understand the
mechanism of inhibition.

EXPERIMENTAL

Arsenical alUminium brass specimens of the composition Cu

77.5%, Zn 20.5%, Al 1.9% and As 0.1% were used for all studies.
Specimens of 5 x 2 x 0.025 cm were used for weight loss measure-
ments. A cylindrical rod of the same composition and embedded in
araldite to expose an area of 0.276 cm2 was used for potentiodynamic
polarisation studies. Triazole derivatives used in this study were
synthesised in the laboratory as per the procedure reported else-
where [17].

Both weight loss measurements and potentiodynamic polarisation

studies were carried out as described earlier [18]. Surfaces of
corroded and inhibited specimens were examined both by UV Spectral
reflectance measurements" and scanning electron microscopic studies
as reported earlier [18J. Corrosion products adhering to the metal
surface were examined by X-ray diffractometry (Model JEOL 8030)
using copper Ka[A = 1.541 AO] as the target material.

RESULTSANDDISCUSSION

Weight Loss Measurements

Table-l gives the values of inhibition efficiency for diffe-

rent concentrations of triazole derivatives for the corrosion of
arsenical aluminium brass in 3.5% NaCl. It is found that the values
of inhibition efficiency obtained by these compounds follow the
order.

AMPT> AMET> AMMT

The inhibition of corrosion by these compounds can be attributed

to the formation of an insoluhle organic film on the metal surface
by their adsorption~ The adsorption of these compounds on the metal
surface can occur through:

1024
1025
(i) the interaction between the n-electrons of triazole ring and
the positively charged metal surface, and

(ii) the interaction between lone pairs of electrons of nitrogen

and sulphur atoms and positively charged metal surface.
\

The order of inhibition shown by these compounds may be due to the

difference in electron releasing tendencies (+1 effect) of different
alkyl substitutes present in triazole derivatives [19]. It can also
be attributed to an increase in the molecular area of these com-
pounds, which leads to more coverage and thereby more corrosion
inhibition.

Application of Adsorption Isotherm

The degree of surface coverage (e) for different concentra-

tions of triazoles has been evaluated from weight loss values as
described earlier [19]. The data obtained were tested graphically
for fitting a suitable adsorption isotherm. Temkin isotherm was
tested by plotting e vs log C for all the compounds. A straight
line was obtained in all the cases, proving thereby that the
adsorption of these compounds on the surface of arsenical aluminium
brass obeys Temkin1s adsorption isotherm.

Potentiodynamic Polarisation Studies

Table-2 gives various corrosion kinetic parameters such as

corrosion current (I Corr ), corrosion potential (ECorr ) and Tafel
slopes (ba and bc) der1ved from potentiodynamic polar1sation curves;
values of ECorr are shifted to less negative values in the presence
of different concentrations of all triazole derivatives. Values
of I Corrare brought down in the presence of different concentrations
of tr1azole derivatives in the order given below

AMPT> AMET> AMMT

An increase in the concentrations of these compounds is found to

increase the values of both ba and bc to almost an equal extent.
So the inhibition of corrosion of arsenical aluminium brass in 3.5%
NaCl is under mixed control. But maximum increase in both the Tafel
slopes is observed in the case of AMPT, followed by AMETand AMMT
in the decreasing order. Values of inhibition efficiency obtained
by weight loss method and from values of ICorragree very well.

Table-3 gives the values of different corrosion kinetic para-

meters for the corrosion of As-AI brass in 3.5% NaCl in the presence
of different concentrations of triazole derivatives at different
temperatures ranging from 30-90C. It can be seen from this table
that ECol;:rvalues become more negative with increase in temperature.
Values ot I increase with increase in temperature. Values of
both the TaWf slopes decrease with increase in the temperature.
These observations bring out the inferior performance of these

1026
1027
1028
compounds at higher temperatures, which may be due to the desorption
of these compounds from the metal surfaces at higher temperatures.

UVSpectral Reflectance Study

The fact that the inhibition of corrosi01'l of arsenical alu-

minium brass in 3.5% NaCl in the presence of triazole derivatives
may be due to the formation of a film on the metal surface is sup-
ported by UV reflectance studies carried out using a spectrophoto-
meter for different specimens under similar conditions. A comparison
of reflectance curves for buffed arsenical aluminium brass speci-
mens with polished specimens dipped in 3.5% NaCl in the absence
and presence of triazoles clearly brings out the fact that the per-
centage of reflectance is maximum for polished specimen. It has
been considerably reduced for the specimen immersed in 3.5% NaC!.
The observation clearly brings out the change in surface charac-
teristics of due to the corrosion of the specimen in NaC!. But in
the presence of triazoles, the reflectance is reduced only to a
small extent. This shows that surface characteristics are
not altered very much due to the formation of a film on the metal
surface by the adsorption of the triazoles.

X-ray diffraction studies on the corroded specimen clearly

shows the formation of an outer oxide layer consisting of cuprous
oxide, cupric oxide and copper oxy chloride. It also shows the pre-
sence of aluminium oxychloride in lesser amounts on the surface
layer to a limited extent.

Scanning electron microscopic studies also reveals the forma-

tion of a thin and very adherent organic film on the metal surface
in all the cases; which is actually responsible for the inhibition
of corrosion of the metal in NaCl solution.

CONCLUSIONS

Studies on the inhibition of corrosion of arsenical aluminium

brass in 3.5% NaCl by triazole derivatives brings out the following
main conclusions.

1. Triazole derivatives inhibit the corrosion of arsenical alu-

minium brass in 3.5% NaCl in the order AMPT > AMET~ AMMT.

2. The inhibition of corrosion of arsenical aluminium brass by

these compounds is under mixed control.

3. The adsorption of triazoles on the metal surface from 3.5%

NaCl obeys Temkin1s adsorption isotherm.

4. The inhibition of corrosion of arsenical aluminium brass in

3.5% NaCl in the presence of triazoles may be due to the for-
mation of a thin insoluble protective surface film.

1029
REFERENCES
1. Unny V.K.P., Shah G.C., Shatiya R.S., Corrosion behaviour of
cupronickel tubes in the sea water of circus nuclear reactor.
Proc. of the Symposium on Corrosion and, its control in power
and chemical industries, M.S. University of Baroda, Baroda,
December 15-17, 1982, pp. 11-3, 1-10.
2. Deshmukh, M.B., Rodrigues, P.V., Iqbal Akhtar, Sea Water Pollu-
tion: Influence of Corrosion of Copper alloys, Proc. of the
Symposium on Corrosion and its control in. Power and Chemical
Industries, M.S. University of Baroda, baroda, Dec. 15-17,
1982, pp. 11-4, 1-6.
3. Vakil B.B., Oza B.N., Influence of halides on the Corrosion
behaviour of 70/30 brass in 3.5% NaCl solution, Proc. Symp.
on corrosion and its control in Power and Chemical Industries,
M.S. University of Baroda, Baroda, Dec. 15-17, 1982, pp. 11-5,
1-7.
4. Habib K., Amin A., Electrochemical behaviour of aluminium brass
in natural sea water, Desalination, Vol. 85, No.3, March 1992,
pp. 2 5 7 - 8 2

5. Narain S., Asad S.H., Corrosion problems in low temperature

desalination units, Materials performance, Vol. 31, No.4,
April, 1992, pp. 64-67.
6. Shalaby H.M., Ai-Hasan A., Ai Muhanna R., Study of the effect
of pollutant additives on corrosion behaviour of aluminium
brass in sea water, British Corrosion Journal, Vol. 31, No.3,
March, 1996, pp. 199-204.
7. Epler D.C., Castle J.E., An XPS study of the behaviour of pro-
tective layer of aluminium brass condenser tubes, Corrosion,
Vol. 35, No.l0, October 1979, pp. 451-455.
8. Castle J.E., Parvizi M.S., Protective surfa~e film characteris-
tics of copper alloys in sea water; Corrosion prevention and
control, Vol. 9, No.2, February, 1986, pp. 5-15.
9. Pryor M.J., Kar-Kheng Giam, "The effect of arsenic on the de-
alloying of a -brass, Journal of Electrochemical Society, Vol.
129, No.l0, October, 1982, pp. 2159-63.
10. Mazza F., Torchio S., Factors influencing the susceptibility
of intergrannular attack stress corrosion cracking and de-
alloying attack of aluminium brass, Corrosion Science, Vol.23,
No.ll, November, 1983, pp. 1053-1057.
11. Beccaria A.M., Poggi G., "Behaviour of aluminium brass in sea
water at various temperatures', British Corrosion Journal,
Vol. 23, No.2, February, 1988, pp. 122-129.

1030
12. Baccaria A.M., Poggi G., Capanelli G., The effect on the beha-
viour of a -brass in sea water of the additionof aluminium and
tin - Parts I & II Corrosion Prevention and Con trol, Vol. 12,
No.3, March, 1989, pp. 169-173.
13. Patel N.K., Makwana S.C., Patel M.M., Actioft of benzimidazoles
on the corrosion of 63/37 brass in NaOH solution, Corrosion
Science, Vol. 14, No.1, January, 1974, pp. 91-94.
14. Soni K.P., Bhatt loM., Some azoles as inhibitors for copper,
brass and aluminium, Journal of Electrochemical Society of
India, Vol. 32, No.2, February 1983, pp. 197-99.
15. Elrahman H.A.A., Evaluation of the triazoles as corrosion inhi-
bitors for alpha-brass in acid chloride solutions, Corrosion,
Vol. 47, No.6, June 1991, pp. 424-28.
16. Dacosta, S.L.F.A., Agostinho S.M.L., Nobe K., Rotating ring
disk of electrode studies of copper - zinc alloy - electro-
dissolution in 1M HCl - effect of benzotriazole, Journal of
Electrochemical Society, Vol. 140, No. 12, December, 1993,
pp. 3483-88.
17. Dubey S.N., Beena Kaushik, Synthesis of triazole and its deri-
vatives, Indian Journal of Chemistry, Vol. 24 A, ~o.8, Septem-
ber, 1985, pp. 950-54.
18. Phani K.L.N., Pitchumani S., Muralidharan S., Ravichandran, S.,
Iyer S.V K., Polymino benzoquinone Polymers : A new class 0 f
corrosion inhibitors for mild steel, Journal of Electrochemical
Society, Vol. 142, No.5, May 1995, pp~ 1478-83.
19. Muralidharan S., Quraishi M.A., Iyer S.V.K., The effect of
molecular structure on hydrogen permeation and corrosion inhi-
bition of mild steel in acidic solutions, Corrosion Science,
Vol. 37, No. 11, November, 1995, pp. 1739-1750.

1031
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Influence of Some Dyes on CorrosioR 'of Mild Steel in

Sulphuric Acid Solution
R.S: Chaudhary and Santosh Sharma
Department of Chemistry, Maharshi payanand University,
Rohtak 124001, India

ABSTRACT: Methylene blue, Auramiile 0, Methyl red, Rhodamine B and Turquoise blue have been
investigated to control the dissolution of mild steel in 1.0 M sulphuric acid sol:ution by weight loss,
electrochemical polarization, scanning electron microscopy (SEM) and electron spectroscopy for chern ical
analysis (ESCA) techniques. The study has been carried at 100, 200, 400 and 800 ppm concentration of
the investigated dyes at 30.40 and 50C. All the dyes act as mixed inhibitor, follow Langmuir adsorption
isotherm equation and are physically adsorbed on the surface of mild steel. Inhibition efficiency increases
wit'" increase in concentration of the inhibitors and decreases with increase in temperature of the system.
Activation energy value of the inhibited sys~em 'is always more than the uninhibited system.

INTRODUCTION: Mild steel comes in contact with sulphuric acid solution in various industries and
suffers corrosion. The dissolution rate of mild steel- sulphuri<: acid system can be effectively controlled
by using corrosion inhibitors. Some times it is necessary to make the acid solutions coloured in industries
for careful handling of acid solution. Dyes have not been investigated in detail for their effectiveness as
corrosion inhibitor. Only a few workers have reported the use of some dyes as corrosion inhibitor.(lo,).

EXPERIMENT AL : For weight loss experiments ractangular specimens of commercial mild steel of
size 1.5 x 3.0 cm. were used whereas for electrochemical studies, the specimens had a working area of
1cm. x 1cm. with a 4 cm. long stem to make electrical contact. All the specimens were polished mechanically
upto 4/0 grade of emery paper and were thoroughly cleaned with distilled water and degreased in acetone.

1032
1033
covered with a protective film in presence of all the dyes. However, in presence of turquoise blue the
surface is not so smooth but still it is in a better condition than blank solution.

Elemental analysis of the surfacl( of mild steel specimen in ab~nce and presence of the dyes was
carried out by ESCA technique. The presence of chlorine, sulphur and nitrogen peaks in addition to
carbon, oxygen and iron peaks in inhibited specimens as compared with those of uninhibited specimens
indicate the adsorptiClft of the dyes on mild steel surface due to which metal surface becomes protective
against corrosion.

In case of Rhodamine B the presence of two nitrogen atoms, one oxygen atom and planer structures
might be responsible for its adsorption over metal surface, whereas in methylene blue adsorption lJ1ay
occur through tertiary nitrogens and sulphur atom. The imino nitrogen in auramine 0 is the point of
adsorption on mild steel surface. Low efficiency of turquoise blue is due to non rigid structure and steric
hindrance between molecules. Tertiary amino nitrogen is the active centre for adsorption on steel surface
in methyl red.

REFERENCES

I. Talati J.D., Gandhi D.K, Journal of Electrochemical society of India, 32, 1983, pp 380.

2. Talati J.D., Daraji J.M., Journal of Electrochemical society of India 35> 1986 pp 175.
3. Talati J.D., Daraji J.M., Journal of Indian Chemical society, LXV, 1988, pp 94.
4. Gupta Pushpa, Chaudhary R.S., Namboodhiri T.K.G., Prasad B.B., Journal of Electrochemical
society of India, 32,1983, pp 27.

1034
1035
la. - Blank solution
lb., lc., ld., le.,lf. - In presence of 800 ppm of Methyleneblu,
Auramine 01 Methyl red, Rhodamine B,
and Turquo1se blue respectively at
40C

1036
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Corrosion Behaviour of Zin<- Coated Steel

(ARC Sprayed) in Chloride Solutions
c. Marikkannu, c. Jeyaprabha and A. Madhavamayandi
Corrosion SCF and Engineering Division,
Central Electrochemical Research Institute,
Karaikudi-630 006, India

ABSTRACT

Recently much interest has been shown towards the corrosion study of galvanized coatings
due to its varied performance in rr..uine environments. In this investigation, corrosion behaviour of
zinc coated steel (metal arc sprayed) has been studied in neutral and alkaline chloride environments.
Effect of coating thickness on the corrosion resistance of the steel has been studied by po1imtial-time
measurements, salt spray test, humidity test, potentiodynamic polarisation and linear polarisation.
Effect of chromate treatment on the corrosion resistance has also been studied:

Results indicate that metal arc sprayed zinc coating improved the corrosion resistance of steel
more in neutral chloride solution than in alkaline chloride solution. Increase of coating thickness
does not have much influence on the corrosion resistance in the studied range 50 to 100 urn. The
corrosion resistance is due to barrier effect as wen as sacrificilal action of zinc. Chromate treatment
improves not only the corrosion resistance of the galvanized layer, but also of steel due to the inlnbiting
nature of the adsorbed chromate ions.

INTRODUCTION:

Galvanizing is one of the methodS adopted to minimize the rate of corrosion of$teeI structures.
Inspite of the wide practical experience gained with this protection method, its usage ~d effectiveness
in marine environments have been a matter of controversy due to its varied performanCe. Galvanizing
can be done by hot-dipping, metal spraying and electrogalvanizing (electrodeposition) methods.
But mostly either hot dip or electrogalvanized steels are in use. Literature on the corrosion behaviour
.of galvanized steel is mostly available for electrogalvanized steel and little on hot-dip galvanized
steel [1-4]. But till date, not much information is available on arc sprayed-galvanized steel. Hence,
attempts have been made to study the corrosion behaviour of arc-sprayed zinc coated steel in chloride
solutions. Moreover, for reducing corrosion in aggressive environments galvanizing alone is not

1037
actually enough and would need an additional treatment to act as barrier between the galvanized
layer and the environment. Generally, the use of chromate is a well known practice for reducing zinc
corrosion [5-7).

Considering the above facts this investigation focuses on ,

i) Corrosion behaviour of arc-sprayed zinc coated steel of various Thicknessin chloride solutions
and
ii) Effect of chromate treatment on the corrosion res;stance of arc- sprayed zinc in chloride
solutions.

EXPERIMENTAL :
Electrodes
Cylindrical mild steel specimens of 1 cm dia. and 5 cm long were used. For electrochemical
measurements, samples of size 0.785 cm2 embedded in Teflon were used.

Metallizing
Metal surface was cleaned by mild sand blasting. For metallizing, a spray gun was used with
an electric arc sustained at the end of continuously red zinc wire, operating typically at 25 V and 250
A to 350 A direct current. The zinc was commercially pure (99%). Thickness of the deposit was
varied by the number of passes.

Chromating
Specimens which were arc-sprayed, were cleaned using hydrochloric acid. Then activated in
1% nitric acid and chromated in OJ, 0.25,0.5, 1 % sodium dichromate solutions and chromating
solution (20% Sodium dichromate containing sulphuric acid) for 30 see at room temperature.

TECHNIQUES:

The thickness of the arc-sprayed zinc layer was determined by chemical stripping method and
using thickness measuring meter. Samples with a coating thickness of 50, 70 and 100 um were taken
for the study.
Corrosion resistance of the zinc coated steel specimens were studied by humidity test, salt
spray test and electrochemical tests such as Potential- time measurements and Polarisation technique
(Tafel extrapolation method and linear polarisation)
Porosity of the coatings was determined by water adsorpiton test, ferroxyl indicator test and
electrochemical method based on potentiostaic polarisation. This m,ethodinvolves the measurement
of cathodic oxygen reduction current in sodium hydroxide solutioq of pH 12.

RESULTS AND DISCUSSION

The thickness of metallic coatings is one of the important properties in the assessment of
quality of the coating. In this investigation, for the measurement of coating thickness, chemical
stripping method and thickness meter based on magnetic principle were used.

1038
 Results show that coating thickness by chemical stripping method"is lesser than that obtained
'It
by the meter. This may be due to the presence of some residual coating on the surface. Porosity of
the coating has been determined by water adsorption method, ferroxyl indicator and cathodic limiting
curr' :nt method and the results are summarized in Table I.

Results of water adsorption study indicates that the coating is highl)J porous. On the other
hand in ferroxyl indicator tests, no blue spot was observed and in electrochemical test also very low
cathodic limiting current was observed. From the results, one can conclude that though it has many
pores, they are not extended upto the base.

Corrosion behaviour of galvanized steel of thicknesses 50, 70 and 100 um were studied in
3.5% sodium chloride solutions under immersed conditions by (i) visual observation (ii) potential-
time measurements, and (iii) corrosion current measurement by polarisation, and weight loss method.
The samples were also subjected to salt spray and humidity test and the results are summarised in
Table I and II. Results show that increase of coating thickness from 50 to 100 micro meter does nto
change the corrosion resistance much. It is in the order of 110 .10 uA / cm2

TABLE I: RESULTS OF POROSITY AND CORROSION STIJDY -

EFFECT OF THICKNESS

(i) By water adsorption test By weight loss method

(ii) By ferroxyl indicator test By tafel extrapolation
(iii) Cathodic limiting current By linear polarisation

1039
 TABLE II : RESULTS OF OTHER TESTS

* Time for start of white rust, days

** Time for start of red rust, days

Visual observation :

A marked change in the appearance has been observed. In alkaline chloride solution, white
gelatinous precipitate has been seen on all the samples with various extend of coverage. With time,
the precipitate grows and covers the entire surface, within '.0 days. On the otherhand, in neutral
chloride solution, the coatings dissolve with time. After 50 days of exposure, the corrosion rates
were calculated by weight loss method and reported in Table III.

Potential-time studies:

Potential of the galvanized steel with and without chromate treatment were monitored as a
function time for 50 days in sat. CaOH2 containing chloride and 3.5% sodium chloride solution.

The data indicated that the trend is same in both solutions. For all the specimens with and
without chromate treatment, the starting potential is more negativ~1nld positive trend appears with
time of exposure irrespective of pH of the solution. This positive shift is due to passivation of the
surface. Chromate treatment does not change the potential mcuh

Electrochemiclil study:

Corrosion rates of the samples with and without chromate treatment in 3.5% NaCland
saturated Ca(OH)2 containing 3.5% NaCl have been determined by (a) Tafel extrapolation and linear
polarisation methods. Polarisation behaviour of galvanized steel of various coating thickness in
alkaline chloride and the effect various chromate treatment on the polarisation behaviour of galvanized

1040
steel of 70 u coating thickness in alkaline chloride solution are as shown in figs I & 2. Similar
behaviour has been observed In neutral 3.5 % sodium chloride solution too. The results of
electrochemical study in neutral 3.5% sodium chloride solution and alkaline chloride solutIOnare
given in Tables III and IV respectively .

TABLE III.: RESULTS OF ELEClROCHEMICAL STUDY IN
ALKALINE CHLORIDE SOLUTION

1041
1042
 The linear polarisation curves for the galvanised steel wIth and without chromate treatment in
the two electrolytes are shown in Figs 3 and 4.

Other tests

The samples have also been subjected to salt-spray, humidly an! immersion tests and the
results ar ~given in Table II.

Discussion:

In chloride solutions a positive potential shift, low corrosion current and a white, adherent
corrosion product have been observed. All the!>e results, clearly indicate the passivation of zinc in
alkaline solution.

Passivation of zinc takes place by the formation of passive layer after an initial dissolution of
zinc as zincate ions. The mechanism of product formed depends upon of the concentration and
nature of the electrolyte used [8-9]. In hydroxide solution of pH 12-13 Zn(OH)2 formation is
responsible for passivation. Initial dissolution takes place as .

Earlier works also support the salcts [10-12] of passivation product formed on zinc in NaOH
with and without calcIum IOns shows that the presence of calcium ion affect the nature of passivation

1043
1044
 product. It IS Zn(OH), in media without calcium Ions and calcium hydroxy zincate Ca[Zn(OH)3L
.2H,O in media contal;'ing calcium ion. In alkaline chloride solution formation of Zn(OH)2 ; and
basl'c ZinC salts such as zinc hydroxy chloride, ZnCI2. 4Zn(OH)2 Zn C126 Zn(OH)2 takes place. The
formation of such salts has also been reported by V.(I.Hime and M.Marchias [13].

In neutral chloride solution, large amount of white powdery com~ound was observed which
settled down at the bottom of the beaker. It may be due to the formation of zinc hydroxy chloride of
formula Zn5 (OH), C12. H20 as identified earlier for zinc in chloride solution and structural studies
[14] shoNed that it has a layered structure ofstructural formula [Zn) (OH),J [Zns C12 HP]. Conversion
of metallic zinc layer to Zns (OH)s C12.HP involved a substantial volume increase of atleast 261.46%
which may be the cause of spalling of the corrosion product.

The results of the studies have also indicated that the galvanized layer completely protect the
base steel in chloride solutions and the degree of protection is more in neutral chloride solution than
in alkaline chloride solution. Galvanizing offer protection to steel in more than one way. Firstly, the
metallic layer of zinc act as a physical barier between the steel and the environment and the corrosion
resistance of steel owes to the corrosion resistance of zinc. Further, wherever steel is exposed due to
the pores or any defects, steel is protected by the sacrificial action of zinc.

EFFECT OF CHROMATE TREATMENT:

Results of all the studies show that chromate treatment improves the corrosion resistance of
the metallized layer. In contrast to the control, the chromated samples withstand the environment
effectively. This improved r.erformance is attributed to the formation ofa chromate coating [15-17]
composed of a continuous layer that consists of insoluble Cr (III) compound and soluble Cr (IV)
compounds.

The Cr (VIi in'1 leacnp< <lnwly when it is in contact with water and finally the film is more of
insoluble Cr (III) compound. In addition to the inhibiting nature ofCr (IV) ions and the barrier effect
of Cr (III) film, chromate reduces the corrosion rate of galvanized layer by suppressing hydrogen
evolution reaction as

Chromate ions were reduced instead of water, and hence no hydrogen evolution. The reduced
Cr (III) is also precipitated on the surface. Even in presence of chloride ions, the passive film
continued to form but at to a lesser extent.

Conclusion

Results of the investigation indicate that metal arc sprayed zinc protect the base steel effectively
even at a lower thickness, of 50 u, But the degree of protection is more in neutral chloride solution

1045
due to the barrier effect and sacrificial action of zinc layer. But, the extent of white corrosion (ZinC
corrosion) is same in both the environments. Increase of thickness does not have much influence on
the corrosion performance. Chromate treatment further improves not only the corrosion resistance
of the galvanized layer 'Jut also the steel due to the inhibiting nature of chromate ions.

REFERENCES ~

1. Sergi, G., Short, N.R., and Page, c.L., Corrosion of Galva'lized and Galvannealed Steel.
Corrosion, Vol: 41, No. 11, (1985) P.618-24.
2. Maahn, E., and Sorensen, B., Influence of Microstructure on the Corrosion Properties of
Galvanized Reinforcement, Corrosion, Vol: 42, No.4 (1986) P. I 87-92.
3. Brain Lansly, Galvanizing-Economical Corrosion Protection, Corrosion Prevention and Control
Vol:34, No.1 I (1987) P.IO-I1.
4. Puech, M., Corrosion Behaviour of Galvanized Steel, Proc. of International Seminar on
Galvanizing Steel, (1975) P.5-15.
5. Blestek, T., and Weber, J., Electrolytic and Chemical Conversion Coatings, Portiullis Press.
Warzava (1976) P.85-95.
6. Helwig, L.E., Chromate treatment for Hot-Dip Galvanized Steel, Metal Finishing Vol: 68,
No.7, (1970), P.54-60.
7. Marikkannu, c., Ph.D. Thesis on Characterization on Chemical Passivation Treatments,
Alagappa University, (1996) P.lI6-130.
8. Graveer, R., and Kaesche, H., Electrochemical Dissolution of Zinc in Hydroxide Solution,
Corr. Sci, Vol: 12 (1972), P.617-23
9. Macias, A., and Andrade, c., Corrosion Behaviour of Galvanized Steel in Alkaline Solution,
Brit. Corr. J.,Vol: 22 No.2, (1987),P. 113-29.
10. Macias, A., and Andrade, C., Corrosion rate of Galvanized Steel in Saturated Calcium
Hydroxide Solution, Brit. Corr. 1., Vol: 18 No.2, (1983), P. 82-87.
11. Blanco, M.T., Andrade, c., and Macias, A., SEM study of Corrosion Products of Galvanized
Steel in Solutions of pH 12.6 - 13.6, Brit. Corr. 1., Vol: 19No I, (1984) PAI-48.
12. Macias, A., and Andrade, c., Corrosion of Galvanized Steel in Calcium Hydroxide Solution,
Brit. Corr. J., Vol: 22, No.3, (1987) P.162-7L
13. Hime, V.G., and Machins, M., Performance Variation of Galvanized Steel in Mortar and
Concrete, Corrosion, Vol: 49, No. 10, (1993) P.858-60.
14. Silverman, J.N., The Crystal structure of zinc hydroxy chlori~ .Univ. of Berlin, (1956).
15. Williams, L.F.G., Rate of Chromate Film Formation on Zinc, Surf. Tech. Vol: 5 (1977)
P.lO~-110
16. c.Marrikkannu and K.Balakrishnan, Electrochemical Evaluation of Chromate Coating on Zinc,
Bull. of Electro Chern. Vol: 4, No.7, (1988) P.625-30.
17. C.Marrikkannu and K.Balakrishnan, Effect of Anions on the Mechanism of Chromate Film
Formation on Zinc, Proc. 10th Inter. Congoon Metall. Corr., Nov. (1987), Madras. P.I133-37.

1046
Proc. Int. ConI'. on Corrosion CONCORN '97
December 3-6, Mumbai, India

High Temperature Corrosion Behaviour of

Ceramics After Excimer Laser Sealing
Gines Nicolast, Michel Autricl and Roland Streiff2
lInstitute for Research on Non-Equilibrium Phenomena (IRPHE),
LP3 Laser Plasma and Photonic Processes Laboratory,
Parc Scientifique et Technologique de Luminy, Case 918,
163 avenue de Luminy, 13009 Marseille, France
2Laboratoire de Physico-Chimie des Materiaux (LPCM)
Universite de Provence Marseille, France

ABSTRACT

The development of materials used in severe environment such as heat exchanger components subjected
to thermomechanical damaging processes is of a considerable interest in order to increase their lifetime.
Ceramics and alloys have the requirements for high temperature applications but after a certain time,
these materials lost their initial properties due to the corrosion phenomenon.
The excimer laser irradiation of such a kind of materials leads to an improvement in the corrosion
resistance with suitable conditions for some of these.
This study is devoted to investigate the modifications which occur during the laser exposure of ceramics.
The principle consists in minimizing the grain boundaries density by melting and adjoining grains to get
sealed, cleaned and smoothed surfaces without pores, pits or cracks where the corrosion attack starts.
Pores, pits and cracks areas are analysed by an image processing technique.
Results on oxidation kinetics at high temperatures show an improvement in the corrosion behaviour on
these ceramics after laser treatment. This is due to the formation, during an oxidation process, of a thin
protective layer upon a reduced porosity surface. The texture and the crystallographic structure have
been analysed in order to determine the properties of the formed oxide.

1. INTRODUCTION
During the last few decades, a great effort has been devoted to the development of materials for the
tribological applications and the hot corrosion protection. Due to their interesting properties, i. e.
toughness, thermal conductivity and hardness, ceramic materials offer the required performances [1]. A
range of nitrides, carbides and oxides can be selected as possible candidates to replace alloys in areas
where a workpiece must survive without protection over long periods in aggressive environments.
Engines and gas turbines operate at elevated temperatures to realize maximum efficiency. Such
applications require materials to withstand damages due to creep, fatigue, corrosion, 'erosion etc. As
compared with traditional gas turbine materials, the ceramic substrates and coatings bring several
advantages such as increase of temperature of combustion gases and reduction of temperature inside the
materia).. However, the use of these ceramics is limited by brittle behaviour [2] and by relatively poor
adhesion to the substrate in the case of coatings. Extensive work has been performed to optimize the
bonding of the ceramic layers and decrease of their porosity [3]. Plasma spraying is one of the most
suitable method for producing ceramic films. Plasma sprayed coatings are formed by superimposed
lamellae created by a stream of molten particles which impact and spread onto the substrate. However,

1047
the films obtained by this method contain a high quantity of pores or cavities which is detrimental for
uses at high temperatures and is a factor responsible of the corrosion phenomena. The corrosion
involves destruction of materials due to their chemical interaction with the surrounding atmosphere [4].
The laser surface treatment is an alternative method which allows to modify directly the ceramic material
by irradiation. As a result of this, a melted layer is produced on surface with different properties leading
to a change in the mechanical and chemical behaviour of the material. ~
In the present study, an attempt has been made to investigate the surface modifications induced by an
excimer laser on two ceramics : aluminum nitride (AIN) and silicon carbide (SiC) in order to enhance
the hot corrosion resistance of these materials after laser treatment.

2. EXPERIMENTAL
2.1 Sample Preparation and Irradiation
The materials under investigation were commercial ceramics. Two kind of samples used in this study
were AlN and SiC. They were obtained from powders by sintering [5].
Samples were prepared from sheet material with dimensions of 25 x 25 x 1 mm. They were placed in
acetone, followed by cleaning in an ultrasonic device.
In order to ensure accurate surface treatment of material by laser, it was essential that the pieces be
irradiated such that the modifications, which take place during the interaction processes, were the same
in all treated zones: This can be achieved using an optical system for focusing and selecting the central
part of laser beam where the energy distribution was homogeneous.
Due to the size of the focalised beam (some mm2), all the areas of the samples were treated by scanning
using a x-y positioning table actuated by microprocessor controlled stepper motors. Irradiations were
performed in air.

2.2 Laser Parameters

The excimer laser used in our experiments was a Lambda Physik LPX 220 operating at a wavelength of
248 nm and a pulse width of 20 ns. A range of laser fluences from 0.5 to 10 lcm-2 was studied and has
corresponded from weak to strong modifications of the materials.

2.3 Oxidation Procedure

The corrosion tests were cyclic with each cycle being of 24 hours duration (20 hours at high
temperature followed by 4 hours cooling period). During the cooling period of each cycle, samples
were removed from the furnace and cooled to room temperature in air. The exposures were conducted
in the furnace with temperature of 1000 0c. Repeated cycles were realized continuously one after
another.

2.4 Analysis Techniques

A scanning electron microscope (SEM) was used to observe surface morphology before and after laser
treatment, and after corrosion tests. From SEM pictures, an image processing technique has allowed to
quantify areas corresponding to the porosity (pores, cracks, pits, voids).
The chemical composition was analysed by Auger electron spectroscopy (AES) to determine the change
of elements ratio and to get elements profiles.
The structure of oxides formed during high temperature oxidation was analysed by grazing X-ray
diffraction (XRD).

3. RESULTS

3.1 Morphological Examination

- Before oxidation
The SEM photographs of the specimens show that the surface is constituted by small grains with an
average size of 1-2 Ilm in both cases (SiC and AIN). The laser irradiation in the UV range induces on

1048
these material several modifications. Firstly, when the incident energy density applied on the surface is
sufficient, the initial granular microstructure disappears and a thin melted layer is produced. In this
uniformly melted layer, the most of defects such as grains boundaries, pores, cracks and pits are
removed. In order to quantify this morphological modification, the SEM images processing show that
the surface porosity of the laser treated areas is strongly reduced: from values about more than 10% for
AlN and 14% for SiC, we obtain 2-4 % in both cases. Figure 1 gives tht evolution of porosity with the
laser energy density (fluence) : we can observe a decrease beyond a value of 0.7 J.cm,2 which
corresponds to the melting threshold, Le. the grains start to melt and to coalesce. Between 1.0-2.0 J.cm'2,
the total surface is melted (12% -> 4%). For fluences greater than 2.0 J.cm,2 (well established plasma
condition), small pores 0.01 J.UI1) probably due to the explosion of air bubbles captured in the melted
pool during the interaction between matter and laser beam exist.

If the fluence is not enough important, the initial characteristics are not removed fully and the areas with
pt>rosity are about 10 %. It is not convenient to irradiate at fluences higher than 4:0 J.cm,2 because, in
this case, complex phenomena due to plasma and hydrodynamic instabilities induce strong degradation
of the treated zones [6]. The pressure induced by the plasma on sample increases. and instabilities
generate periodic structures on the melt during the interaction time.
A second kind of surface modification connected with this concerns the roughness which may develop
on irradiated surfaces upon accumulation of several pulses. Depending on the thermal diffusivity of the
material, the heat is evacuated more or less quickly resulting in an increase or decrease of roughness.
A third modification is the change in chemical composition. Indeed, the UV radiation leads to a
bonding break of Si-C and AI-N, and a redistribution of atoms in the melt. In the two cases studied, the
melted layer is constituted by a rich film of Si for SiC [7] and AI for AIN [8] which changes the
reactivity of atoms on the surface. The depth of the melted layer is less than I J.l.m(400 nm for SiC and
200 nm for AlN).

- After oxidation
In an aggressive environment, material surface is modified due to the growth of oxide. The grains of
untreated materials are covered by oxide but the initial topography remains. A similar behaviour is

1049
observed for laser treated samples but the surface seems to be smoother. For AlN, the structure of
formed oxide was identified by XRD : corundum (a AI203).

3.3 Kinetics

3~1~C I

Figure 2 shows the mass gain of SiC in air at 1000 C for untreated sample and two irradiation
conditions. The curves follow parabolic law at the beginning, but in the case of original material, the
kinetics is lower. After three cycles, oxide scale becomes constant but we didn't observe a weight loss in
the range expected. In this case, the oxidized sample stays stable. For irradiated sample (1.9 J.cm-2), the
kinetics of oxide formation is faster; the weight gain reaches a maximum value after 80 hours. It seems
that there is a balance between mass gain and spallation. When the fluence is higher (3.5 J.cm-2), the
curve indicates an uninterrupted oxidation pattern corresponding to a better hot temperature corrosion
resistance as compared with 1.9 J.cm-2 This result is explained by a higher reduction of porosity (see
fig. 2) and by the presence of a thicker and more homogeneous Si rich layer investigated by AES.

3.3.2 AIN

Figure 3 shows the mass gain of AlN subjected to oxidation at 1000 C in air for untreated sample and
laser treated sample with a fluence of 3.5 J.cm-2 Once again, the curves correspond to parabolic law but
with an increase of weight higher for sample exposed to laser that we can attribute at a .better reactivity
of rich film aluminum towards oxygen. Afterwards, we note a decrease of weight gain which means that
the oxide scale after growing to certain thickness cracks. This cracking may be due to growth of stresses
developed during the oxidation and cooling cycles.
In the case of original sample, after an increase of weight during the first cycle, there is a saturation
effect due to the thermodynamically instable character of nitrides in oxygen attnosphere [9].

1050
 Figure 3 : Cyclic oxidation of 24 H on AlN untreated sample c irradiated sample (3.5 J.cm'Z).

4. CONCLUSION

Laser surface sealing is induced in the near surface by relatively high intensity, short duration laser
interaction (i. e. 108 W.cm'z for 20 ns at 248 om) on two ceramics: SiC and AlN. This can result in
surface properties modifications which concern mainly the morphology and topography of material. By
removal of sites (grain boundaries, pores ...) where corrosion attack starts, the protection against this
aggressive phenomenon can be improved with suitable laser irradiation conditions.

5. REFERENCES

1. Structure and properties of ceramics, vol. ed. R. J. Brook, Materials Science and Technology,
Vol. 11, Weinheim, 1994.
2. Davidge, R. W., Mechanical Behaviour of Ceramics, Cambridge Solid State Sciences Series,
London, 1986.
3. Materials for Advanced Power Engineering 1994, D. Coutsouradis et al. (eds.), Kluwer
Academic Publishers, Dordrecht, 1994.
4. Khanna, A. S., High Temperature Corrosion of Materials, Metallic Corrosion - Principles and
Control, A. S. Khanna et al. (eds.), 1994, pp. 123-136.
5. Processing of ceramics Part. I & II, vol. ed. R. J. Brook, Materials Science and Technology, Vol~ 17A &
17B, Weinheim, 1996.
6. Bauerle, D., Laser Processing and Chemistry - Second Edition, Springer, Berlin, 1996.
7. Nicolas, G., Autric, M., Excimer laser-induced hydrodynamical effects and surface modifications
on silicon carbide, Applied Surface Science, Vol. 96-98, 1996, pp. 296.
8. Nicolas, G., Autric, M., Production of a metallic thin film on AIN surface by UV laser radiation,
Applied Surface Science, Vol. 109-110, 1997, pp. 477.
9. Billy, M., Corrosion des nitrures reramiques it haute temrature, La Corrosion des Materiaux a
Haute Temperature, G. Beranger, J. C. Colson et F. Dabosi (eds.), 1986, pp. 485.

1051
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6. Mumbai. India

Microbiologically Influenced Corrosio"n(MIC) and

Its Mitigation in Industrial Open Recirculati.ng
Cooling Water Systems
G.S. Bhattacharyya
Water R&D Centre, Excel Industries Limited,
V.J.P. Road (Mandai Gathi) Calcutta-700 052, India

ABS1RACf
MiGrobio~ogically influenced
corrosion (MITC) is a type of corrosion where microbes playa dominant role. As an
open recirculating cooling water system is one of the most favoured aquous system
for growth and proliferation of bacteria, bacterial growtbs are more profuse in
Open Cooling water system than any other industrial water system. Overwhelming
majority of the bacterial population in a cooling watersystem, like any other
aquous system, actually live in thick slime-enclosed adherent biofilms on
available submerged surfaces including metals/alloys. The primary mechanism of MITC
of metal surfaces irwolves the creation within the biofilms of local
physicochemical corrosion cells. Biofilm can develop on any metallic surface and
no metal/alloy used in cooling water services is immune to MIC. Mitigation
measures can be so many but the principal measure is proper cooling water
management so as to ensure cleanliness of the cooling water system by subjecting
the same to suitable antiscalant, antifoulant, anticorrosion and antibacterial
cooling water treatment.

The paper incorporates a brief discussion of MIC mechanism, MITC diagnosis and
cooling water treatment that can control MIC.

INTRODUCTION
Present day's industrial open recirculating fresh water cooling systems aim at
operation at highest practically feasible cycle of concentration (C.O.C.), keeping
in mind the limited resources of good quality water and water pollution abatment.
With increase in C.O.C., all the inorganic and organic constituents of
recirculating water increase proportionately but increase of microbial population
becomes infinitely high. So high cycle operation of a cooling water system
increases the deposit forming potential of a cooling water with respect to both
inorganic constituents and microorganisms. Inorganic deposition creates crevices
on metal surfaces where microbes get ready footholds for attachment. Once microbe
attach to form a biofilm, biofilm drags suspended particulate matters in the film
and increases in thickness. So biofilm development and corrosion under the biofilm
(MIC) is a serious problem under modern day's industrial open cooling water
systems. Effective biofouling and MITC control can be achieved in a cooling water

1052
1053
low pH corrosion.

Thus MIC always takes place under biofilm where various species of sessile
bacteria live as a community having symbiotic relationship-one helping the other
for mutual growth and proliferation.

CORRECT MIC MITIGATION MEASURES DEMAND CORRECT "

DIAGNOSIS

Before going for mitigation measures, it is imperative to establish that a

particular corrosion failure is caused by MIC because outwardly most MIC look like
typical chloride induced underdeposit pitting corrosion or crevice corrosion. Thus
comes the necessity of correct identification.

Identification is possible through a combined approach of visual inspection of the

affected part at site and chemical, microbiological and microscopic examination of
deposits properly sampled from the corroded site.

VISUAL INSPECTION

Fresh biofouling deposits are slimy or sticky in touch and often have distinctive
colours and odours. The wet deposits are generally soft or friable and can be
easily deformed in contrast to mineral deposits or ?cales. Deposit colour can also
be telling. Iron-oxidizing bacteria typically produce brown or reddish brown
tubercular deposits on carbon steel and some co loured distinct mounds on
austenitic stainless steel. Through wall penetration of stainless steel tubes due
to gallionella or other iron-oxidizing bacteria generally result in rust coloured
streaks emanating from the penetration and going both up and down. SRB produce
characteristic black pasty deposits on carbon steel and stainless steel with
familier rotten smell of H?S. Slimy deposits on carbon steel and stainless steel
caused by PSEUlXlM::>NASare coloured by the suspended solids they trap from cooling
water environment.
Shape and location of deposits can also be indicative. Distinctive hemispherical
or conical tubercles or nodular mounds on the surface of steel and sub-surface
pitting are characteristic of Iron Bacteria. Pits associated with MIC in most
cases have a small surface opening and a large sub-surface cavity. Tubercles can
be met all over the carbon steel surface wherever cooling water velocity is low or
cooling water flow is intermittent. In the case of stainless steel, small
tubercles or mounds are generally found located at weldments or adjacent areas.

Visual inspection of cooling tower as regards slimy growths on cooling tower

fills, drift eliminators, basin walls or other cooling tower structures coming in
contact with cooling water can also indicate whether potential for MIC ,exists.

CHEMICAL ANALYSES OF DEPOSITS

Presence of high volatile solids (20% or more) in a deposit sample as found by

loss on ignition at 550C + 50C points to high bio-mass content in the deposit
and microbial influence in deposit formation. High iron, manganese, sulphide and
chloride content in deposits disproportionate to their presence in bulk water may
also indicate microbial activities in deposit formation. In recent years ion
chromatography and gas chromatography are being used to analyze deposit samples for

1054
organic acids, hydrogen, CO2, methane other microbial products in deposits.

MICROBIOLOGICAL ANALYSES OF DEPOSITS

methxls
The most familiar am widely practised Afor microqiological analyses are culture
methods. These methods are designed to grow microbes ol>tained from the freshly
collected deposit sample in specific culture media so as to characterize am
enumarate them or isolate them for further stud!es. Traditionally, culture from
suspected MICsites had been attempted only for SRB.But nowit is well recognized
that MICis caused not by SRBalone b..tt a communityof bacteria. Specific media
have come up that can cultivate aerobes, anaerobes, APB am SRB etc. Of late
culture techniques had been further improved am simplified am single mediumhad
comeup which can culture MICinducing r~td forming bacterial communityas a whole
excepting aerobic bacterial species The main problems \11th the culture
methods lie in proper sampling of deposits from the corrosion site so that
microbial population is not disturbed or killed during sampling am proper storage
of the samples till these are used for culturing.
MICKBDPIC ANALYSIS(F IEPa)IT SNfJUS

The microscopic analysis is the simplest, fastest am most precise method' for
identification and enumeration of total numbers of bacteria in a sample.
Microscopic analysis most commonlyinvolve light microscopy am fluorescence
microscopy. Light microscopy can give the total count of bacteria b..tt it can not
distinguish living bacteria cells from the dead cells am bacteria cells from
debris of the same size am shape. Fluoresencce microscopy can differentiate
bacteria cells from debris b..tt like light microscopy fails to differentiate
between living am dead bacteria cells.

CHEMICAL ANDMICROBIOLOGICAL ANALYSES OF COOLINGWATERSAMPLE

HIC potential of a cooling water system can be guessed from chemical am
microbiological analyses of b..tlk cooling water High organics as found from
permanganate value or CODor OOD,high oils/hydrocarbons, high total nitrogen,
high total phosphate, am high HPC/mlor MPNIndex values ~d imicate the
existence of MICpotential.

MANIFESTATIONS
OF MIC IN COOLINGWATERSYSTEMS

In more than 90 percent of cases, MIC takes the form of localized pitting
corrosion urxler tubercles or at crevices. In carbon steel or low alloy steel,
tubercles of various sizes may be rampant am scattered throughout the surface
especially at areas where cooling water velocity is restricted. In stainless steel
too MICmanifest as pitting urxler discrete reddish-brown moundsespecially located
at or near weldments. In copper alloys too MICmostly manifests as ramom pitting
b..tt dealloying attack in admiralty brass am 70/30 ~3)90/10 copper-nickel, because
of microbial activities, had also been reported Few cases have also been
reported where Gallionella, a memberof iron bacteria family, is suspected to have
caused stW corrosion cracking of stainless steel by chloride concentration
mechanism

1055
MIC MITIGATION MEASURES
Whena corrosion failure has been diagnosed to be due to MIC,mitigation measures
can be .taken. 1he measures can be of the following three types :

* Measuresfor a newcooling water system Le. measure$.to be taken at the design

stage, fabrication stage, installation stage and commissioningstage.

* Measuresfor an operating cooling water system.

* Measuresfir idle storage.

MEASURES FOR A NEW SYSTEM

During design stage, due considerat~0n should be given to MICpotential of the
cooling water and design heat exchangers with adequate water flow velocity and
with minimum of crevices. Heat exchangers with shell-side water flow should never
be designed for cooling water systems where cooling water may develop high MIC
potential because of contamination from process and/or environment and high
cycling up.

Correct fabrication, installation and commissioningsteps can eliminate or reduce

manyMICfailures. Inadequate surface preparation, scratches, grinding mark, heat
tints, paint and crayon marking as well as surface defects arising from handling
and fabrication can accelerate MIC.

