Hydrogen Cracking and Stress Corrosion of Pressure Vessel

Steel ASTM A543

by
Ali Hamad AlShawaf
 A thesis submitted to the Faculty and the Board of Trustees of the Colorado

School of Mines in partial fulfillment of the requirements for the degree of Doctor of

Philosophy (Metallurgical and Materials Engineering).

Golden, Colorado
Date

Signed:
Ali Hamad AlShawaf

Signed:
Dr. Stephen Liu
Thesis Advisor

Golden, Colorado
Date
Signed:
Dr. Ivar E. Reimanis
Interim Department Head
Department of Metallurgical and Materials
Engineering

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 Table of Contents

Chapter 1: Introduction ......................................................................................................... 1

1.1 Research Scope ........................................................................................................... 1

1.2 Justification for Research Performed............................................................................ 1

1.1 Plant Process Operation ............................................................................................... 5

1.1.1 Alkalinity of Boiler Water ........................................................................................ 5

1.1.2 pH Level of Boiler Water ........................................................................................ 5

1.1.3 Dissolved Oxygen in Boiler Water .......................................................................... 6

1.1.4 Dissolved Solids in Boiler Water ............................................................................ 6

Chapter 2: Literature Review ................................................................................................ 9

2.1 Hydrogen Damage ....................................................................................................... 9

2.1.1 Hydrogen Cracking Models .................................................................................. 10

2.1.2 Temperature Range for Hydrogen Cracking ........................................................ 11

2.1.3 Sources of Hydrogen ........................................................................................... 11

2.1.4 Presence of Hydrogen in the Weld ...................................................................... 12

2.1.5 Weld Overmatching Condition ............................................................................. 13

2.1.6 Weld Undermatching Condition ........................................................................... 13

2.1.7 Hydrogen Solubility and Diffusivity in HSLA Steel................................................ 14

2.1.8 Hydrogen Trap Sites ............................................................................................ 14

2.1.9 Hydrogen Interaction with Grains & Grain Boundaries ........................................ 16

2.1.10 The Influence of Grain Size & Alloying Elements.............................................. 16

2.1.11 Microstructural Susceptibility ............................................................................ 17

2.1.12 Effect of Hydrogen on Mechanical Properties: .................................................. 18

2.1.13 Hydrogen Damage Prevention ......................................................................... 21

2.2 Weldability Testing ..................................................................................................... 22

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 2.2.1 Implant Testing .................................................................................................... 24

2.2.2 Carbon Equivalent ............................................................................................... 25

2.2.3 Previous Research Studies on Implant Test of HSLA Steels ............................... 26

2.3 Hydrogen Charging .................................................................................................... 33

2.3.1 Electrochemical Charging .................................................................................... 33

2.3.2 Hydrogen Recombination (Poison) ...................................................................... 34

2.4 Fracture Surface Morphology In The Presence of Hydrogen ..................................... 34

2.5 Residual Stresses....................................................................................................... 34

2.6 Corrosion .................................................................................................................... 36

2.6.1 Corrosion in Water-contained Pressure Vessels.................................................. 38

2.6.2 Stress Corrosion Cracking (SCC) ........................................................................ 40

2.6.3 Slow Strain-Rate Testing ..................................................................................... 41

2.6.4 Corrosion Prevention and Protection ................................................................... 42

Chapter 3: Experimental Procedure ................................................................................... 44

3.1 Material Specification ................................................................................................. 44

3.2 Heat Affected Zone (HAZ) Experimental Simulation................................................... 44

3.2.1 Gleeble® 3500 Simulation of HAZ ....................................................................... 44

3.2.2 Furnace Simulation of HAZ .................................................................................. 46

3.3 Hydrogen Charging Set-up ......................................................................................... 47

3.4 Hydrogen Analysis Using LECO H2 Analyzer ............................................................. 49

3.5 Etchant Used for Preparing the Metallographical Samples ........................................ 50

3.6 Weldability Implant Testing ......................................................................................... 51

3.6.1 Gas Metal Arc Welding (GMAW). ........................................................................ 52

3.7 Tensile Testing of simulated HAZ Subzones-Alliance Machine .................................. 52

3.8 Corrosion Study of Q&T HSLA Steel .......................................................................... 53

3.8.1 Slow Strain Rate Testing...................................................................................... 53

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 3.8.2 Electrochemical Test Using Gamry Machine ....................................................... 55

Chapter 4: Weldability and Mechanical Properties ............................................................. 57

4.1 Weldability Implant Testing ......................................................................................... 57

4.1.1 Implant Test Equipment Construction .................................................................. 58

4.1.2 Implant Test Results ............................................................................................ 59

4.2 Mechanical Properties Results ................................................................................... 60

4.2.1 Pre-charged Furnace Simulated Samples ........................................................... 60

4.2.2 Pre-charged Gleeble® Simulated Samples ......................................................... 69

Chapter 5: Fractography & Metallography Analyses .......................................................... 74

5.1 Introduction ................................................................................................................. 74

5.2 Results and Discussion .............................................................................................. 74

5.3 Metallography of Furnace and Gleeble® Samples ..................................................... 76

5.3.1 LePera Colored Etchant ....................................................................................... 91

Chapter 6: Numerical Simulation of Implant Testing .......................................................... 93

6.1 Numerical Simulation Introduction .............................................................................. 93

6.1.1 Simulation Considerations ................................................................................... 94

6.1.2 Rosenthal's Equations ......................................................................................... 95

6.2 Mathcad Calculations ................................................................................................. 97

6.3 ESI-SYSWELD Simulation ......................................................................................... 98

6.3.1 Material Database Manager ............................................................................... 100

6.3.2 Thermal and Mechanical Parameters in SYSWELD .......................................... 102

6.3.3 Modeling of Moving Heat Source (Arc) .............................................................. 105

6.4 Simulated Implant Testing ........................................................................................ 108

6.4.1 Parameters Used in the Simulation .................................................................... 112

6.4.2 Thermo-physical Properties ............................................................................... 113

6.4.3 Mechanical Properties ....................................................................................... 113

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 6.5 Description of the Welding Conditions – Bead-on-Plate Welding Simulation ........... 113

6.5.1 Temperature Distribution and Obtaining Thermal Cycle .................................... 115

6.5.2 Imposing Thermal Cycle on Implant Pin Simulation ........................................... 115

6.6 Simulation Results for Pressure Vessel Steels ......................................................... 119

6.6.1 ASTM A516 Gr. 70 Steel Simulation Results ..................................................... 124

6.6.2 ASTM A533 Steel Simulation Results ................................................................ 126

6.6.3 ASTM A36 Steel Simulation Results .................................................................. 128

6.6.4 ASTM A543 Steel Simulation Results ................................................................ 128

6.7 Discussion of Implant Simulation Results ................................................................. 131

Chapter 7: Corrosion Study of Q&T HSLA A543 Steel ..................................................... 136

7.1 Introduction ............................................................................................................... 136

7.2 Results and Discussion of SSRT .............................................................................. 139

7.3 Electrochemical Impedance Spectroscopy (EIS) ...................................................... 147

7.3.1 Results and Discussion ...................................................................................... 150

Chapter 8: Research Summary ........................................................................................ 159

8.1 Hydrogen Cracking ................................................................................................... 159

8.2 Surface Mobility Mechanism Causing Pits ................................................................ 159

Chapter 9: Conclusions .................................................................................................... 165

9.1 Microstructure, Mechanical Behavior and Weldability Studies ................................. 165

9.2 Numerical Modeling .................................................................................................. 165

9.3 Corrosion Study ........................................................................................................ 166

9.4 Suggested Mitigations .............................................................................................. 166

Chapter 10: Future Works .................................................................................................. 167

Chapter 11: Appendices ..................................................................................................... 178

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 List of Figures

Figure 1.1. A longitudinal cross-section through the weld showing the crack, which exhibits a
jagged path. ................................................................................................................................. 3
Figure1.2. A schematic showing the general assembly of the pressure vessel, E is ethylene,
EO is ethylene oxide. ................................................................................................................... 7
Figure 1.3. Schematic of two drums boiler to generate Boiler Feed Water BFW [5]. ................... 8
Fig. 2.1. Schematic showing location of hydrogen-induced cracks in carbon steel weldments
[9]. ............................................................................................................................................. 10
Figure 2.2. (A)The hydrogen sites in the steel: a) Trap sites. b) Subsurface. c) Surface. d)
GB, vacancies. e) Dislocations. f) Combined Hydrogen, (B)the common hydrogen models
[10]. ........................................................................................................................................... 12
Figure 2.3. Causes of cold cracking in base metal [15]. ............................................................ 13
Figure 2.4. a) Amount of hydrogen absorbed by the molten weld pool varies with
concentration in arc atmosphere at 1900oC. b) Solubility of hydrogen in weld metal
decreases as temperature decreases [15]................................................................................. 15
Figure 2.5. Hardness as function of carbon content as a function of martensite formation in
carbon steel with rapid cooling [13]. .......................................................................................... 18
Figure 2.6. Hardenability curves for five carbon steels as determined by end-quench testing
[13]. ........................................................................................................................................... 19
Figure 2.7. True-stress-strain curve relation with the strain hardening. ..................................... 20
Fig. 2.8. Effect of grain size on mechanical properties. ............................................................. 22
Fig. 2.9. Hydrogen hardening as observed during the hydrogen charging [31]. ........................ 23
Figure 2.10. Schematic representation of an Implant test specimen after welding. The rod is
loaded by tension. ..................................................................................................................... 24
Figure 2.11. The CSM Implant test set up. The plate on top of the set-up is the weld plate.
With the weld plate removed, the notched rod is shown in the small photograph. ..................... 25
Figure 2.12. Carbon equivalent values located on the Graville chart. ........................................ 26
Figure 2.13. Implant test result showing the different charging percentage of hydrogen. .......... 27
Figure 2.14. A chart of the model that developed by Coe and Chano [36]. ............................... 27
Figure 2.16. Implant testing results of the five grades of HSLA steels [38]. ............................... 28

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Figure 2.17. Implant specimen showing the variable parameters used to build up the
numerical model [39]. ................................................................................................................ 30
Figure 2.18. No evidence of cracking in the HAZ and fusion zone [40]. .................................... 31
Figure 2.19. Preheat temperature as a function of hydrogen content [42]. ................................ 31
Figure 2.20. The Percentage of hydrogen diffusion in one of the steel [46]. .............................. 33
Figure 2.21. Intergranular fracture surface of two different materials a) 2507 duplex stainless
steel, b) HSLA AISI 4135 steel [54,55]. ..................................................................................... 35
Figure 2.22. The distribution of residual stresses over the diameter of a quenched bar and
radial directions due to (a) thermal contraction and (c) both thermal and transformational
volume changes [9]. .................................................................................................................. 37
Figure 2.23. Typical distributions of temperature and longitudinal stress (x) during bead on
plate welding showing residual stress development [9]. ............................................................ 37
Figure 2.24. The galvanic series showing active and inactive metals. ....................................... 39
Figure 2.25. Stress corrosion cracking factors. .......................................................................... 40
Researchers have classified the SCC of HSLA steels into two categories, intergranular SCC
(IGSCC) and transgranular SCC (TGSCC). Both intergranular and transgranular SCC may
take place, but the crack always follows a general macroscopic path that is normal to the
tensile component of stress. ...................................................................................................... 40
Figure 2.26. A schematic of the slow strain-rate test set up. ..................................................... 42
Figure 2.27. Stress corrosion cracking factors. .......................................................................... 42
Figure 3.1. Gleeble® 3500 thermo-mechanical simulation system. ........................................... 45
Figure 3.2. Heat treatment temperatures cycles in Gleeble® 3500. .......................................... 46
Figure 3.3. One inch-thick plates for furnace heat treatment. .................................................... 47
Figure 3.4. Cathodically hydrogen charging set-up. .................................................................. 48
Figure 3.5. Hydogen concentrations vs. time for pre-charged specimens analyzed by LECO
analyzer. .................................................................................................................................... 49
Figure 3.6. LECO H2 analyzer machine. .................................................................................... 50
Figure 3.7. Implant weldability test set-up constructed in the welding laboratory. ..................... 51
Figure 3.8. Gas metal arc welding (MIG welding or GMA welding). .......................................... 52
Figure 3.9. Mechanical tensile test using the Alliance machine. ................................................ 53
Figure 3.11. Geometry and dimensions of tensile test specimen for SSRT (in mm). ................. 54
Figure 3.12. Electrochemical test showing the flask and Gamry set-up. ................................... 56

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Figure 4.1. Implant test design and dimensions recommended by ASM handbook [76]. .......... 57
Figure 4.3. The implant test parts, a) general implant test set-up, b) applied load reading, c)
load cell, d) weld bead on implant plate, e) load plates, f) jack sysetm. .................................... 61
Figure 4.4. Schematic showing how the implant test is conducted. ........................................... 62
Figure 4.5. Implant test results for all three conditions (0% H2, 1%H2 and 2% H2). ................... 63
Figure 4.6. Fracture locations in different conditions. ................................................................ 64
Figure 4.7. Microhardness measurements on the implant pin without hydrogen charging, the
sample did not fail. ..................................................................................................................... 65
Figure 4.8. a) the hydrogen diffusion in austenitic materials is lower than ferritic materials, b)
hydrogen cracking after the weld [15]. ....................................................................................... 66
Figure 4.9. Mechanical tensile test results for the furnace samples. ......................................... 68
Figure 4.10. Tensile strength and microhardness results for the furnace samples. ................... 69
The samples were machined according to the standardized low force mode in Gleeble®
machine. The dimensions were 6 mm diameter and 80 mm length. The samples were used
to produce the different subzones in the HAZ along the implant pin. Two more temperatures
were added to assure covering all the regions in between the different microstructures. .......... 69
Figure 4.11. Modified tensile test results using constant load for the furnace samples. ............ 70
Figure 4.12. Modified tensile test results using constant load for each simulated furnace
sample. ...................................................................................................................................... 71
Figure 4.13. Fracture locations in different conditions. .............................................................. 72
Figure 5.1. Schematic showing the possible features happening in the fracture surface. ......... 75
Figure 5.2. The base metal (ASTM A543 steel) and the high temperature simulated
specimens (CGHAZ and FGHAZ) with different hydrogen charging. ......................................... 77
Figure 5.3. The low temperature simulated specimens with different hydrogen charging. ........ 78
Figure 5.4. The base metal (ASTM A543 steel) and the high temperature simulated
specimens (CGHAZ&FGHAZ) with different hydrogen charging at higher magnification. ......... 79
Figure 5.5. The low temperature simulated specimens with different hydrogen charging at
higher magnification. ................................................................................................................. 80
Figure 5.6. Gleeble simulated samples charged with 5 ppm H2 for ASTM A543 steel. .............. 81
Figure 5.7. Gleeble simulated samples charged with 5 ppm H 2 at higher magnification
showing the high hydrogen intergranular cracking in the CGHAZ and reduces as going to low
temperatures in red arrow. ......................................................................................................... 82

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Figure 5.8. Different microstructures (subzones) generated by the weld during implant
testing. ....................................................................................................................................... 84
Figure 5.9. Different HAZ subzones microstructures produced by the furnace.......................... 85
Figure 5.10. Microstructure of the base metal ASTM A543 steel showing the martensite and
bainite with some ferrite. ............................................................................................................ 86
Figure 5.11. The Vickers hardness reading along the implant pin for ASTM A543 steel. .......... 86
Figure 5.12. Different microstructures produced by the Gleeble®. ............................................ 88
Figure 5.14. As-etched microstructures for a) 1200oC and b) 1100oC, CGHAZ simulated
samples. .................................................................................................................................... 89
Figure 5.16. As-etched microstructures for a) 760oC and b) 725oC, and c) 500oC simulated
samples. .................................................................................................................................... 90
Figure 5.17. Lepera etchant for the CGHAZ and FGHAZ samples, ferrite is blue, bainite is
brown, MA consituent is white. .................................................................................................. 92
Figure 6.1. Heat flow around weldment for (a) thick plate and (b) thin sheet. ............................ 94
Figure 6.2. Schematic temperature variations around weld pool. .............................................. 95
Figure 6.3. Rosenthal assumption: point heat source geometry [85]. ........................................ 96
Figure 6.4. Rosenthal equation showing the effect of doubling the welding speed on isotherm
pattern [84]. ............................................................................................................................... 97
Figure 6.5. Graphical repersentation of the calculations resulted in the form of isotherms
using Rosenthal equation. ......................................................................................................... 99
Figure 6.6. Welding advisor: Component (base metal and welding metal) properties, welding
process parameters, cooling behavior, and clamping condition are addressed. ...................... 101
Figure 6.7. Material database manager- start window. ............................................................ 103
Figure 6.8. Material database manager- start window- chemical composition, thermal
conductivity, and yield stress. .................................................................................................. 104
Figure 6.9. Goldak double ellipsoid heat source model [89]. ................................................... 106
Figure 6.10. The weldline in SYSWELD simulation. ................................................................ 107
Figure 6.11. Recommended dimensions for implant test pin in ASM Metals Handbook. ......... 108
Figure 6.12. Simulated model showing the dimensions used in SYSWELD. ........................... 110
Figure 6.13. First model simulation showing the geometry and the mesh distrinution. ............ 111
Figure 6.14. The two models used for the simulation and computational analysis. ................. 112
Figure 6.15. Simulated welding parameters and conditions .................................................... 116

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Figure 6.16. Temperature distribution during the weldability implant testing ........................... 117
Figure 6.17. Thermal cycle obtained from the first model for the second implant pin model. .. 118
Figure 6.18. Displacement (distortion) during the welding process. ........................................ 119
Figure 6.19. Imposing the thermal cycle to the implant pin model. .......................................... 120
Figure 6.20. Thermal cycle obtained from the first model and applied to the second pin
model. ...................................................................................................................................... 120
Figure 6.21. The applied tensile loading in the second simulated pin compared to the implant
testing. ..................................................................................................................................... 121
Figure 6.22. Simulated weldability implant test using ESI-SYSWELD software. Different
colors represent different temperature zone. The warmer the color, the higher is the
temperature. ............................................................................................................................ 122
Figure 6.23. Calculated CE for the three pressure vessel steels and ASTM A36 steel on the
Graville chart. .......................................................................................................................... 123
Figure 6.24. Phase amounts of martensite and bainite for ASTM A516 Gr. 70 steel. .............. 124
Figure 6.25. Austenite fraction for ASTM A516 Gr. 70 steel during welding and after the weld
passes. .................................................................................................................................... 125
Figure 6.26. The susceptible crack initiation phase and location for ASTM A516 Gr. 70 steel.125
Figure 6.27. Phase amounts for ASTM A533 steel after weld cycle. ....................................... 126
Figure 6.28. Phase amounts of bainite and tempered martensite for ASTM A533 steel. ........ 127
Figure 6.29. The susceptible crack initiation phase and locations for ASTM A533 steel. ........ 127
Figure 6.30. Percentage of microstructural constituents for ASTM A36 steel. ......................... 128
Figure 6.31. Phase amounts of martensite, bainite, and other phases for ASTM A36 steel. ... 129
Figure 6.32. The susceptible crack initiation phase and location for ASTM A36 steel. ............ 130
Figure 6.33. Phase amounts of bainite, martensite and tempered martensite for ASTM A543
Gr. B steel................................................................................................................................ 131
Figure 6.34. The susceptible crack initiation phase and locations for ASTM A543 Gr.B steel. 132
Figure 6.35. Implant test fracture of ASTM A543 steel compared to the simulation result of
the same pressure vessel steel. .............................................................................................. 134
Figure 6.36. Microstructures of the four pressure vessel steels a) ASTM A516 Gr.70 steel
(ferrite-pearlite)92, b) ASTM A533 Gr.B steel (bainite)92, c) ASTM A543 Gr.B steel
(Martensite-bainite), d) ASTM A36 steel (ferrite-pearlite)92. ..................................................... 135
Figure 7.1. Stress-strain curves of high strength steels at different temperature [98]. ............. 136

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Figure 7.2. Stress-strain curves of high strength steel at different pH [99]. ............................. 137
Figure 7.3. Stress-strain curves of high strength steel in two different level of oxygen.100....... 138
Figure 7.4. Effect of SCC on the mechanical properties [104]. ................................................ 138
Figure 7.5. Stress-strain curves in air at 25oC for base plate A543 steel. ................................ 141
Figure 7.6. Stress-strain curves (base plate A543 steel) in 3.5%NaCl solution at 100, 125,
150, and 175oC compared to air (25oC). .................................................................................. 142
Figure 7.7. Stress-strain curves (welded-condition) in 3.5%NaCl solution at 100, 125, 150,
and 175oC compared to air (25oC)........................................................................................... 143
Figure 7.8. Stress-strain curves (base plate A543 steel) in 0.1%NaNO2 solution at 100,125,
150, 175oC compared to air (25oC).......................................................................................... 144
Figure 7.9. Stress-strain curves (welded-condition) in 0.1% NaNO2 solution at 100, 125, 150,
and 175oC compared to air (25oC)........................................................................................... 145
Figure 7.10. EpR, RAR and ISSRT results for 3.5%NaCl and 0.1%NaNO2 solutions. ................ 146
Figure 7.11. SEM images for the fractured base plate specimens in air. ................................. 147
Figure 7.12. SEM images for the fractured base plate specimens in 3.5%NaCl solution at a)
175oC and b) 150oC c) 125oC. ................................................................................................. 148
Figure 7.13. SEM images for the fractured specimens in 0.1% NaNO 2 solution for the base
plate A543 steel. ...................................................................................................................... 148
Figure 7.14. The welded specimen showing the fusion zone, HAZ, and base metal A543
steel. ........................................................................................................................................ 149
Figure 7.15. Schematic showing the locations of the extracted samples [105]. ....................... 149
Figure 7.16. SEM images for the fractured specimens for the welded condition. .................... 151
Figure 7.17. Fracture occurred away from HAZ region. ........................................................... 152
Figure 7.18. Schematic of EIS electrical circuit [117]. .............................................................. 152
Figure 7.19. Single and multi pass samples. ........................................................................... 153
Figure 7.20. Nyquist curves showing the 45o straight line in different test samples. ................ 154
Figure 7.21. Modulus impedance and phase as function of frequency curves showing the two
peaks indicated by the arrows. ................................................................................................ 155
Figure 7.22. Pits formation as explained by De Levis and Warburg. ....................................... 156
Figure 7.23. Gamry software suggested CPE with diffusion model. ........................................ 156
Figure 7.24. CPE with diffusion model that fits the EIS results for all the tests. ....................... 157
Figure 7.25. Potentiodynamic results showing the corrosion rate and pits formation. ............. 158

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Figure 8.1. Hydrogen cracking following the MA constituents in the CGHAZ. ......................... 160
Figure 8.2. Surface mobility mechanism in the steam environment. ........................................ 161
Figure 8.3. (a) Anodic pits formation in steam environment, (b)Evans diagram showing the
electrochemical reaction happening most likely in the micro-crack tip. .................................... 162
Figure 8.4. A cross section of a sample taken from the pressure vessel in the plant showing
the stress. corrosion cracking and the branching at the crack tip. .......................................... 163
Figure 8.5. (a) Pits formation during the electrochemical impedance test, (b)pits formation in
a sample taken from the plant. ................................................................................................ 163
Figure 8.6. Flow chart illustrating the possible failure mechansims for A543 steel. ................. 164

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 List of Tables
Table 1.1. Chemical composition of the SA-543 Q&T HSLA steels. .......................................... 3
Table 1.2. Major tasks programmed in this research. ................................................................ 4
Table 2.1. Five different HSLA steels and their carbon equivalent values. .............................. 28
Table 2.2. Some alloys with their susceptibility to SCC in severe environment. ...................... 41
Table 3.1: Chemical composition of the A-543 Q&T HSLA steel and the welding
consumable. .............................................................................................................................. 44
Table 4.1. Heat treated Furnace samples microhardness measurements............................... 67
Table 4.2. Heat treated Furnace samples HEI calculated values. ........................................... 67
Table 4.3. Heat treated Gleeble® samples micro-hardness measurements. .......................... 72
Table 4.4. Heat treated Gleeble® samples microhardness measurements. ............................ 73
Table 5.1. Heat treated Furnace samples hardness measurements. ...................................... 87
Table 5.2. Heat treated Gleeble® samples hardness measurements. .................................... 87
Table 6.1. SYSWELD simulation statistic data of the two models. ........................................ 109
Table 6.2. Chemical composition of all four pressure vessel steels. ...................................... 113
Table.6.3. Thermo-physical and mechanical properties for ASTM A516 Gr. 70 steel. .......... 114
Table.6.4. Stress-Strain properties for ASTM A36 steel. ....................................................... 114
Table 6.5. CE values for all the steels ................................................................................... 123
Table 7.1. The results obtained from stress-strain curves for both alkaline solutions. ........... 140

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 ACKNOWLEDGEMENTS

I’m grateful for the support and the guidance that my Ph.D. advisor, Prof. Stephen Liu provided
during my Ph.D. program. Prof. Liu’s inspiration and enthusiasm helped to make the program
beneficial and enjoyable.
I would like to extend my thanks to all members of the Center of Welding, Joining and Coating
Research (CWJCR). Also, I thank all the staff of the Metallurgical and Materials Engineering
department at Colorado School of Mines (CSM) for the support provided during my Ph.D.
program.
Thanks are due to my employer SABIC (Saudi Basic Industries Corporation) for the trust,
investment, and the financial support especially Mr. Ali Al-Hazemi and STC (SABIC
Technology Center) management.
A special thanks is owed to Brian Shula and Vamsi Kommineni from Engineering System
International (ESI) for the training and the software technical support to successfully complete
the SYSWELD numerical simulation study.
No doubt that my success is a result of the care, emotional support and prayers of my parent,
Hamad Ali AlShawaf and Zahra Ali AlHashim. I thank my family: my wife, Rabab
Alabdulmuhsin, my children, Hamad and Zainab, for being with me in the United States, going
through and sharing all the happy and hard moments.

