Engineering Fracture Mechanics 131 (2014) 485503

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Engineering Fracture Mechanics

journal homepage: www.elsevier.com/locate/engfracmech

Effects of wet H2S containing environment on mechanical

properties of NACE grade CMn steel pipeline girth welds
Tse-Ven Steven Chong a,b,, Shashi Bhushan Kumar b, Man On Lai a, Wai Lam Loh a
a
b

Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117576, Singapore
Det Norske Veritas Pte. Ltd., 16 Science Park Drive, Singapore 118227, Singapore

a r t i c l e

i n f o

Article history:
Received 13 April 2014
Received in revised form 1 August 2014
Accepted 6 September 2014
Available online 16 September 2014
Keywords:
Sour service
Girth weld steel pipes
Hydrogen sulphide
Sulphide stress cracking
Hydrogen embrittlement

a b s t r a c t
Tensile and fracture specimens (pre-charged with H2S) were tested in solution using
customised rigs. When comparing with uncharged specimens, the tensile test results
showed signicant reduction in ductility for base and weld metal. The fracture resistance
test results showed similar reduction of 0.3 times in base and weld metals and heat
affected zone. There was noticeable increase in yield and tensile strength in both base
and weld metals, due to the effect of hydrogen. When using partially coated specimens,
higher fracture resistance was obtained, with reduction of 0.4 times only. This was
mainly contributed by crack tip hydrogen and less so by the bulk hydrogen.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
Subsea pipelines are designed and installed to transport oil and gas in large quantities continuously for offshore eld production. The pipeline which is typically S-layed or J-layed, is fabricated on-board a lay barge by joining several linepipes of
about 12.2-metre length using girth weld conguration. During production welding, it is inevitable that circumferentially
oriented weld imperfections such as lack of fusion and incomplete penetration, etc. may occur in the girth welds. These pipelines are designed to safety considering the static and dynamic stresses and strains anticipated during laying (for example,
sag-bend, over-bend) and in-service including environmental effect, if any (i.e. sour well uids, etc.).
To assess the structural integrity of girth welds in the pipeline, Engineering Critical Assessment (ECA) is commonly performed considering mechanical properties, loading conditions and imperfection size using fracture mechanics principles.
In ECA, a series of fracture mechanics analyses is performed in accordance with the procedures stipulated in codes such as
DNV-OS-F101 [1], BS 7910:2005 [2] and DNV-RP-F108 [3], to establish alternative aw acceptance criteria for non-destructive
testing (NDT) inspection of the eld production girth welds on-board the lay barge.
Often the aw acceptance criteria (acceptance standard) for the pipeline girth weld defects are dened based on
mechanical property data and design parameters using fracture mechanics principles to meet adequate structural integrity
in the weld [4,5]. The mechanical properties of the base (parent) metal (BM), the weld metal (WM) and the heat affected zone
(HAZ) are required as part of the input parameters in conducting an ECA. Such data are derived from an established database
or tested to the specic environments representing the actual or more conservative situations than the pipeline will experience during installation and operation. The main mechanical properties required as input to the ECA are: tensile properties,
Corresponding author at: Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117576, Singapore.
E-mail address: steven.chong@dnvgl.com (T.-V.S Chong).
http://dx.doi.org/10.1016/j.engfracmech.2014.09.005
0013-7944/ 2014 Elsevier Ltd. All rights reserved.

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Nomenclature
A
a
ao
AWTS
B
BM
BMTS
CMOD
ECA
El
Ff
FL
FPZ
H
HAZ
Jtot
Je
Jp
K
Lf
Li
RF
SEM
SENT
Up
W
WM
b

gp
ry
rT
(W-ao)

coefcient of power law t equation

height for surface crack
initial height for surface crack
all-weld tensile specimen
width of the specimen
base metal
base metal tensile specimen
crack mouth opening displacement
Engineering Critical Assessment
elongation
nal load recorder as per load versus CMOD curve
fusion line
fracture process zone
Daylight between the grips of SENT specimen
heat affected zone
sum of elastic and plastic part of the J-integral
elastic part of the J-integral
plastic part of the J-integral
stress intensity factor
gauge length after fracture
initial gauge length
reduction factor
scanning electron microscope
single edge notch tensile
the plastic part of the area under the load versus CMOD curve
wall thickness of the pipeline
weld metal
exponent of power law t equation
dimensionless function of the geometry
yield strength
ultimate tensile strength
the remaining ligament length