Lengthy start-up or commissioning of a plant is also responsible for manyMIC

failures in cooling water systems. There have been cases of manyMICfailures of
coolers and condensers because of left-over hydrotest water in the equipments
after hydrotesting was over. Hydrotesting water should be put into an heat
exchangers just before the facility will be put to service. If this can not be
scheduled, the heat exchanger, after hydrotesting, should be completely drained
out and stored dry. Improper commissioningor commissioningin a hurry has also
resulted in many MIC failures of heat exchangers. The cooling water system
including cooling tower pipe lines and heat exchangers should be thoroughly
flushed with high velocity water .to get rld of foreign materials accumulated
during improper storage. After flushing, the system should be thoroughly inspected
and if there are evidences of adherent mill scale or corrosion product, the heat
exchangers in the system mayhave to be cleaned chemically so as to removethese
adherent deposits from the metal surface, otherwise these deposits may promote
biofilm and MIC.

MITIGATION MEASURES IN AN OPERATING COOLING WATER SYSTEM

If a cooling water system is severely fouled by inorganic and microbiological
slime, the system should be mechanically and chemically cleaned to remove the
fouling deposits to the maximum possible extent. Need for precleaning is promoted
from two principal considerations :

1. Inaccessibility of biocidal chemicals to the lower layers of a thickbiofilm

where corrosive bacteria i.e. SRBand APBremain hidden.

1056
1057
manycases better than chromate based technologies.

COOLINGWATERTREATMENT
: BIOFOULING!BIOFILM
CONTROL

In an open recirculating cooling water system planktonic and sessile bacterial

pOpulations co-exist but there is hardly any co-telation between the t:\\O
population types-neither in numbersnor in types. As sessile populations are more
numerous, more resistant and are directly responsible for MIC, cooling water
treatment for MICcontrol must aim at controlling sessile bacterial populations
that form biofilm. Traditional practice of assessing MICproblems and controlling
the same from enumeration of planktonic populations in bulk cooling water from
grab cooling water sampling is erroneous and practically meaningless because the
biofilm causing sessile bacteria that may be found in planktonic stage in bulk
water at a particular point of time only represent that small proportion of active
sessile population that happen to detach from the biofilm and enter the bulk water
phase because of change in water shear force or other mechanical/chemical
disturbances.

Thus knowingthe types and numbersof sessile bacterial populations in biofilm by

correct sessile sampling procedure is most important so far as MICcontrol by
chemical treatment is concerned. As sessile sampling demandsscrapping of biofilm
from the surface, this is difficult to perform in a running cooling water system
without taking the equipment shut down. An ingeni~ way of sessile sampling is
use of a test tack similar to corrosion coupon rack 8l which maybe installed at
a by-pass of the cooling water outlet line of a critical heat exchanger. Test
coupons similar to corrosion coupons can be inserted at various locations of this
test rack through which cooling water would flow at velocity and temperature
conditions simulating those of the heat exchanger in question. With passage of
time biofilm would grow on the coupons along with other fouling deposits including
corrosion products. After a predetermined exposure time, the coupons ~uld be
taken out and the foulants accumulated on the coupon surface scrapped with a
sterile S.S. spatula/scalpel and the scrapping transferred aseptically into a
sterile culture bottle containing sterile distilled water. The bottle is
thoroughly shaken to disintegrate the mass and homogenizethe sample. This slurry
can serve"the pu~se of sessile bacterial sample for fin:Jirg
responsible for b10film formation and MIC.
BlOCIDES FOR BIOFILMCONTROL

An effective biocide is one which can penetrate the biofilm, kill the biofilm
bacteria layer by layer and dislooge the biofilm completely. This task is made
difficult whenthe biofilm reaches a thickness which does not allow penetration of
biocide to the innermost layer .. In this situation, a dispersant/surfactant/wetting
agent can assist the biocide.
Thu broad types of biocides are used for biofouling control in cooling water
systems viz. oxidizing biocides and non-oxidizing biocides.

OXIDIZINGBIOCIDES

Chlorine, added as chlorine gas or liquid sooiumhypochlorite, is by far the most

commonlyused oxidizing biocide. But toxicity associated with chlorine or
chlorinated organics. loss in efficiency at alkaline pH.or in ammonia/organic

1058
1059
1060
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai. India

Synergistic and Biocidal Effects of a Phosphqnate-Metal Ion-

Biocide System on the Inhibition of Corrosion of Mild Steel
in Neutral Aqueous Environment
Susai Rajendranl, B.V. Apparao2 and N. Palaniswamy3
[Department of Chemistry, G.T.N. Arts College (Autonomous), Dindigul-624 005, Tamilandu, India
2Dept. of Chemistry, Regional Engineering College, Warangal-506 004, India
JCoITosion Science and Engineering Division, Central Electrochemical Research Institute,
Karaikudi-630 006, Tamilnadu, India

ABSTRACT

1061
1062
1063
Figure I Potentiostatic polarisation curves of
mild steel in various environments

(a) Cl-1 60 ppm

(b) Cl-1 60 ppm + PAA 50 ppm
(c) CI-1 60 ppm + HEDP 300 ppm
(d) crl 60 ppm + Zn2'" 50 ppm
(e) cr1 60 ppm + PAA 50 ppm +
HEDP 300 ppm + Zn2 .. 50 ppm

Figure 2 FIlR spectra

(a) PAA
(b) HEDP
(c) Film formed on the surface of the metal
immersed in the environment containing
Cl-1 60 ppm + HEDP 300 ppm +
PAA 50 ppm + Zn2 .. 50 ppm

1064
Figure 3 Luminescence spectra of the film formed on surface of the metal
immersed in various environments

(a) CI-1 60 ppm + HEDP 300 ppm + PAA 50 ppm

(b) CI-1 60 ppm + HEDP 300 ppm + PAA 50 ppm + Zn2+ 50 ppm

1065
 3. The protective film was found to be luminescent.

4. The above formulation controlled the cathodic reaction

predominantly.

5. The above formulation may find apijlication in cooling

water systems. --

REFERENCES

1. Sekine, I. and Kirakawa, Y., Corrosion, Vol. 42, 1986,

p.276.

2. Fang, J.L., Li, Y., Ye, X.R., Wang, Z.W. and Liu, Q.,
corrosion, Vol. 49, 1993, p. 266.

3. Horvath, T., Kalman, E., Kutsan, G. and Rauscher, A.,

Br. Corrosion Journal, Vol.29, 1994, p.215.

4. Du Thanbao, Chen Jiajian, Cao Dianzhen and Cao Chunan,

Bulletin of Electrochem., Vol.13, 1997, p.13.

5. Gunasekaran, G., Palaniswamy, N., Apparao, B.V. and

Muralidharan, V.S., Electrochim. Acta, Vol.49, 1997,
p.1427.

6. Rajendran, 5., Apparao, B.V. and Palaniswamy, N., Proc. 8th

Europ. Symp. Corros. Inhibitors, Ferrara, Italy, Vol. 1,
1995, p. 465.

7. Rajendran, 5., Apparao, B.V. and Palaniswamy N., Bulletin of

Electrochem., VOl.12, 1996, p.15.

8. Rajendran, 5., Apparao, B.V. and Palaniswamy N., Proc.

2nd Arabian Corrosion Conference, Kuwait, 1996, p.483.

9. Rajendran, 5., Apparao, B.V. and Palaniswamy N.,

EUROCORR'97, Trondheim, Norway.

10. Rajendran, 5., Apparao, B.V. and Palaniswamy N., Anti-

Corrosion Methods and Materials, in Press, 1997.

11. Hatch, G.B. and Ralston, P.H., Mat. Pro. Perf., VOl.1l,
1972, p.39.

12. Horner, L. and Horner, C.L., Werkst. Korros., Vol. 27, 1976,
p. 223.

1066
 Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Effect of the Addition of In3+, Sn2+ and Zh2+ Ions on the

Electrochemical Behavior of AI-Zn, AI-In and AI-Sn
Binary Alloys in 3.5% NaCI
A. Venugopa~and V.s. Raja
Corrosion Science and Engineering, Indian Institute of Technology,
Powai, Mumbai-400 076, India

ABSTRACT
3
The effect of the addition of In +, Sn2+ and Zn2+ ions on the electrochemical corrosion behavior of AI-Zn, AI-
In and AI-Sn binary alloys in 3.5% NaCl has been investigated using, polarization and AC impedance and x-
ray photoelectron spectroscopy. It was found that Zn added to AI-In or AI-Sn acts synergistically with the
activators to enhance the dissolution of AI. However, the synergism between Zn and In 'is stronger than that
between Zn and Sn. Based on impedance and XPS results the existence of cations with valencies other than
2 2 4
3 (In+/In + and Sn +/Sn + ions) in the films have been suggested to be responsible for generation of point
defects in the film, which in turn activate AI.

INTRODUCTION

AI-Zn(5wt%) alloys containing either In or Sn as activator are widely employed as sacrificial anodes
for the cathodic protection of steel structures especially in sea water[1,2]. Earlier work on these types of
anodes were directed mainly on the electrochemical corrosion behavior in relation to corrosion potential,
current efficiency and current output as they are primary factors that decide the applicability of these a1loys[3-
5]. Among the above factors, the literature indicates that the anodes offer potentials which are well below the
required value of -1.00 V against saturated calomel electrode. However, with regards to efficiency and current
output there is more scope to improve. To achieve the above, more specifically the current output, it is
essential to understand the role of alloying elements on the dissolution process involved.

The dissolution process can be studied, by deliberately .adding various cations to the solution and
examine the electrochemical behavior of AI. This type of work becomes relevant in the sense that once the
anodes dissolve, metallic cations will be created in solution which in turn may influence the passivation
behavior of AI. Since, In and Sn activated AI-anodes are ternary alloys of Al-Zn-In and Al-Zn-Sn it is worth
while to investigate systematically the role of In3+, Sn2+ and Zn2+ cation on the binary AI-In, AI-Zn and Al-Sn
alloys. One of the authors, as a first step, reported the role of various cations on the electrochemical behavior
of pure Al in 3.5% NaCl solution[6]. The present work is the continuation of the above work to examine the
effect of these cations in the ternary AI-alloy anodes.

1067
EXPERIMENTAL METHOD

Binary AI-5Zn, AI-0.05In, AI-

0.03Sn and ternary AI-5Zn-0.03In, AI-5Zn-
0.03Sn (compositions are in wt%) were
prepared from 99.999% purity aluminum.
These alloys were prepared using graphite
crucibles in a resistance heating furnace
shielded with argon gas atmosphere. The
cast alloys were homogenized at 550C for
24h followed by quenching in water.
Electrodes were made from these alloys
with an area of 0.4cm2 and were mounted
using cold setting resin with one end
soldered to a copper wire. The electrodes
were polished on SiC paper down to the
grade 1000 and finally washed with distilled
water and methanol.

The electrochemical cell used for the present study was a glass vessel similar to ASlM G5
specification. Unstirred 3.5% NaCI solution, prepared using distilled water freely exposed to the atmosphere,
was used as the corrosive environment. An EG&G PARC potentiostat 273 and a Solartron 1255 frequency
response analyzer driven by m352 and m388 softwares were used to carry out electrochemical experiments.
Impedance measurements were made in the frequency range of 105 to 10-2 Hz. The potential measurements
were undertaken with a saturated calomel electrode(SCE) as a reference electrode.

The electrochemical behavior of binary AI-alloys were studied by adding cations of In3+, Sn2+ and
Zn2+ in the form of InCI3, SnCl2 and ZnCl2 salts respectively to the working electrolyte. For XPS(x-ray
photoelectron spectroscopy) study, binary AI-3In, AI-3Sn alloys were used. Spectra were generated using Mg
Ka (1253 eV) x-ray source operated at 8keV and 20mA emission current. Binding energies were normalized
to that of peak at 284.7eV corresponding to adventious hydrocarbon. The variation in the nature of oxide
along the thickness was determined by sputtering the films with.Ar ions of 3keV and 20mA energy.

RESULTS
The polarization behavior of Al and its alloys obtained in 3.5% NaCI is shown in Fig.l. From the
figure it is seen that pure Al exhibits strong passivity with a pitting potential of -O.72V. The binary AI-Zn
alloy exhibits relatively low passivation current density than that of pure Al despite the fact that it has a very
narrow range of passivation ending at the pitting potential of -"V. With respect to binary alloys having
activators, it seems passivity is completely eliminated in the case of AI-Sn, while iIi the case of AI-In, close
to Ecorr the anodic curve exhibits soine sort of resistance of this alloy for complete activation. However, if
Zn is added, the alloy completely becomes active. In the case of AI-Sn system, the addition of Zn seems to
raise the Ecorr. To study the possible effect of In, Sn and Zn on the passivity of binary alloys, impedance
studies were further conducted. This was done by adding various cations in NaCI solution.

The impedance spectrum of AI-Zn shown in Fig.2a exhibits two well separated capacitive loops. The
addition of 0.006M In3+ ions to AI-Zn alloy gives raise to two inductive loops starting at 6.3Hz and 0.15Hz
(Fig.2b) while at the same time eliminating the low frequency capacitive loop. Addition of 0.004M Sn2+ ions
with AI-Zn alloy also exhibits similar behavior with two inductive loops (Fig.2c). Fig.3a shows the impedance
plot of AI-In alloy, which exhibits a single time constant over the entire frequency range with some points

1068
lying scattered in the second quadrant of the
complex plane diagram falling in the very
low frequency range. The data points lying
in the second quadrant is indicative of an
inductive behavior. The addition of O:04M
Zn2+ ions leads to two elongated semicircles
in the Nyquist plot with the absence of
inductive behavior (Fig.3b). The impedance
behavior of Al-Sn alloy shows a definite
high frequency capacitive 100p(Flg.4a).
There seems to be a possibility of the
emergence of another capacitive loop in the
low frequency region. Zn2+ ions added with
AI-Sn alloy (Fig.4b) shows similar behavior
as in Fig.3b, in the sense that two capacitive
semicircles are seen.

Comparison of Figs 4 and 5 clearly

shows that the effect of Zn is same whether
it is added with AI-In or AI-Sn. As Zn ions
readily precipitate on the surface as
Zn(OHh film[7], the appearance of the
second capacitive semicircle can be ascribed
to this phenomenon as has been suggested
by Epelboin et al for Fe-system[8].
Previous investigators have suggested the
inductive loop formation can be as a result
of formation of intermediates during
corrosion process[8,9]. Accordingly the
appearance of one of the inductive loops due
to the addition of In3+ and Sn2+ ions can be
ascribed to the formation and adsorption of
reaction intermediates.

Attempt is made to identify these

intermediates using XPS analysis after
immersing AI-Sn and AI-In alloys in 3.5% NaCI solution for lh. Fig.6 corresponds to Sn(3d) spectra of AI-Sn
alloy clearly showing the existence of 3d3/2 and 3dS/2 energy levels. Notably, the peaks corresponding to
Sn3d3/2 and Sn3ds/2 became broader on sputtering. As the peaks contained shoulders they were deconvoluted
tor further analysis. Fig.7 delineates various deconvoluted peaks. Three deconvoluted peaks at 488.6,486.3
and 484.6 eV corresponding to Sn(3d)s/2 energy level are seen in the figure. Comparing the bindin~ energies
of these peaks with that given in literature these peaks respectively can be attributed. to Sn4+, Sn + and Sn
species[IO]. From the raising intensity of the shoulder with sputtering of the oxide film, it can be said that
1bere was an apparent increase in the concentration of Sn2+ at the expense of Sn4+ in the film as the film was
sputtered .. Now the question arises as to whether Sn4+ got reduced to Sn2+ during sputtering or was the
original constituent of the oxide film. The earlier work by Barr[lO] showed that Sn4+ was stable and did not
zet reduced to Sn2+ and the latter species co-existed with Sn4+ in the film. Nevertheless, the possibility of
air oxidation during the transfer of sample from the solution to vacuum chamber in XPS can not be ruled out
as a cause for absence of Sn2+ in the surface of the film. Efforts to detect the existence of lower valent
(In+/In2"1 ions through XPS were failed as these ions seem to be stable only in aqueous conditions and only

1069
DISCUSSION

The results obtained in the l+resen1

study indicate that the cations Zn + witl1
In3+ and Zn2+ with Sn2+ act synergistically
towards the electrochemical behavior of AI
Zn-In and AI-Zn-Sn anodes in the following
ways. i) optimize the c~rrosion potential
and ii) completely activating the alloy
Optimising Ecorr is essential, because if it i!
too low, then the hydrogen evolution on AI
will be facilitated and thus will reduce it!
life. On the contrary, if the Ecorr is on the
higher side, then there will not be enough
driving potential to protect the steel
structures. Thus Zn along with AI-In
shifted its potential from -0.998V to .
1.018V although this variation is only to a
smaller extent, while the potential of Al-Sn
changed from -1.39V to -1.l2V as a result
of Zn alloying. Hence, Zn optimises the
corrosion potential of binary AI-In and Al-
Sn alloys towards the better performance 01
the ternary anodes, though its effect is more
when it is added with AI-In as compared to Al-Sn. This effect is also reflected in the impedance response of
the alloys in the following manner. The Ry value of AI-In decreases from 2800 to 30 ohms as a result of Zn2+
addition. On the other hand, the ~ value of Al-Sn decreases only from 1250 to to ohms. The larger
reduction in Rp of AI-In due to Zn2 is also seen from the polarization curve in the sense that the small
passivity of AI-In alloy close to Ecorr is completely eliminated in AI-Zn-In alloy'.

As stated above, Zn tends to passivate at pH 7 due to the formation of Zn(OHh film. Since
passivation is a dynamic processes involving dissolution and precipitation, Zn2+ ions can get incorporated into
Al203 oxide film. It has been shown earlier that ZnO forms ZnAl204 phase with Zn2+ in the interstitial
position[l2]. X-ray diffraction study carried out on AI-Zn after immersion in 3.5% NaCl for 48h did not
reveal any information about the oxide film possibly due to smaller thickness of oxide. However, XPS shows
the co-existence of Zn2+ with Al203 indicating that there is a possibility of existence of ZnAl204 phase in the
oxide film (Fig.8). If ZnAl204 is assumed to be formed then Al203 film will have excess electrons and
enhanced cationic mobility. Therefore, the increase in electronic conductivity on one hand reduce the field
across the film enhancing passivity[13] as is evident from polarization measurements. On the other hand,
because of this excess charge the break down potential of the near insulating film comes down.

In general the added cations to the electrolyte decreases the Rp value of binary alloys with a
simultaneous large increase in fmax value corresponding to high frequency capacitive loop. This can arise
when the relaxations with in the film becomes faster. This would be possible only when more defects are
created within the passive film. The rationale behind the generation of defects due to the addition of In and
Sn is discussed below.

Among the cations, In3+ and Sn2+ addition with AI-Zn promotes inductive loops while Zn2+ addition

1070
1071
REFERENCES
1. Reding, J.T., . Newport, J.J, Materials
Performance, Vol. 5, no.9, 1960, p.15
2. Keir, D.S, Pryor, MJ., Sperry, P.R.,
J.Electrochem. Soc., Vo1.114, 1967,
p.777
3. Burri, G., Luedi, W., Hass,O., J.
Electrochem. Soc., Vol. 136, 1989,
p.2l67
4. Lennox, JR., Groover, R.E., and
Peterson, M.H., Materials
Performance, Vol. 10, 1971, p.39
5. Sakano,T., Toda, K., and Hanada, M.,
Materials Protection, 12, no.12, 1966,
p.15
6. Raja, V.S., Proceedings of Second
International Conference on Surface
Engineering 7-10 March (1994),
Adelaide, Australia, p.c380
7. Raymond Jasinski, High-Energy
Batteries, 1967, p.159, Plenum Press,
New York
8. Epelboin, 1., Keddam, M., and J.c.
Lestrade, J.C., Transactions of Faraday
Society, Vol. 56 1973, p.264
9. Venugopal, A., and Raja, V.S.,
Corros. Sci. (In press)
10. Barr, T.L., J. Vac. Sci., Vol. 14, 1977,
p.660
11. Cotton, FA, and Wilkinson, G.,
Advanced Inorganic Chemistry, Inter
Science Publications, New York, 4th Edn., 1980, p.326
12. Donald L. Branson Journal of Am. Ceramic Soc. VolA8, 1965, p.59l
13. Bockris, J.O'M., and Reddy, A.K.N., Modem Electrochemistry, Vo1.2, Plenum Press, New York 1970,
p.13l8
14. Marcel Pourbaix, Atlas of Electrochemical Equilibria in Aqueous Solutions 1st Edn. Pergamon Press,
London, 1966, p.436
15. Idem, ibid, p.477

1072
1073
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Hydrogen Embrittlement BehavioI1-of Three High

Manganese Stainless Steels
V.S. Raja and A. Devasenapathi
Corrosion Science and Engineering,
Indian Institute of Technology,
Powai, Mumbai-400 076, India

ABSTRACT

Hydrogen embrittlement (HE) behavior of three commercial grade high Mn stainless steels with
varying Ni content was examined. Both constant load tests, under continuous cathodic charging, and constant
extension tests of charged samples were carried out. Both the types of tests indicated that the susceptibility
of the alloys towards HE to follow the order Grade 3 > Grade 2 > Grade 1 > AISI 304. Cathodic hydrogen
charging was found result in the appearance of EH martensite in all the three Mn stainless steels, while the
tensile test specimen fractured in air was found to contain stress induced a' martensite. Since the
susceptibility of the alloy towards HE did not seem to correlate with H content of the alloy, the formation of
EH and a' martensites were suggested to be responsible for the higher susceptibility of Mn stainless steels
towards HE.

INTRODUCTION

AISI 304 ss has several attractive properties, such as good corrosion resistance, formability and
weldability that make this material a better choice for a variety of industrial applications. In order to make
this material cost effective, Ni has been replaced partly or fully by Mn as the latter is not only a low cost
element as compared to Ni but also a good austenitic stabilizer. Another beneficial effect of Mn is that in its
presence N content of stainless steels can be significantly increased. The high Mn alloys with higher N
content provide excellent mechanical properties such as high yield strength combined with good ductility.
Systematic studies in our laboratory showed that these alloys offer better stress corrosion cracking resistance
(SCC) (1) and intergranular resistance (IGC) (2) in comparison with AISI 304 ss. It is interesting to examine
the hydrogen embrittlement (HE) behavior of these alloy. While several studies exist on HE behavior of AISI
304 ss (for example ref.3-12) study on Mn stainless steels are sparse (13-16). The role ofMn were reported
to be conflicting in nature. Thus studies involving high Mn stainless steels exposed to high pressure hydrogen
gas at around 200C by Pemg and Altstetter (15) indicated that they are insensitive to HE, while similar
studies by Louthan et al (16) showed that Mn stainless steels were susceptible to HE. The situation is not
different even with respect to SCC of these stainless steels where deleterious (17,18) as well as beneficial
effects (19, 18) ofMn were reported. Therefore, a study was undertaken to examine the HE behavior of three

1074
commercial grade high Mn stainless steels. These
alloys were compared with AISI 304 ss under
identical conditions. The present wode is different
from the previous studies by Pemg and Altstetter
(15) and Louthan et al (16) in the sense that these
studied involved exposing the alloys to high
pressure molecular hydrogen at about 200C while
the present study involved cathodic charging of
hydrogen from an acid solution.

EXPERIMENTAL PROCEDURES

Chemical composition of stainless steels

used for the present study are AISI 3'04: 0.04C-
0.71 Si- I. 72Mn-8.5Ni- I 8.8Cr-0.046P-0.019S-
0.017N-0. 12Cu, Grade I: O.062C-0.38-Si-8.24Mn-
4.62Ni-15.2Cr-0.065P-0.OISO.097N- I .03Cu, Grade
2: 0.057C-0.47Si-9. 14Mn-2.05Ni- 14.64Cr-O.058P-
0.005S-0.092N-I.72Cu, and Grade 3: 0.075C-
O.48Si -9.25 -Mn-O. 87Ni- I 5. 93Cr-0. 060P-0. 0 I 6S-
0.2N-I.8Cu. All three grades ofMn stainless steels
were used in the solutionised condition after heat
treatment at a temperature of I 100C in nitrogen
atmosphere for Ih followed by water quenching.
Studies were carried out with specimens of 600 grit
surface finish.
For hydrogen embrittlement studies flat
tensile specimens' of 25mm gauge length, 6mm
width, Imm thickness and 40mm reduced length
machined from IOOmmlength strips were used (20).
Two different test methods namely continuous
charging under constant load and constant extension
after precharging were carried out to study the
hydrogen embrittlement behavior of stainless steels.
Cathodic hydrogen charging was carried out at a
current density of 2OmA/cm2 in a solution of IN ~ S04 + 25Omg/I of sodium arsenite using Pt foil as an
anode in a manner similar to that reported elsewhere (12).. In continuous charging tests the specimens were
tested at 75% of their yield strength and the time taken for complete fracture was taken as the time to failure.
In constant extension test specimens were tested at a strain rate of 6.6xI0-4/s using a tensiometer. Though the
strain rate used in the case is relatively higher, it was sufficient to bring out the effect of hy4rogen in a relative
sense. Notably Liu eta! (21) and Hanninen and Hakarainen (22) could bring out the effects of hydrogen even
with strain rates of 3.3 xIO-4/s and 8.3xI0-2/s respectively. Specimens were tested both in the uncharged
condition. and after precharging for 24, 48 h respectively to find out the change in material parameters like
yield strength, ultimate tensile strength and elongation to fracture. The specimens after failure were tested
under a scanning electron microscope (SEM) to find out the change in fracture morphology. The quantity of
hydrogen diffused into the alloys after cathodic charging for 48h was calculated using specimens of
20x20xlmm dimension in triplicate. After charging, the specimens were transferred into a hydrogen extraction
cell of a gas chromatograph which was heated to 200C for 6h.. The extracted hydrogen was then carried
using Ar gas to a precalibrated gas chromatographar and analyzed.

1075
 To find out the phase changes during straining the specimens surfaces after tensile testing in air were
analyzed in a x-ray diffractometer (XRD) using Fe Ka radiation. Also to find out the phase changes involved
during hydrogen charging, the specimens were tested using XRD after charging for 48h. The specimens were
also aged .for 24h at room temperature in air after cathodic charging to find out the phase changes involved.

RESULTS AND DISCUSSION

Hydrogen embrittlement results of tests

involving during continuous cathodic charging
under uniaxial tension are given in Table I.
The time to failure, an indication of the
susceptibility of the alloy to HE, decreases in
the order 304 > Grade I > Grade 2 > Grade 3.
The susceptibility of the alloys towards HE was
also examined from the point of view of various
tensile parameters. Table 2 summarizes the
tensile test data for all the four stainless steels
before and after subjecting them to cathodic
charging at 24h and 48h. The reduction in
ductility reflects the same trend as that of
uniaxial tension testing results with respect to
susceptibility of Mn steels towards HE.
However, the yield strengths {If Mn stainless
steels have been found to be higher than that of
304 ss even in the charged conditions suggesting
that Mn addition promotes HE resistance and
continuous charging experiments should have
been carried at one particular stress level for all
the grades. This apparent contradiction can be
resolved by analyzing the data in the following
manner. Notably, the tensile data of the
uncharged samples indicates that Mn imparts high strength as well as high ductility to austenitic stainless
steels. Therefore this increase in yield strength off-sets the actual reduction brought out as a result of hydrogen
in the samples. In order to compare the all the alloys the following factors are used.

These values given in the Table 2 are in close agreement with the trend reflected by the reduction in ductility
and the time to failure determined from two different experiments. In deed it is worthwhile to mention the
fact that the Mn stainless steels would have failed at higher time intervals if the all the grades were tested at
one particular stress level. This would have implied that the modified composition promotes HE resistance.
Which is not the case. Comparison of the data between samples charged at 24h and 48h indicates that the
samples become more susceptible as charging time is increased. This might arise out of the fact that amount
of hydrogen in the sample is expected to go up. Studies reported earlier(23) also show a similar increase in
the degree of embrittlement with charging time.

1076
 Hydrogen content of the alloy is an
important parameter that gives a measure of
diffusivity of hydrogen in an alloy(24). The
diffusible hydrcgen present is Bxpected to migrate
to the crack tip for promoting HE(25,26). The
hydrogen content of alloys after cathodically
charged for 48h was determined by degassing them
at 2000 C for 6h ( Table 3). The hydrogen content
of stainless steels barring Grade 3 alloy, which has
the lowest value, does not seem to differ much.
Therefore the difference in susceptibility of the
alloys can not be explained based on hydrogen
content of the charged alloy.

Possibility of phase transformation

associated with cathodic charging were further
examined by x-ray diffraction. Figure I shows the
appearance of gH martensite phase in the most
susceptible alloy namely, Grade 3 after subjecting
it to cathodic charging. AISI 304, Grade 2 and
Grade 3 alloys after 48h of cathodic charging also
showed the formation of gH phase. Similar gH
martensite phase formation in ternary Fe-Ni-Mn
austenitic steels have been reported by Nishino etal
(27). However room temperature ageing for 24h
leads to a reduction in peak intensity
corresponding to gH. This is in agreement with
Usui and Asano who have reported that gH is stable
only during the alloy exposed to aqueous solutions
and not in air (28). While the transformation from
gH phase to u 'that was reported to take place in
304 ss (28-31) after outgassing, Mn stainless steels
in the present work do not reveal such a
transformation thus behaving in a manner similar to
that of Fe-50Mn (32). Nevertheless these alloys
exhibit (Fig. 2) the presence of u ' martensite
phase after subjecting them to tensile deformation
in air. This observation is in agreement with the
results of Liu et al(21). The presence of
a'martensite can significantly influences the HE
behavior of an austenitic stainless steel(22). It has
also been reported that a' martensite formation increase with decrease in Ni (33), and Cr (21) contents of the
alloy. Thus the variation in composition with the alloys might bring out a similar effect.

Fig.3 shows the fractographs of uncharged and charged (48h) Grade I stainless steel after subjecting
them to tensile tests. The fractograph of uncharged sample shows dimples throughout the fracture surface
revealing a ductile mode of fracture by micro void coalescence. The fractograph of the charged sample on
the otherhand shows a brittle transgranular cleavage mode with several secondary cracks in it. Under
continuous cathodic charging at constant load all the three Mn stainless steels undergo a predominantly
transgranular mode of cracking with small amount of intergranular cleavage, while 304 stainless steel exhibits

1077
 a complete transgranular mode of cracking. The
nature of fracture swface obtained for Grade -2 is
shown in Fig. 4. The fractograph (Fig.4a) shows
that the alloy undergoes a predominantly
transgranular brittle fracture that starts from the
edges and a small amount of intergranular cracking
that ends in the middle of the test specimen. The
high magnification fractograph in Fig.4b reveals the
transgranular mode of failure with the slip lines on
the fracture surface. The fractograph of Grade 3
alloy failed during continuous cathodic hydrogen
charging under constant load is shown in Fig. 5. A
close examination of the fractograph reveals
additional features indicated by arrows. These
feat. ,es are expected to arise due to the fonnation
(indicated by 1) of either a brittle phase(34, 35) or
twins(35). In addition, the fractograph of Grade 3
shows the presence of voids (indicated by 2)
around the precipitates and other boundaries on the
fracture swface. This is reported(31,36) to be due
to the accumulation of hydrogen around precipitates
and bursting of hydrogen bubbles at high pressure.
Since these phases can act as irreversible trap sites
for H, this might be a probable cause for low H
content detected in the chromatograph inspite of the
fact that Grade 3 is the most susceptible alloy to
HE.

SUMMARY

Though the high Mn stainless steels used in

this study posses high yield strength combined with
very good ductility, the following factors
unambiguously illustrate that they are more Fig. 4 Fractographs of Grade 2 alloy: a) predominant
vulnerable to hydrogen embrittlement than that of transgranular cracking at the edges with a small intergra-
304 stainless steel; a) the reduction in time to nular cracking at specimen center and b) transgranular
failure exhibited by constant load experiments, b) mode of cracking with slip lines on the fracture swface
the loss in % elongation shown by tensile test, c) are shown
the low degree of susceptibility as illustrated by
a/uncharged)/o'y<charged) and d) a clear brittle fracture delineated by the fractographs. From the
compositional point of view Mn stainless steels, in general, differ from AISI 304 ss by having significantly
high Mn and low Ni contents and relatively higher levels of Cu, C, N and P contents in comparison with the
latter. With in Mn stainless steels Ni is reduced systematically from 4.62 to 0.87, Cu is increased from 1.03
to 1.87 and with regards to the interstitial elements, namely, C and N there seems to be no systematic order
though Grade 3 alloy has higher C and N content. In the light 'of simultaneous variations in a variety of
clements it would be difficult to attribute which of these elements responsible for the enhanced susceptibility
of the high Mn stainless steels. Conflicting claims have been found in the literature regarding the role of Mn
with regards to SCC and HE. Mn alloys exposed to gas phase at about 200C have been shown to be both
insensitive (15) and susceptible (16) to HE. Based on boiling 42% MgCl2 experiments Kowaka and Fujikawa
(17) have reported an increase in susceptibility due to Mn. On the contrary Bamatt et al (18) and

1078
Devasenapathi et al (1) have reported a marginal raise in resistance to SCe. It is interesting to note that the
only high Mn alloy tested by Kowaka and Fujikawa contained relatively higher amount ofN, which according
them also brings down SCC resistance. In this sense the higher susceptibility of Grade 3 alloy compared to
Grade 2 would be essentially attributed to N as it is only with respect to this element the composition of the
alloy is significantly different and the decrease in Ni content in this range is only expected to reduce
susceptibility. Interestingly though Mn and Ni in Grade 1 differ signific$1tly from AISI 304, there is an
appreciable increase in Cu and N levels in Grade 1 alloy. Since in accordance with Perng and Altstetter(15)
Cu and N promote HE susceptibility of austenitic stainless steels, the role of Mn can not be ascertained
unambiguously.

Detailed microscopic examination by Liu et al (21) brings out the underlying reason behind the
superior resistance of AISI 310 over AISI 304 towards resistance to failure in boiling 42% MgCl ~ solution.
According to them AISI 304 is prone to the formation of brittle a.'martensite and therefore unde;goes both
SCC and HE, while on the other hand AISI 310 resists the formation a.'martensite due high Cr/Ni ratio and
undergoes SCC. Since the XRD data shows that these alloys .give rise to.!;H martensite due to cathodic
charging and a.'martensite due to deformation even in the absence of hydrogen (Fig. 2) it is probable that their
formation during testing would promote HE. The fracture surface of Grade 3 alloy (Fig.5) indeed exhibits
feature similar to formation of martensites. Such features are not very revealing in other alloys which are less
susceptible. A systematic study by Hanninen and Hakarainen (22) further indicates that increasing
a.'martensite content enhances the susceptibility. Therefore an extensive study to quantify the ability of these
alloys to form a. ' martensite and its effect on HE
will be more useful. In this respect it is
worthwhile to compare the present work with our
previous work on SCC of the same alloys in
boiling 42% MgCl2 (1) where we had reported that
they posses better SCC resistance as against the
higher HE susceptibility of these alloys compared
to AISI 304 Examination of the fractographs
indicates the probable reasons behind this. These
alloys fail by intergranular mode in boiling MgCI2,
while they show transgranu1ar cleavage fracture in
the hydrogen charged condition. Since
a.'martensite is expected form even on those
samples subjected to SCC, as they are subjected to
stress, whether or not the formation of !;H
martensite due to hydrogen in the samples is
responsible for the change in mode of fractures
Fig. 5 Fractograph of Grade 3 alloy showing a brittle
needs further examination.
transgranular mode of cracking with a brittle phase or
twins (indicated by I) and voids (indicated by 2)
References
I A. Devasenapathi, G. S. Ramakrishna and V.
S. Raja, 1. Mater. Sci. Let., 14,(1995)1254
2 V. S. Raja and A. Ramkumar, Br. Corrosion J. - in press
3 R.B. Benson, R.K. Dann and LW. Roberts, Trans. TMS-AIME, 242 (1968) 2199.
4 M.L. Holzworth and M.R. Louthan, Corrosion, 24 (1968L 110.
5 AW. Thompson, Metall. Trans. 4 (1973) 2819.
6 M.L. Mehta and 1. Burke, Corrosion, 31 (1975) 108.
7 e.L. Briant, Script, Metall., 12 (1978) 541.
8 M.R. Louthan, G.R. Caskey, 1.A. Donovan and D.E. Rawl, Mater.Sci.Eng., 26 (1972) 357.
9 M.B. Whiteman and A.R. Troiano, Corrosion, 21 (1965) 53.

1079
 10 M.L. Holzworth, Corrosion, 25 (1969) 107.
II M.L. Holzworth and M.R. Louthan, Corrosion, 24 (1968) 110.
12 D. Eliezer, D.G. Chakrapani, C.J. Altstetter and E.N. Pugh, Metall. Trans.A., lOA (1979) 935.
13 A.W. Thompson and I.M. Bernstein, Rev. Coatings Corros, 2,3 (1975)
14 A.W. Thompson, Hydrogen in Metals, Eds., I.M. Bernstein and A.W. Thompson, ASM, Metals Park,
Ohio, (19740 p.91. . t
15 TP. Perng and C. J. Alstetter, Mater. Sci.Engg. A129(1990)99
16 M.R. Louthan, Jf. G.R. Caskey, 1.A. Donovan and D.E. Rawal Jr., ibid,
17 M. Kowaka and H. Fujikawa, Stress Corrosion Cracking of Austenitic Stainless Steels in Chloride
Environments, in Localized Corrosion, Eds. 437
18 A.W. Loginow and J.E. Bates, Corrosion, 25(1969)15
19 Bamatt, R. Stickler and D. van Rooyan, Corros. Sci., 3, (1963)9
20 A. Devasenapathi, R. C. Prasad and V. S. Raja, Scripta Metallurgica et Materialia, 33(1995)pp.233-238
21 R. Liu, N. Narita, C. Altstetter, H. Birnbaum and E. N. Pugh, Metall. Trans. A., llA, 1563 (1980).
22 H. Hanninen and T Hakarainen, Corrosion, 36(1980)47
23 M. B. Whiteman and A. R. Troiano, Corrosion, 21, 53 (1965).
24 T K. G. Namboodhiri, Ind. Inst. of Metals, 37, 764 (1984).
25 A. R. Triano, Trans. ASM., 52, 54 (1960).
26 1. P. Hirth, Metall. Trans A., llA, 861 (1980).
27 Y. Nishino, M. Obata and S. Asano, Scripta. Metall., 24; 703 (1990).
28 Makoto Usui and Shigeru Asano, Scripta. Metall, 31, 445 (1994).
29 M. L. Holzworth and M. R. Louthan, Corrosion, 24, 110 (1968).
30 H. Okada, y. Hosoi and S; Abe, Corrosion, 26, 183 (1970).
31 N. Narita, C. 1. Altstetter and H. K. Birnbaum, Metall. Trans. A., 13A, 1355 (1982).
32 M. Usui and S. Asano, 1. Japan Inst. Met., 50, 943 (1986).
33 V. V. Kutumba Rao and P. Rama Rao, Script. Metall., 6, 1103 (1972).
34 J. Chene, 1. Ovejero Garcia, C. Paes de Oliveira and M. Aucouturier, 1. Microsc. Spectrosc. Electron.,
4,37 (1979).
35 Yutaka Moriya, Haruo Suzuki, Shuji Hashizume, Tetsuya Sampei and Isoo Kozasu, Pro. of Int. Conf. on
stainless steels, Chiba, ISIJ, Japan, Vol. 1 (1991) p.527.
36 C. Zapffe and C. Sims, Trans. AIME., 145, 225 (1941).

1080
1081
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Hydrogen Embrittlement Studies of

API 5LX 52 Pipeline Steel
R.C. Prasad" H. Avinash" T.R. Reddy" Viju Cherian2,
P.F. Anto2 and S.K. Singh2
IDepartment of Metallurgical Engineering and Materials Science,
Indian Institute of Technology, Bombay-400 076, India
21nstitute of Engineering 'and Ocean Technology, ONGC, Panvel-410 221, India

ABSTRACT:

API 5LX steels are widely used in off-shore structures. Despite the fact that these steels
possess good notch toughness, several hydrogen induced failures are reported to have occurred
in the large diameter crude oil pipelines when they are subjected to static and dynamic loads in
the oil field production environment. The presence ofH2S, C~ and brine in crude oil not only
enhance the corrosion rate but also lead to environmental fracture assisted by enhanced uptake
of H atoms in steel. This has prompted the researchers to evaluate steels for resistance to
failure by hydrogen embrittlement in oil field production environment.

The use of slow strain rate test method has become more common in the laboratory.
Furthermore, this is the most severe and positive test method to screen the materials
susceptible to HE in a short duration. In the present investigation , the deleterious effects of
hydrogen on the mechanical and fracture properties of API 5LX steel have been evaluated by
tensile and slow strain rate testing in air and the NACE solution. The susceptibility to HE was
found by comparing the properties in environment to that of air. The tensile and slow strain
rate tested samples were examined in SEM to understand the change in the mode of failure.

INTRODUCTION:

A pipeline is a conduit for carrying produced oil between off-shore platforms and between
platforms and onshore facilities. Hydrogen sulfide present in the sour gas wells give rise to
two main types of corrosion . i) Hydrogen Induced Cracking (HIC) and ii) Sulfide Stress
Cracking (SSC). Hydrogen sulfide affects cracking in two ways i) It acidifies corrosive
medium ii) catalyses the penetration of hydrogen into steel. [I]. Hydrogen sulfide in the
presence of water forms atomic hydrogen by the following reaction.

1082
The hydrogen atoms get transported intemally by diffusion or dislocation motion 'and get
accreted at a site such as internal interface where it influences nucleation and growth of a
crack. earbon and low alloy steels are widely used as pipeline steels. These consist of API
grade steels which have good notch ductility and high tensile strength. In general. higher the
yield strength of a material, the more susceptible it is to see [2].
t
EXPERIMENTAL:

2.1 Material characterization:

The material used in the present investigation is API 5LX 52 grade pipeline steel obtained
from mOT, ONGC, Panvel. The chemical analysis of the studied material was done using
Atomic Absorption Spectroscopy. The results of analysis along with specified elements are
listed in Table I..

2.2 MicrostnJctural examination:

The specimens were polished upto 1 m surface finish using diamond paste and etched with
2% nital. The microstructure was observed at different magnifications under the inverted
metallurgical microscope.

2.3 Specimen preparation:

Smooth round tensile specimens were machined out from a hollow cylindrical pipe in the
direction of rolling. The dimensions of the tensile and SSRT specimens are given in fig 1 &: 2.

Fig 1. The specimen dimensions for tensile tests.

1083
2.4 Hydrogen charging:

To study the effect of hydrogen ingress on the properties of the material, the tensile specimens
were cathodically charged in an electrochemical cell consisting of platinum anodes. The
solution was prepared as per NACE TM-0177 standard consisting of 5% NaCl, .5%
CH3COOH and elemental sulfur. AS203 was added as hydrogen evolution poison. The
specimens were charged for 24 hrs and 48 hrs to study the effect of hydrogen ingress on the
mechanical properties of the material. The amount of diffusible hydrogen was determined by
gas chromatography.

2.5 Tensile tests:

The tensile tests were carried out on Hounsfield tensometer for both charged and uncharged
specimens to study the effect of hydrogen embrittlement. The load Vs extension curves were
obtained and superimposed as shown in the Fig 4.

2.6 Slow strain rate tests:

Slow strain rate tests were also conducted on CORTEST CERT system at a constant strain rate
of I X 10-6 so: Load Vs extension curves were obtained both for as received and specimen
tested in the environment.

3. Results and Discussion:

The microstructures of API 5LX steel under different magnifications is given in fig 3.

1084
The microstructure consists of predominantly ferrite with small amount of pearlite. This is
typical microstructure of a low carbon steel. Besides these, the matrix contains Mns inclusions
which can be detrimental to steel by promoting hydrogen trapping at these sites.

The hydrogen content of the sample charged for 48 hrs was found to be 21 ppm. The presence
of large amounts of diffusible hydrogen is due to I) cathodic cflu.ging and ii) presence of
sulfur in NACE solution. Numerous theories have been proposed to explain the increased
hydrogen transport based on stress assisted bulk diffusion, dislocation transport and grain
boundary tunneling of hydrogen [ 3].

Fig 4 shows the superimposed load Vs extension curves for the tensile specimens charged for
24 hrs and 48 hrs. The comparision of mechanical properties of charged and uncharged
specimens is shown in table 2.

Table 2. Comparision of mechanical properties of specimens tested in air and environment.

The values of mechanical properties obtained in slow strain rate test are shown in table 3.

1085
Table 3: Table showing mechanical properties of API 5LX steel in air and environment by
SSRT.

The ratios of mechanical properties in environment to that of air are less than one which
ll1u1catethat the material is susceptible to hydrogen embrittIement. Also, the decrease in
properties is more pronounced in the case of SSRT compared to tensile tests due to the
continuous charging in the slow strain rate tests. The fractography of the material tested in air
and environment is shown in fig 5.

1086
The fractographs of the samples tested in air showed dimples which is indicative of ductile
failure mode. The material near the surface which is in contact with the environment failed in a
brittle manner,.where as the material towards the center of the specimen lesser impact from the
environment and hence showed ductile fracture .

Conclusions: '
The study of the hydrogen embrittlement of API 5LX steel yielded the following conclusions.
I) The microstructure consists of ferrite and pearlite indicative of ductile nature. But when
charged with hydrogen it showed brittle failure.
2) The tensile properties of specimen show a decrease when charged with hydrogen thereby
proving its detrimental effect.
3) The fractographs of the fractured specimens indicate ductile to brittle transition in the
failure mode when charged with hydrogen.

REFERENCES:

I. Geer and Z.Y. Chen., " Hydrogen embrittlement during the corrosion of steel wet
elemental sulfUr," Corrosion science 37(12):2003 - 11,1995.

2. Witheln S.M, Kaur Sham Lei and Oilfield J.W., " Selection of materials for deep sour gas
wells," proceedings of the second NACE international symposium, U- U8, 1989.

3. Pressoure G.M., " Trap theory of hydrogen embrittlement", Acta Met, 28, (1980), 895.

1087
Proc. Int. ConL on Corrosion CONCORN '97
December 3-6, Mumbai, India

Application of Nuclear Metlt0ds in

Corrosion and Wear Studies
K.G. Prasad1 and A.S. Khanna2
'Tata Institute of Fundamental Research, Homi Bhabha Road,
Mumbai 400 005, India
2Indian Institute of Technology, Powai,
Mumbai 400 076, India

Abstract The application of nuclear methods in investigating the wear and corrosion rates
have several advantages, especially when shallow depths of the samples are involved. We describe
here several such techniques in general and the Rutherford Back Scattering (RBS) in more detail as
applied to a few samples studied by us. The merits and disadvantages will be pointed out.

Introduction: Most of the nuclear techniques yield information regarding relative

compositions of various elements in the samples under investigation. The usual methods employed
are either reactor or accelerator based. The methods depending on reacators require special
handling techniques and complicated laboratories, as radioactive materials are produced. Due to
these reasons we shall confine only to accelerator based methods, which are relatively simple and
straight forward.
We shall describe three methods: (a) Proton induced X-ray emission (PIXIE), (b) Nuclear
reaction analysis and (c) Rutherford Back Scattering (RBS) technique (detailed description of all
these methods are given in ref.1 and the references therein).

