Hydrogen effect on fracture toughness of pipeline steel welds,

with in situ hydrogen charging

E.V. Chatzidouros*, V.J. Papazoglou, T.E. Tsiourva, D.I. Pantelis
Shipbuilding Technology Laboratory, School of Naval Architecture and Marine Engineering, National Technical University of Athens, Greece
a r t i c l e i n f o
Article history:
Received 13 April 2011
Received in revised form
20 June 2011
Accepted 29 June 2011
Available online 30 July 2011
Keywords:
Hydrogen embrittlement
Pipeline steel
Fracture toughness
Microstructure
Welds
Hydrogen charging
a b s t r a c t
The API 5L X70 and X52 pipeline steel weld fracture toughness parameters are measured in
a hydrogen environment and compared to the ones in air. The hydrogen environment is
created by in situ hydrogen charging, using as an electrolyte a simulated soil solution, with
three current densities, namely 1, 5 and 10 mA/cm
2
. A specially designed electrolytic cell
mounted onto a three-point bending arrangement is used and hydrogen charging is per-
formed during the monotonic loading of the specimens. Ductility is measured in terms of
the J
0
integral. In all cases a slight change in toughness was measured in terms of K
Q
.
Reduction of ductility in the base metal is observed, which increases with increasing
current density. A more complex phenomenon is observed in the heat affected zone metal,
where a small reduction in ductility is observed for the two current densities (1 and 5 mA/
cm
2
) and a larger reduction for the third case (10 mA/cm
2
). Regarding microstructure of
tested X70 and X52 base and HAZ metal, it is observed that the hydrogen degradation effect
is enhanced in banded ferriteepearlite formations. The aforementioned procedure is used
for calculating the fracture toughness parameters of a through-thickness pipeline crack.
Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.
1. Introduction
Hydrogen is envisioned to be used as an energy carrier for
future energy needs. The European energy roadmap dictates
the use of many energy sources (renewable, nuclear, petro-
leum, natural gas, etc.), where the need to have one form of
energy for easy distribution among civilian and industrial
sectors is evident. Hydrogen is a promising prospect and
research has been intensied during the last decade in order
to deal with various issues regarding hydrogen utilization
(production, distribution, storage, etc.). Distribution is one of
the key issues regarding hydrogen energy and the natural gas
pipeline infrastructure is envisioned to be used for hydrogen
delivery.
The natural gas pipeline infrastructure is a key ingredient
in the European energy distribution map. A possible
introduction of a hydrogen economy in Europe in the coming
years would be greatly beneted by the utilization of the
existing pipeline infrastructure. The main obstacle for the
hydrogen delivery through the natural gas pipelines is the
effect that hydrogen has on steel. Hydrogen entry into steels
may lead to degradation of its mechanical properties. Addi-
tionally, the susceptibility of pipeline steels to hydrogen is
a key issue in existing pipelines, even without the introduc-
tion of hydrogen. Cathodic protection of pipelines or/and
transporting sour gas may lead to hydrogenating
environments.
The effect of hydrogen in metals is commonly known as
hydrogen embrittlement (HE). HE has been studied during the
past seventy years, but no unique, generally accepted theory
for its full explanation has been identied. Many researchers
have proposed alternative mechanisms regarding hydrogen
* Corresponding author. Tel.: 30 21 07724027; fax: 30 21 07721412.
E-mail address: elchat08@central.ntua.gr (E.V. Chatzidouros).
Avai l abl e at www. sci encedi r ect . com
j our nal homepage: www. el sevi er . com/ l ocat e/ he
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 6 ( 2 0 1 1 ) 1 2 6 2 6 e1 2 6 4 3
0360-3199/$ e see front matter Copyright 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2011.06.140
effect on metals, but four mechanisms are the most widely
accepted ones for explaining the phenomenon. These HE
mechanisms are the hydrogen pressure theory (HP) [1],
hydrogen induced weakness of the metallic lattice or
hydrogeninduced decohesion(HID) [2,3], internal stresses and
toughness decrease due to stress induced formation of
hydrides [4e8], and hydrogen enhanced local plasticity (HELP)
[9e11].
The Hydrogen Pressure (HP) theory dictates that atomic
hydrogen accumulates inside the steel lattice, in reversible
(natural interstitial lattice sites) or irreversible traps (voids,
dislocations, grain boundaries, etc.) and recombines to form
molecular hydrogen. The recombined molecular hydrogen
results in high pressure that may reduce the stress required to
propagate voids.
The mechanism of hydride formation relates to group Vb
metals [5], Ti [7] and Zr. The HELP mechanism is based on
observations that, in a range of temperatures and strain rates,
the presence of hydrogen in solid solution decreases the
barriers to dislocation motion, thereby increasing the amount
of deformation that occurs in a localized region adjacent to
the fracture surface. The fracture process is a highly localized
plastic failure process rather than an embrittlement. There-
fore the HELP fracture process limits the macroscopic ductility
by the onset of extensive localized plasticity and is supported
by microscopic observations. A complement to the HELP
mechanism is the theory of enhanced hydrogen transport by
moving dislocations [12]. The fourth viable mechanism is the
hydrogen-related decohesion mechanism (HID), in which the
atomic bonding at the crack tip is weakened by the presence of
hydrogen in solid solution. HID has also been applied to
particle-matrix or ferrite-second phase decohesion in the
presence of hydrogen in the metal lattice [13]. In the case of
steel the most promising candidates for explaining HE are the
latter two mechanisms, namely HELP and HID.
Hydrogen degradation of pipeline steels has been investi-
gated by many researchers. Various electrolytic solutions
were used ranging from soil [14,15] to NaHCO
3
solution [16,17]
and sulphuric acid [18e21], employing various current densi-
ties or potentials. The majority of studies use cylindrical and
notched specimens [14,16e19] and measure the average
reduction of area in a hydrogenenvironment, while others use
at bar dogbone specimens [15] and thin plate specimens
[21]. On a pipeline, in most cases, failure initiates at a crack
defect which forms either by cathodic protection or corrosion.
Several studies have focused experimentally on the effect of
hydrogen on a crack in pipeline steel [20,22e27] and speci-
cally in [20] the fracture toughness properties of single edge
notch specimens in various current densities were examined.
In the present work, the main goal is to study the effect of
a hydrogen environment acting on a stress concentrator,
namely a crack, located on the base metal and the heat
affected zone (HAZ). Welds are often defect incubators in
pipelines. This can be attributed to the formation of defects
during the welding process or during operation due to the
strength mismatch of base metal and weld. In this paper
hydrogen effect on existing cracks in pipeline welds is thor-
oughly studied and the fracture toughness parameters of the
HAZ with those of the base metal are compared, but also the
microstructural aspects and fracture morphology of hydrogen
effect on pipeline steel is explored. To that end, fracture
toughness three-point bending tests of API 5L X70 and X52
pipeline steel specimens, taken from the HAZ along with the
base metal, are fatigue pre-cracked following the ISO 12135
standard [28] and tested in air and in a hydrogen environment
simulated by electrolytically charging the specimens. The
apparent differences in fracture toughness of the two metals
are then correlated to the apparent different microstructures
and fracture morphologies.
Furthermore the developed testing procedure can be
readily implemented to measure fracture toughness proper-
ties in a hydrogenenvironment of any given metallic material,
following commonly used standards like ISO 12315.
2. Experimental procedure
2.1. Material
The materials used for the testing are API 5L X70 and X52
steels that were cut from a buried in-service pipeline as
illustrated in Fig. 1. The X70 pipeline with dimensions 710 mm
diameter and 13.2 mm wall thickness, was in service for
approximately 8 years till it was cut for testing, while the X52
pipeline with dimensions 610 mm diameter and 10.5 mm wall
thickness, was in service for approximately forty years till it
Fig. 1 e Pipeline and base and HAZ metal specimens, including geometry and testing arrangement.
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 6 ( 2 0 1 1 ) 1 2 6 2 6 e1 2 6 4 3 12627
was cut for testing. The tests were carried out on the base
metal and on the heat affected zone of the longitudinal seam
weld of the pipeline.
The X70 base metal possesses a banded ferritic and mixed
bainiticepearlitic microstructure (Fig. 2), with elongated
grains due to the forming process and indications of partial
recrystallization, with average hardness 212 HV
0.3
. Further-
more the ferrite presented a hardness of 185 5 HV
0.01
, while
the mixed bainiteepearlite in bands presented a hardness of
270 5 HV
0.01
. The X70 heat affected zone metal (HAZ) had an
average hardness of 209 HV
0.3
, with 174 10 HV
0.01
hardness
of ferrite grains and 235 10 HV
0.01
hardness of mixed bai-
niteepearliteeferrite in bands and a banded ferritic, mixed
bainiticepearliticeferritic microstructure, where the pearlite
bands have been partially transformed to ferrite (Fig. 2).
The X52 base metal possesses a banded ferriticepearlitic
microstructure, as illustrated in Fig. 3 and presented a hard-
ness of 185 HV
0.3
. Furthermore the ferrite presented a hard-
ness of 154 5 HV
0.01
, while the pearlite in bands presented
a hardness of 245 5 HV
0.01
. The X52 heat affected zone metal
(HAZ) had an average hardness of 173 HV
0.3
, with
160 10 HV
0.01
hardness of ferrite grains and 212 10 HV
0.01
hardness of pearlite grains and a non banded ferriticepearlitic
microstructure, with various sized grains (Fig. 3).
All specimens were nital etched prior to microstructural
characterization. Hardness was measured using an SHI-
MADZU HMV-2E microhardness tester.
The Scanning Electron Microscope used was a JEOL JSN
6390. The chemical composition of the steel was obtained
through spectrometric analysis following the ASTM E415-99a
[29] standard, while the mechanical properties were derived
following the ASTM E8 [30] standard and are given in Tables 1
and 2, respectively.
2.2. Three-point bend test
The tests conducted were three-point bending fracture
toughness tests following the ISO 12135 standard. The goal
was to simulate a surface defect propagating to a localized
through-thickness hole. In this manner the fracture charac-
teristics of a crack emanating from a defect located on the
outer surface of the pipeline wall, were studied. The specimen
(Fig. 1), with characteristic dimensions presented in Table 3,
had a pre-machined notch on the outer surface of angle 45