stress strain curves, fracture toughness/resistance, fatigue crack growth rate (FCGR) parameters of all relevant material zones
(viz., BM, WM and HAZ). The design parameters required for an ECA include the: peak strain/stress, fatigue histogram, welding
residual stresses, geometrical stress concentration factors and safety factor associated with the zone of operation.
The growing demand of oil and gas resources has inevitably led the industries to explore and produce such resources from
deeper and more complex reservoirs. Field developments with such wells pose a variety of technical challenges as these
complex deepwater wells are also typically associated with sour environments. NACE MR0175/ISO 15156 [6] denes a sour
environment as one that contains sufcient H2S to cause cracking of materials by hydrogen induced cracking mechanisms.
Oil and gas elds can contain signicant amounts of H2S and pipeline steels exposed to a sour environment can be susceptible to a number of different cracking mechanisms. For example, hydrogen induced cracking (HIC) sometimes termed as
hydrogen pressure induced cracking (HPIC), stress oriented hydrogen induced cracking (SOHIC) and sulphide stress cracking
(SSC) [6,7] (Fig. 1). The resultant uid often containing H2S will place a signicant demand on the pipeline mechanical properties such as ductility, fracture resistance and fatigue crack growth rate. The severity of such an environment depends on
the metallurgical characteristics of the materials, well uid composition and operating conditions.
In order to develop such challenging offshore oil and gas elds, new design concepts and materials are required to be
developed and used. When designing and developing pipeline systems to transport highly corrosive oil/gas, NACE grade
CMn linepipe is selected and welded offshore using over-matching welding consumable wires. Recent research using conventional CMn steel material has shown that mechanical properties like fatigue performance degrades in the presence of
H2S containing environment [8,9]. Although NACE grade CMn steels exhibit resistance to SSC, it is expected that properties
like tensile strength and fracture resistance will still be affected to some extent as a result of the high concentration of hydrogen present at the fracture process zone (FPZ). Subsequently, this leads to embrittlement. Fig. 2 provides a schematic illustration of the generation of hydrogen from the metal dissolution and hydrogen sulphide dissociation and Section 3.2
discusses the micro-mechanisms of hydrogen diffusion in detail.
The works performed by various authors [1016] suggest that the effect of hydrogen generated from various methods (i.e.
dry gas charging, electrochemical charging or metal dissolution) play an important role in inuencing the mechanical
properties. However, there has been limited studies performed which give a holistic assessment of the effects of hydrogen

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487

Sulphide stress
cracking

Fig. 1. Macrograph of a non-NACE grade welded coupon failed as a result of severe sulphide stress cracking after being strained in hydrogen sulphide
solution. Such alloys are non-cracking resistant and are susceptible to SSC. Source: DNV GL Materials Technology and Structural Integrity Laboratories,
Singapore.

Fig. 2. Schematic diagram of the hydrogen sulphide dissociation and atomic hydrogen generation process.

embrittlement on the tensile and fracture toughness/resistance of pipeline weldments exposed to wet H2S environment
before and during testing. Furthermore, there has been little work performed to evaluate the effects of using coated versus
un-coated test specimen on the fracture resistance for the related weldments. A coated specimen here refers to specimens
coated with ceramic epoxy on all sides except the top face and the notch. This paper attempts to document experimental techniques to quantify the changes in mechanical properties when welded test coupons are tested in wet hydrogen charged environments. The paper also discusses the role of hydrogen on the fracture morphology of the test specimens used in this study.
2. Experimental procedures
This section describes the design of the test rigs, test materials, specimen preparation methods, testing procedures, data
processing and experimental observation made during the current investigation. Test coupons were prepared and tested
with reference to NACE, ASTM and DNV standards.
2.1. Material
NACE compliant 45.72 mm (18 inch) OD  14.3 mm WT DNV SMLS (seamless) 450 SFD grade linepipe girth welded with
Lincoln MD-SG2 (AWS Class: ER 70S-6/Spec No.: A5.18) were used in the current research. The linepipes were manufactured
by a plug mill seamless pipe fabrication process and the pipe sections were later joined by pulse gas metal arc welding
(p-GMAW) process in 5G downhill position. The chemical composition requirements of the pipe material (i.e. base metal)
and welding consumable are shown in Table 1a and b. A macro-section of the weld prole is shown in Fig. 3 to illustrate
the important features of the girth weld. The different microstructures present in a welded connection such as the base
metal, weld metal and HAZ (also referred as fusion line i.e. FL) were investigated.

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Table 1
Chemical composition requirements (by maximum weight%) of: (a) NACE grade pipeline steel (DNV SMLS 450 SFD, in compliance with DNV-OS-F101
specications). (b) Lincoln weld ller metal (in compliance with AWS ER70S-6 specications).
(a)
Element
Wt%
Element
Wt%

C
0.16
V
0.09

Si
0.45
Nb
0.05

Mn
1.65
Ti
0.06

P
0.02
Other
Notes

S
0.003

(b)
Element
Wt%
Element
Wt%

C
0.060.15
Ni
0.15

Mn
1.41.85
Cr
0.15

Si
0.81.15
Mo
0.15

P
0.025
V
0.03

S
0.035
Cu
0.50

Notes: The sum of niobium, vanadium and titanium contents shall be 60.015%. Cu 6 0.5%, Ni 6 0.5%, Cr 6 0.45%, Mo 6 0.35%, B 6 0.0005%.

Weld cap
Base Metal

Heat Affected Zone (HAZ)

Weld root

Fig. 3. Macrograph of girth weld prole using J-prep bevel and p-GMAW process.