PIXIE: In this method, the sample under study is bombarded by 2-3 MeV protons, obtained
from an accelerator (for e.g. a van de Graaff accelerator). These protons create innershell vacancies
in the target atoms, which in turn are filled by the outer electrons accompanied by emission of
characteristic X-rays.These X-rays are usually detected by a high resolution Si(Li) semiconductor
detector.This process has been well studied and can result in highly accurate compositional analysis
of the sample. However, It is difficult to get reliable depth information of the target atom, since the
energy of the X-rays does not depend on the depth at which they are produced.

Nuclear Reaction Analysis (NRAJ: This method usually requires protons and alpha
particles of enrgy ranging from 100 keV to 10 MeV, although occasionally other ions can also be
used. These particles induce nuclear reactions in target materials. The reaction products, like
gamma rays, protons, neutrons, alpha prarticles etc. are emitted, which are detected using the
nuclear radiation detectors. The nuclear reactions produce radioactive nuclei, which are long lived
(half life >few minutes) and short lived (half life < few seconds). In the former case the samples can
be studied offline (not discussed here for reasons mentioned in the case of reactor based methods),
whereas in the latter, samples are investigated in situ. In many instances the nuclear reactions take
place at a well defined energy, within a narrow energy range (resonant reactions). Under such

1088
conditions it is possible to study the depth distribution of the target atoms by varying the energy of
the projectile. In many cases, where there is no resonance reaction, it is still possible to obtain the
depth information, if the "a" value of the reaction and the energy of the incident particles are known
and the energy of the emitted particles are measured. The usual detectors used are charged particle
semiconductor detectors, neutron counters and gamma ray detectors. The method is well developed
and described in detail in several review articles. !

Rutheford Back Scattering (RBSJ This is a well establshed method of studying the
compositional variation in the near surface regions (typically upto about 2 microns). Usually the
target atomic mass is larger than that of the projectile. In almost all studies the projectile is an alpha
particle in the energy range 1 to 8 MeV. With the advent of heavy ion accelerators several other ions
like B, C, Nand 0 have also been occasionally employed to obtain better mass resolution. The RBS
does not produce nuclear reactions as the measurements are carried out well below the coulomb
barrier for such reactions. The RBS depends on the kinematics of the scattering and the energy loss
of the projectile in the sample. Both these are well understood and well studied and hence can be
directly applied to obtain the concentration of the scattering centre and its depth distribution. The
experimental arrangement is quite simple. The target to be investigated is mounted in a vacuum
chamber (with vacuum of the order of 10-6 torr.) which is situated at the end of a beam line of an
accelerator capable of delivering 1 to 10 MeV ions with good energy resolution and stability.
Typically the electrostatic linear accelerators, either single ended or tandem type are well suited for
this purpose. The scattered charged particle is detected in a simple semiconductor surface barrier
detector. A low noise preamplifier with a suitable linear amplifier and a multichannel analyser are
needed for efficient data collection. The schematic experimental arrangement is shown in fig. 1.

The incoming ion looses its energy both as it travels within the sample before getting
scattered and also on its way out to the detector after scattering. The energy of the detected particle
is a measure of the depth of scattering and the scattered yield is a measure of concentration of the
scattering centres. Let EO be the energy of the incident particle of mass M1 and E1 be the energy of
the particle at the time of scattering. Then the energy E2 of the particle immediately after scattering
by a target atom of mass M2 is given by

1089
 Zl and Z2 being the atomic numbers of the projectile and the scattering atom respectively.
The yield of scattered projectile is proportional to the scattering cross-section. Thus, by measuring
the relative yields of particles scattered from various atomic spieces at same depth one. can easily
determine their relative concentrations.
If a suitable scattering atom (with M2, Z2) is introduced as a "marker" into the sample under
investigation, it is quite straight forward to study the effects of corrosion or wear by monitoring the
depth distribution and concentration of these atoms. It is assumed here that the introduction of these
"marker" does not affect the bulk properties of the substrate significantly. We will now describe a few
examples where this method has been applied to such measurements .

Corrosion: Iron samples of 50 ~ thickness were implanted with 250 keY Sb ions (obtained
.
from the 400 kV accelerator at T.I.F.R., Mumbai, India) to a dose of 5x1015 atoms/Cm2. The
projected range of these ions in Fe is 0.0475~. with a straggling of. 0.017~. The RSS spectrum of
this sample recorded using 2.05 MeV alpha particles is shown in fig.2. Here the flat region
corresponds to the thick substrate while the peak structure is that of implanted Sb. The arrow
indicates the position of Sb if it were at the surface. However, since the implantation energy was 250
keY, the Sb atoms have penetrated deeper into the substrate. The Sb ions have been chosen for
implantation as they are easy to obtain and their atomic mass is heavier compared to that of the
substrate, making the analysis of the data simpler.
We have subjected these samples to corrosion treatment by immersing them in 1N H2S04
for different durations (1 to 5 mins.). The RSS spectra of the implanted Sb in these treated samples
are compared with "as implanted" samples in fig.3. Initially the the Sb profile moves towards the
surface, indicating that the surface layers (where there are no Sb atoms) are being removed. As the
duration of the treatment increases, the Sb atoms have come nearer the surface and are also being
removed from the sample. This clearly shows that the rate of removal of Sb is proportional to the
rate of loss of substrate.

Wear: Samples of several alloys were prepared as above and were subjected to abrasion
by rubbing them with 6/0 grade emery paper. Care was taken to keep the pressure on the sample
same each time to get uniform wear rate. The RSS spectra were recorded at frequent intervals. The
Sb part of the RSS spectra for Fe substrate is shown in fig.4. As in the case of corrosion studies, we

1090
can clearly see the decrease in Sb concentration as the wear increases. In fig.5, the effect of wear
due to abrasion for several samples is shown. The rate of decrease in Sb concentration, relative to
that in "as iimplanted" sample in each case, is clearly proportional to rate of wear in the samples
studied.

Summary We have described several accelerator based nucleal techniques suitable for
corrosion and wear investigations. The RSS method has been applied to such studies.

Acknowledgements: The authors thank the staff of 400 kV accelerator at T.I.F.R., Mumbai,
for Sb implantations and the students and the staff of 3 MV Pelletron Accelerator group at lOP,
Shubaneswar, for help in carrying out the RSS measurements. This work was part of the IAEA
project, contract No. 7047/R2/RS.

Fig.2. RBS spectrum of as implanted steel sample Fig. 3 RBS curves showing the decrease in the 123Sb ions
with 123Sb implantation. level on the implanted ample, as a function of the
dissolution of metal when exposed to IN H2S04
solution for different duration's.

1091
1092
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai. India

Weldment Corrosion in Dissimilar Material Incoloy 800

Vs 2.25 Cr IMo Used in Process and Power Plants
R. Vaideeswaran1, s. Natarajan2 and 'Y.Sivan2
'Plant Laboratory, Bharat Heavy Electricals Limited,
Tiruchirapalli-620 014, Tamilnadu, India and
Part time Ph.D Research Scholar, REC, Tiruchirapalli-620 015, India
2Department of Metallurgical Engineering, Regional Engineering College,
Tiruchirapalli-620 015, Tamilnadu, India

ABSTRACT

It well known that Nickel alloys are widely used in chemical

process plants,oil refineries and in Nuclear power
plants. This paper deals with the corrosion behaviour of the
dissimilar joint Incoloy 800 with 2.25 Cr lMo material in
terms of electrochemical techniques, in HCl medium of
different concentrations at room temperature and at lOOOC.For
the Incoloy 800 material the passivation range is more with
increase in acid concentration at elevated temperature.The
passivation in the weld root is found to be due to the
formation of Nickel oxide as seen in XRD measurements. The
Impedance measurements indicate an inductive loop attributing
to the adsorption-desorption phenomena at the working
electrode surface.

*****

INTRODUCTION

Incoloys and Nickel alloys are widely used in chemical

proce.ss plants,oil refineries and in Nuclear power
plants. They are extremely used for vessels,pipings and pumps
in the production of mineral and organic acids.Incoloy 800 is
on the borderline between austenitic stainless steels and
nickel alloys, from corrosion resistance view point[l] .Ni-Cr-
Fe alloys are more resistant to pitting,crevice corrosion and
chloride SCC than the austenitic stainless stp'~ls. Further,
dissimilar metal welds between low alloy ferritic steels and
austenitic stainless steels are widely used in power station
steam generators.This dissimilar metal joint results in
premature failures well below the designed lifetime.To
overcome the above problem,a transition metal joint with
alloy 800 as transition piece is used between low alloy steel
and austenitic stainless steel [2].

1093
Since welding is the most common method of joining metals,it
is important to effectively evaluate weldment corrosion for
the purposes of quality control,welding process comparison
and alloy development [3,4].The microstructure and mechanical
properties of Incoloy 800 Vs 2.25 Cr lMO have beeq studied by
Bhaduri et al and their study has showed tthat lowering the
post weld heat treatment temperature delays the onset of
deterioration in microstructure and in mechanical properties
of this joint during subsequent ageing [5]. From the
literature,we learn that the data on the corrosion behaviour
of dissimilar joint in Incoloy 800 with 2.25 Cr lMo steel in
HCl medium has not been reported and hence this attempt.

EXPERIMENTAL

Weldments in Incoloy 800 Vs 2.25 Cr lMO steel were prepared

using Shielded Metal Arc Welding process.The chemical
compositions of the materials were as per the
specifications(Table I) .The details of the welding conditions
adopted are listed in Table II.The pipes were post weld heat
treated at 700C.The pipes were further checked for absence
of defects by radiography.The defect free pipes were cut in
the form of small test coupons, each of approximately 50 mm
in length and lSmm in width.Thus each specimen comprises
parent metal,heat affected zone and weld metal.Each test
specimen was surface polished using conventional
methods(degreasing and polishing with abrasive sheets of
various grades) .Parent metal,weld reinforcement,Heat affected
zone on either side of the weld and weld root were chosen as
regions of exposure for corrosion studies.The zones were
identified by macro etching and the unwanted_ regions masked
by teflon tapes.

ELECTROCHEMICAL TECHNIQUE:

Polarisation measurements were made using scanning

potentiostat Model 362 ( EG&G Princeton Applied Research
Corporation, New Jersey,USA) .Open Circuit potential was
recorded in each experiment after it became stable at least
for 30 minutes. Potentials were applied accordingly, in
discrete fashions and thereby noting down the corresponding
current density.The observations were made for all the
regions of the weldment in HCl medium containing 100ppm of
H2S04. The experiments were carried out at room temperature
and at 100C. In each experiment,a plot of potential vs
current density was made.The values of primary passivation
potential,passivation range,critical current density and
passivation current density were found out and are given in
Table III and IV.

1094
TABLE I CHEMICAL COMPOSITION (Wt%):

Incoloy 800

C Mn Si Cr Ni Fe Al t Ti Cu S

0.10 1.5 1.0 19.0- 30.0- 39.5 0.15- 0.15- 0.75 0.015
max max max 23.0 35.0 min 0.60 0.60 max max
ALLOY steel

C Mn Si Cr Mo S P

0.05- 0.30- 0.50 1.90- 0.87- 0.025 0.025

0.15 0.60 max 2.60 1.13 max max
Filler Metal

ERNiCr3 (GTAW):

C Mn Si Cr Ni Fe Cb&Ta Ti S P

0.10 2.5- 0.50 18.0- 67.0 3.0 2.0- 0.75 0.015 0.03
max 3.5 max 22.0 min max 3.0 max max max
ENiCrFe3 (SMAW):

C Mn Si Cr Ni Fe Cb&Ta Ti S Cu

0.10 5.0- 1.0 13.0- 59.0 10.0 1.0- 1.0 0.015 0.50
max 9.5 max 17.0 min max 2.5 max max max
TABLE II WELDING CONDITIONS:

Joint : Butt Joint

Specification : Incoloy 800 and 2.25 Cr 1MO
Pipe diameter : 356 x 12 mm
Process : Root : Gas Tungsten Arc Welding
Further layers: Shielded Metal Arc Welding
Filler Metal : ERNiCr3 for GTAW 2.4 mm 100 Amp
ENiCrFe3 for SMAW 3.15 mm 100 Amp

Condition : Post weld Heat Treated at 715-720oC for

360 mtsiROH 200oC/Hr max,ROC 140oC/Hr max

IMPEDANCE MEASUREMENTS
Impedance measurements were taken for the different zones o~
the Incoloy 800 Vs 2.25Cr1Mo weIdment in HCI medium in
o .1M,o. 5M and 1.OM Concentration at room temperature using
the Electrochemical Impedance Analyser (EG&G Princeton Model
6310) .Bode plots and Nyquist plots were obtained for each
zone.

1095
X-RAY DIFFRACTION STUDIES:

XRD studies have been carried out on different regions

namely weld root ,weld reinforcement and incoloy parent metal
at room temperature and at lOOOC.

MICROSTRUCTURAL FEATURES:

The photomicrographs of the different regions are shown in

Figures II,III and IV.The microstructure of the weld zone
shows columnar grains of austenite,while the incoloy parent
metal consists of twinned grains of austenite.The low alloy
steel has a microstructure of tempered bainite.

POLARISATION STUDIES

The weld root is more anodic compared to weld reinforcement

at all concentrations.The incoloy 800 parent metal exhibits
passivation which increases with acid concentration and with
temperature. The heat affected zone on the incoloy 800 side
shows more passivation than the heat affected zone on the
alloy steel side. This can be attributed to the corrosion
resistance of the Ni-Cr alloying elements in the Incoloy 800.
Higher anodic critical current densities are obtained at
lOOOC for weld reinforcement regions in all
concentrations.Pitting was well observed in Incoloy 800 and
weld reinforcement at elevated temperature at transpassive
potentials.Palumbo G.et al [6] have reported the pitting
corrosion behaviour of Incoloy 800 in chloride-sulphate
media.Decreasing the chloride concentration resulted in noble
shifts of the critical nucleation potential. Immunity to
pitting corrosion was evident at chloride concentration below
O.OlM.Increasing sulphate concentration resulted in improved
chloride pitting resistance,although detrimental effects
associated with pitting at transpassivepotentials were
evident within low level sulphate additions to dilute
chloride media.It is interesting to note that the findings of
t~is present study are also resembling to that of the
predictions made by the aforesaid investigators.Investi-
gations have also been carried out by Briceno D .et al to
study the degradation and failure behaviour of Incoloy 800
subjected to simulated loading and environmental
conditions [7].

1096
 Fig. II Fig. III
Photomicrographs of the Incoloy 800 weldment showing
the HAZ on Incoloy/weld side (Fig. I) and the HAZ on
the 2.25 Cr IMo/weld side (Fig. II). (Mag: 2OOX)

1097
Fig. IV Photomicrograph of the weld zone
of the Incoloy 800/2,25 CrlMo weldment
(Mag: 2OOX)

1098
XRO measurements on the Incoloy 800 parent
metal and the weld zone

1099
1100
XRD ANALYSIS

From XRD measurements it is found that the peak obtained in

the weld root is probably due to the presence of NiO in the
weld root region,which is also corroborated with polarisation
experiments, where passivity is seen.Thet mechanism for the
above observation may be attributed to the one which has been
suggested by Latha G.et al[8] .The passivation of Ni alloys
is by oxide film formation which involves a dissolution-
precipitation process at the active-passive transition for
Nickel.

The process consists of two or three steps in which the

dissolved ion precipitates to form an oxide film.A separate
work by the same authors Vaideeswaran R.et al on Incoloy 825
with SA 516 Gr 70 steel also has revealed more or less
similar observations with regard to formation of a passive
film[9].

IMPEDANCE MEASUREMENTS

Impedance diagrams indicate additional inductive loop at low

frequencies for Incoloy 800 and the low alloy 2.25Cr1MO
parent metal regions.This may be attributed to the adsorption
-desorption phenomena at the working electrode surface.As
regards the weld root region,a typical Nyquist plot has been
obtained.

CONCLUSION:

* The weld root is more anodic compared to the weld

reinforcement at all concentrations and temperatures.

* The heat affected zone (HAZ) on the Incoloy 800 side has
more passivation range than the HAZ on the 2.25 Cr 1Mo side.

* For the Incoloy 800 material,with increase in acid

concentration, at elevated temperature the passivation range
becomes more.

* Being a freely corroding system,the 2.25Cr1Mo material has

not shown ,its active-passive behaviour.

* Higher anodic critical current density values are obtained

at 100C for weld reinforcement region in all concentrations.

* From XRD measurements,it is found that the peak obtained is

possibly due to the presence of nickel oxide in the weld
root region.

1101
* Impedance measurements indicate additional inductive loop
at low frequencies for Incoloy 800 and the low alloy 2.25 Cr
1Mo parent metal regions.This may be attributed to
adsorption-desorption phenomena at the working electrode
surface .As regards the weld root region,a typical Nyquist
plot has been obtained. 1-

Acknowledgements:

The authors thank the BHEL authorities for providing the

material and the Principal, REC for his kind encouragement
and permission to present and publish this paper.

REFERENCES:

1.Denny A.Jones,Principle and prevention of corrosion,

Macmillan Publishing Company,Page 516-517,1992

2.Rajamani G.P.,Shanmuga N.S,Rao K.Prasad,Dissimilar friction

welding of alloy 800 and 2.25 Cr1Mo steel, International
journal for joining of material vol. 3,No.1,Mar.1991,page
25-32.
3.ASTM Gl-72,Recommended practice for preparing,cleaning and
evaluating test specimens,1993.
4.Michael Henthrone,Corrosion Testing of weldments,Vol 30,
No.2,Feb.1974,Corrosion ,NACE.
5.Bhaduri A.K.,Venkatesan S.and Rodriguez P.,Microstructure,
Mechanical property and performance simulation of
alloy 800/2.25 Cr1Mo steel joint,National Welding Seminar,
Dec 1989,pp 4.1-4.7.
6.palumbo G.,King P.J. and Aust K.T., Pitting corrosion
behaviour of alloy 800 in chloride-suiphate media, Vol
43,No.1,Jan.1987,Corrosion,NACE.
7.Briceno D.,Lancha Hernandez A.M. and Castano Marin M.L.,
Theoretical and applied Fracture Mechanics,Vol 21,No.1,
Aug 1994,pp 59-71.
8.Latha G.and Rajeswari S.,Suitability of high Ni-Cr-Mo
alloys as construction materials in sea water
applications,Vol.44,No.1,Feb 1997
9.Vaideeswaran R.,Natarajan S. and Sivan V.,Dissimilar
weldment corrosion in Incoloy 825 Vs SA 516 Gr 70
material,National Welding Seminar, Dec 1997.

***

1102
Proc. In!. ConI'. on Corrosion CONCQRN '97
December 3-6, Mumbai, India

Prevention of Crevice Corrosioa of SS 304 in

Condensers of Power Plants by
Sacrifical Cathodic Protection
Ashwini K. Sinha, V.C. Bhakta, S.D. Chowdhary,
A.K. Mitra and G. Gunasekaran
Research and Development Centre, National Thermal Power Corporation Ltd.,
A-8A, Sector-24, Noida-201 301, Uttar Pradesh, India

ABSTRACT

Instances of 55 tube leakages due to crevice corrosion have

been experienced cU power stations. The joints of tube and
tube plate in the condensers are susceptible to crevice
corrosion resulting in tube leakages. In some of the condensers
low carbon steel (0.03% approx.) are used as sacrifical anode
for preventing crevice/pitting corrosion of 55 tube plate and
55 tube as well as to protect the mild steel water boxes. These
anode materials are imported and maintenance replacement
is difficult. Laboratory studies have been carried out to evalaute
the protection capabilities of such anode materials in preventing
crevice/pitting corrosion of 58 tube plates 88 t.ubes in the
power plant condensers. Alternate indigeneous materials such
as M8-1018, mild steel, Zinc, Magnesium based alloys etc.
have been studied to substitute the imported anode materials.
The tests were conducted in 88-304 material in 5% FeC13,
and 3.5% NaCI in' presence/absence of crevice through
immersion studies and cyclic polarization studies. Differenct
anode materials were also coupled to 88-304 material and
their protective capabilities have been evaluated. Both electro
chemical and immersion studies have indicated that imported
low carbon steel has very good protective capability. M8-1 018
has also good protective properties, however, under continued
immersion in chloride media, the protective properties
decreases. Ordinary mild steel has no protective property
and crevice/pitting corrosiion takes place.

1103
INTRODUCTION:
In many power plants the steam condensers are made of
SS 304 tubes fixed to SS cladded tubsesheetand water boxes
made of mild steel. Some instances of tube leak~ges had been
noticed at the junction of tube and tube plate '(jue to mainly
crevice/pitting attack. In order to prevent the crevice/pitting
corrosion attack some of the manufacturers have used sacrifical
cathodic protection system employing anodes of very low carbon
mild steel. Visual observaton of some of the anodes indicated
that uniform dissolution of the anodes had taken place and no
apparent crevice/pitting attack had taken place on the tube
plates, but corrosion of water boxes were observed.

The anodes used in these condensers are imported and

the replacement is difficult as similar anodes are not available'
in the country. More over the performance of these need to be
evaluated in the laboratory. In view of this, studies have been
initiated to evaluate the performance of the imported anode
material and to find substitute anode material which would be
effective in preventing crevice/pitting attack on the SS 304
material under the operating conditions of steam condensers.
The present paper describes the results obtained in the
laboratory for the effectiveness of imported low carbon steel,
commercial mild steel, mild steel 1018 and Zinc metal in
preventing crevi~e corrosion/pitting of SS 304 under accelerated
conditions of corrosion.

2.0 EXPERIMENTAL:

For evaluating the effectiveness of variou's sacrificial

anodes in preventing crevice/pitting corrosion of SS 304
material, following methodology was adopted.

2.1 Immersion Tests:

A condenser tube made of SS 304 was obtained and plate

samples were prepared. Crevices were created on some of these
samples by Teflon nut bolts & washers. 5% FeCl3 and 3.5%
NaCI were taken for immersion studies. The experiment
conditions for both the solutions were as follows:

1104
(a) Immersion in 5% FeCI3

Size of SS 304 plate sample: 7.5.x 1.5 x 2 cm2

Anode sizes (low carbon steel, MS, MS & 1018): 5 cm2
Duration : 5 days 1-
Conditions: Room temp, static

Anodes connected to SS 304 through insulated copper

wire the ends of which were covered with araldite. The SS
304 samples chosen were with and without crevice. Visual
observations were made after immersion.

(b) Immersion in 3.5% NaCI

Size of SS,plate : 8x2.5x2 cm2

Anode sizes (low carbon steel, MS , MS 1018 & Zinc)
:1cm2
Duration : 30 days
Temp. : 30 C
Condition : Static

Anodes connec.ted to SS 304 through insulated copper

wire, the ends of which were covered with araldite. The SS
304 samples chosen were with crevice. Potentials of SS 304
measured daily with respect to Ag/AgCI reference electrode
through EG&G, Prin'ceton applied research corporation USA,
make potentiostat (273A). Visual and microscopic examinations
made after immersions.

2.2 ELECTROCHEMICAL TESTS

Size of SS 304 plate sample: 7.5 x 1.5 x 2 cm2

Anode size (low carbon steel, MS, M8 1018:Zn) : 5 cm2
Solution: 5% Fe CI3 and 3.0% NaCI
Condition Static, 30 C, Aerated, unaerated.
Reference elctrode : Ag/Ag.CI

Anode connected to SS 304 through insulated copper wire,

the ends of which were covered by araldite. The S8 304 samples
chosen were with and without crevice. Cyclic polarization
experiments were conducted using computer controlled
electrochemical system EG and G, PARC, U.S.A with graphite

1105
rods as counter electrode and Ag/AgCI as reference electrode.
The scan rate' was 0.5 mV/.Sec. Visua.1 and microscopic
examinations were made after completion of tests. Calculations
and quantitative measurements done through EG &G model
352.1 softcorr, software. 1-

3.0 RESULTS

3.1 Immersion Tes,ts:

(a) Immersion in FeCI3 solution:

Crevice corrosion was observed on SS 304 without any

sacrificial anode after 5 days of immersion in 5% FeCI3. N'o
crevice corrosion was observed on SS 304 connected to the'
sacrifical anodes. Some pits were observed on SS 304 coupled
with mild steel. Photograph-1 depic the condition of the samples.

(b) I,mmersion in NaCI solution:

Crevice corrosion was observed on SS 304 without any

sacrificial anode after 30 days of immersion in 3.5% NaCI. No
crevice corrosion was observed on SS 304 cathodically
protected with Zinc but small crevice attack was noticed on SS
304 plate coupled with mild steel, low carbon steel & MS 1018.
Deposition of corrosion products of sacrificial Zinc anode on
SS 304 are noticed. Small pits were noticed on SS 30~
cathodically protected with mild steel, low carbon steel and
mild steel 1018. Below the pits and under the crevice:
Intergranular corrosion was observed under scanning electron
microscope and optical microscope. Photographs -2 & 3 show
the condition of samples after exposure for 30 days in 3.5%
NaCI.

The best protection was observed in case of cathodic

protection with Zino electrode. Low carbon steel gave much
better protection compared to MS 1018 which in turn gave
better protection than mild steel.

1]06
3.2 ELECTROCHEMICAL TESTS

The Ecorr of SS 304 in 3.5% NaCI was lound to be 10

mV vS Ag/AgCI at the initial stage, but after 30 days of
exposure to 3.5% NaCl, it shifted anodically to 65 mV vS Ag/
AgCI. Mild steel connected to SS 304 shifted its potential to -
76 mV vS Ag/AgCI on immediate immersion. Upto seven days
immersion in 3.5% NaCI shifted the potential of SS 304 to
more cathodic value i.e. around-640 mV vS Ag/AgCI .
However, on continuous immersion, the potential shifted
anodically to -390. mV vS Ag/AgCI suggesting improper
dissolution of mild steel and its subsequent failure to act as
an anode material thereby corroding SS 304. Low carbon
steel on other hand showed better performance as it shifted
the potential of SS 304 cathodically from -63 mV vS Ag/AgCI
to around -500 mV vS Ag/AgCI till about 21 days of immersion
then it shifted slightly anodic to around -410 mV vS AgfAgCI.
Accumulation of corrosion products on mild steel anodes,
minimizes the dessolution of mild steel anode. Thus SS 304
becomes less protected.

Zinc anode did not show similar behaviour and from the
begining the potential of SS 304 was shifted cathodically to
around-590 mV vS Ag/AgCI with some transient shifts in
between. The data. suggests uniform dissolution of Zinc
material and continuous protection of SS 304. Detailed
potential measurement record is given in Table -I. The
behaviour was ~onfirmed by visual/microscopic examinations
of sample after immersion.

Cyclic polarization diagrams indicate that the behaviour

of SS 304 changes on being coupled with anode material
(Figs 1 to 7). The galvanic couple shows the corrosion trend
as that of anode material above. The hysteresis loop formed
by increasing the scan shows adminishing trend on coupling
the SS 304 plate with sacrifical anodes, suggesting protection
of SS 304 from localized corrosion attack. As per cyclic
polarization behaviour also best protection is accured by Zinc
in 3% NaCI.

1107
4.0 DISCUSSIONS
The power plant steam condensers work under conditions
of severe corrosion because the cooling water used in the
condensers is taken from either a river or a b(>re well or a sea
or a lake. The flow rate is of the order of 25,0'00 to 30,000 M3
per hour for a 200 MW unit and around 90,000 M3/Gr for a 500
MW unit. The dissolved oxygen content of the cooling waters
especially those which are under open recirculation system is
much more. The operating temp. varies from 30 C to 50 C and
biological growth is also present. Some of the cooling waters
are known to be scaling in nature and in many cooling waters
there is a tendency G)fmechanical fouling due to silt/sand/clay,
foreign materials such as plastics, woods, leaves etc. All these
conditions aggrevate crevice/pitting corrosion.

In condensers made of SS 304 condenser tubes and mild

steel tube plate and mild steel water boxes, the tube/tube pla~e
joint are highly susceptible to crevice/pitting attack. In addition,
if the tube plate is made of cladded SS 304, it is also susceptible
to crevice/pitting attack. To protect the condenser water boxes/
tube plates and inlet corrosion of condenser tubes, attempts
have been made to provide cathodic protection. 'Some of the
manufacturers of steam condensers have utilized impressed
current cathodic protection (1,2), where as some of them utilized
sacrifical cathodic protection (3) for the purpose. In some of
the power plants low carbon steel had been used as an anode
material. These anodes have performed well over a period of 7-
8 years, but corrosion products were observed which inhibited
uniform dissolution of the anode. The condenser water boxes
are coated with good quality anticorrosive coating, in addition,
the nature of the cooling waters in these stations were of scaling
kind. Thus, real behaviour of the anodes could not be established,
in practical conditions.

The results obtained above suggest that low carbon steel

may provide sufficient cathodic protection to the condenser tube
plates and tube/tube plate joints. However, since the low carbon
steel is not available in the country and also because Zinc is
performing better as an anode material, it may be worthwhile to
replace the existing'low carbon steel anodes with high purity
Zinc anodes with suitable alloying elements such as Mg, AI etc.
which can ensure uniform dissolution of Zinc anodes in fresh
waters.
1108
5.0 CONCLUSIONS:

The laboratory studies indicate that sacrificial cathodic

protection system is able to impart sufficient-,:Jrotection to SS
304 material against localized corrosion. Low carbon steel is a
better choice as an anode material amongst the carbon steel,
materials but these also get passivated due to build up of
corrosion products. In case of high chloride concentration the
anodes of carbon steel are not able to prevent localized
corrosion such as IGC, crevice or pitting of SS 304',Zinc anode
can help in preventing localized corrosion attack on the SS
304 provide at the uniform dissolution of Zinc and removal of
corrosion products are ensured. Zinc anodes can also help in
reducing the corrosion of water boxes made of carbon steel.
In such cases the design of the cathodic protection system
plays a crucial role as the water boxes with much larger area
will require greater protective current consequently the localized
corrosion prevention of SS 304 can be hampered,

ACKNOWLEDGEMENT

The authors would like to place on records their gratitude

to Sh. S.K.Sanyal, General Manager (R&D), NTPC for the advice
& guidance in the experimental work and for according
permission for presenting this work. Authors are also thankful
to Dr. Pradeep Jain, Mgr (R&D), Sh. a.p. Rangwani,Sr. Engr.
(R&D), and other colleagues who helped in conducting the
various works connected with this study.

1109
 REFERENCES

1. Process Plant and cooling water systems"

E Burbridge, cathodic Protection, thet>ry & practice
edited by V. Ashworks & CJL Borker, AP 191-213

2. "Cathodic Protection of main condneser circulating

water boxes "Philips D Simon. paper No.192,
Corroison 78.

3. "Design considerations for CP systems with coatings"

WH thomson etal, paper No.424, Corrosion 92.

4. "Corrosion Control" LL Shesier Volll.

5. Use of carbon steel to mitigate crevice Corrosion of

stainless steels in sea water T.S. Lee etal; materials
performance, Jan 1983 PP-48-53.

1110
1111
1112
1113
1114
1115
1116
1117
1118
1119
1120
Proc, Int. ConI'. on Corrosion CON CORN '97
December 3-6, Mumbai, India

Localized Corrosion Behaviour of Argol\ Ion Implanted

Titanium Modified Type 316L Stainless Steel for
Application as Orthopaedic Implant Device
T. Sundararajanl, U. Kamachi Mudali2, K.G.M. Nair,
S. Rajeswaril and M. Subbaiyanl
IDepartment of Analytical Chemistry, University of Madras,
Guindy Campus, Madras-600 025, India
2Metallurgy and Materials Group, Indira Gandhi Centre for Atomic Research,
Kalpakkam-603 102, India

ABSTRACT

Studies on nitrogen ion implanted of titanium modified type 316L stainless steel(SS) showed
an increase in the localized corrosion resistance of the material. X-ray Photoelectron Spectroscopy(XPS}
was employed to identify the chemical state of the elements present in the passive film of implanted
specimen. Argon ion implantation was carried out to confirm whether the improvement in the localized
corrosion resistance of nitrogen ion implantation was due to chemical effect produced by nitrogen or due
to microstructural effect produced by ion implantation. The results showed that nitrogen ion implantation
improved two fold increase in the localized corrosion resistance and the passive film consisted of
oxynitrides along with oxides. The argon ion implantation does not improve localized corrosion
resistance and it was detrimental with increase in doses.

INTRODUCTION

Inherent mechanical properties of metalIic materials have led to their use as orthopaedic implants
for a long time. Three main alIoys, viz, stainless steels, cobalt-chromium' alIoys and titanium and its
alloys are the materials, frequently used for this application (1). Currently, type 316L SS is the mO,st
widely used orthopaedic implant material in India which has a reasonable corrosion resistance and low
cost. However, frequent failures have been reported with them it).the recent past which revealed that this
material can not be used for longer period (2,3). This necessitated the need to look for alternate materials
which possesses good corrosion resistance. Altering the material by means of surface modification is,an
alternate way to increase the corrosion resistance, without affecting the bulk properties, Ion implantation
as a technique, improving the corrosion resistance of various materials has been widely studied (4-7). The
advantage of ion implantation over other surface modification .process are: I) it improves the wear
resistance, ii) it is a non-equilibrium technique where implanting ions (element) can be added into the
material more than its solubility and iii) it is a low temperature process, during which the process material
particularly stainless steels will not undergo sensitization (8-9). The performance of titanium modified
type 316L SS, developed at IGCAR, Department of Atomic Energy, Kalpakkaln, in simulated body
fluids exhibited better corrosion resistance (10),

1121
1122
RESULTS AND DISCUSSION

Figure 1. shows the potentiodynamic polarization curves for pristine and N+ implanted titanium
modified type 316L SS in comparison with the pristine 316L SS. Both pristine specimens showed a
similar passive current density. The pitting potential of 316L SS was + 190 rriV whereas for the titaniuin:
modified type 316L SS it was +280 m V. Many investigation have been reported improved localized
corrosion resistance of' titanium added stainless steels (16-18). Titanium was considered to be helpful
in forming TiS' inclusions which are insoluble in acids in comparison with MnS inclusions '(18). 'IIi'
addition it was suggested that (19) titanium could be playing a major role in stabilizing the passive film
to improving the pitting corrosion resistance.
On anodic polarization titanium also dissolves
along with other -alloying elements such as Cr,
Fe, Ni, and Mo and gets into the Cr-rich mixed
oxide passive film. In general the passive film
of SS have high concentrations of defects with
bound water the competition or absorption
between the oxygen and chloride on the
electrolyte on to the passive film of surface is
the underlying mechanism of passivity. Pitting
is initiated the specific absorption of chloride
ions favoured over Qxygen ions. The presence
of titanium in the passive film may reduce the
defect concentration by occupying the vacant
sites. Also, the absorption of oxygen ions will
be favoured by the titanium in the passive film,
in preference to chloride ions. The passive
current density of Ti-modified 316L SS was
tending to show'lower value than type 316L SS
indicates the film gets stabilized with the addition of titanium.
The specimen implanted with W ions showed a pitting potential of +630 m V which is a two fold
increase in comparisoq with pristine titanium modified type 316 SS (Fig. 1). It has been reported that
nitrogen addition to this material showed an, improvement in localized corrosion resistance and'
mechanical properties (20). According to Speidel(2.1) four different hypothesis are available for die
improvement in locali~d corrosion resistance of nitrogen-bearing stainless steels. I) nitrogen dissolves
during the corrosion reaction and forms NH/ at,the pit sites and'renders the pit. electrolyte less acidic
by increasing the pH (22) ii) nitrogen is enriched at the surface and improve the passivity while other

1123
metal preferentially dissolves (23) iii) nitrogen is incorporated into the passive film to fomi dense
protective oxynitrided layer giving stability to the film (24) and iv) nitrogen dissolves to form stable
nitrite and nitrate compounds which act as inhibitors locally at the pit sites (25).Also the passive current
density of N+ implanted specimen was found considerably decreased. This could be attributed to the
dense" protective, oxynitride formation In the passive film, which'rtinimizes the dissolution. Th~
increase in the pitting resistance may be attributed to the formation of NH4 + ions at the pit sites. The
formation of NH4 + within the pit will increase the pH within the pit sites which hinders the pit
propagation and thus widens the passive range.

XPS Analysis:

Figure 2 shows the N Is high resolution spectra ofN+implanted-passivated specimen of titanium

modified type 316L SS. Deconvolution ofN 1s
energy level yielded five peaks at 395.4, 397.1,
398.2,399.8 and 402.4 eV. The peak at 395.4
is due to the overlapping ofMo 3p peak in this
region and this corresponds to Mo02 (26). The
peaks at 397.1 a,nd 381.2 are accounted for
implanted nitrogen and nitrides of iron
respectively (11,27). The peak at 399.8
corresponds to the N-O as reported by
Marcus et al (11). This confirms the presence
of oxynitrides in the passive film. The shift in
the OCP towards the nobler direction and a
reducti'on in the passive current density of
nitrogen ion implanted specimen would arise
from the stable protective oxynitride film. The
peak at 402.4 was attributed to the NH4 +
indicated the formation of ammonium ions
present in the passive film.

OCP - Time measurements of Ar+ implanted Titanium mo~ified type 316L SS :

, The variation in the OCP (Table 2) as a function of time for argon ion implanted titani~
modified type 316L SS at different doses are represented in Figure 3. The unimplanted specimen showed
initially a higher potential and at the end falls rapidly to the negative direction and reaches a steady stat~'
at -261 mY. The specimen implanted at 1 x 1015 ions/cm2 attained a constant potential with lesser time
compared to unimplanted specimen and the potential was shifted towards the nobler direction (-78 mV).
For the specimens implanted at 1 x 1016 and 1 x 1017 ions/cm, the potential falls gradually and
attains a steady state at -137 and -254 mV, respectively. The increase in the OCP of the implanted
specimen and the attainment of stable potential within a short duration indicated the control in the
dissolution of th~ passive film. This may due to the thickening of the air formed oxide film produced
during implantation. Ashworth et al (28) found that argon ion implantation on pure iron exhibits a nobler
shift in OCP in acidic medium: However there was no improvement in the corrosion resistance of these

1124
implanted samples suggesting that the increase in OCP is due to the thickening of the air formed
oxide layer. The lowering of the OCP at the higher doses may be due to the considerable sputtering
taking place on these oxide film.

Potentiodynamic Anodic Polarization Studies on Ar+ implanted Titanium modified type 316 SS:

The potentiodynamic anodic polarization curves are shown in Figure 4. The pitting potential of
1he implanted specimens varied with the doses (Table 2). The specimen implanted at the dose of 1 x 1015,
ioosIcm2 showed an improvement in the pitting potential (+415 m V) from the pristine specimen (+280
mV). Jedrekowiak et al (6) reported the amorphiza,tion of steel by Ar+ implantation at the dose of 1 x 1015
and Ix 1016 ions/cm2 The improvement in the localized corrosion resistance of the specimen implanted
at 1 x 1015 ions/cm2 could be attributed to the amorphisation near the surface layers which favours the
aeation of more protective passive film. However, the specimens implante~ at the doses 1 x 10 i6 and 1.
x 1017 ionslcm2 showed inferior pitting potential than the pristine specimen. The decrease in the localized
corrosion resistance with increasing doses may be due to the defects generated by ion implantation. This

1125
indicated that the argon ion implantation does not improve the localized corrosion resistance. Whereas
the nitrogen ion implantation showed a two fold increase in the pitting resistance. Thus the improvement
in the pitting resistance after nitrogen ion implantation is due to the chemical effect produced by nitrogen
rather than the microstructural changes produced by ion implantation ..

CONCLUSIONS 1-

The results of the present investigations suggested that the improvement of localized corrosion
resistance by nitrogen ion implantation could be mainly due to the chemical effects produced by
nitrogen such as formation of oxynitride layer in the passive film, dissolution of nitrogen at the pit site
to increase the local pH and to form inhibiting compounds. The argon ion implantation was detrimental
for localized corrosion resistance and a shift in the OCP toward the noble direction could be due to the
thickening of the air formed passive film during implantation.

ACKNOWLEDGMENT

The authors are very much thankful to Prof. Ajay Gupta, Centre Director, IUC-DAEF, Indore'
and Dr. R.K Dayal ,Metallurgy Division, IGCAR for their keen interest and providing the facility. The.
work was carried out under IUC-DAEF collaboration programme at IGCAR.

REFERENCES

1. Williams, D.F., 1. Mater. Sci., Vol 22, 1987, p 3421.

2. Nielsen, K, ~rit. Corros. J., Vol 22, 1987, p 272.
3. Coiagelo, V.J., and Greene,N.D., J. Biomed. Mater. Res., Vol 3, 1969, p 247.
4. Ashworth, V., Baxter, D., Grant, W~A and Procter, R.P.M., Corros. Sci, Vol 16, 1976, p 661
5. Jedrkowiak, J., Martan, J.,Masalski, J. and Bogomolov, D.B., Phys. Stat. Soli., Vol A1l2,
1989, p 357.
6. Tabkowski, P.,Brylowska, 1. and Subotowicz,.M., Phys. Stat. Sol., Vol A112, 1989, p 353 ..
7. Erdemir, A, Carter, W.B,.Hochman, R.F. and Meletis, E.I., Mater. Sci. Eng Vol 69, 1985, p 89.
8. Ashworth, V., Grant, W.A, Procter, R.P.M., Corros. Sci., Vol 16, 1976, p 661.
9. McCafferty, E.; Moore, P.G., Ayers, J.D. and Hubler, G.K, Corrosion ?fMetal Processed by
Directed Energy Beams, eds. Clayton, C.R. and Preece, C.M., The Metallurgical Society AIME,
New York, USA, 1982, pp 1
10. Sundararajan, T.,Karnachi Mudali, 0., Nair, KG.M.,Rajeswari, S. and Subbaiyan; M., presented
at 50th Annual Technical Meeting of Indian Insititute of Metals, New Delhi, Nov 14-17, 1996.
11. Marcus, P. and Bussell, M.E., Appl. Surf. Sci., Vol 59, 1992, p 7.
12. Nair, M.R., Venkatraman, S., Kothari, D.C.,Lal, KB. and Raman, R., Nucl. Instr. Meth. In phys.
Res., Vol B34, 1988, p 53.
13. Sabot, R., Devaux, R., de Becdelievre, AM. and Duret-Thual, C., Corros. Sci., Vol 33,
1992, p 1121.
14. Kamachi Mudali, U., Sundararajan, T., Nair, K.G.M. and Dayal, R.K., this conference.
15. Kamachi Mudali, U., Dayal, R.K., Grianamoorthy, 1.B. and Rodriguez, P., Metallurgical
Transaction A Vol 27 A, 1996, p 2881.
16. Tomashov, N.D., Chamova, G.P. and Marcova, O.N., Corrosion, Vol 20, 1964, p 166.
17. Sydberger, Werkst. und Korros., Vol 32, 1981, p 179.
18. Sedricks, A1., Int. Met. Rev., Vol 28, 1983, p 295.

1126
19. Kamachi Mudali, U., Dayal, R.K., Venkadesan, S. and Gnanamoorthy, lB., Met. Mater. Proc.,
Vol 8, 1996, pp9.
20. Trueman, J.E., Coleman, M.J. and Pirt, K.P.,.Brit. Corros. J., Vol 12, 1.977, p 236.
21. Speidel, M.a.: Proc. Of Int. Conf. On Stainless Steels' 91; Vol 1, ISH, Chiba (1991) p25.
22. Chyou, S.D. and Shih, H.C., Mater. Sci. Eng. Vol A129, 1990, p 109 .
23. Lu, Y.c., Bandy, R., Clayton, C.R. and Newman, R.C.,1. Electrochem. Soc., Vol 130,
1983, p 1175.
24. Willenbruch, R.D.,. Clayton, C.R., Oversluizen, M., Kim, D. and Lu, Y.C., Corros. Sci., V 01.31,
1990,pI79.
25. Kamachi Mudali, U., Dayal, R.K., Gill, T.P.S. and Gnanamoorthy, lB., Werks. und Korros.,
Vol 37, 1986, p 637.
26. Lu, Y.c., Ives, M.B. and Clayton, C.R., Corros. Sci., Vol 35, 1993, P 89.
27. Grabke, H.J., ISH International, Vol 36, 1996, P 777
28. Ashworth, V:, Grant, W.A., Procter, R.P.M. and Wellington, T.e., Corros. Sci., Vol 16,
1976, p 393.

1127
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6. Mumbai. India

Triazoles as Corrosion Inhibitor lor Brass in

Sea Water Environment
I.H. Farooqi1 and M.A. Quraishi2
'Lecturer, Department of Civil Engineering,
A.M.D., Aligarh, India
2Reader, Corrosion Research Laboratory, Department of Applied Chemistry,
A.M.D., Aligarh, India

ABSTRACT
The inhibitive effect oftriazoles on brass in 3% NaCl has been investigated by means of weight
loss, electrochemical polarisation and impedance methods. The present investigation also deals with the
mechanism of dezincification of commercial brass. All the triazoles derivatives, namely, Amino-methyl
mercapto triazoles (AMMT), Amino Ethyl mercapto triazole (AEMT) and Amino propyl mercapto triazole
(APMT) gave inhibition efficiencies in the order APMT (94.5) > AEMT (93.6) > AMMT (91.5). All the
inhibitors were found to be mixed inhibitors. Nyquist plots showed warburg impedance i.e. the reaction
was diffusion control. The inhibition efficiencies of the triazoles did not drop in dynamic flow conditions.
Solution analysis showed selective dissolution of zinc as compared with copper. The dissolution of Zinc
decreased in the presence oftriazoles, to 0.35 mg/l.

INTRODUCTION
Brass has been widely used as components in heat exchangers, pumps and in various industries
such as, sugar, petrochemical, paper, textile and marine industries. Studies on corrosion phenomenon of
brass assumes great significance as they are susceptible to a corrosion process known as dezincification.

Many organic compounds have been used as corrosion inhibitors for brasses in different media. Of
these azoles have shown the greatest efficiency [1,2]. Benzotriazoles have been recognised as effective
inhibitors for copper and its alloys. Recently tolytriazole has been found to have equal or superior inhibitive
action [3].

Dezincification of brass has been studied by various scientists. Heidersback and verink[ 4] have
proposed three hypothesis for the mechanism of dezincification of brass (i) Preferential dissolution of zinc
from the alloy (ii) Simultaneous dissolution of Cu and Zn followed by redeposition of the spongy. copper
on the surface of the alloy (iii) Dezincification by both the above mechanisms operating simultaneously.
Suguwara and Ebiko [5] have reported that the mechanism of dezincification is mainly due to redeposition

1128
of copper. Langenegger & Robinsion [6] observed a linear relationship between 'the rates of dezincmcation
and specimen potential and they have supported the preferential dissolution of zinc theory.

The present investigation is concerned with the study ofinhibitive action oftriazole derivatives,
. namely, amino methyl mercapto triazole (AMMT), amino ethyl mercapto tiazole (AEMT) and amino
propyl mercapto triazole (APMT) on the corrosion of commercial brass in 3% NaCI. The mechanism of
dezincification is also studied.

EXPERIMENTATION
The inhibitors were synthesized in the laboratory following procedures described elsewhere [7].
Coupons of size (5 x 2 x 0.025cm) were cut from commercial grade 70/30 brass sheet for weight loss
studies while for polarisation and impedance studies, brass strips with an exposed area of 1cm2 were
used. Specimens were polished mechanically and then successively with different grades of emery papers
and finally cleaned with acetone. Weight loss experiments were carried out at 40C for 5 days as described
in our earlier work [8]. Samples in triplicate were used for weight loss experiments and the inhibition
efficiencies were calculated from the difference in weight loss values in the presence and absence of
inhibitors.

