international journal of hydrogen energy 34 (2009) 9879–9884

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Effects of hydrogen-charging on the susceptibility of X100

pipeline steel to hydrogen-induced cracking

C.F. Dong a,*, Z.Y. Liu a, X.G. Li a, Y.F. Cheng b,**

a
Corrosion and Protection Center, University of Science and Technology Beijing, Beijing 100083, China
b
Dept. of Mechanical & Manufacturing Engineering, University of Calgary, Calgary, AB, Canada T2N 1N4

article info abstract

Article history: In this work, the hydrogen-induced cracking (HIC) behavior of X100 pipeline steel was
Received 4 August 2009 investigated by a combination of tensile test, electrochemical hydrogen permeation
Received in revised form measurement and surface characterization techniques. The effect of inclusions in the steel
24 September 2009 on the crack initiation was analyzed. Results demonstrated that the amount of hydrogen-
Accepted 26 September 2009 charging into the X100 steel specimen increases with the charging time and charging
Available online 28 October 2009 current density. Hydrogen-charging will enhance the susceptibility of the steel to HIC. The
cracks initiate primarily at inclusions, such as aluminum oxides, titanium oxides and ferric
Keywords: carbides, in the steel. The diffusivity of hydrogen at room temperature in X100 steel is
Hydrogen-induced cracking determined to be 1.04  108 cm2/s.
X100 pipeline steel ª 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
Hydrogen-charging
Inclusions

1. Introduction
In the recent years, with the continuously growing demand in
energy consumption, extensive attentions have been paid to
supply oil and natural oil in a more economic and safer way.
Development of high-strength steel pipelines has enabled the
energy industry to realize significant savings in the total cost
of long-distance oil/gas transmission in view of the pipeline
wall thickness and operating pressure [1–3]. Thus, the primary
interest in the design and manufacture of pipeline steels
meeting the American Petroleum Institute (API) grades is to
obtain the best possible combination of strength, toughness
and corrosion resistance through improving metallurgical and
material processing techniques [4,5].
Hydrogen-induced cracking (HIC) is one of the predomi-
nant failures occurring in high-strength steels, including API
X100 steel [6–12]. HIC results from the entry of atomic
hydrogen into the steel [13]. The penetrated hydrogen atoms
diffuse towards the tri-axial stress zones, and are trapped and
precipitated at sensitive metallurgical defects, such as hard-
ening phases, non-metallic inclusions or micro-cracks to
reduce the local ductility, resulting in HIC [14,15]. It is gener-
ally acknowledged that an elevated strength level tends to
decrease the resistance of the steel to HIC. Hardie et al. [7]
compared the susceptibility of three API grade pipeline steels,
X60, X80 and X100 steels, to HIC. It was found that the loss of
ductility upon hydrogen-charging becomes greater while the
strength level of the steel increases. Almonsour [16] investi-
gated the sulfide SCC of X100 steel in a H2S environment, and
found that HIC cracks nucleated at banded martensite-ferrite
interfaces and propagated along the rolling direction parallel
to the applied tensile stress through the softer ferrite phase.
To date, research on X100 steel has generally focused on
the mechanical and metallurgical aspects in order to improve

* Corresponding author. Tel.: þ86 10 6233 3931.

