Laser Surface Modification of HVOF Coatings For Improvement of Corrosion and Wear Performance

Laser Surface Modification of HVOF Coatings for
Improvement of Corrosion and Wear Performance
A thesis submitted to The University of Manchester for the degree of

Doctor of Philosophy
in the Faculty of Engineering and Physical Science
2013
Mohsen Mohamed Rakhes
School of Materials
TABLE OF CONTENTS
LIST OF FIGURES ............................................................................................ 6
LIST OF TABLES ............................................................................................ 18
ABSTRACT....................................................................................................... 19
DECLARATION ............................................................................................... 21
COPYRIGHT STATEMENT ........................................................................... 22
ACKNOWLEDGEMENTS .............................................................................. 24
NOMENCLATURE .......................................................................................... 25
LIST OF PUBLICATIONS RELATED TO THIS THESIS ........................... 27
CHAPTER 1 INTRODUCTION ................................................................... 29
1.1 RESEARCH MOTIVATION AND RATIONALE...... ..............................................29

1.2 AIMS AND OBJECTIVES OF THE RESEARCH...... ..............................................31
1.3 THESIS OUTLINE.......... ..................................................................................32
CHAPTER 2 LITERATURE REVIEW ....................................................... 34
2.1 INTRODUCTION........... ....................................................................,.............34

2.2 CORROSION OF METALS.......... ......................................................................34
2.2.1 Fundamentals of Electrochemical Corrosion........ ..................................35
2.2.2 The electrode potential.............................................................................38
2.2.3 Corrosion thermodynamics ......................................................................39
2.2.4 Kinetics of corrosion under polarisation... ..............................................40
2.2.5 Types of corrosion ..................................................................................43
2.2.6 Polarisation curve ..................................................................................46
2.2.7 Electrochemical impedance spectroscopy (EIS).... ..................................47
2.3 WEAR............................................................................................................57
2.3.1 Classifications and Types of Wear ..........................................................57
2.3.2 Wear tests... ..............................................................................................59
2.3.3 Pin-on-Disc wear test......... ......................................................................61
2.4 THERMAL SPRAY COATINGS ......................................................................61
2
TABLE OF CONTENTS
2.4.1 Principles of Thermal Spray Coatings....... ..............................................62

2.4.2 Types of Thermal Spray Coatings ..........................................................63
2.4.3 High Velocity Oxy-Fuel Thermal Spraying ..............................................65
2.4.4 Coating materials ..................................................................................66
2.4.5 Microstructure of HVOF-Sprayed coatings........... ..................................67
2.4.6 Corrosion Performance of HVOF-Sprayed WC-Co-base coatings.........69
2.4.7 Wear Performance of HVOF-Sprayed WC-Co-base coatings....... ..........77
2.5 LASER SURFACE ENGINEERING.......... ..........................................................80
2.5.1 Lasers......... ..............................................................................................80
2.5.2 Laser beam Interaction with Materials...... ..............................................91
2.5.3 Laser Surface Treatment.... ......................................................................92
2.5.4 Laser induced rapid solidification ..........................................................95
2.5.5 Effect of laser Surface treatment on microstructure and electrochemical
properties of HVOF Coatings ......................................................................97
2.5.6 Effect of laser Surface treatment on hardness and wear resistance of
HVOF Coatings ............................................................................................101
CHAPTER 3 EXPERIMENTAL PROCEDURES ..................................... 104
3.1 INTRODUCTION........... ................................................................................104

3.2 MATERIALS..... ............................................................................................104
3.2.1 Specimen preparation for laser treatment ............................................105
3.3 LASER PROCESSING..... ................................................................................105
3.3.1 Laser System.......... ................................................................................105
3.3.2 Laser processing setup....... ....................................................................106
3.4 MATERIAL CHARACTERISATION........ ........................................................107
3.4.1 Sample preparation ................................................................................107
3.4.2 Scanning Electron Microscope (SEM/EDS).......... ................................108
3.4.3 X-ray diffraction (XRD)..... ....................................................................110
3.4.4 Surface profile........ ................................................................................111
3.4.5 Porosity measurements...... ....................................................................112
3.4.6 Electron probe micro-analyser (EPMA).... ............................................113
3.5 CORROSION TESTS....... ................................................................................113
3.5.1 Immersion test........ ................................................................................113
3.5.2 Sample preparation for polarisation and EIS tests ................................114
3
TABLE OF CONTENTS
3.5.3 Polarisation ............................................................................................115

3.5.4 Electrochemical Impedance Spectroscopy (EIS) Test........ ....................117
3.6 WEAR TEST ............................................................................................118
3.6.1 Pin-On-Disc tester ................................................................................118
3.6.2 Wear test conditions........... ....................................................................119
3.7 MICROHARDNESS MEASUREMENT...... ........................................................120
CHAPTER 4 OPTIMISATION OF LASER OPERATING CONDITIONS

....................................................................................................................122
4.1 INTRODUCTION........... ................................................................................122

4.2 DEFINITION OF THE TERMS..... ....................................................................122
4.3 FORMATION OF POROSITY WITHIN LASER MELTED SURFACE ....................128
4.4 FORMATION OF CRACKS WITHIN LASER MELTED SURFACE..... ....................131
4.5 OPERATING WINDOWS FOR LASER TREATMENT.......... ................................135
4.6 Summary ...................................................................................................143
CHAPTER 5 MATERIALS CHARACTERISATION............................... 144
5.1 INTRODUCTION........... ................................................................................144

5.2 POWDERS........ ............................................................................................144
5.2.1 Morphological observation ....................................................................144
5.2.2 XRD analysis.......... ................................................................................147
5.3 AS-SPRAYED COATING ................................................................................150
5.3.1 Surface views of HVOF coatings... ........................................................150
5.3.2 Cross sectional view of HVOF coatings.... ............................................158
5.3.3 XRD analysis of HVOF coatings.... ........................................................168
5.3.4 Porosity measurements of HVOF coatings ............................................170
5.4 LASER SURFACE TREATED HVOF COATINGS ............................................172
5.4.1 Surface views of laser melted HVOF coatings....... ................................173
5.4.2 Cross section of laser treated HVOF coatings.......................................180
5.4.3 XRD of laser treated HVOF coatings........ ............................................194
5.4.4 Porosity measurements of laser treated HVOF coatings ....................197
5.5 Summary ...................................................................................................199
CHAPTER 6 CORROSION TESTS ........................................................... 202
6.1 INTRODUCTION........... ................................................................................202

4
TABLE OF CONTENTS
6.2 IMMERSION TEST........ ................................................................................202

6.2.1 Tribaloy 800 (T800) coating.......... ........................................................203
6.2.2 T800+21WC........... ................................................................................206
6.2.3 T800+43WC......... ................................................................................210
6.2.4 T800+68WC.......... ................................................................................212
6.2.5 Inductivity coupled plasma- optical emission spectrometer (ICP-OES)
test........... ........................................................................................................215
6.3 POLARISATION TEST.... ................................................................................217
6.4 ELECTROCHEMICAL IMPEDANCE SPECTROSCOPY TEST (EIS)....................227
6.5 Summary ...................................................................................................243
CHAPTER 7 RESULTS ON HARDNESS AND WEAR RESISTANCE

MEASUREMENTS......................................................................................... 245
7.1 INTRODUCTION........... ................................................................................245

7.2 MICROHARDNESS....... ................................................................................245
7.3 WEAR TEST RESULTS... ................................................................................249
7.3.1 T800........... ............................................................................................250
7.3.2 T800+21WC.......... ................................................................................252
7.3.3 T800+43WC.......... ................................................................................254
7.3.4 T800+68WC..........................................................................................255
7.4 Summary ................................................................................................... 256
CHAPTER 8 CONCLUSIONS AND SUGGESTIONS FOR FUTURE

WORK.............. ....................................................................................................258
8.1 INTRODUCTION...........................................................................................258
8.2 Conclusions................................................................................................258
8.3 Suggestions for future work.......................................................................263
APPENDIX A .................................................................................................. 264
APPENDIX B .................................................................................................. 271
REFERENCES ................................................................................................ 279
Word count: 54,075
5
LIST OF FIGURES
Figure ‎2.1 Current flow in corrosion cell [17] ........................................................ 35
Figure 2.2 Metal in an aqueous solution containing metal ions; an electrical
double layer has formed [19]. ................................................................ 38
Figure 2.3 Determination of electrode potential with the aid of a reference
electrode [19]. ....................................................................................... 39
Figure 2.4 Anodic and cathodic polarisation curves [19]. ...................................... 41
Figure 2.5 Crevice corrosion [27] .......................................................................... 45
Figure 2.6 Pitting corrosion [28]............................................................................ 45
Figure 2.7 (a) Transgranular cracks in an austenitic steel produced in a
chloride environment (100x); (b) Intergranular cracks in a ferritic
stainless steel produced in a high temperature caustic environment
(50x) [30].............................................................................................. 46
Figure 2.8 Schematic diagram of the polarisation behaviour [16]........................... 47
Figure 2.9 AC wave forms for an applied potential and a resulting current ............ 49
Figure 2.10 Complex plane showing impedance vector Z [36]............................... 51
Figure 2.11 Nyquist plot with impedance vector .................................................... 51
Figure 2.12 Bode and phase angle plots [32]. ..................................................... 52
Figure 2.13 Randle equivalent circuit (a) and Nyquist plot (b) ............................... 54
Figure 2.14 The Equivalent circuit for a coated substrate [37]. .............................. 54
Figure 2.15 Abrasion wear [51]. ............................................................................ 58
Figure 2.16 Adhesion wear [51]. ........................................................................... 59
Figure 2.17 Fatigue wear [53]. .............................................................................. 59
Figure 2.18 Diagram of Pin-on-Disk configuration wear test [48]. ......................... 61
Figure 2.19 Basic principle of thermal spraying [55]. ............................................ 63
Figure 2.20 Classification of thermal spray processes [56] .................................... 63
Figure 2.21 Schematic diagram of the HVOF process [57]. ................................... 65
Figure 2.22 Cross-section of T800 HVOF coating on stainless steel substrate ....... 65
Figure 2.23 Schematic diagram of adhesion of a particle to a substrate
asperity. (1) asperities, (2) particle in flight, (3) particle
mechanically locked to the substrate, (4) substrate [55]. ........................ 66
Figure 2.24 Thermal spray coating microstructure showing common features
[56] ....................................................................................................... 68
6
LIST OF FIGURES
Figure 2.25 Cross-section of T800-68WC HVOF coating on stainless steel

substrate................................................................................................ 68
Figure 2.26 Potentiodynamic polarisation curves of different coatings in the
aerated 5 wt. H2SO4 solution [5]. ......................................................... 70
Figure 2.27 Schematic representation of the reaction processes taking place
on the WC-Co surface as a consequence of the galvanic coupling
between Co and WC [77]. ..................................................................... 72
Figure 2.28 Electrochemical polarisation curves of HVOF-sprayed coatings
in 0.1 M HCl solution [70]. ................................................................... 73
Figure 2.29 Potentiodynamic polarisation of Co and WC in aerated 1 N
H2SO4 [85]. ........................................................................................... 74
Figure 2.30 Potential-pH equilibrium diagram for the system cobalt-water, at
25oC, potential with respect to standard hydrogen electrode [85]. .......... 75
Figure 2.31 Potential-pH equilibrium diagram for the system tungsten-water,
at 25oC, potential with respect to standard hydrogen electrode [85]. ...... 75
Figure 2.32 Electrochemical behaviour of Co-W alloys in aerated 1 N H2SO4
[93]. ...................................................................................................... 77
Figure 2.33 Total (pin and disc) specific wear rates for different HVOF
coating composition under dry oscillating wear [105]............................ 80
Figure 2.34 Two-level energy system (a), Spontaneous emission (b),
absorption (c), Stimulated emission (d). ................................................ 82
Figure 2.35 Laser components ............................................................................... 84
Figure 2.36 Amplification process ......................................................................... 85
Figure 2.37 Semiconductor laser-junction region [111]. ........................................ 88
Figure 2.38 Semiconductor laser [111] .................................................................. 89
Figure 2.39 absorption as a function of wavelength for carbon steel and
aluminium [114]. .................................................................................. 90
Figure 2.40 Time resolved intensity distribution within a 1.6 s interval (a)
HPDL system (b) Nd-YAG laser [116]. ................................................ 91
Figure 2.41 Laser surface processing [119]............................................................ 93
Figure 2.42 laser surface treatment techniques; (a) laser transformation
hardening, (b) laser surface melting, (c) laser alloying, (d) laser
cladding ................................................................................................ 94
Figure 2.43 Effect of temperature gradient G and growth rate R on the
morphology and size of solidification microstructure [122] ................... 95
Figure 2.44 SEM morphologies of the laser clad Tribaloy T-800 on stainless
steel (AISI 304), shows: (1) substrate; (2) planar crystallization
region; (3) cellular growth zone; (4) fine dendritic microstructure;
(5) overlap zone between tracks. power density 200 W/mm2 ,
scanning speed 240 mm/min and powder feed rate 10-15 g/min
[123]. .................................................................................................... 96
7
LIST OF FIGURES
Figure 2.45 SEM morphologies of the laser clad Tribaloy T-800 on stainless
steel (AISI 304) power density 200 W/mm2 scanning speed 240
mm/min and powder feed rate 10-15 g/min: (a) Cellular structure;
(b) dendritic microstructure [123].......................................................... 97
Figure 2.46 SEM morphologies of laser clad of the Stellite 6. The dark
dendritic phase is the cobalt-based matrix and the white phase is
formed by the M7C3 eutectic carbides: (a) slow processing
conditions (Vb=1.67 mm s-1); (b) fast processing conditions
(Vb=167 mm s-1) [126]. ......................................................................... 97
Figure 2.47 Potentiodynamic polarisation curves of HVOF WC24Cr 3C2-6Ni
coatings in 3.5% NaCl solution [129]. ................................................... 98
Figure 2.48 Polarisation curves of laser melting and HVOF sprayed Inconel
625 coatings [10]. ................................................................................. 99
Figure 2.49 optical micrograph of (a) HVOF sprayed and (b) laser remelted
high chromium nickel-chromium coating after one week
immersion test in 3.5 wt.% NaCl [11]. ................................................ 100
Figure 2.50 Microhardness of cross-sections of HVOF WC-CoCr coatings
before and after laser treatment [128] .................................................. 101
Figure 2.51 Friction coefficient and wear rate of the coatings [129] ..................... 102
Figure 3.1 Schematic diagram of cutting process ................................................. 105
Figure 3.2 Laser processing setup ........................................................................ 106
Figure 3.3 Laser treatment experiment ................................................................ 107
Figure 3.4 Cross-sectioned of SEM samples mounted using conducting resins .... 108
Figure 3.5 Schematic of scanning electron microscope [133]............................... 109
Figure 3.6 Schematic of electron beam interaction with material [135] ................ 110
Figure 3.7 Waves reflected from successive planes of a crystal . ......................... 111
Figure 3.8 MicroXAM surface mapping microscope [137] .................................. 112
Figure 3.9 Schematic diagram showing sample prepared for the immersion
test ...................................................................................................... 114
Figure 3.10 Sample prepared for polarisation or EIS test ..................................... 115
Figure 3.11 (a) ACM Gill AC instrument, (b) complete setup for the
experiment, (c) A schematic of experimental setup used in
polarisation test ................................................................................... 116
Figure 3.12 Setup of open circuit potential .......................................................... 117
Figure 3.13 Setup of polarisation experiment ...................................................... 117
Figure 3.14: Setup of AC impedance experiment ................................................. 118
Figure 3.15 Diagram of a pin on disc configuration wear test .............................. 118
Figure 3.16 Parameters of wear track (a) track diameter and track width, (b)
track depth .......................................................................................... 120
Figure 4.1 Schematic shown partially laser melting of HVOF coating ................. 123
8
LIST OF FIGURES
Figure 4.2 Overlapping tracks of laser treated T800+21WC HVOF coating

showing surface of partially melting of HVOF coating ........................ 123
Figure 4.3 SEM cross-section image of HVOF T800 (a) partially laser
melting T800 HVOF coating (b) high magnification of melted
T800 HVOF layer ............................................................................... 124
Figure 4.4 SEM cross-section image of HVOF T800+21WC (a) partial laser
melting of T800+21WC HVOF coating (b) high magnification of
melted T800+21WC HVOF layer ....................................................... 124
Figure 4.5 Schematic shown fully laser melting of HVOF coating (a) melting
of HVOF coating only (no dilution) (b) melting of substrate
(dilution) ............................................................................................. 125
Figure 4.6 Overlapping tracks of the laser-treated the T800+43WC HVOF
coating, showing surface of large melting of HVOF+43WC
coating ................................................................................................ 125
Figure 4.7 SEM cross-section image of HVOF coating T800+43WC fully
laser melted (a) without dilution (b) with dilution ................................ 126
Figure 4.8 SEM cross-section image of HVOF coating T800+68WC fully
laser melted (a) without dilution (b) with dilution ................................ 126
Figure 4.9 Schematic illustration of partially and full melting of WC .................. 126
Figure 4.10 SEM cross-section image of HVOF T800+21WC (a) HVOF
coating (b) high magnification of the coating ...................................... 127
Figure 4.11 SEM cross-section image of HVOF T800+21WC (a) partially
laser melted WC near the surface (b) partially melted WC particles
and fully melted T800 ......................................................................... 127
laser melted WC (b) partially melted WC particles and fully
melted T800 ........................................................................................ 128
laser melted WC (b) partially melted WC particles and fully
melted T800 ........................................................................................ 128
Figure 4.14 porosity in laser treated area (a) porosity near the surface and a
vertical crack in T800+43WC HVOF laser-treated (800 W, 40
mm/sec) (b) porosity in T800+68WC HVOF laser treated (800 W,
20 mm/sec) ......................................................................................... 130
Figure 4.15 low porosity in the laser treated area (a) T800+43WC HVOF,
laser-treated (800 W, 5 mm/s) (b) T800+68WC HVOF, laser
treated (800 W, 3 mm/s) ...................................................................... 130
Figure 4.16 porosity in the laser treated area (a) T800 HVOF, laser treated
area (600 W, 20 mm/s) (b) T800+21WC HVOF, laser treated (800
W, 40 mm/s) ....................................................................................... 131
Figure 4.17 low porosity in the laser treated area (a) T800+43WC HVOF,
laser treated (550 W, 3 mm/s) (b) T800+68WC HVOF, laser
treated (500 W, 3 mm/s) ...................................................................... 131
9
LIST OF FIGURES
Figure 4.18 SEM microstructure of the Laves phase in theT800 HVOF

coating after laser treatment ................................................................ 132
Figure 4.19 vertical crack in T800 HVOF laser treated (a) small crack at
(600W, 5 mm/s) (b) big crack with high dilution at (800W, 10
mm/s) ................................................................................................. 132
Figure 4.20 a small vertical crack in T800 HVOF laser treated with a
partially- melted coating (500W, 3 mm/s) ........................................... 133
Figure 4.21 a vertical crack in a T800+21WC HVOF laser-treated surface (a)
a small crack at (800W, 5 mm/s) (b) a large crack and porosity at
laser parameters (600W, 40 mm/s) ...................................................... 133
Figure 4.22 a vertical crack and porosity in a T800+43WC HVOF laser-
treated surface, with a partially-melted coating (800W, 80 mm/s) ....... 133
Figure 4.23 a vertical crack and porosity in a T800+68WC HVOF laser-
treated surface with a partially-melted coating (800W, 20 mm/s) ........ 134
Figure 4.24 The variation of the ratio of melting depth/coating thickness with
scanning speed for different laser powers for a T800 HVOF
coating ................................................................................................ 135
scanning speed for different laser powers for a T800+21WC
HVOF coating..................................................................................... 136
HVOF coating..................................................................................... 136
HVOF coating..................................................................................... 137
Figure 5.1 SEM morphology of T800 powder ..................................................... 145
Figure 5.2 SEM micrographs of the T800 + 21WC powder ................................. 145
Figure 5.3 SEM micrographs of (a) T800 + 43WC (b) T800 + 68WC
powders .............................................................................................. 146
Figure 5.4 Mapping images: (a) T800 powder (b) T800+21WC powder (c)
T800+43WC powder (d) T800+68WC powder ................................... 147
Figure 5.5 XRD pattern of the T800 stock powder .............................................. 148
Figure 5.6 XRD pattern of the T800+21WC stock powder .................................. 148
Figure 5.9 SEM micrographs of surface view of T800 HVOF coatings with
(a) low magnification (b) high magnification ...................................... 150
Figure 5.10 SEM micrographs of surface view of T800+21WC HVOF
coatings with (a) low magnification and (b) high magnification .......... 151
10
LIST OF FIGURES

Figure 5.13 MicroXam (a) 2D and (b) 3D profiles of four different areas on
T800 HVOF surface ............................................................................ 155
T800+21WC HVOF surface ............................................................... 154
T800+43WC HVOF surface ............................................................... 156
T800+68WC HVOF surface ............................................................... 156
Figure 5.17 Comparison of surface roughness of various HVOF coatings............ 157
Figure 5.18 Comparison of surface area ratios of various HVOF coatings ........... 157
Figure 5.19 SEM micrograph of cross section of T800 HVOF coating ................ 158
Figure 5.20 SEM micrographs of T800 HVOF coating at the interface
between the coating and substrate (a) and typical microstructure
(b) ....................................................................................................... 158
Figure 5.21 SEM image of cross-section of T800 HVOF ..................................... 159
Figure 5.22 SEM micrograph of T800 HVOF microstructure .............................. 160
Figure 5.23 EDX results of various phases in T800 HVOF coating (1) Laves
phase (2) Eutectic Laves phase + Co solid solution (3) Co solid
solution ............................................................................................... 161
Figure 5.24 SEM micrograph of cross section of T800+21WC HVOF
coating. ............................................................................................... 161
Figure 5.25 SEM micrographs of T800+21WC HVOF coating at the interface
between coating and substrate (a) and with high magnification (b) ...... 162
Figure 5.26 SEM micrograph of cross section of T800+21WC HVOF coating
with high magnification ...................................................................... 162
with high magnification ...................................................................... 162
Figure 5.28 SEM micrograph of cross section of T800+43WC HVOF coating .... 163
Figure 5.29 SEM micrographs of T800+43WC HVOF coatings at interface
between coating and substrate (a) and with high magnification (b) ...... 163
Figure 5.30 SEM micrograph of cross section for T800+68WC HVOF
coating ................................................................................................ 163
Figure 5.31 SEM micrographs of T800+68WC HVOF coating at interface
between coating and substrate (a) and with high magnification (b). ..... 164
Figure 5.32 EDX results of various phases in T800+WC HVOF coating (1)
White phase, (2) dark matrix and (3) grey phase............................... .... 165
11
LIST OF FIGURES
Figure 5.33 (a) SEM micrographs of T800+68WC HVOF coating and (b)
EDX line scan analysis of the line marked in (a). ................................ 165
Figure 5.34 EDX analyses at splat boundary (1) and near splat boundary
(2) for T800 HVOF coating................................................................166
Figure 5.35 Line scan for oxygen trough splat boundary for T800 HVOF
coating ................................................................................................ 166
Figure 5.36 EPMA mapping of T800 HVOF coating ........................................... 167
Figure 5.37 EPMA mapping of T800+43WC HVOF coating............................... 167
Figure 5.38 XRD pattern of T800 HVOF coating ................................................ 168
Figure 5.39 XRD pattern of T800+21WC HVOF coating .................................... 169
Figure 5.40 XRD pattern of T800+43WC HVOF coating .................................... 169
Figure 5.41 XRD pattern of T800+68W HVOF coating ...................................... 170
Figure 5.42 Porosity of T800 HVOF coating ....................................................... 171
Figure 5.43 Porosity of T800+21WC HVOF coating ........................................... 171
Figure 5.44 Porosity of T800+43WC HVOF coating ........................................... 171
Figure 5.45 Porosity of T800+68WC HVOF coating. .......................................... 172
Figure 5.46 SEM micrographs of laser treated surface view of T800 HVOF
coating at low magnification (a) and high magnification (b) ................ 173
Figure 5.47 SEM micrographs of laser treated surface of T800+21WC HVOF
coating at low magnification (a) and high magnification (b) ................ 173
coatings at low magnification (a) and high magnification (b) .............. 174
Figure 5.49 SEM images of surface of laser treated T800+68WC HVOF
coating at low magnification (a) and high magnification (b). ............... 174
laser treated T800 HVOF coating ........................................................ 175
laser treated T800+21WC HVOF coating ............................................ 176
Figure 5.54 Surface roughness of various laser treated HVOF coatings ............... 179
Figure 5.55 Average of surface area ratio of laser treated HVOF coatings ........... 179
Figure 5.56 SEM micrograph of cross section of laser treated T800 HVOF
coating. ............................................................................................... 180
Figure 5.57 SEM micrograph of laser melted T800 HVOF coating. ..................... 181
12
LIST OF FIGURES
Figure 5.58 EDX analysis of various phases in laser melted T800 HVOF
coating (1) Laves phase (2) Eutectic (Laves phase + Co solid
solution) (3) Co solid solution ............................................................. 182
Figure 5.59 SEM micrograph of cross section of laser treated T800+21WC of
HVOF coating..................................................................................... 182
Figure 5.60 SEM micrographs of laser treated T800+21WC HVOF coating
showing (a) interface between the coating and substrate (b)
microstructure in laser melted area ...................................................... 183
Figure 5.61 SEM micrograph of cross section for laser treated T800+21WC
HVOF coating..................................................................................... 183
Figure 5.62 EDX results of various phases in T800+21WC HVOF coating
after laser treatment (1) Co-Cr binder phase (2) Co solid solution
phase (3) partially melted WC ............................................................. 184
Figure 5.63 SEM micrograph of cross section of laser treated T800+43WC
HVOF coating showing partially melted WC ...................................... 185
Figure 5.64 SEM micrograph of laser treated T800+43WC HVOF coating
showing (a) interface between the substrate and the coating (b)
microstructure in laser melted area ...................................................... 185
HVOF coating showing partially melted WC. ..................................... 185
Figure 5.66 EDX results of phases (marked as 1, 2, 3 in Figure 5.65) in
T800+43WC HVOF coating (1) T800 matrix (2) Co-Cr binder
phase (3) partially melted WC. ............................................................ 186
Figure 5.67 (a) SEM micrograph of laser treated T800+68WC (b) EDX line
scan analysis on T800 and WC particles .............................................. 186
Figure 5.68 EPMA mapping of laser treated T800 HVOF coating ....................... 187
Figure 5.69 EPMA mapping of laser treated T800+43WC HVOF coating
with partially melting of WC particles ................................................. 187
Figure 5.70 EDX results of different areas of T800+43WC HVOF coating
after laser treatment............................................................................. 188
Figure 5.71 EDX line scan of laser treated T800+43WC HVOF coating.............. 189
HVOF coating..................................................................................... 190
Figure 5.73 SEM micrographs of laser treated T800+68WC HVOF coating
showing (a) interface between the coating and substrate and (b)
microstructure of melted area. ............................................................. 190
Figure 5.74 SEM micrograph of cross section of laser treated T800+68WC ........ 190
Figure 5.75 EDX results in different areas of laser treated T800+68WC
HVOF coating..................................................................................... 192
Figure 5.76 EDX results in different areas of laser treated T800+68WC
HVOF coating..................................................................................... 193
13
LIST OF FIGURES
Figure 5.77 EDX results of line scan of laser treated T800+43WC HVOF
coating showing Fe distribution along the coating thickness ................ 193
Figure 5.78 XRD pattern of T800 HVOF coating after laser treatment ................ 195
Figure 5.79 XRD pattern of T800+21WC HVOF coating after laser treatment .... 195
Figure 5.82 Porosity of laser treated T800 HVOF coating ................................... 197
Figure 5.83 Porosity of laser treated T800+21WC HVOF coating ....................... 198
Figure 6.1 SEM cross-section images of T800 HVOF coating: a and c as
received HVOF coatings, b and d after laser treatment, all are
immersed for 24 h ............................................................................... 203
immersed for 48 h ............................................................................... 204
immersed for 72 h ............................................................................... 205
immersed for 96 h ............................................................................... 206
Figure 6.5 SEM cross-section images of T800+21WC HVOF coating: a and c
as received HVOF coatings, b and d after laser treatment, all are
immersed for 48 h ............................................................................... 207
immersed for 72 h ............................................................................... 208
immersed for 96 h ............................................................................... 209
immersed for 48 h ............................................................................... 210
immersed for 72 h ............................................................................... 211
Figure 6.10 SEM cross-section images of T800+43WC HVOF coating: a and
c as received HVOF coatings, b and d after laser treatment, all are
immersed for 96 h ............................................................................... 212
14
LIST OF FIGURES
Figure 6.11 SEM cross-section images of T800+68WC HVOF coating: a, c

as received HVOF coatings, b, d after laser treatment, all are
immersed for 48 h ............................................................................... 213
immersed for 72 h ............................................................................... 214
immersed for 96 h ............................................................................... 215
Figure 6.14 Mean concentration of the elements released in 3M H 2SO4 after 7
days of immersion of T800+43WC HVOF coating before and after
laser treatment..................................................................................... 216
Figure 6.15 Polarization curves of the HVOF coatings in 0.5 M H 2SO4
solution. .............................................................................................. 218
Figure 6.16 Polarization curves of HVOF coatings before and after laser
treatment in 0.5 M H2SO4 (a) T800 (b) T800+21WC (c)
T800+43WC (d) T800+68WC ............................................................ 219
Figure 6.17 A typical polarization curve of T800+43WC HVOF coating. ............ 222
Figure 6.18 Microcrevice corrosion of T800+21WC HVOF coating after
immersion in 3 M H2SO4 for 108 h. .................................................... 222
Figure 6.19 Galvanic corrosion of T800+43WC HVOF coating after
polarisation test. .................................................................................. 223
Figure 6.20 Cross section of T800 HVOF coating after polarization test in 0.5
M H2SO4 solution. .............................................................................. 224
Figure 6.21 Surface corrosion of laser treated T800 coating after polarization
test in 0.5 M H2SO4............................................................................. 225
Figure 6.22 Surface of laser treated T800 coating after polarization test in 0.5
M H2SO4 solution. .............................................................................. 225
Figure 6.23 Cross section of laser treated T800+21WC coating after
polarization test in 0.5 M H2SO4 solution ........................................... 225
Figure 6.24 Cross section of T800+68WC HVOF coating after polarization
test in 0.5 M H2SO4............................................................................. 226
Figure 6.25 Cross section of T800+43WC laser treated coating after
polarization test in 0.5 M H2SO4 ......................................................... 226
Figure 6.26 Nyquist plots of HVOF coatings for different times (a) T800 (b)
T800+21WC (c) T800+43WC and (d) T800+68WC ........................... 227
Figure 6.27 Nyquist plots of laser treated HVOF coatings for different times
(a) T800 (b) T800+21WC (c) T800+43WC and (d) T800+68WC....... 228
Figure 6.28 Equivalent circuit proposed for the coating system ........................... 229
Figure 6.29 Impedance spectra after 3 hours of immersion for various
coatings before and after laser treatment: (a) T800, (b)
T800+21WC, (c) T800+43WC, and (d) T800+68WC ......................... 230
15
LIST OF FIGURES
Figure 6.30 Impedance spectra after 12 hours of immersion for various

coatings before and after laser treatment: (a) T800, (b)
T800+21WC, (c) T800+43WC, and (d) T800+68WC ......................... 232
Figure 6.31 Coating resistance Rp before and after laser treatment for various
time of immersion (a) T800 (b) T800+21WC (c) T800+43WC (d)
T800+68WC ....................................................................................... 235
Figure 6.32 Charge transfer resistance R ct before and after laser treatment for
various time of immersion (a) T800 (b) T800+21WC (c)
T800+43WC (d) T800+68WC ............................................................ 236
Figure 6.33 Cross section of T800 HVOF coating after EIS test at 12h
immersion time (a) cross section of the coating (b) interface ............... 237
immersion time (a) surface of the coating (b) corrosion of Co solid
solution within splats (c) cracks within splats ...................................... 237
Figure 6.35 Cross section of laser treated T800 HVOF coating after EIS test
at 12h immersion time (a) cross section of the coating (b) zoom of
the upper side of the coating ................................................................ 238
Figure 6.36 Cross section of T800+68WC HVOF coating after EIS test at
12h immersion time (a) cross section of the coating (b) interface
(c) zoom of upper side of the coating .................................................. 239
Figure 6.37 Cross section of laser treated T800+68WC HVOF coating after
EIS test at 12h immersion time (a) cross section of the coating (b)
corrosion area ..................................................................................... 239
immersion time (a) cross section of the coating (b) corrosion at the
upper side of the coating ..................................................................... 240
at 48h h immersion time (a) cross section of the coating (b) zoom
at the upper side of the coating ............................................................ 240
48h immersion time (a) upper side of the coating (b) interface ............ 241
at 48h immersion time (a) cross section of the coating (b) upper
side of the coating ............................................................................... 241
48h immersion time (a) cross section as HVOF coating (b) cross
section after laser treated (c) upper side of HVOF coating (d)
upper side of laser treated coating ....................................................... 242
Figure 7.1 Hardness profiles of various HVOF coatings before and after laser
treatment (a) T800 (b) T800+21WC (c) T800+43WC
(d) T800+68WC...................................................................................247
16
LIST OF FIGURES
Figure 7.2 SEM micrographs of microhardness indentations on different phases of

T800+43WC HVOF coating................................................................248
Figure 7.3 SEM micrographs of microhardness indentations on different
phases of laser treated T800+43WC coating. ...................................... 249
Figure 7.4 SEM micrographs of microhardness indentations (a) on as-
received HVOF coating and (b) after laser treatment. .......................... 249
Figure 7.5 Wear rates for various coatings before and after laser treatment. ........ 250
Figure 7.6 SEM micrographs of worn surface of T800 HVOF coating. ............... 251
Figure 7.7 SEM micrographs of worn surface of laser-treated T800 HVOF
coating. ............................................................................................... 252
Figure 7.8 SEM micrographs of worn surface of T800 + 21 WC HVOF
coating. ............................................................................................... 253
Figure 7.9 SEM micrographs of worn surface of laser-treated T800 + 21 WC
HVOF coating. .................................................................................... 254
Figure 7.10 SEM micrographs of worn surface of T800+43 WC HVOF
coating. ............................................................................................... 255
Figure 7.11 SEM micrographs of worn surface of laser-treated T800+43 W
coating. ............................................................................................... 255
Figure 7.12 SEM micrographs of worn surface of T800+68 WC HVOF
coating. ............................................................................................... 256
Figure 7.13 SEM micrographs of worn surface of laser-treated T800+68 WC
coating. ............................................................................................... 256
17
LIST OF TABLES
Table ‎2.1 Equivalent circuit elements [34]............................................................ 53
Table ‎2.2 Comparision of characteristics for various thermal spraying
processes [3]. ...................................................................................... 64
Table 2.3 Main lasers and their properties [110] ................................................... 87
Table 2.4 Wavelengths of a selected range of diode laser materials [112] ............. 89
Table 3.2 Conditions of wear test ....................................................................... 119
Table 4.1 A laser operating conditions used for various HVOF coating with
observations ........................................................................................ 138
Table 4.2 Laser operating conditions and coating characteristics of the
selected coatings ................................................................................. 142
Table 5.1 Surface roughness and surface area ratios of various HVOF
coatings............................................................................................... 157
Table 5.2 EDX chemical analysis of T800 HVOF coating, wt.%. ....................... 159
Table 5.3 Coating thickness measured ................................................................ 164
Table 5.4 Measurement of porosity of various HVOF coatings. .......................... 170
Table 5.5 Optimum parameters obtained in laser processing and coatings
features ............................................................................................... 172
Table 5.6 Surface roughness parameters of laser treated surface ......................... 179
Table 5.7 Measurement of porosity of various HVOF coatings after laser
treatment ............................................................................................. 197
Table 6.1 Mean concentration of the elements (units of µg/ml) released into
the electrolyte solution after 7 days of immersion of T800+43WC
HVOF coating before and after laser treatment.................................... 216
Table 6.2 Corrosion current density (Icorr) and corrosion potential (Ecorr)
of HVOF coatings before and after laser treatment in 0.5 M
H2SO4 solution .................................................................................. 220
Table 6.3 Electrochemical parameters obtained from EIS spectra of HVOF
coatings after 3 hours of immersion..................................................... 230
Table 6.4 Electrochemical parameters obtained from EIS spectra of laser
coatings after 3 hours of immersion..................................................... 231
Table 6.5 Electrochemical parameters obtained from EIS spectra of HVOF
coatings after 12 hours of immersion ................................................... 232
Table 6.6 Electrochemical parameters obtained from EIS spectra of laser
coatings after 12 hours of immersion ................................................... 233
Table 7.1 Microhardness values of various HVOF coatings before and after
laser treatment..................................................................................... 247
18
ABSTRACT
Metal Matrix Composite (MMC) coatings, comprised of a hard ceramic phase

embedded in a metallic matrix, are increasingly being applied for many industrial
applications to provide cost effective protection against wear and corrosion. Such
coatings are commonly produced by thermal spray. Although the most advanced
thermal spray techniques, such as high-velocity oxy-fuel (HVOF), produce MMC
coatings with total porosity levels lower than 1%, due to the nature of thermal
spray MMC coatings, corrosion still takes place. The corrosion processes are
dominated by the complex microgalvanic and interfacial mechanisms, as well as by
porosity, due to the existence of various defects in HVOF MMC coatings. As a
result, HVOF coatings do not ultimately meet the requirements in certain service
conditions in operating environments. Therefore, there is a need to find a method of
modification of coatings, with significantly reduced microstructural defects and
improved cohesive and adhesive strength so that the service life of the coated
components can be increased.
This work aims to investigate the effects of laser surface treatment on the corrosion
and wear performance for Tribaloy 800 (T800), and T800-based WC HVOF-
sprayed MMC coatings onto 316L stainless steel substrate. Laser surface
treatments have been carried out using a 1.5 kW high power diode laser. Laser
operating windows for various coatings have been established for the relationships
between the laser operating conditions and melt pool dimensions, in the
consideration of formation of cracks and porosity within laser-treated surface
layers. Microstructural analysis of the powders, and various coatings before and
after laser treatments has been conducted by means of optical and SEM (with
EDX) microscopy, electron probe micro-analysis (EPMA), white-light
interferometery, and X-ray diffraction, to characterise morphology, chemical
composition and phase. Corrosion performance of various coating was evaluated
using immersion testing in 3 M H2SO4 at pH ~ 1.27 at room temperature for
different periods of time (including 24, 48, 72, 96 and 168 hours), followed by
Inductivity Coupled Plasma-optical emission spectrometer (ICP-OES) technique,
potentiodynamic polarisation in 0.5 M H2SO4, and electrochemical impedance
19
ABSTRACT
spectroscopy studies in 0.5 M H2SO4 solution after 1, 3, 6, 12, 24, and 48 hours.
Inaddition, dry sliding wear behaviour measured by pin-on-disk and microhardness
test of various coatings before and after laser treatment were evaluated.
The results indicated that it was possible to achieve full control of melt depth and
the degree of melting, particularly full or partial melting of WC particles by proper
selection of the laser processing parameters while preventing dilution. Significant
improvement of corrosion and wear resistance has been achieved after laser
treatment as a result of the elimination of discrete splat-structure, removal of
microcrevices and porosity, as well as the reduction of microgalvanic driving force
between the WC and the metal matrix by formation of new phases at the interfaces.
The degree of melting of WC particles controls the corrosion properties of the
laser-treated HVOF coatings. Moreover, the results also suggested that partial
melting of WC had positive effect on wear resistance of the coatings.
20
DECLARATION
No portion of the work referred to in this thesis has been submitted in support of an
application for another degree or qualification of this or any other university or
other institution of learning.
2013
MOHSEN RAKHES
21
COPYRIGHT STATEMENT
[i] The author of this thesis (including any appendices and/or schedules to
this thesis) owns any copyright in it (the “Copyright”) and he has given
The University of Manchester the right to use such Copyright for any
administrative, promotional, educational and/or teaching purposes.
[ii] Copies of this thesis, either in full or in extracts, may be made only in
accordance with the regulations of the John Rylands University Library
of Manchester. Details of these regulations may be obtained from the
Librarian. This page must form part of any such copies made.
[iii] The ownership of any patents, designs, trade marks and any and all
other intellectual property rights except for the Copyright (the
“Intellectual Property Rights”) and any reproductions of copyright
works, for example graphs and tables (“Reproductions”), which may be
described in this thesis, may not be owned by the author and may be
owned by third parties. Such Intellectual Property Rights and
Reproductions cannot and must not be made available for use without
the prior written permission of the owner(s) of the relevant Intellectual
Property Rights and/or Reproductions.
[iv] Further information on the conditions under which disclosure,

publication and exploitation of this thesis, the Copyright and any
Intellectual Property Rights and/or Reproductions described in it may
take place is available from the Head of School of Materials.
22
THIS WORK IS DEDICATED TO MY
PARENTS
&
WIFE
23
ACKNOWLEDGEMENTS
I am extremely thankful to Allah for help me to carrying out this research.
I would like to express my thanks for my kind supervisor Dr Zhu Liu for her great
guidance, help, and encouragement. Very special thanks to Dr Gareth Littlewood
and Dr Karen Shapiro for their help, support, and comments on the work.
I am thankful to all staff and research assistants working in both centres (CPC and
LPRC) for their support. I am thankful to the experimental officers in LPRC, Dr
Marc Schmidt and Dr David Whitehead for their help.
I want to express my gratitude to Dr. Elena Koroleva, Prof. Peter Skeldon, Ms
Judith Shackleton, Mr Teruo Hashimoto, Mr Mark Harris, Paul Jordan, Steve
Blatch, Peter Carroll, and Mr Kenneth Gyves for their help and support.
I wish to thank my colleagues: Ejaz, Zakria, Sohaib, Yasir, Ismail, Wei, Abdeslam,
Bader, Ahmed, Dr Fernando, and Dr Ana for their advice.
I am thankful to my father and my mother and all my family members for their
efforts and pray to provide me strength to compete this work. I would like to
express my indebtedness to my wife for her support during my work.
Finally, I would also like to express my gratitude to the people who have
contributed in different ways towards the completion of this thesis.
24
NOMENCLATURE
NOMENCLATURE
HVOF High Velocity Oxygen Fuel
GNP Gross National Product
EDL Electrical Double Layer
OCP Open Circuit Potential
EIS Electrochemical Impedance Spectroscopy
AC Alternating Current
DC Direct Current
CPE Constant Phase Element
pF Pico-Farad
nF Nano-Farad
MMC Metal Matrix Composite
AFM Atomic force microscope
ICP Inductively coupled plasma
HPDL High Power Diode Laser
SEM Scanning Electron Microscope
EDS Energy Dispersive Spectrometry
EBSD Electron Back-Scattered Diffraction
FEG Field Emission Gun
SE Secondary Electrons
BSE Backscattered Electrons
XRD X-ray Diffraction
EPMA Electron Probe Micro-Analyser
WDS Wavelength Dispersive Spectroscopy
SCE Saturated Calomel Electrode
OCP Open Circuit Potential
G Gibbs Free-Energy
EMF Electromotive Force
F Faraday’s Constant
E Electromotive Force of the Electrochemical Cell
Eref Electrode Potential of Reference Electrode
Etest Electrode-Potential-of-the-Test-Electrode
25
NOMENCLATURE
 Polarisation
Cdl Double-Layer Capacitance
Rct Charge-Transfer Resistance
Rs Electrolyte Resistance
Ccoat Capacitance of coating
Rpore Pore Resistance
CPE Constant Phase Element
Ra Roughness
E1 Energy level for upper state
E0 Energy level for lower state
Cp Heat Capacity
K Thermal Conductivity
h Thermal Diffusivity
G Temperature Gradient
R Growth Rate
WDS Wavelength Dispersive X-ray
Sdr Surface Area Ratio
ICP Inductivity Coupled Plasma
OES Optical Emission Spectrometer
26
LIST OF PUBLICATIONS RELATED TO THIS THESIS
Journal papers
Rakhes, M. E. Koroleva, and Z. Liu, Improvement of corrosion
performance of HVOF MMC coatings by laser surface treatment, Surface
Engineering, 2011. 27(10): p. 729-733.
Oral/ Poster papers