(My Lord, Increase me in knowledge)

xv
 ABSTRACT

The purpose of conducting this research is to develop fundamental understanding of the

weldability of the modern Quenched and Tempered High Strength Low Alloy (Q&T HSLA)
steel, regarding the cracking behavior and susceptibility to environmental cracking in the base
metal and in the heat affected zone (HAZ) when welded. A number of leaking cracks
developed in the girth welds of the pressure vessel after a short time of upgrading the material
from plain carbon steel to Q&T HSLA steel. The new vessels were constructed to increase the
production of the plant and also to save weight for the larger pressure vessel.

The results of this research study will be used to identify safe welding procedure and design
more weldable material. A standardized weldability test known as implant test was constructed
and used to study the susceptibility of the Q&T HSLA steel to hydrogen cracking. The charged
hydrogen content for each weld was recorded against the applied load during weldability
testing. The lack of understanding in detail of the interaction between hydrogen and each HAZ
subzone in implant testing led to the need of developing the test to obtain more data about the
weldability. The HAZ subzones were produced using two techniques: standard furnace and
Gleeble® machine. These produced subzones were pre-charged with hydrogen to different
levels of concentration. The hydrogen charging on the samples simulates prior exposure of the
material to high humidity environment during welding process. Fractographical and
microstructural characterization of the HAZ subzones were conducted using techniques such
as SEM (Scanning Electron Microscopy). A modified implant test using the mechanical tensile
machine was also used to observe the effects of the hydrogen on the cracking behavior of
each HAZ subzone.

All the experimental weldability works were simulated and validated using a commercial
computational software, SYSWELD. The computational simulation of implant testing of Q&T
HSLA with the previously used plain carbon steel and other currently used pressure vessel
steels was successfully completed. The experimental and computational results of the Q&T
HSLA steel agreed well with each other.

xvi
The susceptibility of the Q&T A543 steel to stress corrosion cracking was investigated using
the slow strain rate testing under different environments and conditions. Also, advanced
corrosion study using the electrochemical impedance spectroscopy was done at different
conditions. The corrosion study revealed that this A543 steel is prone to form pits in most of
the conditions. The model results in the corrosion study were validated with the Gamry Echem
Analyst software that A543 steel tends to form pits in the tested environment.

xvii
 CHAPTER 1: INTRODUCTION
This chapter discusses the research objective and scope of the work. The plant
operation process, which shows the environment to which this modern Q&T HSLA steel
is exposed, is briefly mentioned in this chapter.

1.1 Research Scope

The primary goal of this research is to obtain fundamental understanding of the
weldability of modern quenched and tempered high strength low alloy (Q & T HSLA)
steels. In parallel, this research will collect and compile welding data on A543 steel
regarding weldability, hydrogen cracking susceptibility, cracking behavior and corrosion
behavior. A standardized weldability implant testing was constructed and used for the
cold cracking evaluation. Slow strain rate testing was used to examine the susceptibility
of Q & T HSLA steels to stress corrosion cracking. The samples were cathodically
hydrogen charged to simulate prior exposure of the material to high humidity
environment.

1.2 Justification for Research Performed

High strength alloys, whether iron-based, aluminum-based or titanium-based, are
susceptible to hydrogen cracking. Fabrication using these materials for structural
applications must exercise care to minimize the effect of hydrogen cracking. High
strength low alloy (HSLA) quenched and tempered (Q&T) structural steels typically
contain less than 0.25 wt.pct. carbon and less than 5 wt.pct. total alloy content. These
steels possess high yield and tensile strengths, good ductility and notch toughness, and
good atmospheric corrosion resistance. They are strengthened primarily by quenching
and tempering to produce microstructures that contain martensite, bainite, and, in some
compositions, ferrite. Some types are produced with a precipitation-hardening treatment
that follows hot rolling or quenching. The yield strength values range from approximately
345 to 895 MPa (50 to 130 ksi), and tensile strength values range from 485 to 1035
MPa (70 to 150 ksi), depending on chemical composition, thickness, and heat
treatment. High-strength low-alloy (HSLA) steels are used widely in the fabrication of
heavy structures such as pressure vessels. However, they are difficult to weld due to
their high hardenability and susceptibility to cold cracking [1].

1
In the fabrication of a pipeline or a chemical reactor, circumferential or girth welds are
often required to join sections of tubular structures together. In the presence of
hydrogen during the fabrication and welding processes, hydrogen pick up is expected
which together with thermal stresses, can lead to hydrogen cracking in the weld zone.
Hydrogen cracking is also referred to as delayed cracking, because cracking is often
delayed for minutes, hours, or even longer after solidification has completed. Requisites
for cold cracking include tensile stress (external loading and/or residual stress from
welding), crack-susceptible microstructure (martensite), and the presence of hydrogen.
Cold cracking can occur in the weld fusion zone in the form of microfissuring, or in the
HAZ as underbead cracking [2, 3].

There has recently been a trend towards manufacturing large pressure vessels using
SA-543 Grade B Class 1 steel. This type of Q&T HSLA steel (Table 1.1) has been
selected because of its high strength and also because of the weight savings, which is a
critical factor when manufacturing, transporting and erecting such large vessels [1].
However, the increase in carbon, chromium, nickel, and molybdenum content has great
influence on the carbon equivalent value of the alloy. The carbon equivalent of SA-543
steel is 0.93 wt. pct. (minimum nominal chemical composition) and 1.16 wt. pct.
(maximum nominal chemical composition). Both carbon equivalent values are located in
the third zone of the Graville chart, which indicates that the steel is difficult to weld and
that proper heat treatment would be required [4]. The ASME Section VIII Div. 2 code,
however, does not mandate or prohibit the requirement of pre- and post-weld heat
treatment for this type of steel, so the fabrication specification of one such reactor did
not include any heat treatment. Recently, some cracks were discovered in the closing
V-groove welds in the coolers. A micrograph of the weld cross-section showing the
crack propagation is presented in Figure 1.1. The electrodes and the welding processes
used to construct the pressure vessel are A5.28 ER110S-G grade for gas metal arc
welding (GMAW) and gas tungsten arc welding (GTAW), E12018M grade for shielded
metal arc welding (SMAW), and F11A6-EM3-M3 or A5.23 / F12A10-EG-G consumables
for submerged arc welding (SAW).

2
 Table 1.1. Chemical composition of the SA-543 Q&T HSLA steels.
Minimum Minimum
Composition, wt.pct. tensile yield
ASTM strength strength
Grade
spec.
C Mn P S Si Cr Ni Mo Cu V MPa ksi MPa ksi

0.20- 1.50- 2.60- 0.45- .. 620- 90- 480- 70-

B 0.23 0.40 0.020 0.020 0.03
A 543 0.40 2.00 4.00 0.60 . 930 135 700 100

WELD

HAZ

Figure 1.1. A longitudinal cross-section through the weld showing the crack, which
exhibits a jagged path.

Pre- and post-weld heat treatment is generally effective in eliminating hydrogen

cracking, but they add cost to the manufacturing process. Newer steels reduce their
carbon content to minimize the impact of hydrogen cracking. With bainitic or
bainitic/martensitic matrix and usually higher dislocation density, the stability of these
microstructures in weld thermal cycles of these newer steels is less known [2, 3]. Their
resistance to hydrogen cracking needs also be thoroughly characterized to ensure safe
application. In particular, the notch sensitivity of hydrogen cracking in these modern
Q&T HSLA steel must be clearly defined using weldability tests. It is crucial to prevent
failures and extend useful service life of the pressure vessel in modern petrochemical
plants. The failure of a pressure vessel can result in huge direct and indirect economic
losses that include replacement and repair costs along with unscheduled shutdowns
and loss of production. This study of the newly used Q&T HSLA steel is necessary to
understand the steel behavior and also to collect sufficient data about the metallurgical
properties of the welds to avoid future failures.

3
The main focus of this research is to evaluate the hydrogen cracking susceptibility of
modern high strength steels. The research objectives have been established to answer
the following fundamental questions:

1. Is A543 steel susceptible to hydrogen cracking, to stress corrosion cracking or to

both mechanisms?
2. What is the nature of the cracking in the A543 steel weldment HAZ?
3. What are the roles of HAZ subzones and phase transformations in A543 steel
weld and their relationship to the cracking behavior?
4. Can SYSWELD software simulate the weldability implant test for pressure vessel
steels with respect to:
a. Thermal experience effect?
b. Subzones microstructure?
c. Crack location in the subzones?
5. Can the simulation data be used to achieve better understanding of the evolution
of microstructure and cracks in subzones in HAZ?

The research work encompasses the tasks listed in Table 1.2 below.
Table 1.2. Major tasks programmed in this research.

# Task(s)
1. Design and construct an implant testing equipment.
2. Test Q&T A543 steel and gather data from the weldability tests ( implant test).

3. Design and set-up cathodic hydrogen charging and measure the hydrogen
content of the pre-charged samples using LECO analyzer.
4. Simulate HAZ microstructures using the furnace and Gleeble 3500 thermo-
mechanical system.
5. Study the susceptibility of the Q&T A543 steel to stress corrosion cracking.
6. Study the effects of hydrogen on the simulated HAZ microstructures on
cracking behavior.
7. Study the fractography of the fractured samples using SEM.
8. Quantify the hydrogen content in the Q&T A543 steel welded joints prepared
using enriched hydrogen shielding gas and cathodically pre-charging method.

9. Simulate the welding/heat treating conditions using computational software

SYSWELD.

4
1.1 Plant Process Operation
In this reactor, the Q&T A543 steel is exposed to Boiler Feed Water (BFW). The medium
temperature range is between 270 and 300ºC (518 and 572oF) and the pressure range is
from 35 to 40 bar. This industrial plant oxidizes ethylene in the reactor to form ethylene
oxide and then to finally produce ethylene glycol. Figure 1.2 is a sketch of the general
arrangement of the reactor and cooler assembly. In the reactor, the ethylene gas passes
through the tubes and gets oxidized to go to the cooler.

In the cooler, the ethylene oxide passes through the cooler tubes and the boiler feed
water (BFW) is used as a cooling medium on the shell side to further cool it down. The
BFW has to be controlled and maintained to certain quality. Figure 1.3 shows a general
schematic of two drum boiler generating the BFW for the plant. So, the reactor
chemistry plays a very important role in corrosion. Corrosion occurs by electrochemical
reactions and is influenced by chemical factors. These factors like pH, alkalinity, oxygen
and dissolved solids play a significant role in controlling the quality of the BFW. Their
effects will be briefly mentioned below.

1.1.1 Alkalinity of Boiler Water

Alkalinity is the ability of natural water to neutralize acid. Alkalinity in water is due to the
presence of bicarbonates, carbonates and hydroxyl ions. In raw water alkalinity is
mainly due to bicarbonates. Carbonates and particularly hydroxyl ions are rarely
encountered in untreated waters. Hydroxyl ions normally get introduced during
treatment of water [5,6].

1.1.2 pH Level of Boiler Water

Water pH is a measure of its relative acidic or alkalinity. Neutral water will give pH equal
to seven (7). A number lower than 7 is acidic and higher than 7 is alkaline. Both
extremes are corrosive to steel. In acidic range the protective layer of magnetite is not
able to form resulting in corrosion. In very high pH range the protective layer of
magnetite breaks down leading also to corrosion. pH is defined as negative logarithm of
H+ ions concentration and it is calculated as pH = -Log [H+]. For corrosion prevention,
maintaining proper pH is very important [5, 6].

5
1.1.3 Dissolved Oxygen in Boiler Water
Oxygen is considered as one of the most corrosive components in water chemistry.
Dissolved oxygen with traces of chloride or solids can cause pitting corrosion of metallic
surface. The resulting condition may be severe, even at low pressure [5, 7,8].

1.1.4 Dissolved Solids in Boiler Water

Dissolved solids or salt content of water present as ion increases electrical conductivity
of water. The higher the conductivity, the greater will be the possibility of corrosion to
occur. Other elements like silica, chloride, copper and sulfate need to be strictly
controlled and limited to assure the quality of BFW [5,7,8].

6
 E

BFW & Steam

Diameter = 5 meter (16.4feet)

Hight = 13 meter (42.7feet)
Shell side = Boiler Feed Water
Around 19000 tubes (BFW)

Reactor

BFW

BFW

Around 4000 tubes

Cooler

BFW

EO

Figure1.2. A schematic showing the general assembly of the pressure vessel, E is

ethylene, EO is ethylene oxide.

7
Figure 1.3. Schematic of two drums boiler to generate Boiler Feed Water BFW [5].

8
 CHAPTER 2: LITERATURE REVIEW
This Chapter discusses the recent literatures about the influence of hydrogen and
interaction with the Q&T HSLA steel. Also, the weldability and hydrogen cracking will be
addressed in this chapter.

2.1 Hydrogen Damage

There are two types of cracking that can happen during and after welding. These
cracking are hot and cold cracking. Hot cracks are also called solidification cracks. Cold
cracks form in the weld at some point in time after the weld has cooled down. Cold
cracking, which is the focus of this research, usually form as a result of residual
stresses in the weld and hydrogen diffusion in steels. There are numerous standardized
weldability tests to investigate the cold cracking mechanism. One of the weldability
tests, called implant testing, has been constructed in the welding laboratory at CSM.
Hydrogen-induced cracking, HIC, is the most serious problem affecting weldability. This
type of cracking results from the combined effects of four factors: a susceptible (brittle)
microstructure, the presence of hydrogen in the weld metal, tensile stresses in the weld
area, and a specific temperature range, -100 to 200°C. Changes in one factor can affect
changes in the other three. For example, a change in welding parameters, which
changes the weld metal cooling rate, will most likely change the hydrogen
concentration, the residual stresses, and likely the microstructure [9,10].

Hydrogen-induced cracking, also known as cold cracking, delayed cracking, or

underbead cracking is the most serious problem affecting steel weldability. Any
hardenable steel is susceptible to hydrogen-induced cracking. Figure 2.1 shows the
most common cracking that could happen after the weld cools down in carbon steel.
The weld metal cracks could initiate and propagate either in the longitudinal or
transverse directions. The longitudinal weld metal cracks are caused by the stress
concentrations at the root of the weld. While, the transverse weld metal cracks are
caused by the hydrogen-containing defects plus the tensile stresses. The underbead
cracks usually happen more or less parallel to the fusion line. The toe cracks and root
cracks initiate usually in regions having a high stress concentration. The least common
cracking is the transverse cracking which happen in the HAZ. These types of cracks

9
could occur in the steel under the right conditions like high tensile stresses and the
presence of hydrogen [11,12].

Fig. 2.1. Schematic showing location of hydrogen-induced cracks in carbon steel

weldments [9].

2.1.1 Hydrogen Cracking Models

Generally speaking, HIC susceptibility of a microstructure increases with increasing
hardness or strength [9]. There are models simulating the hydrogen cracking behavior
as a function of hydrogen diffusion behavior e.g. the Pressure Theory, Hydrogen
Enhanced Decohesion (HEDE) and Hydrogen Enhanced Localized Plasticity (HELP).
These models are illustrated in Figure 2.2 and described in the following [9]:

2.1.1.1 The Pressure Theory

It is one of the oldest models for hydrogen damage. This model points out that hydrogen
embrittlement occurs when the diffused atomic hydrogen into the metal combines to
form molecular hydrogen which will gather at voids or other internal discontinuities. The
gathering of molecular hydrogen will increase the concentration of hydrogen leading to
increases in the internal pressure. The internal pressure will then enhance void growth
or crack initiation. This model does not explain other hydrogen damages like hydrogen
cracking but can be used to explain some of the hydrogen damage like hydrogen
blistering [9,11].

2.1.1.2 Hydrogen Enhanced Decohesion (HEDE)

Hydrogen can affect the cohesive force between the atoms in the alloy matrix. Since
high hydrogen concentrations will accumulate ahead of a crack tip, hydrogen will lower

10
the cohesive force between metal atoms. So, the local tensile stress perpendicular to
the plane of the crack may become equivalent to or greater than the lattice cohesive
force, and fracture results [9,12].

2.1.1.3 Hydrogen Enhanced Localized Plasticity (HELP)

It is related to hydrogen-dislocation interactions and is primarily based on fractographic
observations. This model proposes that atomic hydrogen enhances dislocation motion
(generally, screw dislocations) and the generation of dislocations at surfaces and/or
crack tips, leading to softening of the material on a localized scale. High resolution
electron microscopes have been used to study the brittle cleavage or intergranular
fracture surfaces. These high resolution electron microscopes showed evidence of
crack tip plasticity in support of this model [9,10].

2.1.1.4 Hydride Formation

Group Vb metals in periodic table like niobium, vanadium, tantalum, zirconium, titanium,
and magnesium is degraded in hydrogen environments and that brittle metal hydrides
form at the crack tip. The crack will be arrested in the more ductile matrix or will be
continued and grow between hydrides resulting in ductile rupture. The crack
propagation and growth is enhanced by the applied stress [9,11].

2.1.2 Temperature Range for Hydrogen Cracking

Hydrogen cracking will not normally occur outside of the temperature range of -100 to
200°C (-150 to 390°F). Below -100°C (-150°F), the hydrogen probably diffuses too
slowly to reach a critical concentration in a susceptible area, while above 200°C (390°F)
the hydrogen diffuses so rapidly out of the weld area that hydrogen will not have time to
reach a critical accumulation [9,11].

2.1.3 Sources of Hydrogen

Hydrogen exists in many industrial applications like oil, chemical, petrochemical and
even during the steel-making process. Moreover, any corrosive environment can
produce hydrogen from the corrosion reactions and that will result in hydrogen uptake.
In industries, extra care is needed especially for the steel grades that are potentially
susceptible to hydrogen during welding [13, 14].

11
 (A) (B)

Figure 2.2. (A)The hydrogen sites in the steel: a) Trap sites. b) Subsurface. c) Surface.
d) GB, vacancies. e) Dislocations. f) Combined Hydrogen, (B)the common hydrogen
models [10].

2.1.4 Presence of Hydrogen in the Weld

Hydrogen presence is necessary for the hydrogen cracking. Hydrogen is generally
introduced into the weld region during the welding process. The principle source of
hydrogen is the welding consumable. Other sources for hydrogen during welding are
moisture in the flux coating in the electrodes, hydrogen-containing lubricants left on the
surface of wire electrodes, hydrogen-containing compounds such as grease, oil, paint,
and rust left on the plate surface, and leaking gas lines. Many specifications provide
consumable classification based on the diffusible hydrogen levels of their deposited
weld metals, e.g. AWS A4.3 and ISO 3690 [13,14].

The distribution of hydrogen in the weld metal and HAZ and the subsequent
susceptibility to cold cracking is a function of the phase transformations that take place
upon cooling as shown in Figure 2.3. Hydrogen is usually decomposed to its atomic
form during welding with high solubility in molten iron as well as in austenite phase as
shown in Figure 2.4. Solubility of hydrogen decreases with decreasing temperature.
Rapid cooling after the weld can result in significant supersaturation of atomic hydrogen
in the solidified metal. Because atomic hydrogen diffuses relatively easily through
ferrite, a certain amount of the initial hydrogen present will subsequently diffuse out of
the weld metal [14,15,16].

