Hydrogen Attack A516 G70

i
EFFECTS OF ABSORBED HYDROGEN ON FRACTURE

TOUGHNESS OF WELDED SA516 GRADE 70 STEEL
MOHAMAD HAIDIR BIN MASLAN
A project report submitted in partial fulfillment of the

requirements for the award of the degree of
Master of Mechanical Engineering
(Mechanical Engineering)
Faculty of Mechanical Engineering

Universiti Teknologi Malaysia
OCTOBER 2007
iii
Dedicated to
my parents, Maslan bin Isa and Kaujah binti Yahok,
my wife, Noraini binti Kurdi,
my daughter, Nazurah Hana,
and all my family and friends
for their immensurable support and love.
iv
ACKNOWLEDGEMENTS
Thanks to God, the most gracious and the most merciful, for His guidance to
accomplish this research. Without His help and mercy, this would not been possible.
He is the one who knows the hardship and He is the one I seek his satisfaction and
ask His acceptance.
I would like to express my deepest gratitude towards my advisor, Professor
Dr Mohd Nasir Tamin for his guidance, encouragement, and valuable comments
during the research and writing of this dissertation. His attention and technical
expertise were key elements to my success. I feel that I gained a deep knowledge
from him in area of fracture mechanics and hydrogen embrittlement, which will have
a significant impact on my future career.
I wish to express my appreciation to my project committee members, Mr Adil
Khattak, Mohamad Hafizuddin and Sebastian for their generous cooperation,
hospitality, time and insight on related matters during this research. My appreciation
also to Mr Rizal bin Khaus, Mr Fadlisah b Abd Kadir , Mr Sazali bin Duki and all
technicians that are contribute in this study for their assistant in laboratory work.
My appreciation goes to Universiti Teknikal Malaysia Melaka (UTeM) and
my colleagues in the Faculty of Manufacturing Engineering for their understanding
and support throughout my part time Master study. The working environment here
was very pleasant, encouraging and supportive towards my work and study loads.
Special thanks goes to my parents for their patient and sacrifice during my
academic career. Their concern, encouragement, moral and financial support over the
years has always been a source of motivation that enables me to achieve this degree.
Finally, and most importantly, special thanks to my beloved wife, Noraini
binti Kurdi, for her unconditional love and support during my education. Thanks for
taking care of our daughter, Nazurah Hana, and for tolerating my absence from
family activities during this challenging time.
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ABSTRACT
Effects of absorbed hydrogen on structure and properties of welded A516 Grade-70

steel are investigated. Emphasis is placed on ductility measure of the crack-tip plastic
zone under Mode I loading. Specimens are cathodically charged in a cell with dilute
sulphuric acid and corrosion inhibitor with uniform charging current density of 20
mA/cm2 and at different exposure time. Results indicate a change from coarse- to
fine-grained microstructures in the weld region and heat affected zone (HAZ) of
hydrogen-charged specimen. Well-defined ferrite-pearlite bands in the base metal are
transformed into coarse-grain structure. Hardness variation along radial distance
indicates higher values towards the center of the bar, possibly due to faster diffusion
rate but limited solubility of hydrogen. Load-COD responses indicate that slow,
stable crack propagation occurred in both base metal and HAZ. The measured
provisional fracture toughness, KQ is higher for HAZ than that for the base metal.
The toughness values decreases significantly for the initial three hours of hydrogen
charging. The tensile fracture region in the immediate fatigue pre-crack tip forms a
triangular (rough) zone due to limited constraint to free surface deformation in the
thin specimen. Fracture surface of HAZ is dominated by intergranular fracture with
localized cleavage facets.
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ABSTRAK
Kesan penyerapan hidrogen ke atas struktur dan sifat bahagian kimpalan pada besi
A516 Gred 70 adalah dikaji. Penekanan diberikan kepada pengukuran kemuluran
pada bahagian plastik di hujung retak dengan pembebanan mod 1. Spesimen dicaj
pada bahagian katod dalam sel elektrolisis yang menggunakan cecair campuran asid
sulfurik dan perencat kakisan, dengan arus caj malar 20 mA/cm2 dan tempoh
mengecas yang berbeza. Keputusan mendapati terdapat perubahan dari mikrostruktur
kasar kepada mikrostruktur berbijian halus di bahagian kimpalan dan bahagian kesan
pemanasan bagi spesimen yang dicaj dengan hidrogen. Jalus ferit pearlit pada logam
asas bertukar kepada struktur bijian yang kasar. Variasi kekerasan pada jarak
sepanjang jejarian didapati nilainya meningkat ke arah pusat rod. Berkemungkinan
ianya disebabkan oleh kadar serapan yang pantas tetapi dengan keterlarutan hidrogen
yang terhad. Bebanan perubahan pembukaan retak mendapati berlakunya perambatan
retak yang perlahan dan stabil berlaku pada kedua-dua logam asas dan bahagian
kesan pemanasan. Pengukuran kekuatan patah sementara, KQ bagi bahagian kesan
pemanasan adalah lebih tinggi berbanding bahagian logam asas. Nilai kekuatan
berkurangan dengan ketara selepas tiga jam pertama dicaj hidrogen. Bahagian
permukaan patah pada pra-retak lesu berbentuk segitiga akibat dari kekurangan
pergantungan kepada perubahan bentuk permukaan bebas di dalam spesimen nipis.
Permukaan patah bahagian kesan pemanasan di dominasi oleh patah antara bijian
dengan celah segi setempat.
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TABLE OF CONTENTS
CHAPTER TITLE PAGE

TITLE i
DECLARATION ii
DEDICATION iii
ACKNOWLEDGEMENT iv
ABSTRACT v
ABSTRAK vi
TABLE OF CONTENTS vii
LIST OF TABLES x
LIST OF FIGURES xi
LIST OF SYMBOLS xiii
LIST OF APPENDICES xv
1 INTRODUCTION 1
1.1 Introduction 1
1.2 Background 1
1.3 Research Problems and Hypothesis 3
1.3.1 Statement of Research problem 3
1.3.2 Research Questions 3
1.4 Hypothesis 4
1.5 Objectives 5
1.6 Scope 5
1.7 Significance of Findings 5
2 LITERATURE REVIEW
2.1 Introduction 6
viii
2.2 Hydrogen Damage 7

2.2.1 Types of Hydrogen Damage 8
2.2.2 Hydrogen Diffusion mechanism 12
2.3 Welding 18
2.3.1 Submerged Arc Welding 19
2.3.2 Weld Stress 20
2.3.3 Post Weld Heat Treatment 20
2.3.4 Weldment Microstructure and Properties 21
2.3.5 Effect of HAZ in Hydrogen Environment 23
2.4 Fracture Mechanics 24
2.4.1 Linear Elastic Fracture Mechanics 24
2.4.2 Elastic Plastic Fracture Mechanics 27
2.4.3 Plane Stress and Plane Strain 27
2.4.4 Shear Lip Formation During Crack Growth 29
3 RESEARCH METHODOLOGY 30
3.1 Introduction 30
3.2 Research Design 30
3.3 Material 30
3.4 Sample Preparation 33
3.5 Hydrogen Charging Process 35
3.6 Experimental Design 36
3.6.1 Vickers Hardness Test 36
3.6.2 Microscopic Analysis 37
3.6.3 Tensile Test 37
3.6.4 Fracture Toughness Test 38
3.6.5 Fractography 42
4 RESULTS AND DISCUSSION 43

4.1 Introduction 43
4.2 Microstructure 43
4.3 Hardness 45
ix
4.4 Stress and Strain Curve 47

4.4 Fracture Toughness 48
4.5 Fractographs 50
5 CONCLUSION 53
6.1 Conclusions 53
6.2 Suggestions for Future Work 54
REFFERENCES 55
APPENDICES 58
x
LIST OF TABLES
TABLE NO. TITLE PAGE
2.1 ASTM specification for pressure vessel quality steel plate 7

2.2 Description mode of fracture and types of materials 9
3.1 Composition of A516-Grade 70 pressure vessel steel (wt. %) 32
4.1 Results from Tensile Test 47
4.2 Results from Fracture Toughness Test 48
xi
LIST OF FIGURES
FIGURE NO. TITLE PAGE
2.1 Process of hydrogen evolution and adsorbtion 13

2.2 Hydrogen discharge process in metal membrane and
hydrogen concentration through thickness 13
2.3 Hydrogen concentration in pressure vessel steel 14
2.4 Autoclave set up 15
2.5 Electrochemical hydrogen diffusion set-up 16
2.6 High temperature electrochemical hydrogen diffusion set up 17
2.7 Common practice to assemble pressure vessel using fusion
welding processes as gas metal arc welding 19
2.8 Post Welding Heat Treatment process 20
2.9 Longitudinal Residual stress at well after post weld heat treatment 21
2.10 Temperature Gradien vs Length in welding process 22
2.11 Stress at crack tip 25
2.12 The cross hatched area represent load that must be redistributed,
resulting in a large plastic zone 26
2.13 Stress Triaxiality at crack tip effect from plane stress 28
2.14 Fracture toughness versus thickness 29
2.15 Ductile growth of an edge crack 29
3.1 Research Design 31
3.2 Weld Radiograph of pressure vessel steel 32
3.3 Slice remark on the curve plate to produce straight plate 33
3.4 Flat plate after applying nital 34
3.5 Fracture toughness sample after applying nital 34
3.6 Electrolytic cell for hydrogen charging experiment 35
3.7 Location for hardness test sampling 36
xii
3.8 Shape and dimension For Rectangular Tension Test Specimens 38

3.9 Specimen for Fracture Toughness Test 38
3.10 Principal Types of Force-Displacement (CMOD) Records 40
3.11 Load-displacement curve for an invalid fracture toughness test 42
4.1 Microstructure of welded ASTM A516 steel as received (10x) 44
4.2 Microstructure of welded ASTM A516 steel 3 Hr hydrogen
charging (10x) 44
4.3 Hardness profile along radial locations of 0.30 wt%C steel rod
after 6-hour hydrogen charging 45
4.4 Vickers Hardness value distribution in pressure vessel steel
non-hydrogenate and 3 Hours hydrogenate time 46
4.5 Stress and strain curve for ASTM A 516 steel before and
after charging 47
4.6 Comparison between KQ value for base metal and HAZ vs
hydrogen charging time 49
4.7 SEM of fracture surface of tensile specimen for base metal as
received 50
4.8 SEM of fracture surface of tensile specimen for base metal
3 Hr hydrogen charge 51
4.9 Morphology of fracture surfaces of HAZ in the immediate
region of the fatigue pre-crack tip. (a) as-received condition
and (b) 3-hour hydrogen charged sample. 52
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LIST OF SYMBOLS
YS Yield strength (MPa)
Poisson ratio
a Crack length (mm), includes notch plus fatigue pre-crack
Atomic radius
B Specimens thickness (mm)
BM Base Metal
C(T) Compact Test
CH4 Methane
CTOD Crack tip opening displacement
E Modulus Young
EPFM Elastic plastic fracture mechanics
F Frequency
Fe Ferrum
Fe3C Cementite
H2 Hydrogen gas
HAZ Heat affected zone
KI Stress intensity factor (MPa m )
KIC Plane strain fracture Toughness (MPa m )
KQ Critical stress intensity factor (MPa m )

LEFM Linear elastic fracture mechanics
P Load (N)
Pmax Ultimate Load
PQ 5% secant line to elastic loading slope (N)
R Load ratio
r Radius of the plastic zone
S Span (mm)
xiv
SAW Submerged arc welding

W Specimen width
WM Weld metal
xv
LIST OF APPENDICES
APPENDIX TITLE PAGE
A1 Project Schedule (Gantt Chart) for semester 1 59