Rakhes, M. and Z. Liu, Laser surface modification of HVOF MMC
coatings for improvement of tribological performance, NASM 3, 11-15
April 2010, Manchester, UK, (Oral Presentation).
Rakhes, M. E. Koroleva, and Z. Liu, Improvement of corrosion

performance of HVOF MMC coatings by laser surface treatment, 36 th
International Matador conference, 14-16 July 2010, Manchester, UK, (Oral
Presentation).
Rakhes, M. and Z. Liu, Laser surface modification of HVOF coatings for

improvement of corrosion and wear performance, NACE – Corrosion 2010,
14-18 March 2010, San Antonio, Texas, USA, (Poster Presentation).
Local Seminars/ Posters

improvement of corrosion resistance, PG Conference, School of Materials,
The University of Manchester, Manchester, UK, May 2008, (Oral
Presentation).

improvement of corrosion and wear performance, PG Conference, School
of Materials, The University of Manchester, Manchester, UK, May 2009,
(Poster Presentation).
27
LIST OF PUBLICATIONS RELATED TO THIS THESIS

improvement of corrosion resistance, PG Conference, School of Materials,
The University of Manchester, Manchester, UK, May 2010 , (Oral
Presentation).
Awards
First Prize in Corrosion for best poster at Postgraduate Student Conference
2009, School of Materials, The University of Manchester.
28
Chapter 1 Introduction
This chapter presents the motivation and rationale of this research, and defines the
overall aim of the work. The structure of the thesis is also provided.
1.1 Research motivation and rationale

Thermal spray processes, especially high velocity oxygen fuel (HVOF), are widely
used coating techniques in many gas and oil industrial applications to protect
materials from various degradation processes such as wear, erosion, high
temperature and corrosive atmosphere [1-3]. Metal matrix composite (MMC)
coatings, in which a mixture of hard particles and metallic binder materials are
normally applied on metal substrates by HVOF spraying, provide advantages to the
surface mechanical properties especially wear resistance. A typical example of
such coatings is tungsten carbide (WC) particles with metallic binders of Co, Ni or
Co–Cr which has been applied extensively in heavy-loaded conditions, due to its
excellent wear resistance [4-7]. However, when applied in corrosive environments,
such coatings must exhibit an acceptable resistance against corrosion. Corrosion
resistance of thermal spray coatings depends on many factors. Among them, the
corrosion behaviour of metallic binders, especially the content of chromium [5, 8],
is a determining factor, while the microstructure of the thermal spray coatings [9]
also plays an important role. Due to the defects of thermally sprayed coatings
including pores (isolated or interconnected), micro-cracks, gaps and oxide
inclusions between splats and the bond strength at the coating/substrate interface by
mechanical interlocking mechanism, these coatings might be insufficient to protect
the surface in severe service conditions containing aggressive chemicals. In
addition, inhomogeneous structures of the HVOF coatings limit their effectiveness
to be used as physical barriers to inhibit corrosive species from getting into contact
with the substrate to be protected. As a result, improvement against corrosion by
29
CHAPTER 1 INTRODUCTION
such coatings is limited in most cases. In order to further improve the corrosion
resistance of the coating properties, laser surface modification could be considered
as a potential technique to eliminate or reduce the defects of the coatings. Laser
surface modification via re-melting, or heat treatment, offers many advantages
including precisely controlled treatment dimensions, particularly in depth, and
minimum heat-affected zones, resulting in no thermal effects on substrate
materials. Moreover, the laser processes are non-contact, suitable for components
with complicated geometry, and easy to automate. Laser surface melting of HVOF
coatings to improve corrosion resistance and/or wear resistance has been
investigated by a number of researchers. Tuominen et al. [10, 11] reported the
improvement of corrosion properties of Inconel 625 and nickel-chromium HVOF
coatings on mild steel substrate using Nd:YAG laser surface melting. Liu et al.
[12], at the University of Manchester, studied the effect of High Power Diode Laser
(HPDL) surface melting on the corrosion and wear performance for Inconel 625
and Inconel 625 based WC HVOF coatings, showing that the laser treatments
improved both corrosion resistance and wear resistance. Some other researchers
intended to improve hardness and wear resistance of HVOF coatings using lasers.
Chen et al. [13] attempted to improve wear resistance of WC-12Co HVOF coatings
using CO2 laser surface melting, showing that the wear resistance was reduced as a
result of decreasing WC particle size by laser treatment. From the previous work, it
is clear that laser surface melting of HVOF coatings reduced/eliminated various
defects of the coatings and subsequently improved the properties of the coatings,
particularly in corrosion resistance. However, one of the main purposes of applying
such coatings is for protection against wear. If laser surface treatment is only
capable of improving corrosion properties, but deteriorating the wear performance,
it would be less beneficial to apply such laser techniques. Therefore it is essential
to ensure that laser surface treatment is able to improve corrosion resistance at least
without sacrificing wear performance. It would be an extra bonus if laser surface
treatment could improve both corrosion and wear resistance. From the literature, it
was also realised that different degrees of laser surface melting, especially for
metal matrix composite coatings, in terms of fully/partially melting of the ceramic
particles and formation of new phases, had significant impacts on the resultant
properties. Therefore, it was believed that proper controlling of laser operating
30
conditions to achieve different degrees of melting of HVOF coatings, would be a

major issue to achieve optimised improvement of properties.
In this project, a HPDL has been applied for surface modification of Tribaloy
(T800) and T800-based WC metal matrix composite HVOF coatings, to gain
detailed knowledge of how laser surface modification affects corrosion and wear
performance of those coatings.
1.2 Aims and objectives of the research

This work aims to improve corrosion resistance of the following HVOF coatings on
316L stainless steel substrate by laser surface melting using HPDL, with possibility
of improving wear performance:
Tribaloy 800 (T800)
T800 + 21WC (wt.%)
T800 + 43WC (wt.%)
T800 + 68WC (wt.%)
The investigations include microstructural analysis, corrosion behaviour, wear

resistance and hardness testing of various coatings before and after laser surface
treatments. The specific objectives of this project are:
1) To establish laser operating windows for various HVOF coatings to achieve
i) defect-free layers, i.e. elimination of porosity, microcracks and splats

microstructure.
ii) control of the melt pool dimensions, in particularly melt depth;
iii) control of the degree of full/partial melting of the WC particles.
2) To investigate the microstructural changes of various HVOF coatings before and

after laser treatments, in terms of surface morphology, phase transformation and
homogenisation of WC particles;
31
3) To study the corrosion behaviour of various HVOF coatings before and after
laser surface treatments in different laser operating conditions, and to understand
the corrosion mechanisms of various coatings;
5) To investigate the wear performance and hardness of various HVOF coatings

before and after laser surface treatments in different laser operating conditions, and
to understand the wear mechanisms of various coatings;
6) To establish the best laser operating conditions for various coatings with respect
to wear performance and corrosion properties.
1.3 Thesis outline

This thesis comprises eight chapters and two appendices, of which this first chapter
is an introduction.
Chapter 2 covers the fundamental aspects of corrosion and various corrosion

techniques such as polarisation and electrochemical impedance spectroscopy (EIS).
Also, the principles of laser theory, laser beam interaction with materials and
various laser treatment techniques are introduced. In addition, wear performance
and hardness are discussed. It also presents a review of the HVOF thermal spray
technique. This chapter also reviews the state-of-art literature on the subjects
related to corrosion and wear performance of WC-Co HVOF sprayed coatings,
along with laser surface treatment of HVOF coatings for improvement of corrosion
and wear properties.
Chapter 3 gives details of the experimental equipment and procedures used in this
thesis. It includes the materials used for HVOF coatings, laser processing setup,
and preparation of the samples for laser treatment and for different characterisation
techniques adopted in this work before and after laser treatment.
Chapter 4 presents the optimisation of laser operating conditions by studying the

influence of laser operating conditions on melting of various HVOF coatings, and
establishment of laser operation windows to produce the melted layers of the
HVOF coatings being crack-free and porosity-free.
32
Chapter 5 presents the results and discussion on materials characterisation of

powders, then HVOF coatings before and after laser treatment, in terms of surface
morphology, phase transformation, elemental and WC particle distribution within
the laser-treated layers.
Chapter 6 presents the results obtained from the different corrosion techniques used
to evaluate corrosion performance of the different HVOF coatings before and after
laser treatment, and discussion on corrosion mechanisms involved.
Chapter 7 presents results obtained from the wear and hardness tests of HVOF
coatings before and after laser treatment, and discussion on possible wear
mechanisms involved.
Chapter 8 is the last chapter of this thesis, which presents general conclusions
reached from this work. It also makes recommendations for future work.
Appendix A presents Nyquist plots with tables of electrochemical parameters

obtained from EIS test for various HVOF coatings before and after laser treatment
at 1, 6, 24, 48 hours of immersion in 0.5M H2SO4 electrolyte.
Appendix B presents Bode plots obtained from EIS test for various HVOF coatings
before and after laser treatment at 1, 3, 6, 12, 24, 48 hours of immersion time.
33
Chapter 2 Literature Review
2.1 Introduction
This literature review explores various subjects related to this work. The main
contributions of the literature include discussion of the fundamental mechanism of
corrosion and various corrosion techniques such as polarisation and
electrochemical impedance spectroscopy (EIS). Definition of wear, types of wear,
wear mechanisms and wear tests are introduced. It also presents a review of
thermal spray coating techniques and focuses on HVOF. Laser theory, types of
lasers and laser beam interaction with materials have been discussed. Previous
work on corrosion and wear performance of WC-Co HVOF sprayed coatings has
been reviewed. Also previous work of laser surface treatment of HVOF coatings
for improvement of corrosion and wear properties has been presented.
2.2 Corrosion of Metals

Corrosion is defined as “The destructive result of chemical reaction between a
metal or a metal alloy and its environment” [14]. Most metals after being reduced
from their ores are thermodynamically unstable, and tend to change their state to
more stable state. Furthermore, almost all metals are found as a combination with
other elements such as sulphur or oxygen. In order to change it to pure metal, it is
essential to provide a large amount of energy to the system. This energy will be
stored in the pure metal. However, from the laws of thermodynamics, a higher
energy state of material tends to transform into a lower energy state. This energy
which is stored in the metallic system must be restored by turning back to its
oxidized state by recombination with the environment. In general, the more energy
absorbed by the metal, the more readily the metal corrodes [15].
34
CHAPTER 2 LITERATURE REVIEW
2.2.1 Fundamentals of Electrochemical Corrosion

Corrosion process of a metal is electrochemical reactions. A corrosion cell (figure
2.1) is essential for corrosion to take place, containing anode, cathode, electrolyte
and metallic path. Almost all corrosion processes concern transfer of charges in
aqueous solutions (electrolyte). The mechanism of corrosion is based on anodic and
cathodic reactions in an electrolyte. The anodic reaction (oxidation) releases
electrons, while the cathodic reaction (reduction) consumes electrons. Moreover,
there are three general cathodic reactions, namely: oxygen reduction, hydrogen
evolution from water, and hydrogen evolution from acid [16].
Current Flow by Ionic

Conduction Electrolyte
Cathode
Anode
Current Flow by Electron

Conduction
Figure 2.1 Current flow in corrosion cell [17]
Anode:
Anode is an electrode in an electrolyte cell, at which oxidation occurs producing
electrons. Moreover, it is the zone where the metal dissolves into the solution. This
reaction is called an anodic reaction. Metal ion formation in the solution may occur
by one of a number of ways:
Production of metal cations
The sample M represents a metal atom having n valence electrons, and converted
into an ion Mn+.
Oxide-formation
35
Hydroxide formation
Formation of an insoluble salt
Cathode
The second element in the electrolyte cell is the cathode. Cathode reactions involve
electron consuming and are essential in controlling the rate of corrosion which
takes place at the anodes. The cathode reactions are important to neutralize the
electrons which are produced by anodic reactions [18]. The reaction in the anode
cannot be at a high rate unless the electrons produced can be consumed at the
cathode. The consumption or neutralization of the electrons could occur by
different reactions, as follows:
In alkaline and neutral aerated solutions,
In acid solutions with high concentration of hydrogen ions:
In acid solutions with dissolved oxygen:
Total reduction of metal ions to metallic state:
36
Electrolyte
The electrolyte is the third important element in the corrosion cell. The electrolyte
is the solution which covers the metal and acts as a medium to form the electric
circuit. Moreover, the corrosion rate depends on the conductivity of the electrolyte;
high conductivity produces rapid corrosion. The electrolyte contains ions so as to
be conducting, for example, in the case of seawater, the corrosion is rapid, where
the seawater has a high conductivity [18].
External Circuit
The anode and cathode are present on the metal surface. Furthermore, the metal
itself here acts as the external circuit. In other words, the anode and cathode should
be connected by an external circuit to complete the corrosion process, also
conductivity for external circuit plays important role in the rate of corrosion.
Corrosion in acid environment

In acidic environments, even without oxygen, the metal can be attacked
aggressively at the anode, while hydrogen ions in the electrolyte become hydrogen
gas at the cathode. Furthermore, corrosion by acids can produce salt which slows
down the reaction, because it is formed on the surface being attacked. One of the
examples of these reactions is when iron is placed in dilute sulphuric acid. The iron
can be attacked and hydrogen gas is produced as shown in equation 2.11. This
reaction can be considered as the sum of two different reactions occurring at
different sites on the metal surfaces:
Anodic reaction
Cathodic reaction
37
2.2.2 The electrode potential

When metal M is in an electrolyte which contains ions of the metal M n+, the
equilibrium stage will reached after electrode reactions take place at the surface of
metal [19]:
These reactions will create an electrical double layer (EDL) as shown in figure 2.2.
This will result in a potential called Galvani potential E 1 which is different from
solution potential E2. EDL is associated with a polarized electrode, and the charge
cannot transfer without imposing an external potential voltage source.
M
+ _ _ +
+ _ _ +
+ E_ + E2
n+ __ 1_
M + +
+
+ + +
Figure 2.2 Metal in an aqueous solution containing metal ions; an electrical double
layer has formed [19].
The difference ∆E=E1–E2 in Galvani potential cannot be measured directly.

However, this value can be measured by using a relative value, where a reference
electrode such as saturated calomel electrode (SCE) is connected via an electrolyte
to the test electrode, for which the electrode potential is to be determined (figure
2.3). The circuit contains a half cell, but with a potentiometer, the electromotive
force (∆E) of the electrochemical cell is produced and measured. These
measurements are taken, where the flow of current should be as low as possible:
Where, ∆E is electromotive force of the electrochemical cell measured by a

potentiometer. Furthermore, when this potential difference in the absence of an
external potential source, it is called open circuit potential (OCP). Eref is the
38
electrode potential of the reference electrode (constant) and E test is the absolute
value of the electrode potential of the test electrode [19].
Potentiometer
__ ________ _____- _
-- -- _ _ _ ______-
_ _ _ _ _-
Reference -- --
_ _ _ - ___ __
electrode
-- -- _ _- ___ Test
_ - __ __ _ _ _
-- -- _ -_ _ _ _ electrode
-- -- _ -_ ______ _ _ _
-- -- _ _ -__ _ _ _______ __ _ Electrolyte
-- -- ___
-- -- __ _ _ __ _ _ __ _____
___ __
Figure 2.3 Determination of electrode __
_ potential with the aid of a reference electrode
-- -- __
_ [19].
-- --
_
2.2.3 Corrosion thermodynamics
_
From the thermodynamic point of_view, the tendency of a metal to corrode can be
predicted. However, thermodynamics
_ provides no information about the details of
the reaction, such as indication of corrosion rate. The rate of corrosion can be
indicated by kinetic theory. This tendency of the reaction can be measured by the
Gibbs free-energy change, ∆G. For a spontaneous reaction to take place, ∆G must
be negative, and the more negative the magnitude of ∆G, the higher the tendency
will be for reaction to occur [20].
The tendency for corrosion can be presented in terms of the electromotive force
(EMF) of the corrosion cells by the following relation:
F = Faraday’s constant 96.500 coulombs mole-1,
Faraday’s constant represents the charge transported by one mole of electrons. ∆E

is the electromotive force (EMF). The number n is the number of electrons
transferred in the corrosion reaction [15].
39
2.2.4 Kinetics of corrosion under polarisation

As discussed in Section 2.2.3, the thermodynamics does not predict the corrosion
rate. In order to understand how fast a corrosion reaction is, it is important to have
a clear understanding of the corrosion kinetics that occur on an electrode surface in
contact with an electrolyte.
When a metal is exposed to an aqueous solution, two complementary reaction

processes will take place on the surface simultaneously, i.e. an oxidation of the
metal atoms to metal ions by losing electrons, and a reduction of metal ions by
accepting electrons. These reactions at equilibrium can be explained as follows,
The free energy of activation (∆E) for the anodic and cathodic reactions in this case
has the same level [16]. This equilibrium is dynamic, where the two reactions occur
at equal rates in opposite directions. Any changes in the conditions such as
temperature, pressure, and concentrations of the participants may move the reaction
from its equilibrium state. The reaction rate in both directions (anodic and
cathodic) can be expressed by current or current densities, for cathodic reaction
and for anodic reaction , both can exist because of an exchange of electrons
between the metal and the electrolyte.
At equilibrium , , where called exchange current density,

and it depends strongly on many parameters such as electrode material, electrolyte,
temperature and ion concentrations in the electrolyte [21]. Furthermore, if there is
current applying to the surface that will make , so that the applied
cathodic current density is:
The applied anodic current density is:
When the current is applied to the surface, the potential electrode will change to ,
the change in electrode potential is called Polarisation .
40
As figure 2.4 shows, the polarisation of a cathode is negative, on the other hand the
polarisation of an anode is positive [19].
Figure 2.4 Anodic and cathodic polarisation curves [19].
The polarisation can be classified into three groups:
Concentration polarisation
This type of polarisation is caused as result of the difference in concentration in an
electrolyte near the electrode surface. This means either that there is deficiency of
reactants near the electrode surface, or that an increase of reaction products takes
place. For example [21], if the concentration of hydrogen ions in a solution is
relativity low, the neutralization of hydrogen ions by the electrons will depend on
the rate of hydrogen ions diffusing through the solution, and the number of
hydrogen ions available. In this case, the corrosion will be controlled by the
diffusion of hydrogen ions in the solution. However, in high concentrations of
hydrogen ions, as in acid solutions, the electrochemical reactions go rapidly.
Resistance (Ohmic) polarisation

Metal surfaces might have high ohmic resistance. This is, for example, due to oxide
films on aluminium, stainless steels etc. The resistance will decrease when the
41
current flows through the film. If the resistance of the film is R (Ω), the resistance
polarisation can be presented by η = RI. Moreover, anodic resistance polarisation
has an influence on surfaces which are passivated by oxides or other materials [21].
Activation polarisation
This polarisation takes place by the resistance opposed to the reaction itself at the
metal surface. For example, the rate of gradual development of hydrogen at the
cathode is dependent on the rate of the electron transfer from the anode. Therefore,
the rate of evolution hydrogen will change at the cathode as the anode varies in its
ability to give up electrons. In general, the controlling factor in corrosion with high
concentration of hydrogen ions as in strong acids is activation polarisation.
However, at low concentration of hydrogen ions as in aerated water or salt solution,
the controlling factor in corrosion is concentration polarisation [18].
The relationship between activation polarisation η, that can be definite as

overpotential (because it is described potential changes from equilibrium corrosion
potential Ecorr), and the rate of reaction, can be represented by current density ia or
ic.
For anodic polarisation:
For cathodic polarisation:
Where and are the anodic and cathodic Tafel constants. is positive so
must be positive too, and is negative because is negative [14]. Equation
(2.20) and (2.21) might be re-written in exponential form as follows,
42
By substitution into equation (2.17), we obtain:
By rearrangement of equation (2.24) and differentiation , an

expression of the polarisation resistance is
Thus, the slope at the origin of the polarisation curve is inversely
proportional to the corrosion rate [14], where:
B is the proportionality constant.
2.2.5 Types of corrosion

There are several types of corrosion, although all corrosion involves
electrochemical reactions. Each type of corrosion has a specific features occurring
in specific locations. Corrosion can be generally divided into two types, uniform
corrosion and non-uniform (localised) corrosion.
2.2.5.1 Uniform corrosion

“Uniform or general, corrosion is a type of corrosion attack uniformly distributed
over a metal surface” [22]. In uniform corrosion, multiple anodes and cathodes are
working on the metal surface at any time, and their areas continually move on the
surface, causing uniform corrosion [23]. Uniform corrosion normally occurs when
there is no high macroscopic concentration differences across the metal surface, the
metal is nearly homogeneous, and the material has not significant passivation
tendency in the particular environment [24]. Uniform corrosion can be prevented
by using coatings or inhibitors, or proper material selection. It is usually treated by
establishing a corrosion allowance into the structure of the substrate. However, this
43
type of corrosion is not very dangerous from a technical standpoint because the life
time of equipment can be estimated by simple immersion tests which allow
calculation of the weight (mass) loss, and the dissolving of the thickness as a
function of time [23].
2.2.5.2 Localised corrosion

“Localised corrosion is a corrosion phenomenon concentrated at some specific sites
of a metal surface, which are very small relative to the surface of the metal that
does not corrode” [22]. In general, localised corrosion can be more severe than
uniform corrosion because it can take place after a short time period of use or
exposure without warning [25]. Some types of localised corrosion are described
below.
Galvanic corrosion
Galvanic (dissimilar metals) corrosion occurs when two metals with different
electrode potential are coupled together in a corrosive electrode environment. In
general any metal or alloy has a unique corrosion potential E corr. When dissimilar
metals are connected together in an electrolyte, a flow of electrons is produced
between the two metals as a result of the potential difference. One of the dissimilar
materials becomes the anode and corrodes faster than it would by itself; the other
material becomes the cathode and corrodes slower than it would alone [26].
Galvanic corrosion can take place at either macroscopic or microscopic levels.
Furthermore, different phases and microstructure at the microscopic level can be
subjected to galvanic corrosion. The corrosion in anodic materials will be more
rapid and more damaging when the potential difference between the two materials
in the galvanic series increases and when the cathode area increases relative to the
anodic area [19]. To control galvanic corrosion, metals closer to each other in the
galvanic series should be used, or by isolating metals from each other.
Crevice corrosion
Crevice corrosion is a form of localised corrosion which takes place at narrow
openings gaps between adjoining surfaces (figure 2.5). This type of corrosion
44
results from a concentration cell created between the solution within the crevice,
that is oxygen starved, and the solution outside the crevice, where the oxygen
concentration is high. Moreover, the material inside the crevice (less oxygen) acts
as an anode, and the exterior material (high oxygen) becomes a cathode [23].
Figure 2.5 Crevice corrosion [27]
Pitting corrosion
Pitting corrosion is a form of localised dissolution of a metal resulting from the
breakdown of the protective film on the metal surface (figure 2.6). Furthermore,
small areas corrode leading to the creation of cavities or pits, and the bulk of the
surface remains unattacked. The driving force for pitting corrosion is the reduction
of oxygen around the small area (at the bottom of the pit). This area becomes an
anode while the area (at the top of the pit) with excess of oxygen will become a
cathode leading to localised galvanic corrosion. As a result of the pitting corrosion
mechanism, the pH value at the bottom of the pit becomes extremely low, with
increasing chloride concentration with time, the pit depth increases. [16].
Figure 2.6 Pitting corrosion [28]
For this type of corrosion, it is difficult to predict the location and the degree of
pitting corrosion attack. Also, pits are generally small and difficult to detect by
45
simple visual examination [23]. Furthermore, the shape of the pits depends on
metallurgy of the surface alloy and chemistry of the environment, pits might be
deep, subsurface, undercut, shallow, or elliptical [29].
Stress corrosion crack

This type of corrosion results in cracking which is induced from the combined
influence of tensile stress and a corrosive environment, especially in chloride-rich
environment like sea water and at high temperature. There are two kinds of crack
propagation: cracks that propagate across grains which are called Transgranular
and those which follow grain boundaries are called Intergranular (figure 2.7).
Figure 2.7 (a) Transgranular cracks in an austenitic steel produced in a chloride

environment (100x); (b) Intergranular cracks in a ferritic stainless steel produced in a
high temperature caustic environment (50x) [30]
2.2.6 Polarisation curve

Polarisation curves represent the relationship between the logarithm of current
density and potential, which illustrates active and passive behaviour of a metal
(figure 2.8). The polarisation curve has three main regions which are: active,
passive, and transpassive. From figure 2.8, OD represents anodic behaviour, and
AO represents the cathodic behaviour. The two dashed lines AB and CD represent
Tafel lines. Furthermore, the anodic and cathodic polarisation curves intersect in
the active region at point O, which is called corrosion potential Ecorr, the net current
at this point is zero. The corrosion rate increases at potentials higher than the
potential at O, and reaches a maximum at the primary passive potential Epp.
Moreover, at potentials higher than Epp the passive film stays stable, and the growth
46
of the protective film causes the sudden fall in corrosion current density from icrit to
ipass. The region from E to F called the passive region, this region shows the full
passivity on the metal surface as a result of film formation [16]. At point F, the
passive film breaks down, so pits grow and propagate. The potential at F is called
the pitting potential Ep. The region from F to G denotes transpassive corrosion.
Potential
Passive film breaks down
(V) G
Ipass
Ep F
(+)
Passive
E Active-passive transition
Epp D
B Anodic reaction
Ecorr O Icrit
C A Cathodic reaction Active
(-) G
Icorr Log Current Density (mA/cm2)
Figure 2.8 Schematic diagram of the polarisation behaviour [16].
2.2.7 Electrochemical impedance spectroscopy (EIS)

The Electrochemical Impedance Spectroscopy (EIS) technique based on alternating
current (AC), and can be used to understand corrosion mechanisms, and to evaluate
the efficiency of corrosion control methods, for instance, coatings and inhibiters.
Furthermore, EIS is used extensively as a tool for investigating complex and
difficult systems [31]. The advantages of EIS over DC methods are: (1) it can
measure solution resistance easily, so it can provide more precise information about
polarisation resistance for high solution resistance. (2) having the complete
information over the whole frequency range, can provide useful information about
the corrosion behaviour. (3) during EIS studies, a very small amplitude AC signal
is applied which causes very little perturbation to the system. (4) the measurements
47
of EIS can provide useful information on electrode capacitance and charge transfer
resistance. In addition, EIS can measure changes in the porosity, and
simultaneously monitor the corrosion rate of the coatings [32, 33].
2.2.7.1 Principles of EIS

The principle of the impedance method is to apply a small amplitude AC sinusoidal
excitation signal to the system, and then measure the response. Generally, a small
voltage signal is applied and the resulting current is measured.
For direct current (DC), Ohm’s law represents the relationship between voltage and
current.
Where R is resistance in ohms, V is voltage in volts, and I is current in amperes.

Unfortunately, this relationship is limited to the ideal resistor. The ideal resistor has
many simplifications such as: its resistance follows Ohm’s law, the resistance value
is independence of frequency, and the AC and voltage signals through a resistor are
in phase with each other. In the real world, many systems show behaviour that is
more complex. In this case, impedance is used in place of resistance, which is a
measure of the ability of the circuit to resist (or impede) the alternating current. The
relationship which is equivalent to Ohm’s law is:
Where, Z is the impedance of the circuit in ohm’s (Ω). The impedance Z is almost
always depends on frequency (f). For an AC signal, the frequency is measured in
cycles per second (Hz) [31].
Equation (2.28), represents the impedance of the system at a certain frequency

which can be defined by another two terms, related to the current and voltage.
These terms are the amplitude (A) of the signal (AC), and the phase difference (ϕ)
between the current and the voltage (see figure 2.9). The following figure illustrates
a standard sine wave voltage (V) applied to an electrochemical cell and the current
48
response (I) is also sine wave. However, the two sine waves are not in phase.
Moreover, the two sine waves will only have same phase and different amplitude in
a purely resistive network [34].
V
Io
ϕ Time
Figure 2.9 AC wave forms for an applied potential and a resulting current
The current sine wave can be represented by the equation:
Where is instantaneous current, is the maximum amplitude, is the angular

frequency in radians per second , and ( where, is
frequency in Hertz. t is time in seconds and is the phase shift in radians.
The voltage sine wave can also be expressed as a function of time, and has the
form:
is the voltage at time t, is the amplitude.
The impedance of the system can be calculated by the following expression

which analogous to Ohm’s law:
Where the ratio of the size of the voltage sine wave to that of the current sine wave
( is the magnitude or the size of the impedance in Ohms of this system. The
49
magnitude value is usually written as: . As can seen from equation (2.31), the
impedance can be expressed in terms of a magnitude, , and a phase shift .
From Euler relationship
Where is a complex number ( [35].
It is possible to represent the impedance as a complex function. The current can be

described as,
and the voltage can be expressed as in the following equation,
The total impedance of the system can represented as a complex number,
The impedance of the system can be written in vector form as a complex number:
and (2.37)
Where, and are the real and imaginary parts for the impedance respectively.
Equation (2.36) may be plotted in polar coordinates as shown in the following

graph (figure 2.10):
50
θ
o
Figure 2.10 Complex plane showing impedance vector Z [36].
Data Presentation
There are two common methods to present the data, which are, Nyquist and Bode
plots. In a Nyquist plot which is used in this research, it is common to plot on
the Y axis against on X axis of the chart (figure 2.11). In this plot the Y-axis is
negative and each point on the plot represent the impedance at one frequency. As
shown in figure 2.11, the low frequency data are on the right side of the plot and
higher frequencies are on the left. Furthermore, the impedance can be represented
as a vector with magnitude . The impedance usually reduces with increasing
frequency. However, this behaviour is not true for all circuits. The phase angle:
and the magnitude of Z:
Figure 2.11 Nyquist plot with impedance vector
The Nyquist plot has one limitation, which is that the frequency does not appear in
the plot. The other popular presentation method is the Bode plot. The Bode plot for
51
a system consists of two graphs: one showing the magnitude of the impedance as a
function of frequency; the other showing the phase angle as a function of
frequency. The scales used for the axes can vary but the most popular format is to
plot and phase angle against log frequency, as shown in figure 2.12.
Figure 2.12 Bode and phase angle plots [32].
Equivalent circuit elements

Very often it is difficult to know everything about the process and the mechanism
in the electrochemical study, because of the complexity of the process where
several processes could contribute to the system’s EIS spectra. These factors
include: Electrode double layer capacitance, electrode kinetics, diffusion layer and
solution resistance. However, by using EIS and fitting the practical data to
equivalent circuit models, it is possible to understand and get a clear picture of the
corrosion behaviour and other useful information, such as solution resistance and
porosity in the coating. The equivalent circuit should be as simple as possible, and
it should provide the best possible match between the measured (Real) impedance
and the model’s impedance. Usually, the system depends on more than one cell
element. The common method used to investigate the EIS spectra is predicting the
process and the mechanism, and describing it by electrical components (resistors,
capacitors and inductors). Building these components into logical series and
parallel combinations is very important to simulate the real electrochemical
process.
52
The impedance of the system will depend on the value of the impedance of the
individual elements. The following table shows the equivalent circuit elements with
their impedance equation:
Table 2.1 Equivalent circuit elements [34].
Circuit Element Impedance Equation
Resistor
Capacitor
Inductor
Electrochemical systems such as coated surfaces or corroding metals can usually be

described as simple electronic circuits.
The Randles cell

The Randles cell is the most common and simplest model of an electrochemical
interface which can be used in bare metals [16]. Figure 2.13 shows the equivalent
circuit and Nyquist plot for a Randle cell. In this circuit Rs denotes the electrolyte
resistance. Cdl is the double-layer capacitance which is modelled in this circuit as a
pure capacitance. Rct is the charge-transfer resistance.
53
Figure 2.13 Randle equivalent circuit (a) and Nyquist plot (b)
As seen from figure 2.13 the Nyquist plot of a Randle cell is a semicircle. At high
frequencies the impedance of the double-layer capacitance (Cdl) will become very
low, so the evaluated impedance will be close to Rs. Moreover, at very low
frequencies the impedance of C dl becomes very high, so the measured impedance in
this situation will be close to Rct + Rs. The charge-transfer resistance is equal to the
diameter of the semicircle. The Randle equivalent circuit is useful as a starting
model to build up more complicated models for more complicated systems [33].
EIS of a coated substrate

To understand the use of equivalent circuits in real electrochemical system, EIS of
a coating system cell will be discussed. This equivalent circuit contains a
combination of two capacitors and three resistors as shown in figure 2.14.
Figure 2.14 The Equivalent circuit for a coated substrate [37].
EIS can quantitatively determine resistances and capacitances in the

electrochemical system and through these values, many properties of the coating
54
can be evaluated. By this technique, changes in a coating behaviour during

exposure to an electrolyte can be detected [38]. The equivalent circuit shown in
figure 2.14 is the one most commonly used for coating on metal substrates [37, 39,
40]. As the coating degrades with time during the exposure to an electrolyte, EIS
can track changes which could occur in the capacitance of the coating (C coat), and
also evaluates changes in the porosity of the coating through the pore resistance
(Rpore). Furthermore, EIS simultaneously monitors the rate of the corrosion by
tracking the charge transfer resistance (Rct) value [37, 41].
Electrolyte resistance (Rs)

The electrolyte resistance (Rs) is the resistance between the working electrode
surface and the reference electrode. The values of Rs usually are low (1-50Ω) and
can be ignored because the electrolyte is very conductive.
Coating capacitance (Ccoat)

The coating capacitance usually has a low value because most coatings are
relatively thick. It is caused by dielectric properties of the coating, and physical and
chemical properties of the coating that affect the capacitance. It can be described
by the following relation:
Where is the permittivity of vacuum ( ), is the

dielectric constant of the coating, is the surface area of one plate and is the
distance between two plates (coating thickness) [42, 43].
Pore resistance (Rp)

Pore resistance is also known as coating resistance (Rcoat). It is the resistance of the
coating which changes during the exposure as a result of penetration of electrolyte
into micro-pores of the coating. Moreover, it is usually inversely proportional to the
exposure time and to the porosity of the coating. The higher the value of (Rp), the
55
lower the value of porosity and the higher the protective ability of the coating.
However, Rp usually increases after a long time of exposure as a result of corrosion
products blocking the pores in the coating [38, 44].
Double layer capacitance (Cdl)

An electrochemical double layer occurs at the interface between an electrode and
the surrounding electrolyte. The double layer is created as a result of attraction
between the negative ions (anions) and positive ions (cations), and repulsion
between similar charged ions (see Section 2.2.2). When an equilibrium between the
electrolyte and the metal is established, charges in the electrode are separated from
the charges of the ions in the electrolyte. Furthermore, this separation is very small,
and will create high capacitance. The electric field of double layer capacitance
prevents easy charge transfer, which limits the electrochemical interactions at the
surface. Many parameters could affect on the value of double layer capacitance, for
instance: electrode potential, types of ions, oxide layers, temperature, electrode
roughness, ionic concentrations and impurity adsorption [16, 29].
Charge transfer resistance (Rct)

Charge transfer resistance (Rct), also called polarisation (Rp), describes the rate of
the corrosion reaction and is inversely proportional to the corrosion rate; this
parameter can be represented by a Nyquist plot (figure 2.10b).
Constant phase element (CPE)

Constant phase elements have been used widely in equivalent circuits to fit the
experiment data. Many research groups have shown that using CPE instead of pure
capacitance produce better fitting [45]. In some systems the Nyquist plot has been
expected to be an ideal semi-circle with the centre on the X-axis. However, in some
real impedance experiments, the plot was not an ideal semi-circle, but an arc with
the centre located somewhere below the X-axis. This ‘depressed arcs’ behaviour
has been investigated in terms of the nature of the system. In other words, the
system will not follow the ideal capacitance behaviour if the system is not
56
homogeneous or has dispersion of the values of physical properties, such as

roughness, electrode porosity and different current and potential distributions
associated with electrode geometry. As shown in table 2.1, the impedance of a
capacitor is:
where is the inverse of the capacitance.
is an exponent which equals 1 for a capacitor.
For CPE, the exponent is less than one, and can be treated as an empirical
constant [42, 46, 47].
2.3 Wear
Wear is gradual loss or deterioration of material surface caused by relative
movement with respect to another substance [48]. In order to reduce wear, it is
important to understand the mechanism of wear. Moreover, there are several types
of wear with very complex mechanisms which do not lend themselves to precise
theoretical treatment without serious simplifications. Furthermore, wear is system
property dependent. For instance, it is dependent on material properties,
environmental conditions and the dynamics of relative movement, and also,
chemical reaction and/or phase transformations that may also be involved [49].
2.3.1 Classifications and Types of Wear

There are three ways of classifying wear. In the first case, wear can be classified in
terms of the appearance of the wear track, such as, scratched, pitted, or scuffed. In
the second case, wear is classified in terms of the physical mechanism which
removes the material or produces damage to the surface, such as, adhesion,
abrasion, and oxidative. The third classification of wear is in terms of conditions
surrounding the wear location, such as, lubricated wear, unlubricated wear, and
57
high temperature metallic wear [48]. Descriptions of wear types by thephysical

mechanism classification are presented in the following sections.
2.3.1.1 Abrasion wear

This is the material removal and cutting action due to hard particles or hard
protuberances forced against and moving along its solid surface. Furthermore, it
takes place in mechanical operations such as grinding, cutting, and polishing [50].
Two-body abrasive wear takes place when one hard surface plastically cuts
material away from other softer surface (figure 2.15). In most cases, this
mechanism changes to three body abrasive wear, which occurs when an abrasive
particles such as debris becomes entrained in the operation and where it is
sufficiently hard, and it is acts between two solid bodies that are in relative motion
[48].
Figure 2.15 Abrasion wear [51].
2.3.1.2 Adhesion wear

Adhesion wear is material removal and surface damage which can take place when
two smooth surfaces slide against each other (figure 2.16). There is no perfectly
smooth surface. The surfaces have some high spots where contact between the
surfaces occurs. Because of high local pressure between these contact points,
plastic deformation, surface damage and material removal could take place.
Furthermore, the distance between the surfaces becomes of the same order as the
inter-atomic spacing in the material, and where the adhesive forces are higher than
the cohesive forces, shearing of welded junctions can take place in the material of
lower cohesion [51, 52].
58
Figure 2.16 Adhesion wear [51].
2.3.1.3 Fatigue wear

Fatigue of a surface can also cause loss of material. When materials are subjected
to severe contact forces and repeated stress cycling, it can lead to cracking. The
linked cracks result in the formation of loose wear particles [49] (figure 2.17).
Figure 2.17 Fatigue wear [53].
2.3.1.4 Corrosion wear

Corrosion wear takes place when sliding occurs in a corrosive environment. In this
situation, the sliding movement can cause wear on the passivation film, which has
been created by the corrosion processes, which will expose the fresh surface to the
corrosive environment. Usually, there is a combination of the mechanical processes
operating separately or together, which produce wear [49].
2.3.2 Wear tests

Wear tests can be classified into two categories, which are, phenomenological wear
tests and operational wear tests.
2.3.2.1 Phenomenological wear tests

Phenomenological wear tests have a tendency to focus on the general type of wear
situation, such as, sliding wear and low-stress cutting abrasion. Moreover, these
59
tests provide general information, and present either first or second order
simulation, providing useful information to understand and characterise basic wear
behaviour of materials. Typical phenomenological wear tests are [48]:
 Dry sand-rubber wheel abrasion test
 Wet sand-rubber wheel abrasion test
 Slurry abrasivity
 Erosion by solid particle impingement using gas jets
 Vibratory cavitation erosion test
 Block-on-Ring wear test using wear volume
 Crossed-Cylinder wear test
 Pin-on-Disc wear test (this type of test has been used in this
research, and will be introduced in detail in next section)
 Rolling wear test
 Impact wear test
 Scratch wear test
2.3.2.2 Operational wear tests

Operational wear tests focus on particular applications, and usually the name of the
test indicates the specific application, such as a wear test for brake liners. In these
tests, simulation of the test is concerned with the application more than the wear
mechanisms. However, wear mechanisms can be evaluated from the results of the
test. This category of tests presents useful information about understanding wear
behaviour of certain applications. Typical operational wear tests are [48]:
 Cylindrical abrasive test
 Coin wear test
 Brake material wear tests
 Engine wear tests
 Drill wear tests
 Bearing tests
60
2.3.3 Pin-on-Disc wear test

The Pin-on-Disc wear test has been used widely to investigate and evaluate wear
rate. A stationary pin or ball (usually made of cemented carbide) is used against a
rotating disc of the material to be tested (figure 2.18). This standard test can be
used to measure friction and wear resistance of dry and lubricated surfaces of bulk
materials and coatings. In most cases, users can choose the normal load, rotational
speed of the disc, wear track diameter, and the duration of the test. The ASTM
standard for this test is ASTM G99, which indicates the use of a rounded pin.
However, this standard does not specify certain values for the parameters, but users
can choose those parameters to provide simulation of an application. The ASTM
standard allows researchers to measure the wear rate by geometrical or mass loss
methods. In the case of the mass loss method, the volume loss can be evaluated by
dividing the mass loss by the density. In a geometrical method, volume loss can be
measured by converting a measured linear dimension, to a volume using suitable
mathematical relations of the geometry of the wear track [48].
Load Specimen
Rotating
Disc
Figure 2.18 Diagram of Pin-on-Disk configuration wear test [48].
2.4 Thermal Spray Coatings