2.2. Tensile test

The tensile tests were carried out in both an air environment and NACE Solution A (i.e. sour service environment). In the
latter case, the specimens were pre-charged and tested in a special purpose Perspex test cell containing H2S solution (NACE
Solution A). Round bar specimen was used to generate the tensile properties and the tensile stressstrain curves of the base
and weld metal.
2.2.1. Design of test rig
The test rig was designed and fabricated based on the research works performed by Yang et al. [17] on single edged notch
tension (SENT) specimens and with reference to NACE TM0177-2005 [18]. The objective of the test cell, which made up the
rig, was to isolate the specimen in the intended test environment during the charging and testing phases. Test xtures with
internal screw threads were used to hold the specimen and to increase the gripping area. It also allowed the specimen to be
encapsulated within the test cell and submerged in the test solution. The xtures extended outside the test cell while the
design provided for sufcient freedom in the vertical extension during the test, yet with sufcient sealing capacity to prevent
leakage of the hazardous gas.
Considerations were made for the measurement of the elastic strain since the conventional extensometer could not be
used when the specimens were submerged in the solution during the test. Hence, the design accommodated for two (2)
water-proof strain gauges, installed on the reduced section of the specimen for the purpose of recording the stressstrain
data in the elastic regime.
2.2.2. Preparation and testing
Round bar specimens were machined from two locations: at the base metal and at the girth weld. The parent (base) metal
tensile specimen was extracted in the axial direction of the pipe while the weld metal tensile specimen was extracted from
the circumferential direction with reference to Appendix B of DNV-OS-F101. The testing was performed in accordance with
ASTM A370-13 [19]. Fig. 4 illustrates the locations where the tensile specimens were extracted.
For the tests conducted in NACE Solution A, the test solution consisted of 5 wt% NaCl and 0.5 wt% CH3COOH in distilled
water with a pH of approximately 2.7, which was thoroughly deaerated with high purity nitrogen prior to the introduction of
99.5% (min) purity H2S at 1 bar. The specimens were pre-charged in the simulated sour service environment for 168 h (7-day

T.-V.S Chong et al. / Engineering Fracture Mechanics 131 (2014) 485503

BMTS

489

AWTS

Fig. 4. Extraction plan for the tensile tests (BMTS base metal tensile, AWTS all weld tensile).

duration) at ambient temperature of 24 C + 3 C and at atmospheric pressure prior to actual testing. The schematic sketch of
the test apparatus and setup for the pre-charging phase is illustrated in Fig. 5.
Upon completion of pre-charging, the test cell was isolated by closing off all external valves and the test rig was transferred to a 25 ton Instron universal test machine. For pipeline in operation condition that is governed by displacement controlled loading, the displacement rate in mm/s in more relevant. Henceforth, both the tensile and fracture tests used similar
displacement rate of 0.02 mm/min (3.3  104 mm/s) which is also within the range specied in ASTM G129-00 [20] for
standard slow strain rate tests involving environmentally assisted cracking. The tests were conducted at ambient temperature of 24 C + 3 C using displacement/position control mode. During the rising load test, the test specimens were kept
immersed in the NACE Solution A with H2S at 1 bar.
The details of test specimens and setup are illustrated in Fig. 6. After the completion of the tests, the test solution was
extracted and analysed to conrm that the pH and hydrogen sulphide concentration were maintained within range of
2.62.8 and 23003500 ppm respectively as per NACE Solution A test requirements.
For the tests conducted in an air environment, the specimens were directly mounted onto the grips of the machine. An
extensometer was attached to the reduced section to record the strain data at the elastic regime. The loading rate was maintained between 3 mm/min and 6 mm/min in displacement/position control mode. The test matrix for the tensile tests is
summarised in Table 2.
2.3. Fracture resistance test
The fracture resistance tests were carried out in an air environment and in NACE Solution A. In the latter case, the specimens were pre-charged and tested in a customised Perspex test cell containing H2S solution, with reference to the design
proposed by Yang et al. [17] but with some modications. SENT geometry specimens were employed to generate the J Rcurves for the base, weld metal and HAZ. DNV-OS-F101/Appendix A, allows SENT testing at operation environments since
SENT specimen is designed to give a crack tip constraint close to that of the pipe with a aw. Furthermore, weld related
imperfections are controlled by the weld pass height which is relatively small in the typical range of 26 mm. Therefore
as per DNV-RP-F108, a SENT specimen with notch depth of a/W = 0.20.5 is considered to have a realistic crack depth. Here,
a represents the notch depth after fatigue pre-crack and W represents the wall thickness. If the cracks have realistic crack
depths, not only the crack tip elds in the pipe and specimen are similar, but also the deformation in the whole remaining
ligament is more accurately replicated. Moreover as the SENT specimen has been widely accepted for pipeline girth weld
fracture resistance tests, it was chosen to be used in the present investigation.
2.3.1. Preparation and testing
The specimens were machined from the steel pipes in the LR orientation according to ASTM E1823-13 [22], with the
notch running from the inner surface of the pipe coupon. The notches were machined at the base metal, weld metal centre

Fig. 5. Schematic sketch of test apparatus and setup for the pre-charging phase.