A2 Project Schedule (Gantt Chart) for semester 1 59
B1 Stress Strain Curve for as received material 60
B2 Stress Strain Curve for 3 hr hydrogen charging material 60
C1 CTOD curve for Base Metal (as received) 61
C2 CTOD curve for Base Metal (3 hr hydrogen charging) 61
C5 CTOD curve for HAZ (as received) 63
CHAPTER ONE
INTRODUCTION
1.1 Introduction
Today business sector economics compel industrial units to attain ever-higher

capacity factors, yet materials aging and the other forms of degradation are
increasing the potential for components failure, derating or outages and higher
operation and maintenance costs. Thus managing materials degradation and aging is
one of the major technical and economic challenges facing today industry. For plants
approaching the license renewal stage, assuring regulators of the continuing
reliability and safety of in-service materials adds another dimension to this challenge.
The rate of materials degradation, and consequently plant component or system
availability, are strongly affected by a plants operating environment, including
temperatures and corrosiveness. Thus, a comprehensive, integrated understanding of
materials characterization with respect to their resistance to load, temperature and
corrosive environment are a fundamental consideration in the development of overall
plant business and operating strategies.
1.2 Background
Pressure vessel and piping system form a class of components for which
particularly high levels of integrity and reliability are required. This is due the
potential hazards which are associate with many industrial processes combined with
their high capital value. In oil and gas industries, and chemical processing plants, the
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reactor pressure vessel often operate in aggressive environment. In this study, the
environment is focusing the presence of corrosive gases. The loadings constitutes of
high pressure with fluctuating as in services operation and shut down. Such condition
leads to environment-fatigue interaction of the material. The vessel provides the
integrity of the reactor pressure boundary and function as a barrier for preventing the
leakage of isolated chemical. In addition, the continued safety of the reactor pressure
vessel is a key factor in ensuring the feasibility of implementing plant life extension
program.
Reactor pressure vessel failures have caused extensive damage to the plant,
people and environment. The explosion of Union Oil amine absorber pressure vessel
in 1984 has resulted in causing 17 fatalities and extensive property
damage(Challenger et al., 1995). The explosion of boiler/pressure vessel on-board
the Mississippi steamship Sultana in 1965 have claimed 1238 lives, although more
souls were lost when ship sank within 20 min after the explosion. In 1999, 23 percent
of a total of 138 explosion and 82 percent of a total of 150 accidents involved failure
of boilers, resulting in 21 fatalities(Spence et al., 2004). The situation worsened in
2001 where 158 people died and 342 were injured in boilers, pressure vessel and
pressure piping related accidents. Many of these reported mishaps were due to non-
conforming design and fabrication of pressurized vessels and components and
inadequate in-service inspection.
Pressure vessel are often used in the temperature range 480-565oC with the
stresses about 15-30 MPa over time periods of some 30 years. The main factor
responsible for the good creep resistance of this low alloy steel is the formation of
fine and highly stable dispersions of alloy carbides, although a significant
contribution also comes from solid solution strengthening (Tsai, 2003). In heavy-
wall vessels operating in similar service environment, it is common to apply welded
austenitic steel inlay to low carbon steels, Thereby, taking advantage of the high
strength and low cost of the base metal while retaining the superior corrosion
resistance of the stainless steel weld inlay(Nasman, 1982). The low carbon steel and
stainless steel inlay of the vessel is primarily constructed by welding resulting in
different microstructure in the welded zone(Krisnan et al., 2005). The application of
heat for the fusion process greatly transforms the microstructure; induce phase
changes and mechanical properties of the steel in the vicinity of the welded region.
These changes often lead to a decrease in toughness of the weld and heat affected
3
zone (HAZ) resulted in different microstructures throughout the HAZ and the
associated residual stresses.
Several commercially available steel have been studied for applications in
reactor pressure vessel. Although these studies have contributed to better
understanding of the microstructures of these welded joints, little information is
available in correlating the observed microstructures with the mechanical responses
of the alloy.
An experimental research, establishing the processing, heat treatment-
structure-properties relationship of the alloy is therefore necessary. The result is
essential in generating relevant failure data and quantifying factors that can explain
fracture mechanism for both static and fluctuating load at elevated temperatures and
in corrosive environment.
This research is aimed at discovering and understanding the underlying
fracture mechanism with environment interaction of welded connection and to
examine the effect of the HAZ in both static and fatigue responses of the welded
ASTM SA516 Grade 70 steel connection.
1.3 Research Problem And Hypothesis
1.3.1 Statement of Research Problem
How does the material damage evolve in the process zone of welded ASTM SA 516
Grade 70 steel subjected to hydrogen absorption?
1.3.2 Research Questions
1. What are the damage parameters for the HAZ of welded ASTM SA516
Grade 70 steel under hydrogen environment?
2. What are the evolution characteristics of these parameters and its limiting
values?
4
3. What type of hydrogen concentration sequence that should be applied to

test specimens in accelerated tests for a given operative conditions?
4. What are mechanism-base of life prediction models are proposed to
represent the Hydrogen interaction failure of welded ASTM SA516 steel?
1.3.3 Hypothesis
Physical-based damage parameters for the HAZ include the different

microstructural features of the zone, resulting from steep temperature gradient during
the fusion process. These range from grain size, types of microstructures and surface
defects. Hardness measurements may also indicated the material damage. In addition,
initiation of microcracks may be quantified in terms of crack density (crack length
per unit area sampled)
Non-linear or logarithmic-type evolution characteristic is expected for the
chosen damage parameter. For example, hardness measures decreases rapidly after
half design-life of the vessel has been reached. This is expected due to synergistic
environment effect especially at elevated temperature when creep might be present.
Typical operating conditions for hydrocracking pressure vessel are 380oC-
455oC along with hydrogen pressure of 17 MPa. This condition has cause critical
point in the wall to experience increasing of hydrogen concentration up to 4.28ppm.
Temperature is set at ambient temperature as a control process, and different
hydrogen concentration will be applied to get the relation of material degradation to
the hydrogen concentration.
Two approaches are proposed for the mechanics-based life prediction models.
In the damage mechanics approach, damage will be plotted against component
life(years) throughout designed life of the component. Damage parameters in this
approach are hardness variation and microstructure degradation. In the fracture
mechanics approach, damage parameters are fracture toughness (KIC) and stress
intensity factor (KI). KI can be calculated through non-destructive testing (NDT)
during in-service conditions and curve for KIC will be established through
experimental setup.
5
1.4 Research Objectives
The objectives of this research are to quantify the effect of absorb hydrogen on crack
tip ductility in welded SA516 grade 70 steel
1.5 Research Scope
Scope of this research is:

Critical literature review on welded ASTM SA516 Grade 70 steel, hydrogen
embrittlement of steel, and fracture mechanics
Development accelerated hydrogen absorption test cell. Establish absorption
characteristics.
Mechanical test of ASTM SA516 Grade 70 steel- Tension and fracture
toughness tests, fractographic and metallurgical analysis on welded samples
and base metal samples.
Establish damage evolution characteristics of ASTM SA 516 Grade 70 steel
in prolonged hydrogen environment. Damage parameters include fracture
toughness, hardness and microstructure.
1.6 Significance of Study
This research directly addresses and ensures safety and integrity of vessel
throughout desired life. Moreover this research will help to avoid any expected
pressure vessel failure events thereby improving plant capacity, realibility and
availability. Last but not least, life-extension program can successfully be achieved
through this research.
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CHAPTER TWO
LITERATURE REVIEW
2.1 Introduction
ASTM A516 Grade 70 steel is one of the most commonly used material in
the fabrication of low temperature pressure vessels. Steel used in the fabrication of
pressure vessel steel is in two kinds, carbon steel and alloy steel. Those type of
pressure vessel steel is grades by ASTM as shown in Table 2.1.
In pressure vessel steel, carbon is of prime importance because of its
strengthening effect. It also raises the transition temperature, lower the maximum
energy values and widens the temperature range between completely tough and
completely brittle behaviour. Pressure vessel steel generally contain less than 0.25 wt
% C or in other word, those steel are categories in low carbon steel.
When two or more parts of pressure vessel steel are welded together, the
properties of the metal in weldment vary significantly. Weldment here are
heterogeneus structural elements composed of three microstructural region, base
metal (BM), weld metal(WM) and heat affected zone(HAZ). Properties in those
regions are different due to high heat input during welding, slag inclusions, and
disproportionate heat or cooling rate(Kou 2003).
During service, these pressure vessel steels, especially 2.25Cr1Mo steel, are
susceptible to temper embrittlement and/or hydrogen damage(Tan, 2005). Several
7
type of hydrogen damage such as hydrogen embrittlement, and hydrogen attack are
commonly occur at the pressure vessel material.
In this chapter, adequate detail description will be conduct to understanding
the hydrogen damage, welding effects, fracture mechanics in order to answer the
research question.
Table 2.1 ASTM Specification for Pressure Vessel Quality steel Plate (Sharma,
1998)
Specification Steel type and Condition

A285 Carbon steel plates of low or intermidiate tensile strength
A299 Carbon manganese silicon steel plates
A442 Carbon steel plates for applicatios requiring low transition
temperature
A455 Carbon Manganese steel plates of high tensile strength
A515 Carbon silicon steel plates of high tensile strength
A516 Carbon silicon steel plates for moderate and lower temperature
A537 Heat treated carbon manganese silicon steel plates
A562 Titanium bearing carbon steel plates for glass or diffused
metallic coatings
A612 Carbon steel plates of high tensile strength for moderate and
lower temperature
A662 Carbon manganese steel plates for moderate and lower
temperature
A724 Quenched and tempered carbon steel plates for layered pressure
vessel not to subject to post weld heat treatment
A738 Heat treated carbon manganese silicon steel plates for moderate
and lower temperature
2.2 Hydrogen Damage
Hydrogen damage refers to the degradation of physical and mechanical

properties of metals resulting from action of hydrogen, which may be initially
present inside the metal or accumulated through absorbtion. (Chatterjee, 2001, Sinha,
2003, Baecham, 1977). The damage may manifest itself in several way, loss of
ductility, tensile strength, fracture toughness, creating microscopic and macroscopic
damage beginning with void to internal flaking, blistering, fissuring and cracking
(Chatterjee, 2001).
8
Hydrogen can be retained in steels and other metals internally as a result of

melting and casting, and present externally in the atmosphere around the alloy
material as a gas or constituent of gas as a result of pickling, electroplating,
cathoding process, sour environment, contact with water or other hydrogen-
containing liquid or gases and so forth (Chatterjee, 2001). Hydrogen damage can
develop in a wide variety of environments and circumstances and also variety of
materials but it is more predominant in carbon and low alloy steel (Sinha, 2003).
Although hydrogen damage presence may have been suspected by makers
and users of steel product long ago, but according to Buzzard and Cleaves, in 1873,
the first recorded hydrogen damage in the form of hydrogen embrittlement as a cause
of metal failure was made by W. H. Johnson (Beachem, 1977).
2.2.1 Types of Hydrogen Damage
Hydrogen damage has been classified into several terminologies base on

hydrogen damage encounter under different conditions. The specific types of main
hydrogen damage that occur on low strength steel may be categorized as follows:
2.2.1.1 Hydrogen Embrittlement
Hydrogen embrittlement can be describe as a process resulting as materials

exposed to hydrogen in low temperature(less then 200oC). Hydrogen embrittlement
resulting in the degradation in any one or more of a number of mechanical properties
such as ductility, work hardening rate, tensile and yield strength, fracture toughness,
and so on, depending on its application.
Hydrogen embrittlement damage could be occur in several types of damage
such as loss in tensile ductility, hydrogen stress cracking and hydrogen environment
embrittlement and hydride formation.
Loss in tensile ductility is a damage process when decrease in elongation and
reduction in area without the formation of any visible defects, chemical product or
cracking cause by hydrogen atoms collecting interstitially between metal atoms
9
causing local distortion of the metal lattice observe in lower strength alloy: steels,
stainless steel, nickel base alloy, aluminium alloy. This damage is temporary and
could be accomplish by heating.
Hydrogen stress cracking or in the other name called hydrogen assisted
cracking (HAC) and hydrogen induced cracking (HIC) is a brittle fracture of a
normally ductile alloy under sustained load in presence of hydrogen. This damage
often initiate at subsurface sites where triaxial stress is highest. Hydrogen stress
cracking could be observe in lower strength alloy: steels, stainless steel, nickel base
alloy, aluminium alloy, and in ferrous metal but restrict to alloy having hardness of
22 HRC. This damage could be observe in temperature -100 to 100C, brittle fracture
could be avoided if hydrogen if hydrogen is move out from metal by bake the
materials.
Hydrogen environment embrittlement encounter in an essentially hydrogen-
free material when mechanically tested in gaseous hydrogen. These types of
hydrogen embrittlement observe in ferritic steels, nickel base alloy, aluminium alloy
and some metastable stainless steel. Hydrogen environment occur in gas pressure 34-
70MPa and most severe in room temperature.
The fracture modes for hydrogen embrittlement can vary from intergranular
fracture, transgranular ductile failure, cleavage fracture of mixed fracture depends on
the materials as shown in Table 2.1.
Table 2.2 Description mode of fracture and types of materials(Chatterjee, 2001)

