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TESTS

AN D STAN DAR D S
I N T ER P R ETATIO N
2ND E D I T I O N

@
INTERNATIONAL
EDITOR
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Corrosion Tests
and Standards:
Application and
In t e r p r e t a t i o n - - S e c o n d Edition

Robert Baboian, Editor

Section Editors
Robert Baboian
Sheldon W. Dean, Jr.
Harvey P. Hack
Edward L. Hibner
John R. Scully

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Library of Congress Cataloging-in-Publication Data

Corrosion tests and standards : application and interpretation /


Robert Baboian, editor ; section editors, Robert Baboian ...
[et al.].--2nd ed.
p. cm.--(ASTM manual series ; MNL 20)
ASTM Stock Number: MNL20--2nd
ISBN 0-8031-2098-2
1. Corrosion and anti-corrosives---Testing. I. Baboian, Robert.
II. Series.

TA462.C666 2005
620.1'1223---dc22
2004025972

Copyright © 2005 ASTM International, West Conshohocken,


PA. All rights reserved. This material may not be reproduced
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E D W A R D L. H I B N E R is a Sen-
ior Metallurgist and Code Manager at Special
ROBERT BABOIAN, Metals Corporation, formerly Inco Alloys Interna-
tional, in Huntington, West Virginia. He received
Editor his B.S. in Chemistry from Marshall University
Robert B a b o i a n is a corrosion c o n s u l t a n t w i t h RB and in Metallurgy from the University of Cincin-
Corrosion Service. He received his B.S. degree in chem- nati. He is the recipient of the ASTM Award
istry from Suffolk University in 1959 a n d his Ph.D. in of Merit, the ASTM Committee G-1 Francis L.
physical c h e m i s t r y from R e n s s a l a e r Polytechnic Insti- LaOue Memorial Award, the ASTM Committee
tute in 1964. He did postdoctoral research at the Uni- G-1 Certificate of Appreciation, and the NACE
versity of Toronto i n 1964 a n d subsequently received a Fellow Award, and is currently Vice-Chairman
and the Editorial Review Chairman of ASTM
faculty a p p o i n t m e n t to Senior Research Associate in
Committee G-1 on Corrosion of Metals. He has
1965. He joined the Materials a n d Controls Group of
Texas Instruments, Inc. in 1966, w h e r e he established served as Chairman and as Trustee of the West
Virginia Section of NACE International and is
the E l e c t r o c h e m i c a l a n d Corrosion Laboratory. He
currently serving on the NACE MR0175/ ISO
retired from Texas I n s t r u m e n t s in December 1996 as
15156 Maintenance Panel. He has extensive ex-
Principal Fellow a n d H e a d of the Electrochemical a n d
perience in alloy development for chemical proc-
Corrosion Laboratory. The Principal Fellow position a t
ess, flue gas desulfiarization, marine, and oil field
TI is the company's highest honor for scientific and
applications. He has written widely on materials
technical achievement. He is a n ASTM Honorary Mem- applications and corrosion topics in these fields
ber, a Fellow of ASTM, NACE, a n d SAE, and was a Ford and has four patents and 60 publications. In addi-
Foundation Postdoctoral Fellow in 1964. tion to ASTM International, he is a member of the
Dr. B a b o i a n has b e e n d e d i c a t e d to the r e s e a r c h a n d d e v e l o p m e n t of c o r r o s i o n r e s i s t a n t mate- International Desalination Association, the Soci-
rials a n d devices, e n v i r o n m e n t a l effects o n materials, a n d the use of e l e c t r o c h e m i c a l tech- ety for Petroleum Engineers, ASME International,
n i q u e s in corrosion testing for a l m o s t 40 years. He holds 15 U.S. patents, is the e d i t o r of 13 SAE International, NACE International, and the
books, a n d has a u t h o r e d over 170 t e c h n i c a l publications. He has served o n a n u m b e r of Gov- Naval Submarine League.
e r n m e n t a n d Academic C o m m i t t e e s a n d h a s lectured t h r o u g h o u t the world, a n d his services
w e r e d o n a t e d b y TI to the National P a r k Service as a c o r r o s i o n c o n s u l t a n t o n the Statue of J O H N R. S C U L L Y receivedhis B.S,
Liberty r e s t o r a t i o n program. Recently, he has r e s e a r c h e d the sinking of the Titanic a n d h a s M.S., and Ph.D. Jn Materials Science and Engi-
p r o p o s e d theories o n corrosion m e c h a n i s m s c a u s i n g the failure. neering from Johns Hopkins University. While
Recognized for his active involvement in the technical c o m m u n i t y , Dr. Baboian has received the pursuing his Ph.D., he worked at David Taylor
C a v a n a u g h Award a n d the Award of Merit from ASTM, the ASTM Dudley Award for publica- Naval Ship R&D Center in Annapolis, Maryland in
tions, the ASTM LaQue Award for outstanding contributions to corrosion testing and evaluation, the Marine Corrosion Branch. He then joined
the Speller Award for o u t s t a n d i n g contributions in corrosion engineering, a n d the T. J. Hull Sandia National Laboratory after a term as a Visit-
Award for publications from NACE, the Science a n d Technology Award of the Suga W e a t h e r i n g ing Scientist at AT&T Bell Laboratories. In 1990,
Technology F o u n d a t i o n in Japan, the Vittorio de Nora Award from the Electrochemical Society, he joined the faculty of the Department of Materi-
the Francis L. LaQue Award for contributions to m a r i n e corrosion a n d prevention from the als Science and Engineering at the University of
LaQue Center Sea Horse Institute, a n d the National Materials A d v a n c e m e n t Award from the Virginia and is a full professor and co-directs the
F e d e r a t i o n of Materials Societies. He has served o n the Executive C o m m i t t e e a n d the B o a r d of Center for Electrochemical Science and Engineer-
Directors of ASTM a n d NACE a n d was the C h a i r m a n of the ASTM Board of Directors in 1987. ing. Professor Scully received the 1985 A. B.
He also has chaired ASTM C o m m i t t e e G-1 o n Corrosion of Metals, the SAE Automotive Corro- Campbell Young Author Award from NACE. He
sion and Protection Committee, a n d the NACE Research Committee. has also been selected as a National Science Foun-
dation Young Investigator, and has received the H.
H. uhlig Award from NACE and the William Blum
Award from the Electrochemical Society. Professor
Scully has published over 100 technical papers and
edited several books on corrosion.
SHELDON W. DEAN, JR. HARVEY P. H A C K Dr. Hackis a n
is currently the President of Dean Corrosion Advisory Engineer for Northrop Grumman Corpo-
Technology, Inc., a consulting finn in Allentown, ration, where he does materials selection and cor-
Pennsylvania that provides expert advice on rosion control for underwater vehicles and systems
matters involving corrosion of metals. He is also for the Department of Defense. He received his B.S.
Editor in Chief of the Journal of ASTM Interna- and M.S. from Carnegie-Mellon University, and his
tional. He received his A.B. from Middlebury Ph.D. in Metallurgy from The Pennsylvania State
College and his B.S. and Sc.D. from the Massa- University. He is the recipient of the ASTM Interna-
chusetts Institute of Technology. He has received tional Award of Merit, and is past Chairman of the
the ASTM Award of Merit, the Charles B. Dudley Board of Directors of ASTM International. Dr. Hack
Award, the Sam Tour Award, the Francis L. has received the Distinguished Service Award from
LaOue Memorial Award, the ASTM Committee NACE International, the Francis L LaOue Memo-
on Publications Award for Excenence, the ASTM rial Award from ASTM Committee G-1 on Corro-
Committee G-1 Certificate of Appreciation, the sion of Metals, and the Francis L. LaOue Award
NACE Frank Newman Speller Award, the NACE from the Sea Horse Institute. He is a NACE Corro-
Fellow Honor, and was named a Fellow of the sion Specialist, Cathodic Protection Specialist, and
American Institute of Chemical Engineers and Coatings Inspector, a Fellow of NACE Interna-
the Materials Technology Institute. He has served tional, ASTM International, the Washington Acad-
as chairman of ASTM Committee G-1 for four emy of Sciences, and the Institute of Corrosion in
years. He also served on and chaired the ASTM the United Kingdom, and is a Registered Profes-
Committee on Publications and the ASTM Board sional Engineer in Maryland. Dr. Hack is the Asso-
of Directors, and chaired the Finance and Audit ciate Editor for the Materials Performance and
Committee. He has also served on and chaired Characterization section of the Journal of ASTM
the Board of Directors of the Materials Technol- International (JAI), is on the Materials Advisory
ogy Institute. He has 12 U.S. patents, 96 publica- Board for the National Air and Space Museum of
tions, and has co-edited eight books. the Smithsonian Institution, and is a past President
of the Council of Engineering and Scientific Specialty
Boards. Dr. Hack has approximately 70 publications
and is the author, editor, or major con-tributor to five
books. He is the author of a regular column on corro-
sion in Underwater Magazine.
.o.
III

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Reviewers

Dinesh Agarwal Jim Gossett Sankara Papavinasam


Vinod Agarwala Richard Granata Frederick Pettit
Hira Ahluwalia Harvey Hack Bopinder Phull
Paul Aimone William Hartt Robert Puyear
George Andersen Gardner Haynes David Reiser
Frank Ansuini George Hays Pierre Roberge
Peter Ault Edward Hibner Paul Rothman
Denise Aylor Stanley Hirozawa Ken St. John
Robert Baboian F. Galen Hodge Alberto Sagues
Brian Baker Alfred Hopkins Stuart Saunders
Milan Bartos William Jarosinski John Schemel
Neal Berke James Jenkins George Schick
Thomas Britton Denny Jones John Scully
C. Sean Brossia Russell Jones K. Anthony Selby
Rudolph G. Buchheit Robert Kain David Shifter
Kenneth Budinski Mike Katcher Tetyana Shmyreva
James Bushman Robert Kelly David Silverman
Paul Brewer Gerhardus Koch J. Douglas Sinclair
Julie Brown Simeon Krumbein Raymund Singleton
Kirk Bundy Paul Labine Joseph Slusser
Gustavo Cragnolino Herbert Lawson Gaylord Smith
Lee Craig Jason Lee John Snodgrass
Sheldon Dean Daoming Li Donald Snyder
Terry DeBold Brenda Little Narasi Sridhar
Stephen Dexter Daryl Little Sridhar Srinivasan
George DiBari Frank Lutze Anthony Stavros
Jeffrey Didas Florian Mansfeld T. J. Summerson
Charles Dillon Charles Marsh William Tillis
Marcia Domack James Martin Herbert Townsend
George Downs Peter Mayer Hector Videla
Dave Duqnette Joseph Menke Yash Virmani
K. Daniel Efird Jean-Marc Meyer George Waid
Nathan Eisinger Harold Michels Robert Wei
Peter Elliott Tom Mills Paul Whitcraft
David Enos James Moran Ian Wright
Ed Escalante Patrick Morris George Young
John Fitzgerald Max Moskal Walter Young
Anna Fraker Jim Myers
Gerald Frankel James Noel

iv

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Foreword

THE REVISEDPUBLICATION,Corrosion Tests and Standards: Application and Interpretation,


is sponsored by ASTM Committee G1 on Corrosion of Metals and edited by Robert
Baboian, RB Corrosion Service. Section editors include Robert Baboian, Sheldon
W. Dean, Dean Corrosion Technology, Harvey P. Hack, Northrup G r u m m a n Corpora-
tion, Edward Hibner, Special Metals Corporation, and John R. Scully, University of
Virginia. This is the second edition of Manual 20 in the ASTM Manual series.

Preface

CORROSION CONTINUES to be a problem of worldwide importance. The second edition


of this manual has been prepared and published to address this form of degradation.
Corrosion is often neglected, but it seriously impacts our economy, jeopardizes hu-
m a n health and safety, and impedes technological progress. The most important fac-
tors in addressing corrosion and its control are: (t) recognizing and understanding
the mechanisms, (2) developing solutions to the problems, and (3) implementing
those solutions. Corrosion tests and standards are very significant in addressing each
of these factors. Therefore, this manual includes guidelines for recognizing types of
corrosion as well as fundamentals of testing and provides the tools required for mak-
ing calculations, interpretations, and correlations. It serves as a source book of proce-
dures, equipment, and standards used in testing.
The editor and section editors have coordinated the revision and update of this
book so that most recent technologies are included in each section. In most cases, the
original authors of chapters have made the revisions. In some cases, new authors
needed to be chosen, or the editors performed that task. Users of the manual will find
that it is an invaluable and instructive tool, as well as a source book on how to con-
duct corrosion tests, interpret results, and use standards.
The second edition of the manual is the result of a massive effort of planning, writ-
ing, reviewing, editing, production, and marketing. It would not have been possible
without the outstanding efforts of the ASTM staff and the valuable and competent
work of the editors and over 400 experts in the field that donated their time as au-
thors and reviewers. They represent industrial, educational, and government organi-
zations, and their contributions are greatly appreciated.

Robert Baboian
Editor

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Contents

Introduction

I: GENERAL INFORMATION--R.Baboian, Section Editor

Unified Numbering System for Metals and Alloys 4


Examples of Common Names of Selected UNS Alloys 5
Standard Terminology Relating to Corrosion and Corrosion Testing 7
Glossary of Corrosion-Related Acronyms 12
Standard Abbreviations and Unit Symbols 14
International System of Units (SI) 17
General Conversion Factors 18
Condensed Metric Practice Guide for Corrosion 20
Multiplication Factors (SI Prefixes) 22
Corrosion Rate Conversion Factors 22
Corrosion Rate Calculation (from Mass Loss) 23
Corrosion Rate Conversion Factors 24
Densities/K Factors for Alloys 25
Overvoltage Values 26
Reference Potentials and Conversion Table 27
Equivalent Weight Values for Metals and Alloys 28
Constants Used in Faraday's Equation 30
Physical Properties of Gases and Liquids 31
Physical Properties of Elements 32
Densities of Metals and Alloys 33
Density of Materials 35
Thermal Expansion Coefficients for Alloys 36
Physical Properties of Water 37
Dew Point of Moist Air 38
Chemical Cleaning Procedures for Removal of Corrosion Products 43
Electrolytic Cleaning Procedures for Removal of Corrosion Products 46

II: TESTING AND EVALUATION--R.Baboian, Section Editor

Chapter 1--Planning and Design of Tests 49


Stephen D. Cramer and Barnie P. Jones

Chapter 2--Types of Data 59


David C. Silverman

Chapter 3--Metallographic Analysis 66


Richard L. ColweU

vii

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viii C O R R O S I O N T E S T S AND S T A N D A R D S MANUAL

Chapter 4---Surface Analysis 76


Alfred G. Hopkins

Chapter 5~Statistical Treatment of Data, Data Interpretation, and Reliability 83


Fred H. Haynie

Chapter 6---Computer Based Data Organization and Computer Applications 89


Pierre R. Roberge

III: TYPES OF TESTS---H. P. Hack, Section Editor

Chapter 7--Electrochemical Tests 107


John R. Scully

Chapter 8--Cabinet Tests 131


Cynthia L. Meade

Chapter 9--Immersion Testing 139


Richard A. Corbett

Chapter 10--High-Temperature and High-Pressure Corrosion Testing 147


Russell D. Kane

Chapter I 1--Atmospheric 159


Sheldon W. Dean, Jr.

Chapter 12---Seawater 170


James F. Jenkins

Chapter 13--Freshwater 175


Walter T. Young and Philippa Fairer

Chapter 14--Soils 181


Edward Escalante

Chapter 15--Industrial Applications 187


Allan Perkins

Chapter 16--High-Temperature 194


Gaylord D. Smith

IV: TESTING FOR CORROSION TYPES--J. R. Scully, Section Editor

Chapter 17--Uniform Corrosion 205


James A. EUor and John Repp

Chapter 18--Pitting 211


Robert G. Kelly

Chapter 19--Crevice Corrosion 221


Narasi Sridhar, Darrell S. Dunn, C. S. Brossia, Gustavo A. Cragnolino, and Jeffery R. Kearns

Chapter 20--Galvanic 233


Harvey P. Hack

Chapter 2 1 - - I n t e r g r a n u l a r 244
Michael A. Streicher

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CONTENTS ix

Chapter 22--Exfoliation 266


Donald O. Sprowls; revised by Kevin R. Cooper

Chapter 23--Erosion, Cavitation, and Fretting 273


W. A. Glaeser

Chapter 24---Dealloying 278


Ann Chidester Van Orden

Chapter 25--Environmental Cracking--Stress Corrosion 289


W. Barry Lisagor

Chapter 26--Environmental Cracking---Corrosion Fatigue 302


Richard P. Gangloff

Chapter 27--Hydrogen Damage 322


C. G. Interrante and L. Raymond

V: T E S T I N G IN ENVIRONMENTS---H. P. Hack, Section Editor

Chapter 28---Outdoor Atmospheres 343


Herbert H. Lawson

Chapter 29--Indoor Atmospheres 349


J. D. Sinclair

Chapter 30---Seawater 362


David A. Shifter and Denise M. Aylor

Chapter 31--Freshwater 380


Walter T. Young and Philippa Fairer

Chapter 32--Soils 387


Lucien Veleva

Chapter 33--Concrete 405


Neal S. Berke

Chapter 3 A. Industrial Waters 413


A. S. Krisher

Chapter 35--Industrial Chemicals 418


Robert B. Puyear

Chapter 36---Petroleum 425


K. Daniel Efird

Chapter 37--High-Temperature Gases 434


Gaylord D. Smith and Brian A. Baker

Chapter 38--Organic Liquids 448


C. S. Brossia and D. A. Shifter

Chapter 39--Molten Salts 457


F. S. Pettit

Chapter 40--Liquid Metals 465


Chris Bagnall, Peter F. Tortorelli, Steven J. Pawel, Jack H. DeVan, and Steven L. Schrock

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x CORROSION TESTS AND STANDARDS MANUAL

Chapter 4 1 - - C o r r o s i o n I n h i b i t o r s 480
Rudolf H. Hausler

Chapter 42--Corrosion Testing in In Vivo Environments 500


K. J. Bundy

Chapter 4 3 - - M i c r o b i o l o g i c a l E f f e c t s 509
Stephen C. Dexter

VI: MATERIALS TESTINC,---E. L. Hilmer, Section Editor


Chapter 4 4 - - Z i n c 525
Frank E. Goodwin and Safaa J. Alhassan

Chapter 45--Lead (and Alloys) 531


Safaa J. Alhassan and Frank E. Goodwin

Chapter 46--Magnesium (and Alloys) 537


James E. Hillis

Chapter 47--Aluminum (and Alloys) 547


Bernard W. Lifka

Chapter 48--Steels 558


M. E. Komp, D. L. Jordan, and R. Baboian

Chapter 49--Copper (and Alloys) 565


Arthur Cohen

Chapter 50~Nickel (and Alloys) 580


Edward L. Hibner

Chapter 51--Stainless Steels 585


James W. Martin

Chapter 52--Cobalt-Base Alloys 591


P. Crook

Chapter 53--Titanium 598


Ronald W. Schutz

Chapter 54--Zirconium and H a f n i u m 613


Te-Lin Yau

Chapter 55--Tantalum and Niobium Alloys 617


E. B. Hinshaw and K. D. Moser

Chapter 56---Metallic Coatings on Steel 620


T. C. Simpson and H. E. Townsend

Chapter 57--Nonmetallic Coatings 632


Richard D. Granata

Chapter 58--Metal-Matrix Composites 637


L. H. Hihara

Chapter 59--Electrodeposits 656


T. P. Moffat

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CONTENTS

Chapter 60---Powder Metallurgy (P/M) Materials 664


Erhard Klar and Prasan K. Samal

VII: TESTING IN INDUSTRIES---S. W. Dean, Jr., Section Editor


Chapter 6 l - - A u t o m o t i v e 673
Robert Baboian

Chapter 62--Commercial Aircraft 687


A. A. Adjorlolo and J. A. Marceau

Chapter 63--Military Aircraft and Associated Equipment 693


Earl C. Groshart

Chapter 64---Pipeline 696


Paul S. Rothman and Walter T. Young

Chapter 65--Highways, Tunnels, and Bridges 706


James B. Bushman and Victor Chaker

Chapter 66---Marine--Piers and Docks 716


James F. Jenkins

Chapter 67--Electric Power 722


P. Mayer and A. D. Pellgrini

Chapter 68--Nuclear Power 727


George J. Licina

Chapter 69---Steam Generation 738


Otakar Jonas

Chapter 70---Flue Gas Desulfurization 746


Harvey S. Rosenberg and Eldon R. Dille

Chapter 7 l--Electronics 754


Robert Baboian

Chapter 72--Telecommunications 762


George Schick

Chapter 73--Metals Processing 769


Terry A. DeBold

Chapter 74--Chemical Processing 779


Bert Moniz and Shi Hua Zhang

Chapter 75--Pulp and Paper 795


Angela Wensley

Chapter 7 6 - - P e t r o l e u m P r o d u c t i o n a n d R e f i n i n g 812
R. N. Tuttle

Chapter 77--Food and Beverage 822


W. E. Clayton and B. Tholke

Chapter 78--Water Handling Systems 826


Bennett P. Boffardi

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xii C O R R O S I O N TESTS AND S T A N D A R D S M A N U A L

Chapter 7 9 - - M e d i c a l a n d Dental 834


Anna C. Fraker

Chapter 8 0 - - P h a r m a c e u t i c a l 846
David F. Jensen

VIII: CORROSION-RELATED STANDARDS--H.P. Hack and R. Baboian, Section Editors

LIST OF CORROSION-RELATED STANDARDS 851

Author Index 865

Subject Index 867

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Introduction

ASTM'S AWARD-WINNINGManual 20 has been revised and interpret, and evaluate the technology. This section is greatly
updated to include current and state-of-the-art technologies expanded and includes a unified numbering system for met-
in corrosion testing and standardization. The editors of this als and alloys and their common names, standards terminol-
manual have many years of experience in this field and are ogy, a glossary of terms and acronyms, abbreviations and
well qualified in leading the task to provide state-of-the-art units symbols, International System of Units and matrix
information on this subject for corrosion scientists and guide, general conversion tables, corrosion rate calculations
technologists throughout the world. The work of 80 highly and all necessary conversion factors, chemical and physical
qualified chapter authors and numerous reviewers has properties of materials, properties of water and moist air,
resulted in a revised, expanded, and updated Manual 20 on chemical and electrolytic cleaning procedures for corrosion
Corrosion Tests and Standards, Application and Interpre- products, physical properties of gases, liquids and elements,
tation. and densities of metals and alloys.
Corrosion is the chemical or electrochemical reaction be- Section II on Testing a n d Evaluation (R. Baboian,
tween a material, usually a metal, and its environment that Section Editor) is designed to provide important informa-
produces a deterioration of the material and its properties. tion on planning and design of tests and interpretation of
The direct cost of corrosion in countries throughout the results. This topic provides a foundation for corrosion test-
world is estimated to be between 3 % and 4 % of the gross ing and the use of corrosion standards. It includes chapters
domestic product of each country. For example, that cost in on planning and design of tests, types of corrosion data,
the United States was estimated to be $276 billion annually, metallographic and surface analysis, statistical treatment of
for recent years. It was determined that a significant por- data and data computerization and computer applications.
tion of these costs could be avoided through the more effec- Section III covers Types o f Tests (H. Hack, Section Edi-
tive use of existing technologies and the use of sound tor) including laboratory-accelerated tests, field tests, and
corrosion management techniques. This manual is a key service tests. The chapters in this section provide basic
resource in addressing both of these subjects. principles, describe test techniques and specific considera-
Corrosion testing is one of the most important aspects of tions such as specimen preparation, test duration and
corrosion control because it is used to advance technology acceleration factors, and cite pertinent standards. Chapters
and to determine the most effective and economical means included under laboratory tests are electrochemical, cabi-
to achieve acceptable performance. A large number of fac- net, immersion, high temperature, and high pressure. Field
tors affect corrosion behavior so that there is no universal Tests chapters include atmospheric exposure, seawater,
corrosion test. ASTM and other organizations such as NACE, fresh water, and soil. Under service tests are industrial
ISO, and others have standardized many tests and practices. applications and high temperature environments.
However, industry, government, and academic laboratories Section IV on Testing for Corrosion Types (J. Scully,
sometimes utilize in-house tests. Thus, this Manual provides Section Editor) describes the major forms of corrosion, how
a valuable resource describing and listing a large number of to recognize them and factors of influence. Each chapter
tests ranging from highly accelerated laboratory tests to includes an overview of basic principles and also descrip-
field service trials. tions of test techniques, methods of evaluation of test re-
Since gtandards are universally recognized as an important sults, and standards used for testing. Subjects included are
tool in effective corrosion control management, this Manual uniform, pitting, crevice, galvanic, intergranular, exfoliation,
not only provides information required to find and use erosion, cavitation, fretting, dealloying, stress corrosion, cor-
proper standards in specific applications, it also includes a rosion fatigue and hydrogen damage.
CD with almost 200 of the most widely used ASTM and Section V on Testing in E n v i r o n m e n t s (H. Hack, Section
NACE corrosion standards. All of the chapter authors have Editor) includes chapters on outdoor and indoor atmos-
included important standards specific to their topic and the pheres, seawater, flesh water, soils, concrete, industrial wa-
Manual includes lists of standards according to subject, of ters, industrial chemical, petroleum, high-temperature gases,
which the most important are included in the CD. organic liquids, molten salts, liquid metals, corrosion inhibi-
The revised Manual is organized into eight sections. tors, in-vivo, and microbiological effects. Each chapter pro-
Section I on General I n f o r m a t i o n (R. Baboian, Section vides a descriptive overview of the environment and factors
Editor) provides tools necessary for the corrosionist to define, and variables affecting corrosion rates and mechanisms,

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2 C O R R O S I O N TESTS A N D S T A N D A R D S M A N U A L

unique characteristics of testing, descriptions of appropriate and equipment, pipeline, highways, tunnels and bridges,
laboratory and field tests and lists of standards used for cor- marine piers and docks, electric power, nuclear power, steam
rosion testing in these environments. generation, flue gas desulfurization, electronics, telecom-
Section VI is on Materials Testing (E. Hibner, Section munications, metal processing, chemical processing, pulp
Editor). This section provides overviews of important tests and paper, petroleum production and refining, food and
used in evaluating the corrosion behavior of metals and alloys. beverage, water handling systems, medical and dental, and
In addition, this testing information provides the means for pharmaceutical.
the development of new and improved corrosion resistant Section VIII on Corrosion-Related Standards (H. Hack
materials. Each chapter includes a discussion of the nature of and R. Baboian, Section Editors) is a comprehensive list
the material, such as the effect of composition, alloying, met- of standards developed by various organizations including
allurgical treatments, microstructure, surface effects and the American Petroleum Institute, American Waterworks
natural films on the corrosion behavior. The chapter also in- Association, ASME International, ASTM International,
cludes descriptions of tests used for specific types of corrosion International Electrotechnical Commission, ISO, NACE
for the metals and alloys, methods of evaluation of corrosion International, SAE International, and the Steel Structures
damage and standards used for corrosion testing of the vari- Painting Council. The standards are listed and grouped ac-
ous materials. The chapters are zinc, lead (and alloys), alumi- cording to subject within each organization. The accompa-
num (and alloys), steels, copper (and alloys), nickel (and nying CD includes many of the ASTM and NACE corrosion
alloys), stainless steels, cobalt-base alloys, titanium, zirconium standards.
and hafnium, tantalum and niobum alloys, metallic coatings The revised Manual 20 on Corrosion Tests and Standards
on steel, nonmetallic coatings, metal matrix composites, elec- is certain to serve as a valuable resource for those in indus-
trodeposits, and powder metallurgy materials. try, government, and academia. Acknowledgment is given to
Section VII on Testing in Industries (S. Dean, Section the many authors who wrote the chapters providing the
Editor) provides an overview of corrosion testing unique to important information in this revision. Also acknowledged
each industry and how these tests are used to address cor- are the reviewers who work anonymously to help maintain
rosion problems. Included are descriptions of environments a high level of quality throughout the book. The work of the
encountered and materials used in specific industries. Test editors can only be completed through the dedication and
methods for corrosion control and evaluation are described competence of these persons.
along with appropriate standards. Chapters in this section Robert Baboian
include automotive, commercial aircraft, military aircraft Editor

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MNL20-EB / Jan. 2005

Section I: General Information


R. Baboian, Editor

Contents
Reference
Unified Numbering System for Metals and Alloys NACE
Examples of Common Names of Selected UNS Alloys NACE
Standard Terminology Relating to Corrosion and Corrosion Testing ASTM G 15
Glossary of Corrosion-Related Acronyms NACE
Standard Abbreviations and Unit Symbols ASTM
International System of Units (SI) ASTM E 380
General Conversion Factors ASTM E 380
Condensed Metric Practice Guide for Corrosion ASTM
Multiplication Factors (SI Prefixes) ASTM E 380
Corrosion Rate Conversion Factors Wrangl6n
Corrosion Rate Calculation (from Mass Loss) ASTM G 1
Corrosion Rate Conversion Factors NACE
Densities/K Factors for Alloys NACE
Overvoltage Values Various
Reference Potentials and Conversion Table ASTM G 3
Equivalent Weight Values for Metals and Alloys ASTM G 102
Constants Used in Faraday's Equation ASTM G 102
Physical Properties of Gases and Liquids ASTM
Physical Properties of Elements ASTM
Densities of Metals and Alloys ASTM G 1
Density of Materials ASM
Thermal Expansion Coefficients for Alloys NACE
Physical Properties of Water Various
Dew Point of Moist Air NACE
Chemical Cleaning Procedures for Removal of Corrosion Products ASTM G 1
Electrolytic Cleaning Procedures for Removal of Corrosion Products ASTM G 1

Copyright © 2005 by ASTM International

3
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Unified Numbering System
for Metals and Alloys
U N S SERIES Metal
Nonferrous MetalsandAlloys
A00001-A99999 Aluminum and aluminum alloys
C00001-C99999 Copper and copper alloys
E00001-E99999 Rare earth and rare earth-like metals and alloys
L00001-L99999 Low melting metals and alloys
M00001-M99999 Miscellaneous nonferrous metals and alloys
N00001-N99999 Nickel and nickel alloys
P00001-P00999 Gold
P01001-P01999 Iridium
P02001-P02999 Osmium
P03001-P03999 Palladium
P04001-P04999 Platinum
P05001-P05999 Rhodium
P06001-P06999 Ruthenium
P07001-P07999 Silver
R01011-R01999 Boron
R02001-R02999 Hafnium
R03001-R03999 Molybdenum
R04001-R04999 Niobium (Columbium)
R05001-R05999 Tantalum
R06001-R06999 Thorium
R07001-R07999 Tungsten
R08001-R08999 Vanadium
R10001-R19999 Beryllium
R20001-R29999 Chromium
R30001-R39999 Cobalt
R40001-R49999 Rhenium
R50001-R59999 Titanium
R60001-R69999 Zirconium
Z00001-Z99999 Zinc and zinc alloys
Ferrous Metals and Alloys
D00001-D99999 Specified mechanical properties steels
F00001-F99999 Cast irons
G00001-G99999 AISI and SAE carbon and alloys steels (except tool steels)
H00001-H99999 AISI H-steels
J00001-J99999 Cast steels (except tool steels)
K00001-K99999 Miscellaneous steels and ferrous alloys
S00001-$99999 Heat- and corrosion-resistant (stainless) steels
T00001-T99999 Tool steels
Welding Filler Metals, Classified
by Weld Deposit Composition
W00001-W09999 Carbon steel with no significant alloying elements
W10000-W19999 Manganese-molybdenum low-alloy steels
W20000-W29999 Nickel low-alloy steels
W30000-W39999 Austenitic stainless steels
W40000-W49999 Ferritic stainless steels
W50000-W59999 Chromium low-alloy steels
W60000-W69999 Copper-base alloys
W70000-W79999 Surfacing alloys
W80000-W89999 Nickel-base alloys

iSee NACE Corrosion Engineers Reference Book, Third Edition,


R. Baboian, Ed., NACEInternational, 2002, p. 233.

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Examples of Common Names
of Selected UNS Alloys
Nonferrous
A02420 Al 242.0 A02950 Al 295.0 A03560 A1 356.0
A05140 Al 514.0 A05200 Al 520.0 A24430 A1 B443.0
A91060 A1 1060 A91100 A1 1100 A92014 A1 2014
A92024 Al 2024 A93003 Al 3003 A95052 A1 5052
A95083 Al 5083 A95086 A1 5086 A95154 A1 5154
A96061 Al 6061 A96063 Al 6063 A97075 Al 7075
C10200 OF Copper C11000 ETP Copper C12200 DHP Copper
C14200 DPA Copper C22000 Commercial Bronze C23000 Red Brass
C26000 Cartridge Brass C27000 Yellow Brass C28000 Muntz Metal
C44300 Admiralty Brass, As C44400 Admiralty Brass, Sb C44500 Admiralty Brass, P
C46500 Naval Brass, As C51000 Phosphor Bronze A C52400 Phosphor Bronze D
C60600 Aluminum Bronze, 6 % C61300 Aluminum Bronze, 7 % C61400 Aluminum Bronze D
C63000 Nickel Aluminum Bronze C65500 High-Silicon Bronze C67500 Mangenese Bronze A
C68700 Aluminium Brass, As C70600 90-10 Copper-Nickel C71500 70-30 Copper-Nickel
C75200 Nickel Silver C83600 Ounce Metal C86500 Mangenese Bronze
C90500 Gun Metal C92200 M Bronze C95700 Cast Mn-Ni-A1 Bronze
95800 Cast Ni-Al Bronze C96400 Cast 70-30 Cu-Ni
L50045 Common Lead L51120 Chemical Lead L55030 50/50 Solder
Ml1311 Mg AZ31B Ml1914 Mg AZ91C M12330 Mg EZ33A
M13310 Mg HK31A
N02200 Nickel 200 N02201 Nickel 201 N02230 Nickel 230
N04400 400 Alloy N04405 R-405 Alloy N05500 K-500 Alloy
N05502 502 Alloy N06002 X Alloy N06007 G Alloy
N06022 C-22 Alloy N06030 G-30 Alloy N06110 Allcor
N06333 RA333 Alloy N06455 C-4 Alloy N06600 600 Alloy
N06601 601 Alloy N06617 617 Alloy N06625 625 Alloy
N06690 690 Alloy N06975 2550 Alloy N06965 G-3 Alloy
N07001 Waspaloy N07031 31 Alloy N07041 Rene 41
N07090 90 Alloy N07716 625 Plus N07718 718 Alloy
N07750 X-750 Alloy N08020 20Cb-3 N08024 20Mo-4
N08026 20Mo-6 N08028 Sanicro 28 N08320 20 Mod
N08330 RA-330 N08366 AL-6X N08367 AL-6XN
N08700 JS700 N08800 800 Alloy N08801 801 Alloy
N08810 800H Alloy N08811 800HT Alloy N08825 825 Alloy
N08904 904L Alloy N08925 25-6Mo N09706 706 Alloy
N09925 925 Alloy N10001 B Alloy N10002 C Alloy
N10003 N Alloy N10004 W Alloy N10276 C-276 Alloy
N10685 B-2 Alloy
R03600 Molybdenum R03630 Molybdenum Alloy R03650 Molybdenum, low C
R04210 Niobium (Columbium) R05200 Tantalum R07005 Tungsten
R30003 Elgiloy R30004 Havar R30006 Stellite 6
R30031 Stellite 31 R30035 MP35N R30155 N-155

1See NACE Corrosion Engineers Reference Book, Third Edition,


R. Baboian, Ed., NACE International, 2002, pp. 234-235.
5

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6 C O R R O S I O N T E S T S AND S T A N D A R D S M A N U A L

Nonferrous
R30188 HS-188 Alloy R30260 Duratherm 2602 R30556 HS-556
R30605 L-605 Alloy R50250 Titanium, Gr 1 R50400 Titanium, Gr 2
R50550 Titanium, Gr 3 R50700 Titanium, Gr 4 R52250 Titanium, Gr 11
R52400 Titanium, Gr 7 R53400 Titanium, Gr 12 R54520 Titanium, Gr 6
R56260 Ti6M6Mo2Sn4Zr R56320 Titanium, Gr 9 R56400 Titanium, Gr 5
R58640 Beta-C R60702 Zr 702 R60704 Zr 704
R60705 Zr 705
Z13000 Zinc Anode Type II Z32120 Zinc Anode Type I Z32121 Zinc Anode Type III
Ferrous
F10006 Gray Cast Iron F20000 Malleable Cast Iron F32800 Ductile Iron 60-40-18
F41000Ni-Resist Type 1 F41002 Ni-Resist Type 2 F41006Ni-Resist Type 5
F43000 Ductile Ni-Resist D2 F43006 Ductile Ni-Resist D5 F47003 Dunron
G10200 1020 Carbon Steel G41300 4130 Steal G43400 4340 S t e d
J91150 CA-15 J91151CA-15M J91153 CA-40
J91540 CA-6NM J91803 CB-30 J92500 CF-3
J92600 CF-8 J92602 CF-20 J92603 HF
J292605HC J92615 CC-50 J92701CF-16F
J92710 CF-SC J92800 CF-3M J92900 CF-8M
J93000 CG-8M J93001CG-12 J93005HD
J93370 CD-4MCu J93402 CH-20 J93423 CE-30
J93503HH J94003 HI J94202 CK-20
J94203HK-30 J94204HK-40 J94213HN
J94224HK N08604 HL N08002HT
N08007 CN-7M N08004HU N08705 HP
K01800 A516-55 K02100 A516-60 K02403 A516-65
K02700 A516-70 K02801 A285-C K03005 A53-B
K03006 A106-B Kl1510 0.2Cu Steel Kl1522 C-0.5Mo
K11576 HSLA Steel Kl1597 1.25Cr-0.5Mo K21590 2.25Cr-lMo
K41545 5Cr-0.5Mo K81340 9NiSteel K90941 9Cr-lMo
K94610 KOVAR
S13800 PH 13-8 Mo S15500 15-5 PH S15700 PH 15-7Mo
817400 17-4 PH S17600 Stainless W S17700 17-7 PH
$20100 2 0 1 S S $20200 202 SS $20910 22-13-5
$21400 Tenelon $21600 216 SS $21800 Nitronic 60
821900 21-6-9 $24000 18-3Mn $28200 18-18 Plus
830200 302 SS $30300 303 SS $30400 304 SS
830403 304L SS $30409 3 0 4 H S S $30451 304NSS
830453 304LN SS $30500 305 SS $30800 308 SS
$30815 253MA $30900 309 SS $30906 3098 SS
$31000 310 SS $31006 3108 SS $31200 44LN
$31254 254 SMO $31260 DP-3 $31400 314 SS
831500 3RE60 $31600 316 SS $31603 316L SS
831609 3 1 6 H S S $31635 316Ti SS $31640 316Cb SS
$31651 3 1 6 N S S $31635 316LNSS $31700 317 SS
831703 317L SS $31725 3 1 7 LMS S $31726 317L4 SS
$31803 2205Mloy $32100 3 2 1 S S $32109 321H SS
$32304 8AF 2304 $32404 Uranus 50 $32550 Ferr~ium255
$32900 329 88 $32950 7-Mo Plus $34700 347 SS
$34709 3 4 7 H 8 8 $34800 348 SS $35000 A M3 5 0
$35500 AM355 S36200Almar362 $38100 18-18-2
840300 403 SS $40500 405 SS $40900 409 SS
$41000 410 88 $41400 414 SS $41600 416 SS
$41800 Greek Ascoloy $42000 420 SS $42200 422 SS
842400 F6NM $42900 429 SS $43000 430 SS
$43100 431 88 $43400 434 SS $43500 436 SS
844002 440A $8 $44003 440B SS $44004 440C SS
$44200 442 88 $44400 18-2 $44600 446 SS
844625 26-1 $44626 26-1Ti $44627 26-1Cb
844635 26-4-4 $44660 SC-1 $44700 29-4
$44735 29-4C $44800 29-4-2 $45000 Cu st o m 4 5 0
845500 Custom455 $50100 5C~0.5Mo $50200 5Cr-0.5Mo
850300 7Cr-0.5Mo $50400 9Cr-lMo $66286 A286

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Designation: G 15-04

Standard Terminology Relating to


Corrosion and Corrosion Testing I

This standard is issuedunder the fixed designationG 15; the numberimmediatelyfollowingthe designationindicatesthe yearof
originaladoptionor, in the case of revision,the year of last revision.A numberin parenthesesindicatesthe year of last reapproval.
Asuperscriptepsilon(e) indicatesan editorialchangesincethe last revisionor reapproval.
This standard has been approved for use by agencies of the Department of Defense.

1. Scope anodic protection--a technique to reduce the corrosion


1.1 This terminology covers commonly used terms in the rate of a metal by polarizing it into its passive region
field of corrosion. Related terms may be found in Terminol- where dissolution rates are low.
ogies D 16, D 4538, G 40, or other ASTM terminology stan- a n o l y t e - - t h e electrolyte adjacent to the anode of an electro-
dards. All terms defined by ASTM committees may be fotmd lytic cell.
in the ASTM Dictionary o f Engineering & Technology. auxiliary electrode--See counter electrode.
2. Referenced D o c u m e n t s b r e a k d o w n p o t e n t i a l - - t h e least noble potential where pitting
2.1 ASTM Standards: 2 or crevice corrosion, or both, will initiate and propagate.
D 16 Terminology for Paint, Related Coatings, Materials, cathode--the electrode of an electrolytic cell at which re-
and Applications duction is the principal reaction. (Electrons flow toward
D 4538 Terminology Relating to Protective Coating and the cathode in the external circuit.)
Lining Work for Power c a t h o d i c corrosion---corrosion of a metal when it is a
G 40 Terminology Relating to Wear and Erosion cathode. (It usually happens to metals because of a rise
3. Terminology in pH at the cathode or as a result of the formation of
AC impedance--See e l e c t r o c h e m i c a l i m p e d a n c e . hydrides.)
active--the negative direction of electrode potential. (Also cathodic i n h i b i t o r m a corrosion inhibitor whose primary
used to describe corrosion and its associated potential action is to slow the kinetics of the cathodic reaction,
range when an electrode potential is more negative than producing a negative shift in corrosion potential.
an adjacent depressed corrosion rate [passive] range.) c a t h o d i c p o l a r i z a t i o n - - t h e change of the electrode poten-
a n i o n - - a negatively charged ion. tial in the active (negative) direction due to current flow.
a n o d e - - t h e electrode of an electrolytic cell at which oxida- (See polarization.)
tion is the principal reaction. (Electrons flow away from cathodic protection--a technique to reduce the corrosion
the anode in the external circuit. It is usually the electrode rate of a metal surface by making it the cathode of an
where corrosion occurs and metal ions enter solution.) electrochemical cell.
anode corrosion efficiency--the ratio of the actual corro- c a t h o l y t e - - t h e electrolyte adjacent to the cathode of an
sion (weight loss) of an anode to the theoretical corro- electrolytic cell.
sion (weight loss) calculated by Faraday's law from the catiou--a positively charged ion.
quantity of electricity that has passed. caustic crackingmstress corrosion cracking of m e t a l s in
anodic i n h i b i t o r - - a corrosion inhibitor whose primary caustic solutions. (See also s t r e s s - c o r r o s i o n cracking.)
action is to slow the kinetics of the anodic reaction, pro- caustic embrittlement--See caustic cracking.
ducing a positive shift in corrosion potential. cavitation--the formation and rapid collapse within a liquid
a n o d i c p o l a r i z a t i o n - - t h e change of the electrode potential of cavities or bubbles that contain vapor or gas or both.
in the noble (positive) direction due to current flow. (See cavitation corrosion--the conjoint action of cavitation-
polarization.) erosion and corrosion.
cavitation damage---the degradation of a solid body result-
ing from its exposure to cavitation. (This may include
loss of material, surface deformation, or changes in
1 This terminology is under the jurisdiction of ASTM Committee properties or appearance.)
G01 on Corrosion of Metals and are the direct responsibility of cavitation-erosionmloss of material from a solid surface due
Subcommittee G01.02 on Terminology.
Current edition approved Jan. 1, 2004. Published January 2004. to mechanical action of continuing exposure to cavitation.
Originally approved in 1971. Last previous edition approved in c h e m i c a l c o n v e r s i o n c o a t i n g - - a protective or decorative
2003 as G 15-03a. nonmetallic coating produced in situ by chemical reaction
2For referencedASTMstandards,visitthe ASTMwebsite,www.astm.org, of a metal with a chosen environment. (It is often used to
or contact ASTM Customer Service at service@astm.org. For Annual prepare the surface prior to the application of an organic
Book of ASTM Standards volume information, refer to the standard's coating.)
Document Summary page on the ASTM website.
Copyrigh@ASTMInternational,100Ban"HarborDrive,PO Box C700,WestConshohocken,PA 194282959, UnitedStates.

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8 CORROSION TESTS AND STANDARDS MANUAL

concentration c e l l - - a n electrolytic cell, the emf of which is diffusion limited current d e n s i t y - - t h e current density,
caused by a difference in concentration of some component often referred to as limiting current density, that corre-
in the electrolyte. (This difference leads to the formation sponds to the m a x i m u m transfer rate that a particular
of discrete cathode and anode regions.) species can sustain due to the limitation of diffusion.
c o r r o s i o n m t h e chemical or electrochemical reaction be- electrochemical a d m i t t a n c e - - t h e reciprocal of the elec-
tween a material, usually a metal, and its environment that trochemical impedance, MIAE.
produces a deterioration of the material and its properties. electrochemical c e l l - - a n electrochemical system consisting of
corrosion f a t i g u e - - t h e process in which a metal fractures an anode and a cathode in metallic contact and immersed in
prematurely under conditions of simultaneous corrosion an electrolyte. (The anode and cathode may be different
and repeated cyclic loading at lower stress levels or fewer metals or dissimilar areas on the same metal surface.)
cycles than would be required in the absence of the cor- electrochemical i m p e d a n c e - - - t h e frequency dependent,
rosive environment. complex valued proportionality factor, AE/M, between
corrosion f a t i g u e s t r e n g t h - - t h e m a x i m u m repeated stress the applied potential (or current) and the response cur-
that can be endured by a metal without failure under defi- rent (or potential) in an electrochemical cell. This factor
nite conditions of corrosion and fatigue and for a specific becomes the impedance when the perturbation and re-
number of stress cycles and a specified period of time. sponse are related linearly (the factor value is independ-
corrosion i n h i b i t o r ~ a chemical substance or combination ent of the perturbation magnitude) and the response is
of substances that, when present in the proper concen- caused only by the perturbation. The value may be re-
tration and forms in the environment, prevents or re- lated to the corrosion rate when the m e a s u r e m e n t is
duces corrosion. made at the corrosion potential.
corrosion potential~the potential of a corroding surface electrochemical n o i s e - - f l u c t u a t i o n s of the current, or
in an electrolyte relative to a reference electrode meas- both, originating from uncontrolled variations in a cor-
ured under open-circuit conditions. rosion process.
corrosion rate---the a m o u n t of corrosion occurring in unit electrochemical potential (electrochemical t e n s i o n ) m
time. (For example, mass change per unit area per unit the partial derivative of the total electrochemical free en-
time; penetration per unit time.) ergy of the system with respect to the n u m b e r of moles of
counter e l e c t r o d e - - t h e electrode in an electrochemical cell the constituent in a solution when all other factors are
that is used to transfer current to or from a test electrode. constant. (Analogous to the chemical potential of the
crevice c o r r o s i o n ~ l o c a l i z e d corrosion of a metal surface constituent except that it includes the electrical as well as
at, or immediately adjacent to, an area that is shielded the chemical contributions to the free energy.)
from full exposure to the environment because of close electrode potential--the potential of an electrode in an
proximity between the metal and the surface of another electrolyte as measured against a reference electrode.
material. (The electrode potential does not include any resistance
c r i t i c a l a n o d i c current density~the m a x i m u m anodic losses in potential in either the solution or external cir-
current density observed in the active region for a metal cuit. It represents the reversible work to move a unit
or alloy electrode that exhibits active-passive behavior in charge from the electrode surface through the solution to
an environment. the reference electrode.)
critical h u m i d i t y m t h e relative humidity above which the at- electrolysis---production of chemical changes of the electrolyte
mospheric corrosion rate of some metals increases sharply. by the passage of current through an electrochemical cell.
c r i t i c a l pitting potential--the least noble potential where electrolytic c l e a n i n g - - a process of removing soil, scale or
pitting corrosion will initiate and propagate. (See break- corrosion products from a metal surface by subjecting it
down potential.) as an electrode to an electric current in an electrolytic
current d e n s i t y ~ t h e electric current to or from a unit area bath.
of an electrode surface. Electromotive Force Series ( E M F S e r i e s ) - - a list of ele-
current e f f i c i e n c y ~ t h e ratio of the electrochemical equiva- ments arranged according to their standard electrode po-
lent current density for a specific reaction to the total tentials, with "noble" metals such as gold being positive
applied current density. and "active" metals such as zinc being negative.
d e a c t i v a t i o n - - t h e process of prior removal of the active cor- e m b r i t t l e m e n t - - t h e severe loss of ductility or toughness or
rosive constituents, usually oxygen, from a corrosive liquid both, of a material, usually a metal or alloy.
by controlled corrosion of expendable metal or by other environmentally-assisted c r a c k i n g - - t h e initiation or accele-
chemical means, thereby making the liquid less corrosive. ration of a cracking process due to the conjoint action of
deaUoying--See p a r t i n g . a chemical environment and tensile stress.
depolarization--not a preferred term. (See p o l a r i z a t i o n . ) e q u i l i b r i u m ( r e v e r s i b l e ) p o t e n t i a l - - t h e potential of an
deposit c o r r o s i o n ~ l o c a l i z e d corrosion under or a r o u n d a electrode in an electrolytic solution when the forward
deposit or collection of material on a metal surface. (See rate of a given reaction is exactly equal to the reverse
also crevice corrosion.) rate. (The equilibrium potential can only be defined with
dezincification--See p a r t i n g ; specific to copper-zinc alloys. respect to a specific electrochemical reaction.)
differential aeration cell (oxygen concentration c e l l ) - - a erosion--the progressive loss of material from a solid sur-
concentration cell caused by differences in oxygen con- face due to mechanical interaction between that surface
centration along the surface of a metal in an electrolyte. and a fluid, a multi-component fluid, or solid particles
(See c o n c e n t r a t i o n cell.) carried with the fluid.