** Corresponding author. Tel: þ1 403 220 3693.
E-mail addresses: dongchf@hotmail.com (C.F. Dong), fcheng@ucalgary.ca (Y.F. Cheng).
0360-3199/$ – see front matter ª 2009 Professor T. Nejat Veziroglu. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2009.09.090
9880 international journal of hydrogen energy 34 (2009) 9879–9884
Fig. 1 – Micrograph of the microstructure of X100 pipeline
steel.
the strength and roughness of the steel [17,18]. In this work,
the HIC behavior of X100 steel was investigated to simulate
the inside pipeline environmental condition by a combination
of tensile test, electrochemical hydrogen permeation
measurement and surface characterization techniques. The
influences of inclusion and microstructure on the crack initi-
ation and propagation were analyzed, and the cracking
mechanism of X100 steel upon hydrogen-charging was
determined. A H2S environment could also be caused due to
the microbiological activity outside the pipelines, and the
relevant research is still going and not included in this work.
2. Experimental
The material used in this work was cut from a sheet of API
X100 steel plate, with the chemical composition (wt%): C 0.064,
Si 0.13, Mn 1.56, Cu 0.38, Al 0.030, Nb 0.089, Ti 0.011, Ni 0.54, Mo
0.28, S 0.0024, P 0.024, and Fe balance. The metallographic
15
Hydrogen concertation (ppm)
12
9 a PAR 2273 potentiostat.
6 the steady state hydrogen current density, IN, which was
0.05 M H2 SO4 , 50mA/cm2, 1h
3 0.05 M H2 SO4 , 50mA/cm2, 3h
0.05 M H2 SO4 , 50mA/cm2, 5h
0 where A is the specimen area and F is Faraday constant. The
0 400 800 1200 1600 2000
Time (min)
Fig. 2 – The amount of hydrogen released from the steel
specimen that was charged at 50 mA/cm2 in 0.05 M
H2SO4 D 250 mg/L As2O3 solution at various times.
24 0.1 M H 2 SO 4 , 20mA/cm 2
Hydrogen concertation (ppm)
0.5 M H 2 SO 4 , 20mA/cm 2
0.5 M H 2 SO 4 , 50mA/cm 2
20
0.5 M H 2 SO 4 , 100mA/cm2
16
12
4
1 2 3 4 5
Hydrogen Charging Time (h)
Fig. 3 – Steady state concentrations of hydrogen released
from the steel under various charging conditions.
observation showed that it contained predominantly bainite
and ferrite, as shown in Fig. 1.
Specimen used for electrochemical hydrogen-charging was
machined into a rectangle shape, with a dimension of
1.10 cm  1.60 cm  0.05 cm. The specimen was grounded
sequentially to 1200 grit emery paper, and then polarized
cathodically in 0.05 M and 0.5 M H2SO4 solutions at 20 mA/cm2
and 200 mA/cm2 cathodic current densities for 1 h, 3 h, and 5 h,
respectively. The solutions also contained 250 mg/L arsenic
trioxide (As2O3). The addition of As2O3 was to enhance the
hydrogen atom permeation, and avoid their recombination.
After charging, the specimen was immersed immediately into
a liquid paraffin to measure the release flux of hydrogen.
The electrochemical hydrogen permeation test was per-
formed in a modified double-cell, as described previously [5].
The hydrogen-charging side of the double-cell contained 0.5 M
H2SO4 þ 250 mg/L As2O3. The hydrogen ingress into the steel
specimen was facilitated by applying a constant cathodic
current density of 10 mA/cm2. The hydrogen-detecting side
contained 0.1 M NaOH, and a potentiostatically polarized
potential of 300 mV (vs. saturated calomel electrode, SCE) was
applied on the specimen. Prior to the hydrogen permeation test,
the cell was purged with a high-purity nitrogen (99.99%) to
remove the dissolved oxygen in the solution. All electro-
chemical control and measurement was conducted through
The hydrogen flux through the specimen was measured by
converted into hydrogen permeation flux, JN, by [9]:
IN
JN ¼ (1)
FA
effective hydrogen diffusivity, Deff, can be calculated by [19]:
d2
Deff ¼ (2)
6tL
where d is the specimen thickness and tL is the time-lag,
corresponding to the point on the hydrogen permeation curve
 international journal of hydrogen energy 34 (2009) 9879–9884
Fig. 4 – Surface morphology of the steel specimen after 1 h (a), 3 h (b), 5 h (c) and 8 h (d) of hydrogen-charging in 0.5 M H2SO4
solution at a current density of 20 mA/cm2.
at which it ¼ 0.63iN. The sub-surface hydrogen concentration
at the charging side, C0, can be estimated by [19]:
JN  d
C0 ¼ (3)
Deff
For mechanical tensile test, the X100 steel specimen was
machined into a flat bar along the rolling direction of the steel
sheet according to GB T15970 specification [20]. The tensile
specimen was grounded longitudinally with 1200 grit emery
paper. After degreasing, the specimen was masked with
a LECO sealant, except the gauge length. The rate of tensile
test was 0.02 mm/s. The susceptibility of the steel to HIC was
assessed by calculating the elongation and reduction in area
before and after hydrogen-charging. The fracture morphology
Fig 5 – View of micro-crack present on the specimen.
9881
was observed by a Model Philips XL30 scanning electron
microscopy (SEM), and the crack length was determined by
SEM observation. The crack depth was measured by adjusting
the focuses of SEM at the crack mouth and the crack bottom.
All the tests were conducted at ambient temperature
(w21  C) and open to air.
3. Results and discussion
3.1. Amount of hydrogen in the steel under various
charging conditions
Fig. 2 shows the amount of hydrogen released from the steel
that was charged at 50 mA/cm2 in 0.05 M H2SO4 þ 250 mg/L
As2O3 solution at various times. It is seen that the released
hydrogen reached a steady state concentration after about
400 min. The steady state hydrogen concentration released
from the steel increased with the charging time.
Fig. 3 shows the steady state concentrations of hydrogen
released from the steel under various charging conditions. It is
seen that, generally, the measured hydrogen concentration in
the steel increased with the increases of the H2SO4 concen-
tration and charging current density. Apparently, the
hydrogen permeation into the steel is driven by the external
charging conditions, such as the hydrogen ion concentration
and cathodic charging current density.
The time dependence of the amount of the charged hydrogen
is quite complex, depending on the solution chemistry and
charging current density. At a solution with low concentration,
the amount of the charged hydrogen increases with the
charging time, as shown in Fig. 2. However, when the solution
concentration increases, a drop of the amount of the charged
9882 international journal of hydrogen energy 34 (2009) 9879–9884