The anodic and cathodic polarisation behaviour of 70/30 brass in 3% NaCI was determined
using EG & G potentistat 1galvanostat (model 173). Impedance studies were performed using a computer
controlled EG & G PAR system model M 6310 with software M398. A platinum foil was used as a
counter electrode and all potentials were measured against a saturated calomel electrode.

Dynamic studies were also performed to assess the performance oftriazoles under flow conditions.
Brass coupon was made to rotate in inhibited solution with the help of a motor using aJar test apparatus.

Solutions collected during the weight loss experiments were analyzed with digital portable
voltameter for determining Zn and Cu concentrations in the solution.

OBSERVATIONS AND DISCUSSION

Weight loss measurements
Table 1 gives the values of inhibition efficiencies obtained at different concentrations of three
triazoles derivatives, namely, AMMT, AEMT & APMT. All the compounds were found to inhibit
corrosion of brass in 3% NaCI water. The inhibition efficiency increased with an increase in the triazole
concentration till maximum efficiency was obtained at an optimum concentration of 200 mg/l. The
order of inhibition efficiency was as follows:

APMT (94.5%) > AEMT (93.6%) > AMMT (91.5%).

The inhibition efficiency of APMT was more than that of AEMT. This may be due to higher +1
(Inductive effect) of propyl group in comparision to ethyl group. Same is true for ethyl derivative in
comparision with methyl derivative.

Table 1 also gives the results of dynamic studies. It is seen that the inhibition efficiencies remained

1129
almost same under dynamic conditions, which are more realistic for the evaluation of cooling water
inhibitors.

Polarisation studies

The anodic and cathodic polarisation curves in the absence and presence of inhibitors at optimum
concentrations are shown in Fig. 1. Figure shows that the curves, in the presence of inhibitors, have
shifted to lower. current regions showing the inhibition tendency of triazoles. The values of various
electrochemical parameters are summarised in table 2. It can also be noted from table 2 that the presence
oftriazoles has not shifted the EoolT values considerably. Hence all the triazoles are mixed inhibitors.

Impedance Studies

Table 2 also gives the results of impedance tests. Fig 2 shows the nyquist plots in the absence
and presence of optimum concentration of inhibitors. It is seen that Rt values have increased and Cd]
values decreased in the presence of inhibitors. For all the three inhibitors nyquist plot shows warburg
impedance thereby meaning that the reaction was diffusion controlled. This situation occurs wlien the
electrode surface is covered with reaction product of limited solubility [9]. It has been reported by
various scientists that triazoles form complexes with copper [10]. The decrease in the Cd] values in the
presence of inhibitors show the coverage of metal surface with reaction product that results in decrease
in double layer thickness.

1130
Solution Analysis

Table 1 also shows the results of solution analysis. It is seen that preferential dissolution of zinc
occurs in the absence of inhibitors. However, the dissolution of zinc decreases as the concentration of
inhibitor increases. At optimum concentration. The zinc concentration in the solution was minimum in
the presence of optimum concentrations of inhibitors. Hence it can be said that the inhibitors under study
also minimises the dezincification of brass.

CONCLUSIONS

All the triazole derivatives were found to perform well as corrosion inhibitors for brass in 3%
NaCI water and the order ofinhibition efficiencies were: APMT > AEMT > AMMT. The inhibitors were
found to perform well under dynamic conditions also. The inhibition efficiencies obtained through
polarisation and impedance studies were in agreement with those obtained in weight loss method.
Polarisation curves reveal that all the triazole derivatives are mixed inhibitors. Nyquist plots show warburg
impedance thereby indicating that the reaction was diffusion controlled. Solution analysis showed selective
dissolution of Zinc as compared with copper. The dissolution of zinc decreases, in presence oftriazoles,
to 0.35 mg/I, a value considered environmentally safe for the disposal of cooling water blowdowo.

1132
 REFERENCES

1. Walker, R. Ibid, Vol. 32 (Ie), 1976, p-414.

2. Patel, N.K., Makawana, S.C., & Patel, M.M., Corros. Sci., Vol. 14, no. 1, 1974, p-91.
3. Hallander Orin and Roger C. May, Corrosion, Vol. 41, No.1, 19l1t5.
4. HeidersbackR.H., & Verink, e., Corrosion, Vol. 10, no. 7, 1972, p-897.
5. Suguwara, R., & Ebiko, H., Corros. Sci., Vol. 7, 1967, p-513.
6. Langenegger, E.E., & Robinson, F.P.A., Corrosion, Vol. 25, no. 2, 1969, p-59.
7. Dhaka, K.S., Jag Mohan, Chadha, VB. & Pujari, H.K., Ind. 1. Chern., Vol. 12, 1974, p-288.
8. Minhaj, A., Saini, P.A., Quraishi, M.A. and Farooqi, I.H., accepted for publication is Corr. Prevo
& Control, UK, 1997.
9. ASTM Designation, G-I06, 1994, pp. 427-435.
10. Chadwick, Rashami, T., Corros. Sci., Vol. 18, 1978, pp. 39.

1133
Proc. Int. Cant'. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Integrity of Incoloy-825 Cladded Mild Steel in

Sour Gas Service
A.S. Khanna1, A.K. Pattanaik1, P.F. Anto2 and S.K. Cliugh2
ICorrosion Science & Engineering, IIT Bombay, India
210ET, ONGC, Panvel, New Bombay, India

Abstract

The corrosion of pipeline which carries crude petroleum products is a serious problem in petroleum industries.
Thus selection of material for combating pipeline corrosion is an important aspect. Various kinds of pipelines
with different kinds of coatings from inside or use of inhibitors or other control methods are usually employed to
combat the corrosion of pipelines. A recent concept is the use of nickel base alloy cladding in the inside of the
mild steel pipe to control the corrosion from the highly sour gas environment. Recently Mis ONGC, an Indian
company, laid Incloloy c1added mild steel gas pipelines for their transportation. In the present work, the
corrosion behavior of this Incoloy and Incoloy c1addedmild steel in sour gas environment was investigated using
high pressure high temperature tests, sulfide stress corrosion cracking test, stress corrosion cracking and
constant extension rate tests. The results of High Pressure High Temperature tests help to predict life of the
material as well as suggest a method of repairing the defect if it is formed during service conditions. The results
of Sulfide Stress Corrosion Cracking and Constant Extension Rate tests revealed that the suceptibility of the
material to Sulfide Stress Corrosion Cracking was not affected by welding. The' C' ring and ' U' bend test
results showed that the material was not susceptible to Stress Corrosion Cracking. The present work justifies
the selection of Incoloy c1addedMild Steel for sour gas service.

1. Introduction

The selection of materials for pipeline construction is limited when all of the aspects of safety, structural
integrity, operating life and economic considerations are taken into account and acted upon. Carbon steel is
almost exclusive choice of pipeline designers. They are used to gather or collect natural gas, crude oil , refined
liquids, water etc. Cast iron is extensively used in water and atural gas distribution systems. Carbon steels and,
in certain types of service and environmental conditions, alloy steels are by far the most commonly used pipeline
material of construction.

The exploitation of various energy resources is becoming important because of recent shortages and increase in
energy demand. With the rise in the price of energy, several unconventional fossil fuel projects are. becoming
economically feasible. Among the projects, the production of oil from deep sour gas wells and the enhanced
recovery of petroleum reserves appear to be most promising. Deep sour gas exploration involves environment
containing H2S and CO2 gases. As a result of which corrosion of equipment and failure due to stress corrosion

1134
cracking are usually encountered. Similarly, the enhanced recovery using CO2 injection is expected to encounter
some corrosion problems. These corrosion problems would not be as severe as those encountered and/or
anticipated in deep sour gas wells. However, the high pressure and high temperature along with the presence of
H2S and chloride ions in the CO2 environment can induce severe corrosive attack in the form of high corrosion
rates, localized corrosion and/or stress corrosion cracking. 1.

Thus material selection for sour gas service, is an important aspect in curtailing these corrosion problems. High
performance Nickel and Cobalt base alloys are being evaluated for their resistance to various "sour gas"
conditions. The duplex-ferritic-austenitic and high Nickel stainless steel have been reported to offer improved
resistance to stress corrosion cracking in sour gas atmosphere. Highly alloyed stainless steel could be the
solution to some of the problems encountered in the inhibition of stress corrosion in sour gas wells.

The Nickel base alloys (Incoloy 825 and Hastealloy) offer the best resistance to corrosive attack by H2S stress
cracking at room temperature and to chloride! sulfide stress corrosion cracking at. elevated temperature. These
alloys show excellent performance in simulated CO2 well environment [1,2]. The materials which are in sour
gas service, undergo anyone or combination of the following corrosion problems.

I. Sulfide Stress Corrosion Cracking (SSC)

2. Hydrogen Induced Cracking (HIC)
3. Stress Corrosion Cracking (SCC)
4. Weight loss Corrosion.

A lot.of research [3-7] has been carried out to choose a proper materials which can withstand severe corrosive
conditions in the pipelines.

Cladding offers the strength and economy of one metal and the corrosion resistance of another. The material
which are used in deep sour gas wells, experiencing severe corrosive conditions, such as high temperature
exceeding 200C and the pressure in the range of 138 MPa with hydrogen sulfide, chlorides and salts. In these
environments, low alloy and stainless steel perform very badly. The corrosion resistant material has been
obtained by cladding the surfaces , which are in contact with the well eftluents, with a high alloy material. The
cladding material is selected primarily for its corrosion resistance properties or for other desired properties and
the base material is selected for its low cost and strength.

2. Experimental Details
2.1. Materials

Incoloy 825 cladded mild steel pipelines which are being used by ONGC for their gas transportation, are
subjected to various accelerated tests to study their behaviour in different service conditions. For this purpose,
Incoloy 825 cladded mild steel plates obtained from Japan Steel Works, Tokyo were used for testing their
integrity. The cladding of mild steel and Incoloy 825 Plate was carried out using HOt Rolling'technique with a
thickness of 2.5 mm (lncoloy 825) on a 16mm Mild Steel plate [8]. The tensile specimens for Sulfide Stress
Corrosion Cracking and Constant Extension Rate tests were made from Incoloy 825 rods. The following
accelerated tests were carried out for studying the integrity of the cladded materials.

2.2. High Pressure and High Temperature Tests ( HPHT)

A reactor vessel which is made up of Hastealloy HC276, was used for HPHT test. It has a capacity of one litre.
The maximum operating pressure is 6600 psi and temperature is 350C. There is a provision for water sampling

1135
which is useful in the study of corrosion products. The testing solution can be stirred with varying speeds ( 0 -
600 rpm ). The major application of this instrument is its versatile nature for corrosion testing in various
simulated service conditions. The environment which was used through out the experiments is :

Sodium Chloride (NaCI) 3.5 % /5.0 % 1-

Acetic Acid (CH3 COOH) O.lM
Carbon dioxide ( CO2) 7 Kg! cm2
Hydrogen Sulfide Saturation level (around 1600 - 2400 ppm)
Temperature 50/125 0 C
RPM ( Stirring) 200 or 500
Duration 96 hours

2.3. Sulfide Stress Corrosion Cracking Tests (SSC)

Sulfide stress corrosion cracking test was carried out on clad material Incoloy 825, to know whether the cladd
material is succeptible to sulfide SCC or not. The tensile specimen was made from Incoloy 825 rods with the
specifications: Gauge length = 33mm; Gauge Diameter = 6.3 mm ; Length = 10.2 em. Incoloy 825
specimens without any defect ( only clad material ) were prepared by removing the clad portion of the cladded
plate by milling. The SSC test was also carried out on welded specimens to know whether welded specimens are
susceptible to SSC or not.

The environment was set up according to NACE TMOl77-86. According to this specification, fifty grams of
Sodium Chloride and 5g of Acetic acid were dissolved in 945 ml of water. ( i.e. 5 % NaCI & 0.5 0/0( - 0.3M )
AcOH). The pH of the solution was approximately 3. Care was taken to ensure that the pH of the solutioh did
not exceed 4.5. The specimens were polished to a diamond surface finish. Before exposing to the environment,
the specimens were cleaned with acetone and the dimensions of the specimens were measured. The cleaned
specimens were then subjected to a stress equal to 80 % of the yield load of the material. ( 80 % of 10260.8 =
8208.64 N). The test solution was deaerated by purging with nitorgen for 1 hour. The deaerated solution was
then saturated with hydrogen sulfide before pouring to the corrosion cell, inorder to maintain the
concentration, the solution was continuously bubbled with hydrogen sulfide ( @ few bubbles per minute). The
time to failure was noted by a hour meter which is available with equipment.

2.4. Stress Corrosion Cracking Tests( SCC )

The 'c' rings were made from Incoloy 825 sheet according to the NACE specification :
Outer Diameter = 40 mm ; Internal Diameter = 34 mm ;
Thickness = 3 mm; Width = 20 mm ; Angle = 60 o.

The 'U' bend specimens were made from Incoloy 825 according to the following NACE specification :
L= 100m; M=90mm; W= 9mm; T= 3.Omm; X=25 mm;
y= 38 nun; R= 16mm; D=7 Mm.

The advantage of 'c' ring specimen is its versatility for determining the susceptibility to cracking of various
alloys. The 'c' ring specimens can be stressed to predetermined levels, using simple equipment, for the
application of either constant load or constant strain. The 'U' bend usually contains large amounts of elastic
and plastic strain. Thereby it provides one of the severe tests available for smooth SCC specimens. Another

1136
reason for selecting 'U' bend is its simplicity and economic feasibility. The environment for determining the
susceptibility of the material to stress corrosion cracking was in accordance with the standard NACE TMOI77-
86 at ambient temperature (room temperature) and 50C. The machined 'c' rings and 'U' bends were polished
to a surface of diamond finish. The polished specimens were cleaned with acetone for degreasing. The coating
was given to small portion of 'C' ring and 'U' bend specimens to ensure there was no galvanic couple formation
with coated nuts and bolts. 1-

Both 'C'ring and 'U' bend specimens were stressed to 90% of their yield load (90% of 10260.8 N = 9234.7 ).
The amount of compression ( change in diameter of the ring ) required on the 'c' ring to produce only elastic
straining, and the degree of elastic strain was calculated as follows:

2.5. Constant Extension Rate Tests ( CERT)

The tensile specimens were made from Incoloy 825 (non-weld) and Incoloy 625 (weld ) rods for carrying out
CERT test with the following specifications: ( Gauge length ~ 25 mm; Gauge diameter = 6.35 mm; Length=
17.6 cm ).

The machined specimens were polished to a diamond surface finish. Before exposing the specimen to the
environment, it was cleaned with acetone and the dimensions were measured. Then the tensile specimens were
subjected to the environment, 3.5 % NaCI with O.IM acetic acid pressurized by carbon dioxide ( 7 Kg/cm2).
The test solution was deaerated by purging with nitrogen for 1 hour. The deaerated solution was then saturated
with hydrogen sulfide before pouring to the corrosion cell. The temperature of the corrosion cell was maintained
around 50C. The specimens were subjected to the extension rate of 2.946 X 1O-~mm / sec (at the strain rate of
1.179 X 10-6sI) and the data were stored in a file by using a data acquisition software, the facility which is
available with the CERT machine.

2.6. Microstructural Analysis

The microstructural analysis of the exposed and un-exposed specimens to diferent testing conditions were.
analysed using optical and SEM/EDAX. The specimens were observed in optical microscope before exposing
the specimen to the environment. The microstucture were observed after properly etching the specimen. The
etchant used for Mild steel was 2% Nital and Aqua regia for Ni-alloys ( Incoloy 825 and Inconel 600). Before
etching, the specimens were polished upto fine diamond.

3. Results and Discussion

The corrosion .rates of Incoloy in different environments and temperatures using high pressure and high
temperature (HPHT) tests are shown in Fig.l& 2. It shows that there is an increase in the corrosion rates as the
temperature increases (both in 3.5% and 5.0 % NaCI ). The effect of temperature on corrosion rate is not very
high, it is evident from the fact that there is 1.5 times increase in corrosion rate as the temperature is increased
from 50 to 200C (both in 3.5% and 5.0% NaCI and 200 rpm). In the case of 3.5% NaCI solution ( 500 rpm),
decrease in corrosion rate is observed as the temperature is increased from 50 to 200C. But with increasing the

1137
concentration of the solution, i.e. 5.0% NaCI ( 500 rpm ), there is an increase in the corrosion rate. With
increasing the concentration of NaCl from 3.5%to 5.0% (at 200 rpm), the corrosion rate increases, but at 500
rpm, reverse trend is noticed. This trend is noticed at all temperatures. The increase in flow velocity from 200
to 500 rpm showed mixed trends. In the case of 3.5% NaCI, corrosion rate increases whereas at 5.0% NaCI
solution, corrosion rate decreases.

Similarly, the corrosion rates of Incoloy cladded Mild Steel ( with defect ) in different environments and
temperatures were also carried out. It was found that there was an increase in the corrosion rate as the
temperature increases (both in 3.5% and 5.0 % NaCI). But the effect of temperature on corrosion rate was very
high, it was four times increase in corrosion rate as the temperature was increased from 50 to 200C ( in the
case of 3.5% NaCI and 200 rpm ) and in the case of 5.0 % NaCI solution and 200 rpm , there was six times
increase in the corrosion rate. When the flow velocity was increased from 200 rpm to 500 rpm, in 3.5% NaCI
solution, there was a decrease in the corrosion rate whereas in 5.0% NaCI solution, corrosion rate increased.

The optical micrograph shows that the corrosion product are visible near the defects, rest of the area not
affected much as shown in Fig. 3. The SEM micrograph observation revealed the same points as shown by
optical, but the corrosion products deposition were clearly seen (Fig.4 ).

The corrosion near the defect was more compared to other places. The mild steel portion of the specimen comes
in contact with the environment through the defect. Since, the corrosion resistivity of Incoloy is more ( since
corrosion rate ofIncoloy 825 is less), the corrosion is more near the defect. (corrosion product which comes out
of the defect are deposited near the defect ). The hole is created by drilling and defects are created by using
electrical sparks, the temperature of the latter process is more, thereby leading to a zone ( similar to heat
affected zone during welding) which is prone to corrosion. The elemental composition of corrosion products
formed near the defect in Incoloy cladded mild steel specimens were analyzed using EDAX. One of the results is

1138
shown in Fig.4. The EDAX resuhs were not sufficient enough to know the nature of corrosion products in
decisive manner. But at the same time, the results indicates there might be formation of either nickel sulfide or
iron sulfide or chromium sulfide. Since the free energy formation [9] of nickel sulfide is very less, the possibility
for the formation of nickel sulfide is more feasible.

If the pipeline is made up of only Incoloy 825, then the pipeline will last for many years because the effect of
temperature, concentration of NaCl and flow velocity is very less on the corrosion rate of the material. The
economic viability of the material is not encouraging one, the cladding with mild steel is opted. If the clad
material is alone exposed to the environment ( mild steel is not in contact with the environment ) then the
pipeline will survive for many years. But if any defects are created during the service conditions, the life of the
pipeline decreases. For example, at 500C and 3.5% NaCl environment and the thickness of pipeline is around
16mm ( only the mild steel thickness is taken in to account, as the corrosion rate of clad metal is very less
and the thickness is around 2.5 - 3.0mm ), then the life of the pipeline is around 37 years. ( The defect size is
around 0.5 to 0.6 mm and depth is around 2.2 - 2.5mm ). If the defect size is not that large size to reach mild
steel portion then life of the pipeline is not affected much.

From the sulfide stress corrosion cracking results, it was found that the non-welded and welded tensile
specimens which were exposed to NACE TM-OI-77 conditions for 720 hours ( 30 days ), showed no crack
during the entire test time. This leads to the conclusion that the welded and non-welded specimens are not
susceptible to Sulfide Stress Corrosion Cracking (SSC).

1139
Similarly, the 'C' ring 'U' bend specimens which were exposed to NACE TM-01-77 conditions for a period of
14 days also showed no crack during the testing time. Even the rise in temperature to 50C, had not affected the
susceptibility of the material to Stress Corrosion Cracking ( SCC).These tests supports the fact that the Incoloy
825 is not susceptible to SCC .

The results obtained from the CERT test for non-welded speimen is shown in\ig.5. The cracked specimens are
observed under scanning electron microscope for understanding the mode of failure. The observations revealed
that the specimen failed because of ductile fracture. This is evident from the SEM micrograph ( Fig.6 )
indicating the presence of dimples, which indicates the typical ductile mode of failure for both welded and non-
welded specimens. This further revealed that the specimens are not susceptible to Sulfide Stress Corrosion
Cracking.

From the data obtained, a plot of load Vs % elongation is made (Fig.5) from this curve, the tensile strength and
the yield strength of the materials are calculated.

The parameters which are

calculated from the results
obtained is given in Table 1

From the results, it is found

that the strength of the
material is unaffected by
the environment. The %
elongation, which is main
parameter in deciding the
susceptibility to stress
corrosioncracking, speci-
men has acceptable %
elongation and strength. The
specimen is cracked by
ductile failure, this indicates
that the specimen is not
susceptible to stress
corrosion cracking.

1140
4. Conclusions

The following conclusions can be drawn from the present investigations:

The high pressure and high temperature tests demonstrated that Incoloy 825 cladding can provide corrosion
free service for more than 35 years in sour gas environment.

Both non-welded and welded specimens are not susceptible to Sulfide Stress Corrosion Cracking. This
supports the use of Incoloy 825 in sour gas pipelines and the welding technique as mode of repairing.

The life of the cladded material decreases if defects are created during service conditions.

Constant Extension Rate Test resuhs of non-welded and welded specimens indicates that both the specimens
are not susceptible to Sulfide Stress Corrosion Cracking. The strength and other properties ( like %
elongation, % reduction in area etc.,) are not affected much because of welding.

1141
References

1. A.T.Asphahani," Evaluation of Highly Alloyed Stainless Steel materials for CO2 / H2 S environment",
Corrosion, TI. No.6, 327, June (1981).

2. W.K.Unl and M.R.Pendley, "HIP clad Nickel base alloy 625 for deep four well", Materials Performance,
~ No.5, 30, May (1989).

3. B.FWilde, C.D.Kim and E.H.Phelps, "Some observations on the role of inclusion in Hydrogen Induced
Blister Cracking (HlBC) of line pipe steels in sulfid environments", Corrosion, J, No.ll, 625, Nov
(1990).

4. T.Taira etaI., "SSC of line pipe for sour gas service", Corrosion, TI. No.1, 5, Jan (1981).

5. R.M.Thompson and G.B.Kohul et aI., " SSC failures of 12 Cr and 17-4PH Stainlees Steel well head
equipment", Corrosion, 17, No.3, 216, Mar (1991).

6. M.Kimura and N.Totsuka et aI., "Sulfide Stress Cracking ofline pipe", Corrosion, ~ No.4, 346, Apr
(1989).

7. T.Nakayaman and S.K.Fujiwava et aI., "Development of high strength, high corrosion resistant austenitic
stainless steel for sour gas service", Corrosion, 45, No.9, 749, Sept (1989).

8. Product Literature, Research Laboratory, Japan Steel Works, Tokyo, R(PL) 87-07493-041, Aug (1993)

9. AJohn Sedriks, "Stress Corrosion Cracking - Test Methods", Corrosion Testing Made Easy, 1.. NAC~
(1990)

1142
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Performance and Cost Evaluation of S9me Glass Fibre

Reinforced Polyesters and Steels for Hopper Box used in
=-
Seed-Cum-Fertilizer Drill Agricultural Machine
Kavita Gidwanit, A.K. Singh2, V.S. Muneshwa~ and A.K. Gupta2
1M. Tech. MACT, Bhopal
2Scientist, Regional Research Laboratory, Bhopal, India

Seed-cwn-fertilizer drill machine!!have been introduced and popularised to facilitate seeding operation and
to maximize crop yields. It saves 50-75% time, 45-800,4 sowing cost & labour, productivity can be increased
and yield is increased by.11-37% in ploughed and irrigated land over the traditional sowing devices. Seed
drill or combine drill have major components like seed and fertilizer hopper box, metering device, seed!
fertilizer distribution (fluted roller), furrow opener, wheel drive depth control-cum-transport wheels etc.
Hopper box is an important component of tractor and animal drawn seed-C'llItlfertilizer drill machine. It is
used as a storage bin for seed and fertilizer during sowing operation. It is generally made of mild steel sheet
of various thickness varies from 0.50 to 1.5 mm. The boxes are coated with enamel paint from inside and
outside to avoid corrosion due to atmospheric exposure and other reasons.

The hopper box corrodes very filst and the life was reported to have around one to two years. The present
.study has been confined to upgrade corrosion and abrasion characteristic of the box material for quality
upgradation for better performance. In order to develop better alternate appropriate material for the hopper
box different materials such as enamel coated mild steel, uncoated mild steel, galvanized mild steel, tin
coated mild steel, glass fibre reinforced epoxy (GFR-Epoxy), GFR-Bisphenol, GFR-IsopthaIic, GFR-Gen-
eral Purpose, GFR-HDPE polyesters have been characterised under different corrosive medias for their per-
formance evaluation.

The extent of loss were determined in terms of weight/volwne loss of the materials in different corrosive
environments viz (i) dilute Solution ofHCL, HN03, ~S04 and NaOH (ii) Concentrate solution of fertilizer
like DAP, Urea. ~so 4' KCl. These materials have also been tested for abrasion characteristics using Suga
Abrasion test setup. It is a standard equipment for two-body abrasion test which is recognised by ASTM.
The aurface topology using SEM to examine the extent of attack of fertilizer and chemical and also
worn surface have been carried out. It was found that the glass reinforced polyester resin was much superior
and four to five times better abrasion and corrosion resistant as compared to mild steel materials. Further-
more, am~ polyester resin glass fibre reinforced HDPE was found to be the best and may be suggested
81 suitable material for this application. The performance was also evaluated considering the abrasion and
corrosion behavior of the materials and their corresponding <;ost.

1143
INTRODUCTION :-
Hopper box is an important component of tractor and animal drawn seed-cum-fertiliZllr drill machine. It is
used 8S 8 storage bin for seeds & fertilizer during sowing operation.

BSI Specification for the hopper box is as follows; 1-

1. Mild Steel sheet ofl6-22 gauge thickness or 1.6-0.7 nun thick:cold and rolled shoet.(IS:11691, 226)
2. Galvanised sheet (IS : 11691, 227)
3. Seasoned wood (IS: 11691, 289)

Conventional hopper box is fOlmd to he corroded very fiIst by the combined action of fertiliZllrand atmo-
spheric exposure and generally life span has been recorded to' be aroood 1-2 yean. The degradation is ~
cause of high rate of corrosion and Erosion - Abrasion in the form of pits, deep holes and rust The visible
reasons for this high corrosion are chemical attack of fertilizers, preBeDCeof moisture & oxygen in the
atmosphere and Erosion-Abrasion by the seed and fertilizer.

Urea, DAP and potash based fertilizers are mostly used for various crop production in India. In contains

suitable salt ion ofNa+, K+Mg*, Ca*, NH4*, Cl", 804-- and No]" etc. When it expose to moisttn and oxygen
of the atmosphere various types of inorganic acids and alkalis. are formed and corrosion in steel/Jron take
place in the form of etch pits. Erosion Abrasion occur due to impact and rubbing action of the seeds and
fertilizer particles against the box during pow1ng of the grains rubbing in course of downward movement of
the particles during sowing operation.

Considering are all these observations OR Polymer was found to be used for hopper box as followed by
improvements
1. Corrosion resistance against mild acid and alkalies.
2. Moderate abrasiOJiresistance
3. Moderate erosion resistance
4. Easy fabricatability & formability
5. Cost effective.

2.0 Materials aIId Experimeat :

The following materials were selected for study and characterisation as alternative appropriate materials for
the hopper box as to improve the life and perfonnance of hopper box. These are easily available and cost
effective materials.
Material Studied for Iaopper bos
1. Enamel paint coated mild steel.
2. Galvanized mild steel
3. Tin Coated mild steel
4. Uncoated mild steel
Polymeric Material
5. Glass Fibre Reinfoced Epoxy
6. Glass Fibre Reinforced Bisphenol
7. Glass Fibre Reinforced Isopthalic
8. Glass Fibre Reinforced General Purpose
9. High Density Polyethylene

1144
2.1 Material C.cterisation
2.1.1 Corrosion studies were caniod out in the following solution using dip test tectmique - where the
spec~ were kept in solutions and the latter was agitated by a stirrer.

'1. 50% DAP Solution in water 1.

2. 5ooA.Urea Solution in water
3: 20% KCl Solution in water
4. loGA.~S04 Solution in water
5. 01% HCl Solution in water
6. 01% ~S04 Solution in water
7. 01% HNO) Solution in water
8. 01% NaOH Solution in water

2.1.2 Abrasion - Corrosion

The experiment worlc was carried out in sand bed in which the samples were rotated with low r.p.m. These
sands were of the two type.
A Sand mixture containing 2% of 50% water solution of DAP fertilizer
B. Sand mixture containing 2% of 50% water solution of Urea fertilizer.

3.0 Res.1t & DUcu.lon :

The performance in the term of material loss under different sets of test condition are calCulated and also
compared with material cost and cost of processing.

The analysis-are based on the following assumption.

1. Negative values indicates the degradation due water absorption and is considered IS a kind of material
Iou.
2. performance were determined on the basis of the actual test run.
3. Cost ofmatorial based on volume loss.
4. Lamination of 1 nqn thick polymeric material is quit enough on mild st~l, therefore the calculations
were based on the loss of 1 mm thick plate.
5. Performance and cost analysis were determined considering the cost of piocessing and matorialloss
during the stipulated test run.

The results obtained have been presented in the fonn of (table 1 - 4) and cost'analysis data are given in table
4. Material loss has been calculated by weight by volume and volume loss per unit area.

3.1 : Mild steel is low cost and easily available material. In order to protect against corrosion mild steel
boxes are coated with enamel paint. Therefore, enamel coated mild steel was taken as a reference for
performance and cost comparision. Regarding tin coated and galvanised steel, their repairing and replace-
ment cost are high therefore it has not been considered in latter studies. Corrosion test under mild steel acid.
base and water solution of various fertilizer were also carried out to simulate corrosion in the hopper box.

Abrasion corrosion test under 2% of 500!OUrea & n l\ 1 water solution sand mixture was carried out to
simulate the rubbing action that occur during downwards movement of the fertilizer, and seeds their and
impact action.
1. Enamel Paint coating was found to be the least corrosion resistant as compared to galvanized and tin
plated mild steel (table 4).

1145
Galvanized sheets are better then enamel coated and tin plated mild steel sheet. Further Lab findings indicate
that galvanized and tin plated sheets have shown limited life after that either it has to be fully replaced or to
be protected by means of coating which will be an expensive Job: Because of their high cost of replacement
and protection hence they are not economically viable (table 4).

2. Polymer materials have been fOWldto be better alternative material. Lab bding indicates that lamination
of high density polyethylene (HDPE) foWld to be the best material followed by general purpose and
epoxy polymer. It is to be noted that addition of 100/0 of glass fibre in the polymer would double the
strength at the rruuginal increase in the cost at the most by 5 to 8% (table 4).

1146
1147
3. Based on laboratory experimental tests and the severity of the test conditions. The life of the polymer
material obserbed to be around 5 times more then the enamel coat mild steel sheet. Suggested polymeI1l are
cheap and easily available, it can work satisfactorily under mild ~dic and basic conditions mostly encoun-
tered on seed-cum- fertilizer -drill machine. Capital investment on equipment and other maintenance are nil.
It can be repaired by finther coating and welding. It has got sufficient strength to bear load and jerks of the
machine. The polymer materials can be brush coated, rivited and laminated. 11' box can be straightway made
out of polymeric material using hand moulding and casting.

Conclusions:

1. Polymeric material in general was found to be better altCma1ive material compared to mild steeL

2. Among polymeric materials high density polyethylene was fOWld to be the be8t material
followed by general purpose and epoxy polymer.

3. Addition of glass fibres in polymer by 10% would double the strength of the material at
additional margional cost only by 5 to 8%.

4. Metallic materials such as g1avanised sheet and tin coated sheet are not teclntoeconomical feasible.

5. Fabrication of glass reinforced polymeric materials are S1raigthforward and can be done by hand
moulding and casting. it can be cladded with steel sheet or component may directly be made out
of polymer inateria1.

Referecences :

1. Directory of Agricultural Machinery & Manufactures. P - 101, Compeled by G. Singh & K.K.
Bhardwaj, Technical Bulletin CIAE 85/47, CIAE.
2. G.R. DIMs, Proceeding, Ins. Mech. Engg., 1965-66 Vol. 180 (2A) pp -237-247.
3. R.W. Johnson, Wear, 1968, Vol. 12 PP 213-216.
4. Kirk, R.E. and Ot1uner, D.F. Encyclopedia of Chemical Teclmology, 3rd edn, Jolm Wiley,
New York, 1978.
5. SheD, F.D. and Hilton, C.L. Encyclopedia ofIndus1rial Chemical Analysis, Interscience,
. New York, 1966 ..
6. Engineering Materials and Design, Oct. 1975, p. 46; Januaty 1976, p. 40; Feb. 1976, p. 13
7. Electrical Review, 12 March 1976, Volume 198, Number 10, p. 32

Acknowledgement:

Authors wish to thank Director RRL, Bhopal for the permission to publish the work.
Authors are thankful to Sh. Mohan Gurjar, Vmmdra Singh, P.N. Patil and other staff members of
RRL, Bhopal for their help in the experimental work

1148
Proc. In!. ConI'. on Corrosion CONCORN '97
December 3-6. Mumbai. India

Corrosion Behaviour of Magnesiulp Alloys in

Chloride Medium
Inder Singh and A.K. Bhattamishra
National Metallurgical Laboratory,
Jamshedpur-831 007, India

ABSTRACT

Magnesium and its alloys find wide application as sacrificial anode in cathodic protection of
pipelines and burried structures where hot zones exist. Magnesium alloys containing different
alloying elements, such as Sn, Cd and Zn were cast in the form of rod of dia. 1/2" and studied
potentiodynamically and galvanostatically. PARC-273 was used for the polarization studies.
OCP,E and
cOlT were measured. The total immersion test was also carried out to record weight
L:OIT

loss. It was obseIVedthat alloy containing Cd and Zn showed higher corrosion rate in comparison to
other alloys studied under identical conditions. Addition of Sn to the alloy improves the corrosion
resistance properties marginally. Magnesium alloy containing Sn and Cd only was found to have
superiority over other alloys in respect to corrosion resistance properties. The weight loss data
substantiate the polarization data. The data are discussed in detail in the paper.

INTRODUCTION

Magnesium and its alloys have been well accepted as sacrificial anodes for cathodic
protection of pipelines, buried structures, hot spot areas, etc. The performance of the alloys, in
general, is dependent on their chemistry, micro-structural features, the environments, nature of film
formation in the specified medium, ect.. Also, the dissolution of the alloys varies with the media and
the alloying elements or impurities in the magnesium alloys. As reported, cathodic impurities, like
Cd,Tin and Zn have substantial influence on the performance of magnesium anodes in corrosion
media. Still, systematic studies on the corrosion behaviour of the magnesium alloys containing these
elements are lacking. The paper discusses the data generated on corrosion rates as a function of
composition ofMg- alloys, containing Cd, Tin and Zn.

EXPERIMENTATION

Four magnesium alloys containing Cd, Tin and Zn were cast and machined upto 12.5 mm dia
rod (Table-I). These alloys were mechanicallypolished upto 600 grit finish, washed, cleaned and

1149
degreased with acetone. Samples for different experiments were cut as per the requirement from
these cast rods.

Total immersion test was carried out using cut slice (2 rom thick x 12.5 rom dial of the rod
samples in 3.5 % NaCl solution for 96 hours, Initial and final weights of the samples were measured,
using Metler Digital balance. Corrosion products from the surface after the exposure were removed
by chromate solution as per ASTM-G(I). Corrosion rates were determined., Data are set-forth in
Table-2.

Electrochemical tests on four Mg-alloys were carried out using PARC-273

Potentiostat/Galvanostat in 3.5 % NaCl solution. Surface area of I cm2 was used for polarization
studies at the scan rate of 2 mY/Sec. Saturated calomel electrode and graphite rod were used as
reference and auxiliary electrodes respectively. L:OIT EcolT,OCP and corrosion rate were measured.
(Table-3).
Table-3
Electrochemical test data on Mg-aUoys exposed in 3.5 % NaO solution
( Potentiodynamic polarization)

1150
 RESULTS AND DISCUSSION

Data on total immersion test in 3.5 % NaCl solution indicate that the corrosion rate of the
Mg-Zn-Cd alloy is on higher side followed by Mg-Zn-Cd-Sn alloy. The alloy containing Zn and Sn
has slightly better corrosion resistance, but Mg-alloy with Sn andtCd only has shown superior
corrosion resistance in comparison to other alloys studied.

Potentiodynamic polarization studies in chloride medium also reveal that Mg-alloy containing
Cd and Sn only has lowest Ico.,. as well as the corrosion rate, but Mg -alloy containing Zn and Sn has
slightly improved corrosion resistance. The highest Ico.,. as well as the corrosion rate have been
observed in case of Mg-Zn-Cd alloy which may be due to higher dissolution rate under galvanic
actions. It has also been observed (Fig. 1) that all the alloys are showing strong anodic polarization
whereas the alloy containing Sn and Cd is cathodically controlled to a great extent. Also, in the
galvanostatic polarization experiment, the Mg-alloy containing Sn and Cd develops lowest negative
potential at equihorium condition.

CONCLUSIONS

l.Alloying addition ofZn in Mg-Sn-Cd system is not beneficial from corrosion resistance
point of view.

2.Addition of Cd has deleterious effect in Mg-Zn alloys

3.Dissolution tendency of the alloys studied in 3.5 % NaCI solution decreases in the
following order

B > A > C >0

ACKNOWLEDGMENT
,
The authors record their sincere thanks to PrOL P.Ramchandra Rao, Director, NML,
Jamshedur for giving permission to publish this paper.

1151
1152
Fig. 2 Galvanostatic polarization of magnesiwn alloys in 3.5 % NaCI solution

1153
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Effect of Mixed Cationf on

Phosphate Coating of Steel
D.D.N Singh and Bijay Kumar Singh
National Metallurgical Laboratory,
Jamshedpur-831 007, India

Abstract

Effecs of ~ariat~ons in t~ constituents of phosphating

baths having Zn +, Mn +, Ni + and Ca + on performance of produced
coatings on steel surfaces, have been studied. It is observed
that a bath having Zn + Mn + Ni as their phosphates and Ca as
nitrate, provides excellent coating on the surface. Addition of
urea (U), hexamine (HA), guanidine nitrate (GN) and nickel nitrate
(NIN) provides different types of effects. HA doubles the rate of
coating formation but produces a coarser and poorer corrosion
resistant film. Thermal resistance, spot corrosion resistance,
alkali resistance tests and immersion resistance tests have been
performed to determine the characteristics of the coatings. Salt
spray resistance (8 117) studies indicate that the phosphated
surface having passivation treatment of Phosave (a trade name)
provides an excellent improvement in controlling of appearance of
brown rust on the surface. Electrochemical studies indicate that
the produced coating is more resistant in saline environment than
sulphurous acidic environments. SEM studies indicate that the
addition of GN in phosphating baths has a strong influence in
transf0rming the morphologies of phos1:hatecrystal structure from
coarse to finer one.

1154
 Zinc phosphate coatings on steel surfaces are applied to
achieve conversion coatings of zinc andiron phosphate. These
coatings provide good corrosion resistance, .act ~s absorbent for
lubricant in contact of lubricating agents and i~crease the life
of dies, provide excellent base for the applications of paints and
sometimes also used to harden the surface to achieve abrasion
resistance. OUt of these applications, the application of paints
and coatings on phosphated surface is the most cri~ically affected
due to the variation in morphology of structure of phosphate
layer. In recent years, attempts are being made to modify the
coating structures by providing appropriate optimized treatments
by incorporation of cations, surfactants and changing paIameters
of bath to achieve high degree of corrosion resistance (Salt s:gy
and immersion tests), thermal resistance and alkali resistance .
Amongst the various types of cations, zinc in combination
of Mn ++ and Ni ++ is reported to provide superior performance.
However, the studies in our lab have shown that incorporation of
Ca++ in the coating improves the performance to a great extent,
especially in changing the morphology of structure of the
coatings. The types of passivation treatments provided on the
phosphated surface also affect the degree of corrosion resistance
to a considerable extent. A Literature survey of last 10 years has
shown that the details about such types of phosphatings are not
reported in research papers. The Present work was undertaken to
have a detailed investigation o~ the 2 coat~g prov~ded by a
phosphating composition having Zn +, Mn +, Ni Tand Ca + and also
incorporation of some surfactants in the coating bath.

2(a). Composition of substrate: Mild steel coupons having 0.15%

C, 0.6% Mn, 0.055% Sand 0.09% P were used as the substrate to
provide coating. Reagent grade chemicals were used for the
preparation of baths. The steel coupons of size 7.5 cm x 2.5 cm
x 0.05 cm were cut and pickled in 10% HCI. The specimen were then
exposed in phosphating bath maintained under different
conditions.

2(b). Phosphating bath compositions and deposition of coatings:

Following are the compositions of baths chosen for the
studies :

1155
In all th'e cases, the pH of the bath was maintained at 3.5 by
addition of appropriate amount of phosphoric acid: The
experiments were performed in beakers keeping them in
thermostatically controlled water baths. In each sets of
experiments, 6 samples. were tested simultaneously and average
results were calculated. To determine the coating weight, the
weight of samples were taken prior to and after phosphating. The
final weights were taken after dissolving the phosphated specimen
in 10% NaOH for 20 minutes.

2(c). Salt spray resistance tests: These tests were performed as

per B 117. The observations were made after each 8 hours of
exposure time .

2(d). rmm&rsion tests.: Immersion tests were performed by dipping

the specimen in 3.5% NaCl solution at 30 C. After 360 hours of
exposure , the iron leached out in the solution was determined by
titration method. Spot corrosion resistance tests were performed
by making cross scratches on the painted panels (provided with 3
coats of acrylic paints and dried for 72 hours prior to giving
scratch tests) and dipping in 5% NaCl +0.5% CuSO solution for
4
50 minutes. The corrosion of spots appeared on the surface
were counted by visible observations ..

2 (e). Thermal resistance tests : In this test, the phosphated

0
specimen were placed in oven at 100 C for 10 minutes. The
0
temperature was increased from 100 to 180 C in 45 minutes.
After this heat shock, the specimen were removed and kept in
dessicator and cooled there. Th~ weight changes were determined
after 6 hours.
2 (f). Alkali solubility tests: Tne pnospnaced sUrt-ace- was-
dipped in O.lN NaOH for 60 minutes. The coupons were then
removed and dried with hot air. Percentage coating weights left
on the surface were recorded by loss in weight divided by the
original weight of coating multiplied by 100.

1156
2 (g). Electrochemical studies,: Electrochem~cal studies were
performed by cutting the specimen of 1 cm area from the
phosphated panels. The edges of the panels were coated with
acrylic paint. The tests specimen had stem of 5 cm length through
which electrical contacts were made. Potentiodynamic polarization
tests were run in 3.5% NaCI and in acidic distil1ed water (pH =
3.5 brought down by the addition of sulphuric acid) .. The
specimen initially were put in the electrolyte to achieve a steady
state open circuit potential. The polarization runs were then
performed first starting the potential from negative potentials to
positive potentials. The scan rate in all the cases was maintained
at 100 mv/min, using a potentiodyne analyser (supplied by M/S
Petrolyte Corporation, U.S.A.). All the potentials were measured
against saturated calomel electrode (SCE).

Total acidity, free acidity, acid ratio values before

and after phosphate treatments and coating weights are given in
Table I.

Table II: Total acidity {TA}, fr!e acidity {PA}, acid ratio
{R},Coating weight {gms/m} in different baths.

Treatment time : lS min~tes

Total area phosphated : 0.g3 m
Temperature of bath :90 oC {Bl, B2 and B3}
80 C {B4 and B4 + additives}

1157
 The above Table shows that baths B1, B2 and B3 provide
very high weight of coating and also cause severe dissolution of
iron. These baths were, therefore, not further investigated.
Bath B4, which was prepared by mixing of Zn, Mn, Ni and Ca was
taken as an ideal bath as the acid ratio of the bath before and
after phosphating was the s.ame. This type of batJ1s are considered
ideal from stability point of view. Addition of HA in this bath
has a strong accelerating effect on the coating formation. The
coating weight has almost doubled in this case, in comparison to
the blank and other additives. Iron dissolution in presence of HA
is also increased to some extent but not in ratio of increase in
the coating weight. A careful examination of the results indicate
that in the presence of all the additives, the change in total
Cicidity of the bath after experiments, is of the order of 4
pointage as compared to only 2 in blank (B4) $olution. The
deposition of coat~g weight in all the cases except HA is of the
order of 9-10 gm/m. These observations indicate that HA helps
in converting of maximum soluble metal phosphates (present in the
form of total acidity) into insoluble phosphates who crystallize
on the steel surface. Very limited amount is wasted in the form
of sludge. In contrast to this,the other additives convert a
greater fraction of phosphates into insoluble phosphates in the
form of sludge. The greatest disadvantage associated with HA
however, is its tendency to drastically increase the acid ratio
value of bath 'after the coating treatment which is 12.5 against
its original (prior to coating) value of 6.3. The other additives
change the acid ratio values of the order of 3 only. A negligible
effect in acid ratio is noted for the bath having no additive.

Salt spray resistance tests on the performance of

different types of coatings and effect of passivation treatment'
have been incorporated in Table III.

1158
 The above table shows that the baths 84 and,84 having
urea exhibit extremely poor salt spray resistance under
unpassivated conditions and the whole surface is rusted
within 24 hours of exposure. The baths having GN and NIN,
however, provide superior performance and almost no attack is
noted upto 48 hours of exposure. A drastic improvement is noted
when the phosphated sur!aces !ere passivated in 2~ of NML-Phosave
(a passivator having Cr +, Cr + and organic chemicals). The baths
84 and 84+U exhibit salt spray resistance of over 72 hours under
passivated conditions compared to hardly -8 hours in the
conditions of unpassivated surface. GN and NIN provided further
improved life of 144 hours under passivated conditions. These
improvements were achieved clearly due to the blocking effects of
Phosave on the pores existing in phosphated layers (The phosphated
layers produced by 84, 84 + U had very bigger size of crystals
and the surface had appreciable amount of porosity, as discussed
later) .

The change in open circuit potential of unpassivated

phosphated surface with passage of time is shown in figure 1.
In all the cases, it is noted that the potential shifts in -ve
direction with the passage of time and stabilize almost after one
hour. The trend in case of passivated surface had also been the
same except that the stabilized potential values varied
considerably in comparision to the passivated potential. These
potentials are shown in Table IV.

1159
is the cathodic reaction. A shift of potential in active
direction indicates the polarization of this reaction. A faster
rate of polarization is obderved in passivated
surface of phosphate coating provided in the presence of GN
and NIN, as evident from the time required to stabilize the
potential. This is attributed to the blocking effect of Phosave
of pores of phosp~ate layer with increase in pH at the interface,
as a result of OH ions generated by the reaction (i).

The results showing the effect of type of phosphate

coating on thermal resistance (TR), corrosion resistance (CR),
alkali resistance (AR) and immersion resistance (IR)are tabulated
in table V.