,
notch depth a
n
2 mm and a
n
2.5 mm for the X52 and X70
steel respectively and notch root radius of 0.15 mm. All
specimens were fatigue pre-cracked according to the proce-
dures described in ISO 12135.
The alignment of the bands in relation to the crack plane
and the crack propagation direction can be observed in Fig. 4,
which is a representation of a base metal specimen cut at the
fatigue pre-crack plane, illustrating the alignment of the
bands and the vector of hydrogen entry.
The machine used was a 250 kN MTS hydraulic testing
machine. The displacement rate of the tests was 0.01 mm/
min. Kyowa 5 mm crack gages were used to measure the
fatigue pre-crack. A crack gage is essentially a 45 grid circuit
that is glued on the side of the specimen ahead of the notch.
As the crack propagates ahead of the notch, the crack gage is
ripped and changes its electrical resistance, which in turn is
Fig. 2 e SEM micrographs of X70 base a), b) and HAZ c), d) metal at two magnications.
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 6 ( 2 0 1 1 ) 1 2 6 2 6 e1 2 6 4 3 12628
measured. The crack faces after the testing were examined in
a Leica MZ6 stereoscope to measure the fatigue pre-crack
length.
The introduction of hydrogen into the steel was accom-
plished by hydrogen charging the specimen in an electrolytic
solution, where the specimen was used as the cathode (see
Section 2.3). The base and HAZ metal specimens were tested in
air andina hydrogenenvironment simulatedby appliedcurrent
densities in the NS4 electrolytic solution (Table 4). For the
hydrogen environment the applied current densities were 1, 5
and10mA/cm
2
. For eachsteel, atotal of 12basemetal specimens
were tested, 3 for each case (air and the three applied current
densities); 12 respective HAZ specimens were also tested.
2.3. In situ hydrogen charging
Hydrogen can be introduced in steel specimens either by
electrolytically charging the specimen or by gaseous hydrogen
in a closed chamber under pressure. In the rst case the steel
specimen is used as the cathode where hydrogen enters the
crystal lattice through electrolysis. Hydrogen charging can be
accomplished before or during the testing of the specimen.
Hydrogen pre-charging, followed by testing of the specimen in
air, hints at the possibility of hydrogen escaping the metal and
results might be erroneous. API X70 and X52 have a bcc
structure and, as pointed out in [14], bcc metals have large
interstitial lattice sites so hydrogen that resides there escapes
quickly. It is stated in [14] that for an X70 steel, after 10 h 65%
of the hydrogen has escaped from the steel after hydrogen
pre-charging. Furthermore Fang et al. used cylindrical speci-
mens with total area exposed to hydrogen uptake and diffu-
sion of approximately 123 mm
2
. The X52 specimens have
exposed area of 130 mm
2
and for the X70 specimens the
exposed area of approximately 156 mm
2
. These values are
close and can give a qualitative correlation to the tests
reported in this work In the scenario of an in-service pipeline
which transfers hydrogen or a mixture of methane with
hydrogen, or a pipeline with cathodic protection, the pipeline
steel is constantly bombarded by hydrogen under a given
pressure or current. Therefore, it is critical to simulate the
constant hydrogen interaction with the pipeline steel.
Furthermore, hydrogen entry is enhanced in defected regions
such us crack tips, where the population of dislocations and
general lattice defects is larger than in the bulk of the metal. In
the case of an in-service pipeline containing a defect the
interaction of hydrogen with this defect is constant, so it is
crucial to charge the specimen while it is being deformed.
In the present work in situ hydrogen charging was used
(Fig. 5). The developed procedure benets fromusing standard
three-point bending tests, which are commonly used to
Fig. 3 e SEM micrographs of X52 base a), b) and HAZ c), d) metal at two magnications.
Table 1 e Chemical composition of the tested steels (wt.%).
C Si Mn P S Cr Ni Mo Al Cu Nb N
X70 0.116 0.26 1.67 0.012 <0.01 0.05 0.04 0.02 0.03 0.04 0.03 0.009
X52 0.205 0.29 1.29 0.013 0.011 0.02 0.02 0.01 0.03 0.01 0.03 0.006
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 6 ( 2 0 1 1 ) 1 2 6 2 6 e1 2 6 4 3 12629
calculate fracture toughness properties of metallic materials,
to measure fracture toughness in a hydrogen environment. In
this manner commonly used standards such as ISO 12135 can
be implemented, to measure fracture toughness properties of
steel specimens from large diameter pipelines, in air and in
a hydrogen environment.
Regarding the hydrogen environment, the specimen was
continuously charged with hydrogen, during the three-point
bending fracture toughness tests. This was accomplished by
mounting an electrolytic cell made of PVC on the three-point
bending xtures and using acetal casings (Table 5) for
encompassing the bending xtures along with high strength
Alumina ceramic rollers (Table 6). The whole arrangement
used high strength non-conductive materials in order to
exclude extra deformations owing to the xtures, and to
eliminate stray currents. Additionally, the cell was sealed in
order to make it watertight using polyurethane.
The composition of the electrolytic solution was NS4 (Table
4), which simulates the electrolyte trapped between coating
and the pipe steel. The electrolytic solutions pH was kept at
6.7e7 and was purged with 5% CO
2
and balanced with N
2
gas.
Accordingly the pHof the solutionwas continuously monitored
throughout the experiment in order to maintain it within the
desired values. The area around the notch and the crack was
polished using a 600 grade emery paper, cleaned with distilled
water and acetone and dried. The whole specimen was coated,
excluding the notch and pre-crack, by polyurethane in order to
promote hydrogen entry only in the defect area. During the
electrolysis the specimen was used as the cathode and a plat-
inum electrode was utilized as an anode.
Previous works have indicated that pipeline steels exhibit
large degradation of mechanical properties till applied current
density (c.d.) of 10 mA/cm
2
, and small above that c.d. value.
Specically Hardie et al. [18] after studying X60, X80 and X100
cylindrical steel specimens, reached to the conclusionthat after
cathodic charging with various current densities ranging from3
to 66 mA/cm
2
the degree of embrittlement tended to increase
with increasing current density, reaching a maximum around
10 mA/cm
2
. The variations above 10 mA/cm
2
are negligible
regarding steel X60. For steels X80 and X100 results indicate that
there is noadditional deleterious hydrogeneffect for appliedc.d.
of 11e44 mA/cm
2
. Another work that focused on fracture
toughness of X70 single edge notch steel specimens under
dynamic hydrogen charging conditions [20], clearly states that
for current densities between 1 and 10 mA/cm
2
the reduction of
the fracture toughness parameter K
Q
is fast and slow above
applied current density of 10 mA/cm
2
. In light of the afore-
mentioned studies it was chosen to test the steels in three
current densities, namely 1, 5 and 10 mA/cm
2
where hydrogen
degradation effects on pipeline steels increase fast with
increasing current density. Moreover current density is moni-
tored and controlled throughout the experiment, in order to
keep it constant.
Before the tests depicted inthis work, several pre-tests were
conducted regarding hydrogen pre-charging durations.
Hydrogen pre-charging tests with 1 mA/cm
2
applied current
density were conducted, for durations of 24, 7, 4 h and no pre-
charging. The results indicated that there is no difference on
hydrogen effect on fracture toughness parameters of studied
steels for 24, 7 and 4 h hydrogenpre-charging, realizing that 4 h
is sufcient time for establishing a steady hydrogen concen-
tration in the crack tip. In contrast higher J integral values were
observed for the case of no hydrogen pre-charging, in
comparisonto 24, 7 and 4 h pre-charging. Thus in every test the
specimens were pre-charged for 4 h prior to the application of
the monotonic loading, in order to establish a steady hydrogen
concentration in the crack tip, using the same current density
that was applied during the monotonic loading.
3. Results and discussion
3.1. Fracture toughness parameters
During the three-point bending test the forceeload line
displacement (FeL) diagram was recorded (Fig. 6). Fracture
toughness parameters were calculated according to ISO12135.
The fracture parameter K
Q
corresponds to the intersection of
the ForceeLoad line displacement curve with line (OB) of
Fig. 6. Line (OB) is drawn through the origin with a slope equal
to DF/F less than that of the tangent (OA) to the linear portion
of the record. The magnitude of DF/F is 0.04 for load line
displacement record. The J
0
integral is measured at the point
of the maximum force on the ForceeLoad line displacement
diagram. In Fig. 6 the points where forces F
Q
and F
max
are
measured can be identied. The stress intensity factor K
Q
and
the J
0
integral are given by equations (1) and (2), respectively.
K
Q