12
 Figure 2.3. Causes of cold cracking in base metal [15].

2.1.5 Weld Overmatching Condition

Weld overmatching is when the weld metal has a higher strength than the base metal
and its martensite start temperature below that of the base metal as such, the austenite
in the HAZ starts decomposing before the austenite in the weld metal. Therefore, the
HAZ immediately adjacent to the fusion zone will transport hydrogen at a higher rate
than that in the weld metal. If the martensite forms at a high temperature in the HAZ,
then the hydrogen will be able to transport a significant distance into the parent metal.
However, hydrogen transport cannot proceed until the weld metal transforms because
austenite has high hydrogen solubility but not good diffusivity. Hydrogen cannot diffuse
fast enough to the fusion line. If the weld metal martensite temperature happens at low
temperature, then the hydrogen transport from the weld metal is limited. Very little
hydrogen can reach the heat affected zone adjacent to the fusion line. The high amount
of hydrogen in the weld metal may finally lead to weld metal hydrogen cracking or
microfissuring [15, 16, 17].

2.1.6 Weld Undermatching Condition

If the weld metal is undermatched with respect to the base metal, the heat affected zone
transforms from austenite to ferrite at lower temperatures. So, the HAZ would be an
austenite diffusion barrier for hydrogen transport and so a high hydrogen accumulation
occurs near the fusion line. This situation promotes underbead hydrogen cracking.

13
Thus, a HAZ with lower martensite temperature may result in underbead hydrogen
cracking and localized weld metal cracking along the fusion line [15, 16, 17].

2.1.7 Hydrogen Solubility and Diffusivity in HSLA Steel

Modern Q&T HSLA Steels alloys generally contain two phases, a body centered
tetragonal (BCT) martensite (α’) and body centered cubic (BCC) ferrite (α). Martensite
and ferrite are expected to have similar hydrogen transport properties since both are
open structure. The open-packed structures like BCT & BCC provide greater hydrogen
diffusivities than close-packed structures like face centered cubic (FCC) austenite ().
The transport aspect is important because of the lower hydrogen solubility but higher
hydrogen diffusion in ferrite (BCC) and martensite (BCT) which is opposite from
austenite (FCC). The solubility of hydrogen in austenite is three orders of magnitude
higher than the solubility in ferrite. So, a non-uniform hydrogen distribution may result
across the weldment according to the austenite decomposition behavior of the alloys.
The reported values for hydrogen diffusivities in ferrite at room temperature range from
10-4 to 10-6 cm2/s [18,19], whereas the common reported value for austenite is 10 -12
cm2/s [18,20]. The solubility of hydrogen is related to the interstitial sites. The atomic
radius size of hydrogen is reported to be 0.37 Å and the reported radius size of the
octahedral site in austenite is 0.52 Å and in ferrite is 0.19 Å [20]. The radius size of the
tetrahedral sites, which is between the two phases, is 0.28 Å in austenite and 0.35 Å in
ferrite [21].

2.1.8 Hydrogen Trap Sites

Trapping sites are very important factor to understand the hydrogen cracking fracture
mechanism and also to evaluate the susceptibility of steel to hydrogen cracking. There
are trapping sites in the steel like the impurities (inclusions), structural defects, and
microstructural constituents. Binding between hydrogen and the trapping sites usually
happen due to physical trapping, electric field, stress field, temperature gradient, or
chemical gradient. The trapping sites can generally be identified as two types.

14
 (a)
(b)

Figure 2.4. a) Amount of hydrogen absorbed by the molten weld pool varies with concentration in arc atmosphere at 1900 oC.
b) Solubility of hydrogen in weld metal decreases as temperature decreases [15].

15
They are mobile trapping sites and stationary trapping sites. Examples of the mobile
trapping sites are dislocations and stacking faults. Grain boundaries, carbide particles,
inclusions, and individual solute atoms are examples of the stationary trapping sites.
Trapping of hydrogen may also be reversible or irreversible. Reversible traps are short
duration traps of hydrogen in which the occupancy time is short or limited. While, the
irreversible traps are a longer staying and attachment time for hydrogen because of the
high binding energy. Inclusions are as mentioned earlier is one of the important
stationary trapping sites. Nonmetallic inclusions like manganese sulfides are examples
of hydrogen trapping sites in steels. The solubility of hydrogen depends not only on the
content but also on the shape of manganese sulfide particles. For example, the
elongated manganese sulfides increase hydrogen solubility and decrease its effective
diffusion coefficient in direction perpendicular to the planes. Whereas, the rounded
manganese sulfides decreases the hydrogen solubility and increases the diffusion
coefficient [22, 23].

2.1.9 Hydrogen Interaction with Grains & Grain Boundaries

Many researchers reported that hydrogen enters only into grain boundaries of the
body-centered cubic (BCC) phase. They reported that the solubility of hydrogen was
0.01 ppm [22]. However, this solubility value was determined by the gas equilibration
method, where the pressure has high influence on the solubility of hydrogen. The
recent researches showed that hydrogen most likely enters the solid granular particles
rather than grain boundaries. They cathodically hydrogen charged a steel which had
two different grain sizes. They found that the same hydrogen concentration was
obtained in the two steels. So, as the grain size to grain boundary area increases, the
solubility of hydrogen in the metal becomes greater which indicate that hydrogen
most likely enters the grains rather than the grain boundaries [22, 24].

2.1.10 The Influence of Grain Size & Alloying Elements

Grain size plays a big role in the formation of the martensite microstructure. After the
weld is completed, the Heat Affected Zone (HAZ) would have large austenite grains
which will easily allow the formation of martensite microstructure than smaller grains.
The literatures have different opinions in regard to the effect of grain size on hydrogen

16
cracking. One of the reasons that cause the different opinions is because different
microstructures can result from different grain sizes. It was reported that fine carbide
and grain sizes have good mitigation effect on hydrogen cracking because the hydrogen
is distributed evenly and uniformly [22]. Ryder et al. [25] reported that crack growth
kinetics are affected mostly by a diffusion-controlled process, which may either be
related to the area of the grain boundary or the amount of retained austenite at the
boundary and proposed that coarse austenite grain size provides interfaces that
promote crack branching which improves the steel toughness. It is good to mention that
most of the grain refinement alloying elements like niobium and vanadium would raise
the HAZ hardness in higher heat input welding or in longer cooling time welding,
through the precipitation hardening by their carbonitrides [4, 26].

Regarding the alloying elements, the main purpose of adding the alloying elements to
HSLA steels is to obtain good physical and mechanical properties but however these
elements may or may not contribute to the hydrogen cracking. It was reported that
manganese (Mn) has a strong influence on the hydrogen cracking, while additions of
silicon, vanadium, niobium, cobalt, and palladium are good for the resistance of the
hydrogen cracking [27]. Hence, the hydrogen cracking is influenced by the combination
of microstructure and the alloying elements.

2.1.11 Microstructural Susceptibility

The understanding of the four well-established metallurgical strengthening mechanisms
will definitely help to improve the welding microstructural and mechanical properties. So,
it is desired to increase the strength of the material without negatively impacting other
properties like the material toughness often represented in the form of brittle-ductile
transition temperature diagrams. The four strengthening mechanisms are solid-solution
strengthening, grain size refinement, precipitation strengthening, and microstructural
strengthening. Different heat treatments and different composition of the welding wires
will result in different microstructures, different toughness and resistance to hydrogen-
induced cracking in the weld metal and HAZ of this modern Q&T HSLA steel. The hard
and brittle microstructure formed in the HAZ or weld metal is a susceptible
microstructure to hydrogen cracking. Martensite is the most susceptible microstructure

17
to hydrogen cracking because of its high hardness, depending on its carbon content
[13]. High carbon content in martensite will make microstructure harder, more brittle,
and more susceptible to cracking. Figure 2.5 shows the effect of carbon content on the
hardness of carbon steel for different percentages of martensite formed by quenching
the steel [27, 28, 29]. The susceptibility to hydrogen cracking of other microstructures
that formed in the weld metal and HAZ depends on the level of hardening.

Figure 2.5. Hardness as function of carbon content as a function of martensite formation

in carbon steel with rapid cooling [13].

The hardenability of the steel is also influenced by the carbon content. Figure 2.6 shows
the hardenability curves for five carbon steels as determined by the Jominy bar test. As
the cooling rate decreases, hardness decreases and less martensite is formed. So
higher cooling rate for the high carbon steel will result in more martensite formation
which makes the steel harder and more susceptible to hydrogen-induced cracking [13].

2.1.12 Effect of Hydrogen on Mechanical Properties:

It was reported [27] that dislocation trapping sites can act as rapid and efficient carriers
of hydrogen. Also, they studied the relationship between the kinetics of embrittlement
under loading and the transport of hydrogen to critical failure sites within the material.

18
 Figure 2.6. Hardenability curves for five carbon steels as determined by end-quench
testing [13].

A mathematical relationship between the motion and velocity of dislocation (V) and the
hydrogen atom was developed as follow [27]:

V = (D/k T) F (2.1)

where D is the lattice diffusivity of hydrogen and F is the effective driving force for the
formation of the hydrogen-dislocation pair.

During the bending and tension testing, some mechanical properties such as yield (σy)
and tensile strength (σUTS), total percent elongation (%), and work hardening exponent
(n) need to be considered. Also, other mechanical properties that can be calculated are
the true stress-true strain data which can be fitted to the Hollomon equation to relate
them to the strain hardening behavior of the tested material.

σ = K εn (2.2)
r = εw / εt (2.3)

19
where σ is the true stress, ε is the true strain, K is the flow strength and n is the work or
strain hardening exponent that is illustrated in Figure 2.7.

Figure 2.7. True-stress-strain curve relation with the strain hardening.

These properties change depending on material properties as seen in Figure 2.8. For
example the flow stress is affected by grain size according to the Hall-Petch relation.
During the tension process, the interaction between hydrogen with the dislocation is
very important. In Figure 2.7, the stress-strain relation remains linear during the
deformation till a point where the dislocations move irreversibly. A curve starts to form
on the stress-strain graph and the deviation point is the start of the plastic region (yield
stress). Then, the curve continues to rise to a maximum stress level representing the
maximum resistance of the material to further deformation (ultimate tensile stress). The
portion of the curve between the yield stress and the maximum stress illustrated strain
hardening. This behavior can be described by the Hollomon equation [30]. The
hydrogen interaction with the dislocations was studied by Oriani et al. [31] who
suggested that solute hydrogen can increase the yield or flow stress of steels by
hydrogen drag on moving dislocations, or impeding cross-slip. Hydrogen hardening is
also expected from the fact that trapped hydrogen can make dislocation nucleation
difficult from grain boundary dislocations and other possible sources as shown in Figure
2.9 [31,32].

20
2.1.13 Hydrogen Damage Prevention
One of the serious problems with hydrogen-induced cracking is the difficulty in detecting
the presence of a crack. The delayed nature of some of the cracks demands that
inspection not be carried out too soon, especially in welds that will have external loads
applied when put in service. Because some of the cracks do not extend to the surface,
they are not detectable by visual inspection methods (for example, liquid penetrant, or
magnetic particle inspection, which requires the defect to be near the surface).
Radiography is most sensitive to volumetric flaws, but it may not detect cracks that are
too fine or of the wrong orientation. Ultrasonic inspection is capable of detecting cracks
within the detectable limits [33].

Preheating of the weld area is the most effective and widely used method for avoiding
hydrogen cracking. Its primary function is to reduce the weld metal cooling rate so that
transformation to martensite is avoided or reduced below a certain critical level. The
slower cooling also gives hydrogen more time to diffuse out of the weld area and delays
the onset of maximum residual stresses. Many specifications and codes require the use
of specific preheat and interpass temperatures for welding hardenable steels. AWS
D1.1 code specifies minimum preheat and interpass temperatures for various
thicknesses of structural carbon steels [16].

Hence, the major preventative measures to avoid cold cracking can be summarized as
follow:
• Preheat, including maintenance of proper interpass temperature.
• Heat input control.
• Postweld heat treatment.
• Bead tempering.
• Use of low-hydrogen processes and consumables.
• Use of alternate filler materials (for example, austenitic electrodes) [33].

21
 Fig. 2.8. Effect of grain size on mechanical properties.

2.2 Weldability Testing

Weldability is defined as the capacity of a material to be welded under the imposed
fabrication conditions into a specific, suitably designed structure and to perform
satisfactorily in the intended service. The weldability tests are used to evaluate the
effects of welding on the base metal and weld metal properties. Because weldability
testing is used to evaluate the welding characteristics of the base materials, many of
these weldability tests are laboratory or research tests rather than production tests.
Weldability tests are used extensively during alloy development. However, many are
also used during weld procedure development to ensure the weldability of base
materials before production commences. Each test is designed to evaluate the material
susceptibility to a specific weldability problem. In this research, implant testing was
selected as the methodology to characterize the weldability of A543 steel and
susceptibility to hydrogen cracking. An implant testing equipment was constructed [34,
35] and used in this investigation.

22
Fig. 2.9. Hydrogen hardening as observed during the hydrogen charging [31].

23
2.2.1 Implant Testing
The implant weld hydrogen cracking test originated from the studies by Granjon et al. in
1964 and Cabelka et al. in 1967. The International Institute of Welding (IIW) adopted
and recommended the test in 1973 as a complementary information test for steels. The
recommended procedure is detailed in IIW-93- 62 and IIW-Doc. No IX-1240-82. As
shown in Figure 2.10 below, a rod of the steel base metal to be tested is machined to
specified dimensions, with either a circular groove or a helical groove machined into the
end of the rod. The rod is placed inside a hole in the center of a plate so the top of the
rod is flush with the top of the plate. A load is then attached to the bottom end of the
rod. A weld bead is made on the top surface of the plate passing directly over the top of
the rod. By making the weld over the rod, the groove (notch) in the rod is thus located in
the coarse-grained HAZ, which is most susceptible to HIC in structural steels. The time
to failure is plotted as a function of the loading stress. The crack susceptibility of the
base metal is measured by the degree to which the failure stress is reduced with time.
More data can be obtained from the implant test like the hardness distribution along the
rod and thermal history of the weld by inserting a thermocouple. The Implant test set-up
is shown in Figure 2.11 [9]. More details about the construction of the system can be
found in Chapter 3 (implant testing construction).

Figure 2.10. Schematic representation of an Implant test specimen after welding. The
rod is loaded by tension.

24
 Figure 2.11. The CSM Implant test set up. The plate on top of the set-up is the weld
plate. With the weld plate removed, the notched rod is shown in the small photograph.

2.2.2 Carbon Equivalent

It is well known that both the weldability and weldment toughness are inversely related
to the Carbon Equivalent (CE) value, especially at high carbon contents. It is also
known that carbon equivalent and micro-alloying elements such as vanadium (V) and
niobium (Nb) can seriously affect the fracture properties. Vanadium and niobium are
very often added to HSLA steels to improve the strength and low temperature
toughness. For this reason, calculating the CE for Q&T HSLA steel is important and
locating the CE value in the Graville [4] chart (Fig. 2.12) can relate the CE on the
weldability of the steel. The CE equation used in this research is according to AWS
Specification and it is given as follow:

(%𝑴𝒏+%𝑺𝒊) (%𝑪𝒓+%𝑴𝒐+%𝑽) (%𝑪𝒖+%𝑵𝒊)

𝑪𝑬 = %𝑪 + [ ]+[ ]+[ ] (2.4)
𝟔 𝟓 𝟏𝟓

The carbon equivalent for Q&T ASTM A543 steel is 0.93 considering minimum typical
chemical composition and 1.16 at maximum typical composition. The CE values of A36
steel and A543 steel are marked on the Graville [4] chart in Figure 2.12.

25
There is a criterion that categorizes the CE values and evaluates the need for the heat
treatment. Carbon steels with less than 0.2 wt. pct. carbon content are generally not
susceptible to cracking, and additional precautions are usually unnecessary. Thus, mild
steels can be welded but their hardness may need to be controlled. If the CE value of
the steel is less than 0.40 or it is located in the first zone on the Graville chart, preheat is
usually not necessary. If the CE value is above 0.40 and it is located in the second zone
on the Graville chart, pre-heat is recommended. However, if the CE is above 0.4 and
located in the third zone of the Graville [4] chart, then pre- and post-weld heat treatment
are recommended. Generally, the use of low hydrogen consumables is recommended
for HSLA steels.
Pre- and post-heat recommended
.
Preheat
recommended

A3 A543

Easy to weld
Figure 2.12. Carbon equivalent values located on the Graville chart.

2.2.3 Previous Research Studies on Implant Test of HSLA Steels

There are numerous technical papers that discuss the cracking behavior during and
after welding common HSLA steels but a very limited and almost none found that
investigated the newer Q&T HSLA steels, especially ASTM A543. Hence, the following
is a brief summary of literatures that investigated the behavior of other grades of HSLA
steels.

Gedeon and Eagar [36] cathodically charged one specific grade of the HSLA steel with
different percentage of hydrogen and analyzed the results of the implant test and the

26
diffusible weld hydrogen as shown in Figure 2.13. A reduction of the load that the tested
steel can withstand was observed as the hydrogen concentration increases. They
determined the amount of hydrogen present at the crack location at the time of fracture.
They determined the amount of hydrogen using a model initially developed by Coe and
Chano [36] as shown in Figure 2.14.

H2 increase

Figure 2.13. Implant test result showing the different charging percentage of hydrogen.

Figure 2.14. A chart of the model that developed by Coe and Chano [36].

Pircher et al. [38] examined the influence of welding on the resistance to hydrogen-
induced cracking of five different HSLA steels (A, B, C, D and E) as shown in Table 2.1.
The multi pass welded joints and single-pass bead-on-plate welds with varying cooling
times, t8/5, were discussed. Constant load tests were conducted according to NACE TM-
01-77 with H2S saturated NACE test solution of pH 3 (Fig.2.16). The results showed
that steels with lower hardening tendency exhibited greater resistance to HIC.

27
 Table 2.1. Five different HSLA steels and their carbon equivalent values.
Tensile strength
HSLA Steel Alloying components CE wt.pct.(IIW eq.)*
(N/mm2)
A C, Mn, Ni 535 0.46
B C, Mn 520 0.4
C C, Mn, Nb, V 575 0.39
D C, Mn, Cr, Mo 605 0.38
E C, Mn, Cr, Mo, Ni, V 850 0.79
*CE: carbon equivalent values according to IIW specification.

Figure 2.16. Implant testing results of the five grades of HSLA steels [38].

Biswas [39] used Rice’s path-independent J integral (Fig. 2.17) to correlate the crack
growth initiation for materials under extensive plastic deformation. An elastic-plastic
finite element analysis suitably formulated to accommodate linear work hardening of
materials for a circumferentially notched axisymmetric implant specimen was carried out
under contained yielding and monotonically increasing tensile loads. The numerical
results include notch tip parameters and near-tip deformation fields. Also, the effects of
the difference in weld and base metal properties on J integral were investigated. Even
though his results did not predict a unique J value, these results may still be employed
confidently for engineering purposes in view of the justification demonstrated by the
nearly path-independent J solutions obtained from a rather crude finite element
formulation based on linear displacement distributions. The author concluded that the
results of J integral analysis suggest that the parameter largely depends on the material
and geometric interactions of the test specimen and the numerical models agreed with
the published analytical results.

28
Murti et al. [40] studied the susceptibility of specific grade of HSLA steel (0.26C-0.65Mn-
0.01S-0.01P-1.7Cr-1.8Ni-0.05Al) to hot and cold cracking using 309L stainless steel
welding wire. He used five different standard tests. These tests were (i) Tekken test for
HAZ cracking, (ii) Tied tee test for fusion zone cracking, (iii) Electron microprobe
analyzer for composition, (iv) Metallographic test for microstructure and (v) Vickers
microhardness. The results showed no evidence of fusion zone or underbead cracking
for all the heat inputs as shown in Figure 2.18. The hardness results showed lower
hardness at high heat input.

Reddy et al. [41] studied the weldability of high strength low alloy steel (0.3C-3Ni-2.5Si-
0.87Cr-0.52Mn-0.29Mo) using austenitic filler metals (309L and 18Cr-8Ni-6Mn stainless
steel). Hot and cold cracking tests (T-type weld cracking test and Tekken test) were
carried out to study the cracking tendency in the weldment. The results showed that
these steels are not prone to hot and cold cracking and the toughness of the weld was
improved by a factor of nearly 1½ compared to that of the base metal in case of type
309L stainless steel while it was lower in case of type 18-8-6 austenitic steel.

Brozda’s paper [42] contains information about methods of selection of welding

conditions (the liner energy and preheat temperature) as functions of the thickness of
the parts to be welded and of the volume of diffusing hydrogen (Fig. 2.19). The author
determined the preheat temperature according to the European standard prEN1011
(BS5135). He concluded that the method of assessing the minimum preheat
temperature to prevent cold cracking as proposed by Uwer and Hohne and quoted in
the guidelines of SEW088 is the best approximation to the experimental results of the
Tekken test and because of its simplicity.

Zrilic et al. [43] studied the crack properties of a high strength steel welded joint.
Experimental investigations of toughness and crack resistance parameters through
static and impact tests of HSLA steel (with a nominal yield strength of 700 MPa) and its
welded joint were performed on Charpy specimens, V-notched and pre-cracked, of the
parent metal, weld metal and HAZ. The selected electrode was slightly undermatching
and enabled the welded joints to be manufactured without cold cracks.

29
Figure 2.17. Implant specimen showing the variable parameters used to build up the numerical model [39].

30
 Figure 2.18. No evidence of cracking in the HAZ and fusion zone [40].

Figure 2.19. Preheat temperature as a function of hydrogen content [42].

The impact energy and its parts responsible for crack initiation and propagation were
determined by toughness evaluation. Crack sensitivity, defined as the ratio of the impact
energy for V-notched and for pre-cracked specimens, enabled a comparison of the
homogeneous microstructure of the parent metal and the weld metal, and of the
heterogeneous microstructure of the heat-affected-zone (HAZ). The results obtained
showed that the toughness and crack resistance of the weld metal were significantly
lower than those of the parent metal and the HAZ.

Mayudeeswaran et al. [44] investigated the hydrogen-induced cracking mechanism that

could happen in the HAZ after welding in Q&T steels. The use of austenitic stainless
steel consumables to weld the HSLA steel was the only available remedy because of
higher solubility for hydrogen in austenite. The use of stainless steel consumables for a

31
non-stainless steel base metal is not economical. Hence, alternate consumables for
welding Q&T steels and their vulnerability to HIC need to be explored. Recent studies
proved that low hydrogen ferritic steel consumables can be used to weld Q&T steels
which can give very low hydrogen levels in the weld deposits. The investigation studied
the influence of welding consumables and welding processes on hydrogen-induced cold
cracking of armor grade Q&T steel welds by implant testing.