Modes of HE Fracture Types of materials
mixed mode high strength steel
Intergranular nickel alloy and steel with segregation of impurities
elements such as S, As, Sb
Cleavage Ti, Nb, Zr based alloy- form stable hydrid, exhibitting a
stress-induced hydride formation and cleavage mechanism
Transgranular nickel alloy and steel with segregation of impurities
elements such as S, As, Sb, but with high tensile stress
10
2.2.1.2 Hydrogen Attack
The first report on hydrogen attack of steels appeared in 1933. Inspection

reports revealed internal de-carburization and cracking found in plain carbon steel
vessels used in ammonia synthesis. Since that time, more hydrogen attacks were
observed. In 1940s, Nelsons aggregate data regarding the operation experience in
Petroleum and petrochemical industry were published. He develops a set of curves
known as Nelson curves, for design and fabrication of pressure vessel and
pumping at moderate temperatures and high hydrogen pressure. The Nelson curve
have been accepted by the American Petroleum institute(API 941). The Nelson curve
provide operating limits for the combination of temperatures and hydrogen partial
pressure above which partial hydrogen attack occur.
Hydrogen attack is damage process that are usually occur at petrochemical
plant equipment and hydrosulfurization reactor where the materials exposed to high
pressure hydrogen and temperature above 200oC(Chatterjee, 2001, Sinha, 2003). The
industrial failures due to hydrogen attack are an integral part of the wider category of
failures due to hydrogen damage, where related accidents have been estimated to cost
equivalent to about 100 billion dollars/year in the USA and are responsible for
several deaths and many injuries of workers (Kim, 2002).
Hydrogen attack is an irreversible damage and leads to both surface and
internal decarburization. The former is encountered on the surfaces directly exposed
to high temperature and high pressurized hydrogen(Nasman, 1982). Surface
decarburization leads to the formation of a decarburized layer whose thickness
depends upon the operational (or testing) conditions; the composition of the steel; the
history of the steel (treatment received, eventual cold work, etc.); the geometry of the
component (e.g. the thickness); the surface finish (Manna, 2007).
Internal decarburization takes place at temperature and pressure below the
sursace decarburization process (partial pressure>200psia(1379kPa) and
o o
Temperature>430 F (221 C) (Nasman, G. D., 1982). The process start with hydrogen
permeates into steel, Hydrogen reacts with carbon atoms in cementite to form
methane.
2H2+Fe3C=CH4+3Fe
11
These reactions reduce the content of carbon, a strengthening constituent, in

solution in the steel. Accumulate methane at grain boundaries and at voids also
contributes to the loss of strength and ductility. Molecular size of methane is too
large to diffuse out of the carbon steel lattice (Nasman, 1982). These undesired
methane molecules are trapped in cavities (voids) at the grain boundaries, and the
high methane pressure which builds up in the cavities is responsible for cavity
growth. This results in intergranular fissuring and can lead to catastrophic failure
(Schlogl, 2001).
2.2.1.3 Hydrogen Induced Blistering
Hydrogen induced blistering is more common in low strength steels, and it is

observed in metals exposed to sufficiently higher hydrogen-charging conditions such
as acid pickling, electroplating, cathodic processes, or in service corrosive
environment. This damage could occur in low temperature and in the unstressed
condition.
Hydrogen blistering literally means the formation of surface bulging
resembling a blister. This type of damage is caused by the pressure generated by the
process of combination of atomic hydrogen into molecular hydrogen. The diffusion
hydrogen atoms accumulate at internal micro defects such as voids, lamination, or
inclusion-matrix interfaces already present in steel. At sufficiently high
concentrations, they tend to combine into molecular hydrogen, exerting an estimated
pressure of several thousand atmospheres, which brings about the damage.
2.2.1.4 Shatter Cracks, Flakes and Fish Eyes
Shatter cracks, flakes and fish eyes are common features of hydrogen damage
in forgings, castings, and weldments. This types of damage refers to small internal
fissures that occur is steels when cooled from high temperature.
At higher temperature of melting or welding or heat treatment in austenite
range, the solubility of hydrogen in steel is higher than in the solidified or low
12
temperature bcc state. The excess released hydrogen accumulates at internal defects,
combine to form hydrogen gas, and cause these types of damage.
The cracks produced are detectable by radiographic or ultrasonic inspection,
or by visual and microscopic observation of transverse sections. The extent of
damage is dependent on the time of exposed to a hydrogen-containing environment.
2.2.2 Hydrogen Diffusion Mechanism
Hydrogen has an atomic radius of 0.25-0.54 which compared with the

diameter of other metallic atoms is much smaller(Eliaz, 2002). This characteristic
gives hydrogen significant mobility (diffusion) in metals. Hydrogen can be
introduced in a material through a variety of ways such as by electrochemical,
hydrogen gas atmospheres, plating process, etc. Diffusion by electrochemical will be
the elaborate in this chapter since the method will be used in this study.
In order for hydrogen to go through a material it must be transported to the
surface of the material, followed by adsorption, absorption and eventually
transported to the material bulk. For electrochemical Hydrogen Diffusion, hydrogen
was produced at the cathodic sites when acid solution molecule was receiving
electron.
1
H 3O + e H 2 + H 2O
2
Hydrogen adsorption into a metal could be explain by characteristic of
hydrogen evolution reaction. Figure 2.1 shows the process of hydrogen evolution
reaction when a metal is in an acid solution. It shows the distinct steps associated
with the entire process. First hydrated atoms are transported to the double layer
(surface), a separation of hydrogen proton and water by adsorption, electro donation
with the charge of electrons of material thereby producing a discharge; the process of
hydrogen combination can occur by two ways atom-atom or ion-atom or both. The
ultimate stage are eventually the desorption and entry into the material, with
accompanying hydrogen evolution reaction culminating in the formation and
hydrogen diffusion(Mamani, 2005).
13
1-Transport
2-Seperation
O O H+
H
H+
O O
H
H
H+ -
H 3-Adsorption
H+ -
7-Evolution of
hydrogen diffusion H+ -
H
H H H H H
6-Desorption
4-Discharge
or Entry
5-Combination
Figure 2.1 Process of hydrogen evolution and adsorbtion
Rajan then show the hydrogen diffusion process in metal by applies the
hydrogen evolution and adsorption information as shown in Figure 2.2. As we can
see, at the surface of adsorption, the process of recombination and evolution results a
maximum concentration of hydrogen occur in some distance from adsorb surface.
Metal Membrance
Hydrogen rich recombination

environment H
discharge diffusion H
H H
H
evolution
Hydrogen
Concentration
0 l1 L Thickness
Figure 2.2 Hydrogen discharge process in metal membrane and hydrogen

concentration through thickness(Mamani, 2005)
14
This theory is support by hydrogen concentration in pressure vessel diagram

develop by Askari and Fujii. In his study for hydrogen diffusion in 300mm thick
pressure vessel wall, the maximum hydrogen concentration is 4.16 ppm located
about 22.85mm inside the base metal.
Figure 2.3 Hydrogen concentration in pressure vessel steel(Askari, 2004)
All solid materials contain structural defects; more so crystalline solids such
as the metallic ones have certain imperfections such as vacancies, dislocation, grain
boundaries areas, voids, inclusions, etc. Although these defects lead the formation of
internal corrosion such as blister in the material, its also retard hydrogen diffusion.
When hydrogen accumulates on these defects, it becomes difficult for subsequent
hydrogen diffusion or transport while the hydrogen resident time on these sites
increases correspondingly in comparison to the case for normal lattice distribution.
(Mamani S.C 2005).
2.2.2.1 Experimental Hydrogen Adsorption method
There is two general approach used to introduce hydrogen into metal. The
first one is using gaseous, and the second one is by using electrochemical.
I. Gaseous Approach
Gaseous hydrogen charge is a traditional approach to introduce hydrogen into

the materials. Usually, the specimens are placed in an oxygen-free, high-conductivity
15
copper chamber with tantalum hydride. The tantalum hydride decomposes and
creates a high partial pressure of hydrogen gas at high temperatures (above 973 K) to
drive hydrogen diffusing into the specimens. Up to 40 ppm of hydrogen can be
introduced into steels and alloys by this technique. (Ming Au, 2007)
High-pressure hydrogen autoclave is another technique using gaseous
hydrogen to charge materials. Specimens are explored to hydrogen for a long period
of time (days or weeks) at high pressure (2035MPa) and high temperature (above
623 K). At the same pressure and temperature, the hydrogen concentrations of 304
stainless steel calculated by different researchers using the equation
C H = kP1 / 2 exp(H / RT ) vary largely from 16 to 118 ppm. The actual hydrogen
concentrations measured by the experiments are much less than the calculated
values. The main explanation is that hydrogen desorption occurred during autoclave
cooling down. Some researchers were able to introduce up to 50 ppm of measurable
hydrogen into 304 steel using this technique in their best effort. (Ming Au, 2007)
Figure 2.4 Autoclave set up (Manna, G., 2007)
II. Electrochemical Method
Electrochemical method introduced hydrogen into the specimens by cathodic

charging in a melted salt bath that consisted of sodium bisulfate monohydrate and
potassium bisulfate. The mixed salt was melted and maintained at 473K in a glass
16
kettle. In this work, 1500 g mixed salt (2.03 g/ml bulk density) was used. Most
evaporated water was collected and dripped back to the salt bath through a
condenser. The water was maintained at a constant level through the dynamic
evaporationcondensation process and periodical water injection. Cathodic charging
was conducted under a 0.850V Ag/Ag+ fixed potential and at 423K with the
specimens acting as the cathode.
Reference Platinum (anode)

