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Environment hydrogen embrittlement of pipeline steel X70 under various gas

mixture conditions with in situ small punch tests

Article in Materials Science and Engineering A · February 2020

DOI: 10.1016/j.msea.2020.139114

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 international journal of hydrogen energy xxx (xxxx) xxx

Available online at www.sciencedirect.com

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

Effect of low partial hydrogen in a mixture with

methane on the mechanical properties of X70
pipeline steel

Thanh Tuan Nguyen a, Jaeyeong Park a, Woo Sik Kim b,

Seung Hoon Nahm a,**, Un Bong Beak a,*
a
Center for Energy Materials Measurement, Division of Industrial Metrology, Korea Research Institute of Standard
and Science (KRISS), 267 Gajeong-Ro, Yuseoung-Gu, Daejeon 34113, Republic of Korea
b
Korea Gas Corporation, Gyeonggi-do, 163-754, Republic of Korea

highlights graphical abstract

Tensile, notched tensile, and

toughness of X70 steel under a low
partial hydrogen in natural gas
mixture were investigated.

Significant loss of the reduction in
the area was only observed when
tested with a sharp notched
specimen.

Fracture toughness of X70 pipeline
steel was reduced markedly under
a gas mixture with 1% H2.

Long-term exposure to hydrogen/
natural mixture had no remark-
able effect.

article info abstract

Article history: In this study, the effect of a low partial hydrogen in a mixture with natural gas on the
Received 6 September 2019 tensile, notched tensile properties, and fracture toughness of pipeline steel X70 is inves-
Received in revised form tigated. An artificial HE aging is simulated by exposing the tested sample to the mixture gas
30 October 2019 condition for 720 h. In addition, a series of tests is conducted in ambient air and 10 MPa of
Accepted 3 November 2019 100% He and H2. Overall, 10 MPa of 100% H2 significantly degrades the mechanical prop-
Available online xxx erties of an X70 pipeline steel. However, it is observed that the 10 MPa gas mixture with 1%
H2 does not affect the mechanical properties when tested with a smooth tensile specimen.
Keywords: In the notched tensile test, a significant reduction in loss in the area is observed when
X70 pipeline steel tested with a notched specimen with a notch radius of 0.083 mm. It is also confirmed that a
Hydrogen embrittlement 10-MPa gas mixture with 1% H2 causes a remarkable reduction in the toughness. The
Notched-tensile