The basic idea of thermal spray coating comes from Dr. Max Schoop, who
invented thermal spraying in the early of 1900s. Due to the increasing demand for
surfaces which can serve in aggressive environments, significant improvements of
spray techniques were made between the 1920s and 1930s. The combustion powder
and plasma powder processes were developed in the early 1960s, and since that
time, thermal spray techniques have been developed very rapidly, developing to the
61
low pressure plasma spray and high velocity oxy fuel (HVOF) techniques.
Nowadays, thermal spraying can be controlled by microprocessors to produce high
quality coatings [3]. Thermal spray coatings have been used widely to improve
corrosion resistance, conductivity, surface hardness, wear resistance, and repair
surface damage of engineering components. These coatings are becoming
important for a wide range of industrial applications such as aero engines, oil
industry components, gas turbines, and automotive industry components [54].
Thermal spray coating technology uses different forms of materials as a coating
such as: powders, wires, or rods. These stock materials are heated by different
heating sources, depending on the used technology, like flames or plasma, in which
molten or softened particles are accelerated before impacting on the substrate
surface. Moreover, repeating the transition of the spray gun across the substrate
will build up the coating layer, which has thickness from ten microns to hundreds
of microns. Furthermore, the thermal spray technique is an effective, economical
method for improving the surface of components facing aggressive environments.
This technology can be divided into three main groups, which are: flame spray,
electric arc spray, and plasma spray [55].
2.4.1 Principles of Thermal Spray Coatings

The thermal spray technique is a group of processes which start by feeding the
coating material such as powder to the heating source, which is usually a thermal
gun that generates the necessary heat by using combustible gases or an electric arc.
When the coating material is heated, it changes to a molten or semi-molten state.
These molten or semi-molten particles are rapidly accelerated by a compressed gas
stream directed towards the substrate (figure 2.19). When the particles strike the
prepared substrate, they will deform to thin platelets (splats) which adhere to
irregularities of the prepared substrate and to each other. As the sprayed particles
collide on the surface, they cool rapidly and construct splat over splat to form a
laminar structure. Usually this structure has porosity, gaps, and oxide inclusions.
The bond between the coating and the substrate is formed by mechanical
interlocking. The properties of this type of coating will depend on the material used
and the thermal spray parameters.
62
Figure 2.19 Basic principle of thermal spraying [55].
2.4.2 Types of Thermal Spray Coatings

Thermal spray processes can be classified into three main coating process groups:
plasma arc, electric arc, and flame, along with another process which is referred to
as cold spray. These processes have a number of subsets as can seen in figure 2.20.
Furthermore, each of these methods has its own unique characteristics as shown in
table 2.2.
Figure 2.20 Classification of thermal spray processes [56]
63
Table 2.2 Comparison of characteristics for various thermal spraying processes [3]
Deposition Heat Propellant Material Spray Particle Coating Porosity

technique source feed type gun velocity materials level
temp. m/s vol. %
(°C)
Electric arc Arc Air Wire 6000 240 Ductile 8 – 15

between materials
electrodes
Metallic,
Plasma Inert gas Powder 16000 120-600 ceramic, 2-5

Plasma arc
plastic, and
arc
spraying
compounds
Metallic,
Low Plasma Inert gas Powder 16000 900 ceramic, 5

arc plastic, and
pressure
compounds
plasma
spraying
Fusible
Spray & - - Powder - - metals  0.5
fuse
Oxyacetyl
Flame ene/ Air Powder 3000 30-120 Metallic and 10-20
spraying oxyhydro ceramics

gen
Oxygen /
Detonation acetylene/ Detonation Powder 4500 800 Metallic, 0.1 - 1
gun nitrogen shock waves ceramic,

gas plastic, and
spraying
detonation compounds
Oxypropy
High- lene/ Combustion Powder/ 3000 800 Metallic and 0.1 - 2
velocity hydrogen/ jet wire ceramic

propane/
oxy-fuel
LPG
(HVOF)
64
2.4.3 High Velocity Oxy-Fuel Thermal Spraying

This type of spraying differs from conventional flame spraying in that the
combustion process is internal, and the gas pressure is much higher than that used
in the atmospheric burning flame spraying processes. In this process the
combustion fuel gas (hydrogen, propane, or propylene) and oxygen are fed to the
spray gun together with the spray material. The combustion of gases will produce
high temperature and high pressure in the spray gun (figure 2.21). The burning gas
mixture will accelerated to supersonic speeds, and the spray powder is ejected to
the hot gas stream. The spray powder is heated and accelerated by the hot gas
stream and projected into the substrate, the bonding between the substrate and the
coating is usually mechanical bonding (figure 2.22).
Figure 2.21 Schematic diagram of the HVOF process [57].
Figure 2.22 Cross-section of T800 HVOF coating on stainless steel substrate
2.4.3.1 Splat formation and structure of HVOF coating

The splat is the base building block of the structure in HVOF coating. These splats
are formed when a stream of molten and semi molten particles impacts on the
substrate (figure 2.23). The molten droplets are in general spherical in shape before
65
impacting on the substrate surface, followed by flattening, rapid solidification and

cooling processes [56]. Then continuous impacting of particles will increase the
thickness of the coating. The produced microstructure of this thermal spray is a
complex mixture of lamellas (figure 2.24).
Figure 2.23 Schematic diagram of adhesion of a particle to a substrate asperity. (1)

asperities, (2) particle in flight, (3) particle mechanically locked to the substrate, (4)
substrate [55].
2.4.4 Coating materials

There are a large number of modern coating materials available and suitable for
thermal spray technology. In fact, any material that has a well known melting point
and which is not easily decomposed or evaporated when heated can be used in the
thermal spray process [55]. These materials can be classified into three basic types
[56]:
Single-phase materials
Metals: Most pure metals and metal alloys have been thermally sprayed, such as
cobalt-based (Setllites and Tribaloys), nickel-based (Inconel 625), zinc, aluminium,
tungsten, stainless steels, and NiCrBSi (self-fluxing) alloys.
Ceramics: Most ceramics can be thermally sprayed, such as metallic oxides

(Al2O3, stabilized ZrO2, TiO2); carbides (Cr3C2,TiC, WC, SiC), usually these
carbides are used in a more ductile supporting metal matrix such as cobalt or NiCr.
Intermetallics: Most of intermetallics are very sensitive to high temperature and to

oxidation, so shielding gas must be used in the spraying process. The most
common intermetallics are TiAl, Ti3 Al, Ni3 Al, and MoSi2.
66
Metal matrix composite (MMC)materials

Metal matrix composite material is a mixture of metal as a matrix with less than
80% of ceramic or another metal. They are fabricated to have the optimal
properties of a ceramic, such as hardness and wear resistance, and the optimal
properties of a metal, such as the ability to undergo plastic deformation. The metals
most commonly used as a matrix in MMC are cobalt, nickel, and molybdenum.
These metals are usually used as a matrix for an oxide, boride, or carbide. MMCs
are used as binder coatings in thermal barrier systems to solve thermal mismatch
between substrate and the oxide ceramic top coating. One of the most popular
MMCs is tungsten carbide and cobalt (WC-Co) which is used widely to produce
very dense, hard and wear resistant coatings [55, 58, 59]. However, cermets can be
regarded as a special type of MMC, where in this case, ceramic particles are
bonded together by a small proportion (less than 20%) of metallic phase [60].
2.4.5 Microstructure of HVOF-Sprayed coatings

The HVOF coating generally consists of lamellar splats (droplets of semi-molten or
molten powders), unmelted particles, voids and oxidised particles (figure 2.24).
The typically HVOF coating also contains certain defects, such as oxide inclusions
in metallic coatings, which are usually seen as dark phase areas in the coating cross
section. As a result of the low temperature, only mechanical bonding is produced
between the coating and the substrate. Also, HVOF coatings may contain unmelted
particles and pores, which produce an inhomogeneous structure.
67
Figure 2.24 Thermal spray coating microstructure showing common features [56]
A typical cross section of HVOF sprayed coating is shown in figure 2.25. The
powder will fully melt or partially melt due to flame temperature which varies from
2500 oC to 3200 oC depending on the fuel, fuel/oxygen ratio and gas pressure. Use
of the HVOF process has been growing rapidly specially for materials which are
sensitive to phase transformations due to oxidation, decarburisation, or evaporation,
because this process has relatively low flame temperatures and low exposure time
in the flame. The high kinetic energy and low thermal energy will result in better
adhesive bonding and high density coating with relatively low residual thermal
stress which results in coating thicknesses between 100 m and 300 m [61].
Figure 2.25 Cross-section of T800-68WC HVOF coating on stainless steel substrate
In recent years, there has been a significant growth in the use of this technique to
spray cermets, metallics and ceramics. HVOF coatings have recently gained more
popularity and are now extensively studied for protection against corrosion and
wear [12, 58, 62-65]. Furthermore, HVOF technology has found many
68
applications such as automotive, aircraft, oil and other industries, the goal of this
technique in all applications is to increase the lifetime of the surfaces as compared
with uncoated substrate surfaces [66-68].
2.4.6 Corrosion Performance of HVOF-Sprayed WC-Co- base coatings

HVOF WC-Co MMC coatings are widely used to improve wear resistance.
However, in some cases, the service environment is corrosive, so it is necessary to
understand how the coatings behave in these corrosive environments. In this
section a review of some work on corrosion of HVOF sprayed WC-Co coatings is
presented.
Galvanic Coupling between WC and Co

From previous studies, it has been found that the corrosion mechanisms of HVOF
WC-Co coatings are very complex, as a result of the heterogeneous microstructure
and binder phase composition [69]. It is believed that the corrosion mechanism in
this system is controlled by the galvanic coupling between the hard phase (WC)
and the metal matrix [5, 9, 69-75]. For example, Perry et al [75] studied the
corrosion and erosion characteristics of HVOF thermally sprayed 86WC-10Co-4Cr
coatings on a stainless steel (UNS S31603) substrate, by examining these samples
in artificial seawater under the influence of an impinging jet of liquid free from
solids and containing solids. In static conditions, they noted micro-galvanic and/or
crevice corrosion are concentrated at metallic/ceramic interfaces, and the corrosion
attack occurred on metal phase, because the hard phase WC particles have a lower
corrosion rate compared with the metal phase. The dissolution of metal phase led to
extensive removal of carbide particles from the surface, as a result, surface
roughness (Ra) increased from 10 ± 3 nm to 48 ± 5 nm. Monticelli et al [9] has
studied the corrosion process of carbon steel coated by HVOF WC-12Co and WC-
17Co with different coating thickness in 3.5% NaCl solution. They showed the
corrosion resistance of the coatings depended on the cermet layer porosity.
Increasing the coating thickness from 0.05 to 0.2 mm in WC-17Co, offered the
highest hindrance to the anodic oxidation of the substrate, where the access of the
aggressive solution to the substrate was more difficult. They suggested the cobalt
69
and iron dissolution were enhanced by the WC coupling, where, a galvanic current
was between steel or cobalt (anodic) and WC (cathodic). Cho et al [5] have studied
the open circuit potentials between WC and different matrix metals in aerated 5
wt.% H2SO4 solution, and showed considerable microgalvanic corrosion occurred,
where the WC is cathodic and the binder material becomes anodic. They also
assumed that the potentiodynamic polarisation behaviour of the WC coating layers
is related to corrosion of the binder material in region I and to WC oxidation in
region II as shown in figure 2.26.
Figure 2.26 Potentiodynamic polarisation curves of different coatings in the aerated 5

wt. H2SO4 solution [5].
Schnyder et al [73] have investigated the corrosion behaviour of WC-15Co in

different environments (acidic, neutral, and alkaline solutions) in order to study the
effect of pH on the corrosion behaviour. In their study, they concluded that WC-Co
system showed high dissolution rate in all types of electrolyte, and they believed
that WC is significantly noble and has much less corrosion rates than Co. Also,
galvanic coupling between Co and WC increased the dissolution rate of the Co
binder in the hard metal, and they noted very high dissolution rate of Co led to a
loss of the WC particles. Lekatou et al [76] studied the electrochemical behaviour
of HVOF WC-17Co with Ni-5Al bonding layer coatings on Al7075 substrate. The
top surface was WC-17Co. Firstly; they investigated the corrosion behaviour of the
coating in 3.5% NaCl solution, and they noted that during anodic polarisation,
pseudopassivation (will be discussed in more detail in next section) occurred.
Moreover, there was parallel active corrosion induced by the inhomogeneous
binder composition at the same time as pseudopassivation. Also, they investigated
70
the same coating in 0.5 M H2SO4 solution [7], and they noted that the corrosion
behaviour of the WC-Co composite was affected by the galvanic effect of the WC-
Co couple and by the galvanic effect between matrix regions with different content
of WC and Co. Furthermore, they believed the dissolution of Co was greater at the
WC/Co interface, at W-rich/W-poor matrix interface and along lamellae formed of
well-melted particles. A previous study by Hochstrasser-Kurz et al [77] used
scanning Kelvin probe force microscopy (SKPFM) under controlled humidity to
measure the local electrochemical potential distribution of WC grains and Co
binder, and showed for the first time, increasing the humidity allowed
demonstration of coupling mechanisms of the two phases [77, 78]. As a result of
their study, in humid environments the WC grains were the cathodes and the cobalt
binder was active. Moreover, the electrochemical potential difference between the
two phases was measured, to be around 200-250 mV. The mechanisms of corrosion
as a result of this galvanic coupling have been discussed in this study (figure 2.27)
as follows.
Co dissolves in neutral and acidic solutions, and is passivated in alkaline solutions,

showing higher dissolution rates for decreasing of pH. However, WC shows
dissolution in alkaline solution and continuous stabilisation with decreasing pH.
The galvanic coupling causes accelerated anodic dissolution of the less noble phase
(Co) as shown in the following equation:
The reduction reaction then occurred on the WC phase, which can be one of the
following reactions:
The cathodic reaction from reactions 2.43 and 2.44 creates a local increase in the
solution pH. Using inductively coupled plasma mass spectroscopy (ICP-MS)
analysis, WC is instable in alkaline solution has been confirmed. In aerated
conditions, the WC surface becomes covered by a tungsten oxide layer, which is
71
WO3 as shown in figure 2.27. This oxide can be dissolved in aqueous solution as
shown in the following reaction:
As seen from reaction (2.45), no electron takes part in this reaction, so it cannot be
detected by electrochemical techniques. This oxide dissolution can decrease the
local pH, and that can possibly initiate accelerated Co dissolution around the WC
grains [77].
Figure 2.27 Schematic representation of the reaction processes taking place on the
WC-Co surface as a consequence of the galvanic coupling between Co and WC [77].
The same process has been reported by Souza and Neville [79] in studies of the
corrosion behaviour of 86WC-10Co-4Cr HVOF coating in 3.5% NaCl using in situ
atomic force microscope (AFM) and ICP analysis. They concluded that, not only
the matrix material underwent dissolution, but the hard phase WC had oxidation
and dissolution at much higher potentials than Co, where, WC oxidizes to WO 3
then dissolves into WO42-. However, when the potential is high (0.7 V(SCE)), the
formation of WO42- can also take place directly. Corrosion of Co in the solution
takes place in the early stages of the process but is slowed down by the Cr2O3 oxide
layer, which is formed from the Cr in the matrix. The initial dissolution of Co
creates conditions and interactions such as reduction of localized pH, which
promotes oxidation/dissolution of WC particles. The WC particle can be removed
from the surface if the surrounding area has been corroded.
72
Pseudopassivation behaviour
Many studies [71, 72, 80] have confirmed that the reactions which occur on the
hardmetal surface depend on the potential of the system. At low applied potentials
or at open-circuit potential, the dissolution starts at the matrix phase, while only in
the higher potential range does the dissolution of the WC phase occur.
Some researchers have reported that the WC-Co system has a passive behaviour
[81]. However, it was also reported that the system did not show any passivation,
just active dissolution throughout the potential range studied [82]. Conversely,
some researches confirmed that the passivation behaviour of this composite was
kind of pseudo-passive state. The HVOF sprayed alloy coatings may not reach the
perfect passive state as a result of defects, pores and oxidation inclusions [70, 83].
Bolelli et al [84] has studied the effect of heat treatment on corrosion properties of
three different HVOF coatings: Co-28Mo-17Cr-3Si (T800), Ni-20Cr-10W-9Mo-
4Cu-1C-1B-1Fe (Diamalloy-4006) and Ni-32Mo-16Cr-3Si-2Co (T700). The
corrosion tests were performed in 0.1 M HCl solution. A passive-like state
(pseudopassive) has been observed in anodic polarisation curves. It has been
confirmed that the anodic polarisation curves cannot be described as a complete
true passivation, and the current density is too high for a perfect passivity state.
However, T800 showed significant active corrosion, where the current density
increased slowly over a large potential range (figure 2.28) [70]. The lack of full
passivation has taken place because of defects, porosity and lamellae boundaries.
Figure 2.28 Electrochemical polarisation curves of HVOF-sprayed coatings in 0.1 M

HCl solution [70].
When the porosity defects due to imperfect interlamellar cohesion exist, these will
be preferential sites for corrosion to take place, since the diffusion of oxygen into
73
these defects is much slower than that of small Cl- ions, which limits passivation
occurring [70]. Sutthiruangwong and Mori [85] studied the corrosion properties of
WC-Co in deaerated and aerated acidic solutions (H2SO4 and HCl), the polarisation
test with saturated calomel references electrode shows that dissolved oxygen has
little influence on the anodic behaviour. Moreover, polarisation curves for Co and
WC in 1N H2SO4 solution have been discussed. Corrosion potential (Ecorr) of Co
was found to be about -460 mV, the current density (icorr) was 0.68 mA/cm2, the
corrosion potential (Ecorr) of WC was 110 mV, and the corrosion current density of
WC was 6.2 × 10-4 mA/cm2 as shown in figure 2.29.
Figure 2.29 Potentiodynamic polarisation of Co and WC in aerated 1 N H2SO4 [85].
Pseudopassive behaviour has been observed in their study, which concluded that
the anodic film caused the current density reduction. The same conclusion was
reached by Human et al [86]. Another explanation for pseudopassive behaviour is
the Co2+ ions taking a longer path through the porous tungsten carbide after
dissolution of Co, where the diffusion for these ions through the WC skeleton is
slower than free diffusion [85]. Furthermore, the stability of Co and WC in acidic
environments has been discussed, as shown in the Pourbaix diagram of cobalt
(figure 2.30); there is no stability of Co at anodic (between -390 and -330 mV) and
pseudopassive (+200 mV) potentials and pH 0 where, the Co is dissolved as Co 2+
into the solution.
74
Figure 2.30 Potential-pH equilibrium diagram for the system cobalt-water, at 25oC,
potential with respect to standard hydrogen electrode [85].
However, tungsten exhibits a different behaviour, as shown in Pourbaix diagram of

tungsten (figure 2.31); W is stable at the anodic potentials (between -390 and -330
mV) and pH 0. However, at the pseudopassive potential (+200 mV) and pH 0, it
shows instability, and can be oxidized to oxide compounds (WO2, W2O5 and WO3)
[85].
Figure 2.31 Potential-pH equilibrium diagram for the system tungsten-water, at 25oC,
potential with respect to standard hydrogen electrode [85].
Many researchers have concluded that in H2SO4 solution, at the low potentials, the
pseudopassivation state (region I in figure 2.26) is closely related to the oxidation
of Co and W [5, 81, 87] whereas, at the high pseudopassive potentials (region II in
figure 2.26) it is related to the oxidation of W and C [5, 7, 71, 72, 88, 89].
75
Effect of porosity
In general, spraying unmelted/semi-melted powders leads to a low spraying
efficiency and high porosity in the coating layers. Sufficient melting of the sprayed
powders is important in order to create coatings with low porosity and excellent
properties [90]. It has been reported by Guilemany et al [91] that, more micro
cracks and porosity in coating layer will produce more corrosion, as a result of
infiltration of the electrolyte into the coating layer/substrate interface. Godoy et al.
[92] have reported that the pathways generated by interconnected porosity caused
corrosion of WC-Co HVOF coatings due to formation of galvanic couples between
the coating and substrate. Magnani et al [58] have sprayed WC-Co on aluminium
alloy by the HVOF technique, and they noted that optimization of thermal spray
parameters can produce low porosity and homogeneous coatings, which provide
good corrosion resistance. Liu et al. [12] concluded that the existence of inter-
connected porosity and lamellar grains within the splat-structures with oxide
inclusions at interlayer boundaries is the main reason for the failure of the coatings
due to corrosion penetration into the interlayer which could cause de-bonding of
the coatings. In general corrosion resistance can be improved by decreasing the
porosity, avoiding cracks, and enhancing inter splat adhesion [91].
Effect of WC percentage and particle size in WC-Co alloy

As discussed above, the chemical stability of WC is higher than that of Co in acidic
media [71, 80]. Moreover, the current density which was measured in polarisation
tests of WC-Co alloy was mostly from oxidation of binder phase, especially at low
potentials. Consequently, it might be expected that as the binder content increased,
the corrosion current density will increase proportionally. However, Human and
Exner have concluded that the corrosion rate increased with increasing proportion
of matrix phase because the fraction of the phase area was increased. However, the
kinetics of the binder phase corrosion are not changed [72]. It has been proved that
the electromechanical behaviour of WC-Co can be modelled using a simple linear
rule of mixtures which was proposed by Stern [72, 80].
76
Where is the electrochemical current density of the WC-Co composite,

is the cross-sectional area fraction of the WC phase, is the current density
of WC, is the cross-sectional area fraction of the binder phase and

is the current density of a Co(W,C) alloy (matrix composition). It has been shown
that the corrosion behaviour of WC-Co was similar to the corrosion behaviour of
pure Co in 0.1 M NaCl solution, and strong dissolution of the Co binder may cause
the loss of WC particles that might fall out of the surface [5, 73, 75, 93].
Sutthiruangwong et al [93] studied the influence of W on the corrosion behaviour
of W-Co alloys in 1N H2SO4 solution, it showed that (figure 2.32) the corrosion
current density decreased with increasing tungsten content in the binder.
Figure 2.32 Electrochemical behaviour of Co-W alloys in aerated 1 N H2SO4 [93].
Many researchers reported that the size of the WC particle size does not result in
any effect on the corrosion behaviour of WC-Co alloys [71, 72, 80]. However,
Tomlinson and Ayerst [94] have reported a decrease in passive current density by
reducing the grain size of WC.
2.4.7 Wear Performance of HVOF-Sprayed WC-Co-base coatings

WC-Co cermets are extensively used as wear resistance materials as a result of
their favourable combination of toughness and hardness. These composite coatings
used on engineering components by the thermal spray processes, especially the
HVOF technique, result in a dense structure that shows excellent resistance against
conditions where erosion, abrasion and other forms of wear exist. The HVOF
technique is performed at a lower temperature compared with other thermal
77
techniques such as plasma spray. For this reason it is suitable for spraying low
melting point alloys and cermets. Furthermore, HVOF spray creates the highest
mechanical properties and wear resistance compared with plasma spray or lower
velocity combustion [95].
Due to the wide application of these coatings where good abrasion, erosion or
sliding wear resistance is needed, there are a number of researchers concerned with
the improvement of the wear resistance of these coating materials and studying the
factors which could affect the tribological properties of the coating. Guilemany et
al [96] studied the mechanism of wear on WC-12Co HVOF coating and indicated
that the wear started by removing the binder phase which takes place mainly by
abrasion (two body abrasive wear) and the fine debris cause three-body abrasive
wear, followed by pull out the carbides. However, the three-body abrasive wear is a
function of the quantity and hardness of the debris. The oxide layers which are
produced on the surface will decrease the friction. But, will be removed by the
abrasive effect, and the debris will cause an increase in the friction parameters
again. Similar mechanisms of wear have also been reported by Shipway et al [97]
in WC-17Co, Stewart et al [98] in WC-12Co and Kumari et al [99] in WC-10Co-
4Cr.
It was found that the wear behaviour of WC-Co HVOF sprayed coatings is
different from wear behaviour of bulk sintered WC-Co as a result of inhomogeneity
and phase transformations which occur during the thermal spray process, and that
has a significant effect on the tribological properties of the coatings. Liao et al
[100] reported for WC-17Co HVOF coating that hardness and cohesion of the
material are very important for resistance to abrasive wear in cermets such as WC-
Co, where, in this type of material, more hard WC particles means increasing the
average hardness. The cobalt matrix in this coating operates as a binder for carbide
particles. So, to improve the wear resistance of these materials the cohesion
between the carbides and cobalt matrix should be increased, which influences the
microstructure and phases in the coatings at the interface between hard WC
particles and the cobalt matrix. Appearance of M6C or M12C gives a good
indication of improvement of cohesion between hard carbide and the cobalt matrix,
which enhances the abrasive wear resistance [100]. Furthermore, it was found the
78
smaller the carbide size, the better the abrasive wear resistance, because pull out of
single carbide particles produces less damage to the finer coating and the debris for
the finer carbides have less influence as the third body abrasive [100-102].
However, Guilemany et al [63] have observed that in WC-12Co coatings, the
mixture of nanostructure and conventional coatings (which is called bimodal
coating) has higher wear resistance than nanostructure or conventional coating
individually. They suggest that this is because the mixture of nano-sized carbides
hardens the matrix and improves the cohesion for hard micro-sized WC particles
with the cobalt matrix, which creates a strong, tough surface which leads to
improve the wear resistance.
Optimization of thermal spray parameters has a significant influence on coating

properties and wear resistance. Zhao et al [103] have reported that for WC-CoCr
and under the experimental conditions, the particle velocity has more effect on
coating properties than the particle temperature, and the total gas flow rate has a
significant influence on wear resistance.
Heat treatment has a significant effect on microstructure and coating properties.

Stewart et al [104] have studied the influence of heat treatment on abrasive wear
behaviour of WC-17Co HVOF coatings, and reported that the heat treatment
reduced the residual stresses in the coatings. Low temperature treatment has
improved the abrasive wear resistance. They also observed that heat treatment at
temperature above 600oC produced low carbon  phase Co6W6C [65, 104].
However, Asl et al [64] found heat treatment of WC-17Co HVOF sprayed coatings
at high temperature (1100oC) decreased the wear resistance of the coatings.
The decomposition of WC and subsequent decarburisation due to the hot gas jet in
HVOF, typically WC to W2C has a negative effect on wear resistance of the
coating. It has been reported that the wear resistance decreased due to brittle phases
which are produced from decarburisation mainly WC  W2C [98]. Karimi and
Verdon [95] showed that in WC-CoCr coating, during the spray, some of the WC
could decompose into W2C or interact with cobalt and form Co 3W3C. It has been
reported that adding Cr to this composite could have a positive effect on wear
resistance, where Cr could inhibit the decomposition of WC to a large extent [95].
79
Wood [105] reported that the tribological properties of the spray coatings are
functions of a wide range of parameters such as: composition (figure 2.33), phases
and their distribution, microstructure, residual stress and porosity. These
parameters have a direct influence on the hardness of the coating, which are used as
initial correlation factors to evaluate the wear resistance. Also another important
factor which can influence the tribological performance of HVOF WC-Co coatings
is the adhesion of the coating to the substrate.
Figure 2.33 Total (pin and disc) specific wear rates for different HVOF coating
composition under dry oscillating wear [105].
The inhomogeneous microstructure of WC-Co-Cr thermal sprayed coatings,

especially the low fracture toughness in a direction parallel to the substrate, is the
main factor which affects the nature of crack formation under erosion conditions.
These cracks could start at voids, splat boundaries and interfacial inclusions [105].
However, brittle phases in the thermal spray coating can be avoided by employing
suitable spraying parameters [106].
2.5 Laser Surface Engineering

2.5.1 Lasers
In 1917, Albert Einstein illustrated the phenomenon of stimulated emission. This
process is important for amplification of light, and for laser operation. During the
period of time from 1920 to 1940, there were many discoveries in quantum
mechanics physics, which made it possible to progress towards the establishment of
the first laser. Moreover, during World War II experience was gained during the
80
improvement of radar, in particular, the important work in the field of microwave

radiation. That work led scientists to analyse the conditions that are important for
the laser process to succeed. In 1960 the first ruby laser was operated successfully
by T. H. Maiman. After that many substances were discovered as the active laser
medium, such as Helium-Neon gases, crystals and dye solutions [107]. Lasers have
since been used in many applications in our life for instance in medical
applications, communications, material processing, holography and isotope
separation.
2.5.1.1 Basic Principle of Lasers

Laser stands for Light Amplification by Stimulated Emission of Radiation. In every
laser device three conditions should exist. Firstly, it has an active medium, which
contains atoms, molecules, or ions. Secondly, it supports population inversion, this
condition does not exist in nature, but it is created in laser by a process known as
pumping. Finally, for a laser beam to be generated, there must be a pumping
process to give energy to the system.
The Active Medium

The active medium is the main material, which is responsible for laser action. This
material can also be considered as an atomic system. Every material in the world
can be regarded as having energy levels, and the energy level contains atoms. The
number of atoms in each energy level depends on the energy of this level [107].
The atoms can transit from one level to another level. Physics laws control these
transitions. In the following paragraph, the relationships between energy levels and
the important transitions are discussed briefly.
Absorption and Emission

Although not true of real materials, these phenomena can be described using a
theoretical material which has just two energy levels (figure 2.34). The ground state
with energy E0, and the excited state with energy E 1.
81
E1
E1  E0 Photon
Emitted
E0 h
(a) (b)
E1
Photon h
Absorbed
h
h
E0
(c) (d)
Figure 2.34 Two-level energy system (a), Spontaneous emission (b), absorption (c),
Stimulated emission (d).
If the atom in the upper level E 1 makes a transition to the lower level E 0, it will
emit energy. This energy could be in the form of radiation. The frequency of this
radiation is given by equation (2.47). This kind of transition is called spontaneous
emission (figure 2.34 (b)).
Where: E1 Energy level for upper state. E0 Energy level for lower state.
Planck constant = 6.626×10-34 J.s
Frequency of the radiation.
An atom initially at the lower energy level (ground state) E0, must absorb energy to
transit to the upper level E1 (figure 2.34 (c)). The frequency of this energy is given
by the above equation [108]. There is another kind of emission called stimulated
emission. This type of emission is different from the spontaneous emission, which
occurs randomly in time. However, the stimulated emission occurs when an atom
in the higher energy state interacts with a photon, which stimulates it to go down to
the lower state. In this case the result of stimulated emission is two photons (figure
2.34(d)), these photons are coherent [108].
82
Population Inversion
In normal conditions (Thermal Equilibrium), the population (number of atoms) in
the lower level is greater than the population in the higher level. The distribution is
known as a Boltzmann distribution, which can be expressed in this equation [108]:
Where: Population of upper level.
Population of lower level.
Energy level for upper state.
Energy level for lower state.
Boltzmann constant = 1.38×10-23 m2 kg s-2 K-1
Absolute temperature (K).
From equation (2.48) when E1 > E0 (normal condition) then N0 > N1. Any photons
will be absorbed rather than causing stimulated emission. To make stimulated
emission happen, it is necessary to increase the population of the upper energy
level. This situation is known as a population inversion [108]. In fact population
inversion can be achieved only in non-equilibrium conditions, where Boltzmann’s
law does not apply.
Laser pumping
Pumping is an important to reach a population inversion. Population inversion is
obtained in a laser by exciting or pumping the atoms in the laser medium to a non
thermal equilibrium state using an external source of energy [107]. The most well
known methods of laser pumping are optical pumping to provide the system with
energy; a flash lamp is fixed near the active medium (used especially in solid state
lasers), electrical pumping uses an external high voltage as a source of energy for
gas lasers.
83
Laser components
Any laser device must contain an Active medium, a Pumping source and two
mirrors (Resonator), one with 100% reflectivity and the other with partial
reflectivity. Figure 2.35 shows the main parts for every laser device.
Laser
Active Medium
R=100% R= Partially %
Pumping
Process
Figure 2.35 Laser components
How a laser works

Population inversion is the important condition of the laser process, which is
reached by pumping the active medium using an external source of energy.
Stimulated emission is the following process, then immediately after that, the
amplification for coherent radiation, which occurs by a resonator, where the
mirrors will reflect the two photons into the active medium and these photons will
stimulate more photons. Afterword, the new photons which have been reflected
from the other mirror again pass into the active medium (figure 2.36). This process
will continue until the radiation reaches a high enough power to emit from the
partial reflectivity mirror as laser radiation. At the same time, the pumping process
continues to give the system energy for population inversion [107].
84
Active Medium
R=100% Pumping R= Partially %

Process
Active Medium
R=100% R= Partially %
Pumping
Process
Laser
Active Medium
R=100% Pumping R= Partially %

Process
Figure 2.36 Amplification process
2.5.1.2 Properties of laser radiation

As a result of the unique properties of laser radiation, it is the perfect tool for many
areas of industrial and research.
Monochromaticity
The word, Monochromatic, means laser has single wavelength. From Greek
language monos means “single” and chroma means “colour” [107]. In fact, the
laser light is emitted over a very narrow range of wavelength compared with
conventional light sources. Ordinary white light is a mixture of many different
wavelengths (colours).
Directionality
A laser beam is directional; it is nearly parallel when emitted from the resonator.
This means it has very small divergence angle. This property comes from the fact
85
that laser radiation emits from the resonator cavity, and only the waves propagating
along the optical axis stay in the cavity and are amplified [107].
Coherence
Coherence is one of the unique properties of the laser. This fascinating radiation is
totally coherent whereas, ordinary light sources are incoherent. This property
comes from the stimulated emission process which produces the amplification. The
emitted photons have a defined phase relation to each other. This coherence is both
temporal and spatial mean that the photons at any point along the laser beam are in
phase and remain in phase throughout the time that the laser is operating [108].
High power density

A laser beam can be focused by special optical instruments such as lenses to a
small spot area with high power density. This is important in laser material
processing, which require high power density, like drilling, alloying, cutting and
welding [107].
2.5.1.3 Types of laser

The different laser types developed to date have a wide range of physical and
operating parameters. Moreover, lasers are classified according to the physical state
of the active material, which are: solid state, liquid or gas lasers, depending on the
active medium state [109]. The main laser types are as follows:
Solid state lasers

Ruby laser, Nd: YAG (Neodymium: Yttrium-Aluminium Garnet) laser and
Semiconductor laser. In these lasers the active medium is solid material, for
example, the Ruby laser which emits visible light at wavelength 694.3 nm, and
Nd:YAG laser emits infrared light at 1064 nm [109].
86
Gas laser
The most important gas lasers are Helium-Neon laser, Argon laser, Carbon dioxide
laser, Excimer laser and Nitrogen laser. In gas lasers He-Ne (Helium-Neon) laser is
the most common gas laser used in laser labs for beam alignment, which has a
radiation of visible red light, and its usual operation wavelength is 632.8 nm.
Moreover, Carbon dioxide laser operates in the infrared at 10.6 m [109].
Liquid laser (Dye laser)

Dye lasers use complex organic dyes. They are tuneable over a broad range of
wavelengths [109].
The following table shows most types of lasers and their properties.
Table 2.3 Main lasers and their properties [110].
Laser Wavelength Power Operation mode
CO2 laser 10.6 m 1 W – 40 kW Continuous/ pulsed
193 nm/ 248 nm/ 308

Excimer laser 1 kW-100 MW Continuous/ pulsed
nm
He-Ne laser 632.8 nm 1 mW-1W Continuous
Argon laser 515 nm/ 458 nm 1 mW-1W Continuous
Dye laser Between IR and UV 1 mW-1 W Continuous/ pulsed
Nd:YAG laser 1064 nm 1 W-3 kW Continuous/ pulsed
Ruby laser 694.3 nm Several MW Pulsed
Semiconductor From infrared to

1mW-100 mW Continuous/ pulsed
laser visible
87
2.5.1.4 Semiconductor Laser
A diode laser is made by forming a junction between (positive) and (negative)

types materials in the same host material, known as a - junction. Figure 2.37
shows that the lower part of the conduction band of the n-type material is filled
with electrons and in the p-type material, the top is filled by holes. Moreover, a
high voltage needs to overcome the energy gap V. The n-type is connected to the
negative part of a potential supply and the p-type is connected to the positive part
of the potential supply, called forward bias. Under this condition, the electrons in
the n-type region are driven towards the junction and combined with holes to
produce photons. Furthermore, when the forward bias is increased, the photons
emmision will be increased and intensity of light becomes higher.
Figure 2.37 Semiconductor laser-junction region [111].
The most common semiconductor material used in semiconductor lasers is gallium

arsenide, and there are other semi conductor materials used in this laser type such
as indium phosphide, gallium antimonide, and gallium nitride. Moreover, in this
type of laser the resonator is different from conventional lasers, where the resonator
in this laser is affected by the semiconductor structure itself using the polished
faces as mirrors. These lasers are pumped by applying an electrical current (figure
2.38). The energy gap for gallium arsenide is 1.4 eV and the wavelength emitted is
840 nm.
88
Figure 2.38 Semiconductor laser [111]
In this system without stimulated emission conditions, it is possible for the

electrons and holes to be near each other without combination. The time to remain
without this interaction is called the recombination time (about one nanosecond).
The stimulated emission occurs when a nearby photon with energy equal to the
recombination energy can cause recombination, and this will generate other
photons at the same frequency, direction, phase and polarisation as the original
photon. Moreover, to complete the laser process, the stimulated photons are
constrained by an optical cavity. The stimulated light passes through the cavity and
is amplified by stimulated emission. However, there is some loss in light due to
absorption. When the amplification is greater than the losses in the cavity, the laser
is generating [111]. The wavelength of a diode laser is dependent on many
parameters such as; band gap energy, cavity length and refractive index of the
semiconductor. The following table shows the wavelengths of some semiconductor
laser materials [112].
Table 2.4 Wavelengths of a selected range of diode laser materials [112]
Materials AlGaAs InGaAs AlGaInP
Wavelengths (nm) 720-880 940-990 630-690
89
2.5.1.5 Characteristics of high power diode laser

Characteristics of high power diode lasers (HPDL) make them suitable for many
material processes. HPDL usually works in continuous mode. However, by
controlling of current, the output power can be switched off and on rapidly to
generate a pulsed mode. HPDL has a high optical/electrical efficiency of 20-50%,
which is higher than other high power lasers. Furthermore, HPDLs are smaller in
size than other lasers of the same output power level [113]. The short output
wavelength of most practical HPDLs (between 800 and 940 nm) can be absorbed
by most metals compared with CO2 and Nd-YAG lasers (figure 2.39). This reduces
the need of surface preparation [114].
Figure 2.39 absorption as a function of wavelength for carbon steel and aluminium
[114].
A single diode laser has a low power of less than 5 W. To increase the output
power, practical HPDLs are based on several individual emitters which are
arranged either in a one dimensional linear array, as a high power diode laser bar
(30-50 W), or a two dimensional multi-layer array to produce a rectangular shape
of laser beam profile [112]. The average output power of HPDLs after using this
focusing technique reaches up to 6 kW [115]. However, HPDL have relatively poor
beam quality. Consequently, it is not suitable for precision materials processing
such as cutting and welding. Moreover, the beam profile of a HPDL generally is
‘top-hat’ in the slow axis direction and Gaussian in the fast axis direction with a
rectangular shaped spot, which is suitable for surface engineering. The HPDLs
have high beam stability compared with other conventional lasers such as Nd-YAG
and CO2 lasers, where, the conventional lasers have a single beam which has
intensity fluctuations, apparent as irregular spikes in beam profile, as a result of
small variations during the excitement of the laser active medium. However, the
90
great number of laser beams of a HPDL system reduces fluctuations, and giving the
combined beam an outstanding modal stability. Consequently, the beam profile of
HPDL appears smoother and has very little variation in shape and peak power as
shown in figure 2.40 [115, 116].
Figure 2.40 Time resolved intensity distribution within a 1.6 s interval (a) HPDL
system (b) Nd-YAG laser [116].
As a result of these unique features, HPDLs provide better surface finish, fewer
cracks, more uniform melt zones, have more repeatable results than other lasers and
now increasingly used in surface treatment [112].
2.5.2 Laser beam Interaction with Materials

When a laser beam is incident on the surface of material, such as a metal (Opaque
material), some of the energy is absorbed into the near-surface regions, and some
reflected. In these materials, Absorptivity depends on the material, laser
wavelength, temperature of material, and surface roughness [108]. The portion of
the incident optical energy that is absorbed is of interest in material processing. The
absorbed optical energy (photons) is immediately transformed to cause vibrational
motion of electrons in the affected zone by the excitation of electrons from their
equilibrium states to some excited states. These vibrations are transmitted into the
structure of the material within an extremely short period of time. The optical
energy is converted to heat, which gradually transfers to adjacent atoms. The
temperature will increase as more photons are absorbed. Moreover, the temperature
will rise rapidly, and the near-surface region undergoes extreme heating and
cooling rates (103-1010 K/s), very high thermal gradient (106-108 K/m) and a rapid
91
solidification velocity (1-30 m/s) [117]. The flow of heat in the material can be
described by conventional heat equation
Where: h Thermal diffusivity
K Thermal conductivity
Q Heat production per unit volume time
And Cp is heat capacity, and  is density of material
The thermal diffusivity determines how rapidly a material will conduct thermal
energy. The heat equation (2.49) is a non-linear partial differential equation that
makes the solution difficult. However, the equation can be solved by numerical
techniques such as finite difference or finite element [118].
2.5.3 Laser Surface Treatment

Lasers have been used in numerous applications, such as communication, medical
and material processing. Laser surface treatment is used to change the surface
microstructures to enhance locally some specific properties of the surface such as
hardness, wear and corrosion resistance. This process includes surface heating,
alloying and cladding. Figure 2.41 is schematic showing a simple classification of
laser surface treatment. Figure 2.42 depicts the different techniques of laser surface
treatment.
92
Figure 2.41 Laser surface processing [119].
2.5.3.1 Laser Transformation Hardening

When the laser beam heats the surface of material, the surface may be hardened by
a solid state transformation mechanism. Following heating, the laser energy is
reduced or switched off or the beam moved off to another area, and the cold bulk
material then quenches the heated surface; this will cause extremely rapid cooling.
Diffusion occurs at high temperatures and the material is unable to be transformed
back to its origin phases on rapid cooling; causing martensite transformation [108].
The factors which will affect hardening are speed of scanning, intensity of the laser
radiation and type of metal. Laser surface hardening will increase hardness, wear
resistance, and fatigue life [108, 119].
2.5.3.2 Laser Surface alloying