1160
 Phosphated surfaces are exposed to thermal treatments
during the baking of the paints ap~lied over the surfaces. This
baking is carried out at about 180 C in heating ovens. During this
baking process, the water of crystallization present in the
coating is lost and results in changing of microstructure of
coating. The corrosion resistance and adhesion properties of the
phosphate coating is adversely affected due to the loss of water
of crystallization. Calculation of percentage of water in coating
weight [zn3(po4)2. 4H2o+FeZn2(P04)2.4H20] shows that about 20% of
weight of coating is the water of crystallization. For a good
coating, the loss of water should not go beyond 10% A pure Zinc
phosphate coating exhibits loss of water > 15%. A tricationic
phosphating , however, resists the dehydration of coating during
the baking process. This is evident from the above table where
the TR values in all the compositions are almost of the order of
the 10% loss of coating weight. Appearance of the rusted spots on
cross hatched surface is the lowest in the bath having no
additive. Alkali resistance of coating is also lowest in the
case of blank bath having no additive. This is best in case of
the bath having HA as the additive.

Immersion resistance 0f coating is best achieved in the

2
bath having GN (0.85 mg/cm of iron leached out from the
coating/substrate) 2 whereas it is worst' for the blank solution
+ HA (1.32 mg/cm ). This observation is totally in contrast
with the observations noted for alkali resistance. Where B4 + HA
provides higher value of coating weight left on the surface (92%).

Potentiodynamic polarization plots for the phosphate

coatings produced in bath B4 (Zn+Mn+Ni) and having passivation and
no passivation treatments are shown in figure 2. These plots have
been drawn in 3.5% NaCl and in acidic distilled water (pH=3.5)
brought down by the addition of sulphuric acid. These studies
were performed to study the effect of saline environments

1161
(experienced in coastal areas) and sulphurous environment
(experienced in industrial are'as) on deterioration of phophate
coatings. It is observed from the figure that the corrosion
rate in acidic environments, where hydrOgen evolution is the
cathodic reaction, is more (about 100 times) than in chloride
environments, where aggressive ion is chlotide and oxygen
reduction is the cathodic reaction. In both the cases, the
passivation treatment provided by Phosave has a pronounced effect
on the dissolution of phosphate (anodic polarization) and the
cathodic reaction. Passivation effect is more pronounced on the
cathodic reduction of oxygen.
Microstructures of phosphated surface produced in the
presence of B4 bath and having GN and HA are shown in figures 3
(a), (b) and (c) respectively. It is eviden~ from the
microphotographs that in the absence of any 'additive, the bath B4
produces coarse and fine crystals of phosphate. EDX analysis of
these cystals exhibited that the majority of the constituent was
zinc followed by iron and manganese phosphates. Trace amount of
nickel was also noted. It, further reveals that the growth of
crystal was not uniform. When GN was present in the same bath,
very fine and uniform types of crystals were produced (figure
3-(b) ). Addition of HA, on the other hand, produced very coarse
structures (figure 3-(c) ). These structures have' strongly
influenced the corrosion resistance properties of the coatings
produced on the surface.

(i) The phosphate coatings produced by Zn+Mn+Ni phosphate baths

provide excellent resistance towards thermal resistance,
corrosion resistance and alkali resistance.

(ii) Addition of HA in the bath strongly enhances the coating

weight formation but has adverse effects on other properties.

(iii}Presence of guanidine nitrate (GN) in the bath has a strong

positive influence on corrosion resistance properties of
tricationic phosphating.

(iv) Passivation of phosphated surface using NML-Phosav8 strongly

enhances the protect ive propert ies of the coat ings . This
improvement is reflected in salt spray, immersion and other
tests.

(v) The phosphate layer produced is more resistant in saline

environment than in sulphurous acidic environments.

(vi) Microstructures reveal that GN addition in the bath helps in

producing smaller and uniform crystals of phosphates.

1162
1163
1164
1165
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6. Mumbai. India

Passivation of Galvanized Surfaces,.to Improve their

Corrosion Resistance
D.D.N. Singh, A.K. Dey and Israr Khan
National Metallurgical Laboratory,
Jamshedpur-831 007, India

1167
 Freshly galvanized surfaces are very prone to interact
with the surroundings and form white powdery corrosion pr.oduct
which is generally hydroxide, carbonate or chlori~s / sulphates.
These powdery corrosion products are known as wfiite rust. The
protective properties of this white rust is 'extremely poor and the
attack on the base metal i.e., Zinc is aggravated ow~ng to the
absorption of moisture and gases in this porous film. To avoid
the formation of these powdery products on zinc surface, a
protective film is applied to the surface which makes the surface
resistant to the reduction of oxygen or water (in normal
atmospheric corrosion these are the cathodic reactions).
Literature survey has revealed that chemical conversion coatings
based on chromium compounds, tungstate and molybdate l<:~e applied
to zinc surface to control the white rusting problems . Out of
these coatings provided on the surface of zinc, the coating based
on chromium compounds is considered to be the most effective under
the influence of variable parameters. This i~ owing to the fact
that over a wide range of pH values, the Cr + ions are reduced
easily to form protective chromic hydroxide film at a nobler
potential than the corrosion potential of corroding zinc in an
aqueous electrolyte. The mechanism of the action of: this anion on
the zinc surface to form protective layer is, however, not fully
understood. Moreover, the influence of plant parameters and the
correlation of the performance of the passivators based on
chromium compounds with the electrochemical parameters; effect of
cold forming and influence of some ions have also been scarcely
attempted. These correlations are very important in view of the
fact that they provide a quick result on the performance of
passivators to be used in a system or in developmental programmes
of passivators. In the present paper, an attempt has been made to
address the above lacunae existing in the literature and suggest
remedial measures.

(a) Salt spray resistance tests : Salt spray resistance tests

for the galvanized coatings were performed as per the
specifications of B 117. Duplicate samples of size 5 cm x 7.5 cm
were cut from the same sheet (origirial size of the sheet was 300
cm x 100 cm ) produced in hot dip batch type of galvanizing. The
sheets were collected from the plant in unpassivated state. To
remove any trace of grease/oil or other impurities present on the
specimen during its handling, they were degreased with MgO paste
and then washed thoroughly. All the edges of the specimen were

1168
covered with a good quality water resistant tape. The passivation
treatment to the surface was provided by instantaneous dipping of
the specimen in passivation bath and then taking tpem out through
a structure having rubber lining. This completely wipped off the
passivation solution from the surface of the specimen. It was
observed that the contact time between the 1solution and the
specimen was about 1-2 seconds. After giving the treatment to the
specimen, they were hanged in laboratory atmosphere for 48 hours
to stabilize the passivation film on the surface. After exposing
the specimen in the salt spray chamber, observations were made
after every 8 hours. Out of the two specimen, the specimen which
lasted for maximum period of exposure again!3t white rusting was
taken as the right specimen and observations were recorded for
that specimen only. This technique was adopted due to the reason
that the white rusting could start due to some other defects
already present on the galvanized coating.

To determine the role of corrugation on the performance

of the coating, the specimen were passivated in the laboratory and
corrugation was carried out in the plant. Different periods of
stabilizing time to the film was allowed prior to corrugation.
Some panels were cut from the corrugated sheets passivated ~nd
corrugated in the plants.

(b) ,Electrochemical studies : Electrochemical st~dies were

p~rformed by cutting the flag types of specimen of 1cm area from
the same sheets as used for the salt spray tests. The procedures
for the preparation of the specimen 'were the same as described for
the salt spray tests coupons. The potentials were measured
against saturated calomel electrode. A potentiodyne analyser
(MiS Petrolite Corporation, USA) was used to .run potentiodynamic
polarization studies.

Variation in salt spray resistance ( white rusting ) against the

concentration of chromic acid (CA) is shown in figure 1. These
observations were noted by maintaining the temperature of the
treatment bath at room temperature (R T = 300C) , 600 and 800C.
Another set of exeperiments were also performed by keeping the
0
specimen in oven at 90 C for 10 minutes and then passivating
them in the chromic acid baths. This was carried out to study the
effect of sheet temperature at the time of treatment, on salt
spray resistance. In general, it is observed that the salt spray

1169
resistance increases with increase in concentration of CA
solution. Above 0.5% of the concentration of CA, the surface
appearance was having yellow tinge which is objectionable to sheet
galvanizers. A 100 hours of salt spray resistance which is
considered as the landmark for providing a considerable life of
sheets against white rusting, is achieved,. only when the
concentration of the bath is maitained >= 1.5% CA .

The plot showing the effect of temperature on salt spray

resistance (S S R) for the specimens treated in 1% CA bath,
indicates that the performance increases with rise in temperature
(fig-2) . The sheet which was having 900C temperature prior to
passivation, has however, shown very poor performance.

Effect of the addition of some metal cations namely Na+,

Cu++, and Ni++ as their sulphates on W.R. is shown in figure 3.
An improvement in resistance against W.R. is observed in all the
cases up to the concentration of 0.1% of cations. Above this
concentration, a deterioration in W.R. resistance is noted in all
the cases. The most pronounced effect is noted for Cu ++ . It 'is
to be noted here that although a deterioration has taken place at
the higher concentrations of cations, the ~erformance is still
superior than in their absence except Cu +, who exhibits the
greater degree of deterioration at 0.5%, but has a W.R. resistance
equivalent to in its absence i.e, 30 hours.

Na+ is not expected to have any influence on the passive

film formation. An improvement in W.R. in the presence of Na~S04
therefore, may be attributed to SO4 This anion is indeed
reported to have a positive role on the film formation 6. Copper
and Nickel which are cathodic to zinc are expected to deteriorate
the corrosion resistance of galvanized coating,howeverr, appear to
have an improving effect due to the presence of SO --
4

Effect of some proprietary passivators : Two proprietary

passi vators designated as 'c ' and 'P , were also evaluated to
control W.R. in salt spray exposure and actual field exposure in
marine environment of Digha (Bay of Bengal). These passivators
were also evaluated for their performance to control W. R. on
corrugated sheets. The results are summarized in Table I. It is
evident from the Table that 'P , provides optimum resistance to
W.R. at the concentration of 2%, both in plain and corrugated
sheets.

1170
Table I : Performance of 'P , and 'C ' passivators on W.R, surface
reflectance and corrugation effect, bath temperature 500C,
contact time, = 1-2 sec.

Table II : Effect of stabilizing time allowed for curing of

passive film formed in presence of 2% of 'P'on galvanized surface,
prior to corrugation, treatment time 1-2 seconds, squeezing of
solution just after treatment.

The surface appearance was also quite brright in this

case. Passivator 'C' however, provided only 30 and <24 hours of
SSR at 1% of its concentration for plain and corrugated sheets,
respectfully. Above this concentration an yellowish tinge
appeared on the surface. Corrosion resistance of the film was
also found to be deteriorated at the higher concentration. of 'C'.
Very interesting observations were noted during the study of
effect of curing time prior to corrugation on resistance to W R

1171
In case of 'C', a drastic reduction in S.S.R. was noted after
corrugation. No effect of time of curing was observed in this
case. In - case of passivation by 'P', on the other hand, an
improvement in S.S.R. was noted when the passivated surface was
quickly (within 1/2 hour) corrugated (Table II). This was perhaps
due to the reason that 'P' in its composition inc~porates certain
ingredients which retains passivating solution in invisible form,
on galvanized surfaces, even after squeezing and drying. During
corrugation, the additional compression energy supplied to the
surfacce, helps in faster reaction of the passivator . and it
covers and passi vates the broken film which may had been taken
place due to the pressing effect of corrugation machine. This
view is further corroborated with the microstructure of film
formed in the presence of 'P' and 'C' (Figure - 4). It is
observed that 'C' provides a lamellar type of structure on the
zinc surface which is liable to be broken easily. In contrast to
this, the film formed in the presence of 'P' is amorphous in
nature and can withstand the cold deformation of the surface.
Some photographs showing the effect of passivators on S.S.R. to
W.R. are shown in figure - 5.

Changes in open circuit potential (OCP) of galvanized

sheets with passage of time in different concentrations of CA are
shown in figures 6. In very dilute solution of CA (0.1%), the
potential initially jumps in more active direction. After 2
minutes of exposure, it gradually moves in nobler direct ion and
stabilizes after 5 minutes. In 0.5%, the trend is reversed. The
potential moves towards nobler direction and remains stable
between 2-3 minutes. After this period of exposure, a continuous
shift in active direction is observed. In concentrated solutions
of CA i.e., 1% and 1.5%, the potential is stable initially for 3-4
minutes and then moves continuously in active direction.

Shifting of potential in active direction indicates

either. a cathodic polarization or an anodic depolarization, wheras
an anodic shift indicates that the reaction is either anodically
polarized or cathodically depolarized. During the film formation
on zinc surface in the presence of hexavalent chromium solution, a
cathodic depolarization reaction is - always preferred. For an
optimum film formation a treatment time of 1-2 minutes is
sufficient. It is, therefore, this initial period of exposure
(1-2 minutes) which is important in deciding the nature of
passive film. In 0.1% CA, an initial shift of potential in active
direction may 6be tak~ as the cathodic polarization (here
reduction of Cr + to Cr +) as anodic depolarization is ruled out

1172
due to very low amount of acidity present in the bath. After 2
minutes of exposure, an anodic polarization starts taking place.
In this situation., the passive film f9rmed on the surface is
expected to be very weak resulting in poor protection. This is
indeed observed during the salt spray test. In O. 5%' CA, on the
other hand, the potential immediately after e~osure starts moving
in nobler direction. This is a clear case of cathodic
depolarization and following reactions take place :

A chromium chromate film is formed on the surface. This film is

quite tenacious and protective and provides high degree of
protection. A shift of potential in nobler direction may be
attributed to the activation of reaction (ii).

In 1 and 1.5%' of CA, an instantaneous thick film of

chromium chromate is formed. Any further exposure of the
specimen, a thickening in the passive film (potential shifting in
active direction) takes place. This film provides an yellow
colouration of the surface and does not have good corrosion
resistance. This finding is also corroborated with the results
as shown in figure - 6. The steady state corrosion potential of
galvanized coating moves in nobler direction with increase in the
strength of the acid, which is again an indication of facilitation
of reaction (ii) which helps in the thickening of chromium
chromate film formed on the surface, with time. Changes in OCP of
the specimen treated in different concentrations of CA and exposed
in 3.5%' NaCl are shown in figures - 7 (A.D.). The specimen
treated in 0.1%' CA exhibits a continuous shift of OCP in active
direction, indicating the formation of an inadequate thick film to
stop the ionizatiDn of zinc from the surface (depolarization of
anodic reaction). In case of 0.5%' of CA treated specimen,
however, the potential continuously moves in nobler direction
(7-B) which indicates that the anodic polarization (zinc
ionization) reaction dominates the corrosion process. The specimen
having the treatment of 1%' CA, exhibits an initial enobling of
potential but after 4-5 minutes, a continuous shift of OCP takes
place in active direction. This plot suggests that the film
formed on the surface has an initial role in control of zinc
ionizat ion from the surface. However, with passage of time , a
polarization of cathodic reaction (oxygen reduction) takes place.
Passivation treatment using 1.5%' of CA, exhibits a continuous
enobling of potential which suggests that the passive treatment
film is quite thick and during the period of exposure (10 minutes)

1173
 the film is sufficiently strong to withstand the ionization of
zinc from the galvanized surface.

Chromium compounds are considered to be one of the ~~~t

effective passivating species towards the metals and alloys .
Acgording to the widely held views, the passivation of metals by
Cr + is due to their affecting the dissolution of metals through
the formation of a complex oxide of dissolved metal (here zinc)
and chromium. During the dissolution of zinc in acidic
environments, dissolved oxygen is cathodically reduced at the
interface of the corroding metal :

As is evident from equation (iv), the rate of reaction of

formation of Zn (OH)2 ads. at the corrosion potential region is
controlled by the concentration of generated hydroxyl ions in the
electrical double layer. This reaction. is expected to be
6
facilitated by the reduction of Cr +present in the solution :

1174
The hydroxide formed at reaction (iv) and (vii) precipitates out
the dissolved zincsimultaneously at the surface and provides the
protective film to the galvanized surface. The above discussion
clearly ind~cates that it is not simply the reaction products of
zinc and Cr + compounds who decide the protective properties on to
zinc surface but it is their mode of precipitation !at the surface
who decides the extent of protection. If above compounds are
precipitated in such a fashion that an amorphous and adherent type
of layer is formed at the surfaqe, the passivator should provide a
high degree of protection. This is indeed observed during the
study of surface by SEM (fig - 4). An amorphous layer is produced
in case of passivator 'P' which has provided very high degree of
protection (Tables I & II)

The authors are thankful to the Director, NML, Jamshedpur to

permit the publication of this' paper. We also express our
gratitudes to the managements of Tinplate Company of India
Limited, Jamshedpur for providing the galvanized sheets and allow
to conduct some experiments in their plants.

References
1. D.D.N. Singh, B. Gaur and' A.K.Dey, Inter finishing 1996,
Birmingham.
2. F. Rodelas, S.A.Procoat and S.A. Barcelona, Metal finishing,
87(1989)29.
3. G.A. Reghi, US Patent 4812175, 1989
4. L.D. ronis, T.M. bersadskaya, T.M. Lippin, A.I. Kozminskaya,
Razumov Yu G, Sov. Electrochemistry, 24(1988)1421.
5. N.M. Mart yak, J.E. Mccaskie and L. Harrison, Met. Finishing,
94(1996)65
6. D.D.N. Singh and A.K. Dey, Development of passivator for
Galvanized surfaces, NML Techn. report # 05489127(1990).
7. I.L. Rozenfel, d, Corrosion Inhibitors, Khimiya, Moscow 1997.

1175
1178
1179
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Corrosion Behaviour of Rapidly So~dified' Lead

Aluminium Alloys for Battery Grids
T.B. Singh, K. Lal, R.K. Mohanty and C.S. Shivaramakrisnan
National Metallurgical Laboratory,
Jamshedpur-831 007, India

. ABSTRACT

Rapidly solidified (RS) Pb-AI alloy in If2S04 sohrtion at room temperature (30C) wasfOlmd to be
more corrosion resistant to that of conventional Pb-Sb alloy. PoJariDtion CUlVes,for RS and as cast
Pb-4Al, Pb-5Sb alloys and Pb, indicated that the critical and passive current densities were lowest in Pb-AI
alloys. Further, RS alloy showed more corrosion resistant behaviour than all other alloys and metallDlder
investigation. Oxygen evohrtion reaction potential was not affected by lIbnnininm addition to the lead'alloy.

INTRODUcnON

Lead grid alloys used in battery indusny generally contain 6-12% antimony. Though the addition of
antimony in this range leads to desirable mechanical and casting properties, it makes the alloys less
corrosion resistant mostly due to overcharging and self:. dischargingl-4. Under anodic attack of the grid,
during overcharge, antimony can also pass into the sohrtion, (in the +5 oxidation state), and be transferred
to the negative grid, where it is reduced. The antimony ultimately deposited on the electrode surmce and
thus lowers the hydrogenevohrtion potential than lead This process leads to ~ evohrtion on the negative
electrode with subsequent water loss and self. discharging ofbatte.y-7. Attempts have been made either to
reduce the level of Sb in the grid or to replace it completely. The most successful ones were, addition of
calcium, tin, magnesium and aluminium8, which modified the electrochemical properties of the alloys.

The objective of the present work is to explore the effect of AI addition to lead, on the corrosion
behaviour ofPb-AI alloys. The paper reports a comparative swdy on the corrodibility of commercial Pb,
Pb-Sb and Pb-Al,as cast as wen as RS alloys in sulphuric acid potentiodynamically. The metallographic and
mechanical properties are also studied.

1182
EXPERIMENTAL PROCEDURE

RS n1>bonsofPb-4Al alloy were produced by meh spinning the cast ingots prepared by mechanical
mixing. The n1>bonswere cut into small pieces and compacted in hydraulic press to produce compacts of
35 mm diameter. Metallographic examinations were carried out on tte ribbons as well as on the
mechanically mixed and RS, compacted samples. Mechanical properties were determined using
Hounsefield Tensometer.
The working electrodes were prepared by cold mounting of 1 sq. em of alloys in acid resistant
resin. The electrolyte used for polarization study was 10M H2S04 and was-prepared from Analar- grade
reagent and double distilled water. All measurements were made at room temperature (30 1C) with
respect to the Hg/ Hg: S04 reference electrode. The electrical contacts were made through copper rods
from the back side of the mold by drilling and making threads into the mold. Before introduction to the
electrolyte, the electrode surface was prepared by polishing on % to 4/0 grades emery papers, cleaned
thoroughly on wet tissue paper and finally, rinsed with distilled water. Polarization experiments were
performed using an E & G Princeton Applied Research PotentiostatiGalvanostat Model 273A - Two
cylindrical graphite electrodes were used as counter electrode.

RESULTS AND DISCUSSION

MetaUographic Examination

Figure 1 shows the optical micrographs ofPb-4Al alloys (a) as cast and (b) rapidly solidified n1>bon.
It may be noted that aluminium has a tendency to solidifYin the form of globules due to surface tension in
the pool of mohen lead (Fig.la). A single phase morphology is seen in figure Ib, which is due to the
dissolution aluminium in the matrix. due to rapid cooling. SEM micro-photograph and EDAX of RS
compacted peUet of Pb-4Al alloy reveals the distribution of aluminium particles embedded in lead matrix
(Fig. 2).

Mechanical Properties

Tensile testing of Pb-4Al alloy, produced by mechanical mixing route, carried out by tensometer
and values are summarized in Table-I. The values for Pb-5Sb are also given for comparative study.

Table-l Mechanical properties ofPb-4Al and Pb-5Sb aUoys

The mechanical properties ofPb-4Al are comparable with conventional Pb-5Sb alloy. The fractography of
tensile tested samples, which is not shown here. indicates the ductile nature ofPb-4Al alloy.

1183
Potentiodynamic Polarization

Prior to polarization experiments, the working electrodes were cathodically pretreated at potential
-1.6V for 30 minutes to remove any reducible species present on the surface. The polarization of the
electrode was conducted in the potential range of-1.4 to 1.4V to cover pa~e and oxygen evolution range.
Figure 3 shows the polarization cwves for as cast and RS compacted Ph-4AI alloys in 10M H2S04
solution. It is noted from the figure that an activation-passivation reaction phenomenon is involved in both
the alloys anode reaction. The extent of activation polarization does not depend on the process of alloy
preparation as is seen by the critical current density (l:nt) for RS, 2.84 mA/cm2 and for as cast alloy, 2.89
mA/cm2. Further, passive current density (Ip) for RS as well as cast alloys is 0.05 mA/cm2 and 0.22
mA/cm2 respectively, which frames an idea that RS alloy is more corrosion resistant to that of as cast one.
Transpassive region which is found to attain at about IV is mainly due to the oxygen evolution reaction and
formation ofPb~ layer from PbS04 present on the surface27.

The polarization plots for Pb, Pb-5Sb and RS Pb-4AI alloys in 10M H2S04 solution are shown in
figure 4. A significant role of rapid solidification was observed towards the passive film formation on the
electrode surface. Though the passive region in all the cases is almost same, passive current density for RS
compacted electrode was the lowest. The first active-passive transition, which is resuhed around -IV, is
due to sulphation reaction. In this region (-1.2 to Ec), the current increases due to the dissolution of Pb to
Pb2+ 7!) until a critical passivation potential(Ec) is attained where lead sulphate starts precipitating. PbS04
forms a passive film on the electrode surface and thus resuhs in a rapid decrease in current density. A close
look devides the polarization plots into three different regions. The first one is due to formation and
deposition of lead sulphate around -1.1 to - 1.0V; second region belongs to the formation of PbO
underneath PbS04 layer which starts around -0.6V with slight increase in current density and third region is
transpassive region at about IV, where PbS04 is oxidized to a polymorphic Pb~ film 7.10.11. Oxygen
evolution occurred after the formation ofPb~ on the surface.

Table-l
Qpen circuit potential (Eoc). critical current density Oati.),passivation current density (1,), critical
passivation potential (Ec) and passivation potential (Ep) for lead and lead aUoys in H;zSO .

The electrochemical parameters recorded in H2S04 solution are shown in Table-2. The open circuit
potential (Eoc), observed in all the cases was quite stable and very close to the reverSlvle potential of
PbS04 formation. Lower critical (Icrit) and Passive (Ip) current densities for Ph- AI alloys indicates that the
addition of aluminium provides better corrosion resistant property to the alloys. Further lowering in Ip

1184
value ofRS alloy by one order of magnitude to that of as cast one imparts best corrosion resistant property
to the RS Pb-Al alloy.

CONCLUSIONS

1. Addition of ahmlinium, to replace antimony, improves the corrosion resistant behaviour, however,
no DDlchimprovement is observed on mechanical properties.
2. Rapid solidification route makes the Pb-Al alloy more corrosion resistant further.
3 Oxygen evolution potential was found to be almost same in all the cases shows that the RS Pb-AL
alloy can be used as grid material in the battery industry.

REFERENCES

1. V.lliev, D.Pavlov, IElectrochem.Soc. 129(1982)458.

2. AG.Gad-Allah, HAAbd EI-Rehman, M.Abd EI-GaliI, IAppl Electrochem. 25(1995)689.
3. IF. Cole, F.E. Goodwin, 10M 42 (1990) 41.
4. HBode, Lead-Acid Batteries, John Wily & Sons, NY (1977),p.238
5. S.Webster,P.IMitchell, NAHampson, J.I.Dyson, IElectrochem.Soc.
133(1986)133.
6. S.Webster,P.I Mitchell, NAHampson, ibid. 133(1986)137.
7. M.N.C. Ijomah, Ibid. 134(1987)2960.
8. IK Gibson, Chloride Technical Ltd., Project Rpt.No.2480, Chloride
Technical, Swinton, UK(1981).
9. L.M.Baugh, KL.Bladen, F.L.Tye, IElectrochem.Soc. 145(1983)355.
10. KR.Bullock,G.M Trischan,R.G.Burrow, I Electrochem. Soc. 130(1983)
1283.
11. Y.Yamamoto,F.Koichi,TVeda,M.Nambu, Electrochim Acta,37(1992)199.

1185
Fig. 2 (a)SEM rnicrograph of RS compacted Pb-4AI alloy
showing spherical Al particles embedded in Pb
martix, (b) EDAX of spherical particles
confirms the presence of Al

1186
Fig. 4. Comparison of polarization behaviour of (a) Pb,
(b) Pb-5Sb and (c) Pb-4Al alloys in 10 M H2S04

1187
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

A Direct Electroless Process for N\.-P Protective

Coating on Aluminium
L.G. Bhatgadde and Sharlet Joseph
Advanced Centre for Research in Electronics,
Indian Institute of Technology, Mumbai-400 076, India

ABSTRACT

Ni- P coating is known to protect aluminium against corrosion under

severe conditions of atmospheric exposure. Conventionally, Ni-P is deposited on
aluminium after giving a thin layer of Zn followed by an overlay of Cu.
However, recent years have witnessed direct Ni-P plating processes on
aluminium without applying an intermediate Zn layer.

In the present work attempt has been made to initially apply a thin
layer of 99.9% Ni by using a hydrazine containing Ni - ethylene diamine bath
followed by deposition of Ni-P with sodium hypophosphite from the same bath.
This process in volves fewer number of steps, since it eliminates both Zn and
Cu coatings and hence faster and more cost effective. The Ni-P plated Al
substrates have been found to withstand 48 hour salt spray as well as humidity
resistance tests without deterioration.

INTRODUCTION

Ni-P coating is known to protect Al against severe conditions of

corrosion and erosion [1]. The famous Alniclad process developed in 1950' s is
used for plating aluminium propeller blades, light alloy fistons, connector
backshells and other accessories of aircraft components [2 . Presently Ni-P
coated aluminium is also employed in a large number of automotive, chemical,
plastic and food processing equipments besides being used in electronic
packages and computer memory devices [3].

Aluminium 'is known to be a difficult-to-plate metal owing to the

presence of oxide film resulting in poor adhesion of the coated metal. Even if
the coating is applied after meticulous surface deoxidation minute pores /

1188
discontinuities in plating can accelerate corrosion, since aluminium with a
standard potential of -1. 53 volts is anodic to most of the depositing metals
such as Zn, Cu and Ni . An electroless process is known to produce a pore free
coating at lower thicknesses than that of electroplating. Besides, electroless
baths possess a 100% throwing power, which ensures uniform plating of small
diameter tubes, threaded parts, tanks and large vessel~ [4] .

The conventional pretreatment process for Ni-P plating of aluminium

consists of i)degreasing, ii)alkaline cleaning, iii)acid etching, iv)zincating,
v)stripping of Zn, viJre zincating, viUCu striking and viii)Ni-P plating with
rinsing followed between two steps. Some proprietary processes employ
immersion Sn instead of Zn from a stannate bath and electroless brass/bronze
before Ni-P plating [5], while others have retained zincating but avoided a Cu
or brass strike before applying Ni-P coating [6].

The aim of the present work was to evolve a direct electroless

process, which eliminates both Zn and Cu/brass coatings thus resulting in a
decrease in total number of processing steps without sacrificing the protective
value of the final electroless coating.

EXPERIMENTAL

Imm. thick general purpose aluminium alloy sheet was cut into 5 X
2.5 as well as 1 X 1 cm sized subtrates. The plating cycle is shown in
Table I.
 Mter degreasing with trichloroethylene and/or acetgne the substrates
were cleaned with a 5% solution of sodium hyc;lroxide at 50 C. This step was
found to be more effective than conventional alkaline mixture of sodium
carbonate and trisodium orthophosphate. This was followed by chemical
polishing treatment, which etches the surface by removing adherent oxide and
other smut and smoothens it thus improving its wetplbility in the subsequent
electroless bath. The chemical polishing bath had tht!' following spectification:

Sulphuric acid (98%) 40 ml

Orthophosphoric acid(88%) 20 ml
Distilled water 40 ml'
Propionic acid 0.1 ~
Temperature 80-85 C

The composition and operating prameters of electroless baths are given in

Table II.

Table II. Bath Composition and Operating Parameters of Electroless Baths

1190
and the values were cross checked by using a microsectioning technique.
Coating adhesion was found qualitatively by scoth tape and quantitatively by a
tensile pull tester.
The XRD patterns were recorded on a Philips X-ray diffractometer
using &uK~ radiation and a tube current of 35 mA at 45 tkV in the Z6 range of
40-110 .
The coating was dissolved in a 50% HN03 solution and its - P content
was analysed by inductively coupled plasma spectroscopy.

The corrosion resistance of the plated samples was evaluated by

exposure to salt spray. The samples were suspended in the spray cabinet
containing 3% naCl solution at 400C at a rate of 8 hours spraying followed by a
16 hour rest for a total of 48 hours.

Humidity resistance tests were performed in a humidity resistance

oven as per MIL-STD-883C given below:

At the end of the tests the samples were rinsed dried and evaluated for
discoloration/blistering by both visual inspection and optical microscopy.
RESUL TS AND DISCUSSION

It was observed that the thickness of the pure Ni on aluminium could

not be increased above O.l-O.Z urn even by increasing the plating time or
changing the bath composition and pH. It is known that in a true electroless
plating process, coating 2hickness increases with plating time. Although, the
present bath contained Ni + ions in the form of a complex, [NiCen)Z(N03)2] and
hydrazine is a strong reducing agent under alkaline conditions due fo the
following reaction: .

Once, AI is completely covered with a thin monolayer of Ni, no

furthet plating occurs. The adhesion of Ni to Al increased after heat treating
at Z50 C.
The X-ray diffractograms in Fig 1. revealed that patterns of Ni/AI
were identical to that of Al except that in the former the (ZOO) orientation
was weaker. Since, the thickness of Ni was extremely small (O.l-O.Z urn), its
peak was absent in Fig.l(b). Mter Ni-P plating peak heights of (ZOO) and
(311) have decreased and a new amorphous phase of NiZP appeared as shown in
Fig.l(c). Mer the heat treatment, this amorphous phase became
microcrystalline [Fig.l(d)]. From the ICP analysis it was found that it had an
average P content of 6.4%.

1191
 From a comparison of corrosion behaviour in Table III as well as photomicrographs in
Fig. II it was seen that as deposited Ni-P coating had minimum discoloration/attack and a
negligible weight loss.

1192
This is attributed to an amorphous (glass like) phase of Ni2P, which is corrosion resistant.
However, microcrystallinity after heat treatment decreases corrosion resistance as seen from
the blisters in Fig: II (c). Needless to say that the unprotected aluminium had maximum number
of brown spots (Fig. II (a)). The results of humidity resistance tests supported the observations
of the salt spray test. However, the weight increases of sample~in humidity resistance tests
may be attributed to the formation of oxides on their surfaces.

1193
 Since the elimination of both Zn and Cu/brass undercoats has been
achieved, a large number of chemicals as well as additional process steps have
been saved. This modification makes the proposed process economically more
attracti ve than the conventional process.

1.
CONCLUSIONS
A direct electroless process for Ni-P plating on aluminium is
characterised by deposition of a thin film of Ni in lieu of the conventional
zincating and Cu/brass coatings.

The Ni-P plated aluminium was able to withstand both salt spray and
humidity resistance cycles with minimum degradation.
ACKNOWLEDGEMENT
The authors are grateful to DRDO, Ministry of Defence for support and Mr.
Sumit Sharma for cooperation.

REFERENCES
l. Hajdu J., Plating and Surface Finishing, Vol.83, no.9, Sept.1996,pp.29-33.
2. Laitnen G.A., Metal Finishing, Vol.90,no.4,April 1992,pp.13-15.
3. Bowdrand W. and Malik M., Metal Finishing, Vol.84,no.3 ,Mar.1986,pp .15-20.
4. Wernick S. and Pinner R., The Surface Treatment of Aluminium and its
Alloys, Vol.2, Fourth edition, Robert Draper Ltd.,1972.
5. Lashmere D.S., Plating and Surface Finishing,Vol.72,no.6,June 1985,pp.36-39.
6. Rajgopal 1. et.al., Metal Finishing, Vol.92,no.3,Mar.1994,pp.29-3l.

1194
Proc. In!. Cont". on Corrosion CONCORN '97
December 3-6. Mumbai, India

Fouling and Under Deposit Corrosion in

CW System--A Case Study
D.K.N. Kutty and A. Periaswami
National Thermal Power Corporation Ltd.,
NTPC-Jhanor, NTPC Township,
Bhamch, 392 215, India

SUMMARY:
Proprietary formulation from a renowned multinational company was used in conjunction with
sulphuric acid and chlorine dosing to reduce scale, corrosion and bio-fouling at one of the Gas Based
Combined Cycle Power Plant, with 225 MW steam turbine. Water requirement for auxiliary
equipments cooling and fire fighting which comprise mainly of MS components with small dia
pipelines are drawn from the main CW system. Clarified water with turbidity less than 20 NTU is used
as make up and 5% of the CW flow is subjected to side filtration. During the one and half years of
operation. of the systems, the monitoring equipments showed corrosion and scale within prescribed
limits of 3 mpy for MS and 15 mglsq.dm respectively. However, heavy loose sludge was observed in SS
coolers impairing the heat transfer, while fouling with under deposit corrosion were restricting the free
flow in MS pipelines. This paper gives an inlook into the treatment program adopted, analysis of the
problem and the system requirements.

INTRODUCTION:
Quantity and quality requirement of water varies from process to process. Oflate, conservation of water
has come as the top most national agenda. Accordingly, industries have resorted to recycling and reuse
of water. While coal-based thermal power plants can use blow down water from cooling tower in ash
handling, combined cycle gas power plants have to operate at higher cycles of concentration (COe) to
conserve water. With purer water removed as evaporation loss and low blow down of salt containing
water, the salt concentration in the system increases.

Increase in ions like Ca and HC03 can give rise to hard scales in the heat exchangers reducing the heat
transfer efficiency. Similarly, increase in dissolved gases and acidic ions like chlorides and sulphates
induce corrosion, especially pitting, which results in the outage of equipments and fouling. Slime
d~posits can be centers for micro biological growth and under deposit corrosion and subsequent fouling,
affecting the heat transfer.

Raw water at this project is essentially scale forming. Clarified water, as per theoretical Langlier or

1195
Ryznar indices is slightly corrosive but is scaling above 1.3 cae. Hence, requirement for CW treatment
was envisaged from the design itself. Scaling can be prevented by sulphuric acid dosel which converts
the less soluble Ca(HCO~)2 and CaCa3 into more soluble CaSa4. Main heat exchanger i.e. the
condenser is of SS metallurgy. The highly aerated water in re-circulation makes the MS components of
auxiliary system corrosive. While some part of the auxiliary system is PIftected from corrosion another
part with varying temperature and flow conditions may get corroded. The makeup water characteristics
also changes which calls for ac\ose look into the water characteristics and control of the operational
parameters like blow down, acid dose etc.

Cooling water (CW) treatment to reduce the above said water borne problems, has advanced from the
polyphosphate treatments during 1930's and the much acclaimed chromate treatment during 1950's to
the recent all organic treatments2.

THETREATMENTPROGRAM:
As per design, the CW circulation rate for the system is 42000 M3fhr, with hold up volume of 15000
M3. Differential temperature across condenser is 10.5 C. pH control is automated by on line
measurement and stroke control of acid dosing pump. The chemical treatment was started by the plant
supplier on a new system with slug dose of PC1, an organic phosphate for deposit control and PC2 a
polyglycol based bio-dispersant after stopping the blow down.

Monitoring equipments viz. coupon rack, deposit and bio-fouling monitors were placed in the CW inlet
to condenser. Regular dosing of PC I and PC2 were started and recirculated for 48 hours. The maximum
rise in iron and turbidity levels observed were 0.12 mg/I and 16 NTU respectively. Increase in iron and
turbidity during the cleaning/passiv~tion step is a measure of system fouling and the efficiency. of the
chemical. Blow down was resorted after 48 hours.

Chlorine used as biocide was dosed 14 hours a day to maintain free chlorine upto 0.6 mg/l. During night
the residual chlorine used to be nil for 4-5 hours. The system was initially operating at 2 cac and
7.6-7.8 pH. Coupons showed high corrosion rate of 6 mpy for MS. Though pH was increased towards
the higher limit of 8.0-8.2 and cac to 4.0, corrosion rate was still 4 mpy and higher. The chemical
supplier changed PC 1 to PC3 stating that they had considered only SS metallurgy initially and the all
organics PC3 with prism crystal modifier mechanism protects MS components better. The product
catalogue or MSDS states that the patented polymer ofPC3 prevents dirtincrustation and sedimentation
with excellent dispersing and stabilizing properties even under extreme conditions. Recommended
control limits for cooling water were as below:

1196
As against 8 ppm dose rate of PC1 the requirement ofPC3 is based on COC and varied from 8 ppm for
2 COC to 16 ppm for 4 COe. These chemicals were introduced in Jan'96 without any pre cleaning.
With the new chemicals, the corrosion rate with passivated and unpassivated MS coupons showed 1-1.5
mpy and 2-2.5 mpy respectively.

THE PROBLEM AND ITS ANALYSIS: 1-

The program was apparently showing good control on general corrosion, scale & biofouling through
coupons, deposit monitor and biofouling monitor. Unit was running at half load conditions and no
indication of vacuum drop was observed in condenser. But, towards the end of Sept.'96, one of the
pumps with service water for cooling failed on account of restricted water flow. Different flow
indicator glasses were getting coated with black particles. Physical examination of various half inch and
one inch MS pipelines of auxiliary system showed heavy fouling with iron oxide. The top layer of the
deposit was covered with whitish layer. Towards the metal, it was blackish and the rest brownish red.
Thinning of the pipes were also observed. Fouling was observed in the inlet and outlet pipelines,
irrespective of temperature difference.

Reduced flow were observed in some of the coolers of SS tubes. Here, the problem was mainly because
of acid insoluble components of white gelatinous precipitate. Cooling towers were inspected during
shut down. Heavy deposits with acid insoluble were observed on the PVC fills of CT, which on drying
collected on the basin as thick layers. Analysis of the deposits didnot show significant faal out of scale
forming ions. The samples showed 8.6% and 90% loss on drying for 1 hour respectively for the deposits
from MS pipes and that from SS coolers. Analysis of the dry sample showed following composition:

Nature of both the deposits points towards slime deposition with organics and in MS subsequent under
deposit corrosion. Plant supplier initially attributed the problem to inadequate chlorination. However,
the deposits and the water samples did not show any signs of micro biological problems. Then they
attributed the problem to a) Extraneous ingress of Si02 to the system and b) Carryover of corrosion
products from other areas to the low velocity area and proposed to add two more chemicals PC4, an
iron specific dispersant and PCl, used earlier.

As the make up is clarified water, ingress of Si02 in the system can only be expected from the
deterioration of the concrete structure with high sulphate addition. The maximum Si02 measured in
CW system was 90 mg/I, against the tolerance limit of 150 mg/1. As the corrosion rate was higher
during the initial operations, carry over of corrosion products can be expected since no pre cleaning was
done during change over from PCl to PC3. While the make up was having turbidity around 10 NTU

1197
and total iron 0.3 mg/l, the circulating water was having only 2 NTU turbidity and 0.15 mgll iron,
indicating deposition. Also the COC based on soluble Si02 was around 3.0-3.2 against 4.0-4.2 on Ca,
Mg or Na. It was thought that side filtration is helping in reducing the suspended matter and silica. It
was claimed that Si02 analysis will not be representative because of dilution during test.

Crystal modifiers3 keep the salt forming substances in solution by changing the crystal structure. For
e.g. from the cubic shaped CaC03 crystals to spherical shaped ones which changes the crystal property
from hard scales to loose sludge. These sludges are kept in solution by stabilizers or dispersants and
removed through side filtration or blow down. An under dose of these polymer dispersants produces
coagulation! flocculation. The crystal modifiers can interact with higher cations like iron and
aluminium flocs loosing their characteristics ..

It appears that the treatment chemical comprising of crystal modifier, selected for the system had poor
dispersing ability for slime and instead acted as flocculant. The sludge thus formed settled on low
velocity areas like SS coolers, CT fills and on rough MS pipelines. Underdeposit corrosion started on
the MS pipes with this slime deposition. Since, the foulants are not sticking on the polished coupon
surfaces, it does not give rise to corrosion. The cleaned MS pipes over a period of 2 months were again
found to have a reduction in dia of 2 mm with iron oxide foulants.

OBSERV AnONS:
The treatment in use was part of the turn key project and so the performance requirement and
monitoring methods were not clearly spelt out apart from that corrosion rate should be less than 3 mpy
and scale should be less than 15 mg/dm2 Failure of the treatment can be attributed to the following
points.
a) Arbitrariness of Program Selection:
The initial program of PC 1+PC2 was changed to PC2+PC3 during the course of implementation to
control MS corrosion. Later, when this change was also not effective, the supplier proposed to introduce
two more new chemicals. The same supplier came up with a much more economical package

1198
comprising of zinc, orthophosphate, organophosphonate and polymer combine at almost one third of
the earlier program !:ost, when the treatment program was open for tendering. This indicates the
arbitrariness of program selection without studying the water chemistry and system requirement in a
scientific way,
b) Imvrover Start Up & Program imvlementation: !
While change over to the second chemical from the first, no cleaning was identified and done, which
failed to relT!0ve the initial corrosion products. This might also have lead to the ineffectiveness of the
crystal modifier. The plant supplier entrusted the program implementation to a water treatment agency
and the chemicals formulation supply was from a third agency affecting the proper implementation and
system review. No procedure was made to check the healthiness of critical exchangers and pipes on
regular basis. Removable spool pieces could have been introduced to cross check the performance of
the chemicals. Deterioration in heat transfer coefficient can be used'in seeing the trend offouling.
c) Inadequate Monitoring:
Underdeposit corrosions may not be reflected through the coupons as foulants may not stick to the
coupons at the flow conditions. Monitoring equipments were installed in inlet header instead of return
header having maximum potential for fouling and corrosion. Data from deposit monitor appears to be
overlooked in this case. Analytical results were not properly evaluated, particularly, w.r.t silica
deposition. The software based data management system, Trend Check was not supported with
adequate data. It did not have the basic calculations for heat exchanger performance.
d) Commercial Avvroach of the Chemical Supplier:
Under the pretext of proprietary chemicals, the supplier did not share vital information on :
I) Laboratory methods for checking and ascertaining the amount of the active components. As a result
the correct dose of the chemicals could not be properly estimated. Crude method of dosing a fixed
quantity of chemicals through metering pumps was done, even without knowing the exact blow down
and make up quantities.
2) Methods for quality check ofthe product.
3) Single formulation is used for both corrosion and scale control. With this dose adjustments can be
difficult at times.
4) Mechanism of working of the formulations and their limitations were not revealed to operating staff
e) Interruvted Use of Biocide:
No biocide was being used in the night which can lead to slime deposits. For a re-circulating cooling
water system working at high COC, continuous chlorination to maintain free residual chlorine between
0.2-0.5 mg/I is a requirement. Chlorine more than I mg/I can cause corrosion in copper. Below 0.2
mg/I, its effect is poor. Phosphate based treatment chemicals act as food for these organisms.
f) Inadequate lab facilities for microbial tests:
Fouling and associated corrosion attributed to biological deposits cannot be fully eliminated in this
case. Difficulties in sampling and analysis compound the problem by identification of micro
biologically induced corrosion4 as the organism die off when removed from their habitat unless
favourable temperature, moisture and other conditions are maintained. As the site lab is not equipped,
bacteriological tests were carried out from outside lab, which may not give clear picture.
g) Design Drawbacks :
I. Blow down is taken from the CW pump discharge instead of from CT basin or return header. As
chemicals are added in the pump suction, part of freshly added chemicals is lost through blow down.

1199
2. For dilution of Chlorine, treated cooling water is used. High level of chlorine destroys the polymer
chain of the organics already present in the treated water. Organophosphonates get converted to
orthophosphates with heavy chlorine, reducing their effectiveness.
3. No measurements are provided for blow down and make up. Metering of blow down and make up
water can help in finding out the COC maintained and comparing with the lab results.
4. Side filtration tanks are open and because of the warm sunlight, 021md the presence of organic and
inorganic nutrients in the system algae formations were heavy in the tanks.
5. Auxiliary cooling systems where multi metallurgies are involved with different heat duties and
velocities are connected to the main CW system. These can be isolated and given closed cooling system
with DM water and preservatives which can reduce the treatment cost and better control on operation.

CONCLUSION:
Each cooling water system will present unique challenges based on design, operating practices, water
quality and treatment program employed. There is no established laboratory methods to simulate the
actual conditions of system and test before hand the effectiveness of the chemicals in use. Suppliers of
proprietary formulations will be more commercial than technical and can pose more problems.
Generally, 2-6 mg/l dose levels of active components are only required control the water borne
problems. An under dose generally reduces their effectiveness towards these problems while overdose
increases sludge formation and treatment cost. Hence, proper selection of the treatment program, its
implementation and monitoring is a musr. Pilot cooling towers can be designed and used for every
treatment system for properly controlling the feed rate and effect of the treatment program. Software
program can be prepared as per the specific requirements of the plant w.r.t existing water chemistry and
system. Increased corrosion and fouling problems can be expected in areas where water stagnancy can
occur as that of fire fighting line in this case. System design should be in line with the limitations of the
treatment chemicals identified to get best results.

ACKNOWLEDGMENT:
The authors express their sincere gratitude to all their colleagues who gave important tips in bringing
out this paper. They are also thankful to the NTPC management for giving permission in presenting this
paper.