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STANDARD TERMINOLOGY 9

erosion-corrosion--a conjoint action involving corrosion hydrogen e m b r i t t l e m e n t - - h y d r o g e n - i n d u c e d cracking or


and erosion in the presence of a moving corrosive fluid, severe loss of ductility caused by the presence of hydro-
leading to the accelerated loss of material. gen in the metal.
exchange current density--the rate of charge transfer per i m m u n i t y - - a state of resistance to corrosion or anodic dis-
unit area when an electrode reaches dynamic equilibrium solution of a metal caused by thermodynamic stability of
(at its reversible potential) in a solution; that is, the rate the metal.
of anodic charge transfer (oxidation) balances the rate of impingement corrosion--a form of erosion-corrosion gen-
cathodic charge transfer (reduction). erally associated with the local impingement of a high-
e x f o l i a t i o n - - c o r r e c t i o n that proceeds laterally from the velocity, flowing fluid against a solid surface.
sites of initiation along planes parallel to the surface, impressed current--an electric current supplied by a device
generally at grain boundaries, forming corrosion prod- employing a power source that is external to the electrode
ucts that force metal away from the body of the material, system. (An example is dc current for cathodic protection.)
giving rise to a layered appearance. intensiostatic--See galvanostatic.
e x t e r n a l c i r c u i t - - t h e wires, connectors, measuring devices, intercrystalline corrosion--See i n t e r g r a n u l a r corrosion.
current sources, and so forth, that are used to bring i n t e r g r a n u l a r c o r r o s i o n - - p r e f e r e n t i a l corrosion at or ad-
about or measure the desired electrical conditions within jacent to the grain boundaries of a metal or alloy.
the test cell. internal oxidation--the formation of isolated particles of corro-
fillform corrosion--corrosion that occurs under some coatings sion products beneath the metal surface. (This occurs as the
in the form of randomly distributed threadlike filaments. result of preferential oxidation of certain alloy constituents by
f r e t t i n g c o r r o s i o n - - t h e deterioration at the interface be- inward diffusion of oxygen, nitrogen, sulfur, and so forth.)
tween contacting surface as the result of corrosion and k n i f e - l i n e a t t a c k - - i n t e r g r a n u l a r corrosion of an alloy, usu-
slight oscillatory slip between the two surfaces. ally stabilized stainless steel, along a line adjoining or in
g a l v a n i c c o r r o s i o n - - a c c e l e r a t e d corrosion of a metal be- contact with a weld after heating into the sensitization
cause of on electrical contact with a more noble metal or temperature range.
nonmetallic contactor in a corrosive electrolyte. local action c o r r o s i o n - - c o r r o s i o n caused by local corro-
galvanic c o u p l e - - a pair of dissimilar conductors, commonly sion cells on a metal surface.
metals, in electrical contact (See g a l v a n i c corrosion.) local corrosion c e l l - - a n electrochemical cell created on a
g a l v a n i c c u r r e n t - - t h e electric current between metals or metal surface because of a difference in potential be-
conductive nonmetals in a galvanic couple. tween adjacent areas on that surface.
g a l v a n i c s e r i e s - - a list of metals and alloys arranged ac- l o c a l i z e d c o r r o s i o n - - c o r r o s i o n at discrete sites, for example,
cording to their relative corrosion potentials in a given pitting, crevice corrosion, and stress corrosion cracking.
environment. long-line c u r r e n t - - e l e c t r i c current through the earth from
g a l v a n o d y n a m i c - - r e f e r s to a technique wherein current, an anodic to a cathodic area of a continuous metallic
continuously varied at a selected rate, is applied to an structure. (Usually used only where the areas are sepa-
electrode in an electrolyte. rated by considerable distance and where the current re-
g a l v a n o s t a i r c a s e - - r e f e r s to a galvanostep technique for sult from concentration-cell action.)
polarizing an electrode in a series of constant current Luggin probe or Luggin-Haber c a p i l l a r y - - a device used
steps wherein the time duration and current increments in measuring the potential of an electrode with a signifi-
or decrements are equal for each step. cant current density imposed on its surface. (The probe
g a l v a n o s t a t i c - - a n experimental technique whereby an dec- minimizes the IR drop that would other, vise be included
trode is maintained at a constant current in an electrolyte. in the m e a s u r e m e n t and without significantly disturbing
g a l v a n o s t e p - - r e f e r s to a technique in which an electrode is the current distribution on the specimen.)
polarized in a series of current increments or decrements. macrocell corrosion--corrosion of a metal embedded in po-
g r a i n d r o p p i n g - - t h e dislodgement and loss of a grain or rous media (for example, concrete or soil) caused by con-
grains (crystals) from a metal surface as a result of inter- centration or galvanic cells which exist on a scale at least as
granular corrosion. large as the smallest major dimension of the corroding item
graphitic corrosion--the deterioration of metallic con- (for example, the diameter of a bar pipe).
stituents in gray cast iron, which leaves the graphic par- metal d u s t i n g - - a c c e l e r a t e d deterioration of metals in car-
ticles intact. (The term "graphitization" is commonly bonaceous gases at elevated temperature to form a dust-
used to identify this form of corrosion but is not recom- like corrosion product.
m e n d e d because of its use in metallurgy for the decom- metallizing--See thermal spraying.
position of carbide to graphite.) microbial c o r r o s i o n - - c o r r o s i o n that is affected by the
hot corrosion--an accelerated corrosion of metal surfaces action of microorganisms in the environment.
that results from the combined effect of oxidation and reac- m i c r o b i o l o g i c a l l y influenced corrosion (MIC)---corrosion
tions with sulfur compounds and other contaminants, such inhibited or accelerated by the presence or activity, or
as chlorides, to form a molten salt on a metal surface which both, of microorganisms.
fluxes, destroys, or disrupts the normal protective oxide. m i x e d p o t e n t i a l - - t h e potential of a specimen (or speci-
hydrogen b l i s t e r i n g - - t h e formation of blisters on or below mens in a galvanic couple) when two or more electro-
a metal surface from excessive internal hydrogen pres- chemical reactions are occurring simultaneously.
sure. (Hydrogen m a y be formed during cleaning, plating, n o b l e - - t h e positive (increasingly oxidizing) direction of
corrosion, and so forth.) electrode potential.

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10 C O R R O S I O N TESTS AND STANDARDS MANUAL

noble m e t a l - - a metal with a standard electrode potential density (critical anodic current density) of an electrode
that is more noble (positive) than that of hydrogen. that exhibits active-passive corrosion behavior.
occluded c e l l ~ a n electrochemical cell created at a local- protection p o t e n t i a l - - t h e most noble potential where pit-
ized site on a metal surface which has been partially ob- ting and crevice corrosion will not propagate.
structed from the bulk environment. redox p o t e n f i a l m t h e potential of a reversible oxidation-
open-circuit p o t e n t i a l m t h e potential of an electrode reduction electrode measured with respect to a reference
m e a s u r e d with respect to a reference electrode or an- electrode, corrected to the hydrogen electrode, in a given
other electrode when no current flows to or from it. electrolyte.
overvoltage---the change in potential of an electrode from its reduction--the gain of electrons by a constituent of a
equilibrium or steady state value when current is applied. chemical reaction.
o x i d a t i o n - - l o s s of electrons by a constituent of a chemical reference e l e c t r o d e - - e l e c t r o d e having a stable and repro-
reaction. (Also refers to the corrosion of a metal that is ducible potential, which is used in the m e a s u r e m e n t of
exposed to an oxidizing gas at elevated temperatures.) other electrode potentials.
p a r t i n g - - t h e selective corrosion of one or more compo- rest potential--See o p e n - c i r c u i t p o t e n t i a l .
nents of a solid solution alloy. r u s t - - a corrosion product consisting primarily of hydrated
p a r t i n g l i m i t ~ t h e m i n i m u m concentration of a more noble iron oxide. (A term properly applied only to ferrous alloys.)
component in an alloy, above which parting does not oc- s a m p l e - - a portion of material taken from a larger quantity
cur in a specific environment. and representative of the whole, to be used for test pur-
passivation--the process in metal corrosion by which met- poses.
als become passive. (See passive.) season cracking--See s t r e s s - c o r r o s i o n c r a c k i n g .
p a s s i v a t o r - - a type of inhibitor which appreciably changes s e n s i t i z a t i o n m a process resulting in a metallurgical condi-
the potential of a metal to a more noble (positive) value. tion which causes susceptibility of an alloy to intergranu-
p a s s i v e - - t h e state of the metal surface characterized by low lar corrosion or intergranular environmentally assisted
corrosion rates in a potential region that is strongly oxi- cracking in a specific environment.
dizing for the metal. specimen~a prepared portion of a sample upon which a
passive-active c e l l - - a corrosion cell in which the anode is test is intended to be performed.
a metal in the active state and the cathode is the same stray current corrosion--the corrosion caused by electric
metal in the passive state. current from a source external to the intended electrical
pitting---corrosion of a metal surface, confined to a point or circuit, for example, extraneous current in the earth.
small area, that takes the form of cavities. stress-corrosion c r a c k i n g - - a cracking process that requires
pitting f a c t o r ~ r a t i o of the depth of the deepest pit result- the simultaneous action of a corrodent and sustained
ing from corrosion divided by the average penetration as
tensile stress. (This excludes corrosion-reduced sections
calculated from weight loss.
which fail by fast fracture. It also excludes intercrystal-
p o l a r i z a t i o n ~ t h e change from the open-circuit electrode
line or transcrystalline corrosion which can disintegrate
potential as the result of the passage of current.
an alloy without either applied or residual stress.)
p o l a r i z a t i o n a d m i t t a n c e - - t h e reciprocal of polarization
subsurface corrosion~See i n t e r n a l o x i d a t i o n .
resistance (di/dE).
s u l f i d a t i o n - - t h e reaction of a metal or alloy with a sulfur-
p o l a r i z a t i o n r e s i s t a n c e - t h e slope (dE/di)at the corrosion
potential of potential ( E ) - - c u r r e n t density (i) curve. (It is containing species to produce a sulfur c o m p o u n d that
inversely proportional to the corrosion current density forms on or beneath the surface of the metal or alloy.
when the polarization resistance technique is applicable.) Tafel slope---the slope of the straight line portion of a
p o t e n t i o d y n a m i c - - r e f e r s to a technique wherein the poten- polarization curve, usually occurring at more than 50 mV
tial of an electrode with respect to a reference electrode from the open-circuit potential, when presented in a
is varied at a selected rate by application of a current semi-logarithmic plot in terms of volts per logarithmic
through the electrolyte. cycle of current density (commonly referred to as volts
potentiostaircase--refers to a potentiostep technique for per decade).
polarizing an electrode in a series of constant potential t h e r m a l s p r a y i n g - - a group of processes wherein finely
steps wherein the time duration and potential incre- divided metallic or nonmetallic materials are deposited
ments or decrements are equal for each step. in a molten or semimolten condition to form a coating.
potentiostat---an instrument for automatically maintaining (The coating material m a y be in the form of powder, ce-
an electrode in an electrolyte at a constant potential or con- ramic rod, wire,or molten materials.)
trolled potentials with respect to a stfitable reference electrode. t h e r m o g a l v a n i c c o r r o s i o n - - t h e corrosive effect resulting
potentiostatic~the technique for maintaining a constant from the galvanic cell caused by a thermal gradient
electrode. across the metal surface.
p o t e n t i o s t e p - - r e f e r s to a technique in which an electrode is transpassive r e g i o n - - t h e region of an anodic polarization
polarized in a series of potential increments or decrements. curve, noble to and above the passive potential range, in
poultice corrosion--See deposit corrosion. which there is a significant increase in current density
Pourbaix diagram (electrode potential-pH diagram)ma (increased metal dissolution) as the potential becomes
graphic representation showing regions of thermodynamic more positive (noble).
stability of species in metal-water electrolyte systems. t u b e r c u l a t i o n - - t h e formation of localized corrosion prod-
p r i m a r y passive potential (passivation p o t e n t i a l ) ~ t h e ucts that appear on a surface as knoblike prominences
potential corresponding to the m a x i m u m active current (tubercules).

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STANDARD T E R M I N O L O G Y 11

u n i f o r m c o r r o s i o n - - c o r r o s i o n that proceeds at about the that occurs as the result of sensitization in the heat-
same rate over a metal surface. affected zone during the welding operation.
w e l d d e c a y - - n o t a preferred term. Integranular corrosion, w o r k i n g e l e c t r o d e - - t h e test or specimen electrode in an
usually of stainless steels or certain nickel-base alloys, electrochemical cell.

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Glossary of Corrosion-Related
Acronyms
ABS Acrylonitrile-butadiene-styrene plastics FBC Fluidized bed combustion
AC Air-cooled FBE Fusion-bonded epoxy coating
AE Acoustic emission FC Furnace cooled
AES Auger electron spectroscopy FCGR Fatigue crack growth rate
ANN Annealed FEP Fluorinated ethylene propylene polymer
AUSS Austenitic stainless steel FGD Flue gas desulfurization
AVT All volatile treatment for BFW FPM Fluorocarbon elastomers
BFW Boiler feedwater FRP Fiber-reinforced plastic
BWR Boiling water reactor FSS Ferritic stainless steel
CAB Cellulose acetate-butyrate GMAW Gas metal arc welding
CCI Crevice corrosion index GTAW Gas tungsten arc welding
CCT Critical crevice corrosion temperature HAZ Heat-affected zone
CD Current density HB Brinell hardness number
CDA Corrosion data acquisition HE Hydrogen embrittlement
CF Corrosion fatigue HIC Hydrogen induced cracking
CH Cold work hardened HK Knoop hardness number
CHA Cold work hardened, aged HLLW High level liquid waste (nuclear)
CN Concentric neutral HPW High-purity water
CP Cathodic protection HR Hot-rolled
CPP Critical pitting potential HRA Hot-rolled, aged
CPT Critical pitting temperature HRB Rockwell B hardness number
CPVC Chlorinated poly(vinyl chloride) HRC Rockwell C hardness number
CR Cold-rolled HSC Hydrogen stress cracking
CRA Corrosion-resistant alloy HSLA High-strength low-alloy steel
CS Carbon steel HTR Heat treatment
CSE Copper/copper sulfate electrode HVN Vickers hardness number
CW Cooling water IGC Intergranular corrosion
DCB Double cantilever beam test IGSCC Intergranular stress corrosion cracking
DIMA Direct imaging mass analyzer IMMA Ion microprobe mass analyzer
DSS Duplex stainless steel IOZ Inorganic zinc coating
DTA Differential thermal analysis ISS Ion scattering spectroscopy
DW Distilled water ISWS Illinois State Water Survey tester
EC Environmental cracking KIC Critical stress intensity
EDXA Energy dispersive X-ray analysis LAS Low-alloy steel
EIS Electrochemical impedance spectroscopy LMC Liquid metal cracking
ELN Electrochemical noise technique LSI Langelier saturation index
EPMA Electron beam microprobe analysis MAS Maraging steels
EPDM Ethylene propylene elastomer MCA Multiple crevice assembly
EPR Electrochemical potentiokinetic MIC Microbial induced corrosion
reactivation MSS Martensitic stainless steel
ER Electrical resistance MT Magnetic particle inspection
ESCA Electron spectroscopy for chemical analysis NG Nuclear grade
EW Electric welded NHE Normal hydrogen electrode
NMR Nuclear magnetic resonance
1See NACE Corrosion Engineers Reference Book, Third Edition, NPS Nominal pipe size
R. Baboian, Ed., NACEInternational, 2002, p. 33. NT Normalized and tempered

12

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G L O S S A R Y OF CORROSION-RELATED A C R O N Y M S 13

OCTG Oil country tubular goods SIMS Secondary ion mass spectroscopy
OQ Oil-quenched SMAW Shielded metal arc welding
OTEC Ocean thermal energy conversion SMLS Seamless pipe or tubing
OZ Organic zinc coating SMYS Specified minimum yield strength
PC Polycarbonate SRA Stress relief anneal
PD Pit depth SRB Sulfate-reducing bacteria
PE Polyethylene SRC Solvent-refined coal
PFA Perfluoro(alkoxy-alkane) copolymer S/N Fatigue test
PHSS Precipitaion hardenable stainless steel SRE Scanning reference electrode
PPC Polymer modified portland cement SS Stainless steel
PP Polypropylene SSC Sulfide stress cracking
PR Polarization resistance SSMS Spark sources mass spectroscopy
PT Dye penetrant survey SSR slow strain rate test
PTA Polythionic acids SSW Substitute seawater
PTFE Polytetrafluoromethylene STA Solution treated and aged
PU Polyurethane STEM Scanning transmission electron microscopy
PVC Poly(vinyl choloride) STQ Solution treated and quenched
PVDC Poly(vinylidene chloride) SW Seawater
PVDF Poly(vinylidene fluoride) TEM Transmission electron microscopy
PWHT Post-weld heat treatment TFE Tetrafluoroethylene
PWR Pressurized water reactor TS Tensile strength
QT Quenched and tempered TTS Temperature, time, sensitization diagram
RH Relative humidity URD Underground residential distribution systems
RSI Ryzner saturation index UT Ultrasonic survey
RT X-ray or gamma ray survey UV Ultraviolet spectroscopy
RTP Reinforced thermoset plastics VCI Volatile corrosion inhibitor
RX Recrystallized WFMT Wet fluorescent magnetic particle inspection
SAM Scanning Augar microscopy WQ Water-quenched
SAW Submerged arc welding WOL Wedge-opening load test
SBR Styrene-butadiene rubber XPS X-ray photoelectron spectroscopy
SCC Stress-corrosion cracking XRD X-ray diffraction
SCE Saturated calomel electrode YS Yield strength
SEM Scanning electron microscopy ZRP Zinc-rich paint

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ASTM Standard Abbreviations
and Unit Symbols
absolute abs Department Dept. b
academic degrees use periods and run together diameter dia (in figures and tables only)
(M.S., Ph.D., etc.) differential d
alternating current, n. AC direct current, n. DC
alternating current, adj. A-C direct current, adj. D-C
American Am.a Division Div.b
American wire gage AWG dollar $
ampere A effective horsepower ehp
ampere hour Ah electromotive force emf
angstrom A electronvolt eV
ante meridiem a.m. Engineers Engrsf
Association Assn. b equation(s) Eq(s)
atmosphere atm farad F
average avg figure(s) Fig(s).d
barrel bbl foot ft
becquerel Bq footcandle fc
billion electronvolts (use GeV, gigaelectronvolts) foot pound-force ft- lbf (use for work, energy)
Birmingham wire gage BWG (see lbf. ft)
brave horsepower bhp gallon gal
brake-horsepower hour hhp - h gauss G
Brinell hardness number HB (see ASTM E 10) gilbert Gb
British thermal unit Btu grain spell out
Brown and Sharpe (gage) B&S gram g
bushel bu gravity (acceleration) g
calorie cal gray Gy
candela cd half hard :AH
centimetre cm henry H
centipoise cP hertz Hz
centistokes cSt horsepower hp
circular mil cmil horsepower hour hp.h
coefficient spell out hour h
Company Co.b Hurter and Driffield scale H&D
Corporation Corp. b (film density)
coulomb C hydrogen ion concentration, pH
cubic use exponential formc negative logarithm of
cubic centimetre cm 3 inch in.
cubic decimetre dm 3 inch of mercury in. Hg
curie Ci inch of water in. H20
cycles per minute cpm inch pound-force in- lbf (use for work, energy)
cycles per second (use Hz. hertz) (see lbf. in.)
day spell out inclusive incl (in figures and tables only)
decibel dB Incorporated Inc.b
degree (angle) ° indicated horsepower ihp
degree Celsius °C inside diameter ID (in figures and tables only)
degree Fahrenheit °F Institute Inst. b
degree Rankine °R integrated neutron flux nvt. n/cm 2
degrees of freedom df iron pipe size IPS

14

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ASTM STANDARD ABBREVIATIONS AND UNIT SYMBOLS 15

joule J millimetre mm
K alpha radiation Ktx millimetre of mercury mm Hg
kelvin K million electronvolts MeV
kilocalorie kcal milliroentgen mR
kilocycle per second (see note on cycles per second) millisecond ms
kilogram kg millivolt mV
kilogram-calorie kg. cal milliwatt mW
kilogram-force kgf minimum min (in figures and tables only)
kilogram metre kg.m minute min (spell out when used with
kilometre km minimum)
kilovok kV molal spell out
kilovolt ampere kVA molar M
kiloelectronvolt keV mole mol
kilovolt peak kVp month (When followed by a spell out
kilowatt kW date use Jan., Feb., March,
kilowatt hour kWh April, May, June, July, Aug.,
kip (1000 lbf) spell out Sept., Oct., Nov., Dec. When
kip (1000 lbf) per square inch ksi there is no date, spell out.
Knoop hardness number HK (see ASTM E 384) Examples: Jan. 15, 1983;
lambert L January 1983)
linear spell out nanometre (formerly nm
litre L millimicron)
logarithm (common) log National Nat. a
logorithm (natural) In newton N
lumen lm nOITFlal N
lux lx number(s) (This abbreviation No(s). d
magnetomotive force mmf can often be omitted
mass-to-charge ratio m/e entirely. It is usually
maximum max (in figures and tables only) understood (as in STP 325,
maxwell Mx Specimen 8, Test 14, etc).)
median effective concentration EC50 oersted Oe
median effective dose EDs0 ohm
median lethal concentration LCs0 ortho 0
median lethal dose LDs0 ounce OZ
megacycles per second (see note on cycles per second) outside diameter OD (in figures and tables only)
megawatt MW page p.
meta m pages pp.
metre m para P
mlcroampere pA parts per billion ppb
mlcrocurie pCi parts per million ppm
mxcrofarad pF pascal Pa
mmrogram Pg per use the diagonal line in express-
mmrohenry pH ions with unit symbolse
mlcroinch pin. percent %
mmrolitre pL pico (prefix) P
mmro-micro (prefix. use pico) P picofarad pF
mmrometre (formerly micron) pm pint pt
mmroroentgen pR poise P
microsecond ps Poisson's ratio p (v is preferred in applied
mlcrovolt pV mechanics)
mlcrowatt pW post meridiem p.m.
mil spell out pound lb
mile spell out pound-force lbf
miles per hour mph pound-force foot lbf. ft (use for torque)
milliampere mA (see ft. lbf)
milli-angstrom mA pound-force inch lbf- in. (use for torque)
millicurie mCi (see in. lbf)
milliequivalent meq pound-force per square foot lbf/ft2
milligram mg pound-force per square inch psi or lbf/in. 2
millihenry mH pound-force per square inch psia
millilitre mL absolute

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16 C O R R O S I O N TESTS AND STANDARDS MANUAL

pound-force per square inch psig standard taper (tables and


gage quart drawings only)
quart qt steradian sr

rad (dose unit) rd stokes St


radian rad tensile strength spell out
radio frequency, n. rf tertiary tert
radio frequency, adj. r-f tesla T
radius R (in figures and tables only) thousand electronvolts keV
Railway Ry.b thousand pounds kip
Railroad R.R. b thousand pounds-force per ksi
reference(s) Ref(s) square inch
relative humidity RH (in figures and tables ton spell out
only) torr spell out
revolution per minute r/rain United States, n. spell out
revolution per second r/s United States, adj. U.S.
Rockwell hardness, C scale HRC (see ASTM E 18) United Status Pharmacopeia USP
roentgen R versus spell out
root mean square rms Vickers hardness number HV (see ASTM E 92)
Saybolt Furol seconds SFS volt V
Saybolt Universal seconds SUS volume (of a publication) Vol a
second s watt W
secondary sec watt hour Wh
siemens S weber Wb
Society Soc.b week spell out
socket joint (tables and § yard yd
drawings only) year spell out
specific gravity sp gr Young's modulus E
square use exponential form
(exception: psi, ksi) c

aIn footnotes and references only.


bAt end of name only.
cWith unit symbols only.
dOnly when followed by a number.
eExceptions: cpm, mph, psi.

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International System of Units (SI)'
Quantity Unit Formula
Base Units
length metre (m)
mass kilogram (kg)
time second (s)
electric current ampere (A)
thermodynamic temperature Kelvin (K)
amount of substance mole (mol)
luminous intensity candela (cd)
Supplementary Units
plane angle radian (rad)
solid angle steradian (sr)
Derived Units
acceleration metre per second squared n3/s 2

activity (of a radioactive source) disintegration per second (disintegration)/s


angular acceleration radian per second squared rad/s 2
angular velocity radian per second rad/s
square metre m 2
area
density kilogram per cubic metre kg/m 3
electric capacitance farad (F) A • s/V
electric conductance siemens (S) A/V
electric field strength volt per metre Wm
electric inductance henry (H) V . s/A
electric potential difference volt (V) W/A
electric resistance ohm (f~) V/A
electromotive force volt (V) W/A
energy joule (J) N.m
entropy joule per kelvin j/K
force newton (N) kg - m/s 2
frequency hertz (Hz) (cycle)/s
illuminance lux (Ix) lm/m 2
luminance candela per square metre cd/m 2
luminous flux lumen (lm) cd • sr
magnetic field strength ampere per metre A/m
magnetic flux weber (Wb) V.s
magnetic flux density tesla (T) Wb/m 2
magnetomotive force ampere (A)
power watt (W) J/s
pressure pascal (Pa) N/m 2
quantity of electricity coulomb (C) A.s
quatity of heat joule (J) N.m
radiant intensity watt per steradian W/sr
specific heat joule per kilogram-kelvin J/kg. K
stress pascal (Pa) N/m 2
thermal conductivity watt per metre-kelvin W/m • K
velocity metre per second rn/s
viscosity, dynamic pascal-second Pa.s
viscosity, kinematic square metre per second m2/s
voltage volt (V) W/A
volume cubic metre m3
wavenumber reciprocal metre (wave) m
work j o u l e (J) N.m

xSee ASTM E 380, Practice for Use of the International System of


Units (SI) (The Modernized Metric System).
17

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General Conversion Factors
Unit Conversion to Multiply by Reciprocal
Linear Measure
mil (0.001 inch) micrometre 25.4 0.03937
rail (0.001 inch) millimetre 0.0254 39.37
inch millimetre 25.4 0.03937
foot metre 0.3048 3.281
yard metre 0.9144 1.0936
mile kilometre 1.6093 0.6214
nautical mile kilometre 1.8532 0.5396

Square Measure
square inch square millimetre 645.2 0.00155
square inch square centimetre 6.452 0.155
square foot square metre 0.0929 10.764
square yard square metre 0.8361 1.196
acre hectare 0.4047 2.471
acre square metre 4047. 0.0002471
acre square foot 43560. 0.00002296
square mile acre 640. 0.001562
square mile square kilometre 2.590 0.3863

Volume
cubic inch cubic centimetre 16.387 0.06102
cubic foot cubic metre 0.02832 35.31
cubic foot gallon (U.S.) 7.48 0.1337
cubic foot litre 28.32 0.03531
cubic yard cubic metre 0.7646 1.3079
ounce (U.S., liq.) cubic centimetre 29.57 0.03382
quart (U.S., liq.) litre 0.9464 1.0566
gallon (U.S) gallon (Imperial) 0.8327 1.2009
gallon (U.S) litre 3.785 0.2642
barrel (U.S. Pertoleum) gallon (U.S) 42. 0.028
barrel (U.S. Pertoleum) litre 158.98 0.00629

Mass
grain milligram 64.8 0.01543
ounce (avoirdupois) gram 28.35 0.03527
p o u n d (avoirdupois) kilogram 0.4536 2.205
short ton metric ton 0.9072 1.1023
long ton metric ton 1.0161 0.9842

Pressure or Stress
atmosphere m m Hg (@ 0°c) 760. 0.001316
atmosphere p o u n d force per inch 2 14.696 0.06805
atmosphere bar 1.013 0.9872
atmosphere megapascal (MPa) 0.1013 9.872
torr (ram Hg) pascal 133.32 0.007501
inch of water pascal 248.8 0.004019

1See ASTM E 380, Practice for Use of the International System of


Units (SI) (The Modernized Metric System).
18

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GENERAL CONVERSION FACTORS 19

Unit Conversion to Mukiplyby Reciproc~


foot of water p o u n d force per inch 2 0.4335 2.307
dyne per centimetre 2 pascal 0.1000 10.00
pound force per inch 2 (psi) kilopascal (kPa) 6.895 0.1450
kip per inch 2 (ksi) megapascal (MPa) 6.895 0.1450
p o u n d force per inch 2 bar 0.06895 14.50
kitp per inch 2 kilogram per millimetre2 0.7031 1.4223

Work, Heat, and Energy


British thermal unit (Btu) joule 1055. 0.0009479
foot pound-force joule 1.356 0.7375
calorie joule 4.187 0.2389
Btu foot pound-force 778. 0.001285
kilocalorie Btu 3.968 0.252
Btu kilogram metre 107.56 0.009297
Btu per hour watt 0.2929 3.414
watthour joule 3600. 0.0002778
horse power kilowatt 0.7457 1.341

Thermal Properties
(Btu per foot 2, hour, °F) per inch (kilocalorie per metre 2, hour, °C) 0.1240 8.064
per metre
(Btu per foot 2, hour, °F) per inch watt per metre, K 0.144 6.944
Btu per foot 2, hour, °F kilocalorie per metre 2, hour, °C 4.882 0.2048
Btu per foot 2, hour, °F watt per metre 2, K 5.674 0.1762
Btu per foot 2 kilocalories per metre 2 2.712 0.3687
Btu per foot 2 joule per metre 2 11360. 0.00008803

Miscellaneous
pound per foot 3 kilogram per metre 3 16.02 0.06242
p o u n d per gallon (U.S) gram per litre 119.8 0.00835
grains per 100 foot 3 milligram per metre 3 22.88 0.0437
ounces per foot 3 gram per metre 2 305.2 0.003277
p o u n d mole (gas) cubic foot (STP) 359. 0.00279
gram mole (gas) litre (STP) 22.4 0.0446
day minute 1440. 0.000694
week hour 168. 0.00595
year hour 8766. 0.0001141
U.S. bag cement kilogram 42.63 0.02346
gallon (U.S) per bag cement litre per kilogram 0.0888 11.26
ksi (inch) 1/2 megapascal (metre) 1/2 1.0989 0.9100
cubic foot of water (60°F) p o u n d of water 62.37 0.01603
board foot cubic metre 0.00236 423.7
milliampere per foot 2 milliampere per metre 2 10.76 0.0929
gallons (U.S.) per minute metre 3 per day 5.451 0.1835
pound-force newton 4.448 0.2248

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Condensed Metric Practice
Guide for Corrosion"2
Mukiply By To Convert to SI Units:
Area
inch 2 645.2 millimetre 2 (ram 2)
inch 2 6,452 centimetre 2 (cm 2)
foot 2 0.092 90 m e t r e 2 (m 2)
foot 2 929.0 centimetre 2 (cm 2)
yar,d 2 0,836 1 metre 2 (In 2)
Bending M o m e n t (Torque)
dyne centimetre 0.000 000 1 n e w t o n metre (N.m)
pound-force inch 0.113 0 n e w t o n metre (N.m)
pound-force foot 1.356 n e w t o n m e t r e (N.m)
Corrosion Rate
rail p e r year (mpy) 0.025 40 millimetre per year (mm/y) a
rail per year 25.40 m i c r o m e t r e per year (ram/y)
inch per year (ipy) 25.40 millimetre per year (mm/y)
inch p e r m o n t h (ipm) 304.8 millimetre per Y2ear (mrrgy)
milligram per decimetre 2 day (mdd) 0.100 0 g r a m per metre day (g/m 2.d) a
milligram per decimetre 2 day 0.004 167 g r a m p e r metre 2 h o u r (g/m 2.h)
milligram p e r decimetre 2 day 100.0 milligram per metre 2 day (mg/m 2. d)
Current Density
milliampere per millimetre 2 1000. a m p e r e p e r m e t r e 2 (Mm 2)
milliampere p e r centimetre 2 10.00 a m p e r e per metre 2 (A/m 2)
m i c r o a m p e r e p e r centimetre 2 0.010 00 a m p e r e per metre 2 (A/m 2)
milliampere p e r metre 2 0.001 000 a m p e r e per metre 2 (Aim 2)
m i c r o a m p e r e per millimetre 2 1.000 a m p e r e p e r metre z (A/m z)
m i c r o a m p e r e p e r foot 2 10.76 milliampere p e r metre 2 (mA/m 2)
a m p e r e p e r inch 2 1 550. a m p e r e p e r metre 2 (A/m 2)
a m p e r e per foot 2 10.76 a m p e r e p e r metre 2 (A/m 2)
a m p e r e per centimetre 2 10 000. a m p e r e per metre 2 (A/m 2)
a m p e r e per decimetre 2 100.0 a m p e r e per metre 2 (Mm 2)
Energy
British thermal unit (Btu) (60°F) 1055. joule (J)
calorie (mean) 4.190 joule (J)
foot-pound-force 1.356 joule (J)
kilocalorie (mean) 4190. joule (J)
kilowatt hour 3.600 megajoule (MJ)
Flow, Volume Per Unit Time
foot 3 per second 0.028 32 metre 3 p e r second (mS/s)
foot 3 per second 2445. metre 3 per day (m3/d)
foot 3 p e r m i n u t e 40.78 m e t r e 3 per day (ma/d)
gallon (U.S. liquid) per m i n u t e 5.451 m e t r e 3 per day (m3/d)
gallon (U,S. liquid) per h o u r 0.090 85 m e t r e 3 per day (m3/d)
gallon (U.S, liquid) p e r day 0.003 785 metre 3 per day (m3/d)
Force
dyne 0,000 01 newton (N)
kilogram-force 9.807 newton (N)
ounce-force 0.278 0 newton (N)
pound-force 4.448 newton (N)
Length
angstrom 1 x 10-1° m e t r e (m)
angstrom 0.100 0 n a n o m e t r e (nm)
micron 0.001 0 millimetre (mm)
micron 1,000 m i c r o m e t r e (~tm)
mil 0.025 40 millimetre (mm)
mil 25.40 m i c r o m e t r e (~tm)

20

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C O N D E N S E D M E T R I C PRACTICE GUIDE FOR C O R R O S I O N 21

Multiply By To Convert to SI Units:


inch 2.540 centimetre (cm)
inch 25.40 millimetre (mrn)
inch 25 400. micrometre (~tm)
foot 0.304 8 metre (m)
yard 0.914 4 metre (m)
mile 1.609 kilometre (km)
Mass
grain 64.80 milligram (mg)
ounce 28.35 gram (g)
pound 0.453 6 kilogram (kg)
pound 453.6 gram (g)
ton (short, 2000 lb) 907.2 kilogram (kg)
Mass Per Unit Area
ounce-mass per foot 2 305.1 gram per metre 2 (g/m E) 2
pound-mass per foot 2 4.882 kilogram per metre 2 (kg/m)
pound-mass per foot 2 4882. gram per metre 2 (g/zm2) z
pound-mass per inch 2 703.1 kilogram per metre (kg/m)
Mass Per Unit Volume (Density)
gram per centimetre 3 1000. kilogram per metre 3 (kg/m 3)
ounce (mass) per inch 3 1730. kilogram per metre 3 (kg/m 3)
ounce (mass) per gallon (U.S. liquid) 7.489 kilogram per metre 3 (kg/m 3)
ounce (mass) per gallon (U.S. liquid) 7.489 gram per litre (g/L)
pound (mass) per foot 3 16.02 kilogram per metre 3 (kg/m 3)
pound (mass) per gallon (U.S. liquid) 119.8 kilogram per metre 3 (kg/m 3)
Power
Btu (thermochemical) per second 1054. watt (W)
horsepower (electric) 746.0 watt (W)
kilocalorie (thermochemical) per second 4184. watt (W)
Pressure or Stress
atmosphere (normal = 760 tort) 101 300. pascal (Pa)
centimetre of mercury (0°C) 1 333. pascal (Pa)
dyne per centimetre 2 0.100 0 pascal (Pa)
inch of mercury (60°F) 3377. pascal (Pa)
inch of water (60°F) 248.8 pascal (Pa)
kilogram-force per metre 2 9.807 pascal (Pa)
kip per inch 2 6.895 megapascal (MPa)
pound-force per inch 2 6.895 kilopascal (kPa)
pound-force per foot 2 47.88 pascal (Pa)
Stress Intensity
(pound-force per inch 2) inch v2 0.034 75 newton per millimetre 3/2 (N/mITI3/2)
(kip per inch 2) inch u2 34.75 newton per millimetre 3a (N/mm 3/2)
(pound-force per inch 2) inch 1/2 0.001 099 megapascal metre 1/2 (MPa .ml/2) a
(kip per inch 2) inch u2 1.099 megapascal metre 1/2(MPa .ml/2) a
Temperature
degree Celsius TK = ~c + 273.15 kelvin (k)
degree Fahrenheit ~c = (2~e- 32)/1.8 degree Celsius (°C)
Time
hour (mean solar) 3600. second (s)
day (mean solor) 86 400. second (s)
m o n t h (calendar) 2.628 megasecond (Ms)
year (calendar) 31.54 megasecond (Ms)
Velocity (Speed)
inch per second 25.40 millimetre per second (ram/s)
foot per second 0.304 8 metre per second (m/s)
Inch per minute 0.423 3 millimetre per second (ram/s)
mile per hour 1.609 kilometre per hour (kin/h)
mile per hour 0.447 0 metre per second (m/s)
Volume
inch 1 16.39 centimetre 3 (cm 3)
fluid ounce (U.S.) 29.57 centimetre 3 (cm3)
pint (U.S. liquid) 473.2 centimetre 3 (cm 3)
quart (U.S. liquid) 946.4 centimetre 3 (cm a)
gallon (U.S. liquid) 0.003 785 metre a (m 3)
gallon (U.S. liquid) 3.785 litre (L)
1This condensed guide is under the jurisdiction of ASTM Committee G-1 on Corrosion of Metals.
2This guide is based on ASTM E 380.
~Preferred units.

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Multiplication Factors
Multiplication Factor Prefix Symbol
1 000 000 000 000 000 000 = 1018 exa E
1 000 000 000 000 000 = 1015 peta P
1 000 000 000 000 = 1012 tera T
1 000 000 000 = 109 giga G
1 000 000 = 104 mega M
1 000 = 103 kilo k
1 00 = 102 hecto ~ h
1 0 = 101 deka ~ da
0.1 = 10 -1 deci ~ d
0.01 = 10 -2 centi~ C
0.001 = 10 -3 milli m
0.000 001 = 10 ~ micro ~t
0.000 000 001 = 10 -9 nano n
0.000 000 000 001 = 10 -12 pico P
0.000 000 000 000 001 = 10 -15 femto f
0.000 000 000 000 000 001 = 10 -18 atto a
~To be avoided where practical.

Relationships among Some


of the Units Commonly Used
for Corrosion Rates 2
F a c t o r for C o n v e r s i o n to
Unit todd g/m2/d txm/yr mm/yr mils/yr in./yr
Milligrams per square decimetre 1 0.1 36,5/d 0.365/d 1.144/d 0.00144/d
per day (mdd)
Grams per square metre per day 10 1 365/d 0.365/d 14.4/d 0.0144/d
(g/m2/d)
M i c r o m e t r e s p e r y e a r (~m/yr) 0.0274d 0.00274d 1 0.001 0.0394 0.0000394
Millimetres per year (mm/yr) 27.4d 2.74d 1000 1 39.4 0.0394
Mils p e r y e a r (mils/yr) 0.696d 0.0696d 25.4 0.0254 1 0.001
I n c h e s p e r y e a r (in./yr) 696d 69.6d 25400 25.4 1000 1
NOTE: d is metal density in grams per cubic centimetre (g/cm3).

1See ASTM E 380, Practice for Use of the International System of


Units (SI) (The Modernized Metric System).
2 Wrangl6n, G. An Introduction to Corrosion and Protection of
Metals, Chapman and Hall, 1985, p. 233.
22

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Corrosion Rate Calculation
(from Mass Loss)'
Corrosion rate = (K x W)
(A×r×D)
where
K =
a c o n s t a n t (see below),
T =
t i m e of exposure in h o u r s to the nearest 0.01 h,
A =
a r e a in c m 2 to the nearest 0.01 c m 2,
W =
m a s s loss in g, to nearest 1 m g (corrected for any loss d u r i n g
c l e a n i n g (see 9.4)), and
D = density in g / c m 3, (see Appendix X1 of ASTM G 1).

M a n y different units are u s e d to express c o r r o s i o n rates. Using the


above units for T, A, W, and D, the c o r r o s i o n rate can be calculated in a
variety of units w i t h the following a p p r o p r i a t e value of K:

Constant (K) in Corrosion


Corrosion Rate Units Desired Rate Equation
mils p e r y e a r (mpy) 3.45 x 106
inches p e r y e a r (ipy) 3.45 x 103
inches p e r m o n t h (ipm) 2.87 x 102
millirnetres p e r y e a r (ram/y) 8.76 x 104
m i c r o m e t r e s p e r y e a r (~trn/y) 8.76 x 107
p i c o m e t r e s per s e c o n d (pro/s) 2.78 x 104
g r a m s p e r square m e t r e p e r 1 . 0 0 x 104 x D ~
h o u r (g/m 2. h)
m i l l i g r a m s p e r square 2.40 x 106 x D ~
d e c i m e t e r p e r day (mdd)
micrograms per square metre 2.78 x 1 0 6 x D a
p e r s e c o n d ([.tg/m2- s)
aDensity is not needed to calculate the corrosion rate in these units. The density
in the constant K cancels out the density in the corrision rate equation.

1See ASTM G 1, Practice for Preparing, Cleaning and Evaluating


Corrosion Test Specimens.

23

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Corrosion Rate Conversion Factors
weight loss
Mils/year(mpy) = C x × K
area x time

Millimetres/year (mm/y) = 0.0254 mpy

Weight C Factors
Loss Area Hour Day Week Month Year
mg cm 2 437 18.2 2.59 0.598 0.0498
dm 2 4.37 0.182 0.0259 5.98 x 10 -3 4.98 x 104
m2 0.0437 1.82 × 10 -3 2 . 5 9 × 10 -~ 5 . 9 8 x 10 -5 4.98 × 10 -6
in 2 67.7 2.82 0.402 0.0927 7.72 x 10 -3
ft 2 0.470 0.0196 2 . 7 9 × 10 -3 6.44 × 104 5.36 × 10 -5
g cm 2 4 3 7 × 103 182 x 102 2590 598 49.8 K is a d e n s i t y factor
dm 2 4370 182 25.9 5.98 0.498 K = 1.000 for c a r b o n steel
m2 43.7 1.82 0.259 0.0598 4 . 9 8 x 10 -3 K factors for o t h e r alloys
in 2 6 7 7 × 102 2820 402 92.7 7.72 are given o n t h e next page
ft 2 470 19.6 2.79 0.644 0.0536
lb cm 2 198 × 106 825×104 118 x 104 2 7 1 x 103 226x 102
dm 2 198 × 10 4 825 X 102 118 X 102 2710 226
m2 198 × 102 825 118 27.1 2.26
in 2 307 × 105 128 × 104 182 x 103 4 2 0 x 102 3500
ft 2 213 × 103 8880 1270 292 24.3

EXAMPLE: A 5.0 square i n c h s p e c i m e n of copper h a s a weight loss of 218 nag in 40 h o u r corrosion test.

218
mpy = 67.7 × - - × 0 . 8 8 = 65
5.0×40

mm/yr = 0 . 0 2 5 4 × 65 = 1.65

iSee NACE Corrosion Engineers Reference Book, Second Edition,


R. S. Treseder, R. Baboian, a n d C. G. Munger, Eds., NACE
International, H o u s t o n , TX, 1991.

24

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Densities of Common Alloys
(K = r a t i o o f c a r b o n steel d e n s i t y to t h a t o f alloy)

Density Density
UNS Common Name g/cm3 K UNS Common Name g/cm 3

A91100 Al 1100 2.72 2.89 N06007 G Alloy 8.34 0.94


A93003 Al 3003 2.74 2.87 N06022 C-22 Alloy 8.69 0.90
A95052 Al 5052 2.68 2.93 N06030 G-30 Alloy 8.22 0.96
A96061 AI 6061 2.70 2.91 N06455 C-4 Alloy 8.64 0.91
A97075 A1 7075 2.80 2.81 N06600 600 Alloy 8.47 0.93
C11000 ETP Copper 8.94 0.88 N06601 601 Alloy 8.11 0.97
C22000 Commercial Bronze 8.89 0.88 N06625 625 Alloy 8.44 0.93
C23000 Red Brass 8.75 0.90 N06985 G-3 Alloy 8.30 0.95
C26000 Cartridge Brass 8.53 0.92 N07001 Waspaloy 8.19 0.96
C27000 Yellow Brass 8.39 0.94 N07041 Rene 41 8.25 0.95
C28000 Muntz Metal 8.39 0.94 N07718 718 Alloy 8.19 0.96
C44300 Admiralty brass. As 8.52 0.92 N07750 X-750 Alloy 8.28 0.95
C46500 Naval Brass. As 8.41 0.93 N08020 20Cb-3 8.08 0.97
C51000 Phosphor Bronze A 8.86 0.89 N08024 20Mo-4 8.11 0.97
C52400 Phosphor Bronze D 8.78 0.90 N08026 20M0-6 8.13 0.97
C61300 A l u m i n u m Bronze 7 % 7.69 1.00 N08028 Sanicro 28 8.0 0.98
C61400 A l u m i n u m Bronze D 7.78 1.01 N08366 AL-6X 8.0 0.98
C63000 Ni-Al Bronze 7.58 1.04 N08800 800 Alloy 7.94 0.99
C65500 High-Silicon Bronze 8.52 0.92 N08825 825 Alloy 8.14 0.97
C67500 Manganese Bronze A 8.36 0.94 N08904 904L Alloy 8.0 0.98
C68700 A l u m i n u m Brass. As 8.33 0.94 N08925 25-6Mo 8.1 0.97
C70600 9-10 Copper-Nickel 8.94 0.88 N09925 925 Alloy 8.05 0.98
C71500 70-30 Copper-Nickel 8.94 0.88 N10003 N Alloy 8.79 0.89
C75200 Nickel Silver 8.73 0.90 N10004 W Alloy 9.03 0.87
C83600 Ounce Metal 8.80 0.89 N10276 C-276 Alloy 8.89 0.88
C86500 Manganese Bronze 8.3 0.96 N10665 B-2 Alloy 9.22 0.85
C90500 Gun Metal 8.72 0.90 R03600 Molybdenum 10.22 0.77
C92200 M Bronze 8.64 0.91 R04210 Niobium 8.57 0.92
C95700 Cast Mn-Ni-A1 Bronze 7.53 1.04 R05200 Tantalum 16.60 0.47
C95800 Cast Ni-A1 Bronze 7.64 1.03 R50250 Titanium, Gr 1 4.54 1.73
F10006 Gray Cast Iron 7.20 •.09 R50400 Titanium, Gr 2 4.54 1.73
F20000 Malleable Cast Iron 7.27 1.08 R53400 Titanium, Gr 12 4.52 1.74
F32800 Ductile Iron 7.1 1.11 R56400 Titanium, Gr 5 4.43 1.77
F41002 Ni-Resist Type 2 7.3 1.06 R60702 Zr 702 6.53 1.20
F43006 Ductile Ni-Resist, D5 7.68 1.02 $20100 201 SS 7.94 0.99
1747003 Duriron 7.0 1.12 $20200 202 SS 7.94 0.99
G10200 1020 Carbon Steel 7.86 1.00 $30400 304 SS 7.94 0.99
G41300 4130 Steel 7.86 1.00 $30403 304L SS 7.94 0.99
J91150 CA-15 Cast SS 7.61 1.03 $30900 309 SS 7.98 0.98
J91151 CA-15M Cast SS 7.61 1.03 $31000 310 SS 7.98 0.98
J91540 CA-6NM Cast SS 7.7 1.02 $31254 254 SMO 8.0 0.98
J92600 CF-8 Cast SS 7.75 1.01 $31500 3RE60 7.75 1.01
J92800 CF-3MN Cast SS 7.75 1.01 $31600 316 SS 7.98 0.98
J92900 CF-8M Cast SS 7.75 1.01 $31603 316L SS 7.98 0.98
J94204 HK-40 Cast SS 7.75 1.01 $31700 317 SS 7.98 0.98
J95150 CN-7M Cast SS 8.00 0.98 $32100 321 SS 7.94 0.99
Kl1597 1.25Cr-0.5Mo Steel 7.85 1.00 $32550 Ferralium 255 7.81 1.01
K81340 9Ni Steel 7.86 1.00 $32950 7 Mo Plus 7.75 1.01
L51120 Chemical Lead 11.3 0.70 $34700 347 SS 8.03 0.98
Ml1311 MgAZ31B 1.77 4.44 $41000 410 SS 7.70 1.02
N02200 Nickel 200 8.89 0.88 $43000 430 SS 7.72 1.02
N04400 400 Alloy 8.80 0.89 $44600 446 SS 7.65 1.03
N05500 K-500 Alloy 8.44 0.93 $50100 5Cr-0.5Mo Steel 7.82 1.01
N06002 X Alloy 8.23 0.95 $50400 9Cr-lMo Steel 7.67 1.02

1See NACE Corrosion Engineers Reference Book, Third Edition,


R. Baboian, Ed., NACE International, 2002, p.105.

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Table 1--Overvoltage values
n=blogi/i 0

HYDROGEN OVERVOLTAGE
Ovevoltage (Volts) at 1 ma/cm 2
Material 25°C, 2 N HzSO 4
Platinum (Platinized) 0.0005
Platinum (Smooth) 0.15
Palladium 0.05
Nickel 0.25
Iron 0.40
Tungsten 0.2
Molybdenum 0.15
Bismuth 0.70
Lead 1.2
Tin 0.65
Carbon 0.5
Aluminum 0.70
Mercury 1.15
Cadminum 0.9
Zinc 0.85
Gold 0.15
Silver 0.30
Copper 0.5

OXYGEN OVERVOLTAGE
Overvoltage (Volts) at 1 maJcm2
Material 25°C, 1 N KOH
Platinum (Platinized) 0.52
Platinum (Smooth) 0.82
Nickel 0.53
Graphite 0.89
Gold 0.96
Silver 0.73
Copper 0.58

Data from: The Encyclopedia of Electrochemistry, Reinhold, NY, 1964. Glasstone's Textbook of Physical Chemistry, Van
Nostrand, NY, 1958. Kochler's Electrochemistry, 2nd Edition, Wiley, NY, 1950. Uhilg's Corrosion and Corrosion Control,
Wiley, NY, 1971.