Laser surface alloying is variation on the surface melting process by adding another
material into the melt pool. This process produces a surface layer which is different
from the substrate. Nowadays many researchers have reported this technique
improves wear and corrosion resistance for some specific parts which are target at
corrosive environments [108, 119, 120].
2.5.3.3 Laser Cladding

This method involves melting and adding another material as in the alloying
process. However, dilution in this process is kept to minimum. This technique
93
creates metallurgical bonding of the clad layer with the substrate to improve the
surface properties of a material which will be subjected to corrosion, erosion or
wear [108].
Figure 2.42 laser surface treatment techniques; (a) laser transformation hardening,
(b) laser surface melting, (c) laser alloying, (d) laser cladding
2.5.3.4 Laser Surface Melting

In this type of processing, the laser beam is used to melt a small region of the
substrate surface. This processing does not change chemical compositions within
the melted layer, but changes its microstructure, in terms of a refined and possibly
metastable microstructure in small localised areas of base material. The features of
this process are: flexibility resulting from possibilities of computerisation (software
control) of the process and automation, and it has small thermal penetration and
therefore minimum distortion. By this procedure fine homogeneous structure can
be obtained due to rapid cooling rates, where the unaffected substrate acts as a heat
94
sink. When the beam traverses past, the solidification process starts from the
solid/melt interface towards the surface.
2.5.4 Laser induced rapid solidification

The microstructural features during solidification are controlled by the shape of the
solid-liquid interface. The nature and stability of the produced solid-liquid interface
depend on the thermal and compositional conditions in the melted layer. The main
variables in determining the morphology of solidification are, the temperature
gradient G in the liquid, the growth rate R, and the alloy composition. Depending
on these conditions, the interface between liquid state and solid state, might grow
by planar, cellular or dendrite mechanisms. The temperature gradient G and growth
rate R are important in the combined forms GR (cooling rate) which influence the
scale of the solidification microstructure and the ratio G/R determines the
solidification morphology [119],[121] . Figure 2.43 summarises the effect of the
temperature gradient G and the growth rate R on the solidification microstructure
of alloys.
Figure 2.43 Effect of temperature gradient G and growth rate R on the morphology
and size of solidification microstructure [122]
11
During laser surface treatment, cooling rates are very high between 103-10 Ks-1
depend on treatment conditions. The solidification velocity is also high between
0.01-1 ms-1, and the temperature gradients between 104-106 K m-1 [119]. Rapid
solidification induced by laser melting can produce materials with superior distinct
95
physical and mechanical properties. The cooling rate decreases from the maximum
on the surface to a minimum at the bottom of the molten pool and also decreases
from a maximum at the centreline to zero at the edge of the molten pool. This
variation in cooling causes a variation of microstructure in the molten pool [108].
For high cooling rates, the liquid might under-cool which results in protrusions at
the solidification front. These protrusions will develop as cellular or dendritic
structures depending on cooling rate (figure 2.44).
Figure 2.44 SEM morphologies of the laser clad Tribaloy T-800 on stainless steel
(AISI 304), shows: (1) substrate; (2) planar crystallization region; (3) cellular growth
zone; (4) fine dendritic microstructure; (5) overlap zone between tracks. power
density 200 W/mm2 , scanning speed 240 mm/min and powder feed rate 10-15 g/min
[123].
In most cases in substrate-quenched alloys as in laser surface treatment, nucleation

leads to columnar growth dendrites, which start at the surface in contact with the
quenching substrate [124, 125]. Figures 2.45 and 2.46 show different
microstructures which might be created by rapid solidification induced by laser
treatment for different materials.
96
Figure 2.45 SEM morphologies of the laser clad Tribaloy T-800 on stainless steel
(AISI 304) power density 200 W/mm2 scanning speed 240 mm/min and powder feed
rate 10-15 g/min: (a) Cellular structure; (b) dendritic microstructure [123].
Figure 2.46 SEM morphologies of laser clad of the Stellite 6. The dark dendritic
phase is the cobalt-based matrix and the white phase is formed by the M7C3 eutectic
carbides: (a) slow processing conditions (Vb=1.67 mm s-1); (b) fast processing
conditions (Vb=167 mm s-1) [126].
2.5.5 Effect of laser Surface treatment on microstructure and

electrochemical properties of HVOF Coatings
Laser treatment promotes homogenisation of the surface composition, and
increases the density of the HVOF coating by eliminating porosity to provide a
better barrier to the substrate [11]. This section summarises the previous work of
the consideration of corrosion properties after surface treatment by various lasers.
Heat treatment can be an effective way of enhancing the overall corrosion

resistance of the Co alloy, as has been reported lately by Bolelli et al [84], where,
the heat treatment for one hour at 600oC of AISI 1040 steel plates coated by T800,
T700, and other alloys HVOF coatings, showed enhancement of corrosion
properties. It has been suggested the heat treatment improved the interlamellar
cohesion which reducing the activation of corrosion through the interlamellar
97
boundaries. Marginean et al. [127] studied the oxidation behaviour of CoNiCrY

HVOF coating after laser heat treatment. After treatment without protective inert
gas, an oxide layer was formed on the surface. Also the oxide layer had poor
adhesion to the surface and cracks. Zhang et al. [128] found that porosity of WC-
CoCr HVOF coating was reduced after laser heat treatment by a factor of
approximately five compared to HVOF coating. Neither Co nor CrCo was detected
in the coating after HVOF process, suggesting that most of Co is retained in the
nano-crystalline binder phase. However, WC and W2C were still present in the
coating, and a new phase (Co 4W2C) has appeared in the LH treatment.
Furthermore, Argon gas was used for shrouding the laser treated region and no
oxide formation has been detected in the HVOF coating before or after laser
treatment. In another paper [129] recently the authors investigated the corrosion
properties of HVOF sprayed WC-24%Cr3C2-6%Ni before and after LH treatment.
They observed that the performance against corrosion has been improved after heat
treatment. Their polarisation test results are shown in figure 2.47. It has been
concluded that the improvement in corrosion resistance was as a result of
decreasing the size and the number of porosity, and creating a compact interface
between the coating and the substrate, compared with HVOF coating without LH
treatment. They reported that the coating with LH treatment was more successful in
hindering the solution from reaching to the interface between the coating and the
substrate.
Figure 2.47 Potentiodynamic polarisation curves of HVOF WC24Cr3C2-6Ni

coatings in 3.5% NaCl solution [129].
98
Corrosion properties of HVOF sprayed Inconel 625 on mild steel using laser
melting has been studied by Tuominen et al. [10]. The coatings obtained after laser
melting are metallurgically denser than HVOF, and also crack- and porosity-free.
In an immersion test in 3.5% NaCl solution for one week, it was observed for the
HVOF samples, that the coating materials had corroded selectively. The corrosion
started along splat boundaries and corroded the material nearby, and as a result of
splat boundaries, interconnected pores, and micro-cracks of sprayed coatings, the
electrolyte quickly reached to the substrate and caused corrosion at the interface.
However, for laser melted samples in certain laser parameters, the surface after one
week of immersion was still free from any corrosion products. For some laser
parameters the electrolyte can reach the substrate through the interconnected pores.
It has been supposed that the reason of these pores is atmospheric gases which
dissolved in melting pool during laser treatment, and at the high speed laser
scanning the air bubbles do not have time to escape before solidification. On the
other hand low scanning speed could cause high dilution from the substrate,
therefore, appropriate processing parameters should be chosen. In the polarisation
test they observed improvement in corrosion resistance after laser treatment as
shown in figure 2.48.
Figure 2.48 Polarisation curves of laser melting and HVOF sprayed Inconel 625
coatings [10].
The same researchers in another paper [11] studied laser melting of high chromium
(53.5%) nickel-chromium HVOF coatings to improve corrosion behaviour. They
conclude that the corrosion behaviour of the coating can be improved by laser
melting, only if the appropriate laser parameters have been chosen. Parameters
which create high energy densities cause high iron dilution which decreases pitting
99
corrosion resistance, and high cooling rates should be avoided by using low
traverse speed because high chromium alloys are sensitive to cracking. The
immersion test showed very positive results, after one week of immersion test in
3.5% NaCl solution. The HVOF sample showed corrosion at the interface whereas
the laser melted coating was unaffected (figure 2.49).
Figure 2.49 optical micrograph of (a) HVOF sprayed and (b) laser remelted high
chromium nickel-chromium coating after one week immersion test in 3.5 wt.% NaCl
[11].
Suutala et al. [62] reported producing coatings by a laser-assisted spraying

process; also called laser hybrid spraying, where thermal spraying and laser melting
processes were combined to get denser coatings of different Ni-base materials on
low carbon steel substrate. Laser-hybrid Inconel 625 coatings showed poor
corrosion behaviour, as a result of cracks and high iron dilution from the substrate.
Furthermore, they reported that the Nd:YAG laser is not ideal for real applications
due to the inhomogenity in its power intensity in beam profile. Corrosion
properties in 3.5% NaCl solution of pure Inconel 625 HVOF coating, and Inconel
625 with WC as MMC HVOF coating on 316 L steel substrate has been studied
before and after HPDL laser remelting by Liu et al. [12]. The results showed that
laser treatments improved the corrosion resistance due to a reduction of
compositional gradient between the WC and the matrix metallic, and also due to
elimination of the discrete splat-structure and micro-crevices. Moreover, they
reported that 22.3% of Fe caused by dilution within the treated surface layer did not
affect significantly the corrosion behaviour. Recently Ahmed et al. [130] studied
the corrosion properties in 0.5 M H2SO4 solution of Inconel 625 as a bulk material
and HVOF sprayed coating before and after HPDL remelting. They concluded that
the difference between bulk and HVOF sprayed coating is due to galvanic
100
corrosion between Cr-depleted in resolidified regions and non-melted material with

the original Cr in the coating. Furthermore, the non-interconnected porosity has a
negative effect on the corrosion behaviour of the as sprayed coating. Laser
treatment largely reduced the difference between the corrosion behaviour of HVOF
as sprayed and bulk material by elimination of both porosity and regions of
material depleted in Cr.
2.5.6 Effect of laser surface treatment on hardness and wear resistance

of HVOF Coatings
Laser treatment of HVOF sprayed coatings has been performed by some
researchers in an attempt to improve their hardness and wear resistance. This
section contains a review of this work. Micro-scale abrasive wear behaviour of
HVOF sprayed and laser remelted WC-12Co HVOF coatings has been studied by
Chen et al. [13]. They found that the wear resistance was decreased by laser
remelting, due to reducing the carbide size and fracture of carbide during laser
treatment. Zhang et al. [128] studied the effect of laser heating on the hardness of
WC-CoCr HVOF sprayed coating. The results showed that the average value of the
microhardness of the coating increased after laser heating from 1161.7 Hv to
1579.8 Hv (figure 2.50). Furthermore, the microhardness is increased with
decreased porosity of the coating.
Figure 2.50 Microhardness of cross-sections of HVOF WC-CoCr coatings before and

after laser treatment [128]
The same researchers recently studied the effect of laser heating on tribological
performance of HVOF sprayed WC-24%Cr3C2-6%Ni coating [129]. They found
101
after laser heating there was a reduction in roughness level, and an improvment in
hardness. Moreover, remarkably reduction of wear rate and friction coefficient has
been noted (figure 2.51).
Figure 2.51 Friction coefficient and wear rate of the coatings [129]
They proposed the following wear mechanism; for the HVOF sprayed coating, the
wear started by severe deformation of Cr3C2 and Ni phases (matrix) between WC
particles. These deformed matrix phases then extruded, and microcracking and/or
pull-out of WC particles when there is no support of WC particles from the matrix.
These processes produce wear debris, and that caused more damage on both sides
as a third-body abrasive. However, they noted laser heating improved wear rate by
densifying the coating as a result of compressive thermal stress, and that is useful
to form denser tribofilm and enhance the cohesion between the matrix and WC
particles. Moreover, they reported that the thin oxide film which was created during
the test has a significant influence on adhesive wear, and for laser treated surface,
the wide area of oxides helps to reduce roughness, and increase the lubrication of
sliding surface, and that led to a decrease in friction coefficient during the wear test
[129].
Morimoto et al. [131] found that laser melting has improved both hardness and
wear resistance of Cr3C2-NiCr cermet coatings. Furthermore, the laser melting
improves the solid particle erosion resistance for this cermet coating by twice the
amount. Liu et al. [12] has been studied the effect of laser remelting on the
mechanical properties of Inconel 625 and Inconel 625 with WC as MMC HVOF
102
sprayed on 316L steel substrate. They observed that wear resistance increase by
increasing the percentage of WC in the coating material. They explained the
increase of wear resistance by elimination of the discrete splats and porosity.
Furthermore, laser melting creates faceted dendritic WC phases, and increases the
bonding between WC particles and the surrounding matrix. However, wear
resistance reduced as a result of fully melted WC particle.
103
Chapter 3 Experimental Procedures
3.1 Introduction
This chapter describes the materials (i.e. powders and coatings), the laser and the
laser operating conditions applied in the project. Examination and assessment of
the coating microstructures, in terms of surface morphology, porosity, cracks,
chemical composition, phase constituents, was carried out using scanning electron
microscopy (SEM)/energy-dispersive x-ray spectroscopy (EDX), electron probe
micro-analysis (EPMA), optical interferometry, and x-ray diffraction (XRD).
Images processing and analysis was performed to establish the extent of the
coatings’ porosity. The corrosion performances of the coatings both before and
after laser treatment were evaluated using electrochemical tests and immersion
tests. The electrochemical tests included anodic polarisation and Electrochemical
Impedance Spectroscopy (EIS) in 0.5M H2SO4 solution. The immersion test was
carried out using 3M H2SO4 solution. The corrosion morphology of coatings was
observed using Scanning Electron Microscope (SEM) and solution after the tests
was analysed using Inductivity Coupled Plasma-optical emission spectrometer
(ICP-OES) to understand the corrosion mechanisms. Wear resistance of the
coatings were also conducted using pin-on-disk, along with the Vickers hardness
test
3.2 Materials
Powders
The feedstock powders were produced by an agglomeration method. The four types
of powders used are:
Tribaloy 800 (T800) (29 wt. %Mo, 18 wt. %Cr, and 3.5 wt. %Si and Co based)
104
CHAPTER 3 EXPERIMENTAL PROCEDURES
T800+21wt.%WC(tungstencarbide)
T800 + 43 wt.% WC
T800 + 68 wt.% WC
Coatings
All the coatings were applied onto 316L stainless steel substrate using the HVOF
technique. The dimensions of the samples were (10 mm thickness × 20 mm × 15
mm). The coated samples were supplied by Bodycote Metallurgical Coatings
Limited; UK using a JP5000 gun, with liquid kerosene as the fuel source. The
coatings’ thicknesses were ~ 250 µm for T800 coating, ~ 230 µm for T800+21WC,
~ 220 µm for T800+43WC and ~ 165 µm for T800+68WC.
3.2.1 Specimen preparation for laser treatment

Before laser processing, each sample was cut to the size of 20 mm × 15 mm × 10
mm (figure 3.1) using Accutom-5 (Struers) and Brillant 250 H machine with
coolant.
Figure 3.1 Schematic diagram of cutting process
3.3 Laser processing

3.3.1 Laser System
A high-powered diode Laser (HPDL) generated by a Laserline Diode Laser 150-
1500 has been used for laser processing. This HPDL consists of a compact laser
beam source (laser head), a mobile power supply unit, and a laser cooling. All the
105
operating and monitoring functions are on the control panel. A diode laser bar, on
which a number of separate emitters of the size of 0.5 × 3 µm2 are aligned, is
mounted on a dissipater. The power generated by this single diode laser is 40 – 50
W. These separate components are stacked on top of each other. This allows the
laser to increase the power per compact stack to several hundred Watts. The
rectangular laser spot measures 3.5 mm × 2.5 mm at focal position, with an output
power of up to 1500 W. It works in continuous-wave mode and pulsed mode with
wavelengths of 808 nm - 940 nm.
3.3.2 Laser processing setup

The laser processing setup is shown in figures 3.2 and 3.3. The laser head was
fixed, while the samples were clamped to a base which can be controlled (travelling
speed and position) by a PC. All the laser processes were carried out in an argon
gas environment to avoid/reduce oxidation caused during laser process in the
interaction zone. The samples were placed in metal box covered by a Perspex sheet
that allows penetration of the laser beam (figure 3.3). The box was purged with
argon gas with flow rate 10 l/min for 5 min before laser processing and was also
purged continuously during each process.
Figure 3.2 Laser processing setup
106
Figure 3.3 Laser treatment experiment
3.4 Material characterisation

3.4.1 Sample preparation
The HVOF samples before and after laser treatment were characterised to
investigate the chemical composition, microstructure, morphology and porosity.
The samples were sectioned, mounted, ground and polished. The mounting process
carried out by using a cold conductive resin in ratio 8:5 powder and liquid
respectively (see figure 3.4). The grinding was performed with abrasive SiC
grinding paper with increasing mesh number in the following order: 220, 230, 500,
800, 1000, 1200, and the polishing was performed on a rotating wheel covered by
polishing cloth using 6 m, 3 m and finished in 1 m diamond paste. The laser
treated samples (T800-WC) were etched to reveal the microstructure. The etching
solution used is Murakami’s reagent (10 g potassium ferricyanide + 10 g sodium
hydroxide +100 ml distilled water) [132]. The sample surface was dipped into the
etching solution for 1 min then removed and quickly rinsed with water to remove
all traces of the solution, and then rinsed with distilled water and dried by means of
cold air blower.
107
Figure 3.4 Cross-sectioned of SEM samples mounted using conducting resins
3.4.2 Scanning Electron Microscope (SEM/EDS)

Scanning electron microscopy (SEM) is an important tool for studying of surface
morphology and chemical composition. Two electron microscopes were used in
this project and each microscope is equipped with Energy Dispersive Spectroscopy
(EDS) to carry out the chemical analysis.
SEM Philips XL-30-FEG (Field Emission Gun) equipped with EDS and EBSD
(Electron Back-Scattered Diffraction) patterning analysis system EISS EVO-50
SEM
The resolution in SEM is close to the bonding distance of atoms, and that results in
useful information at high magnifications which reach up to 200000×. Moreover,
another feature of SEM is its large depth of field in the sample surface that
produces a three-dimensional appearance of an object. The main component parts
of SEM are illustrated in figure 3.5. The source of electrons can be a tungsten (W)
a filament, lanthanum hexaboride (LaB6) or Schottky emitter. The highest
resolution in images can be produced by a field emission electron gun.
108
Figure 3.5 Schematic of scanning electron microscope [133]
These electrons are focused using electron lenses to a beam with a range of
diameter between 1-1000 nm which affects the resolution, and then the focused
electrons are scanned across the sample by the deflecting coils. The cavity of
electrons tracks is under vacuum because electrons can be absorbed by air. The
electron beam spot size might be of the order of 7 nm from W or LaB6 filament
guns, whereas spot sizes in order 1 to 2 nm are produced by field emission guns.
There are two factors affecting the resolution: the minimum electron spot size that
can be focused on the sample, and how much current in the electron beam to
extract a clear measurable signal. These measured signals are the electrons which
are emitted by interaction between the incident focused electrons and sample
surface. There are two types of emitted electrons: (1) secondary electrons (SE)
produced from inelastic scattering, which have low energy (less than 10 eV). These
electrons are emitted from near-surface layers (which is about 50 Å) of the sample.
This operation mode provides images of surface morphology. (2) Backscattered
electrons (BSE) produced from elastic scattering have high energy, approaching the
energy of incident electrons. BSE mode provides image contrast as a function of
composition, where higher atomic number material appears brighter than low
atomic number. The secondary electrons which are created near to the surface can
109
escape to the vacuum; usually the escaping electrons are created within a small
depth less than 2 nm beneath the surface (figure 3.6). Therefore, the SE images are
representative of the surface structure and morphology of the sample. On the other
side, the backscattered electrons with kinetic energy have sufficient energy to
escape from the solid to the vacuum (figure 3.6), the distance in this case is of the
order of tens or hundreds of nanometres. Therefore, the BSE technique detect the
differences in atomic numbers on and below the surface sample [133, 134].
Figure 3.6 Schematic of electron beam interaction with material [135]
3.4.3 X-ray diffraction (XRD)

X-ray techniques are used to investigate the structure for crystals and chemical
composition of materials. When an X-ray beam with wavelength λ is incident on a
crystalline material at angle θ, the constructive interference (diffraction) occurs
only when the distance travelled by the X ray beam reflected from the material
(electrons) differs by an integer number n of wavelengths (nλ). In 1912 W. L.
Bragg observed important relation which is named Bragg’s Law:
n  2d sin (3.1)
Where: d is the distance between similar atomic successive planes in the material
(the interatomic spacing) measured in angstroms.  is the angle of diffraction. For
practical reasons, a diffractometer measures 2θ. λ is the wavelength of the incident
X-ray radiation (figure 3.7).
110
Figure 3.7 Waves reflected from successive planes of a crystal .
Based on this phenomena, a diffractometer can be used to obtain a diffraction

pattern for crystalline solid material, and by a diffraction pattern, one can identify
unknown phases, where the intensities of the individual patterns are proportional to
the concentrations of the phases present [136]. In this project, phase analysis were
undertaken to identify the phases for coating materials as a powder and HVOF
coatings before and after laser treatment. Powders were examined by Philips X-ray
diffraction machine with CuK radiation, and the applied voltage of 50 Kv with a
40 mA current. The range of 2θ was from 5 o to 85o with a step size 0.05 o and a step
time of 2 s.
HVOF coatings before and after laser treatment were examined by an X-ray
diffractometer (Philips x’pert) to identify the phases produced during HVOF
thermal spray and laser melting. The XRD for HVOF coatings before and after
laser treatment was performed with CuK radiation and the applied voltage was 45
Kv with a 40 mA current. The range of 2θ was from 5 o to 85o with a step size 0.05 o
and a step time of 30 s.
3.4.4 Surface profile

The MicroXAM is an optical interferometer using white light. The device measures
fields of view from microns to millimetres depending on the objective lens used. It
splits a beam of light, then reflecting it off both the sample and reference surface
111
(see figure 3.8). The lights then recombine and interference patterns are detected by
a high resolution camera. The information can be interpreted via a 3D
representation of the surface. By using computer software, it provides precise
surface measurements with advanced image processing, in terms of surface
roughness, surface area and texture of surface [137].
Figure 3.8 MicroXAM surface mapping microscope [137]
A MicroXAM profilometer was used to measure surface roughness of the HVOF

coatings before and after laser treatments. Additionally, Developed Interfacial Area
Ratio (Sdr) has been calculated. Sdr is the ratio of the increment of the interfacial
area of a surface over the measured area (flat) x-y plane. In this project, four
different areas (163 m × 124 m) for each sample were measured, and then the
average values for roughness and Sdr were calculated.
3.4.5 Porosity measurements

Pores within HVOF coatings before and after laser melting were observed and
captured using SEM. The pores were then characterised using Image Processing
and Analysis in Java (ImageJ 1.43u) software developed by National Institute of
Health, USA.
112
3.4.6 Electron probe micro-analyser (EPMA)

A Cameca SX100 EPMA has been used for quantitative precise microchemical
analysis. This technique is based on wavelength dispersive X-ray spectroscopy
(WDS). Unlike EDS, the specific X-rays in WDS, instead of using solid state
detectors collects and counts all of the emitted X-rays. WDS analysis results in a
spectral resolution and sensitivity which is an order of magnitude better than EDS
analysis. In comparison to EDS, WDS offers quantitative analysis, especially for
light elements. It also provides better resolution of overlapping X-rays peaks for
element identification and quantification.
3.5 Corrosion tests

Corrosion behaviour of HVOF thermal spray coatings before and after laser
treatment has been studied by immersion tests and by using electrochemical
methods. The results from both tests are compared to determine the effects of laser
surface treatment on corrosion behaviour.
3.5.1 Immersion test

Immersion tests were performed in 3M H2SO4 at pH ~ 1.27 at room temperature
for different periods of time, including 24, 48, 72, 96 and 168 hours. The test was
performed for all the HVOF coatings and for selective samples after laser
treatment. The HVOF samples were washed in acetone using an ultrasonic bath and
then dried. In order to make around 1 cm2 of the surface area exposed to the H2SO4
solution, the rest of the area was masked by lacquer then by wax to ensure good
insulation as shown in figure 3.9. Each specimen was placed in a beaker containing
500 ml of H2SO4. During the test, the level of the solution was monitored, and
distilled water was added to replenish the evaporated solution as required.
113
Figure 3.9 Schematic diagram showing sample prepared for the immersion test
After the test the specimens were washed in distilled water and then dried. For
SEM observation, the specimens were sectioned, mounted in conductive resin, and
then ground and polished by diamond paste up to 1 m.
3.5.1.1 Chemical analysis

Inductivity Coupled Plasma-optical emission spectrometer (ICP-OES) technique
has been used to analyse the H2SO4 solution after 7 days of immersion testing for
T800+43WC HVOF coating before and after laser treatment. The instrument used
in this analysis is Perkin Elmer Optima 3300DV by Intertek ASG.
3.5.2 Sample preparation for polarisation and EIS tests

Samples to be tested had copper wire welded to their sides by spark welding
machine, to ensure good electric connection between the sample and the working
electrode. The samples were cleaned with ethanol and dried before applying
lacquer 45. By using a small brush, the sample was covered by lacquer 45, except
for an area of ~ 1 cm2 left exposed. Samples were kept in air to dry for about 3
hours, and then a subsequent layer was added to ensure better insulation. The
copper wire was covered with plastic coating and exposed to hot air until the plastic
adhered to the copper wire, such that there were no air gaps in order to avoid any
contact between the solution and the wire (figure 3.10)
114
Figure 3.10 Sample prepared for polarisation or EIS test
3.5.3 Polarisation
The polarisation test was used to study the propensity of the HVOF to corrode both
before and after laser treatment. This process has many advantages, for example
only a few minutes or hours are required to perform a test, whereas the
conventional methods such as weight loss measurements require days or more [29].
A ACM (Gill AC) potentiostat was used to apply a potential on a test sample to a
selected value with respect to a reference electrode. The ACM instrument is
computer-controlled, and the electrolyte solution is 0.5 M of H2SO4 solution at pH
~ 1.57. The solution was prepared by diluting the as-received 18 M sulphuric acid
to obtain one litre (0.5 M concentration) of sulphuric acid, by using the dilution
equation:
One litre (0.5M) of sulphuric acid solution was prepared by 27.7 ml of 18 M

concentrated sulphuric acid.
The technique that was used in this test was cyclic polarisation, and before this test
voltage and current versus time plots were produced for 1-hour to ascertain the
open circuit potential (OCP) to stabilise the experiment. As shown in figures 3.12
and 3.13 the sweeping rate was 0.25 mV/s, and the scanned potential range was -
500 mV to +1500 mV. The complete electrochemical cell (figure 3.11) contains the
test sample that is usually referred to as the working electrode, and the reference
115
electrode has constant electrochemical potential, and it is used as a reference point

from which to measure the potential of a test sample. The reference electrode that
was used in this test was a saturated calomel electrode (SCE). The other electrode
used in the electrochemical cell is the auxiliary electrode (counter electrode), which
is used to supply the required current and controlling the potential of the working
electrode, where its main function is to ensure that current does not pass through
the reference electrode.
Figure 3.11 A schematic of experimental setup used in polarisation test
In general, potentials measured in electrochemical tests represent a value of the

driving force for the corrosion reaction to proceed, and the current provides a
measure of rate at which reactions take place. The operation method of the
potentiostat is that the potential difference between the reference and the sample is
kept constant and equal to Vc, and the instrument applies a current between the
auxiliary electrode and the sample to fix the desired working electrode potential.
The cell voltage or the driving voltage is the voltage difference between the
auxiliary electrode and working electrode [138].
116
Figure 3.12 Setup of open circuit potential
Figure 3.13 Setup of polarisation experiment
3.5.4 Electrochemical Impedance Spectroscopy (EIS) Test

The EIS test has been performed using ACM (Gill AC) potentiostat. The
experiments were performed at open circuit potential. The parameters for this test
as shown in figure 3.14 were, a frequency range of 30000 Hz to 0.005 Hz, with an
amplitude of 10 mV, and reading per test of 50. These experiments were carried out
every 1, 3, 6, 12, 24, 48 hours accordingly. A 0.5M H2SO4 solution was used.
117
Figure 3.14 Setup of AC impedance experiment
3.6 Wear test

3.6.1 Pin-On-Disc tester
Pin-on-disc tests are used for evaluating sliding wear behaviour. The basic
configuration of this test is shown in figure 3.15. It consists of a pin in contact with
a rotating disc. Either the pin or the disc can be the test piece of interest. The
contact surface of the pin could be spherical, or flat. These experiments were
conducted in accordance with ASTM G99, which specifies the use of a rounded
pin, but does not specify specific values for the parameters, and therefore these are
selected by the users to suit the application. The other variables of interest are the
load, speed, materials, and size and shape for the pin [48].
Figure 3.15 Diagram of a pin on disc configuration wear test
118
The wear rate here has been measured using the pin on disc principle. The wear
machine was provided by Teer Coatings Limited. The device consists of a  5 mm
diameter WC-Co ball as a pin; the wear pin creates a circular wear track on the
sample surface. As a result of sliding motion of the sample under the wear pin, a
frictional force is generated and detected by the load cell, which is recorded by the
computer wear machine. The load can be varied by adjusting the amount of weight
been hanging at the end of the loading beam.
The wear pin creates a circular wear track which can be controlled by offsetting the
pin relative to the sample’s centre of rotation. Loads can be changed from 10 N to
100 N, and the rotational speed and time of the test can be pre-selected. These input
values are used to calculate the wear rate.
3.6.2 Wear test conditions
The diameter of the wear track for all samples was 8 mm. The speed of rotation for
all samples was 500 rpm. The load used for all samples was 40 N, and the testing
time was varied from sample to sample, because of the different coatings that had
been applied in each case (refer to table 3.2).
Table 3.2 Conditions of wear test
Sample Test time (min.)
T800 (HVOF & Laser) 20
T800 + 21 WC (HVOF & Laser) 50
T800 + 43 WC (HVOF & Laser) 120
T800 + 68 WC (HVOF & Laser) 120
Parameters for all samples (Load= 40 N, Rotation speed=

500 rpm, diameter track= 8 mm)
The temperature and relative humidity were at 22oC and 40%, respectively. After
the wear test is complete, the track dimensions (width (w) and depth (t)), were
measured using an optical microscope (Polyvar MET). The width was measured
119
directly by the optical microscope, but to measure the depth of wear track, every
wear scar was cut diagonally and then the cross section was ground and polished,
for measurement using SEM. The worn volume and the wear rate were calculated
as in Equations 3.3 and 3.4.
Where: Number of revolutions = r.p.m. × testing time in minutes
w is track width,
t is wear depth, and
d is the diameter of the track (see figure 16).
Figure 3.16 Parameters of wear track (a) track diameter and track width, (b) track
depth
3.7 Microhardness measurement

To measure the microhardness of the cross sections for both HVOF and laser
treated samples, the preparation of the samples were prepared as follows. The
120
samples for HVOF and after laser treated were cut along the plane passing
perpendicular to the sample surface. The cut was made using an automatic cutting
machine (Struers Accutom-5). The specimens were mounted and ground and
polished in the conventional way. After polishing the HVOF coating and the laser
treated pool sections can be seen by the naked eye. Profiles of microhardness along
the coating depth and laser treated depth were obtained using a Buehler tester,
using a load of 100 g for all measurements.
121
Chapter 4 Optimisation of Laser Operating
Conditions
4.1 Introduction
This chapter presents the investigation of the influence of laser operating
conditions on melting of various T800, T800+21WC, T800+43WC and
T800+68WC HVOF coatings. It is aimed to establish laser operation windows to
achieve crack-free, porosity-free HVOF coating melting layers.
4.2 Definition of the terms

The laser operating conditions were determined by appropriately selecting laser
power and scanning speed conditions that allow:
A suitable melt depth within the HVOF coating to achieve partial melting of the
HVOF coating (melt depth < HVOF coating thickness); or full melting of the
HVOF coating (melt depth  HVOF coating thickness) as shown in the schematic
in figures 4.1 and 4.5.
Melted layers to be free from porosity and cracks.
Minimal dilution in the fully melted HVOF coating.
Control of the melting of the hard carbide (WC) inside the melting pool, see figure
4.9
122
(a) Partial-melting of HVOF coating

The HVOF coating in this state was partially melted as shown in the schematic in
figure 4.1. The depth of laser melted layer < coating thickness. In this case, the
interface between the coating and substrate is not affected (mechanical bonding).
Figure 4.1 Schematic shown partially laser melting of HVOF coating
Figure 4.2 shows surface views of a laser melted T800+21WC HVOF coating. The
surface became smoother after laser treatment, and no cracks or porosity were
observed on the surface under this magnification. From the observing of the melted
surface, it is clear that a small amount of melting of the HVOF coating occurred.
Figure 4.2 Overlapping tracks of laser treated T800+21WC HVOF coating showing
surface of partially melting of HVOF coating
Figures 4.3 and 4.4 show partially melted HVOF coating for T800 and
T800+21WC respectively. Table 4.2 shows the laser parameters used in each case.
123
Figure 4.3 SEM cross-section image of HVOF T800 (a) partially laser melting T800
HVOF coating (b) high magnification of melted T800 HVOF layer
Figure 4.4 SEM cross-section image of HVOF T800+21WC (a) partial laser melting of
T800+21WC HVOF coating (b) high magnification of melted T800+21WC HVOF
layer
(b) Full-melting of HVOF coating

Where the HVOF coating melted completely, the melting depth ≥ the coating
thickness. The full melting of the HVOF coating could be with very small dilution
if the interface between the coating and the substrate has been melted or without
dilution if there is no melting of the substrate or the interface between the HVOF
coating and the substrate, as demonstrated in the schematic in figure 4.5 (a). Also,
full melting could be with dilution by the melting of the interface between the
HVOF coating and substrate and some of the substrate. In this case the type of
bonding between the coating and interface will change from mechanical bonding to
fusion bonding. The full melting eliminates the defects in the interface between the
coating and substrate as shown in the schematic in figure 4.5 (b), and figures 4.7,
4.8.
124
(a) (b)
Figure 4.5 Schematic shown fully laser melting of HVOF coating (a) melting of
HVOF coating only (no dilution) (b) melting of substrate (dilution)
Figure 4.6 shows extensive melting of the HVOF coating. No oxidation has been
observed on the surface after laser melting due to Ar gas shielding during the laser
melting process.
Figure 4.6 Overlapping tracks of the laser-treated the T800+43WC HVOF coating,
showing surface of large melting of HVOF+43WC coating
In this research full melted of HVOF coating with small dilution was used in
T800+43WC and T800+68WC HVOF coatings.
125
Figure 4.7 SEM cross-section image of HVOF coating T800+43WC fully laser melted
(a) without dilution (b) with dilution
Figure 4.8 SEM cross-section image of HVOF coating T800+68WC fully laser melted
(a) without dilution (b) with dilution
(c) Partial-melting of WC
The results of the partial melting of the WC particles by the laser, is shown in the
schematic in figure 4.9.
Figure 4.9 Schematic illustration of partially and full melting of WC
Figure 4.10 shows the cross-section of the as received T800+21WC HVOF coating.
The carbide particles have a bright white colour and are polygonal in shape. Due to
the lower melting point of T800 ~ 1352 oC [139] compared to the melting point of
126
WC ~ 2785 oC [140], under some conditions the T800 can be melted while the WC
particles remain unmelted or partially melted. When the melt pool temperature
reaches around the melting point of WC (T~Tm,WC), the T800 can be melted fully
and WC melted partially. The melting of WC starts from the particle edges. See
figures 4.11 to 4.13.
Figure 4.10 SEM cross-section image of HVOF T800+21WC (a) HVOF coating (b)
high magnification of the coating
Figure 4.11 SEM cross-section image of HVOF T800+21WC (a) partially laser melted
WC near the surface (b) partially melted WC particles and fully melted T800
127
WC (b) partially melted WC particles and fully melted T800
WC (b) partially melted WC particles and fully melted T800
To obtain optimum operating conditions for the laser treatment, various different
laser conditions have been used by changing scanning speed and power (see table
4.1). Inappropriate laser parameters in processing can lead to defects in laser
melted zone such as porosity, cracks and high dilution from the substrate, which in
turn reduce the beneficial properties and the function of the HVOF coating.
4.3 Formation of porosity within laser melted surface

Porosity is the presence of gas pores or pockets in the melted zone. It is caused by
the gases in the melted pool which are released during cooling due to reduced
solubility in solids. This is caused mostly when the gases have amounts more than
their solubility limit in the solid [141], and when there is not sufficient time for air
bubbles to escape from melted pool. The source of the gas could be from porosity
present in the HVOF coating or from the reaction of metallic oxides with carbon to
form CO and CO2 [142, 143]. In this work, as shown in figure 4.14, there was a
128
substantial amount of large diameter porosity formed within the laser melted layer
of T800+43WC and T800+68WC HVOF coating. When laser treatment was
carried out using relatively high scanning speed (figure 4.14 (a)), vertical cracks
were observed in the melting layer as well as large diameter porosity near to the
surface. In lower scan speed (20 mm/s) the melting depth was higher, however still
there was large diameter porosity (figure 4.14 (b)). The formation of porosity might
be due to the faster cooling rates resulting from these high scanning speeds
(interaction time is very low), which results in less time for the release of the gases
within the HVOF coatings. Consequently, these become trapped in the melt zone
instead. Furthermore, the dissolved carbides have an effect of hindering the escape
of bubbles to the surface of the molten pool [144]. Thus, the air bubbles are
captured as a result of dissolved carbides in T800+43WC and T800+68WC.
However, at the same power (800W), and with reducing the scanning speed to
given level (high interaction time), there would be sufficient time to reduce the
porosity. Figure 4.15 shows a low porosity in the laser-melted layer of
T800+43WC and T800+68WC HVOF coating after using low scanning speeds of 5
mm/s and 3 mm/s respectively at 800 W. In T800 HVOF and T800+21WC laser
treated, the porosity was lower, and it has occurred only in relatively high speed
scans (figure 4.16). The same conclusion has been reached in previous work by
Tuominen et al. [10]. The authors have studied the corrosion behaviour of HVOF
sprayed Inconel 625 by using a high power Nd:YAG laser. Their study showed that
the inappropriate laser parameters cause porosity in laser melted layer. Previous
work [145] has studied the effects of laser parameters, such as scanning speed on
the porosity of HVOF thermally sprayed WC-CrC-Ni coatings. The results of this
work suggested a decrease in porosity of the laser treated coating was a result of
the laser scanning speed reduction. Goswami et al. [146] studied laser surface
alloying chromium on mild steel and molybdenum on stainless steel surfaces, using
a Nd:YAG laser. This work has yielded a similar result with a higher scan speed
producing a higher cooling rate, with greater porosity.
129
Figure 4.14 porosity in laser treated area (a) porosity near the surface and a vertical
crack in T800+43WC HVOF laser-treated (800 W, 40 mm/sec) (b) porosity in
T800+68WC HVOF laser treated (800 W, 20 mm/sec)
Porosity can be prevented or reduced by proper selection of scanning speeds and

power density; very high scanning speeds should be avoided [10, 121]. In addition,
high power should be avoided to avoid a large melting depth and a large amount of
dilution from the substrate (as shown in figure 4.17).
Figure 4.15 low porosity in the laser treated area (a) T800+43WC HVOF, laser-
treated (800 W, 5 mm/s) (b) T800+68WC HVOF, laser treated (800 W, 3 mm/s)
130
Figure 4.16 porosity in the laser treated area (a) T800 HVOF, laser treated area (600
W, 20 mm/s) (b) T800+21WC HVOF, laser treated (800 W, 40 mm/s)
Figure 4.17 low porosity in the laser treated area (a) T800+43WC HVOF, laser
treated (550 W, 3 mm/s) (b) T800+68WC HVOF, laser treated (500 W, 3 mm/s)
4.4 Formation of cracks within laser melted surface

T800 has a large volume fraction (~ 60%) of a hard, intermetallic Laves phase in a
much softer matrix (figure 4.18). T800 is also hard, but has little capacity for
plastic flow and has low fracture strength due to the hard brittle nature of the Laves
phase [139, 147-149]. The laser parameters (scanning speed and power) were
optimized for each type of HVOF coating to minimise cracks within the treated
zone in the T800 HVOF coating, and to produce crack-free laser-melted layer for
T800+WC HVOF coatings. The T800 HVOF coating showed high sensitivity to
cracking, particularly in high scanning speed (figure 4.19(b)). T800 HVOF had
some vertical cracks after the application of a relatively low power and scan speed
(as shown in figure 4.19(a)). T800 and T800+21WC HVOF show higher sensitivity
to cracks than T800+43WC and T800+68WC HVOF. Additionally, it has been
131
observed that more cracks were produced by increasing the melt depth. The
sensitivity of T800 HVOF to cracking can be seen in figure 4.24. Figures 4.24 to
4.27 show that clearly T800 alloy has the narrowest range of laser permissible
operation window. This behaviour might because of high percentage of Laves
phase in these alloys.
Figure 4.18 SEM microstructure of the Laves phase in theT800 HVOF coating after
laser treatment
Figure 4.19 vertical crack in T800 HVOF laser treated (a) small crack at (600W, 5
mm/s) (b) big crack with high dilution at (800W, 10 mm/s)
It was found that the optimal laser parameters for T800 are a power of 500W and at
scanning speed of 3mm/s; however, these parameters sometimes could cause very
small cracks as can be seen in figure 4.20.
132
Figure 4.20 a small vertical crack in T800 HVOF laser treated with a partially-
melted coating (500W, 3 mm/s)
The other T800+WC HVOF coatings are less sensitive to cracks, in particular
T800+43WC and T800+86WC as a result of reduction of a brittle phase (Laves). It
can be observed in figures (21-23) that cracks in the treated zone in all HVOF
coatings increase with an increase in the scanning speed.
Figure 4.21 a vertical crack in a T800+21WC HVOF laser-treated surface (a) a small
crack at (800W, 5 mm/s) (b) a large crack and porosity at laser parameters (600W, 40
mm/s)
Figure 4.22 a vertical crack and porosity in a T800+43WC HVOF laser-treated

surface, with a partially-melted coating (800W, 80 mm/s)
133
Figure 4.23 a vertical crack and porosity in a T800+68WC HVOF laser-treated

surface with a partially-melted coating (800W, 20 mm/s)
The main factor responsible for cracking during the solidification phase is thermal
stresses. High thermal gradients and high scan speeds could cause higher thermal
stress as a result of the larger cooling and solidifying rate [150]. The stresses will
build up during the cooling stage, and if the thermal stress is higher than the
strength of the coating material, cracks will occur in the melted layer [151]. It is
reported [146, 152] that the misfit between the HVOF coating and the substrate
during the thermal expansion or thermal shrinkage in the melted pool could cause
residual stresses in the melted layer. The results in this research further
demonstrate that the integrity of the laser treated zone is largely dependent on laser
scan speed. In all HVOF coatings (except T800 which still contains small cracks), a
crack-free zone could be achieved at the lower scanning speed of ≤ 3 mm/s, and the
faster scanning speed the greater the number and the size of the cracks and pores
created. Accordingly, to decrease the number of cracks, slower scan speed has been
used, but concurrently, the laser power must be relatively low to avoid high melting
depth and consequently high dilution between the coating and substrate. The same
behaviour has been described by Pokhmurs’Ka [153] using a CO2 laser to treat
electric–arc spray Fe-Cr-B-Al thermal coatings. Also Tuominen et al. [154] have
studied laser-remelted nickel-chromium HVOF by a Nd-YAG laser. It has been
concluded that laser parameters which produce high specific energy should be
avoided; hence iron dilution from the substrate has a negative effect on the
corrosion properties of the coating. Additionally, it has been observed that high
scanning speeds should be avoided in laser remelting to avoid high solidification
rates, which cause more cracks in the melted layer.
134
4.5 Operating windows for laser treatment