REFERENCES:
1. R.P.Mittal and D.K.N.Kutty, Scale and its prevention in condensers of open recirculating cooling
water systems, National Workshop on Chemistry in coal and gas based thermal power stations,
6th & 7th July, 1994.
2. D.K.N.K.utty and A.Periaswami, CW Treatment Formulations For Open Re-Circulation, ibid.
3. Sheldon D.Strass, Water Treatment, Power, June -1993.
4. Sheldon D.Strass, Barrier dispersion mitigates biofouling, MIC effects, Power, March 1992.

1200
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Prediction of Pitting Corrosion Tendenc, of Materials

During Extended Storage of Spent Nuclear Fuels
Vivekanand Kaint, s.s.Shinde2 and P. Seetharamiah3
IMaterials Science Division, 2Fuel ReprocessingDivision and 3SpentFuel Handling Section,
Bhabha Atomic Research Centre, Trombay, Mumbai-400085, India

ABSTRACT

Spent fuels from nuclear reactors are predominantly stored in spent fuel storage pools (SFSP)
for their wet storage. In order to store these for extended periods in SFSP, it has to be qualified against
corrosion degradation. Generally, the water chemistry of the pool water is benign and at ambient
temperatures general corrosion rates are too low to be of any concern. However, the localized
corrosion resistance of the fuel clad materials and the lining of the pool have to be ensured for extended
storage of spent fuels. To predict the tendency of materials (stainless steel type 304, aluminum - IS and
Zircaloy -2) in various heat treated and surface finish conditions to pitting corrosion, anodic polarization
experiments have been carried out. Demineralized water containing diffetent levels of chloride ions (50-
10,000 ppm) is used for these experiments. IR compensation is applied for experiments in solutions
upto 100 ppm cr . Correlations between the pitting potentials and chloride content are obtained for
stainless steel. Ranking of these alloys in order of decreasing susceptibility to pitting corrosion is made.
Comparison of these results with field experience is also made.

1.0 INTRODUCTION

Spent fuels from nuclear power and research reactors are predominantly stored in SFSP for
their wet storage. The SFSPs use light water and capacities of the pools vary with anticipated
requirement from site to site. Generally continuous on-line ion exchange columns are. used for water
purification to keep specific conductivity of water less than 1-5 IlS/cm. The pools are designed to
provide cooling by heat exchangers, if the temperature of water exceeds about 40 C. These
underground pools are generally in a covered building. The spent fuels are stored either on aluminum or
stainless steel racks. The pool walls and bottom are made of concrete and in some cases, as in India,
lined with type 304 / 304L stainless steel (SS). The storage racks are also mostly made of type 304 /
304L SS. In India the materials stored in the SFSPs are natural uranium cladded with high purity
aluminum 1S and U02 fuel cladded with Zircaloy.

1201
 Some countries have to store the spent fuels for long periods either due to legislation or other
constraints[ 1]. In such a scenario, accumulation oflarge quantities of spent fuel takes place which has to
be stored in SFSPs for extended periods. This calls for evaluating the corrosion degradation aspects of
spent fuels during extended wet storage, even though the SFSP environment is benign. Experience with
storage of spent fuels over last 27 years have shown[2,3] that aluminupl clad of spent fuels has shown
severe pitting corrosion in many pools whereas in other pools, with good water chemistry, the localized
corrosion has not occurred. Generally the water chemistry of the pool water is benign (demineralized
water) and at ambient temperatures, the general corrosion rates are too low to be of any concern.
However, localized corrosion resistance of the fuel clad materials and the lining of the pool has to be
ensured for extended storage of spent fuels.

Since a number of cases of pitting corrosion of aluminum clad of spent fuels has been
encountered at various locations, it is of utmost importance to predict the pitting corrosion tendency of
materials during extended storage of spent nuclear fuels. This paper describes various methods
employed in evaluating the pitting corrosion of materials, available information on pitting corrosion
behaviour of the materials of interest viz. SS, AI-IS and Zircaloy-2 and the results of anodic
polarization experiments in solutions containing 50-10,000 ppm cr. The correlations of pitting
potentials obtained in such experiments with field corrosion behaviour are also discussed.

2.0 PITTING CORROSION

Pitting is a localized form of corrosion[4,5] in which metal is removed preferentially at point

locations on the surface and it manifests in cavities or pits. The attack is generally limited to extremely
small areas while the remaining surface is relatively unaffected. It is a particularly dangerous form of
corrosion as it can result in through penetration of the fuel clad and consequent leaching of the fuel.

Pitting corrosion starts by initiation -of pits wherein the passive film on the metallic surfaces is
breached locally. Aggressive species known to penetrate oxide films in decreasing order are: chloride,
bromide, iodide, fluoride, sulfate, nitrate and phosphate. Following the initiation of a pit, the pit growth
is by an autocatalytic process. The corrosion processes within a pit produce conditions which are both
stimulating and necessary for continuing activity of the pit. In a situation where a metal is being pitted
by an aerated chloride containing electrolyte, rapid dissolution occurs within the pit, while oxygen
reduction takes place on the adjacent surfaces. This rapid dissolution within the pit tends to produce
excess positive charge in this area and results in the migration of chloride ions into the pit to maintain
neutrality. The metal chlorides hydrolyze rapidly to produce metal hydroxide and free chloride and
hydrogen ions[4,5]. Thus in a pit, there is high concentration of chlorides and hydrogen ions. As a
result, the pits become more acidic, and contain high levels of chlorides. These processes stimulate the
dissolution of most metals.

2.1 Tendency for Pitting: Different Methods of Evaluation

In order to determine the resistance of a material to pitting, several methods may be used[5,6].
The most common method is the anodic polarization technique in which the breakdown potential is
measured. Another common method is to determine the lowest concentration of aggressive ions (e.g.
Cn necessary to nucleate the pits. The third method consists of measuring the loss in weight and the
number, depth and width of the pits formed under some arbitrary conditions leading to an accelerated

1202
1203
3.0 EXPERIMENTAL AND RESULTS

Anodic polarization experiments were carried out to determine the pitting potential. These
experiments were carried out in demineralized (DM) water having varying amount of cr, in the range of
50-10000 ppm, which was obtained by adding NaCl to DM water. The flodic polarization experiments
were carried out on the following material samples:
(a) Type 304-SS- as received and mechanically polished on emery paper, grit 120,
(b) Type 304-SS - as received and sensitized at 6750 C for one h and mechanically polished with emery
paper, grit 120,
(c) Aluminum-1S- as received and mechanically polished on emery paper, grit 120,
(d) Aluminum-1 S as received and autoc1aved in water at 1500 C for 15 days,
(e) Zircaloy-2, as received and mechanically polished on emery paper, grit 120.

All the experiments were carried out using saturated calomd electrode (SCE) as the reference
electrode. A potential scan rate of 20 mV/min. was employed and about 5 cm2 surface area of sample
was exposed to the solution. The current density was recorded with the potential and the plots of
potential - current density were prepared for each material. These experiments were carried out in
solutions containing 50, 100, 1000 and 10,000 ppm cr and separate samples were used for each
experiment.

The pitting potentials were identified from these potential - current density experiments and
are listed in Table-1 for all the material samples in solutions containing various levels of cr. The
presence/absence of pits was confirmed after observations under an optical microscope on the samples
after the anodic polarization experiments.

Anodic polarization experiments were also carried out in IN H2S04 solution at room
temperature for all the material samples. In these experiments also, a scan rate of 20 mY/min. was
employed and the potential-current density plots were prepared. The transpassive potentials obtained

1204
from these curves are +900 mV(SCE) for type 304 SS(annealed and polished), +IOOOmV(SCE) for
Zircaloy-2(as received and polished) and over +1000 mV(SCE) for aluminum-IS(annealed and
oxidized).

Since the resistance of the solutions with 50 and 100 ppm ct-
was quite high, the effects
of the resistance of the solution was compensated by applying IR drop for each of the material samples.
This was done by using a.c. impedance spectroscopy. Individual samples were immersed in the solution
with 100 ppm cr and the frequency was decreased from 100 KHz to about 10KHz. The resistance of
the solution material surface ~as calculated from the extrapolated values of Z/. The IR compensated
values of pitting potentials are shown in ( ) in Table I itself.

The pitting potential thus obtained were plotted with the cr concentration, on a semilog graph.
The plot is shown in Fig. I for the stainless steel samples thus tested. The curve fitting was done for
these material samples and following are the equations obtained correlating the pitting potential with the
concentration of chloride ions in DM water.
For type 304 SS(annealed & polished) : Bpit = 600-1 87.210g [Cr]
For type 304 SS(sensitized & polished) : Bpit = 242.2-148.910g[Cr],where the cr content is in ppm.

Fig.I. Correlation of the pitting potentials with the concentration of chloride ions.Point A
is for SS (annealed) and point B for SS (sensitized).

4.0 DISCUSSION

The presence of low conductivity solutions, as commonly used in spent fuel storage pools,
makes the task of predicting the tendency of materials to pitting corrosion quite difficult. While use of
accelerated tests has applications particularly for in situ experiments in SFSP, laboratory studies would
also require correlation with field test data. However, anodic polarization experiments yield pitting
potentials, which can be used to rank materials in order of their resistance to pitting corrosion in
environments simulating the SFSP environments. This simulation of SFSP environments has to be done

1205
carefully so that the results are applicable to SFSP conditions. While it is reported[9] that experiments
in O.IN Na2S04 correlate well with the corrosion behaviour in high temperature high purity water, such
simulation of low conductivity water at ambient temperatures is quite questionable. Since trace levels of
anions (S04" ", N03- , P04- - , OR", cr etc.) affect the susceptibility to pitting corrosion in this
environment[6, 10], it was thought prudent to carry out these tests in Dr,J water.The anodic polarization
experiments can not be reliably carried out in low conductivity solution due to high resistance of
solutions and the IR drop. Therefore, for experiments in DM water containing 50 and 100 ppm cr, the
IR compensation was applied. Use of the results of these experiments is also done carefully, basically to
rank the materials in order of their resistance to pitting corrosion. Further inferences based on these
results have to be drawn with care.

The plots of pitting potentials and cr content on a semilog scale (Fig. 1) show a linear
relationship for type 304 and aluminum-IS. Based on the resistance to pitting corrosion, the ranking of
various materials, in decreasing order of their resistance to pitting corrosion in the environments tested,
is as follows: Zircaloy-2 (polished) > aluminum-IS (oxidized) > SS (annealed and polished) > SS
(sensitized and polished) > aluminum-I S (as received and polished).

This shows the superior resistance to pitting corrosion even in the polished condition of
Zircaloy-2 material. During service in reactor, the Zircaloy-2 clad develops on oxide coating which
provides further protection against corrosion. This is corroborated with the lack of any observation of
pits on zircaloy clad spent fuels during last three decades of experience in wet storage facilities. What
comes out as an important observation is that the aluminum-I S material in the oxidized condition
(having an oxide film of ~20 f..lm, developed after the autoclave exposure[II] at 150C for 11 days) is
more resistant to pitting corrosion than even annealed and polished stainless steel. This does not mean
that the aluminum clad spent fuels would not undergo pitting corrosion in SFSP conditions. This is due
to the fact that other factors e.g. scratches on the clad surface (during handling of spent fuels) would
result in development of a galvanic cell on these surfaces. Large surface areas of oxidized aluminum
would act as cathode and the small bare (scratched) surfaces as anode, resulting in fast localized
corrosion. Therefore, the ranking given above is for individual materials in their specified surface
condition and the effects of galvanic/crevice conditions are not included. It is clear from these results
that aluminum-IS (as received and polished) is prone to pitting corrosion in DM water containing
chloride ions.

The next most important aspect is to predict the minimum levels of chloride ions in DM water,
below which pitting corrosion does not occur in these materials. Since high potentials are applied in
anodic polarization experiments which provide extreme conditions generally not encountered in service
environments of SFSP, it is logical to infer that the experiments with a particular level of chloride, which
do not show any pitting during anodic polarization (meaning no thermodynamic possibility of pitting
corrosion) would be the levels of chloride in DM water, in which pitting would not occur in SFSPs. In
such a case, the results in Table 1 show that Zircaloy-2 does not pit below 50 ppm chloride. On the
other hand, stainless steel did show susceptibility to pitting corrosion in DM water with even 50 ppm
chloride ions. The extrapolation of the pitting potentials in Fig. 1 does show possible pitting of SS even
below 50 ppm cr but confirmation of these is not practical by anodic polarization experiments as IR
drop would be very high in such solutions. Even in the DM water with 50 ppm cr, clear and observable
pits could not be seen on SS samples, although the current density- potential curves indicated pitting
corrosion. Exploration of the pitting potential - cr content curve (Fig.7) shows pitting potential of 600

1206
mV (SCE) and 242 mV (SCE) for annealed and sensitized conditioning of SS in DM water with 1 ppb
cr. This is below the trans passive potential of +900 mV (SCE) in IN H2S04 solution. Therefore,
theoretically, pitting is possible even at ppb levels of chlorides. However, kinetic factors determine
whether pitting would actually occur.

The influence of oxide film formation on aluminum-l S in' improving its pitting corrosion
resistance is reflected in pitting potentials reported in Table 1. In case of both the surface conditions,
aluminum-l S shows pitting in DM water with 50 ppm water. Zircaloys do pit in DM water with
chloride ions, but are highly resistant and such extreme conditions of high applied potential are not
encountered in SFSPs. The linear type correlations obtained between the pitting potential and log of cr
content match well with the correlations reported by Smialowska[6] for solutions containing other
cations/anions, for stainless steel.

The pitting corrosion based on observations of pitting potential in anodic polarization

experiments has been questioned recently[12]. While one has to carefully match the environm~nts in
which tests are done with the actual environments, it is logical to at least rank various alloys in order of
their resistance to pitting corrosion in a given environment (of testing). At the same time, existence of
other influencing factors e.g. crevices, galvanic contact, other cations etc. also has to be. taken into
account befor extrapolating laboratory test results to predict corrosion behaviour in field applications. In
case of SFSP, experience over last 30-40 years are in line with the findings ofthis study.

Acknowledgments:
The authors thank Dr. P.K De, Head, Corrosion Science Section, Dr. S. Banerjee, Associate
Director & Head, Materials Group and Dr. K Balu, Director, Nuclear Waste Management & Fuel
Reprocessing Group, for their keen interest and suggestions during the course of these investigations.
This work was part of a coordinated research project on "Irradiation enhanced degradation of materials
in spent fuel storage facilities (1993 -1996) of International Atomic Energy Agency.

References:
[1]. lAEA Technical Reports Series No. 378, Options, Experience and Trends in Spent Nuclear Fuel
Management, lAEA, Vienna, 1995.
[2].Bases to Assess Durability of Spent Nuclear Fuels and Storage Facili./y Components in
Wet Storage, draft report prepared by lAEA coordinated research project on "Irradiation enhanced
degradation of materials in spent fuel storage facilities", April 1997.
[3]. Howell, J.P., CORROSION/96, paper No. 128, Houston, Texas, 1996.
[4]. Fontana, M.G., Corrosion Engineering, 3rd Edition, Mcgraw Hill, New York, 1986.
[5]. Szklarska-Smialowska, S, Pitting Corrosion of Metals, NACE, Katy, Texas, 1986.
[6]. Szklarska-Smialowska, S, in Localized Corrosion, Proceedings of the Conference held at
Williamsburg, Virginia, Dec. 6-10,1971, NACE, Houston, Texas, 1974, p312.
[7]. Godard, H.G., Materials Performance, 20, 1981, p9.
[8]. Truman, J.E., Corros. Sci., 17, 1977, p737.
[9]. De, P.K., Ph.D. Dissertation, I1T(Bombay), 1984.
[10]. Hong, T. and Nagumo, M., Corros. Sci., 39,1997, p961.
[11]. Kain, v., Agarwal, K, De, P.K. and Seetharamih, P., J.Nucl. Mater., communicated, 1997.
[12]. Streicher, M. A., Materials Performance, 36, 1997, p65.

1207
Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Approaches to ISO Certification-

Paint Manufacturing Industry
Jyoti Lata Pandey!, T.B. Rao2, Sandeep Singh2 and M.K. Banerjee3
'Scientist, Corrosion Protection Division
National Metallurgical Laboratory, .Jamshedpur-831 007, India
2M. Tech. Students, Deptt. of Chemistry
Regional Institute of Technology, Jamshedpur 831 014, India
3Assistant Professor, Deptt. of Chemistry
Regional Institute of Technology, Jamshedpur 831 014, India
ABSTRACT
A bird's eye view of global industrial development shows a very large landscape, with
scientific and logical harmony lending every facets. There has been lots of changes in world
wide quality approach. ISO-9000 series has proved to be the record setting standard for
world wide adoption and sell (ISO-9ooo remains record setter in Genius book of world
records). This series of standards are developed as a gist to the standards like BS5750 and
many others which were once called the most suitable and less time killing standards on
quality system - with few loop holes. ISO - 9000 series of standards are most suitable for
batch production and the repeatability of the same tests get eliminated. In the present text it is
attempted to express the 'First step preparation' for an industry who comes up to refresh it's
unit with new energy of disciplined decorum. Here we have cited an example of paint
manufacturing industry. It will be attempted to impress that in an already running industry, if
one wants to take up ISO certification, it is required that a mental frame-up will be all
necessary in the beginning to go ahead. The testing time and fatigue to the inspectors can by
reduced drastically by adopting the proposals furnished in the text.

INTRODUCTION
1.1 SIGNIFICANCE
Abird's eye view of global industrial development shows a very large landscape,
with scientific and logical harmony lending every facets. This huge continuum of
technological pursuits can be easily guessed to obey the basic scientific tenets of
regularity and discipline. As with any scientific achievement, industrial and
technological growth must follow the dectum of regularity and principles of
discipline. Any lack of rhythm will create disharmony in the system, which would
surely give a back pressure and endanger the creative rhythms, besides eddying off a
lot of industrial expenses. If we look at the industrial history of growth and it's
kinetics of any particular developed country, it will be evident that maintenance of
1208
 discipline and regularity, or in other words strict adherence to standardization
methodologies, are the primary criteria or governing principles, which bore fruit.

Realising in principle the importance of above discipline curriculum, today even the
developing countries are rushing towards ISO recognition. 1n India, even after so
much of popular discussions, seminars, conferences etc., there are only a limited
number of industries who could achieve ISO markings. This is not to indicate that
the level of their status is poor, rather, to hint that still the recognition of importance
of such standardization is not in full view. Many industrial organizations still feel
ISO recognition is redundant or it requires an unnecessary investments. It appears
that the output of scientific seminars is not upto its rated maximum; probably this has
something to do with the contents of deliberations. If we adhere to too much of
literary jugglery probably it does not give the proper impetus to the attending
industrial personnel.

In the present text it is attempted to express the 'First step preparation' for an
industry who comes up to refresh it's unit with new energy of disciplined decorum.
It will be attempted to impress that in an already running industry, if one wants to
take up ISO certification, it is required that a mental frame-up will be all necessary in
the beginning to go ahead.

As a case, a discussion will be made of different steps for preliminary preparations

needed for a paint manufacturing industry. The paint manufacturer buys the required
raw material from certified manufacturers (of raw materials). It is intended to state
that the raw materials are of quality origin and each batch of raw materials are quality
tested at the manufacturers premises which is as per recognition/acceptance of the
buyer, i.e., the paint manufacturer.

In the next chapter, steps of preparations as required for ISO certification will be
discussed.

1.2 THE UNIT

There has been lots of changes in world wide quality approach: ISO-9ooo series
has proved to be the record setting standard for world wide adoption and sell (ISO-
9000 remains record setter in Genius book of world records). This series of
standards are developed as a zist to the standards like BS5750 and many others
which were once called the most suitable and less time killing standards on quality

1209
 system - with few loop holes. ISO ~ 9000 series of standards are most suitable
for batch production and the repeatability of the same tests get eliminated.

Production of paints, as involves many complex methods, remains complex in term

of quality aspects. As, the result of a paint synthesis becomel evident c:mly after
prolonged use, no 'go' - 'no go' sort of devise can be designed for testing the
paints quality aspects. Its is a SPECIAL PROCESS.

This document developed and presented here with is a simple plan: how to utilize
the ISO - 9002 in production of paints and allied materials. It covers the overall
quality aspect of a paint company but not any company in particular. We have a paint
manufacturing company which wants ISO - 9002 certification. Looking after
company it may be observed:

~ Customer is fixed,
~ There are boiler reactors, conveyors, etc., inside the company,
~ Fumes and other pollution
~ The safety requirements.

A flow chart of the plant (unit) is given in the Fig. 1.

1210
1211
2.0 Drawing ISO Frame
2. 1 Production Process Approval (ISO : 9002 : 4.4)
On the basis of requirements stated by the customers, the production process and
raw materials will be proposed by the manufacturing expert, A trial production will
be taken up. On the report of the trial production performance the raw materials and
production processes will be amended or approved. Once the process and raw
materials are approved, the production should be taken us strictly in conformance to
this (4.4 and 4.9).

2.2. Document Preparation and Authorization (ISO : 9002 : 4.5)

Based on the properties of raw materials mentioned in the production process
approval documents the necessary tests to be conducted on the raw materials should
be determined and documented. These will include properties likedensity, fluidity,
viscosity, flash point, impurity % etc. On the basis of the list of raw material sources
and their previous performances, the amount-of inspection to be carried out will be
documented and determined.

The customer stated requirements from the basis of documentation and determination
of the tests to be conducted for product approval. The production process approval
documents will give proper guidance about the amount of control necessary to be
exercised. Also, all the chemical and physical parameters to be monitored during
process of production will be obtained from these dOCuments.

At the end, these three set of documents shall be approved and authorized by suitable
authority. So, before production starts following documents will remain duly
approved and authorized.

I. Incoming inspection procedures.

2. In process inspections and monitoring procedures.
3. Final inspection procedures.
Amount of inprocess inspection and monitoring will solely depend on the
experience and qualification and training of the operators (4.18).

2.3 Raw Materials (ISO : 9002: 4.6)

The production, process approval documents will clearly mention the raw materials
and the characteristics of them. It becomes the moral responsibility of the purchaser

1212
 to procure these raw materials from the sources which has proved in past, their
performance in terms of rejection percentage and delivery schedule.

2.4 Incoming Inspection. (for ISO : 9002 :4.10.2)

The bought raw materials should be insP<Ected ancJ tested as per the documents
prepared during stage 2. The records of this inspection and test will give necessary
confidence at all times that raw materials used are proper. Individual testing
procedures may be developed with or without help of standards (national and
international) depending on individual raw material group.

2. 5 Product Identification and Traceaibility (ISO : 9002 : 4.8)

Immediately after the incoming inspection is over, the raw materials that pass the
inspection shall be suitably identified. The identification should be proper enough to
allow traccacibility back to sources, any time required. The norm of identification
leading to thorough treacibility shall be followed through all stages of production
(This shall make easy the treacibility and assignment of reason, if some non non-
formity arises). Identification should be simple enough to be understood by the
workers or operators.

2.5 Production
The production steps shall be strictly as mentioned in the production process
approval documents. All the testing and monitoring should be done in accordance to
the documents established in step 2. Records of these inspection and monitoring
should be mentioned and should be tinked at every stage to the raw material
identification. If, the procedure employs some special purpose machine or
equipments, its performance should be pre-tested and 'qualified' before bringing
into use (4.9).

2. 6 Application and Testing (Product Approval)

After the paint has been manufactured, it must be tested against the requirements as
stated by the customer. As a developing practice ili industries, it remains good to
check all the incoming inspection records, in process monitoring records as well as
all the calibration records of the raw materials and test equipments (4.11) used
during production process. Due authentication of all these records in a must. The
final inspection shall be. done in the condition of application in which the said point
is required to perform; as far as practicable inside the testing laboratory. The steps of

1213
 final inspection shall be in accordance to the final inspection procedure developed in
step 2.

Here, it is worth mentioning that the paint batches which are accepted after
inspection shall be identified. In the event, source batches a! rejected they also shall
be properly identified till they are taken out of the production premises.

2.6.1 Objective and Testing

(i) ProcesslProduction control
(ii) Quality control (closed inspection of each batch within limits)
(iii) Quality assurance/determination of suitability for particular use.
(iv) R and D activity (Minor changes in ingredients - their effect). For products
having large range of possible use, the testing operation may be classified.
(i) Quality assurance (Product approval - with extensive range of tests over
prolonged peirod).
(ii) Quality control
(a) Some quick tests to assure that critical materials have been incorporated.
(b) Batch-wise testing

2.6.2 Selection of Properties for Testing

For testing purpose these properties must be selected which bears major importance
to the ultimate life expectancy of the paints, such as

(a) Paint Properties: (i) Storage, (ii) Application, and (iii) Curing,
Note : - The paint properties are of first importance, because unless a satisfactory
continuous film is produced, the performance properties will be standard. Some film
defects may be visually obvious in the film appearance, while others may not.

(b) Film Properties: (i) Film appearance, (ii) Film performance short, and (iii)
Film performance long-term.
Note: - A considerable amount of film testing is carried out on films less than 7 days
old; the assumption is made that the films will not change essentially in properties
untill the end of their useful lives. Unfortunately, it is rarely the case: films that dry
by oxidation, in particular, continue to harden and shrink over several years with the
result that they became more brittle and less extensible.

2.6.3 Selection of Tests

1214
 Purpose: - A test may be selected because of it's similarity with the actual use,
bec~use the tests are very sensitive and reproducible, because they provide a
permanent record, or because they are cheap or rapid. Considerable experiences
required to determine the most suitable tests for a particular qurpose.

For quality - control purposes rapid simple tests are normally selected to provide a
permanent record. Such tests cause the minimum interference with production while
allowing easy control within close limits.

For research work or quality assurance, tests of high precision are required to
produce a numerical record which allows statistical analysis and possibly an external
audit.

2.6.4 Selection of Equipment

Important in the selection of suitable equipment for testing are
(a) serviceability - ease of cleaning and servicing
.(b) range of operation
(c) postability
(d) necessity for controlled conditions (temperature, humidity, freedom from
vibration or voltage fluctuations)
(e) speed of operation and operate time required (calibration, preparation of
samples, reading, cleaning).
(f) training required for operator.
(g) low repeatability error
(h) capital cost
(i) standardization with other laboratories

Note: for quality control purpose in one production unit, although some times
calibration may seen irrelevant, yet serious problems may result creating all previous
data useless. As part of calibration exercise an equipment register should record the
supplier: data of purchase, service contracts, each service and calibration, with the
corrosion factors.

2.6.5 Precision of Equipment

It is common to assume greater accuracy of a result than is statistically valid. It is
important to know what differences are significant as.to know the actual test results.

1215
 For some standards e.g., ASTM standard precision data and reproducibility R
values have been determined by means of inter laboratory tests on the same sample.

Checks should be carried out on equipment and operato,- to ensure that they fail
within the precision expected of the test methods. This is particularly relevant in the
case of visual colour comparison, where the ability of individuals to differentiate
between colours.

2.6.6 Sampling
Correct sampling is vital to any testing programme. Results are valueless unless the
samples tested are representative of all the materials supplied. Most quality -
control testing in the paint industry is based on the assumption that one sample is all
that is required to define the characteristics of the whole batch. For this reason,
adequate mixing before sampling and filling, and checks to ensure that containers
filled at the start and towards the end of the filling operation are closely similar are
essential.

If it is shown that a sample is not representative of the batch or that a batch is non-
uniform, the quality---control system is invalid and all the testing carried out is
suspect.

2.6.7 Condition of Testing

For quality control process, the testing conditions will usually be controlled as much
as possible to increase the precision of results.

When testing is carried out for quality assurance or development programmes, the
condition may be controlled to the most adverse under which the product is
recommended for use.

The affeCt of variation in the environment on the results should be analysed

statistically, particularly if the conditions cannot be controlled for testing. The
condition of testing should be recorded so that the significance of the results can be
audited or a correction factor applied.

2.6.8 Panel Prepara!ion

Panel preparation is important for reproducible testing, because a number of tests
can be affected by surface contamination and difference in adhesion. The adsorbed

1216
 layers of contaminants on the surface of steel affect the corrosion resistance of
coatings to a greater extent. Adsorbent surfaces that have been metted and allowed to
dry may contain higher than normal levels of extractable materials. These surface
layers must be removed to produce a true reproducible substrat
1
2.6.9 Standardization of Testing and the Reporting of Results
In order that a comparison can be made of results, either the detailed conditions and
test methods must be recorded in each case or a standardize method is used.

The standardize method is one in which the procedure is detailed and the condition
of testing defined. Such methods should be adequately documented and given a
reference number or distinctive name, so that only this reference need to quoted with
the test result. The use of standardized methods enables direct comparison of results
and quick recognition of differences in properties generally with ISO Standards, to
be made.

2.6.10 Packaghig and Storage (ISO: 9002 : 4.15)

Paints, owing to the presence of organic solvents and other chemically active
ingredients deserve to the handled properly (due to properties like high vapour
pressure and inflammability). Depending on the country or locality where these
paints are being manufactured, the package should abide by statutory regulations
governing the area. (for food industries packs are allowed in Switzerland).

If possible, the package shall contain most of the necessary intermission like 'shelf
life time', batch no, handling instruction, etc. The paints, duly packed shall be
stored in a conditions, which does not distroany one of the property established
during final inspection stage.

Conclusion
The testing time and fatigue to the inspectors can by reduced drastically by adopting
the proposals furnished above. The plan includes :
1. Production Process Planning.
2. Production Process Approval.
3. Development of Inspection Documents Based on Production Process Approval
Documents.
4. Correct Raw Material Source Identification and Procurement.
5. Incoming Inspection.

1217
 6. In process Inspection and Monitoring.
7. Final Inspection.
8. Packaging and Storage as per Pre-established Documents.

1-
References
1. BS-5750(1).
2. IS/ISO 9001 (1194).
3. ISO 8490 (Quality Vocabulary).
4. Journals published by TQMI.
5. Introduction to paint technology by W.G. Morogan, Vol. 1.

1218
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Electrochemical Corrosion Behaviour of Carbon Steel in

Morpholine and Sodium Hydroxide
R. 'Ramakrishnan2, S. Rangarajanl, S.V. Narasimhanl and P.K. Mathur3
IWater and Steam Chemistry Laboratory BARC Facilities,
IGCAR Campus, Kalpakkam, 603 102, India
2pRP, IGCAR Campus, Kalpakkam, 603 102, India
3Analytical Chemistry Division, Chemistry Group, BARC, Mumbai, 400 085, India

ABSTRACT

In nuclear power plants, volatile amines are added to maintain an alkaline pH (8.5-9.5) in the steam
generator circuits for minimising the corrosion of structural materials. The corrosion behaviour of
carbon steel has been studied with morpholine and NaOH in a mixture of Na2S04 and NaCI using
potentiodynamic polarisation method. The corrosion potentials shifted towards noble direction and
the extent of passivation increased with pH in both the medium. Under deaerated condition and in
NaOH medium, the corrosion rates decreased with pH, but in morpholine medium there was no
significant change in the corrosion rate. Under aerated condition, the effect of complexation of
morpholine was felt at pH 9.3, unlike at pH 10.3, where passivation by the hydroxyl group dominated
the complexing effect. The study showed that under deaerated conditions, the addition of morpholine
is better than NaOH for the corrosion control of carbon steel.

INTRODUCTION

In nuclear power plants, volatile amines like morpholine, cyclohexyl amine etc. are added in
steam generator circuits to maintain a pH in the range of 8.5-9.5. The alkaline pH is used to reduce
the corrosion damage of steam generator tubes. These volatile amines not only hydrolyse to give the
required pH range in the boiler, but also volatilise to give protection to the steam circuit as well. As
amines are good complexing agents, they form complexes with the corrosion product metal ions and
affect the base metal corrosion. In the steam generator circuit, carbon steel forms the structural
material for the piping, baffle plates and the shell and so the study of its corrosion behaviour under
different conditions becomes important. The electrochemical behaviour of iron has been studied in
NaCl medium by different authors [1-3]. Deegan (4) has studied the stress corrosion cracking of
carbon steel in liquid ammonia environment. Uhlig (5) et.al have studied the stress corrosion cracking
of high and low strength carbon steels in neutral solution containing nitrate. The effect of carbonate
and bicarbonate ions in the electrochemical dissolution of'iron and the susceptibility to fatigue and
stress corrosion cracking has also been studied [6-10]. This paper discusses the electrochemical

1219
corrosion behaviour of carbon steel in the presence of morpho line and sodium hydroxide at pH 9.3 and
10.3 respectively under both deaerated and aerated conditions.

EXPERIMENTAL
1-
Test coupons of carbon steel were mechanically polished with silicon carbide papers
sequentially starting from grade 80 to 800. These polished coupons were washed with demineralised
water, degreased using acetone and dried in air. These coupons were immediately exposed to the test
solution containing sodium chloride and sodium sulphate (each 5XlO-4 M) added to reduce the IR
drop in the cell. The solutions were prepared using AnalaR reagents. 'ION-85' ion analyzer
(Radiometer, Copenhagen) which uses a combined pH electrode was employed to record the pH of the
solution. Electrochemical experiments viz., Potentiodynamic polarisation and Tafel plot analysis were
carried out in a conventional three electrode cell with a platinum plate as a counter electrode and a
saturated calomel electrode as a reference electrode through a Luggin capillary. The experiments were
carrried out under deaerated and aerated conditions at pH 9.3 and 10.3 in morpholine and sodium
hydroxide medium respectively. The deaerated condition was achieved by bubbling argon gas for 45
minutes prior to the immersion of the test coupon and the purging of inert gas continued throughout
the experiment. The electrochemical interface (Model SI 1286, Solartron make) was used to record
the electrochemical measurements.

RESULTS AND DISCUSSION

The electrochemical corrosion parameters of carbon steel in morpho line and sodium hydroxide
mediums at pH 9.3 and pH 10.3 under aerated and deaerated conditions are shown in the Table-I.
As can be seen, the Ecorrvalues were nobler and anodic tafel slopes were higher in aerated condition
than in deaerated condition and this showed that the extent of anodic polarisation was greater in the
former case. As expected, the corrosion rates were smaller as represented by the corrosion current
density values under deaerated condition.

1220
 Fig. 1 shows the potentiodynamic polarisation curves of carbon steel in sodium hydroxide and
morpholine mediums under aerated condition. The corrosion potential shifted to more positive
potentials (noble direction) with the addition of either morpholine or NaOH and the extent of anodic
polarisation was found to increase with pH in both the medium. In both the mediums, the corrosion
rates decreased with increasing pH. However, in morpholine medium,the c~rrosion rate at pH 9.3 was
found to be more than that for blank which was due to the formatf'on of soluble metal amine
complex. This complexing effect was not observed at pH 10.3 which may be due to the higher extent
of passivation in the more alkaline solution.

Fig. 2 gives the potentiodynamic polarisation curves of carbon steel in the sodium hydroxide
and morpholine mediums under deaerated condition. The corrosion potentials were found to shift in
the noble direction in the order: pH 9.3 (NaOH) < pH 10.3 (Morpholine) .( pH 9.3 (Morpholine)
< pH 10.3 (NaOH). In NaOH medium, when pH was increased to 10.3, a sharp current peak was
observed around 0.6 V which then decreased due to a film formation. The breakdown of the film
occured at 0.56 V. In morpholine medium at pH 9.3, a similar current peak was observed at 0.69 V

1221
and the film breakdown occured at 0.5 V. A broader passive region was obtained at pH 10.3 in case
of morpholine when compared with the other cases.

CONCLUSIONS

I. The corrosion potential shifted in the noble direction and the extent of polarisation was found
to increase with increasing pH in both the mediums.

2. The corrosion rates were found to be higher under aerated condition than in deaerated
condition in both the mediums.

3. The effect of complexation of morpholine was felt at pH 9.3 due to formation of a soluble
metal-amine.complex.

4. Under deaerated conditions which prevail in the reactor circuits, the addition of morpholine was
found to be better because of the presence of a wider passive region and a consequent steady
corrosion rate.

1222
 Acknowledgment

The authors gratefully acknowledge the support and encouragement given by Shri. S. Basu,
Engineering-in-Charge, PRP, Kalpakkam.

1-
REFERENCES

1. O.Seri et.al., Corrosion Sci., Vol. 30 No.87 (1990)

2. D.You, et.al., Corrosion Sci., Vol. 34 No. 1,5(1993)

3. S. Wolynec and E.Escalailte, Corrosion, Vo1.36 (1980) pp.327-334

4. D.C.Deegan, Ph.D thesis, Ohio State Univ. (1973)

5. HHUhlig and Aziz Asphahani, Corrosion, Vo1.32 (1976)pp.117-120

6. D.HDavies and G.T.Burstein, Corrosion, Vo1.36 (1980)

7. A.Wieckowski, E.Ghali, M.Szklarezyk and Sobkowski, Electrochim.acta, Vol.28 (1983)

8. T.Hurlan, S.Gunvalelsen and RTunoldetal, J. Electroanal.chem. 180,511 (1984)

9. J.Lee, K.Osseo, Asare and HW.Pickering, J.Electrochem.Soc. 132,550 (1985)

10. E.B.Castro et.al., Corrosion Sci., Vol.26 ,No. 10, 781 (1986)

1223
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Electrochemical Corrosion Studieswn Copper,

Carbon Steel and Monel-400 in Steam Generator
Cleaning Formulations
R. Latha2, s. Rangarajan" S.V. Narasimhan" S. Rajeswari2 and M. Subbaiyan2
[Water and Steam Chemistry Laboratory,
BARC Facilities, IGCAR Campus, Kalpakkam-603 102, India
2Department of Analytical Chemistry,
University of Madras, Guindy Campus, Tamil Nadu-600 025, India

ABSTRACT
Potentiodynamic polarisation experiments were carried out on copper, carbon steel (CS) and
monel-400 in Steam Generator (SG) cleaning formulations. In iron formulation, the corrosion rates and
inhibitor efficiencies of Rhodine 92B were evaluated. The shift in open circuit potential (OCP),
polarisation resistance and the tafel slopes of the anodic reactions showed the anodic nature of the
itlhibitor. In ammonia based copper formulation, the polarisation curves of monel and CS showed
active to passive transition under deaerated and aerated conditions. Copper showed a very high
corrosion rate in the potential range of -O.5~ 0.1 V and hence maximum copper dissolution could be
achieved in the solution with guaranteed protection for monel and CS if the OCP was maintained in
that range. In the EDA based formulations, similar results were obtained and monel did not show the
active to passive transition. The results showed that EDA based copper formulation with 2% H202 is
better.

INTRODUCTION
Steam generators are crucial components of pressurised water reactors in nuclear power
generating stations as they are the main boundary between the pressurised, radioactive, primary
cooling system and the low pressure secondary steam/condensate system. Corrosion product oxides
and contaminants either in the form of particles or ionized salts get deposited either on the surface of
the heat exchanger or on the various structural components like tube sheet, tube support plate etc. or
on crevices of the steam generator circuit. Moreover, the production of steam per se concentrates the
impurities present. Any corrosion damage can lead to spreading of radioactivity to the secondary circuit
and loss of heavy water in case ofPHWRs. The various structural components of the steam generator
act as active sites for the accumulation of corrosion product deposits. This leads to the reduction in
heat transfer. These deposits can also shorten the time required to puncture the steam generator tubes.
Generally, chemical cleaning is carried out to clean the entire steam generator to get rid of the oxides.
Scheffler et.al (1) has been successful in cleaning the steam generator circuit of the Byron unit
of the United States of America using nitrilotriacetic acid as a solvent ( 1-7%) for the removal of iron

1224
deposits. A total of over 6,992 kilograms of deposit was removed from the steam generator unit
leading to 100% cleaning. Odar et.al (2) of Germany has reported 100% cleaning of the KWU steam
generator tubes (nickel based alloys, inconel 690, incolloy 600) in a temperature range of 1400C to
1750C. KWU chemical cleaning process consisted of two single step methods for sludge removal -a
high temperature iron process and a copper process under ambient temperature. Nitrilotriacetic acid
and Ethylene diaf11..minc tetra acetic acid ( 1-20%) had been used as solvents for removing the iron
deposits. The copper removal process was based on ethylene diammine which served as a selective
complexing agent. Fiquet et.al (3) from EDF(Electricit'e de France) has also reported the success of
their steam generator cleaning to be 100% .
This paper discusses a two step cleaning formulation applicable for steam generators using
monel tubes. This paper highlights the electrochemical corrosion behaviour of monel -400, carbon steel
(CS) which are the structural materials in the steam generator circuit and copper. In the iron
formulation (10% EDTA +1% hydrazine hydrate, the pH of the solution was adjusted to 6.0 by NH3)
carried out at a temperature of 950C, the efficacy of a new inhibitor Rhodine 92B was tested on
various coupons of copper, monel-400, and carbon steel. In copper formulation (5% EDTA pH
adjusted to 9.5 either with NH3 or ethylene diammine (EDA corrosion rates of the coupons were
determined under different oxidising conditions.

EXPERIMENTAL
The various test coupons of monel-400, copper and carbon steel were pretreated by polishing
with silicon carbide papers sequentially starting from grade 80 to grade 600. They were washed with
distilled water, degreased with acetone and dried in air. The coupons were immediately exposed to the
test solution. The various solutions were prepared using AnalaR reagents and distilled water. The pH
of the solution was measured with ion meter ('ION-85' ion analyzer, Radiometer, Copenhagen) which
uses a combined pH electrode .
Experiments were conducted in a conventional three electrode cell with a platinum plate as
counter electrode and a SCE as reference electrode through a Luggin capillary. The temperature of the
solution was maintained within 1C. Experiments were carried out both under deaerated and aerated
conditions. The deaerated condition was achieved by bubbling argon gas 30 minutes prior to the
immersion of the coupon and purging of inert gas continued throughout the experiment. The aerated
condition was achieved by means of a mechanical air pump. Potentiodynamic polarisation experiments
were carried out using the SI 1286 electrochemical interface. Two concentrations of the Rhodine
92B inhibitor (0.04% and 0.4%) were tested for minimisation of corrosion on the various test
specimens.

RESULTS AND DISCUSSION

Figures la ,lb and lc give the potentiodynamic polarisation curves of monel, copper and
carbon steel in iron formulation, both in the presence and absence of the inhibitor Rhodine 92B. The
open circuit potential(OCP) of monel was found to shift in the noble direction and the polarisation
resistance and tafel slope of the anodic reaction were found to increase with inhibitor concentration.
These observations showed the anodic nature of the inhibitor. The corrosion rates for various materials

1225
are given in Table I. From the data given in Table 1 , the efficacy of the inhibitor Rhodine 92B was
calculated using the formula,

where E(%) indicates efficiency of the inhibitor, Ca represents the corrosion rate in the absence of
inhibitor and Cb represents the corrosion rate in the presence of inhibitor. For copper and carbon steel,
the corrosion rates were of the same order of magnitude with increasing inhibitor concentration. The
efficiency of the inhibitor for monel, copper and carbon steel was found to be between 70-80%,
80-90% and 90-95% respectively.

Figures 2a, 2b and 2c give the potentiodynamic polarisation curves of monel, copper and carbon steel
in the NH3 based copper formulation under different conditions. The possible cathodic reactions are
reduction of oxygen or hydrogen peroxide or It. The possible anodic reactions are dissolution of
metal to give metal ion and oxidation of hydrogen peroxide. Since the solutions in the copper based
formulations are highly basic, the hydrogen ion concentration is very low, and so the predominant
reactions are either reduction of oxygen or hydrogen peroxide. The reactions are as follows:

1226
 It was observed that the polarisation curves of monel and carbon steel showed an active to
passive transition in the ammonia based copper formulation under both deaerated and aerated
conditions. The passivation was observed in the potential range of -0.3 to +0. 1V and -0.5 to + 0.1V
(vs SCE) respectively. Copper showed a comparatively higher corrosion rate in the above
potential range. The above results indicated that the maximum copper dissolution could be achieved in
the solution with guaranteed protection for monel and carbon steel if the open circuit potential was
maintained in that particular range by addition of some oxidising agent. The aerated condition shifted
the open circuit potential only marginally, whereas the addition of 2% H202 shifted the open circuit
potential to the passive region.

1227
 Figures 3 (a) , 3 (b) and 3 (c) give the potentiodynamic polarisation curves of monel, copper
and carbon steel in the EDA based copper formulation under various conditions. It was observed that
in the EDA based copper formulation, similar results were obtained as that of figure 2. Monel did not
show the active to passive transition but there was a significant difference observed between the
corrosion rates of copper and carbon steel in the potential ranges of passivation.

Table 2 gives the corrosion parameters of the different test specimens involved in the NH3 and
EDA based copper formulations. It is found that the Ecorr values shift towards the more positive side
with increasing oxidising conditions in both the NH3 and EDA based copper formulations. The
corrosion rate is found to increase with increase in oxidising condition in the case of copper coupon in
both the NH3 and EDA based copper formulations. The high cathodic tafe! slope observed under
deaerated condition in NH3 based copper formulation carried out on copper coupon shows that the
cathodic reaction is highly polarised. From the point of view of copper corrosion, 2% hydrogen
peroxide addition seems better for copper removal. However, in the ammonia based formulation the
corrosion rates for the base metal (carbon steel and monel) are higher. Further, in the ammonia based
copper formulation pitting attack is observed on carbon steel. In the EDA based copper formulation,
there is no such localized attack on any coupon. Therefore, from the view point of both localized attack
and base metal corrosion, EDA based copper formulation is considered superior to the NH3 based
copper formulation.

1228
CONCLUSIONS

The following conclusions can be drawn from the present study for cleaning of the steam
generator tubes at the Madras Atomic Power Station:

1. Among the two concentrations studied, 0.4% Rhodine 92B offered better corrosion inhibition.

2. The efficiency of the inhibitor for monel, copper and carbon steel was found to be between 70-80%
80-90% and 90-95% respectively.

3. EDA based copper formulation with 2% hydrogen peroxide was better than the corresponding
ammonia based formulation from the viewpoint of base metal corrosion. Hence it is preferable to use

1229
EDA based copper formulation with hydrogen peroxide as oxidant. However hydrogen peroxide
concentration should be maintained at 2% , if there should be decomposition of hydrogen peroxide by
any means.

Acknowledgment

This work was sponsored by the Board of Research in Nuclear Sciences, DAE. The support
extended by Dr.P.K. De, Head, Corrosion Science Section, MSD, BARC and Dr. P.N. Moorthy,
Associate Director, Chemistry Group, BARC, Bombay is gratefully acknowledged.

REFERENCES
1. ScheIDerW.A., Kerr S.R. , Byron Unit I High temperature Chemical Cleaning, NACE
International Symposium on Environmental Degradation of Materials in Nuclear Power Plants:
Water Reactors. Breckenridge, CO(United States) Aug. 1995. pp.6-10

2. S.Odar and K.Kuhnke, The KWU Chemical Cleaning Process as a Remedial measure to
improve Steam Generator Performance, Water chemistry of nuclear reactor systems 6, (BNES)
VoU ,1992. pp. 113-121

3. P.Saurin, M.Clinard, M.Organisa, lM.Fiquet and lP.Veysset, Copper elimination during

Secondary Side Cleaning, Water chemistry of nuclear reactor systems 6, (BNES) Vol. 1,
1992 pp. 129-133

1230
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Possible Effects of Coal Chlorine on Furnace Wall

Fireside Corrosion in Utility Boilers
A.K. Mehtal, c.J. Davis2, P.J. James2,
L.W. Pinde.-2 and I.G. Wrighf
'Electric Power Research Institute, USA
2Power Gen pic, UK
30ak Ridge National Laboratory, USA

ABSTRACT

Fireside corrosion represents a prominent threat to the integrity of furnace wall tubing in many
pulverized fuel-fired boilers world-wide. This paper is concerned with establishing the factual basis for
the existence of a limitation on chlorine content in coal specifications used by utilities. This limitation
currently is based primarily on information reported by U.K. utilities. A sound understanding of the
effects of chlorine-if any-on fireside corrosion in utility boilers would provide a rational basis for
utility cost-benefit decisions. Such an understanding also could lead to a basis for increasing the interest
of utilities in high chlorine coals, which are currently underutilized. The paper summarizes the results of
(I) a review of the many years of experience that U.K. utilities have had with high-chlorine coals, (2) a
test program in the U.K., employing novel corrosion probe technology in a model test facility, to derive
a relationship for use in coal quality evaluation tools and (3) an overyiew oflessons learned from the
U.K. experience that should allow utilities to develop a more informed position when considering use of
high-chlorinecoal.