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(a)

Test fixtures

Strain gauge
cables

Tensile specimen

(b)

Pre-charging
circuitry

Test cell

4-way valve

Tensile specimen

(c)

Strain gauge
cables

Tensile specimen

Machine

Fig. 6. Tensile test specimens and setup. (a) Specimens fastened to test xtures and with water proof strain gauge installed. (b) Pre-charging circuitry for
test cells in series. (c) Sour service tensile test setup, with dual strain gauges and gas cabinet.

line and HAZ with an a/W ratio between 0.2 to 0.3 after fatigue pre-cracking. The specimen cross section was kept as B  2B
with a daylight between the grips of 10B (where B is the wall thickness of the pipe coupon), as recommended in DNV-OSF101.
The reference study was performed on specimens which were not coated to simulate the case of hydrogen ingress by bulk
charging. To further study the effects of bulk charging versus crack tip hydrogen charging, some of the specimens were sandblasted and subsequently coated with Belzona ceramic epoxy on all sides except the top face and the notch. This additional
study simulates one-sided diffusion to ensure that metal dissolution and hydrogen generation occurs only on the top face
and crack tip, which will also lead to ingress of hydrogen. This will be more representative in the case of uid owing inside
a pipeline.

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491

Table 2
Test matrix for the tensile tests.
Material

No. of specimens

Test environment

Base metal
Weld metal

3
3

Environment: air
Temperature: 24 C 3 C

Base metal

Weld metal

Solution: NACE TM0177 solution A

Gas: 99.5% min purity H2S at 1 bara
pH: 2.62.8
H2S concentration: 23003500 ppm
Temperature: 24 C 3 C

For the tests conducted in NACE Solution A, the pre-cracked SENT specimens were subsequently preloaded in the test rig
to longitudinal axial stresses of about 300 micro-strain (corresponding to typical pipeline operating pressures) to open the
crack mouth for exposure to the test solution. The specimens were subsequently pre-charged, similar to the procedures and
environmental set up as documented in Section 2.2.2 for the tensile tests.
Upon completion of pre-charging process, the tests were conducted at ambient temperature of 24 C + 3 C using displacement/position control mode with a slow displacement rate of 104 mm/s in accordance to ASTM G129-00 [20] and
research works performed by Yuan et al. [21]. During the rising load test, the specimens were immersed in the NACE Solution
A with H2S at 1 bar. For the tests conducted in an air environment, the loading rate was maintained at 0.25 mm/min in displacement/position control mode.
The J R-curves were established by power law t as per DNV-OS-F101/Appendix A, in which multiple specimen approach
(i.e. six specimens) was used. The rst specimen in the test series was tested to a crack mouth opening displacement (CMOD)
value of about 120% of the CMOD value corresponding to maximum load. The 2nd, 3rd, 4th, 5th and 6th specimens for the
series were tested to CMOD values of 100%, 100%, 80%, 60% and 40%, respectively, of the CMOD value corresponding to maximum load from the rst test.
The data were subsequently calibrated to compute for the J integral according to the formulation in DNV-RP-F108. The J
R-curves were calculated from the elastic and plastic component according to Eqs. (1)(4). Subsequently, a power law relation as per Eq. (5) was used to t the J-Da data sets. Eq. (2) was used to derive the J coordinate and Da coordinate was derived
from physical measurements of the fractured specimens.

J tot J el J pl

J tot

gp U p
K 2 1  t2

E
BW  ao

q
 pa 
 

 p a 3

0:752 2:02 Wa 0:37 1  sin 2W

2 tan 2W
p
K
p
a
B W cos2W


 a 5 
 a 4 
 a 3
B
B
B
196:719eW  64:642
493:511eW 138:837
463:503eW  106:207
W
W
W

 a 2 
 a  

B
B
B
W
W
W
34:532
39:413e
 4:525
1:039
2:064e
4
201:862e
W
W

gp 0:85 

J ADab

Here, Je is the elastic part of the J-integral, Jp is the plastic part of the J-integral, gp is the dimensionless function of the geometry, Up is the plastic part of the area under the load versus CMOD curve, K is the elastic stress intensity factor, F is the force at
termination of the test, A is the coefcient of power law t equation and b is the exponent of power law t equation.
After the completion of the tests in the air and sour environment, each specimen was broken to measure the fatigue crack
front and the ductile crack extension Da for computation of J as per DNV-RP-F108. Fractography analysis was also performed
to study the effects of hydrogen ingress on the microstructure. For the tests performed in a sour environment, the test solution was extracted and measured to ensure that the pH and hydrogen sulphide concentration were maintained at pH 2.62.8
and 23003500 ppm respectively as per NACE test requirements. Fig. 7 provides illustrations of the SENT specimen and Fig. 8
gives an overview of the test specimen geometry and setup.
A total of eight (8) sets of tests were performed: with three (3) sets performed at notch location at the base metal, weld
metal and HAZ in an air environment and the other three (3) sets conducted in a sour environment made up of NACE Solution
A at 24 C. Another two (2) sets with coating were performed at notch location at the weld metal and HAZ in a sour environment. The test matrix for the fracture resistance tests is summarised in Table 3.