The figures 4.24 to 4.27 show the variation of melt depth ratio (melt depth/coating
thickness) with scanning speed at various levels of laser powers. The melt depths
range from 30 m - 936 m. It is clear from the graphs, as expected, that the melt
depth for all samples are a function of the scanning speed of the laser. This is
where, high scanning speed result in low melt depths due to a short interaction time
between the laser and the surface, and the melt depths increased by decreasing the
scanning speed.
3.0
T800 300 W
350 W
2.5
400 W
600 W
Ratio (melt depth/coating thickness)
800 W
2.0 1000 W
No cracks- No porosity area
1.5
1.0
Cracks
0.5
Porosity
0.0
0 10 20 30 40 50 60 70 80 90 100 110
Scanning speed (mm/sec)
scanning speed for different laser powers for a T800 HVOF coating
135
2.0 300 W
1.8 T800 + 21 WC 350 W
400 W

1.6 600 W
800 W
1.4 1000 W
1.2
1.0
No cracks- No porosity area
0.8
0.6
0.4
0.2
0.0
0 10 20 30 40 50 60 70 80 90 100 110
scanning speed for different laser powers for a T800+21WC HVOF coating
2.2
2.0
T800 + 43 WC 350 w
400 w
600 w
1.8
800 w
1.6 1000 w
1.4 No cracks- No porosity area
1.2
1.0
0.8
0.6
0.4
0.2
0.0
0 10 20 30 40 50 60 70 80 90
136
The previous figures illustrate, as expected, for that a fixed scanning speed, higher
laser powers result in large melt depths. Furthermore, it is have been demonstrated
that the narrowest operating window was for the T800 HVOF coating; this is may
be due to a high percentage of very brittle Laves phase present in this coating, as
discussed in the previous section.
137
Table 4.1 A laser operating conditions used for various HVOF coating with
observations
T800
Track no. Power (W) Scanning speed (mm/s) Surface and cross-section observations
Track 1 300 3 Low-melting, no cracks, no porosity
Track 2 300 5 Low-melting, small cracks, no porosity
Track 4 300 10 No-melting
Track 5 350 3 Partially-melting, one crack, no porosity
Track 8 350 10 Low-melting, cracks, no porosity
Track 9 350 20 No-melting
Track 12-1 500 2 Fully -melting, one crack, no porosity
Track 12-2 500 3 Partially-melting, no cracks, no porosity
Track 12-3 500 4 Partially-melting, no cracks, no porosity
Track 13 600 3 Fully -melting, no cracks, no porosity
Track 14 600 5 Fully -melting, cracks, no porosity
Track 15 600 8 Partially-melting, cracks, no porosity
Track 16 600 10 Partially-melting, many cracks, no porosity
Track 18 600 40 Low-melting, many cracks, no porosity
Track 19 600 80 Low-melting, many cracks, no porosity
Track 20 800 3 Fully -melting, no cracks, no porosity
Track 25 1000 40 Fully-melting, cracks, no porosity
138
T800 + 21WC
Track no. Power (W) Scanning speed (mm/s) Surface and cross-section observation
Track 5 300 20 No melting
Track 6 350 3 partially-melting, no cracks, no porosity
Track 9 350 20 No melting
Track 11 400 5 partially-melting, small cracks, no porosity
Track 14-1 400 1 partially-melting, no cracks, no porosity
Track 14-2 450 1 Fully melting, small cracks, no porosity
Track 14-3 450 2 partially-melting, no cracks, no porosity
Track 15 600 3 Oxidation problem in the sample
Track 16 600 10 partially-melting, small cracks, no porosity
Track 17 600 5 Fully melting, small cracks, no porosity
Track 19 600 3 (repeated) Fully melting, one crack, no porosity
Track 29 1000 10 Fully-melting, small cracks, no porosity
Track 31 1000 40 Oxidation problem in the sample
Track 34 1000 40 (repeated) Fully-melting, cracks, no porosity
139
T800 + 43WC
Track 1 300 3 Low-melting, no cracks, no porosity and low-
melting of WC
Track 6 400 3 Partially-melting, no cracks, no porosity and
partially melting of WC
Track 9-1 550 3 Fully-melting, no cracks, no porosity and
partially- melting of WC
Track 10 600 3 Fully-melting, no cracks, no porosity and
partially- melting of WC
Track 10- 650 3 Fully-melting, no cracks, no porosity and fully-
1 melting of WC
Track 11 600 5 Fully-melting, no cracks, no porosity and
partially-melting of WC
Track 12 600 8 Partially-melting, no cracks, no porosity
Track 15 800 3 Fully-melting, cracks, no porosity and fully-
melting of WC
Track 23 1000 8 Problem in laser operation
Track 24 1000 8 (repeated) Fully-melting, cracks, no porosity
140
T800 + 68WC
melting of WC
melting of WC
Track 6 400 3 Partially-melting, no cracks, no porosity and
Track 8-1 500 3 Fully-melting, no cracks, no porosity and
Track 8-2 600 2 Fully-melting, no cracks, no porosity and fully-
melting of WC
Track 9 600 3 Fully-melting, no cracks, no porosity
Track 10 600 5 Problem in Laser
Track 12 600 5 (repeated) Fully-melting, no cracks, no porosity
Track 18 800 10 (repeated) Partially-melting, cracks, porosity
Track 19 800 20 Low-melting, cracks, porosity
Track 27 1000 10 (repeated) Fully-melting, cracks, porosity
Track 28 1000 20 Partially-melting, cracks, porosity
Track 29 1000 10 (repeated) Fully-melting, cracks, porosity
Track 30 1000 20 (repeated) Partially-melting, cracks, porosity
Track 31 1000 40 Partially-melting, cracks, porosity
141
Table 4.2 summarises the laser operating conditions for the laser-treated coatings
that were selected to represent partially-melting, fully-melting without defects for
further characterisation and various tests in this project. For T800+43%WC and
T800+68%WC, the coatings were fully-melted and crack-free with low dilution.
For T800 and T800+21WC, the coatings were partially-melted and crack-free.
Table 4.2 Laser operating conditions and coating characteristics of the selected
coatings
Power Scanning Beam size

Coating Treated coating characteristics
(W) speed (mm/s) (mm × mm)
Partially melted HVOF, some cracks,
T800 500 3 3.5  2.5 (No dilution)
Partially melted HVOF, Partially
T800+21 WC
450 2 3.5  2.5 melted WC, Cracks free, (No dilution)
Fully melted HVOF, Partially melted
T800+43 WC
550 3 3.5  2.5 WC, Cracks free, (No dilution)
Fully melted HVOF, Partially melted
T800+68 WC
500 3 3.5  2.5 WC, Cracks free, (No dilution)
In conclusion, laser operating windows for various HVOF coatings have been
established, by formation of porosity-free and crack-free coatings in specific laser
operation parameters. The formation of cracks under some laser processing
conditions was due to thermal stresses. T800 coating was highly prone to cracks
due to the hard and brittle nature of the Laves phase. Furthermore, formation of
porosity under some laser processing conditions was due to trapped gas in the
melted zones that often occurred at high scanning velocities that provided less time
for gas to release. Different coating materials presented different optimised laser
conditions to produce laser melted layers free from defects, when the laser beam
spot size was fixed as 3.5 mm × 2.5 mm at the focal position.
142
4.6 Summary
 Laser operating windows for various HVOF coatings have been

established, indicating the optimised laser operating conditions for
formation of porosity-free and crack-free coatings. A melt depth of 100
m to 210 m for various HVOF coatings can be obtained by controlling
laser operating conditions. Low dilution of the full laser treated HVOF
coatings can be also achieved.
 Formation of cracks under some laser processing conditions was due to

thermal stresses. T800 coating was highly prone to cracks due to the hard
and brittle nature of the Laves phase.
 Formation of porosity under some laser processing conditions was due to

trapped gas in the melted zones that often occurred at high scanning
velocities that provided less time for the gas to release.
 Different coating materials presented different optimised laser conditions

to produce laser melted layers free from defects, when the laser beam
spot size was fixed as 3.5 mm  2.5 mm at the focal position.
 Due to the time limitation of the project, only the following laser
processing parameters were selected to produce laser-melted coatings
which were crack-free, porosity-free, and with or without low dilution.
These coatings were further characterised and evaluated in terms of
corrosion and wear performance:
 T800 (Partial melting of HVOF coating): 500 W, 3 mm/s.
 T800 + 21WC (Partial melting of HVOF coating): 450 W, 2 mm/s.
 T800 + 43WC (Full melting of HVOF coating): 550 W, 3 mm/s.
 T800 + 68WC (Full melting of HVOF coating); 500W, 3 mm/s.
143
Chapter 5 Materials Characterisation
5.1 Introduction
This chapter presents the materials characterisation of the HVOF coatings before
and after laser treatment, in terms of morphology, phases and elemental
distribution. Optical microscopy, scanning electron microscopy (SEM)/energy-
dispersive x-ray spectroscopy (EDX), electron probe micro-analysis (EPMA), X-
ray diffraction (XRD), atomic force microscopy (AFM), and white-light
interferometery have been applied for the above characterisation.
5.2 Powders
Various powders containing Tribaloy 800 (T800) and T800 with variable
percentages of WC have been used for the production of HVOF coatings.
5.2.1 Morphological observation

The T800 powder is almost spherical in shape, with a smooth surface, as shown in
Figure 5.1. The range of the powder size is from 10 to 40 m. SEM micrographs of
the T800 + 21WC powders are shown in Figure 5.2, presenting the porous nature
of an agglomerated powder. This morphology was formed during the powder
manufacturing process. It was believed [58] that such a porous nature promotes
more homogeneity of thermal sprayed coatings, because it provides better heat
distribution inside the powder particles during the spraying process. Figure 5.2 also
shows two different types of powders consisting of WC particles and T800,
respectively. One is smooth T800 powder particles while the other is porous WC
powder particles with binder. The difference makes them easy to distinguish.
144
CHAPTER 5 MATERIAL CHARACTERISATION
Figure 5.1 SEM morphology of T800 powder
Figure 5.2 SEM micrographs of the T800 + 21WC powder
145
Figure 5.3 illustrates the characteristic of an agglomerated T800 + 43WC and T800
+ 68WC powder mixtures. The size range of WC particles is within 15 – 50 m,
while the size range of T800 particles is within 10 – 40 m.
Figure 5.3 SEM micrographs of (a) T800 + 43WC (b) T800 + 68WC powders
146
T800 T800
WC
(a) (b)
WC
T800
WC
(d) T800
(c)
Figure 5.4 Mapping images: (a) T800 powder (b) T800+21WC powder (c)
T800+43WC powder (d) T800+68WC powder
5.2.2 XRD analysis

Figure 5.5 illustrates the X-ray diffraction pattern of the T800 feedstock powder.
The detected phases are Co 3Mo2Si, Co2MoCr and Co. The Co 3Mo2Si phase
represents Laves phase, in which the Si replaced the Cr in its original structure of
Laves phase of Co 2MoCr. Furthermore, the Co phase in fcc form represents the
solid-solution-of-cobalt-[155].
147
5000
T800
powder 1 1 ---- Co
4000 2 ---- Co3Mo2Si
3 ---- Co2MoCr
Intensity (arb)
3000
2000
3
1000 3 3
13
2 3 2
2 2 22 32 2
2
0
0 20 40 60 80 100
Angle
Figure 5.5 XRD pattern of the T800 stock powder
Figures 5.6 to 5.8 show X-ray diffraction patterns of T800+21WC, T800+43WC,

and T800+68WC stock powders respectively. The analysis confirmed the existence
of four phases in all the powders. T800+21WC and T800+43WC have almost the
same phases which are WC, Co, W2Co4C and Co3Mo2Si. Figures 5.6 and 5.7 show
that the WC phase has higher peak intensity in T800+43WC compared with
T800+21WC, reflecting the percentage difference of WC in these powders.
6000
T800+21WC 1 1 ----- WC
5000
powder 2 ----- Co
1 2 3 ----- W2 Co4 C
4 ----- Co3 Mo2 Si
4000
Intensity (arb)
3000
1
2000 1 1
3 1
1
1
1000 2 3
2 1
3 4 3 3 4
0
0 20 40 60 80 100
Angle(2)
Figure 5.6 XRD pattern of the T800+21WC stock powder
148
10000
T800+43WC 1 ---- WC
1
powder 2 ---- Co
8000 1 3 ---- W2 Co4 C
4 ---- Co3 Mo2 Si
Intensity (arab)
6000
2
4000
1
1
1 1 1
3
2000
1
3 3
2 1 2
43 3 41 4
33 3
0
0 20 40 60 80 100
Angle (2)
Due to a low volume fraction of a hard, intermetallic laves phase (Co 3Mo2Si), this
phase was not detected in the X-ray diffraction pattern of the T800+68WC powder
as shown in figure 5.8. However, the other three phases of WC, Co, W2Co4C can
be seen.
18000
T800+68WC 1 1 ---- WC
16000 powder 2 ---- Co
1
14000 3 ---- W2 Co4 C
12000
Intensity (arb)
10000
8000
6000 1 1
1 1
1
4000
1
2000 32 1
3 32 3 3 3
0
0 20 40 60 80 100
Angle (2)
Furthermore, the intensity of Co peaks become lower, while the intensity of WC

peaks becomes higher, as a result of increased percentage of WC.
149
5.3 As-sprayed coating

The HVOF coatings are deposited by melting, partially melting and unmelting of
powder particles which are sprayed at high velocity on the substrate (316L stainless
steel), using a JP5000 gun. Lamellar microstructure is built-up by subsequent
impact and rapid solidification of those molten or semi-molten particles. As a result
of the process, pores are inevitably formed and oxide inclusions are probably
present in typical HVOF coatings [156]. Characteristics of the coatings in terms of
density and porosity strongly depend on coating material and spraying parameters
[157, 158].
5.3.1 Surface views of HVOF coatings

Figures 5.9 to 5.12 illustrate the surface view of the HVOF coatings with various
WC contents. Figure 5.9 (a) shows the presence of micro-cracks on the T800
coating surface. In addition, there are pores and gaps between powder particles, and
the coating surface displays high roughness.
Figure 5.9 SEM micrographs of surface view of T800 HVOF coatings with (a) low
magnification (b) high magnification
150
Figure 5.10 SEM micrographs of surface view of T800+21WC HVOF coatings with
(a) low magnification and (b) high magnification
In order to investigate the surface morphology in more detail, the microXam

mapping was used to obtain (2D, 3D) profiles of the coating surfaces. In addition,
based on the profiles, the surface roughness (Ra) and surface area ratio (Sdr) are
calculated. The surface area ratio (Sdr) is the ratio of the surface (taking the z
151
height into account) and the area of the flat x, y plane [159]. Figures 5.13 (a) and
(b) show 2D and 3D profiles for different areas of the T800 HVOF surface. It
shows that different areas of the same sample present significantly different surface
profiles indicating the high inhomogeneity of the T800 HVOF surface. Table 5.1
displays the values of average roughness (Ra) and the average of surface area ratio
(Sdr) based on four measurements. Similarly, 2D and 3D surface profiles of the
other three coatings with WC are shown in Figures 5.14 – 5.16. The values of
surface roughness and surface area ratios are presented in Table 5.1. In addition,
the comparison of surface roughness and surface area ratios of various HVOF
coatings are presented in Figures 5.17 and 5.18. The results show that the surface
roughness and surface area ratios of T800+21WC coating are similar to those of
T800 coating. However, the increase in the content of WC results in less rough
coatings. The T800+68WC shows the lowest roughness of Ra ~ 4.49 µm, and the
lowest surface area ratio of Sdr ~ 153%.
152
Figure 5.13 Surface profile (a) 2D and (b) 3D profiles of four different areas on T800
HVOF surface
153
Figure 5.14 Surface profile (a) 2D and (b) 3D profiles of four different areas on
T800+21WC HVOF surface
154
155
156
Table 5.1 Surface roughness and surface area ratios of various HVOF coatings.
HVOF coating Average roughness Ra, µm Average surface area ratio Sdr, %
T800 5.05 212
T800+21WC 5.47 223
T800+43WC 4.94 212
T800+68WC 4.49 153
5
Ra (m)
3
T800 T800+21WC T800+43WC T800+68WC
Figure 5.17 Comparison of surface roughness of various HVOF coatings
400
300
Sdr %
200
100
0
T800 T800+21WC T800+43WC T800+68WC
Figure 5.18 Comparison of surface area ratios of various HVOF coatings
157
5.3.2 Cross sectional view of HVOF coatings

Figure 5.19 shows a typical cross sectional view of T800 HVOF coating, indicating
the presence of porosity. The details of the coating microstructure can be seen in
figure 5.20. It shows that the T800 HVOF coating can be characterised as a
lamellar structure with splats and distinct splat boundaries. The interface between
the coating and substrate is mechanical bonding with some defects like pores
appearing at the interface. The coating structure contains Laves phase (white phase)
surrounded by the cobalt solid solution (gray phase).
Figure 5.19 SEM micrograph of cross section of T800 HVOF coating
Figure 5.20 SEM micrographs of T800 HVOF coating at the interface between the
coating and substrate (a) and typical microstructure (b)
158
Table 5.2 presents the EDX chemical analysis of the two areas of S1 and S2, as
marked in Figure 5.21, of the T800 HVOF coating. It appears that the region close
to the surface contains higher oxygen than the inner region.
Figure 5.21 SEM image of cross-section of T800 HVOF
Table 5.2 EDX chemical analysis of T800 HVOF coating, wt.%.
Element O Si Cr Fe Co Mo
Area S1 1.17 3.62 17.52 0.19 48.80 28.63
Area S2 0.12 3.55 17.92 0.17 48.73 29.04
Average 0.65 3.59 17.72 0.18 48.77 28.84
SEM micrograph with higher magnification of T800 HVOF coating is shown in

figure 5.22, further indicating the presence of splats and splats boundaries that are
of importance to its corrosion behaviour to be discussed in Chapter 6.
159
Figure 5.22 SEM micrograph of T800 HVOF microstructure
Chemical compositions of the phases by EDX, marked in T800 HVOF coating are
shown in Figure 5.23. It confirms that phase 1 is Laves and phase 2 is cobalt based
solid solution surrounding the Laves phase.
160
Figure 5.23 EDX results of various phases in T800 HVOF coating (1) Laves phase (2)
Eutectic Laves phase + Co solid solution (3) Co solid solution
Figures 5.24 to 5.31 show the SEM micrographs of cross sections of T800 coatings
with various WC contents. From these micrographs, it can be seen that there are
some different phases presented in the coatings, including white phase, light-gray
phase and dark-gray phase. In addition, the defects can be seen for all the coatings
in the high magnification images. The coating thickness has been measured on the
SEM micrographs. Average values of three measurements were obtained for each
type of coating and are shown in Table 5.3.
Figure 5.24 SEM micrograph of cross section of T800+21WC HVOF coating.
From Figures 5.25 (a), 5.29 (a) and 5.31 (a), the mechanical bonding between the
HVOF coating and the substrate can be clearly seen. Some other defects along the
interfaces are also evident. The black voids at the interface could be formed during
the deposition process due to surface contaminants that are burnt to become gases
and trapped between the coating and the substrate [160]. Islands of sharp corners of
crushed carbides have appeared in the T800+WC HVOF coatings (figures 5.24 to
161
5.31), suggesting that the WC are not fully melted while only the binder alloys are
melted during spraying process. The size of the carbides varies between 100 nm
and 2 µm (Figure 5.27).
Figure 5.25 SEM micrographs of T800+21WC HVOF coating at the interface

between coating and substrate (a) and with high magnification (b)
Figure 5.26 SEM micrograph of cross section of T800+21WC HVOF coating with
high magnification
Figure 5.27 SEM micrograph of cross section of T800+43WC HVOF coating with
high magnification
162
The higher magnification SEM micrographs of the cross sections (Figures 5.25 (b)
and 5.29 (b)) displayed some typical defects of thermal sprayed coatings, such as
porosity and splat boundary separation.
Figure 5.29 SEM micrographs of T800+43WC HVOF coatings at interface between

coating and substrate (a) and with high ma.gnification (b)
Figure 5.30 SEM micrograph of cross section for T800+68WC HVOF coating
163
Figure 5.31 SEM micrographs of T800+68WC HVOF coating at interface between

coating and substrate (a) and with high magnification (b).
Table 5.3 Coating thickness measured
Coating Thickness (µm) Standard deviation
T800 ~ 250 11
T800+21WC ~ 228 0.8
T800+43WC ~ 220 5
T800+68WC ~ 165 9
Figure 5.32 presents the results of EDX analysis of chemical composition of

different phases, as described earlier. From the results, it is believed that the white
phase is WC particles, the dark phase is T800 matrix and the gray phase is CoCr
binder surrounding the WC particles.
164
Figure 5.32 EDX results of various phases in T800+WC HVOF coating (1) White
phase, (2) dark matrix and (3) grey phase
Further chemical analysis by EDX line scan was preformed crossing two clusters of
the WC particles. The line profiles obtained for T800+68WC HVOF coating are
displayed in figure 5.33 (b).
Figure 5.33 (a) SEM micrograph of T800+68WC coating and (b) EDX line scan
analysis of the line marked in (a)
In addition, EDX analysis of the splat boundary is illustrated in Figure 5.34 (1).
Compared with the point close to splat boundary (Figure 5.34 (2)), it was noticed
that there is a small increase in oxygen at the inter-splat boundary. Furthermore,
the EDX line scan across the splat boundary as shown in Figure 5.35 confirms the
increase of oxygen. This is believed to be the oxidation stringers, in which the
molten alloy particles during flight are exposed to air, and oxidation takes place.
Therefore, the oxidation products, i.e. oxide inclusions, are formed between the
splats.
165
Figure 5.34 EDX analyses at splat boundary (1) and near splat boundary (2) for T800
HVOF coating.
Figure 5.35 Line scan for oxygen through splat boundary for T800 HVOF coating
In order to further investigate the elemental distribution of the HVOF coatings,

EPMA was used to obtain elemental mapping. Figure 5.36 illustrates the elemental
mapping images of T800 HVOF coating, showing that oxygen is rich along the
166
inter-splat boundaries. In addition, oxygen is also enriched in specific regions at the

coating/substrate interface.
Figure 5.36 EPMA mapping of T800 HVOF coating
Figure 5.37 shows the elemental mapping of the T800+43WC HVOF coating. As
expected, the coating has a non-uniform composition in which various elements are
concentrated at specific locations. Three different regions were observed including
1) the matrix area (T800) contains Co, Mo and Cr, 2) the binder areas surrounding
the WC particles, are Co- and Cr-rich, and 3) WC particles. In addition, the
T800+43WC HVOF coating has shown the presence of oxygen, especially along
the inter-splat boundaries and at the interface between the coating and the substrate.
Figure 5.37 EPMA mapping of T800+43WC HVOF coating
167
5.3.3 XRD analysis of HVOF coatings

The XRD patterns of various HVOF coatings are shown in figures 5.38 to 5.41.
Compared with the same coating materials in powder form presented earlier in
figures 5.5 to 5.8, the same phases were found in each individual coating,
indicating that there was no detectable phase transformation during the spraying
process. The presence of W2C in HVOF coatings due to undesired decarburisation
which has been reported elsewhere [161, 162], was not observed in the coatings
studied in this work. The occurrence of decarburisation of WC has been reported
to cause loss of hard phase and result in metal matrix embrittlement, which
consequently decreases the mechanical properties and corrosion resistance [161]. In
addition the free carbon which is created by the decarburisation process may
interact with oxygen to produce CO2 gas that can be trapped in the coating to form
porosity [162].
8000
T800
1 ---- Co
HVOF
7000 2 ---- Co3Mo2Si
3 ---- Co2MoCr
Intensity (arb)
6000
1
5000
2
3 23
4000 2 32
2 3 2 2 23 3 2
3000
20 40 60 80 100
Figure 5.38 XRD pattern of T800 HVOF coating
168
T800+21WC 1 ----- WC
6000 HVOF 2 ----- Co
3 ----- W2 Co4 C
4 ----- Co3 Mo2 Si
Intensity (arb)
4000
1
2 1
1
2000
3
3
2 1 1 11 1
4 3 1 3 2 3 4
0
20 40 60 80 100
Figure 5.39 XRD pattern of T800+21WC HVOF coating
25000
T800+43WC 1 ---- WC
HVOF 2 ---- Co
20000 1 1 3 ---- W2 Co4 C
4 ---- Co3 Mo2 Si
15000
10000 1
2
5000 3 1 1
1
1 1
43 3 2
41
1
34
3
0
20 40 60 80 100
Figure 5.40 XRD pattern of T800+43WC HVOF coating
169
T800+68WC 1 ---- WC
15000 HVOF 2 ---- Co
1
3 ---- W2 Co4 C
1
Intensity (arb) 10000
1 1
5000 1
1
1 1
1
3 32 3
3 2 3 3
0
20 40 60 80 100
Angle (2)
Figure 5.41 XRD pattern of T800+68W HVOF coating
5.3.4 Porosity measurements of HVOF coatings

Table 5.4 shows the results of porosity measured and calculated for various HVOF
coatings. It is clear that the T800 HVOF coating has the highest porosity of 4.8%.
Addition of WC reduces the porosity and the porosity decreases slightly with the
increasing WC content.
Table 5.4 Measurement of porosity of various HVOF coatings.
HVOF Coating Porosity %
T800 4.8
T800 + 21WC 2.8
T800 + 43 WC 2.5
T800 + 68WC 2.2
170
Figure 5.42 Porosity of T800 HVOF coating
Figure 5.43 Porosity of T800+21WC HVOF coating
Figure 5.44 Porosity of T800+43WC HVOF coating
171
Figure 5.45 Porosity of T800+68WC HVOF coating.
Figures 5.42 to 5.45 illustrate various HVOF coatings with porosity coloured in red
within the coatings. Apart from the porosity within the coatings, the porosity is also
present at the interface between the coating and substrate.
5.4 Laser surface treated HVOF coatings

High power diode laser (HPDL) has been used for laser surface treatment of
various HVOF coatings, the surface became smoother and no obvious cracks,
porosity, and oxidation were observed on the surface treated at the optimum laser
operating conditions (full laser conditions showed in Chapter 4).
Table 5.5 Optimum parameters obtained in laser processing and coatings features
Scanning Beam size

Coating Power (W) Coatings features
Speed (mm/sec) (mm × mm)
Partially melted HVOF

T800 500 3 3.5  2.5
Partially melted HVOF,

T800+21 WC
450 2 3.5  2.5 Partially melted WC
Fully melted HVOF,
T800+43 WC
Fully melted HVOF,
T800+68 WC
172
5.4.1 Surface views of laser melted HVOF coatings

Figures 5.46 to 5.49 show the surface morphology of various HVOF coatings after
laser treatment under the laser operating conditions that result in either partial
melting or full melting, as described in Chapter 4, with formation of different
microstructures. Figure 5.46 (b) shows the microstructure of the laser-melted
surface of T800 coating at high magnification, containing eutectic Laves phase. For
laser partial melting of T800 coatings with various WC contents, it can be seen
from Figures 5.47, 5.48 and 5.49 that the WC particles on the surface are partially
melted, which is confirmed by EDX analysis presented later.
Figure 5.46 SEM micrographs of laser treated surface view of T800 HVOF coating at
low magnification (a) and high magnification (b)
Figure 5.47 SEM micrographs of laser treated surface of T800+21WC HVOF coating
at low magnification (a) and high magnification (b)
173

coatings at low magnification (a) and high magnification (b)
Figure 5.49 SEM images of surface of laser treated T800+68WC HVOF coating at
low magnification (a) and high magnification (b).
The details of surface morphology after laser treatment have also been investigated
by microXam mapping. The surface parameters such as roughness (Ra), surface
area ratio (Sdr) have been calculated. Figure 5.50 illustrates 2D surface profiles and
3D surface profiles of different areas on T800 HVOF surface after laser melting.
As shown in Table 5.5, the average roughness (Ra) of the T800 HVOF after laser
melting is 0.18 µm. Compared with the roughness of the T800 HVOF before laser
treatment (Table 5.1), the average roughness is reduced by 96%. The surface area
ratio after laser surface melting is 3.4%, which is a 98% reduction compared with
T800 HVOF coating before laser surface melting.
174
Figure 5.50 Surface profile (a) 2D and (b) 3D profiles of four different areas on laser
treated T800 HVOF coating
Figures 5.51 to 5.53 show surface profiles of T800 HVOF coatings with various
WC contents after laser treatment using MicroXam 3D mapping and MicroXam 2D
mapping. The values of average roughness (Ra) and surface area ratios (Sdr) of the
coatings after laser treatment are shown in Table 5.5. Compared with those values
before laser treatment as shown in Table 5.1, it can be seen that the laser treatment
significantly reduces the surface roughness, as well as surface area ratios. For
example, the surface area ratio, Sdr, of T800+21WC HVOF after laser treatment is
9.94%, while for the same HVOF coating, the Sdr is 223% (Table 5.1). The
reduction of surface roughness and surface area ratios can be attributed to the
melting of the top surface.
175
treated T800+21WC HVOF coating
176
177
178
Table 5.6 Surface roughness parameters of laser treated surface
Laser treated HVOF Average roughness Ra Average of surface area ratio

coating (µm) Sdr (%)
T800 0.18 3.40
T800+21WC 1.9 9.94
T800+43WC 2.20 13.94
T800+68WC 4.53 43.30
4
Ra (m)
0
T800 T800+21WC T800+43WC T800+68WC
Figure 5.54 Surface roughness of various laser treated HVOF coatings
60
40
Sdr %
20
0
T800 T800+21WC T800+43WC T800+68WC
Figure 5.55 Average of surface area ratio of laser treated HVOF coatings
179
5.4.2 Cross section of laser treated HVOF coatings

The cross section of T800 HVOF coatings after laser partial melting is shown in
Figure 5.56, demonstrating that only the top part of the coating layer was melted,
and the melted region showed a smooth surface with no visible cracks or porosity.
Below the melted top-layer, there is a heat treated region, i.e. the temperature of the
region was not sufficient to reach the melting temperature of T800. Therefore, the
splat boundaries and small gaps still appear in this region. Furthermore, the
interface between the HVOF coating and the substrate is not affected by the laser
treatment.
Figure 5.56 SEM micrograph of cross section of laser treated T800 HVOF coating.
The backscattered SEM micrograph of the T800 HVOF coating after laser
treatment is presented in figure 5.57, showing a typical solidification
microstructure with dendritic features. The microstructure comprises a few phases
including the white phase representing primary Laves phase, eutectic structure with
white laves phase and the dark Co solid solution. Moreover, it is noted that no
porosity or splat boundaries can be seen after laser melting.
180
Figure 5.57 SEM micrograph of laser melted T800 HVOF coating.
The EDX spectrum in figure 5.58 (1) further confirms the primary Laves phase
contains a higher percentage of Mo (43.18%) and Si (5.07%) and lower percentage
of Cr (12.22%) and Co (39.53%) compared with other phases. The eutectic phase
as shown in Figure 5.58 (2) has a higher percentage of Mo (22.78%) than the Co
solid solution. The highest percentage of Co of 59.33% was in the Co solid solution
phase (Figure 5.58 (3)).
Figure 5.59 is a SEM micrograph of the cross section of T800+21WC HVOF

coating after laser partial melting. The top part of the coating was melted, while the
lower part of the HVOF coating remains unmelted. As can be seen in Figure 5.60
(a), the interface between the coating and the substrate remains mechanically
interlocked. There is some small-scale porosity close to the surface and the WC
particles were melted partially, where the carbides still appear within the upper part
of the coating after laser treatment (Figure 5.60 (b)).
181
Figure 5.58 EDX analysis of various phases in laser melted T800 HVOF coating (1)
Laves phase (2) Eutectic (Laves phase + Co solid solution) (3) Co solid solution
Figure 5.59 SEM micrograph of cross section of laser treated T800+21WC of HVOF
coating
182
Figure 5.60 SEM micrographs of laser treated T800+21WC HVOF coating showing
(a) interface between the coating and substrate (b) microstructure in laser melted
area
The microstructure of partially melted T800+21 HVOF coating with partially

melted of WC showing in Figure 5.61. This complex microstructure was achieved
after a rapid solidification process. Three typical phases can be seen in Figure 5.61,
which are light-gray phase, dark phase and partially melted of WC particles. Figure
5.62 shows the EDX results of the three phases for laser partially melted of
T800+21WC HVOF coating. The light gray phase (1) contains 41.91% of Co and
10.69% of W which was expected because W2Co4C was identified in the XRD
results in Figure 5.92. The dark phase (2) contains 41.11% Co, 29.46% Mo which
is close to the composition of T800 phase. Figure 5.62 (3) illustrates the EDX result
of partially melted of WC particles in T800+21WC HVOF coating. This phase, as
expected, has the lowest percentage of Co (26.56%), and the highest percentage of
W (31.55%).
Figure 5.61 SEM micrograph of cross section for laser treated T800+21WC HVOF
coating
183
Figure 5.62 EDX results of various phases in T800+21WC HVOF coating after laser
treatment (1) Co-Cr binder phase (2) Co solid solution phase (3) partially melted WC
Figure 5.63 shows a SEM micrograph of a cross section for fully melted
T800+43WC HVOF coating. Figure 5.64 (a) illustrates a fusion bond at the
interface between the coating and the substrate was created by laser treatment.
Figure 5.65 shows the complex microstructure of the fully laser melted
T800+43WC HVOF coating. It should be noted that this only indicates the full
melting of the HVOF layer. Due to the large difference in melting temperatures
between WC and the Co-matrix, WC particles were not fully melted, i.e. the
temperature of the melt pool was between the melting temperatures of the two
phases. Figure 5.66 shows the respective EDX results corresponding to the (1), (2),
and (3) locations. In the EDX results, the dark phase (T800) (1) contains higher
concentration of Co and Cr than the other two phases. On the other hand, the gray
phase (2) has 25.7% of Co, 22.6% of W, and 1.05% of C, this indicates that the
gray phase is composed of W2Co4C phase, consistent with the XRD result in Figure
5.92. The white phase (partially melted carbides) (3) has the highest concentarion
of W (80.24%).
184
Figure 5.63 SEM micrograph of cross section of laser treated T800+43WC HVOF
coating showing partially melted WC
Figure 5.64 SEM micrograph of laser treated T800+43WC HVOF coating showing
(a) interface between the substrate and the coating (b) microstructure in laser melted
area
coating showing partially melted WC.
185
Figure 5.66 EDX results of phases (marked as 1, 2, 3 in Figure 5.65) in T800+43WC

HVOF coating (1) T800 matrix (2) Co-Cr binder phase (3) partially melted WC.
Figure 5.67(a) and (b) illustrate that the laser treated T800+68WC HVOF coating
shows improved homogeneity, compared with inhomogeneity in the HVOF coating
as seen in Figure 5.33 before laser treatment. This improvement in homogeneity
might have a positive effect on the mechanical and the electrochemical properties
of the HVOF coating.
Figure 5.67 (a) SEM micrograph of laser treated T800+68WC (b) EDX line scan
analysis on T800 and WC particles
186
Homogeneity of the HVOF coatings by laser treatment can also be observed by

EPMA measurement. Figure 5.68 illustrates the EPMA elemental mapping of the
laser partially melted T800 coating. The laser treated area (top area) has more Mo
which indicates of the existence of Laves phase. Figure 5.69 shows EPMA results
of the laser treated T800+43WC with partial melting of WC particles, indicating
that the melting was mainly in the upper part of the coating. The blue areas in the
Mo image shows the WC particles not completely melted in the coating. The
oxygen distribution shows the presence of oxide inclusions in the splat boundaries
and the interface between the coating and the substrate.
Figure 5.68 EPMA mapping of laser treated T800 HVOF coating
Figure 5.69 EPMA mapping of laser treated T800+43WC HVOF coating with
partially melting of WC particles
187
Figure 5.70 illustrates the dilution changes of laser treated T800+43WC with
partially melted WC particles. A3 in Figure 5.70 represents the bottom part of the
laser melted layer and the EDX result in this area shows that the iron content in this
area is 5.84%. The iron contents gradually reduce to 0.71% for the middle area A2
and then to 0.53% in the top area of the coating (A1). These results were also
confirmed by EDX line scan of iron as shown in Figure 5.71.
Figure 5.70 EDX results of different areas of T800+43WC HVOF coating after laser
treatment
188
Figure 5.71 EDX line scan of laser treated T800+43WC HVOF coating
Laser treated T800+68WC HVOF coating with partially melted WC particles is

shown in figure 5.72. The laser melted layer has some defects including porosity as
shown in Figure 5.73 (b). Fusion bonding was created by laser full melting between
the coating and substrate (figure 5.73 (a)). The microstructure of the melted layer is
shown in Figure 5.74 in which the white phase is partially melted WC particles, the
light-gray phase is the partially melted binder phase, and the dark-gray phase is
T800 (matrix). The T800+68WC HVOF coating shows more partially melted WC
particles compared with T800+43WC (Figure 5.65). This might be due to the
higher percentage of higher melting temperature phase, WC in T800+68WC, so
that the melt pool temperature was not high enough to melt all WC particles.
Although WC has lower thermal conductivity than the surrounding metals, it seems
that the large difference in melting temperatures between the two phases plays a
more important role than thermal conduction. It is also noted that the melting
occurred along the edges of WC particles.
189
coating
Figure 5.73 SEM micrographs of laser treated T800+68WC HVOF coating showing
(a) interface between the coating and substrate and (b) microstructure of melted area.
EDX results of different phases for laser treated T800+68WC HVOF coating are
shown in Figure 5.75. Binder phase (light-gray marked as 1) has higher percentage
of Co (18.15%) compared with the other phases. The percentage of W in the binder
190
phase is 68.24%, indicating partially melting of WC particles. In addition, the T800

matrix shows a high percentage of W (81.51%), also suggesting the melting of WC
particles.
Figures 5.76 and 5.77 illustrate dilution behaviour in laser treated T800+68 HVOF
coating with partially melted WC. As seen in Figure 5.76, Fe percentages in the
upper (A1) and middle (A2) areas are around 0.6%. In the bottom of melted layer
(A3) the percentage of Fe is 7.85%. As confirmed in Figure 5.77 by EDX line
scan, a slightly higher dilution was found in the region of the coating adjoining the
region of substrate melting. It suggested that the melt pool behaviour was not fully
convective, and it seemed that the diffusion at the interface between the coating and
substrate played a more important role.
191
Figure 5.75 EDX results in different areas of laser treated T800+68WC HVOF
coating
192
Figure 5.76 EDX results in different areas of laser treated T800+68WC HVOF
coating
Figure 5.77 EDX results of line scan of laser treated T800+43WC HVOF coating
showing Fe distribution along the coating thickness
193
5.4.3 XRD of laser treated HVOF coatings

Figures 5.78 - 5.81 illustrate the XRD patterns of various HVOF coatings after
laser treatment. From the XRD result for the HVOF coating before laser treatment
(Figure 5.38), it is clear that, before laser treatment, the HVOF coating consists of
pure Co phase and various Co 2MoCr and Co3Mo2Si phases. However, there is no
Co2MoCr phase after laser treatment while the amount of Co 3Mo2Si phase
increases. The typical T800 alloy consists of a large percentage of hard
intermetallic Laves phase distributed in a soft cobalt solid solution. The hard
primary intermetallic phase is a compound of Co, Mo and Si with composition
roughly of Co3Mo2Si [163]. The peaks of the crystal structures Co 3Mo2Si and
Co2MoCr have hexagonal symmetry [155, 164]. Comparing XRD patterns of
T800+21WC and T800+43WC as HVOF coating (Figures 5.39 and 5.40) with
those after laser treatment (Figures 5.79 and 5.80); the WC was a major phase
before the laser treatment while W2Co4C became the major phase after laser
treatment. The W2Co4C phase was formed by the reaction of Co with WC phase
during laser treatment [162]. Cobalt-phase was detected in laser treated T800
coating only. On the other hand, all the spectra indicated the presence of WC
phase. The Co0.9W0.1 was only present in the spectra of laser-treated coatings which
may be caused by the melting of WC and Co. Figure 5.81 shows the XRD pattern
of T800+68WC HVOF coating after laser treatment, the pattern indicates the
presence of W2Co4C and weak peaks of WC. The cobalt peak was very weak in the
as received HVOF coating (figure 5.41) and not seen in laser treated spectra,
suggesting that it has dissolved into the coating.
194
12000
T800 1 ----- Co
10000 Laser 1 2 ----- Co3 Mo2 Si
2
3 ----- Co2 Si
Intensity (arb)
8000
3
3
6000 3
3
4000
2
2000 2
22
2 32 2
3 2 3 3 2 2 332
2
3 3
0
20 40 60 80 100
Figure 5.78 XRD pattern of T800 HVOF coating after laser treatment
6000
2
T800+21WC 1 ----- WC
Laser 2 ----- W2 Co4 C
3 3 ----- Co0.9 W0.1
Intensity (arb)
4000 4 ----- W Co1.5 Si0.5
1 3
2000 4
4 42
1
4
2 1 3
12
2 2 2 24 4
22 2 41
1 4
0
0 20 40 60 80 100
Angle (2)
Figure 5.79 XRD pattern of T800+21WC HVOF coating after laser treatment
195
60000
T800+43WC 2 1 ----- WC
3 ----- Co0.9 W0.1
Intensity (arb) 40000
2
20000
1 2 2
2
2 2
2 2 3 2 2 2
1 123 3 12 2
0
0 20 40 60 80 100
Angle (2)
10000 T800+68WC 1 ----- WC