_

_
_
s
W
_
F
Q
BB
N
W
0:5
_

_
_
g
1
_
a
0
W
__
(1)
where: B
N
B for plain sided specimens; F
Q
, force at
the intersection of the FeL curve with a line that starts
from the origin and has slope equal to DF/F 0.04;
Table 2 e Tensile properties of the tested steel.
Youngs
modulus
E (GPa)
Poissons
ratio n
Yield strength
s
Y,0.2
(MPa)
Tensile
strength
s
TS
(MPa)
X70 206 0.3 556 630
X52 203 0.3 395 560
Table 3 e API 5L X70 and X52 steel specimen characteristic dimensions (mm).
Pipe diameter
(D)
Specimen thickness
(B)
Width
(W )
Span of supports
(S )
Notch depth
(a
n
)
Fatigue pre-crack
(a
c
)
Nominal crack length
(a
o
)
X70 710 10 13.2 53.4 2.5 4.5e5.5 7.5
X52 610 9.9 10.5 53.4 2 4 6
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 6 ( 2 0 1 1 ) 1 2 6 2 6 e1 2 6 4 3 12630
g
1
_
a
0
W
_
3
_
a
0
W
_
0:5
1:99
_
a
0
W
__
1
a
0
W
_
2:15 3:93
a
0
W

2:7
_
a
0
W
_
2
_
=2
_
1 2
a
0
W
__
1
a
0
W
_
1:5
J
0

_
F
max
S
BB
N

0:5
W
1:5
g
1
_
a
0
W
_
_
2_
1 v
2
E
_

2U
P
B
N
Wa
0

(2)
where: F
max
, point of maximum force on the FeL diagram
(Fig. 6); v, Poissons ratio; E, Youngs modulus; U
p
, the area
under the FeL diagram and line DC which is parallel to the
elastic section of the test curve and intersects the curve at the
point of F
max
(Fig. 6)
The maximum stress intensity factor K
Q
is not, however,
the plane strain fracture toughness, because condition (3) is
not satised.
B ! 2:5
_
K
Q
s
Y;0:2
_
2
(3)
The fatigue pre-cracking was achieved using a loading
frequency of 10 Hz at a stress ratio of 0.1. The maximumstress
intensity factor for fatigue pre-cracking was about 20 MPa

m
p
and 18 MPa

m
p
, for X70 and X52 specimens respectively.
The specimen dimensions B and W are well within the
required ratio (equation (4)) of ISO 12135, as is the fatigue pre-
crack a
0
to W ratio (equation (5)). The average values of W/B
were 1.32 and 1.05, for X70 and X52 specimens respectively,
while the averages values of a
0
/W were 0.58 and 0.6, for X70
and X52 specimens accordingly, which are well within the
limits designated by the formulae (4) and (5).
1:0
W
B
4:0 (4)
0:45
a
0
W
0:70 (5)
3.2. Using ISO 12135 for curved samples
The ISO 12135 standard is used for evaluating fracture
toughness parameters on Compact Tension Specimens and
three-point bending rectangular specimens. In the following
paragraph the applicability of equations (1) and (2) of ISO
12135 to curved specimens is investigated, through the use of
the nite element method. More specically, the fracture
toughness parameters K
Q
and J integral are evaluated through
the ISO 12315 equations and compared to the corresponding
values calculated with the use of the nite element method.
Two 3D nite element (FE) models of curved specimens
were created (Fig. 7), representing the X70 and X52 base metal
specimen geometries, with characteristic dimensions depic-
ted in Table 3. The nite element analysis was carried out
using the commercial nite element analysis package
ANSYS