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Standard Reference Potentials
and Conversion Table'
Reference Potentials and Conversion Factors
Thermal Temperature
Potential (V) at 25°C CoefficientA
Electrode E '~ E" c (mV/°C)

(Pt)/H2(ct = 1)/H ÷ (ct = 1)(SHE) 0.000 ... +0.87


Ag/AgCI/1M KC1 +0.235 ... +0.25
Ag/AgC1/0.6 M C1-(seawater) +0.25 . . . . . .
Ag/AgCI/0.1 M C1- +0.288 ... +0.22
Hg/Hg2C12/sat KC1 (SCE) +0.241 +0.244 +0.22
Hg/Hg2C12/1M KC1 +0.280 0.283 +0.59
Hg/Hg2C12/0.1M KC1 +0.334 0.336 +0.79
Cu/CuSO 4 sat +0.30 ... +0.90
Hg/Hg2SO4/H2SO4 D +0.616 . . . . . .
ATo convert from thermal to isothermal temperature coefficients, subtract 0.87 mV/°C. Thus the isothermal
temperature coefficient for Ag-AgC1is - 0.62 mV/°C.
BE' is the standard potential for the half cell corrected for the concentration of the ions.
c E" also inclues the liquid junction potentials for a saturated KC1 salt bridge.
To convert from one scale to another, add the value indicated.
D Potential given is for a range of H2SO 4 molalities as discussed in Ref (10).

From (E') To SHE Scale To SCE Scale (E')


H2/H ÷ ... -0.241
Ag/AgC1/1 M KC1 +0.235 -0.006
Ag/AgC1/0.6 M C1 ( s e a w a t e r ) +0.25 +0.009
Ag/AgC1/0.1 M C1 +0.288 +0.047
Hg/HgE/C12/sat KC1 (SCE) +0.241 ...
Hg/Hg2C12, 1 M +0.280 +0.039
Hg/HgEC12, 0.1 M +0.334 0.093
Cu/CuSO 4 sat +0.30 +0.06
Hg/Hg2SO4/H2SO 4 +0.616 ...
Example:
An e l e c t r o d e p o t e n t i a l o f +1.000 V v e r s u s SCE w o u l d b e (1.000 + 0.241) ± +1.241 V v e r s u s SHE.
An e l e c t r o d e p o t e n t i a l o f - 1 . 0 0 0 V v e r s u s SCE w o u l d give (-1.000 + 0.241) = - 0 . 7 5 9 V v e r s u s
SHE.

1See ASTM G 3, Practice for Conversions Applicable to Electrochemical


Measurements in Corrosion Testing.

27

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Equivalent Weight Values
for Metals and Alloys
Elements Lowest Second Third Fourth
Common w/Constant Variable Equivalent Variable Equivalent Element/ Equivalent Element/ Equivalent
Designation UNS Valence Valence Weight Valence Weight Valence Weight Valence Weight
Aluminum Alloys
AA1100 A91100 A1/3 8.99
AA2024 A92024 Al/3, Mg/2 Cu/1 9.38 Cu/2 9.32
AA2219 A92219 Al/3 Cu/1 9.51 Cu/2 9.42
AA3003 A93003 AI/3 Mn/2 9.07 Mn/4 9.03 Mn 7 8.98
AA3004 A93004 Al/3, Mg/2 Mn/2 9.09 Mn/4 9.06 Mn 7 9.00
AA5005 A95005 AF3, Mg/2 9.01
AA5050 A95050 A1/3, Mg/2 9.03
AA5052 A95052 A1/3, Mg/2 9.05
AA5083 A95083 AI/3, Mg/2 9.09
AA5086 A95086 A1/3, Mg/2 9.09
AA5154 A95154 Al/3, Mg/2 9.08
AA5454 A95454 Al/3, Mg/2 9.06
AA5456 A95456 A1/3, Mg/2 9.11
AA6061 A96061 AF3, Mg/2 9.01
AA6070 A96070 Al/3, Mg/2, 8.98
Si/4
AA6101 A96161 AI/3 8.99
AA7072 A97072 AI/3, Zn/2 9.06
AA7075 A97075 A1/3, Zn/2, Cu/1 9.58 Cu]2 9.55
Mg/2
AA7079 A97079 Al/3, Zrg2, 9.37
Mg/2
AA7178 A97178 AI/3, Zn/2, Cu/1 9.71 Cu/2 9.68
Mg/2
Copper AUoys
CDAll0 Cl1000 Cu/1 63.55 Cu/2 31.77
CDA220 C22000 Zn/2 Cu/1 58.07 Cu/2 31.86
CDA230 C23000 Zrd2 Cu/1 55.65 Cu/2 31.91
CDA260 C26000 Zn/2 Cu/1 49.51 Cu/2 32.04
CDA280 C28000 Zn/2 Cu/1 46.44 Cu/2 32.11
CDA444 C44300 Zn/2 Cu/1, Sn/2 50.42 Cu/1, Sn/4 50.00 Cu/2, Sn/4 32.00
CDA687 C68700 Zn/2, A1/3 Cu/1 48.03 Cu/2 30.29
CDA608 C60800 A1/3 Cu/1 47.114 Cu/2 27.76
CDA510 C51000 Cu/1, Sn/2 63.32 Cu/1, Srd4 60.11 Cu/2, Sn/4 31.66
CDA524 C52400 Cu]l, Sn/2 63.10 Cu/1, Sn/4 57.04 Cu/2, Sn/4 31.55
CDA655 C65500 Si/4 Cu/1 50.71 Cu/2 28.51
CDA706 C70600 Ni/2 Cu/1 56.92 Cu/2 31.51
CDA715 C71500 Ni/2 Cu/1 46.69 Cu/2 30.98
CDA752 C75200 Nil2, Zn/2 Cu/1 46.38 Cu/2 31.46
Stainless Steels
304 $30400 Ni/2 Fe/2, Cr/3 25.12 Fe/3, Cr/3 18.99 Fe/3, Cr/6 15.72
321 $32100 Ni/2 Fe/2, Cr/3 25.13 Fe/3, Cr/3 19.08 Fe/3, Cr/6 15.78
309 $30900 Ni/2 Fe/2, Cr/3 24.62 Fe/3, Cr/3 19.24 Fe/3, Cr/6 15.33
310 $31000 Ni/2 Fe/2, Cr/3 24.44 Fe/3, Cr/3 19.73 Fe/3, Cr/6 15.36
316 $31600 Ni/2 Fe/2, Cr/3, Mo/3 25.50 Fe/3, Cr/3, Mo/4 25.33 Fe/3, Cr/6, Mo/6 19.14 Fe/3, Cr/6, Mo/6 16.111
317 $31700 Ni/2 Fe/2, Cr/3, Mo/3 25.26 Fe/3, Cr/3, Mo/4 25.03 Fe/3, Cr/6, Mo/6 19.15 Fe/3, Cr/6, Mo/6 15.82
410 $41000 Fe/2, Cr/3 25.94 Fe/3, Cr/3 18.45 Fe/3, Cr/6 16.28
430 $43000 Fe/2, Cr/3 25.30 Fe/3, Cr/3 18.38 Fe/3, Cr/6 15.58
446 $44600 Fe/2, Cr/3 24.22 Fe/3, Cr/3 18.28 Fe/3, Cr/6 14.46
20CD3 ~ N08020 Ni/2 Fe/2, Cr/3, Mo/3 23.98 Fe/2, Cr/3, 23.83 Fe/3, Cr/3, 18.88 Fe/3, Cu/6, Mo/6, 15.50
Cu/1 Mo/4, Cu/1 Mo/6, Cu/2 Cu/2

1S e e A S T M G 102, P r a c t i c e f o r C a l c u l a t i o n o f C o r r o s i o n R a t e s a n d
Related Information from Electrochemical Measurements.

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EQUIVALENT WEIGHT VALUES FOR METALS AND ALLOYS 29

Elements Lowest Second Third Fourth


Common w/Constant Variable Equivalent Variable Equivalent Element/ Equivalent Element/ Equivalent
Designation UNS Valence Valence Weight Valence Weight Valence Weight Valence Weight
Nickel Alloys
200 N02200 Ni/2 29.36 Ni/3 19.57
400 N04400 Ni/2 Cu/1 35.82 Cu/2 30.12
600 N06600 Ni/2 Fe/2, Cr/3 26.41 Fe/3, Cr/3 25.44 Fe/3, Cr/6 20.73
800 N08800 Ni/2 Fe/2, Cr/3 25.10 Fe/3, Cr/3 20.76 Fe/3, Cr/6 16.59
825 N08825 Ni/2 Fe/2, Cr/3, Mo/3, 25.52 Fe/3, Cr/3, Mo/ 25.32 Fe/3, Cr/3, Mo! 21.70 Fe/3, Cr/6, Mo/6, 17.10
Cu/1 4, Cu/1 6, Cu/2 Cu/2
B N10001 Ni/2 Mo/3, Fe/2 30.05 Mo/4, Fe/2 27.50 Mo/6, Fe/2 23.52 Mo/6, Fe/3 23.23
C-22b N06022 Ni/2 Fe/2, Cr/3, Mo/3, 26.04 Fe/2, Cr/3, Mo/ 25.12 Fe/2, Cr/3, Mo/ 23.28 Fe/3, Cr/6, Mo/6, 17.88
W/4 4, W/4 6, W/6 W/6
C-276 N10276 Ni/2 Fe/2, Cr/3, Mo/3, 27.09 Cr/3, Mo/4 25.90 Fe/2, Cr/3, Mo/ 23.63 Fe/3, Cr!6, Mo/6 19.14
W/4 6, W/6 W/6
G N06007 Ni/2 (1) 25.46 (2) 22.22 (3) 22.04 (4) 17.03

(1) = Fe/2, Cr/3, Mo/3, Cu/1, Nb/4, (3) = Fe/3, Cr/3, Mo/6, Cu/2, Nb/5, Mn/2
Mn/2

(2) = Fe/2, Cr/3, Mo/3, Cu/2, Nb/5, (4) = Fe/3, Cr/6, Mo/6, Cu/2, Nb/5, Mn/4
Mn/2
Carbon Steel
Fe/2 27.92 Fe/3 18.62
Other Metals
Mg M14142 Mg/2 12.15
Mo R03600 Mo/3 31.98 Mo/4 23.98 Mo/6 15.99
Ag P07016 Ag/1 107.87 Ag/2 53.93
Ta R05210 TaJ5 36.19
Sn L13002 Srg2 59.34 Sn/4 29.67
Ti R50400 Ti/2 23.95 Ti/3 15.97 Ti/4 11.98
Zn Z19001 Zn/2 32.68
Zr R60701 Zn/4 22.80
Pb L50045 Pb/2 103.59 Pb/4 51.80

aRegistered trademark Carpenter Technology.


bRegistered trademark Haynes International.
NOTE 1 --Allo ying e l e m e n t s at c o n c e n t r a t i o n s b e l o w 1 % by m a s s w e r e n o t i n c l u d e d i n t he c a l c u l a t i o n , for e x a m p l e , t h e y w e r e c o n s i d e r e d
p a r t of t h e b a s i s metal.
NOTE 2 - - M i d r a n g e v a l u e s w e r e a s s u m e d for c o n c e n t r a t i o n s of a l l o y i n g e l e m e n t s .
NOTE 3 - - O n l y c o n s i s t e n t v a l e n c e g r o u p i n g s w e r e used.
NOTE 4---E q uation 4 in ASTM G 102 w a s u s e d to m a k e t h e s e c a l c u l a t i o n s .

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Values of Constants for Use
in Faraday's Equation'
Calculation o f Corrosion Rate--Faraday's L a w c a n b e u s e d to
calculate t h e c o r r o s i o n rate, e i t h e r i n t e r m s of p e n e t r a t i o n r a t e
(CR) o r m a s s loss rate (MR)

CR = K 1~ - E W

MR = K2icorEW
where
CR is given in m m / y r , icor in gA/cm 2,
K 1 = 3.27 104 , m m g / g A c m y r ,
9 = d e n s i t y in g / c m 3, (see ASTM G 1 for d e n s i t y values
for m a n y m e t a l s a n d alloys u s e d in c o r r o s i o n testing),
MR = g/m2d, a n d
K 2 = 8.954 x 10 -3, g cm2/gA m 2 d.

O t h e r values for K 1 a n d K 2 for d i f f e r e n t u n i t s y s t e m s are given in t h e


following table.

Rate
A
Penetration
Rate Unit (CR) Icor Unit p Unit KI Units of KIa
mpy ~i/cm 2 g/cm 3 0.1288 mpy g/gA cm
mm/yr bb A/m2b kg/m 3b 327.2 m m kg/A m y
mm/yr gA/cm2 g/cm 3 3.27 x 10-3 m m g/gA cm y
B
Mass Loss Rate
Unit Ico r U n i t K2 U n i t s o f --K2a

g/m2db A/m 2b 0.8953 g/Ad


mg/dm2d (mad) I~dczr~2 0.0895 mg cm2/gA dm 2 d
mg/dm~d (mdd) 8.953 x 10.3 mg mZtA dm 2 d
a .
EW is assumed to be dimensionless.
bsI unit.

1See ASTM G 102, Practice for Calculation of Corrosion Rates and


Related Information from Electrochemical Measurements.

30

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Physical Properties of Gases
and Liquids
Explosive Limits
Melting Boiling Percent by Vol. in
Molecular Density, Point, Point, Auto-Ignition Air
Name Formula Weight g/L °C oC Point °C Lower Upper
Acetylene C2H 2 26.04 1.173 -81 -83.6 335 2.5 80.0
subl.
Air 1.2929
Ammonia NH 3 17.03 0.7710 -77.7 -33.4 780 16.0 77.0
Argon Ar 39.94 1.784 -189.2 -185.7
Butane-n C4H10 58.12 0.601 -138 0.6 430 1.6 8.5
Butylene-n C4H 8 56.10 0.595 -185 -6.3 1.7 9.0
Carbon dioxide CO 2 44.01 1.977 -57 -78.5
5 atm. subl.
Carbon monoxide CO 28.01 1.250 -207 -191 650 12.5 74.2
Chlorine C12 70.91 3.214 - 101 -34
Ethane C2H 6 30.07 0.572 -172 -88.6 510 3.1 15.0
Ethylene C2H 4 28.05 0.384 -169 -103.7 543 3.0 34.0
Helium He 4.003 0.1785 -272 -268.9
Heptane-n C7H16 100.20 0.684 g/cm 3 -90.6 98.4 233 1.0 6.0
Hexane-n C6H14 86.17 0.6594 g/cm 3 -95.3 68.7 248 1.2 6.9
Hydrogen H2 2.016 0.0899 -259.2 -252.8 580 4.1 74.2
Hydrogen chloride HC1 36.47 1.639 -112 -84
Hydrogen fluoride HF 20.01 0.921 -92.3 19.5
Hydrogen sulfide HES 34.08 1.539 -84 -62 4.3 45.5
Methane CH 4 16.04 0.7168 -182.5 -161.5 538 5.3 13.9
Nitrogen N2 28.016 1.2506 -209.9 -195.8
Octane-n C8H18 114.23 0.7025 g/cm 3 -56.8 125.7 232 0.8 3.2
Oxygen 02 32.00 1.4290 -218.4 -183.0
Pentane-n C5H12 72.15 0.626 g/cm 3 -131 36.2 310 1.4 8.0
Propane C3H 8 44.09 0.501 -189 -44.5 465 2.4 9.5
Propylene C3H 6 42.05 0.519 - 184 -48 458 2.0 11.1
Sulfur dioxide SO z 64.06 2.926 -75.7 -10.0
Density of gases in g/L at 0°C and 760 mm Hg.
Density of liquids in g/cm 3 at 20°/4°C.

31

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Physical Properties of Elements
Density
Atomic g/cm3 Melting Crystal
Symbol Weight 20°C Valencies Point, °C Structure
Aluminium A1 29.98 2.70 3 660 1
Antimony Sb 121.75 6.68 3/5 630 5
Argon Ar 39.948 1.784 a 0 -189.2 1
Arsenic As 74.92 5.73 3/5 814 5
Barium Ba 137.34 3.5 2 725 2
Beryllium Be 9.01 1.85 2 1280 3
Bismuth Bi 208.98 9.80 3/5 271 5
Boron B 10.81 2.3 3 2300 --
Bromine Br 79.91 3.12 1/3/5/7 -7.2 6
Cadmium Cd 112.40 8.65 2 321 3
Calcium Ca 40.08 1.55 2 842 1
Carbon C 12.01 2.25 2/3/4 3550 4
Chlorine C1 35.45 1.56 b 1/3/5/7 -103 7
Chromium Cr 52.00 7.2 2/3/6 1890 2
Cobalt Co 58.93 8.9 2/3 1495 3
Copper Cu 63.54 8.92 1/2 1083 1
Fluorine F 19.00 1.69 a 1 223 --
Gold Au 196.97 19.32 1/3 1063 1
Helium He 4.003 0.177 a 0 -272.2 --
Hydrogen H 1.008 0.090 b 1 -259.2 4
Iodine I 126.90 4.93 1/3/5/7 113.5 6
Iron Fe 55.85 7.87 2/3/6 1535 2
Lead Pb 207.19 11.35 2/4 327.4 1
Lithium Li 6.94 0.53 1 186 2
Magnesium Mg 24.31 1.74 2 651 3
Manganese Mn 54.94 7.2 2/3/4/6/7 1260 10
Mercury Hg 200.59 13.55 1/2 -38.9 5
Molybdenum Mo 95.94 10.2 2/3/4/5/6 2620 2
Nickel Ni 58.71 8.90 2/3 1455 1
Niobium Nb 92.91 8.55 3/5 2500 2
Nitrogen N 14.007 1.25 a 3/5 -209.9 4
Oxygen O 15.9994 1.429 a 2 -218.4 10
Phosphorus P 30.98 1.82 3/5 44.1 10
Platinum Pt 195.09 21.37 2/4 1773 1
Potassium K 39.10 0.87 1 62.3 2
Rhodium Rh 102.91 12.5 1/2/3/4 1966 1
Selenium Se 78.96 4.8 2/4/6 220 4
Silicon Si 28.09 2.42 4 1420 8
Silver Ag 107.87 10.50 1 960.5 1
Sodium Na 22.99 0.97 1 97.5 2
Sulfur S 32.06 2.07 2/4/6 119 9
Tantalum Ta 180.95 16.6 3/5 2996 2
Tin Sn 118.69 7.31 2/4 231.9 7
Titanium Ti 47.90 4.5 2/3/4 1800 3
Tungsten W 183.85 19.3 2/4/5/6 3370 2
Vandium V 50.94 5.96 2/3/4/5 1710 2
Zinc Zn 65.73 7.14 2 419.5 3
Zirconium Zr 91.22 6.4 4 1857 3

ag/L (0°C and 760 mm Hg)


bLiquid at boiling point -37°C
CCrystal structures:
1 Face-centered cubic 5 Rhombohedral 9 Face-centered orthorhombic
2 Body-centered cubic 60rthorhombic 10 Cubic (complex)
3 Close packed hexagonal 7 Tetragonal
4 Hexagonal 8 Diamond cubic

32

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Densities for a Variety
of Metals and Alloys
UNS Number Alloy Density, g/cm3
MuminumAlloys
A91100 1100 2.71
A91199 1199 2.70
A92024 2024 2.78
A92219 2219 2.84
A93003 3003 2.73
A93004 3004 2.72
A95005 5005 2.70
A95050 5050 2.69
A95052 5052 2.68
A95083 5083 2.66
A95086 5086 2.66
A95154 5154 2.66
A95357 5357 2.69
A95454 5454 2.69
A95456 5456 2.66
A96061 6061 2.70
* 6062 2.70
A96070 6070 2.71
A96101 6101 2.70
A97075 7075 2.81
A97079 7079 2.75
A97178 7178 2.83

S t a i n l e s s Steels
$20100 Type 201 7.9z
$20200 Type 202 7.9~
$20200 Type 302 7.9z
$30400 Type 304 7.9z
$30403 Type 304L 7.9z
$30900 Type 309 7.9L
$31000 Type 310 7.9
$31100 Type 311 7.9
$31600 Type 316 7.9
$31603 Type 316L 7.9
$31700 Type 317 7.9
$32100 Type 321 7.94
$32900 Type 329 7.98
N06330 Type 330 7.98
$34700 Type 347 8.03
$41000 Type 410 7.70
$43000 Type 430 7.72
$44600 Type 446 7.65
$50200 Type 502 7.82

Other Ferrous Metals


FIXXXX Gray cast iron 7.20
GXXXXX-KXXXXX Carbon steel 7.86
* Silicon iron 7.00
KXXXXX Low alloy steels 7.85

1See ASTM G 1, Practice for Preparing, Cleaning, and Evaluating


Corrosion Test Specimens.

33

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34 C O R R O S I O N T E S T S AND S T A N D A R D S MANUAL

UNS Number Alloy Density, g/cm3

Copper Alloys
C38600 Copper 8.94
C23000 Red brass 230 8.75
C26000 Cartridge brass 260 8.52
C28000 Muntz metal 280 8.39
* Admiralty 442 8.52
C44300 Admiralty 443 8.52
C44400 Admiralty 444 8.52
C44500 Admiralty 445 8.52
C68700 Aluminum brass 687 8.33
C22000 Commercial bronze 220 8.80
C60800 Aluminum bronze, 5 % 608 8.16
* Aluminum bronze, 8 % 612 7.78
* Composition M 8.45
* Composition G 8.77
C51000 Phosphor bronze, 5 % 510 8.86
C52400 Phosphor bronze, 10 % 524 8.77
* 85-5-5-5 8.80
C65500 Silicon bronze 655 8.52
C70600 Copper nickel 706 8.94
C71000 Copper nickel 710 8.94
C71500 Copper nickel 715 8.94
C75200 Nickel silver 752 8.75
Lead
L53305-53405 Antimonial 10.80
L5XXXX Chemical 11.33
Nickel Alloys
N02200 Nickel 200 8.89
N04400 Nickel copper 400 8.84
N06600 Nickel chromium iron alloy 600 8.51
N06625 Nickel chromium molybedenum 8.14
alloy 625
N08825 Iron nickel chromium alloy 825 8.14
N08020 Iron nickel chromium alloy 20 8.08
Cb-3
* Iron nickel chromium cast 8.02
alloy 20
N 10665 Nickel molybedenum alloy B2 9.2
N 10276 Nickel chromium molybdenum 8.8
alloy C-276
N06985 Nickel chromium molybdenum 8.3
alloy G-3
Other Metals
MIXXXX Magnesium 1.74
R03600 Molybdenum 10.22
P04980 Platinum 21.45
P07016 Silver 10.49
R05200 Tantalum 16.60
L13002 Tin 7.30
R50250 Titanium 4.54
Z13001 Zinc 7.13
R60001 Zirconium 6.53
NOTES--All UNS numbers that include the letter X indicate a series
of numbers under one category. An asterisk(*) indicates that a UNS
number not available.

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Density of Materials
Density Density Density Density
Material (g/cm3) (lb/in. 3) Material (g/cm3) (lb/in.3)

Iridium 22.65 0, 82 Nickel aluminide (NiA1) 6.05 0.22


Osmium 22.61 0.82 Gallium 5.91 0.21
Platinum 21.45 0.77 Zirconia (partially stabilized) 5.70 0.21
Rhenium 21.00 0.76 Germanium 5.32 0.19
Tungsten 19.40 0.70 Titanium nitride 5.29 0.19
Gold 19.30 0.70 Titanium carbide 4.94 0.18
Uranium 19.07 0.69 Titanium diboride 4.52 0.16
Tungsten carbide 17.20 0.62 Titanium 4.51 0.16
Tantalum 16.60 0.60 Ti-6A1-4V 4.50 0.16
Tantalum carbide (TaC) 14.53 0.52 Titanium dioxide 4.25 0.15
Hafnium 13.10 0.47 Aluminum oxide 3.98 0.14
Ruthenium 12.45 0.45 Spinel (MgO. Al303) 3.57 0.13
Rhodium 12.41 0.45 Aluminum nitride 3.26 0.12
Palladium 12.02 0.43 Sialon 3.20 0.12
Thallium 11.85 0.43 Silicon nitride 3.19 0.12
Thorium 11.50 0.42 Mullite(3Al203 • 2SIO2) 3.16 0.11
Lead 11.34 0.41 Silicon carbide 3.10 0.11
Silver 10.49 0.38 Hydroxyapatite 3.10 0.00
Molybdenum 10.20 0.37 Aluminum carbide 2.99 0. I 1
Bismuth 9.80 0.35 Wollastonite 2.90 0.10
Thulium 9.31 0.34 Aluminum copper alloy 2.84 0.10
Cast high leaded tin bronze 9.29 0.34 Aluminum zinc alloy 2.78 0.10
Nickel-moly (Hastelloy B-2) 9.20 0.33 Aluminum 2.70 0.10
Copper 8.96 0.32 Cordierite 2.65 0.10
Nickel 8.90 0.32 E-glass fiber 2.62 0.10
Copper nickel (64Cu-14Ni-227n) 8.85 0.32 Pyrex glass 2.52 0.09
Cobalt 8.85 0.32 Boron carbide 2.52 0.09
Nickel silver 8.70 0.31 Boron 2.40 0.09
Brass (61.5Cu-3Pb-35.5Zn) 8.70 0.31 Silicon 2.33 0.08
Bronze (57Cu, 40Zn, 39Pb) 8.70 0.31 PTFE (polytetrafluoroethylene) 2.30 0.08
Cadmium 8.65 0.31 Graphite 2.26 0.08
Niobium (Columbium) 8.57 0.31 Boron nitride 2.25 0.08
Nickel chromimum cobalt alloy 8.21 0.30 Sulfur 2.07 0.07
Nickel-chromium (Inconel 718) 8.20 0.30 Unsaturated polyester 2.00 0.07
Copper zinc alloy 8.19 0.30 Polyimide thermoset 2.00 0.07
Maraging steel 8.02 0.29 Phenolic resin 1.99 0.07
Austenitic stainless steel 8.00 0.29 Beryllium 1.85 0.07
Iron-nickel (Invar) 8.00 0.29 Phosphorus 1.83 0.07
Iron 7.87 0.28 Carbon fiber 1.74 0.06
Nickel iron superalloy 7.86 0.28 Magnesium 1.74 0.06
Chromium steel 7.83 0.28 PPS (polyphenylene sulfide) 1.67 0.06
Nonresulfurized carbon steel 7.83 0.28 Nylon 6 1.64 0.06
Stainless steel (17Cr-4Ni) 7.81 0.28 Acetal resin 1.57 0.06
Hot work tool steel 7.75 0.28 Epoxy resin 1.56 0.06
Aluminum bronze 7.64 0.28 Calcium 1.55 0.06
Babbitt 7.50 0.27 Rubidium 1.53 0.06
Samarium 7.49 0.27 Polycarbonate 1.53 0.06
Manganese 7.43 0.27 Aramid fiber 1.45 0.05
Indium 7.31 0.26 Aromatic polyamide 1.44 0.05
Niobium nitride 7.30 0.26 Bismaleimide resin 1.36 0.05
Tin 7.30 0.26 Silicone 1.35 0.05
Cerium dioxide 7.28 0.26 PEEK (polyetheretherketone) 1.32 0.05
Austempered ductile iron 7.20 0.26 Cellulose acetate 1.30 0.05
Pewter (Sn,Sb,Cu) 7.20 0.26 H u m a n Bone 1.30 0.05
Chromium 7.19 0.26 Polyurethane 1.27 0.05
Zinc 7.13 0.26 ABS (acrylonitrile butadiene styrene) 1.26 0.05
Neodymium 7.00 0.25 Polysulfone 1.24 0.04
Praseodymium 6.77 0.24 Acrylic 1.19 0.04
Cerium 6.77 0.24 Polypropylene 1.05 0.04
Chromium carbide 6.70 0.24 Sodium 0.97 0.04
Antimony 6.65 0.24 PE (polyethylene) 0.95 0.03
Zirconium 6.49 0.23 UHMWPE
Lanthanum 6.15 0.22 (ultrahigh molecular weight PE) 0.93 0.03
Vanadium 6.11 0.22 Potassium 0.86 0.03
Lithium 0.53 0.19
Source: GEM 2001, p. 35, ASM 2000.

35

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Coefficients of Thermal Expansion
of Common Alloys
UNS Common Name in/in/°F x 10-6 mrn/mrrd°C x 10-6 Range, °C

A24430 Cast A1 B443.0 12.3 22 20-100


A91100 A1 1100 13.1 24 20-100
A95052 Al 5052 13.2 24 20-100

C11000 ETP Copper 9.4 16.9 20-100


C23000 Red Brass 10.4 18.7 20-300
C28000 M u n t x Metal 11.6 21 20-300
C44300 Admiralty Brass, As 11.2 20 20-300
C61400 Aluminum Bronze D 9.0 18.2 20-300
C70600 90-10 Copper-Nickel 9.5 17.1 20-300
C71500 70-30 Copper-Nickel 9.0 16.2 20-300
C83600 O u n c e Metal 10.2 18.4 0-100

F10006 Gray Cast Iron 6.7 12.1 0-100


G10200 C a r b o n Steel 6.7 12.1 0-100
J94224 H K Cast SS 9.4 16.9 20-540

L13002 Tin 12.8 23 0-100


L51120 Chemical Lead 16.4 30 0-100
L55030 50/50 Solder 13.1 24 0-100
M11311 Mg AZ31B 14.5 26 20-100
M13310 Mg HK31A 14.5 26 20-100

N02200 Nickel 200 7.4 13.3 20-90


N04400 400 Alloy 7.7 13.9 20-90
N06600 600 Alloy 7.4 13.3 20-90
N10276 C-276 Alloy 6.3 11.3 20-90
N 10665 B-2 Alloy 5.6 10.1 20-90

R03600 Molybdenum 2.7 4.9 20-100


R05200 Tantalum 3.6 6.5 20-100
R50250 T i t a n i u m , Gr 1 4.8 8.6 0-100
R56400 T i t a n i u m , Gr 5 4.9 8.8 0-100
R60702 Zr 702 2.9 5.2 0-100

$30400 304 SS 9.8 17.3 0-100


$31000 310 SS 8.0 14.4 0-100
$41000 410 SS 6.1 11.0 0-100
$44600 446 SS 5.8 10.4 0-100
$50200 5Cr-0.5Mo Steel 7.3 13.1 20-540
Z13001 Zinc 18 32 0-100

1See NACE Corrosion Engineers Reference Book, Third Edition,


R. Baboian, Ed., NACE International, 2002, p. 291.

36

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Physical Properties of Water
Temperature, t Density 1, d Specific Vapor Viscosity3, ~ Dielectric
Volume 1, v Pressure 2, p Constant 4, e
°C g/mL mL/g m m Hg* Centipose
0"* 0.99987 1.00013 4.580 1.787 87.74
5 .99999 1.00001 6.538 1.517 85.76
10 .99973 1.00027 9.203 1.306 83.83
15 .99913 1.00087 12.782 1.138 81.95
18 .99862 1.00138 15.471 1.053 80.84
20 .99823 1.00177 17.529 1.002 80.10
25 .99707 1.00293 23.753 0.8903 78.30
30 .99567 1.00434 31.824 .7974 76.55
35 .99406 1.00598 42.180 .7194 74.83
38 .99299 1.00706 49.702 .6783 73.82
40 .99224 1.00782 55.338 .6531 73.15
45 .99025 1.00985 71.90 .5963 71.51
50 .98807 1.01207 92.56 .5471 69.91
55 .98573 1.01448 118.11 .5044 68.34
60 .98324 1.01705 149.47 .4669 66.81
65 .98059 1.01979 187.65 .4338 65.32
70 .97781 1.02270 233.81 .4044 63.86
75 .97489 1.02576 289.22 .3782 62.43
80 .97183 1.02899 355.31 .3547 61.03
85 .96865 1.03237 433.64 .3340 59.66
90 .96534 1.03590 525.92 .3149 58.32
95 .96192 1.03959 634.04 .2976 57.01
100"** .95838 1.04343 760.00 .2822 55.72

1 - M. Thiesen, Wiss. Abh. der Physikalisch-Technischen Reichsanstalt 4, No. 1, 1904; International Critical Tables 3, 25 (1928).
2 - F. G. Keyes, J. Chem. Phys., 15, 602 (1947).
3 - J. F. Swindells, J. R. Coe, a n d T. B. Godfrey, J. Research Nat. Bur. Standards, 48, 1 (1952); R. C. H a r d y a n d R. L. Cottington,
ibid, 42, 573 (1949); J. R. Coe a n d T. B. Godfrey, J. App. Phys., 15, 625 (1944).
4 - C. G. Malmberg a n d A. A. Maryott, J. Research Nat. Bur. Standards, 56, 1 (1956).
* - 760 m m Hg = 1 atmosphere = 1,013,250 dyn c m -2 = 101,325 newtons m -2 on the Systbme International d'Unites, adopted
in a resolution, 1 l t h General Conference on Weights a n d Measures, Paris, October 1960, the international unit of pressure
is the Newton per square meter.
** - The freezing point is zero degrees Celsius, exactly; the triple point of water is 0.001°C or 273.16°K.
*~* - The boiling point.

37

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Dew Point of Moist Air'
T h e t e m p e r a t u r e d r o p r e q u i r e d f o r c o n d e n s a t i o n to o c c u r at a s p e c i f i e d
a i r t e m p e r a t u r e a n d r e l a t i v e h u m i d i t y is g i v e n i n t h e t a b l e b e l o w . T h e
t e m p e r a t u r e drops are m e a n values for the indicated air t e m p e r a t u r e
ranges.

Air Temperature °C Air Temperature °F


RH % 0-20 20-35 RH % 32-68 68-95
55 9 10 55 16 18
60 7 9 60 13 15
65 6 7 65 11 13
70 5 6 70 9 11
75 4 5 75 8 9
80 3 4 80 6 7
85 2 3 85 4 5
90 1.6 1.8 90 3 3
92 1.2 1.4 92 2.2 2.5
95 0.8 0.9 95 1.4 1.6
98 0.3 0.3 98 0.5 0.5
Example: At 30°C (86°F) and 80 % RH a temperature drop of 4°C (7°F) would
result in condensation.
Dew point temperatures of moist air as a function of air temperature and relative
humidity are tabulated on the following four pages.

1See NACE Corrosion Engineers Reference Book, Third Edition,


R. Baboian, Ed., NACE International, 2002, pp. 69-73.

38

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Dew Point of Moist Air "C
Air Temperature °C

RH% 0 2 4 6 8 10 12 14 16 18 20 22 24
1 -50 -49 -47 --46 -45 -44 -42 -41 -40 -39 -38 -36 -35
3 -40 -39 -37 -36 -34 -33 -32 -30 -29 -28 -26 -25 -24
5 -35 -34 -32 -31 -29 -28 -26 -25 -24 -22 -21 -19 -24
7 -32 -30 -29 -27 -26 -24 -23 -21 -20 -18 -17 -15 -14
9 -29 -27 -26 -24 -23 -21 -20 -18 -17 -15 -14 -12 -11
11 -27 -25 -24 -22 -21 -19 -17 -16 -14 -13 -11 -10 -8
13 -25 -23 -22 -20 -19 -17 -15 -14 -12 -tl -9 -8 -6
15 -23 -22 -20 -19 -17 -15 -14 -12 -11 -9 -7 -6 -4
17 -22 -20 -19 -17 -15 -14 -12 -11 -9 -7 -6 -4 -2
19 -21 -19 -17 -16 -14 -12 -11 -9 -8 -6 -4 -3 -1
21 -20 -18 -16 -15 -13 -11 -10 -8 -6 -5 -3 -1 0
23 -19 -17 -15 -14 -12 -10 -8 -7 -5 -3 -2 0 2
25 -18 -16 -14 -13 -11 -9 -7 -6 -4 -2 -1 1 3
27 -17 -15 -13 -12 -10 -8 -6 -5 -3 -1 1 2 4
29 -16 -14 -12 -11 -9 -7 -5 -4 -2 0 2 3 5
31 -15 -13 -12 -10 -8 -6 -5 -3 -1 1 2 4 6
33 -14 -13 -11 -9 -7 -6 -4 -2 0 2 3 5 7
35 -14 -12 -10 -8 -7 -5 -3 -1 1 2 4 6 8
37 -13 -11 -9 -8 -6 -4 -2 0 1 3 5 7 9
39 -12 -10 -9 -7 -5 -3 -1 0 2 4 6 8 9
41 -12 -10 -8 -6 -4 -3 -1 1 3 5 6 8 10
43 -11 -9 -7 -6 -4 -2 0 2 4 5 7 9 11
45 -11 -9 -7 -5 -3 -1 1 2 4 6 8 10 11
47 -10 -8 -6 -5 -3 -1 1 3 5 7 8 10 12
49 -9 -8 -6 -4 -2 0 2 4 5 7 9 11 13
51 -9 -7 -5 -3 -1 0 2 4 6 8 10 12 13
53 -8 -7 -5 -3 -1 1 3 5 7 8 10 12 14
55 -8 -6 -4 -2 -1 1 3 5 7 9 11 13 14
57 -7 -6 -4 -2 0 2 4 6 8 9 11 13 15
59 -7 -5 -3 -1 1 2 4 6 8 10 12 14 16
61 -7 -5 -3 -1 1 3 5 7 9 11 12 14 16
63 -6 -4 -2 0 2 3 5 7 9 11 13 15 17
65 -6 -4 -2 0 2 4 6 8 10 11 13 15 17
67 -5 -3 -2 0 2 4 6 8 10 12 14 16 18
69 -5 -3 -1 1 3 5 7 8 10 12 14 16 18
7t -5 -3 -1 1 3 5 7 9 11 13 15 17 19
73 -4 -2 0 2 4 6 7 9 11 13 15 17 19
75 -4 -2 0 2 4 6 8 10 12 14 15 17 19
77 -4 -2 0 2 4 6 8 10 12 14 16 18 20
79 -3 -1 1 3 5 7 8 10 12 14 16 18 20
81 -3 -1 1 3 5 7 9 11 13 15 17 19 21
83 -3 -1 1 3 5 7 9 11 13 15 17 19 21
85 -2 0 2 4 6 8 10 12 14 16 18 19 21
87 -2 0 2 4 6 8 10 12 14 16 18 20 22
89 -2 0 2 4 6 8 10 12 14 16 18 20 22
91 -1 1 3 5 7 9 11 13 15 17 19 21 23
93 -1 1 3 5 7 9 11 13 15 17 19 21 23
95 -1 1 3 5 7 9 11 13 15 17 19 21 23
97 0 2 4 6 8 10 12 14 16 18 20 22 24
99 0 2 4 6 8 10 12 14 16 18 20 22 24
Continued on Next Page

1See NACE Corrosion Engineers Reference Book, Third Edition,


R. Baboian, Ed., NACE International, 2002.
39

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40 C O R R O S I O N TESTS AND STANDARDS MANUAL

D e w P o i n t o f Moist Air °Ct (Cont.)

Air Temperature °C
RH% 26 28 30 32 34 36 38 40 42 44 46 48 50
1 -34 -33 -32 -30 -29 -28 -27 -26 -25 -24 -22 -21 -20
3 -22 -21 -20 -18 -17 -16 -14 -13 -12 -11 -9 -8 -7
5 -16 -15 -14 -12 -11 -10 -8 -7 -5 ~, -3 -1 0
7 -12 -11 -9 -8 -7 -5 --4 -2 -1 1 2 4 5
9 -9 -8 -8 -5 -3 -2 0 1 3 4 6 7 9
11 -7 -5 4 -2 -1 1 3 4 6 7 9 10 12
13 4 -3 -1 0 2 3 5 6 8 10 11 13 14
15 -3 -1 1 2 4 5 7 9 10 12 13 15 16
17 -1 1 2 4 6 7 9 10 12 14 15 17 18
19 1 2 4 6 7 9 10 12 14 15 17 19 20
21 2 4 5 7 9 10 12 14 15 17 19 20 22
23 3 5 7 8 10 12 13 15 17 18 20 22 23
25 5 6 8 10 11 13 15 16 18 20 21 23 25
27 6 7 9 11 12 14 16 18 19 21 23 24 26
29 7 8 10 12 14 15 17 19 20 22 24 25 27
31 8 9 11 13 15 16 18 20 21 23 25 27 28
33 9 10 12 14 16 17 19 21 22 24 26 28 29
35 9 11 13 15 16 18 20 22 23 25 27 29 30
37 10 12 14 16 17 19 21 23 24 26 28 30 31
39 I1 13 15 16 18 20 22 24 25 27 29 31 32
41 12 14 15 17 19 21 23 24 26 28 30 31 33
43 13 14 16 18 20 22 23 25 27 29 31 32 34
45 13 15 17 19 20 22 24 26 28 29 31 33 35
47 14 16 17 19 21 23 25 27 28 30 32 34 36
49 15 16 18 20 22 24 26 27 29 31 33 35 36
51 15 17 19 21 23 24 26 28 30 32 34 35 37
53 16 18 20 21 23 25 27 29 31 32 34 36 38
55 16 18 20 22 24 26 27 29 31 33 35 37 38
57 17 19 21 23 24 26 28 30 32 34 36 37 39
59 17 19 21 23 25 27 29 30 32 34 36 38 40
61 18 20 22 24 26 27 29 31 33 35 37 39 41
63 19 20 22 24 26 28 30 32 34 35 37 39 41
65 19 21 23 25 27 28 30 32 34 36 38 40 42
67 19 21 23 25 27 29 31 33 35 37 38 40 42
69 20 22 24 26 28 30 31 33 35 37 39 41 43
71 20 22 24 26 28 30 32 34 36 38 40 42 43
73 21 23 25 27 29 31 32 34 36 38 40 42 44
75 21 23 25 27 29 31 33 35 37 39 41 42 44
77 22 24 26 28 29 31 33 35 37 39 41 43 45
79 22 24 26 28 30 32 34 36 38 40 41 43 45
81 23 25 26 28 30 32 34 36 38 40 42 44 46
83 23 25 27 29 31 33 35 37 39 40 42 44 46
85 23 25 27 29 31 33 35 37 39 41 43 45 47
87 24 26 28 30 32 34 36 37 39 41 43 45 47
89 24 26 28 30 32 34 36 38 40 42 44 46 48
91 25 27 29 31 32 34 36 38 40 42 44 46 48
93 25 27 29 31 33 35 37 39 41 43 45 47 49
95 25 27 29 31 33 35 37 39 41 43 45 47 49
97 26 28 30 32 34 36 38 40 42 44 46 48 50
99 26 28 30 32 34 36 38 40 42 44 46 48 50

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Dew Point of Moist Air "F
Air Temperature °F

RH% 32 35 38 41 44 47 50 53 56 59 62 65 68 71 74
1 -57 -56 -54 -52 -50 -48 -46 -45 -43 -41 -39 -37 -36 -34 -32
3 -40 -38 -36 -34 -32 -30 -28 -25 -23 -21 -19 -17 -15 -13 -11
5 -31 -29 -27 -25 -22 -20 -18 -16 -14 -12 -9 -7 -5 -3 -1
7 -25 -23 -20 -18 -16 -14 -11 -9 -7 -5 -2 0 2 4 6
9 -20 -18 -15 -13 -11 -9 -6 -4 -2 1 3 5 7 10 12
11 -16 -14 -12 -9 -7 -5 -2 0 2 5 7 9 12 14 16
13 -13 -11 -8 -6 -3 -1 1 4 6 8 11 13 16 18 20
15 -10 -8 -5 -3 0 2 4 7 9 12 14 16 19 21 24
17 -8 -5 -3 0 2 5 7 10 12 15 17 19 22 24 27
19 -5 -3 0 2 5 7 10 12 15 17 19 22 24 27 29
21 -3 -1 2 4 7 9 12 14 17 19 22 24 27 29 32
23 -1 1 4 6 9 11 14 16 19 21 24 26 29 31 34
25 0 3 5 8 11 13 16 18 21 23 26 28 31 33 36
27 2 5 7 10 12 15 17 20 23 25 28 30 33 35 38
29 4 6 9 11 14 17 19 22 24 27 29 32 35 37 40
31 5 8 10 13 16 18 21 23 26 29 31 34 36 39 42
33 6 9 12 14 17 20 22 25 27 30 33 35 38 41 43
35 8 10 13 16 18 21 24 26 29 31 34 37 39 42 45
37 9 12 14 17 20 22 25 28 30 33 36 38 41 44 46
39 10 13 15 18 21 23 26 29 32 34 37 40 42 45 48
41 11 14 17 19 22 25 27 30 33 35 38 41 44 46 49
43 12 15 18 20 23 26 29 31 34 37 39 42 45 48 50
45 13 16 19 21 24 27 29 32 35 38 40 43 46 49 51
47 14 17 20 22 25 28 31 33 36 39 42 44 47 50 52
49 15 18 21 24 26 29 32 35 37 40 43 46 48 51 54
51 16 19 22 24 27 30 33 36 38 41 44 47 49 52 55
53 17 20 23 25 28 31 34 37 39 42 45 48 50 53 56
55 18 21 23 26 29 32 35 37 40 43 46 48 51 54 57
57 19 21 24 27 30 33 35 38 41 44 47 50 52 55 58
59 19 22 25 28 31 33 36 39 42 45 48 50 53 56 59
61 20 23 26 29 32 34 37 40 43 46 49 51 54 57 60
63 21 24 27 29 32 35 38 41 44 47 49 52 55 58 61
65 22 25 27 30 33 36 39 42 44 47 50 53 56 59 62
67 22 25 28 31 34 37 40 42 45 48 51 54 57 60 62
69 23 26 29 32 35 37 40 43 46 49 52 55 58 60 63
71 24 27 30 32 35 38 41 44 47 50 53 55 58 61 64
73 24 27 30 33 36 39 42 45 48 51 53 56 59 62 65
75 25 28 31 34 37 39 42 45 48 51 54 57 60 63 66
77 26 29 32 34 37 40 43 46 49 52 55 58 61 64 66
79 26 29 32 35 38 41 44 47 50 52 55 58 61 64 67
81 27 30 33 36 39 42 44 47 50 53 56 59 62 65 68
83 27 30 33 36 39 42 45 48 51 54 57 60 63 66 68
85 28 31 34 37 40 43 46 49 52 55 58 60 64 66 69
87 29 32 34 37 40 43 46 49 52 55 58 61 64 67 70
89 29 32 35 38 41 44 47 50 53 56 59 62 65 68 71
91 30 33 36 39 42 45 48 51 54 56 60 62 65 68 71
93 30 33 36 39 42 45 48 51 54 57 60 63 66 69 72
95 31 34 37 40 43 46 49 52 55 58 61 64 67 70 73
97 31 34 37 40 43 46 49 52 55 58 61 64 67 70 73
99 32 35 38 41 44 47 50 53 56 59 62 65 68 71 74
Continued on Next Page
1
See NAC r E Corroszon
" "
Engineers Reference Book, Third Edition,
R. Baboian, Ed., NACE International, 2002.

41

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42 CORROSION TESTS AND STANDARDS MANUAL

D e w P o i n t o f Moist Air °F (Cont.)