* Corresponding author.
** Corresponding author.
E-mail addresses: shnahm@kriss.re.k (S.H. Nahm), ubbaek@kriss.re.kr (U.B. Beak).
https://doi.org/10.1016/j.ijhydene.2019.11.013
0360-3199/© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article as: Nguyen TT et al., Effect of low partial hydrogen in a mixture with methane on the mechanical properties of
X70 pipeline steel, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.013
2 international journal of hydrogen energy xxx (xxxx) xxx
Toughness influence of the exposure time to 1% hydrogen in a mixture with natural gas was found to
Mixture gas be minor.
© 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Introduction
Pipeline systems are the safest method for transporting pe-
troleum and natural gas from the original extraction to con-
sumption regions. In general, natural gas distribution systems
are designed in accordance with ASME B31.8 [1] and the
structural materials used in the pipeline infrastructure
generally follow the American Petroleum Institute (API) 5L
specifications [2]. To increase the transportation reliability
efficiency, new structural materials should be developed by
focusing on achieving high strength and toughness. The
application of high-strength and high-toughness pipelines
steel has allowed large transmission of oil and gas by the
ability to withstanding high pressures, also resulting in
decreasing the wall thickness of pipes. Because welded pipe-
lines are common in pipeline systems, its good welding ability
provides less installation efforts, reduced transportation, and
low repairing costs. Moreover, to eliminate the dependence on
fossil fuels, hydrogen has been considered as a primary en-
ergy carrier source for future energy needs. To utilize the
existing pipeline systems, blending hydrogen by adding a
certain portion to natural gas pipelines is being considered as
a method to deliver hydrogen to the market [3]. Therefore, for
active maintenance and susceptibility to hydrogen embrit-
tlement, (HE) the maximum/minimum hydrogen concentra-
tion of the hydrogen blend that is required for appliance and
maintenance adjustments needs to be specified [3e6]. Unex-
pected hydrogen concentrations can also be generated by
electro-chemical reactions achieving cathodic protection of
pipelines or transportation sour gas. The actual hydrocarbon
natural gas condition may contain a small portion of hydrogen
and other components such as oxygen and sulfur dioxide.
This can change the nature of the aqueous environment and
exposure conditions on the surface of the metals, and more
specifically, it can degrade the mechanical properties of the
transported materials [3,5,7]. However, most pipeline steels,
which are composed of ferritic steels, are extremely sensitive
to the various forms of environmental attack such as stress
corrosion cracking or hydrogen embrittlement [8e14]. To
enable a pipeline system to be operable for the design life, the
behavior of the used material under various conditions of the
gas mixture should be carefully examined. The material
compatibility in long-term service under hydrogen/natural
mixtures also needs to be evaluated.
In general, the susceptibility to HE can be quantitatively
characterized by the losses in the strength, strain at the
fracture, reduction in the area, or acceleration of the fatigue
crack growth rate [15e17]. Based on the historical service
experience and extensive studies, ferritic stainless steels such
as carbon, low-alloy, and pipeline steels are reported to be
more susceptible to a hydrogen environment compared to
Please cite this article as: Nguyen TT et al., Effect of low partial hydrogen in a mixture with methane on the mechanical properties of
X70 pipeline steel, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.013
austenitic stainless steels [18e20]. This is attributed to the
difference in the crystal structure resulting from the differ-
ence in the hydrogen concentration within the specimen.
Until now, extensive research studied have investigated the
effect of hydrogen on the mechanical properties for various
API pipelines, carbon, and low-alloy steels. Much of the pre-
vious investigations were conducted on electrochemically
pre-charged hydrogen specimens [7,10e12,21e24]. For ferritic
steels, mechanical tests performed in a gaseous hydrogen
environment may be more appropriate compared to with the
electrochemical charging because it can generate a high
hydrogen concentration near the surface, which can cause
some damages on the specimen surface, such as surface
cracking or blistering [25,26].
This current study aims to achieve a better understanding
of the influences of the addition of a small portion of hydrogen
to natural gas on the mechanical properties of API X70 pipe-
line steel. Smooth tensile, notched tensile, and fracture
toughness testing were performed in a gas mixture with 1%
H2. In addition, a series of tests in ambient air, 10 MPa of 100%
He, and 100% H2 was also conducted. Artificial aging to
simulate the long-term operation during service was created
by exposing the test sample to the corresponding mixture gas
condition for 720 h.
Experimental procedure
The material used in this study was API 5L X 70 pipeline
steel, which is used as a domestic natural gas piping mate-
rial in South Korea. The specimens were machined from a
pipe with an external diameter of 762 mm and thickness of
12.7 mm. The chemical composition is listed in Table 1.
Smooth and notched tensile tests were performed in a high-
pressure hydrogen environment following the ASTM G142
standard [27]. A smooth specimen with a 6 mm gauge
diameter and parallel part length of 28.6 mm was machined,
as shown in Fig. 1a. A notched specimen with specific di-
mensions of a notch angle of 60 and a notch radius of 0.083
mm ± 0.013 was prepared, as presented in Fig. 1b. Both the
specimens were machined along the pipeline circumferen-
tial direction along which the subjected stress is expected to
be the largest. A constant crosshead speed of 0.002 mm/s
was applied in the test with the smooth tensile specimen,
whereas a constant speed of 0.02 mm/s was used for the
notched tensile testing.
The fracture toughness was measured by the crack tip
opening displacement (CTOD) method under similar envi-
ronment conditions as those of the smooth tensile and
notched tensile tests, following the BS 7448-1 standard [28].
The geometry of the tested specimen with a thickness of
12.7 mm is shown in Fig. 1c. To resemble the actual crack
 international journal of hydrogen energy xxx (xxxx) xxx 3

Fig. 1 e Schematics of the testing specimens: (a) smooth tensile specimen, (b) notched tensile specimen with R ¼ 0.083 mm,
(c) CTOD specimen.

Please cite this article as: Nguyen TT et al., Effect of low partial hydrogen in a mixture with methane on the mechanical properties of
X70 pipeline steel, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.013
4 international journal of hydrogen energy xxx (xxxx) xxx

Table 1 e Chemical compositions of the API X70 pipeline steel, wt.%.