12.0 Academic. For both the models eight node brick

elements (SOLID 185) were used, while the roller supports
were modelled as being rigid. Contact between specimen and
roller supports was modelled using four node surface to
surface contact elements (CONTA173, TARGET170), with fric-
tion coefcient equal to 0.3.
A static non-linear analysis was performed using large
displacement theory and employing the Newton Raphson
incremental-iterative scheme. Furthermore, only half the
actual specimen geometry is modelled due to symmetry with
respect to the plane AA in Fig. 7, dened by the fatigue pre-
crack plane and extending across the un-cracked specimen
ligament L.
L wa
0
(6)
Boundary conditions were imposed at the rollers. Speci-
cally on the centre line of the roller S (Fig. 7), translations U
X
,
U
Y
, U
Z
and rotation R
Y
are set to zero, while rotations R
X
and R
Z
Fig. 4 e Representation of steel specimen cut at the fatigue
pre-crack plane, illustrating the alignment of bands,
direction of propagating crack (white) and hydrogen entry
vector (black).
Table 4 e Electrolytic solution NS4.
Potassium chloride (KCl) 122 mg/L
Sodium hydrogen carbonate (NaHCO
3
) 483 mg/L
Hydrated calcium chloride (CaCl
2
, 2H
2
O) 181 mg/L
Hydrated magnesium sulphate (MgSO
4
, 7H
2
O) 131 mg/L
Fig. 5 e Schematic representation of the testing
arrangement.
Table 5 e Mechanical properties of acetal casings.
Youngs modulus 3.2 GPa
Compressive modulus 3.2 GPa
Poissons ratio 0.35
Tensile strength 70 MPa
Compressive strength 110 MPa
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 6 ( 2 0 1 1 ) 1 2 6 2 6 e1 2 6 4 3 12631
are free. On roller F (Fig. 7) translations U
Y
, U
Z
and rotations R
X
,
R
Y
are set to zero and rotation R
Z
is free.
For the non-linear analysis employing large displacement
theory, the true Stress Strain Curves of the X70 and X52 base
metals were used which were computed from the experi-
mentally determined stressestrain curves following the
ASTM E8 [30] standard and assuming that plastic deformation
takes place at constant volume.
Regarding the evaluation of the fracture parameters K
Q
and
J using the FE models, force and displacement are applied,
respectively, on roller F. The corresponding forces for evalu-
ating K
Q
, which are depicted in Table 7, are the experimentally
determined F
Q
values.
The comparison of the numerical and experimental eval-
uation of J depends on the agreement of the FeL curves
produced by the two methods. These FeL curves, produced by
the FE simulation of the X70 and X52 base metal models are
shown in Fig. 8, along with the experimental curves. In Fig. 8 it
is observed that the experimental and numerical FeL curves
show good agreement up to displacement values equal to
1.09 mm and 1 mm for the X52 and X70 models, respectively.
These are the points where the experimental and numerical
comparison of J is accomplished. In this respect the afore-
mentioned respective displacements are imposed on roller F
for both the X70 and X52 models.
3.2.1. K
Q
evaluation
The experimentally obtained values of K
Q
are depicted in
Table 8 for both X70 and X52 specimen models. Numerically
the K
Q
values are calculated at every node along the crack
front for both models. The maximumK
Q
which corresponds to
the node located at the centre of the crack front is then
compared to the experimentally calculated value.
The comparison between the experimentally derived K
Q
values using ISO 12315 equations and the numerical ones for
the X70, which are summarized in Table 8, exhibit a 1.5%
difference. Regarding the aforementioned comparison for the
X52 model the difference is 6.5%.
3.2.2. J integral evaluation
The experimentally obtained values of the J integral are
depicted in Table 9 for both X70 and X52 specimen models.
Numerically the J integral values are calculated at every node
along the crack front for both models. The J integral numerical
values along the crack front, that exhibit a uctuation,
between 140 and 144 N/mm for the X70 and between 124.22
and 125.43 N/mm for the X52 model are averaged for each
model. These averaged J integral values for the X70 and X52
models are used for comparison with the experimental ones.
Results are depicted in Table 9.
The comparison between the experimentally derived J
values using ISO 12315 equations and the numerical ones for
the X70, which are summarized in Table 9, exhibit a 2.0%
difference. Regarding the aforementioned comparison for the
X52 model the difference is 5.4%.
Table 6 e Mechanical properties of alumina ceramics
(Al
2
O
3
) [38].
Youngs modulus 380e410 GPa
Shear modulus 158e164 GPa
Poissons ratio 0.24e0.27
Tensile strength 210e500 MPa
Compressive strength >4000 MPa
Fig. 6 e Forceeload line displacement diagram from three-
point bending test according to ISO 12135.
Fig. 7 e Finite element model which represents half the
actual specimen geometry due to symmetry at the fatigue
pre-crack plane, simulating the three-point bending
specimen geometry and roller supports.
Table 7 e Forces and displacements imposed on roller F
for the F.E. models of X70 and X52.
Force F
Q
(kN) Displacement for calculating J (mm)
X70 4.22 1.09
X52 2.42 1.00
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 6 ( 2 0 1 1 ) 1 2 6 2 6 e1 2 6 4 3 12632
3.3. Results for X70 base metal
The ForceeLoad line displacement curves and corresponding
DC lines, for air and all hydrogen charging cases and for
bending tests of specimens having comparable a
0
z 7.6 mm
are depicted in Fig. 9 for the X70 base metal. In Table 10 results
are listed for the X70 base metal specimens.
The standard record of three-point bending tests is the
ForceeLoad line curve, where F
Q
, F
max
and U
P
canbe identied.
High ductility corresponds to high absorbed energy U
P
. The
value of U
P
(Fig. 6) is equal to the area under the ForceeLoad
line curve (FeL) and line DC. InFig. 9 the FeL curves are plotted
for all cases and for the base metal. In this gure the DC lines
are also plotted in order to illustrate the change in U
P
for the
various cases.
Regarding the X70 base metal, a constant reduction of
ductility is observed as the current density increases. The
aforementioned observation is evident in Fig. 9 where the
ForceeLoad line displacement curve with current density
equal to 10 mA/cm
2
exhibits the highest reduction in ductility.
Reduction in ductility is observed sequentially higher for the
specimen constantly charged with 10 mA/cm
2
, second for
5 mA/cm
2
and third for 1 mA/cm
2
in comparison with the case
in air. This effect is expressed as a reduction of J
0
. In Table 11
the average values of the four cases and for the base metal are
listed. These values are plotted (Fig. 11) along with the varia-
tion of the measurements for the specimen tested. The
hydrogen induced reduction of ductility is a common macro-
scopic effect that is observed when hydrogen is introduced in
low carbon steels, regardless of hydrogen charging conditions
or electrolytic solutions. J
0
exhibits 31.6%, 41.1% and 63.4%
reduction for the cases with 1, 5 and 10 mA/cm
2
current
density, respectively, in comparison with the case in air.
Regarding the K
Q
variations for the charging cases, there is
a slight increase for the cases of 5 and 10 mA/cm
2
and an
increase also for the case of 1 mA/cm
2
current density, which
however is well within the experimental margin of error
(Table 11 and Fig. 12).
3.4. Results for X70 HAZ metal
The ForceeLoad line displacement curves and corresponding
DC lines, for air and all hydrogen charging cases and for
bending tests of specimens having comparable a
0
z 7.6 mm
Fig. 8 e Three-point bending X70 and X52 base metal test
comparison (experimental-numerical).
Table 8 e Experimental and numerical K
Q
values for the
X70 and X52 models.
Experimental K
Q
MPa