Material (cathode)
Metal membrane
Figure 2.5 Electrochemical hydrogen diffusion set-up(Rumaih, 2004)
After charging, the specimens were removed from the cell and rinsed with
distilled water. The specimens remained at 233K in the dry ice box to prevent
hydrogen from off gassing.
The second method of electrochemical approach is high temperature
electrochemical charging technique was developed for effective introduction of
hydrogen or tritium into the metallic materials to a high level in a short period of
time. The samples of the steels and alloys, as the cathode, were charged in an
electrochemical cell consists of Pt anode and molten salt electrolyte. After 3, 6 and
12 h charging, the 304 stainless steel absorbed 25, 45 and 60 ppm of hydrogen,
respectively. Correspondingly, the mechanical strength lost 10, 16 and 23%. The
plasticity was also reduced to 20, 23 and 38%. The fractography showed the
hydrogen embrittlement effect on the fractures. The electrochemical hydrogen
charging technique was successfully used for introducing tritium, an isotope of
hydrogen, into the super alloys for visualization of hydrogen trapped in the
microstructure of the materials. It is found that the hydrogen is trapped at the grain
17
boundaries, in inclusions and carbides. The deformed and twisted grain boundaries
trap most hydrogen under stress.
Figure 2.6 High temperature electrochemical hydrogen diffusion set up
2.2.3 Hydrogen Effect on Steel Properties
This study will only focus on effect on Hydrogen effect on steel properties in
room temperature and low pressure. The predominant effect of hydrogen on the
properties of steel at room temperature is a decrease in ductility. This degradation
depends on the hydrogen content and the strength of the material. Several literature
found that small amount of hydrogen can lead to a large change in the ductility of a
high strength steel (Siddique, 2005).
The effect of hydrogen on the yield strength and Youngs modulus of a
material is not as significant as on the ductility. Various researchers have suggested
that hydrogen did not affect the yield stress and the young modulus in low strength
steels but gave marked reduction in both their ductilitys at room temperature. Roger
found that the yield strength of SEA 1020 steel charged with hydrogen at 30 mA/cm2
18
was found to increase, compared to uncharged steel without change of young

modulus. Zhang et al. Studied the effect of hydrogen on Young Modulus of -Fe
(0.13C charged in H2SO4 for 24 hrs) at room temperature found that hydrogen
decreased the modulus of such steel by 0.08-1.83%. They proposed that hydrogen
decreased the modulus by increasing the internal stress at accumulation sites rather
than decreasing the atomic cohesive force. Ortiz and Ovejero measured the modulus
of 1070 and 1005 steels (charged in H2SO4 for 24 hours) and found that hydrogen
slightly changed the modulus about 0.4-1.7% of these materials. With the percent
change being dependent on the steel hardness (the largest reduction of modulus was
found in quenched steels (high hardness) and the smallest in normalized steel (low
hardness)). Bastein and Azou found that the modulus of mild steel (0.12C charged in
10% HCl for 48 hours) decreased by 1.9%. It can be conclude that embrittlement of
a material due to hydrogen could be determine mostly using fractography compare
using tensile data (Tantaseraneewat, 2000).
2.3 Welding
This section of the research considers prediction of thermal effects, and

transient and residual stress field in a welded thick plate. Knowledge of basic
residual stress formation mechanism is necessary to understanding the environment
effect. During welding, a weldment undergoes complex temperature changes that
cause transient thermal stresses, and non-elastic strain in regions near the weld.
The majority of service failures of industrial equipment made of Cr-Mo steels
have been reported to occur in critical parts such as welds, mainly due to the
microstructural changes, due to the composition of the alloy in use and to the thermal
fields produced by the welding process, which give rise to marked variations in the
material properties (Manna, et all, 2007).
19
2.3.1 Submerged Arc Welding
Submerged arc welding (SAW) is an arc welding process in which

coalescence of metals is produced by heating them with an arc between a bare
consumable electrode and the workpiece, with the arc being shielded by a blanket of
granular, fusible material placed over the welding area. In the welding process, flux
closest to the arc melts and form slag on the surface of the weld, thus protecting the
molten metal from reacting with the air.
If the welding parameters are properly set, the appearance of the weld is often
very uniform and bright, merging smoothly into the workpiece material. The slag
also usually comes away by itself. The flus masks the light from the arc and there is
no smoke or spatter from the weld. This improves working conditions as compared
to gas metal arc welding (Weman, 2003).
The SAW process, owing to relatively large volumes of the molten slag and
metal pool, is usually limited to flat position welding and circumferential welding.
Also because of the relatively high heat input and the resulting large weld pool,
coarse columnar grains often form in the fusion zone. This sometimes results in low
toughness or even hot cracking of the weld metal.
Figure 2.7 Common practice to assemble pressure vessel using fusion welding
processes as gas metal arc welding (Askari, 2004)
SAW have good ductility, uniformity and density. Good impact strengths are
obtainable when specific procedures and techniques are evaluated in combination
with the electrode and flux. A proper selection of the electrode and flux provides
good corrosion resistance depending upon the requirement, and ensures mechanical
properties at least equal to that of the base metal(Sharma, 1998).
20
Submerged arc welding is used mainly for large items, such as plates in
shipyards, longitudinal welding of large tubes or beams, or large cylindrical vessel.
2.3.2 Weld Stress
After two plates are welded together, various kinds of transverse and
longitudinal stresses arise in the weldment due to disproportionate heating and
cooling rates. The residual stresses vary from tension on the surface of the weld to
compression in the center. Post weld heat treatment helps reduce these non uniform
stresses in the weldments, but their existence cannot be completely eliminated.
2.3.3 Post Weld Heat Treatment
A post weld heat treatment is needed to reduce the internal stresses that have
developed due to the welding process to an acceptable level. Post weld heat
treatment could be defined as heating to a suitable temperature(recrystaallization
temperature); holding long enough to reduce residual stresses, and then cooling
slowly enough to minimize the development of new residual stress. Heating and
cooling must be done slowly and uniformly, usually 150oC/h. Figure 2.8 show the
heating and cooling process that usually applied to Cr-Mo pressure vessel wall.
Figure 2.8 Post Welding Heat Treatment process(Al rumaih, A.M., 2004)
21
This treatment has a bearing on the quality of weld or the integrity of the
finished weldment, and control of temperature may be rigidly specified. However,
the residual stresses in a structure subjected to PWHT still not reduced to zero
(Askari, 2003).
Figure 2.9 Longitudinal Residual stress at well after post weld heat treatment
(Askari, A. 2003)
Figures 2.9 show the effects of PWHT on the longitudinal residual stresses at
different location on the weldment. The residual stresses in the welded plate
subjected to PWHT were reduced to a much lower value, but not completely
removed. Also PWHT smoothed out the concentrated residual stress into a wider
area. So the high peak values were distributed more uniformly around the welding
area, and the effects of high changes of stress in a small area were reduced.
In the current work, the material used was SA 516 Grade 70. Hence the
welded joint should be post weld heat treated to a temperature of 600oC for one hour
at a rate of 200oC/hr. The structure can be cooled slowly at a rate of 230oC/hr. ASME
recommends this procedure to obtain minimum residual stresses in the welded joints.
2.3.4 Weldment Microstructure and Properties
Microstructure in heat affected zone due to welding in a carbon steel can be

related to the Fe-C phase diagram, as shown in Figure 2.10. Upon high heating rate
22
and short retention time on certain temperature in welding, several types of

microstructure was produce at and near to the welding zone.
Figure 2.10 Temperature Gradien vs Length in welding process (Rumaih, 2004)
Generally, microstructures on welding zone are divides to several area.

Columnar grain was produced at the weld zone. Then at the heat affected zone,
coarse grains are produce following by fine grains and partially refined grains.
For high strength low alloy steel weld using submerged arc weld, metal
microstructures could be dividing in details to five regions. From the closest to the
weld interface, the microstructure are constituent of: (Sharma,1998)
1. Proeutectoid ferrite, either in massive equixed form or as thin veins
delineating prior austenite grain boundaries
2. Sideplate widmanstatten ferrite(parallel ferite laths)
3. Acicular ferrite(a tough structure found within the body of prior austenite
grain that is formed between 592oC to 667oC
4. Retained austenite and twinned or lath mertensite(martensite-austenite
phases)
5. Other-pearlite and bainite
While for C-Mn Steel, the constituent of the HAZ are(Sharma,1998)

1. Proeutectoid ferite at prior austenite grain boundaries
2. Transgranular widmanstatten ferrite
3. High carbide content microstructures such as pearlite
23
4. Upper bainite and lower bainite

5. martensite
Ferrite has a limited solubility of carbon and is thus a relative softer phase. It
exists in other forms as acicular ferrite, side plate ferrite, grain boundary ferrite, etc.
The formation of even a small volume fraction of grain boundary ferrite, ferrite side
plates, or upper bainite is considered detrimental to toughness, since these
microstructures provide easy crack propagation paths.
Acicular ferrite on the other hand is responsible for high toughness. It is
formed intragranularly, resulting in randomly oriented short ferrite needles with
basket-weave like structure. This interlocking nature, together with its fine grain size,
provides the maximum resistance to crack propagation by cleavage and enhances the
yield strength of the metal.
Pearlite consists of alternating layers of lamellae of the two phases, ferrite
and cementite(Fe3C), that form simultaneously from austenite. Mechanically, pearlite
has properties intermediate between the soft, ductile ferrite and the hard, brittle
cementite.
Bainite is the other microcontituent produced during austenite transformation.
It consists of ferrite and cementite phases, and is in the form of needles or plates.
Bainite and pearlite formation are competitive processes during transformation from
austenite. Since bainite is a finer structure (i.e smaller cementite particles in the
ferrite matrix), it is generally stronger and harder than pearlite; yet bainite exhibits a
combination of strength and ductility.
2.3.5 Effect of HAZ in Hydrogen Environment
Welding effect with combination of residual stress and heat affected zone
microstructure received much attention in failure analysis. However, less data could
be achieve from the literature on affected of hydrogen in weldments area. Nelson
curves which published for the first time in 1951 provide data available from
industrial experience and indicate the pressuretemperature ranges in which certain
steels, but not their weldments, may be used without experiencing hydrogen attack.
24
Hydrogen embrittlement in combination with residual stresses is an irreversible

process that can cause permanent damage resulting in degradation of the mechanical
properties and subsequent failures (Tan, 2005).
Several study also have been made to determine effect of microstructure on
hydrogen embrittlement. Microstructure have been ranked from the best to worst
resistance to hydrogen embrittlement as follows(Banerjee, 2002):
1. Spheroidized or normalized structure
2. Martensite, tempered to precipitate a fine dispersion of alloy carbides
3. Lower bainite plus tempered martensite
4. Martensite, tempered near 500C.
2.4 Fracture Mechanics
Fracture mechanics as an engineering dicipline was introduced in 1950s

under the leadership of G. R. Irwin at the Naval Research Laboratory (NRL). The
concepts of fracture mechanics were further developed and refined throughout the
1960s(Sanford R.J.2003). The principle of fracture mechanic is to study the fracture
behaviour of structure and the influence of parameters such as flaw size, applied
stress and fracture toughness of the materials.
2.4.1 Linear Elastic Fracture Mechanics
For many years, linear elastic fracture mechanics (LEFM) has been the
primary method for fracture analysis. LEFM applies when the material undergoes
only a small amount of plastic deformation. Using LEFM, the stress intensity factor,
KI, in the structure is compared with the critical stress intensity factor, KIC, also
called the material fracture toughness. The subscript I stands for mode I crack
opening mode.
Fracture toughness first used when Irwin and Westergaads method shows
that stress and displacement near crack tip completely characterised in LEFM by a
25
single constant called stress intensity factor, K(Anderson, 2005). This was done by
analysing crack near field stress, as shown in Figure 2.11
Figure 2.11 Stress at crack tip
Stress intensity factor describes as

w
K = a f
a
Where = applied stress
a = crack size
w = plate width
w
f = constant depends on the crack geometry
a
Crack in ideally brittle material plates with infinite size is the easiest crack
geometry formula to be develop since the boundary condition could be neglected.
Solution for this case was given by Westergaard, Irwin and Koiter, and further
development done by Feddersen. The result are:
w a
f = sec
a W
Hence, the formula for stress intensity factor for crack in ideally brittle
material plates with infinite size become:
a
K = a sec
W
However, this formula gives a infinite stress values occur at crack tip. But, in
real structures, stresses at crack tip are finite. Once inelastic deformations occur at
26
the crack tip, stresses at the crack tip relax. Hence, elastic analysis becomes
increasingly in accurate as the inelastic region at the crack tip grows.
Figure 2.12 The cross hatched area represent load that must be redistributed,
resulting in a large plastic zone
Irwin noted this, and he proposed plastic zone correction to estimate stress
intensity factor using LEFM for moderate crack tip yielding.
w
K eff = aeff f
a
eff
2
1 K I
For plane stress
Where a eff = a+
2 YS
2
1 K I
For plane strain
a eff = a+
6 YS
Upon further development, Dugdale and Barenblatt created the strip yield
model. This model assumes for a narrow strip plastic zone with the length of p
effective intensity factor for through-thickness crack in an infinite plate under plane
strain condition become:

K eff = a sec
2
ys
In 1966, Further development done by Buderkin. The modified equation to

estimation of the strip yield model become
27
8
K eff = ys a 2 ln sec
2 ys

2.4.2 Elastic Plastic Fracture Mechanics
Linear elastic fracture mechanics (LEFM) can be usefully applied as the

plastic zone is smalls compared to the crack size. However, if the plastic zone is
large compared to the crack size, LEFM do not apply any longer. Therefore, elastic
plastic fracture mechanics(EPFM) analysis is necessary for ductile material such as
low carbon steel and alloy steel. EPFM was first proposed by Wells in 1963.
Wells proposed that the displacement of the crack faces be an alternative
fracture toughness area. As the plastic zone spread through the entire cracked
section, plastic deformation at the crack tip can occur freely. This idea became the
basis of the crack tip opening displacement (CTOD) method.
2.4.3 Plane Stress and Plane Strain
The radius of the Irwin plastic zone is different depending on whether plane
strain or plane stress conditions exist. As in real life, stress and strain exists in all
three planes, but three dimensional stress field are very difficult to solve. For this
reason the assumptions of plane stress and plane strain were made. Plane strain is
used for thick sheets and assumes the stress in z direction (principal direction 3) is
equal to (1 + 2 ) . In other words, the material in the z direction resists the
materials tendency to neck ( Z = 0) .
Plane stress is used for thin sheets and that there is no stress in the z-
direction. In other words, there is not enough material in z-direction for stress
variation to occur ( Z = 0) .
28
As the plane stress and plane strain effects depending on plate thickness,
stress intensity value also different. Figure 2.13 shows a crackes plate with thickness
B subjected to in-plane loading. Assuming that the plastic zone is small, the region of
the plate that is far from the crack tip must be loaded in plane stress. Material near to
the crack tips loaded higher stress then the surrounding material. The high normal
stress at the crack tip causes material near to surface to contract, but the material in
the interior is constrained, resulting in a triaxial stress state. Material on the plate
surface is in a state of plane stress because there are no stresses normal to the free
surface.
Stress intensity
at the crack tip
Figure 2.13 Stress Triaxiality at crack tip effect from plane stress
However, if the thickness of the plate extends to some value, the plane stress
condition will change to plane stress condition where stress normal to the free
surface start to exist. Plane stress reduces the stress intensity different at the surface
and in the interior. This phenomena make the fracture toughness value in the plane
strain lower than plane stress condition, and the value is not dependent to the
thickness value as shown in Figure 2.14
29
Fracture Toughness, KQ
KIC
Plane stress Plane strain
behavior Behavior
Thickness, B
Figure 2.14 Fracture toughness versus thickness
2.4.4 Shear Lip Formation During Crack Growth
When an edge crack in a plate grows by microvoid coalescence, the crack exhibits a
tunneling effect, where it grows faster in the center of the plate, due to higher
triaxiality. The through thickness variation of triaxiality also produces shear lips,
where the crack growth near the free surface occurs at a 45o angle from the
maximum principal stress as illustrated in Figure 2.10
Figure 2.15 Ductile growth of an edge crack

30
CHAPTER THREE
RESEARCH METHODOLOGY
3.1 Introduction
Chapter three clarifies in adequate detail the method and procedure to

perform each essential step in the research in order to obtain accurate and valid
results.
3.2 Research Design
The research is an experimental study on material damage accumulated

during environment fatigue interaction process. The research design is presented in
Figure 3.1
3.3 Material
The material employed in this study is ASTM A516 Grade 70 steel. The
material is 16-mm thick pre fabricated plates using to produce the curvature of a
cylindrical pressure vessel wall. Each plate is receive with dimension 300mm x
300mm with double vee butt welding at the centre of the plate produced by multiple-
ASTM SA516 Grade 70 Steel
Material
Welded Part Base Metal
Tensile Specimen CTOD Fracture Vickers Hardness Microstructure

Toughness Specimen Specimen Specimen at Base
Sample
Preparation
Metal and HAZ
Electrochemical
Hydrogen
Diffusion Process
Grade 70 Steel
Experimental
Tensile Test Fracture Toughness Vickers Hardness Microstructural
Figure 3.1 Research Design

Test test Analysis
ULT
KIC Hv Microstructure
y HAZ
Comparison, before
Base Metal Base Metal
and after charging
E HAZ
Effects of Absorbed Hydrogen on Fracture Toughness of Welded SA516
Expected Result
3 9 Charging 2 3 4 5 6 7 8Charging
Time(h) Time(h)
31
32
pass submerged arc welding(SAW). All the SAW were performed by Hong Weng
Sdn Bhd using ANSI/AWS specification and section IX ASME boiler and pressure
vessel, welding procedure 135.
Post weld heat treatment (PWHT) was carried out at 620oC for 1 hours with
the increasing and decreasing rate for 220oC/Hr and 278oC/Hr performed by Pioneer
Heat Treatment Sdn Bhd. Radiographic inspection for non destructive test is then
performed by Total Sterling (M) Sdn Bhd to indicated complete fusion, free from
crack and found to be satisfactory. Figure 3.2 shows the weld radiograph of pressure
vessel steel showing complete fusion.
Figure 3.2 Weld Radiograph of pressure vessel steel
A516-Grade 70, plain carbon steel contains two main elements and some
other minor ones. The two main constituent elements are carbon (C) and manganese
(Mn). Minor alloying elements include sulfur (S), phosphorus (P), silicon (Si),
chromium (Cr), nickel (Ni), molybdenum (Mo) and Vanadium (V). The relative
amounts of each constituent alloying element shown in Table 3.1
Table 3.1 Composition of A516-Grade 70 pressure vessel steel (wt. %)

Element C Mn S P Si Cr Ni Mo V Fe
ASTM wt% 0.28 1.23 0.035 0.035 0.40 - - - - Bal
Actual wt% 0.26 1.12 0.004 0.015 0.457 0.018 0.021 0.012 0.005 Bal
33
3.4 Sample Preparation
The first task in preparing for the experimental is cutting process for sample
preparation. As mention before, the material come in curve plate shape, hence the
material needs to be slice from the curve plate to produce specimen in straight shape
as shown in Figure 3.2. This slicing process is conduct using EDM wirecut machine
to minimize local heating effect at the material.
Figure 3.3 Slice remark on the curve plate to produce straight plate
The slicing process produce three flat plate with thickness 10mm and width
100mm from each curve plate. Welded location could be define after the slicing
process by applying 2% nital on the material surface. Nital will react with the
material surface and produce a bright colour at the location of welded zone. Figure
3.4 show the flat plate after applying the nital.
34
This bright zone

appears after
applying nital
Figure 3.4 Flat plate after applying nital
After the slicing process complete, further cutting process is to produce the
specimen. Again, using the EDM wirecut, sample for tensile and fracture toughness
is produce. Sample for fracture toughness need to be produce to measure the fracture
toughness exactly for the base metal and for the heat affected zone. Welded zone
could be determine by applying 2% nital at the plate surface. Figure 3.5(a) show the
specimen for fracture toughness after applying 2 % nital. The bright part at the
sample is weld metal. Figure 3.5(b) show the assumption that been made to estimate
that the edge is locate absolutely on HAZ region.
HAZ
Welded Zone
Welded Zone
(a) (b)
Figure 3.5 (a) Fracture toughness sample after applying nital (b) Assumption for
determining location for HAZ for fracture toughness analysis
35
3.5 Hydrogen Charging Process
The SA516 Grade 70 steel specimen was charged with hydrogen using
electrochemical process. Hydrogen charging of the polished test specimen was
carried out using a simple set up comprising of an electrolytic cell (Fig. 3.6) with
stainless steel plate as the cathod and SA516 Grade 70 steel specimen as the anode.
The specimen was mounted in the cell filled with dilute sulphuric acid solution
(0.5M H2SO4 solution) containing 10mm of arsenic oxide (As2O3) as a corrosion
inhibitor.
Previous study showed that this solution with arsenic addition is capable of
introducing high total H concentrations in the Cr-Mo base steel, reaching 9 and 10
ppm when charging at intermediate current densities of 1- to 20 mA/cm2 [Rumaih].
A constant current density of 10 mA/cm2 was maintained for the specimen for 24
hour. After charging, each sample was removed and quickly immersed in liquid
Nitrogen to minimize H loss. The sample was then quickly cleaned by abrasive-paper
grinding to remove any present scale and put back in liquid nitrogen before any
further experiment.
Cathode: SA516 Anode:

Grade 70 Steel Stainless Steel
0.5M H2SO4 + 10g As2O3
Figure 3.6 Electrolytic cell for hydrogen charging experiment

36
3.6 Experimental Detail
The aim of this study was to investigate the effect of absorbed hydrogen on
properties of SA516 Grade 70 steel such as tensile strength, hardness, chemical
composition, microstructure, and fracture toughness for both base metal and HAZ of
the A516 Grade 70 steel.
3.6.1 Vickers Hardness Test
The main purpose of the testing was to compare the effect of hydrogen
adsorption in term of hardness to the material. Two studies on the effect of hydrogen
in material hardness was done to the material. The first study is to evaluate the
hydrogen effect in the cross section of 32-mm diameter steel rod subject to 6 hour
hydrogen charging. The second study is to determine the hardness different on base
metal, HAZ, and weld zone before and after charging. These experiments will be
conduct base on standard ASTM E92.
Sample hardness variation study in cross section of a 32-mm diameter steel
rod subjected to 6 hour charging was prepare by cut the rode after charging process
using EDM wirecut. Then the measurement is taken to measure the hardness
variation for every thickness.
While, for comparison of hardness value in base metal, HAZ and welded
zone, cross section for both virgin material and after charged specimen is cut at the
base metal, HAZ and the welding zone. Then the hardness value is taken across the
welded joint as shown in Figure 3.7
Heat Affected Welded Zone

Zone
Base Metal
Figure 3.7 Location for hardness test sampling

37
For both study, the surface of the cutting surface need to be prepared so that
the ends of the diagonals are clearly defined and can be read with precision of 0.0005
mm or 0.5 % of the length of the diagonals as state in the standard. A vickers
microhardness tester with a 1kgf load maintained for (10-15) seconds was used. Five
data was taken for each sample. The results of this can be seen in chapter four in
form of hardness vs hydrogen concentration graph.
3.6.2 Microscopic Analysis
Microstructural study is performed using optical microscope (OM). The

following sequence of step was utilized to prepare the specimens for microscopic
examination:
a. Grinding on 230 grit silicon carbide paper
b. Drinding on 4000 grit silicon carbide paper
c. Polishing with 15 micron diamond paste on nylon cloth
d. Polishing with 1 micron diamond paste on nylon cloth
e. Etching with 2% nital and 5% picral
The resulting microstructure of the weldment was optically examined using

an (microscope spec) with attached (camera spec). Photomicrographs of various
magnifications at different positions of the weldment were taken. The micrographs
are shown in chapter four
3.6.3 Tensile Test
Tensile test is a testing to get the value of modulus young, yield strength, and
the stress strain plot curve for overall specimen with certain concentration of
hydrogen. This experiment will be conduct base on standard ASTM E8M. Figure
show the shape and dimension for the specimen.
38
C W
G R T
G - Gage length 50 mm
W - Width 40 mm
T - Thickness 5 mm
R - Radius of fillet 12.5 mm
L - Overall length 200 mm
Figure 3.8 Shape and dimension For Rectangular Tension Test Specimens
Specimen for tensile test was prepared for both base metal and welding parts.
Test was done to measure material properties before and after charging. Loading was
done using Instron 100kN with crosshead speed of 2mm/min. Extensometer used to
measure elongation on the gage length.
3.6.4 Fracture Toughness Test
These test are performed in accordance with ASTM E399. This test method
determines the plane strain fracture toughness (KIC) of the materials. Compact C(T)
specimen (Figure 3.9) was chose for this test.
This test is very stringent and a valid test has to satisfy several criteria
regarding specimens thickness, crack length, and crack length to weight ratio.
1.25W
precrack
10 mm <0.1W 1.2W
W B
Figure 3.9 Specimen for fracture toughness test