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Fig. 7. The clamped SENT (Single Edge Notched Tension) specimen geometry. Relationship between aw orientation and height in the pipe and the crack
orientation and size in the specimen.

3. Results and discussion

3.1. Effects of H2S exposure

3.1.1. Tensile properties

The tensile stress strain curves (engineering) and test results for the NACE grade CMn pipeline girth welds are summarised in Figs. 9 and 10 and Table 4. It was observed that the weld metal is overmatching the base metal in terms of yield
strength and tensile strength when tested in an air and in a sour environment. There was no noticeable change in the Youngs
modulus for both base and weld materials in both environments. This was consistent as modulus should not change as a
result of H-embrittlement or any forms of strengthening; it changes as a result of temperature changes and microstructural
change.
The ductility parameter, elongation, is reported as follows:

El

DL L f  L i

L
Li

Here, El is the elongation, Li is the initial gauge length and Lf is the gauge length after fracture. The percentage changes in the
tensile properties i.e. yield strength, tensile strength and elongation when the material was tested in a sour environment
versus an air environment, are calculated as follows:

DEl%
Dry %

Elsour  Elair
Elair
ry;sour  ry;air

ry;air
rT;sour  rT;air
DrT %
rT;air

7
8
9

Here, ry is the yield strength and rT is the ultimate tensile strength. When comparing the results due to the effects of a sour
environment with that of an air environment, both the base metal and the weld metal coupons demonstrated a loss in ductility as a result of hydrogen embrittlement. The embrittlement was most likely caused by atomic hydrogen that has diffused
into the metal lattice through the grain boundaries. The base metal exhibited less reduction in elongation to fracture of 35%
when compared to the weld metal of 51% (calculated with the air environment as the base case). Thus, when exposed to H2S
pre-charging the weld metal was more susceptible to the effects of hydrogen embrittlement and retained less of its initial

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(a)

493

Pre-load frame

SENT specimen

Test cell

(b)

Epoxy coating

SENT specimen

(c)

SENT specimen
Clip gauge

H2S detector
Gas containment
chamber

Fig. 8. Fracture test specimens and setup. (a) Pre-charging of SENT specimen for duration of 7 days. (b) Epoxy coating applied on all sides except notch side
to simulate one-sided diffusion. (c) SENT test setup in a sour environment with data logger and gas cabinet with exhaust venting.

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Table 3
Test matrix for the fracture resistance tests.
Conditions

Material

No. of specimens

Test environment

Air at 24 C

Base metal
Weld metal
HAZ/FL

6
6
6

Environment: air
Temperature: 24 C 3 C

Sour at 24 C w/o coating

Base metal
Weld metal
HAZ/FL

6
6
6

Sour at 24 C with coating

Weld metal
HAZ/FL

6
6

Solution: NACE TM0177 Solution A

Gas: 99.5% min purity H2S at 1 bara
pH: 2.62.8
H2S concentration: 23003500 ppm
Temperature: 24 C 3 C

Fig. 9. Base metal engineering stress strain curves (test environment: in air and in sour).

Fig. 10. Weld metal engineering stress strain curves (test environment: in air and in sour).

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Table 4
Summary of tensile properties (mean of 3 tests) for NACE grade CMn pipeline tested in air and in sour environments.
Material

Test environment

Youngs modulus (GPa)

Yield strength Rp0.2% (MPa)

Tensile strength Rm (MPa)

Elongation (%)

Base Metal

Air
Sour

207
207

464
477

530
554

21.4
13.9

Weld Metal

Air
Sour

207
207

584
658

648
732

16.8
8.2

ductility when compared to the base metal. This was likely attributed to the difference in homogeneity of microstructure
arising from the welding process and the composition of the welding consumable.
Both the base metal and the weld metal exhibited an increase in strength as a result of a sour environment. The base
metal showed slight increase in yield strength (2.7%) and tensile strength (4.5%) when the material was tested in a sour environment. However, the weld metal showed a more signicant increase in yield strength (12.7%) and tensile strength (12.9%),
suggesting that the material is more sensitive to a sour service environment. The percentage changes in tensile properties
(yield strength, tensile strength, Youngs Modulus and elongation to fracture) of specimens tested in sour service environment with respect to the specimens tested in an air environment is summarised in Table 5. Fig. 11a and b further illustrate
the linear relationship between the tensile properties of the base metal and weld metal with the environment.
The fracture surfaces were examined using a scanning electron microscope (SEM). Fractographs of the specimens tested
in an air environment showed fracture characteristic of microvoid coalescence or dimple fracture. It was observed that some
of the small equiaxed dimples nucleate at the inclusions of the metal (Fig. 12a and b). The fractogaphs of specimens tested in
a sour environment showed mix-mode fracture: localised areas of dimpled fracture surrounding relatively at small facets,
which is characteristic of quasi-cleavage (Fig. 12c and d). The presence of such brittle features was likely due to hydrogen
ingress resulting in embrittlement. The fractographs of the weld metal tested in a sour environment showed reduced plasticity as evidenced by a greater degree of cleavage facets when compared to that of the base metal. This was likely due to the
welding process in which brittle microstructures known as local brittle zones were formed resulting in reduced ductility.
The most evident trend presented by the stress strain curves and the fractographs was the mode of fracture for specimens
tested in an air and in a sour environment. Specimens tested in an air environment experienced large elongations to fracture
indicating that the material underwent a large plastic deformation before fracture which was representative of ductile failure of modern pipeline steel materials. However, when the material was tested in a sour environment, it fractured at a much
lower strain with a smaller degree of plastic deformation. Moreover, the H2S charged specimens displayed a slightly higher
strength when compared to non-charged specimens. These observations are consistent with the works by Zaleski [23] and
Wu and Kim [24] on testing hydrogen charged steels in dry environment.
3.1.2. Fracture resistance properties
3.1.2.1. Bulk charging. The fracture resistance J R-curves and test results for the uncoated SENT specimens machined from
NACE grade CMn pipeline girth welds are summarised in Fig. 13 and 14 and Table 6. The reduction factor was calculated
by normalising the coefcient, A, of the power law t Eq. (3) in a sour environment to the value in an air environment. The
reduction factor is dened as:

RF

Asour
Aair

10

Here, RF is the reduction factor and A is the coefcient of power law t equation. It was observed that the weld metal exhibited the lowest fracture resistance followed by the HAZ and the base metal when tested in an air or in a sour environment.
Comparing the results due to the effects of a sour environment with those of an air environment, all the specimens with
notch location at the base metal, HAZ and weld metal demonstrated a reduction in fracture resistance. The slope of the J
R-curves for all 3 materials had a reduction factor of about 0.280.33 times when pre-charged in a sour environment. This
indicates that fracture resistance in a sour environment is controlled by concentration of hydrogen.
It was also observed that the weld metal generally had higher tearing lengths (Da) at each load level followed by the HAZ
and base metal when tested in an air and in sour environment. Furthermore the results showed an increase in tearing length
(Da) associated with each load level by about 1.53 times for the base metal, HAZ and weld metal when tested in a sour
environment, which also contributed to the reduction in the slope of the J R-curve. Thus when exposed to H2S pre-charging

Table 5
Summary of percentage change in tensile properties for NACE grade CMn pipeline tested in air and in sour environments.
Material

Youngs modulus (%)

Yield strength Rp0.2% (%)

Tensile strength Rm (%)

Elongation (%)

Base metal
Weld metal

No signicant change

2.7
12.7

4.5
12.9

35
51

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Fig. 11. Linear relationship between the tensile properties of the base metal and weld metal with the environment, based on mean tting. (a) Yield strength
and tensile strength. (b) Elongation.

the base metal, HAZ and weld metal were more susceptible to the effects of hydrogen charging resulting in reduced tearing
resistance.
As per Section 2.3.1, the J R-curves were derived from the load versus CMOD curves for 6 specimens loaded to different
clip gauge opening displacements. When tested in a sour environment, the curves demonstrated a reduction in clip gauge
opening displacement associated with each load level for the base metal, HAZ and weld metal. Some representative graphs
for the base metal have been illustrated in Figs. 15 and 16. This was likely a result of the effects of hydrogen embrittlement
and reduced plasticity, consistent with the results from the tensile stress strain curves as per Section 3.1.1.
Upon completion of the tests, the SENT specimens were broken apart following soaking in liquid nitrogen. Representative
macro-section examination of the fracture surface of the SENT specimens tested in a sour environment is shown in Fig. 17ac.
Fish eyes were most evident in the fracture surface of the weld metal specimen, which demonstrated that the material had
been saturated with hydrogen and that the fracture process involved hydrogen diffusion. For comparison, the fracture surface
of a SENT specimen tested in an air environment is shown in Fig. 17df. The fracture surface was relatively smooth with no sh
eyes present.
The fracture surfaces were further examined using SEM. The fractographs of SENT specimens tested in a sour environment exhibited predominantly quasi-cleavage features, which was more pronounced at the crack initiation area (Figs. 18a
and b). Dimples were also observed intermittently further away from the initiation site. The overall observation from the
fractographic study indicated that fracture propagation has been dominated by a semi-ductile tearing. This was more evident for the weld metal and could be attributed to its inhomogeneous microstructure. This also revealed that the material

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497

Fig. 12. Representative SEM fractographs of tensile specimens taken at the centre of the fracture surface. (a) in air base metal, (b) in air weld tensile metal,
(c) in sour base metal and (d) in sour weld metal.

Fig. 13. J R-curves determined for in an air environment of base metal, weld metal and HAZ/FL at 24 C.

was susceptible to hydrogen induced fracture requiring low stress/strain. The crack propagation and cracking mechanism
were not characterised as active sulphide stress corrosion cracking since the material has been qualied as per NACE requirements. SEM fractographs of the SENT specimens subjected to an air environment revealed mainly ductile tearing with small
elongated dimples (Fig. 18c).
3.1.2.2. Single sided charging. In hydrogen enhanced cracking, hydrogen may enter the metal through corrosion reactions
occurring on the metal surface exposed to a sour environment (referred to as bulk-charged hydrogen). Another source of diffusible hydrogen may arise during crack extension in which the fresh exposed metal at the crack tip is under plastic deformation. This localised region reacts with the corrosive environment and therefore generates hydrogen (referred to as crack
tip hydrogen). Both these two sources of diffusible hydrogen can potentially impact the fracture resistance of the pipeline
steel.

