Ocean Engineering 146 (2017) 311–323

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Ocean Engineering
journal homepage: www.elsevier.com/locate/oceaneng

Effect of pH and hydrogen on the stress corrosion cracking behavior of

duplex stainless steel in marine atmosphere environment
Wei Wu a, Zhiyong Liu a, *, Shanshan Hu a, Xiaogang Li a, b, Cuiwei Du a
a
Corrosion and Protection Center, University of Science and Technology Beijing, Beijing 100083, China
b
Ningbo Institute of Material Technology & Engineering, Chinese Academy of Sciences, Ningbo 315201, Zhejiang, China

A R T I C L E I N F O A B S T R A C T

Keywords: Electrochemical and stress corrosion cracking (SCC) behaviors of 2205 duplex stainless steel (DSS) of different
pH microstructures in the marine atmosphere environment with various pH values and hydrogen charging current
Hydrogen charging densities were investigated by employing electrochemical measurements and the slow strain rate tensile (SSRT)
Stress corrosion cracking method. Results indicated that the resistance of 2205 DSS to pitting corrosion deteriorated as the pH decreased,
Duplex stainless steel and the susceptibility to SCC improved in spite of the decrease in pH or the increase in hydrogen charging current
Marine atmosphere environment
density. As compared to the microstructure of the as-received specimen, microstructures of the normalized and
especially the quenched samples were more vulnerable to SCC.

1. Introduction
The use of stainless steel in marine engineering to relieve the corro-
sion behavior induced by harsh conditions in marine environment, such
as the high salinity, high humidity, and the presence of various kinds of
microorganisms, is increasing. Duplex stainless steel (DSS) has been
widely applied for offshore construction and platform in recent years.
DSS, generally exhibiting a ferrite/austenite volume ratio of 1:1, usually
shows considerable resistance to pitting and stress corrosion cracking
(SCC) (Lv et al., 2016; Raman and Siew., 2010; Zanotto et al., 2014).
However, the thin electrolyte layer (TEL) environment in marine atmo-
sphere is recognized as a huge threat to metal materials due to its short
distance of diffusion and increased concentration of salinity. The corro-
sion behavior induced by TEL is quite different from that induced by bulk
solutions, which often results in serious localized corrosion (Zhang et al.,
2008; Zhou et al., 2009; Zvirko, 2017), causing many failures and
financial loss (Cheng et al., 2004; Li et al., 2015; Liao et al., 2011).
However, the corrosion behavior, especially the SCC behavior of DSS in
TEL, remains unknown, which seriously affects engineering applications
and service life. Thus, the SCC behavior of DSS in TEL environment has
become an urgent problem to solve.
pH is one of the most vital factors in marine atmosphere environment
that prominently affects the corrosion process (Hu et al., 2011; Li et al.,
2014; Wu et al., 2015). The occurrence of acid rain (Sun et al., 2009; Vera
et al., 2009) and the presence of corrosion products and deposit
sediments (Refait et al., 2013; Skrifvars et al., 2008) can result in
changing the pH of TEL. Furthermore, galvanic corrosion occurring be-
tween dissimilar metals in marine engineering can alter the pH of TEL
covered on cathodic materials (Izquierdo et al., 2013). In addition, the
TEL within the crevice or under the disbonded coating has an extremely
low pH due to the enclosed conditions (Chen et al., 2016; Wang et al.,
2014). A wide range of pH conditions can be present in marine envi-
ronment due to these factors, which may promote SCC of DSS in TEL
environment. More importantly, cathodic hydrogen evolution in TEL
facilitates hydrogen permeation, resulting in the enhancement of
hydrogen content in steel. This may cause hydrogen embrittlement (HE)
or hydrogen-induced cracking (HIC) and aggravation of the SCC sus-
ceptibility (Mohtadi-Bonab et al., 2015; Wan et al., 2016). Zheng et al.
(2007) found the occurrence of distinct hydrogen permeation in TEL
environment on examining the 35CrMo high-strength steel. Furthermore,
the velocity of hydrogen permeation was promoted by stress. Thus, de-
creases in pH and hydrogen permeation usually occur in marine atmo-
sphere environment, and their influence on SCC of DSS is vitally
important. Meanwhile, the microstructure of welded DSS is composed of
coarse grain with significant defects, which results in a worse mechanical
property of welded DSS relative to the as-received material. This means
that the welded DSS is more vulnerable to SCC in a TEL conditions in
marine. However, so far, plenty of studies have been carried out for
understanding the electrochemical behavior and characterizing the pas-
sive film of DSS (Gholami et al., 2015; Luo et al., 2011, 2012; Wang et al.,