m
p _
Numerical K
Q
MPa

m
p _
Difference
K
Q
%
X70 64.1 63.2 1.5
X52 45.1 42.2 6.5
Table 9 eExperimental and numerical J values for the X70
and X52 models.
Experimental
J (N/mm)
Numerical
J(N/mm)
Difference
J%
X70 145.1 142.2 2.0
X52 119.0 124.6 5.4
Fig. 9 e ForceeLoad line displacement curves and
corresponding DC lines from the three-point bending tests
for X70 base metal specimens, having comparable a
0
,
(cd [ current density in mA/cm
2
)
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 6 ( 2 0 1 1 ) 1 2 6 2 6 e1 2 6 4 3 12633
are depicted in Fig. 10 for the X70 HAZ metal. In Table 12
results are listed for the X70 HAZ metal specimens.
The HAZ metal exhibits higher resistance to hydrogen
embrittlement in contrast to the base metal. As illustrated in
Fig. 10, the test in air and the test with 1 mA/cm
2
have
comparable U
P
and values of J
0
250 and 242 N/mm, respec-
tively. These values demonstrate a slight decrease in ductility
which is well within the experimental margin of error. This
trend continues for the case of 5 mA/cm
2
current density and
for specimen 2 (Fig. 10), where J
0
exhibits an increase
compared to the aforementioned cases. Finally for the case of
10 mA/cm
2
there is a substantial decrease in J
0
. Overall the
average values of J
0
are illustrated in Table 13 and Fig. 11.
Regarding K
Q
there is a slight decrease with increasing
current density (Table 13 and Fig. 12).
3.5. Results for X52 base metal
The ForceeLoad line displacement curves and corresponding
DC lines for air and all hydrogen charging cases and for
bending tests of specimens having comparable
a
0
z6.2e6.3 mmare depicted in Fig. 13 for the X52 base metal.
In Table 14 results are listed for the X52 base metal specimens.
Regarding the base metal, a reduction in plasticity (as
expressed in the J
0
reduction) is observed as the current
density increases (Fig. 13). The relative reduction of J
0
for the
base metal is shown in Fig. 15 and Table 15. The dispersion of
the results concerning hydrogen induced J
0
reduction for
applied current densities of 1 and 5 mA/cm
2
, suggests that
there is a clear reduction of plasticity as compared with J
0
in
air. For the applied current density of 10 mA/cm
2
the average
J
0
reduction is higher than the J
0
reduction for applied current
density of 5 mA/cm
2
, but due to the dispersion of results
(Fig. 15) it could be argued that the reduction could be similar
for both applied current densities. This can be attributed to
the fact that for applied current density of 5 mA/cm
2
a critical
hydrogenconcentration might have accumulated onthe crack
tip. Though more hydrogen uptake is facilitated by applying
higher current density the effect on the fracture toughness is
negligible.
Concerning the values of the maximum stress intensity
factor K
Q
, it appears that there is no signicant effect of
hydrogen charging on them. The average values show some
variations in the various applied current densities as
compared with air Table 15, but the dispersion of the indi-
vidual results (Fig. 16) indicates that these variations are well
within the margin of error of the experimental measure-
ments. The aforementioned results for K
Q
indicate that there
Fig. 10 e ForceeLoad line displacement curves and
corresponding DC lines from the three-point bending tests
for X70 HAZ metal specimens, having comparable a
0
,
(cd [ current density).
Table 10 e Results for the X70 base metal specimens.
Specimens K
Q
MPa

m
p _
J
0
N/mm
a
0
(mm)
a
0
/W F
Q
(kN)
F
max
(kN)
Air
1 64.1 290.9 8.3 0.63 4.2 5.1
2 61.1 304.3 7.6 0.58 4.9 5.6
3 65.6 295.2 7.2 0.55 5.9 6.4
4 66.0 250.8 7.4 0.56 5.7 6.5
1 mA/cm
2
1 67.3 204.7 7.8 0.59 5.3 5.7
2 62.5 191.5 7.6 0.58 5.2 5.8
3 65.3 190.7 7.9 0.60 5.1 5.6
5 mA/cm
2
1 66.3 159.8 7.6 0.57 5.5 6.1
2 69.4 179.6 8.1 0.61 4.9 5.6
3 67.1 164.6 7.2 0.55 6.1 6.5
10 mA/cm
2
1 66.1 106.8 8.0 0.60 4.9 5.5
2 65.1 100.4 7.6 0.57 5.5 6.0
3 67.8 105.8 7.9 0.59 5.3 6.0
Fig. 11 e J
0
vs applied cathodic current density i for X70
base and HAZ metal.
Table 11 e X70 base metal average K
Q
and J
0
values and
percent variation as compared with air.
X70 base metal K
Q
MPa

m
p
J
0
N/mm K
Q
% J
0
%
Air 64.2 285.3
1 mA/cm
2
65.0 195.2 1.31 31.57
5 mA/cm
2
67.6 168.0 5.33 41.11
10 mA/cm
2
66.3 104.3 3.33 63.44
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 6 ( 2 0 1 1 ) 1 2 6 2 6 e1 2 6 4 3 12634
is no effect of hydrogen charging on reducing fracture
toughness in the elastic regime of the base metal.
3.6. Results for X52 HAZ
The ForceeLoad line displacement curves and corresponding
DC lines, for air and all hydrogen charging cases and for
bending tests of specimens having comparable a
0
z6 mm are
depicted in Fig. 14 for the X52 HAZ metal. In Table 16, results
are listed for the X52 HAZ metal specimens.
In contrast to the base metal, the HAZ exhibits higher
resistance to hydrogen induced reduction of J
0
. As it is clearly
shown in Fig. 15 and Table 17, in the case of applied current
density equal to 1 mA/cm
2
the J
0
reduction is 6.4% as
compared with air, in contrast to 9.2% reduction of J
0
for the
base metal. Furthermore, at applied current density of 5 mA/
cm
2
the HAZ metals J
0
relative reduction is 12.8% as opposed
to 46.9% of the base metal. Finally, for applied current density
of 10 mA/cm
2
the J
0
relative reduction is more pronounced
with a value of 33.4%.
Concerning the values of K
Q
, results (Fig. 16, Table 17) show
that the same conclusions that were deduced for the base
metal are also applicable in the case of the HAZ.
3.7. Microstructural aspects
3.7.1. API X70
In general, low carbon pipeline steels usually possess a ferri-
ticepearlitic or ferriticebainitic microstructure. The ferri-
ticepearlitic microstructure is met in older grades of pipeline
steels and ferritic-lowcarbon bainitic microstructures are met
in contemporary steels.
Factors that can potentially affect hydrogen trapping and
solubility in the metal lattice are rst and second phases, non-
metallic inclusions, precipitates and the size and shape of
grains. Hydrogen solubility in the metal lattice and in revers-
ible and irreversible traps is greatly affected by continuous
ferriteecementite interfaces along grain boundaries of
banded microstructures and pearlitic grains act as barriers to
hydrogen diffusion path [31e33]. The trapping nature of
cementiteeferrite interface in pearlite grains and ferri-
teecementite grain boundaries, has also been conrmed by
Tritium Autoradiography through Scanning Electron Micros-
copy and Transmission Electron Microscopy [34] in high
strength ferriteecementite steels.
The X70 base metal, as illustrated in Fig. 2, possesses
a banded ferritic and mixed bainiticepearlitic microstructure,
with elongated grains along the rolling direction due to
forming process and indications of partial recrystallization. In
Table 12 e Results for the X70 HAZ metal specimens.
Specimens K
Q
MPa

m
p _
J
0
N/mm
a
0
(mm)
a
0
/W F
Q
(kN)
F
max
(kN)
Air
1 70.9 250.8 7.7 0.58 5.6 6.3
2 69.1 289.4 8.6 0.65 4.1 4.9
3 69.8 258.0 7.2 0.55 6.3 6.8
1 mA/cm
2
1 69.9 242.0 7.7 0.58 5.5 6.4
2 67.3 252.9 7.5 0.57 5.6 6.4
3 69.6 221.7 8.0 0.61 5.02 5.9
5 mA/cm
2
1 65.7 249.5 8.5 0.64 4.1 4.9
2 66.7 270.5 7.6 0.58 5.4 6.2
3 65.0 239.2 7.3 0.55 5.7 6.3
10 mA/cm
2
1 65.1 173.8 8.4 0.64 4.1 5.1
2 65.6 183.1 7.6 0.58 5.3 6.1
3 64.4 167.8 8.0 0.61 4.6 5.3
Table 13 e X70 HAZ average K
Q
and J
0
values and percent
variation as compared with air.
X70 HAZ metal K
Q
MPa