C Mn P S Cr Ni Cu Mo Others
0.07 1.68 0.012 0.01 0.07 0.14 0.10 e Ni þ V þ Ti < 0.15

Fig. 2 e Stressestrain curve for X 70 pipeline steel when tested with the smooth tensile specimen (a) in ambient air, (b) in
10 MPa of He, (c) in 10 MPa gas mixture with 1% H2, (d) in 10 MPa gas mixture with 1% H2, 720-h exposure, (e) in 10 MPa of H2,
and (f) a comparison of a typical stressestrain curve.

presented in the structure, the specimens were pre-cracked by
fatigue loading with loading ratio R 0.1 and frequency 10 Hz.
The load required for fatigue crack formation was considered
not to cause blunting of the crack tip or compressive residual
stress at the crack tip range. The final position of the pre-crack
tip could be observed from the outer surface of the specimen
and was stopped at a ratio of ao/W ¼ 0.58 ± 0.005. During the
test, a clip gauge was used to measure the crack opening
displacement. The loadeline displacement rate was 1 mm/
min. After completing the tests, the specimens were opened
at liquid nitrogen temperature to evaluate the average crack
length of propagation. Average measured crack sizes were
evaluated from nine positions along the crack front on the
broken specimens.

Please cite this article as: Nguyen TT et al., Effect of low partial hydrogen in a mixture with methane on the mechanical properties of
X70 pipeline steel, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.013
 international journal of hydrogen energy xxx (xxxx) xxx 5

Table 2 e Summarized test conditions and results of the smooth tensile specimens.
Test condition Number of Ultimate strength, Reduction area, Fracture elongation,
test (MPa) RA (%) EL (%)
atm, RT 6 632 ± 2 82 ± 0.70 23.3 ± 1.53
1% mixture gH2, 10 MPa 6 624 ± 3 81.7 ± 2.1 22.4 ± 0.81
1% mixture gH2, 10 MPa, 720-h exposure 6 620 ± 3 81.3 ± 1.8 22.7 ± 0.50
100% gHe, 10 MPa 2 628 ± 3 82 ± 0.65 21.15 ± 0.25
100% gH2, 10 MPa 2 628 ± 1 40.2 ± 5.1 15.52 ± 1.42

Table 3 e Summarized test conditions and results of the notched tensile specimens.
Test condition Number of test Ultimate strength, (MPa) Reduction area, RA (%)
R ¼ 0.083 mm atm, RT 2 1251.0 ± 8.53 45.4 ± 3.70
1% gH2, 10 MPa 2 1211.0 ± 0.00 20.2 ± 2.20
1% gH2, 10 MPa, 720-h exposure 2 1223.0 ± 8.49 23.10 ± 0.90
100% gHe, 10 MPa 2 1323.0 ± 5.66 46.3 ± 0.24
100% gH2, 10 MPa 2 1217.0 ± 18.38 21.15 ± 0.25

All the tests were performed at a pressure of 10 MPa at the autoclave was filled with the testing gas to the required
room temperature of 25  C with CH4/H2 mixture gas contain- pressure of 10 MPa, the specimens were exposed to the gas for
ing 1% H2. To simulate long-term usage in service condition, at least 30 min before testing. Fractography analyses were
the tested specimens were artificially exposed to the corre- performed via scanning electron microscopy (SEM) after the
sponding mixture gas conditions for 720 h. Before exposing, test.
the specimens processed in the embrittlement autoclave were
cleaned by an ultrasonic washing machine. After a 720-h
exposure, the test piece was discharged from the autoclave, Test results
moved to the test autoclave, and mounted and tested again
under the same mixture gas conditions. For tensile and Smooth tensile test results
notched tensile testing, a series of tests were also performed
in ambient air, 10 MPa of 100% HE and 100% H2 for compari- Stressestrain curves
son. All the test conditions are summarized in Tables 2e4. Fig. 2aee present the engineering stresseengineering strain
The testing equipment was a particularly designed auto- curves of X70 pipeline steel for the smooth tensile specimens
clave with a maximum pressure of 120 MPa installed on a under five environment conditions: ambient air, 10 MPa of He,
servo-hydraulic material testing frame. The pressure in the 10 MPa of 1% H2 gas mixture, 10 MPa of 1 %H2 gas mixture
autoclave was controlled by a computer in the control room. 720 h exposure, and 10 MPa of 100% H2, respectively. Six tests
The load was measured from a load cell located outside of the were performed under the gas mixture with 1% H2 to determine
pressure vessel, and the strains were measured using a clip- the variability of the tested results, whereas the tests were
on extensometer inside the pressure vessel. A primary repeated twice in the additional tests in 10 MPa of He and H2. As
following procedure including creation of a vacuum condition shown, the obtained result presents a good reproducibility in
to 0.5 torr and purging the corresponding mixture gas up to all the tested environments. A comparison of the typical
5 MPa was repeated at least thrice to ensure gas purity. After stressestrain curves under all the environmental condition is
shown in Fig. 2f. It is observed that hydrogen has no effect on
the yield strength and ultimate tensile strength of the material,
even in the test in 10 MPa of 100% H2. A variation in the elon-
Table 4 e Summarized test conditions of the fracture
toughness testing. gation at the fracture and reduction in the area (RA) is shown in
Fig. 3b. The elongations of the specimen tested in 1% H2
Test Test Initial crack ratio, (ao/ CTOD
condition number W) (mm) mixture gas and 1% H2 gas mixture after 720 h exposure is
approximately 22.5%, which is nearly equivalent to the tested
atm, RT 1 0.5859 0.459
result in ambient air and 10 MPa of He. However, the elongation
2 0.5926 0.404
3 0.5815 0.414 of the specimen tested in 10 MPa of 100% H2 remarkably de-
1% gH2, 1 0.5847 0.214 creases to approximately 15.5% ± 1.4, which is a reduction by
10 MPa 2 0.5829 0.226 31.1% compared to the results in 1% H2 blending gas. The
3 0.5824 0.194 variation in the RA under the different tested conditions pre-
1% gH2, 1 0.5853 0.191 sents a similar tendency to that in the strain at the fracture, as
10 MPa, 2 0.5828 0.220
indicated by the red line in Fig. 3b. The RAs are consistent at
720-h 3 0.5856 0.211
approximately 82% among the four environmental conditions:
exposure
100% gH2, 1 0.5832 0.125 ambient air, 100% HE-10 MPa, 1% mixture H2,1% mixture H2
10 MPa 2 0.5874 0.097 -720 h exposure-10 MPa, whereas the RA in 10 MPa of 100% H2