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Fig. 14. J R-curves determined for in a sour environment of base metal, weld metal and HAZ/FL at 24 C.

Table 6
Summary of J R-curve fracture resistance data for NACE grade CMn pipeline tested in air and in sour environments.
Material

In air environment

In sour environment

Reduction factor

Base metal
Weld metal
HAZ/FL

970Da0.9
720Da0.76
885Da0.75

320Da0.85
237Da0.9
246Da0.9

0.33
0.33
0.28

Fig. 15. F versus V-curves determined for in an air environment of base metal at 24 C.

The role of bulk charging versus crack tip hydrogen has been investigated with a set of SENT specimens (with notch location at the HAZ and weld metal) coated on all sides except the top face and around the crack tip. The fracture resistance J Rcurves and test results for the coated SENT specimens are summarised in Fig. 19.

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Fig. 16. F versus V-curves determined for in asour environment of base metal at 24 C.

Fish eyes

(a)

(b)

(c)

(d)

(e)

(f)

Fig. 17. Representative macro-fracture surface of (a) WM, (b) HAZ/FL, (c) BM specimens tested in a sour environment and (d) WM, (e) HAZ/FL, (f) BM
specimens tested in an air environment. The regions of (A) rising load, (B) fatigue pre-crack and (C) EDM notch are also indicated in (d). Fish eyes are most
evident on the fracture surfaces of the weld metal specimen tested in a sour environment.

There was a consistent reduction in fracture resistance due to the effects of the H2S charged environment. It was further
observed that the reduction factor reduced from 0.28 to 0.33 times for non-coated specimens to 0.330.37 times for coated
specimens. While the fracture resistance was reduced in both the coated and uncoated specimens when tested in hydrogen
charged environment, the amount of reduction differed by about 16%.
It is generally accepted that fracture resistance of steels in a sour environment involves a hydrogen enhanced mechanism.
The present study demonstrated that for the case of SENT specimens tested in hydrogen charged environment, bulk charging
of hydrogen plays an important role in stable crack tearing resistance as with crack tip hydrogen generation.
3.2. Micro mechanisms of fracture behaviour
For the material system in the present study, the failure behaviours of the CMn pipeline steels and related weldments
are primarily governed by the process of hydrogen diffusion. Atomic hydrogen (H0) is produced as a natural byproduct of the
metal dissolution process at local cathodic sites and is readily adsorbed by the metal surface. Substantial levels of hydrogen
are adsorbed on the surface through such electrochemical processes. The kinetics of recombination can be signicantly
retarded in the presence of poisons that consist of sulphur species resulting from H2S (i.e. dissolved H2S, HS and S2) [25].

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Fig. 18. Representative SEM fractograph of weld metal specimens tested in (a) sour environment taken at the crack initiation zone, located at region X. (b)
Sour environment taken further from the crack initiation zone, located at region Y. (c) Air environment, taken at region Z.

Anode :Fe ! Fe2 2e

Cathode :H2 S H2 O ! H HS H2 O
HS H2 O ! H S2 H2 O
Fe H2 S H2 O ! FeS 2H0 H2 O
This leads to increased absorption of atomic hydrogen within interstitial sites in a metallic crystal as well as at grain
boundaries. The solubility of hydrogen is especially high in regions in which the lattice expands as a result of high degree
of stress triaxiality. This is particularly so for the fracture process zone near the crack tip in which hydrogen will be

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501

Fig. 19. J R-curves of coated specimens tested in a sour environment of weld metal and HAZ/FL at 24 C.

Fig. 20. Schematic illustration of the crack tip processes involved in the hydrogen induced fracture mechanism.

concentrated. The high local concentration of hydrogen causes the process zone to be embrittled [26]. Fig. 20 illustrates the
abovementioned crack-tip chemistry. The atomistic mechanisms for hydrogen embrittlement have been reviewed extensively and the three major theories proposed are: hydride-induced embrittlement, hydrogen enhanced localised plasticity
(HELP) and hydrogen enhanced decohesion (HEDE) [27].
The increase in yield strength was likely associated with the diffusion of hydrogen atoms into the metal interstitial sites,
pinning down any dislocations, and hence an additional stress is required to free the dislocations causing an increase in yield
strength and ultimate tensile strength. However the decrease in elongation to fracture is most likely due to embrittlement.
Hydrogen diffusion is a time dependent process and the crack extension occurs via diffusion of hydrogen through a critical distance associated with the fracture process zone [28,29]. The presence of absorbed hydrogen in the region of material
directly ahead of a crack tip is known to have an adverse effect on the properties of common pipeline steels. It was observed
from the SEM fractographs as per Sections 3.1.1 and 3.1.2.1, that quasi-cleavage features were more pronounced at the crack
initiation area and this was consistent with the higher concentration of absorbed hydrogen ahead of the crack tip during the