39
The dimension of the C(T) specimen are W=35mm, a=15.75mm(notch +

precrack) and the thickness, B=10mm. These dimensions were chose such that
a/W=0.45 which satisfy the ASTM E399 section 7.3.2.1 according to which:
0.45 a / W 0.55
Base on the standard, the specimens thickness (B) must be greater than half
of the widthness(W).
KQ
B
YS
The second rules is to make sure that the test is in plane strain condition, as
plane stress and plane strain conditions varies base on thickness as discuss is
previous chapter.
However, thickness available for the material received is just 10mm
compared to 30mm that required from the standard. Then, result for experiment will
be consider as stress intensity factor for plane stress condition. Hence, stress intensity
factor for the material is higher than results from this study.
The sample was cut using CNC wire cut to develop the v sharp notch.
Location in front of the v sharp notch is the region to be evaluated. Specimen for
fracture toughness test was prepared to evaluate fracture toughness on the base metal
and the heat affected zone.
3.6.4.1 Fatigue Precracking
Before start with testing, precracking need to be produced at the v notch. A

fatigue crack is generated by cyclic loading the specimens until a crack of the desired
length is made. Base on the ASTM standard, the stress intensity factor during any
stages of precracking shall not exceed 80% of the KIC. The standard also state that
the fatigue crack length was not more than the minimum of 1.3mm or 0.025W and
the crack length fell between 45-55% of the width.
Based on preliminary calculation, values of Kmax is 23 MPa m , load ratio
(R) of 0.1 and frequency (f) of 10 Hz were assigned to the software to generate the
crack. 1.3mm crack is indicate at the notch after 2 hour cyclic loading. The load ratio
40
and the frequency also satisfied with ASTM E399, which according to the standard,
load ratio and frequency must:
1 R +0.1 and
f < 100Hz
Hence, the fatigue pre-cracking process is approve following procedure of

standard ASTM E399.
3.6.4.2 Fracture Loading
After, fatigue cracking, the test specimens were slowly loaded until they
failed. The loading was between 0.55 to 2.75 MPa m per second. During testing,
the displacement of the crack mouth and the load applied are recorded. Clip gauge
was used to measure the displacement of the crack mouth. These data are then used
to plot force vs displacement graph. Principle types of load-displacement plot shown
in Figure 3.11
A A
Force, P
Pmax Pmax
A
PQ
PQ PQ and Pmax
Displacement, V
Figure 3.10 Principal Types of Force-Displacement (CMOD) Records

41
3.6.4.3 Fracture Test Results Analysis
The critical load, PQ is defined in one of several ways, depending on the type
of curve. A line from origin with a slope of 95% of the initial elastic loading slope is
constructed to determine P5. The force PQ is then defined as follows: if the force at
every point on the record which precedes P5 is lower than P5, then P5 is PQ; if,
however, there is a maximum force preceding P5 which exceeds it, then this
maximum force is PQ. The determination of PQ and crack length are used in the
computation of provisional fracture toughness, KQ, from the following relationship
PQ S a
KQ = f
B W W
Where f(a/w) is a dimensionless function of a/w and is expressed as:
a a
2 3 4
a a a
2 + 0.886 + 4.64 13.32 + 14.72 5.6
a w w w w w
f =
w
3/ 2
a
1
w
The KQ value computed from equation could be said as valid KIC result,
only if all the validity if all the validity
Pmax 1.10 PQ
The ratio Pmax/PQ, where Pmax is the maximum force the specimen was able to
sustain (see 8.4.1), shall be calculated. If this ratio does not exceed 1.10, proceed to
calculate KQ as described in the Annex appropriate to the specimen configuration.
If Pmax/PQ does exceed 1.10, then the test is not a valid KIc test and the user is
referred to Test Method E 1820 on elastic-plastic fracture toughness.
42
Load
Pmax
PQ
Displacement
Figure 3.11 Load-displacement curve for an invalid fracture toughness test
3.6.5 Fractograph Analysis
The fractured pressure vessel steel surfaces were analyzed under a scanning
electron microscope(SEM) to observe the brittle and ductile fractured surfaces. The
analysis are presented in detail in chapter four.
43
CHAPTER FOUR
RESULTS AND DISCUSSION
4.1 Introduction
The main purpose of this research was to study the effect of adsorb hydrogen
on fracture toughness in the weldment of A516-Grade 70 steel. In this chapter,
results for each experimental done to determine the properties of the microstructure
on heat affected zone (HAZ) and the base metal before and after charging with
hydrogen will be reported. Then, the effect of hydrogen on fracture toughness is
discussed based on mechanical and metallurgical knowledge gathered from hardness,
microstructure, tensile properties, literature, etc.
4.2 Microstructure
The ground specimen was fine polished and etched with 2% nital. The
resulting microstructure was analyzed and image analyser using the inverted Nikon
microscope. Photomicrographs of varying magnifications were taken at various
position of base metal and heat affected zone and weld metal. Figure 4.1 show the
micrograph for the SA 516 grade 70 steel in the as received condition, while Figure
4.2 shows the micrograph after 3 hour charging.
It is found that the microstructure of base metal (Figure 4.1a) displays an
aggregate of well defined ferrite-pearlite bands. The HAZ(Figure 4.1b) is dominated
by a well defined network of equiaxed grain boundary ferrite with colonies of fine
44
grain acicular ferrite while the weld metal(Figure 4.1c) is composed of course grains
of cross hatched appearance Windmanstatten ferrite microstructure.
(a) Base metal (b) HAZ (c) Welded metal

Figure 4.1 Microstructure of welded ASTM A516 steel as received
After Charging
(a) Base metal (b) HAZ (c) Welded metal

Figure 4.2 Microstructure of welded ASTM A516 steel 3 Hr hydrogen
charging (10x)
Microstructure of similar welded joint after a 3-hour hydrogen charging is
compared in Figure 4.2. The base metal (Figure 4.2a) is transformed into coarse
grained ferrite pearlite. The HAZ (Figure 4.2b) shows a shift from a well defined
network of equiexed grain boundary ferrite with colonies of fine grain acicular ferrite
45
to coalescence of fine pearlitic and ferritic regions. Weld metal region (Figure 4.2c)
is transformed into a fine grain cross hatched appearance widmanstatten ferrite.
Adsorbed hydrogen seem have change a little the microstructure at weldment
region and base metal. This situation was predicted, as literature review has
described that effect of hydrogen adsorption in room temperature cause hydrogen
embrittlement. As hydrogen embrittlement is a reversible phenomenon, hence, its
will not cause a major defect or permanent damage on the microstructure (Banerjee,
2002).
4.3 Hardness
4.3.1 Hardness profile along radial for steel rode subjected to hydrogen
adsorption
Hydrogen absorption characteristics of steel is represented by the variation of

hardness in the cross-section of a 32-mm diameter steel rod (0.30 wt.%C) subjected
to 6-hour hydrogen charging, as shown in Figure 4.3 It is noted that the central
portion of the cross-section is harder (HV = 250) than the exposed surface of the
material (HV = 200).
Figure 4.3 Hardness profile along radial locations of 0.30 wt%C steel rod after 6-
hour hydrogen charging
This is likely due to a faster diffusion rate of hydrogen into the material but
hindered by limited solubility of the hydrogen atoms in the matrix. Excess hydrogen
46
reacts to form molecular hydrogen that increases local pressure in the grain boundary
region leading to increased hardness and brittleness of the material. In a welded joint,
the residual tensile stress induced in the fusion zone could easily results in
microcrack initiation. A gradual increase in hardness towards the center of the rod
reflects a single diffusion mechanism for hydrogen absorption.
This phenomenon was discuss in Section 2.2. Hydrogen diffusion model by
Rajan show that at the outer surface, hydrogen diffusion is influence by
recombination and evolution process. Only after certain distance, fully diffusion
mechanism will occur. If we change the phenomenon from membrane to rod,
hydrogen diffusion will come from all direction. Hence, the maximum concentration
will occur at the center of the material.
4.3.2 Hardness Profile across welded joint
Vickers hardness measurements across the welded joint for as-received and
3-hour hydrogen charged specimens are compared in Figure 3. The HAZ registered
highest hardness number (HV = 136 5) compared with the base metal (HV = 104
5). Scatter of the measured hardness data is primarily due to in-homogeneity of the
microstructure in the welding process zone.
Figure 4.4 Vickers Hardness value distribution in pressure vessel steel non-
hydrogenate and 3 Hours hydrogenate time
47
4.4 Stress and Strain Curve
Tensile test were conduct to gain mechanical properties of the material such
as modulus young, yield strength, tensile strength. These data will be compared to
mechanical properties data from standard for ASTM A 516 grade 70 steel. Beside
that, other data such as elongation before fail and time to fail is also gather to find
deferent properties for each sample.
Table 4.1 Results from Tensile Test

Specimen Yield Tensile Elongation
Strength Strength at failure
(MPa) (MPa) (%)
Nominal Data 260 485
SA grade 70 steel 311 497 11.35
SA grade 70 steel, 3 277 447 9.38
hour hydrogenate
Figure 4.5 Stress and strain diagram for ASTM A 516 steel before and after charging
Table 4.1 and Figure 4.5 show the comparison tensile data for the SA 516
Grade 70 specimen as received and after charging with hydrogen. As we can see, for
both specimen, the yield strength and tensile strength, and elongation before fail was
decrease as compared to non-hydrogenated material. The effect show that a
degradation occur in the specimen.
The effect of hydrogen on the yield strength and Youngs modulus of a
material is not as significant as on the ductility. Furthermore, various researchers
48
have suggested that hydrogen did not affect the yield stress and the young modulus
in low strength steels but gave marked reduction in both their ductilities at room
temperature. Some researcher also found that the yield strength of SEA 1020 steel
charged with hydrogen at 30 mA/cm2 was found to increase, compared to uncharged
steel without change of young modulus(Siddique, 2005).
Decreasing in elongation at failure display decreasing in plasticity for the
sample. This give evident that the material is become more brittle as the charging
process take part.
4.5 Fracture Toughness
The fracture toughness tests were performed on servo-hydraulic testing

system machine, Instron 8801, a software based on ASTM standard E399-90. Aim of
the testing is to get the effect of hydrogen adsorption on base metal and heat affected
zone. While doing the experiment, a problem occur to the specimen label HAZ non-
hydrogenate, hence study had to take data from literature to replace the sample. Refer
to sharma thesis(Sharma S, 1998), average of KIC value for HAZ is 55 MPa m . For
this study, value for HAZ must be above that value as stress intensity value for plane
strain condition is lower that plain stress condition.
Table 4.2 Results from Fracture Toughness Test