Air Temperature °F
RH% 77 80 83 86 89 92 95 98 101 104 107 110 113 116 119 122
1 -30 -28 -27 -25 -23 -21 -20 -18 -16 -14 -13 -11 -9 -7 -6 -4
3 -9 -7 -5 -3 -1 1 2 4 6 8 10 12 14 16 18 20
5 1 3 5 8 10 12 14 16 16 20 22 24 26 28 30 32
7 8 1l 13 15 17 19 22 24 26 28 30 32 35 37 39 41
9 14 16 19 21 23 25 28 30 32 34 36 39 41 43 45 47
11 19 21 23 26 28 30 32 35 37 39 41 44 46 48 50 53
13 23 25 27 30 32 34 37 39 41 44 46 48 51 53 55 57
15 26 28 31 33 35 38 40 43 45 47 50 52 54 57 59 61
17 29 31 34 36 39 41 44 46 48 51 53 55 58 60 63 65
19 32 34 37 39 42 44 46 49 51 54 56 59 61 63 66 68
21 34 37 39 42 44 47 49 52 54 56 59 61 64 66 69 71
23 37 39 42 44 47 49 51 54 56 59 61 64 66 69 71 74
25 38 41 44 46 49 51 54 56 59 61 64 66 69 71 74 76
27 41 43 46 48 51 53 56 58 61 64 66 68 71 74 76 79
29 42 45 48 50 53 55 58 60 63 65 68 71 73 76 78 81
31 44 47 49 52 55 57 60 62 65 67 70 73 75 78 80 83
33 46 48 51 54 56 59 61 64 67 69 72 74 77 80 82 85
35 47 50 53 55 58 60 63 66 68 71 74 76 79 81 84 87
37 49 52 54 57 60 62 65 67 70 73 75 78 81 83 86 89
39 50 53 56 58 61 64 66 69 72 74 77 80 82 85 87 90
41 52 54 57 60 62 65 68 70 73 76 78 81 84 86 89 92
43 53 56 58 61 64 68 69 72 75 77 80 83 85 88 91 93
45 54 57 60 62 65 68 70 73 76 78 81 84 87 89 92 95
47 55 58 61 63 66 69 72 74 77 80 82 85 88 91 93 96
49 56 59 62 65 68 70 73 76 78 81 84 87 89 92 95 98
51 58 60 63 66 69 71 74 77 80 82 85 88 91 93 96 99
53 59 62 64 67 70 73 75 78 81 84 86 89 92 95 97 100
55 60 62 65 68 71 73 76 79 82 85 87 90 93 96 98 101
57 61 64 66 69 72 75 78 80 83 86 89 91 94 97 100 103
59 62 64 67 70 73 76 78 81 84 87 90 92 95 98 10l 104
61 63 66 68 71 74 77 80 82 85 88 91 94 96 99 102 105
63 64 66 69 72 75 78 81 83 86 89 92 95 98 100 103 106
65 64 67 70 73 76 79 82 84 87 90 93 96 98 101 104 107
67 65 68 71 74 77 80 82 85 88 91 94 97 100 102 105 108
69 66 69 72 75 78 80 83 86 89 92 95 98 100 103 106 109
71 67 70 73 76 79 81 84 87 90 93 96 99 101 104 107 110
73 68 71 74 76 79 82 85 88 91 94 97 100 102 105 108 111
75 69 71 74 77 80 83 86 89 92 94 97 100 103 106 109 112
77 69 72 75 78 81 84 87 90 93 96 98 101 104 107 110 113
79 70 73 76 79 82 84 87 90 93 96 99 102 105 108 111 114
81 71 74 77 80 82 85 88 91 94 97 100 103 106 109 112 115
83 71 74 77 80 83 86 89 92 95 98 101 104 107 109 112 115
85 72 75 78 81 84 87 90 93 96 99 102 105 108 110 113 116
87 73 76 79 82 85 88 91 94 96 99 102 105 108 111 114 117
89 73 76 79 82 85 88 91 94 97 100 103 106 109 112 115 118
91 74 77 80 83 86 89 92 95 98 101 104 107 110 113 116 119
93 75 78 81 84 87 90 93 96 99 102 105 108 111 114 117 120
95 76 79 82 85 87 90 93 96 99 102 105 108 111 114 117 120
97 76 79 82 85 88 91 94 97 100 103 106 109 112 115 118 121
99 77 80 83 86 89 92 95 98 101 104 107 110 113 116 119 122

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Chemical Cleaning
Procedures for Removal
of Corrosion Products
Designation Material Solution Time Temperature Remarks
C.I.1 A l u m i n u m and 50 mL phosphoric acid 5 to 10 m i n 90°C to Boiling If corrosion product films
A l u m i n u m Alloys (H3PO 4, sp gr 1.69) remain, rinse, then
20 g chromium trioxide (CrO 3) follow with nitric acid
Reagent water to make procedure (C. 1.2).
1000 mL
C.1.2 Nitric acid (HNO3, sp gr 1.42) 1 to 5 m i n 20 to 25°C Remove extraneous de-
posits and bulky corro-
sion products to avoid
reactions that may
result in excessive
removal of base metal.
C.2.1 Copper and Copper 500 mL hydrochloric acid 1 to 3 m i n 20 to 25°C Deaeration of solution
Alloys (HC1, sp gr 1.19) with purified nitrogen
Reagent water to make will minimize base
1000 mL metal removal.
C.2.2 4.9 g sodium cyanide (NaCN) 1 to 3 m i n 20 to 25°C Removes copper sulfide
Reagent water to make corrosion products that
1000 mL may not be removed by
hydrochloric acid
treatment (C.2.1).
C.2.3 100 mL sulfuric acid 1 to 3 m i n 20 to 25°C Remove bulky corrosion
(H2SO4, sp gr 1.84) products before
Reagent water to make treatment to minimize
1000 mL copper redeposition on
specimen surface.
C.2.4 120 mL sulfuric acid 5 t o lOs 20 to 25°C Removes redeposited
(H2504, sp gr 1.84) copper resulting from
30 g sodium dichromate sulfuric acid
(Na2Cr207 •2H20) treatment.
Reagent water to make 1000 mL
C.2.5 54 mL sulfuric acid 30 to 60 rain 40 to 50°C Deaerate solution with
(H2804, sp gr 1.84) nitrogen. Brushing
Reagent water to make of test specimens to
1000 mL remove corrosion
products followed by
re-immersion for 3 to 4 s
is recommended.
C.3.1 Iron and Steel 1000 mL hydrochloric acid 1 to 25 m i n 20 to 25°C Solution should be vigor-
(HC1, sp gr 1.19) ously stirred or specimen
20 g antimony trioxide (5b203) should be brushed.
50 g stannous chloride (SnC12) Longer times may be
required in certain
instances.

i See ASTM G1, Standard Practice For Preparing, Cleaning,


and Evaluating Corrosion Test Specimens.
43

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44 C O R R O S I O N T E S T S AND S T A N D A R D S MANUAL

Designation Material Solution Time Temperature Remarks


C.3.2 50 g sodium hydroxide (NaOH) 30 to 40 m i n 80 to 90°C Caution should be
200 g granulated zinc or zinc exercised in the use of
chips any zinc dust since
Reagent water to make 1000 mL spontaneous ignition
upon exposure to air can
OCCL1F.
C.3.3 200 g sodium hydroxide (NaOH) 30 to 40 m i n 80 to 90°C Caution should be
20 g granulated zinc or zinc chips exercised in the use of
Reagent water to make 1000 mL any zinc dust since
spontaneous ignition
upon exposure to air can
occur.
C.3.4 200 g d i a m m o n i u m citrate 20 m i n 75 to 90°C Depending upon the com-
((NH4)aHC6H507) position of the corrosion
Reagent water to make 1000 mL product, attack of base
metal may occur.
C.3.5 500 mL hydrochloric acid 10 m i n 20 to 25°C Longer times may be
(HC1, sp gr 1.19) required in certain
3.5 g hexamethylene tetramine instances.
Reagent water to make 1000 mL
C.3.6 Molten caustic soda (NaOH) with 1 to 20 m i n 370°C For details refer to Tech-
1.5-2.0 % sodium nical Information Bulle-
hydride (Nail) tin SP29-370, "DuPont
Sodium Hydride Descal-
ing Process Operating
Instructions."
C.4.1 Lead and Lead 10 mL acetic acid (CH3COOH) 5 min Boiling
Alloys Reagent water to make 1000 mL
C.4.2 50 g a m m o n i u m acetate 10 m i n 60 to 70°C
(CHaCOONH 4)
Reagent water to make 1000 mL
C.4.3 250 g a m m o n i u m acetate 5 rain 60 to 70°C
(CHaCOONH 4)
Reagent water to make 1000 mL
C.5.1 Magnesium and 150 g c h r o m i u m trioxide (CrO 3) 1 min Boiling The silver salt is present
Magnesium 10 g silver chromate (AgECrO4) to precipitate chloride.
Mloys Reagent water to make 1000 mL
C.5.2 200 g c h r o m i u m trioxide (CrO3) 1 rain 20 to 25°C The b a r i u m salt is present
10 g silver nitrate (AgNO 3) to precipitate sulfate.
20 g b a r i u m nitrate (Ba(NO3)2)
Reagent water to make 1000 mL
C.6.1 Nickel and Nickel 150 mL hydrochloric acid 1 to 3 m i n 20 to 25°C
Alloys (HC1, sp gr 1.19)
Reagent water to make 1000 mL
C.6.2 100 mL sulfuric acid 1 to 3 m i n 20 to 25°C
(H2SO4, sp gr 1.84)
Reagent water to make 1000 mL
C.7.1 Stainless Steels 100 mL nitric acid (HNO 3, 20 m i n 60°C
sp gr 1.42)
Reagent water to make 1000 mL
C.7.2 150 g d i a m m o n i u m citrate 10 to 60 m i n 70°C
((NH4)2HC6H507)
Reagent water to make 1000 mL
C.7.3 100 g citric acid (C6H607) 5 rain 60°C
50 mL sulfuric acid (H2504, sp gr
1.84) 2 g inhibitor (diorthotolyl
thiourea or quinoline ethylio-
dide or betanaphthol quinoline)
Reagent water to make 1000 mL

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CHEMICAL CLEANING PROCEDURES FOR REMOVAL OF CORROSION PRODUCTS 45

Designation Material Solution Time Temperature Remarks


C.7.4 200 g sodium hydroxide 5 min Boiling ...
(NaOH)
30 g potassium permanganate
(KMnO 4)
Reagent water to make 1000 mL
followed by
100 g d i a m m o n i u m citrate
((NH4)2HC6H5OT)
Reagent water to make 1000 mL
C.7.5 100 mL nitric acid (HNO3, 5 to 20 m i n 20 to 25°C
sp gr 1.42)
20 mL hydrofluoric acid (HF,
sp gr 1.198-48 %)
Reagent water to make 1000 mL
C.7.6 200 g sodium hydroxide 20 m i n Boiling Caution should be exer-
(NaOH) cised in the use of any
50 g zinc powder. Reagent zinc dust since sponta-
water to make 1000 mL neous ignition upon ex-
posure to air can occur.
C.8.1 Tin and 150 g trisodium phosphate 10 m i n Boiling
Tin Alloys (Na3PO4 • 12H 2O)
Reagent water to make 1000 mL
C.8.2 50 mL hydrochloric acid 10 m i n 20°C
(HC1, sp gr 1.19)
Reagent water to make 1000 mL
C.9.1 Zinc and 150 mL a m m o n i u m hydrox- 15 to 20 s Boiling The silver nitrate should
Zinc Alloys ide (NH4OH, sp gr 0.90) be dissolved in water
Reagent water to make 1000 mL and added to the boiling
followed by chromic acid to prevent
50 g c h r o m i u m trioxide (CrO3) excessive crystallization
10 g silver nitrate (AgNO3) of silver chromate. The
Reagent water to make 1000 mL chromic acid must be
sulfate free to avoid at-
tack of the zinc base
metal.
C.9.2 100 g a m m o n i u m chloride 2 to 5 m i n 70°C
(NH4C1)
Reagent water to make 1000 mL
C.9.3 200 g c h r o m i u m trioxide 1 min 80°C Chloride contamination of
(CrO3) the chromic acid from
Reagent water to make corrosion products
1000 mL formed in salt environ-
ments should be
avoided to prevent at-
tack of the zinc base
metal.
C.9.4 85 mL hydriodic acid (HI, sp 15s 20 to 25°C Some zinc base metal may
gr 1.5) be removed. A control
Reagent water to make 1000 mL specimen (3.1.1) should
be employed.
C.9.5 100 g a m m o n i u m persulfate 5 min 20 to 25°C Particularly recom-
(NH4)2S208) mended for galvanized
Reagent water to make 1000 mL steel.
C.9.6 100 g a m m o n i u m acetate 2 to 5 rain 70°C
(CH3COONH4)
Reagent water to make 1000 mL

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Electrolytic Cleaning
Procedures for Removal
of Corrosion Products:
Designation Material Solution Time Temperature Remarks
E. 1.1 Iron, Cast Iron, Steel 75 g sodium hydroxide 20 to 40 rain 20 to 25°C Cathodic treatment with 100 to
(NaOH) 200 A/m2 current density.
25 g sodium sulfate (Na2SO4) Use carbon, platinum or
75 g sodium carbonate stainless steel anode.
(Na2CO3)
Reagent water to make
1000 mL
E.1.2 28 mL sulfuric acid 3 min 75°C Cathodic treatment with 2000
(H2SO4, sp gr 1.84) A/m2 current density. Use
0.5 g inhibitor (diorthotolyl carbon, platinum or lead
thiourea or quinoline anode.
ethyliodide or betanaphthol
qninoline). Reagent water
to make 1000 mL
E. 1.3 100 g d i a m m o n i u m citrate 5 min 20 to 25°C Cathodic treatment with 100
A/m2 current density. Use
((NHa)2HC6H507)
Reagent water to make 1000 mL carbon or platinum anode.
E.2.1 Lead and Lead Alloys 28 mL sulfuric acid (H2SO4, 3 min 75 ° C Cathodic treatment with 2000
sp gr 1.84) A/m2 current density. Use
0.5 g inhibitor (diorthotolyl carbon, platinum or lead
thiourea or quinoline anode.
ethyliodide or betanaphthol
quinoline)
Reagent water to make 1000 mL
E.3.1 Copper and Copper 7.5 g potassium chloride (KC1) 1 to 3 20 to 25°C Cathodic treatment with 100 A/m2
Alloys Reagent water to make current density. Use carbon
1000 mL or platinum anode.
E.4.1 Zinc and Cadmium 50 g dibasic sodium phos- 5 rain 70°C Cathodic treatment with 110 A/m2
phate (Na2HPO4) current density. Specimen
Reagent water to make 1000 rnL must be energized prior to
immersion. Use carbon, plati-
n u m or stainless steel anode.
E.4.2 100 g sodium hydroxide 1 to 2 m i n 20 to 25°C Cathodic treatment with 100 A/m2
(NaOH) current density. Specimen
Reagent water to make 1000 mL must be energized prior to
immersion. Use carbon, plati-
n u m or stainless steel anode.
E.5.1 General (excluding 20 g sodium hydroxide 5 to 10 rain 20 to 25°C Cathodic treatment with 300
Aluminum, Magne- (NaOH) Aim2 current density. A
sium and Tin $31600 stainless steel anode
Reagent water to make 1000 mL
Alloys) may be used.

2See ASTM G 1, Standard Practice for Preparing, Cleaning, and Evaluating


Corrosion Test Specimens.
46

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Section II: Testing and Evaluation
R. Baboian, Editor

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Planning and Design of Tests
S t e p h e n D. C r a m e r 1 a n d B a r n i e P. Jones 2

CORROSION TESTS ARE an i m p o r t a n t tool for evaluating the While corrosion testing of metallic materials is the focus
performance of materials used in scientific, industrial, en- here, planning and design of environmental performance
gineering, consumer, and aesthetic applications, where tests for nonmetallic materials, such as paints, plastics,
corrosion was estimated to cost the U.S. economy $276 ceramics, and refractories is similar. Specific corrosion test
billion in direct costs annually in 1998, or 3 . 1 % of the U.S. methods have been developed by ASTM International
Gross Domestic Product [1-3]. Corrosion tests are widely [10-12], NACE International [13], and the International
used to evaluate the durability of materials of construction Organization for Standardization (ISO) [14].
in reactive environments. They have a profound impact on Corrosion test planning and design typically involves the
society by the influence they have on the choice of materi- following five steps:
als used, for example, in chemical plants, drilling and
9 Define goals and objectives
mining equipment, energy production facilities, communi-
9 Design corrosion test
cations equipment, buildings, bridges, spacecraft, monu-
9 Develop test protocol
ments, computers, food processing equipment, medical
9 Engineer test
implants, automobiles, and manufacturing facilities. Cor-
9 Modify test
rosion tests evaluate a range of material degradation proc-
esses that affect the final performance of these materials These steps are affected by the nature of the corrosion
and directly influence the materials chosen for these appli- process, the types of data acquired, the analytical resources
cations. These processes involve chemical and electro- available, the statistical treatments to be applied, and the
chemical reactions, and include mechanically assisted outcomes sought. Preliminary or early data can help deter-
corrosion processes and synergies between wear and corro- mine whether the fifth step, modification of the test design,
sion. Corrosion tests are used to examine the performance will be needed.
of materials, evaluate alternate materials, develop strate- As with other technical endeavors, adequate and ongoing
gies for protection of materials, and determine the documentation is a necessary element of planning, design-
corrosivity of specific environments. ing, and conducting corrosion tests [15]. It is the basis for
Typical corrosion and materials engineering requirements effective communications between m a n a g e m e n t and the
are shown in Fig. 1 for three stages in the evolution of a corrosionist from the earliest planning stages, ensuring
manufacturing process for the chemical process industries agreement on goals and objectives and the availability of
(CPI) [4]. Thorough corrosion test planning and design is necessary resources. It provides a way to assess, review, and
essential to achieve satisfactory materials performance for modify the test plan with regard to data quality objectives,
each of these stages. Corrosion tests lay the foundation for use of resources, a n d the outcomes achieved. It provides the
obtaining adequate information on materials performance continuity for other investigators to continue and complete
in the process environments, for ensuring resources are tests and to evaluate the results when personnel changes
efficiently used, and that materials choices are compatible occur, especially when tests are conducted over long time
with long-term economic goals for the plant. The corrosion- spans.
ist is challenged to influence materials decisions in each of
these stages. This is particularly true of the first stage where
trends in process simulation have greatly reduced the time D E F I N E GOALS A N D OBJECTIVES
between research and development and plant design.
Corrosion test planning and design has been discussed by Clearly defined goals and objectives are needed if corro-
others [5-9]. This chapter provides a general background sion tests are to produce results that affect materials selec-
for planning and design of corrosion tests and the basic tion, and methods of corrosion protection and corrosion
statistical considerations affecting the design of these tests. control. Goals and objectives define test purpose and what
is to be achieved. Economic considerations are always a
factor in defining goals and objectives, along with other
1Materials Conservation Division, Albany Research Center, 1450
Queen Ave. SW, U.S. Department of Energy, Albany, OR 97321. considerations (workforce, public safety, and environment).
2Research Unit, Oregon Department of Transportation, 200 Hawthorne Figure 2 shows some of the quality criteria that affect plant
SE, Suite B-240, Salem, OR 97310. economics in the CPI. The criteria have been grouped
49

Copyright* 2005 by ASTM International www.astm.org


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50 C O R R O S I O N T E S T S A N D S T A N D A R D S MANUAL

PreliminaryPlantDesignDetailed
Research and Development, Engineering,Procurement,Fabrication Plant Operation,CodeInspection,
Pilot Plant Materials Selection and ConstructionConsiderations MaintenanceConsiderations
9 Corrosion resistance 9 Operating conditions 9 Corrosion monitoring
9 Ductility 9Corrosion performance at operating 9 NDT in maintenance strategy
9 Weldability conditions, start-up and shutdown 9 Inspection program
9Long time performance conditions 9 Maintenance and repair
9 Non-destructive testing (NDT) 9Design demands on materials selection 9 Failure analysis
9 Corrosion effects on product 9 NDT
9Availability 9 Inspection

FIG. 1--Corrosion and materials engineering requirements characteristic of research and development, plant
design, and plant operation in the CPI [4]. 9 Copyright 1993 by NACE International. All rights reserved by
NACE; reprinted by permission.

Qualitycriteria Effect on Objective


Materials
Design
Dimensioning
Manufacturing componentsafety reliablyoperatingcomponent
Testing
Construction

Materials behavior
Mode of operation
Operation
Instrumentation operationalsafety ~ safe plantwithlow shut-down
rate
NDT
Maintenance
+
Environmental environmental meets standards
standards safety

Economic
factors
productionsafety ~ low
cost
downtimeand low operating

FIG. 2mComponent, operational, and production safety as criteria of plant eco-


nomics [4]. 9 Copyright 1993 by NACE International. All rights reserved by NACE;
reprinted by permission.

according to their effect on a hierarchy of safety factors that Failure analysis is an important aspect of corrosion test-
determine the long-term economic success of the plant. ing since failed components inform the corrosionist about
These safety factors are component safety, operational the severity of actual steady-state and transient operating
safety, and production safety, and represent, in increasing conditions, improperly identified or selected materials, and
order of importance, the economic risks associated with the faulty equipment design. Figure 4 outlines typical steps in
plant. Corrosion tests establish some of the quality criteria failure analysis that are applicable to the CPI and other in-
for these safety factors. The corrosionist must ultimately dustries. At the heart of this process is testing to determine
help balance the costs of corrosion control against the bene- chemical, corrosion, and mechanical contributions to the
fits to be achieved in each of these areas. failure and to validate the results of the analysis. Failure
I n the CPI, m a i n t e n a n c e is one of the quality criteria analysis is an effective means to lower maintenance costs
i n o p e r a t i o n a l safety a n d involves the i m p a c t of c o r r o s i o n and a strategy to limit risk to operational safety.
on the service life of c o m p o n e n t s , on p l a n t productivity, In each of these examples, the crucial issue for the corro-
a n d on m a i n t e n a n c e strategies. Figure 3 shows how sionist is to identify what information is to be generated by
c o m p o n e n t exploitation a n d risk factors are affected the corrosion test, and the connection of that information to
by three different m a i n t e n a n c e strategies, a n d the m a i n - production safety. While asking the right technical ques-
t e n a n c e actions that result from these strategies. To tions is a necessary element of the p l a n n i n g and design
be able to i n f l u e n c e m a i n t e n a n c e costs, the goals a n d process, in an increasingly important sense, the definition
objectives m u s t be guided by p r a g m a t i c c o n s i d e r a t i o n s of goals and objectives can reach beyond the corrosionists
of p l a n t operation. expertise and require input from the public. Thus, in addition

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CHAPTER 1 - - P L A N N I N G A N D D E S I G N OF TESTS 51

Component Exploitation and Risk Maintenance Strategy


Factors; Maintenance Action State of Component Monitored
Waiting for Component Failure Preventive Maintenance in Real Time
Component exploitation 9 operate up to failure 9 repair after assigned time 9 repair according to test of state
9 exploiting component 100 pct intervals 9exploiting component 60-80 pct
9 redundance necessary * exploiting component 60-80 pct 9 diagnostic method necessary
9life time assignment necessary
Failure risk 9 no influence on plant avail- * influence on plant availability 9 influence on plant availability
ability * important plant components 9 important plant components
9 secondary plant components 9 risking future failures 9 risking future failures
9 no risk of consecutive failures 9 examining state of component
uneconomical
Maintenance action 9exchange of component * setting repair schedule Early failure diagnosis by:
9 plant supervision

* recurrent testing

FIG. 3--Maintenance strategies and their effects on component exploitation, failure risk, and plant availability [4].
9 Copyright 1993 by NACE International. All rights reserved by NACE; reprinted by permission.

Operationalunit ]*= DESIGN CORROSION TEST

Corrosion
i failure I Corrosion data are developed from service experience,
field tests, pilot plant tests, and laboratory tests. Confidence
l
Visual inspection, NDT l_
in the reliability of corrosion data increases the more
closely results are based on performance in similar or iden-
I-
tical process environments, Table 1 [16]. Understandably,
i the most reliable information on corrosion performance is
I Failure analysis of component
developed from service experience in identical or nearly

Mechanicaland
i identical process environments. Laboratory tests offer the
corrosive Ioodlng l
flexibility of a broad range of standard and fundamental
of components
i Testing corrosion measurements. Sound practice requires that labo-
Metollographic investigotion
Chemicalanalysisof material ratory tests be verified by pilot plant tests and/or field tests
(Eiectrochem.) corrosion tests before materials specifications are adopted.
Comparisonwith
nominalloads Standard corrosion tests such as those developed by
ASTM, NACE, and ISO often will address the technical
1 Results
i requirements established in the goals and objectives though,
9 Materialmlsidentificotion I in some cases, they may need to be modified. The quality of
Overload Wrongrnateriol selection data produced by standard tests has been well established
Unfavorable design I by critical evaluation and review, and results can readily be
Operating excursions / compared to others obtained using the same test. Even the
Unforeseen operatingconditions/ highly specialized techniques used in fundamental corro-
I I sion research, while not especially amendable to standard-
ization, eventually achieve codification through continued
i
damage ~ l Feed-back of e x p e r i e n c e ]
0ocumentotion
= Expertsystem
~-
/
publication and use [9,17-20].
As a practical matter, corrosion tests are integrated with
other functions in plant development at the laboratory and
pilot plant stage in the ongoing process of specifying mate-
rials of construction, Fig. 5. At each stage the corrosionist
FiG. 4--Corrosion failure analysis in the CPi [4]. 9 Copyright
1993 by NACE international. Aii rights reserved by NACE; must evaluate and re-evaluate the material properties and
reprinted by permission. performance necessary to achieve the production safety
(Fig. 2) defined by plant management. This is done by con-
sidering the operating environment, extremes in the operating
environment, and startup and shutdown conditions. Table 2
identifies reasons why the corrosionist may consider select-
to the expected economic and safety issues, corrosion test- ing more expensive materials than those judged to provide
ing can involve legal [15], regulatory, health, and envi- adequate performance at the laboratory or pilot plant stage.
ronmental issues. I n this context, the goals and objectives Critical or key components in a process may warrant the
may include not only technical but nontechnical factors. added expense of more corrosion resistant materials.
Ultimately, the goals and objectives may include standards The service conditions u p o n which materials selection is
of quality, quantity, and timeliness on matters that are both based are most often the n o m i n a l process or environmental
technical and nontechnical. conditions. However, transients at startup and shutdown,

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52 CORROSION TESTS AND STANDARDS MANUAL

TABLE 1--Corrosion data reliability levels [16]. TABLE 2--Reason for selecting more expensive materials [4].
Corrosiondata source A Concern Importance
Plant performance data obtained in identical processes / h ~ ' ~ x Component/material cost ratio high moderate
Coupon or equipment data obtained in similar Risk of pitting high
processes Risk of stress-corrosion cracking high
Laboratory coupon (including electrochemical tests) Environmental consequences high
data obtained in simulated service conditions Safety consequences highest
Published data in recognized journals Key component failure results in plant highest
Advertising literature from industrial sources shutdown

and during operating excursions, can produce service con- an evaluation is often daunting, p a r t i c u l a r l y since most
ditions that require consideration when selecting a material. c o r r o s i o n testing is c o n d u c t e d over relatively short time
Less obvious factors such as trace reactant levels, stray cur- frames relative to the service life of the c o m p o n e n t
rents, mechanical energy bursts, or combinations of these or structure. Nevertheless, with necessary a s s u m p t i o n s
m a y also be important. Finally, stability of corrosion prod- r e g a r d i n g long-term corrosion p e r f o r m a n c e , lifetime cost
ucts, inhibitors, and coatings m u s t be considered. Potential- estimates can provide an effective m e a n s for evaluating
pH diagrams [21-23] are a valuable resource for showing materials choices.
conditions that may lead to corrosion, immunity, or passivity Cited here are some corrosion studies requiring differ-
of metals in m a n y applications. ing levels of p l a n n i n g and statistical design. Materials
Corrosion tests must address m a n y types of corrosion selection and p r o t e c t i o n strategies for specific environ-
[2,$,25]. These include uniform corrosion, galvanic corro- ments are widely d e t e r m i n e d in pilot plant tests and by
sion, and various forms of localized corrosion, such as inter- p e r f o r m a n c e in service e n v i r o n m e n t s [27-31]. Under-
granular, crevice, or pitting corrosion, that can rapidly standing the m e c h a n i s m and kinetics of specific corrosion
cause materials failure without apparent uniform damage. processes u n d e r one set of conditions provides a funda-
Mechanically-assisted corrosion, such as stress-corrosion mental basis for transferring that knowledge to related
cracking (SCC) [26], corrosion fatigue, erosion corrosion, corrosion processes u n d e r s o m e w h a t different conditions
and wear/corrosion synergism, are complex and important [32,33]. Corrosion testing in specific environments
corrosion processes, about which better understanding is includes acceptance testing for m a t e r i a l s and for envi-
being achieved through ongoing research. r o n m e n t s [34,35], corrosivity m a p p i n g [36], and modeling
Corrosion tests are i n t e n d e d to identify materials that the effects of e n v i r o n m e n t a l factors on materials per-
provide a d e q u a t e corrosion p e r f o r m a n c e and service life f o r m a n c e [37-40].
at a low materials cost. To ensure this, as noted earlier,
corrosionists evaluate the p e r f o r m a n c e of materials, the B a s i c Statistical T o p i c s
effectiveness of p r o t e c t i o n strategies (coatings, inhibitors,
cathodic protection), and the m e c h a n i s m and kinetics of Corrosion test design should reflect the statistical basis of
c o r r o s i o n processes in specific environments in service the data analyses (see ASTM G 16, Guide for Applying Sta-
tests, pilot p l a n t tests, and l a b o r a t o r y tests. Increasingly, tistics to Analysis of Corrosion Data; and E 1488, Guide for
m a t e r i a l s costs are being evaluated in the context of com- Statistical Procedures to Use in Developing and Applying
p o n e n t or structure service life. In this way, factors such ASTM Test Methods; or for a general statistical reference
as m a i n t e n a n c e , repairs, r e p l a c e m e n t , rehabilitation, see Snedecor and Cochran [411). Whether done intuitively
process downtime, and interest rates are a d d e d into the or deliberately, this is a necessary step towards achieving
cost of providing adequate c o r r o s i o n p e r f o r m a n c e over the goals and objectives of the test. However, corrosion test
the service life of the c o m p o n e n t or structure. Finding or design is more encompassing than the application of statis-
p r o d u c i n g the necessary d a t a from corrosion tests for such tical methods alone. The design must efficiently provide the
needed information. In this regard, the design should em-
ploy both statistical and economic types of analyses and
address the range of technical and nontechnical issues that
Materials Behavior in Identical Processes are important. Fortunately, most statistical designs are both
Test Specimen Behavior in Identical efficient and economical.
Processes Five statistical topics are introduced here in increasing
Materials Behavior in Similar Processes order of complexity. They are:
Material Behavior in Pilot Plants
Electrochemical/Conventional Data from 9 Probability sampling and r a n d o m i z a t i o n
Laboratory
Corrosion Literature
9 Determining the required numbers of observations
Commercial Reference Publications 9 Curve fitting and simple statistical modeling
9 Designing experiments
9 Statistical tests for experiments
FIG. 5--Materials selection in research and de-
velopment for CPI plant facilities [4]. 9 Copyright These represent only a fraction of the techniques a n d ap-
1993 by NACE International. All rights reserved p r o a c h e s that are available to the corrosionist. Chapter 5,
by NACE; reprinted by permission. "Statistical T r e a t m e n t of Data, Data Interpretation, a n d

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C H A P T E R 1 - - P L A N N I N G A N D D E S I G N OF T E S T S 53

Reliability," covers some of these topics in detail a n d Statist~d confidencecurve


s u m m a r i z e s the statistical t e r m i n o l o g y (see also ASTM
E 456, T e r m i n o l o g y Relating to Quality and Statistics;
and E 1325, Terminology Relating to Design of Experiments).

Probability Sampling and Randomization 6


c3~s)
There are two related but conceptually different uses of Magnitude of variability=
probability sampling, sampling from a larger population, 0,5
,,1
and randomization. Sampling from a population is usually 4
Statistical en,or curve 92
10
intended to establish external validity, or to obtain a sample
: t l e t e e t a 40 ee ee e e e oa e* e 9 aa eao eo
that can be used to make an inference to the larger popula-
-10
tion. An example might be quality control sampling of
coated steel from a production line, corrosion resistance Number of Observations per Variable
measurements on a medical implant, or samples of rein-
forced concrete from bridges of a particular type. FIG. 6--Statistical confidence and statistical error curves as a
Randomization is largely an identical process, except its focus function of the number of observations per test variable [42].
is on internal validity. An example might be random assign- 9 Copyright 2001 by NACE International. All rights reserved
ment of 48 p r e p a r e d material specimens to three groups. In by NACE; reprinted by permission.
this example, three "samples" of 16 observations (speci-
mens) each are drawn from the "population" of 48 material observations per variable, confidence in the results is high
specimens. The purpose is to create three test groups that are and the error is small regardless of the variability. For small
equivalent and statistically independent of one another. In both numbers of observations per variable, the confidence de-
situations, chance alone determines assignment of observa- creases substantially and is sensitive to the n u m b e r of ob-
tions (observations and cases are interchangeable terms) to servations taken. With only three observations per variable,
a given sample (the aggregate of observations or cases). the level of confidence is only 55 %, corresponding to a risk
level of 45 %, i.e., a 45 % risk that the wrong conclusion
Determining the Required Number may have been reached about corrosion performance or
of Observations service life. W h e n resources permit, some statisticians rec-
o m m e n d 12-18 observations p e r variable corresponding to
There are three considerations in determining the num- 90-93 % confidence in the data, or a 10-7 % level of risk [42].
ber of observations to be included in the case of sampling
from a larger population or in randomization. One consid-
eration is the variance in the dependent variable. Other Curve Fitting and Simple Statistical Modeling
things being equal, the larger the variance, the larger the Often a relationship is sought between corrosion per-
required n u m b e r of observations. A second consideration is formance and some controllable variable, such as exposure
the n u m b e r of factors that will be included in any statistical time. R a n d o m error can produce enough scatter in the data
analysis. The larger the n u m b e r of variables, the more to make visual curve fitting imprecise. W h a t is desired is the
observations that are needed. best data fit. One way used frequently to accomplish a good
Finally, the level of precision required to successfully fit is to use regression analysis to minimize the sum of the
complete the study affects the required n u m b e r of observa- square of the data deviations about the fitted curve. This is
tions. Again, the same considerations apply in randomiza- the "method of least squares." Many physical relationships
tion and in sampling from a larger population: other things are not linear functions. F o r example,
being equal, a large n u m b e r of observations is needed to
detect a small change or to obtain a higher level of confi- logarithmic y = a + blnX (I)
dence in the result. F o r example, larger samples are needed
to accurately predict whether there is a difference in exponential y = be ax (2)
corrosion performance between two alloys with similar power y = bX a (3)
compositions. Also, since statistical tests and estimates are
conditioned by probabilities, larger samples reduce the risk However, they can be put in linear forrn by data transfor-
of drawing the wrong inference from a sample (see the mation. Fitting these functions by least squares is not
discussion of probability distributions and confidence limits necessarily straightforward, but fortunately there are user-
in Part II Chapter 5.) friendly curve fitting software utilities included with most
The effect of replicate samples for each variable on statis- major spreadsheets and statistical packages that will find
tical error and confidence is illustrated in Fig. 6. The top the best fit for these and other functions.
curve is the statistical confidence as a function of the Another m e t h o d is to use a polynomial in the independent
n u m b e r of observations p e r test variable, with the n u m b e r variable and then use multiple linear regression, consider-
of observations and the corresponding statistical confidence ing each p o w e r of the independent variable in the polyno-
(as a percent) also shown in parentheses. The bottom mial as a separate linear variable. Powers of a single
curve is the statistical error, which was generated for three independent variable can be used to fit a complex curve in two
magnitudes of variability in the data. For large numbers of dimensions (Eq 4). For example, many growth processes in

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54 CORROSION TESTS AND STANDARDS MANUAL

nature, when charted over time, will tend to follow a sinu-


soidal curve as they transition from one state of equilibrium
to another. This can be approximated using a third-order
polynomial regression with one independent variable. With
two independent variables, a complex surface can be fit in
three dimensions. A second order example with two inde-
p e n d e n t variables is given in Eq 5 and the approach can be
extended to third and higher order models.

y = a + biX + bllX2 +billX3 + . . . blll..aX k (4)

y = a +blX 1 +b2X 2 +bll X12+b22X2 +bl2X1X 2 (5)

An estimate for a multiplicative model (Eq 6) can be ob-


tained through simple log transformations as shown in Eq 7.
FIG. 7--Cyclic polarization curves from six nominally identical
y=aX1 blx2 b2 23 b3 (6) samples of UNS C10920 copper exposed to a high viscosity,
high pH solution [42]. 9 Copyright 2001 by NACE International.
In y = In a + bl lnXa + b2 lnX2 + b3 lnX3 (7) All rights reserved by NACE; reprinted by permission.

Each of these approaches will yield a best fit based on the


criterion of least squares. A standard measure to express whenever X and Z can be made statistically independent, and
this is the coefficient of determination, R 2. R 2 has a range this can be accomplished in a variety of ways. Referring
from 0 to 1 and can be expressed as the ratio: back to the previous example, atmospheric corrosion ex-
periments can be conducted in chambers, where both
R 2 =1- SSE/SST (8) temperature and moisture (rainfall) can be controlled
completely and independently, or experiments can be con-
where:
ducted in a climate where moisture does not vary signifi-
S S T = sum of squared deviations of y from the m e a n of y. cantly compared to temperature.
S S E = sum of squared deviations of y from the fitted An experiment in which all other relevant variables are
curve or trend line. held constant is an effective approach when it can be
achieved. However, all relevant factors may not be known.
However, in interpreting R 2 and especially in comparing R 2 Furthermore, circumstances often preclude the ability to hold
values, it is important to keep in m i n d that a perfect fit can some variables constant. For example, there may be unfore-
always be obtained with a sufficiently complex curve. An seen factors that affect the course of a corrosion experiment,
alternative is the "adjusted R2, " which is a more realistic as in the polarization curves in Fig. 7 for nominally identical
measure of goodness of fit and expressed as: samples of copper (UNS C10920). Most of the curves indicate
A d j u s t e d R E = 1 - (n-I/n~p)SSE/SST (9) the copper will actively corrode in the solution. However, one
curve indicates the copper will passivate over a narrow range
where n is the n u m b e r of observations and p represents the of potentials. Had a structure or device been built based on
n u m b e r of predictors in the regression equation. Note that the passive curve it would have failed unexpectedly. Fortu-
if p is greater than 1, the "adjusted R 2" will always be nately, enough replicate curves were measured to show that
smaller than R 2. the passive curve was the exception [42].
Completely R a n d o m i z e d D e s i g n s - - T h e concept of ran-
Designing Experiments domization was discussed above in relation to probability
sampling, and also with regard to two sample tests. Given
I n statistical terms, the primary goal of an experimental sufficient sample size, r a n d o m assignment of observations
design is to introduce controls that eliminate or signifi- to two or more groups will tend to result in statistical inde-
cantly reduce statistical dependence between the factor of pendence between the groups. The larger the groups, the bet-
interest and other factors that might influence the test out- ter the approximation to perfect statistical independence.
come or dependent variable. To illustrate, consider three As an example, reinforced concrete slabs are prepared for
variables: X, Y, and Z. X is an experimental factor, Y is a an experiment to compare effectiveness of arc-sprayed zinc
test outcome measure or dependent variable, and Z is an and titanium anodes. All the slabs will be put under im-
independent variable that is correlated with both Y and X. pressed current cathodic protection, and exposed to con-
For example, in atmospheric corrosion, the corrosion rate trolled applications of chloride to the concrete to promote
(Y) is influenced by both temperature (X) and rainfall (Z). corrosion of the reinforcing bar. Slabs are assigned ran-
However, a wet season will also tend to be a cool one in the domly to be coated with either arc-sprayed zinc or titanium.
natural environment, so temperature and rainfall will be In this case, randomization is a desirable precaution to con-
correlated, or confounded. trol small inconsistencies due to mixing of the concrete, the
Controlling Z makes it possible to assess the influence chemical composition of the concrete, or the distribution of
that X and only X has on Y. Z is effectively controlled aggregate in the concrete.

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CHAPTER 1 - - P L A N N I N G AND D E S I G N OF TESTS 55

An i m p o r t a n t advantage of r a n d o m i z a t i o n is that it will concrete test slabs left over from o t h e r experiments, a n d
effectively control not only factors that are known, but also we will assume for the p u r p o s e of illustration that they are
factors that are not known. Consequently, randomization is suitable for use in this new test. The test slabs have been
particularly useful in studies where no well-developed coated with either a carbon, titanium, or zinc anode, a n d
knowledge base exists. The p r i m a r y disadvantage of a com- as a result of a previous e x p e r i m e n t they have been elec-
pletely r a n d o m i z e d design is that, other things being equal, t r o c h e m i c a l l y aged to simulate in-service lives ranging
it requires more cases than other designs. In determining from 0-20 years.
the required n u m b e r of test cases for a completely random- Conceptually, the simplest design would involve using all
ized design, the same considerations apply that were dis- 120 test slabs in the experiment, and randomly assigning
cussed earlier in this chapter under "Probability sampling the slabs to three groups, one for each humectant, and one
and randomization." to serve as a control group. This would constitute a simple
Factorial Designs--Sometimes more than one treatment r a n d o m i z e d experiment. However, the efficiency of the ex-
variable is of interest in an experiment. Whenever an ex- p e r i m e n t could be improved by using a randomized block
p e r i m e n t involves the manipulation of two treatments, it is design. This would involve, as a first step, specifying levels
referred to as a factorial design. F o r example one might of each blocking factor to include in the experiment. In this
wish to test the effects of a chemical wetting agent on the instance there are the three "levels" of anode type. In addition,
conductivity of concrete at varying levels of relative humid- three age categories can be established representing: young
ity. A full factorial design involves testing all combinations (0-6 years), m e d i u m (7-13 years), and old (14-20 years)
of two or more treatment factors. A fractional factorial slab electrochemical age. The advantage introduced by
study excludes some treatment combinations [43]. blocking is that it assures that two variables known to be
Block Designs--As noted already, the p r i m a r y disadvan- important (anode type and slab electrochemical age) are
tage of a r a n d o m i z e d design is the n u m b e r of observations forced to be independent of the treatment. Also, by group-
that m a y be required to effectively control other factors. ing the blocked factor, variance is reduced.
The n u m b e r of required observations can often be reduced The next step would be to assign slabs to the blocks based
through blocking. Blocking can be applied to single factor on the three levels of treatment (and control). Assignment
or multi-factor studies. Variables m a y be incorporated as should be r a n d o m within the nine blocks defined by anode
blocking factors or as additional treatment factors. A treat- electrochemical age and anode type. A r a n d o m process
m e n t factor is usually part of the p r i m a r y focus of an ex- would assign three slabs within each of the nine blocks to
periment, while a blocking factor is more typically a the three levels of treatment/control; remaining slabs would
"nuisance" factor to be controlled. More important, a be d r o p p e d from the experiment. This process requires only
treatment factor is manipulated directly by the corrosionist, 3 (anode type) x 3 (anode age) x 3 (treatment/control) = 27 slabs.
while a blocking factor is controlled indirectly through Organization of the experiment is described in Table 3.
selection and organization of observations. This is the m i n i m u m n u m b e r of slabs required for the ex-
Consider the simplest case for blocking in which one par- perimental design. In some cases it might be advisable to
ticular independent variable is known to have a strong include replications within blocks. The purpose of replica-
statistical relationship (correlation) with the dependent tions would be to preclude unanticipated attrition (e.g., a
variable in an experiment. Observations can be sorted on test accident) or to control unidentified variables through
that independent variable and formed into homogeneous randomization. If the experimenter is confident that no
groups. Treatments are then conducted within each of these uncontrolled or unidentified variables are present, there is
homogeneous groupings of the blocking variable. Blocking no need for replications within blocks.
effectively holds the criterion variable constant within By using a r a n d o m i z e d block design the n u m b e r of test
blocks, and therefore the treatments will be statistically specimens was reduced from 120 to 27. However, to do so
independent of the blocking variable. Also, because the required some assumptions. One assumption was that no
blocking variable is known to be correlated with the de- unidentified or uncontrolled variables were present to con-
pendent variable, blocking will reduce the variance of the found the experiment; hence there was no benefit in includ-
dependent variable within blocks. It is this latter conse- ing replications within blocks. The second was that the
quence of blocking that improves efficiency over a fully factors used in blocking were in fact correlated with the
r a n d o m i z e d design. treatment; if not, nothing was gained through blocking.
More than one variable can be used as blocking criteria, To improve the efficiency of the experiment even further
hut adding blocking criteria increases the n u m b e r of blocks, one could go to an incomplete block design. An incomplete
and this c o m p o u n d s the n u m b e r of times an experiment block design does not run all treatments in all blocks. The
must be replicated. Consider an experiment in which a most extreme case is the Latin square design. In a Latin
treatment is administered at six levels. Consider further that
two blocking factors have been selected, and that each of
TABLE 3--A randomized block experiment,a
these has six levels. The m i n i m u m required cases for a ran-
domized block design is 6 x 6 x 6 = 216. Electrochemical Anode Type
To illustrate r a n d o m i z e d block designs, consider the fol- Age Carbon Titanium Zinc
lowing example: an e x p e r i m e n t is c o n d u c t e d to test the Young AI1,Bll,Cll A21,B21,C21 A31,B31,C31
effectiveness of two h u m e c t a n t s (wetting agents) on the Medium AI2,B12,C12 A22,B22,C22 A32,B32,C32
operation of impressed current cathodic protection systems Old A13,B13,C13 A2s,B23,C23 A33,B33,C33
on r e i n f o r c e d concrete bridges. There are 120 reinforced aA, B, a n d C represent h u m e c t a n t treatments.

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56 C O R R O S I O N T E S T S AND S T A N D A R D S MANUAL

TABLE 4---A Latin square designfl F ratio is n a m e d for R. A. Fischer [41]. The simplest exten-
Electrochemical Anode Type sion involves comparisons of three o r more groups. Another
Age Carbon Zinc Titanium involves introduction of more than one factor. Also, it
Young B 11 A21 C31 should be noted that whenever m o r e than one factor is in-
Medium A12 C22 B32 cluded in an experiment, it becomes possible to test for in-
Old C13 B23 A33 teraction effects. Interaction refers to a situation in which
~A, B, and C represent humectant treatments. the effects of two variables are nonadditive, or that the ef-
fect of one variable depends on the level of a second variable.
Analysis of variance becomes m o r e complicated with
square design each level of each blocking factor receives more complex designs. It is often the case with incomplete
each treatment just once, as in Table 4. However, note that block and fractional factorial designs that some or all inter-
each row and each column contains all three treatments. actions cannot be tested. In the case of more complex de-
The primary advantage of a Latin square is that the experi- signs, it is advisable to consult an experienced statistician
m e n t can be conducted with nine specimens. One important for assistance, both in the design of the experiment and in
disadvantage is that a Latin square requires two blocking setting up the analysis.
factors, and both blocking factors, along with the treatment
factor m u s t have the same n u m b e r of levels. However, the
m a i n disadvantage of a Latin square, and to some extent all
incomplete block designs, is that interactions are con- DEVELOP TEST PROTOCOL
founded. For instance, suppose that the different humectant
treatments affect the anodes very differently. What is actually A test protocol transforms the corrosion test design into a
an interaction between anode type and the treatment, would set of reliable and reproducible measurements that achieve
be impossible to disentangle from the effects of anode age. the goals and objectives of the test. The test protocol may
simply be a guide or "road map" to the raw or un-
interpreted measurements defining methods and standards.
Statistical Tests for Experiments W h e n measurements must meet legal, regulatory, o r cus-
t o m e r challenges, the test protocol m a y be codified into a
In a statistically designed corrosion experiment the goal is
quality assurance (QA) plan [45,46]. The test protocol typi-
to infer a cause and effect relationship between a treatment
cally specifies criteria for precision, accuracy, completeness,
variable and a dependent variable. By whatever means this
representativeness, and comparability of the corrosion and
is achieved, there is an implicit assumption that, except for
related measurements. It can address sampling and analyti-
the treatment itself, there is an equivalence between the
cal procedures, calibration procedures and standards, data
sample of units that received a treatment and the sample
reduction and processing methods, data validation, data
(controls) that did not. In statistical analysis of results from
reporting, and data audits.
experiments, all tests start with this assumption of equiva-
Many of the measurements involved in corrosion tests
lence between or among groups in all regards except for the
are defined in standards to establish precision, accuracy,
factors being tested. Experimental designs are intended to
representativeness, and comparability [10-14]. Analytical
assure, or at least approximate, conditions that make that
techniques and measurements used to characterize the en-
assumption credible.
vironment and corrosion product chemistry, and to evaluate
The simplest category of testing in an experimental design
coatings properties and inhibitor performance, are largely
is the two-sample test. There are a n u m b e r of nonparamet-
covered by "good laboratory practices" standards [45]. In
ric tests that are appropriate for comparisons of two
addition, the requirements for certain analytical and envi-
groups. The most familiar is the two-sample Chi square (~2)
ronmental measurements used in regulatory efforts have
test, but there is also Fisher's Exact Test, the m e d i a n test,
been established in the Code of Federal Regulations (CFR)
Mann and Whitney's U, and m a n y others [44]. Nonparamet-
[47]. The corrosionist should become familiar with and use
ric tests are usually applicable when the dependent variable
these sources of information as they apply to the goals and
is categorical, b u t whenever the dependent variable will
objectives of the study. Table 5 lists some of the ASTM stan-
support computation of a mean, the most typical test to be
dards that are m o r e widely used by corrosionists.
applied is the difference of means test. If two groups are
created through r a n d o m assignment from a c o m m o n pool,
differences can be expected to be attributable to either
sampling error or some external influence occurring subse- ENGINEER TEST
quent to assignment. By effectively ruling out chance on the
basis of probability, one is left with the implication that Engineering the test assures that materials, equipment, in-
some factor subsequent to assignment accounts for the dif- strumentation, personnel, and supporting services are avail-
ference. In a well-designed experiment, the only possible able and used in a timely and effective manner. The test plan
candidate should be the treatment factor. must be examined with a clear understanding of problems
This same basic a p p r o a c h can be extended to any of the that may arise to thwart its successful completion. Critical
experimental designs discussed above using analysis of supplies, equipment, and schedule steps must be identified;
variance (ANOVA). ANOVA was developed early in the options developed; tasks simplified; resources allocated; and
1920s by the British statistician, R. A. Fischer, to apply adequate time allotted. The cost and effort of this step is usu-
statistical methods to agricultural experiments. In fact, the ally recouped in a more efficient, trouble-free corrosion test.