Please cite this article as: Nguyen TT et al., Effect of low partial hydrogen in a mixture with methane on the mechanical properties of
X70 pipeline steel, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.013
6 international journal of hydrogen energy xxx (xxxx) xxx

decreases by approximately 40%. It is noted that the loss in the
RA when tested in 10 MPa of 100% H2 is more pronounced than
the reduction in the strain at the fracture.
Factography analysis
Fig. 4 shows a comparison of necked and fracture surface
characteristics at low magnifications under the performed
conditions. Because the result in 10 MPa of He gas is identical
to that in ambient air, the fracture surface of the specimen
tested in ambient air will be representative for both. As shown
from Fig. 4aec, there is no apparent difference in the macro-
scopic appearances of the fracture surfaces of the specimens
tested in ambient air, 1% H2 gas mixture, or 1% H2 gas mixture
after the 720-h exposure. All the surfaces are elliptical in

Fig. 3 e Comparison of the strength and ductility properties under the different hydrogen conditions (a) for ultimate tensile
strength, (b) for reduction in the area and elongation at the fracture.

Please cite this article as: Nguyen TT et al., Effect of low partial hydrogen in a mixture with methane on the mechanical properties of
X70 pipeline steel, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.013
 international journal of hydrogen energy xxx (xxxx) xxx 7

shape and reveal a typical cup-cone fracture, which includes a
purely normal stress fracture at the central region and a
shearestress fracture region near the external surface. The
short axis of the ellipse fracture surface is roughly parallel to
the radial direction of the parent pipe. No secondary cracks
are detected on the longitudinal of the gauge body section of
these specimens even close to the rupture location. However,
the fracture surface of the specimen in 10 MPa of 100% H2 is
macroscopically flat, presenting a minor necking. A high
density of circumferential cracks, perpendicular to the loading
direction is clearly visible on the external surface on the body
gauge length. A remarkable distinction of the fracture mode
can be observed between the microscopic images of the
fracture surface in the five environments. Fig. 5 presents a
comparison of these fracture appearance was taken from the
central area of each rupture surface as indicated in Fig. 4. The
specimens tested in ambient air, 10 MPa of He, 1% H2 mixture
H2 -10 MPa, and 1% mixture H2 -10 MPa-720 h exposure un-
dergo a completely ductile fracture of micro-void coalescence.
By contrast, the sample tested in 100% H2 gas presents a
completely brittle fracture mode with quasi-cleavage fracture
features, as shown in Fig. 4d.
Notched tensile test results
Stresseextension curves
Fig. 6 depicts the stresseextension curves of the notched
specimens with the variation in the environmental test con-
dition. It is apparent that the hydrogen environment has an
insignificant effect on the stresseextension curves. The vari-
ability in the maximum notched stress and RA with the
environmental conditions are shown in Fig. 7 and summa-
rized in Table 3. To compare, the results of the smooth tensile
specimen are also included. As shown in Fig. 7a, the
maximum stresses are basically unchanged when tested with
a single type of specimen and sharply increases with
decreasing notched radius. Conversely, unlike the results
from the tests conducted on the smooth specimen, the RA of
the notched sample with radius R ¼ 0.083 mm exhibits a sig-
nificant decrease when tested in 1% H2 gas mixture and 1% H2
gas mixture after 720-h exposure compared to the test in
ambient air or 10 MPa of He gas, as presented in Fig. 7b. The RA
also shows a downward trend with increasing of H2 portion up
to 100%.
Fractography analysis
Fig. 8 presents a comparison of the typical fracture surface of
the notched specimen with radius, R ¼ 0.083 mm, when tested
under the four environmental conditions. As shown in Fig. 8a,
the fracture surface of the specimen tested in ambient air
shows a completely ductile fracture with dimples. However,
the normal stress-fracture and shear stress-fracture regions
are not distinguished clearly similar to the results in Fig. 4
when tested with the smooth tensile specimens. By contrast,
the samples tested under either 1% H2 gas mixture or 100% H2
condition show two distinctive regions with remarkably
different characteristics. In the central regions, the fracture
surface is characterized by a dimple fracture feature, which is