6.0 hydrogen is observed at a long changing time (Fig. 3). It is

attributed to the fact that a lot of hydrogen bubbles are formed
16
5.5 on the electrode surface, affecting the further permeation of
The maximum of crack

The maximum of crack

hydrogen atoms. The bubbles are also formed on electrode in
5.0 solution with a low concentration, but not as significant as that
length (mm)

14

width (µm)
formed in the solution with a high concentration.
4.5

12
4.0 3.2. Hydrogen-induced cracks associated with inclusions
The maximum of crack length
The maximum of crack width in the steel
3.5
10
Fig. 4 shows the surface morphology of the specimen after
3.0
0 2 4 6 8 charging at 20 mA/cm2 in 0.5 M H2SO4 þ 250 mg/L As2O3
Hydrogen Charging Time (h) solution with various times. A significant number of
hydrogen-induced blisters were observed on the surface of the
Fig. 6 – The crack length and width as a function of specimen. With the charging time, the size of the blisters
hydrogen-charging time. increased. Furthermore, the micro-crack present on the
specimen was observed, as shown in Fig. 5. The length and

Fig. 7 – Inclusions included in X100 steel. a – Titanium oxide and aluminum oxide; b – iron carbide and aluminum oxide.
 international journal of hydrogen energy 34 (2009) 9879–9884 9883

3.3. Hydrogen permeation and diffusion in X100 steel

-6
5.0x10
Permeation current (A)

Fig. 8 shows the hydrogen permeation curve of X100 steel in

-6
4.0x10 the test solution. In this work, the area of the specimen, A, was
1.767 cm2, the thickness, d, was 0.0542 cm, the steady state
-6
3.0x10 hydrogen current, IN, from the hydrogen permeation curve
was about 4.5 mA, and the time-lag was 47078 s. Therefore, we
-6
2.0x10 have

-6 IN 4:5  106
1.0x10 JN ¼ ¼ ¼ 2:65  1011 mol$cm2 $s1 (4)
FA 96500  1:767
0.0
0.0
4 4 4 4
2.0x10 4.0x10 6.0x10 8.0x10 1.0x10 1.2x10
5 5
d2 0:05422
Deff ¼ ¼ ¼ 1:04  108 cm2 $s1 (5)
Time (s) 6tL 6  47078

Fig. 8 – Hydrogen permeation curve of the X100 steel. JN  d 2:65  1011  0:0542
C0 ¼ ¼ ¼ 1:34  104 mol$cm3 (6)
Deff 1:04  108
depth of the cracks were summarized as a function of The hydrogen trap density can be estimated by [8]:
hydrogen-charging time in Fig. 6. It is apparent that, with the  
increase of charging time, both length and depth of the cracks DL NT Eb 1
ln  1 ¼ ln þ  (7)
increased. The surface observations thus provide indirect Deff NL R T
evidences that enhanced hydrogen permeation would result where NT is the number of hydrogen trapping sites per unit
in generation of hydrogen-induced blisters and cracks. volume in cm3, DL is the lattice diffusion coefficient of
Generally, the local irregularities, such as cavities, disloca- hydrogen in cm3 s1, NL is the density of the interstitial sites
tions, grain boundaries and inclusions, are primarily the in the steel in cm3 and Eb is the hydrogen trap binding energy
hydrogen traps in the steel, which are of great importance for in eV. Due to the unavailability of relevant parameters such as
HIC. Various types of inclusions have been identified in X100 DL, Eb and NL for X100 pipeline steel that is relatively new to
steel, such as aluminum oxide, titanium oxide, ferric carbide, the materials science area, we used the parameters obtained
and a trace amount of calcium, magnesium and silicon oxides on a-Fe [15] i.e. DL ¼ 1.28  104 cm2 s1, Eb ¼ 0.3 eV,
and carbides [3]. Fig. 7 shows the primary inclusions contained NL ¼ 7.52  1022 cm3. The value of Deff was then determined
in the steel. Aluminum oxide and titanic oxide were identified from Eq. (5), and the density of hydrogen traps in the steel was
in Fig. 7a, and ferric carbide was found in Fig. 7b. Furthermore, estimated from Eq. (7) by
the cracks were found to be associated with the inclusions.
It is acknowledged [7] that HIC usually generates from the   Eb
Dl
inclusions in the steel. Cavities often generate at the interface NT ¼ NL   1  e RT
Deff
 