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CHAPTER 1 - - P L A N N I N G AND D E S I G N OF TESTS 57

TABLE 5--Widely used ASTM corrosion and related standards [10-12].


Standard Standard Title
G1 Preparing, Cleaning, and Evaluating Corrosion Test Specimens
G3 Conventions Applicable to Electrochemical Measurements in Corrosion Testing
G4 Conducting Corrosion Coupon Tests in Plant Equipment
G5 Making Potentiostatic and Potentiodynamic Anodic Polarization Measurements
G15 Terminology Relating to Corrosion and Corrosion Testing
G16 Applying Statistics to Analysis of Corrosion Data
G31 Laboratory Immersion Corrosion Testing of Metals
G38 Making and Using C-Ring Stress-Corrosion Test Specimens
G 40 Terminology Relating to Wear and Erosion
G 46 Examination and Evaluation of Pitting Corrosion
G 50 Conducting Atmospheric Corrosion Tests on Metals
G57 Field Measurement of Soil Resistivity Using the Wenner Four-Electrode Method
G59 Conducting Potentiodynamic Polarization Resistance Measurements
G71 Conducting and Evaluating Galvanic Corrosion Tests in Electrolytes
G 82 Development and Use of a Galvanic Series for Predicting Galvanic Corrosion Performance
G 102 Calculation of Corrosion Rates and Related Information from Electrochemical Measurements
G 119 Determining Synergism Between Wear and Corrosion
C 876 Half Cell Potentials of Uncoated Reinforcing Steel in Concrete
E 380 Use of the International System (SI) of Units
E 527 Numbering Metals and Alloys

Pilot plant and service tests may be more vulnerable to in the corrosive environment, lost or damaged corrosion
unforeseen difficulties as a consequence of constraints and samples, or loss or failure of monitoring capability.
demands from external technical and nontechnical sources. Comparing test results with the goals and objectives of
Laboratory tests avoid some of these difficulties because the test is the clearest measure of the success of the test. In
there is usually more flexibility in the allocation of supplies this way, opportunities to improve the test by revising its
a n d equipment and in the scheduling of personnel. Certain design, exploiting scientific and technological advances, and
c o m m o n sense practices can improve laboratory, pilot considering new or additional information can be achieved.
plant, and service tests. Use good quality water for the
preparation of aqueous solutions (systems are available at
reasonable cost that routinely supply Type 1 water) (see SUMMARY
ASTM D 1193, Specification for Reagent Water, part 9).
Provide regulated and filter power for operating critical Corrosion tests provide information about materials and
electronic instruments and computers. Establish a well- their applications that have an important effect on the eco-
defined ground system for test equipment. nomic vitality and quality of life. An overview of the key
Support personnel provide a valuable base of additional steps in planning and designing corrosion tests includes
experience and often serve as assistants to the investigator. identifying goals and objectives, developing a test design
To use support personnel effectively, they must understand using statistical and economic analysis, establishing the
the goals and objectives of the test, have adequate training, protocol for reliable and reproducible measurements, effi-
and clearly understand their role and responsibilities. ciently engineering the corrosion test with limited re-
sources, and coping with modifications to the test plan.

MODIFY TEST
REFERENCES
Test plan execution is the point where the corrosionist
[1] "Corrosion Costs and Preventive Strategies in the United
must cope with changes that affect resource allocation,
States," in a supplement to Materials Performance, NACE
personnel schedules, and goals and objectives. These changes International, Houston, TX, July 2002, 11 pp.
may alter the test design, the nature of the results, and the [2] Virmani, Y. P., "Corrosion Costs and Preventive Strategies in
analysis and interpretation of results. Even when external the United States," Tech Brief, FHWA-RD-01-157, Federal
factors cause no changes, the investigator should examine Highway Administration, U.S. Department of Transportation,
data early in the test, incomplete as they may be, to ensure Washington, DC, March 2002.
that the results will meet the goals and objectives of the test [3] Koch, G. H., Brongers, M. P. H., Thompson, N. G., Virmani, Y. P.,
while time and resources may exist to modify the plan. and Payer, J. H., "Corrosion Cost and Preventive Strategies in
Many changes can be anticipated and their impact on the the United States," FHWA-RD-156, Federal Highway Admini-
test plan minimized. Changes arise in the planning and de- stration, U.S. Department of Transportation, Washington, DC,
sign stage through interactions with others who manage, March 2002.
[4] Spahn, H., "Corrosion Control for Low-Cost Reliability," Pro-
operate, oversee, study, maintain, or fund related technical
ceedings of 12th International Corrosion Congress, NACE
areas. Changes that cannot be anticipated have a more sig- International, September 1993, Plenary 4-19.
nificant impact on the plan. These can range from loss of [5] Ailor, W. H., Handbook on Corrosion Testing and Evaluation,
personnel, damaged equipment, vandalism, major changes John Wiley and Sons, New York, 1971, pp. 1-112.

Copyright by ASTM Int'l (all rights reserved); Wed Feb 10 11:00:35 EST 2010
Downloaded/printed by
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58 CORROSION TESTS AND STANDARDS MANUAL

[6] Dean, S. W., Jr., Atmospheric Corrosion, W. H. Ailor, Ed., John [26] McElvily, A. J., Jr., Atlas of Stress-Corrosion and Corrosion Fa-
Wiley and Sons, New York, 1982, pp. 195-216. tigue Curves, ASM International, Materials Park, OH, 1990.
[7] Sprowls, D. O., Corrosion, ASM Metals Handbook, Vol. 13, 9th [27] Schlain, D., Corrosion Properties of Titanium and Its Alloys,
ed., ASM International, Metals Park, OH, 1987, pp. 193-196 Bulletin 619, U.S. Bureau of Mines, 1964.
and pp. 316-317. [28] Corrosion in Sulfuric Acid, Symposium Proceedings,
[8] Fontana, M. G. and Greene, N. D., Corrosion Engineering, CORROSION/85, NACE International, Houston, TX, 1985.
McGraw-Hill, NY, 1978. [29] Corrosion Rates of Steel in Concrete, ASTM STP 1065, N. S.
[9] Haynes, G. S. and Baboian, R., Laboratory Corrosion Tests Berke, V. Chaker, and D. Whiting, Eds., ASTM International,
and Standards, ASTM STP 866, ASTM International, West West Conshohocken, PA, 1990.
Conshohocken, PA, 1985. [30] Effects of Soil Characteristics on Corrosion, ASTM STP 1013,
[10] "American Society for Testing and Materials, Wear and Ero- V. Chaker and J. D. Palmer, Eds., ASTM International, West
sion; Metal Corrosion," Annual Book of ASTM Standards, Conshohocken, PA, 1989.
Vol. 03.02, ASTM International, West Conshohocken, PA, 1993. [31] Corrosion, ASM Metals Handbook, Vol. 13, 9th ed., ASM Inter-
[11] "American Society for Testing and Materials, General Methods national, Metals Park, OH, 1987, pp. 377-1367.
and Instrumentation," Annual Book of ASTM Standards, [32] Mansfeld, F., Corrosion Mechanisms, Marcel Dekker, NY, 1987.
Vol. 14.02, ASTM International, West Conshohocken, PA, 1993. [33] Szklarska-Smialowska, Z., Pitting Corrosion of Metals, NACE
[12] ASTM International, 100 Barr Harbor Drive, West Conshohocken International, Houston, TX, 1986.
PA 19428-2959; see also http://www.astm.org/; make the following [34] Baloun, C. H., Corrosion, Metals Handbook, Vol. 13, 9th ed.,
selections: ASTM Store; Search for individual standards; ASTM ASM International, Materials Park, OH, 1987, p. 207.
Designation only - Search for "corrosion." [35] Corbett, R. A. and Saldanha, B. H., Corrosion, Metals Hand-
[13] NACE International, 1440 South Creek Drive, Houston TX book, Vol., 13, 9th ed., ASM International, Materials Park, OH,
77084-4906; see also NACE Standards at http://www.nace.org/ 1987, pp. 239-240.
nace/content/nacesecure/standards.cfm. [36] King, G. A., "Corrosivity Mapping--A Sensitive and Cost Effec-
[14] International Organization for Standardization (International tive Means of Characterizing a Region's Level of Atmospheric
Standards Organization, ISO), 1, rue de Varemb6, Case postale Corrosion," Paper 93638, CORROSION/93, NACE Interna-
56, CH-1211 Geneva 20, Switzerland; see also http://www.iso.ch/ tional, Houston, TX, 1993.
iso/en/ISOOnline.openerpage. Make the following selections: [37] Spence, J. W., Haynie, F. H., Lipfert, F. W., et al., "Atmospheric
International Standards; ICS field 77 (Metallurgy); 77.060 Corrosion Model for Galvanized Steel Structures," Corrosion,
(Corrosion of Metals). Vol. 48, No. 12, 1992, pp. 1009-1019.
[15] Rak, G. F., "The Corrosion Professional's Role in a Regulated [38] Graedel, T. E., Nassau, K., Franey, J. P., et al., "Copper Patina
and Litigious Environment," Materials Performance, Vol. 40, Formation," Corrosion Science, Vol. 27, No. 7, 1987, pp. 639-782.
No. 5, 2001, pp. 18-21. [39] Cramer, S. D., Matthes, S. A., Covino, B. S., Jr., Bullard, S. J.,
[16] Verink, E. D., Koltz, J., Rumble, J., and Ugiansky, G. N., "Cor- and Holcomb, G. R., "Environmental Factors Affecting the At-
rosion Data Program Workshop Summary," Materials Perform- mospheric Corrosion of Copper," Outdoor and Indoor Atmos-
ance, Vol. 26, No. 4, 1987, pp. 55-60. pheric Corrosion, ASTM STP 1421, H. E. Townsend, Ed., ASTM
[17] Mansfeld, F. and Bertocci, U., Electrochemical Corrosion Test- International, West Conshohocken, PA, 2002, pp. 245-264.
ing, ASTM STP 727, ASTM International, West Conshohocken, [40] Cramer, S. D., Matthes, S. A., Holcomb, G. R., Covino, B. S., Jr.,
PA, 1981. and Bullard, S. J., "Precipitation Runoff and Atmospheric
[18] Geef, R., Peat, R., Peter, L. M., et al., Instrumental Methods in Corrosion," Paper No. 00452, CORROSION~2000, NACE Inter-
Electrochemistry, John Wiley and Sons, NY, 1985. national, Houston TX, 2000.
[19] Electrochemical Impedance: Analysis and Interpretation, ASTM [41] Snedecor, G. and Cochran, W., Statistical Methods, Eighth ed.,
STP 1188, J. R. Scully, D. C. Silverman, and M. W. Kendig, Iowa State University Press, Ames, Iowa, 1989.
Eds., ASTM International, West Conshohocken, PA, 1993. [42] Tait, W. S., "Increase Your Confidence in Corrosion Test Data,"
[20] Bard, A. J. and Faulkner, L. R., Electrochemical Methods, John Materials Performance, NACE International, Houston TX,
Wiley and Sons, NY, 1980. Vol. 40, No. 3, 2001, pp. 58-61.
[21] Pourbaix, M., Atlas of Electrochemical Equilibria in Aqueous [43] Neter, J., Kutner, M., Nachtsheim, C., and Wasserman, W.,
Solutions, NACE International, Houston, TX, 1974. Applied Linear Statistical Models, 4th ed., McGraw-Hill, Boston,
[22] Frankenthal, R. P. and Kruger, J., Equilibrium Diagrams---Localized 1996, pp. 795-797.
Corrosion, Electrochemical Society, Pennington, N J, 1984. [44] Siegel, S., Chapters 5 and 6, Nonparametric Statistics for the
[23] Chen, C. M., Aral, K., and Theus, G. J., Computer-Calculated Behavioral Sciences, McGraw-Hill Book Company, NY, 1956.
Potential pH Diagrams to 300C, Vol. 2, EPRI NP-3137, Electric [45] Garner, W. Y., Barge, M. S., and Ussary, J. P., Good Laboratory Prac-
Power Research Institute, Palo Alto, CA, 1983. tice Standards, American Chemical Society, Washington, DC, 1992.
[24] Shreir, L. L., Jarman, R. A., and Burstein, G. T., Eds., Corro- [46] Ratliff, T. A., Jr., The Laboratory Quality Assurance System, Van
sion: Metal~Environmental Reactions, Vol. i, 3rd ed., Nostrand Reinhold, NY, 1990.
Butterworth/Heinemann, Oxford, U.K., 1994. [47] Code of Federal Regulations, U.S. Government Printing Office,
[25] Uhlig's Corrosion Handbook, 2nd edition, R. W. Revie, Ed., Office of the Federal Register, National Archives and Records
Wiley, NY, 2000. Service, General Services Administration, Washington, DC, 1993.

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Types of Data ~------ :=::== . . . . . .
::::::::::::::::::::::::::::::::::::::

D a v i d C. S i l v e r m a n ~

CORROSION TESTS ARE performed to provide information on electrode measured at open circuit in an electrolyte. The
material degradation in specific environments, information voltage is measured relative to a reference electrode. For
that is not available from other sources. Corrosion testing can example, ASTM G 69, Practice for Measurement of Corro-
be divided into two broad categories, electrochemical and sion Potentials of A l u m i n u m Alloys, describes how to meas-
nonelectrochemical. Within these categories, test results are ure the corrosion potential of a l u m i n u m alloys, and ASTM
presented in a n u m b e r of ways, ranging from numerical out- G 82, Guide for Development and Use of a Galvanic Series
put to qualitative examination of the test specimen. Both for Predicting Galvanic Corrosion Performance, describes
types of data are represented in each category. A very com- the development and use of a practical galvanic series for
plete listing of data formats for collection and compilation predicting relative corrosion performance. Very often, the
for computerized databases is presented in ASTM G 107, attempt is made to relate the measured potential to poten-
Guide for Formats for Collection and Compilation of Corro- tials calculated from thermodynamic data, e.g., as presented
sion Data for Metals for Computerized Database Input. The in Pourbaix Diagrams [1], in order to understand better the
information in that standard includes a significant portion of corrosion mechanism. One reason this approach requires
the type of test data that might be recorded during corrosion caution is that the measured corrosion potential is at best a
testing. Since required data are test-dependent, not every test steady state potential in which reactions are not at equilib-
would include all of the data listed, but the standard does r i u m and the potential on the Pourbaix diagram is a ther-
provide a reasonable, first pass checklist and should be used modynamic or equilibrium potential.
to ensure that needed information is not overlooked. Confusion sometimes exists with the sign convention
The purpose of this chapter is to provide an overview of when reporting voltage with respect to the reference elec-
types of corrosion data for metals and alloys that might be trode. The thermodynamic electrochemical potential of a
obtained from or be relevant to different types of corrosion reaction written as oxidizing (M-->Mn++ne-, where M is the
tests. The examples discussed are not meant to be all-inclusive. metal and e is the electron) has the opposite sign as when
They are meant to provide a flavor of the types of data that the same reaction is written as reducing (Mn++ne-~M). The
might be recorded. The reader is strongly encouraged to refer recommended approach is to use the Stockholm sign
to the references and cited standards for a more complete dis- invariant convention. I n this convention, the positive direc-
cussion of the types of data relevant to the test discussed. tion (increasing potential) implies increasingly oxidizing
conditions at the electrode surface (noble). The negative
direction (decreasing potential) implies increasingly reduc-
ELECTROCHEMICAL TEST DATA ing conditions at the electrode surface (active). For exam-
ple, the potential of the gold couple with its ion would be
The m a i n variables that are measured in an electrochemi- more positive than the couple of zinc with its ion. Care
cal test are the voltage and the current. The goal is to trans- must be taken when recording the potential of a specimen
late this information into a corrosion rate or some other in an electrolyte relative to a reference electrode so that the
information that describes the corrosion process. ASTM G 3, recorded potentials are consistent with this convention. One
Practice for Conventions Applicable to Electrochemical can always make sure that the connection is correct, i.e., the
Measurements in Corrosion Testing, provides guidelines for leads are hooked up properly, by checking against a known
conventions for reporting a myriad of electrochemical data couple (see ASTM G 3).
for the more c o m m o n tests.
Current or Current D e n s i t y
Potential
Measurement of current or current density is the most
One very common electrochemical measurement is the cor- c o m m o n output of electrochemical corrosion tests. This
rosion potential. This potential is the voltage of the corroding quantity is usually related either to the corrosion rate or to
some features of the corrosion process, such as surface re-
dox reactions that can change the corrosion characteristics.
1principal Consultant, Argentum Solutions, Inc., 14314 Strawbridge Ct.,
Chesterfield, MO 63017, e-marl: dcsflverman@argentums~176176 The relationship between the measured current and the
web site:www.argentumsolutions.com. corrosion rate or m e c h a n i s m depends to some degree on
59

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60 C O R R O S I O N T E S T S AND S T A N D A R D S MANUAL

Related Information from Electrochemical Measurements,


o
provides the methodology and equations. The method is

o
~ Stope- P~
summarized as follows. The slope actually contains contri-
butions from the polarization resistance (shown) and the
uncompensated resistance. The latter term contains several
contributions, two of which are the electrical resistance in
u.i
the solution between the reference electrode sensing point
and the working electrode and the electrical resistance of
r the leads and measuring circuit. This u n c o m p e n s a t e d solu-
tion resistance m u s t be subtracted from the resistance cal-
o culated from the slope to obtain the actual polarization
resistance. The corrosion current is estimated from this
corrected value. The procedure is to divide the Stern Geary
: I I I I I I I I I ~ constant by the polarization resistance. ASTM G 102 and
AnodLc Currenl: 0enss Refs 2 and 3 provide details on how the Stern Geary con-
(-) Cathods162
CuJ~'enl~F
stant might be estimated. If the current m e a s u r e m e n t is in
current, e.g., amp, and not current per unit area of working
electrode, e.g., amp/cm 2, the corrosion current density is
estimated from the corrosion current by dividing it by the
exposed specimen surface area. The specimen area must be
measured. Finally, the corrosion rate as a mass loss is ob-
tained from the corrosion current density. The corrosion
current density is divided by the density of the alloy and is
multiplied by the alloy equivalent weight and a constant to
obtain the corrosion rate in the proper units. The alloy
equivalent weight is the reciprocal of the sum taken over all
FIG. lmHypothetical polarization resistance or linear polariza- of the elements in the alloy of the valence of the element
tion plot (from ASTM G 3). times its mass fraction divided by its atomic weight. The reader
is referred to ASTM G 102 for the details and justification of
the technique used to obtain the current. The type of data using the alloy equivalent weight. Thus, more information
obtained and the format by which the information is than that in Fig. 1 is needed for the corrosion rate to be es-
displayed depend on the test. Some tests display voltage timated from polarization resistance measurements.
versus current, others display voltage versus the logarithm A second type of presentation of current is as the plot of
of the current, others display information about the imped- voltage versus logarithm of the current density (current di-
ance (voltage divided by the current), and others examine vided by the surface area). ASTM G 5, Standard Reference
fluctuations in the current a r o u n d some average value. Test Method for Making Potentiostatic and Potentiodynamic
These different types of current data have different uses and Anodic Polarization Measurements, and ASTM G 61, Test
m a y require additional types of data or analysis programs Method for Conducting Cyclic Potenfiodynamic Polarization
to translate the data into usable information.
Polarization resistance or linear polarization measure-
i.2
ments are used to determine the polarization resistance, a
quantity related to the corrosion rate. Current is measured
I.O
as a function of vokage in the vicinity of the corrosion po-
tential. The two values are plotted as voltage versus current.
The polarization resistance is the slope of the curve at the
At.I.OYC-2/1;
corrosion potential. The importance of this quantity lies in UNSNaOZ?S
the fact that it is (usually) inversely proportional to the cor- LQ
.i
rosion current, the proportionality constant being related to
the Tafel slopes. ASTM G 59, Practice for Conducting Poten- o
tiodynamic Polarization Resistance Measurements, de-
scribes a m e t h o d by which these measurements are made 0.2
a n d the polarization resistance is calculated. Figure 1 shows
a hypothetical plot as a function of current. A very extensive o

discussion of the historical development, theory and assump-


tions, and pitfalls provides an excellent background to -o.s TYPE304STAINLESSSTEEL
UNS $30400
ASTM G 59 [2]. Additional experimental artifacts have also
been discussed [3].
Data in addition to the slope as estimated from a curve, |o 0 io I io,2 io ]
CUNRKNTO(NSITY ( ] , / ~ t / c m 2 )
such as in Fig. 1, are required when calculating the corro-
sion rate from polarization resistance measurements. ASTM FIG. 2mRepresentative cyclic potentiodynamic polarization
G 102, Practice for Calculation of Corrosion Rates and curves (from ASTM G 61).

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CHAPTER 2 - - T Y P E S OF DATA 61

Measurements for Localized Corrosion Susceptibility of divided by the surface area, and the impedance has the
Iron-, Nickel-, or Cobalt-based Alloys, show examples of units of ohm-cm 2. Details are provided in ASTM G 106,
these types of plots. They are generated by ramping the Standard Practice for Verification of Algorithm and Equip-
voltage at a preset rate in the anodic direction with respect m e n t for Electrochemical Impedance Measurements. The
to the corrosion potential. Sometimes, the voltage ramp is impedance is usually plotted in one of two ways, as the in-
then reversed so that the potential is driven at a slow rate verse of the imaginary component versus the real compo-
back to the corrosion potential. This procedure of using a nent, as in Fig. 3a, or as a pair of plots in which the
forward and reverse ramp of voltage is called cyclic poten- magnitude of the impedance and the inverse of the phase
tiodynamic polarization. Figure 2 shows an example of a angle are plotted as function of the logarithm of the fre-
cyclic potentiodynamic polarization scan. One of the pur- quency, as in Figs. 3b and 3c (see ASTM G 106 and G 107).
poses of performing this type of experiment and presenting A plethora of literature exists that discusses how to relate
the data in this m a n n e r is to estimate the susceptibility of the structure of the impedance spectrum to the corrosion
an alloy to undergo localized corrosion in the form of crev- mechanism and corrosion rate. In the limit of zero fre-
ice corrosion and pitting. Certain relationships among quency, the impedance becomes equal to the polarization
"characteristic" voltages, e.g., the difference between the resistance discussed above. Situations arise in which this
"repassivation potential" and the corrosion potential and value is not inversely related to the corrosion rate [5]. The
the difference between the "pitting potential" and the corro- reader is referred to two recent symposia on electrochemi-
sion potential, as well as other features related to the cur- cal impedance spectroscopy that provide excellent "snap-
rent, can be used to make a j u d g m e n t about corrosion [4]. shots" of the state of the art in determining corrosion rates
Both quantitative and qualitative information constitute the and mechanisms from the impedance spectra and provide
data that are used to interpret the polarization scan. information on the additional types of data needed to make
The electrochemical reactivation technique provides a dif- the connection [6,7]. In addition, Ref 3 provides an over-
ferent way of presenting and using current (see ASTM G view of practical applications of this technology, as well as
108, Test Method for Electrochemical Reactivation (EPR) those mentioned previously [3].
Test Method for Detecting Sensitization of AISI Type 304
and 304L Stainless Steels). This test, like the one above,
Electrochemical Noise
involves a voltage ramp, but in this case, the voltage ramp is
from the passive region of the alloy to the active region. The The technique that has been labeled as electrochemical
required test result is the integration of the current or the noise is the m e a s u r e m e n t and analysis of fluctuations in
total charge passed. This charge is related to the degree of potential or current that arise from uncontrolled variations
sensitization of the alloy. In this case, the charge is divided in a corrosion process. This technique has received much
by both the surface area and often the average grain size so attention both for laboratory studies and on-line monitoring
it, too, must be measured. for localized corrosion (pitting, crevice corrosion, and stress
Coupling of dissimilar metals can create a current caused corrosion cracking), coating degradation, and general corro-
by the potential difference between the two alloys. Such sion [8]. Though no ASTM standard yet exists with respect
galvanic currents are measured by a zero resistance amme- to measurement procedure or analysis algorithm, a brief
ter placed in an external circuit that connects the two alloys discussion of types of data associated with this technique
immersed in an electrolyte (see ASTM G 71, Guide for Con- is warranted because of the attention that this technique has
ducting and Evaluating Galvanic Corrosion Tests in Electro- received. The recorded data themselves are current and volt-
lytes). Sometimes, the current when divided by the surface age recorded at constant time intervals. The method used to
area can be used to calculate the corrosion rate from analyze the data points is as important as the data points
Faraday's law. Often when using this type of test the coupled themselves.
specimens have different surface areas so the surface area of The methods used for expressing the data fall into two
each specimen is a type of data. If corrosion is localized on categories, time domain techniques and frequency domain
the alloy surfaces, however, conversion of current to a mass- techniques. The two methods are related because frequency
loss based corrosion rate may not be meaningful. and time are the reciprocals of each other. The analysis
technique influences the data requirements. Reference 9
provides a brief overview of the various mathematical
Impedance
methods and a multitude of additional references. Special-
Measurement of impedance of a corroding electrode has ized transforms (Fourier) can be used to transfer informa-
become important in corrosion prediction for such diverse tion between the two domains. Time domain measures
applications as coatings and corrosion rate estimation in include the normal statistical measures such as mean,
low conductivity media. As most commonly practiced, an variance, third moment, skewness, fourth moment, kurto-
electrode is subjected to a small amplitude (e.g., 5-10 mV) sis, standard deviation, coefficient of variance, and root
sinusoidal variation in the voltage of varying frequency, m e a n square as well as an additional parameter, the ratio of
usually about the corrosion potential. The current is mea- the standard deviation to the root m e a n square value of the
sured. The applied voltage is divided by this measured cur- current (when measuring current noise) used in place of the
rent. Since both the voltage and current have a sinusoidal coefficient of variance because the m e a n could be zero. An
component with respect to time and are usually out-of- additional time d o m a i n measure that can describe the de-
phase, the division results in the impedance, which itself gree of randomness is the autocorrelation function of the
has real and imaginary contributions. Often, the current is voltage or current signal. The m a i n frequency domain

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62 C O R R O S I O N TESTS AND S T A N D A R D S MANUAL

EQUlVALgNTOROJIT measure is the power spectral density of the corrosion


potential noise or the current noise. The power spectrum is
the Fourier Transform of the autocorrelation function and
100.0 -
is the distribution of power of the signal in the frequency
domain. The power spectral density is usually estimated by
J~
the Fast Fourier Transform algorithm or the m a x i m u m en-
~o ~.0- tropy algorithm. Another transform that is presently being
C
investigated but has not found widespread use is the wave-
O
let transform [IO]. This transform has been proposed to
50.0. A A overcome some of the shortcomings of the more traditional
A

&
4= Fourier transform by using a family of basis functions that
&
O
_= &
are localized in both the time and frequency domains. De-
A == bate remains as to which measures provide the most infor-
25.O-
_E
!
&
== mation, so all are found in the literature.
A The types of data m e n t i o n e d in the previous paragraph
0.0
A

| | pertain to the results from analyzing fluctuations in either


0.0 ='.0 =o'.o 7s'.o ~o;.o ,,~.0 the voltage or current signal individually. One additional
Real Resistance (ohm) analysis is to divide the standard deviation of the voltage
signal by the standard deviation of the current signal to ob-
tain the noise resistance [11]. This parameter can be equiva-
lent to the polarization resistance discussed i n the previous
section.

I
,~ 10=".
NONELECTROCHEMICAL TEST DATA
&
&
Though a significant fraction of metallic corrosion in-
/, volves electrochemical processes, much of corrosion testing
:IE ==
Q involves techniques that do not have as the m a i n goal the
A&&AID.&&&&A&&AA &
10' m e a s u r e m e n t of current or voltage. These techniques are
"10 used to examine a n u m b e r of different forms of corrosion.
o
Q.
_E Sometimes the data that result from the tests are quantita-
tive. Sometimes the data are qualitative. Pictures of either
the actual corroded sample or magnified portions of the cor-
lO0 i ,I , , 'l'J, , , i t ll,,~'ll
roded sample are often very useful and must be considered
1r '"i) .... .... lo" as types of data.
b Fr~uenc~ (h=)

Corrosion Rate from Mass Loss


60-
The most c o m m o n method for estimating the corrosion
- == rate is from the mass loss of a metal specimen of known
dimensions immersed in a fluid for a k n o w n amount of
A
O
time. The weight of the specimen is obtained before and
A after the exposure. The corrosion rate is obtained by divid-
ing by the exposed area, the time, and the density. The pro-
c- &
& cedure is outlined in ASTM G 31, Practice for Laboratory
O
A
&
Immersion Corrosion Testing of Metals. An example of a
OrO"20" A typical vessel for conducting such a test is shown in that
et &
standard. Different units exist for expressing the corrosion
! A
A
&

A
& rate (mils/year for penetration rate or mg/dm2/day for mass
A ~ A loss rate). Though a n u m b e r of assumptions are made about
A * ^A~ A~I~II' AI)'II'AI~'A~
the test and specimen when making this estimate, reasona-
o i i. , i i H . I i ~ ; , i ,~,,~ bly reliable values can be obtained when corrosion is not
o:' ..... lo' ..... ;7 ..... le localized but extends reasonably uniformly across the
r Frequency (hz) specimen. Guidelines have been presented as to the error
associated with measurements of weight, time, and surface
FIG. 3--Plot of electrochemical impedance spectrum in:
area when these are the only sources of error [12].
(a) Nyquist format, inverse of the imaginary impedance
versus real impedance; (b) Bode format, logarithm of In the case of rectangular panels or coupons, the area
the impedance magnitude versus logarithm of the may be calculated from the exposed flat sides plus the four
frequency; (c) Bode format, inverse of the phase angle edges. Many investigators have chosen not to include the
versus logarithm of the frequency (from ASTM G 106). edge area, though its inclusion is fairly easily done. In the

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C H A P T E R 2 - - T Y P E S O F DATA 63

case of a wire specimen, the exposed area decreases as cor- above, certain features of the cyclic potentiodynamic polar-
rosion proceeds. In order to take this effect into account, a ization scan are used to estimate somewhat qualitatively the
somewhat different approach must be used to calculate the risk of localized corrosion in the form of pitting and crevice
mass loss per unit area. corrosion. Likewise, the results from coupon immersion
tests used to estimate the risk of crevice corrosion and pit-
Flat panel: ting also contain both types of information. I n the case of
A - 2lw + 2lt +2wt (1) crevice corrosion, a c o m m o n procedure is to immerse a
coupon u p o n which is m o u n t e d an artificial crevice former.
where ASTM G 78, Guide for Crevice Corrosion Testing of Iron-Base
l = length, and Nickel-Base Stainless Alloys in Seawater and Other
w = width, Chloride-Containing Aqueous Environments, describes a ty-
t = thickness, pical procedure. Typical observations include a recording
A = exposed specimen area. of the general appearance of the specimen, its mass change,
the m a x i m u m depth of corrosion in each crevice, the n u m b e r
Wire specimen radius loss:
of crevices that had attack under them, and the severity
of that attack. A picture sometimes becomes part of the
data. This information might be used to rank alloy perform-
ance in the environment either qualitatively or even semi-
quantitatively.
~r = radius reduction from corrosion loss,
Similar types of qualitative and quantitative data are also
d i = initial diameter before exposure,
combined when examining pitting. When a specimen is ex-
mi = initial mass,
posed to an environment, the depths of pits are often mea-
m f = final mass after exposure,
sured. However, the relationship between such depth and a
Am = mass loss.
pitting growth rate is not straightforward because pits do
The specimen must be cleaned after exposure in order to not necessarily grow at a continuous rate. Sometimes a
obtain mass loss results. In m a n y cases weighing the panel sample is sectioned near the pit to examine its structure.
before cleaning is desirable so that an estimate of the corro- ASTM G 46, Guide for Examination and Evaluation of Pit-
sion product thickness or mass can be obtained. In some ting Corrosion, provides a standard rating chart for pits in
cases, removal of the corrosion products should be done which the density of pits on a surface is rated on a scale of
nondestructively from at least a small area on some of the 1-5 (1 being the fewest pits, shallowest attack), as well as
panels so that chemical analyses of the corrosion products diagrams of different types of pit shapes. Comparing actual
may be carried out. Such removal may be done by scraping appearance to that shown in the standard can provide im-
the surface or by using replicating tape. Replicating tape is portant information about the resistance of the alloy, how it
not very effective in removing rust from steel specimens. is being attacked, and possible ways to overcome the attack.
ASTM G 1, Standard Practice for Preparing, Cleaning, and The appearance of the specimen is a type of data. ASTM G
Evaluating Corrosion Test Specimens, provides additional 46 discusses a n u m b e r of detection and analysis techniques
information. that could be used for analyzing pitting and the types of
The laboratory immersion test in which a specimen is ex- data that each technique can supply. In addition, the stan-
posed for a period of time and then removed for examina- dard provides a methodology by which a pitting probability
tion assumes that the corrosion rate remains constant with might be estimated from an immersion test.
time. This assumption is not completely valid, even if the Pitting corrosion is a p h e n o m e n o n that may or may not
e n v i r o n m e n t remains static over the exposure time. The proceed at a constant rate. Pitting can initiate, propagate,
corrosion rate might decrease from a high rate during stop, reinitiate, propagate, stop, etc., many times before the
which passivation occurs or inhibitors adsorb, or the corro- entire specimen is penetrated completely. The mere pres-
sion rate might increase as different kinetic processes estab- ence of pitting does not necessarily indicate failure. Only
lish themselves. When the a m o u n t of change is great, one when the deepest pit has penetrated and a leak has occurred
might use a modified immersion test in which identical has the alloy actually failed. The time for such penetration
specimens are immersed for differing time periods in the to occur may be impossible to estimate. I n the laboratory,
same e n v i r o n m e n t [13]. The mass loss, exposure time asso- test time and specimen surface area can be far different
ciated with that mass loss, and area are used to calculate from the expected field exposure time and surface area of
the corrosion rate for each interval. By comparing the rates the equipment being used. One method that has been pro-
during the different time periods, one can judge if the corrosion posed to bridge the large differences in space and time is
rate is constant, increasing, or decreasing. Again, the types using the statistical theory of extreme values [14,15]. The
of data needed are time, mass, and dimensions, but the ex- test and actual environments are assumed to be the same.
posure intervals are shorter than the total time of the test. Pit depths are measured on the laboratory specimen. The
values are fit to a probability distribution function. If the fit
is good, then by introducing the concept of return period,
Localized Corrosion
which is the ratio of the surface area of the object to the
Required data can sometimes be a mixture of qualitative surface area of the specimen, the m a x i m u m pit depth can,
observations and quantitative measurements that are com- in principle, be estimated for the object. The technique still
bined to provide an overall picture of corrosion. As mentioned requires more validation to determine the extent of usefulness.

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64 CORROSION TESTS AND STANDARDS MANUAL

If valid, it could provide a quantitative methodology for Velocity Sensitive Corrosion (Single Phase Flow)
relating m e a s u r e d pit depths to equipment life. In terms of
Corrosion can be sensitive to fluid motion, and often, fluid
required data, one needs to know the surface area of both
motion is included when testing for corrosion susceptibility.
the laboratory coupon and the object being examined by the
W h e n fluid motion becomes part of the experimental proto-
coupon and the depths of the pits on the coupon.
col, measurements not only have to be m a d e under dynamic
Types of data recorded for detection of intergranular cor-
conditions, but the data recorded m u s t characterize the fluid
rosion are both qualitative and quantitative. Qualitative data
m o t i o n in addition to corrosion rate or other indications of
are visual. They are obtained by examining under magnifica-
corrosion. This brief discussion is provided only to point out
tion a m o u n t e d a n d polished specimen that is etched appro-
the type of information that must be obtained and recorded
priately. The etched structure is usually c o m p a r e d to
to integrate fluid motion into the estimation of corrosion.
photographs of specimens suffering similar types of corro-
Though ASTM standards for testing for velocity sensitive
sion (see ASTM A 262, Practices for Detecting Susceptibility
corrosion do not yet exist, a recent NACE International Report
to Intergranular Attack in Austenitic Stainless Steels) to de-
reviews several methods for making these measurements
termine if intergranular corrosion is observed on the speci-
[19]. While the techniques described all have different geo-
m e n u n d e r examination [16]. The observed surface structure
metries, certain types of data are c o m m o n to all. Merely
becomes the data. Characteristic information that might be
recording fluid velocity or agitation rate is not sufficient to
recorded are evidence of grains missing from the structure,
characterize the relationship between fluid motion and cor-
pits in the grain ends, and ditches between the grains.
rosion. Fluid motion is often quantified in terms of the dimen-
Quantitative d a t a relating to i n t e r g r a n u l a r corrosion are
sionless group the Reynolds number (Re). Quantities such as
actually relative c o r r o s i o n rates between different materi-
fluid shear stress at the wall and the friction factor used to
als or the same m a t e r i a l t r e a t e d differently. F o r example,
characterize the relationships between fluid flow field and
the alloy u n d e r e x a m i n a t i o n is exposed to a strongly acidic
the geometry are functions of this dimensionless group. If
solution (see ASTM G 28, Test Methods of Detecting Sus-
mass transfer controls or influences corrosion, the Schmidt
ceptibility to I n t e r g r a n u l a r Attack in Wrought, Nickel-
number (Sc) and Sherwood number (Sh) are included in the
Rich, C h r o m i u m Bearing Alloys) for a specified length of
description. These dimensionless groups are:
time [16]. The c o r r o s i o n rate is calculated from the mass
loss of the specimen, its area, and the time of exposure Re - (velocity)(characteristic_ length) (3)
(see ASTM G 31). This rate is c o m p a r e d to that o b t a i n e d
(kinematic _ viscosity)
for a p r o p e r l y a n n e a l e d material. Large differences be-
tween the two c o r r o s i o n rates can m e a n the presence of
i n t e r g r a n u l a r corrosion.
Sc - (kinematic_viscosity)
(4)
( diffusivity )
Stress Corrosion Cracking
The most c o m m o n form of evaluation is time to failure
S h - (mass_transfer_coefficient)(characteristic_length) (5)
for stress corrosion specimens. Failure usually means
observation of the first crack. In relatively brittle materials, ( diffusivity )
small cracks propagate rapidly causing the material to
break into pieces. For specimens with constant loads, the The dimensionless groups can usually be related by the fol-
rate of crack propagation increases as cracking proceeds, lowing equation:
and failure is usually manifested as breaking of the speci-
men. Most specimens, however, are stressed by means of a S h = a Re b Sc c (6)
constant strain. In such cases, the rate of propagation de-
creases after the initial crack is formed and, consequently,
the best measure of time to failure is the time to observa- where a, b, and c are constants that d e p e n d on the geometry
tion of the first crack. of the test apparatus.
A n u m b e r of tests are available that are used to estimate Equation 6 is usually assumed to model the relationship
the alloy most resistant to stress corrosion cracking in an among these dimensionless groups and the variables a, b,
environment or to estimate a relative ranking of resistance and c are determined by curve-fitting to actual data for the
among alloys. These tests employ a n u m b e r of different geometry in question.
types of specimens including U-bends, C-bends, precracked Finally, when the corrosion rate is u n d e r complete mass
(Fracture Mechanics) specimens, tuning fork specimens, transfer control, the corrosion rate can be derived from an
tension specimens, etc. The type of data generated depends equation of the form:
on the specimen and the test. The reader is encouraged to
consult two reviews [17,18] and the considerable n u m b e r of Corrosion Rate = (Mass Transfer Coefficient)
(7)
citations to which the articles refer. These references dis- x (Concentration Gradient)
cuss the type of data obtainable in stress corrosion cracking
tests in considerable detail, as well as the behavior of a In theory, one could estimate the mass transfer controlled
n u m b e r of alloys. One of the reviews also contains refer- corrosion rate from knowledge of velocity, the characteristic
ences to a n u m b e r of the ASTM standards that discuss test dimension, and certain physical properties. In practice,
methods for stress corrosion cracking [17]. such a simplified approach would not be prudent though

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C H A P T E R 2 - - T Y P E S OF DATA 65

differences between measured and calculated values might Science and Engineering, M. G. Fontana and R. W. Staehle,
provide insight into the corrosion mechanism. Eds., Vol. 6, Plenum Press, NY, 1976, p. 163.
The background and methodology for using these parame- [3] Silverman, D. C., "Practical Corrosion Prediction Using Electro-
ters in real situations to relate the laboratory geometry to the chemical Techniques," Chap. 68 in Uhlig's Corrosion Handbook,
field and estimate corrosion rates are presented in detail 2nd ed., R. W. Revie, Ed., John Wiley and Sons, 2000, p. 1179.
[4] Rosen, E. M. and Silverman, D. C., "Corrosion Prediction from
elsewhere [20,21]. The equations point to the information
Polarization Scans Using an Artificial Neural Network Integrated
deficiency if only velocity is recorded. Such physical proper- with an Expert System," Corrosion, Vol. 48, No. 9, 1992, p. 734.
ties as the diffusivity, viscosity (kinematic viscosity = abso- [5] Gabrielli, C., Keddam, M., and Takenouti, H., "The Use of AC
lute viscosity/density), and density need to be included in the Impedance Techniques in the Study of Corrosion and Passiv-
recorded data. The characteristic length is a parameter that ity," in Treatise in Materials Science Technology, J. C. Scully,
scales the geometry to the flow field and is used as a scaling Ed., Vol. 23, Academic Press, San Diego, CA, 1993, p. 395.
factor for distance from the wall. Examples are the diameter [6] Electrochemical Impedance: Analysis and Interpretation, ASTM
of a rotating cylinder or the diameter of a pipe. The concen- STP 1188, J. R. Scully, D. C. Silverman, and M. W. Kendig,
tration gradient between the corroding surface and the bulk Eds., ASTM International, West Conshohocken, PA, 1993.
fluid can often be approximated by the bulk concentration [7] Proceedings of the Second International Conference on Electro-
(e.g., oxygen diffusion controlling) or the saturation concen- chemical Impedance Spectroscopy, Santa Barbara, CA, 1992,
D. D. Macdonald, Ed., in EIectrochimica Acta, Vol. 38, 1993.
tration (e.g., steel corroding in concentrated sulfuric acid).
[8] Eden, D. A., "Electrochemical Noise," Chap. 69 in Uhlig's Cor-
Either should be measurable. The reader should consult the rosion Handbook, 2nd ed., R. W. Revie, Ed., John Wiley and
references for more details. Sons, 2000, p. 1227.
[9] Eden, D. A., "Electrochemical Noise - The First Two Octaves,"
Paper 386, presented at CORROSION~98, March, 1998, reprint
O T H E R DATA available from NACE International, Conferences Division, P. O.
Box 218340, Houston, TX 77218-8340.
Though this brief discussion has focused on the various [10] Motard, R. L., Dai, X. D., Joseph, B., Silverman, D. C., "Im-
types of corrosion data that might be recorded during cer- proved Discrimination of Electrochemical Noise Signals Using
tain corrosion tests or upon the analysis of the data, there Wavelet Analysis," Corrosion, Vol. 57, No. 5, 2001, p. 394.
[11] Chen, J. F. and Bogaerts, W. F., "The Physical Meaning of Noise
also are noncorrosion data that should be recorded. Tem-
Resistance," Corrosion Science, Vol. 37, No. 11, 1995, p. 1839.
perature, alloy type, heat number, surface condition, and [12] Freeman, R. A. and Silverman, D. C., "Error Propagation in
e n v i r o n m e n t chemistry are a few examples. Many more Coupon Immersion Test," Corrosion, Vol. 48, No. 6, 1992, p. 463.
exist and may be required to complete the analysis. ASTM G [13] Fontana, M., Corrosion Engineering, McGraw-Hill Book Com-
107, and especially its Table 1, contains a reasonably com- pany, New York, 1986, p. 164.
prehensive list of the type of data that might be recorded [14] Shibata, T., "Corrosion Probability and Statistical Evaluation of
during a corrosion test. ASTM G 161, Standard Guide for Corrosion," Chap. 22 in Uhlig's Corrosion Handbook, 2nd ed.,
Corrosion Related Failure and Analysis, and especially its R. W. Revie, Ed., John Wiley and Sons, New York, 2000, p. 367.
Appendix Xl, list the type of qualitative and quantitative [15] Ault, J. P. and Gehring, G. A., "Statistical Analysis of Pitting
data that should be considered when analyzing corrosion- Corrosion in Condensor Tubes," in Corrosion Testing in Natural
Waters, ASTM STP 1300, Vol. 2, ASTM International, West
related failures. Though not all of the data types listed are Conshohocken, PA, 1996.
relevant to every test, the contents serve as a useful check- [16] "Failure Analysis and Prevention," Metals Handbook, Vol. 11,
list. Experimenters are encouraged to consult these listings 9th ed., ASM International, Metals Park, OH, 1986.
prior to setting up an experiment to help ensure that key [17] Phull, B., "Evaluating Stress-Corrosion Cracking," Corrosion:
data and observations are not omitted from the measure- Fundamentals, Testing, and Protection, ASM Handbook, Vol. 13A,
ments or records during the testing. An important concept Materials Park, OH, 2003, p. 575.
to keep in m i n d is that recording too m u c h information is [18] Corrosion--Metal~Environmental Reactions, L. L. Shreir, R. A.
always better than not recording enough information. Jarman, and G. T. Burstein, Eds., Vol. 1, Chap. 8, Butterworth-
Heinemann, Oxford, 1998.
[19] "State-of-the-Art Report on Controlled-Flow Laboratory Corro-
sion Tests," NACE Publication 5A195, NACE International,
REFERENCES Houston, TX, 1995.
[20] Silverman, D. C., "Rotating Cylinder Electrode-Geometry Rela-
[1] Pourbaix, M., Atlas of Electrochemical Equilibria in Aqueous tionships for Prediction of Velocity-Sensitive Corrosion," Cor-
Solutions, National Association of Corrosion Engineers, rosion, Vol. 44, 1988, p. 42.
Houston, TX, 1974. [21] Efird, K. D., "Flow-Induced Corrosion," Chap. 14 in Uhlig's
[2] Mansfeld, F., "The Polarization Resistance Technique for Corrosion Handbook, 2nd ed., R. W. Revie, Ed., John Wiley and
Measuring Corrosion Currents," in Advances in Corrosion Sons, 2000, p. 233.