Specimen PQ (N) Pmax (N) Pmax/ PQ KQ ( MPa m )
Base Metal 7849.5 16200.3 2.06 38.95
Base Metal- 3 Hr Charge 8481.9 18899.7 2.23 40.62
HAZ- 3 Hr Charge 10687.5 20550.9 1.92 49.86
HAZ- 9 Hr Charge 10450.1 10613.8 1.97 50.05
49
56
FractureToughness (Mpam)
54
52
50
48 HAZ
46
44
42
40
38
36 Base
34
0 2 4 6 8 10 12 14 16
HydrogenChargingTime(Hours)
Figure 4.6 Comparison between KQ value for base metal and HAZ vs hydrogen
charging time
From the data in Table 4.2, Pmax/PQ ratio in all the cases is more than 1.10.
Thus they do not satisfy the plain strain condition, as specified in equation, which
states that critical stress intensity factor(KQ) is a valid plane strain toughness
value(KIC), only when Pmax/PQ<1.10. These values when plotted, essentially
represent figure 3.6, where the specimens fails well beyond PQ, and so, the KQ value
thus grossly underestimates the true toughness of the material. This suggest that
A516 Grade 70 steel used in the present study is quite ductile, as its toughness and
thickness precludes a valid KIC test. Therefore the data in the table and figure cannot
be used to evaluate the fracture toughness of the material and could only be used for
comparison purposed between base metal and double vee welded plate before and
after charging with hydrogen, as it still gives qualitative idea regarding critical stress
intensity factor.
Figure 4.6 show the comparison of KQ values for the crack tip at the base
metal and heat affected zone. For both material, KQ values shows a decreasing
pattern compare to charging time. This pattern show that during the charging
process, hydrogen has diffuse in the material and decrease the fracture toughness of
the material.
The graph also shown that fracture toughness for the crack tip at the heat
affected zone is higher compared to base metal in all case. From literature, it has
shown that acicular ferrite(microstructure for HAZ) is responsible for high
toughness. Acicular ferrite formed intergranular, resulting randomly oriented short
50
ferrite needles with basket-weave like structure. This interlocking nature, together
with its fine grain size, provides the maximum resistance to crack propagation by
cleavage and enhances the yield strength of the metal.
However, literature also show that acicular ferrite, together with martensite,
have worse resistance to hydrogen embrittlement(Banerjee 2002)). This statement
show that, although the haz has better fracture toughness value compare to base
metal, the degradation on haz due to hydrogen embrittlement is also higher. It is
suggested that after several hour of hydrogen charging, fracture toughness for haz
will become lower compare to base metal.
4.6 Fractographs
The Fractured specimen from tensile and fracture toughness testing were
observed in the SEM. Some of the fractographs are shown in Figure 4.7 to 4.10
For tensile sample, we can see clearly that the fracture pattern for as received
sample (Figure 4.7) is fully ductile. This is due to all fracture region is dominate with
equiaxed dimple that will only occur in ductile region.
However, after the material has being charged with hydrogen for 3-hr, we can
see that the fracture pattern has change to a brittle fracture as the fractograph show
Figure 4.7 SEM of fracture surface of tensile specimen for base metal as received
51
Figure 4.8 SEM of fracture surface of tensile specimen for base metal 3 Hr hydrogen
charge
Figure 4.9 compares fracture surfaces in the immediate region ahead of the
fatigue pre-crack tip following crack propagation in HAZ under tensile load for the
as-received (Figure 4.9(a)) and 3-hour hydrogen charged samples (Figure 4.9(b)).
Fatigue pre-crack plane appeared as a smooth surface on the left side of the
fractographs. The tensile fracture region forms a triangular (rough) zone due to
limited constraint to free surface deformation in the thin specimen under plane stress
condition. Fracture surface of HAZ is dominated by intergranular fracture with
localized cleavage facets. Deep secondary cracks between the grains are also
observed. Fracture features are smaller for the hydrogenated HAZ due to finer grain
size than that found in the as-received sample.
52
(a)
(b)
Figure 4.9 Morphology of fracture surfaces of HAZ in the immediate region of the
fatigue pre-crack tip. (a) as-received condition and (b) 3-hour hydrogen charged
sample.
53
CHAPTER FIVE
CONCLUSIONS
The present study was carried out to determine the propagation behaviour of
a fracture crack with effect of hydrogen, in C-Mn pressure vessel steel of the type
A516-drade 70. This steel was welded using submerged arc welding.
Electrochemical method was chosen as a method to hydrogenate the sample. Tensile
test, hardness test, microstructure analysis, fractography analysis was carried out to
the sample.
6.1 Conclusions
Effects of absorbed hydrogen on properties and tensile response of fatigue

pre-crack tip in HAZ of welded A516 Grade 70 steel have been investigated. Results
show that:
The network of equiaxed grain boundary ferrite with colonies of fine-grain

acicular ferrite in the HAZ coalesce to form pearlitic and ferritic regions.
Hardness variation along radial distance in a 0.30 wt.%C steel rod indicates
higher values towards the center of the rod after 6-hour hydrogen charging.
Three-hour hydrogen charging does not produce significant change in hardness
of the welded joint measured on the exposed surface.
From tensile test results, three-hour hydrogen charging give significant effect to
the plastic zone phase.
54
The rate of decrease in toughness due to the presence of hydrogen is faster in the
HAZ compared to that in the base metal.
Fracture surface of HAZ is dominated by transgranular fracture with localized
cleavage facets.
In this study, fracture toughness in this study is not the exact fracture
toughness(KIC) for the material, as some of the criteria for plane strain fracture
toughness is not fulfil. Hence the exact KIC value for the material supposed to be
higher than the results indicate in this study.
6.2 Suggestions for Future Work
Some Suggestion for future work are:
Since the present material ASTM A516 Grade 70 exhibits significant ductility,
and nonlinear material behaviour becomes significant, fracture toughness testing
of the specimens with the same dimensions as used in this study should be done,
using cract tip opening displacement (CTOD) or the J integral. These tests
discard stress intensity and adopt crack tip parameter that takes material behavior
into account. It would be interesting to explain the fracture crack behavior in
term of fracture toughness value.
In this study, hydrogen adsorption is indicate by the charging time. It would be
interesting to explain the effect of hydrogen adsorption in term of part per million
(ppm), as this indicator is used in real life
This study incorporated fracture tests. Similar tests using fatigue tests should be
designed, to see the crack behavior, when a cyclic fatigue crack approaches the
interface at different orientations, from different points in weldment.
56
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59
APPENDIX
Appendix A1
Appendix A2
60
Appendix B1
Appendix B2
61
Appendix C1
Load vs CTOD curve for base metal

18000
16000
Load (N)
14000
12000
10000
8000
6000
4000
2000
0
0 0.5 1 1.5 2 2.5 3
CTOD (mm)
Appendix C2
Load vs CTOD for base metal (3Hr hydrogen charging)
20000
18000
16000
Load (N)
14000
12000
10000
8000
6000
4000
2000
0
0 0.5 1 1.5 2 2.5 3
CTOD (mm)
62
Appendix C3
Load vs CTOD curve for base metal (9 Hr Hydrogen Charging)

18000
16000
14000
12000
Load (N)
10000
8000
6000
4000
2000
0
0 0.5 1 1.5 2 2.5
CTOD (mm)
Appendix C4
Load vs CTOD curve for base metal (16 hr hydrogen charging)

16000
14000
12000
Load (N)
10000
8000
6000
4000
2000
0
0 0.5 1 1.5 2 2.5 3
CTOD (mm)
63
Appendix C5
Load vs CTOD curve for HAZ

25000
Load (N) 20000
15000
10000
5000
0
0 0.5 1 1.5 2 2.5 3
CTOD (mm)
Appendix C6
Load vs CTOD curve for HAZ (3 Hr hydrogen charging)

25000
20000
Load (N)
15000
10000
5000
0
0 0.5 1 1.5 2 2.5 3
CTOD (mm)
64
Appendix C7
Load vs CTOD curve for HAZ (9Hr Hydrogen Charging)

25000
Load (N) 20000
15000
10000
5000
0
0 0.5 1 1.5 2 2.5 3
CTOD (mm)
65
Effects of Absorbed Hydrogen on Crack-tip Ductility

in the Welded A516 Steel
1
M.A. Khattak, 2M.H. Maslan and 3M.N. Tamin
1,3
Faculty of Mechanical Engineering
Universiti Teknologi Malaysia
81310 UTM Skudai, Johor
3
e-mail: taminmn@fkm.utm.my
2
Faculty of Manufacturing Engineering
Universiti Teknikal Malaysia Melaka
75450 UTeM Ayer Keroh, Melaka
Abstract Effects of absorbed hydrogen on the steel [3]. Failures of pressure vessels and pressure
structure and properties of welded A516 Grade-70 piping related accidents are often fatal and involved
steel are investigated. Emphasis is placed on ductility loss of capital investment [eg. 1-2].
measure of the crack-tip plastic zone under Mode I
loading. Specimens are cathodically charged in a cell Previous research has identified possible mechanisms
with dilute sulphuric acid and corrosion inhibitor of hydrogen reaction embrittlement in steels, namely
with uniform charging current density of 20 mA/cm2 hydrogen blistering, internal embrittlement and
and at different exposure time. Results indicate a environmental embrittlement. The presence of internal
change from coarse- to fine-grained microstructures hydrogen produces a plastic loss in austenitic stainless
in the weld region and heat affected zone (HAZ) of steel [4]. At high temperature and pressure, this
hydrogen-charged specimen. Well-defined ferrite- internal hydrogen facilitates de-carburization,
pearlite bands in the base metal are transformed into promotes intergranular cracking and forms blistering
coarse-grain structure. Hardness variation along in steels [5]. The pressure of molecular hydrogen
radial distance indicates higher values towards the causes the formation of brittle cracks in hydrogenated
center of the bar, possibly due to faster diffusion rate low carbon steel [6]. Constant extension-rate test on
but limited solubility of hydrogen. Load-COD Type 216 steel samples pre-exposed to concentrated
responses indicate that slow, stable crack propagation synthetic ground water at 80-150 oC showed evidence
occurred in both base metal and HAZ. The measured of environmental (hydrogen)-assisted cracking and
provisional fracture toughness, KQ is higher for HAZ moisture-induced ductility loss [7]. The susceptibility
than that for the base metal. The toughness values of steels with different heat treatment to hydrogen
decreases significantly for the initial three hours of embrittlement was evaluated in terms of mechanical
hydrogen charging. The tensile fracture region in the properties [8]. While tensile strength, yield and
immediate fatigue pre-crack tip forms a triangular hardness increase with increasing hydrogenation time
(rough) zone due to limited constraint to free surface up to five hours, significant reduction in ductility was
deformation in the thin specimen. Fracture surface of measured.
HAZ is dominated by intergranular fracture with
localized cleavage facets. In a welded joint, the application of immense heat to
fuse the base plate and weld metal (electrode) for a
1. Introduction strong permanent joint resulted in a heterogeneous
heat affected zone (HAZ). This zone is a common
Chemical reactor vessels and pipelines are commonly source for defects such as hard inclusions, blisters by
constructed using welded steels and stainless steel trapped gas and microcracks that developed during
liners. In oil refineries and chemical plants these steel fast cooling of the welded joint. Exposure to absorbed
vessels operate in corrosive environments where high hydrogen can cause deleterious effects including the
concentration of hydrogen sulphide is present. The formation and propagation of brittle cracks. In
operating temperature typically ranges from -29 to controlled laboratory experiment hydrogen can be
427 C. Prolonged exposure of the steel to these introduced in the specimen by gaseous hydrogen
conditions could lead to deleterious effects such as charging in an oxygen-free copper chamber with
embrittlement, loss of toughness and creep rupture of tantalum hydride at temperature in excess of 700 oC
[9]. Others use high-pressure (20-35 MPa) hydrogen
65
66
autoclave at 350 oC [10]. In the electrochemical fracture toughness of the material, thus provisional
method the metal specimen is soaked in dilute solution fracture toughness values, KQ were reported. Hardness
of sulphuric acid with a corrosion inhibitor. A measurements across the fusion zone of the welded
controlled current is supplied to the cathodically- joint were made using Vickers hardness tester with
charged sample in the cell. The concentration of 10-kg indentation load. Microstructure study was
absorbed hydrogen is quantified in part-per-millon performed on optical micrographs while scanning
(ppm) or represented by hydrogen charging time electron microscope (SEM) was employed in
duration. fractographic analysis.
The objective of this study is to establish effects of Hydrogen charging of the polished CT specimens was
absorbed hydrogen on microstructure and properties of carried out in an electrolytic cell with a stainless steel
welded A516 Grade 70 steel. Emphasis is placed on rod as anode and the A516 steel as cathode. The
ductility measure of the crack-tip plastic zone under specimen was mounted in the cell filled with dilute
Mode I loading. sulphuric acid solution (0.5M H2SO4 solution)
containing 1.97 gm of arsenic trioxide (As2O3) as
corrosion inhibitor. A constant current density of 20
2. Materials and Experimental Procedures mA/cm2 was maintained for all the specimens. After
hydrogen charging to preset time duration, the
The material employed in this study is an ASTM specimens were removed from the cell and rinsed with
A516-Grade 70 steel. The 16-mm thick pre-fabricated distilled water.
plates were butt welded to produce the curvature of a
cylindrical vessel wall. The welded joint was produced
by multiple-pass submerged arc welding (SAW) 3. Results and Discussion
process to ANSI/AWS specifications. Post weld heat
treatment (PWHT) was carried out at 620 oC. The Effects of absorbed hydrogen in steel and welded steel
different regions of the welded zone, namely weld joint are presented and discussed in terms of
metal, heat affected zone (HAZ) and the base metal microsructural changes, measured hardness and
are illustrated in Figure 1(a). The chemical toughness values and crack growth behavior under
composition of the base plate is shown in Table 1. tensile load.
Tensile and yield strength of welded samples in the as-
received condition is 480 and 360 MPa, respectively. 3.1 Microstructures
Table 1. Microstructures of the various phases of the welded
Chemical composition of A516 Grade 70 steel (wt. %) A516 steel in the as-received condition are shown in
C Mn Si Cr Cu Mo S P Figure 1(b). The base metal displays an aggregate of
0.263 1.12 0.46 0.02 1.41 0.01 0.01 0.004 well-defined ferrite-pearlite bands. The HAZ is
characterized by a network of equiaxed grain
Si Ni V Fe
boundary ferrite with colonies of fine-grain acicular
0.015 0.02 0.005 Bal. ferrite while the weld metal consists of coarse-
grained Widmanstatten ferrite microstructure.
Microstructures of similar welded joint after a 3-hour
Compact tension (CT) specimens were fabricated hydrogen charging is compared in Figure 1(c). The
using wire cutting process to minimize local heating. base metal is transformed into a coarse-grained
A sharp notch is machined to facilitate fatigue pre- ferrite-pearlite structure. The HAZ showed
cracking in the HAZ. Surface porosity and coalescence of pearlitic and ferritic regions. Fine-
irregularities were removed by fine grinding. Fracture grained Widmanstatten structure of the weld metal is
toughness test was conducted according to ASTM noted.
E399 procedures. The 10-mm thickness of the CT
specimens is insufficient for establishing plane strain
66
67
Figure 2. It is noted that the central portion of the