BACKGROUND

The experience of the U.S. electric utilities is that boiler tube failures are the primary cause ofloss of
power plant availability [1]. Analyses of the root causes of these failures indicated that a small but
significant proportion of the furnace wall and superheater and reheater tube failures are the result, either
directly or indirectly, of excessive metal loss by fireside corrosion. The main causes of fireside corrosion
are impurities in the fuel (such as sulfur, and alkali metals), lack of control of the combustion process
such that the gaseous environment experienced by the tube surfaces is not always oxidizing, and failure
to control the tube metal temperatures to the desired ranges. Because of concern that coals containing
elevated levels of chlorine may lead to increased rates of fireside corrosion, many U.S. utilities have

1231
historically restricted their use of domestic coals containing more than about 0.3 percent chlorine. Such
concern is a direct consequence of relationships reported by the former U.K. utility, the Central
Electricity Generating Board (CEGB), in which the coal chlorine content was directly correlated with the
rate of fireside corrosion.

Because this restriction on chlorine-containing coals results in under-utilization of a significant resource

of bituminous coal and has an economic impact on the Illinois Basin, the Electric Power Research
Institute (EPRI) and the Illinois Clean Coal Institute (ICCI) undertook a joint project to examine the
experience of U.S. utilities that have burned high-chlorine coal, to critically review the data that formed
the basis of the chlorine-corrosion relationships developed by the CEGB, and to make definitive
measurements to determine if any similar relationships applied to U.S. coals. A report of the experience
of U.S. utilities was put together by Battelle for EPRI [2]. A review of the U.K. experience was
undertaken of the original CEGB data, and includes information on the prevailing operating conditions of
the specific boilers in which much of the information was generated [3,4]. This review indicated that
very rapid furnace wall fireside corrosion rates (in excess of 100 nm/hr; 34 mil/yr) typically were
experienced by u.K. boilers only during operation when low oxygen partial pressures (high CO and H2S
levels) and substantial quantities of unburned fuel were ~easured at the furnace walls. These conditions
are consistent with impingement of the flame envelope onto the furnace wall tubes. The experience of the
CEGB was that only where such conditions persisted would an increase in coal chlorine content cause a
detrimental change in furnace wall corrosion rate. In addition, this increased corrosion rate was confined
to those areas where the corrosion rate already exceeded a nominal I 00 nm/hr in the absence of elevated
coal chlorine levels.

Such conditions at the furnace walls may arise as a result of general operational degradation of the overall
combustion plant: the coal mills, fans, and the burner controls, or from inherent deficiencies in the air
and/or coal supply during operation of the boiler at loads near or in excess of its maximum rating.
Operation under 10w-NOx conditions also could result in the persistence of reducing conditions near the
furnace walls if measures are not taken to direct air along the walls, using air blanketing or curtain air
techniques. Specifically-designed 10w-NOx burners, with their improved control of fuel and air flows, are
expected to provide the most efficient air blanketing effect. Experience of operating such burners in U.K.
boilers where severe furnace wall corrosion had been experienced prior to their installation has been that,
where the burners have been adjusted to prevent direct impingement of the lean, long flames onto the
furnace walls, the rate of corrosion has been reduced from of the order of 1,000 nm/hr (340 mil/yr) to less
than 100 Ill1l1'hr(34 mil/yr), at which point the problem was considered to have been resolved [5]. Note
that a wastage rate of 100 nm/hr represented an upper bound that was considered tolerable by the
CEGB; other utilities might use a different value as an indicator. In other U.K. boilers the operation of
10w-NOx burners did not significantly change the rate of corrosion, although its location was shifted.

1232
Overall, the important points from the review of the CEGB experience of furnace wall fireside corrosion
are that chlorine was found to increase the rate of corrosion of furnace wall tubes only when all three of
the following conditions were present:

i. persistent sub stoichiometric conditions (>3.0 percent CO) at the walls,

ii. a high level of unburned coal particles was found near the walls (which implies flame impingement
conditions and a high heat flux), and
iii. the rate of corrosion or wastage of the tube was already> 100 nm/hr (>34 millyr).

Further, the important corollary is that a unit that is not suffering from furnace wall corrosion when
burning its current coal is very unlikely to experience accelerated corrosion when burning a high-chlorine
coal with similar combustion characteristics.

In seeking to apply lessons learned from U.K. experience to the use of high-chlorine coals by U.S.
utilities, it is important to recognize differences among U.S. and U.K. boiler design and operating
characteristics that can significantly influence their relevance [6]. For instance, whereas flame
impingement conditions have been widely experienced in U.K. boilers, they are less frequently
encountered in U.S. boilers. However, as found by the CEGB, conditions that result in persistent
substoichiometric conditions or flame impingement can develop as a result of degradation of the
combustion process through wear of maladjustment of the components. In addition, shortcomings in the
performance of these components are likely to become more obvious, typically in terms of an inability
to maintain the desired combustion envelope, when the boiler is run near or in excess of its maximum
rating. Hence, persistent substoichiometric conditions, and even flame impingement may become
possible as a result of the typical mode of operation of older U.S. boilers. In addition, although
retrofitting with low~NOx burners would be expected to provide tighter control of the combustion
process, persistent sub stoichiometric conditions or flame impingement may be possible where, for
instance, such burners are wrongly sized or inappropriately operated through overfIring, or as a result of
difficulties encountered from switching among coals with different combustion characteristics. In fact,
the accelerated furnace wall corrosion recently reported in a number of U.S. boilers has been
characterized by a rate of wastage in the range 290 to 350 nm/hr (100 to 120 millyr), with deposits
containing FeS together with unburned carbon, and measurements of the local gas composition in the
areas experiencing this attack indicated CO levels in excess of 5 percent, and HzS levels over 500 ppm
[7]. These conditions are very similar to the CEGB criteria for accelerated furnace wall corrosion.

Despite the wealth of plant data, the complex, and often synergistic interaction between varying boiler
operating parameters have compounded difficulties in achieving a definitive, quantitative relationship
linking the rate of furnace wall corrosion with measurable parameters. A joint EPRI/PowerGen
sponsored project is underway to derive a relationship for use in coal quality evaluation tools [8].

1233
CURRENT EXPERIMENTAL WORK

Combustion Test Facility

The 1 MWth combustion test facility (CTF) sited at the PowerGen, Power Technology Centre, which
was designed to closely simulate the conditions in full-scale coal-fired boilers, while providing a
relatively low cost combustion testing environment, is shown schematically in Fig. 1. The furnace shape
gives aerodynamic patterns typical of power generation boilers, reproducing near burner flame conditions
and giving realistic in-furnace residence times. The refractory lined, water cooled furnace chamber is
complemented by a long flue gas conditioning stream, with variable heat removal rate, so that the
temperature-time history of combustion gases follows full scale plant all the way from the burner to the
stack. A comprehensive array of ports is provided on the walls of both the "furnace chamber and
convective duct, which facilitates the location of corrosion and sampling probes.

Figure 1. Schematic of the Combustion Test Facility

The CTF runs were planned to maximize the potential for subsequently performing a multiple regression
analysis on the acquired corrosion rate data. Three U.K. coals were used, selected specifically on the
basis of chlorine and sulfur content: Thoresby (0.55% CI, 1.74% S); Welbeck (0.41 % Cl, 1.90% S); and
Haworth (0.25% CI, 2.49% S). At each coal chlorine level, corrosion probes were exposed under full load
(1.0 MWth) and 80% load (0.8 MW). The capacity of the coal silo limited the duration of each test run
to 50 hours. During the course of these runs, 58 individual corrosion specimens were exposed.

In each run, specimen temperatures were controlled at nominal values of 380, 400, 420 or 450C (716,
752, 788 or 842F), the first three being considered representative of furnace wall tube operating
temperatures in conventional plant and the last being more typical of tubing in supercritical boilers.
Prior to commencing the first test run, a pre-trial operational audit of the combustion test facility, firing
on Thoresby coal, was performed. This involved flue gas analysis and heat flux measurements being
made at ,each prospective probe port location. The results of this audit were subsequently used
strategically to locate the nine/ten corrosion probes used in each run around the CTF furnace chamber
walll>. This ensured a broad spread in flue gas chemistry, from strongly oxidizing (9% O2, 0% CO) to
strongly reducing (7% CO, 0% O2), and incident heat flux.

Corrosion Probes

The furnace wall corrosion probe design co~sisted essentially of a simple tube, one end of which had a
flat disc specimen held in place by a screwed collar (Fig. 2). The corrosion specimens were 31 mm (1.22
in) in diattleter and 5 mm (0.2 in) thick, precision machined from flat carbon steel strip of a specification
comparable to that used for conventional furnace wall tubing. This design provides a gas-tight seal
around the coupon to eliminate dilution of the local gaseous environment by cooling air egress.
Temperature control and cooling of the corrosion specimen was effected by the incorporation of a central
tube down which cooling air could be blown. Four swirl vanes were fitted to the end of the air tube to

Figure 2. Schematic ofFumace Wall Corrosion Probe

promote a uniform air feed onto the rear of the specimen, and spent cooling air was vented to
atmosphere from the rear of the probe tube.

Test specimen temperature was monitored by means of two K-type thermocouples mounted in holes
I
drilled into the rear of the specimen, positioned 10 mm apart symmetrically about the coupon center.

1235
The thermocouples were sited 1.0 mm (0.04 in) and 3.5 mm (0.14 in) from the front surface respectively.
Temperature control was achieved via a Eurotherm controller using the lead thermocouple.

In order to enable relatively short-term corrosion exposures to be made, a methodology was developed to
significantly minimize errors in measuring specimen dimensions before and after exposure [8]. For
instance, measurements made using micrometers or vernier calipers have an accuracy of 5!Jl11(0.2 mil),
and further errors arise in metallographic measurements when the sample is not mounted perfectly
normal to the polishing plane, introducing a geometric magnification error, related to the angle of
sectioning (Fig. 3). For example, a 5 mm (0.2 in) thick satnple at an inclination of just 2.50 to the true
vertical will give an apparent increase in the remaining thickness of nearly 5!Jl11(0.2 mil), so that the
geometric magnification error can far outweigh all other errors and dominate the derived corrosion rate.

In the approach used here, the accuracy of measurement was improved dramatically by obviating the
need to measure the original coupon thickness, by establishing a permanent surface datum on the
corrosion specimens. The test surface of each furnace wall sample was precision machined flat to a 0.4
Ra surface finish. A 1-2 mm (40-80 mil) wide annulus of nickel p~ate was then deposited around the
coupon rim. Previous studies established that nickel plate is highly resistant to the CTF environment

Figure 3. Source of Error in Thickness Measurement due to Sectioning Off-Angle to the Normal

over the test duration; nevertheless, the annulus was further protected from the corrosive furnace gases
by locating-it under the sample mounting ring on the probe (Fig. 2).

Metal loss determinations were performed on a Leica Cambridge Q570 image analysis facility. A
software routine was used to map the x-y co-ordinates of the corroded surface which were then related
to the original metal surface, as defined by the nickel plate reference points at either end of the sample, to
determine the metal loss (Fig. 4). A compromise between the maximum amount of data required to
characterise the surface and the time taken to obtain the measurement was adopted, measurements being
taken at 300Jlm (11.8 mil) intervals across the prepared surface. To eliminate any possible errors

1236
associated with edge effects, such as increased heat input from the uncooled sample mounting ring or
electrochemical interference from the nickel plate, measured losses within 5 mm (0.2 in) from each end of
the diameter were excluded from the analysis. To ensure a representative measure of the metal loss
unbiased by outlying readings, the metal loss values used in subsequent regression analyses were taken
as the upper 95 percentile value of measured readings.

Figure 4. Schematic Diagram Showing Measurement of Metal Loss Relative to Original Surface Datum

EXPERIMENT AL RES ULTS

Corrosion Scale Morphologies

Specimens exposed to predominantly oxidizing environments generally exhibited adherent, thin, compact
scales composed primarily of oxides, with only discrete quantities of iron sulfide present. On some
specimens, the scale was intermittently isolated from the substrate by a thin, dark, interfacial phase. X-
ray analysis of this interfacial layer found significant concentrations of chlorine. No chlorine was
detected elsewhere in the scale.

Exposure to predominantly redu~ing environments led to the development of much thicker, and often
highly porous scales composed of magnetite and iron sulfide. The proportion of iron sulfide in the scale
generally increased as the severity of the reducing environment increased. This scale was separated from
the steel substrate on many samples by a dark phase, up to 30J.lm (1.18 mil) thick (Fig. 5). The detection
of chlorine in the corrosion scale was again confined to this interfacial layer. The presence of sulfur was
barely discernible in this chlorine rich band. Based on previous experience, corrosion was assumed to
progress linearly with time. Hence, corrosion rates were simply derived by dividing the metal loss by the
exposure time.

Regression Analysis

The objective of the multiple regression analysis of the acquired dataset was to describe the rate of
furnace wall fireside corrosion in terms of the following measured parameters:

surface temperature (1),

1237
 time weighted mean concentrations of carbon monoxide (CO),
time weighted mean concentrations of oxygen (02),
fuel chlorine content (Cl) ,
fuel sulfur content (S),
heat flux (HF), and
interactive combinations of the above.

Under most circumstances, the presence of CO and O2 were found to be mutually exclusive in the flue
gas environment local to the probe ports. This enabled use of a single term [CO-02l in the regression
analysis to express the magnitude of the reducing/oxidizing potential in preference to employing [COl
and [02l as discrete terms. Both species were only detected together, and at relatively low levels, in the
vicinity of the oxidizing-reducing transition. When performing the analysis, it was appropriate to
consider this neutral environment as equal to 'zero'

Although the CEGB experience indicated that heat flux is a prerequisite for accelerated attack, it was not
possible to quantify its role in these tests because of scaling/slagging of the samples, changes in burner
settings to maintain gaseous conditions, and problems encountered with some specimen thermocouples.
Although the absence of heat flux from the regression analysis is considered likely to have encouraged a
spread in the data fit, a correlation coefficient (?) marginally better than 0.7 was obtained to an
expression of the form:

This relationship at the four test temperatures and at a nominal fuel sulfur content of 2% is illustrated
graphically in Figs. 6 to 9.

1238
1239
DISCUSSION

Corrosion Rates and Scale Morphologies

As with all laboratory simulations of corrosion processes, the validity of any conclusions drawn from
the present study is subject to confirming that the corrosion rates and scale morphologies developed by
specimens exposed in the CTF are representative of those observed from operating boilers under similar
environmental conditions. A program using corrosion probes in a 500 MWe coal-fired boiler in the D.K.
has been initiated to obtain such data.

1240
The corrosion rates measured in the CTF were in the range 2-1,800 nm/hr (0.7-620 mil/yr), the highest
values being measured on the hottest specimens being exposed to the most stron~ly reducing
environments when firing a high chlorine coal. The highest rates measured in U.K. boilers have been
slightly in excess of 1,200 nm/hr (413 mil/yr). Given the assumptions of linear corrosion rate and the
lower operating temperatures (400C/752F) of furnace wall tubes in U.K. boilers, this agreement is
regarded as very encouraging.

The observation of an increased proportion of iron sulfide in the corrosion scales with increased
corrosion rate, and the detection of chlorine within a dark phase between the steel substrate and the bulk
scale is consistent with observations made on furnace wall tubing removed from service in U.K. boilers.

Effect of Temperature

Previous work has suggested that, if chlorine is an active participant in the wastage mechanism, furnace
wall corrosion may exhibit a 'bell-shaped' temperature dependence comparable to that observed in
molten sulfatic attack. It is proposed that chlorine participates by permeation of HCI from the flue gas
through the corrosion scale to react with the substrate to form FeCh. The thermodynamic stability of
FeCh is a function of the local HCI partial pressure and, at upper bound HCI concentrations measured in
coal-fired boilers (up to 350-400 ppm), FeCh will be unstable above approximately 450C (842F). The
inference is that above this threshold temperature, the intensity of corrosive attack will decline to a level
associated with the other corroding species present.

Figures 6-9 show that there is little discernible difference in the pattern of corrosion at each test
temperature with respect to gaseous environment and fuel chemistry. The effect of temperature alone on
the peak corrosion rate was found to be moderate when compared to other key variables (Fig. 11). Thus
a 10% increase in the absolute temperature, from 653K (380C /71 6F) and 723K (450C/842F) was
responsible for a 25% increase in the peak corrosion rate, being relatively uniform across the temperature
range. If a 'bell-shaped' dependence exists, the inference from the present study is that it is above the
normal operating temperature of furnace wall tubing.

Effect of Flue Gas

Significant furnace wall fireside corrosion in operating boilers (> 100 nm/hr (>34 mil/yr)) has only ever
been reported coincident with the measurement of low oxygen 0.1 ppm) and high carbon. monoxide
(>3%) partial pressures. Results from the present investigation are consistent with this experience.

All samples exposed to predominantly oxidizing environments exhibited negligible corrosion rates which
showed no dependence on fuel chemistry. The transition to a reducing environment, generally above a
3% CO threshold, exerted the greatest influence on metal loss relative to the other test variables. Wastage
rates increased from virtually negligible levels to approximately 2,000 nm/hr (688 mil/yr) over the range 0

1241
to 9% CO. Under these substoichiometric conditions, fuel chlorine and sulfur contents were found to
influence the rate of metallos$.

Effect of Chlorine

Although the role of chlorine in furnace wall fireside corrosion has been subject of great debate, a
chlorine-rich phase is frequently identified at the scale-metal interface on corroded tubes from U.K.
boilers. As discussed earlier, the U.K. experience is that chlorine influences fireside corrosion only in
those sections of the furnace wall exposed to persistent substoichiometric gaseous environments.

The corrosion patterns established in the present study share many common features with the earlier
three-dimensional interpretation of the corrosion process (Fig. 12), although fuel chlorine appears less
influential relative to combustion related parameters than inferred previously. Under reducing
environments, increases in fuel chlorine above 0.3% have been found to exacerbate metal wastage,
consistent with empirical data. However, an unexpected, moderate reduction in corrosion rate is indicated
between the low and high coal chlorine levels at high CO levels. The nature of this effect is currently
unresolved, and may be attributable to only a few data points being available at high CO values as a
result of experimental difficulties experienced when firing the mid-chlorine Welbeck coal (0.45% CI). A
further CTF run is planned to help to resolve this issue, burning a low-chlorine, high-sulfur U.K. coal
(Oxcroft). The confinement of a chlorine effect to severely reducing environments is consistent with
experience in U.K. boilers. Stations able to maintain tight control over combustion and prevent flame
impingement on the furnace walls have demonstrated the ability to tolerate deliveries of high-chlorine
coals (>0.4%) without experiencing catastrophic wastage rates.'

1242
Effect of Sulfur

As discussed earlier, empirical studies in the U.K. relating fuel chemistry to the rate of furnace wall
fireside corrosion have focused primarily on the impact of chlorine content. Although the scales on
corroded furnace tubes invariably contain a significant sulfide fraction, it has been the nature of the
sulfidizing species present in the flue gas, rather than the level present in the coal, which has been of
concem. Where oxidizing environments are dominant, the principal sulfur bearing species is S02' Under
increasingly sub-stoichiometric environments, typically above 3% CO, flame derived H2S becomes the
dominant sulfur species and its proportion, relative to S02, increases with the intensity of these
conditions. This progressive increase in sulfidizing potential, particularly with respect to the reduction in
O2 partial pressure, is reflected by the greater sulfide fraction in the corrosion scales as wastage
increases. This has been observed in the corrosion scales grown in the present study.

Fig. 10 suggests that the impact of sulfur content on the wastage rate is comparable to that observed for
chlorine. Over the relatively narrow spread of fuel sulfur contents in the coals fired during these tests,
increases in the sulfur level caused increased corrosion only under strongly reducing gaseous
environments. Although the fuel sulfur level will not influence the relative proportions of S02 and H2S
(which is dictated by the reducing nature of the flue gas) it will affect the H2S partial pressure and
therefore the sulfidizing and corrosion potential of the flue gas.

Figure 12. Schematic Description of the Influence of Combustion Parameters and Fuel Chlorine Content
on Fireside Corrosion.

1243
SUMMARY AND CONCLUSIONS

A detailed review of the experience of furnace wall fireside corrosion in U.K. boilers from the original
CEGB data and from current U.K. utility practice indicated that chlorine has been found to increase the
rate of corrosion of furnace wall tubes, but only when all three of the following conditions were present:

i. persistent substoichiometric conditions (>3.0 percent CO) at the walls,

ii. a high level of unburned coal particles was found near the walls (which implies flame impingement
conditions and a high heat flux), and
iii. the rate of corrosion or wastage of the tube was already> 100 nm/hr (>34 miVyr).

It is also important to note that a boiler that is not suffering from furnace wall corrosion when burning its
current coal is very unlikely to experience accelerated corrosion when burning a high-chlorine coal with
similar combustion characteristics.

Some recent reports of accelerated fireside corrosion of furnace wall tubes in U.S. boilers suggest that
wastage rates are being experienced that are as high as those considered to constitute accelerat~d
corrosion by the CEGB. The conditions measured in these locations appear to approximate the three
criteria discussed above, and the corrosion product morphologies are similar to those reported by the
CEGB. The boilers involved typically have been retrofitted with 10w-NOx burners, so that there is an
expectation that readjustment of the burners to attain the desired combustion environment near the
affected walls and so mitigate corrosion will be a po'ssibility.

The observations from the current rig experimental work to date underpin the previously held view of
the CEGB from empirical studies that furnace wall fireside corrosion is caused primarily by localized
reducing conditions, and that only under these conditions does increasing the coal chlorine content
exacerbate the corrosion rate. The new data also show that, under localized reducing conditions, the rate
of corrosion for the lower chlorine coals used is high [certainly> 100 iun!hi (>34 mil/yr)], although the
validity of or basis for the apparent minimum in corrosion rate at low-to-moderate chlorine levels is not
understood. Although carbonaceous deposits were observed on the probes on which accelerated wastage
occurred, the concomitant existence of a high heat flux could not be tested be~ause of experimental
difficulties. For the first time, the influence of coal chlorine content has been shown to hold true at metal
temperatures which are applicable to modem 500 MWe boiler (450C/842F). However, confirmation of
linear corrosion kinetics, and validation of these data in operating boilers will be required before the
parametric equation derived from the present investigation can be considered suitable for practical use,
such as an addition to the EPRI CQIM code.

1244
ACKNOWLEDGEMENTS

The authors wish to acknowledge the co-sponsorship, in part of the program, of the Illinois Clean Coal
Institute (ICCI) through Dr. Ken Ho. The technical contributions by Drs. 1Stringer and R B. Dooley,
Applied Science and Technology, Strategic Research and Development at EPRI, and of a technical
steering committee: Dr. J. L. Blough of Foster Wheeler Development Corp.; Mr. R J. Clarkson, Jr. of
Southern Company Services; Dr. E. P. Doane of the Kerr-McGee Coal Company; Mr. D. Eadey of the
Tennessee Valley Authority; Dr. S. C. Kung of Babcock & Wilcox Co.; Dr. A. L. Plumley of ABB
Power Plant Laboratories; and the late Dr. D. B. Meadowcroft, of ERA Technology, U.K., also are
gratefullyacknowledged.

REFEREN CES

1. Dooley, RB. and McNaughton, W.P., Boiler Tube Failures: Theory and Practice, Electric Power
Research Institute, Palo Alto, California (1996).
2. Wright, I.G. and Krause, H.H., Survey of the Effects of Coal CWorine Levels on Fireside Corrosion
in Pulverized Coal-Fired Boilers, Vol. 1 ofEPRI Report No. TR-I08107, Possible Efficts of the
Chlorine Content of Coal on Fireside Corrosion in Pulverized Coal-Fired Boilers, 1997 (Battelle
Final Report on EPRI Research Project RP 9002-08).
3. James, P.J., and Pinder, L.W., Impact of Fuel Chlorine on Fireside Corrosion of Boiler Tubing, Paper
133, NACE CORROSION '97, New Orleans (1997).
4. James, P.J., Robinson, M.T., Gibb, W.H., and Pinder, L.W., Effect of Fuel Chlorine on the Fireside
Corrosion of Ferri tic Furnace Wall and Superheater/Reheater Tubing-a U.K. Perspective, Vol. 2 of
EPRI Report No. TR -108107, Possible Effects of the Chlorine Content of Coal on Fireside Corrosion
in Pulverized Coal-Fired Boilers, August 1997. (PowerGen Report No. PT/951KA657/R, 1996).
5. James, P.l, Power Technology pIc., Ratcliffe-on-Soar, England, private communication with I.G.
Wright, September, 1996
6. Wright, I.G., Dooley, R.B., and Mehta, A.K., U.S. Perspective on the Effects of Fuel Chlorine on
the Fireside Corrosion of Furnace Wall and Superheater/Reheater Tubing, Vol. 3 ofEPRI Report No.
TR -108107, Possible Effects of the Chlorine Content of Coal on Fireside Corrosion in Pulverised
Coal-Fired Boilers, August 1997.
7. Blough, lL., Foster Wheeler, data presented at a Workshop on Materials Issues Associated With
Low-NO" Combustion Conditions in Fossil-Fired Boilers, Tenth Annual Conference on Fossil
Energy Materials, Knoxville, Tennessee (1996).
8. Davis, C.J., James P.J., and Pinder, L.W., Combustion Rig Studies of Fireside Corrosion in Coal-
Fired Boilers, presented at the 5th Inti. Con! on the Effects of Coal Quality on Power Plants, Kansas
City, Kansas, May 1997.

1245
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

The Effect of Dilution on Corrosion and

Wear of Superalloy Weld Overlays
Ram N. Chattopadhyay
Wear Prognose Technology,
Mumbai-400 053, India

Introduction

A series of nickel and cobalt based alloys are used as.were and corrosion resistance
weld overlays. The unique properties of these alloys are basically due to alloy design.
Any major change in alloy composition with respect to vital alloying elements shall
result in drastic reduction in wear and corrosion resistance properties.
During the fusion welding process for deposition of the superalloy overlay on
cheaper mild steel base, the iron and other elements from the base metal are picked up
by the weld deposit with the corresponding decrease in percentage of elements constituting
the superalloy.
The degree of dilution depends basically on the welding process and partly on
the parameters. The MMAW welding leads to maximum dilution and the PTA process
can result in minimum dilution. In order to overcome the heavy dilution problem in
MMAW, the number of weld overlay layers are increased so as to provide the top layer
material within specified compositional limits. In the multilayer deposition, not only
large quantity of costly superalloys are used but can also cause severe distortion.
The dilution and the corresponding change in wear and corrosion properties of
two superalloy weld overlays deposited by MMAWand PTA processes are discussed
in this paper.

Experimental

The composition of the two consumable alloys are shown in Table 1. The alloy
compositions correspond to ECoCrA and ENiCrMo-4. In MMAW, 4 mm diameter
electrode is used, while for PTA, the powder alloys in the size range of (-) 100 to (+)
325 ASTM mesh are used. The elemental scan across the section of the deposit is made
by Energy Dispersive X-ray Analysis attached to SEM. The microstructural features of
the weld deposits are observed in both optical and scanning electron microscopes. 'The
wear tests are carried out on standard pin-on-disc type apparatus as per ASTM G99-90.
The corrosion studies are conducted in Potentiostat.

1246
1247
from consumable can result in the iron content of the weld to exceed the limit specified
for the alloy, inspite of the number of passes as indicated in Table 3.
The diluted percentages with respect to vital alloying elements in the alloy 1 and
alloy 2 in MMA W and PT A single layer deposits are indicated in Table 4.

The main alloying elements in ECoCrA, such as Cr is reduced to 21.5% (MMA W)

and 28.5% (PT A), W to 3.25% (MMA W) and 4% (PT A). The reduction in chromium
level from 28.5 in PTA to 21.5 in MMAW has resulted in increase in corrosion rate
from 1.5 times in 10% HClto 135 times in 10% HN03. (Table 5); For ENiCrM04, the
main elements, Cr and Mo, are diluted from 15.2 in PT A deposit to 11.5 in MMA W,
resulting in increase in corrosion rate 2 times in 10% HCl and 2.6 times in HN03.

The decrease in Cr and W, the two main carbide formers, in MMAW compared
to PT A in CoCrA has been reflected in the increase in wear rate by 2.4 times in the
former against later.
Similarly decrease in Cr & Mo in ENiCrM04 due dilution and iron enrichment
have resulted in increase in wear rate of MMA W overlay by more than twice than that
of PT AW oveday.
The microstructures of ECoCrA overlays by PT A and MMA W are shown in
Figs. la & Ib respectively. The hypereutectic structure consists of Cr & W carbides in
cobalt rich solid solution. The microstructures of ENiM04 welds for PT A and MMA W
are shown in Figs. 2a & 2b respectively.
The reduction in Cr and increase in iron may result in brittle TCP phases, such
as CJ, ).t, X etc. phases (2). The higher dilution and thicker deposition in MMA W process
can result in TCP phase formation during terminal solidification of low melting phases
(3, 4). The formation of the brittle phase can cause reduced ductility in the weld and
crack formation in MMA W deposit (5)

1248
1249
Conclusions:
I. The dilution of superalloy weld overlay is maximum in MMA Wand minimum in PTAW
process.
2. The higher the dilution higher is the wear and corrosion rate of the protective weld overlay.
3. The dilution results in lowering of the percentages of vital alloying elements of superalloys
due to iron enrichment from substrate mild steel. In order to reduce the effect of high
dilution in MMA W process the multiple layers are to be deposited, while single layer
deposit of PTAW is required for similiar wear and corrosion resistance properties of superalloy
overlays.

References
I. Chattopadhyay, R. & Kammer, F.A.: 3rd Int. Conf. in Int. Trends in Welding Technology,
ASM&AWS, 1-5 June, Gatlingburg. Tennessee USA.
2. Heubner U., Hoffmann T., Rudolph G.: Proc. Conf. on Weldability of Materials, Detroit, MI
8-12 Oct, 1990, 175-182.
3. Chattopadhyay R.: Microstructural Science, vol. 9, ASM, 1991.
4. Stephenson N.: Welding & Metal Fabrication, August-September, 1990, 376-384.
5. ibid, October, 1990, 446-452.

1250
Proc. Int. ConI'. on Corrosion CONCORN '97
December ,-6, Mumbai, India

Corrosion Behaviour of Cobalt Based Metallic Glasses

K. Vinita, S.N. Malhotra and A.N. Tiwari
Department of Metallurgical Engineering and Materials Science,
Indian Institute of Technology, Powai,
Mumbai 400 076, India

ABSTRACT

In this investigation, the corrosion behaviour of soft magnetic cobalt based metallic glasses has been
studied in an aqueous medium containing 0.1 to 2.0 wt% of NaCI. Four cobalt based glasses: C-1924, 6025X,
6025 alld 6030 (Vitrovac(R)codes) have been used in as-spun and annealed states. The corrosion behaviour was
studied by electrochemical polarization as well as by the weight loss methods. The 6025X glass was found to
have the best corrosion resistance as measured by corrosion current density. The corrosion rate was found to
vary linearly with NaCI concentration. Anpealing at 673K for l-hr was found to improve the corrosion'
resistance.

INTRODUCTION

Cobalt based metallic glasses have found extensive applications in audio, video and digital tape heads
because they exhibit a unique combination of the following properties: very high magnetic permeability, very
low hysteresis loss, near zero magnetostriction and high hardness leading to superior wear resistance [1]. In
metallic glasses having curie temperature (Tc) below crystallization temperature (TJ an annealing treatment
between Tc and Tx can further improve soft magnetic properties due to relaxation [2]. The corrosion behaviour
of chromium free cobalt based metallic glasses has not been reported in literature, but their commercial
importance make them very interesting for the study of their corrosion behaviour.

It is known that the passivation of iron, cobalt, nickel alloys in sulphuric media is quite pronounced and
the presence of chloride ions can increase the passivation potential and critical current density [3]. In the present
study chloride media (0.1 to 2.0 wt.% NaCl) were chosen to simulate severe corrosive environment. The
corrosion behaviour of four chromium free cobalt based metallic glasses exhibiting very high magnetic
permeability has been studied by potentiodynamic polarization and weight loss methods. The glasses were
supplied by Vacuum Schmelze GmbH, Germany under the designations ofVitrovac(R) C-1924, 6025X, 6025
and 6030. The glasses were evaluated in the as-spun (as received) and annealed conditions.

1251
MATERIALS AND METHODS

The composition of Vitrovac(R)metallic glasses is given in Table 1. These glasses were in the form of
ribbons of thickness - 30 J.Ul1 and width 10 to 20 mm. Some important properties of these glasses are given in
table 2 [2].

The electrochemical polarization studies were made using EG&G model 363 potentiostat in conjunction
with Tacussel Model GSTP 3 ramp generator. The studies were made in Tacussel CECffH cell in which the
ribbon samples were held in a stop cock shaped Teflon tube which exposed 1 cm2 s1;1rfaceto the corrodant. In the
cell the electrical connection is provided by a platinum plate pressed against the sample by a thick walled Teflon
tube through which a permanent contact lead to the platinum plate is provided. The assembly holding the sample
was inserted on the side of the cylindrical cell through a ground glass joint. Platinum disc held in a similar
assembly was used as counter electrode and saturated calomel electrode' (SCE) was used as the reference
electrode. Polarization scans were carried out in aerated aqueous NaCI solutions. A conditioning time of 30
minutes was given before the polarization scan. The samples (air side exposed to the electrolyte) were polarized
from -2.5 volts to 0 voh w.r.t. SCE at a scan rate of 1.0 mY/sec. Corrosion current density (1) was determined
from the Tafel slopes, 13. & I3c and the polarization resistance, Rp, determined by the following formula:

The corrosion current density, t, of the samples was determined in the as-spun as well as in annealed
conditions. The annealing was done at 673 K for 1 hour in vacuum (0.015 mbar). Corrosion rates of the samples
were also measured by immersion tests (wt% loss method) in aerated NaCI solution for 108 hours.

1252
RESULTS & DISCUSSION

The anodic polarization curves showed that all the glasses had slight tendency to passivate. The cathodic
polarization curves were not smooth and showed some noise. This is attributed to non-uniform passive film due
to inherent microsurface roughness. All the samples after polarization studies exhibited uniform corrosion.

Fig.1 shows that the corrosion potential, E, where the current changed from cathodic to anodic, becomes
more active (moves in downward direction) with increase of NaCI concentration. It indicates that the glasses
become more active as the concentration ofNaCI goes up. However, in the case of C-1924 an opposite trend is
observed. In all these cases, the variation ofE with NaCI concentration is found to be linear. The slopes of these
lines are small (maximum variations are within 100 mV range)

Fig.1 also shows that corrosion potentials of all the glasses in the annealed condition are higher than
those of corresponding as-spun specimens. The slopes of E vs. concentration of NaCI lines for the as-spun
samples and the annealed samples are almost the same for all the glasses.

The variation of corrosion current density (I) with the concentration of NaCI is shown in Fig.2. The
relationship is again found to be linear. The slopes of the lines are positive in all the cases. The corrosion current
densities for as-wun samples are always higher than those of annealed samples. The dependence of corrosion
current density on NaCI concentration is significantly less fo: annealed specimens.

Fig.fshows the correlation obtained between the results of immersion test (corrosion rate in mpy) and the
corrosion current density for 2% NaCI sOlution for alJ the four glasses in as-spun as well as in annealed
conditions. A very good correlation is observed (correlation coefficient = 0.95). This study suggests that the
cobah based metallic glasses without Cr should contain at least 68 Co, I Mo, and 17 Si (at.%) to have good
resistance to corrosion along with the excellent soft magnetic properties.

1253
1254
1255
CONCLUSIONS

1. All the glasses showed uniform corrosion in aerated NaCI solutions containing up to 2 wt.% NaCI.
2. The annealing treatment below the crystallization temperature significantly improves the corrosion resistance
of the glasses.
3. Vitrovac 6025X glass has been found to be the most corrosion resistant glass among all the four glasses
studied.
4. A linear correlation between corrosion cumnt density and the corrosion rate by weight loss (ropy) shows that
electrochemical polarization studies can be used to assess the corrosion performance of metallic glasses.

REFERENCES

1. Shoo, K., Otomo, S. and Kudo, M., Magnetic Properties, Ageing Effects and Application Potential for
Magnetic Heads ofCo-Fe-Si-B Amorphous Alloys, J. Appl. Phys., Vol. 52, no. 3, (1981) pp 2483-5.
2. Balasubramaniwn, G, Tiwari, A. N., and Srivastava, C. M., Effects of Composition and Annealing on
Magnetic Properties and Wear Resistance in some Co-based Metallic Glasses, in Advances in Ferrites, Vol.
2, eds. Srivastava, C. M., and Patni, M. J., Oxford and IBH, New Delhi, 1989, pp 825-829.
3. Libermann, H. H. (Ed.), Rapidly Solidified Alloys: Processes, Structures, Properties, Applications: Marcell
Dekker, NY (1993) pp 591-616.

1256
 Proc. In!. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Electrochemical Corrosion Studies of

Propeller-Bronze in Binary Mixtures of
Acetonitrile and Water
Lal Bahadur and M.A. Emami
Department of Chemistry, Faculty of Science,
Banaras Hindu University, Varanasi-221 005, India

Propeller-bronze (82% Cu, 9% AI, 4% Fe, 4% Ni, 1% Mn) has been studied for its
corrosion behaviour in aqueous binary mixtures of ACN containing O.IM NaCI04 as.
supporting electrolyte. The open circuit potential of the test alloy was fOund to shift toward
active side with the increasing content of ACN upto 25 IDol % , remain unchanged in the range
of25-80 mol % and become more negative with further increase in ACN content. Polarization
curves showed that the test alloy passivates in solvent mixtures containing 2-10 & 70-85
mol% ACN and also in pure ACN solution. Polarization resistance (Rp) derived from
impedance data did not show any systematic variation with solvent composition.

l. INTRODUCTION additions of Ta, and Nd in propeller-bronze (19)

Bronzes are generally more resistant to
corrosion than brasses in a given environment
and hence they are preferred over brasses in many
practical applications. The corrosion behaviour of
bronzes studied during early stage showed that
'during corrosion bronzes generally undergo
dealuminization (excessive dissolution of
aluminium than copper as compared to their
proportion in the alloy) (1-7). Subsequently,
considerable efforts have been made to eliminate
or reduce the dealloying of these bronzes by
proper optimization of compositional and as well
as foundry and heat treatment variables which
govern the formation of different phases in the
alloy and in turn its corrosion behaviour (5, 6, 8-
14). Corrosion of aluminium- and nickel-bronzes
in sea water is well documented (15-18) The
minor additions of alloying elements ( Ni , Mn,
Sn, Cr) have been found to improve the corrosion
resistance of aluminium-bronze in different acidic
and neutral solutions (11-14). Singh and co-
workers have studied the influence of minor
and of Ta, La, Ce, and Nd in aluminium-bronze
(20-23) on their corrosion behaviour in aqueous
solutions of HCI, HNO" and H2S04 and
observed some improvement in their corrosion
resistance. Bastidas and co-workers (24) reported
that the corrosion rate of patinated and
unpatinated bronze in gaseous environments
( acetic and formic acid vapours, S02, and NaCI
particles) was found to be quite high Most
recently Hashem et at (25,26) reported the results
of their investigations on the role of cavitation in
corrosion of nickel-aluminium bronze in sea
water. From this brief review it is evident that
though the substantial amount of work has been
carried out in the past ori corrosion behaviour of
different types of bronzes but all these studies
have been confined to aqueous solutions only and
no attempt seems to have been made to
investigate the corrosion behaviour of bronzes in
non-aqueous' and aqueous binary mixtures of
organic solvent(s) inspite of their wide practical
applications in va~ous industries such as non-

1257
aqueous batteries, chemical and fuel processing, 2.2 Instrumentation
pharmaceutical works, electrochemical
Electrochemical experiments were carried
preparations, etc.,.(27-32). As physico-chemical
out in an indigenously designed four-neck Pyrex
properties of aqueous binary mixtures of organic
glass cell of 200 ml capacity A bright platinum
solvents can easily be varied many fold simply by
foil (1 cm2) was used as counter electrode and
changing their composition they get wide
sodium chloride saturated calomel electrode
industrial applications. However, such mixed
(SSCE) as reference. Reference electrode was
solvents have at times difficult-to-predict
separated from the cell solution by using a
properties particularly with regards to their
Luggin capillary containing agar salt (NaCl)
aggressiveness towards metals and alloys .. This
bridge, the tip of which was kept quite close (~1
makes it quite desirable to investigate the
mm) to the working electrode to minimize the iR
corrosion behaviour of metals and alloys in
drop.
aqueous binary mixtures of organic solvents.
Keeping these points in view, binary mixtures of
For the electrochemical measurements, an
acetonitrile and water have been selected as
EG & G , PARC Model 388 Electrochemical
media for the present investigation.
Impedance System was used. For current-
potential and impedance measurements, corrosion
2. EXPERIMENTAL software Model 352 and impedance software
2.1 Materials Model M388, all supplied by EG & G P ARC,
USA, were used.
Acetonitrile (HPLC grade, Qualigens,
India,) was used as obtained. Solvent mixtures
Before each measurements, solution was
were prepared using triply distilled water.
degassed (when experiment was to be conducted
Anhydrous NaCl04 (F1uka) was used as
in deaerated solution) by bubbling through it
supporting electrolyte (O.IM) in all the solutions purified nitrogen. Potentiodynamic polarization
The propeller-bronze studied during present curves were determined at a potential scan rate of
work was prepared and supplied by Sharan and 0.5 mY/so To examine the effect of dissolved
co-workers (33). oxygen in the solution, the experiments were
carried out in 'non-deaerated' solutions also.
To carry out the electrochemical
measurements (polarization and impedance), the Impedance was measured as a function of
test alloy was used in the form of circular disks of frequency (0.1 Hz to 100 kHz ) of the applied
2 cm diameter and 0.2 - 0.3 cm thickness taken signal at the open circuit potential (OCP) of the
from the as-cast alloys. Before using the working electrode in respective solutions .. In all
specimens as working electrode, they were the cases, alternating potential of very low
mechanicalfy polished first with different grades amplitude (10m V) was emp"Ioyed
( 1/0 -1/4 ) of emery papers ( John Oakey & Sons
Ltd, England) and then with sylbeth cloth using 3. RESULTS AND DISCUSSION
alumina powder. After polishing, these specimens
were cleaned with soap, washed under running

3.1 Open circuit potential (OCP) measurements
tap water and finally with distilled water. For
degreasing the surface, the samples were washed The variation of OCP of propeller bronze
with acetone in ultrasonic cleaner and in turn with as a function of solvent composition determined.
distilled water. under deaerated and non-deaerated conditions are
shown in Fig. 1.

1258

As is evident from this figure; the OCP shifts
progressively towards active (more negative) side
with the increasing content of ACN from 2 to 25
mol% and thereafter it remains virtually constant
till the ACN content reaches to 80 mol%. Further
increase in ACN content makes the OCP more
negative. From such observation it can be
inferred that in water-rich region the gradual
addition of ACN makes the solution aggressive
towards the corrosion of propeller-bronze but a
sort of saturation is attained when ACN-content
reaches to 25 mol%. This saturation state is again
disturbed when solution becomes highly rich in
ACN (>80 mol%) This shift in OCP towards
more active side with the increasing content of
ACN in the lower region can possibly be ascribed
to better stabilization of monovalent 'copper ion
(Cu-) in ACN-containing solution than in water.
A comparison of curve b with curve a in
Fig.1 clearly shows that in non-deaerated solution
also, the variation. in OCP with the solvent
composition follows the same trend as in the case
of deaerated solutions but the presence of
dissolved oxygen makes the OCP more nobler.
Hence, it can be concluded that the presence of
1259
oxygen helps in making the propeller-bronze
more resistant to corrosion, at least in free
corrosion condition. Similar effect of dissolved
oxygen was observed in the case of aluminium-
bronze also in the same aquo-organic solvent
mixtures.
3.2 Potentiodynamic polarization studies
(a) Polarization behaviour in deaerated ACN-
water mixtures
The anodic and cathodic polarization
curves of propeller-bronze determined in
deaerated ACN-water mixture of different
compositions arc shown in Fig.2. From this
figure, it is clear that propeller-bronze dissolves
actively in pure aqueous solution (curve a)
without showing any tendency of active-passive
transition even upto a current density of about 10
mA / cm2. But in the presence of even small
quantity (2 mol %) of ACN in the solution, the
anodic polarization behaviour of PB is changed
as it undergoes active-passive transition and
remains passive in about 500 mV potential range
(curve b). In both these solutions, the cathodic
polarization curves exhibit almost similar nature
and current remains below 3 /lAlcm2 even upto a
cathodic potential of about -0.8 V. At higher
cathodic potential, the reduction of water takes
place with almost the same rate (as indicated by
the same slope of the latter parts of the cathodic
curves) in both. these solutions. The nature of the
anodic polarization curves c, d and e obtained in .
solvent mixtures containing 3.6 , 5 and 10 mol %
ACN respectively' is almost similar to that of
curve b but the critical potential .is reduced by
about 250 mY. Further, as ACN content
increases from 3.6 to 10 mol%, the passivation
current decrases from 5.1 to 3 mA / cm2 So far
as cathodic polarization curves in these solvent
mixtures are concerned, they are similar in the
cases of 3.6 and 10 mol % ACN-water mixture
but in the solvent mixture containing 5 mol %
ACN, a cathodic passivation is observed, the
cause of which is not very clear. In' ACN-water
mixtures containing 25 and 50 mol% ACN, the
test alloy exhibits active dissolution with no
indication of any active-passive transition even
2
upto a current density of more than 10 mAlcm
The cathodic polarization curves obtained in
these solutions exhibit three distinct features in
different ranges of potential. In lower cathodic
overpotential range the current increases sharply
but with further increase in potential current
ceases to change and cathodic process seems to
be complete under diffusion control over a wide
range of potential. Finally, when applied potential
becomes sufficiently negative (~ -1.2 V vs SSCE)
the hydrogen evolution starts and current begins
to increase again.

In ACN-rich solvent mixtures (70-85

mol% ACN), the test alloy exhibits distinct
active-passive transition in comparatively lower
anodic over potential range and critical currents
are also lower than those deserved in solvent
mixtures containing 2-10 mol% ACN (curve b-e).
Further, with the increasing content of ACN from
70 to 85 mol%, the cathodic polarization curve
was found to shift towards higher current density
side, though the nature of the polarization
remained the same. In solvent mixture extremely
rich in ACN (95 mol%), the PB showed aCtive
dissolution with no indication of any sort of
passivation (curve k). In pure ACN solution,
active-passive transition was observed but
passivation potential range was quite narrow
(-100 mY).