1
8000 1 3 ----- Co0.9 W0.1
Intensity (arb)
6000 2
1
4000 2
1
2000 3 1 1
2 1 1
1 1 2 1 2 2
2 11
0
0 20 40 60 80 100
Angle (2)
196
5.4.4 Porosity measurements of laser treated HVOF coatings

Table 5.7 along with Figures 5.82 to 5.85 illustrate the results of porosity measured
for various HVOF coatings after laser treatment. Compared with the porosity
before laser treatment (Table 5.4), there is significant reduction of porosity after
laser treatment. T800 has the lowest porosity after laser treatment of 0.1 %, and
T800+68WC has the highest porosity after laser treatment of 1 %. Furthermore, the
significant porosity reduction is an important factor for protecting the substrate in
corrosive environments as will discussed in electrochemical tests in Chapter 6.
Table 5.7 Measurement of porosity of various HVOF coatings after laser treatment
Laser treated HVOF coating Porosity %

T800 0.1
T800 + 21WC 0.3
T800 + 43WC 0.3
T800 + 68WC 1
Figure 5.82 Porosity of laser treated T800 HVOF coating
197
Figure 5.83 Porosity of laser treated T800+21WC HVOF coating
198
5.5 Summary
 The surface of various HVOF coatings shows the presence of defects

such as micro-cracks, micro-crevices, and pores.
 The surface roughness and surface area ratio slightly decreased by

increasing the content of WC. The Ra of T800 ~ 5.05 µm decreased to ~
4.49 µm for T800+68WC. The S dr of T800 ~ 212 % decreased to ~153 %
for T800+68WC.
 Cross sections of various HVOF coatings show lamellar, splat structure

with high levels of defects such as porosity, and splats boundaries.
 The addition of WC reduced the porosity of the coatings. The values of

porosity for T800, T800+21WC, T800+43WC and T800+63WC are
4.8%, 2.8%, 2.5% and 2.2% respectively.
 EDX and EPMA analysis showed the presence of oxide inclusions along
the splat boundaries and at the interface between the HVOF coatings and
the stainless steel substrate.
 The interface between the HVOF coatings and the stainless steel substrate
exhibited-porosity-and-crevices.
 The phases observed by XRD of T800 in a powder form were Co,

Co3Mo2Si, and Co2MoCr. The phases observed in T800+21WC and
T800+43WC in a powder form were WC, Co, W2Co4C, and Co3Mo2Si.
The phases observed in T800+68WC in a powder form were WC, Co,
and W2 Co4C. The HVOF coatings indicated the same phases as those in
powder forms.
199
 Laser surface melting of various HVOF coatings successfully eliminated

various defects in the HVOF coatings, such as porosity, cracks, and splat
structure.
 New microstructure has been achieved after laser treatment. T800 HVOF
coating after laser partial melted showed elimination of the splat
structures and boundaries with increase of eutectic and Laves phase
percentages. T800+WC HVOF coatings after laser treatment showed
partial melting of WC particles.
 After laser treatment there was significant reduction in the roughness (Ra)
and surface area ratio (Sdr). The Ra of T800 HVOF coating was reduced
after laser treatment by 96%, and the Sdr reduced from 212% for HVOF
coating to 3.4%. The Ra of T800+21WC HVOF coating was reduced after
laser treatment by 65%, and the Sdr reduced from 223% for HVOF
coating to 9.94% after laser treatment. For T800+43WC the R a was
reduced after laser treatment by 55%, and the S dr reduced from 212% for
HVOF coating to 13.94% after laser treatment.
 EDX and EPMA results show improvement of elemental homogeneity

after laser treatment.
 There was significant reduction of porosity after laser treatment. The

value of porosity for T800 reduced from 4.8% of HVOF coating to 0.1 %
after laser treatment, for T800+21WC reduced from 2.8% of HVOF
coating to 0.3% after laser treatment, for T800+43 reduced from 2.5% of
HVOF coating to 0.3% after laser treatment, and for T800+68WC
reduced from 2.2% of HVOF coating to 1% after laser treatment.
 XRD results after laser treatment showed the changes in some phases. In
T800 HVOF coating there was an increase in Co 3Mo2Si phase indicating
200
an increase in Laves phase. W2Co4C became a major phase in

T800+21WC and T800+43WC HVOF coatings after laser treatment
suggesting the reaction between Co and WC. In T800+68WC HVOF
coating after laser treatment, it mostly contained W2Co4C phase and a
small amount of WC, while Cobalt solid solution was not seen in all the
laser treated T800 with WC coatings.
201
Chapter 6 Corrosion Tests
6.1 Introduction
This chapter presents the corrosion performance of various HVOF coatings before
and after laser treatment in various corrosion tests, including immersion test,
polarisation test, and electrochemical impedance spectroscopy (EIS) test. Corrosion
morphologies of the coatings after the corrosion tests were characterised using
SEM. Concentrations of the solutions after the immersion test were analysed by
Inductivity coupled plasma- optical emission spectrometery (ICP-OES), to
investigate the corrosion mechanisms. The complete laser melted conditions are
shown in Table 5.5, where T800 HVOF, T800+21WC HVOF were partially melted
coatings (figure 4.1), and T800+43WC, T800+68WC were fully melted coatings
(figure 4.4), and partially melted WC.
6.2 Immersion test

Samples of various as received and laser treated HVOF coatings were immersed in
3M H2SO4 for 24, 48, 72 and 96 hours and observed using SEM. In general, there
was no obvious weight loss after immersion testing for all the coatings. This is
believed to be due to the difficulty of removing corrosion products that may be
trapped at the interface between the coating and the substrate and inside the pores.
In this section only the corrosion at the interface and improved substrate protection
by laser treatment will be discussed. The corrosion which occurred at the surface
and through the coating will be discussed in the following sections.
202
CHAPTER 6 CORROSION TESTS
6.2.1 Tribaloy 800 (T800) coating

From the SEM images of the cross section of the samples after immersion test, it is
obvious that all the as received HVOF coatings had interconnected pores, so that
the electrolyte can reach the substrate, causing corrosion at the interface between
the coating and substrate. Due to the galvanic couple between the coating and
stainless steel substrate, the substrate acted as an anode while the coating was
cathode, leading to anodic dissolution. As shown in tables 5.4 and 5.7, the as
received HVOF coatings had higher percentage of porosity than the laser treated
HVOF coatings. The number of cracks and pores are higher for T800 (Table 5.4)
which also contributed to the electrolyte penetration through the coatings.
6.2.1.1 Samples Immersed for 24 hours

As shown in figure 6.1, after 24 hours of immersion, the as-received HVOF coating
shows signs of corrosion attack at the interface between the coating and substrate,
indicating the penetration of the electrolyte reaching the substrate. However, the
laser-treated coating shows no sign of corrosion.
HVOF Laser Treated
(c)
Figure 6.1 SEM cross-section images of T800 HVOF coating: a and c as received
HVOF coatings, b and d after laser treatment, all are immersed for 24 h
203

By increasing in the immersion time to 48 hours, the as-received HVOF coating
shows more significant corrosion at the interface, as shown in figure 6.2 (a and c).
For laser treated coatings, after 48 hours, still no sign of corrosion was found as
shown in figure 6.2 (b) and (d).
HVOF Laser Treated
(a) (b)
(c) (d)
204

After 72 hour immersion, obviously, the as-received HVOF coating showed a
much increased level of corrosion attack at the interface, but no sign of coating
spallation, while slight corrosion was also observed at the interface for the laser-
treated coating, as shown in figure 6.3. This suggested that a small amount of
electrolyte penetrated through some defects existing in the laser-treated coatings.
HVOF Laser Treated
(a) (b)
(c) (d)

After 96 hours, the as-received HVOF coating presented a much increased level of
corrosion at the interface, leading to the spallation of the coating as shown in figure
6.4a and c. This means that the penetration of the electrolyte had resulted in a large
amount of corrosion products that accumulated along the interface and volume
expansion. However, following the treatment of the HVOF coating by the laser, the
HVOF coatings show a much higher protection against the penetration of the
205
electrolyte through the coating that eliminated/reduced the corrosion at the

interface.
HVOF Laser Treated
(a) (b)
(c) (d)
6.2.2 T800+21WC
In general, the anodic dissolution of the substrate at the interface for T800 HVOF
coating was more severe than that at the interface for T800+WC. This indicated
that the coatings with WC had a denser structure than T800 coating, due to
different operating parameters applied during the thermal spraying of different
HVOF coatings [165]. The HVOF samples with WC did not show any corrosion at
the interface after immersion for 24 hour.
206

As seen in figure 6.5 (a) and (c), the electrolyte penetrated into the as-received
HVOF coating and reached the interface between the coating and the substrate,
resulting in corrosion attack at the surface. On the other hand, there was no obvious
corrosion attack at the interface for the laser-treated coating as shown in figure 6.5
b and d.
HVOF Laser Treated
(a) (b)
(c) (d)
Figure 6.5 SEM cross-section images of T800+21WC HVOF coating: a and c as

received HVOF coatings, b and d after laser treatment, all are immersed for 48 h
207

As shown in figure 6.6 (a) and (c), longer immersion time resulted in more anodic
dissolution of the substrate at the coating/substrate interface. After laser treatment,
still no obvious corrosion attack was found at the interface as shown in figure 6.6
(b) and (d).
HVOF Laser Treated
(a) (b)
(c) (d)

208

After 96 hour immersion, it was obvious that for the as-received HVOF coating,
corrosion occurred at the interface as shown in figure 6.7 (a) and (c). For laser
treated HVOF coating as shown in figure 6.7 (b) and (d), none or very low
dissolution occurred at the interface, as a result of laser melting of the upper side of
the coating which sealed the interconnected porosity.
HVOF Laser Treated
(a) (b)
(c) (d)

209
6.2.3 T800+43WC
No corrosion at the interface was observed for the HVOF coatings with and
without laser treatment after 24 hour immersion test.

As shown in figure 6.8, the penetration of electrolyte in the as-received samples
became obvious, causing anodic dissolution of the substrate after 48 hour, while no
sign of corrosion was observed for the laser-treated coatings.
HVOF Laser Treated
(a) (b)
(c) (d)


After 72 hour immersion, the dissolution of the substrate in the as-received samples
became more severe at the interface (figures 6.9). On the other hand, for laser
treated samples, no corrosion was observed
210
HVOF Laser Treated
(a) (b)
(c) (d)


Further increasing in the immersion time to 96 hours resulted in more significant
corrosion at the interface in the as-received samples with serious dissolution of the
substrate. However no coating spallation was observed, showing better corrosion
protection than the T800 HVOF coating. Again, no corrosion was observed for the
laser treated coating.
211
HVOF Laser Treated
(a) (b)
(c) (d)

6.2.4 T800+68WC
In general, the T800+68WC HVOF coating presented the best protection with
reduced level of electrolyte penetration compared with other HVOF coatings. This
is consistent with the data presented in table 5.4 showing the lowest level of
porosity.
No corrosion was observed after 24 hour immersion.

After 48 hour immersion, only a small amount of corrosion was observed at the
interface for the HVOF coating as shown in figure 6.11 (a) and (c). After laser
treatment (figure 6.11 (b) and (d)), no dissolution occurred at the interface,
suggesting no electrolyte reached to the substrate as a result of sealing the
212
interconnected porosity by the laser. The relatively large pores presented in laser-
treated coating were considered to be isolated.
HVOF Laser Treated
(a) (b)
(c) (d)
Figure 6.11 SEM cross-section images of T800+68WC HVOF coating: a, c as received

HVOF coatings, b, d after laser treatment, all are immersed for 48 h

After 72 hour immersion, the as-received HVOF coating presented obvious
corrosion attack at the interface as shown in figure 6.12 (a) and (c), revealing the
dissolution of the substrate. However no corrosion was observed for laser partially
melted samples as seen in figure 6.12 (b) and (d)
213
. HVOF Laser Treated
(a) (b)
(c) (d)

6.2.4.3 Samples Immersed for 96 hour

Figure 6.13 (a) and (c) shows slightly increased corrosion at the interface.
Compared with other HVOF coatings described earlier, much improved corrosion
protection was found. On the other hand, no corrosion occurred at the interface for
the laser treated samples (figure 6.13 (b) and (d)).
214
HVOF Laser Treated
(a) (b)
(c) (d)

6.2.5 Inductivity coupled plasma- optical emission spectrometer (ICP-

OES) test
ICP-OES was used to analyse the solutions after the immersion tests to gain
information of the concentrations of a few representative elements like Co, W, Mo
and Cr that were released from the samples to the solutions. Such information is
related to the corrosion dissolution which occurred during the immersion test and
aids understanding of the corrosion mechanisms involved in the HVOF coatings
with and without laser treatment. The solutions after 7 days of immersion in 3M
H2SO4 acid for the T800+43WC coatings before and after laser treatment were
selected to be analysed. Table 6.1 and figure 6.14 illustrate the mean concentrations
of those elements released to the electrolyte after 7 days of immersion.
215
Table 6.1 Mean concentration of the elements (units of µg/ml) released into the
electrolyte solution after 7 days of immersion of T800+43WC HVOF coating before
and after laser treatment.
Sample Fe Co W Mo Cr
HVOF 1.873 0.101 0.091 0.012 0.509
Laser treated 0.311 2.691 0.221 0.076 0.407
Reference Standard 0.00075 0 0.058 0.0013 0.0002
2.8
HVOF coating
2.4
Laser treated
2.0
2
g/cm
1.6
1.2
0.8
0.4
0.0
Fe Co W Mo Cr
Figure 6.14 Mean concentration of the elements released in 3M H2SO4 after 7 days of
immersion of T800+43WC HVOF coating before and after laser treatment.
For the T800+43WC coating, the results showed that relatively large amounts of
the Cr and Fe dissolved in the electrolyte. The Fe was from the substrate while the
Cr could be from both the coating and substrate, indicating severe dissolution of
the substrate. This is consistent with the finding described in Section 6.2.3 although
the immersion time was 7 days. On the other hand, the Co, W and Mo were hardly
dissolved, indicating a low level of corrosion occurred of the coating. A similar
finding was also observed for Cr, W, and Mo in 5M H2SO4 by Lee et al [166].
After laser treatment there was no significant change in the dissolution of Mo, Cr
216
and W. However, a large amount of the Co, 2.69 µg/ml, was observed in the
solution showing the highest dissolution of the coating. On the other hand, the
dissolution of Fe from the substrate significantly decreased, indicating a very low
level of corrosion at the interface. These results were consistent with the
observation using SEM as displayed in Section 6.2.3. It can be explained by the
observation described in Chapter 5. In summary, the HVOF coatings allowed the
electrolyte to penetrate easily through the interconnected pores to the interface
between the substrate and the coating, cause high anodic dissolution of the
substrate. That was reflected by the high percentage of Fe in the solution. After
laser partially melting of WC, the high concentration of the Co in the electrolyte
showed the corrosion of the coating, while the electrolyte did not penetrate to the
interface.
6.3 Polarisation test

Figure 6.15 shows the polarisation curves obtained for the HVOF coatings in the
aerated 0.5 M H2SO4 solution at room temperature. Comparison between
polarisation curves of the as-received HVOF coatings, all the coatings presented a
similar value of Ecorr, but there is a slight decrease in the values of Icorr with
increasing the content of WC. A similar observation was also reported by Human
[86], suggesting that addition of carbon and tungsten reduces the corrosion current
density below that of pure cobalt. As seen in figure 6.15, the passivation range was
wider in T800, but become narrower by adding WC due to the reduction of Cr
content which is responsible for passive film formation. Moreover, cathodic
regions of the polarisation curves in figure 6.15 for all the coatings are similar,
implying that all the coatings presented a same cathodic reaction, which might be a
simple hydrogen evolution progressed by the same mechanism [167].
217
1500
HVOF
1000 T800
T800+21WC
T800+43WC
Potential (mV)
500 T800+68WC
-500
1E-4 1E-3 0.01 0.1 1 10 100 1000

2
Current density (mA/cm )
Figure 6.15 Polarization curves of the HVOF coatings in 0.5 M H2SO4 solution.
Figure 6.16 illustrates comparisons of the polarisation curves for various HVOF
coatings before and after laser treatment. Ecorr, Icorr and corresponding breakdown
potentials (Eb) are summarised in table 6.3. Obviously there is an improvement in
corrosion behaviour after laser treatment for all the coatings. As shown in figure
6.16 (a) the Ecorr of T800 HVOF coating was shifted in a positive direction from -
325 mV to -304 mV after laser treatment and corresponding corrosion current
density reduced about 20 times from 0.67 mA/cm2 to 0.033 mA/cm2. In addition,
the breakdown potential increased from 907 mV to 1002 mV. For T800+21WC
HVOF coating, the Ecorr of -312 mV was increased to be more positive after laser
treatment to -243 mV. The current density reduced about 13 times after laser
treatment. Furthermore, the current density reduced about 14 times after laser
treatment of T800+43WC HVOF coating. The current density of T800+68 HVOF
coating decreased after laser treatment about 5 times.
218
1500 1500
T800 T800+21WC
1000 Laser 1000 Laser
HVOF
HVOF
Potential (mV)
Potential (mV)
500 500
0 0
-500
-500
1E-5 1E-4 1E-3 0.01 0.1 1 10 100 1000

1E-4 1E-3 0.01 0.1 1 10 100 1000
2
Current Density (mA/cm ) 2
Current Density (mA/cm )
(a) (b)
1500
1500 T800+43WC T800+68WC

1000 Laser
Laser
1000
HVOF HVOF
Potensial (mV)
Potential (mV)
500
500
0
0
-500 -500
1E-5 1E-4 1E-3 0.01 0.1 1 10 100 1000 1E-4 1E-3 0.01 0.1 1 10 100 1000
2 2
Current Density (mA/cm ) Current Density (mA/cm )
(c) (d)
Figure 6.16 Polarization curves of HVOF coatings before and after laser treatment in
0.5 M H2SO4 (a) T800 (b) T800+21WC (c) T800+43WC (d) T800+68WC
219
Table 6.2: Corrosion current density (Icorr) and corrosion potential (Ecorr)
of HVOF coatings before and after laser treatment in 0.5 M H2SO4 solution
Icorr Ecorr (mV) Eb

Sample
(mA/cm2) (mV)
T800 HVOF 0.670 -325 907
T800 Laser 0.033 -304 1002
T800+21WC HVOF 0.130 -312 922
T800+21WC Laser 0.01 -243 970
T800+43WC HVOF 0.071 -309 922
T800+43WC Laser 0.005 -185 923
T800+68WC HVOF 0.062 -304 986
T800+68WC Laser 0.012 -255 1002
As shown in figure 6.16 (a) the anodic polarisation curve of T800 HVOF coating
show an initial active stage, followed by short stage of passivation which might be
due to the formation of Cr2O3 film [5], suggesting that the coating became pseudo-
passive, until the breakdown of the oxide laser at the potential of 907 mV. The
laser treated T800 HVOF coating, started with an active stage followed by pseudo-
passive stage until breakdown potential reached. The same observations were also
found for T800+21WC before and after laser treatment. The T800+43WC HVOF
coating before laser treatment has the same observation. However, after laser
treatment, the anodic polarisation curve shows firstly active stage followed by
pseudo-passive stage. T800+68WC HVOF coating have the same observation.
However, after laser treatment it shows initially active stage, then a reduction of
current density might be due to the formation of Cr2O3 and/or WO3 oxide films
[168] followed by pseudo-passive stage until breakdown potential. In theory, the
T800 and T800+WC HVOF coatings should be able to passivate as a consequence
of the presence of high amount of Cr (18%) as shown in table 5.2 in a metal matrix
[161]. However, all the HVOF coatings did not present a true passive regime that
220
required much lower current density (below 10 µA/cm2) and the behaviour was
termed as pseudo-passive [70, 72]. The polarisation curves before and after laser
treatment (figure 6.16) show different activation stages, indicating changes in the
corrosion mechanism. The high defect density of HVOF coatings such as weak
splat boundaries, oxide inclusions, etc. could provide many different corrosion
initiation sites, which make the corrosion current density specially for HVOF
coatings relatively high (10-4 A/cm2) . Similar results were also observed by Bolelli
[161]. It reported that pseudo-passivation behaviour occurred as a result of
increasing the length of cobalt diffusion path. Where after Co dissolution, Co 2+
should diffuse out through the porosity and gaps of the HVOF coatings and in the
WC skeleton, which is slower than the free diffusion and much slower than
convection. As a result of diffusion limitation of mass transport, current flow is
decreased causing pseudo-passive behaviour [85].
It was found from the previous studies that the corrosion mechanism of HVOF
WC-Co coatings is complex due to the heterogeneous microstructure and binder
phase composition [69]. The cobalt binder phase is most susceptible to dissolution
in acidic media [72]. Some previous studies [5, 79, 169] believed that there are two
distinctive regions in the polarisation curve as shown in figure 2.26. They assumed
that region I at low potential, related to corrosion of the matrix material and leads
to a rapid release of Co 2+, and region II at higher potential was related to WC
oxidation. It was found that the hard phase WC had oxidation and dissolution at
much higher potential than Co, and oxidize to WO3 at low pH. The oxidation of
WC increases with increasing pH [169]. Furthermore, the dissolution of Co takes
place on the early stages of the process but slowed down by formation of oxide
layer (Cr2O3) [79, 168]. However, in this study, the same trend was noticed; where
the polarisation curves for HVOF T800+WC coatings have two regions as shown
in figure 6.17. There is no evidence of dissolution of Co at low potential (region I)
and WC at high potential (region II). However, the ICP results (table 6.1 and figure
6.14) showed evidence of Co and W in the electrolyte after 7 days of immersion for
T800+43WC HVOF coating in 0.5 M H2SO4 which indicated dissolution of Co and
WC.
221
Figure 6.17 A typical polarization curve of T800+43WC HVOF coating.
Figure 6.18 shows microcrevice corrosion occurred at the splat boundaries of

T800+21WC. The existence of porosity in the HVOF coatings influenced the
corrosion behaviour significantly, mainly due to the electrolyte reaching deeper
areas and resulting in crevice corrosion as evident in figure 6.20. Moreover, the
corrosion was initiated preferentially around the splat boundaries, as a result of
microcrevice corrosion mechanism [170]. The initiation of corrosion at splat
boundaries of HVOF coatings was reported as a result of the presence of oxide
“stringers” in the splat boundaries [171]. The crevice effects of porosity could be
significant in the corrosion action especially at the top layers of the HVOF coating.
Figure 6.18 Microcrevice corrosion of T800+21WC HVOF coating after immersion

in 3 M H2SO4 for 108 h.
It was also found that the cobalt alloy matrix corroded more at the WC/Co
interface. As shown in figure 6.19 the corrosion resulted in dissolution of the
222
matrix near the hard carbides due to micro-galvanic effects. From previous studies,
as discussed in section 2.4.6, Co dissolves in neutral and acidic solutions, and
shows higher dissolution rates with decreasing in pH. However, WC shows more
stabilisation with decreasing in pH. The galvanic coupling between WC and
surrounding metal matrix causes accelerated anodic dissolution of the less noble
phase (Co) as follows.
(6.1)
The reduction reaction (cathodic) occurred on the WC phase, which can be one of
the following reactions:
The corrosion mechanism in this system is controlled by the galvanic coupling

between the WC and the matrix [5, 9, 69-75].
Figure 6.19 Galvanic corrosion of T800+43WC HVOF coating after polarisation test.
The improvement in corrosion behaviour for the coatings after laser treatment is
believed to be due to the elimination of the defects such as porosity, microcracks
and gaps which were found in the HVOF coatings as shown in table 5.7. In
addition, decrease in the difference of electrochemical potentials between the WC
223
and the matrix was achieved by formation of interfacial phases (W2Co4C) between
the two phases [12]. Figure 6.20 illustrates the T800 HVOF coating after
polarisation test. It is obvious that there was a typical corrosion attack at splat
boundaries in the upper part of the coating. Figure 6.21 shows the surface of laser
treated for T800 HVOF coating after polarisation test. The dissolution of Co solid
solution was confirmed by ICP results (figure 6.14) and can be also seen from
figure 6.21, in which the Co solid solution was more anodic than Laves phase that
contains a high percentage of Mo (43%) which was confirmed by EDX (figure
5.58). As shown in ICP results, Mo had a low dissolution in H2SO4 solution. Some
portions of the Laves phase pulled out of the surface showing a shape of flowers
that was the original Laves phase when the around Co phase dissolved. As seen in
figure 6.22, T800 HVOF coating after polarisation test the corrosion attack
occurred at the splat boundaries and the Co solid solution inside the splat, and
cracks have observed in specific areas within brittle splats that might be due to the
oxide expansion around splat boundaries [172]. Figure 6.23 shows the corroded
area of T800+21WC coating after polarisation test. The dissolution occurred on the
surface at T800 matrix, the WC almost disappeared in the matrix. There are no
obvious boundaries between T800 and WC.
Corroded area
Corrosion in the splat boundaries
Figure 6.20 Cross section of T800 HVOF coating after polarization test in 0.5 M
H2SO4 solution.
224
Figure 6.21 Surface corrosion of laser treated T800 coating after polarization test in
0.5 M H2SO4
Figure 6.22 Surface of laser treated T800 coating after polarization test in 0.5 M
H2SO4 solution.
Figure 6.23 Cross section of laser treated T800+21WC coating after polarization test
in 0.5 M H2SO4 solution
225
As shown in figure 6.24 the dissolution in the T800 with WC HVOF coatings
occurred at the T800 matrix (anodic), and at higher potentials some dissolution in
WC occurred, which can be confirmed from ICP test (figure 6.14). After laser
treatment the WC melted partially in T800+43WC and T800+68WC, and as can be
seen in figure 6.25 for T800+43WC, the dissolution occurred around the partially
melted carbides. Also there is dissolution in the not melted WC particles and
phases that new phases such as W2Co4C, this dissolution confirmed by ICP test.
Corroded area in
Corroded area T800 matrix
Figure 6.24 Cross section of T800+68WC HVOF coating after polarization test in 0.5
M H2SO4
Corroded area in
Corroded area matrix
Figure 6.25 Cross section of T800+43WC laser treated coating after polarization test
in 0.5 M H2SO4
226
6.4 Electrochemical Impedance Spectroscopy (EIS) Test

Impedance diagrams obtained in 0.5 M H2SO4 solution at various immersion times
for HVOF coating and after laser treatment are presented in this section. Four
impedance measurements were made for each sample to give an idea about
reproducibility. Figure 6.26 shows Nyquist curves of HVOF coatings at various
immersion times. For all HVOF coatings, after 1 h of exposure, only a large
capacitive semi-circle is observed expanded with further immersion times.
1200 50 30
40 T800 HVOF 700 25 T800+21WC HVOF

20
30
1000 20
1h 600
15
10
10 3h 5
1h
-Z" (ohm.cm )
6h 3h
2
800
0 500 0
0 5 10 15 20 25 30
-Z" (ohm.cm )
0 10 20 30 40 50
6h
2
12h
24h 400 12h
600 48h 24h
300 48h
400
200
200 100
(b)
(a) 0
0
0 100 200 300 400 500 600 700
0 200 400 600 800 1000
' 2
'
Z (ohm.cm )
2 Z (ohm.cm )
700 30
700
50
T800+43WC HVOF 25 T800+68WC HVOF
40
600 20
30
600 15
20 10
10
1h 500 5
500 1h
-Z" (ohm.cm )
3h
-Z" (ohm.cm )
0 0
2
0 5 10 15 20 25 30
0 10 20 30 40 50
6h 3h
400
400 12h 6h
24h 12h
300 24h
300 48h
48h
200 200
100 100
(c) (d)
0 0
0 100 200 300 400 500 600 700 800 0 100 200 300 400 500 600 700
' 2 ' 2
Z (ohm.cm ) Z (ohm.cm )
Figure 6.26 Nyquist plots of HVOF coatings for different times (a) T800 (b)
T800+21WC (c) T800+43WC and (d) T800+68WC
As shown in figure 6.26 there was expansion of the semi-circle by increasing time
due to the oxide layer of chromium oxide formed at the electrode surface.
However, in Nyquist plot T800+68WC HVOF coating (figure 6.26 (d)) there was
small decrease in the semi-circle, probably due to dissolution of matrix material.
The same behaviour was noticed after laser treatment as can seen in figure 6.27. By
increasing the time of immersion there was expansion of the semi-circle of the total
impedance as a result of created oxide layer.
227
7000 5000 500

500
400
T800 Laser 400
T800+21WC Laser
6000 300
300
200
4000 200
100
5000 100 0
0 100 200 300 400 500
-Z" (ohm.cm )
0
2
0 100 200 300 400 500
1h
-Z" (ohm.cm )
3000
2
4000 3h 1h
6h 3h
3000 12h 2000 6h
24h 12h
2000 48h 24h
1000 48h
1000
(a) (b)
0 0
0 3000 6000 9000 12000 15000 0 3000 6000 9000 12000
' 2 ' 2
50
600
50
1200 40 T800+43WC Laser 40 T800+68WC Laser
30
30
20 500 1h
20
1000 10
0
0 10 20 30 40 50
10 3h
400 0 6h
0 10 20 30
800
-Z" (ohm.cm )
12h
2
-Z" (ohm.cm )
1h 24h
2
3h 300 48h
600
6h
12h 200
400
24h
48h
200 100
(c) (d)
0 0
0 500 1000 1500 2000 2500 3000 0 200 400 600 800 1000 1200
' 2
Z (ohm.cm ) '
Z (ohm.cm )
2
Figure 6.27 Nyquist plots of laser treated HVOF coatings for different times (a) T800
(b) T800+21WC (c) T800+43WC and (d) T800+68WC
The Nyquist plots (figures 6.29) showed clearly the different responses of EIS for
the as received coatings (HVOF) and after laser treatment after 3 hours of
immersion. The Nyquist plots obvious illustrated the positive effect of laser
remelting of HVOF coating for all types of coating with different percentage of
WC. The equivalent circuit model was proposed in figure 6.28 which was found to
fit all the HVOF coatings before and after laser treatment. In this model, R S is the
resistance of the solution, RP is the resistance of the coating that is directly linked
to the coating defects such as porosity and microcracks, CPE P is the constant phase
element that is used instead of pure capacitance where it showed better fitting.
Because the real surface area which is exposed to the electrolyte is greater than the
geometric one as shown in tables 5.1 and 5.6, and the roughness of the surface
increases by increasing the exposure time, also due to splat boundaries, and
porosity. Rct is the charge transfer resistance and CPE dl is associated with capacitor
behaviour of the double layer. The corrosion resistance of the coatings can be
evaluated by Rct. The higher the value of Rct, the less easily the charges transferred
through the electrolyte/substrate interface and the higher the resistance to the
228
corrosion. Tables 6.3 and 6.4 summarise the electrochemical parameters of HVOF
coatings before and after laser treatment respectively after 3 hours of immersion,
using the circuit described in figure 6.28. Table 6.3 shows that the values of Rct for
all HVOF coatings after 3 hours of immersion were in the range of 580 – 12768 Ω
cm2, and decreased with the addition of WC. Also RP decreased slightly by
addition of WC with the range 26-55 Ω cm2. However, Rct increased significantly
after laser treatment for all the HVOF coating, which indicates improvement of
corrosion resistance. In T800 HVOF coating, the laser treatment increased the
value of Rct from 12768 to 16529 Ω cm2. For T800+21WC Rct increased from 631
to 10205 Ω cm2. The percentage of corrosion improvement after laser treatment for
T800 and T800+21WC was 23% and 94% respectively. However, the
improvement in corrosion resistance for T800+43WC and T800+68WC was 77%
and 30% respectively. The higher percentage of WC the lower percentage of
corrosion improvement. With increasing content of WC, more WC grains remained
unmelted in the coating after laser treatment. Therefore, the reduction of
microgalvanic activity between the two phases became less effective.
Figure 6.28 Equivalent circuit proposed for the coating system
229
6000 4000
500
T800 after 3h HVOF 500
400 400 T800+21WC after 3h

300 Laser 300
5000 200 200
HVOF
100
0.005 Hz 3000 100
0 0
0 100 200 300 400 500
Laser
4000 0 100 200 300 400 500
-Z" (ohm.cm )
0.034 Hz
2
-Z" (ohm.cm )
2
3000 0.034 Hz 2000 0.005 Hz
2000
1000
1000
30000 Hz
(a) 30000 Hz
(b)
0 0
0 2000 4000 6000 8000 10000 12000 14000 0 2000 4000 6000 8000 10000
' 2 ' 2
1000 50 1000
50
40
30
T800+43WC after 3h 40
T800+68WC after 3h (d)
30
20
800 10
HVOF 800 20
HVOF
0
0 10 20 30 40 50
0.034 Hz
Laser 10
0 Laser
0 10 20 30 40 50
-Z" (ohm.cm )
-Z" (ohm.cm )
2
600 600
2
0.005 Hz
400 400
200 200 0.034 Hz
0.005 Hz
30000 Hz (c) 30000 Hz
0 0
0 500 1000 1500 2000 2500 0 200 400 600 800 1000
' 2 ' 2
Figure 6.29 Impedance spectra after 3 hours of immersion for various coatings before
and after laser treatment: (a) T800, (b) T800+21WC, (c) T800+43WC, and (d)
T800+68WC
Table 6.3 Electrochemical parameters obtained from EIS spectra of HVOF coatings
after 3 hours of immersion
Electrochemical HVOF after 3h of immersion

parameters T800 T800+21WC T800+43WC T800+68WC
Rs (Ω.cm2) 2 1.6 2 1.8
Rp (Ω.cm2) 55 42 40 26
Rct (Ω.cm2) 12768 631 597 580
CPEp (mF.cm-2) 3.7 7.7 7.5 6.5
CPEdl (mF.cm-2) 4.7 4.9 4.8 7.7
np 0.64 0.63 0.64 0.65
ndl 1 1 1 1
230
Table 6.4 Electrochemical parameters obtained from EIS spectra of laser coatings
Electrochemical Laser / after 3h of immersion

Rs (Ω.cm2) 1.56 1.68 1.77 1.85
Rp (Ω.cm2) 8688 349 180 226
Rct (Ω.cm2) 16529 10205 2583 831
CPEp (mF.cm-2) 0.083 0.079 0.26 0.63
CPEdl (mF.cm-2) 0.86 0.19 0.63 1.7
np 0.77 0.83 0.9 0.87
ndl 0.63 0.59 0.56 0.45
Figure 6.30 illustrates the Nyquist plots of EIS spectra of various HVOF coatings
before and after laser treatment after immersion time of 12 h in 0.5 M H2SO4
solution. It is obvious there was improvement in corrosion resistance after laser
treatment especially in T800 and T800+21WC HVOF coating as seen in figure
6.30 (a) and (b). Tables 6.5 and 6.6 show the electrochemical parameters using the
equivalent circuit in figure 6.28. Table 6.5 illustrates that the values of Rct for all
HVOF coatings were in the rage of 2400 to 10200 Ω cm2, and decreased with
increasing WC. Also, RP reduced slightly by adding WC. However, after laser
treatments, the value of Rct for T800 coating was increased from 10200 to 17617 Ω
cm2, which indicates an improvement of corrosion resistance of the coating after
laser treatment. For T800+21WC coating, the Rct increased after laser treatment
from 3750 to 15100 Ω cm2, representing a significant improvement of corrosion
resistance of the coating after laser treatment. Furthermore, the percentages of
corrosion improvement of T800 and T800+21WC coatings after laser treatment
were 42% and 75% respectively. There was no clear improvement in corrosion
resistance for T800+43WC and T800+68WC HVOF coating after laser treatment.
231
8000 5000
1000 1000
800 T800 after 12h HVOF 800

T800+21WC after 12h
7000 600 600
Laser HVOF
400
4000 400
6000 200 200

Laser
0
0 200 400 600 800 1000 0.005 Hz 0
0 200 400 600 800 1000
-Z" (ohm.cm )
5000
-Z" (ohm.cm )
0.034 Hz
2
3000
2 0.005 Hz
4000
2000
3000 0.034 Hz
2000
1000
1000
30000 Hz (a) 30000 Hz (b)
0 0
0 2000 4000 6000 8000 10000 12000 14000 16000 0 2000 4000 6000 8000 10000 12000
' 2 ' 2
1000 50
1000 50
40
T800+43WC after 12h 40 T800+68WC after 12h
30 30
800
20
10
HVOF 800
20
10
HVOF
0
0 10 20 30 40 50
Laser 0
0 10 20 30 40 50 Laser
-Z" (ohm.cm )
600
-Z" (ohm.cm )
600
2
2
0.034 Hz
400 0.005 Hz 400
0.034 Hz 0.005 Hz
200 200
30000 Hz (c) 30000 Hz

(d)
0 0
0 500 1000 1500 2000 0 200 400 600 800 1000
' 2 ' 2
Figure 6.30 Impedance spectra after 12 hour of immersion for various coatings
before and after laser treatment: (a) T800, (b) T800+21WC, (c) T800+43WC,
and (d) T800+68WC
Table 6.5 Electrochemical parameters obtained from EIS spectra of HVOF coatings
Electrochemical HVOF after 12 hour of immersion

Rs (Ω.cm2) 2.2 1.7 1.9 1.8
Rp (Ω.cm2) 46 29 33 24
Rct (Ω.cm2) 10200 3750 2400 2600
CPEp (mF.cm-2) 3.8 6.1 6.4 7.6
CPEdl (mF.cm-2) 4.4 6.6 8.5 11.2
np 0.64 0.63 0.64 0.65
ndl 1 1 1 1
232
Table 6.6 Electrochemical parameters obtained from EIS spectra of laser coatings

Rs (Ω.cm2) 1.5 1.0 1.8 1.6
Rp (Ω.cm2) 8427 200 370 207
Rct (Ω.cm2) 17617 15100 1800 2500
CPEp (mF.cm-2) 0.1 0.2 0.8 0.3
CPEdl (mF.cm-2) 0.8 0.4 1.2 0.65
np 0.69 0.77 0.84 0.77
ndl 1 0.7 0.65 0.55
The decreasing of Rct with the addition of WC in the HVOF coatings might be
associated with several reasons. First, the addition of WC increased the surface
area of the T800 coating matrix by introduction of numerous interfaces between the
matrix and carbides. Such interfaces can be subjected to dissolution governed by
galvanic corrosion (figure 6.19) and form interconnected channels which are
responsible for the electrolyte penetration through the coating and at the
coating/substrate interface. Second, the value of RP decreased with an increase in
the content of WC, indicating the increased porosity with WC during the test.
These interconnected porosity provided channels allowing the electrolyte to
penetrate through the coatings to reach the interfaces at the coating/substrate,
which might leading to galvanic corrosion on the steel substrate. Third, for all
HVOF coatings, the splat boundaries that might be sites of oxide inclusions could
be the common sites for initiation of crevice corrosion [130]. Furthermore, the splat
boundaries became less pronounced with increasing content of WC. It is believed
that the overall corrosion resistance of the HVOF coatings could be considered as a
combined effect. The addition of WC reduced the values of R ct by the first two
mechanisms dominating the corrosion process, but increasing the content of WC
233
did not affect Rct significantly due to the third mechanism contributing to the
overall process of corrosion [173].
After laser treatment as shown in figure 6.29 with tables 6.3 and 6.4 after 3 hours
of immersion corrosion resistance improved for all HVOF coatings, where R ct
increased after laser treatment for all HVOF coatings. Also, R p increased for all
HVOF coatings which indicate reduction of porosity due to remelting of HVOF
coating, same results were shown in porosity measurement (tables 5.4 and 5.7).
However, after 12 hour of immersion the results show significant improvement in
corrosion resistance in T800 and T800+21WC coatings by laser treatment. Also the
results show significant reduction of porosity after laser treatment as RP increased.
The improvement of corrosion resistance was due to reduction of porosity and splat
boundaries, also due to the formation of a new phase of W2Co4C at the interface of
WC/T800 matrix to reduce the microgalvanic activity. In T800+43WC and
T800+68WC there is no obvious improvement in corrosion after 12 hour because
of adding more WC which could cause more galvanic action and more WC grains
remained unmelted in the coating after laser treatment. Therefore, the reduction of
microgalvanic activity between the two phases becomes less effective.
The following figures 6.31-6.32 show the relation between the logarithm of coating
resistance and charge transfer resistance with various immersion times (1, 3, 6, 12,
24, and 48 hour) for as-received HVOF coatings and after laser treatment. The full
results of EIS for all immersion times (graphs and tables) for various HVOF
coatings before and after laser treatment can be found in Appendices (A) and (B). It
is observed from figures 6.31-6.32 that the laser treated samples have different
electrochemical impedance spectroscopy behaviour compared to as-received
HVOF for all coatings. The general trend for almost all the HVOF coatings (as
seen in figure 6.31) is that the coating resistance (Rp) decreased slightly by
increasing time of immersion; this might be because of increased interconnected
channels and defects in the HVOF coating. After laser treatment T800 and
T800+21WC (figure 6.31 (a) and (b)) almost have the same values of Rp which
indicate no porosity increase by increasing immersion time in these coatings.
However, in T800+43WC and T800+68WC coatings (figure 6.31 (c) and (d)) the
values of Rp increased by increasing immersion time, that might be as a result of
234
oxidation in the splat boundaries and corrosion products partially filling the gaps
and impeding the electrolyte to penetrate through the coating surface. In figure
6.32 (a) and (b) there was improvement in corrosion resistance of T800 and
T800+21WC after laser treatment during all immersion times. However, corrosion
resistance was improved in T800+43WC (figure 6.32 (c)) before the first 10 hours
then the HVOF coating might create oxidation layer (WO3) on the WC [69, 169]
that increase the values of Rct. T800+68 WC coating (figure 6.32 (d)) showed no
improvement in corrosion resistance for this coating. As a general behaviour all
T800 with WC HVOF coatings Rct increased gradually with immersion time which
might because of creating of oxide layer (WO3) [69].
10000 T800+21WC HVOF