m
p
J
0
N/mm K
Q
% J
0
%
Air 69.9 266.1
1 mA/cm
2
68.9 238.9 1.43 10.23
5 mA/cm
2
65.8 253.1 5.87 4.89
10 mA/cm
2
65.0 174.9 7.02 34.27
Fig. 13 e ForceeLoad line displacement curves and
corresponding DC lines from the three-point bending tests
for X52 base metal specimens, having comparable a
0
,
(cd [ current density in mA/cm
2
).
Fig. 12 e K
Q
vs applied cathodic current density i, for X70
base and HAZ metal.
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 6 ( 2 0 1 1 ) 1 2 6 2 6 e1 2 6 4 3 12635
contrast, the HAZ metal possesses a banded ferritic and mixed
bainiticepearliticeferritic microstructure, but as illustrated in
Fig. 2 the amount of cementite in the mixed bainiticepearlitic
bands is considerably less than the one in the bands of the X70
base metal.
The main attributes of the X70 base metal that potentially
favour the hydrogen induced reduction of J
0
are the banded
microstructure, the elongated grains along the rolling direc-
tion due to the forming process, the deformation gradient that
exists between the ferrite and the mixed bainiteepearlite
band and the MnS and Al
2
O
3
inclusions that are observed
(Fig. 17) parallel to the bands. The inclusions are the best
candidates for facilitating microcracking since this is the
dominant characteristic of the fracture surfaces of X70 base
metal as observed in Figs. 17 and 20.
Regarding the banded microstructure it can be observed
that both X70 base metal and HAZ have banded structure but
with X70 HAZ having less amount of cementite in the bands
and a larger portion of ferrite compared to the X70 base metal.
Interfaces between the ferrite and the pearlite in the mixed
bainiteepearlite bands for the X70 HAZ are not so apparent as
in the X70 base metal.
Second the elongated ferrite grains in the X70 base metal
have transformed in more equiaxed grains (Fig. 2), a fact that
be explained by the different microhardness of the ferrite in
the X70 base metal and the X70 HAZ. This fact alone is not
sufcient to give an explanation of the large differences
observed in hydrogen induced reduction of J
0
between the X70
base metal and the X70 HAZ. On the other hand considering
the microhardness difference between the bands of the X70
base metal which is approximately 85 HV
0.01
and microhard-
ness difference between the bands in the X70 HAZ metal
which is approximately 61 HV
0.01
, it can be observed that there
is a larger deformation gradient between the bands of the X70
base metal compared to the X70 HAZ metal.
Inclusions such as the ones illustrated in Fig. 17 are present
for X70 base and HAZ metal. The X70 base metal main fracture
characteristic is microcracking (Figs. 17, 20) which is present
parallel to the bands and perpendicular to the direction of the
propagating crack. In the X70 base metal the best candidate
for the initiation of microcracking are the inclusions that are
parallel to the bands (Figs. 17, 20). On the other hand the X70
HAZ also has inclusions but microcracking is not the main
characteristic of the fracture surfaces (Fig. 21). So the inclu-
sions by themselves cannot explain the initiation of micro-
cracking in the X70 base metal. There is a strong indication
that the synergistic effect of the existence of the inclusions
along the bands and the trapping of hydrogen along the
continuous ferrite-mixed bainiteepearlite interface between
Fig. 14 e ForceeLoad line displacement curves and
corresponding DC lines from the three-point bending tests
for X52 HAZ metal specimens, having comparable a
0
,
(cd [ current density).
Fig. 15 e J
0
vs applied cathodic current density i, X52 base
and HAZ metal.
Table 15 e X52 base metal average K
Q
and J
0
values and
percent variation as compared with air.
X52 base metal K
Q
MPa

m
p
J
0
N/mm K
Q
(%) J
0
(%)
Air 45.1 147.3
1 mA/cm
2
46.1 133.8 2.4 9.2
5 mA/cm
2
45.4 78.2 0.8 46.9
10 mA/cm
2
43.6 72.1 3.3 51.1
Table 14 e Results for the X52 base metal specimens.
Specimens K
Q
MPa

m
p
J
0
N/
mm
a
0
(mm)
a
0
/
W
F
Q
(kN)
F
max
(kN)
Air
1 45.2 151.9 6.8 0.6 2.0 2.5
2 44.9 148.1 5.8 0.6 2.8 3.7
3 45.1 141.8 6.2 0.6 2.4 3.3
1 mA/cm
2
1 46.1 126.2 6.3 0.6 2.4 2.9
2 46.3 138.0 6.7 0.6 2.1 2.6
3 46.1 137.0 6.2 0.6 2.5 3.1
5 mA/cm
2
1 45.8 83.6 6.3 0.6 2.4 2.7
2 45.0 69.2 5.8 0.5 2.9 3.2
3 45.4 81.8 6.6 0.6 2.1 2.5
10 mA/cm
2
1 43.3 73.7 6.0 0.6 2.5 3.1
2 41.7 71.0 5.8 0.6 2.6 3.2
3 45.7 71.7 6.3 0.6 2.5 3.0
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 6 ( 2 0 1 1 ) 1 2 6 2 6 e1 2 6 4 3 12636
the bands of the X70 base metal compared to the reduced
ferriteepearlite interface of the X70 HAZ metal, might be
responsible for the large differences observed between the
hydrogen induced reduction of the two metals. The afore-
mentioned synergistic effect is also aided by the larger
deformation gradient between the bands for the X70 base
metal compared to the X70 HAZ metal. A possible mechanism
that can explain the microcracking phenomena is the
hydrogen dragging by moving dislocations. It is well known
that non-metallic inclusions act as important hydrogen traps
and a higher hydrogen concentration can be expected in their
vicinity, even without external stresses. Nevertheless, during
plastic deformation, the hydrogen concentration around the
inclusions can increase considerably due to the hydrogen
which is transported by the dislocations. As the dislocations
are blocked from moving by the non-metallic inclusions, they
release transported hydrogen in the vicinity of the inclusions
[35]. The existence of inclusions along banded formation can
add more hydrogen to the already accumulated portion of
trapped hydrogen in the ferrite-mixed bainiteepearlite inter-
faces along the bands. This can lead to the supersaturation of
the ferrite-mixed bainiteepearlite interfaces, sufcient to
cause the formation of micro-cracks (Figs. 17, 20).
3.7.2. API X52
The X52 base metal fracture mode is governed by the banded
ferriteepearlite morphology of the microstructure. Pearlite
bands according to [33] can affect hydrogen diffusion and
permeation. While conducting permeation tests they found
that when hydrogen diffusion is perpendicular to the bands
the permeability is lower than the permeability parallel to the
bands and on randomly distributed ferriteepearlite micro-
structure, indicating that pearlite layers act as blockers to
hydrogen diffusion. In the same paper and in [31] the ferrite
layers between the pearlite layers are portrayed as the pref-
erential hydrogen diffusion paths. As hydrogen diffuses
through the ferrite layers, ferriteepearlite interfaces become
saturated with hydrogen which in turn interacts with the
deformation between the ferrite and pearlite bands [31].
Similar conclusions are also indicated in [36,37].
Another fact that must be accounted for regarding the
different behaviour of the X52 base metal and the X52 HAZ, is
the microhardness difference between the ferriteepearlite
bands of the X52 base metal and the ferriteepearlite grains of
the X52 HAZ. From the values depicted in paragraph 2.1, it can
be observed that the difference in hardness for the base metal
ferrite and pearlite is about 90 HV
0.01
and for the HAZ ferrite
and pearlite the difference is about 52 HV
0.01
. The values for
the base metal indicate that there is a greater deformation
gradient between the ferrite and pearlite bands than between
the ferrite and pearlite grains in the HAZ. This deformation
gradient seems to be augmented by the facilitation of
hydrogen in the ferriteepearlite interfaces existing between
the bands. The synergistic effect of the hydrogen diffusion
paths dictated by the banded structure and the higher ferri-
teepearlite deformation gradient which is augmented by the
accumulation of hydrogen in ferriteepearlite interfaces
between the bands, play a critical role in the hydrogen
induced J reduction differences observed between base and
HAZ metal.
To illustrate the aforementioned fact and for the applied
current density of 1 mA/cm
2
, the fracture morphology was
characterized by the tearing of the crack faces in bands,
perpendicular to the direction of the propagating crack and
parallel to the ferriteepearlite banding alignment (Figs. 4, 18
and 22).
Again in this steel the hydrogen dragging by moving
dislocations mechanism can be employed to explain the
hydrogen accumulation in the ferriteepearlite interfaces
Fig. 16 e K
Q
vs applied current density i, X52 base and HAZ
metal.
Table 16 e Results for the X52 HAZ metal specimens.
Specimens K
Q
MPa