Fig. 4 e SEM fractography images of X70 pipeline steel under various environmental tested conditions: (a) in ambient air, (b)
in 10 MPa gas mixture with 1% H2, (c) in 10 MPa gas mixture with 1% H2, 720-h exposure, (d) in 10 MPa of H2.

Please cite this article as: Nguyen TT et al., Effect of low partial hydrogen in a mixture with methane on the mechanical properties of
X70 pipeline steel, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.013
8 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 5 e Microscopic images of the fracture appearances at the central area of each rupture surface as indicated in Fig. 4 (a) in
ambient air, (b) in 10 MPa gas mixture with 1% H2, (c) in 10 MPa gas mixture with 1% H2, 720-h exposure, (d) in 10 MPa of H2.

similar to the results obtained in ambient air. The external
region close to the notch root reveals a brittle fracture with a
quasi-cleavage. The thickness of the brittle ring layer of the
sample tested in 100% H2 is wider than that tested in 1% H2 gas
mixture. Some secondary cracks can be also observed at the
interface between the ductile and brittle fracture zone on the
surfaces of the specimens tested in the presence of either 1%
H2 or 100% H2. However, the number and average length of the
cracks is increased significantly in the specimens tested with
100% H2, as shown in Fig. 8. The high-magnification images
captured in the outer region near the notch root under the four
environmental conditions are compared in Fig. 9.
Toughness test results
A comparison of the fracture toughness values (CTOD), which
were evaluated from the loadecrack opening displacement
curves and average crack length measured from the broken
specimen, is shown in Fig. 10. The toughness of the specimen
tested in ambient air is approximately 0.42 mm, whereas its
value is almost significantly reduced by 49%, decreasing to
0.211 mm when tested with 1% H2 gas mixture. The CTOD
values of the specimen tested in 1% H2 gas mixture after a 720-
h exposure is consistent to the results obtained when tested in
1% H2. Furthermore, the CTOD of the specimen tested in
10 MPa of 100% H2 is remarkably reduced to 0.1 mm. The
corresponding fracture surfaces of the cracking zone ahead of
the fatigue pre-crack are shown in Fig. 11. In ambient air, the
fracture surface is characterized with a ductile fracture with
dimples (Fig. 11a), whereas a quasi-cleavage fracture mode is
observed when tested in 1% H2 gas mixture and 1% H2 gas
mixture after 720 h of exposure. Numerous secondary cracks
are observed at the interface between the fatigue pre-cracked
and crack propagation zone. The fracture surface appearance
of the specimen tested in 10 MPa of 100% H2 is also comprised
of quasi-cleavage and secondary cracks, but the density of the
secondary cracks is increased compared to that in the tests in
1% H2 as shown in Fig. 11d.

Discussion

The investigation of the influence of a gaseous hydrogen

Fig. 6 e Stresseextensions curves in the notched tensile environment on the mechanical properties of the ferritic
tests with different environmental conditions.