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iiiiiiiiiiiiii !ii!i

Metallographic Analysis iiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiiii!iiiiiiiiiiiiiiiiiiiiiiiiii

R i c h a r d L. C o l w e l l 1

A NEW DOOR opened into the study of materials in the late chemical species responsible for damage m a y dissolve and
19th century (1863) when a British geologist n a m e d Henry be washed away.
C. Sorby decided to polish a piece of steel, etch it with acid,
and examine it u n d e r a microscope. Since that time, metal-
lographic examinations have been performed on most every
PROCEDURES FOR SAMPLE PREPARATION
engineering material developed.
Metallographic examination is a valuable tool in provid-
Fixturing and Mounting
ing an understanding of structure/property relationships in
m a n y engineering materials. The true value in these exami- Once a sample has been obtained, it can be prepared for
nations cannot be obtained without an intimate knowledge metallographic examination. Preparation usually involves
of a materials t h e r m o d y n a m i c phase equilibria, and the taking a representative sample of usable size and fixturing it
effects of environmental factors on that equilibria. While for easy handling during grinding. The sample may be
this knowledge can be gleaned from the numerous technical fixtured in a mechanical assembly by using a clamping load
volumes available, first h a n d experience can be a far better supplied by threaded fasteners. Most often the sample is
teacher. sandwiched between two pieces of material of similar hard-
ness. This sandwiching promotes good edge retention. One
should be sure that the sandwich material is nonreactive
SAMPLE SELECTION with the sample, especially in the presence of water and
other fluids. In order to prevent capillary draw of fluid into
The selection of samples can be very important to the out- the crevices inherent to the clamping fixture, paraffin can
come of metallographic analysis. If the component is very be used to fill the voids and gaps.
large, it m a y require sectioning to provide manageable Another fixmring technique involves the use of either ther-
metallographic samples. The location for removal of metal- moplastic, or thermosetting polymer granules and powders.
lographic samples should be considered carefully. Samples These powders and granules have different values of wearabil-
should contain areas representative of the corroded or frac- ity. Mounting resins with high wear resistance promote good
tured component. Samples of unaffected areas can reveal edge retention, but slow the material removal rate. Mounting
contrasting structures, thus distinguishing damage. Some- polymers can also be transparent and electrically conductive.
times multiple samples must be taken at different orienta- Conductive mounts are required to keep the sample from
tions to understand the true nature of failure mechanism. charging when examination using a scanning electron micro-
W h e n sectioning, care should be taken to keep the sample scope is required.
cool. Elevated temperatures can promote phase transforma- Mounting involves inserting a specimen, to-be-polished
tions and exfoliation of surface deposits and scales. Heat side down, into a heated cylindrical cavity of fixed diameter
can also p r o m o t e volatilization of chemical species on the so that the area to be examined is flat against one end of the
surface. Keeping the sample cool m a y require slow cutting cylinder. The sample may require support, such as clip
to avoid heat generation. If samples must be cut using a rings, to keep it in the desired position. Next, polymer gran-
torch, make sure that large areas are removed, thus leaving ules or powder, or both, are carefully added to the cavity,
enough unaffected area for later saw cuts. Recently, the care being taken to not disturb the sample. Once sufficient
p l a s m a cutting torch has gained m u c h acceptance for use in material has covered the sample, the other end of the cylin-
obtaining samples in steels. The plasma torch transfers very der is secured, and the cylinder is pressurized. Heat and
little heat to the steel, thus creating very small heat-affected pressure cause the polymer to liquify and then set, thus
areas. encapsulating the sample. Thermoplastic polymers should
Cutting may also require use of a coolant. One should be be allowed to cool to near r o o m temperature before releas-
careful of liquid coolants, especially if chemical analysis of ing pressure. At temperatures above their glass transition,
surface scales and deposits will be required. Introduction of flow will result, causing the polymer to pull away from the
cooling liquids can contaminate areas of interest. In addition, sample.
When encapsulating samples, it is advisable, if possible,
1Bechtel Corporation, Houston, TX. to remove any sharp corners, sharp protrusions, and burrs
66

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CHAPTER 3 - - M E T A L L O G R A P H I C A N A L Y S I S 67

from the sample edges. Their presence tends to concentrate


stresses during polymer cool-down and can promote crack-
ing. Once cool, the sample can be handled easily during
grinding and polishing.
Another method of sample fixturing uses cold-set epoxy
resins. This m e t h o d is helpful when samples are large or
when cutting affects the physical integrity of the sample.
Samples can be m o u n t e d in mold release coated metal
molds or bakelite preforms. Molds or preforms, or both, are
then affixed (rubber cement, Seal-AllTM, etc.) to an alumi-
n u m foil or PTFE covered flat surface. The sample is then
placed on the flat foil/PTFE surface, in the preform, side-to-
be polished down. Mixed, bubble-free epoxy resin is then
p o u r e d over the sample, filling the mold. When using epoxy
resins, it is helpful to have access to a bell jar and vacuum
pump. A few minutes u n d e r vacuum tends to draw any air
and gas bubbles out of the sample. The best method using
liquid resins involves introducing it to the sample while
u n d e r vacuum. Upon venting to atmosphere, resin is actu-
ally forced into microcavities. The sample is then placed in
the preform mold and resin is added to fill the mold.
For some resins, raising the temperature of reaction sig-
nificantly reduces the time required for the resin to cure, but
there are some drawbacks. If the temperature is too high, the
resin can oxidize, causing discoloration, thus decreasing visi-
bility of the sample. More important, the amount of shrink-
age is significantly higher for resins cured at temperatures
above room temperature. This shrinkage can lead to cracking
FIG. 1--Mounting arrangement for preserving oxide scales.
of the epoxy glass. Curing at high temperatures can also
cause the epoxy to pull away from the sample, which pro-
motes staining during etching.
If metallographic examination of coatings, specifically using rotating abrasives, or automatically (usually encom-
oxide coatings, is required, the following special techniques passing rotating abrasives, a counterrotating sample platen,
are helpful in preserving the integrity of the coating. The and downwards pressure of the sample onto the abrasive).
basis of coating preservation involves minimizing shrinkage The choice between these methods depends on the n u m b e r
associated with the curing resin. Blank mounts are made by of samples and economy.
filling bubble-free liquid resin in 1.25 in. diameter bakelite Whatever method is used, the principle is still the same:
preforms. After a 24 h cure, two parallel saw cuts are made material removal. Material is removed for two reasons. The
(approximately 7/8 in. apart) through the sample, creating first involves removal of gross scratches and deformities from
flats (Fig. 1). Next, a thin slot is cut n o r m a l to the fiats, half- the surface. The second, which is equally important, espe-
way through the m o u n t thickness. The ends of the slot are cially for softer materials, is to remove subsurface damage.
d a m m e d up using cellophane tape. The sample is vacuum During grinding, abrasive particles actually cut gouges in the
impregnated and then placed in the slot. The sample is then sample surface. While cutting, the material just beneath the
s h i m m e d up using thin stainless steel strips. "The strips surface of the gouge is plastically deformed. This plastically
minimize rounding and reduce the chance of separation at deformed material has a higher dislocation density, and is
the specimen-resin interface by providing a preferential site therefore higher in internal strain energy than the material
for such separation, if any should occur" [1]. around it. During etching, these higher energy areas are pre-
Other methods are available and the reader is advised ferentially attacked, thus leaving traces of scratches and etch
to explore them. A good outline of additional mounting pits. It is very important to not only remove the scratches you
methods and materials is given in Metallography Principles see, but remove subsurface damage you cannot see.
and Practice by G. Vander Voort, Ref 2, section 2.4, During grinding, the metallographer should keep in mind
and ASTM E 3, Methods of Preparation of Metallographic that increasing the pressure on the sample will result in
Specimens, sections 7 through 9. greater material removal rates, but will not increase the
a m o u n t of subsurface damage [3]. The m a x i m u m depth of
subsurface damage is independent of pressure [4].
Grinding Traditionally, grinding starts at grits numbered 60 or 120,
Once the sample is fixtured properly, the Surface should depending on the initial condition and flatness of the sample.
be ground smooth and flat. Grinding is traditionally per- Grinding should start with the finest grit capable of rendering
formed using silicon carbide papers, but sometimes dia- a flat specimen and removing damage from sectioning. Coarse
m o n d impregnated grinding media are used. Grinding can grinding should be minimized in order to limit subsurface
be done manually with stationary abrasive papers, manually deformation. Figure 2 shows the relationship between scratch

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68 C O R R O S I O N T E S T S AND S T A N D A R D S MANUAL

20 TABLE 1--Polishing cloth selection table.*


~ Total Depth'of D i s l u ~ ~ .... "-"
Cloth RecommendedUses
Canvas Rough general polishing. Use with
r
O
I- Depth ~f Deforrr~t,on coarse grades of SiC and A120~.
a
.g Billiard Cloth (Sheared Rough general polishing of ferrous-
E 12
O / Virgin Wool) based materials.
13. Red Felt (Plucked Virgin Rough or intermediate polishing.
o o o Wool Pile)
o o .t
Cotton-Medium Nap Intermediate polishing. Commonly
s
?
to
0J used with diamond, 111203, and
r~ colloidal silica.
Cotton-Fine Nap Rough diamond polishing of soft
metals. Use with polishing grades of
Al203, Cr203, and silica.
Nylon Rough polishing with diamond. Helps
10 20 30 t.O 50 60 70 80 maintain flatness.
Porticle Size of Grinding Compound ~n pm Silk Use with diamond in rough polishing
of extremely friable materials and
rough polishing of metals.
FIG. 2--Depth of scratches (roughness) and subsurface Woven Wool Rough and intermediate polishing of
deformation in steels as a function of abrasive grit size. hard materials.
Wool (Short Pile) Use in all final polishing stages.
Rayon (Flock on Cotton Final polishing with diamond, A1203.
Backing)
depth (roughness) and depth of deformation in steels for Rayon-Fine Superior final polishing with dia-
various grit sizes [5]. Additional grinding is performed mond, A 1 2 0 3 , and colloidal silica.
using successively finer abrasives, typically using 240, 400, Synthetic Velvet Intermediate and final polishing.
and 600 grit abrasives sequentially. Minimizes relief and edge rounding.
During grinding, the sample surface should be kept cool. Synthetic Velvet-Fine Use in vibratory polisher, especially
with soft materials.
Cooling is usually provided by use of water, alcohol, or Medium Napped Polishing oxide films. Use with cerium
other organic compounds. Nonaqueous coolants are used Polyurethane Cloth oxide.
to inhibit leaching of water soluble compounds from the on Polyester
sample or oxide scales. * C o u r t e s y of S o u t h B a y T e c h n o l o g y , Inc.
Once grinding using 600 grit p a p e r is completed, it is usu-
ally a good idea to chamfer the edges of the sample mount.
This chamfer minimizes damage to the polishing cloth nap.
A diamond extender (i.e., fine cutting oil) is used during
polishing. This oily compound allows diamond particles to
Polishing adhere to the fibers of the polishing cloths, removes abraded
There are basically two types of polishing: electrolytic material, and permits dissipation of heat during polishing.
(electrochemical) and mechanical. Each will be discussed F o r very soft materials, it is sometimes necessary to etch
separately. the sample and repeat the previous step before continuing.
This repetition is required to remove subsurface damaged
Mechanical Polishing material.
Subsequent to grinding and prior to polishing, the metal- Once the sample has been polished to 3 gm, a final step
lographer's hands and the sample should be thoroughly wa- (fine polishing) usually involving either an alumina slurry
shed. Washing keeps any residual grinding abrasives from or colloidal silica slurry is used. The size of particles in
contaminating the polishing cloth. these aqueous slurries can be as small as 0.02 gm. Once
The polishing operation is very similar to grinding, but finished with this step, the sample is ready for etching.
the size of the polishing abrasives is considerably smaller If elemental analysis of the polished sample is to be
than the size of grinding abrasives. Again, the sample performed using SEM/EDS or other X-ray techniques, extra
should be washed between each polishing step to inhibit care should be taken. Often times artifact silicon or alumi-
abrasive carryover and contamination of the polishing n u m peaks ,can be introduced by accumulation of polishing
cloths. Ultrasonic baths are highly r e c o m m e n d e d for clean- abrasives in cracks and pores, and sometimes, depending
ing during polishing. Ultrasonic waves promote superior on the metal hardness, by intrusion into the sample surface.
cleaning by agitating small particles out of cracks and voids.
However, metallographers beware: extended use can result Vibratory Polishing
in cavitation and pitting on the sample surfaces. Vibratory polishing is another method commonly used.
Typically, a sample will first be rough polished using 6 gm Mounted samples are weighted down and allowed to randomly
or 3 gm d i a m o n d compound, or similarly sized alumina circulate on a cloth covered vibrating platen. The platen holds
slurries. Choice of polishing cloth is a function of sample an aggressive slurry of polishing abrasives and is usually cov-
material hardness, polishing rate, desired edge retention, ered to avoid evaporation and splashing. The downside of
and relief. A listing of various polishing cloths and their vibratory polishing is that it requires much more time than
uses is presented in Table 1, It is a good idea to keep sepa- traditional mechanical or electrolytic polishing. Fortunately,
rate wheels for both soft and hard materials. this time is unattended. Vibratory polishing is very good at

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CHAPTER 3--METALLOGRAPHIC ANALYSIS 6 9

Fig. 4~Simplistic representation of the principle of chemical


etching.

Fig. 3--Diagram of a simple electrolytic polishing cell.


In other words, some microstructural constituents are anodic
to others. Grain boundaries and twin boundaries are more
producing scratch-flee samples for soft metals. After polishing, energetic (anodic) than the material in the center of a grain.
samples should be washed, rinsed in alcohol, and blown dry to Likewise, regions under elastic tensile strain, or regions that
avoid staining. have undergone plastic deformation will etch faster than
nonstrained, nondeformed material. In a multiphase material,
Electrolytic Polishing one phase may be more reactive than another.
Electrolytic polishing is a convenient way to polish metal- Similarly, grain orientation on polished surfaces can af-
lic samples in the fine grinded (600 grit) or machined sur- fect the degree of etching. Close packed orientations can
face states. This method requires formation of an electrical etch slightly faster than lesser packed planes.
circuit in which the sample is the anode (Fig. 3). A suitable Under reflected light, etched material will appear darker
electrolyte flows across the surface of the sample. The cur- than the unetched material. Indentations created by etching
rent density is adjusted for the type of material a n d size of act as holes, reflecting light away at different angles. The
the polished sample to facilitate suitable dissolution of "off-reflected" light cannot be reflected back to the objective
metal ions from the to-be-polished surface. As the electro- lens, and therefore appears as regions of darkness (Fig. 4).
lyte washes over the sample, any perturbations in the sur- Some materials etch more easily than others. Grain
face (high energy sites) are selectively dissolved. The result b o u n d a r y delineation in a l u m i n u m alloys is perhaps one
is a flat surface with no mechanical damage. of the most difficult tasks for a metallographer. In alumi-
Although this m e t h o d is easy to use, storage and use of n u m alloys, it is sometimes necessary to experiment with
potentially dangerous electrolytes limit its use. For example, m a n y etchants in order to obtain the desired grain bound-
some solutions of perchloric (HC104) can become explosive ary resolution.
if allowed to evaporate to concentrated solutions. Table 2 contains a n u m b e r of chemical etchants that have
proved useful for a limited n u m b e r of the more popular
Etching engineering alloys. Included are the microstructural charac-
teristics highlighted by the etch.
Etching is performed in order to observe microstructural After chemical etching, samples should be rinsed in wa-
constituents, including grain boundaries, twin planes, slip ter, followed by alcohol and blown dry to avoid staining.
lines, and second phase particles. In addition, etching can Samples should be stored in desiccators to inhibit corrosion
sometimes, as will be discussed later, reveal a material's on the highly polished surfaces. If a desiccator is not avail-
propensity towards certain corrosion mechanisms. able, use of commercial clear coat paints is recommended.
Safe laboratory work practices are very important. A met- Electrolytic etching is similar to chemical etching, but the
allographer is useless without his or her eyes. Use proper electrochemical reaction is forced by means of an externally
protective equipment (gloves, safety glasses, etc.) when using applied potential. If the sample is e m b e d d e d in a polymeric
laboratory chemicals. mounting material, provisions for making electrical contact
There are three basic types of etching mechanisms: chem- m u s t be made (i.e., prepared mount, drilling through the
ical etching, staining, and optical etching. Chemical etching mount, removal from mount, etc.).
uses the anisotropy in a material. The reaction rates A family of chemical etchants known as deposit etchants
of the chemical etchant on a polished sample's surface are works slightly different than chemical etchants. Like elec-
dependent on the energy state of materials microstructure. trolytic etchants, deposit etchants promote dissolution of
The higher the energy state of one region, the faster it will metal on the polished surface. However, the dissolved metal
react, and more etching (localized material removal) occurs. ions react with agents in the etchant solution, promoting

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70 C O R R O S I O N TESTS AND S T A N D A R D S MANUAL

TABLE 2--A brief list of etchants for revealing microstructure in popular engineering alloys.
Alloy Etchant Uses
Aluminum and Al Alloys 0.5-25 g NaOH General purpose etch.
1 g zinc chloride Grain boundary delineation.
100 mL water Immerse up to 2 rain.
1 m L HF (48 %) Outlines microconstituents.
200 mL water Immerse for 30-40 s.
12.5 mL HNO 3 (conc.) General purpose etch.
2.5 mL HF (48 %) Grain boundary delineation.
85 mL water Immerse up to 1 rain.
2 mL HF (48 %) Modified Keller's Rgnt.
3 mL HCl (conc.) General purpose etch for A1 & A1 alloys. Immerse 10-60 s.
20 mL HNO 3 (conc.) Wash in warm water, blow dry.
175 mL water
Copper and Copper Alloys 10 mL NH4OH General purpose etch.
10 mL H202 (3 %) Grain boundary delineation.
Can dilute up to 20 mL water Use fresh, swab, or immerse up to 1 min.
10 g (NH4)2S20 s General purpose etch.
90 mL water Grain boundary delineation.
Immerse up to 1 min.
10 g Cr203 Swab or immerse up to 30 s.
4 drops HC1
75-100 mL water
Nickel and Nickel Alloys 20 mL HNO 3 AquaRegia
60 mL HCL Grain boundary, carbide, and ~ contrast. Use fresh and under
hood. Discard after use.
Swab or immerse up to 1 rain.
3 parts glycerol Glyceregia.
2-3 parts HCl Popular etch. Use fresh and under hood. Discard after use.
1 part HNO 3 Swab or immerse up to 1 rain.
10 g CuSO 4 Marble's Reagent.
50 mL HC1 Grain boundary delineation
50 mL water Swab or immerse up to 1 rain.
A few drops of H2SO4 increase etch activity.
Iron and Iron Alloys 2 mL HNO 3 Nital.
98 mL ethanol Gives good pearlite-ferrite-grain boundary contrast in carbon
and low alloy steels.
Swab or immerse up to 1 rain.
4 g picric acid Picral. Promotes good resolution of pearlite, bainite,
100 mL ethanol martensite, and carbides.
4-5 drops of zephiran Swab or immerse up to 1 rain.
chloride (wetting agent)
100 mL picric acid (sat.) Reveals prior austenitic grain boundaries in martensitic steels.
1 g tridecylbenzene
Stainless Steel 1 part HNO 3 General purpose etch for stainless steels.
1 part HC1 Promotes grain boundary contrast.
1 part water Immerse in a gently stirred solution.
1 g picric acid Viella's Reagent.
5 mL HC1 Outlines carbides, 6, and &
100 mL ethanol Immerse up to 1 rain.
1 part glycerol Glyceregia for SS's.
3 parts HCI Reveals grain structure.
1 part HNO 3 Outlines ~ and carbides.
Use fresh and under hood. Discard after use.
Swab or immerse up to 1 min,
10 g oxalic acid Electrolytic etch (sample is anode). Use at 1-6 V @ 0.1-1.0 A/cm2.
100 mL water Resolves c in 5-10 s. Resolves carbides in 15-30 s. Resolves
grain boundaries in 45-60 s.

p r e c i p i t a t i o n o f i n s o l u b l e c o m p o u n d s o n t h e s a m p l e sur- i d e n t i f i c a t i o n a n d d i f f e r e n t i a t i o n o f oxide films t h a n in out-


face. The relative t h i c k n e s s o f t h e c o a t i n g is d e p e n d e n t o n lining microstructural constituents.
t h e r e a c t i o n rate, w h i c h a g a i n is v a r i a n t d e p e n d i n g o n mi- Optical e t c h i n g is a n o n d e s t r u c t i v e m e t h o d . The t e r m opti-
crostructure and chemical composition. cal e t c h i n g is a m i s n o m e r . Optical m e t h o d s d o n o t involve
H e a t t i n t i n g is a n o t h e r type o f d e p o s i t etch. E x p o s i n g a etching, b u t are useful in s h o w i n g m i c r o s t r u c t u r a l features in
p o l i s h e d s a m p l e ( n o t i n a p l a s t i c m o u n t ! ) to e l e v a t e d t e m - c e r t a i n alloys. In this m e t h o d , m i c r o s t r u c t u r a l contrast, spe-
p e r a t u r e s i n air c a u s e s o x i d a t i o n t o occur. On t h e m i c r o - cifically crystallographic c o n t r a s t of p o l i s h e d samples, is pro-
s c o p i c level, o x i d a t i o n r a t e s o f m i c r o s t r u c t u r a l c o n s t i t u e n t s d u c e d b y u s i n g the "Kohler" principle of i l l u m i n a t i o n (Fig. 5).
v a r y a c c o r d i n g to t h e i r r e a c t i v i t y i n a g i v e n e n v i r o n m e n t . M o d e s o f i l l u m i n a t i o n i n c l u d i n g p o l a r i z e d light, differential
T h e s e c o n d type o f e t c h i n g is m o r e o f a s t a i n i n g o p e r a - i n t e r f e r e n c e c o n t r a s t (Nomarski), a n d d a r k field illumination
t i o n t h a n e t c h i n g . S t a i n i n g h a s b e e n m o r e i n v o l v e d w i t h the c a n p r o d u c e vivid a n d s o m e t i m e s colorful contrast.

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CHAPTER 3 - - M E T A L L O G R A P H I C A N A L Y S I S 71

-- m --f'--" First ,mage plane


cracking. TGSCC is best revealed by etching materials to
reveal grain boundaries (Fig. 6). In addition, the magnitude
of crack branching and crack initiation sites is best re-
vealed by metallographic examination.
fl /t /
~ lens lens set C~ ~t
Susceptibility of SCC is highly dependent on the metals
stress state. Tensile stresses, either applied or residual, above
a threshold value (material dependent), are required for
cracking to occur. Chemical etching of metals can sometimes
provide clues into a material's thermomechanical history.
Signs of plastic deformation (deformation twins, slip lines),
and thus knowledge of exceeding of material yield strength,
Back focal plane ___ I Illumination Radiant
of the objective lens -- ~--F-- condenser field stop can be revealed through etching.
aperture
Some stainless steels can be m a d e susceptible to IGSCC
by exposure to elevated temperatures (823~ < T < 1073~
Objective lens
At these temperatures, carbon atoms migrate to grain
boundaries where they combine with c h r o m i u m atoms to
produce c h r o m i u m carbides. Since c h r o m i u m atoms are
tied up as carbides, they are not available for matrix corro-
FIG. 5~The Kohler Principle of Illumination. sion resistance, and the near-grain boundary regions are
locally depleted in c h r o m i u m (Fig. 7). This depletion ren-
ders grain b o u n d a r y regions susceptible to corrosion, and
A comprehensive list of chemical etchants and etching
procedures can be found i n Refs 2, 6, and 7. the alloy is then termed "sensitized." The degree of sensitiza-
tion is a function of t e m p e r a t u r e and time at temperature.
In many cases, a prediction of the susceptibility of austen-
Metallographic Interpretation itic stainless steels to IGSCC can be obtained by a simple
In the preparation of metallographic samples, not only electrolytic etch (ASTM A 262, Practices for Detecting Sus-
are good hygiene and technique required, but also a good ceptibility to Intergranular Attack in Austenitic Stainless
understanding of the sample material and its properties. Steels, practice A).
Most metallographers have at least once been surprised by a
structural anomaly that turned out to be an artifact. Experi-
Pitting
ence and an inquisitive nature are necessary for good metal-
lographic interpretation. Metallographic examination can be quite useful in deter-
mining severity of pitting, and can also be used to qualify
materials for use in specific environments. A procedure for
METALLOGRAPHIC EXAMINATION metallographic preparation of pitted samples is cited here,
AND EVALUATION
quoting ASTM G 46, Guide for Examination and Evaluation
OF CORROSION MECHANISMS of Pitting Corrosion, section 5.1.5: "Select and cut out a
representative portion of the metal surface containing pits
Stress Corrosion Cracking (SCC)
and prepare a metallographic specimen in accordance to
The nature of stress corrosion cracking (SCC) can be the r e c o m m e n d e d procedures in Methods E 3. Examine
directly observed by metallographic examination. The dis- microscopically to determine whether there is a relation
tinction between intergranular (IGSCC) and transgranular between pits and inclusions or microstructure, or whether

FIG. 6--Transgranular (left) and intergranular (right) stress corrosion cracking in type
304 stainless steel (magnification 200 x,)

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72 C O R R O S I O N TESTS AND S T A N D A R D S MANUAL

20

-+++++ ~ .t-+ +~..+..~

) 15 - -
g
f (a) Narrow, Deep (b) Elliptical (r Wide, Shallow

-_-.

lo - t
/
(d) Subsurface (e) Undercutting

s I I I l i !
-1200 -cO0 -404 0 t,O0 800 1200
(h) Distance from lt'ain boundary Into)

FIG. 7--Electron microprobe analysis showing depletion


of chromium at and near grain boundaries of sensitized (Horizontal)
type 304 stainless steel [14]. (Vetlical)
(I) Microstn~ctural Orientation

the cavities are true pits or might have resulted from metal FIG. 9 ~ A S T M pitting chart for pit shape (see ASTM G 46).
dropout caused by intergranular corrosion, dealloying, etc."
Evaluation of the metallographic samples of pitted mate-
rials can be performed easily using charts A, B, and C in polishing. Material removal can eliminate overly conserva-
ASTM G 46, section 7.2.1. (Figs. 8 and 9). These charts tive measurements caused by the three-dimensional (3-D)
characterize a sample's pit density, pit size, and pit depths. travel path of corrosion pits.
These data are convenient ways of relating and illustrating Another way to quantify the extent of pitting is to just exam-
the severity of pitting to the lay person. It is sometimes ine the pitted surface of an unprepared sample under a labo-
helpful to reassess a sample after additional grinding and ratory microscope. By measuring the vertical difference, via
micrometer measurements on focus knob, between the top of
sample and bottom of pit, the pit depth can be measured.
____A _L C One should use this method with caution because pits are not
DENSITY SIZE DEPTH always straight. Pits m a y travel a circuitous path, and mea-
surement of the perceived pit bottom will result in an overly
conservative depth.

Dealloying
2 . 5 x 103,tin2 0. Smm 2 0.4 mm

Dealloying is a corrosion m e c h a n i s m where one element


in a multielement system is selectively leached from the
matrix by action of a fluid system. Two alloy systems that
are widely known for dealloying are cast iron (graphitic cor-
I x 1041m 2 2.0ram 2 0.Smm
rosion) and copper zinc (Zn > 15 wt. %) brasses. In gray cast
irons (in the presence of sulfate reducing bacteria, salt wa-
ter, or weak acids), alpha iron is anodic to graphite and cor-
rodes, leaving behind a porous mass of graphite and iron
sulfates. In brasses, zinc is selectively leached from the
$ x 104/m 2 8.0 mm 2 1.6ram matrix, leaving behind a porous mass of copper [8, 9]. Deal-
loying severely reduces the mechanical properties of compo-
nents made from them. Metallographic examination can
confirm visual indications of dealloying (Fig. 10). Not only
will the microstructure appear changed as one element is
I ~ t0$1m 2 12.5mm 2 3.2 mm
selectively leached from the matrix, but changes in micro-
chemistry can also be observed. Dealloying can be observed
optically or by analyzing the polished specimen in a scan-
5
ning electron microscope (SEM). Back scatter electron
images will show contrast in regions of varying atomic
$ 9 1051 m 2 24.5 mm 2 6 94 mm
number. Another SEM method that graphically displays dif-
FIG. 8 - - A S T M pitting chart for density, size, and depth ferences in microstructural elemental composition is the
(see ASTM G 46). digital X-ray line scan or X-ray dot map. The line scan can

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CHAPTER 3 - - M E T A L L O G R A P H I C A N A L Y S I S 7 3

FIG. 12--Photomicrograph showing o phase precipita-


FIG. 10~Photomicrograph showing selective dezinci- tion along austenitic grain boundaries in a type 310
fication of the continuous phase in an c~-~ brass stainless steel (magnification 500 x).
(magnification 200 x),

show variations in elemental composition along a line Cr exposed to temperatures between 1100 ~ and 1700~ (593.3 ~
(Fig. 11). The dot map shows compositional differences over and 926.7~ over long periods of time [10]. Sigma phase is an
the examined area. Depending on c o m p u t e r capabilities and iron chromium rich phase that precipitates along austenitic
software, some systems can m a p out the concentrations of grain boundaries and delta ferrite precipitates (Fig. 12). Test
up to 16 elements simultaneously. results have shown that sigmatized austenitic stainless steels
undergo significant intergranular corrosion in boiling 65 %
HNO 3 and in hot concentrated sulfuric acid solutions. Sigma
Corrosion Due to Phase Changes (~ Phase phase formation also results in loss of room temperature base
Formation in Cr-Ni-Fe and Fe-Cr Alloys) metal ductility.
Exposure of certain alloys to elevated temperatures can pro- Sigma phase formation can be easily assessed by metal-
duce phase changes within the alloy. These phase changes can lographic examination. One of the easiest ways of determining
sometimes lead to corrosive attack of the alloy. Corrosion can the presence of sigma phase is by using a 45 % aqueous KOH
occur if the phase change alters the formation of protective solution as an electrolytic etch. Sigma grains are revealed as
barriers on surface. Examples of this mechanism are sensitiza- distinct reddish-brown islands in the austenitic matrix,
tion of stainless steels (discussed earlier) and sigma phase (o)
formation. Sigma phase formation occurs in nickel-chromium-
iron and chromium-iron alloys containing a ~xfinimum of 16.5 % General Corrosion
In conditions where general corrosion occurs, metallo-
graphic samples can be used to verify the extent of metal
loss through microscopic measurements of sample thick-
ness. Reduction of thickness coupled with weight loss in-
formation provides a checks and balances p r o g r a m into the
analysis and reveals any corrosion rate differences due to
anisotropy.

Liquid Metal Embrittlement


Liquid metal embrittlement (LME) is not a very c o m m o n
mechanism. Only a small n u m b e r of liquid metals can cause
LME in any given alloy system. LME is an inter- and intra-
granular cracking m e c h a n i s m p r o d u c e d by a liquid metal
on the surface of a sensitive solid metal in the presence of a
tensile stress, either applied or residual. The mechanism
occurs only above a threshold stress value and has an incu-
bation period. Table 3 shows a few of the solid and liquid
systems exhibiting LME. More alloys systems exhibiting
FIG. 11--EDS line scan showing a reduction in zinc concen- LME are tabulated in the ASM Metals Handbook, 9th edi-
tration across a dezincified interface in an ~-~ brass alloy. tion, Vol. 11, p. 238.

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74 C O R R O S I O N T E S T S AND S T A N D A R D S M A N U A L

TABLE 3--Solid and liquid systems exhibiting LME. transforms to a brittle ferromagnetic material and can be
Solid Metal Liquid MetalsPromotingEmbrittlement checked with a simple magnet.
Aluminum Alloys Mercury, Gallium, Sodium, Indium, Tin Metallographic examination reveals an inward diffusion
Brass (70/30-Cu/Zn) Mercury, Lithium Bismuth layer of gross carburization and grain "pop out".
Iron or Steel Lithium
Nickel Copper Alloys Mercury, Lead
Stainless Steels Zinc, Cadmium
Ni-Cr-Fe Alloys Lead Sulfidation
Metallographic examination of metals which have exhib-
ited wastage due to sulfidation usually show a two-layer
Metallographic examination can assist in identifying LME. scale, the upper layer being red, the lower being black and
Liquid metal penetration can be observed readily, usually shiny. A few drops of aqueous hydrochloric acid on the
without use of an etchant (Fig. 13). However, etching for deposit can release a noticeable H2S odor and verify the
grain boundaries can distinguish between inter- and intra- presence of sulfides. In addition, creation of a "sulfur print"
granular cracking. In addition, SEM/EDS (energy dispersive can verify sulfidation damage. A cross section sample of
spectroscopy) analysis, as discussed in the section covering thinned metal with surface scale is sanded to a 120 grit
Dealloying, can positively identify the presence of foreign finish. Next, wash a piece of black and white photographic
metals at grain boundaries within a matrix. Care should p a p e r in 2-3 % sulfuric acid. Wipe away excess acid with a
be taken when trying to identify mercury using SEM/EDS. clean sponge. The sample is placed on the photographic
High v a c u u m and electron beams promote evaporation of p a p e r for a few seconds. The p a p e r is then stopped and
mercury. Low kV settings should be used over wide areas to fixed as in normal circumstances. An image of the sulfide
inhibit burning off highly volatile mercury. In addition, mer- distribution on the tube will appear [11].
cury X-ray energy peaks (M) and sulfur (Kr peaks are easily
mistaken for each other. Wet chemical spectroscopy is per-
haps the best m e t h o d for absolute identification of liquid Oxidation
metal species.
Radiography can be used as a check for LME in large Oxidation, perhaps the most visible of all corrosion mech-
structures. By virtue of the large difference in liquid and anisms, is responsible for consuming a significant amount of
solid metal system densities, cracks can be revealed easily maintenance dollars. Metallography of oxidized metals can
on X-ray film, even when they are not visible on the surface. provide information about the type of reaction. Types of oxida-
tion reactions (general, internal, intergranular) can be differen-
tiated by microexamination. Knowing the oxide scale thickness
High Temperature Corrosion--Metal Dusting and composition can provide data on time-temperature expo-
Metal dusting of heat-resistant alloys (Ni-Cr-Fe) occurs in sure by knowing the oxidation rate laws of the material. In ad-
carbonaceous atmospheres at temperatures above 800~ dition, knowledge of the mass ratio of oxide species in the scale
(426.7~ with very high activity in the temperature range can determine exposure temperature.
of 1450~ to 1550~ (787.7 ~ to 843.3~ and above 1700~ Metallographic examination of different phases within
(926.6~ In metal dusting environments, a black "sooty" oxide scales has proven difficult, but some techniques are
residue (graphite) usually covers the surface in most of the available. For example, in steels the scales formed at high
wasted areas. The residual metal is usually thinned and con- temperature are generally composed of three layers: wtistite
tains multiple r o u n d e d pits. The originally austenitic matrix (FeO), hematite (Fe203), and magnetite (Fe304). The forma-
tion of these three oxides can be described by the following
reactions:

Fe + 8902 = FeO
3Fe + 202 = F%O 4
2Fe304 + 7102 = 3Fe203

The mineralogical names are used to emphasize their spe-


cific physical and chemical properties. Wiistite forms at
high temperatures (>565~ adjacent to the steel surface.
Magnetite is an intermediate layer and hematite is the outer
layer. Usually a layer of mixed hematite and magnetite is
observed.
An etchant containing 0.5 % selenic acid (HaSeO4) and 4 %
HCI in ethanol can produce a nice contrast between the
oxide phases on polished samples after immersion at r o o m
temperature [12]. Selected dyes have also been used with
FIG. 13~Unetched photomicrograph showing diffu- various degrees of success. The reader is encouraged to read
sion of Pb/Sb into steel (magnification 500x). Ref 13 for further information on dying oxide scales.

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CHAPTER 3 METALLOGRAPHIC ANALYSIS 75

REFERENCES [8] Uhlig, H. J., Corrosion Handbook, John Wiley and Sons, 1948,
pp. 139-198.
[1] Hussey, R. J., Beaubien, P. E., and Caplan, D., "Metallography of [9] Corrosion, Vol. 1, L. L. Shreir, Ed., Newnes-Butterworths, re-
Oxide Scales on Metals," Memllography, Vol. 6, 1973, pp. 27-36. printed 1977, pp. 446-447.
[2] Vander Voort, G., Metallography Principles and Practice, [10] Gaertner, D. J., "Characterization of Sigmatized Austenitic
McGraw-Hill, 1984. Stainless Steels," Materials Performance,January 1985, pp. 18-24.
[3] Samuels, L. E., Metallographic Polishing by Mechanical Methods, [11] Gaertner, D. J., "Characterization of Sigmatized Austenitic
ASM, Materials Park, OH, 1982, p. 57. Stainless Steels," Materials Performance, January 1985, p. 15.
[4] Samuels, L. E., MetaUographic Polishing by Mechanical Methods, [12] Chicco, B. and Heijkoop, T., "Metallographic Reagent for the
ASM, Materials Park, OH, 1982, p. 111. Characterization of Oxide Scales on Iron and Steel," Prakt.
[5] Petzow, G., MetaUographic Etching, ASMI, Materials Park, OH, Metallographic, Vol. 20, 1983, pp. 321-326.
1978, pp. 10-11. [13] Chicco, B., "Dye Adsorption--A New Technique for the Color
[6] Petzow, G., Metallographic Etching, ASMI, Materials Park, OH, Metallography of Oxide Scales on Steels," MetaIlography,
1978, pp. 30-101. Vol. 14, 1981, pp. 319-328.
[7] ASM Metals Handbook, 9th ed., Vol. 9, ASMI, Materials Park, OH, [14] Tekin, A., Martin, J., and Senior, B., Journal of Materials Science,
1985. Vol. 26, 1991, pp. 2458-2466.

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Surface Analysis
Alfred G. Hopkins 1

BECAUSE CORROSIONis fundamentally a surface phenomenon, This limits the n u m b e r of analysis points that can be ob-
those interested in the fundamental processes of corrosion tained. All of the above limitations result in most studies
have always been among the first to explore the utility of being done on stable films on metals and making these
surface analysis techniques. These techniques have had, and techniques of lesser utility on unstable or rapidly changing
will continue to have, great success in illuminating m a n y systems.
facets of corrosion phenomena.
For those seeking a more detailed treatment of the appli-
cation of surface analysis techniques to the study of corrosion GENERAL PRINCIPLES
than can be given here, there are a n u m b e r of S y m p o s i u m
Proceedings from the Electrochemical Society and from These techniques generally require the sample to be placed
ASTM that are of great utility [1-6]. For those interested in an ultrahigh vacuum (on the order of 10-7 P a / 1 0 - 9 torr)
in more depth on the subject of surface analysis in general to prevent contamination from residual gases in the analy-
or on particular surface techniques, the following are some sis chamber. A rule of t h u m b is that up to an atomic layer
useful references [7-13]. Systems that are particularly ame- per second can be formed at pressures of 10-4 Pa (10-6 torr)
nable to surface analysis include inhibitor films and protective if each collision of a gas molecule results in its sticking to
coatings, stable oxide films, and corroded surfaces. the surface. Fortunately, the sticking coefficients are often
m u c h less than unity, especially for oxidized samples such
as often are of interest in corrosion studies. Some samples
LIMITATIONS are especially prone to reacting with residual gases; this is
often accelerated by electron beam-induced degradation at
There are, however, a n u m b e r of limitations that have the sample surface with techniques such as Auger. In these
prevented these techniques from being even more widely cases, it m a y be necessary to bake the analysis system to
used. The first is that corrosion is inherently a dynamic reach vacuums in the low 10-8 Pa range or better. With some
process, while these techniques are essentially static in na- techniques (such as Secondary Ion Mass Spectroscopy), the
ture. They can only give a snapshot in time of the chemical v a c u u m requirements can be relaxed since the surface that
state of the system. These techniques are obviously of m o r e is actually being analyzed will only be exposed to the vacuum
use in those systems that change slowly in time versus those for a very short period of time.
that change rapidly. Near surface techniques, in contrast to true surface tech-
The second limitation is that most of these techniques re- niques, do not require an ultrahigh vacuum. Secondary Elec-
quire that the sample be removed from the corrosive envi- tron Microscopy-Energy Dispersive X-ray Spectroscopy (SEM-
r o n m e n t and placed into a high vacuum environment before EDS) is an example of a particularly useful near surface
analysis can be performed. This is a major problem for technique that will be discussed in a later section. Micro
those systems that can change structure u p o n drying or loss surface electrochemical techniques, such as the Scanning
of absorbed water. Kelvin probe, overcome these limitations and do give detailed
The third major limitation is that the analysis process electrochemical (rather than elemental) information about
itself can change the composition of the surfaces to be ana- the system in question.
lyzed. The two most c o m m o n types of this problem are In classic surface analysis techniques, the surface is illu-
analysis beam-induced damage and inhomogeneities caused m i n a t e d (interrogated) with high-energy electrons, photons,
by the sputtering process, which is used often to probe past or ions. Depending on the illuminating species, any or all of
the topmost surface of the sample. these types of species will be generated from the ensuing
The final major limitation is cost/availability. Some of the collision. Elemental identification is then made based on
techniques are not widely available, and even those that are characteristic energies or masses of the ejected species. One
easily available (XPS and Auger) are still quite expensive. c o m m o n way of characterizing surface analysis techniques
is by tabulating the incoming and outgoing particles. Table 1
shows such a table, which was adapted from previously
IDistinguished Member, Technical Staff, Texas Instruments Inc., published ones [8-10]; this paper will concentrate on the
Attleboro, MA 02703-0964. most frequently used techniques. Because surface analysis
76

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CHAPTER 4 - - S U R F A C E A N A L Y S I S 7 7

TABLE 1--Comparison of surface analysis techniques.


Category Incident Analyzed Measured AnalysisDepth Sample Sensitivity Standardless
Technique Particle Particle Quantity in Monolayers Damage (AtomicFraction) Quantification
Auger Electron Auger Electron Energy 2-10 No-Mod 10 -3 fair
XPS-ESCA X-Ray Photo-Electron Energy 2-10 No-Min 10-3 fair
Dynamic Sims Ions Sec Ions Mass 10-20 Mod-Ext 10-7 poor
Static Sims Ions Sec Ions Mass 1-2 Mid-Mod 10-8 poor
SNMS Ions Neutrals Mass 5-10 Min-Ext 10-7 fair
SALI Ions Neutrals Mass 1-2 Min-Ext 10-7 fair
RBS Ions Input Ions Energy many Min-Mod 10-3 good
ISS Ions Input Ions Energy- 1 No 10-3 good
NOTES---NO: NONE; MOD: MODERATE; MED: MEDIUM, EXT: EXTENSIVE.

is an extremely specialized field, it has its own nomencla- in a Wilson Cloud Chamber and first described it in 1923)
ture; the reader is referred to ASTM E 673, Terminology [14]. Because the emission of a n Auger electron is, in real-
Relating to Surface Analysis. ity, a three-electron process, Auger transitions are n a m e d
Surface analysis is mainly used in two separate modes. for the energy levels of the three-electron orbitals involved,
One is in surface science where the goal is to fundamentally such as KLL.
u n d e r s t a n d the root causes and mechanisms that are occur- The Auger process releases electrons of characteristic en-
ring in a system. Usually a model system is picked to elimi- ergy for each element, which are d e t e r m i n e d by the differ-
nate as m a n y confounding variables as possible to get a ences in energy of the orbitals involved. In addition to the
system about which firm conclusions can be drawn. Often, Auger electrons, there are also m u c h more plentiful sec-
m a n y different techniques wilt he used o n the same prob- ondary electrons with a broad energy distribution that
lem i n order to illuminate as m a n y facets of the problem as overlay the characteristic peaks. To highlight the charac-
possible. The other mode is failure analysis. The goal here is teristic peaks, differentiation is performed on a plot of the
to determine which of the failure modes (previously discov- n u m b e r of electrons emitted by the sample versus the
ered by surface science) is the most important one for a energy of those electrons. This results in a spectrum that
particular failure. The samples are real, and hence, non- ignores the more plentiful b a c k g r o u n d (secondary) elec-
ideal. This analysis mode is often used to identify the ele- trons and emphasizes the characteristic electrons that are
ments present, their distribution pattern and their oxidation used to identify the elements present. In some cases, the
state. exact peak shape a n d energy can be used to identify the
The first and second most c o m m o n of the true surface oxidation state of the elements present. To more clearly
analysis techniques are Auger Electron Spectroscopy (AES) discern the peaks, the spectra are derivatized; such a spec-
and X-ray Photoelectron Spectroscopy. They are electron t r u m is shown in Fig. 1.
spectroscopies that quantify the energy of electrons that are One of the attractions of Auger analysis is that it is quite
emitted by the surface during analysis. A good reference for surface-sensitive since an Auger spectrum typically repre-
those seeking more detail is "Uses of Auger Electron and sents information about the composition of the top (0.5-2 nm)
Photoelectron Spectroscopes in Corrosion Science" by of the surface depending on the sample analyzed and the
McIntyre and Chan in Practical Surface Analysis [12]. analysis conditions. Although Auger electrons can be gener-
ated at depths of several micrometers into the sample, in
order to be detected, the Auger electrons must be able to
AUGER ELECTRON SPECTROSCOPY (AES) escape to the surface without undergoing an inelastic colli-
sion. The presence of overlaying material exponentially
AES is the most commonly used surface technique on decreases the probability of the electron reaching the detec-
metal samples because of the following advantages: tor unscathed. The exponential constant is the inelastic
mean-free path of the electron, which depends on the kine-
9 High-surface sensitivity.
tic energy of the Auger electron and the material it must
9 Acceptable detectability for m a n y corrosion problems.

9 Simultaneous detection of all elements (except hydrogen


and helium).
9 Very good small area analysis (mapping).
9 Ability to probe deeper into the surface by sputter profiling.
9 Analysis time not excessively long.
9 Readily available instrumentation.

With AES, the sample is subjected to a high-energy (typi-


cally 2-20 KeV) electron beam that can cause ejection of a
core electron from an atom to form an atomic inner shell
vacancy. An outer-level electron will then fill the inner-level
vacancy, which will induce an excited state. One of the ways
46.9 240~9 4,t9.0 640.0 84P.0 1040.9 12~.0 1~.9 I~9.6 184P.0 20~.(
that the atom can then relax is by emitting another electron IQHETIC ~ ' / ,
to form a doubly ionized species. This electron is the Auger
electron (named for Pierre Auger, who recognized the effect FIG. 1--Auger spectra of stainless steel surface.

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78 CORROSION TESTS AND STANDARDS MANUAL

traverse in order to reach the detector. Empirical graphs of are shown in Fig. 2. Variations in signal intensity caused by
the relationship between the electron kinetic energy and its geometric effects can often be eliminated b~" ratioing the
mean-free path are often of use in understanding detect- intensity of the peak of interest to that of adjoining back-
bility issues. The effective depth of analysis varies from ground areas. Elemental m a p p i n g is also an important tool
element to element, even varying between lines of a particu- in techniques such as SIMS, SEM-EDS, Scanning Kelvin
lar element. This results in high-energy Auger electrons Probe and others.
being detectable from deeper in the surface than low-energy As in most surface analysis techniques, qualitative identi-
ones. For example, a thin, adsorbed carbon (organic) film fication of the elements present is the easiest type of analy-
will preferentially mask the low-energy (68 eV) peak of sis. Most elements have more t h a n one Auger peak due to
a l u m i n u m as c o m p a r e d to the high energy one (1396 eV). having either multiple transitions or fine structure within a
These same types of considerations are applicable to all transition. It is fairly easy to identify from an Auger spec-
related electron spectroscopies such as XPS. t r u m what elements are present on the surface of the sam-
Auger spectroscopy also offers acceptable detectibility for ple based on the following: peak position, peak intensity
m a n y situations encountered in corrosion science. This can ratios for a particular element, and peak shape. Compila-
be as low as 0 . 0 1 % , although this is seldom realized in tions of elemental spectra and charts of atomic n u m b e r
c o m m o n practice since low detectibility conflicts with other versus electron energy are available to help assign peaks.
desirable qualities such as resolution, analysis time, and the Modern data processing (background subtraction, peak fit-
need to minimize b e a m current to minimize b e a m damage. ting to standard spectra) has m a d e it possible to correctly
Almost all Auger spectrometers have a scannable incident resolve m a n y peak identification problems caused by peak
electron b e a m such as is used in a Scanning Electron Mi- overlap. The analyst should be familiar with ASTM E 827,
croscope (SEM). Such an instrument can also be called a Standard Practice for Identifying Elements In Auger Elec-
Scanning Auger Microscope (SAM). This can provide spatial tron Spectroscopy. There have been some variations in peak
resolution as low as 15 nm. The ability to scan allows ele- electron energy between different systems and handbooks,
mental concentration maps of the surface to be generated. but this should be minimized in the future as a result of
This qualitative analysis of small areas is AES's greatest standardization efforts of ASTM.
strong point. Its ability to determine element identity and Both peak energy and peak shape can vary depending
distribution via mapping provides insights into m a n y corro- u p o n the chemical state of the element. This is particularly
sion problems. In particular, the breakdown of passivity true for the low-energy transitions of valence electrons. It
and the initiation of pitting corrosion are often associated can also be seen in core-level transitions in those cases
with the presence of heterogeneous elements, which include where the electrons experience strong energy losses in
both internal inclusions and corrosive species. Auger maps escaping from metallic surfaces b u t not from the oxide; for

FIG. 2mAuger elemental distribution maps.