m
p _
J
0
N/mm
a
0
(mm)
a
0
/W F
Q
(kN)
F
max
(kN)
Air
1 46.1 108.3 6.0 0.6 2.7 3.3
2 45.8 104.4 6.3 0.6 2.4 3.0
3 45.3 94.2 6.5 0.6 2.2 2.8
1 mA/cm
2
1 48.5 84.5 6.0 0.6 2.8 3.1
2 47.7 95.1 5.8 0.6 3.0 3.3
3 47.6 107.5 6.5 0.6 2.3 2.7
5 mA/cm
2
1 45.9 83.6 6.0 0.6 2.7 3.1
2 48.8 92.9 6.2 0.6 2.7 2.9
3 46.5 91.2 5.8 0.6 2.9 3.3
10 mA/cm
2
1 48.7 75.1 6.3 0.6 2.6 2.8
2 48.8 56.4 6.0 0.6 2.9 3.1
3 48.1 72.9 5.8 0.6 3.0 3.2
Table 17 e X52 HAZ average K
Q
and J
0
values and percent
variation as compared with air.
X52 HAZ metal K
Q
MPa

m
p
J
0
N/mm K
Q
% J
0
%
Air 45.8 102.3
1 mA 47.9 95.7 4.7 6.4
5 mA 47.1 89.2 2.9 12.8
10 mA 48.5 68.1 6.1 33.4
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 6 ( 2 0 1 1 ) 1 2 6 2 6 e1 2 6 4 3 12637
between the bands. In this steel though there is no apparent
microcracking, not in the X52 base metal or in the X52 HAZ.
The other different characteristic from the X70 steel is the
larger difference between the ferrite-banded pearlite
microhardness of the X52 base metal compared to the X52
HAZ metal.
Generally the J
0
results for the HAZ metal, as already
mentioned in paragraph 3.6, indicate higher resistance to
Fig. 17 e a) MnS and Al
2
O
3
inclusions existing along the bands in the X70 base and HAZ metal, b) and c) micro-cracks for X70
base metal and for the case of applied current density of 1 mA/cm
2
.
Fig. 18 e SEM micrographs illustrating the banding fracture morphology of X52 base metal; a) microstructure and alignment
of ferriteepearlite banding, b) ruptured surface at applied current density of 1 mA/cm
2
showing fracture in bands.
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 6 ( 2 0 1 1 ) 1 2 6 2 6 e1 2 6 4 3 12638
hydrogen induced reduction of plasticity, as compared to the
base metal. The X52 base metal, as illustrated in Fig. 3,
possesses a banded ferriticepearlitic microstructure. In
contrast, the HAZ metal possesses a non banded ferri-
ticepearlitic microstructure which is more pronounced as the
HAZ metal is closer to the welding. In order to illustrate this
fact, several SEM micrographs of the HAZ were obtained,
following the plane of the fatigue pre-crack and the variations
of the microstructure, as illustrated in Fig. 19. As shown in
Fig. 19, zone I, which is closer to the weldment, possesses
a ferriticepearlitic microstructure with no apparent forma-
tions and bands, zone II possesses a banded ferriticepearlitic
microstructure, with individual pearlite bands affected by the
heat treatment, whereas zone III is basically the base metal.
These variations of microstructure can be attributed to the
effect of heat treatment due to welding, which is more intense
closer to the weldment. In Fig. 19 the SEM micrographs were
taken at each zone and at a distance of approximately 6 mm
from the outer wall of the pipeline, along line (xx).
Furthermore, the size of zones I and II varies in each
specimen due to the size of the weldment, the welding
processes etc. These latter observations (Fig. 19) lead to the
conclusion that the crack plane crosses zones I and II and the
fatigue pre-crack tip may exist in zone I or II. When the fatigue
pre-crack tip is placed in zone I, with the non banded ferri-
ticepearlitic microstructure, the specimen exhibits higher
resistance to hydrogen reduction of J
0
, as compared to the
fatigue pre-crack tip being placed in zone II, with the banded
ferriticepearlitic microstructure.
The aforementioned observations regarding the micro-
structure of the HAZ metal affect the J
0
results for applied
current densities of 1, 5 and 10 mA/cm
2
, which exhibit large
dispersion for the individual specimen results (Fig. 15).
Furthermore, the J
0
results in air and in applied current
density of 1 mA/cm
2
exhibit overlapping results for individual
specimens, e.g. specimen 1 in air and specimen 3 at applied
c.d. of 1 mA/cm
2
(Table 16). These results can be attributed to
the variations in microstructure, where the tip of the fatigue
pre-crack in specimen 3 and for applied current density of
1 mA/cm
2
is located at zone I (Fig. 19).
The same dispersion of results (Fig. 11), can be observed for
the X70 HAZ metal and the same conclusions can be derived
as to the location of the fatigue pre-crack plane in relation to
the microstructure as in X52 HAZ.
3.8. Fractography
3.8.1. API X70
Fractography of the X70 base metal exhibited mixed ducti-
leebrittle rupture when tested while hydrogen charged and
Fig. 19 e Variations in microstructure in the X52 HAZ-base
metal along the direction of the propagating crack.
Fig. 20 e SEM micrographs showing the fracture morphology of X70 base metal; a) in air, b) at applied current density of
1 mA/cm
2
, c) at applied current density of 5 mA/cm
2
, d) at applied current density of 10 mA/cm
2
.
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 6 ( 2 0 1 1 ) 1 2 6 2 6 e1 2 6 4 3 12639
ductile when tested in air. More specically, the base metal
exhibited a 100% ductile fractured morphology with dimples
(Fig. 20a), without hydrogen charging. Regarding the charging
case with applied current density of 1 mA/cm
2
, the rupture
was mixed with ductile and brittle areas (Fig. 20b). For the
cases of applied current densities of 5 and 10 mA/cm
2
, the
fracture morphologies illustrated a mixed aspect of the tran-
sition zone from the ductile zone with dimples to the brittle
Fig. 21 e SEM micrographs showing the fracture morphology of X70 HAZ metal; a) in air, b) at applied current density of
1 mA/cm
2
, c) at applied current density of 5 mA/cm
2
, d) at applied current density of 10 mA/cm
2
.
Fig. 22 e SEM micrographs showing the fracture morphology of X52 base metal; a) in air, b) at applied current density of
1 mA/cm
2
, c) at applied current density of 5 mA/cm
2
, d) at applied current density of 10 mA/cm
2
.
i nt e r na t i ona l j o ur na l o f hy d r o g e n e ne r g y 3 6 ( 2 0 1 1 ) 1 2 6 2 6 e1 2 6 4 3 12640
zone (Fig. 20c and d). In all hydrogen charging cases micro-
cracking was observed along and parallel to the mixed baini-
teepearlite bands.
The fracture morphology of the HAZ without hydrogen
chargingwas100%ductile(Fig. 21a). Regardingthechargingcase
with applied current density of 1 mA/cm
2
the fracture surface
illustrated a mixed rupture (Fig. 21b). For the case of applied
current density of 5 mA/cm
2
the fracture surface also indicated
mixed rupture (Fig. 21c), indicating areas of ductile and brittle
rupture. Finally, for applied current density of 10 mA/cm
2
the
rupture was again mixed but with more brittle areas (Fig. 21d).
3.8.2. API X52
Fractography of the X52 base metal (Fig. 22) exhibited mixed
ductileebrittle rupture when tested while hydrogen charged
and ductile when tested in air. More specically, the fracture
morphology of the X52 base metal in air indicates ductile
rupture (Fig. 22a). Fractography for applied c.d. of 1 mA/cm
2
is
predominantly ductile with fracture arranged in bands,
following the banded ferriteepearlite microstructure (Figs. 18
and 22b). In contrast, fractography for applied c.d. of 5 mA/
cm
2
is cleavage with micro-cracks and nally for applied c.d.
of 10 mA/cm
2
is cleavage (Fig. 22c,d).
Fractography of the X52 HAZ metal (Fig. 23) exhibited
mixed ductileebrittle rupture, with dimples when tested