1000 Laser
T800
RP (ohm.cm )
HVOF
RP (ohm.cm )
2
1000
Laser 100
100 10
(a) (b)
0 10 20 30 40 50 0 10 20 30 40 50
Immersion time (h) Immersion time (h)
10000
HVOF T800+43WC T800+68WC
HVOF
Laser
600 Laser
1000
RP (ohm.cm )
2
RP (ohm.cm )
2
400
100
200
10
(c) (d)
0
0 10 20 30 40 50 0 10 20 30 40 50
Figure 6.31 Coating resistance Rp before and after laser treatment for various time of
immersion (a) T800 (b) T800+21WC (c) T800+43WC (d) T800+68WC
235
25000 100000
T800 T800+21WC HVOF
HVOF Laser
20000 Laser
Rct (ohm.cm )
10000
Rct (ohm.cm )
15000
2
10000
1000
5000
(a) (b)
0 100
0 10 20 30 40 50 0 10 20 30 40 50
5000
T800+43WC HVOF T800+68WC HVOF
Laser Laser
4000 10000
Rct (ohm.cm )
2
Rct (ohm.cm )
2
3000
2000
1000 1000
(c) (d)
0
0 10 20 30 40 50 0 10 20 30 40 50
Figure 6.32 Charge transfer resistance Rct before and after laser treatment for
various time of immersion (a) T800 (b) T800+21WC (c) T800+43WC (d) T800+68WC
Figure 6.33 (a) illustrates the cross section of T800 HVOF coating after EIS test at
12h immersion time. In figure 6.33 (b) it is clear the network of pores within the
coating provides a path for electrolyte to penetrate through the coating and reach
the interface causing corrosion of the steel substrate which is confirmed by ICP test
(figure 6.14). Figure 6.34 (a) shows general view of T800 HVOF after EIS 12 h of
immersion test. It was observed that splat boundary regions start to corrode
preferentially. Also corrosion occurred within splats at Co solid solution (figure
6.34 (b)), where Laves phase contains high percentage of Mo which shows low
dissolution in the electrolyte as confirmed by ICP test (figure 6.14). These splat
boundaries have higher oxide contents as seen in EDX results (figures 5.34 and
5.35), and confirmed by EPMA mapping (figure 5.36). Moreover, lateral cracking
within splats has been observed as shown in figure 6.34 (c), these cracks may have
occurred because of oxide induced expansion in splat boundaries which initiate
cracks in the very fragile splats material (T800) [172].
236
Figure 6.33 Cross section of T800 HVOF coating after EIS test at 12h immersion time
(a) cross section of the coating (b) interface
(a) surface of the coating (b) corrosion of Co solid solution within splats (c) cracks
within splats
Figure 6.35 (a) illustrates the cross sectional view of T800 HVOF coating after
laser treatment following EIS test at 12h of immersion time in 0.5M H2SO4. The
coating was attacked slightly at the surface in the Co solid solution as can seen
from figure 6.35 (b) and the difference can be noticed by comparison with as-
sprayed condition in figure 6.34 (c). The interface was not attacked by corrosion, as
237
the laser treatment significantly reduced the porosity at the surface of the coating.
The improvement of corrosion resistance was due the significantly reduced
porosity (table 5.4 and table 5.7) which protected the substrate from corrosion.
Also, the improvement of corrosion behaviour was as a result of reduced or
eliminated the oxide inclusion around splat boundaries.
Figure 6.35 Cross section of laser treated T800 HVOF coating after EIS test at 12h
immersion time (a) cross section of the coating (b) zoom of the upper side of the
coating
Figure 6.36 illustrates cross section of T800+68WC HVOF coatings after EIS test
at 12h of immersion time. After adding WC carbides, the corrosion occurred at the
matrix (T800) regions as can see from figure 6.36 (c). The corrosion attacked the
upper side of the coating as shown in figure 6.36 (a). The electrolyte penetrated
through the interconnected pores to the interface and caused corrosion of substrate
(figure 6.36 (b). The dissolution of T800 as a result of galvanic corrosion, where
WC works as cathodic and T800 works as anodic.
238
Figure 6.36 Cross section of T800+68WC HVOF coating after EIS test at 12h
immersion time (a) cross section of the coating (b) interface (c) zoom of upper side of
the coating
Figure 6.37 shows laser treated T800+68 WC HVOF coating after EIS test at 12h
of immersion. Small corrosion at the interface has been noticed which indicates
that laser treatment sealed the defects within the HVOF coating and protected the
substrate from the corrosion (figure 6.37 (a)). However, as a result of existence of
partially melted of WC, the coating still contains regions of WC and small regions
of T800 (figure 5.74), this microstructure will create galvanic coupling between the
wide area of WC particles and the small area of T800 (figure 6.37 (b)).
Figure 6.37 Cross section of laser treated T800+68WC HVOF coating after EIS test
at 12h immersion time (a) cross section of the coating (b) corrosion area
239
Cross section of T800 HVOF coating after EIS test at 48h of immersion time
showed in figure 6.38 (a). The coating faced severe corrosion attack around the
splat boundaries and within splats (figure 6.38 (b)), also the steel substrate
corroded extensively, where the electrolyte found its way easily through the
connected pores in the HVOF coating. After laser treatment (figure 6.39 (a)) the
protection of substrate of electrolyte penetration has been significantly improved,
even though there was a small amount of corrosion attack at the interface. Figure
6.39 (b) shows corrosion attack of Co solid solution, a very small amount of attack
noticed at Laves phase, these results have been confirmed by ICP test (figure 6.14).
The improvement in corrosion behaviour was clearly due to modification of the
morphology of the coating and reduction in the defects within the coating.
(a) cross section of the coating (b) corrosion at the upper side of the coating
Figure 6.39 Cross section of laser treated T800 HVOF coating after EIS test at 48h h
immersion time (a) cross section of the coating (b) zoom at the upper side of the
coating
240
Figure 6.40 illustrates cross section of T800+21WC HVOF coating after EIS test at
48h of immersion. The corrosion attacked the surface of the coating and as shown
in figure 6.40 (a) galvanic coupling between WC and T800 control the corrosion
action. The figure shows some WC particles moved from their positions due to
corrosion of the surrounding T800. Also, there was corrosion attack at the
interface where the electrolyte penetrated the coating as a result of interconnected
pores in the coating (figure 6.40 (b)). However, after laser treatment T800+21WC
HVOF coating did not show corrosion attack at the surface as can see in figure 6.41
(b). Moreover, a very small amount of corrosion attack was noticed at the interface
(figure 6.41 (a)). The excellent improvement of corrosion behaviour of this coating
was due to greater melting of WC particles which form a new phase of W2Co4C to
reduced microgalvanic activity between carbides and the matrix.
immersion time (a) upper side of the coating (b) interface
Figure 6.41 Cross section of laser treated T800+21WC HVOF coating after EIS test
at 48h immersion time (a) cross section of the coating (b) upper side of the coating
241
Figure 6.42 shows cross section of T800+68WC HVOF coating before and after
laser treatment after EIS test at 48h of immersion test. As shown in figure 6.42 (a),
in the as sprayed coating, the corrosion attacks the upper region of the surface, and
the interface between the coating and substrate, which indicates there was
penetration of the electrolyte to the interface through the interconnected porosity.
After laser treatment as shown in figure 6.42 (b) there was corrosion at the surface.
However, there is no indication of corrosion at the interface which confirms that
laser treatment reduced the interconnected pores in the coating, making the coating
more protective to the substrate against attack of the electrolyte. Figure 6.42 (c)
illustrates that corrosion occurred on the upper regions of surface which are anodic
(matrix). After laser treatment (figure 6.42 (d)) the corrosion attacks the small areas
between the carbides (gray areas) which work as anodic, where the laser did not
melt the carbides completely and still there is galvanic activity in the partially
melted area.
immersion time (a) cross section as HVOF coating (b) cross section after laser treated
(c) upper side of HVOF coating (d) upper side of laser treated coating
242
In conclusion, laser surface treatment of HVOF sprayed Co based WC MMC

coatings significantly reduced the microstructural defects such as porosity and splat
boundaries. Laser surface treatment also resulted in the formation of new phase due
to the interdiffusion and interaction between the WC and Co matrix. Immersion
tests, polarisation tests, and electrochemical impedance spectroscopy analysis
along with ICP test and the SEM examination of corrosion morphology confirmed
that the densification of the coatings by laser treatment prevented the electrolyte
penetration and subsequent corrosion attack of the steel substrate for laser treated
HVOF coatings. For the laser treated T800+21WC coatings, EIS analysis showed
significant improvement in the corrosion resistance due to the fully melting of the
WC resulting in reduction of microgalvanic corrosion between the WC and Co
matrix. However, for the T800+43WC and T800+68WC coatings, the laser
treatment under the current processing conditions did not produce sufficient
melting of the WC to reduce the microgalvanic activity.
6.5 Summary
 Immersion tests followed by ICP tests for the as-received HVOF coatings
show that the electrolyte can penetrate easily through the interconnected
pores of HVOF coating to reach the interface between the substrate and
the coating, causing corrosion and dissolution of the substrate and
delamination of the HVOF coatings.
 Immersion tests followed by ICP tests for the laser treated HVOF
coatings show that after laser treatment the HVOF coatings with
significant reduction of defects become more effective barrier coatings in
protecting the substrate from corrosive attack.
 Polarisation tests in aerated 0.5M H2SO4 solution show a positive shift of

corrosion potentials and reduction of corrosion current density after laser
treatment, indicating that the laser treatment improves corrosion
resistance of HVOF coatings.
243
 Electrochemical Impedance Spectroscopy (EIS) tests in aerated 0.5M

H2SO4 solution show that there is an oxide layer of chromium oxide
formed at the electrode surface with increasing time of immersion. In
general the Nyquist plots clearly illustrated the positive effect of laser
remelting of HVOF coating for all types of coating with different
percentage of WC. The degree of WC melting affect the corrosion
behaviour of the MMC laser treated HVOF coatings, the higher the
percentage of WC the lower the percentage of corrosion improvement.
This is because, by increasing the content of WC, more WC grains
remain umelted in the coating after laser treatment, so the reduction of
micro-galvanic activity between the two phases became less effective.
Also EIS showed significant reduction of porosity in HVOF coatings
after laser treatment.
 The corrosion starts to attack the micro-crevices within splat boundaries,

and the boundaries between the carbides and the matrix as a result of
galvanic coupling between the WC and the T800 matrix. Laser surface
treatment improved the corrosion properties of T800 and T800+WC
HVOF coatings because of: 1) significantly reduction of defects such as
porosity, micro-crevices, and splat boundaries. 2) high melting of WC
formed new phase as a result of interaction between the WC and T800
matrix, which reduced the micro-galvanic coupling between the WC and
the T800.
244
Chapter 7 Hardness and Wear Resistance
Measurements
7.1 Introduction
This Chapter presents the results of Vickers microhardness and wear rate tests to
evaluate the wear performance of various HVOF coatings before and after laser
treatment. SEM was used to investigate the worn areas to understand the wear
mechanisms involved for the various coatings.
7.2 Microhardness
Vickers microhardness under a 100 g load was measured on ground and polished
cross-sections of various coatings from the top of the coating surface to the base
stainless steel, to produce hardness profiles along the melt depth. The distance
between indentations remained large enough to avoid interaction between the new
indentation and any micro-cracks caused by the previous indentations. Figure 7.1
shows microhardness profiles for various HVOF coatings before and after laser
treatment. It can be seen that for the T800 HVOF coating, there was an
improvement in homogeneity after laser treatment. The improvement was due to
the elimination of the defects from the HVOF coating such as splat boundaries,
inhomogeneity, and porosity (as shown in Figures 5.20 and 5.42). However, the
average values of the microhardness for T800 HVOF coatings before and after
laser treatment were 909 HV0.1 and 912 HV0.1 respectively, indicating that laser
treatment led to no significant change of microhardenss. The value of the hardness
for the laser-treated coating was higher than the value of 850 HV0.3 reported for a
laser-clad layer of T800 coating on stainless steel (AISI 304) by Navas et al. [123].
Fig. 7.1(b) illustrates the microhardness for T800+21WC coating before and after
laser treatment and the results show that the laser treated specimen presented
245
CHAPTER 7 HARDNESS AND WEAR RESISTANCE MEASUREMENTS
a more homogenous microhardness distribution, and higher microhardness values

in the laser treated area were found close to the surface. Within the HVOF coating,
obviously the hardness of the WC cluster was up to 1254 HV0.1, while the hardness
of the T800 matrix was around 687 HV0.1, giving the average value of
microhardness of the HVOF coating of 729 HV0.1. After laser treatment, the
average hardness was increased to 955 HV0.1. The inhomogenity in microhardness
for HVOF can be explained from figure 7.2, where when the indentation was on
WC phase as shown in figure 7.2 (b) the microhardness value was high. If the
indentation was on T800 phase as shown in figure 7.2 (a) the microhardness was
much lower. The high microhardness in some points on HVOF coating might be
due to the presence of big WC particles in the untreated layer. As expected, the
same behaviour has been observed in T800+43WC and T800+68WC coatings, in
which only a small improvement in microhardness after laser treatment was
obtained, while significant improvements in homogeneity have been achieved, as
can be seen in figures 7.1, 7.2, and 7.3. The complete results of microhardness tests
are shown in Figure 7.1 and Table 7.1.
As shown in Table 7.1 the values of standard deviation indicate the inhomogeneity
in the coating. The higher the standard deviation, the more the inhomogeneity in
the coatings is. The results in the table also illustrate that the laser treatment
improves homogenisation of the coatings which obviously reduces the standard
deviation values after laser treatment. This improvement in homogenisation was
due to the spread of the partially melted WC particles over a wider area in the
coating as can be seen in figure 7.3. Moreover, the indentations on the coating after
laser treatment have more symmetrical shape than the indentations on the HVOF
coatings due to the homogeneity of the laser treated coating in figure 7.4.
246
Figure 7.1 Hardness profiles of various HVOF coatings before and after laser
treatment (a) T800 (b) T800+21WC (c) T800+43WC (d) T800+68 WC
Table 7.1 Microhardness values of various HVOF coatings before and after laser
treatment
T800 T800+21WC
Laser HVOF Laser

HVOF
854.1 532.4 1001

808.5
937.7 687.4 1022

889.6
935.5 1254 808.2

893
921.6 441.9 989.8

1046
912 729 955

909
± 39* ± 364* ± 99*
± 99.2*
247
T800+43WC T800+68WC
Laser HVOF Laser

HVOF
1188 981.2 1331

788
1190 1061 1325

915.8
1250 1323 1288

1113
1100.9 1105 1332

1104
1182 1118 1319

980
± 61* ± 146* ± 21*
± 157*
n* Standard deviation

T800+43WC coating.
248

laser treated T800+43WC coating.
Figure 7.4 SEM micrographs of microhardness indentations (a) on as-received HVOF

coating and (b) after laser treatment.
7.3 Wear test results

Figure 7.5 illustrates the results for the wear test of various HVOF coatings before
and after laser treatment. It is obvious that in T800 coating, there was a significant
improvement in wear resistance, in which the wear rate of the HVOF coating was
0.43 m3/Nm while after laser treatment it was reduced to 0.017 m3/Nm,
indicating 25 times reduction in wear rate after laser treatment. Furthermore, the
improvement in wear resistance was observed for the other coatings. Where, the
wear rate in T800+21WC decreased by around 9 times after laser treatment. In
T800+43WC and T800+68WC the wear rate decreased 3 times and 5 times after
laser treatment respectively. Also from figure 7.1 it is clear that the coatings with
higher percentage of WC, have higher wear resistance for both as-received HVOF
249
and laser treated. In previous work, Liu et al [12] used HPDL remelting for Iconel
625 with WC HVOF coatings. The results showed that wear volume loss has been
decreased for Inconel 625-22 wt.% WC by ~ 80% and by ~ 50% for Inconel 625-
42 Wt.% WC.
0.43 Wear rate for HVOF and after laser treatment
HVOF
0.4
Laser
Wear rate (m /N m)
3
0.055
0.05
0.04
0.03
0.02 0.017
0.011
0.01 0.006 0.007
0.0048
0.0013
0.00
T800 T800+21WC T800+43WC T800+68WC
Figure 7.5 Wear rates for various coatings before and after laser treatment.
7.3.1 T800
In order to understand the improvement in wear resistance and wear mechanisms
involved in various coatings before and after laser treatment, SEM images for the
worn areas have been taken. Figures 7.6 and 7.7 show the surface morphology of
the worn areas for T800 coating before and after laser treatment respectively. The
T800 alloy is a very brittle material as reported in some previous studies [155, 174-
177]. As shown in Figure 5.9 in Chapter 5, the T800 HVOF coating contained gaps
and micro-cracks between the splats. Surface fatigue led to mixture of severe
plastic deformation, and fracture wear. During sliding cracks occurred in the wear
track. Subsequently large wear layers tend to be produced during surface breakup.
In the surface fracture wear the amount of damage is increased by increasing
sliding distance (figure 7.6). In addition, the high wear rate can also be attributed to
the high surface roughness of T800 HVOF coating (Ra ~ 5µm) (Table 5.1). Where,
the brittle protrusions on the T800 surface are easily removed by the abrading
particles.
250
On the other hand, the laser-treated T800 coating (figure 7.7) shows much denser
layers, due to the elimination of the defects such as porosity and gaps. Therefore,
the laser treatment improved the cohesion between the splats and the adhesion
strength at the coating/substrate interface due to the formation of fusion bonds by
laser treatment. The wear mechanism in this case might be mixed of adhesion and
oxidation wear. Furthermore, harder phases precipitated after laser treatment such
as eutectic (Laves phase + Co) had increased the hardness and positively affected
wear resistance [178, 179]. Also the significant reduction in surface roughness in
T800 after laser treatment (Ra = 0.18 µm) (Table 5.6) also contributed to the
reduction of the wear rate.
Figure 7.6 SEM micrographs of worn surface of T800 HVOF coating.
251
Figure 7.7 SEM micrographs of worn surface of laser-treated T800 HVOF coating.
7.3.2 T800+21WC
Figure 7.5 shows an improvement in wear resistance for the T800+21WC coating
after laser treatment. It has been observed from figures 7.8 and 7.9 there was
abrasion wear before and after laser treatment. In general there are two important
factors which affect the wear rate. One is hardness and the other is cohesion of
material. For this MMC material, the hard WC particles increase the average
hardness as shown in figure 7.1 and Table 7.1. The T800 matrix acts as a binder
material between these hard particles. As shown in Figure 7.8, due to the nature of
thermal spray processes, the cohesion between WC particles and the matrix is not
strong, the wear process resulted in many fractured particles appearing in worn
tracks (figure 7.8 (d)). It suggested that some material loss took place firstly by
removal of the binder phase (matrix) due to fracture wear and cracks in the
subsurface, followed by pullout of the carbides. The resultant fine debris from the
matrix and fractured WC, caused further sharp cutting abrasive wear, promoting
further removal of the matrix. The high surface roughness (R a = 5.47 µm) (Table
5.1) could be an important factor in the high wear rate.
252
Figure 7.8 SEM micrographs of worn surface of T800 + 21 WC HVOF coating.
Figure 7.9 shows the worn area of T800+21WC after laser treatment. The
improvement of wear resistance after laser treatment as shown in figure 7.1 was
mainly due to the combination of partially melted carbides and fully melted
substrate that increased the cohesion between the carbide particles and the matrix.
Also the elimination of porosity and gaps by laser treatment affected wear
resistance positively. In this case the wear performance has the same mechanism as
described for the HVOF coatings above. However, for laser-treated surface, pulling
out the hard particles may take a longer time so that the harder particles fractured
and remained in the matrix longer as shown in figure 7.9 (d), (e). And meanwhile,
the laser re-melting reduced the lamellar nature of the structure, and increased the
average hardness value, and reduced surface roughness to 1.9 µm (Table 5.6).
These factors also contributed to the improvement of the wear resistance positively.
253
Figure 7.9 SEM micrographs of worn surface of laser-treated T800 + 21 WC coating.
7.3.3 T800+43WC
The same wear mechanism which occurred in T800+21WC coating before and
after laser treatment can be observed on the T800+43WC coating. As shown in
figures 7.10 and 7.11, it can be seen that some small WC particles (Figure 7.10d)
after fracturing were pulled out the matrix. On the other hand, it is obvious that a
higher percentage of WC particles in this case improved the wear resistance for
both HVOF and laser-treated, compared with T800+21WC coating. This indicates
that the WC particles are resistant to wear and are successfully retained by the
matrix especially after laser partial melting.
254
Figure 7.10 SEM micrographs of worn surface of T800+43 WC coating.
Figure 7.11 SEM micrographs of worn surface of laser-treated T800+43 W coating.
7.3.4 T800+68WC
Figure 7.12 shows the worn regions of the T800+68WC coating. The increased
WC percentage in the matrix further improved the wear resistance. The wear
mechanism in the HVOF coating had the same wear process as described for the
lower WC content coatings (T800+21WC and T800+43WC) in which the loss of
materials was due to fracture wear in T800 matrix caused by fracturing WC and
pulling out the carbides (figure 7.12). However, after laser treatment (figure 7.13),
the grooves running parallel to the slide direction became more obvious, indicating
a mainly abrasive wear mechanism. Also, the small WC particles can be seen in the
255
worn area which took a longer time to be pulled out due to the fusion bonding
between the partially melted WC particles and the Co-matrix.
Figure 7.12 SEM micrographs of worn surface of T800+68 WC coating.
Figure 7.13 SEM micrographs of worn surface of laser-treated T800+68 WC coating.
7.4 Summary
 The microhardness distribution became uniform within the HVOF

coatings, due to homogenisation of microstructures by laser remelting,
and elimination of porosity and gaps from the coating. For T800 coating,
the hardness was increased as a result of formation of Lavas phase; For
T800+WC coatings, more uniform distribution of microhardness was
observed.
 Wear test (pin on disk) showed that the wear process was dominated by
the fracture wear mechanism in T800 HVOF coatings and in the matrix of
T800+WC HVOF coating. There was significant improvement in wear
256
resistance after laser remelting for T800, by reducing the wear rate from
0.43 m3/N m to 0.017 m3/N, indicating 25 times reduction of wear
rate after laser treatment. For T800+21WC, the wear rate was decreased
by 9 times after laser treatment, from 0.055 m3/N to 0.006 m3/N. For
T800+43WC and T800+68WC coatings, the wear rates were decreased 3
times and 5 times after laser treatment respectively.
 The HVOF coatings with higher percentage of WC have higher wear

resistance before and after laser treatment.
 The improvement of wear resistance was due to a number of reasons,

including 1) increase in hardness, particularly for T800 coating; 2) more
homogenisation of microhardness, particularly for T800+WC coatings as
a result of elimination of porosity and inter-splat gaps; 3) the formation of
new microstructure such as dendritic structure for T800 coating and much
improved compacted T800+WC coatings; 4) for T800+WC coatings, the
improvement of the cohesion between the WC hard particles and the
matrix that was believed to play a major role in improvement of wear
resistance after laser treatment.
257
Chapter 8 Conclusions and suggestions for
future work
8.1 Introduction
This chapter summaries the conclusions that are presented at the end of each
chapter, in order to address the aims and objectives described in Section 1.2. The
conclusions are then followed by the recommendations that are made for carrying
out further research related to this area of research.
8.2 Conclusions
This work aimed to improve corrosion resistance of T800 and T800 with varying
amount of WC HVOF coatings on 316L stainless steel substrate by laser surface
melting using a high power diode laser, with the possibility of improving wear
performance. The outcomes of the work, through detailed microstructural
characterisation, evaluation of corrosion and wear performance, are summarised
and presented in correspondence to the objectives described in Section 1.2 as
follows.
1) To characterise the HVOF coatings of T800 and T800 composites with

varying amount of WC
All the HVOF coating surface show the presence of defects such as
porosity, micro-cracks, and micro-crevices between the splats. The surfaces
of the coatings are rough with a high surface area. It has been shown that
both surface roughness and surface area ratio (over a flat surface) were
slightly decreased by increasing the content of WC. The Ra of T800 is ~
5.05 µm, compared with ~ 4.49 µm for T800+68WC. The Sdr of T800 is ~
258
CHAPTER 8 CONCLUSION AND SUGGESTIONS FOR FUTURE WORK
212 % compared with ~ 153 % for T800+68WC. The cross-sections of

various HVOF coatings revealed the coating thickness of 250, 230, 220 and
165 µm respectively for T800, T800+21WC, T800+43WC and
T800+68WC, and non-homogeneous lamellar structures. The
microstructures show the presence of defects such as porosity, micro-
cracks, and micro-crevices and oxide stringers around splats. The addition
of WC reduces the porosity of the coatings. The values of porosity for
T800, T800+21WC, T800+43WC and T800+68WC are 4.8, 2.8, 2.5 and
2.2% respectively. The EDX and EPMA cross-sectional examinations
showed the presence of oxide inclusions along the splat boundaries and at
the interface between the HVOF coatings and the stainless steel substrate.
The XRD results indicate that there is no change of phases in HVOF
coatings, compared with the same materials in the form of powders. The
phases observed for T800 both in a powder form and as a HVOF coating
are Co, Co3Mo2Si, and Co2MoCr. The phases observed in T800+21WC and
T800+43WC in powder form and HVOF coating are WC, Co, W2Co4C, and
Co3Mo2Si. The phases observed in T800+68WC in a powder form and
HVOF coating are WC, Co, and W2Co4C. Co3Mo2Si was absence.
2) To establish laser operating windows for various HVOF coatings to

achieve i) defect-free layers, ii) control of the melt pool dimensions, in
particularly melt depth; iii) control of the degree of fully/partially melting
of the WC particles.
Under some laser processing conditions, it is possible to form cracks as a

result of thermal stresses. The T800 coating is highly prone to cracks due to
the hard and brittle nature of the Laves phase. Additionally, some laser
processing conditions produced porosity due to trapped gas in the melted
zones. This often occurred at high scanning velocities that provided less
time for the gas to release. In order to optimise the laser surface melting of
various HVOF coatings for formation of porosity-free and crack-free
coatings, the laser operating windows for various HVOF coatings have been
established. A range of melt depths, from 100 µm for partially melting, to
210 µm for fully melting, can be achieved for various coatings by
259
controlling the laser operating conditions. Low dilution of laser fully-

melted HVOF coatings can be also achieved.
Due to the time limitation of the project, only the following laser processing
parameters were selected to produce laser-melted coatings which were
crack-free, porosity-free, and with low dilution. When the laser beam size
was fixed as 3.5 mm x 2.5 mm at the focal position, the best laser operating
conditions were the following:
T800 (Partial melting): 500 W, 3 mm/s.

T800 + 21WC (Partial melting): 450 W, 2 mm/s.
T800 + 43WC (Full melting): 550 W, 3 mm/s.
T800 + 68WC (Full melting); 500 W, 3 mm/s.
3) To investigate the microstructural changes of various HVOF coatings

before and after laser treatments, in terms of surface morphology, phase
transformation and homogenisation of WC particles;
Laser surface melting of various HVOF coatings successfully eliminated

various defects in the HVOF coatings. There is significant reduction in
terms of porosity, roughness (Ra) and surface area (Sdr) after laser treatment.
The Ra of T800 HVOF coating was reduced after laser treatment by 96%,
and the Sdr reduced from 212% for the HVOF coating to 3.4%. The Ra of
T800+21WC HVOF coating was reduced after laser treatment by 65% and
the Sdr reduced from 223% for the HVOF coating to 9.94% after laser
treatment. For T800+43WC the Ra was reduced after laser treatment by
55%, and the Sdr reduced from 212% for the HVOF coating to 13.94% after
laser treatment. In general, EDX and EPMA results show an improvement
of elemental homogeneity after laser treatment. It has been shown that there
was significant reduction of porosity after laser treatment. The porosity for
T800 reduced from 4.8% for the HVOF coating to 0.1% after laser
treatment; for T800+21WC, it reduced from 2.8% of the HVOF coating to
0.3% after laser treatment; for T800+43WC, it reduced from 2.5% of
HVOF coating to 0.3% after laser treatment; and for T800+68WC, it
reduced from 2.2% of HVOF coating to 1% after laser treatment. XRD
260
results after laser treatment show the changes in some phases. For the T800
HVOF coating there was an increase in Co3Mo2Si phase indicating an
increase in Laves phase. W2Co4C became a major phase in the
T800+21WC, T800+43WC, and T800+68WC HVOF coatings after laser
treatment suggesting the reaction between Co and WC. The T800+68WC
HVOF coating after laser treatment mostly contained W2Co4C phase and a
small amount of WC. Cobalt solid solution was not detected in any of the
laser treated T800 coatings with WC.
4) To study the corrosion behaviour of various HVOF coatings before and

after laser surface treatments in different laser operating conditions, and to
understand the corrosion mechanisms of various coatings;
Immersion tests followed by ICP tests in 3M H 2SO4 solution for the as-
received HVOF coatings show that the electrolyte can penetrate easily
through the interconnected pores of HVOF coatings to reach the interface
between the substrate and the coating, causing corrosion and dissolution of
the substrate and delamination of the HVOF coatings. However, after laser
treatment, the HVOF coatings with significant reduction of defects become
more effective barriers in protecting the substrate from corrosive attack. In
the second electrochemical examination, the polarisation tests in aerated 0.5
M H2SO4 solution show a positive shift of corrosion potentials and
reduction of corrosion current density after laser treatment, indicating that
the laser treatment improves corrosion resistance of HVOF coatings. The
third electrochemical technique used was electrochemical impedance
spectroscopy in aerated 0.5 M H2SO4 solution. The results of EIS tests
show that there is a layer of chromium oxide formed on the coating surface
with increasing in time immersion. The Nyquist plots clearly illustrated the
positive effect of laser remelting of HVOF coating for all types of coating
with different percentage of WC. The degree of WC melting affects the
corrosion behaviour of the laser treated HVOF composite coatings. The
higher the percentage of WC, the lower the percentage of improvement in
corrosion resistance. This might be because, by increasing the content of
WC, more WC grains remain unmelted in the coating after laser treatment,
261
so the reduction of micro-galvanic activity between the two phases became

less effective. Also EIS results show significant reduction of porosity in the
HVOF coatings after laser treatment. The investigation of corrosion
morphology after polarisation and EIS tests for both as-received HVOF
coatings and after laser treatment show that the corrosion initiated at the
micro-crevices within splat boundaries, and at the boundaries between the
carbides and the matrix as a result of galvanic coupling between the WC
and the T800 matrix. The improvement of corrosion properties of the T800
and T800+WC HVOF coatings was due to the significant reduction of
defects such as porosity, micro-crevices, and splat boundaries. Also,
melting of WC formed new phase as a result of interaction between the WC
and T800 matrix, which reduced the micro-galvanic coupling between the
WC and the T800 matrix.
5) To investigate the wear performance and hardness of various HVOF

coatings before and after laser surface treatments in different laser
operating conditions, and to understand the wear mechanisms of various
coatings;
For the T800 coating, the hardness was increased as a result of formation of
Laves phase after laser treatment. On the other hand, the T800+WC
coatings show more uniform distribution of microhardness as a result of
homogenisation of microstructures by laser melting and elimination of
porosity and gaps from the coatings. There was significant improvement of
wear resistance for all the HVOF coatings after laser melting. The
improvement was due to a number of reasons, including: increase in
hardness, particularly for the T800 coating, more homogenisation of
microhardness distribution, and the formation of new microstructures, such
as a dendritic structure for T800 coating and a much improved compactness
for T800+WC coatings. Also, the improvement of the cohesion between the
WC hard particles and the matrix was believed to play a major role in
improvement of wear resistance after laser treatment. During the pin-on-
disk wearing test, it was believed that surface fatigue creates significant
cracks. The observation suggested that a fracture wear mechanism was
262
involved in degradation of the coatings, due to the lamellar microstructure

of T800 HVOF coating; after laser treatment of the T800 HVOF coating,
the microstructure was completely changed, becoming much more compact.
The wear mechanism then changed from fracture wear to another
mechanism that might be a combination of adhesion and oxidation wear. In
the case of T800+WC HVOF coatings, the wear mechanism within the
T800 matrix is the same as the one in T800 coating, and meanwhile, the
carbides were pulled out leading to a different wear mechanism involving
abrasive wear. After laser treatment of T800+WC HVOF coatings, the
bonding between the matrix and carbides becomes much stronger, which
requires a longer time for the carbides to be pulled out.
8.3 Suggestions for future work
 To investigate erosion-corrosion properties of various HVOF coatings

before and after laser treatment.
 To further investigate the laser operating parameters to achieve full melting

of WC with controllable dilution to further optimise the combined
corrosion and wear performance.
 To study the corrosion properties for various HVOF coatings before and
after laser treatment in different corrosion environment, such as
electrolytes containing Cl- ions.
 To investigate the corrosion properties of various HVOF coatings before

and after laser treatment using other corrosion techniques such as salt spray
test.
263
Appendix A
EIS Nyquist plots of HVOF coatings before and after laser
treatment
The following graphs are additional Nyquist plots of the HVOF coatings before
and after laser treatment corresponding to the results shown in section 6.4.
5000 7000
500 800
400 T800 after 1h 600 T800 after 6h HVOF

300
6000 400 Laser
4000 200
100
HVOF 200
0
0 100 200 300 400 500
Laser 5000 0
0 200 400 600 800
0.005 Hz
-Z" (ohm.cm )
3000 -Z" (ohm.cm )

2
0.005 Hz 4000
0.034 Hz
2000 3000
0.034 Hz
2000
1000
1000
30000 Hz (a) 30000 Hz
(b)
0 0
0 2000 4000 6000 8000 10000 12000 0 2000 4000 6000 8000 10000 12000 14000
' 2 ' 2
8000 8000 1200

1200
1000 T800 after 24h HVOF 1000
T800 after 48h HVOF
7000 800
7000 800
600 Laser 600

Laser
400 400
6000 200
6000 200
0
0
0 200 400 600 800 1000 0 200 400 600 800 1000 1200
-Z" (ohm.cm )
-Z" (ohm.cm )
0.005 Hz
2
0.005 Hz
5000 5000
4000 4000
0.034 Hz 0.034 Hz
3000 3000
2000 2000
1000 1000
30000 Hz
(c) 30000 Hz
(d)
0 0
0 2000 4000 6000 8000 10000 12000 14000 16000 0 2000 4000 6000 8000 10000 12000 14000 16000
' 2 ' 2
Figure A.1 Nyquist plots of T800 HVOF coatings before and after laser
treatment at different immersion times in 0.5 M H 2SO4 solution: (a) after 1h, (b)
after 6h, (c) after 24h, and (d) after 48h
264
APPENDIX A
4000 4000 500

500
400
T800+21WC after 6h
300
300 200
200 HVOF 100

HVOF
3000 3000 Laser
100
0
Laser 0
0 100 200 300 400 500 600
0 100 200 300 400 500 0.034 Hz
-Z" (ohm.cm )
-Z" (ohm.cm )
2
2
0.034 Hz 0.005 Hz
2000 0.005 Hz 2000
1000 1000
30000 Hz
(a) 30000 Hz (b)
0 0
0 2000 4000 6000 8000 0 2000 4000 6000 8000 10000
' 2 ' 2
5000
600 T800+21WC after 24h 6000 600 T800+21WC after 48h
400
400
HVOF HVOF
4000 200 5000
200
Laser 0
Laser
0 0 200 400 600
0 200 400 600
-Z" (ohm.cm )
2
-Z" (ohm.cm )
4000 0.005 Hz
2
0.034 Hz
3000 0.005 Hz
0.034 Hz
3000
2000
2000
1000 1000
30000 Hz
(c) 30000 Hz (d)
0 0
0 2000 4000 6000 8000 10000 0 2000 4000 6000 8000 10000 12000
' 2 ' 2
Figure A.2 Nyquist plots of T800+21WC HVOF coatings before and after laser
1000 1000 50
40
T800+43WC after 1h 40 T800+43WC after 6h
30
800
20
HVOF 800
20
HVOF
10
0
0 20 40
Laser 0 Laser
0 10 20 30 40 50
0.034 Hz
-Z" (ohm.cm )
2
600 600 0.034 Hz

-Z" (ohm.cm )
2
0.005 Hz
0.005 Hz
400 400
200 200
(a) (b)
30000 Hz 30000 Hz
0 0
0 500 1000 1500 2000 2500 0 500 1000 1500 2000
' 2 ' 2
1000 50
1000 50
40 T800+43WC after 24h 40 T800+43WC after 48h
30
30
800
20
10
HVOF 800 20
HVOF
10
0
0 10 20 30 40 50
Laser 0
0 10 20 30 40 50
Laser
-Z" (ohm.cm )
600
2
600
-Z" (ohm.cm )
2
0.005 Hz
0.034 Hz
400 0.005 Hz 400
0.034 Hz
200 200
30000 Hz
(c) 30000 Hz
(d)
0 0
0 200 400 600 800 1000 1200 1400 0 200 400 600 800 1000
' 2 ' 2
Figure A. Nyquist plots of T800+43WC HVOF coatings before and after laser
265
APPENDIX A
1000 1000
50
40
T800+68WC after 1h (a) 50
40
T800+68WC after 6h (b)
30
30
800 20
HVOF 800 20
10
HVOF
10
0
Laser 0
0 10 20 30 40 50
Laser
0 10 20 30 40 50
-Z" (ohm.cm )
-Z" (ohm.cm )
600
2
600
2
400 400
0.034 Hz
200 0.034 Hz
200 0.005 Hz
0.005 Hz
30000 Hz 30000 Hz
0 0
0 200 400 600 800 1000 0 200 400 600 800 1000
' 2 ' 2
1000 1000
50
40 T800+68WC after 24h (c) 50
40 T800+68WC after 48 (d)

30 30
800 20
HVOF 800 20
10 10
HVOF
0
0 10 20 30 40 50 Laser 0
0 10 20 30 40 50 Laser
-Z" (ohm.cm )
2
-Z" (ohm.cm )
600 600
2
400 400
0.005 Hz 0.005 Hz
0.034 Hz
200 200 0.034 Hz
30000 Hz
30000 Hz
0 0
0 200 400 600 800 1000 0 200 400 600 800 1000
' 2 ' 2
Figure A.4 Nyquist plots of T800+68WC HVOF coatings before and after laser
266
APPENDIX A
Tables of electrochemical parameters obtained from EIS spectra of

HVOF coatings before and after laser treatment for different
immersion times
Electrochemical HVOF / after 1h of immersion

Rs (Ω.cm2) 2 2 2 2
Rp (Ω.cm2) 66 45 41 27
Rct (Ω.cm2) 13661 490 406 3008
CPEp (mF.cm-2) 3.9 7.7 6.9 6.3
CPEdl (mF.cm-2) 4.7 4.5 4.6 6.6
np 0.64 0.63 0.64 0.65
ndl 1 1 1 1

Rs (Ω.cm2) 1.48 1.67 1.73 1.85
Rp (Ω.cm2) 8766 346 152 148
Rct (Ω.cm2) 15144 9465 2508 885
CPEp (mF.cm-2) 0.084 0.085 0.18 0.36
CPEdl (mF.cm-2) 1.1 0.2 0.39 1.1
np 0.76 0.82 0.89 0.87
ndl 0.67 0.55 0.53 0.52
267
APPENDIX A

Rs (Ω.cm2) 2 2 2 2
Rp (Ω.cm2) 52 34 39 25
Rct (Ω.cm2) 11459 1423 1418 2541
CPEp (mF.cm-2) 3.6 7.0 7.5 6.7
CPEdl (mF.cm-2) 4.6 5.9 7.5 8.9
np 0.64 0.63 0.64 0.65
ndl 1 1 1 1

Rs (Ω.cm2) 1.55 1.66 1.79 1.87
Rp (Ω.cm2) 8597 400 245 204
Rct (Ω.cm2) 15036 10858 2166 1393
CPEp (mF.cm-2) 0.082 0.08 0.43 1
CPEdl (mF.cm-2) 1.2 0.2 0.83 2.3
np 0.77 0.83 0.87 0.87
ndl 0.76 0.61 0.56 0.34
268
APPENDIX A

Rs (Ω.cm2) 2 2 2 2
Rp (Ω.cm2) 34 26 30 22
Rct (Ω.cm2) 9110 3324 2680 3963
CPEp (mF.cm-2) 3.9 5.7 6.9 10
CPEdl (mF.cm-2) 4.2 9.8 12.2 16.5
np 0.64 0.63 0.64 0.65
ndl 1 1 1 1

Rs (Ω.cm2) 1.5 1.66 1.84 1.87
Rp (Ω.cm2) 8448 436 471 439
Rct (Ω.cm2) 16588 13198 1320 1138
CPEp (mF.cm-2) 0.08 0.08 1.66 3.1
CPEdl (mF.cm-2) 0.71 0.27 1.86 9.2
np 0.78 0.84 0.78 0.84
ndl 0.65 0.62 0.63 0.64
269
APPENDIX A

Rs (Ω.cm2) 2 2 2 2
Rp (Ω.cm2) 25 24 31 24
Rct (Ω.cm2) 7095 3168 2700 6000
CPEp (mF.cm-2) 4.0 6.7 11 15
CPEdl (mF.cm-2) 4.1 13.8 19.9 25
np 0.64 0.63 0.64 0.65
ndl 1 1 1 1