cross-section is harder (HV = 250) than the exposed
surface of the material (HV = 200). This is likely due
to a faster diffusion rate of hydrogen into the material
but hindered by limited solubility of the hydrogen
atoms in the matrix. Excess hydrogen reacts to form
molecular hydrogen that increases local pressure in
the grain boundary region leading to increased
(a) hardness and brittleness of the material. In a welded
joint, the residual tensile stress induced in the fusion
zone could easily results in microcrack initiation. A
gradual increase in hardness towards the center of the
rod reflects a single diffusion mechanism for
hydrogen absorption.
BM HAZ WM
(b)
Figure 2. Hardness profile along radial locations of

0.30 wt.%C steel rod after 6-hour hydrogen charging.
Vickers hardness measurements across the welded

joint for as-received and 3-hour hydrogen charged
specimens are compared in Figure 3. The HAZ
registered highest hardness number (HV = 136 5)
compared with the base metal (HV = 104 5). Scatter
of the measured hardness data is primarily due to in-
homogeneity of the microstructure in the welding
process zone.
BM HAZ WM
(c)
Figure 1. (a) Cross-section of the fusion zone of the

welded joint, (b) Microstructures of base metal (BM),
HAZ and weld region (WM) of as-received sample
and (c) microstructures for a 3-hour hydrogen
charged sample. Mag. 10X.
3.2 Hardness Measurements

Hydrogen absorption characteristics of steel is
represented by the variation of hardness in the cross- Figure 3. Hardness profile across the fusion zone of
section of a 32-mm diameter steel rod (0.30 wt.%C) welded A516 steel for as-received and 3-hour
subjected to 6-hour hydrogen charging, as shown in hydrogen charged sample.
67
68
It is noted that the 3-hour hydrogen charging does not Fatigue pre-crack plane appeared as a smooth surface
produce significant change in hardness of the welded on the left side of the fractographs. The tensile
joint measured on the exposed surface. It is believed fracture region forms a triangular (rough) zone due to
that exposure of the welded joint to longer hydrogen limited constraint to free surface deformation in the
charging time will cause an observable increase in thin specimen under plane stress condition. Fracture
hardness. Such effects of increased hardness in surface of HAZ is dominated by intergranular
different heat-treated 0.31 wt. %C steels were fracture with localized cleavage facets. Deep
reported for hydrogen charging beyond 3-hour period secondary cracks between the grains are also
[8]. observed. Fracture features are smaller for the
hydrogenated HAZ due to finer grain size than that
3.3 Tensile Crack Growth Behavior found in the as-received sample.
The effect of absorbed hydrogen on fracture

toughness of the HAZ is presented in Figure 4.
Results show that the apparent fracture toughness (in
plane stress condition) for HAZ is higher than that for
the base metal. Since hardness of both phases is
similar (see Figure 3), the difference in measured
toughness is likely due to significant difference in
microstructures of HAZ compared with the base
metal. Absorbed hydrogen decreases the toughness of
the materials with prolonged exposure time. It is
worth noting that the rate of decrease in toughness
due to the presence of hydrogen is faster in the HAZ
for the first 3-hour of charging, as reflected in the
steep (negative) slope of the curve. The continuous
decrease in toughness with prolonged exposure to
hydrogen favors crack propagation leading to
premature failure of the material.
(a)
Figure 4. Variation of fracture toughness (KQ) of

HAZ and base metal with different hydrogen
charging time.
(b)
Figure 5 compares fracture surfaces in the immediate Figure 5. Morphology of fracture surfaces of HAZ in
region ahead of the fatigue pre-crack tip following the immediate region of the fatigue pre-crack tip.
crack propagation in HAZ under tensile load for the (a) as-received condition and (b) 3-hour hydrogen
as-received (Figure 5(a)) and 3-hour hydrogen charged sample.
charged samples (Figure 5(b)).
68
69
4. Conclusions [6] Izotov VI, Pozdnyakov VA, Filippov GA.

Effect of the initial structure on the fracture
Effects of absorbed hydrogen on properties and of a hydrogenated low carbon steel.
tensile response of fatigue pre-crack tip in HAZ of Metallovedenie 2002;93(6):1017.
welded A516 Grade 70 steel have been investigated. [7] Tae A. Corrosion of low carbon cast steel in
Results show that: concentrated synthetic ground water at 80
150 OC. Waste Manage 1995;15(7):4716.
The network of equiaxed grain boundary ferrite [8] R.A.Siddiqui, Hussein A.Abdullah, Hydrogen
with colonies of fine-grain acicular ferrite in the embrittlement in 0.31% carbon steel used for
HAZ coalesce to form pearlitic and ferritic petro-chemical applications, Journal of
regions. Material Processing Technology 170 (2005)
Hardness variation along radial distance in a 0.30 430-435
wt.%C steel rod indicates higher values towards [9] R. Garber, I.M. Bernstein, A.W. Thompson,
the center of the rod after 6-hour hydrogen Effect of hydrogen on ductile fracture of
charging. spheroidized steel, Scripta Met. V10 (1976)
241244.
Three-hour hydrogen charging does not produce
[10] R. Garber,M. Bernsten, Conference on
significant change in hardness of the welded
Environmental Degradation of Engineering
joint measured on the exposed surface.
Materials, Blacksburg, Virginia, 1997.
The rate of decrease in toughness due to the
presence of hydrogen is faster in the HAZ
compared to that in the base metal.
Fracture surface of HAZ is dominated by
transgranular fracture with localized cleavage
facets.
Acknowledgement
This project is supported by the Ministry of Science,
Technology and Innovation (MOSTI), Government of
Malaysia through e-Science Fund Project No. 79058.
References
[1] N.V.Challenger, R.Phaal and S.J.Garwood

(1995). Fracture mechanics assessment of
industrial pressure vessel failures
[2] J. Spence, D.H. Nash, Milestones in pressure
vessel technology, International Journal of
Pressure Vessels and Piping 81 (2004) 89118
[3] Tesman, A.B, Materials of construction for
process plants - I, Chemical engineering, 19-
02-1973. Reproduced by courtesy of Japan
steel works.
[4] Y. Tan, D.H. Zhou, J. Feng, Influence of
internal hydrogen on the hydrogen
embrittlement of austenitic stainless steel, Acta
Metall. Sin., Ser. A Phys. Metall. Mater. Sci.
10 (June) (1997) 228232
[5] H. Hagi, Hydrogen embrittlement of mild steel
cathodically charged with hydrogen (effect of
dissolved hydrogen and hydrogen damage on
elongation of mild steel), Trans. Jpn. Soc.
Mech. Eng., Part A 60 (576) (1994) 1729
1733.
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EFFECTS OF ABSORBED HYDROGEN ON FRACTURE

MOHAMAD HAIDIR BIN MASLAN

A project report submitted in partial fulfillment of the

Faculty of Mechanical Engineering

Effects of absorbed hydrogen on structure and properties of welded A516 Grade-70

CHAPTER TITLE PAGE

2.2 Hydrogen Damage 7

4 RESULTS AND DISCUSSION 43

4.4 Stress and Strain Curve 47

TABLE NO. TITLE PAGE

2.1 ASTM specification for pressure vessel quality steel plate 7

FIGURE NO. TITLE PAGE

2.1 Process of hydrogen evolution and adsorbtion 13

3.8 Shape and dimension For Rectangular Tension Test Specimens 38

YS Yield strength (MPa)

KIC Plane strain fracture Toughness (MPa m )

KQ Critical stress intensity factor (MPa m )

SAW Submerged arc welding

APPENDIX TITLE PAGE

A1 Project Schedule (Gantt Chart) for semester 1 59

Today business sector economics compel industrial units to attain ever-higher

1.3 Research Problem And Hypothesis

1.3.1 Statement of Research Problem

1.3.2 Research Questions

3. What type of hydrogen concentration sequence that should be applied to

Physical-based damage parameters for the HAZ include the different

1.4 Research Objectives

1.5 Research Scope

Scope of this research is:

1.6 Significance of Study

Specification Steel type and Condition

2.2 Hydrogen Damage

Hydrogen damage refers to the degradation of physical and mechanical

Hydrogen can be retained in steels and other metals internally as a result of

2.2.1 Types of Hydrogen Damage

Hydrogen damage has been classified into several terminologies base on

2.2.1.1 Hydrogen Embrittlement

Hydrogen embrittlement can be describe as a process resulting as materials

Table 2.2 Description mode of fracture and types of materials(Chatterjee, 2001)

2.2.1.2 Hydrogen Attack

The first report on hydrogen attack of steels appeared in 1933. Inspection

These reactions reduce the content of carbon, a strengthening constituent, in

2.2.1.3 Hydrogen Induced Blistering

Hydrogen induced blistering is more common in low strength steels, and it is

2.2.1.4 Shatter Cracks, Flakes and Fish Eyes

2.2.2 Hydrogen Diffusion Mechanism

Hydrogen has an atomic radius of 0.25-0.54 which compared with the

Figure 2.1 Process of hydrogen evolution and adsorbtion

Hydrogen rich recombination

Figure 2.2 Hydrogen discharge process in metal membrane and hydrogen

This theory is support by hydrogen concentration in pressure vessel diagram

Figure 2.3 Hydrogen concentration in pressure vessel steel(Askari, 2004)

2.2.2.1 Experimental Hydrogen Adsorption method

Gaseous hydrogen charge is a traditional approach to introduce hydrogen into

Figure 2.4 Autoclave set up (Manna, G., 2007)

II. Electrochemical Method

Electrochemical method introduced hydrogen into the specimens by cathodic

Reference Platinum (anode)

Figure 2.5 Electrochemical hydrogen diffusion set-up(Rumaih, 2004)

Figure 2.6 High temperature electrochemical hydrogen diffusion set up

2.2.3 Hydrogen Effect on Steel Properties

was found to increase, compared to uncharged steel without change of young

This section of the research considers prediction of thermal effects, and