Yayla et al. [45] used different welding techniques in his study to evaluate the
mechanical performance of weldments of HSLA HY-80 steel. Weldments were prepared
using different welding processes such as shielded metal arc welding, gas metal arc
welding, and submerged arc welding. The objective was to determine the optimum
welding method for the steel. The effects of welding methods on weld metal
microstructure and mechanical properties including weld metal tensile strength and
Charpy V-notch impact toughness over the temperature range -20 to 20°C were
investigated. Charpy impact and tensile tests were performed on standard notched
specimens obtained from the welded and main sections of the material. They concluded
that with the optimum welding parameters the HY80 steel could be welded effectively
without any post-weld heat treatment.

Kim et al. [46] studied the resistance of two HSLA steels (Steel A and B, composed of
0.03%C–0.25%Cr and 0.05%C–0.25%Cr, respectively) to HIC. It was evaluated in
various test solutions with different H2S partial pressures and pH values. The results
showed that H2S partial pressure is the key parameter affecting the HIC resistance.
Hydrogen permeation rate was affected by both H2S partial pressure and pH of test
solutions, whereas the apparent hydrogen diffusivity was determined mainly by pH
value in case of H2S partial pressure less than 0.1 atm (Fig. 2.20). The results showed
also that hydrogen cracking in the steels primarily nucleated at inclusions and/or
clusters of Al and Ca oxides.

Beldokhti et al. [47] investigated the HIC and sulfide stress cracking (SSC) susceptibility
of the submerged arc welded pipeline steel. Different amounts of titanium at two levels
of manganese (1.4 and 2 wt. pct.) were studied. The centerline segregation region

32
(CSR) observed in the steel played an important role in the HIC susceptibility. Increased
acicular ferrite content in the microstructure improved HIC resistance and SSC
resistance, while bainite and martensite/austenite constituents deteriorated the
workability of the welded specimens in sour environments. The 2 wt. pct. Mn-series
welds showed higher SSC susceptibility than the 1.4 wt. pct. Mn-series welds due to the
higher hardness values of the welds. The precipitated titanium carbonitrides in the
welds acted as beneficial hydrogen traps and can delay cracking in hydrogen sulfide
environments. By further addition of titanium, the appearance of bainite and
martensite/austenite in the microstructure outweigh any beneficial effect of titanium
carbonitrides. The weld metals contained high percentage of acicular ferrite and good
distribution of titanium carbonitrides yielded the best performance in sour environments.

Figure 2.20. The Percentage of hydrogen diffusion in one of the steel [46].

2.3 Hydrogen Charging

To be able to relate weld cracking behavior with hydrogen, the amount of hydrogen in
the base metal and weld metal must be known. Two tests are proposed for examination.
The first one is pre-charging the specimen with hydrogen using electrochemical cells.
The second test is varying the hydrogen content through the shielding gas during the
gas metal arc (GMA) welding process [48].

2.3.1 Electrochemical Charging

The electrochemical evolution of atomic hydrogen is the most common cathode reaction
in cathodic protection, electroplating and other corrosion processes. In all cases most of
hydrogen atoms may encounter each other and quickly recombine to H2 molecules.

33
Atoms enter the metal surface and remain as individual atoms in metal as shown in the
chemical reactions below. However hydrogen absorbed by steels has a devastating
effect on strength and ductility of metal resulting in high risk of brittle failures [49, 50].

 H+ (solution) + e- → H• (adsorbed) ↔ ½ H2 (adsorbed) →½ H2 (bubbles)

 H+ (solution) + e- → H• (adsorbed) → H• (absorbed)

2.3.2 Hydrogen Recombination (Poison)

There are certain compounds that can affect the adsorption of hydrogen on steel. The
elements of these compounds are from groups VA and VIA in the periodic table known
as hydrogen recombination poisons. These compounds are added into the chemical
solution when the steel is cathoically charged with hydrogen. The most common
poisoned compounds that are typically used are arsenic (used in this research),
antimony, cyanides, and selenium compounds. These compounds are added to
electrolytes like H2SO4 before starting the cathodic charging process. The poisoned
compound will slow the recombination rate (kr) and will increase the likelihood that
hydrogen will be absorbed into the charged steel [51, 52].

2.4 Fracture Surface Morphology In The Presence of Hydrogen

The fracture surface morphology depends on the material properties and the loading
and environment conditions to which the metal is exposed. In the presence of hydrogen,
the fracture surface of the body centered cubic structures changes from ductile void
coalescence to intergranular or transgranular cleavage [53]. There are many research
studies that show that the pre-charged samples exhibited greater area fractions of
intergranular or transgranular fracture than the uncharged samples [54,55]. Figure 2.21
showed SEM images of pre-charged hydrogen samples that have different material
compositions with intergranular fracture surface [56, 57].

2.5 Residual Stresses

The stresses that a weldment is subjected to may be produced either externally or
internally. External stresses are those applied when the weld is in-service.

34
 (a) (b)
Figure 2.21. Intergranular fracture surface of two different materials a) 2507 duplex
stainless steel, b) HSLA AISI 4135 steel [54,55].

While, internal or residual stresses are produced during the welding process due mainly
to thermal gradients, unequal thermal expansion and contraction of the base metal and
weld metal, and volume changes resulting from phase transformations during cooling as
shown in Figure 2.22. The material will distort during welding if the thermal stresses are
higher than the yield strength of the material because of the thermally induced stresses.
When the stresses cannot cause macroscopic distortion, because the component is
constrained in some way, they either cause microscopic deformation like cracks or they
are locked into the structure to become residual stresses. Residual stresses in welded
structures can be very harmful because that the fracture may take place at a lower
externally applied stress than expected. Residual stresses can be reduced by
unrestrained movement of the parts being welded, thermal treatments, and proper weld
design. There are two main causes of the thermally-induced stresses:
 A volume change associated with a phase change (solidification or melting).
 High heating or cooling rates leading to a significant change in temperature and
temperature gradient.

Movement of the parts can be actual physical displacement or an elastic or plastic

deformation. Using a lower strength ferritic filler metal or austenitic filler metal to weld

35
the steel will help to minimize the residual stresses. The ductile filler metal is able to
absorb some of the stresses by elastic or plastic deformation and reduce the stress
level in the HAZ. Any condition that limits the movement of welded parts will increase
the residual stresses and the likelihood of hydrogen cracking.

Figure 2.23 shows the welding heat source which is moving at a constant speed along
the line O-x (x – axis). The area where plastic deformation occurs during the weld
thermal cycle is shown by the shaded area M–M. The temperature distribution and the
residual stresses build up are compared in four different locations namely A, B, C and
D. Along A-A, the material is unaffected with zero thermally-induced stresses because
the heat source is still far away. Along B-B, the temperature changes very rapidly
through the fusion zone because it is the location of the welding arc (heat source) and
has zero stress in the liquid weld pool itself. In the HAZ close to the weld pool, the metal
is trying to expand as it is heated but is prevented from doing so by the cooler material
ahead and behind it, so a compressive stress develops. Further away, the stress
becomes tensile to balance the compressive stresses in the B-B plane. Along C-C, the
arc or the heat source passed and the temperature decreases significantly. At C-C the
weld metal is solidified and the HAZ is cooled. Plastic deformation may occur in the hot
weld metal during cooling to result in residual stresses. Finally, along D-D, the
temperature is back to the ambient temperature [9, 58].

2.6 Corrosion
The selection of any material depends on the environment of application, whether at
elevated or cryogenic temperature, in aggressive seawater or acidic solutions. Any
metal generally loses some of its material either by corrosion or by forming a
nonmetallic film as protective layer. Corrosion, which comes from the Latin word
"corrodere" means gnawing to pieces, is a result of the interaction between the material
and the severe environment. It can be defined as breakdown or deterioration of the
metal that material loss results from the electrochemical reactions [60]. There are
mainly two reactions occurring in corrosion. They are anodic and cathodic reactions.
When a metal atom loses or gives up electrons, it is an anodic reaction that is also
known as oxidation.

36
 Figure 2.22. The distribution of residual stresses over the diameter of a quenched bar
and radial directions due to (a) thermal contraction and (c) both thermal and
transformational volume changes [9].

Figure 2.23. Typical distributions of temperature and longitudinal stress (x) during bead
on plate welding showing residual stress development [9].

37
On the other hand, the process in which a second metal atom receives these electrons,
a cathodic or reduction reaction occurs. Also, there are some factors which can
accelerate the corrosion process like temperature, acidity level, oxygen rate, micro-
organisms, velocity of the media and the contaminations. For example, increasing the
velocity will enhance the corrosion rate due to the erosive effects and increasing the
acidity level will also enhance the corrosion rate due to the increase of the corrosion
reactions [61, 62,63].
There are some basic terms which are related to the corrosion process. The rate of
material removal as a result of the electrochemical reactions is called the Corrosion
Penetration Rate (CPR) and it can be calculated as following:
𝑘𝑤
𝐶𝑃𝑅 =
𝜌𝐴𝑡
where k is constant and depends on the unit used (87.6 for mm/year). w is the weight
loss and A is the area of the sample, t is the time and ρ is the density.
Passivity occurs when the active metal or alloy loses its chemical reactivity and
becomes inactive. The galvanic series in Figure 2.24 shows the relative reactivity of
selected active and inactive metals.

Generally speaking, corrosion can be classified into two: wet and dry corrosion based
on the environment. However, there are eight classified forms of corrosion that may
happen in metals. These forms are uniform, galvanic, crevice, pitting, intergranular,
selective leaching, erosion-corrosion, and stress corrosion. Some forms of corrosion
can happen only in severe environments. For example, intergranular corrosion which
can occur in some alloys when heated to temperatures between 500 and 800oC. At this
elevated temperature these alloys become sensitized to intergranular corrosion in the
presence of some aggressive elements [64, 65].

2.6.1 Corrosion in Water-contained Pressure Vessels

The most common cause of corrosion in water-containing pressure vessels is dissolved
oxygen entering the system. Excessive oxygen causes localized corrosion in the form of
rounded pits.

38
 Figure 2.24. The galvanic series showing active and inactive metals.

The pits are small but deep, pinpoint holes which eventually can penetrate the metal to
cause failure. Oxygen can enter the process system at any point due to unexpected
leakage or upset. When the oxygen is dissolved, corrosion attack of the pipelines,
pumps and other equipment can be expected [66]. The severity of the attack depends
upon the concentration of the oxygen and the temperature of the water. Another
common cause of corrosion is the low pH. There are many contaminants which can
cause low pH levels to develop. Other problems that corrosion may cause are thinning
of the metal, metal perforation, interference with the production process, contamination,
and finally unscheduled shutdowns of the plant.

Water chemistry in the pressure vessels plays a very important role in corrosion.
Uniform corrosion of steel surfaces is expected to occur and is not of much concern as
all steels experience a small amount of general corrosion. However, localized corrosion
like pitting is of great concern, although metal loss is very small. Corrosion underneath

39
the contamination or solid deposited on the metal surface can weaken the steel and
cause failure. Typical types of corrosion found in pressure vessels depending on the
environments are stress corrosion cracking whether it is acid corrosion or caustic
corrosion, galvanic corrosion, and corrosion fatigue [67, 68, 69].

2.6.2 Stress Corrosion Cracking (SCC)

There are four factors that must be present in order for the SCC to occur. The four
factors are tensile stress, corrosive environment, susceptible material and enough time
for the failure to occur, as shown schematically in Figure 2.25. It must be noted that
removal of any of these factors will decrease the potential for SCC. Stress corrosion
cracking of an alloy in corrosive environment is specific and depends on the metal and
the environment. For example, stainless steels are generally susceptible to SCC in hot
chloride solutions but these solutions do not have the same effect on carbon steels,
HSLA steels, aluminum, or other nonferrous alloys. Table 2.2 shows some alloys with
susceptibility to SCC in severe environments [62,70].

TIME

MATERIAL STRESSES
SCC

ENVIRONMENT

Figure 2.25. Stress corrosion cracking factors.

Researchers have classified the SCC of HSLA steels into two categories, intergranular
SCC (IGSCC) and transgranular SCC (TGSCC). Both intergranular and transgranular
SCC may take place, but the crack always follows a general macroscopic path that is
normal to the tensile component of stress.

40
 Table 2.2. Some alloys with their susceptibility to SCC in severe environment.
Alloy Environment
Aluminum Chloride-containing solution, including contaminated water
vapor
Gold Chlorides, ammonium hydroxide, nitric acid
Steels Hot chloride solutions, caustics, saline solutions
Nickel Hot caustics
Copper Ammonia

Intergranular cracking proceeds along grain boundaries suggesting some

inhomogeneity along grain boundaries. For example, segregation of sulfur and
phosphorous at the grain boundaries is the probable cause of intergranular SCC in low
alloy steels. On the other hand, in transgranular SCC, cracks propagate across the
grains usually on specific crystal planes, generally with low indices such as {100}, {110},
and {210}. Both transgranular and intergranular SCC may occur in the same system or
even in the same part, depending on the right conditions [90, 91].

2.6.3 Slow Strain-Rate Testing

A recent advance in stress corrosion cracking (SCC) characterization technology is the
slow strain rate or continuous extension rate test. A conventional tensile specimen with
either round or rectangular cross section, tensile specimen is slowly pulled at a constant
strain rate to failure while exposed to a corrosive environment. The result is a stress
versus strain curve at a very low rate of loading. A schematic of the slow strain-rate test
set up is shown in Figure 2.26.

Stress corrosion cracking is critically influenced by electrochemical potential. Schematic

of the potentiodynamic anodic polarization curve for a typical active-passive corrosion
resistant alloy is shown in Figure 2.27. The two hatched lines indicate the occurrence of
SCC in susceptible alloy-solution combinations. The passive film is an apparent
prerequisite for SCC, but the two zones of susceptibility appear at the potential
boundaries where the passive film is less stable. Usually pitting and SCC start below
the bottom hatched line or adjacent potentials [71, 72].

41
 Figure 2.26. A schematic of the slow strain-rate test set up.

Figure 2.27. Stress corrosion cracking factors.

2.6.4 Corrosion Prevention and Protection
The selection and control of chemicals for preventing corrosion requires an
understanding of the causes and corrective measures. The common methods for
protecting the metal from corrosion are corrosion inhibitors, protective coating, on-line
corrosion monitoring and cathodic protection, which is divided into two types, namely

42
sacrificial anodes and impressed current. The corrosion inhibitors can be classified into
two types, environment modifiers and adsorption. In the case of environment modifiers,
the action and mechanism of the inhibition is a simple interaction with the aggressive
species and thus reduce the attack. On the other hand, the action and mechanism of
the adsorption corrosion inhibitors is to adsorb on the metal surface and inhibit the
corrosion. The protective coating may be accomplished by barrier coating, inhibitive
primers or cathodic protection. Other methods for prevention of corrosion include
filtration of solid suspended impurities and particles, removing dissolved oxygen,
maintaining the right recommended conditions for the process, keeping the internal
surfaces clean during off-days, using a chemical treatment program, and perform
regular inspections using appropriate NDT methods [73, 74].

Generally speaking, inhibitors are most commonly used in controlling corrosion in the
water-containing pressure vessels. They are long chain compounds, usually
nitrogenous such as amides, amines, imides, imidazolines but organophosphates can
also be used. These compounds are either polar or ionized salts with charge centered
on the nitrogen, oxygen or phosphorus groups which make them surface active. Since
metal surface in aqueous environment have a surface charge, inhibitors will rapidly
adsorb onto the metal surface. Once adsorbed, charge transfer takes place between the
metal surface and the inhibitor to form a stable chemical bond. This process leads to the
formation of a stable film of inhibitor on the surface of the metal, which retards the
corrosion process [75].

43
 CHAPTER 3: EXPERIMENTAL PROCEDURE
This chapter describes the experimental techniques and equipment used during the
research study and also the procedures involved for simulating the HAZ microstructure
and analyzing the hydrogen content.

3.1 Material Specification

The implant plates and pin are made of A543 Type B Cl1 steel. It is Q&T HSLA steel.
The A543 steel has an ultimate tensile strength of 930MPa (135 ksi) and yield strength
of 700MPa (100 ksi). The chemical composition is listed in Table 3.1. The material was
provided by the sponsor of this research, SABIC. The as-received material was
analysed using X-ray Fluorescence technique and the results are shown in Table 3.1.

Table 3.1: Chemical composition of the A-543 Q&T HSLA steel and the welding
consumable.
Composition, wt.pct.

C Mn P S Si Cr Ni Mo Cu V Fe

A 543 (ASTM 1.50- 2.60- 0.45-

0.23 0.40 0.020 0.020 0.20-0.40 ... 0.03 Bal.
spec.) 2.00 4.00 0.60

Results 0.1 0.35 0.01 0.01 0.25 1.63 3.23 0.58 0.01 0.01 Bal.

Wire type / wt.pct. Mn Ni Mo Cu Fe

AWS ER110S-G (MG-S80) < 5.0 < 5.0 0.5 < 0.5 Bal.

3.2 Heat Affected Zone (HAZ) Experimental Simulation

Laboratory simulation heat treatments were conducted using Gleeble® 3500 machine
and Carbolite furnaces.

3.2.1 Gleeble® 3500 Simulation of HAZ

Using a Gleeble® 3500 thermo-mechanical simulation system (Fig. 3.1), the HAZ of
Q&T HSLA A543 steel was simulated. Seven temperatures were selected based on the
numerical simulation results along the HAZ region along the implant pin. Solid
cylindrical samples of 6.0 mm diameter and 80 mm length were machined from the
provided plates from the sponsor. The specimens were subjected to thermal cycles to
44
mimic the cooling behavior that austenite in steels undergoes after welding. The
temperatures of the samples were measured by thermocouples welded to its middle
surface circumference. The high temperature samples go through austenization and
then cool down. For example, the simulated 1200oC sample was austenitized at 1200C
for sixty seconds, followed by grip cooling to ambient temperature. The low temperature
samples go up to the selected temperature and then grip cooled to ambient temperature
as shown in Figure 3.2. Dilatometry curves were also determined for the samples. The
heating and austenitization process was conducted under a vacuum at almost 10-6 Torr,
and the cooling was in the vacuum.

Control panel

Parameters Gleeble 3500

Max heating rate 10,000oC/s
Max quenching rate 10,000oC/s
Max stroke 100 mm
Max stroke rate 1000 mm/s
Max force (metric tons) 10 tons
Max specimen size 20 mm diameter
Figure 3.1. Gleeble® 3500 thermo-mechanical simulation system.

45
 Austensization

Cooling rate for

o
1000 C sample

Martensitic
transformation

Ms

Figure 3.2. Heat treatment temperatures cycles in Gleeble® 3500.

3.2.2 Furnace Simulation of HAZ

Carbolite furnaces were also used to simulate the HAZ microstructure of the Q&T HSLA
steel. Five heat treatment temperatures were selected to simulate the heat affected
zone. These temperatures are 1100, 900, 760, 725, and 500oC. The temperature was
monitored and measured with an external thermocouple to assure the accuracy of the
tested temperature. Furnace was heated till the desired temperature was reached.

46
Then, the one inch-thick plate was loaded inside the furnace and heated in the furnace
for one hour. The plate was then pulled out from the furnace to cool down in air
(normalized). The samples were then machined out from these plates for the hydrogen
cracking study as shown in Figure 3.3.

Figure 3.3. One inch-thick plates for furnace heat treatment.

3.3 Hydrogen Charging Set-up

Electrochemical hydrogen charging was used to charge the samples. The cell is a
simple beaker that holds the electrolyte and the electrodes (steel is the cathode and the
graphite is the anode) as shown in Figure 3.4. It is important to monitor the electrical
parameters because the current within the system tends to vary when the system is
voltage controlled, or voltage varies if the applied current is controlled. The slight
variation in the electrical response has to be monitored in order to assess the reliability
of the charging process. Current was controlled using a potentiostat DC power supply,
while voltage varied based on the electrochemical nature of the reactions occurring
between the two electrodes in the test setup. The hydrogen charging procedure steps
are as follow:
• Calculate Asurface, the exposed surface area of the steel.
• Recommended current density (id) is 10 mA/cm2 based on literatures and
previous research works.
• Exposed Asurface x (id) = applied current (Iapp).
• Put sample into the solution (1N H2SO4 + 1mg/L As2O3) .
• Turn on the potentiostat DC power supply.

47
 • Run test and record the time.
The applied current can be calculated as in the following:
 Sample diameter (d) = 0.25 in (0.635 cm).
 Sample height (h) = 0.6 cm.
 Surface area = 2 x  (3.14) x (d/2)2 +  (3.14) x d x h = 1.83 cm2
 Applied current = 1.83 cm2 x 10 mA/cm2 = 18.3 mA

H SO solution
2 4
with As2O3

Sample holder

Graphite (anode) Beake

Charged sample

Anode
wire

Cathode
wire
Figure 3.4. Cathodically hydrogen charging set-up.

48
The electrochemical hydrogen charge is a special technique to introduce high
concentrations of hydrogen into materials in a relatively short period of time. Two
hydrogen concentrations were selected, after multiple charging as function of time tests,
to study the interaction between hydrogen and the simulated microstructure. The
selected hydrogen concentrations were 2 and 5 ppm hydrogen concentration as shown
in Figure 3.5.

5ppm

2ppm

Figure 3.5. Hydogen concentrations vs. time for pre-charged specimens analyzed by
LECO analyzer.

3.4 Hydrogen Analysis Using LECO H2 Analyzer

The tested sample is melted in a graphite crucible in an argon shielded environment.
Hydrogen is released from the sample during melting and detected by the analyzer. A
thermal conductivity cell determines the hydrogen content from which the weight
percent of hydrogen in the sample is calculated. Readings from calibration samples are
always advised to do before testing the actual sample to verify that the hydrogen
content is within the calibration range. The LECO analyzer set-up is shown in Figure
3.6. So, the calibration steps are as follow:
a. Enter the weight of the sample.
b. Press loader switch on front of furnace, the loading head slide block will
open.
c. Press loader switch again, the loading head slide block will close and the
lower electrode will open.

49
 d. Place one graphite crucible.
e. Press loader switch, the lower electrode will close and the analysis sequence will
start automatically.
The sample size is limited by weight and physical dimensions. The maximum diameter
for a sample that can be dropped through the loading head of the electrode furnace is
7.5 mm (0.3 inch). The maximum length of a sample that can be tested is 18 mm (0.7
inch) and the normal sample weight ranges from 0.5 to 1.0 g.

Figure 3.6. LECO H2 analyzer machine.

3.5 Etchant Used for Preparing the Metallographical Samples

The steel microstructure needs to be studied thoroughly after each test. The etchants
that were used to examine the general and specific features in the microstructure are
2% Nital and LePera etchants, respectively. The Nital etchant has around 98 wt. pct. of
ethanol and 2 wt.pct. of Nitric acid and is used to reveal the general microstructural
features. LePera etchant consists of two separate solutions to develop specific
microstructural features like martensite and retained austenite (MA) constituents. The
first solution of LePera etchant has 1 g of sodium metabisulfite in 100 ml of deionized
water. The second solution has 4 g of picric acid and 100 ml of ethanol. The two
solutions have to be mixed in an equal quantity to obtain the microstructure.