Rs (Ω.cm2) 1.45 1.58 1.7 1.84
Rp (Ω.cm2) 8514 466 1322 676
Rct (Ω.cm2) 15459 15796 1390 2387
CPEp (mF.cm-2) 0.08 0.082 4.4 7
CPEdl (mF.cm-2) 0.71 0.32 8.1 56
np 0.78 0.83 0.69 0.79
ndl 0.66 0.61 0.22 1
270
Appendix B
EIS Bode plots (Impedance Vs. Frequency and Phase angle Vs.
Frequency) of HVOF coatings before and after laser treatment
The following graphs are the Bode plots of the HVOF coatings before and after
laser treatment at different immersion times in 0.5M H2SO4 solution
90
(a) (b)
10000 T800 after 1h T800 after 1h
80
HVOF HVOF
70 Laser
Laser
1000 60
log (Z/ohm)
50
 (deg.)
100 40
30
10 20
10
1 0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000
log(f/Hz) log(f/Hz)
90
T800 after 3h (c) T800 after 3h (d)
10000 80
HVOF
HVOF 70 Laser
Laser
1000 60
50
log (Z/ohm)
 (deg.)
100 40
30
10 20
10
1 0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000
log(f/Hz) log(f/Hz)
90
T800 after 6h (e) T800 after 6h (f)
10000 80
HVOF
HVOF 70 Laser
Laser
1000 60
log (Z/ohm)
50
 (deg.)
100 40
30
10 20
10
1 0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000
log(f/Hz) log(f/Hz)
271
APPENDIX B
90
(g) (h)
T800 after 12h T800 after 12h
10000 80
HVOF HVOF
Laser 70 Laser
1000 60
log (Z/ohm) 50
 (deg.)
100 40
30
10 20
10
1 0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000
log(f/Hz) log(f/Hz)
90
T800 after 24h (i) (k)
80
T800 after 24h
10000
HVOF
HVOF 70 Laser
Laser
1000 60
 (deg.)
50
log (Z/ohm)
100 40
30
10
20
10
1
0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000
log(f/Hz) log(f/Hz)
(l) 90
T800 after 48 T800 after 48h (m)
10000 80
HVOF
HVOF 70 Laser
Laser
log (Z/ohm)
1000 60
 (deg.)
50
100
40
30
10
20
10
1
0
0.01 0.1 1 10 100 1000 10000 100000
0.01 0.1 1 10 100 1000 10000
log(f/Hz) log(f/Hz)
Figure B.1 Bode plots of T800 HVOF coatings before and after laser treatment
at different immersion times in 0.5 M H2SO4 solution
272
APPENDIX B
90
10000 (a) (b)
T800+21WC after 1h T800+21WC after 1h
80
HVOF
70 Laser
HVOF
1000
log (Z/ohm)
Laser 60
50
 (deg.)
100
40
30
10
20
10
1
0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000
log(f/Hz) log(f/Hz)
90
10000 (c) (d)
80
HVOF
HVOF 70 Laser
1000 Laser
60
log (Z/ohm)
 (deg.)
50
100
40
30
10
20
10
1
0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000
log(f/Hz) log(f/Hz)
90
10000 (e) (f)
80
HVOF
HVOF 70 Laser
1000 Laser
60
log (Z/ohm)
 (deg.)
50
100
40
30
10 20
10
1 0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000
log(f/Hz) log(f/Hz)
90
T800+21WC after 12h (g) T800+21WC after 12h (h)
10000 80
HVOF
HVOF 70 Laser
Laser
log (Z/ohm)
1000 60
50
 (deg.)
100 40
30
10 20
10
1 0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000
log(f/Hz) log(f/Hz)
273
APPENDIX B
90
T800+21WC after 24h (i) T800+21WC after 24h (k)
10000 80
HVOF
HVOF 70 Laser
1000
Laser
60
log (Z/ohm)
 (deg.)
50
100 40
30
10 20
10
1
0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000
log(f/Hz) log(f/Hz)
90
(l) (m)
10000 T800+21WC after 48h T800+21WC after 48h
80 HVOF
HVOF 70 Laser
Laser
1000 60
 (deg.)
log (Z/ohm)
50
100 40
30
10 20
10
1 0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000
log(f/Hz) log(f/Hz)
Figure B.2 Bode plots of T800+21WC HVOF coatings before and after laser
treatment at different immersion times in 0.5 M H 2SO4 solution
274
APPENDIX B
90
T800+43WC after 1h (a) (b)
80 T800+43WC after 1h
1000 HVOF
HVOF 70 Laser
Laser
60
log (Z/ohm)
 (deg.)
100 50
40
30
10
20
10
1 0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000
log(f/Hz) log(f/Hz)
90
T800+43WC after 3h (c) (d)
80
T800+43WC after 3h
1000 HVOF
HVOF 70
Laser
Laser
60
log (Z/ohm)
100 50
 (deg.)
40
30
10
20
10
1
0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000
log(f/Hz) log(f/Hz)
90
T800+43WC after 6h (e) T800+43WC after 6h (f)
80
1000 HVOF
HVOF 70 Laser
Laser
60
log (Z/ohm)
100 50
 (deg.)
40
30
10
20
10
1 0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000
log(f/Hz) log(f/Hz)
90
(g) T800+43WC after 12h (h)
1000
HVOF 70 HVOF
Laser Laser
60
log (Z/ohm)
 (deg.)
100 50
40
30
10
20
10
1 0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000
log(f/Hz) log(f/Hz)
275
APPENDIX B
10000 90
T800+43WC after 24h (i) T800+43WC after 24h (k)
80
HVOF
HVOF 70 Laser
1000
Laser
60
log (Z/ohm)
 (deg.)
50
100
40
30
10
20
10
1 0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000
log(f/Hz) log(f/Hz)
10000 90
T800+43WC after 48h (l) T800+43WC after 48h (m)
80
HVOF
1000 HVOF 70 Laser
Laser 60
log (Z/ohm)
 (deg.)
50
100
40
30
10
20
10
1 0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000
log(f/Hz) log(f/Hz)
treatment at different immersion times in 0.5 M H2SO4 solution
276
APPENDIX B
120
T800+68WC after 1h (a) T800+68WC after 1h (b)
1000
100
HVOF HVOF
Laser 80 Laser
60
log (Z/ohm)
100
 (deg.)
40
20
10 0
-20
-40
1
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000 100000
log(f/Hz) log(f/Hz)
120
1000 T800+68WC after 3h (c) T800+68WC after 3h (d)
100
HVOF HVOF
80 Laser
Laser
60
log (Z/ohm)
100
 (deg.)
40
20
10
0
-20
1 -40
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000 100000
log(f/Hz) log(f/Hz)
120
T800+68WC after 6h (e) (f)
1000 T800+68WC after 6h
100
HVOF HVOF
80 Laser
Laser
60
100
log (Z/ohm)
40
 (deg.)
20
10 0
-20
-40
1 -60
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000 100000
log(f/Hz) log(f/Hz)
120
1000 T800+68WC after 12h (g) (h)
100 T800+68WC after 12h
HVOF HVOF
80 Laser
Laser
100 60
log (Z/ohm)
 (deg.)
40
20
10
0
-20
1 -40
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000 100000
log(f/Hz)
log(f/Hz)
277
APPENDIX B
100
(i) (k)
1000 T800+68WC after 24h T800+68WC after 24h
HVOF
HVOF
80 Laser
Laser
log (Z/ohm) 100 60
 (deg.)
40
10
20
1
0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000 100000
log(f/Hz) log(f/Hz)
90
(l) (m)
1000 T800+68WC after 48h 80 T800+68WC after 48h
HVOF
HVOF 70 Laser
Laser
60
100
log (Z/ohm)
50
 (deg.)
40
10 30
20
10
1
0
0.01 0.1 1 10 100 1000 10000 100000 0.01 0.1 1 10 100 1000 10000 100000
log(f/Hz) log(f/Hz)
treatment at different immersion times in 0.5 M H 2SO4 solution
278
REFERENCES
1. Chidambaram, D., C.R. Clayton, and M.R. Dorfman, Evaluation of the

electrochemical behavior of HVOF-sprayed alloy coatings. Surface and
Coatings Technology, 2004. 176(3): p. 307-317.
2. Allcock, B. and P. Lavin, Novel composite coating technology in primary and
conversion industry applications. Surface & Coatings Technology, 2003: p.
62-66.
3. Sidhu, T.S., S. Prakash, and R.D. Agrawal, Studies on the properties of high-
velocity oxy-fuel thermal spray coatings for higher temperature applications.
Materials Science, 2005. 41(6): p. 805-823.
4. Verdon, C., A. Karimi, and J.L. Martin, A study of high velocity oxy-fuel
thermally sprayed tungsten carbide based coatings. Part 1: Microstructures.
Materials Science and Engineering A, 1998. 246(1-2): p. 11-24.
5. Cho, J.E., S.Y. Hwang, and K.Y. Kim, Corrosion behavior of thermal
sprayed WC cermet coatings having various metallic binders in strong acidic
environment. Surface and Coatings Technology, 2006. 200(8): p. 2653-2662.
6. Godoy, C., Structural changes in high-velocity oxy-fuel thermally sprayed
WC–Co coatings for improved corrosion resistance. Surface and Coatings
Technology, 2004. 188–189(0): p. 1-6.
7. Lekatou, A., E. Regoutas, and A.E. Karantzalis, Corrosion behaviour of
cermet-based coatings with a bond coat in 0.5 M H2SO4. Corrosion Science,
2008. 50(12): p. 3389-3400.
8. Perry, J., T. Hodgkiess, and A. Neville, A comparison of the corrosion
behavior of WC-Co-Cr and WC-Co HVOF thermally sprayed coatings by in
situ atomic force microscopy (AFM). Journal of Thermal Spray Technology,
2002. 11(4): p. 536-541.
9. Monticelli, C., A. Frignani, and F. Zucchi, Investigation on the corrosion
process of carbon steel coated by HVOF WC/Co cermets in neutral solution.
Corrosion Science, 2004. 46(5): p. 1225-1237.
279
REFERENCES
10. Tuominen, J., Improving corrosion properties of high-velocity oxy-fuel

sprayed inconel 625 by using a high-power continuous wave neodymium-
doped yttrium aluminum garnet laser. Journal of Thermal Spray Technology,
2000. 9(4): p. 513-519.
11. Tuominen, J., Corrosion properties of HVOF sprayed and Nd-YAG laser
remelted high-chromium nickel-chromium coatings. Thermal Spray 2001:
New Surfaces For a New Millennium, 2001: p. 1203-1212.
12. Liu, Z., Improving corrosion and wear performance of HVOF-sprayed
Inconel 625 and WC-Inconel 625 coatings by high power diode laser
treatments. Surface & Coatings Technology, 2007: p. 7149-7158.
13. Chen, H., Micro-scale abrasive wear behaviour of HVOF sprayed and laser-
remelted conventional and nanostructured WC-Co coatings. Wear, 2005: p.
333-338.
14. Jones, D.A., Principles and Prevention of Corrosion. 1992, Singapore:
Macmillan.
15. Roberge, P.R., Corrosion engineering principles and practice. 2008, USA:
McGraw-Hill.
16. Ahmad, A., Principles of Corrosion Engineering and Corrosion Control.
2006: Elsevier Science & Technology Books.
17. information, C.M. http://www.corrosion-club.com/basictheory.htm. 2011.
18. Munger, C.G., Corrosion and prevention by protective coatings. 1984, Texas:
NACE.
19. Mattsson, E., Basic Corrosion Technology for Scientists and Engineering.
Ellis Horwood Series in Corrosion and its Prevention. 1989, UK:
Mattsson/Ellis Horwood Limited.
20. Winston Revie, R., Corrosion and corrosion control, An introduction to
corrosion science and engineering. Fourth ed. 2008, New Jersey: John Wiley
& Sons.
21. Einar, B., Corrosion and protection. Engineering materials and processes.
2004, USA: Springer-Verlag London.
22. Groysman, A., Corrosion for everybody. 2010, New York: Springer.
23. Davis, J.R., Corrosion understanding the basics. 2000, USA: ASM
International.
280
REFERENCES
24. Bardal, E., Corrosion and protection. Engineering materials and processes.
2004, USA: Springer-Verlag London.
25. Nimmo, B., Beginners guide to corrosion. 2003: Life time management of
materials (LMM).
26. Dexter, S.C. Galvanic corrosion. 2003.
27. Callow, J. www.amteccorrosion.co.uk (Guide to corrosion). 2003.
28. Carther, M. water and infrastructure data system
http://octane.nmt.edu/waterquality/. 2006.
29. Jones, D.A., Principles and Prevention of Corrosion. Second ed. 1996, USA:
Prentice-Hall, Inc.
30. Sedrikes, A.J., Corrosion of stainless steels. 1996, New York: John Wiley &
Sons.
31. Loveday, D., P. Peterson, and B. Rodgers, Evaluation of organic coatings
with electrochemical impedance spectroscopy, Part 1: Fundamentals of EIS.
JCT Coatings Tech., 2004. 8(1): p. 46-52.
32. Cottis, R. and S. Turgoose, Electrochemical impedance and noise. 1999,
USA: NACE International.
33. Yuan, X., Electrochemical Imedance Spectroscopy in PEM Fuel Cells,
Fundamentals and Applications. 2010, New York: Springes.
34. Basic of electrochemical impedance spectroscopy-Application Note AC-1.
EG & G Princeton Applied Research. 1989, NJ.
35. Marsden, J.E. and J. Hoffman, Basic complex analysis. Third ed. 1999, USA:
W. H. Freeman and Company.
36. Barsoukov, E. and J.R. Macdonald, Impedance Specroscopy Theory and
Applications Second ed. 2005, New Jersey: John Wiley & Sons.
37. Verdian, M.M., K. Raeissi, and M. Salehi, Corrosion performance of HVOF
and APS thermally sprayed NiTi intermetallic coatings in 3.5% NaCl
solution. Corrosion Science, 2010. 52(3): p. 1052-1059.
38. Loveday, D., P. Peterson, and B. Rodgers, Evaluation of organic coatings
with electrochemical impedance spectroscopy, Part2: Application of EIS to
coatings. JCT Coatings Tech, 2004. 10(1): p. 88-93.
39. Cahan, B.D. and C.T. Chen, Questions on kinetics of O2 evolution on oxide-
covered metals. Journal of Electrochemistry Society, 1982. 129: p. 700-705.
281
REFERENCES
40. Park, C.-G., A study on corrosion characterization of plasma oxidized 65/35

brass with various frequencies. Surface and Coatings Technology, 2005.
200(1-4): p. 77-82.
41. Liu, X., Study on corrosion electrochemical behavior of several different
coating systems by EIS. Progress in Organic Coatings, 2009. 64(4): p. 497-
503.
42. Orazem, M.E. and B. Tribollet, Electrochemical impedance spectroscopy.
First ed. The Electrochemical Society Series. 2008, New Jersey: John Wiley
& Sons, Inc.
43. Mirabedini, S.M., Corrosion performance of powder coated aluminium using
EIS. Progress in Organic Coatings, 2003. 46(2): p. 112-120.
44. Wang, Y., Microstructure, spallation and corrosion of plasma sprayed
Al2O3-13%TiO2 coatings. Corrosion Science, 2009. 51(12): p. 2924-2931.
45. Suegama, P.H., Electrochemical and structural characterization of heat-
treated Cr3C2-NiCr coatings. Journal of the Electrochemical Society, 2006.
153(10).
46. Jorcin, J.-B., CPE analysis by local electrochemical impedance spectroscopy.
Electrochimica Acta, 2006. 51(8-9): p. 1473-1479.
47. Pajkossy, T., Impedance spectroscopy at interfaces of metals and aqueous
solutions -- Surface roughness, CPE and related issues. Solid State Ionics,
2005. 176(25-28): p. 1997-2003.
48. Bayer, R., Mechanical Wear Fundamentals and Testing. 2004, New York:
Marcel Dekker.
49. Rabinowicz, E., Friction and Wear of Materials. Second ed. 1995, USA:
John Wiley & Sons.
50. Buckley, D.H., Surface Effects in Adhesion, Friction, Wear, and Lubrication.
Tribology. 1981, New York: Elsevier.
51. England, G. Wear (www.gordonengland.co.uk/wear.htm). 2010.
52. Neale, M. and M. Gee, Guide to Wear Problems and Testing for Industry.
First ed. Tribology in Practice. 2000, London: Professional Engineering.
53. Corporation, P. Wear (www.pall.com/Aerospace_18167.asp). 2010.
54. Strafford, K., P. Datta, and C. Googan, Coatings and Surface Treatment for
Corrosion and Wear Resistance. First ed. 1984, UK: Ellis Horwood Limited.
282
REFERENCES
55. Burnell-Gray, J. and P. Datta, Surface Engineering Casebook. First ed. 1996,
UK: Woodhead Publishing.
56. Davis, J.R., Hand book of thermal spray technology. 2004: ASM
International.
57. Metco,S.www.sulzermetco.com/de/desktopdefault.aspx/tabid-008/3390_read-
5302. 2008.
58. Magnani, M., Influence of HVOF parameters on the corrosion and wear
resistance of WC-Co coatings sprayed on AA7050 T7. Surface and Coatings
Technology, 2008. 202(19): p. 4746-4757.
59. Valentinelli, L., Mechanical and tribocorrosion properties of HVOF sprayed
WC-Co coatings. Corrosion Engineering Science and Technology, 2004: p.
301-307.
60. Clyne, T.W., Metal Matrix Comosites: Matrices and Processing, in
Encyclopaedia of Materials: Science and Technology2001: Cambridge.
61. Turunen, E., Diagnostic tools for HVOF process optimization, in Materials
Science and Engineering2005, University of Technology: Helsinki. p. 144.
62. Suutala, J., J. Tuominen, and P. Vuoristo, Laser-assisted spraying and laser
treatment of thermally sprayed coatings. Surface & Coatings Technology,
2006: p. 1981-1987.
63. Guilemany, J.M., S. Dosta, and J.R. Miguel, The enhancement of the
properties of WC-Co HVOF coatings through the use of nanostructured and
microstructured feedstock powders. Surface and Coatings Technology, 2006.
201(3-4): p. 1180-1190.
64. Asl, S., Effect of heat treatment on wear behavior of HVOF thermally
sprayed WC-Co coatings. Wear, 2006: p. 1203-1208.
65. Asl, S.K., Study of phase transformations in heat treatment of HVOF
thermally sprayed WC-17Co coating, 2008. p. 161-166.
66. Gerard, B., Application of thermal spraying in the automobile industry.
Surface & Coatings Technology, 2006: p. 2028-2031.
67. Koutsky, J., High velocity oxy-fuel spraying. Journal of Materials Processing
Technology, 2004. 157-158(SPEC. ISS.): p. 557-560.
68. Ballard, W., Metal Spraying and the Flame Deposition of Ceramics and
Plastics. Fourth ed. 1963, London: Charles Griffin and Company Limited.
283
REFERENCES
69. Hochstrasser, S., Analytical characterization of the corrosion mechanisms of

WC-Co by electrochemical methods and inductively coupled plasma mass
spectroscopy. Corrosion Science, 2007. 49(4): p. 2002-2020.
70. Bolelli, G., L. Lusvarghi, and R. Giovanardi, A comparison between the
corrosion resistances of some HVOF-sprayed metal alloy coatings. Surface
and Coatings Technology, 2008. 202(19): p. 4793-4809.
71. Tomlinson, W.J. and C.R. Linzell, Anodic polarization and corrosion of
cemented carbides with cobalt and nickel binders. Journal of Materials
Science, 1988. 23(3): p. 914-918.
72. Human, A. and H. Exner, The relationship between electrochemical
behaviour and in-service corrosion of WC based cemented carbides.
International Journal of Refractory Metals & Hard Materials, 1997: p. 65-71.
73. Schnyder, B., Investigation of the electrochemical behaviour of WC-Co
hardmetal with electrochemical and surface analytical methods. Surface
Science, 2004. 566-568(Part 2): p. 1240-1245.
74. Lekatou, A., Electrochemical behaviour of cermet coatings with a bond coat
on Al7075: Pseudopassivity, localized corrosion and galvanic effect
considerations in a saline environment. Corrosion Science, 2010. 52(8): p.
2616-2635.
75. Perry, J.M., Assessment of the corrosion rates and mechanisms of a WC-Co-
Cr HVOF coating in static and liquid-solid impingement saline
environments. Surface and Coatings Technology, 2001. 137(1): p. 43-51.
76. Lekatou, A., D. Zois, and D. Grimanelis, Corrosion properties of HVOF
cermet coatings with bond coats in an aqueous chloride environment. Thin
Solid Films, 2008: p. 5700-5705.
77. Hochstrasser-Kurz, S., ICP-MS, SKPFM, XPS, and Microcapillary
Investigation of the Local Corrosion Mechanisms of WC--Co Hardmetal.
Journal of The Electrochemical Society, 2008. 155(8): p. C415-C426.
78. Yee, S., R.A. Oriani, and M. Stratmann, Application of a kelvin microprobe
to the corrosion of metals in humid atmospheres. Journal of the
Electrochemical Society, 1991. 138(1): p. 55-61.
79. Souza, V. and A. Neville, Using in situ atomic force microscopy to
investigate the kinetics of corrosion of WC-Co-Cr cermet coatings applied by
284
REFERENCES
high-velocity oxy-fuel. Journal of Engineering Materials and Technology-

Transactions of the Asme, 2007: p. 55-68.
80. Human, A.M. and H.E. Exner, Electrochemical behaviour of tungsten-
carbide hardmetals. Materials Science and Engineering: A, 1996. 209(1-2):
p. 180-191.
81. Ghandehari, M.H., Anodic behavior of cemented WC-6% Co alloy in
phosphoric acid solutions. J. Electrochem. Soc., 1980. 127: p. 2144-2147.
82. Bozzini, B., Corrosion behaviour of WC-Co based hardmetal in neutral
chloride and acid sulphate media. Materials and Corrosion, 2002. 53(5): p.
328-334.
83. Souza, V.A.D. and A. Neville, Linking electrochemical corrosion behaviour
and corrosion mechanisms of thermal spray cermet coatings (WC-CrNi and
WC/CrC-CoCr). Materials Science and Engineering: A, 2003. 352(1-2): p.
202-211.
84. Bolelli, G., L. Lusvarghi, and M. Barletta, Heat treatment effects on the
corrosion resistance of some HVOF-sprayed metal alloy coatings. Surface
and Coatings Technology, 2008. 202(19): p. 4839-4847.
85. Sutthiruangwong, S. and G. Mori, Corrosion properties of Co-based
cemented carbides in acidic solutions. International Journal of Refractory
Metals & Hard Materials, 2003: p. 135-145.
86. Human, A.M., B. Roebuck, and H.E. Exner, Electrochemical polarisation
and corrosion behaviour of cobalt and Co(W,C) alloys in 1 N sulphuric acid.
Materials Science and Engineering A, 1998. 241(1-2): p. 202-210.
87. Scholl, H., B. Hofman, and A. Rauscher, Anodic polarization of cemented
carbides of the type [(WC,M): M = Fe, Ni or Co] in sulphuric acid solution.
Electrochimica Acta, 1992. 37(3): p. 447-452.
88. Bozzini, B., G.P. De Gaudenzi, and C. Mele, An in-situ FT-IR investigation
of the anodic behaviour of WC-Co hardmetal. Materials and Corrosion, 2003.
54(9): p. 694-696.
89. Bozzini, B., Anodic behaviour of WC-Co type hardmetal. Materials and
Corrosion, 2003. 54(5): p. 295-303.
285
REFERENCES
90. Lee, C.W., A study on powder mixing for high fracture toughness and wear
resistance of WC–Co–Cr coatings sprayed by HVOF. Surface and Coatings
Technology, 2010. 204(14): p. 2223-2229.
91. Guilemany, J.M., Study of the properties of WC-Co nanostructured coatings
sprayed by high-velocity oxyfuel. Journal of Thermal Spray Technology,
2005. 14(3): p. 405-413.
92. Godoy, C., Structural changes in high-velocity oxy-fuel thermally sprayed
WC-Co coatings for improved corrosion resistance. Surface & Coatings
Technology, 2004: p. 1-6.
93. Sutthiruangwong, S., G. Mori, and R. Kösters, Passivity and pseudopassivity
of cemented carbides. International Journal of Refractory Metals and Hard
Materials, 2005. 23(2): p. 129-136.
94. Tomlinson, W. and N. ayerst, Anodic polarization and corrosion of wc-co
hardmetals containing small amounts of Cr3C2 and or VC. Journal of
Materials Science, 1989: p. 2348-2354.
95. Karimi, A., C. Verdon, and G. Barbezat, Microstructure and hydroabrasive
wear behaviour of high velocity oxy-fuel thermally sprayed WC---Co(Cr)
coatings. Surface and Coatings Technology, 1993. 57(1): p. 81-89.
96. Guilemany, J., Role of three-body abrasion wear in the sliding wear
behaviour of WC-Co coatings obtained by thermal spraying. Surface &
Coatings Technology, 2001: p. 141-146.
97. Shipway, P., D. McCartney, and T. Sudaprasert, Sliding wear behaviour of
conventional and nanostructured HVOF sprayed WC-Co coatings. Wear,
2005: p. 820-827.
98. Stewart, D., P. Shipway, and D. McCartney, Abrasive wear behaviour of
conventional and nanocomposite HVOF-sprayed WC-Co coatings. Wear,
1999: p. 789-798.
99. Kumari, K., Effect of microstructure on abrasive wear behavior of thermally
sprayed WC-10Co-4Cr coatings. Wear, 2010: p. 1309-1319.
100. Liao, H., B. Normand, and C. Coddet, Influence of coating microstructure on
the abrasive wear resistance of WC/Co cermet coatings. Surface & Coatings
Technology, 2000: p. 235-242.
286
REFERENCES
101. Li, C.-J., A. Ohmori, and K. Tani, Effect of WC Particle Size on the Abrasive
Wear of Thermally Sprayed WC-Co Coatings. Materials and Manufacturing
Processes, 1999. 14(2): p. 175 - 184.
102. Yang, Q., T. Senda, and A. Ohmori, Effect of carbide grain size on
microstructure and sliding wear behavior of HVOF-sprayed WC-12% Co
coatings. Wear, 2003: p. 23-34.
103. Zhao, L., Influence of spray parameters on the particle in-flight properties
and the properties of HVOF coating of WC-CoCr. Wear, 2004: p. 41-46.
104. Stewart, D., P. Shipway, and D. McCartney, Influence of heat treatment on
the abrasive wear behaviour of HVOF sprayed WC-Co coatings. Surface &
105. Wood, R., Tribology of thermal sprayed WC-Co coatings. International
Journal of Refractory Metals & Hard Materials, 2010: p. 82-94.
106. Basak, A.K., Effect of Al and Cr addition on tribological behaviour of HVOF
and APS nanostructured WC–Co coatings. Transactions of the Institute of
Metal Finishing, 2007. 85: p. 310-315.
107. O'shea, W. and W. Rhodes, An Introduction to lasers and their applications.
1978, Canada: Addison-wesely.
108. Steen, W., Laser Material Processing. Third ed. 2003, London: Springer.
109. Svelto, O., Principles of lasers. 1998, New York: Plenum Press.
110. Thyagarajan, K. and A. Ghatak, Lasers fundamentals and applications. 2010,
London: Springer.
111. Beesley, M., Lasers and thier applications. 1976, London: Taylor & Erancis
Ltd.
112. Li, L., Advances and characteristics of high-power diode laser materials
processing. Optics and Lasers in Engineering, 2000. 34(4-6): p. 231-253.
113. Vuoristo, P., Laser coating and thermal spraying - process basics and
coating properties. Thermal Spray connects: Explore its surfacing potential,
2005: p. 1270-1277.
114. Parker, K. Heat Treating with High Power Diode Lasers.
www.Coherent.com 2010.
287
REFERENCES
115. Kennedy, E., G. Byrne, and D.N. Collins, A review of the use of high power
diode lasers in surface hardening. Journal of Materials Processing
Technology, 2004. 155-156: p. 1855-1860.
116. Haag, M. and T. Rudlaff. Assessment of different high power diode lasers for
material processing. 1997.
117. Dutta Majumdar, J. and I. Manna, Laser processing of materials. Sadhana -
Academy Proceedings in Engineering Sciences, 2003. 28(3-4): p. 495-562.
118. Sugioka, K., M. Meunier, and A. Pique, Laser precision microfabrication.
Materials Science. 2010, New York: Springer.
119. Ion, J.C., Laser Processing of Engineering Materials. First ed. 2005, Oxford,
UK: Elsevier Butterworth-Heinemann.
120. Zhong, M., W. Liu, and H. Zhang, Corrosion and wear resistance
characteristics of NiCr coating by laser alloying with powder feeding on grey
iron liner. Wear, 2006: p. 1349-1355.
121. Jones, H., Rapid solidification of metals and alloys. 1983, London:
Chameleon Press Ltd.
122. Kou, S., Welding metallurgy. 2003, New Jeresy: John Wiley & sons.
123. Navas, C., Microstructure and sliding wear behaviour of Tribaloy T-800
coatings deposited by laser cladding. Wear, 2006: p. 838-846.
124. Kurz, W. and R. Trivedi, Rapid solidification processing and microstructure
formation. Materials Science and Engineering: A, 1994. 179-180, Part 1(0):
p. 46-51.
125. William J, B., Microstructural variations in rapidly solidified alloys.
Materials Science and Engineering, 1988. 98(0): p. 123-130.
126. Frenk, A. and W. kurz, High-speed laser cladding - solidification conditions
and microstructure of a cobalt-based alloy. Materials Science and
Engineering a-Structural Materials Properties Microstructure and Processing,
1993: p. 339-342.
127. Marginean, G., Influence of Electron Beam and Laser Remelting on the
Oxidation Behaviour of HVOF-sprayed CoNiCrAlY Coatings. BHM Berg-
und HÃ¼ttenmÃ¤nnische Monatshefte, 2007. 152(1): p. 32-38.
128. Zhang, S.H., Characterization of microstructure and surface properties of
hybrid coatings of WC-CoCr prepared by laser heat treatment and high
288
REFERENCES
velocity oxygen fuel spraying. Materials Characterization, 2008. 59(10): p.

1412-1418.
129. Zhang, S.H., Influence of CO2 laser heat treatment on surface properties,
electrochemical and tribological performance of HVOF sprayed WC-
24%Cr3C2-6%Ni coating. Materials Chemistry and Physics, 2010. 119(3): p.
458-464.
130. Ahmed, N., The effects of microstructural features on the performance gap in
corrosion resistance between bulk and HVOF sprayed Inconel 625. Surface
& Coatings Technology, 2010: p. 2294-2301.
131. Morimoto, J., Surface modification of Cr3C2-NiCr cermet coatings by direct
diode laser. Vacuum, 2006: p. 1400-1405.
132. Kim, C.S., T.R. Massa, and G.S. Rohrer, Interface character distributions in
WC-Co composites. Journal of the American Ceramic Society, 2008. 91(3):
p. 996-1001.
133. Oliveira, U., Laser treatment of alloys: processing, microstructure and
structural properties, in Netherlands Institude for metals research2007,
Groningen University: te Natal-Brazilie. p. 124.
134. Williams, D.B. and A.R. Pelton, Images of materials. 1991, Oxford: Oxford
University press.
135. Company, S. Backscatter Imaging
http://www.semitracks.com/index.php/reference-material/failure-and-yield-
analysis/die-level-analysis/imaging/backscatter-imaging. 2011.
136. Whiston, C., X-Ray Methods. 1987, Great Britain: John Wiley & Sons.
137. Shift,A.P.
http://www.ccmr.cornell.edu/facilities/images/fac_equipment/MicroXam%20
specs.pdf. 2002.
138. Thompson, G.N., DC electrochemical test methods. 1998, Houston: NACE
International.
139. Yao, M., J. Wu, and R. Liu, Microstructural characteristics and corrosion
resistance in molten Zn-Al bath of Co-Mo-Cr-Si alloys. Materials Science and
Engineering a-Structural Materials Properties Microstructure and Processing,
2005: p. 299-305.
289
REFERENCES
140. Kim, H.C., Rapid sintering process and mechanical properties of binderless
ultra fine tungsten carbide. Materials Science and Engineering A, 2006. 435-
436: p. 717-724.
141. Kannatey, E., Principles of Laser Materials Processing. 2009, New Jersey:
John Wiley & sons.
142. Colangelo, V.J. and F.A. Heiser, Analysis of Metallurgicall Failures. 1974:
John Wiley & Sons, Inc.
143. Zhou, S., Analysis of crack behavior for Ni-based WC composite coatings by
laser cladding and crack-free realization. Applied Surface Science, 2008.
255(5, Part 1): p. 1646-1653.
144. Zhou, S., Y. Huang, and X. Zeng, A study of Ni-based WC composite
coatings by laser induction hybrid rapid cladding with elliptical spot.
Applied Surface Science, 2008. 254(10): p. 3110-3119.
145. Zhang, S.-H., Investigation on microstructure, surface properties and anti-
wear performance of HVOF sprayed WC–CrC–Ni coatings modified by laser
heat treatment. Materials Science and Engineering: B, 2009. 162(2): p. 127-
134.
146. Goswami, G.L., Control of defects during laser surface alloying. Surface
Engineering, 1999. 15(1): p. 65-70.
147. Xu, W., Mechanical and tribological properties of newly developed Tribaloy
alloys. Materials Science and Engineering a-Structural Materials Properties
Microstructure and Processing, 2007: p. 427-436.
148. Halstead, A. and R.D. Rawlings, The effect of iron additions on the
microstructure and properties of the "Tribaloy" Co-Mo-Cr-Si wear resistant
alloys. Journal of Materials Science, 1985. 20(5): p. 1693-1704.
149. Halstead, A. and R.D. Rawlings, The fracture behaviour of two Co-Mo-Cr-Si
wear resistant alloys ("Tribaloys"). Journal of Materials Science, 1985.
20(4): p. 1248-1256.
150. Wang, A.H., CO2 laser-induced structure changes on a zircon refractory.
Applied Surface Science, 2004. 227(1–4): p. 104-113.
151. Zhou, S., Analysis of crack behavior for Ni-based WC composite coatings by
laser cladding and crack-free realization. Applied Surface Science, 2008: p.
1646-1653.
290
REFERENCES
152. Kong, D.J., F. Yuan, and H. Miao, Effects of residual stress on interfacial
bonding strength of WC coating, 2009. p. 10-14.
153. Pokhmurs'ka, H.V., Crack Formation in Gas-Thermal Coatings Depending
on the Conditions of Their Laser Remelting. Materials Science, 2003. 39(1):
p. 64-68.
154. Tuominen, J., Corrosion behavior of HVOF-sprayed and Nd-YAG laser-
remelted high-chromium, nickel-chromium coatings. Journal of Thermal
Spray Technology, 2002. 11(2): p. 233-243.
155. Tobar, M.J., Characteristics of Tribaloy T-800 and T-900 coatings on steel
substrates by laser cladding. Surface and Coatings Technology, 2008.
202(11): p. 2297-2301.
156. Vreijling, M., Electrochemical Characterisation of Metallic Thermally
Sprayed Coatings. First ed. 1998, Netherlands: M.P.W. Vreijling.
157. Lih, W.-C., Effects of process parameters on molten particle speed and
surface temperature and the properties of HVOF CrC/NiCr coatings. Surface
and Coatings Technology, 2000. 133–134(0): p. 54-60.
158. Lugscheider, E., C. Herbst, and L. Zhao, Parameter studies on high-velocity
oxy-fuel spraying of MCrAlY coatings. Surface and Coatings Technology,
1998. 108–109(0): p. 16-23.
159. Gentile, M., Influence of zinc on surface treatments of aluminium-zinc alloys,
in Corrosion and protection centre 2010, University of Manchester:
Manchester.
160. Abdollah, S., Evaluating Properties of Corrosion Resistance in Thermal-
Sprayed (HVOF) Coatings, in Corrosion and Protection Centre2008,
University of Manchester.
161. Bolelli, G., Corrosion resistance of HVOF-sprayed coatings for hard chrome
replacement. Corrosion Science, 2006. 48(11): p. 3375-3397.
162. Celik, E., Assessment of microstructural and mechanical properties of HVOF
sprayed WC-based cermet coatings for a roller cylinder. Surface & Coatings
Technology, 2006: p. 4320-4328.
163. Zhang, Y.D., Oxidation Behavior of Tribaloy T-800 Alloy at 800 and
1,000 °C. Oxidation of Metals, 2008. 70(3): p. 229-239.
291
REFERENCES
164. Sahraoui, T., HVOF-sprayed TribaloyÂ©-400: Microstructure and first

principle calculations. Materials Letters, 2004. 58(19): p. 2433-2436.
165. Kawakita, J., S. Kuroda, and T. Kodama, Evaluation of through-porosity of
HVOF sprayed coating. Surface & Coatings Technology, 2003: p. 17-23.
166. Lee, C. and K. Min, Effects of heat treatment on the microstructure and
properties of HVOF-sprayed Ni-Cr-W-Mo-B alloy coatings. Surface &
167. Sunada, S., Evaluation of corrosion resistance of WC-Co based alloys in
H2SO4, 2007. p. 2147-2150.
168. Souza, V.A.D. and A. Neville, Mechanisms and kinetics of WC-Co-Cr high
velocity oxy-fuel thermal spray coating degradation in corrosive
environments. Journal of Thermal Spray Technology, 2006. 15(1): p. 106-
117.
169. Harnisch, F., Electrocatalytic and corrosion behaviour of tungsten carbide in
near-neutral pH electrolytes. Applied Catalysis B-Environmental, 2009: p.
63-69.
170. Gil, L. and M.H. Staia, Influence of HVOF parameters on the corrosion
resistance of NiWCrBSi coatings. Thin Solid Films, 2002. 420-421: p. 446-
454.
171. Shrestha, S., A. Neville, and T. Hodgkiess, The effect of post-treatment of a
high-velocity oxy-fuel Ni-Cr-Mo-Si-B coating Part I:
Microstructure/corrosion behavior relationships. Journal of Thermal Spray
Technology, 2001. 10(3): p. 470-479.
172. Khaled, M.M. and B.S. Yilbas, Corrosion properties of HVOF-coated steel
in simulated concrete pore electrolyte and concentrated chloride
environments. Surface and Coatings Technology, 2007. 202(3): p. 433-438.
173. Rakhes, M., E. Koroleva, and Z. Liu, Improvement of corrosion performance
of HVOF MMC coatings by laser surface treatment. Surface Engineering,
2011. 27(10): p. 729-733.
174. Bolelli, G., Microstructural and tribological comparison of HVOF-sprayed
and post-treated M–Mo–Cr–Si (M = Co, Ni) alloy coatings.
Wear, 2007. 263(7–12): p. 1397-1416.
292
REFERENCES
175. Liu, C.T., Physical metallurgy and mechanical properties of transition-metal

Laves phase alloys. Intermetallics, 2000. 8(9-11): p. 1119-1129.
176. Thoma, D.J., Intermetallics: Laves Phases, in Encyclopedia of Materials:
Science and Technology. 2001, Elsevier: Oxford. p. 4205-4213.
177. Yao, M.X., High temperature wear and corrosion resistance of a Laves
phase strengthened Co-Mo-Cr-Si alloy. Materials Science and Engineering
A, 2006. 435-436: p. 78-83.
178. Navas, C., Microstructure and sliding wear behaviour of Tribaloy T-800
coatings deposited by laser cladding. Wear, 2006. 260(7-8): p. 838-846.
179. Halstead, A. and R.D. Rawlings, Structure and hardness of Co–Mo–Cr–Si
wear resistant alloys (Tribaloys). Metal Science, 1984. 18: p. 491-500.
293

Laser Surface Modification of HVOF Coatings For Improvement of Corrosion and Wear Performance

Încărcat de

Informații document

Titlu original

Drepturi de autor

Formate disponibile

Partajați acest document

Partajați sau inserați document

Opțiuni de partajare

Vi se pare util acest document?

Este necorespunzător acest conținut?

Drepturi de autor:

Formate disponibile

Laser Surface Modification of HVOF Coatings For Improvement of Corrosion and Wear Performance

Încărcat de

Drepturi de autor:

Formate disponibile

Laser Surface Modification of HVOF Coatings for

Improvement of Corrosion and Wear Performance

A thesis submitted to The University of Manchester for the degree of

Mohsen Mohamed Rakhes

LIST OF TABLES ............................................................................................ 18

COPYRIGHT STATEMENT ........................................................................... 22

LIST OF PUBLICATIONS RELATED TO THIS THESIS ........................... 27

CHAPTER 1 INTRODUCTION ................................................................... 29

1.1 RESEARCH MOTIVATION AND RATIONALE...... ..............................................29

CHAPTER 2 LITERATURE REVIEW ....................................................... 34

2.1 INTRODUCTION........... ....................................................................,.............34

2.4.1 Principles of Thermal Spray Coatings....... ..............................................62

CHAPTER 3 EXPERIMENTAL PROCEDURES ..................................... 104

3.1 INTRODUCTION........... ................................................................................104

3.5.3 Polarisation ............................................................................................115

CHAPTER 4 OPTIMISATION OF LASER OPERATING CONDITIONS

4.1 INTRODUCTION........... ................................................................................122

CHAPTER 5 MATERIALS CHARACTERISATION............................... 144

5.1 INTRODUCTION........... ................................................................................144

CHAPTER 6 CORROSION TESTS ........................................................... 202

6.1 INTRODUCTION........... ................................................................................202

6.2 IMMERSION TEST........ ................................................................................202

CHAPTER 7 RESULTS ON HARDNESS AND WEAR RESISTANCE

7.1 INTRODUCTION........... ................................................................................245

CHAPTER 8 CONCLUSIONS AND SUGGESTIONS FOR FUTURE

APPENDIX A .................................................................................................. 264

APPENDIX B .................................................................................................. 271

REFERENCES ................................................................................................ 279

Word count: 54,075

Figure 2.25 Cross-section of T800-68WC HVOF coating on stainless steel

Figure 4.2 Overlapping tracks of laser treated T800+21WC HVOF coating

Figure 4.18 SEM microstructure of the Laves phase in theT800 HVOF

Figure 5.11 SEM micrographs of surface view of T800+43WC HVOF

Figure 6.11 SEM cross-section images of T800+68WC HVOF coating: a, c

Figure 6.30 Impedance spectra after 12 hours of immersion for various

Figure 7.2 SEM micrographs of microhardness indentations on different phases of

Metal Matrix Composite (MMC) coatings, comprised of a hard ceramic phase

[iv] Further information on the conditions under which disclosure,

Oral/ Poster papers

Rakhes, M. E. Koroleva, and Z. Liu, Improvement of corrosion

Rakhes, M. and Z. Liu, Laser surface modification of HVOF coatings for

Local Seminars/ Posters

Rakhes, M. and Z. Liu, Laser surface modification of HVOF coatings for

Rakhes, M. and Z. Liu, Laser surface modification of HVOF coatings for

1.1 Research motivation and rationale

conditions to achieve different degrees of melting of HVOF coatings, would be a

1.2 Aims and objectives of the research

Tribaloy 800 (T800)

T800 + 21WC (wt.%)

T800 + 43WC (wt.%)

T800 + 68WC (wt.%)

The investigations include microstructural analysis, corrosion behaviour, wear

1) To establish laser operating windows for various HVOF coatings to achieve

i) defect-free layers, i.e. elimination of porosity, microcracks and splats

ii) control of the melt pool dimensions, in particularly melt depth;

iii) control of the degree of full/partial melting of the WC particles.

2) To investigate the microstructural changes of various HVOF coatings before and

5) To investigate the wear performance and hardness of various HVOF coatings

1.3 Thesis outline

Chapter 2 covers the fundamental aspects of corrosion and various corrosion

Chapter 4 presents the optimisation of laser operating conditions by studying the

Chapter 5 presents the results and discussion on materials characterisation of

Appendix A presents Nyquist plots with tables of electrochemical parameters