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CHAPTER 4 SURFACE A N A L Y S I S 79

instance; aluminum, magnesium, and silicon. A more detailed quantifiable peaks from the spectra and in minimizing inter-
description can be found in ASTM E 984, Guide for Identi- i n s t r u m e n t a n d i n t e r - l a b o r a t o r y variations. ASTM Com-
fying Chemical Effects and Matrix Effects in Auger Electron mittee E-41 on L a b o r a t o r y Apparatus has a n u m b e r of
Spectroscopy. s u b c o m m i t t e e s dealing with these issues for a n u m b e r of
Auger spectrometers are normally equipped with ion- surface analysis techniques including Auger, ESCA, and SIMS.
b e a m sputter guns that can slowly remove the surface while A relevant p u b l i c a t i o n is ASTM E 995, Guide to Back-
the sample is being analyzed in the vacuum chamber. This g r o u n d S u b t r a c t i o n Techniques in Auger Electron Spec-
results in a depth profile that plots the composition of the troscopy. Auger analysis is subject to a n u m b e r of possible
freshly generated surface as it varies with depth into the artifacts due to effects such as sample charging, electron
surface. The following three basic issues must be faced when b e a m desorption, electron b e a m decomposition, and varia-
sputter profiling is employed: difficulties in determining the tions i n d u c e d by sputter profiling. These are treated in
sputter rate, variations in depth resolution, and changes in ASTM E 983, S t a n d a r d Guide for Minimizing Unwanted
the sample that are induced by the ion beam. Electron B e a m Effects in Auger Electron Spectroscopy. To
Sputter rates vary greatly depending on such factors as prevent the analyst from adding c o n t a m i n a t i o n to the
the identity of the ions (argon is most typical), the accelerat- sample, he should be a w a r e of ASTM E 1078, Guide for
ing voltage, the angle of incidence, the chemical nature of S p e c i m e n Handling in Auger Electron Spectroscopy, X-
the sample, and sample surface structure. Although pub- Ray Photoelectron Spectroscopy, and S e c o n d a r y Ion Mass
lished sputtering yields can be helpful, they cannot replace Spectrometry.
running known thickness standards on an individual instru-
ment. Two standards that are easiest to accurately fabricate,
and therefore are the most common, are tantalum oxide on X-RAY PHOTOELECTRON SPECTROSCOPY
tantalum and silicon oxide on silicon. Further complica- (XPS)
tions are added by the dependence of sputter yield on depth
and on surface roughness. Einstein received the Nobel Prize for his explanation of
Depth resolution can be considered to be equal to the ob- the photoelectric effect in which atoms can be ionized by an
served broadening of an originally atomically sharp inter- incoming p h o t o n [16]. Siegbahn's [17] realization that the
face. It is not constant; it worsens as one sputters into the energy of the ejected photoelectron could be used to deter-
material. Inert gas ion sputtering is used in the great major- mine the chemical state of an a t o m caused him to coin the
ity of surface analysis techniques, either as a method of name ESCA (Electron Spectroscopy for Chemical Analysis).
seeing deeper into the sample (Auger, XPS) or as a way Because X-ray photons are necessary to generate appropri-
of generating particles to be analyzed (SIMS). A discussion ate electrons, the technique is also called X-ray Photoelec-
of some of the effects of the sputtering process is given in tron Spectroscopy (XPS).
the SIMS section of this chapter. An important publication XPS shares the Auger characteristics of good surface sen-
on the subject is ASTM E 1127, Guide for Depth Profiling in sitivity since this is driven by the same need for the electrons
Auger Electron Spectroscopy. A review of sputtering is given to be able to reach the detector unscathed. It is possible to
in "Depth Profiling in Corrosion Research" in Ref 15. F o r vary the depth of analysis in both techniques by varying the
Auger spectroscopy, a simplistic m e t h o d of generating a tilt angle with regard to the detector. This technique is used
sputter profile by plotting net p e a k heights works well if more extensively in XPS where it is often called angle resolved
there are no p r o b l e m s such as: p e a k overlap, peak shape depth profiling.
change, a n d p e a k shift. M o d e r n d a t a m a n i p u l a t i o n tech- XPS also has the very i m p o r t a n t advantage of being able
niques such as factor analysis minimize the effects of these to obtain chemical state information on most atoms. It be-
problems. An Auger sputter profile is shown in Fig. 3. comes easy to observe the effect of differing chemical envi-
Absolute quantification of surface composition by electron- ronments in both the photoelectron peaks and in the Auger
energy spectral techniques such as Auger and ESCA is a very peaks, which are also generated by XPS's X-ray excitation.
difficult goal. Current efforts are concentrated in abstracting Often, the chemical shifts in the Auger peaks of an XPS
spectrum are larger than the shifts in the photoelectron
peaks. Another aid to assigning the proper oxidation state to
--. i I i 1 ~ I I I IF e P ~I F~2
l 1 I ]e2 a peak is the presence of satellite shake-up lines due to a
.
simultaneous promotion of a valence electron to a higher
9 Fe2~ ~ orbital as the photoelectron is being ejected. Proper interpre-
tation of the implications of peak shifts requires the knowl-
edge of sample charging on the spectra. A useful reference is
ASTM E 1523, Guide to Charge Control and Charge Refer-
encing Techniques in X-Ray Photoelectron Spectroscopy.
Crl -- --
Another advantage of XPS is that peak identification is more
easily done than in Auger because of the narrow line width,
as well as the presence of both Auger peaks and photoelec-
. L $12
tron peaks in the spectra as is shown in Fig. 4.
,.0 1." 2.0 3.0 4.0 5." 6.0 7.0 8.0 $." 1"."
&oUIIER lINE. NIN. XPS is also preferable in that it is able to analyze non-
conducting samples and has a lesser tendency towards sample
FIG. :}--Auger sputter profile. degradation than other techniques. XPS is not as preferable

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80 C O R R O S I O N TESTS A N D S T A N D A R D S M A N U A L

Mgls Ols hydrorJde~mg~


1320 1310 1300 $45 $35 525
BndlngEnergyleV) BindingEnergy(eV)
Magnesium Is Spectra. Oxygen Is Spectra.

Mg 2s Mg KLL
hydroxide/oxlde~metal Auger
corroded~~xlde/oxlde
coclearn~
" -

e4 54 !lee.e Hea.e
BindingEnergy(eV) Klnettc Energy leV)

Magnesium 2s Soectra. Magnesium KLL Auger Spectra.

FIG. 4--Ultraviolet photon spectroscopy: uses of narrow scans for corrosion problem solving.

because it does not have Auger's very small spot size since it A major disadvantage of SIMS is that there is a very great
is m u c h more difficult to focus X-ray beams than electron range of ionization rates for different elements. Further-
beams. Therefore, it is necessary to mask or abstract only a more, the rates will vary depending on the other species
portion of the available analysis area which negatively impacts present (matrix effects). Either a beam of positive or nega-
the signal to noise ratio. Relevant information is found in tive ions can be used as the exciting beam, although the
ASTM E 1217, Practice for Determination of Specimen Area response factors are m u c h different between them. The
Contributing to the Detected Signal in X-Ray Photoelectron biggest differences are found with the very electronegative
Spectroscopy and Auger Electron Spectroscopy. However, halogens and the electropositive alkali metals. The variabil-
10-30 gm size analysis is possible on a routine basis. The ity in response factors makes quantification very difficult
longer time necessary for an XPS spectrum often results in and closely matched standards critical. Of use is ASTM E
the analyst settling for a lower signal-to-noise ratio and, hence, 1505, Guide for Determining SIMS Relative Sensitivity Factors
poorer detectibility than with Auger. from Ion Implanted External Standards.
In SIMS, as in sputter profiling in Auger and XPS, there
are other effects in addition to simply removing the surface
SECONDARY ION MASS SPECTROSCOPY atoms. For instance, there is implantation of the sputtering
(SIMS) gas and a rearrangement or interfacial mixing of the surface
layers. Also, compositional changes caused by preferential
Secondary Ion Mass Spectroscopy (SIMS) is the third of sputtering of one element versus another also occur. This is
the three most c o m m o n surface analysis techniques. A good actually a bigger problem for Auger and XPS, which mea-
reference to SIMS and other ion spectroscopies is Czanderna's sure the surface, as compared to SIMS, which measures the
and Hercules' "Ion Spectroscopies for Surface Analysis" in elements ejected from the surface which soon reach an
Ref 11. In SIMS, the sample is irradiated with a primary ion equilibrium with the actual composition.
beam (normally argon), the impact of which sputters away Static SIMS uses a much less intense ion beam than Dyn-
the surface atoms, some as neutrals and others as ions. Those amic SIMS. This gives the advantage of not destroying all
atoms that become ionized are then detected in a mass the molecular species on the surface, which results in one
spectrometer where their masses are measured. The most being able to obtain significant chemical information from
c o m m o n variant is Dynamic SIMS in which a high-energy the surface. It also maintains the integrity of the surface dur-
ion beam is used that removes layers of the surface. The ing analysis so that it is much more of a surface technique
beam is so energetic that little chemical information is re- than Dynamic SIMS. Time of Flight (TOF) SIMS refers to the
tained since the vast majority of any molecular species is mode of analysis of the ionized particles rather than their
fragmented. Although destroying the surface obviously pre- generation process. It provides a very wide mass range plus
vents its re-examination, it is not a total disadvantage since very high sensitivity.
it allows depth profiling to occur.
Some of the advantages of SIMS are that it has a very low
detection limit (PPM to PPT) and it can detect all elements. OTHER SURFACE TECHNIQUES
These advantages make it able to address many problems
that neither AES nor XPS are suitable for. Reasonably small The highly variable response factors that are the main limi-
(micrometer or smaller) spot sizes allow elemental mapping. tation of SIMS are almost eliminated by Secondary Neutral

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CHAPTER 4 - - S U R F A C E A N A L Y S I S 81

Mass Spectroscopies (SNMS), which provides relatively non- Spectrometer (EDS). Quantification can be quite good if
selective i o n i z a t i o n of the s p u t t e r e d species. S e p a r a t i n g appropriate standards are used. The X-ray detector can be
the sputtering a n d ionizing functions of SIMS not only set to only detect and count X-rays that have energies
eliminates m a t r i x effects b u t also allows for m u c h less within a n a r r o w range. This output can then be used to
aggressive sputtering conditions. The h i g h e r cost of the generate elemental distribution maps, or line scans. Newer
systems is an inevitable trade-off. There are three ways detectors with ultrathin windows can easily detect all ele-
that the s p u t t e r e d n e u t r a l species can be ionized. Surface ments with an atomic n u m b e r of 5 (boron) or greater. Some
Analysis by Laser Ionization (SALI) uses a high-power laser applications of SEM-EDS analysis are given in the metal-
for p h o t o i o n i z a t i o n , while Glow Discharge Mass Spectros- lography chapter of this manual.
copy ionizes the neutrals in a glow discharge plasma. The Particle Induced X-Ray Emission (PIXE) is similar to EDS
t h i r d m e t h o d is Electron I m p a c t Ionization, and it is la- analysis except that it uses high-energy particles instead of
beled by the n a m e of the overall technique, SNMS. Both electrons to create the vacancies that lead to X-ray emission.
Electron I m p a c t SNMS and SALI can give SIMS-type in- It offers orders of magnitude better detection limits for trace
f o r m a t i o n on p o i n t defects w i t h o u t the quantification elements than does EDS. Transmission Electron Microscopy
p r o b l e m s that SIMS is prone to. SALI is available with a (TEM) and Scanning Transmission Electron Microscopy
time of flight (TOF) mass s p e c t r o m e t e r which is desirable (STEM) require extensive sample preparation. When coupled
if h i g h e r mass range a n d r e s o l u t i o n is n e e d e d t h a n can be with another technique (EDS for example), they can be useful
p r o v i d e d by s t a n d a r d mass spectrometers. in determining the nature of surface films or in illuminating
Rutherford Backscatter Spectroscopy (RBS) requires a the microstructural causes of corrosion. Environmental Sca-
monoenergetic b e a m of high-energy particles (helium ions) nning Electron Microscopes (ESEM) that are equipped with
that is bounced off of the surface to be analyzed. By analyz- EDS spectrometers allow SEM-EDS type data to be obtained
ing the energy of the backscattered particles, a standardless, from samples in the hydrated state.
nondestructive, quantitative depth profile of the top several Fourier Transform Infrared Spectroscopy (FTIR) and
m i c r o m e t e r s of the surface can be obtained. A related tech- Laser R a m a n Spectroscopy (LRS) provide complementary
nique is Ion Scattering Spectroscopy (ISS) in which a low- views of chemical bonding in a sample by studying the
energy monoenergetic b e a m of ions is directed onto the vibrational energies of the bonds. Surface Enhanced R a m a n
surface and the energy of the scattered ions is measured. Spectroscopy (SERS) can give vibrational spectra of in situ
This technique is perhaps the most selective technique of all films. A useful review of the application of these vibrational
with regard to only analyzing the t o p m o s t layer of atoms. spectroscopies is available [19].
Its major limitations are that it is not able to detect ele-
ments at low concentration levels, and it has poor ability to
discriminate between elements with similar atomic mass. IN SITU M E T H O D S

Because of the changes that can occur in preparing and


N E A R SURFACE TECHNIQUES analyzing surfaces for high-vacuum techniques, there is great
interest in techniques that can obtain information as to the
Although not a true surface technique, SEM-EDS often chemical state of metal surfaces while they are in aqueous
provides useful information in regard to surface corrosion environments. Some of the most exciting research on the
mechanism. The ubiquitous nature, low cost, and ease of fundamentals of corrosion are using these new techniques.
use of this technique cause it to be used as a tool in m a n y Scanning Tunneling Microscopy (STM) a n d especially
failure analyses involving corrosion. Because its analysis Scanning Force Microscopy (SFM) were the first techniques
depth is m u c h larger (approximately a micrometer) than the to give an atomic scale and three-dimensional (3-D) image
true surface techniques, it is not necessary to analyze samples of a surface that would p e r m i t observation in aqueous envi-
that are high-vacuum compatible. This restflts in the necessity ronments. Since the first scanning probe microscope was
of almost no sample preparation for m a n y different kinds of invented in 1981 by Gerd Binnig and Heinrich Rohrer, a
samples. whole family of scanning probe microscopies have evolved.
The sample is scanned with a high-energy (typically 5-30 All of these Scanning Probe Microscopies operate by scan-
KeV) electron b e a m in a raster pattern, which causes the ning a small probe tip over the surface to be imaged and
ejection of a n u m b e r of particles including secondary creating distributional maps of the response. Two of the most
electrons, backscattered electrons, and X-rays. Secondary useful for corrosion science are Scanning Kelvin Probe
electrons (with energies less than 50 eV) are only detectable Atomic Force Microscopy (SKPAFM) and Scanning Elec-
if they are generated in the top surface of a sample; this trochemical Microscopy (SECM). Two valuable resources
causes the secondary electron output to be responsive to on these and other techniques are the Electrochemical Society's
topographical detail and therefore gives an image that is Proceedings on the Symposium on Localized In Situ Methods
r e m a r k a b l y similar to that seen with an optical microscope. for Investigating Electrochemical Interfaces [2] and Scanning
Added advantages are greater magnification and depth of Electrochemical Microscopy, which has been edited by Bair
field. The contrast in backscattered electron images is mainly and Mirkin [20].
dependent on atomic number, so these images provide rough SECM is discussed elsewhere in this handbook. The Scan-
elemental distribution information. ning Kelvin Probe is an updating and miniaturization of
Element identification is provided by analysis of the char- the classic method that was first postulated by Lord Kelvin
acteristic X-rays that are emitted with an Energy Dispersive in 1861. It is essentially a non-contact vibrating capacitor

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82 CORROSION TESTS AND STANDARDS MANUAL

f o r m e d b e t w e e n t h e s a m p l e a n d a v i b r a t i n g electrode tip, [6] Application of Surface Analysis Methods to Environmental/


w h i c h m e a s u r e s t h e w o r k f u n c t i o n of t h e sample. S i n c e Material Interactions, D. R. Baer, C. R. Clayton, and G. D.
t h e w o r k f u n c t i o n is e x t r e m e l y d e p e n d e n t o n s u r f a c e c o n - Davis, Eds., The Electrochemical Society, Inc., Pennington,
dition, the SKP can be used to study such p h e n o m e n a as oxide NJ, 1991.
layer imperfections, surface and bulk contamination, surface [7] Surface Analysis--The Principal Techniques, J. C. Vickerman
Ed., John Wiley & Sons, 1997.
c h a r g i n g , etc.
[8] Encyclopedia of Materials Characterization: Surfaces, Interfaces,
The a v a i l a b i l i t y of h i g h intensity, s y n c h r o n o u s X - r a y Thin Films, C. R. Brundle, C. A. Evans, Jr., and S. Wilson,
s o u r c e s at n a t i o n a l s y n c h r o t r o n c e n t e r s has a l l o w e d t h e Eds., Butterworth-Heinemann, Boston, MA, 1992.
d e v e l o p m e n t of a n u m b e r of n e w tools t h a t c a n study pas- [9] Powell, C. J., et al., "Methods of Surface Characterization,"
sive o r c o r r o s i o n films as t h e y are f o r m i n g in a q u e o u s en- Beam Effects, Surface Topography and Depth Profiling in Sur-
v i r o n m e n t s . S u r f a c e X - R a y D i f f r a c t i o n (SXRD) p r o v i d e s a face Analysis, Vol. 5, Kluwer Academic Publishers, 1998.
d i r e c t d e t e r m i n a t i o n of the crystal s t r u c t u r e of the a t o m s [10] Surface Characterization: A User's Sourcebook, D. Brune et al.,
of t h e surface. S u r f a c e E x t e n d e d X - R a y A b s o r p t i o n F i n e Eds., John Wiley & Sons, 1997.
S t r u c t u r e ( S E X A F S ) c a n p r o v i d e i n f o r m a t i o n on t h e geo- [11] Ion Spectroscopies for Surface Analysis, A. W. Czanderna and
m e t r i c s t r u c t u r e of a t o m s w i t h i n a few a n g s t r o m s a r o u n d D. Hercules, Eds., Plenum, New York, 1991.
[12] McIntyre, N. S. and Chan, T. C., "Uses of Auger Electa-on and
the a b s o r b i n g a t o m .
Photoelectron Spectroscopes in Corrosion Science," Practical
These are truly exciting t i m e s for the application of sur- Surface Analysis, 2nd ed., Vol. A, Auger and X-Ray Photoelec-
face analysis to c o r r o s i o n problems. tron Spectroscopy, John Wiley & Sons Ltd., Chichester,
U.K., 1990.
[13] Thompson, M., Baker, M. D., Christie, A., and Tyson, J. F., Auger
REFERENCES Electron Spectroscopy, John Wiley & Sons, New York, 1985.
[14] Auger, P. J., JPhys Radium, Vol. 6, 1925, pp. 205-208.
[1] Baer, D. R., Clayton, C. R., Halada, G. P., and Davis, G. D., [15] Hoffman, S., "Depth Profiling in Corrosion Research," The
"State-of-the-Art Application of Surface and Interface Analysis Application of Surface Analysis Methods to Environmental/
Methods to Environmental material Interactions," The Elec- Material Interactions, The Electrochemical Society, Pennington,
trochemical Society, Inc., Pennington, N J, 2001. NJ, 1991.
[2] Hillier, A. C., Seo, M., and Taylor, S. R., Proceedings of the [16] Einstein, A., Annals Physik, Vol. 17, 1905, p. 132.
Symposium on the Localized In Situ Methods for Investigating [17] Siegbahn, K., et al., "Electron Spectroscopy for Chemical
Electrochemical Interfaces, The Electrochemical Society, Inc., Analysis Atomic, Molecular and Solid State Structure Studies
Pennington, NJ, 1999. by Means of Electron Spectroscopy," Nova Acta Gegiae Society
[3] Hebert, K. R., Lillard, R. S., and MacDougall, B. R., Oxide Science Upsaliensis, Series IV, No. 20, 1967.
Films, The Electrochemical Society, Inc., Pennington, NJ, 2000. [18] Czanderna, A. W., "Ion Spectroscopies for Surface Analysis,"
[4] Mansfeld, F., Huet, F., and Mattos, O., "New Trends in The Application of Surface Analysis Methods to Environmental/
Electrochemical Impedance Spectroscopy and Electrochemical Material Interactions, The Electrochemical Society, Penningtou,
Noise Analysis," The Electrochemical Society, Inc., Pennington, NJ, NJ, 1991.
2000. [19] Czanderna, A. W. and Hercules, D. M., "Methods of Surface
[5] Hansen, D. C., Isaacs, H. S., Sieradzki, K., and Porter M. D., Characterization," Surface Infrared and Raman Spectroscopy,
"Scanning Probe Microscopy for Electrode Characterization Vol. 3, Kluwer Academic Publishers, 1998.
and Nanometer Scale Modification," The Electrochemical [20] Bard, A. J. and Mirkin, M., Scanning Electrochemical Micros-
Society, Inc., Pennington, NJ, 2000. copy, 2001, Marcel Dekker, New York.

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Statistical Treatment of Data,
Data Interpretation,
and Reliability
Fred H. H a y n i e 1

MOSTPHYSICALANDCHEMICALmeasurements, performed under Unfortunately, all experiments have limitatfons and these
n o m i n a l l y identical conditions, yield differing data. The limitations cause the existence of error. Whereas r a n d o m
results of corrosion tests are no exception. Sometimes the error is acceptable, biased error is not. For example, if, when
difference between values is less t h a n the m e a s u r e m e n t comparing the corrosion resistance of two alloys in a salt
accuracy and cannot be detected. At other times the difference cabinet, the replicate samples of one alloy are placed at one
approaches the magnitude of the values. Unfortunately, corro- end of the cabinet and the other alloy at the other end, it is
sion test data tend to be in the latter category more often possible that the results will be biased by the spray pattern.
t h a n in the former. The within-sample error may be small, and the difference
Because of this variation in results it is necessary to apply between samples may appear to be significant when the only
some type of statistical t r e a t m e n t to the data (e.g., the true significance is a difference in spray pattern. The same
arithmetic averaging of replicate values). W h e n analyzing type of biased error may be introduced when results obtained
data, however, it helps to know some basics. Statistical tech- on a new alloy are compared to previously obtained results
niques can be misused and give the researcher a false sense on an old alloy. Because such environmental conditions cannot
of security. One must be aware of limitations as well as be controlled exactly, it is necessary to compensate for them
advantages. in the experimental designs by r a n d o m exposure of sample
Statistics in Research by Bernard Ostle [1] is an excellent replicates in both time and space. This procedure tends to
text that can be used as a handbook. I n addition, Standard counteract the effects of biased error but generally increases
G 16 (Guide for Applying Statistics to Analysis of Corrosion the within-sample error. Both effects reduce the probability
Data) is a useful document. Statistical techniques are par- of producing results from which erroneous conclusions are
ticularly useful in planning and designing experiments. This made.
chapter describes some of the advantages and limitations of
applying statistical techniques in corrosion research. Population, Sample, and Replication
All units having a c o m m o n set of conditions form a popu-
lation described by those conditions. For example, if we
BASICS wish to determine the corrosion behavior of an alloy in a
particular type of chemical solution, the population consists
Three statistical methods that are often important in cor- of all heats of that alloy exposed to all solutions of the speci-
rosion experiments are (1) probability distributions, (2) design fied type. A m u c h smaller population would be one parti-
of experiments, and (3) analysis of data. Most investigators cular heat of the alloy exposed to a single batch of the
use some kind of data analysis technique. Less attention is solution. It would be incorrect to assume that the smaller
given to experimental design, and probability distribution is population is representative of the larger population.
the most neglected of the three methods. A sample is some fraction, usually small, of the popula-
tion. A good sample is representative of the population.
Random selection of the proper n u m b e r of units from a
Terminology
population should assure a good sample. In chapter 1 on
Certain words have specific m e a n i n g s to the statistic- PLANNING AND DESIGN OF TESTS both r a n d o m selection
ians. These same words may have different m e a n i n g s to and m i n i m u m sample size are discussed.
those who are not familiar with statistics. In order to avoid Replication is the repetition of a specified set of experi-
confusion, a discussion of some of the basic terminology is mental conditions that describe the population. Repeated
presented. measurements on a single specimen constitute replication
only if the population is the set of all such measurements on
Error the specimen.
Error is the a m o u n t by which a value is incorrect or
inaccurate. Probability Distribution
If mass losses on a large n u m b e r of replicate specimens
1Corrosion consultant, Cary, NC 27511, and updated and revised are determined, it is often observed that there is one most
by S. W. Dean. frequently occurring value, and as other values deviate from
83
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84 CORROSION TESTS AND STANDARDS MANUAL

it, their frequencies of occurrence decrease. This peak is estimate of variance (s2). Equation 2 is used to estimate var-
called the mode, and the shape of the curve produced by iance by substituting (~) 1 for n.
plotting frequency versus measured value is the probability
distribution. Most such curves are symmetrical about the Confidence L i m i t s for the Mean
mode and have a bell-shaped normal distribution as shown In general the larger the sample size, the more closely the
in Fig. 1. sample average (x) approaches the population mean since,
A normal distribution can be mathematically described if the entire population were measured, we could calculate
with two terms: (a) the arithmetic m e a n (x) of all values in the population mean. As the sample size decreases, how-
the population, and (b) the standard deviation (6). The ever, the sample average probably deviates more from the
mean, which is a measure of central tendency, is equal to population mean. We would like to know how the sample
the mode for a normal distribution. It is determined from average deviates from the population m e a n in order to have
the relationship confidence in the calculated average value.
Gossett [2] (who signed his article "Student") provided a
_ n

x = y x~/n (1) relationship from which the confidence limits on the true
i=1 m e a n can be estimated. The relationship is

where n is the n u m b e r of units in the population. The stan- x - x = +_s~.t (3)


dard deviation (6) is the square root of the variance (o~) and
is a measure of the dispersion of values about the mean. where sm is the square root of the best estimate of sample
The variance is the arithmetic average of all the squares of variance of the m e a n (s 2) and t is the tabular value "Stu-
the deviations about the mean. Mathematically dent's t" [which is a function of the degrees of freedom and
probability (P)]. If, for example, a sample of five specimens
n
is available and it is desired to establish 95 % confidence
0"a = ~ ( x i - x) 2in (2)
z=l
limits for the true m e a n (x) (i.e., it is desired to have some
measure of assurance that 19 out of 20 times the true m e a n
Thus, 68.26 % of all the population will be contained within will lie within these limits), the table of "t" values is con-
1 standard deviation either side of the mean. Similarly, sulted at 4 degrees of freedom (fi) 1 and a probability P of
95.46 % and 99.73 % will be contained within 2 and 3 stan- 0.05, and a value of 2.776 for "t" is found. If the best estimate
dard deviations, respectively. of variance is 10, sm is calculated to be +1.414. Therefore, the
95 % confidence limits for the true m e a n x are x = _+3.92.
Best E s t i m a t e o f Variance a n d S t a n d a r d Deviation
The sample sizes in corrosion work are usually not large
enough to establish either a true m e a n (x) or a true variance PROBABILITY DISTRIBUTION
(62). Therefore, best estimates must be made. The n u m b e r
of bits of information that possibly can be obtained from a Probability distribution was introduced in the section in
finite sample is restricted by the data collected. This restric- this chapter on Terminology, and the components of a
tion is known as the total degrees of freedom. As bits of normal distribution and how to work with them were dis-
information are obtained from the sample, the degrees of cussed. Some distributions are not normal because they are
freedom are reduced. Thus, in order to estimate both a skewed to one side of the mode. Unless the values can be
m e a n (x) and a variance (s2), which are two bits of informa- treated by some mathematical function to yield a new set of
tion, we must have a m i n i m u m sample size of two. The best values that approximates a normal distribution, the use of
estimate of the m e a n (x) is calculated from the sample data normal statistical techniques could lead to erroneous con-
using Eq 1. With any size sample (n), 1 degree of freedom clusions. Sometimes the distribution is skewed in such a
is said to be used in estimating the mean, thus leaving way that the logarithms of the values have a normal distri-
(fi) 1 degrees of freedom with which to calculate the best bution. Fortunately, although the values are not amenable
to standard statistical methods, their logarithms are. In con-
trast, m a x i m u m pit depths have an extreme value distribu-
0.5 tion and should be treated with extreme value statistics. We
will discuss these three distributions.
0.4

,~, 0.3
Normal Distribution
The normal distribution has the familiar symmetrical bell
M.
0.2 shape as shown in Fig. 1 and is the basis for the most com-
m o n statistical techniques of experimental design and data
0.1 analysis. The characteristics of this distribution are described
in the section on Terminology. Mass loss, mass gain, thick-
0 ness loss, corrosion potential, corrosion rate, and pitting area
-4 -3 -2 -1 0 1 2 3
DEVIATION FROM MEAN - - ET may have a normal distribution. Although this may not be an
established fact, in the past many researchers have assumed
FIG. 1 - - N o r m a l distribution. normal distributions for such data with apparent success.

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CHAPTER 5--STATISTICAL TREATMENT OF DATA 85

Log-Normal Distribution statistical methods. The purpose of any experimental design


should be to efficiently provide a m a x i m u m amount of rele-
In some cases better results can be produced by assuming
vant information. In this optimization process, statistical
a log-normal distribution. A log-normal distribution is sim-
methods, economic analysis, as well as knowledge of corro-
ply data that have a normal distribution after they are con-
sion processes is normally employed. Therefore, the use of
verted to logarithms. The data then can be analyzed using
statistical techniques in design of experiments, is covered in
n o r m a l statistical techniques.
m o r e detail in the chapter on PLANNING AND DESIGN OF
Some indicators that generally indicate a log-normal dis-
TESTS. It is discussed here to show how it subsequently
tribution are: (a) data values that physically cannot be nega-
affects the analysis of data.
tive, (b) normal standard deviations that are proportional to
arithmetic means, (c) arithmetic means that are consistently
greater than median values, and (d) dependent parameters Types of Experiments
whose logarithms are proportional to the values of independ- Corrosion scientists work with two basic types of experi-
ent parameters. Some types of corrosion data that are likely ments, (1) controlled a n d (2) uncontrolled. In controlled
to be log-normally distributed are: (a) mass loss, (b) thickness experiments, levels of i n d e p e n d e n t variables (factors such
loss, (c) time to initial stress corrosion cracks, (d) time to as t e m p e r a t u r e and chemical composition) are controlled
stress-corrosion cracking failures, and (e) polarization cur- a n d the d e p e n d e n t variables (corrosion rate, pitting poten-
rents in the Tafel slope range. tial, etc.) are measured. In u n c o n t r o l l e d experiments such
as a t m o s p h e r i c exposures, u n c o n t r o l l e d i n d e p e n d e n t vari-
Extreme Value Distribution ables such as t e m p e r a t u r e and relative h u m i d i t y are mea-
sured along with the d e p e n d e n t c o r r o s i o n results. Properly
The depths of deepest pits on specimens, the times to first
designed controlled experiments are m u c h m o r e a m e n a b l e
leaks in pipe lengths, times to initial stress-corrosion crack-
to statistical analysis of variance than are properly designed
ing failures, and the n u m b e r of cycles to first corrosion-
uncontrolled experiments. Many scientists prefer some form
fatigue failures are, by definition, extreme values. The depth
of factorial design for controlled experiments.
of the deepest pit on a specimen is the upper tail of the
distribution of depths of all pits on that specimen. Factorial E x p e r i m e n t s
The Weibull distribution [3] often is used in analyzing
E a c h controlled variable with m o r e t h a n one controlled
extreme value data. Expressed in a linear form [4]
level is considered a factor in an experiment. The m a i n
ln[- ln[1 - F(x)] ] = cln(x - a) - cln(1/b) (4) advantage of a factorial design e x p e r i m e n t is that interac-
tion as well as direct effects can be studied with less
where F(x) is cumulative probability, x is a ranked measured replication than several one-way analyses of variances. An
value equal to or greater than a, a is the m i n i m u m value of x example of an i n t e r a c t i o n effect is a change of slope of a
and is equal to or greater than 0, b is a scaling parameter, and corrosion rate versus relative humidity curve with a change
c is a shape factor. When working with finite samples, the in temperature.
cumulative probability or plotting position is estimated by [5] Researchers use two-level factorial experiments to deter-
mine which variables or factors cause direct or interaction
F(xm) = m/(n + 1) (5) (synergistic) effects on the measured parameter. Each new
factor introduced, however, doubles the n u m b e r of test
where m is the ordered rank of the measured value (1,2,3 . . . . . n) conditions. Thus, the need to include a large n u m b e r of fac-
and n is the total n u m b e r of the sample. tors in a complete experimental design often results in an
impractical n u m b e r of test conditions. To circumvent this
Data Distribution Evaluation problem, statisticians can design fractional experiments
that produce nearly all of the information that researchers
Corrosion scientists seldom have enough replicate data to need by confounding some possible effects such as higher
analyze distributions using such techniques as histograms order interactions. At this point, corrosion researchers have
and tests of fit. Sometimes, however, enough data are avail- the knowledge and background to assess which physical
able to order and plot as a function of linearized forms of the and chemical relations may control the corrosion process.
different kinds of probability distributions. Also, nonlinear Some high-order interaction effects m a y be physically im-
least squares curve fitting may be used. The best approach is possible or very unlikely, and statisticians may be able to
to choose the type of distribution that clearly produces the confound these with direct or lower-order interaction effects
best approximation to a straight line. If an extreme value dis- that m a y be possible. Without such guidance, statisticians
tribution is only slightly better than a normal distribution, a normally will assume that the higher-order interactions will
normal distribution may be assumed because the statistical have little effect, and therefore will design a fractional factorial
techniques are easier to use and more universally understood. experiment accordingly.
The Greco-Latin square is a fractional, four-level, four-
factor factorial experiment composed of a total of 16 sets of
D E S I G N OF E X P E R I M E N T S conditions. The complete factorial experiment requires 256
test conditions. It is a very efficient experiment when the
The philosophy incorporated into the design of corrosion data are commensurate with a model containing no interac-
experiments is m o r e encompassing than the application of tion terms. Unfortunately, in corrosion experiments it is a

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86 CORROSION TESTS AND STANDARDS MANUAL

rare situation when a study of four variables does not involve Most of the popular spreadsheet programs can perform mul-
some interaction effects. tiple regression analysis, and most of the information that is
needed can be obtained from this process. Regression
Uncontrolled Experiments analysis as well as other techniques that deal with normal
In the real world, metals are seldom exposed to controlled statistics are based on two basic assumptions that are seldom
environments. Thus, the development of materials for use in completely accurate; these are (1) independent variables
the real world normally requires exposure studies in uncon- upon which dependent variables are regressed are truly in-
trolled environments. dependent, or not associated with each other in any way,
A properly designed uncontrolled experiment is one that and (2) the values of the independent variables are fixed
considers all the possible effects of uncontrolled variables. The (that is, each one is not just a sample of a distribution of
corrosion researcher's knowledge of physical and chemical values and thus is not subject to error). In the real world of
processes is most valuable in this respect. Changes in variables corrosion research, it is extremely difficult to design or
that are believed to cause effects along with the resulting conduct an experiment where these criteria are met. Thus,
effects should be measured. If an important variable is missed, it is necessary to evaluate how these assumptions might
all of the other data become less meaningful. affect the data analysis. The different statistical techniques
For proper subsequent analysis, uncontrolled experiments discussed in the following paragraphs consider the effects
require the collection of considerable data. For example, it is of these assumptions.
possible to collect ten sets of data involving nine uncontrolled
variables and the measured corrosion results. The total is 100 Simple Linear Regression
bits of information that can be subjected to multiple regres- This technique fits a straight line to data as dependent
sion analysis. If all of the variables are included in the analy- values related to a single set of values of an independent
sis, a perfect mathematical fit can be obtained that is both parameter. The set of equations that are used minimizes the
physically and statistically meaningless. The experimental de- sum of the squares of differences between the dependent
sign does not consider the possibility of nonlinearity effects, values and the line.
interaction effects, nor error effects. One approach to assure This technique may be illustrated by the analysis of a
that enough data sets are collected is to count all of the physi- conceptually simple experiment, galvanic current as a func-
cally and chemically (not mathematically) possible direct and tion of dewpoint-temperature a n d a m b i e n t - t e m p e r a t u r e
interaction effects of the measured variables and multiply by differences. Assume the experiment was conducted in a n
4 or 5 to account for possible nonlinearity and error. e n v i r o n m e n t a l c h a m b e r that can control conditions uni-
formly within the m e a s u r e m e n t accuracy of temperature
and dewpoint. We have spaced replicate specimens ran-
ANALYSIS OF DATA domly in the c h a m b e r and have measured currents from
each very accurately. Three tests were performed at each
With the use of desktop computers and work stations now of three levels of dewpoint (28, 26, and 24~ holding tem-
common, it is possible for corrosion researchers to put in perature c o n s t a n t at 30~ For each new test, at each level,
their data and come out with analysis of variance tables for old specimens were retained while new specimens were
factorial experiments and multiple linear regression analysis added and m e a s u r e m e n t s made on both. If three speci-
tables for uncontrolled experiments. Most such tables include mens were added for each test replication, there would
a statistical test of significance for observed effects. That test be 18 c u r r e n t m e a s u r e m e n t s at each level for a total of
(such as a F test) is a measure of the probability that an ob- 54 measurements. That may seem like a lot of measure-
served effect either exists or is caused by random error. ments just to establish two points that define a straight
Handbooks usually tabulate F values for 0.05 and 0.01 line. This approach has taken into consideration that both
probability levels. If a proper probability distribution has time and space may have a n unexpected effect o n our cur-
been assumed and an experiment has been designed and rent responses, a n d that our e n v i r o n m e n t a l m e a s u r e m e n t s
executed properly, calculated F values exceeding tabulated a n d their resulting controls on c h a m b e r conditions truly
values at the 0.05 probability level indicate that the observed may not be fixed. For example, although c o n t i n u o u s tem-
effect is likely to he caused by r a n d o m error only one in 20 perature m e a s u r e m e n t s may be within a tenth of a degree,
or more times. Those are rather good odds involving rela- dewpoint m e a s u r e m e n t s may be accurate only within a
tively little risk. Such odds establish a relatively high degree degree.
of confidence in the decisions that are based on the corre- Spreadsheet programs consider independent variables as
sponding experimental results. When complex tradeoff deci- in the x range and the dependent variable as the y range.
sions are to be made, it may be necessary to assume a higher The resulting statistics are placed in an output range in the
degree of risk. More complete F tables are available that in- form of a table. The primary results of interest are the inter-
clude other probability levels; nothing is magical about 95 or cept (a), the slope (b), the estimated standard deviation of
99 % confidence levels. Researchers should be able to weigh the slope (Sb), the square of the correlation coefficient (R2),
the involved risks in decisions and act accordingly. and the n u m b e r of degrees of freedom for error. I n simple
linear regression, only one independent value or one col-
u m n for x is considered. I n multiple regression, several
Analysis Techniques
variables (xl) may be included in a like n u m b e r of columns
A lot of sophisticated statistical software can he used to and the results include a coefficient (hi) and estimated stan-
analyze data. These comprehensive packages can be expensive. dard deviation (Sbi) for each.

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C H A P T E R 5 - - S T A T I S T I C A L T R E A T M E N T OF D A T A 87

T A B L E 1--Fractional factorial design and results.


Natural Logarithmof Currentin Microamps
28~ 26~ 24~
1st Time 2nd Time 3rd Time 1st Time 2nd Time 3rd Time 1st Time 2nd Time 3rd Time
First Exposure 2.0656 . . . . . . 1.4563 . . . . . . 0.2700 . . . . . .
2.0656 . . . . . . 1.5195 . . . . . . 0.3075 . . . . . .
2.1294 1.4231 ... 0.4055
SecondExposure 2.2905 2.3224 iii 1.3762 1.2i'19 ... -0.3011 -0.3011 iii
2.3523 2.4105 ... 1.2641 1.3762 ... -0.1744 -0.4463 ...
2.3523 2.2905 ... 1.2119 1.1410 -0.4463 -0.2107
Third Exposure 1.8625 1.8991 1.8625 1.2613 1.1086 1.i725 0.0862 0.2390 0.0862
2.0980 2.1564 2.0360 1.1725 0.9670 1.1410 0.1484 -0.0513 0.0198
1.8991 2.1282 1.9359 1.0750 1.2326 1.0403 0.0198 0.1222 0.1823

The resuks of a simple linear regression of our data are: error degrees of freedom are 46. The F tables are entered
-a = 44.01, b = 1.859, s b 0.094, a n d R 2 = 0.882 (the fraction of the
= with 1 DF for the greater mean square and 46 DF for the
variability explained by the regression). However, it is known lesser mean square. The F values associated with better
that current is an exponential function of dewpoint, and the than 0.95 and 0.99 probabilities of statistical significance
current values are log-normally distributed. One reason to for these DFs are 4.05 and 7.21, respectively.
think so is that current cannot be negative when the dew- The results of regression analysis and analysis of variance
point is zero as is indicated by the intercept value. Regressing are given in Table 2. Only those effects containing dewpoint
the natural logarithms of the current with dewpoint yields are statistically significant at greater than 0.95 or 0.99 pro-
-a = 12.68, b -- 0.532, sb = 0.018, and R 2 -- 0.943. The exponential bability. A regression including only those terms yields the
model produces a better fit than the linear model. results in Table 3. Only the intercept is slightly different
How does dewpoint not being fixed affect these coeffi- from that in Table 2. The best estimate of the functional
cients? If dewpoint is regressed with log-current and the relationship between current and dewpoint at a constant
resulting equation transposed, the coefficients a and -b are temperature of 30~ is Current = exp [0.581(DP- 24.2)].
13.52 and 0.563, respectively. This result shows that the
inability to precisely measure and control the dewpoint re- Covariance o f "Independent" Variables
sults in an underestimate of the slope and an overestimate
In many corrosion experiments, exposure conditions are
of the intercept.
uncontrolled and the independent variables of interest are
Multiple Regression Analysis a n d Analysis o f Variance measured and recorded. Multiple regression analysis is very
useful in analyzing these data. The results of multiple re-
The hypothetical experiment described previously was per-
gression analysis of uncontrolled experiments do not within
formed considering the possibility that time and space effects
themselves prove cause-effect relationships. Possible corre-
could bias our results. This possibility can be tested using
lations between supposedly independent variables are a
multiple linear regression and analysis of variance. The ex-
serious problem. When two "independent" variables are
perimental design has included two variables (other than
perfectly correlated, it is impossible to determine which
dewpoint) we will call time and exposure. Values for expo-
variable actually correlates with the dependent variable re-
sure are 1, 2, and 3 for the first, second, and third exposures
sults. Thus, when such strong correlations exist, although
at a set dewpoint, respectively. Values for time are 1, 2, and 3
one variable may appear to be statistically more significant
for specimens exposed only to the first exposure, to the first
than the other, it may be mathematically serving as the
and second exposures, and to the first, second, and third
other variable's proxy or stand-in a cause-effect relation-
exposures, respectively. With three variables, four interaction
ship. Such might be the case when the error of measure-
effects are possible: (1) dewpoint X time, (2) dewpoint X
ments for the proxy variable is much less than the error of
exposure, (3) time X exposure, and (4) dewpoint X time X
measurements for the variable actually causing the effect.
exposure. The values for these interactions are the products
Significant proxy variables may be used within limits with
of the differences between the values and their means. For
some success as predictors and still not have any real physi-
example, a value for dewpoint X exposure is (28 - 26) X (-12.33)
cal significance. A good example is corrosion rates that cor-
= -2.67. By using formulas in a spreadsheet it is possible to
relate with distance from a seashore when the actual cause is
create an x matrix of 7 columns with 54 rows that can be
the a m o u n t of salt spray deposited on the specimens.
regressed against the measured current data y. The data in
Simple linear regressions between each of the independent
this fractional factorial experiment are presented in Table 1.
variables can be used to produce a correlation matrix. The
Multiple regression of the data for this three-factor, three-
values of R in this matrix can be used to identify possible
level factorial experiment can produce an analysis of variance.
covariance problems. Once statistical significance of various
Calculated values for F are used to determine statistical sig-
factors is established, the corrosion researcher should con-
nificance of direct and synergistic effects. F may be deter-
sider the corrosion processes and first principles in reaction
mined using the following relationship
kinetics to evaluate the consistency of the statistical model
r = (b/sb) 2 (6) with a physical model. Best fits of data to physical models
can yield valuable information such as activation energies
Each coefficient uses one degree of freedom (DF). In this that can point toward diffusion controlled or activation con-
experiment with an intercept and 7 slopes the remaining trolled processes.

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88 C O R R O S I O N TESTS AND S T A N D A R D S MANUAL

TABLE 2--Regression analysis and analysis of variance. an e x p e r i m e n t n o r analyze the resulting d a t a w i t h o u t the
Intercept a help of corrosion researchers. Statistical techniques have both
-13.81 R2 0.9643 DF 46 advantages and limitations related to the types of data to be
Effect b Sb F collected. Overall, c o r r o s i o n r e s e a r c h e r s s h o u l d have a bet-
Dewpoint (DP) 0.5809 0.0196 876.70 ter feel for the physical constraints that m a y limit statistical
Time (T) -0.0457 0.0513 0.79 m o d e l s t h a n do statisticians. The statistician will have a
Exposure (E) -0.0533 0.0513 1.08 b e t t e r feel for h o w t h e s e constraints can be i n c o r p o r a t e d
DP x T 0.0836 0.0314 7.08
DP x E -0.1087 0.0314 11.96 into the layout of the design w h i c h p r e d e t e r m i n e s the style
TxE 0.0778 0.0728 1.14 of statistical analysis to be used. Statistical t e c h n i q u e s
DP x T x E -0.1811 0.0446 16.52 s h o u l d n o t control the r e s e a r c h to the p o i n t t h a t it b e c o m e s
the "tail that wags the dog." The r e s e a r c h objectives m u s t be
kept in sight, and statistics is one of m a n y tools that can be
v a l u a b l e to r e a c h them.
TABLE 3--Regression analysis of significant effects.
Intercept a
-13.99 R2 0.9572 DF 49 REFERENCES
Effect b Sb F
Dewpoint (DP) 0.5809 0.0208 778.21 [1] Ostle, B., Statistics in Research, Second Edition, Iowa State
DP x T 0.0836 0.0334 6.28 College Press, Ames, IA, 1963, pp. 585.
DP x E -0.1087 0.0334 10.62 [2] Micldey, H. S., Sherwood, T. K., and Reed, C. E., Applied
DP • T x E -0.1811 0.0473 14.66 Mathematics in Chemical Engineering, Second Edition,
McGraw-Hill, New York, 1957, pp. 46-99.
[3] WeibuU, W., "A Statistical Distribution of Wide Applicability,"
Journal of Applied Mechanics, Vol. 18, 1951, pp. 293-297.
SUMMARY [4] Harshbarger, J. H., Kemppinen, A. I., and Strum, B. W., "Statis-
tical Treatment of Nonnormally Distributed Stress-Corrosion
Data," Handbook on Corrosion Testing and Evaluation, W. H.
C o r r o s i o n r e s e a r c h e r s can gain a g r e a t e r degree of confi- Ailor, Ed., John Wiley and Sons, New York, 1971, p. 90.
d e n c e in t h e i r e x p e r i m e n t a l results if t h e y have a basic un- [5] Pathak, B. R., "Testing in Fresh Waters," Handbook on Corro-
d e r s t a n d i n g a n d use statistical t e c h n i q u e s of e x p e r i m e n t a l sion Testing and Evaluation, W. H. Ailor, Ed., John Wiley and
design and data analysis. Statisticians c a n n o t properly design Sons, New York, 1971, p. 568.

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Computer Based Data
Organization and Computer
Applications
i!ii!!ii161iiii!!i
i~•i!~i!~i!!~•!•i~ii~i!~i•i•!i~i~•ii~!ii~i•ii~ii~!ii~!i~i•i!i!i~i•i~ii!i~•i!i!~i!i~i!~iii~•ii~•ii~!•i~i!i!ii~ii~iii~ii•~ii!~ii~ii~i!i~i•i~ii~!•i~ii~i•i~ii~iiiiiiiiiii•ii•
Pierre R. Roberge 1

INTRODUCTION as it relates to computerization. ASTM G 107, Guide for For-


mats for Collection and Compilation of Corrosion Data for
COMPUTERS PLAYIMPORTANTroles in d a t a a c q u i s i t i o n in labo- Metals for Computerized Database Input, serves as a master
r a t o r y and field e n v i r o n m e n t s , d a t a p r o c e s s i n g and analysis, list with a total of 125 individual data entry fields, each defined
data s e a r c h i n g a n d d a t a p r e s e n t a t i o n in u n d e r s t a n d a b l e and with preferred units and category sets (acceptable entries) to
useful formats. The r a p i d d e v e l o p m e n t of accessible c o m - assure consistency. Not all fields are required for any one data
p u t i n g p o w e r since the 1980s has led to the use of c o m - record, but an estimated 25-50 often are required to fully de-
p u t e r s a n d direct o r i n d i r e c t applications of m a c h i n e scribe the material, environment, and test results for an indi-
intelligence in every sphere of science a n d engineering. As a vidual test. Table 1 describes the eight basic data categories
m o d e r n science p h i l o s o p h e r has written, "The e m e r g e n c e of detailed in the standard as being considered essential for the
m a c h i n e intelligence d u r i n g the s e c o n d half of the t w e n t i e t h complete documentation of corrosion data. Rarely is this detail
c e n t u r y is the m o s t i m p o r t a n t d e v e l o p m e n t in the e v o l u t i o n provided in the published literature, a factor that compounds
of this p l a n e t since the origin of life two to three t h o u s a n d the difficulties in comparing published data from different
m i l l i o n years ago" [1]. C o m p u t e r s also assist e n g i n e e r s to sources [2].
t r a n s f o r m data into usable and r e l e v a n t i n f o r m a t i o n . The
c o n n e c t i v i t y of c o m p u t e r s to the outside w o r l d t h r o u g h the
TABLE 1--Corrosion database input categories for metals in
I n t e r n e t and the W e b has o p e n e d up t r e m e n d o u s c h a n n e l s ASTM G 107.
of c o m m u n i c a t i o n that n e v e r existed before. Type of Test 9 Standardized test
9 Laboratory or field test
Compilation of Corrosion Data 9 Relation to specific process (e.g., pulp bleaching)
9 Relation to specific application
Corrosion data for metals are measures of time dependent (e.g., production tubing)
material/environment interactions that are manifested in m a n y Test Emphasis 9 Type(s) of corrosion evaluated
forms; for example, pitting, stress corrosion cracking, corrosion- Environment 9 Generic description
fatigue, crevice corrosion, and fretting. If nonmetals are consi- 9 Concentration and state of principal components
9 Contaminants
dered, swelling, property changes, and cracking are i m p o r t a n t 9 Form (e.g., solid, liquid, aqueous solution)
m a n i f e s t a t i o n s . D a t a are available f r o m m a n y s o u r c e s in- Exposure 9 Duration
c l u d i n g s t a n d a r d i z e d l a b o r a t o r y and field tests, industrial Conditions 9 Temperature
exposures, and the results of failure analyses, and are recorded 9 pH
9 Hydrodynamic conditions
in m a n y formats that m a y or m a y not include sufficient infor-
9 Aeration
mation for independent understanding and reliability assess- 9 Agitation
ment. As with m a n y other material property studies, the data Material 9 Class(e.g., metals)
often are developed for proprietary purposes by an individual Identification 9 Subclass
or a small group of users w h o have a c o m m o n understanding 9 Family
9 Common name
of unique terminology, algorithms, test methods, and data re- 9 Standard designation
port formats and have no motivation to modify their data 9 Condition
compilations for sharing with other potential users [2]. 9 Manufacturing process
9 Product form
Standardized Data Recording Formats Specimen 9 Specimen no.
Identification 9 Size
The need to develop standardized data recording formats was 9 Surface condition
9 Composition
recognized by Committee G01 on Corrosion of Metals. The 9 Properties
committee efforts addressed material identification and re- Specimen 9 Mass change
cording of test details along with guidelines for assessing data Performance 9 Property change
quality, data interchange formats, and consistent terminology 9 Type and severity of localized attack
(e.g., pitting, crevice corrosion,
stress corrosion cracking)
1 Department of Chemistry and Chemical Engineering, Royal Mili- Documentation 9 Reference or source
tary College of Canada, Kingston, Ontario K7K 7B4, Canada. 9 Published or unpublished data
89

Copyright 9 2005 by ASTM International www.astm.org


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90 CORROSION TESTS AND STANDARDS MANUAL

FIG. 1--Time and environment dependency of databases and models.