(b) Polarization behaviour in non-deaerated

ACN-water mixtures
In order to examine the effect of dissolved
oxygen on the dissolution behaviour of propeller-
bronze, polarization curves were determined in
non-deaerated solutions also and two
representative curves are shown in Fig.3 along
with those obtained under deaerated condition.
From this figure it can be seen that in the
presence of dissolved oxygen in the solution,
the cathodic

1260
polarization curves are invariably shifted towards
higher current density .side irrespective of the
ACN-content in the solvent mixtures. However,
the dissolved oxygen causes cathodic passivation
also in most of the cases which was not observed
in deaerated solutions. Thus, the process which
leads to cathodic passivation of the test alloy
seems to occur only in the presence of oxygen.

Fig.3 further reveals that the nature of

anodiC polarization curves of propeller-bronze is
not altered by the presence of dissolved oxygen in
the solution. However, it (oxygen) increases the
passivation current to some extent in the solvent
mixtures containing 3.6 and 10 mol% ACN.
Contrary to this, the anodic dissolution current is
reduced in the presence of dissolved oxygen in all
other in solvent mixtures. It is also to be noted
that in the case of 75 mol % ACN-water mixture,
the passivation potential range. is widened under
non-deaerated condition. Thus, the dissolved
oxygen helps in reducing the anodic dissolution
current of propeller-bronze in ACN-water
mixtures particularly when ACN-content is more
than 25 mol%.

3.3 AC impedance studies

(a) AC impedance response of propeller-bronze
in t/eaerated ACN-water mixture .

As mentioned above, the impedance

measurements were made at open circuit
potential of the test alloy in ACN-water mixtures
of varied composition under deaerated condition
and the results are shown as Bode plots in FigA.
The various impedance parameters derived from
these graphs are given in Table 1.

From the values given in Table. 1 it is

clear that the polarization resistance of the
propeller-bronze does not follow monotonic

trend with the increasing content of ACN in the

solution. However, in broader sense it can be said
that the Rr value decreases with the

1261
increasing content of ACN upto 3.6 mol% and
thereafter it increases till ACN content reaches to
10 mol%. Subsequently, R., value follows more
or less a decreasing trend with the increasing
content of ACN upto 95 mol%, except in the
case of 85 mol% ACN-water mixture. In pure
acetonitrile solution the R., value was found to be
higher again. As the R., value is a measure of
corrosion resistance of the test alloy in the
respective solution, the trend followed by R.,
values would be the trend of corrosion resistance
also but this influence would be applicable only
under free corrosion potential because impedance
measurements were carried out at OCP not at
bias potential.

(B) The effect of dissolved oxygen on A C

impedance response of propeller-bronze

Impedance parameters derived from Bode.

plots for propeller-bronz in non~deaerated
solutions are given Tablel. Fig.5 shows the
Nyquistplot of the propeller-bronze in 75 mol %
ACN-water mixture determined under non-
deaerated condition. The Nyquist plots obtained
in other solvent mixtures were found to be of
usual nature (single capacitance loop) and hence
they are not shown.
As it is evident from Fig.5, Nyquist plots
obtained in 75 mol% ACN-water exhibit two
time constants. From the values given in Table I
it can also be seen that except in one case (95
mol% ACN-water mixture), the R., values
obtained.in all other solvent mixtures under non-
deaerated condition are lower than' those
obtained in deaerated condition. Based on this
observation it can be inferredthat in general the

1262
 dissolved oxygen has adverse effect on corrosion
~sistance of the propeller-bronze.
~EFERENCES
I. R. A. Wilkins, Mech.Eng. 58, 51 (1936).
2. S. C. Britton. J Inst. Metals, 67, 119 (1941).
3. M. Schussler and D. S. Napolitan, Corrosion, 12,
107' (1956).
t. M.L .Williams, J Am. Soc. Naval Engrs., 69,
453 (1957)
5. 1. F. Tabor, Am. Water Works Assn., 48, 239
( 1963)
6. S .Goldspeil, J. Kirshner, and G. Wacker, Modern
Castings, 47, 818 (1965).
7. R. Heidersbach, Corrosion, 24, 38 (1968).
8. B. Upton. Corrosion, 19, 204t (1963).
9. R. E.Maersch and J. M. Cieslewicz, ProtoMatels,
3.54 (1964)
10. C. A. Zanis and R. J. Ferrara. Transactions AFS,
71. (1974)
II. Z. Ahmad. M. Ghafelehbashi, and S. Nategh,
Anlicorrosion. 13 (1974)
12. Z Ahmad. Anticorrosion. 8 (1977).
13. Z. Ahmad and A. Afshar, Anticorrosion, 10
( 1978)
J.I R. 1. F.Ferrara and T. E. Caton, Material
Perjhrmance. 22, 30 (J 982).
1263
15. B. G. Ateya, E. A. Ashour, and S. M. Sayed. .I
Electrochem. Soc., 141. 78 (1994).
16. R. B. Niederberger, Modern Castings. 45, /10
(1964).
17. C .A. Zanis and R. 1. Ferrara. Transations AF5;.
259 (1972)
18. A. Schussler, H. E. Exner, Corro. Sci., 34. 1793
(1993): Corros. Sci. 34,1803 (1993)
19. R. N. Singh, S. K. Tiwari. and N. Vem1a.
Corrosion Prevo & Cont.. 43 (1988).
20. R. N. Singh. N. Verma and W. R. Singh
Corrosion, 45, 222, (1989).
21. N. Verma, W. R. Singh, S. K. Tiwari, and R. N.
Singh, Br. Corms. J, 25, 131 (1990)
22. R. N. Singh, S. K. Tiwari, and W. R. Singh, J
Appl. Electrochem., 22, 1175 (1992).
23. R. N. Singh, N. Verma, S. K. Tiwari, and W. R.
Sin~h, IndianJ Chem. Techno!.. 1, 103 (1994)
24. 1. M. Bastidas, M. P. Alonso, E. M. Mora, and B.
Chico, Mater. Corros. 46,515 (1995).
25. A. AI-Hashem, P. G. Caceres. W. T. Riad. and
H. M. Shalaby, Corrosion, 51. 331 (1995).
26. H. M. Shalaby,A AI-Hashem . H. Al-Mazzeedi.
A. Abdullah, Br. Corros. .J, 30.63 (1995)
27. E. Compaign and W. Archer, JAm. Chem. Soc.,
75, 983 (1953)
28. R. Jasinski. in "Advances in Electrochemistry
and Electrochemical Engineering". Vol.8. (P.
Delahay and C. Tobias, Eds.), Wiley & Sons,
New York (1971), p. 253.
29. E. Heitz, in "Advances in Corrosion Science and
Technology", Vol. 4, (M.Fontana and R. Staehle,
Eds.), Plenum Press, New York (1974), p.149
30. E. Blomgren, in " Lithium Batteries", (1. P.
Gabano, Ed.), Academic Press, New York
(1983), p. 13.
31. M. Fukuda and T. Tigima, in "Lithium
Batteries". Academic Press, New York (1983). p.
211.
32. P. L. de Anna, Corros. Sci., 25, 43 (1985).
33. R. Saran and B. Kumar, 12th AIMGDR ConL
lIT Deihl, India, 1986. p. 228
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Water Treatment and Corrosion Control in Oil Field

Water Injection Schemes of Upper Assam
B.P. Babu, Jolly Joseph, S.K. Sahota and H.C. Dhawan
RCL, ONGC, Sibsagar, Assam, India

ABSTRACT

Water injection for pressure maintenance is one of the most widely used method of secondary
recovery world over. Water quality requirement for water flooding is very stringent in the sense
that the injection water should not adversely affect the permeability of the producing reservoir.
Suspended solids, corrosion and scaling products formed often plug the formation thereby reducing
the injectivity. Hence water quality plays a significant role in the success ofany water injection
scheme.

In the Upper Assam field.of ONGC both produced as well as tube well waters are used for the
injection purposes. Targets of water injection could not be achieved due to poor quality of the
water which necessitates further improvement. The laboratory study conducted on injection
waters ofLakwa and Geleky reflects that the treatment of Potassium permanganate in the alkaline
media considerably improves the quality of injection waters, when used along with other water
injection chemicals. The source water contains dissolved iron and/or organic matter in the form of
tloe suspended particles. Potassium Permanganate in the alkaline media oxidizes the dissolved iron
and/or the organic matter present in the source waters to form insoluble flocks which are removed
by the filters. Study shows that there is a three to five times increase in filterabilities of Lakwa
injection waters and two times increase in Geleky after the treatment of alk.Potassium
Permanganate. Corrosion rates of the injection waters reduced from 0.8-1.5 mpy to 02-0.5 mpy
after the treatment. Field implementation of the study shows remarkable improvement in the
quality of the injection waters in terms of fIlterability, total suspended solids and corrosion
tendency.

INTRODUCTION

Wa~r injection for pressure maintenance is one of the most widely used method of secondary oil
recovery world over because of its easy availability, better oil sweep etliciency and its low cost. In
water injection operation it primarily concerns with those ions, physical properties which are
important for the stand point of plugging or corrosion. Suspended solids present in the water and
the corrosion products from the transporting lines all lead to the plugging of the formation thereby
reducing its injectivity. Hence water for injection requires an extensive treatment to make it free:
from suspended solids, free from micro organisms, non-corrosive and compatible with the
fornlation for the long term success of the injection scheme.

In Upper ASSaDl1ieldsofONGC trial water injection plant was commissioned in 1982 to arrest the
pressure decline in the reservoir sands of Tipam and Barail. At present approximately 5000 M3 of
treated water is injected daily into TS-l,TS-2A.,TS-3A.,TS-4,TS-5A.,T~ and BMS sands from

1264
seven water injection plants viz. Lakwa-IJUII, Geleky, Lakhmani, Demulgoan and Rudrasagar.
Present study is focussed on Lakwa and Geleky waters as they contribute about 75 % of total water
injection.

WATER COMPOSmON AND CORROSION

The etl'ects of various dissolved ions on the corrosivity of the water are:

Dissolved Salts; Dissolved salts increases the conductivity of the water and thereby increasing
electrochemical corrosion. The effect of Chloride ion is very severe.
Dissolved Gases: Oxygen, Carbon-di-oxide and Hydrogen Sulphide dissolved in water drastica11y
increases the corrosivity.
Oxygen: It is a major cause of corrosion in oil field waters. It causes severe corrosion even if it is
present in smaller concentrations of <0.1 ppm. The action of Oxygen is two fold. It acts as Ii
cathodic depolarizer and also it removes Iron by precipitating iron oxide at anode.
Carbon-di-Oxide ; It forms carbonic acid when dissolved in water and decreases the pH of the
water and hence increases the corrosivity.
Hydrogen Sulphide: It rew.:tswith iroD and produce sulphide which fonus an insoluble precipitate
on the metal surfaces.

Other factors:

pH : The corrosivity of the water generally increases as the pH decreases to acidic region.
Suspended Solids: High suspended solids causes settling of solids at the bottom of the lines
promoting .formationof sludge under which bacteria develops causing bacterial corrosion.
Microbial factors: Sulphate reducing bacteria and iron bacteria causes the two most widely known
fonns of bacterial corrosion. Iron bacteria produce tubercles of iron oxide below which sulphate
reducing bacteria grow and bring about severe localized corrosion due to generation of Hydrogen
Sulphide.

CORROSION CONTROL

Various methods generally applied for controlling corrosion in oil field water injection schemes are:

-' Removal of suspended solids by coagulation-tlocculaltion and filteration.

-. Remov-alofOAygen by deaeration and with chemical scavenger .
.- Use ofsuitab1e corrosion inhibitor.
Chlorination and use of bactericide to kill the bacteria.

Potassium Pemlanganate in alkaline media is Ii good oxidizing agent to oxidize iron and the
organic matter present in the water which forms insoluble flocks. In the present study this
property is used to treat the water for improving its quality.

MONITORING

The quality of the injection waters are assessed by monitoring the various parameters like
tilterability, total suspended solids and corrosion tendency.

1265
Filterability: It gives the plugging tendency of the injection water, It is measured by using millipore
f1lteration apparatus. Injection waters are passed through 0.45 J.I. filter paper' under pressure and
the volume collected in 30 mins. is taken as the filterability.

Total suspended solids: It is calculated by taking the weight of the solids remaining on the filter
paper after the ftltemtion test.

Corrosion rate: Corrosion rates are estimated by the coupon weight loss method. Steel coupons are
exposed .in the injection waters for five days at 502C under static conditioin. The weight loss of
the coupons are taken for calculating the rates by using:

RESULTS AND DISCUSSION

In Geleky the water is a mix of tube well and river water. This wa.ter is treated with Alum and
Lime to remove suspended solids and after passing through tilters, clay stabilizer, Oxygen
scavenger and bactericides are dozed before injection. Remarkable improvement in the water
quality has been observed after treatment with optimum dose of 2 ppm KMTl04 and 40 ppm
Caustic along with other water injection chemicals. Result reflects tllat the filterability increases
from 2.7 lit to 5.6 lit Bud suspended solids decreases fiom 4.7 to 2.0 mg/lit (Tltble-l). The
corrosion rate of the raw water is 2.04 mpy. After treating with Alum and Lime corrosion rate is
reuuced to 1.23 mpy, but alter adding 0.2 % KCI it is raised sharply to 1.94 mpy, It has been
found that when the raw water is treated with 2 ppm ofKrv1n04 and 40 ppm ofNaOH along with
other wak:r injection chemicalswitllout corrosion inhibitor the corrosion rates is reduced to 0.51
mpy (Table-3).

In Lakwa water injection plants UI & ill the source water is the treated effluent (produced water)
from effiuent treatment plant. This water contains organic matter in the foml of tiny suspended
particles. At present this water is treated only with bactericide before injection. The water is
having fllterability 0.68-0.95 lit. After the treatment '\\-ith optimum dose tlf 12 ppm of KMn04
and 40 ppm of NaOH the filterability increases to 302-397 lit. and total suspended solids
decreases from 12.2-14.0 mgllit to 2.6-3.2 mgllit (Table-2). The corrosion rate of raw water is in
the range of 0.95-1.32 mpy and with the treatment of bactericide the rate has been shghtly
reduced to 0.83-1.l2mpy. After the treatment of alk.KMn04 the corrosion rate reduced to 0.23-
0.51 mpy (Table-4).

The improvement in the quality of injection water atler the treatment of alk.KMnO. is due to the
oxidation of iron and other oxidisable prganic matter which forms insoluble flocks and are removed
by the filters. The reduction in corrosion rates is due to the removal of suspendeu solids and the
overall improvement in the quality of the ~iection water.

1266
FJELD IMPLEMENTATION

Field trials of the treatment of alkaline Potassium Pennanganatc in Lakwa and Geleky water
injection plants gave encouraging results (Table-5 & 6).

CONCLUSION

The treatment of alkaline Potassium pennanganate shows remarkable improvement in the overall
quality of injection water in terms of fIlterability, total suspended solids and corrosion tendency.
The study also shows encouraging results in the real field conditions.

ACKNOWLEDGEMENT

Authors express their sincere gratitude to Dr.D.M.Kale, General Manager (Exploration) for
encouragement and tor granting permission to publish this paper.

1267
1268
1269
Proc. Int. Cont. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Effect of Addition of Admixture on Strength and

Corrosion Behaviour of Concrete
A. Bhattacharyya, S.K. Ghosh, S. Srikanth and K.B. Mishra
R&D Centre for Iron & Steel,
Steel Authority of India Limited, Ranchi-834 002, India

Abstract

Concrete structures of M-20 grade exposed to hot phenolic water in steel plants are
undergoing considerable corrosion in a short time. The phenolic water is quite
corrosive due to the presence of inorganic impurities such as cyanides, sulphides,
sulphates, ammonia, carbon dioxide and oxygen in small concentrations. The present
work was initiated to assess the performance of concrete with the addition of
admixture in the above environment. Two types of samples were cast.

(i) 18 numbers of beams of 1500mm length and 150mm x 150mm cross section
(ii) 18 numbers of cubes of 150mm size

Both the types were cast with and without admixture. Admixture used was polymer
based Superseal-lOO. The optimum percentage i.e. 0.75% by weight of the admixture
with respect to cement has been obtained after conducting a series of tests on 100mm
cement mortar cubes having different percentages of admixture

Six numbers of beams and six numbers of cubes with 0.75% admixture were exposed
to hot phenolic water for six months. Also six numbers of beams and six numbers of
cubes without admixture were exposed to same phenolic water for comparative
evaluation. All the cubes were tested for compressive strength after exposure and the
beams were tested for flexural strength. It was observed that compressive strength of
cubes with 0.75% admixture did not change before and after exposure in hot phenolic
water whereas cubes without admixture showed 14% reduction in compressive
strength after exposure possibly due to the deterioration und~r exposed condition.
Similarly in the flexural strength tests the beams with admixture exhibit nearly equal
values before and after exposure. Since flexural strength is governed by steel, the
above results indicate that there is no evidence of reduction in the cross sectional area
of reinforced steel bars due to exposure conditions. Bnt the beams without admixture
show 16.8% reduction in flexural strength after exposure in hot phenolic water. From
the results it may be concluded that 0.75% admixture in cement reduces the concrete
corrosion significantly.

1270
Introduction

Phenolic water vapour as well as hot phenolic water cause severe corrosion to
surrounding concrete structures in Coke ovens in SAIL steel plants. Phenolic water is
quite corrosive due to the presence of inorganic impurities such as cyanides,
sulphides, sulphates, chlorides, ammonia, carbon dioxide and oxygen in small
concentrations. Diff~rent treatments have been proposed by a number of research
' , " to reduce th e above ImpuntIes
workers 12345 .... In t he pheno l'ICwater.

The need to make cement concrete highly resistant to Ghemical attack is becoming
increasingly important nowadays. It is reported that addition of certain additives in
cement improves the corrosion properties of concrete6. Buenfield7 and Gerwisk8
reported that concrete structures can be protected .from chemical attack by applying
suitable coatings on the concrete surface. The present investigation was carried out to
assess the performance of concrete with the addition of admixture in the above
mentioned environment.

Experimental

Preliminary study was carried out to find out the optimum percentage of admixture to
be added in the cement. For this purpose cement mortar cubes of standard size
(lOOmmcubes) were cast with the admixture, "Superseal-lOO", in varying percentages
as 0, 0.125, 0.25, 0.50, 0.75 and 1.0% respectively. Three samples were cast for each
of the above percentages of admixture. The samples were removed from the mould 48
hours after casting and then kept in water for curing. These samples were tested for
compressive strength in 100 tons capacity machine.

Also, a set of experiments were carried out to find out the proper time of opening of
moulds after casting in case of concrete with admixture to avoid disintegration of
cubes or beams before curing in water.

Finally, two types of concrete samples were cast to study corrosion behaviour in hot
phenolic water.

(i) 18 numbers of beams of 1500mm length and 150mm cross section

(ii) 18 numbers of cubes of 150mm size

Both the types were cast with and without admixture. Admixture used was polymer
based "Superseal-lOO" supplied by Mis Manikant Bros, Bombay. Admixture added
was 0.75% by weight with respect to cement and in all the beams cover thickness was
25mm.

1271
Six numbers of beams and six numbers of cubes with admixture along with equal
numbers of beams and cubes without admixture were exposed to hot phenolic water
for six months. The remaining beams and cubes were kept in air after curing in water
for 28 days. These were tested along with exposed beams and cubes after six months.
Compressive tests were carried out for all the cubes in 100 tons capacity machine.
Flexural tests were carried out for all the beams in SEGAR, German make 20 tons
capacity machine with four point load method.

Results and discussion

The compression tests show that with increasing admixture percentage in cement the
compression strength of the cement mortar cubes remains more or less equal upto
0.75% admixture. Beyond this percentage the strength of the cubes drops drastically
and the cubes disintegrate during mould opening.

The proper duration of keeping the samples in mould when admixture is added has
been studied and the experimental results are shown in Table-I. The gain in
compressive strength of the cubes with 0.75% admixture with age is fairly alright as
the fck values increased from 153 kg/cm2 to 213 kg/cm2 i.e. an increase of about 40%
in seven days as shown in Table-I. This indicates that the addition of admixture does
not have any adverse effect on the 20 days compressive strength. However, there is no
evidence of any gain also. It is also observed that keeping the samples in the mould
for seven days appears to reduce the compressive strength to 141 kglcm2 The
optimum demoulding period was found to be two days (48 hours).

1272
The compressive strength of six numbers of unexposed cubes with 0.75% admixture
were measured (Table-2) along with 0.75% admixture added cubes exposed to hot
phenolic water for more than six months (Table-3). Results show that both exposed
and unexposed cubes have nearly same compressive strength i.e. 318 kg/cm2 and 311
kg/cm2 respectively. This indicates that there is no deterioration in concrete which has
been exposed more than six months to the corrosive environment. However the
compressive strength of the cubes without admixture shows lower values (273
kg/cm2) when exposed to above corrosive environment for similar duration as given in
Table-4. This may be due to deterioration of concrete when exposed to corrosive
environment.

1273
The flexural strength of six numbers of unexposed beams (l500mm long) with 0.75%
admixture were measured (Table-5) along with 0.75% admixture added beams
exposed to hot phenolic water for more than six months (Table-6). Results show that
the admixture added beams both unexposed and exposed have nearly same flexural
strength. The average ultimate moments at failure (Mu) are 10.63 and 10.39 kNm
respectively. The flexural strength is governed by reinforcing steel bar. It therefore
appears that there is no evidence of reduction in sectional area of reinforced bar
embedded in concrete when exposed to agressive environment for more than six
months. However the flexural strength (Mu) of the beams without admixture shows
lower value (8.84 kNm) when exposed to above corrosive environment for similar
duration as shown in Table-7. This indicates that corrosion of reinforced bars might
have started and cross sectional area is reduced.

1274
Conclusions

Based on the results the following conclusions are drawn.

(i) The optimum percentage of admixture (Superseal-l00) used was found to be

0.75% by weight of the admixture with respect to cement.

1275
(ii) Compression tests of the 100mm size cubes with and without admixture
showed that the admixture did not have any adverse effect on the compressive
strength.

(iii) Compressive strength of cubes with 0.75% admixture did not change before
and after exposure to hot phenolic water whereas cubes without admixture
showed 14% reduction in compressive strength after exposure due to the
deterioration under the exposed condition.

(iv) In the flexural strength tests the 1500mm long beams with admixture exhibited
nearly equal values of ultimate moment at failure (Mu) before and after
exposure. This indicates that reinforced bars were unaffected by the corrosive
environment even after six months possibly due to sealing of pores in concrete
by the admixture. But the beams without admixture showed 16.8% reduction
in flexural strength after exposure in hot phenolic water.

References

1. J.E.Barker and R.J.Thompson, EDA-R2-73-167, April (1973), P 178

2. J.E.Abson and K.H.Todhunter, COMA Yearb, Waverly House, Yorkshire,

England, (1960), PP 283-319

3. R.L.Cooper and J.R.Catchpole, Information Symp, Coke Oven Technique,

EVR 5342, May (1975), P 149

4. W.G.Cousins and A.B.Mindler, J. Water Pollution, Control-Fed, 44(4), 1972,

P 606

5. Ohio River Valley water sanitation cp., ossopm, phenol wastes, treatment by
chemical oxidation, Cincinnati, (1951)

6. COI11parisionof polarisation resistance technique, N.S.Berke, D.F.Shen and

K.M.Sundberg, Corrosion rates of steel in concrete, Proc. of Symp. ASTM,
J!lne (1988), P 38

7. N.R.Buenfield, Imperial College ofSci. & Tech., Proj. Rep., (1992)

8. Design and construction of concrete ocean structures to ensure long term

durability, B.C.Gerwisk, Int. conf. on evaluation of materials performance in
severe enviroment, Japan, 20-23rd Nov (1989), PP 527-534

1276
ABSTRACT: Conosion is an electrochemical process which occurs when there
exists considerable electron gradient between any two zones or sites in any system
considered For any study on corrosion in relation to its cause, ongoing and factors
influencing it, a proper quantification of the criterion for corrosion is required. In this
paper the quantification of the criterion for corrosion is stated as a fundamental theorem
in the form of an equation This equation governs the initiation of corrosion process in
any system considered Also this equation becomes the fundamental equation from
which any other corrosion equation can be formulated in different cases corresponding
to different factors aiding and abetting corrosion. The quantification principle involves
accounting for the difference of the electrode potentials of the localised anodic and
cathodic zones operating in the system considered and thereby assessing its value.

KEY WORDS : Corrosion, equivalent anodic zone!, equivalent cathodic zone, metals.

INTRODUCTION :

Most of the literature in corrosion is in a very raw and theoretically verbal form
rather than a mathematically quantified perspective. For understanding the corrosion
process i.e. onset, ongoing and factors influencing it, a mathematically quantifiable
assessment enables us to account for the different factors causing corrosion and their
magnitude in a precise manner. A mathematically modelled criterion for corrosion is
stated and a fundamental equation for corrosion onset is formulated

1. By equivalent zone (anodic or cathodic) we mean that in a system having many minute corrosion celIs
operating in the system (Le. having many anodic and cathodic zones in it) the equivalent cathodic zone
represents the contribution of all the localised cathodic zones electrode potentials. Similar is the case
of equivalent anodic zone.
1277
THERMODYNAMIC CONCEPTS OF CORROSION :

For electrochemical corrosion to occur, precurSors are

1. Formation of anodic and cathodic areas within the medium.

a) The anode corrodes by forming ions and the cathode reduction takes place.
b) More than one element should be present.2

2. Electrical contact between anode and cathode for conduction of electrons

3. Electrolytic conduction usually provided by the presence of moisture.

Factors affecting corrosion rate :

Relative proportion of anodic and cathodic areas. Large cathodic area and small
anodic area causes intense corrosion (Bannerjee, 1985).

FORMULATION OF THE FUNDAMENTAL EQUATION OF CORROSION

ONSET :(Quantification of the Criterion for corrosion onset)

In any existing system there would be many minute thermodynamic (corrosion)

cells (Alexander William & Arthur Street, 1989), whose net emf is vety low and without
loss of generality we may assume it to be zero. The presence of a gradient in charge
concentrations at two zones (in metals or non-metals) causes the formation of an anodic
zone and a cathodic zone and therefore constitutes formation of a minute corrosion
cell. The summation of the net emf's of the many such minute corrosion cells operating
in the system gives the net emf gradient which is the potential between the equivalent
anodic zone and equiyalent cathodic zone of the system.

2 For electrochemical corrosion presence of different metals with marked differences in their electrode
potentials should be present, these elements may be metals, also non-metals. For eg. S,P,C etc. which
have considerable electronegativity thus having higher electrode potentials as compared to other non-
metals. 1278
1279
DEDUCtION OF THE CORROSION EQUATION :

1. Any intricate phenomenon of nature is governed by a very simple and feasible law:

2. Though corrosion appears to be a very complex process? in reality it is an outcome

of a low but finite level of interplay of electrons and electron concentraitons in a
given system considered.

3. Corrosion will start in a system if the net emf difference due to the active electron
gradient is finite enough or large enough to create marked anodic or cathodic zones
in the system. Any system as such found in its most naural state has its own finite
difference of net emf between anodic and cathodic zones. But this may be vel)' low
which attributes to its vey low degree of distintegration (or corrosion). But any
external parameters which become an external source of emf cause the initial active
emf gradient of low amount to increase and increase the barrier between the net
anodic and cathodic zones. This external emf is in excess of the already existing
small active electron gradient of emf in the system.

The initial emf can be quantified by the state of the matter and also by its form
(metal?non metal? etc.) and the external emf can be quantified by knowing the external
causes and the science behind their quantificaiton. A similar such quantification of
external emf has been done'.

But this is only one example of external emf quantification. We can also quantify
..
the source of emf and thereby adding it to the initial emf (may also be approximated to
zero in some cases) we can know the susceptibility of the system to get corroded (or
diintegrated) which is due to down the large amount of active electron gradient between
the anodic and cathodic zones.
3. RAMESH CHANDRA.B and RAMESH REDDY.R (1997), "Corrosion of Galvanised Reinforcement Bars due to
an Electrothennodynamic parameter: Pyroelectricity." Proceedings of the International Conference on
Maintenance and Durability of Concrete Structures, Universities Press, ISBN No.8173710686.

1280
1281
Now an extern~ sour~ of emf when acts on this system, it boosts each of the minute
corrosion cell operating in it and thereby causing the difference in the net emf between
the. anodic and cathodic zones to widen. This occurs because of the change in the
concentration of electrons at their initial sites caused by the external emf, which results
in a sea change in the concentration of electrons at those corresponding anodic and
cathodic zones creating marked electron gradient between anodic and cathodic zones.
This in turn sets up a large gradient in electron concentration between the anodic and
cathodic zones. This phenomenon is not limited to one minute corrosion cell but to
many localised minute corrosion cells of the system considered This therefore increases
the net emf between the equivalent anodic and equivalent cathodic zones of the system
considered and hence the corrosion process accelerates.

Now, this net emf is not negligible and this is the precursor for enhancement of
corrosion.. (See elctrochemical theory of corrosion).

The external source of emf which can be known by inspection of the mechanics
(Ramesh Chandra, Ramesh Reddy, 1997) of the system helps us to understand the
various types of causes for corrosion and their quantified values precisely. This precise
quantification of the corrosion contribution magnitude by external sources of emf helps
us in having corrosion resistant designs for a system considered. The system considered
can be as diverse as anything, ranging from a remote insulator such as a rock to a
highly conducting metal.
1282
EXPERIMENT :

AISI-4340 specimen of steel was taken for this experiment of corrosion

quantification. The specimen was a fixture and the emf drop between two selected points
was measured before exposing it to the severe corrosive environment. The emf drop was
measured using a multimeter (KEITHELEY, 2001 SCAN, DIGITAL) of high precision and
having a least count of 0.01 micro volts (for measuring voltage). The distance between
the two selected points is 20 rom. The dimensions of the specimen are 150 rom x 50
rom x 10 rom. It was kept in an extremely moist environment for 72 hours to corrode.
Water drops were allowed to trickle down on the specimen althrough the above mentioned
duration.

The emf drop was measured again after it was left to corrode in a severe corrosive
environment as mentioned earlier i.e., after a duration of 72 hours. Both the measurements
were made under identical environmental conditions of temperature and relative humidity.

Results :

Graph No.1 represents the inital emf (m V DC) present between the two selected points
in the specimen. To know its steady and true value its plot has been taken with time on
x-axis. We see that it is of a sinusoidal nature with a steady average value (EJ

Graph No.2 represents the final emf (m V DC) present between the same two selected
points in the specimen. Also to know its steady and true value its plot has been taken
with time on x-axis. We see that it is mostly linear in nature (as compared to the
above graph No.1) with a steady average value (Ez).

Graph No.3 represents both the above two graphs superimposed enabling us to see the
marked difference in their true steady values of emf i.e. we can know the difference,

1283
From the experiment and from the equations we find that any system comprising as
such in its original state has operating in it, afini~ number of minute thermodynamic
corrosion cells which attribute to the system a small and at times negligible emf values
of the corrosion cells already operating in it. These emf of the corrosion cells change
markedly when an external factor causes the change in the magnitude of the emf of the
the corrosion cells and the number of corrosion cells operating in the system earlier.
This change when intense proliferates corrosion which was not so expressed earlier.
The external factors can be varied and diverse such as the factors mentioned earlier. In
nature these factors are nothing but climatic conditions and the diversity of nature's and
man's manifestations or activities.

This quantification enables us to assess the value of threshold or initial emf of the
combined action of the cOrrosion cells of any. system when extensive corrosion is. not
occuring or when corrosion is not expressed or for our convenience at any state of the
system when we ~ent and find its value. It also gives the critical emf value due
to the combined action of the corrosion cells acting in the system which can be assessed
as the maximum value of the emf due to combined action of the corrosion cells operating
in that system when seemingly or truly no severe or corrosion has occured which can
be a precursory value to initiate further corrosion. When the value of the emf of the
combined action of corrosion cells in any system becomes more than its critical emf
value due to the combined action of the corrosion cells acting in the system, the
difference between the cathodic and anodic potential of the combined action of the
corrosion cells widens which causes extensive corrosion in that system.

1284
CONCLUSION :

In this investigative study, basic causes in AISI 4340, 36 HRC (steel) have been
evaluated Based on the experimental observations, it is felt that the process of
corrosion initiation and proliferation may be explained with the help of following
fundamental relations :

APPENDIX: REFERENCES

ALEXANDER WILLIAM & ARTHUR STREET, (1989). "Metals in the Service of

Man", 91h ed, Penguin Books Ltd, London, England

BANERJEE,S.N. (1985). An introduction to the Science of Corrosion and its Inhibition,

Oxonian Press Private Ltd New Delhi, India

HELMS, S.B. & BOWMAN, AL. (1968). Corrosion of steel in lightweight concrete
specimens, ACI Journal, December, pp 1011-1016.

NOVOZHll.,()V,yv. & YAPPA,YU.A (1981). Electrodynamics,Mir Publishers Moscow:

PARKHOMENKO, E.I. (1972). Electrical properties of solids, (Plenum Press).

1285
RAMESH CHANDRAB., and RAMESH REDDY, R, (1997). "Corrosion of galvanised
reinforcement bars due to an electrothermodynamic parameter: Pyroelectricity".
pp.238-242, Proceedings of the International Conference on Maintenance and
Durability of Concrete Structures, March 4-6, JNT University, Hyderabad,
Publishers:Universities Press (India) Limited ISBN 81 7371 0686.

RUDOLPH SZILARD. (1969). A survey of the state-of-the-Art. Corrosion and

corrosion protection of Tendons in prestressed concrete Bridges, ACI Journal/January,
pp.42-56.
Proc. Int. Conf. on Corrosion CONCORN '97
December 3-6, Mumbai, India

Development of In-Service Inspection Techniques for

Monitoring Intergranular Stress Corrosion Cracking in
AISI 304 Core Shroud Welds of Boiling Water Reactors
A.K. Bandyopadhyay, M. Bandyopadhyay, P.P. Nanekar,
R. Ramanathan, B.K. Shah and P.G. Kulkarni
Atomic Fuels Division, Bhabha Atomic Research Centre,
Mumbai-400 085, India

1.0 Introduction

The twin reactors (210 MWe) at Tarapur Atomic Power Station (TAPS) at Tarapur, India
belongs to the early class of Boiling Water Reactors (BWRs). In BWR. core shroud is J!
stainless steel (AISI 304) cylinder which partitions feed water in the reactor vessel down-
comer annulus region from cooling water flowing through the reactor core. It directs the flow
of coolant to the core region, provides ~ctural support' for the core and also provides lateral
support to maintain control rod insertion geometry. Number ofBWRs all over the world are
inspected and in many of them cracks were observed in the core shroud welds. These cracks
were confined to the weld heat affected zone (HAZ). The mechanism of cracking was
identified as intergranular stress corrosion cracking (IGSCC) which is sensitive to combination
of material choice, water chemistry, stress level and to a lesser extent on neutron fluence. It
was decided to carry out in-service inspection (ISI) of core shroud at TAPS to monitor the
extent ofIGSCC. The inspection methodology involved under-water visual examination from
inside of the core shroud for detection and ultrasonic examination for detection and sizing of
IGSCC. The evaluation of IGSCC depth by ultrasonics is based on comparing signal
amplitude from the crack with that from the reference notch. This approach results in
undersizing of the flaw, as signal amplitude is a function of other factors not related to
reflector size. Such factors include roughness, transparency, branching, orientation etc. This
limitation can be overcome by two approaches viz. using known depth IGSCC as reference
standard instead of machined notch and tip diffiaction techniques for flaw sizing which are
based on time of travel rather than amplitude. This paper describes in brief the examination
procedure followed for visual and ultrasonic examination of BWR core shroud welds. It also
describes the procedures standardised in the author's laboratory to generate IGSCC reference
defect standard and the flaw siting results obtained by following the above two approaches.

1287
2.0 Experimental

Pre-cleaning visual inspection, cleaning of core shroud surface of any loose scale that can
mask discontinuities, visual examination of core shroud welds after cleaning and ultrasonic
testing of few selected welds of core shroud form part of the inspection programme.

The under water visual examination from inside of the core shroud was canied out using
CCTV system. The camera was suspended inside the Reactor cavity with the help of special
manipulators and the welds were inspected from a distance of 300 mm to 900 mm (approx.).
Before every insertion the visual examination system was qualified using Sensitivity,
Resolution and Contrast Standard (SRCS). The SRCS panel comprises of 4 horizontal and 4
vertical wires of dia. 14, 30, 40 and 75 microns fixed on a 4-inch x 4-inch SS plate. These
wires were resolved during qualification from minimum and maximum distances required
during actual inspection. In all, three circumferential welds and one lug welds (12 locations)
were visually examined prior to and after cleaning.

After visual examination, ultrasonic examination was carried out at selected location for two
circumferential welds. Two systems, one for spot UT and the other for extended coverage
were developed for this purpose. A 6.25mm deep and 25 mm length EDM notch in HAZ of
SS weld plate was used as reference standard. 1 MHz, 1 inch dia unfocussed immersion probe
was used for ultrasonic examination.

In order to improve the sizing capability of IGSCC by UT, IGSCC of varying depths were
developed in 19 and 25 mm thick AlSI 304 SS plate. The plate was heat treated at 677'C for
5 hours for sensitisation. A partial wall circular groove of dimension 24 mm ID x 6 mm wide
x 15 mm deep was machined at the centre of the plate. AlSI 308 material was deposited in the
groove by welding under restraint. During deposition the plate was clamped between mild
steel plates to develop residual stresses of sufficient magnitude in the heat affected zone. The
weld deposited sensitised plate was then exposed to polythionic acid which was prepared by
passing HzS gas through sulphurous acid and qualified by exposing V-bent sensitised
8:ustenitic stainless steel sample as per the guidelines of ASTM G35. After overnight exposure
0
to polythionic acid, a 360 continuous crack encircling the weld was generated in the plate.
The presence of crack was also confirmed by fluorescent penetrant testing. The plate was
ultrasonically' examined and the depth of IGSCC was evaluated at different locations using
10% machined notch as reference standard. The plate was then cut at one of the locations and
the actual' depth of IGSCC was measured by metallography. The plate was then again
examined using this known depth IGSCC as reference standard for UT. The IGSCC was also
sized at these locations by tip diffraction techniques. The above experiments were canied out
for number of plates in order to standardise the procedure for sizing ofIGSCC in Reactor core
shroud.

1288
3.0 Results and Discussions

The visual examination of 4 welds in core shroud does not reveal any crack like indication.
The ultrasonic examination detected one indication in one of the circumferential welds. The
OD indication having 35 rom length is found to be less than the reference (75% of reference
machined notch).

The IGSCC generation trials in laboratory were observed to' be successful. Figure 1 shows the
IGSCC generated in the plate as revealed by liquid penetrant testing. Figure 2 shows the
photomicrograph ofIGSCC in test plate.

1289
Normally IGSCC tests are performed on V-bend samples. Since the objective of the present
study is to fabricate IGSCC reference standards for ultrasonic examination, it was necessary to
generate IGSCC in flat and thicker sections. This necessitated that IGSCC should be
generated under the action of residual stress alone. The results of our investigation shows that
the weld configuration followed generate residual stresses of sufficient magnitude to cause
IGSCC in thick section of flat geometry.

Table 1 gives the comparison between various techniques employed for sizipg ofIGSCC. The
results obtained clearly reflect the limitations of the amplitude based sizing technique. The
two approaches followed for IGSCC sizing were found to be more accurate.

TABLE -1

1290
4.0 Conclusions

1) In-service Inspection (ISI) of reactor core shroud does not reveal any unacceptable
indication during visual and ultrasonic examination.

2) The weld configuration used for the present study can generate IGSCC under the influence
of residual stress alone in thick sections offlat geometry.

J) Amplitude based sizing technique using machined notch as reference standard undersizes
IGSCC.

4) The two new approaches; viz known depth IGSCC as referepce and tip diffraction
technique are found to be more accurate for sizing ofIGSCC.

1291
 Author Index

Agarwala Vinod S. 140 Cavallaro G. 367

Aggarwal L.K. 81 Cayard M.S. 128. 451
Aiyar R.K. 914 Chakarbarti S.C. 81
Ajmal M. 634 Chakradhar B. 1009
Alice Arul Antony A. 871 Chatterjee Indira 831
Anand Vijay R. 961 ChatteDee U.K. 432
Anandaraj T. 375 Chattopadhyay Ram N. 1246
Anto P.F. 463. 484. 1082. 1134 Chattoraj I. 582
Antonyraj A. 968 Chaudhari R.I. 700
Aouniti A. 672 Chaudhary R.S. 1032
Apparao B.V. 1061 Chaudhuri S.K. 751
Aride 1. 662 Cherian Viju 1082
Arora R.C. 443 Chidambaram Devicharan 1013
Augustin C.O.. 968 Chowdhary S.D. 1103
Autric Michel 347. 1047 Chugh S.K. 1134
Avinash H. 1082
Azim Syed S. 902 Das Chintamani 640
Dash S. 939
Babu B.P. 1264 Datta P.K. 176
Bagadi Ramesh Chandra 1277 Davis C.I. 1231
Bahadur Lal 1257 Dayal R.K 323. 566. 930
Balakrishnan K. 375. 712. 871 De A.K. 751
Balasubramanian V. 700 De P.K. 258. 458
Bandyopadhyay A.K. 1287 Desai Vimal 216
Bandyopadhyay M. 1287 Deshmukh M.B. 727
Banerjee M.K. 1208 Deuis R.L. 367
Banerjee N. 776 Devasenapathi A. 1074
Banerjee S. 258 Dey A.K. 227.1167
Barbian O.A. 679 Dey Mahuya 227
Bekkouch K. 672 Dhawan H.C. 1264
Berchmans John L. 1013. 1023 Dickie Neil 691
Bhakta U.c. 783. 1103 Du HL 176
Bhardwaj Anil 484
Bhatgadde L.G. 1188 Elfarissi M. 672
Bhattacharya A. 574. 751. 1270 Emami M.A. 1257
Bhattacharya B. 776 Ennis P.I. 199
Bhattacharyya G.S. 1052 Evans P.M. 679
Bhattamishra A.K. 1149
Bhaumik T.K. 695 Fanse P.M. 443
Bhor P.K. 751 Farooqi I.H. 1128
Blank Nellv 757 Figovsky Oleg L. 757
Bougrin K. 662
Burnell-Gray 1.S. 176 Gadiyar H.S. 640
Gandhi P. 390
Calla Eklavya 816 Ganguly A. 914
1294 Author Index

Gasser A. 333 Khan Israr 1167

Gaur B. 548 Khanna A.S. 188,727,990,997, 1088, 1134
George Lai Y. 493 Khanna J.L. 736
George RP. 924 Khanra Amit 984
Ghosh J.K. 695 Khatak H.S. 249, 621, 878, 924
Ghosh S.K. 1270 Khazraji A. 662
Gidwani Kavita 1143 Kihara S. 99
GiII T.P.S. 398 Kihira Hiroshi 527
Gleeson B. 301 Krishnan R 939
Gnanamoorthy J.B. 621, 878, 924 Krishnan S.M. 375
Gopalan A. 871 Kulkarni P.G. 1287
Grabke HJ. 89 Kumar Arun S.N.S. 961
Gunasekaran G. 1103 Kumar Vinod 751
Gupta A.K 1143 Kutty D.K.N. 533, 1195
Gustafson David P. 46
Lal K. 1182
Hammouti B. 672 Latha R. 1224
Hansel M. 36 Lee H.J.V. 301
Heggen P. 519 Li Ming 216
Lira-Oliveres J. 357
Ishwar Venkat R 493
Iyer Venkatakrishna S. 952, 974, 1023 Madan Anil 885
Madhavamayandi A. 1037
Jain Pradeep 783 Madhavan K. 952
Jain S.K 751 Malhotra S.N. 1251
James PJ. 1231 Mani A. 891
Jana S. 914 Marikkannu C. 1037
Jayakrishnan P. 902 Maruthamuthu S. 891
Jayakumar T. 117,615,946 Masuda Kazuhiro 527
Jayaraman A. 477 Mathur P.K 1219
Jayaraman T.R. 559 Mehta A.K. 1231
Jenkinson D. 176 Mehta G.N. 909
Jeyaprabha C. 891, 1037 Mehta Raj 831
Joseph Jolly 1264 Mishra KB. 574, 1270
Joseph Sharlet 1188 Misra A.N. 909
Joshi Rajnish 540 Misra D.C. 885
Joshi S.D. 802 Mitra A. 582
Joshi Shrikant V. 163 Mitra A.K. 1103
Miyazaki Hironobu 809
Kain Vivekanad 258, 1201 Modi S.C. 816
Kajigaya I. 99 Mohan P.S. 375
Kalaignan Paruthimal G. 871 Mohanty RK 1182
Kalpana Y. 559 Morishige Norio 208
Kamachi Mudali U. 930 Mudali Kamachi U. 566, 1121
Kane R.D. 128, 280, 451 MukeQee D. 776
Kapali V. 961, 1013 MukheQee A.K. 751
Karthik P.V. 1013 Mukherjee A.N. 815
Kasiviswanathan K.V. 946 Mukhopadhyay C.K. 615
Kaur G. 793 Muneshwar V.S. 1143
KeIlner J.D. 718 Muraleedharan P. 924
Kertit S. 662, 672 Muralidhar S. 695
1296 Author Index

Singh A.K. 1143 Takahashi M. 357

Singh B.K. 227 Teichmann H. 199
Singh Bijay Kumar 1154 Tersmeden Knut 470
Singh D.D.N 227, 1154, 1167 Thiele M. 199
Singh Gyanendra 695 Thomas S. 463
Singh I.B. 1004, 1009 Tiwari A.N. 1251
Singh Inder 291, 742, 815, 1149 Tiwari S.N. 503
Singh M.N. 742 Totlani M.K. 640
Singh S.K. 1082 Tsuzuki Takashi 527
Singh Sandeep 1208 Tyagi A.K. 939
Singh T.B. 1182
Singh V.K. 751 Upadhyay R.K. 513
Sinha A.K. 783 Uzelac N.J. 679
Sinha Ashwini K. 1103
Sivaibharasi N. 621, 878 Vaideeswaran R. 1093
Sivan V. 652, 1023, 1093 Varma M.P. 736
Soufiaoui M. 662 Varma M.P. 885
Sreekumari K.R. 924 Vasudevan T. 712, 871
Sridhar K. 727 Venkatachalam K. 764
Srikanth S. 1270 Venkatesh D. 695
Srinivasan H.S. 548 Venkatnath K. 627
Srinivasan S. 128, 280 Venugopal A. 1067
Stella C. 891 Venugopal K. 559
Strafford K.N. 176 Verity B. 519
Streiff Roland 347, 1047 Vidyasankar K. 961
Stringer John 13 Vinita K. 1251
Subbaiyan M. 1121, 1124 Viswanathan R. 151, 595
Subramanian A. 712
Subramanian C. 367, 519 Willems H.H. 679
Suca1dito Regina 831 Wissenbach K. 333
Sundarajan G. 588 Wright A. 519
Sundararajan T. 566, 1121 Wright I.G. 1231
Sunthankar M.B. 802
Suresh Babu R.H. 902 Yamamoto Masahiro .270,527
Suri S.B. 764 Young DJ. 301