50
3.6 Weldability Implant Testing
A schematic diagram of the Implant test set up is shown in Fig. 3.7. Each sub-zone in
the HAZ is characterized by a different microstructure and hence different mechanical
properties. The presence of a susceptible microstructure in the HAZ is one of the factors
besides stress and diffusible hydrogen responsible for HIC. So, during welding, the
chemical composition along with the cooling rate/time are two factors that can develop
different sub-zone microstructures in the HAZ.

A series of tests with hydrogen introduced through the shielding gas was done to Q&T
HSLA A543 steel. The selection of AWS ER100S-G (MG-S80) wire was based on the
practical use in the industrial plant.

Figure 3.7. Implant weldability test set-up constructed in the welding laboratory.

51
3.6.1 Gas Metal Arc Welding (GMAW).
A brief review of GMA welding will be given here to accompany the implant test
description. In the welding process, heating metals with an arc between a continuous-
feeding filler metal (consumable) electrode and the workpiece. So, the electrode is
usually the anode (positive) to maximise heating and metal melting. The arc, electrode
tip and molten weld metal are shielded from the atmosphere by a shielding gas. The
GMA welding process is shown in Figure 3.8.

Figure 3.8. Gas metal arc welding (MIG welding or GMA welding).

3.7 Tensile Testing of simulated HAZ Subzones-Alliance Machine

Tensile specimens were machined according to ASTM E8/E8M-13a specification. An
extensometer was used to measure the elongation of the specimens during the tensile
test at displacement rate of 0.2 in/min. Mechanical testing was carried out in the
research work to evaluate the elongation and strength of the hydrogen charged samples
and compare them with the uncharged ones for all different simulated heat treated
samples as shown in Figure 3.9. Vickers microhardness measurements were made on
cross sections of the fractured samples with a load of 1000 gmf and dwell time of ten
seconds.

52
 Figure 3.9. Mechanical tensile test using the Alliance machine.

3.8 Corrosion Study of Q&T HSLA Steel

Two standardized corrosion tests to study the susceptibility of this steel to stress
corrosion cracking and also study the response of this steel in a DI-water with sodium
nitrite medium. The two corrosion tests are the slow strain rate test and the
electrochemical test using Gamry software and apparatus.

3.8.1 Slow Strain Rate Testing

Slow strain rate tests (SSRTs) were carried out using a constant extension rate test
(CERT) machine that is activated by a 1⁄4 HP, 1725 rpm, 0-90 VDC permanent magnet
motor. The equipment set up is shown in Figure 3.10. Stress corrosion cracking
susceptibility of Q&T HSLA steel was studied at different temperatures. Experiments
were conducted according to the standards in two alkaline solutions, 3.5 wt. pct. NaCl
(pH range from 6.5 to 7.5) and 0.1 wt. pct. NaNO2 (pH range from 6 to 7) aqueous
solutions. Tension test specimens were machined and the geometry and dimensions
are shown in Figure 3.11. The samples were machined and ground to 0.25 μm (10 μin.)
surface roughness. Before testing, the specimens were washed with deionized water,
rinsed with acetone and dried with blowing air.

To perform the experiments in a corrosive environment, 850 ml of 3.5 wt. pct. NaCl or
0.1 wt. pct. NaNO2 aqueous solutions were poured inside the autoclave. After tightening
the autoclave, nitrogen gas was purged during one hour to deaerate the solution. Finally

53
the solution was heated to the desired test temperature using a proportional integral
derivative (PID) temperature controller. The PID controller was able to control the
temperature inside the autoclave within ±2 °C of the desired test temperature. Once the
temperature reached the selected value, SSRT starts. Upon failure of the specimens,
the cover of the autoclave was opened. The specimens were taken out, rinsed with
acetone, dried with blowing air and stored for further studies. For experiments
conducted at higher temperatures, the furnace was first turned off after the experiment
and allowed to cool below 100°C, the pressure was released and then the autoclave
opened.

3.5% Chemical
NaCl (pH
solution
6.5 - 7.5)
Or 0.1% NaNO2
(pH 6 - 7)

Specimen

Figure 3.10. Schematic assembly shown the SSRT.

Figure 3.11. Geometry and dimensions of tensile test specimen for SSRT (in mm).

54
3.8.2 Electrochemical Test Using Gamry Machine
A Gamry Reference 600™ Potentiostat/Galvanostat/ZRA was used to conduct the
electrochemical experiments and Gamry Echem Analyst software was used to analyze
the electrochemical measurements as shown in Figure 3.12. Electrochemical
experiments were conducted to measure the corrosion rate using the linear polarization
resistance (LPR) technique and to determine the evolution of corrosion and interfacial
processes using electrochemical impedance spectroscopy (EIS). Experiments were
carried out in the 1-liter round bottom flask corrosion cell as shown in Figure 3.12. The
flask or corrosion cell with multiple necks permits the insertion of electrodes, gas inlet
and outlet tubes and thermometer. The reference electrode (RE) was located close to
the working electrode using a bridge tube. One liter of 0.1 wt. pct. NaNO2 dissolved in
deionized (DI) water was prepared. The electrochemical test specimens were made of
the A543 steel with four different conditions. The A543 steel was welded with Low
Transformation Temperature Welding (LTTW) wire, MG-S80 in a single pass, and three-
pass weld. There are two samples of the three pass welds. The two three-pass weld
had different interpass temperature, (150oC) and (25oC). The LPR technique was
applied to measure the solution resistance and corrosion rate. The working electrode
was polarized at ±5 mV and the scan rate was 0.125 mV s-1. To measure the rate of
corrosion, Tafel graphs were constructed. The EIS measurements were conducted
using 5 mV rms AC voltages in a frequency of 100,000 Hz.

55
Figure 3.12. Electrochemical test showing the flask and Gamry set-up.

56
 CHAPTER 4: WELDABILITY AND MECHANICAL PROPERTIES
This chapter discusses one of the weldability tests called implant test. Constructing and
using the Implant test to study the susceptibility of A543 steel to hydrogen cracking is
discussed.

4.1 Weldability Implant Testing

As mentioned earlier in the introduction and literature review chapters, the weldability of
A543 steel is questionable after having cracks develop in the girth welds in a short time
of service. Also, the nominal carbon equivalent values of the steel are located in the
third zone of the Graville chart considering the minimum and maximum chemical
composition requirement.
The implant test is one of the weldability tests recommended in ASM handbook. It is
used to evaluate the susceptibility of HAZ to hydrogen cracking. As shown in Figures
4.1, a rod or implant pin of the steel base metal to be tested was machined to specified
dimensions [76]. The time to failure is plotted as a function of the loading stress. The
crack susceptibility of the base metal is measured by the degree to which the failure
stress is reduced with time. While depositing the weld bead on the plate, hydrogen can
be introduced through the shielding gas. Hydrogen will be picked up in the implant
specimen which will change the time to failure.

Figure 4.1. Implant test design and dimensions recommended by ASM handbook [76].

57
The thermal cycle produced by the weld bead causes phase transformations in the
implant pin. Therefore, heat input and heat distribution along the implant pin are very
important for the phase transformations and will determine the cracking location.
Modeling and analyzing the thermal cycles will greatly assist in understanding the phase
transformations developed along the implant pin.
In general, metallographic analyses of steel HAZ microstructures reveal that
there are four main regions, coarse-grained region, fine-grained region, inter-critical
region, and sub-critical tempering region, based on the arc temperature during the weld.

4.1.1 Implant Test Equipment Construction

A brief description of the construction of the implant test is given in the following. Figure
4.3(a) shows the implant test equipment that was constructed in the welding shop. A
free motion joint system is attached to the shaft which connects to the load system with
the vertical load reading and testing systems to ensure vertical linear movement when
the load is applied as shown in Figure 4.3(b). The top testing area is supported by a
frame consisting of four beams to withstand the applied load as shown in Figure 4.3(c).
The vertical load reading system has a load cell on which the implant pin is secured.
Once the implant pin is attached to the load cell, the applied load can be measured and
shown in the control panel as shown in Figures 4.3(a) and (d). The implant pin goes
through the middle of the top plate and inserted in the middle of the backing plate where
the weld can be deposited. As mentioned earlier that the implant pin is threaded in the
top end according to ASM Vol. 6 handbook. The threading causes an equal stress
concentration in each of the threads along the pin after applying the load. So, after
depositing the weld on the backing plate, a HAZ with different microstructures will be
generated along the pin and the load/threads would cause the pin to crack upon loading
in the most susceptible region along the pin. The load will be applied, after the weld
cools down according to ASM handbook, by gently opening the valve of the hydraulic
jack, thus releasing the load without causing a bending or impact shock on the implant
pin. A schematic showing how the load is applied to the implant pin is illustrated in
Figure 4.4.

58
4.1.2 Implant Test Results
The susceptibility of the HAZ to hydrogen cracking of the A543 steel is tested in three
different conditions using the implant test. The three conditions are no-hydrogen, 1%
hydrogen, and 2% hydrogen. Hydrogen is introduced through the shielding gas while
depositing the weld bead on the base plate and the implant pin. So, hydrogen picked up
during welding will diffuse into the implant pin. During each test, the time to fracture and
the applied load are recorded. The applied load can be changed based on the time to
fracture, e.g. if the time to fracture is very short then the applied load is decreased till
the implant pin sample can withstand the load for at least 24 hours. After the 24 hours,
that applied load will be considered as the lower critical load. Figure 4.5 shows the
results of the implant test for all three conditions. As noticed the applied load-to-fracture
decreased when hydrogen was introduced in the shielding gas. Larger decrease in the
applied load as well as the time to fracture when hydrogen in the shielding gas
increased from 1% to 2%. Also, it is observed that the fracture happens always either in
the first or second thread in the implant pin. In the case of the 2% of hydrogen, most
cracking occurred in the first thread or near to the fusion line as shown in Figure 4.6. It
seemed that hydrogen introduced from the shielding gas concentrating near to the
fusion line and sometimes diffusing into the first thread leading to cracking of the pin.
Figure 4.6 shows the cross sections of several implant pins with their respective fracture
profiles. These samples were macroetched using Nital etchant. Microhardness
measurements were taken along the implant pin that were not hydrogen charged and
that did not fracture even after 24 hours. The result of the microhardness readings is
shown in Figure 4.7. It was observed that the highest microhardness values were near
the second thread of the implant pin. This location is very close to the CGHAZ. More
detailed characterization of the HAZ subzones of the peak microhardness will be shown
in a later section.

Figure 4.8a shows clearly that the hydrogen diffusion in austenitic materials is
significantly lower than ferritic materials. During welding, the different solubility in ferrite
and austenite also creates hydrogen transport gradient. After the weld pool (initially with
high hydrogen content) cools down, the hydrogen will diffuse towards the austenite in
the HAZ, further cooling and transforming into martensite will result in cracking as

59
shown in Figure 4.8b. Hydrogen remains in austenite until martensite transformation
because of the low diffusivity and high solubility.

After completing all the implant tests with three different hydrogen charging, implant test
was able to provide information about the load causing the sample to fracture and also
the time for the sample to fracture. However, there were still some questions about the
amount of hydrogen causing the fracture and also the temperature distribution along the
implant pin generating the microstructural gradient. Hence, each microstructure along
the implant pin needs to be produced and charged with known hydrogen concentration
prior to tensile testing. The temperature gradient along the implant pin must also be
identified in order to produce the microstructure.

4.2 Mechanical Properties Results

After the weldability study, there is a need to know and understand the influence and
the interaction of hydrogen with each microstructure along the HAZ of the implant pin.
The temperatures to produce each microstructure are selected based on the finite
element SYSWELD modeling which is discussed in detail in chapter 6. The mechanical
tensile test results of the pre-charged hydrogen samples simulated by the furnace and
Gleeble® simulation are consistent and in agreement with each other. A comparison
heat treatment is given in the following sections between the Furnace and Gleeble®
simulated samples in regard to the fracture cross-section, load-to-fracture, time-to-
fracture.

4.2.1 Pre-charged Furnace Simulated Samples

As mentioned in the experimental procedure chapter, the samples were machined from
the plates that were heat treated at a specific temperature. Five temperatures were
selected to produce the different microstructures along the HAZ in the implant pin
namely, 1100oC (coarse-grained HAZ), 900oC (fine-grained HAZ), 760oC (upper inter-
critical zone), 725oC (lower inter-critical zone), and 500oC (subcritical, tempered zone).
The dimensions of these machined samples were identical to the implant pin
dimensions. It was the intent of this work to use the mechanical tensile testing machine

60
as a modified implant testing with a hydrogen pre-charged specimen. Specific grips
were designed and machined to hold the samples during the mechanical testing.

(a)

(b) (c) (d)

(e (f)
Figure 4.3. The implant test parts, a) general implant test set-up, b) applied load
reading, c) load cell, d) weld bead on implant plate, e) load plates, f) jack sysetm.

61
 Weld

Implant test
sample
Load cell

Weld

HAZ

Tensile load

Figure 4.4. Schematic showing how the implant test is conducted.

62
 H2 increases

24hr

Welding Parameters:
oltage ( ) = 21
Current (I) = (125, 128, 129, 131, 132)
Wire speed = 133 ipm
Travel speed = 2.56mm/s

Figure 4.5. Implant test results for all three conditions (0% H2, 1%H2 and 2% H2).

63
No-H2 charging- 1%-H2 charging- 2%-H2 charging-
2600kg 5900kg 5900kg

No-H2 charging- 1%-H2 charging- 2%-H2 charging-

5900kg 5900kg 4600kg

2%-H2 charging- 2%-H2 charging- 1%-H2 charging-

7300kg 5900kg 5900kg

Figure 4.6. Fracture locations in different conditions.

64
Figure 4.7. Microhardness measurements on the implant pin without hydrogen charging,
the sample did not fail.

The samples were initially tested with no hydrogen charging and the results are shown
in Figure 4.9(a). Then, the samples were cathodically pre-charged with 2 ppm hydrogen
and tensile tested with the results shown in Figure 4.9(b). Further hydrogen charging of
the samples was done to read around 5 ppm hydrogen concentration and then tensile
tested. The results for these tests are shown in Figure 4.9(c). As noticed from the three
results that the ductility as well as the strength decreased as the hydrogen
concentration increased. It is also observed that the strength increased with 2ppm H2
which was perhaps caused by the hydrogen hardening phenomenon. This phenomenon

65
has been observed by other researches like Oriani et al. [31]. They stated that solute
hydrogen can increase the yield or flow stress of steels by hydrogen drag on moving
dislocation or cross-slip.

(a)

(b)

Figure 4.8. a) the hydrogen diffusion in austenitic materials is lower than ferritic
materials, b) hydrogen cracking after the weld [15].

66
They also said that hardening is expected from the fact that trapped hydrogen may
make dislocation nucleation difficult from grain boundary dislocations and other possible
trapping sources. The microhardness results for all the five simulated temperatures are
shown in Table 4.1. The microhardness for the charged samples was also measured as
shown in Figure 4.10. The Hydrogen Embrittlement Index (HEI) is calculated based on
the reduction of the fractured area as expressed in the following equation:

HEI = (RAH2 - RAA / RAA) (4.1)

where RAH2 and RAA are the reduction of area in the hydrogen charged sample and
non-charged one, respectively. So, the further the index value deviates from unity, the
higher the susceptibility to hydrogen cracking. The calculated hydrogen index values
are reported in Table 4.2. As observed, higher susceptibility to hydrogen cracking is in
the coarse-grained HAZ and followed by fine-grained HAZ. Other zones are susceptible
to hydrogen cracking as well but it is extremely higher in the CGHAZ and FGHAZ.

Table 4.1. Heat treated Furnace samples microhardness measurements.

Heat treated Sample HV (1000gmf)

o
1100 C 351±10
o
900 C 342±5
o
760 C 310±12
o
725 C 278±8
o
500 C 243±6

Table 4.2. Heat treated Furnace samples HEI calculated values.

Furnace Simulated Temp. HEI (2ppm H2 charging) HEI (5ppm H2 charging)
o
( C) (±0.005) (±0.005)
Base metal 0.58 0.36
1100 0.09 0.06
900 0.18 0.11
760 0.20 0.13
725 0.21 0.15
500 0.21 0.18

67
 o
900 C
o
1100 C o
900 C
o o
1100 C 760 C
o
500 C
Base
o
725 C

o Base
760 C
Nominal

Nominal
o
725 C
o
500 C

Nominal Nominal

(a) (b)
Nominal

Nominal
(c)

Figure 4.9. Mechanical tensile test results for the furnace samples.

68
 Figure 4.10. Tensile strength and microhardness results for the furnace samples.

The mechanical tensile test machine was set to apply a constant load to the sample. By
applying a constant load, the machine will act similar to the implant test, but in the
presence of a known hydrogen concentration. The furnace simulated samples were pre-
charged with 2 ppm hydrogen concentration and tested at constant loads to record the
time for the sample to fracture and also recording the lower critical load that the sample
can withstand. Figure 4.11 shows the results for the samples with no hydrogen
charging. It is observed that samples simulated to different microstructures exhibited
different behavior. Samples were pre-charged with 2 ppm hydrogen and tested at the
same loading condition as the no hydrogen samples. The results of the constant load
for both the non-charging and 2 ppm hydrogen charging are shown in Figure 4.12. Also,
the base A543 steel was tested with 2 ppm charging and compared to the non-charging
condition.

4.2.2 Pre-charged Gleeble® Simulated Samples

The samples were machined according to the standardized low force mode in Gleeble®
machine. The dimensions were 6 mm diameter and 80 mm length. The samples were
used to produce the different subzones in the HAZ along the implant pin. Two more
temperatures were added to assure covering all the regions in between the different
microstructures.

69
 o o
1100 C, 900 C

Lower critical load

o
760 C, base metal

Lower critical load

o o
725 C, 500 C

Lower critical load

24hr

Figure 4.11. Modified tensile test results using constant load for the furnace samples.

The temperatures were 1200 and 1100oC (CGHAZ), 1000 and 900oC (FGHAZ), 760
and 725oC (inter-critical zone), and 500oC for the subcritical tempered zone. The results
of the mechanical tensile tests are the same as the furnace simulated samples as
shown in Figure 4.13(a). A lost in ductility and strength are observed when charging the
samples with 5 ppm hydrogen, Figure 4.13(b). The microhardness for the no hydrogen
samples is tabulated in Table 4.3. The HEI values were also calculated and agreed with
the furnace samples as shown in Table 4.4.

70
Figure 4.12. Modified tensile test results using constant load for each simulated furnace sample.

71
 Nominal

Nominal
(a)
(b)
Figure 4.13. Fracture locations in different conditions.

Table 4.3. Heat treated Gleeble® samples micro-hardness measurements.

Heat treated Sample HV (1000gmf)

1200oC 360±5

o
1100 C 355±4

1000oC 353±7

o
900 C 345±3

o
760 C 316±6

o
725 C 283±4

o
500 C 239±8

72
Table 4.4. Heat treated Gleeble® samples microhardness measurements.

Gleeble® Simulated Temp. (oC) HEI (5ppm H2 charging) (±0.005)

1200 0.03
1100 0.04
1000 0.05
900 0.07
760 0.11
725 0.10
500 0.20

73
 CHAPTER 5: FRACTOGRAPHY & METALLOGRAPHY ANALYSES
In this chapter, the fractography and metallography of the fractured tensile samples are
discussed. Scanning Electron Microscopy (SEM) technique is used to study the features
of the fracture surface. The fractured samples were cross-sectioned, mounted, grinded,
and polished to study the microstructural features.

5.1 Introduction
Fracture characterization in steels can vary from dimple to quasi-cleavage, cleavage, or
intergranular cracking. These features may not exist over the entire fracture surface.
The damage effects of hydrogen on the tensile properties are caused by the interaction
of hydrogen with dislocations and the movement of hydrogen decanted dislocation. So,
the fracture surface morphology depends on the material properties and the loading and
environment conditions to which the metal is exposed [77, 78].

The samples examined and analyzed in this chapter were heat treated by either
standard furnace or Gleeble® 3500 machine to simulate the different subzones along
the HAZ in the implant pin. After the heat treatment, mechanical tensile testing of the
pre-charged hydrogen samples was conducted.

5.2 Results and Discussion

To investigate hydrogen effects on mechanical strength of A543 steel, tensile
specimens were prepared from the two heat treatments mentioned earlier. The fracture
surface was examined and analyzed based on the features that exist on the surface like
intergranular cracking, micro-voids, and mixed zone as shown in Figure 5.1 Generally,
the two heat treatments resulted in similar fracture behavior, i.e. similar interaction
between hydrogen and the different simulated microstructures. The first observation is
that high temperature simulated microstructure like CGHAZ (1200 oC, 1100oC) is very
susceptible to intergranular hydrogen cracking. The susceptibility also increases as the
hydrogen concentration increases in the CGHAZ. It is also observed that increasing the
hydrogen concentration promotes multiple crack initiation and branching and secondary
cracks. Similar behavior was noticed in the FGHAZ (1000oC, 900oC) simulated

74
microstructures but with much less intergranular cracking. A more detail discussion of
these observations is stated in the following paragraphs.

Figure 5.1. Schematic showing the possible features happening in the fracture surface.

The observation in the uncharged samples is described in the following. The freshly
broken specimens were examined using Scanning Electron Microscope. Ductile fracture
was observed in all the HAZ simulated heat treated uncharged samples. Typical ductile
fracture like cup and cone surface are shown in Figures 5.2 and 5.3 for the 0 ppm
samples. At high magnification, the fracture is characterized by the presence of a great
number of microvoids (dimples) as shown in Figures 5.4 and 5.5.

After one hour of cathodic charging, around 2 ppm hydrogen was introduced into the
specimen. Samples that were treated to 1100 and 900oC showed fracture composed of
two parts: a brittle area near the sample surface followed by a ductile part in the center
and in the remaining area of the surface as shown in Figure 5.2. It seems that hydrogen
is migrating from the outer surface to the center of the specimen. Most fractures on
samples treated to low temperatures like 760, 725, and 500oC still show the ductile
fracture mode with dimples and micro-voids at higher magnification as shown in Figure
5.3. Intergranular brittle fracture is observed only along some of the surface area of the
CGHAZ and FGHAZ specimens.