Please cite this article as: Nguyen TT et al., Effect of low partial hydrogen in a mixture with methane on the mechanical properties of
X70 pipeline steel, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.013
 international journal of hydrogen energy xxx (xxxx) xxx 9

Fig. 7 e Comparison of the notched maximum stress and reduction in the area of the different environmental conditions
when tested with the notched specimen (a) for maximum stress, (b) for a comparison of the reduction in area.

stainless steel group has been extensively reported in the
literature. The HE susceptibility is shown to be highly sensi-
tive to the strength of the material and environmental pres-
sure. Nagginga et al. reported that the HE increased with
increasing gas pressure, and the downtrend of the HE sus-
ceptibility decreased from the high-strength steel, X100, to
low-strength materials, X65 and X52 [9]. In the similar works,
Xu et al. found that the reduction in the tensile ductility of
carbon and low-alloy steels reached saturation at approxi-
mately 6.9 MPa H2, and no further reduction occurs at a rela-
tively higher pressure [29]. Moro et al. also indicated that no
further reduction of strain at a fracture or reduction was
observed when the pressure was higher than 5 MPa [30].
Relating to the effect of hydrogen on the fracture properties,

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X70 pipeline steel, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.013
10 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 8 e Comparison of a typical fracture surface appearance when testing with the notched specimen of R ¼ 0.083 mm for (a)
in ambient air, (b) in 10 MPa gas mixture with 1% H2, (c) in 10 MPa gas mixture with 1% H2, 720-h exposure, (d) in 10 MPa of
H2.

An et al. showed that the fatigue crack growth rate increased
approximately seven times under a pressure of 0.2 MPa
hydrogen [4]. Chatzidouros et al. obtained a trend of
decreasing ductility expressed in the variations in the fracture
toughness with increasing current density during the electro-
chemical charging process [22]. The authors found a decrease
in the fracture toughness range from 32% to 64% when the
current density ranged from 1 mA/cm2 to 10 mA/cm2. How-
ever, there are few studies on the effect of blending hydrogen.
Meng et al. found that X80 pipeline steel was susceptible to a
gas mixture of methane and H2 and that the susceptibility
increased with the increase in the hydrogen portion [5]. Most
recently, Briottet et al. determined that 1% hydrogen in a
mixture with nitrogen significantly reduced the fracture
toughness of X80 pipeline steel [6].
In the aforementioned results, a significant degradation of
the strain at fracture and RA is observed under 10 MPa of 100%
H2 when tested with either the smooth or notched tensile
specimen. This is a general result, which even occurs with
some alloys belonging to the group 300 austenitic stainless
steel [16e18,31e35]. The fracture surfaces are entirely covered
with a quasi-cleavage fracture mode, which is a typical
hydrogen-induced fracture mode. The high density of
circumferential cracks forming in the longitudinal section
around the fracture location is a result of the hydrogen-
enhanced surface crack occurring after reaching the ulti-
mate tensile strength point. This consequently leads to a
considerable decrease in the elongation at the fracture and a
RA. Conversely, the presence of 1% H2 in 10-MPa gas mixture
containing methane does not cause any degradation of the
reduction in the strength and ductility of the present material,
even though it is exposed for 720 h. The microscopic fracture
surfaces of those tests are also comparable to the results when
tested in ambient air. This may be explained by the fact that
1% H2 in a 10-MPa mixture with natural gas is equivalent to
0.1-MPa partial hydrogen. Because a high pressure may
enhance the increase in the surface cover and hydrogen sol-
ubility in the specimen, the 0.1-MPa partial hydrogen may not
be sufficiently high to favor the susceptibility to HE. The pre-
sent result is coincident with those obtained by Moro et al. [6]
and shows that the smooth tensile testing under 0.1-MPa H2
does not reveal any effect of hydrogen on the mechanical
properties of X80 pipeline steel. It is also noted that the results
of the performed under 10 MPa of H2 present a larger standard
deviation compare to those observed in air or low partial
hydrogen. This phenomenon may result from the appearance
of abrupt small cracks formed on the surface, which mainly
control the strain at fracture.
The notched tensile test results discussed in the previous
section apparently revealed that the present material

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 international journal of hydrogen energy xxx (xxxx) xxx 11

Fig. 9 e Comparison of the microscopic fracture surfaces near the outer surface of the notched specimen with R ¼ 0.083 mm
tested under different environmental conditions: (a) in ambient air, (b) in 1% H2, (c) in 1% H2, 720-h exposure, (d) in 100% H2.