* Corresponding author.
E-mail address: liuzhiyong7804@163.com (Z. Liu).

https://doi.org/10.1016/j.oceaneng.2017.10.002
Received 2 May 2017; Received in revised form 4 July 2017; Accepted 1 October 2017
Available online 7 October 2017
0029-8018/© 2017 Published by Elsevier Ltd.
W. Wu et al. Ocean Engineering 146 (2017) 311–323

Table 1
Element composition of 2205 duplex stainless steel in this work (mass, %).

Element C Si Mn P S Cr Ni Mo N
content 0.029 0.59 1.20 0.029 0.004 22.57 4.63 2.62 0.13

Fig. 1. Microstructures of different 2205 DSS samples as observed by LSCM. The black part corresponds to the ferrite phase and the white part represents the austenite phase. (a) As-
received, (b) normalized, and (c) quenched samples.

2. Experimental procedure

2.1. Materials

2205 DSS was used as the test material in this study, the element
composition of which is given in Table 1. Two kinds of heat treatments
were finished to simulate different microstructures at the heat-affected
zone. The specimens were heated at 1,350
C and held for 10 min fol-
lowed by normalizing the samples in air and quenching in normalized
water. The different microstructures obtained were etched with aqua
regia solution (HCl 75%, HNO3 25%) and were examined using a KEY-
ENCE VK-X200 laser scanning confocal microscope (LSCM). The ratio of
the austenite and ferrite phases was roughly calculated using Photoshop
Fig. 2. Three-electrode system for performing electrochemical measurements in TEL
6.0, as shown in Fig. 1. The as-received 2205 DSS specimen is mainly
environment.
composed of ferrite and austenite with an approximate ratio of 1.05:1
with the two phases uniformly distributed at regular intervals. However,
2015a,b), only a few studies have focused on the SCC behavior and
in the case of 2205 DSSs obtained with air cooling and water cooling, the
mechanism in TEL environment. Furthermore, the influence of welding
two phases are distributed intricately. The normalized 2205 DSS spec-
to the SCC behavior of DSS in TEL is rarely discussed in these years. Thus,
imen contains more austenite phase than the quenched 2205 DSS
it is necessary to study the effect of pH and hydrogen on the electro-
because of the slower cooling velocity employed in the phase change
chemical properties and SCC behavior of welded DSS in marine TEL
process. The ratios of ferrite and austenite in normalized and quenched
environment.
2205 DSS specimens are 1.22:1 and 1.75:1, respectively.
In this paper, DSSs were prepared using different heat treatment
processes to simulate the weld microstructure. Electrochemical mea-
2.2. Electrochemical measurements
surements and slow strain rate tensile (SSRT) tests combined with elec-
trochemical hydrogen charging tests were conducted to study the effect
Electrochemical measurements were conducted on a P2273 electro-
of pH and charging hydrogen current density on the SCC behavior and
chemical workstation using a three-electrode system, as shown in Fig. 2.
mechanism of DSS in marine TEL environment.
The 2205 DSS sample was used as the working electrode (WE), Ag/AgCl
electrode served as the reference electrode (RE), and Pt plate as the