75
After about nine hours of charging, more hydrogen (around 5 ppm) entered the
specimens. The brittle fracture grew toward the central area for the CGHAZ as shown in
Figure 5.2 and 5.4. Due to the loss of ductility and plasticity, the intergranular brittle
fracture area increased in comparison to the specimen after one hour of charging.
Although the overall hydrogen level in the specimens is about 5 ppm, it appeared that
the hydrogen concentration is much higher near surface area, which demonstrates
typical brittle fracture mode with some secondary cracking as shown in Figures 5.2 and
5.4. In the central region of the sample, a mixed fracture mode was observed due most
likely to the lower hydrogen concentration. So, the specimens were mostly brittle with
intergranular cracking in the high temperature simulated CGHAZ and intergranular
cracking with secondary cracking in the FGHAZ simulated samples.

Tensile mechanical tests showed that the strength and ductility decreased dramatically
in the charged samples. The influence of hydrogen on ductile fractures can be attributed
to an accumulation of hydrogen in the trap sites, which lowers the mechanical strength.
The fracture of the nine-hour charging CGHAZ specimens shows the flat and clear
brittle feature as shown in Figure 5.4. Under high magnification, intergranular brittle
rupture dominates the fracture of CGHAZ specimen. On the other hand, ductile feature
like dimples and micro-voids can be observed in the lower temperature heat treated
simulated samples even after nine hours of charging as shown in Figures 5.3 and 5.5.
The observations of the fracture surface of the Gleeble® simulated samples agreed with
the furnace treated ones as shown in Figure 5.6. Figure 5.7 shows clearly that the
hydrogen intergranular cracking is minimized in the low temperature heat treated
specimens when compared to the high temperature simulated heat treated specimens.

5.3 Metallography of Furnace and Gleeble® Samples

After the weldability implant testing, an understanding of the interaction between
hydrogen and the different microstructures that are generated by the weld along the
implant pin is needed to understand the hydrogen cracking mechanism in A543 steel.
These different microstructures are shown in Figure 5.8.

76
 Base-0ppm H2 Base- 2ppm H2 Base- 5ppm H2

1100oC- 0ppm H2 1100oC- 2ppm H2 1100oC- 5ppm H2

900oC- 2ppm H2 900oC- 5ppm H2

900oC- 0ppm H2

Figure 5.2. The base metal (ASTM A543 steel) and the high temperature simulated
specimens (CGHAZ and FGHAZ) with different hydrogen charging.

77
760oC- 0ppm H2 760oC- 2ppm H2 760oC- 5ppm H2

725oC- 0ppm H2 725oC- 2ppm H2 725oC- 5ppm H2

500oC- 0ppm H2 500oC- 2ppm H2 500oC- 5ppm H2

Figure 5.3. The low temperature simulated specimens with different hydrogen charging.

78
 Base-0ppm H2 Base- 2ppm H2 Base- 5ppm H2

1100oC- 0ppm H2 1100oC- 2ppm H2 1100oC- 5ppm H2

900oC- 0ppm H2 900oC- 2ppm H2 900oC- 5ppm H2

Figure 5.4. The base metal (ASTM A543 steel) and the high temperature simulated
specimens (CGHAZ&FGHAZ) with different hydrogen charging at higher magnification.

79
760oC- 0ppm H2 760oC- 2ppm H2 760oC- 5ppm H2

725oC- 0ppm H2 725oC- 2ppm H2 725oC- 5ppm H2

500oC- 0ppm H2 500oC- 2ppm H2 500oC- 5ppm H2

Figure 5.5. The low temperature simulated specimens with different hydrogen charging
at higher magnification.

80
 o o o
1200 C 1100 C 1000 C

o o
o
900 C 760 C 725 C

o
500 C

Figure 5.6. Gleeble simulated samples charged with 5 ppm H2 for ASTM A543 steel.

81
 o
o o
1100 C 1000 C
1200 C

o o o
900 C 760 C 725 C

o
500 C

Figure 5.7. Gleeble simulated samples charged with 5 ppm H2 at higher magnification
showing the high hydrogen intergranular cracking in the CGHAZ and reduces as going
to low temperatures in red arrow.

82
As mentioned earlier, two heat treatment techniques were used to produce these
microstructures, namely, standard furnace and Gleeble® simulation. The temperatures
are selected based on the numerical SYSWELD modeling of the implant test as explain
in Chapter 6.

For the furnace heat treatment, five temperatures are selected to simulate the CGHAZ
(1100oC), FGHAZ (900oC), upper inter-critical zone (760oC), lower inter-critical zone
(725oC), and tempering zone (500oC) as shown in Figure 5.9. The CGHAZ is
predominant with lath martensite microstructure while the FGHAZ is a mixture of bainite
with martensite. The inter-critical zone is a mixture of two or more phase like martensite,
ferrite, and some bainite. The tempering zone has tempered martensite and bainite. The
hardness of these produced microstructures was measured and compared to the
microstructures along the implant test as shown in Figure 5.10 and Table 5.1. The
Vickers microhardness agreed very well with each zone along the implant pin (Fig.
5.11).

For the Gleeble® heat treatment, two more temperatures were added besides the five
temperatures selected as described above in the furnace treated samples (Fig. 5.12).
These two temperatures were 1200oC which also represents the CGHAZ, and 1000oC,
the FGHAZ. Adding these two temperatures will assure an accurate representation for
each zone along the HAZ in the implant pin. The microhardness measurements were
performed for all the produced simulated samples as shown in Table 5.2. The Vickers
microhardness results agreed well with the furnace simulated as well as the
measurement along the implant pin.

After tensile testing of the Gleeble® simulated samples, a cross section of the fracture
surface was extracted to examine the microstructural features after hydrogen charging.
Figure 5.13 shows the hydrogen crack in the as-polished 1100oC simulated sample.
The crack is propagating into the microstructure in an intergranular manner. Figure 5.14
clearly shows two different cracks in two different simulated samples namely 1200 oC
(CGHAZ) and 1100oC (CGHAZ).

83
 CGHAZ

FGHAZ

Intercritical

Subcritical
tempered

Figure 5.8. Different microstructures (subzones) generated by the weld during implant
testing.

84
 o
1100 C
Tempered Martensite
and bainite

o Predominant
500 C martensite

o
900 C

o o
725 C 760 C

Bainite with
martensite

martensite, ferrite, and some bainite

Figure 5.9. Different HAZ subzones microstructures produced by the furnace.

85
 Mixed lath martensite and Bainite.

Figure 5.10. Microstructure of the base metal ASTM A543 steel showing the martensite
and bainite with some ferrite.

Figure 5.11. The Vickers hardness reading along the implant pin for ASTM A543 steel.

86
Table 5.1. Heat treated Furnace samples hardness measurements.

Heat treated Sample HV (1000 gmf)

o
1100 C 351±10

o
900 C 342±5

o
760 C 310±12

o
725 C 278±8

o
500 C 243±6

Table 5.2. Heat treated Gleeble® samples hardness measurements.

Heat treated Sample HV (1000 gmf)

1200oC 360±5

o
1100 C 355±4

1000oC 353±7

o
900 C 345±3

o
760 C 316±6

o
725 C 283±4
o
500 C 239±8

87
 o
1000 C
o
o
1200 C 1100
C

o
900 C

o
760 C

o
725 C
o
500 C

Figure 5.12. Different microstructures produced by the Gleeble®.

88
These cracks also propagated in an intergranular manner. The same behavior is
observed in the FGHAZ simulated samples as shown in Figure 5.15. While a small
crack is noticed in the upper inter-critical zone simulated sample, no cracks are
observed in the lower inter-critical and subcritical tempering zones as shown in Figure
5.16.

Figure 5.13. As-polished microstructure showing the hydrogen crack propagation.

(a) (b)

Figure 5.14. As-etched microstructures for a) 1200oC and b) 1100oC, CGHAZ simulated
samples.

89
 (a) (b)

(c)

Figure 5.15. As-etched microstructures for a) & b) 1000oC and c) 900oC, FGHAZ
simulated samples.

(a) (b)

(c)

Figure 5.16. As-etched microstructures for a) 760oC and b) 725oC, and c) 500oC
simulated samples.

90
5.3.1 LePera Colored Etchant
Color etching is widely used for visualizing different phases in the metals. It produces
different colors for different phases. Color metallogaphy is an excellent way to recognize
phases such as martensite, austenite and bainite. The etchant solution produces thin
chemical films on the surface of the specimens that appear in different colors under
polarized light. The etchant used in this work is called LePera. If the steel is etched with
Lepera solution, ferrite appears as blue or dark blue, bainite is brown and both
martensite and retained austenite are white [79].

After etching CGHAZ and FGHAZ simulated samples as seen in Figure 5.17, it is
observed that the cracks follow the white phase which is believed to be the Martensite
Austenite (MA) constituents. Most of these constituents are located near the grain
boundaries. As stated in the literature review chapter, there are many hydrogen trapping
sites in the steel and the grain boundary has some of these trapping sites. So, the
cracks are propagating into the microstructure and following either the grain boundary
and/or the MA constituent which is also a hydrogen trap site.

91
Figure 5.17. Lepera etchant for the CGHAZ and FGHAZ samples, ferrite is blue, bainite
is brown, MA consituent is white.

92
 CHAPTER 6: NUMERICAL SIMULATION OF IMPLANT TESTING

This chapter discusses the numerical simulation of the weldability implant testing. In the
beginning, MathCAD software was used to show the temperature distributions caused
by bead-on-plate welding using the Rosenthal equations. Then, a more detailed
simulation using SYSWELD [80] software was used to more accurately show the
thermal and the mechanical properties that resulted from the weld bead on the implant
pin.

6.1 Numerical Simulation Introduction

MathCAD [81] is a calculation software for solving engineering equations. Mathcad was
used in the beginning to determine the temperature distribution along the implant pin
specimen. The application of finite element (FE) modelling methods to predict thermal
history and residual stresses is relatively well established. Earlier work focused on the
determination of the temperature distribution resulting from the welding process. In
particular, Goldak [82] made significant advances in the modeling of heat transfer
between the weld electrode and the plate. One of the earliest studies to compare FE
predictions with measured temperatures and stresses was by Leung et al. [83] who
carried out a two-dimensional thermal and mechanical FE analysis of a stainless steel
single pass weld [82]. Good agreement was found between the predicted and measured
temperature and stress distribution, using thermocouples and neutron diffraction
measurements, respectively. SYSWELD simulation software has the ability to predict
the influence of welding on the metallurgical and mechanical properties of a specific
grade of steel. The software mainly gives two outputs, thermal-metallurgical results and
mechanical results. It is important to mention that there are simplifications and
assumptions made to save computation time regarding weld geometry or the use of
partial models while taking advantage of mirror or rotational symmetry. Also, the
boundary conditions are important in the simulation of welding process, filler type, weld
travel speed, and applied welding energy. Examples from the mechanical properties for
the boundary conditions are the applied clamping conditions, clamping and unclamping
time.

93
6.1.1 Simulation Considerations
Heat input to a material to form a fusion weld has both positive and negative issues. On
the positive side, heat is required to melt the surfaces to be joined and the filler wire
needed to fill the joint gap. On the negative side, heat is conducted away into the base
material which creates HAZ. In the HAZ, the structure and properties of the base metal
are changed in an undesirable way. During welding, heat is conducted away from the
hot weld pool into the base metal. The distribution of heat directly affects the following:
1) Rate of melting and size of melt pool.
2) Rate of cooling and solidification structure.
3) Maximum temperature and rate of cooling in HAZ.
4) Build up of residual stresses and/or distortion in the component.
The four points above affect the mechanical properties and performance of the
component. The distribution of heat depends on whether the weld is deposited on what
can be considered as a thick plate or a thin sheet [83, 84]. The heat flow in thick plate is
three-dimensional whereas for a thin plate is two-dimensional as shown in Figure 6.1.

2D
3D

Figure 6.1. Heat flow around weldment for (a) thick plate and (b) thin sheet.

Taking any point near the weld In Figure 6.2, the temperature first rises as the torch
approaches, then falls as the torch goes away. The peak temperature (Tp) decreases
with distance from the fusion boundary. It is important to know that heating causes
metallurgical changes and these changes depend on the temperature reached. These
changes are not necessarily harmful if the temperature is low. For some alloys, there
may be a critical temperature, below which no transformations happen. But the heating
and cooling cycle to temperatures above the critical temperature can bring changes in
the materials properties.

94
 Figure 6.2. Schematic temperature variations around weld pool.

The affected region is called HAZ [85, 86]. The maximum temperature reached is
mainly affected by
 Power input and welding speed.
 Material properties, melting temperature, thermal conductivity, and thermal
diffusivity [87].
The mathematical analysis to predict the temperature distribution in the weld metal
included a number of assumptions. The first model was developed by Rosenthal [85]
where the heat source was assumed as a point source.

6.1.2 Rosenthal's Equations

Rosenthal (1946) [85] specified heat flow equations that have become a source of
reference for much of the work on welding that has followed. A number of assumptions
were made in the original analysis, and they are as follows:
 The heat source moves along the surface of a plate with uniform speed, Figure
6.3.
95
  Heat is delivered from a point source, that is, from an origin which is of infinitely
small size.
 The latent heat of fusion of the weld bead, and the latent heat of any phase
transformations that might occur in the weld, are ignored.
 There are no heat losses from the surface of the plate.
 The thermal properties of the material are temperature independent.
 Convective effects in the weld pool due to electromagnetic and other forces are
neglected.
 The speed of the heat source and the rate of heat input are constant [84,87].

Figure 6.3. Rosenthal assumption: point heat source geometry [85].

The differential equation that describes heat transfer in weld is expressed in orthogonal
coordinates (x,y,z) in reference to a fixed origin in the solid has the following form, which
is also known as the Fourier's equation:

dT   2T  2T  2T 
 2  2  2 
dt  x y z 
(6.1)
where T is the temperature, t is the time and  the thermal diffusivity.
Appling the boundary conditions and assumptions listed earlier, Rosenthal arrived in the
following two equations, describing the heat flow in thick plate (3D heat flow),

q  v 
T  To  exp    R  
2 R  2a  (6.2)

96
and in thin plate (2D heat flow),

q     r  
T  T0  exp  K0   (6.3)
2 d  2   2 
where (d) is the plate thickness and (q) is the arc power which is the product of the arc
current, the arc voltage and the arc efficiency, () is thermal diffusivity, (I) is the arc
current, (R) is the radial distance from the heat source, (r) is the distance from the weld
centreline, (r') is the distance from the heat source, (t) is the time, (T) is the
instantaneous temperature, (To) is the interpass temperature, (v) is the welding
speed,(V) is the arc voltage, (x,y,z) are coordinates fixed with respect to the workpiece,
() is the arc efficiency, () is the distance from the moving source measured along the
positive x-axis (=x- vt), () is the density, (Cp) is heat capacity, and () is the thermal
conductivity of the material. Figure 6.4 shows Rosenthal results for two different weld
travel speeds [84, 87].

Figure 6.4. Rosenthal equation showing the effect of doubling the welding speed on
isotherm pattern [84].

6.2 Mathcad Calculations

MathCad software has mathematical notation, units intelligence, and powerful
calculation capabilities. The software can solve complex and powerful equations and

97
can provide graphical plots as well. This software was used to calculate the temperature
distribution in the implant plate while welding using the Rosenthal three-Dimensional
equation [81]. Steps of the calculations are as follows and the resulted plots are shown
in Figure 6.5.:

Arc voltage Varc  21V

Arc current I  133  A

Arc efficiency   0.75

Welding heat input Q  VarcI  2094.75W

cm
Welding travel speed v  10 
min

W
Thermal conductivity k  50 
m K

J
Specific heat c  530 
kg  K

kg
Density   7850 
3
m
2
k 5m
Coefficient of diffusivity    1.202  10
c  s


v
  2 2 2
x  y  z x 
Q 2 
Rosenthal equation:  ( x y z )  e
2 2 2
2  k  x  y  z

 ( 0  mm 2  mm 2mm )  1664.432  °C

6.3 ESI-SYSWELD Simulation

SYSWELD simulation software is well-recognized commercial finite element software.
The software is developed by Engineering Systems International (ESI-group). The
software is capable of numerically simulating most of the welding processes and
predicting the influence of welding on the steel properties. The software is user-friendly
and can be easily understood. One of the advantages which makes SYSWELD
simulation different from other commercial finite element software is the ability to model
and analyze metallurgical transformations in steels.

98
 T emp.-Dist (T op View)

T emp.-Dist (Side view)

Tco n t

Tco n t

Figure 6.5. Graphical repersentation of the calculations resulted in the form of isotherms
using Rosenthal equation.

99
Metallurgical transformations include volume changes and phase amounts during
transformations along with the resulting mechanical properties. The software is also
supported with a material database that is filled with industrial models and a large
variety of steel grades. The materials database includes also nonferrous such as
aluminum, nickel alloys, stainless steel, and titanium. The software has additional
options to use either two-dimensional (2-D) or three-dimensional (3-D) models and to
perform multi pass welds. It also includes a large number of material behavior models
including elastic-perfectly plastic, isotropic strain hardening, kinematic strain hardening,
and allows for the use of temperature dependent material properties. Using “SYSWELD
welding advisor” interface the time needed to set up computations for heat treatment
and welding is reduced. The welding advisor has nine steps as shown in Figure 6.6.
These steps start from the type of the steel to be welded and the type of filler, and cover
the welding process and parameters, cooling condition, clamping condition, load
applied, etc. [80].

Simulating the weldability implant testing will help to understand the metallurgical
changes and phases created by the weld and to determine the susceptibility of these
phases to cracking. Four different steels were chosen for this study. Three of them are
pressure vessel steels and one is plain carbon steel. The SYSWELD simulation results
will show the temperature gradient along the implant pin and the susceptible phases to
cracking. The software is also able to show the distortion results, residual stresses
results, and plastic strains results but the focus will be on the temperature gradient,
most susceptible phase to cracking, and the amount of the phases.

6.3.1 Material Database Manager

Material properties parameters must be defined in order for SYSWELD to complete the
predication calculations. Examples of the parameters that need to be defined for the
thermal section are the specific heat capacity, material density, and thermal
conductivity. For the mechanical section, some of the parameters are Young’s modulus,
Poisson’s ratio, yield limit, and strain hardening. Material Database Manager (MDM)
(Figure 6.7) is used to view and modify material properties for SYSWELD.

100
 Figure 6.6. Welding advisor: Component (base metal and welding metal) properties,
welding process parameters, cooling behavior, and clamping condition are addressed.

101
The material properties (thermal as well as mechanical) for each phase are given in
graphical and tabular format. The steel properties can be viewed and easily edited using
Microsoft Excel.

As with any finite element model, the first step in a weld analysis is the creation of the
weld assembly and finite element mesh. After the mesh is created, it is necessary to
apply the material properties (MDM), select the metallurgical model, and apply thermal
and mechanical boundary conditions. The heat source parameters and the molten pool
dimensions (length, width, and depth) are also specified for the welding simulation.
Other parameters that can be entered through the welding advisor are the clamping
condition, external loading, and heat transfer behavior prior to computation. Depending
on the computer system capability and geometry weld joint complexity, computation
may take several hours to few days to complete.

6.3.2 Thermal and Mechanical Parameters in SYSWELD

SYSWELD software is programed based on advanced metallurgical principles. It uses
continuous cooling temperature (CCT) diagrams and material dilatometry data to
analyze and relate thermal properties to phase transformations. The CCT and
dilatometry data can be compiled data from international literatures and also results
from dedicated experiments. Depending on the heating and cooling rates, the phases
can be predicted. The phases in steel have different structural volumes. When heating
the steel to elevated temperatures reaching the austenization temperature, austenite
that has a specific structural volume forms. When cooling the steel, austenite transforms
to bainite, martensite, or pearlite depending on the cooling rate. These phases have
their own structural volumes. The software is able to predict the phase that will be
generated based on the heating and cooling rates. The software can also relate phase
transformations to mechanical properties. The software requires the user to enter the
chemical composition, thermal properties like thermal conductivity, and mechanical
properties like yield stress for all the phases as shown in Figure 6.8. This Figure is a
print screen of the material database manager requirements that must be entered to
initiate the simulation computation process.

102
Figure 6.7. Material database manager- start window.

103
Figure 6.8. Material database manager- start window- chemical composition, thermal
conductivity, and yield stress.

104
6.3.3 Modeling of Moving Heat Source (Arc)
The physical phenomena associated with the interaction of the welding arc and the weld
pool is complex and a number of models are available to describe the heat source to
represent the weld torch. The Goldak ellipsoidal heat source model used has been
widely employed in many literatures [88]. This model takes into account the heat which
is transported below the surface when the weld bead is deposited. The ellipsoidal
distribution is defined by the non-dimensional effective torch radius (re) which
represents the distance from the torch center,

(6.1)
The volumetric heat input (q) has a spatial variation based on this effective torch radius
with its peak at the center of the torch position,

(6.2)
xo, yo and zo give the torch position relative to the Cartesian axes and x, y and z
represent the position where the heat flux is to be evaluated. Assuming an ellipsoid
centered at (xo, yo, zo) with semi-axes a, b, and c, as shown in Figure 6.9, the constants
A, B and C may be evaluated, by assuming that the flux decays to 5% of the maximum
value at the ellipse boundaries. The shape of the simulated heat flux is based on the
weld bead profile measurement. Hence, A is taken to be the distance from the weld
bead start point to the weld torch center, B is the half bead width, and C is the bead
height [89, 90]. This procedure will give:

(6.3)
Substituting this equation into the previous one, the heat flux (q) as a function of
position, x, y, z is obtained,

(6.4)
As the heat input at different positions of the weld bead depends on the position of the
weld torch as it travels along the centerline (z axis), the current position can be
calculated according to the welding time [89, 90].

105
The modeling and the phase transformations equations are calculated based on
experimental and literature data. For example, the diffusion-controlled equation for
carbon during phase transformations is based on Leblond and Johnson-Mehl-Avrami
JMA model [89]. The martensitic transformation is based on the Koistinen and
Marburger model [89]. For modeling of the heat source, SYSWELD utilizes the three-
dimensional double ellipsoid model for the weld arc proposed by Goldak et al. [88] as
shown in Equation [6.4]. The double ellipsoid geometry is used because the size and
the shape of the heat source can be easily changed to model different welding
processes, e.g. shallow or deeper penetration processes. The power of heat flux
distribution is Gaussian along the longitudinal weld direction axis. If the cross section of
the molten zone is known from experiment, this information can be used to set the heat
source dimensions. If precise data does not exist, Goldak et al. suggest that it is
reasonable to take the distance in front of the source equal to one half the weld width
and the distance behind the source equal to two times the weld width [89, 90].

Figure 6.9. Goldak double ellipsoid heat source model [89].