exhibited a significant susceptibility to HE in 10 MPa gas with 100% H2 indicates the high partial pressure of hydrogen
mixture with 1% hydrogen when tested with the notched induces more solubility than a small portion of hydrogen
specimen with a notch radius R ¼ 0.083 mm. It was manifested pressure, resulting in a thick brittle region. The present
by the considerable loss of the RA, and those changes in the investigation is correlated well with the pressure dependency
RA were also accompanied by noticeable changes in the of the hydrogen-assisted fatigue propagation mechanism
fracture morphology, as shown in Fig. 8. The presence of the
quasi-cleavage fracture ring on the fracture surface of the
rupture specimen indicates the presence of hydrogen-induced
brittle fracture modes when tested in 1% H2 mixture gas and
100% H2. The thickness of the brittle fracture ring is related to
the H distribution in the sample. The susceptibility to HE is not
only dependent on the local diffusible hydrogen concentra-
tion but also on the local stress state during testing. The dif-
ference in the HE susceptibility grade of the results of the
smooth and notched specimens is attributed to the difference
in the stress/strain state in the gauge section of the testing
specimen. The presence of a notch provides a high stress/
strain concentration in the gauge section at the notch section.
It also affects the stress triaxiality, which enhances the
hydrogen local concentration, resulting in a relatively more
pronounced effect. It is argued that a certain large stress
concentration factor is also required to attain the critical
concentration of hydrogen to induce HE when testing in the
gas mixture with 1% H2. However, a high portion hydrogen
pressure may decrease the level of the stress concentration
factor to reach the critical state of the hydrogen concentra-
tion. As presented in Fig. 8, a large portion of the brittle frac-
Fig. 10 e CTOD test results under the four environmental
ture ring on the fracture surface of the specimens when tested
conditions.

Please cite this article as: Nguyen TT et al., Effect of low partial hydrogen in a mixture with methane on the mechanical properties of
X70 pipeline steel, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.013
12 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 11 e Fracture surface at the crack initiation zone of the fracture toughness specimens under three environment
conditions, (a) in ambient air, (b) in 10 MPa of gas mixture with 1% H2, (c) in 10 MPa of gas mixture with 1% H2, 720-h
exposure, (d) in 10 MPa of 100% H2.

reported by Ogawa et al. [36] The authors found that a large
stress intensity factor was needed to attain the concentration
of hydrogen when tested under such a low-pressure hydrogen
gas, e. g., at 0.7 MPa. In comparison, at an extremely high
pressure, the critical condition for HE was easily achieved
even in a low stress intensity level. In addition, by introducing
a notch mounted on an X70 pipeline body, Capelle et al. also
emphasized that the critical hydrogen concentration could be
a function of numerous factors such as the radius of the notch
tip, rate of loading, geometry of the specimen, and hydrogen
charging method [24,25].
It is well known that the group 300 austenitic stainless steel
is less susceptible to HE than pipeline steels. However, a
ductile fracture region does not appear in the result of the
austenitic stainless steel when tested with the notched spec-
imen under the same conditions as the X70 pipeline steel
examined in this study. Song et al. [37] presented that the
entire fracture surface of austenitic stainless steels such as
304H or 316L material changed to a brittle fracture mode when
tested with a pressure of 10 MPa of 100% H2. However, in X70
pipeline steel, only the ring region near the notch root shows a
brittle fracture, with the inner region still revealing a ductile
fracture that is similar to that when tested in ambient air, as
shown in Fig. 8. To understand the mechanism explaining the
different fracture behaviors of two alloys, attention should be
focused on the characteristic of the stressestrain/
stresseextension curves during the mechanical testing pro-
cess. It is well-known that pronounced susceptibility to
hydrogen environment embrittlement only occurs when the
stress/strain curve exceeds the ultimate tensile strength
point. Overall, the strain at the fracture of the austenitic
stainless-steel specimen is relatively higher than that when
tested with pipeline steel. In addition, the strain value when
the stress/strain curve reaches the ultimate tensile strength
point is relatively much higher in the austenitic stainless
steel. For similar specimen geometries, a high strain leads to
high plastic deformation and long exposure time to the
hydrogen environment. The high plastic deformation can in-
crease the hydrogen trap sites, such as dislocations, va-
cancies, and grain boundaries [38]. Also, crack initiation may
occur earlier in the X70 pipeline steel compared to that in the
tests of austenitic stainless steel. Once an initial crack is
formed, the crack propagation rate is higher than the
hydrogen migration. Then the time is not sufficiently long to
allow hydrogen absorption. For some alloys belonging to the
group 300 austenitic stainless steel, such as type 304 and low-
nickel content type 316, the occurrence of strain-induced
martensite transformation also increases the susceptibility
to HE embrittlement [16,18,33e35]. These combined condi-
tions will increase the probability of hydrogen-assisted frac-
ture and result in a severe susceptibility.
The loss in the toughness has the same tendency with
decreasing reduction in the area of the notched tensile spec-
imen with a sharp notch radius of R ¼ 0.083 mm when tested
in the gas mixture with 1% H2. Also, the similarity of the
fracture surface appearance strongly indicates a similar