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pre-charging stage. Dimples were observed intermittently further away from the initiation site as a result of the reduced
concentration of hydrogen within the metal matrix.
The sh eyes in the SENT specimens were likely to be induced by the crack tip strain and the molecular hydrogen accumulated at inclusions. The atomic hydrogen that had diffused to the HAZ or weld metal had recombined at the discontinuity
sites, e.g. interstitials or small inclusion cavities, to form molecular hydrogen. The applied pressure by the hydrogen gas created location deformations, forming a blister or sheyes. This may have resulted in a further reduction in fracture resistance
after the hydrogen exposure [30].
3.3. Relevance of the research ndings for engineering critical assessments
Fracture limit states are required to be evaluated for the girth welds in pipelines in order to avoid failure during the
installation and operation phases by determining the criticality of the possible weld aws. Unstable fracture, plastic collapse,
tearing and fatigue crack growth assessments are assessed under both static and dynamic (fatigue) loading. The aw acceptance criteria for the pipeline girth weld defects are dened based on mechanical properties and design parameters using
fracture and fatigue assessments procedures as detailed in DNV-OS-F101. It has been shown from this study that the
mechanical properties of the pipeline girth welds are sensitive to the environmentally induced embrittlement and degrade
due to effects of hydrogen ingress. In such situation, when performing the ECA, the mechanical properties i.e. tensile, fracture
resistance and fatigue properties shall be representative of the actual environment [1].
It is imperative to use an appropriate test methodology to obtain an estimate of tensile stress strain properties as well as
toughness, to generate the relevant material input parameters for the fracture mechanics-based structural integrity assessments. This may not be straightforward approach as hydrogen embrittlement is itself affected by the materials microstructure, the specimen geometry, the amount of bulk hydrogen and the concentration of the test solution. In this study, NACE
Solution A with pH 2.7 was selected with reference to NACE TM0177-2005 which provides guidance for sulphide stress
cracking test of metals exposed to oileld environments containing H2S. This is a standard test solution and the pH value
is on the conservative side as a result of the built in safety margin. Engineering projects involving sour service pipelines typically lie in the range of pH 34. It is therefore recommended that test solution be formulated in accordance with the specic
uid composition, taking into consideration the presence of inhibitors, the H2S and CO2 ppm and pH of the solution.
The data established from this study may be used to bridge with the existing material database performed by other
authors in the same eld. This will serve the purpose of establishing a reference database for use in the desk-top or actual
ECAs based on numerical and analytical methods. The material database will be essential in evaluating the fracture capacity
of NACE grade CMn pipelines operating in a sour service environment.
4. Conclusions
The current research documents the effects of wet H2S containing environment on the tensile and fracture properties of
NACE grade CMn pipeline girth welds. Tensile and fracture test specimens (pre-charged with H2S) were tested in solution
using customised test rigs. The following conclusions are drawn:
 The tensile test results demonstrated different degrees of reduction in ductility i.e. 35% in BM and 50% in WM as compared to a non-sour environment.
 Similarly, the fracture resistance test results of the BM, WM and HAZ showed reduction of 0.3.
 However, there was noticeable increase in the yield strength i.e. 3% in BM, 13% in WM and the tensile strength i.e. 5%
in BM and 13% in WM.
 When using specimens coated with ceramic epoxy on all sides except the top face and the notch, higher fracture
resistance J R-curves were obtained, with reduction in the fracture resistance by about 0.4 times and this was mainly
contributed by crack tip hydrogen and less so by the bulk hydrogen. It is recommended to use coated specimens during
testing as it is more representative in the case of uid owing inside a pipeline
 Fractographs of the tensile specimens tested in an air environment showed fracture characteristic of microvoid coalescence or dimple fracture. The fractogaphs of specimens tested in a sour environment showed mainly quasi-cleavage
features. The presence of such brittle features was likely due to hydrogen ingress resulting in embrittlement.
 Macro-section examination of the fracture surface of the SENT specimens tested in a sour environment contained sh
eyes, which demonstrated that the material had been saturated with hydrogen and that the fracture process involved
hydrogen diffusion. The fracture surface of specimens tested in an air was relatively smooth with no sh eyes present.
 The fractographs of SENT specimens tested in a sour environment exhibited predominantly quasi-cleavage features,
which was more pronounced at the crack initiation area.
 The data established from this study will serve the purpose of establishing a reference database for use in the desk-top or
actual ECAs based on numerical and analytical methods.
 It is recommended to formulate the test solution in accordance with the specic uid composition, taking into consideration the presence of inhibitors, the H2S and CO2 ppm and pH of the solution.

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503

Acknowledgement
The authors acknowledge the Economic Development Board (EDB) of Singapore and Det Norske Veritas Pte. Ltd. (DNV) for
the nancial support in pursuing this research via National University of Singapore (NUS) project number R265000440.
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