From the point of view of finite elements, a heat source is modelled in SYSWELD by a
volume density of energy applied to the elements, which move along the weldline. The
weldline is a SYSWELD feature which contains information about the description of the
trajectory and reference lines that are created during the simulation to represent the
actual weld information.

106
The trajectory line is a group of one dimensional elements which are linked to the mesh
along the welding path. The reference line provides information to compute the local
frame at the centre of the heat source. When the computation process reaches
the starting time, the heat source will be switched on. When the whole path is
described, then the source is switched off. The source is programmed in a reference
frame (OXYZ) as shown in Figure 6.10. All process parameters like energy, efficiency
coefficient, torch shape, plastic effects due to phase transformations are included in the
definition of heat source. In case the reference line is applied, another node should be
set as the starting point of the reference and both nodes must be the first nodes in this
group (the starting side of the weld). On the other hand, the end nodes are the nodes
defining the points of the trajectory and the reference line. The start element defines the
direction of the trajectory and reference line and must be the first element. A close up
view of these parameters along the weld path is illustrated in Figure 6.10. If no
reference line is created, the source must be axial-symmetric around the trajectory. The
start node is then only one node that defines the starting point of the trajectory. The
parameters that should be entered are of course identical to the parameters of the
actual weld.

Start node

Trajectory
End nodes O
Y Reference
X

Z Representing a
Random
trajectory

Figure 6.10. The weldline in SYSWELD simulation.

107
6.4 Simulated Implant Testing
A weld bead was deposited along the plate using Gas Metal Arc welding (GMA welding)
process. The welding was performed at an ambient temperature of 20oC. Using a
moving heat source, SYSWELD analyzes each individual weld and demonstrates the
effect of phase transformations caused by the weld. The numerical analysis was
considered for a single bead-on-plate weld. The plate would be one of the four grades
of steels mentioned earlier. The three pressure vessel steels are ASTM A543 Gr. B
Cl.1, ASTM A516 Gr. 70, ASTM A533 steels. ASTM A36 structural carbon steel is used
as reference for comparison. The simulation model was built according to ASM Metals
Handbook vol. 6 and the standardized dimensions are shown in Figure 6.11. The
dimensions for the implant supporting plate are shown in Figures 6.12.

Figure 6.11. Recommended dimensions for implant test pin in ASM Metals Handbook.

Since the weld heat source causes high peak temperatures, and large temperature
gradient and fluctuations, it is important to have fine meshing system around the weld
joint, i.e. very small element size, and consistent time steps. The fine mesh helps to
capture thermal gradients in small time steps to resolve the large temperature variations
for a given mesh. This procedure is important for conducting detailed and accurate
analysis in and near the weld interfaces. Coarser meshes expanding away from the

108
boundary of the heat flux can be applied to obtain adequate accuracy with reasonable
calculation time as shown in Figure 6.13.

The simulation was divided into two models (Figure 6.14) due to the large number of
elements required for the solid element model to describe the weld plate and weld bead
and also to focus on the transformational changes happening along the implant pin. So,
a simplified model was created first for the plate with the bead-on-plate weld and a
cylindrical-shaped pin was inserted in the middle. To reduce the number of solid
elements, fine meshes were used only in and near the weld area to focus on the heat
affected zone. These dense meshes and very small time steps allow for capturing the
high temperature variations for detailed and accurate analysis. Coarser meshes were
adopted at locations farther away from the heat flux boundary where the analysis is not
that critical compared to the area of the weld joint. The second model is just the meshed
implant pin with an extra thermal layer (weld bead) on the top. The thermal cycle
obtained from the first model is imposed on the second implant pin model. The thermal
cycle is applied to the extra thermal layer on top of the implant pin.

So, two separate analyses were performed by the welding simulation and the simulation
data is given in Table 6.1. The first one is for the implant bead-on-plate weld which
begins at time zero and completes at t=60 seconds. Then, the thermal cycle from t=0 to
t=60s is applied onto the second model. After the thermal cycle is finished, a load will be
applied at time equal 61 seconds and stays applied until 3600 seconds.

Table 6.1. SYSWELD simulation statistic data of the two models.

Simulation data Plate Pin
No. of nodes 46108 127732
No. of elements (3D) 40672 673738
Type of mesh Hexagonal Tetragonal
Size of mesh (mm) 1.19 (HAZ), 2.9 (rest of 0.14 (HAZ), 0.33 (the
the plate) rest of pin)

109
 6mm

60o

Nodes (yellow color)

12.7mm

Finer mesh
100mm
100mm

Figure 6.12. Simulated model showing the dimensions used in SYSWELD.

110
Figure 6.13. First model simulation showing the geometry and the mesh distrinution.

111
 Meshed implant Interior mesh
pin

Backing plate with

the weld bead

Figure 6.14. The two models used for the simulation and computational analysis.

6.4.1 Parameters Used in the Simulation

The material properties for the ASTM A516 Gr.70, ASTM A533, ASTM A543, and
ASTM A36 steels were obtained from the ASME Boiler Pressure Vessel Code, Section
II Part D (ASME BPVC, 2004) and from steel welding literature. The material properties
were inserted in the MDM. The chemical compositions and the mechanical properties of
the four steels are shown in Table 6.2. For ASTM A516 Gr.70 steel, the thermo-physical
material properties like thermal conductivity and specific heat and the mechanical
properties like Young’s modulus and yield strength are listed in Tables 6.3 and 6.4,
respectively.

112
 Table 6.2. Chemical composition of all four pressure vessel steels.
Minimum
ASTM Composition, wt.pct. yield
Grade
spec. strength
C Mn P S Si Cr Ni Mo Cu V others MPa ksi
0.20- 1.50- 2.60- 0.45- 480- 70-
A 543 B 0.23 0.40 0.020 0.020 --- 0.03
0.40 2.00 4.00 0.60 700 100
A 533 B 0.25 1.5 0.025 0.025 0.025 0.6 1.0 0.6 --- --- --- 345 50
Al, Ti,
A 516 70 0.22 1.7 0.03 0.03 0.6 0.3 0.3 0.08 0.3 0.03 262 38
Nb
A 36 --- 0.26 1.0 0.04 0.05 0.4 --- --- --- 0.2 --- --- 250 36

6.4.2 Thermo-physical Properties

Table TCD from ASME BPVC Section II Part D-Subpart 2 provides the thermal
conductivity and thermal diffusivity of many materials, including those needed for the
computation in this work. The materials were divided into groups and listed according to
their chemical composition. The specific heat is related to the thermal conductivity and
thermal diffusivity is given by:

Specific heat  J 
Thermal conductivity W  m  C

 kg  C   m2  (1)
Densitykg 3   Thermal diffusivity  
 m   s 
6.4.3 Mechanical Properties
Table 6.3 is an excerpt from the ASME database for the specifics in this work. The
modulus of elasticity (Young’s modulus) can be obtained from Table TM-1 of ASME
BPVC Section II Part D-Subpart 2. Yield strength properties of many materials are listed
in Tables Y1 and U. Table 6.4 is extracted from the ASME database for this research.

6.5 Description of the Welding Conditions – Bead-on-Plate Welding Simulation

As mentioned earlier that one of the simulation model was used to obtain the thermal
cycle caused by the bead-on-plate welding. Then, the thermal cycle was imposed on
the implant pin in a separate simulation model. The welding advisor in SYSWELD-
Visual Weld software was used to apply the bead-on-plate weld.

113
 Table.6.3. Thermo-physical and mechanical properties for ASTM A516 Gr. 70 steel.

Young's Modulus Specific heat Yield strength

2
Conductivity (W/(m.°K) 2
Temperature (N/mm ) (kJ/(kg.°K) (N/mm )
(°C)
Other Other Austenite Austenite Martensite
Austenite Austenite other phases
phases phases
20 200000 201000 450 430 0.015 0.046 320 863
100 197856 473 00 0.046 884
200 196395.24 194000 495 50 0.045 280 832
300 512 80 0.043 730
400 162932.38 184000 523 610 0.041 665
500 178863 533 650 0.038 163
600 82897.14 103853 541 710 0.035 160 119
700 548 790 0.029 101
800 37430.45 78000 556 865 0.024 0.024 50
900 15000 565 565 50 10
1440 4761.91 1000 630 630 10
1490 1840 1840 0.032 0.032
1540 952.38 1000 2470 2470 0.032 10

Table.6.4. Stress-Strain properties for ASTM A36 steel.

Strain (pct.)

0 0.003 0.004 0.005 0.01 0.05 0.1 0.15 0.2 0.5 1

Temp (°C)

20 0 73 79 84 102 160 194 217 236 305 370

100 0 73 79 84 102 160 194 217 236 305 370
200 0 73 79 84 102 160 194 217 236 305 370
300 0 69 75 80 97 152 184 207 224 289 351
400 0 58 63 67 81 128 155 174 189 244 296
500 0 44 47 50 61 96 116 130 141 183 222
600 0 33 35 38 46 72 87 98 106 137 166
700 0 14 16 17 20 32 39 43 47 61 74
800 0 7 8 8 10 16 19 22 24 30 37
900 0 4 4 4 5 8 9.7 11 12 15 18
1000 0 4 4 4 5 8 10 11 12 15 18
1100 0 4 4 4 5 8 10 11 12 15 18
1200 0 1 1 1 1 2 2 2 2 3 4
1300 0 2 2 2 2 3 4 4 5 6 7

114
The applied welding parameters were according to the recommended industrial welding
parameters used in constructing pressure vessels. The arc properties and weld puddle
parameters are shown in Figure 6.15. The arc length and width were selected based on
recommended practices. Clamping conditions is applied while depositing the bead on
the plate. Also, the implant plate is exposed to cooling condition which is set to ambient
temperature. Figure 6.15 shows the steps (modules) of the computing process for
thermo-metallurgy and mechanical predictions.

6.5.1 Temperature Distribution and Obtaining Thermal Cycle

After completing the computation, the temperature needs to be further calculated
separately through the plate and along the cylindrical implant pin can be viewed and
evaluated. Figure 6.15 shows the welding process starting at one second and finishing
at sixty seconds. The temperature at the side of the implant plate image is ranging from
20oC (ambient temperature) till the melting temperature of the steel (1530 oC) as shown
in Figure 6.16. The gray color in the middle of the weld represents the melting
temperature of the steel. The thermal cycle that the cylindrical implant pin is exposed to
is shown in Figure 6.17. This thermal cycle is imposed to the second detailed simulation
implant pin as shown in Figure 6.17. Furthermore, other results like distortion and
residual stresses can also be viewed and evaluated. Figure 6.18 shows the
displacement (distortion) result caused by the weld as it is applied.

6.5.2 Imposing Thermal Cycle on Implant Pin Simulation

The Welding Advisor in SYSWELD-Visual Weld is used to impose the thermal cycle as
shown in Figure 6.19. An extra layer is added on top of the implant pin for imposing the
thermal cycling. Figure 6.20 shows the thermal cycle that was obtained from the implant
plate simulation. Also, very fine meshes were applied in the top threads because it is
the region of the heat affected zone. Similar conditions from the implant plate
simulation, like cooling and clamping conditions, were implemented in this implant pin
simulation. Loading condition was added to this second simulation. As in the case of
the standardized implant testing after the weld is deposited, a tensile load is applied to
the implant pin simulation. The applied tensile loading condition is shown in Figure 6.21.

115
Figure 6.15. Simulated welding parameters and conditions
116
Figure 6.16. Temperature distribution during the weldability implant testing

117
Figure 6.17. Thermal cycle obtained from the first model for the second implant pin
model.

118
 Welding

Figure 6.18. Displacement (distortion) during the welding process.

A schematic of the simulated weldability implant test is also shown in Figure 6.22.
During the computational process, the implant pin is exposed to the thermal cycling for
sixty seconds then the tensile load is applied till the computational process is finished. A
schematic of the thermal and the tensile load steps is shown in Figure 6.20. The tensile
load value can be changed for different simulations as in the case when executing the
standardized weldability implant test.

6.6 Simulation Results for Pressure Vessel Steels

The Welding Adviser in SYSWELD-Visual Weld is used to study the metallurgical
changes caused by the weld on the pressure vessel steels. The applied boundary
conditions, like thermal cycle and tensile loading, are the same for all the steels. The
simulation results reported in this section are the phase amounts, the susceptible phase
to cracking and the crack location. The CE for all the steels was calculated for
comparison purposes. The CE values were plotted in the Graville chart as shown in
Figure 6.23 and listed in Table 6.5.

119
 Layer on which the
Fine thermal energy from
mesh the bead-on-plate
weld is applied.

Coarse
mesh

Figure 6.19. Imposing the thermal cycle to the implant pin model.

Fine
mesh

Coarse
mesh

Figure 6.20. Thermal cycle obtained from the first model and applied to the second
pin model.

120
 Weld

HAZ

Tensile load

HAZ
Fine
mesh

Unaffected
zone

Coarse
mesh

ad

Figure 6.21. The applied tensile loading in the second simulated pin compared to the
implant testing.

121
1. 2.

Load

Load applied
after 60 seconds
Time to fracture

Figure 6.22. Simulated weldability implant test using ESI-SYSWELD software. Different
colors represent different temperature zone. The warmer the color, the higher is the
temperature.

122
The calculated CE is according to AWS specification (1). Ignore the shaded area on the
Graville chart which represents steels outside the scope of this work. As can be seen,
ASTM A36 steel can be welded with preheat alone. The three pressure vessel steels
will require both pre- and post-heat treatment for safe welding.

(%𝑀𝑛+%𝑆𝑖) (%𝐶𝑟+%𝑀𝑜+%𝑉) (%𝐶𝑢+%𝑁𝑖)

𝐶𝐸 = %𝐶 + [ ]+[ ]+[ ] (6.5)
6 5 15

Table 6.5. CE values for all the steels

ASTM Carb n (wt. %) CE value
A543 Gr. B 0.23 0.93
A533 0.25 0.81
A516 Gr. 70 0.22 0.73
A36 0.26 0.33

Pre- and post-heat

recommended

Preheat
recommended

A36
A533
A543
A516

Easy to weld

Figure 6.23. Calculated CE for the three pressure vessel steels and ASTM A36 steel on
the Graville chart.

123
6.6.1 ASTM A516 Gr. 70 Steel Simulation Results
The phases generated by the weld on the top threads (HAZ region) of the implant pin
are bainite and martensite. The amount of bainite phase is higher than martensite as
shown in Figure 6.24. Also, austenite formation during and after the weld passes in the
implant pin is shown in Figure 6.25. As seen in Figure 6.24, martensite is highest near
the fusion line (around 37 pct.) and it decreases in the HAZ region away from the weld
till reaching around 8 pct. On the other hand, the formed bainite phase immediately next
to the weld is around 60 pct. and the amount increases in the HAZ (away from the weld)
till reaching around 95 pct.

Martensite phase Bainite phase dist. (After

dist. (After welding) welding)

Figure 6.24. Phase amounts of martensite and bainite for ASTM A516 Gr. 70 steel.

124
 Austensite phase dist.
(during welding) Austensite phase dist.
(after the weld passes
over the pin)
Figure 6.25. Austenite fraction for ASTM A516 Gr. 70 steel during welding and after the
weld passes.
Figure 6.26 shows the susceptible crack initiation phase for A516 steel. The crack
started in the second thread of the implant pin where there is around 20 pct. of
martensite phase and around 80 pct. of the bainite phase. So, the location of the crack
initiation has high amount of bainite. The bainite phase features are addressed in the
discussion section.

Figure 6.26. The susceptible crack initiation phase and location for ASTM A516 Gr. 70
steel.

125
6.6.2 ASTM A533 Steel Simulation Results
Bainite and tempered martensite were formed by the weld on the top threads (HAZ
region) of the implant pin. The bainite amount is higher than the tempered martensite as
shown in Figures 6.27 and 6.28. Also, as seen in these Figures, the amount of bainite is
high near the fusion line (around 95%) and the amount gradually decreases in the HAZ
region till reaching around 5 pct. As expected, the susceptible crack site is within the
CGHAZ where bainite is dominant in the microstructure as shown in Figure 6.29. The
crack started at the region that contains around 96% of bainite and tempered
martensite. Also, there are other susceptible crack initiation sites (secondary cracks) but
they are located in the interior of the implant pin within the bainite phase region.

Figure 6.27. Phase amounts for ASTM A533 steel after weld cycle.

126
 Bainite phase dist. Bainite + tempered martensite
phase dist.

Figure 6.28. Phase amounts of bainite and tempered martensite for ASTM A533 steel.

Secondary cracks

Figure 6.29. The susceptible crack initiation phase and locations for ASTM A533 steel.

127
6.6.3 ASTM A36 Steel Simulation Results
In this plain carbon steel, bainite and tempered martensite have the highest amount in
the HAZ region as shown in Figures 6.30 and 6.31. Other phases like martensite mixed
with ferrite and pearlite also formed on the HAZ. The amount of martensite is highest
near the fusion line and it decreases in the HAZ as shown in Figure 6.30. The
susceptible crack initiation site is in the CGHAZ where the martensite is dominant as
shown in Figure 6.32.

Figure 6.30. Percentage of microstructural constituents for ASTM A36 steel.

6.6.4 ASTM A543 Steel Simulation Results

In Q&T HSLA A543 steel, bainite and tempered martensite have the highest amount in
the HAZ region. The amount of martensite is high near the fusion line and it decreases
in the HAZ as shown in Figure 6.33. The susceptible crack initiation site is in the
CGHAZ where the amount of martensite is around 0.24 as shown in Figure 6.34.

128
 Bainite + tempered
martensite propt. Ferrite + pearlite
phase propt.

Martensite propt.

Figure 6.31. Phase amounts of martensite, bainite, and other phases for ASTM A36
steel.

129
Figure 6.32. The susceptible crack initiation phase and location for ASTM A36 steel.

130
 Bainite +Tempered Martensite propt.16
martensite

Figure 6.33. Phase amounts of bainite, martensite and tempered martensite for ASTM
A543 Gr. B steel.

6.7 Discussion of Implant Simulation Results

Microstructural transformation causes variations in mechanical and physical properties,
and affects the behavior of the metal being processed. Microstructure prediction is one
of the main challenges in modeling of heat treatment. A three-dimensional (3-D) finite
element model for prediction of transient temperature distribution and locations of
highest stresses in the implant pin welded by Gas Metal Arc (GMA) welding process
was developed.

The first model was able to predict the temperature distribution in the welded implant
plate. The thermal cycle applied to the welded implant plate was then applied to the
second implant pin model. The temperature reached above 1400◦C suggesting melted
material in the fusion zone (FZ).

131
Figure 6.34. The susceptible crack initiation phase and locations for ASTM A543 Gr.B
steel.

132
High temperatures were observed from the calculation in the immediate vicinities of the
FZ, which confirms the development of heat affect zone in these fine-meshed top
threads. Subsequent cooling rate would determine the final microstructure.

The typical microstructure of the pressure vessel steels ASTM A516 Gr.70 steel is
ferritic-pearlitic structure as shown in Figure 6.36a [91]. Its carbon equivalent (CE) is
0.73 wt. pct. using AWS recommended equation and 0.53 wt. pct. using Yurioka
equation. Using SYSWELD FEA software, the microstructure resulted in the HAZ after
welding was martensite and bainite. After applying the tensile load, the location that
showed the highest stresses was the root of the second thread. This location contained
20 pct. martensite and around 80 pct. bainite. Even though actual implant testing was
not conducted on the steel, it is very likely that crack initiation would also be located at
the root of the second thread.

ASTM A533 Grade B steel is also a pressure vessel steel for water-cooled nuclear
reactors. The microstructure of this steel is shown in Figure 6.36b. The simulation
showed that the highest stresses or the suspected crack initiation site would be in the
interface between the martensite and bainite. This interface contained around 96 pct.
bainite and 4 pct. martensite.

ASTM A543 Grade B steel has recently been used to construct the pressure vessel in
question. The microstructure of this steel is shown in Figure 6.36c. SYSWELD
simulation showed that the highest stresses were located in the second thread where
martensite was around 22 pct. and tempered martensite and bainite were about 78 pct.
Comparing the simulation results with the experimental findings, the results agreed well
with each other. The experimental results showed that the crack initiated almost always
in the second thread. With hydrogen added to the shielding gas, the location of crack
shifted to the first thread.

ASTM A36 steel was used for comparison purposes since this steel was used to build
the pressure vessel before upgrading to the HSLA steel. The microstructure of this steel

133
is shown in Figure 6.36d. It is noted in the simulation that the highest stresses were
located in CGHAZ where the martensite was dominant.

Figure 6.35. Implant test fracture of ASTM A543 steel compared to the simulation result
of the same pressure vessel steel.

As noted from the four simulation results, martensite with tempered martensite and
bainite located in the CGHAZ and FGHAZ are responsible for crack initiation in these
steels. It is clear that in ASTM A36 steel simulation that crack initiated in the interface
between martensite and other phases.

134
(a) (b)

(d)
(c)

Figure 6.36. Microstructures of the four pressure vessel steels a) ASTM A516 Gr.70
steel (ferrite-pearlite)92, b) ASTM A533 Gr.B steel (bainite)92, c) ASTM A543 Gr.B steel
(Martensite-bainite), d) ASTM A36 steel (ferrite-pearlite)92.

135
 CHAPTER 7: CORROSION STUDY OF Q&T HSLA A543 STEEL
This chapter discusses the susceptibility of this steel to stress corrosion cracking. The
corrosion behavior in a boiler water medium is also characterized using conventional
and advanced electrochemical techniques.

7.1 Introduction
The behavior and the interaction between the hydrogen and each subzone in the HAZ
along the implant pin were studied in the previous chapters. For safe practices of
pressure vessels, the effects of the environment on the base and welded steel were
investigated. In this chapter, the ASTM A543 steel was welded and samples were
extracted from the weld region [94, 95]. The samples were exposed to similar conditions
to which the base metal was exposed. The electrode used in this part of the welding
was A5.28 ER110S-G grade for gas metal arc welding (GMAW).

The objective of conducting the SSRT research work is to characterize the behavior of
welded steel in the alkaline solution and compare the results with the base metal
results. The alkaline solutions have been chosen based on the chemical treatment
commonly given to the boiler feed water. Amongst the many factors discussed in the
background sections, temperature accelerates all the chemical and electrochemical
reactions (corrosion) between the steel and the medium [98]. Figure 7.1 shows the
additional influence of the temperature on the mechanical properties of the high strength
steels [96, 97].

Figure 7.1. Stress-strain curves of high strength steels at different temperature [98].
The pH of the solution strongly influences the mechanical properties of a steel and also

136
the corrosion rate (Fig. 7.2). pH affects the electrochemical reactions that lead to iron
dissolution and the precipitation of protective scales and corrosion products. It has been
reported that the solubility of the corrosion products released during other corrosion
processes would be reduced by five times when the pH is increased from 4 to 5, but
when pH increases from 5 to 6, the solubility would be reduced by a hundred times [99,
100]. Therefore, increasing pH beyond 5 significantly increases the possibility of forming
the protective oxide layer on the steel.