Please cite this article as: Nguyen TT et al., Effect of low partial hydrogen in a mixture with methane on the mechanical properties of
X70 pipeline steel, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.013
 international journal of hydrogen energy xxx (xxxx) xxx
hydrogen-induced fracture mechanism. This is well-
agreement with the results presented in the literature
[13,21,30]. As already explained, owing to an existing fatigue
pre-crack, H concentration is accumulated at the crack tips
where the hydrostatic stress is relatively high [39]. The
hydrogen accumulation may lead to the localization of plas-
ticity within the plastic zone with a high hydrogen content,
which is consistent with the features of the hydrogen
enhanced-localized plasticity mechanism [40,41].
It is important to note that the high pressure of either the
gas mixture or 100% H2 does not have pronounced effects on
the yield and ultimate tensile strength of the pipeline steels.
Thus, designing by the stress approach may not be applicable
for a hydrogen service component because degradation is
nearly observed in the loss of the ductility. In actual condi-
tions, it is not common to use pipeline steel for structural
components containing high-pressure pure H2 gas. The ob-
tained results with a low partial hydrogen described here
provide some useful information for designing as well as
service appliance and maintenance adjustments. Both the
tensile strength and ductility of the present material were not
affected by 10 MPa of gas mixture with 1% H2 when tested with
the smooth tensile specimen. Therefore, stress analysis for
the structural integrity evaluation of a pipeline system under
the low partial H2 is strictly not of concern. However, the
significant degradation in the ductility when tested with the
sharp notched tensile specimen and the remarkable decrease
in the toughness may provide some useful information for
designing as well as service appliance and maintenance ad-
justments. The level of the stress concentration factor may
play an important role in achieving the critical hydrogen
concentration. Structural design should be noted to avoid any
high stress concentration to achieve the critical hydrogen
concentration. The presence of any defect such as a crack flaw
appearing on the interior of the pipeline can cause a large
increase in the stress/strain at the notch tip. It may pose a
potential safety risk to the operation of the pipeline despite
the relatively low partial hydrogen. In this aspect, pipeline
systems are routinely required to inspect their condition to
ensure safe and efficient operation. Finally, the fracture me-
chanics approach of fitness-for-service should be adapted to
evaluate the conservative life assessment results for pipelines
distributing mixtures of natural/hydrogen gas [42,43].
Conclusions
The effect of 10-MPa hydrogen/natural gas mixture with 1% H2
on the mechanical properties of API X70 pipeline steel was
investigated via tensile, notched tensile, and toughness tests.
From the above results and discussion, the following are the
conclusions:
(1) The X70 pipeline steel exhibits a significant reduction in
the ductility in 10 MPa of H2. However, the 10-MPa
hydrogen/natural gas mixture with 1% H2 does not
cause any degradation of the mechanical properties of
X70 pipeline steel when tested with the smooth tensile
specimen.
Please cite this article as: Nguyen TT et al., Effect of low partial hydrogen in a mixture with methane on the mechanical properties of
X70 pipeline steel, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2019.11.013
13
(2) A substantial loss of the RA under 10-MPa gas mixture
with 1% H2 is only observed when tested with the sharp
notched specimen with a notch radius of 0.083 mm. The
presence of a sharp notch provides a higher stress/
strain concentration in the gauge section, enhances the
stress triaxiality, which favors the hydrogen local con-
centration, and results in a more pronounced effect.
(3) The fracture toughness of X70 pipeline steel is reduced
markedly under gas mixtures with 1% H2 from 0.42 mm
in ambient air to 0.21 mm. Under 10 MPa of 100% H2, the
CTOD is only 0.11 mm.
(4) The long-term exposure to low partial hydrogen has no
effect on the mechanical properties of X70 pipeline
steel.
Acknowledgement
This research was supported by Development of Reliability
Measurement & Standard Technology for Hydrogen Fueling
Station funded by Korea Research Institute of Standards and
Science (KRISS e 2019 e GP2019-0012). This study was also
supported by supported by the 2019e2021 KAIA/MOLIT Project
(No.19TLRP-C152334-01) leaded by Korea Research Institute of
Standards and Science (KRISS), Republic of Korea.
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