while hydrogen charged and ductile when tested in air. The
fracture surface of the X52 HAZ metal in air indicates ductile
rupture (Fig. 23a). Fractography for applied c.d. of 1 mA/cm
2
is
mixed ductileebrittle fracture (Fig. 23b). The fracture
morphology for applied c.d. of 5 mA/cm
2
is also mixed ducti-
leebrittle rupture (Fig. 23c) and 10 mA/cm
2
is also mixed
ductileebrittle rupture with brittle areas (Fig. 23d).
4. Conclusions
With regard to the X70 steel fracture toughness parameters
the tests showed:
The X70 base metal exhibits a reduction in ductility as
expressed in changes to the J
0
parameter in comparison to
the tests in air, ranging from 32% for the charging with
1 mA/cm
2
, to 41% for 5 mA/cm
2
and 64% for the charging
case with 10 mA/cm
2
. For the base metal the K
Q
parameter
showed a slight increase, but it could be argued that it is
well within the margin of error of the experimental
results.
The X70 HAZ, in contrast to the base metal, exhibited only
a slight reduction in ductility for the charging cases of 1 and
5 mA/cm
2
as expressed in changes to the J
0
parameter in
comparison to the tests in air. Eventually the J
0
for the HAZ
metal under hydrogen charging with current density of
10 mA/cm
2
was reduced by 34% as compared to the J
0
in air.
For the X70 HAZ the K
Q
parameter showed a slight decrease
for the charging cases of 5 and 10 mA/cm
2
. For the case of
1 mA/cm
2
the decrease was well within the margin of error
of the produced results.
The methodology used here to assess the validity of the ISO/
ASTMstandard equations, originally derived for rectangular
specimens, in evaluating the fracture toughness parameters
of curved test pieces should be extended to other curved
geometries. Two key issues for three-point bend specimens
are the curvature of the test piece and the span of the
supports. Clearly such a study will be of benet to the
pipeline industry since it is highly desirable to machine
Fig. 23 e SEM micrographs showing the fracture morphology of X52 HAZ metal; a) in air, b) at applied current density of
1 mA/cm
2
, c) at applied current density of 5 mA/cm
2
, d) at applied current density of 10 mA/cm
2
.
i nt e r na t i o na l j our na l o f hy d r og e n e ne r g y 3 6 ( 2 0 1 1 ) 1 2 6 2 6 e1 2 6 4 3 12641
specimens from pipelines when carrying out fracture
mechanics assessments.
Withregard to the X70 microstructural aspects of hydrogen
embrittlement it was observed that:
The material under study was an API 5L X70 steel, where the
base metal had a banded ferritic and mixed baini-
ticepearlitic microstructure. The HAZ also had a banded
ferritic and mixed bainiticepearlitic microstructure, but
with partially transformed pearlite to ferrite in the mixed
bainiticepearlitic bands. The ferritic and mixed baini-
ticepearlitic banded base metal was proven more suscep-
tible to hydrogen embrittlement than the banded ferritic
and mixed bainiticepearliticeferritic of the HAZ metal. The
continuous interface between the ferrite and the banded
mixed bainiteepearlite of the X70 base metal was super-
saturated with hydrogen aided by the existence of inclu-
sions parallel and along the bands. Hydrogen dragging by
moving dislocations is a possible mechanism for the accu-
mulation of hydrogen in these interfaces, which in turn
facilitate microcracking. The deformation gradient that
exists between ferrite and mixed bainiteepearlite bands
might also aid in the larger hydrogen reduction of J
0
of the
X70 base metal compared to the HAZ metal.
With regard to the X52 steel fracture toughness parameters
the tests showed:
The base metal exhibits a reduction in ductility as expressed
in changes to the J
0
parameter in comparison to the tests in
air, ranging from 9.2% for the charging with 1 mA/cm
2
, to
46.9% for 5 mA/cm
2
and 51.1% for the charging case with
10 mA/cm
2
. For the base metal the K
Q
parameter and for all
applied c.d. showed no distinctive variations.
The HAZ, in contrast to the base metal, exhibited only
a slight reduction in ductility of 6.4% for the charging case of
1 and 12.8% for the charging case of 5 mA/cm
2
, as expressed
in changes to the J
0
parameter in comparison to the tests in
air. Eventually the J
0
for the HAZ metal under hydrogen
charging with current density of 10 mA/cm
2
was reduced by
33.4% as compared to the J
0
in air. Large dispersion of J
0
results were observed for the charging case of 1 and 5 mA/
cm
2
, which can be attributed to the non-uniform micro-
structure of the HAZ metal along the fatigue pre-crack
plane. For the HAZ the K
Q
parameter showed a slight
increase for all charging cases, but it could be argued that it
was well within the margin of error of the produced results.
With regard to the X52 steel microstructural aspects of
hydrogen embrittlement it was observed that:
The material under study was an API 5L X52 steel, where the
base metal had a banded ferriticepearlitic microstructure.
The HAZ had a non banded ferriticepearlitic microstruc-
ture, with grained pearlite close to the weldment and more
pronounced band effect further from the weldment. The
ferriticepearlitic banded base metal was proven more
susceptible to hydrogen embrittlement than the grained
ferriticepearlitic microstructure of the HAZ metal. The
continuous interface between the ferrite and banded
pearlite of the X52 base metal leads to hydrogen trapping of
these interfaces, as hydrogen is forced to follow the ferrite
band as it diffuses. Aided by the large deformation gradient
between the ferrite and pearlite bands these interfaces are
supersaturated and the deformation gradient is furtherly
augmented as it is portrayed in the fracture mode which is
arranged in bands. In contrast the X52 HAZ with the non
banded ferriticepearlitic and the small microhardness
difference between the ferrite and pearlite grains, exhibits
larger resistance to the hydrogen reduction of J
0
compared
to the X52 base metal. Microcracking is not dominant in the
X52 base and HAZ metal.
Results of hydrogeninducedreductionof J
0
intheX70andX52
HAZ metal exhibit large dispersion which is attributed to the
non-uniform microstructure at the fatigue pre-crack plane.
Acknowledgements
The present work was partially based on experimental results
produced for the European Project NATURALHY (Contract
No. 502661). The aforementioned issue of utilizing the existing
pipeline infrastructure to carry mixtures of hydrogen with
natural gas was the subject of the NATURALHY Project,
which was funded by the Directorate-General for Research
under the 6th Framework Programme of the European
Commission. Within NATURALHY, 39 partners tackled the
issues regarding transporting, distribution and end use of
hydrogen gas within the envelope of a natural gas infrastruc-
ture. The project tackled key issues, ranging from durability of
pipeline steels and integrity management, to social-economic
assessment and end use. We would also like to thank Gaz De
France for the supply of the piece of the X52 pipeline and two
members of the Shipbuilding Technology Laboratory, Mr.
Daniolos Nikolaos for his assistance in microstructural char-
acterization and microhardness testing and Ms. Charikleia
Sarafoglou for her help and time regarding SEM fracture
micrographs.
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