Figure 7.2. Stress-strain curves of high strength steel at different pH [99].

In industry, oxygen may enter the process line through any leaks in operations and also
perhaps by injection of inhibitors. It was found that addition of oxygen in the process
(between 10 ppb and 1500 ppb) resulted in an increase in corrosion rates [100, 101].
The level of oxygen that dissolved in the medium affects the mechanical properties of
the steel (Fig. 7.3). Generally, the rate of cracking decreases with decreasing oxygen
content. However, oxygen may also promote the formation of protective layers,
retarding the corrosion process.

Inhibitors play a significant role in controlling the corrosion associated with the oil and
gas production and transportation as discussed earlier [101, 102].

As explained in the background section, stress corrosion cracking (SCC) is a very

common cracking mechanism observed in the steel equipment in the oil and gas
industries. Given the required combination of stress and environment, stress corrosion
cracks may propagate and eventually result in leak(s) or sudden catastrophic failure(s)

137
[102, 103]. Figure 7.4 shows the effect of the stress corrosion cracking on the
mechanical properties of the steels.

Figure 7.3. Stress-strain curves of high strength steel in two different level of oxygen.100

Figure 7.4. Effect of SCC on the mechanical properties [104].

Due to localized heating by the welding process followed by rapid cooling, tensile
residual stresses may build up. High tensile residual stresses in regions near the
weld may promote stress corrosion cracking due to the combined effect of the
stress and the harmful environment. So, the tensile residual stresses are usually
undesirable and need to be reduced.

138
7.2 Results and Discussion of SSRT
To calculate the SCC susceptibility for both the base and welded metal, the plastic
strain-to-failure ratio (EPR) and reduction-in-area (RAR) were determined from the
stress-strain curve (Figure 7.5) and the fracture surface of the broken specimens,
respectively. Plastic strain-to-failure was obtained by subtracting the elastic strain at
failure from the total strain at failure. Reduction-in-area was measured from the
difference between the initial area of the specimens at the middle of the gauge length
and the reduced area after fracture. Table 7.1 shows the data obtained from the stress-
strain curves for both base metal and welded conditions. The reduction-in-area ratio
(RAR) can be calculated using equation 1,

RAR (%) = (RAE / RAA ) x 100 (7.1)

where RAR is the reduction-in-area ratio, RAA is the reduction-in-area in air and RAE is
the reduction-in-area in the corrosive environment. The plastic strain-to-failure ratio
(EpR) can be calculated using equation 2. Figure 7.5 shows how to obtain the EPA value
from the stress-strain curve.

EPR (%) = (EPE / EPA) x 100 (7.2)

where EpR is the plastic strain-to-failure ratio, EPA and EPE is the plastic strain failure in
air and in the corrosive environment, respectively. Also, the slow strain rate test index
(ISSRT) can be calculated using equation 3,

ISSRT = 1 – [ (σfw(1 + δfw) / (σfA(1 + δfA) ] (7.3)

where σfw and δfw stand for the tensile strength and elongation obtained from tests in the
corrosive environment. The strength and elongation values in air are σ fA and in solution
δfA, respectively.

139
 Table 7.1. The results obtained from stress-strain curves for both alkaline solutions.
Yield Yield UTS
UTS Elongation
Environment Elongation strength Strength (ksi) (ksi)
(ksi) (W)*
(ksi) (W)* (W)*
Air 0.135 93 102 0.097 112 125
3.5%NaCl-
0.09 83 90 0.025 90 95
175oC
3.5%NaCl-
0.099 85 93 0.06 97 105
150oC
3.5%NaCl-
0.103 87 95 0.065 96 105
125oC
3.5%NaCl-
0.105 89 96 0.066 95 104
100oC
0.1%NaNO2-
0.105 86 96 0.06 98 105
175oC
0.1%NaNO2-
0.107 87 96 0.065 99 109
150oC
0.1%NaNO2-
0.118 89 97 0.07 99 108
125oC
0.1%NaNO2-
0.128 91 100 0.08 100 110
100oC
*(w): welded-condition

Hence, the reduced area after fracture was measured using SEM images. The ratio of
plastic strain-to-failure and reduction-in-area in the corrosive environment (EPE and
RAE) to plastic strain-to-failure and reduction-in-area in inert and air environment (EPA
and RAA) are determined as ductility ratios (EPR% and RAR%), which represent a
measure of SCC susceptibility. The higher the ductility ratios, with values close to
100%, the greater is the material resistance to environmental cracking. Departure of the
SSRT index from unity would mean lower resistance of the steel to SCC.

The stress-strain curves of the tests in NaCl and NaNO2 solutions for both welded and
base plate conditions are shown in Figures 7.6 to 7.9. In general, the ASTM A543 steel
offered lower resistance to environmental cracking in the NaCl solution, particularly at

140
higher temperatures. At 175oC for the base plate condition, the ultimate tensile strength
decreased by approximately 10 ksi and the elongation at failure also decreased from
0.135 to 0.09. The weld deposited on the steel offers higher strength but lower ductility
which was 0.025 at 175oC in NaCl solution. In comparison, the steel exhibited better
corrosion resistance in the NaNO2 environment. The strength did not reduce by any
significant amount (< 5 ksi) in both welded and base plate conditions. It is noted that the
weld gave more strength to the steel as well. The ultimate tensile strength increased
from 91 ksi (at 100oC) in the base plate condition to 100 ksi (at 100oC) for the welded
condition. The elongation at failure in the base plate condition varied between 0.128 (at
100oC) and 0.105 (at 175oC) but dropped to 0.08 (at 100oC) and to 0.06 (at 175oC).

E
pA

Figure 7.5. Stress-strain curves in air at 25oC for base plate A543 steel.

Figure 7.10 shows almost consistent SCC resistance based on RAR and EpR ratios in
NaNO2 solution. The RAR and EpR ratios decrease as the temperature increases in
NaCl solution for both welded and base plate conditions. ISSRT index dramatically
dropped in the welded condition for both solutions. The I SSRT index results are in
agreement with the ductility ratio results. Index values close to unity were observed in
the samples exposed to NaNO2 solutions for the base plate A543 steel.

141
Figure 7.6. Stress-strain curves (base plate A543 steel) in 3.5%NaCl solution at 100,
125, 150, and 175oC compared to air (25oC).

142
Figure 7.7. Stress-strain curves (welded-condition) in 3.5%NaCl solution at 100, 125,
150, and 175oC compared to air (25oC).

143
Figure 7.8. Stress-strain curves (base plate A543 steel) in 0.1%NaNO2 solution at
100,125, 150, 175oC compared to air (25oC).

144
Figure 7.9. Stress-strain curves (welded-condition) in 0.1% NaNO2 solution at 100, 125,
150, and 175oC compared to air (25oC).

145
 Figure 7.10. EpR, RAR and ISSRT results for 3.5%NaCl and 0.1%NaNO2 solutions.

Figure 7.11 shows the fracture morphology of the specimen exposed to air. The fracture
of the specimen was ductile and the cup and cone features can be seen in the images.
Cracking was observed on the surface of the specimens exposed to NaCl solution and
in particular in the necking area of the specimens as shown in Figure 7.12. Increasing
temperature in NaCl solution increased the depth of the cracks as well as the length of
the cracks. The specimen that was tested at 125 oC showed a smaller number of cracks

146
as well as a smaller volume of material that exhibited cracking (~ 1.5mm to either side
of the fracture). The specimen tested at 175oC had a larger number of cracks as well as
a larger volume of material affected by cracking (> 2mm to either side of the fracture).
This observation also indicates that large deformation occurred around the fracture
surface of the specimens at higher temperatures. For the NaNO 2 environment, the
fracture behavior of the specimen was similar to that described above for the NaCl tests
but the cracking and the degradation were less than in NaCl solution (Figure 7.13). The
welded specimens were tested in similar conditions (Figures 7.14 and 7.15). Figure 7.16
shows the cracking and the fracture morphology of the welded condition for both
environments. The cracking and the degradation were more in the NaCl solution than
NaNO2 solution. However, the fracture had always occurred outside the HAZ for both
solutions as seen in Figure 7.17.

7.3 Electrochemical Impedance Spectroscopy (EIS)

The development of the double layer theory which was introduced by Frumkin and
Grahame led to the development of the equivalent circuit modeling which followed by
the representation of impedance data by Randles and Warburg [117]. EIS involves the
use of a potentiostat for applying a potential (voltage) relative to a reference electrode
and measuring the current flowing from the working electrode (specimen) to the counter
electrode as shown in Figure 7.18.

Figure 7.11. SEM images for the fractured base plate specimens in air.

147
 ~2mm
cracked area

(a)

~1.7m
~1.5mm
m
(b)
(c)

Figure 7.12. SEM images for the fractured base plate specimens in 3.5%NaCl solution
at a) 175oC and b) 150oC c) 125oC.

At 100oC At 100oC Fractured

At 100oC At 150oC At 175oC

Figure 7.13. SEM images for the fractured specimens in 0.1% NaNO2 solution for the
base plate A543 steel.

148
 HAZ HAZ

Figure 7.14. The welded specimen showing the fusion zone, HAZ, and base metal A543
steel.

Samples taken for

SSRT

HAZ

Figure 7.15. Schematic showing the locations of the extracted samples [105].

Electrical impedance (Z) is related to the ability of a circuit element (the sample) to
resist the flow of electrical current. The impedance can be defined by Ohms law as
follow:

149
 Et E0 sin t  sin t 
Z   Z0
I t I 0 sin t    sin t    (7.4)

where (I) is the current, (E) is the voltage,  is phase shift,  is radial frequency ( =2
f), and t is the time.
Generally speaking, impedance analysis is based on detection of the processes that
occur in response to external AC voltage applied to the surface of the sample and
measuring the corresponding AC current [118].

7.3.1 Results and Discussion

Electrochemical Impedance Spectroscopy (EIS) has been successfully used to study
the corrosion systems because of the advantage of using small amplitude signals
without disturbing the properties of the sample. The Q&T A543 steel was tested in
different conditions in DI-water with 0.1% sodium nitrite solution. The base metal was
welded with two different wires. These wires were ER110 MG-S80 wire and a LTTW
wire. Also, a multi pass weld using ER110 MG-S80 wire with two different inter-pass
temperatures (25oC and 150oC respectively) was tested. The electrochemical test set-
up was explained in the experimental procedure chapter and selected test samples are
shown in Figure 7.19. The test results for all different condition including the base metal
gave a 45o straight line in Nyquest graph even after leaving the sample immersed in the
solution and tested again after 24 hours as shown in Figure 7.20. The straight line is
explained by Warburg and De Levie [24] that there is an activity of mass transport on
the sample surface because of pore formation. Also, the Bode curves which showing
the frequency for the phases and the impedance modulus, confirm that there are two
activities happening on the sample surface by detecting two different signal peaks as
shown in Figure 7.21.

Looking at the surface of the sample after completing the test, many pores were
detected especially on the HAZ as shown in Figure 7.22. Generally speaking, when
comparing the MG-S80 with LTTW wire, the MG-S80 wire curves had lower frequencies
which indicate the fluctuation of a more compact oxide film that is formed in the solution.

150
 






At 100oC At 125oC Fractured surface

At 150oC At 150oC At 175oC

At 100oC (50X) At 125oC At 150oC

NaNO2 (49X)NaNO2

At 175oC At 175oC

Figure 7.16. SEM images for the fractured specimens for the welded condition.

151
 WM HAZ Base metal

Fracture

HAZ

Figure 7.17. Fracture occurred away from HAZ region.

Figure 7.18. Schematic of EIS electrical circuit [117].

The base metal A543 steel Nyquist graph is somehow an intermediate case between
the MG-S80 and the LTTW wire. The compact oxide film is less formed in the inter pass
welds cases. All phase plots show higher phase angles at intermediate and low
frequencies suggesting the capacitive behavior of the oxide layer. Also as seen in the
case of the LTTW and the base metal, the phase angle at lower frequencies would
decline but remained stable in the MG-S80 wire case. The impedance modulus curve

152
show higher impedance in low frequencies when compared to the base metal A543
steel and the base metal A543 steel show higher impedance when compared to the
LTTW.

Gamry instruments version 5 software (Electrochemical Analyst) was used to fit the
results and to suggest an appropriate model that would explain the electrochemical
activity between the sample and the medium. After fitting the results, the software
suggested Constant Phase Elements (CPE) with diffusion model which confirms that
there were two activities happening on the sample metal surface as shown in Figures
7.23 and 7.24.

The corrosion rate was also measured using the Potentiodynamic test. The results for
all the tests are shown in Figure 7.25. It is noticed that the lowest corrosion rate was
observed for the base metal A543 steel welded with MG-S80. However, the corrosion
rate increased with the multi pass welds. Pore formation was observed for all samples
except when welded with the LTTW. It is shown clearly in the potentiodynamic graph
that the passivation film is formed and stayed longer in the LTTW case. It is different
from the case for MG-S80 wire where pits formed and broke the passive film.

Figure 7.19. Single and multi pass samples.

153
 Warburg and De Levie model

Figure 7.20. Nyquist curves showing the 45o straight line in different test samples.

154
Figure 7.21. Modulus impedance and phase as function of frequency curves showing
the two peaks indicated by the arrows.

155
Figure 7.22. Pits formation as explained by De Levis and Warburg.

CPE

Resistor of the
passive film
Resistor of
Porous Warburg
the pits

Figure 7.23. Gamry software suggested CPE with diffusion model.

156
Figure 7.24. CPE with diffusion model that fits the EIS results for all the tests.

157
 Potential (V)

2
Current density A/cm
Potential (V)

2
Current density A/cm

Figure 7.25. Potentiodynamic results showing the corrosion rate and pits formation.

158
 CHAPTER 8: RESEARCH SUMMARY
This chapter describes the integrated models explaining the possible failure
mechanisms that ASTM A543 steel most likely encountered during construction and
during service.

This research study concluded that ASTM A543 steel is susceptible to both hydrogen
cracking and stress corrosion cracking (SCC). Both mechanisms require the presence
of residual stresses, hydrogen (for hydrogen cracking) and salt ions (for SCC), and a
susceptible microstructure. For SCC, there is usually an incubation time leading to
crack initiation, propagation and eventual material failure. Hydrogen cracking, on the
other hand, commonly happens during the welding process or shortly after fabrication. It
is a combination of the two mechanisms that caused the failure of the pressure vessel in
steam environment described in this work.

8.1 Hydrogen Cracking

There are two possible sources of hydrogen. Hydrogen can be introduced during
fabrication to result in microfissuring (inside weld metal) and cold cracks (within HAZ). It
is possible that the cold cracks were small and below the detection limit of the Non-
Destructive Examination (NDE) methods applied. It is also possible that NDE was not
performed at the completion of the vessel. The second possible source of hydrogen is
during service. Dissociated hydrogen ions from the cathodic reaction in the boiler feed
water may diffuse into the steel and the circumferential welds. With sufficient hydrogen
and high enough residual stresses, cracking may start and propagate following a
specific microstructural feature in the steel. The HAZ of the circumferential welds with
coarsened grain structure and martensite/austenite (MA) constituent as shown in Figure
8.1 are likely paths for easy crack propagation. Residual tensile stresses further
aggravate crack opening and propagation.

8.2 Surface Mobility Mechanism Causing Pits

The surface mobility mechanism causes anodic pits to form on the metal surface. It is
controlled by the rate of movement of the vacancies along the surface of the pit and by
the environment. The surface mobility mechanism assumes that the stress

159
concentration because of the oxidation process at the tip of a pit generates a localized
vacancy region.

Figure 8.1. Hydrogen cracking following the MA constituents in the CGHAZ.

Vacancy generation at the stressed micro-crack tip is responsible for the crack
propagation process. Figure 8.2 depicts a schematic drawing of the surface mobility
process. The reaction of iron to steam, which produces oxide films, injects vacancies in
the surface. At high temperature, there is a clear difference between the growth
mechanism of oxides films like FeO, Fe2O4 and Fe2O3. The growth of FeO and Fe2O4
films take place by outward movement of iron ions. While, the growth of Fe 2O3 films is
inward movement of oxygen anions or oxide ion vacancies which keeps the growth of
the oxide passive film. This anodic reaction increases the number of pits formed on the
metal surface. It is completed by the cathodic reaction to complete the electrochemical
reaction in the micro-crack tip. Figure 8.3a shows the anodic reaction of the pits and
Figure 8.3b shows the Evans diagram of the anode and cathode electrochemical
reactions.

With the right residual stresses, stress corrosion cracking failure of the steel occurred,
Figure 8.4. Figure 8.5a shows the pits that formed during the electrochemical
impedance test. A cross section of a sample taken from the pressure vessel in the plant
confirmed the pits formation on the metal surface as shown in Figure 8.5b. The two
possible scenarios are summarized in the flow chart in Figure 8.6.

160
Figure 8.2. Surface mobility mechanism in the steam environment.

161
 (a)

(b)
Figure 8.3. (a) Anodic pits formation in steam environment, (b)Evans diagram showing the electrochemical reaction happening
most likely in the micro-crack tip.

162
HAZ

BASE
METAL

Figure 8.4. A cross section of a sample taken from the pressure vessel in the plant
showing the stress. corrosion cracking and the branching at the crack tip.

(a)

(b)

Figure 8.5. (a) Pits formation during the electrochemical impedance test, (b)pits
formation in a sample taken from the plant.

163
Figure 8.6. Flow chart illustrating the possible failure mechansims for A543 steel.

164
 CHAPTER 9: CONCLUSIONS
This research work thoroughly investigated the metallurgical behavior of the Q&T A543
steel newly used in the construction of pressure vessels for chemical plants. The major
findings of this research have been summarized into three categories below.

9.1 Microstructure, Mechanical Behavior and Weldability Studies

1. Using both furnace and Gleeble® simulated specimens, the presence of
hydrogen was found to affect not only CGHAZ but also FGHAZ and other
subzones.
 Contrary to other structural steels, the region with the highest susceptibility
to hydrogen cracking was not located only in the CGHAZ. Instead, the
lower intercritical and subcritical HAZ exhibited lower load to fracture
during modified implant testing as well as shorter time to fracture than the
CGHAZ.
 Hydrogen cracks were found to follow the MA constituents leading to
failure of the modified implant test specimens with microstructure
simulated to CGHAZ temperatures using the Gleeble machine. The
presence of MA constituents provide easy path for crack propagation in
the simulated coarse grained heat affected zone.
2. It is also likely that weld cracking started with anodic pits during service of the
pressure vessel followed by propagation by the superposition of stresses and
corrosive environment.
3. Even though heat treatment is not recommended by ASME standard as part of
the fabrication procedure for A543 steel, both pre- and post-weld heat treatment
should be prescribed for the construction of the pressure vessels using this
material.

9.2 Numerical Modeling

1. A two-part model combining welding over the implant plate and heating of the
implant pin was built using SYSWELD as platform for simulating the implant
testing with accurate predictions of temperature, microstructure and crack
location. The predictions were validated by experimental implant test results.

165
  For the HSLA pressure vessel grade steels, cracking occurred near or at
the root of the second thread of the implant pin which corresponded to a
microstructure of predominately bainite and tempered martensite. The
location of the crack, whether surface or internal, was a result of
susceptible microstructure and magnitude of residual stresses that
developed as a function of thermal experience of the implant pin.
 A modified implant test (using a tensile testing setup) was successfully
developed to allow testing of specimens with simulated microstructure
according to SYSWELD modeling that contained selected hydrogen
content to characterize their weldability and fracture mode.

9.3 Corrosion Study

1. The Q&T A543 steel weldment showed higher susceptibility to stress corrosion
cracking in both NaCl and NaNO2 solutions.
 Bode curves obtained from electrochemical testing determined that the
corrosion behavior can be described by the occurrence of two metal
surface activities (surface mobility mechanism). The first one is the
formation of a passive film followed by the development of pits that breaks
the passivation process.
2. The pitting that formed during the electrochemical test in the sodium nitrite
medium can become stress concentration points that can potentially develop into
cracks in the weld regions.

9.4 Suggested Mitigations

1. Heat treatment to modify the cracking susceptible microstructure and redistribute
stresses.
2. Modify welding practice to minimize residual stress. Multiple smaller beads will
reduce residual stress and distortion.
3. Select a moderate strength alloy to optimize the strength and chemical process
performance.
4. Promote cathode inhibition by selected chemical addition.

166
 CHAPTER 10: FUTURE WORKS
Modifications to the weldability implant test are needed to assist in evaluating the
susceptibility of HAZ of any steel to hydrogen cracking. Some of these modifications are
as follow:
 Addition of on-line hydrogen charging electrolytic cell because of hydrogen
outgassing during the time of transporting the pre-charged sample to the implant
test area and also during the welding process. So, adding the on-line electrolytic
cell will help to assure the availability of enough hydrogen to activate the cracking
mechanisms.
 Addition of a data acquisition for more accuracy of recording the test data.
 Addition of multiple thermocouples to read the temperature distribution on the
implant pin and plate.
 The lowest detection level of the Leco hydrogen analyzer used in this work is
0.5ppm. However, the sensitivity of the latest generation LECO machines has
been improved to detect down to 0.001ppm.
 Using the colored etchant worked to reveal MA constituents in CGHAZ
microstructure. However, other techniques like XRD, EBSD and TEM to analyze
the different phases may be desirable.

Corrosion Study:
A detailed study of the weld with different filler metals and if possible using different
welding processes should be conducted to gain better understanding of the corrosion
behavior in the specific process medium. Modifying the slow strain rate test to study in
detail the hydrogen cracking and the stress corrosion cracking mechanisms where the
anodic corrosion process generating the hydrogen and the hydrogen diffuse in the
cathode area to embrittle the steel is also desirable.

Finite Element Modeling Study:

Simulating other weldability tests using numerical methods will save time, money, and
resources (materials, machining, and welding) and such a study is highly
recommended.

167
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 CHAPTER 11: APPENDICES
Appendix-A: Implant test pin drawing

Implant test pin drawing.

178
Appendix-B (residual stresses and distortion measurement cause by the weld on
the plate).

Stresses in XX- direction.

Stresses in YY-direction.

179
Stresses in ZZ-direction.

Distortion measurements.

180
Displacement measurements.

181
Appendix-B (Residual stresses caused by the weld bead for ASTM A533 steel).

Stresses in XX-direction for ASTM A533 steel.

Stresses in YY-direction for ASTM A533 steel.

182
Stresses in ZZ-direction for ASTM A533 steel.

183