ASTM G 135, Guide for Computerized Exchange of Corro- 9 Evaluated data, representing parametric analysis of data
sion Data for Metals, defines the techniques used to encode sets, including in some cases judgmental interpretation by
corrosion of metals test results for exchange between computer one or more experts.
systems. The guide establishes formalism for transferring cor- 9 Certified values, representing approval by some referee on
rosion test data between computer systems in different labora- certification groups for some specific application (for ex-
tories and defines a generic approach to structuring data files. ample, design).
The guide is designed for standards developers to help them
specify the format of files containing test results and create Several distinct steps should be taken to assess the quality
programs that read and write these files. of any material property or performance data. While the
data evaluation and validation steps reflect more on the
Data Quality quality of the data generated, data verification reflects on
the data search and retrieval system used to ensure the re-
Physical and mechanical property data are normally gener- trieved data are consistent with the original source [2].
ated using established standard test procedures that permit
direct comparisons of test results. However, the transforma- 1. Evaluation: The process of establishing the accuracy and
tion of corrosion testing results into usable real life functions integrity of data. Evaluation may involve examination and
for service applications can be a rather difficult task, often appraisal of the data presented, assessment of experimen-
generating unreliable or questionable data as illustrated in tal technique and associated errors, consistency checks for
Fig. 1 [3]. In the best cases, laboratory tests can provide a allowed values and units, comparison with other experi-
relative scale of merit in support of the selection of materials mental or theoretical values, reanalysis and recalculation
exposed to specific corrosive conditions and environments. of derived quantities as required, selection of best values,
Data can be classified by a variety of schemes that reflect the and assignment of probable error or reliability.
extent of the data generated and the level to which the data 2. Validation: The process of substantiating that the data have
have been processed [2]: been generated according to standard methods and prac-
tices or other indices of quality, reliability, and precision.
9 Raw (unanalyzed) individual test results. 3. Verification: The process of substantiating the accuracy
9 Analyzed individual test results. of the data transcription and manipulation within the
9 Mathematically reduced (average or statistically based) val- data system.
ues representative of sets (multiple replicates) or results.
9 Validated data, meeting the validity requirements of the A n u m b e r of corrosion data evaluation studies have de-
appropriate test standards. scribed the scope of the effort required [4]. Unfortunately,

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CHAPTER 6--COMPUTER BASED DATA 91

the complexities of corrosion data tend to discourage at- the most important factors leading to different forms of cor-
tempts to undertake this type of rigorous data analysis. A rosion failures. An obvious application of the results shown
more accepted approach is to develop expert consensus, in Fig. 2 would be to help optimize the n u m b e r of fields
often through peer review or technical committee activities, required for the development of an efficient knowledge
resulting in publication of s u m m a r y documents addressing based system.
specific environments or applications with judgmental ap- Context sensitivity is fundamental to failure analysis. For
praisals of the quality, reliability, and adequacy of available one, the criticality of a specific failure is very much system
data for the intended purpose or application. dependent. While the general description of the corrosion
types presented in Table 2 is sufficient to explain the gen-
eral appearance of most specific problems, it can lead to
Overcoming Knowledge Gaps great confusion when one tries to quantify the attributes
Humans are used to working with imprecise information. associated with them. Pitting corrosion, which, for example,
They naturally accept vague use of language, making continu- is almost a c o m m o n denominator in all types of localized
ous interpretations of the information they receive based upon corrosion attack, may assume different shapes. Pitting cor-
context. Computers are much less forgiving. This section in- rosion can produce pits with their m o u t h open (uncovered)
troduces a generic framework linking mechanistic principles or covered with a semipermeable m e m b r a n e of corrosion
leading to corrosion damage with the observable signs of a products. Pits can be either hemispherical or cup-shaped. In
corrosion attack. some cases, they are flat-walled, revealing the crystal struc-
Six important corrosion factors have been identified in a ture of the metal, or they may have a completely irregular
review of scientific and engineering work on SCC damage [5], shape [8]. The severity associated with pitting corrosion can
generally regarded as the most complex corrosion mode. also vary greatly and is directly dependent on the criticality
According to Staehle's materials degradation model, all engi- of the systems subjected to this form of damage.
neering materials are reactive and their strength is quantifi- A more detailed analysis of these survey results reveals some
able, if all the variables involved in a given situation are interesting features that relate to the terminology used in corro-
properly diagnosed and their interactions understood. For sion science and engineering. The results of interviews were
characterizing the intensity of SCC the factors were material, analyzed with Box-and-Whisker plots. These plots divide the
environment, stress, geometry, temperature and time. These data for each sample into four areas of equal frequency. A box
factors represent independent variables affecting the intensity encloses the middle 50 %, and the median is drawn as a vertical
of SCC. Furthermore, a n u m b e r of subfactors have been iden-
tified by Staehle for each of the six main factors, as shown in TABLE2--Factors and subfactors controlling the occurrence of a
Table 2. corrosion failure.
The term "form" of corrosion is generally well k n o w n Factor Subfactors and contributingelements
from Fontana's popular corrosion engineering textbook [6].
Material Chemical composition of alloy
The different forms of corrosion represent corrosion phe- Crystal structure
n o m e n a categorized according to their visual appearance. Grain boundary (GB) composition
Dillon [7] considered Fontana's eight basic forms of corro- Surface condition
sion and divided them into three groups, based on their Environment
chemical definition Type, chemistry, concentration, phase,
ease of identification: conductivity
circumstance Velocity, thin layer in equilibrium with rela-
9 Group 1--readily identifiable by ordinary visual examination tive humidity, wetting and drying, heat
9 Uniform corrosion transfer boiling, wear and fretting, deposits
9 Pitting Temperature At metal surface exposed to environment
9 Crevice corrosion Change with time
Stress
9 Galvanic corrosion stress definition Mean stress, maximum stress, minimum
9 Group 2 - - m a y require supplementary means of examination stress, constant load/constant strain, strain
9 Erosion rate, plane stress/plane strain, modes I, II,
9 Cavitation III, biaxial, cyclic frequency, wave shape
sources of stress Intentional, residual, produced by reacted
9 Fretting products, thermal cycling
9 Intergranular Geometry Discontinuities as stress intensifiers
9 Group 3--verification by microscopy is usually required Creation of galvanic potentials
9 Exfoliation Chemical crevices
9 Dealloying Gravitational settling of solids
Restricted geometry with heat transfer
9 Stress corrosion cracking leading to concentration effects
9 Corrosion fatigue Orientation versus environment
Time Change in GB chemistry
An empirical correlation was established between the fac- Change in structure
tors listed in Table 2 and these forms of corrosion. Fifteen Change in surface deposits, chemistry,
or heat transfer resistance
recognized corrosion experts agreed to complete an opinion Development of surface defects, pitting,
poll listing the m a i n subfactors and the c o m m o n forms of or erosion
corrosion. The responses were then analyzed and repre- Development of occluded geometry
sented in a graphical way, such as illustrated in Fig. 2, for Relaxation of stress

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92 CORROSION TESTS AND STANDARDS MANUAL

O
t- ~ t,-
o .O c <i.

,'n,
Material
Composition i-i
Crystal Structure L
. GB Composition ,_ :; ........................

9 Surface Condition 9 ,
Environmental
Nominal
Circumstantial
Stress
Applied , t ~ 9 9
Residual ' t [
!
• I
,
Product Build-Up
Cyclic
Geometry
Galvanic Potentials
..... 4 .......... t ...... i . . . . . . . . . . . ~ i ......
Restricted Geometries : "I 9 i
Settlinq of Solids
Temperature
Changing Temperature

Time
lemperature of Surface t ! ! : -

Changes Over Time 9 I ii ]

Based on resloonse where x>7 and ~<3

FIG. 2 - - R e s u l t s of an expert opinion poll indicating the most important factors causing
different types of corrosion failures.

line inside the box. Horizontal lines or whiskers extend on each managers the corrosion performance or under-performance of
side of the box to represent the smallest data point within 1.5 materials has a very different meaning. In the context of life
interquartile for the lower quartile (left) and the highest data cycle management, corrosion is only one element of the whole
point within 1.5 interquartfle for the upper q u a ~ l e (right). In- picture, and the main difficulty with corrosion knowledge is in
dividual points drawn outside of these ranges signify the pres- incorporating it at the system management level.
ence of data values within three interquarfile ranges (suspect
outliers) or even farther apart as outliers.
Figure 3 presents the Box-and-Whisker plots of the results Bottom Up Approach
obtained with pitting corrosion, and Table 3 summarizes Scientific models can take m a n y shapes and forms, but
two features of the plot by prioritizing the importance asso- they all seek to characterize response variables through rela-
ciated with each subfactor included in the framework (the tionship with appropriate factors. Traditional models can be
median) and the sharpness of the responses (inverse of the divided into two m a i n categories: mathematical or theoreti-
b r e a d t h of the whiskers). W h e n presented in this fashion, cal models and statistical or empirical models [9]. Mathe-
such results provide a useful spectrum of factor and subfac- matical models have the c o m m o n trait that the response and
t a r confidence levels. While the important and sharp subfac- predictor variables are assumed to be free of specification
tars can be used reliably to predict the occurrence of pitting error and m e a s u r e m e n t uncertainty [10]. Statistical models,
corrosion, the least focused results provide a good indication on the other hand, are derived from data that are subject to
of the ambiguities related to this form of corrosion. various types of specification, observation, experimental and/
or m e a s u r e m e n t errors. In general terms, mathematical
models can guide investigations while statistical models are
MODELING AND LIFE PREDICTION used to represent the results of these investigations.
Models of materials degradation processes have been devel-
oped for a multitude of situations using a great variety of M a t h e m a t i c a l Models
methodologies. For scientists and engineers working at devel- Some specific situations lend themselves to the develop-
oping materials, models have become an essential benchmark- m e n t of useful mechanistic models that can account for
ing element for the selection and life prediction associated with the principal features governing corrosion processes. These
the introduction of new materials or processes. For systems models are most naturally expressed in terms of differential

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CHAPTER 6--COMPUTER BASED DATA 93

Material Factor Stress Factor

I. . . . . ~pli~d stress
I
Composition

Cwstal structure R e s i d u a l stress

GB ~mpOsltlon P r o d u c t build-up stress

l ..... :
Surface ~ndltlon C y c l i c stress

Environment Factor
Geometry Factor

Nomlnat environment ',


Galvanic potentials

Circumstantial environment

Temperature Factor
Io i
Restricted geometries

Changing temperature Settling o f solids

Time Factor

. . . . . so.2oo ,&pJ~,ore' ..... I

FIG. 3--Box-and-whisker plots of the survey results obtained for the factors and
subfactors underlying the appearance of pitting corrosion.

equations or in another nonexplicit form of mathematics. have made it possible to cope with relatively complex prob-
However, modern developments in computing facilities and lems. A mechanistic model has the following advantages [11]:
in mathematical theories of nonlinear and chaotic behaviors
* It contributes to our understanding of the p h e n o m e n o n
u n d e r study;
TABLE 3--Ranking of the subfactors causing pitting corrosion in 9 It usually provides a better basis for extrapolation;
decreasing order of importance and distribution sharpness. 9 It tends to be parsimonious, i.e., frugal, in the use of pa-
Orderofimportance* Order ofsharpness** rameters and to provide better estimates of the response.
Factor Subfactor Factor Subfactor The m o d e r n progress in understanding corrosion phe-
Material Composition Environment*** Nominal n o m e n a and controlling the impact of corrosion damage
Temperature Surface Environment Circumstantial
was greatly accelerated when the thermodynamic and ki-
Environment Nominal Material Composition
Environment Circumstantial Geometry*** Settling netic behavior of metallic materials was made explicit in
Material GB Temperature Surface what became known as E-pH or Pourbaix diagrams (ther-
Material Surface Material Surface modynamics) and mixed potential or Evans diagrams (ki-
Geometry Setting Stress Residual netics). These two models, both established in the 1950s,
Geometry Galvanic Stress Applied
Geometry Restricted Material Microstructure have become the basis for most of the mechanistic studies
Time Stress Product carried out since then. The multidisciplinary nature of cor-
Temperature Changing Stress Cyclic rosion science is reflected in the multitude of approaches
Material Microstructure Material GB that have been proposed to explain and model fundamental
Stress Product Geometry Galvanic corrosion processes. The following list illustrates some sci-
Stress Applied Temperature Changing
Stress Residual Geometry Restricted entific disciplines with examples of modeling efforts one
Stress Cyclic Time can find in the literature:
*The median 9 S u r f a c e s c i e n c e : atomistic model of passive films
**Theinverseof the breadth of the whiskers
***Presenceof one suspectoutlier 9 Phys/ca/chem/stry: adsorfion behavior of corrosion inhibitors

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94 CORROSION TESTS AND STANDARDS MANUAL

9 Q u a n t u m mechanics: design tool for organic inhibitors / \Ilk


F(x)=expl-l-kX;U j (2)
9 Solid state physics: scaling properties associated with hot
corrosion
9 Water chemistry: control model of inhibitors and anti- and Eq 3 when x > u and k = 0.
scaling agents
9 B o u n d a r y element mathematics: cathodic protection
F(x) = e x p ( - e x p - f ~ ) (3)
Statistical Models
Mechanisms underlying corrosion processes are frequently EVS were put to work on real systems on several occasions
not understood sufficiently well or are simply too complica- in the oil and gas industries for two main reasons. The 1st rea-
ted to allow an exact model to be built from theory. In such son was the critical nature of many operations associated
cases empirical models m a y be useful. The degree of com- with the transport of gas and other petroleum products, and
plexity that should be incorporated in an empirical model the 2nd is the predictability of localized corrosion of steel, the
can seldom be assessed in the initial phase of designing such m a i n material used by the oil and gas industry. Meany has,
model. A most c o m m o n approach is to first build a simple for example, reported four detailed cases where extreme
model based on a limited set of variables and increase its value distribution proved to be an adequate representation of
complexity with growing evidence and confidence. corrosion problems in u n d e r g r o u n d piping and power plant
Statistical assessment of time to failure is a basic topic in condenser tubing [15]. In another study, data from water
reliability engineering for which m a n y mathematical tools injection pipeline systems and from the published literature
have been developed. Evans, who also pioneered the mixed were used to simulate the sample functions of pit growth on
potential theory to explain basic corrosion kinetics, launched metal surfaces [16]. It was concluded that maximum pit depths
the concept of corrosion probability in relation to localized were adequately characterized by extreme value distribution,
corrosion. According to Evans, an exact knowledge of corro- that a Gaussian distribution could model corrosion rates for
sion rate was less i m p o r t a n t t h a n the ascertainment of the water injection systems, and that an exponential pipeline leak
statistical risk of its initiation [12]. The following examples growth model was appropriate for all operation regimes.
illustrate the application of empirical modeling in two areas
of high criticality.
P R O P A G A T I O N OF P R O B A B I L I T Y
FUNCTIONS
Extreme Value Statistics
A n u m b e r of statistical transformations have been pro- The regulations pertaining to the geologic disposal of
posed to quantify the distributions in pitting variables. high-level nuclear waste, in the U.S. and Canada, require
Gumbel is given the credit for the original development of that the radionucleides remain substantially contained within
extreme value statistics (EVS) for the characterization of pit the waste package for 300-1000 years after permanent clo-
depth distribution [13]. The EVS procedure is to measure sure of the repository. The current concept of a waste pack-
m a x i m u m pit depths on several replicate specimens that age involves the insertion of spent fuel bundles inside a
have pitted, then arrange the pit depth values in order of container that is then placed in a deep borehole, either verti-
increasing rank. The Gumbel distribution expressed in Eq 1, cally or horizontally, with a small air-gap between the con-
where )~ and (~ are the location and scale parameters, re- tainer and the borehole. For vitrified wastes, a pour canister
spectively, can then be used to characterize the dataset and inside the outer container acts as an additional barrier. Cur-
estimate the extreme pit depth that possibly can affect the renfly, no other barrier is being planned, making the success-
system from which the data was initially produced. ful performance of the container material crucial to fulfilling
the containment requirements over long periods of time.
A model developed to predict the failure of Grade-2 tita-
F(x) = e x p ( - e x p l - ~ - - ~ ] / (1) nium was published in which two major corrosion modes
were included [17]: failure by crevice corrosion and failure
In reality there are three types of extreme value distribu- by hydrogen induced cracking (HIC). A small n u m b e r of con-
tions [14]: miners were assumed to be defective and fail within 50 years
of emplacement. The model was probabilistic in nature, and
9 Type 1: exp(-exp[-x]) or the Gumbel distribution
each modeling parameter was assigned a range of values re-
9 Type 2- exp(-x -~) Cauchy distribution sulting in a distribution of corrosion rates and failure times.
9 Type 3: exp(-[co - x] k) Weibull distribution
The crevice corrosion rate was assumed to be only dependent
where x is a r a n d o m variable, and k and co are constants. on properties of the material and the temperature of the
A goodness-of-fit test is required to verify which of these vault. Crevice corrosion was also assumed to initiate rapidly
three distributions best fits a specific data set. The Chi square on all containers and subsequently propagate without repas-
test or Kolmogorov-Simirnov test has often been used for sivation. Failure by HIC was assumed to be inevitable once
this purpose. A simpler graphical procedure is also possible a container temperature fell below 30~ However, the con-
using a generalized extreme value distribution with a shape centration of atomic hydrogen to render a container suscep-
factor dependent on the type of distribution. There are two tible to HIC would occur only very slowly and might even be
expressions for the generalized extreme value distribution, negligible if that container had never been subject to crevice
i.e., Eq 2 when kx _<(ct + uk) and k ~eO, corrosion.

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CHAPTER 6--COMPUTER BASED DATA 95

Normal distribution in corrosion rates


(temperature dependent)

p(r,) / ~I Corrosion rate sampled


from experimental data

p(r") dr" = p(t) dt

rt = rt ---y oc
Skewed distribution in failure times

~
p(t) x normalization factor

p(t)

Failure rate as a function of time t=t,

Fraction failed at time t


= f~' fdt

j/
t t,

FIG. 4~Procedure used to determine the failure rate of hot containers as a function of time.

The mathematical procedure to combine various probabil- management. Others are specifically related to the impact of
ity functions and arrive at a failure probability of a hot con- corrosion damage on system integrity and operating costs.
tainer due to crevice corrosion at a certain temperature is The following examples illustrate how these considerations
illustrated in Fig. 4. The failure rate due to HIC was arbitrar- are put into practice and integrated into efficient manage-
ily assumed to have a triangular distribution in order to sim- ment systems.
plify the calculations, and knowing that HIC is only a predicted
marginal failure mode in the considered burial conditions. A Fault Tree for the Risk Assessment of Gas Pipeline
On the basis of these assumptions and the calculations des- This first top-down model example briefly describes the fault
cribed in the till paper, it was predicted that 96.7 % of all contai- tree analysis (FTA) methodology adopted by Nova Corporation
ners would fail by crevice corrosion and the remaining by HIC. for the risk assessment of its 18 000 km gas pipeline network
However, only 0.137 % of the total n u m b e r of containers were [18]. FTA is a very efficient method for reviewing and analyti-
predicted to fail before 1000 years (0.1% by crevice corrosion cally examining a system or equipment in its details to empha-
and 0.037 % by HIC) with the earliest failure after 300 years. size the lower level fault occurrences that directly or indirectly
could contribute to a major fault or undesired event. By per-
forming an FITA from lower-level failure mechanisms, a global
Top Down Approach
overview of the system is achieved. Once completed, the fault
Some of the issues involved in deciding on a cost-effective tree allows the risk engineer to evaluate fully a system safety or
solution for combating corrosion are generic to sound system reliability by altering the various lower-level attributes of the

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96 CORROSION TESTS AND STANDARDS MANUAL

Pipeline Outage
{Corrosion]

Corrosion Leak
Probability Factcr

/ Probability of Severe
and Active COrrOSion

Probability = 1 [

L...................................................... 1

FIG. 5~Fault tree for natural gas pipeline outage due to general corrosion.

tree. Through this type of modeling, a number of variables may values for a n entire system. The probabilities of operating
be visualized in a cost-effective manner. at m a x i m u m permitted pressure and the presence of elec-
The Nova rupture risk FTA is normally performed for the trolyte were both set at value u n i t y in Fig. 5, therefore
review and analytical e x a m i n a t i o n of systems or equip- forcing the focus on worst case scenarios. Other more veri-
m e n t to emphasize the lower-level fault occurrences, a n d fiable variables can be developed fully, as is shown in Fig 6
the results of the FTA calculations are regularly validated for the two basic events describing the probable impact of
with inspection results. These results also serve to sched- a cathodic protection deficiency on the pipeline network.
ule m a i n t e n a n c e operations, c o n d u c t surveys, and plan As can be seen in this figure, the probability values used for
research and development efforts. Figure 5 presents the fault-tree calculations are written directly in the database
u n i f o r m corrosion b r a n c h pipeline outage FTA system. program.
Each element of the b r a n c h in this figure contains n u m -
eric probability i n f o r m a t i o n related to technical and Maintenance Steering Group (MSG) System
historical data for each segment of the 18 000 km pipeline. The aircraft industry and its controlling agencies have de-
I n some cases, it is simpler to assume some probability veloped, over the past few decades, a top down system to

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CHAPTER 6--COMPUTER BASED DATA 97

function PCPSH
private PCPSH_Value

PCPSH Value = 0.05


if COAT~ = "FBE"
....................... . ....................... PCPSH_Value = iif( DIST = 1, 0.05, PCPSH_Value )
PCPSH_Value = iif( DIST = 2, 0,05, PCPSH_Value )
PCPSH_Value = iif( DIST = 3, 0.05, PCPSH_Value )
PCPSH_Value = iif( DIST = 4, 0.05, PCPSH Value )
I cothoOc Protec~on I endif
Deficiency
if COAT1 = "EP"
PCPSH_Value = iif( DIST = 1, 0.05, PCPSH_Value )
PCPSH Value = iif( DIST = 2, 0.05, PCPSH Value )
PCPSH_Value = iif( DIST = 3, 0.05, PCPSH Value )
PCPSH_Valua = iif( DIST = 4, 0.05, PCPSH_Value )
endif

if COAT1 = "AE" .or. COAT1 = "CTE"


PCPSH_Value = iif( DIST = 1, 0.46, PCPSH_Value )
PCPSH_Value = iif( DIST = 2, 0.56, PCPSH_Value )
PCPSH_Value = iif( DIST = 3, 0.30, PCPSH_Value )
PCPSH_Value = iif( DIST = 4, 0.55, PCPSH Value )
endif

if COAT1 = "PT" .or. COAT1 = "PT2" .or. ;


" - ' " - / ..................................... 9 COAT1 = "SRT" .or. COAT1 = "HHT"
PCPSH Value = iif( DIST = 1, 0.80, PCPSH_Value )
PCPSH_Value = iif( DIST = 2, 0.88, PCPSH Value )
PCPSH_Value = iif( DIST = 3, 0.51, PCPSH Value )
PCPSH_Value = iif( DIST = 4, 0.79, PCPSH_Value )
endif

function PCPINAD
private PCPINAD_Value

PCPINAD_Value = 0.0
PCPINAD Value = iif( DIST = 1, 0.000152, PCPINAD_Value )
PCPINAD_Value = iif( DIST = 2, 0.007100, PCPINAD_Value )
PCPINAD_Value = iif( DIST = 3, 0.000134, PCPINAD_Value )
PCPINAD_Value =iif( DIST = 4, 0.000388, PCPINAD_Value )

FIG. 6---Detailed code for the basic events leading to a cathodic protection deficiency.

represent potential failures of aircraft components, the The MSG-3 (Revision 2) structures analysis begins by de-
Maintenance Steering Group (MSG). The first generation of veloping a complete breakdown of the aircraft systems, down
formal air carrier maintenance programs was based on the to the component level. All structural items are then either
belief that each part on an aircraft required periodic over- classified as Structure Significant Items (SSIs) or other struc-
haul. As experience was gained, it became apparent that ture. An item is classified as an SSI depending on considera-
some components did not require as m u c h attention as oth- tion of consequences of failure and likelihood of failures as
ers and new methods of maintenance control were devel- well as material, protection, and probable exposure to corro-
oped. Condition monitoring was, thus, introduced in the sive environments. All SSIs are then listed and categorized
decision logic of the initial maintenance steering group as damage tolerant or safe life items to which life limits are
d o c u m e n t (MSG-1) and was applied to Boeing 747 aircraft. assigned [19]. Accidental damage, environmental deteriora-
The most recent major update to the system was initiated tion corrosion prevention and control, and fatigue damage
in 1980. The resultant MSG-3 system is based on the basic evaluation are then performed for these SSIs following the
philosophies of MSG-1 and MSG-2, but prescribes a different logic diagram illustrated in Fig. 7. Once the MSG-3 structure
approach in the assignment of maintenance requirements. In analysis is completed, each element of the structural analysis
1991, industry and regulatory authorities began working to- diagram (Fig. 7) can be expanded right to the individual
gether to provide additional enhancements to MSG-3. As a re- components and associated inspection and maintenance
sult of these efforts, Revision 2 was submitted to the Federal tasks. The logic of the EDA, illustrated in Fig. 8, requires the
Aviation Administration (FAA) in September 1993 and accepted input of a multitude of parameters such as component part
a few weeks later. One particularly interesting addition in this number, location, material composition, and protective coat-
revision is a procedure for incorporating corrosion damage in ing that can be actuated in practical templates.
the MSG logic. The environmental deterioration analysis (EDA)
involves the evaluation of the structure against probable expo- A Corrosion Index for Pipeline Risk Evaluation
sure to adverse environments. The evaluation of deterioration is The third example of top down models is the pipeline risk
based on a series of steps supported by reference materials con- assessment methodology that is described in much detail in
taining baseline data expressing the susceptibility of structural the 2nd edition of a popular b o o k on pipeline risk manage-
materials to various types of environmental damage. m e n t [20]. Since this book was published, m a n y systems

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98 C O R R O S I O N T E S T S AND S T A N D A R D S MANUAL

permits an assessment of the pipeline risk picture in two gen-


eral parts:

First Part: In the first part, a detailed itemization and


relative weighting of all reasonably foresee-
able events that m a y lead to the failure of a
pipeline are carried out. The itemization is
further broken into the four indexes illustrated
in Fig. 9, corresponding to typical categories
of pipeline accident failures. By considering
each item in each index, an expert evaluator
arrives at a numerical value for that index.
The four index values are then summed to ob-
tain the total index value.
Second Part: The second part of the scoring system is a de-
FIG. 7mOverall MSG-3, Revision 2, structural analysis logic tailed analysis of potential consequences of each
diagram. failure, considering product characteristics, pipe-
line operating conditions, and line location.
based on similar logic have been p r o d u c e d with m u c h m o r e The risk of a pipeline failure caused by corrosion, directly
data and complexity. Thus, the following description should or indirectly, is a c o m m o n hazard associated with steel
serve more as an example than a state-of-the-art description pipelines. The corrosion index was organized in three cate-
of the technology. gories to reflect three types of environment to which pipe-
The methodology proposed in that document is based on lines are typically exposed, i.e., atmospheric corrosion, soil
subjective risk assessment, a method particularly well adapted corrosion, and internal corrosion. Table 4 contains the ele-
to situations where knowledge is incomplete and judgments ments contributing to each of the contributing type of envi-
are based on opinions, experience, and other nonquantifiable ronments and suggested weighting factors. Building the risk
factors. The technique used for quantifying risk factors is assessment tool is said to require the following four steps:
described as a hybrid of several methods allowing the user to
confide in scores obtained by combining statistical failure 1. Sectioning: Dividing a system into smaller sections. The
data with operator experience. The subjective scoring system size of each section should reflect practical considerations

Material & Temper i


L__ - ~-I~el"eimine Co~r~ionChaiactefisfics 1

Type of Corrosion
.................... ~ ~__ '-,m-pioved Access....
ISystematic--i ~-Random~!!~i_ / and/or Redesign
L_~/[ _. -.~- -- ~equired
Deterr~ine R-atino .;............
- stress corrosion cracking i
i other corrosion mode
~. - protection potential
I - environment ~ ~ ,P o s s l binspection
lPobesile Possible
.......... Yes t i Yes i i
Combine Rating -.+ .... i '
........................................................ i Establish _..._.l
Establish 1
i ........l"hre-sh~ nspect on TaskJ
9 _ ~ ........... i

Select Repeat Intervali ............................

FIG. 8---Environmental deterioration analysis logic diagram.


l
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CHAPTER 6--COMPUTER BASED DATA 99

Relative managed. In an age of conservation and recycling, it is im-


Risk portant to recognize the fact that the most valuable com-
........ Score [Dispersion factorl modities are information as a vehicle and knowledge as the

T Le.k=aii-J essence. It is surely sensible to preserve and reuse these


most valuable commodities. The adequate transfer and re-
use of information coveting corrosion problems and solu-
tions involve the development of information-processing
Index
Sum
I ~-roduct hazard]
................
strategies that can become very complex. Some of the artifi-
cial intelligence tools that have been developed recently in
support of corrosion control and protection will be reviewed
T in the following sections.

-i i Incorrect
C~176176 ! Design i ]operations Expert Systems (ESs)
[_ !nie_x......... ~ ~inde-x--' [ index j

T __ ...... 1k
During the 1970s, research in Expert Systems (ES) was
mostly a laboratory curiosity. The research focus then was
really centered on developing ways of representing and rea-
Data gathered ! soning about knowledge in a computer, and m u c h less on
from records designing actual systems [21]. In 1985 approximately 50
and interviews systems were deployed and reported, but the success of
some of these captured the attention of many organizations
FIG. 9~Pipeline risk assessment model.
and individuals. The corrosion c o m m u n i t y reacted with
interest to the advent of these new information-processing
of operation, maintenance, and cost of data gathering ver-
technologies by establishing programs to foster and encour-
sus the benefit of increased accuracy; age the introduction of ES in the workplace. While some of
2. Customizing: Deciding on a list of risk contributors and
these programs were relatively modest, others were quite
risk reducers and their relative importance; ambitious and important both in scope and in funding. The
3. Data Gathering: Building the database by completing an advantages and limitations of using ES technology were ana-
expert evaluation for each section of the system;
lyzed in great detail in one of the first reported efforts on
4. Maintenance: Identifying when and how risk factors can combating corrosion with ES [22]. The Stress Corrosion
change and updating these factors accordingly. Cracking (SCC) ES (SCCES) had been created to calculate
the risk of various factors involved in SCC, such as crack ini-
A P P L I C A T I O N S OF ARTIFICIAL tiation, when the user supplied evidence. The main goal of
INTELLIGENCE this effort was to support the decision process of "general"
materials engineers. The system would initially play the role
The m o d e r n world has produced an unprecedented level of a consultant, but it was anticipated that SCCES had the
of technical information that merits being preserved and potential to become:

9 An intelligent checklist;
TABLE 4---Pipeline Corrosion Risk Subjective Assessment. 9A trainer;
Corrosionproblem Risk weight 9 An expert sharpener;
Atmospheric corrosion 9A c o m m u n i c a t i o n medium;
1. Facilities 0-5 pts 9A demonstration vehicle.
2. Atmospheric type 0-10 pts
3. Coating inspection 0-5 pts
The transfer of corrosion expertise into ES has been real-
total 0-20 pts
ized in a multitude of projects. The NACE Conference Pro-
Internal corrosion
ceedings, for example, regularly contain papers that illustrate
1. Product corrosivity 0-10 pts
2. Internal protection 0-10 pts the continuous interest in the application of knowledge engi-
total 0-20 pts neering to corrosion. Unfortunately, many systems reported
Soil corrosion in the literature have never been commercialized. This has
1. Cathodic protection 0-8 pts resulted in a lack of impartial and practical information con-
2. Coating condition 0-10 pts cerning the performance and accuracy of these systems. It is,
3. Soil corrosivity 0-4 pts indeed, very difficult to believe everything that is said in a
4. Age of system 0-3 pts
5. Other metals 0-4 pts paper, or even more so when the information is some form of
6. a-c induced currents 0-4 pts publicity. To remedy this situation, the European Federation
7. SCC and HIC 0-5 pts of Corrosion (EFC) and Materials Technology Institute (MTI)
8. Test leads 0-6 pts have performed two surveys, between 1988 and 1990, request-
9. Close internal surveys 0-8 pts ing recognized developers of ES in corrosion-related areas to
10. Inspection tool 0-8 pts
provide very specific information concerning the availability,
total 0-60 pts
scope, and performance of their systems [23]. A review of the
Total 0-100 pts information presented in these reports was summarized [24]

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100 C O R R O S I O N T E S T S A N D S T A N D A R D S M A N U A L

X1

X2

Wl
W2

x3

Output path
weights. . ~ . ~ ~

- w, Processing
x, J element

FIG. 10~Schematic of a single processor or neuron in an artificial neural network.

and other developments in expert systems for corrosion pre- techniques where the functions have to be specified before
vention and control reported subsequently [25]. performing the analysis.
9 Corrosion Prediction f r o m Polarization Scans: ANN
was put to the task of recognizing certain relationships in
Neural Networks
potentiodynamic polarization scans in order to predict the
An artificial neural network (ANN) is a network of m a n y occurrence of general or localized corrosion, such as pit-
very simple processors or neurons (Fig. 10), each possibility ting and crevice [27]. The initial data inputs were derived
having a small a m o u n t of local memory. The interaction of by carefully examining a n u m b e r of polarization scans for
the neurons in the network is roughly based on the princi- a n u m b e r of systems and recording those features that
ples of neural science. Unidirectional channels that carry were used for the predictions. Table 5 lists the initial in-
n u m e r i c data based on the weights of connections connect puts used and how the features were digitized for com-
these neurons that operate only on their local data and on puter input. The variables shown were chosen because they
the inputs they receive via the connections. Most neural were thought to be the most significant in relation to the
networks have some sort of training-rule. The training algo- predictions (Table 5). The final ANN proved to be able to
rithm adjusts the weights on the basis of presented patterns. make appropriate predictions using scans outside the ini-
In other words, neural networks "learn" from examples. tial training set. The resulting ANN was imbedded in an ES
ANNs excel particularly at problems where pattern recogni- to facilitate the input of data and the interpretation of the
tion is important and precise computational answers are numerical output of the ANN.
not required. When ANNs inputs and/or outputs contain 9 Modeling CO z Corrosion: A CO 2 corrosion "worst case"
evolved parameters, their computational precision and ex- model based on an ANN approach was developed and the
trapolation ability significantly increases and can even out- model validated against a large experimental database [28].
perform m o r e traditional modeling techniques. Only a few An experimental database was used to train and test the
applications of ANN to solving corrosion problems have ANN. It consisted initially of six elemental descriptors
been reported so far. Some of these systems are briefly de- (temperature, partial CO z pressure, ferrous and bicarbon-
scribed here: ate ion concentrations, pH, and flow velocity) and one out-
put, i.e., the corrosion rate. The system demonstrated
9 Predicting the SCC R i s k o f Stainless Steels: The risk of superior interpolation performance c o m p a r e d to two other
encountering a stress corrosion cracking (SCC) situation well known semi-empirical models. The ANN model also
was functionalized in terms of the main environment vari- demonstrated extrapolation capabilities comparable to a
ables [26]. Case histories reflecting the influence of tem- purely mechanistic electrochemical CO 2 corrosion model.
perature, chloride concentration, and oxygen concentration 9 Predicting the Degradation o f N o n m e t a l l i c Lining
have been analyzed by means of a back-propagation net- Materials: An ANN was trained to recognize the pattern be-
work. Three neural networks were developed. One was cre- tween results from a sequential immersion test for nonme-
ated to reveal the temperature and chloride concentration tallic materials and behavior of the same material in field
dependency (Fig. 11) and another to expose the combined applications [29]. Eighty-nine cases were used for the su-
effect of oxygen and chloride content in the environment. pervised training of the network. Another 17 cases were
The third ANN was trained to explore the combined effect held back for testing of the trained network. An effort was
of all three parameters. ANNs were found to outperform, made to ensure that both sets had experimental data taken
during this project, traditional mathematical regression from the same test but using different samples. Appropriate

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CHAPTER 6 - - C O M P U T E R B A S E D DATA 101

Log(Cr) [~ * SCC

Temperature No SCC

/, .

Hidden layer 1

FIG. 11--Neural network architecture for the prediction of SCC risk of austenitic stainless
steels in industrial processes,

choice of features enabled the ANN to mimic the expert reminded of previous problems they have faced. For m a n y
with reasonable accuracy. The successful development of years, both law and business schools have used cases as the
this ANN was another indication that ANNs could seriously foundation for knowledge in their respective disciplines.
aid in projecting laboratory results into field predictions. Within AI, when one talks of learning, it usually means the
9 Validation and Extrapolation of Electrochemical Im- learning of generalizations, either through inductive or
pedance D a t a : The ANN developed in this project had through explanation-based methods. Case-Based Reasoning
three independent input vectors, frequency, pH, and the (CBR) is unique in making the learning little more than a
applied potential [30]. The ANN was designed to learn byproduct of reasoning [31]. CBR has met with tangible
from the invisible or hidden information at high and low success in such diverse h u m a n decision-making applications
frequencies and to predict in a lower frequency range than as banking, auto-clave loading, tactical decision-making, and
that used for training. Eight sets of impedance data ac- foreign trade negotiations. The CBR approach is particularly
quired on nickel electrodes in phosphate solutions were valuable in cases containing ill-structured problems, uncer-
used for this project. Five sets were used for training the tainty, ambiguity, and missing data. Dynamic environments
ANN and three for its testing. ANN proved to be a powerful can also be tackled, or when there are shifting, ill-defined,
technique for generating diagnostics in these conditions. and competing objectives. Cases where there are action feed-

Case-Based
Reasoning back loops, multiple h u m a n involvement, and multiple and
potentially changing organizational goals and norms can also
be tackled.
Much of h u m a n reasoning is case-based rather than rule- A critical issue for the successful development of such
based. When people solve problems, they frequently are systems is the creation of a solid indexing system, since the
success of a diagnosis depends heavily on the selection of
TABLE 5--Data inputs and outputs for predicting corrosion out of the best stored case. Any misdirection can lead a query down
polarization scans with an Artificial Neural network.
a path of secondary symptoms and factors. Therefore, it is
Input parameter Value of feature very important to establish an indexing system that will
Repassivation potential Eprot- Eco~ effectively indicate or counter-indicate the applicability of a
Pitting potential Epit - Eco~r stored case. Three issues are particularly important in de-
Hysteresis +1 = Positive
0 = None ciding on the indices [32]:
-1 = Negative
Current density at scan reversal pA cm-~ 9 Indices must be truly relevant;
Anodic nose + 1 = Yes 9 Indices must be generalized, otherwise only an exact
0 = No match will be the criterion for case applicability;
Passive current density pA cm-2 9 But indices shall not be over-generalized.
Potential at anodic-cathodic transition EAto c - Ecorr
Output parameter Value of feature Failure analysts and corrosion engineers also reason by
Crevice corrosion predicted + 1 = Yes analogy when faced with new situations or problems. Two
0 = No CBR systems have been developed recently in support of
Pitting pedicted + 1 = Yes corrosion engineering decisions. Both systems derived their
0 = No
Should general corrosion be considered +1 = Yes reasoning from a combination of two industrial alloy per-
0 = No formance databases. The general architecture of these two

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102 C O R R O S I O N TESTS AND S T A N D A R D S MANUAL

User External Interface


(input)

. : . [
\
/ 9
Feature
. /
/'~ indexing /
Case / ..............
istories ~/~
/ r" Case
' \\\, l / / -*Y retrieval
/.

~
Temporary m e m o r y ........
/~- . . . . . . . . . . . . . . . . . ..~ Case
"
i
...................................................................................... \ .........................
adaptation / '

I Solutions ............... ~........


/ -\

+ (output) .....~ - . / Solution ',


"~.. evaluation ,/

FIG. 12--Case-based reasoning architecture for the prediction of materials behavior.

FIG. 13--Compilation of the results to the questions, "What is the most dependable information
source you depend upon to carry your w o r k ? " and "What is the least dependable information
source you depend upon to carry your w o r k ? "

CBR systems is presented in Fig. 12. The first, "M-BASE," INTERNET AND THE WEB
facilitates the process of retrieving materials according to a
given set of desired properties and/or specifications. The The Internet has revolutionized both the computer and
second, "C-BASE," helps the materials engineer in the diffi- communication worlds like nothing before. The invention
cult task of selecting materials for corrosion resistance in of the telegraph, telephone, radio, and computer set the
complex chemical environments. stage for this unprecedented integration of capabilities. The

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CHAPTER 6--COMPUTER BASED DATA 103

Internet is at once a world-wide broadcasting capability, a line the exchange of information between organizations.
m e c h a n i s m for information dissemination, and a m e d i u m However, it is evident that the progress made in recent
for collaboration and interaction between individuals and years with c o m m u n i c a t i o n tools and protocols has been
their computers without regard for geographic location. much greater than the progress in the quality of data that
Besides being extremely efficient tools for transferring are generated and cumulated. Improvement in this area has
documents and data of all types, the Internet and the Web are to precede the development of generalized models of corro-
also gigantic repositories of information. However, there are sion failures and the subsequent reuse of the information by
some doubts concerning the quality of that information. The applying methodologies related to artificial intelligence.
confidence professionals have in the information currently
available on the Web was verified during a survey carried out
directly from a Web site. That survey was conducted by invit-
ing the active participants of two well-known Internet corro-
REFERENCES
sion discussion groups [33,34], totaling approximately 1200
[1] Stonier, T., Beyond Information, London, UK: Springer-Verlag,
active members, to reach a specific page of the Corrosion
1992.
Doctors site and answer a set of both short and specific ques- [2] Anderson, D. B., "Computerization of Data," Corrosion Tests
tions. In the survey designed to reveal the importance of dif- and Standards: Application and Interpretation, R. Baboian, Ed.,
ferent information sources used by corrosion engineers, the ASTM International, West Conshohocken, PA, 1995, pp. 68-72.
participants were asked to select among a series of optional [3] Tomiura, A., "Lessons for a Case Study of Property Databases
answers the one that best fitted a specific question: in Materials Development," Computerization~Networking of
Materials Databases, ASTM STP 1311, S. Nishijirna, S. Iwata,
9 Books C. H. Newton, Eds., West Conshohocken, PA, ASTM Interna-
9 Journals tional, 1996, pp. 3-20.
9 Conferences and their associated activities and publica- [4] Anderson, D. B., "Evaluation of Corrosion Data--A Review,"
tions Computer Modeling in Corrosion, R. S. Munn, Ed., ASTM In-
ternational, West Conshohocken, PA, 1992, pp. 162-173.
9 Software systems (databases, CDs, etc.)
[5] Understanding "Situation-Dependent Strength": a Fundamental
9 Own network of friends and contacts Objective in Assessing the History of Stress Corrosion Cracking,
9 Internet discussion groups such as UMIST, NACE, and NACE International, Houston, TX, 1989.
others [6] Fontana, M. G., Corrosion Engineering, 3rd ed., McGraw Hill,
9 Internet sources others than above, e.g., Web sites New York, NY, 1986.
9 Other [7] Dillon, C. P., Forms of Corrosion: Recognition and Prevention,
NACE International, Houston, TX, 1982.
The questions themselves were semirepetitive, asking of [8] Szldarska-Smialowska, Z., Pitting Corrosion, NACE Interna-
the 52 participants that registered to this particular survey tional, Houston, TX, 1986.
to identify which of the proposed information sources was [9] Box, G. E., Hunter, W. G., and Hunter, J. S., Statistics for
either the most dependable, the least dependable, or a gra- Experiments, New York, NY, John Wiley and Sons, 1978.
[10] Mason, R. L., Gunst, R. F., and Hess, J. L., Statistical Design
dation of these questions. Fig. 13 shows the breakdown of
and Analysis of Experiments, John Wiley and Sons, New York,
answers to the question, "What is the most dependable in- NY, 1989.
formation source you depend u p o n to carry your work?" [11] Box, G. E. P. and Draper, N. R., Empirical Model-Building and
and to the question, "What is the least dependable informa- Response Surfaces, John Wiley and Sons, New York, NY, 1987.
tion source you depend u p o n to carry your work?" The in- [12] Evans, U. R., Mears, R. B., and Queneau, P. E., "Corrosion
formation explaining the survey and the survey results have Probability and Corrosion Velocity," Engineering, 1933, Vol.
been edited and processed into a page of the site for further 136, p. 689.
consultation. The histograms presented in Fig. 13 indicate [13] Gurnbel, E. J., Statistical Theory of Extreme Values and Some
rather clearly that the confidence level people have on the Practical Applications, Vol. 33, 1954, Washington, D.C., Na-
information displayed on the Web in general or shared in tional Bureau of Standards, Mathematics Series.
[14] Shibata, T., "Statistical and Stochastic Approaches to Local-
discussion lists is presently rather low. This situation will
ized Corrosion," Corrosion, Vol. 52, No. 11, 1996, pp. 813-830.
probably change as the technology matures into a credible [15] Meany, J. J. and Auk, J. P., "Extreme Value Analysis of Pitting
repository of useful information. Corrosion," Life Prediction of Corrodible Structures, R. N. Parkins,
Ed., Vol. 1, NACE International, Houston, TX, 1994,pp. 306-319.
[16] Sheikh, A. K., Boah, J. K., and Hansen, D. A., "Statistical
SUMMARY Modeling of Pitting Corrosion and Pipeline Reliability,"
Corrosion, Vol. 46, No. 3, 1990, pp. 190-197.
The difficulties associated with recording corrosion in- [17] Shoesmith, D. W., Ikeda, B. M., and LeNeveu, D. M., "Model-
formation are many, ranging from the basic lack of details ing the Failure of Nuclear Waste Containers," Corrosion,
in failure analyses to the i n h e r e n t complexity of the vari- Vol. 53, No. 10, 1997, pp. 820-829.
[18] Roberge, P. R., "Eliciting Corrosion Knowledge through the
ables involved. The complexities associated with corrosion
Fault-Tree Eyeglass," Modelling Aqueous Corrosion: From In-
damage information are c o m p o u n d e d by a general lack of dividual Pits to Corrosion Management. K. R. Trethewey and
standard schemes to represent materials in their opera- P. R. Roberge, Eds., Kluwer Academic Publishers, Dorchrecht,
tional environments. Data gathered in controlled laboratory The Netherlands, 1994, pp. 399-416.
environments can usually be obtained with more precision [19] BBAD Maintenance Program: Policy and Procedures Handbook,
and for such data standards have been developed to stream- Montreal, Canada, Bombardier, 1994.

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104 CORROSION TESTS AND STANDARDS MANUAL

[20] Muhlbauer, W. K., Pipeline Risk Management Manual, 2nd ed., [27] Rosen, E. M. and Silverman, D. C., "Corrosion Prediction from
Gulf Publishing Company, Houston, TX, 1996. Polarization Scans Using Artificial Neural Network Integrated with
[21] Durkin, J., Expert Systems: Design and Development, MacMil- an Expert System," Corrosion, Vol. 48, No. 9, 1992, pp. 734-745.
lan Publishing Company, New York, NY, 1994. [28] Nesic, S. and Vrhovac, M., "A Neural Network Model for CO2
[22] Basden, A., "On the Applications of Expert Systems," Interna- Corrosion of Carbon Steel," Journal of Corrosion Science and
tional Journal of Man Machine Studies, Vol. 19, 1983, Engineering, Vol. 1, No. 6, 1998, pp. 1-11.
pp. 461-472. [29] Silverman, D. C., "Artificial Neural Network Predictions of
[23] MTI, Report of Task Group 1 of the Working Party on Expert Degradation of Nonmetallic Lining Materials from Laboratory
Systems in Materials Engineering, Materials Technology Insti- Tests," Corrosion, Vol. 50, No. 6, 1994, pp. 411418.
tute, Vol. 1-124, 1990, St. Louis, MO. [30] Urquidi-Macdonald, M. and Egan, P. C., "Validation and
[24] Roberge, P. R., "Bridging the Gap Between the World of Extrapolation of Electrochemical Impedance Spectroscopy
Knowledge and the World that Knows," Materials Perform- Data," Corrosion Reviews, Vol. 15, Nos. 1-2, 1997, pp. 169-194.
ance, Vol. 33, No. 3, 1994, pp. 52-56. [31] Kolodner, J., Case-Based Reasoning, Morgan Kaufmann
[25] Roberge, P. R., "Expert Systems for Corrosion Prevention and Publishers, San Mateo, CA, 1993.
Control," Corrosion Reviews, 1997, Vol. 15, No. 1-2, pp. 1-14. [32] Explanation-Based Indexing of Cases, MIT Press, Cambridge,
[26] Smets, H. M. G. and Bogaerts, W. F. L., "SCC Analysis of Aus- MA, 1988.
tenitic Stainless Steels in Chloride-Bearing Water by Neutral [34] CORROS-L: The corrosion discussion list, http://www.cp.
Network Techniques," Corrosion, Vol. 48, No. 8, 1992, pp. umist.ac.uk/
618-623. [35] NACE International List Servers, http://www.nace.org/

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