between non-metal inclusions and the metal lattice due to ¼ 7:52  1022  1:2810
4 0:3
 1  e 8:3145300 (8)
1:04108
their different thermal expansion coefficients. Hydrogen 26 3
¼ 9:25  10 cm
would be trapped in these cavities. The hydrogen-enhanced
stress concentration results in the crack initiation. In this
work, hydrogen-induced cracks are associated with a large 3.4. Effect of hydrogen-charging on stress-strain
quantity of inclusions including aluminum oxide, titanium behavior of the steel
oxide and ferric carbide.
The stress-strain curves of the X70 steel specimen upon
1000 various hydrogen-charging times at 20 mA/cm2 in 0.5 M
H2SO4 þ 250 mg/L As2O3 solution measured in the charging
solution are shown in Fig. 9. The percentage of elongation (Id)
800
and reduction-in-area factor (IJ) are used to estimate the
susceptibility of the steel to HIC, where
Stress (MPa)

600
Id ¼ ðd0  dH Þ=d0  100% (9)

400 4 3 2 1
1: Uncharged Ij ¼ ðj0  jH Þ=j0  100% (10)
2: 0.5 M H2 SO4 , 20mA/cm 2, 1h and d0 and dH are the elongation of the steel before and after
200 2
3: 0.5 M H2 SO4 , 20mA/cm , 5h hydrogen-charging, respectively. The J0 and JH are the
4: 0.5 M H2 SO4 , 20mA/cm 2, 8h reduction-in-area before and after hydrogen-charging,
0 respectively. Fig. 10 shows the dependences of percentage of
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
elongation and reduction-in-area factor on the charging time.
Displacement (mm)
It is send that, with the increase of the charging time, both Id
Fig. 9 – Stress-strain curves of X100 steel under various and Ij decreased, indicating the increasing HIC susceptibility
charging times. of the steel.
9884 international journal of hydrogen energy 34 (2009) 9879–9884
35
30 Elongation
Plasticity Loss (%)
Reduction in area
25
20
15
10
5
0 2 4 6
Charging Time (h)
Fig. 10 – Reduction of plasticity as a function of charging
time.
Upon hydrogen-charging, the charged hydrogen atoms
tend to diffuse and accumulate at local irregularities, such as
inclusions, micro-defects, etc., with a high stress concentra-
tion [21]. Hydrogen atoms would result in the initiation of
micro-cracks locally by either decreasing the cohesion of Fe–Fe
bonds or increasing the local brittlement. As demonstrated in
this work, cracks are always found at or across the inclusions
contained in the charged steel. Once the micro-cracks are
initiated, the accumulated hydrogen atoms also contribute to
the crack propagation by increasing the local dissolution rate at
the crack tip [22], or decreasing the surface energy of the newly
formed planes and lowering the work of fracture [21]. There-
fore, there is a high susceptibility of the charged steel to SCC.
4. Conclusion
The amount of hydrogen-charging into the X100 steel spec-
imen increases with the charging time and charging current
density. Hydrogen-charging will enhance the susceptibility of
the steel to HIC. The cracks initiate primarily at inclusions,
such as aluminum oxides, titanium oxides and ferric carbides,
in the steel. The diffusivity of hydrogen at room temperature
in X100 steel is determined to be 1.04  108 cm2/s.
Acknowledgements
This work was supported by National Nature Science Foun-
dation of China (Grant No. 50401016), and Canada Research
Chairs Program.
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