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W. Wu et al. Ocean Engineering 146 (2017) 311–323

Fig. 3. Schematic diagrams of the (a) atomization device and (b) SSRT experimental set-up in TEL environment.

counter electrode. WE was sealed by epoxy resin with a working area of
1 cm2 followed by grinding sequentially by abrasive paper and cleaning
with distilled water and acetone. The marine TEL environment was
accomplished using an atomization device, as shown in Fig. 3a and 3.5%
(mass fraction) NaCl solution with a pH of 3.0, 6.5, 7.5 was selected as
the atomizing solution to simulate the marine atmosphere. During the
tests, moisture was supplied constantly to maintain the humidity in the
three-electrode system as 100%. A moisture meter was used to monitor
the experiment conditions.
Prior to the tests, WE was held in TEL environment for 30 min to
obtain a steady-state potential, and electrochemical impedance spec-
troscopy (EIS) measurements were conducted from 100 kHz to 10 mHz
with the AC amplitude of the sinusoidal perturbation of 10 mV. Poten-
tiodynamic polarization curves were acquired by scanning from 1.0 V
to 1.2 V vs. Ag/AgCl at a sweep rate of 0.5 mV/s. All the electrochemical
tests were conducted at ambient temperature and were repeated
three times.
2.3. SSRT tests
selected according to the previous papers (Dunne et al., 2016; Saleh et al.,
2016) and trying to avoid the effect of hydrogen-induced plasticity (HIP).
Meanwhile, relevant discussion of hydrogen blister is ignored to simplify
the study of SCC mechanism of 2205 DSS in a marine TEL environment.
Before charging, the solution was deoxidized with high purity nitrogen
for 2 h. All SSRT tests were conducted at ambient temperature and were
repeated at least three times to ensure veracity. After performing the
experiments, the elongation (φ) and reduction of area (δ) were calculated
from Eqs. (1) and (2) to obtain the susceptibility of 2205 DSS to SCC:
Δl
φ¼1 (1)
l0
ΔS
δ¼1 (2)
S0
where Δl and ΔS are the change in specimen length and cross section
area, respectively. l0 and S0 are the original values for the specimen
length and cross section area, respectively.

3. Results
SSRT specimens were prepared according to Chinese National Stan-
dards GB/T 15970. Prior to testing, the steel samples were ground with a
3.1. Electrochemical behavior of 2205 DSS in TEL environment with
fine emery paper along the tensile direction and washed with ethyl
various pH values
alcohol followed by maintaining the samples in an atmosphere with
100% relative humidity for 24 h to ensure the formation of an electrolyte
3.1.1. EIS results
film on the surface. Moisture was continuously pumped during the
Fig. 4 shows the Nyquist curves for 2205 DSS in TEL environment
experiment. SSRT experiment was conducted with a strain rate of
with different pH values. All the curves are mainly composed of two
1  106 s1 using a WDML-30KN Materials Test System, as shown in
capacitive arcs. In general, the high-frequency capacitive arc provides
Fig. 3. Two kinds of SSRT experiments were performed to study the in-
information about the double electrode layer, whereas the low-frequency
fluence of pH and hydrogen content on the SCC behavior of 2205 DSS in
capacitive arc accounts for the capacitance of the passive film. As pH
marine TEL environment. For the first group, 3.5% NaCl with a pH 3.5,
decreases, the impedance arc radius of all the 2205 DSS specimens de-
6.5, and 7.5 was used as the atomizing solution and relevant SSRT
creases, indicating the weakening of resistance of 2205 DSS to corrosion.
specimens were not imposed with the hydrogen charging process. The
Furthermore, the impedance arc radius of the quenched sample sharply
specimens in the second group were charged in 0.25 mol/L NaOH and
diminishes when the pH of moisture changes from 7.5 to 3.0, which in-
0.25 g/L thiourea for 24 h with different hydrogen charging current
dicates that the quenched microstructure is more susceptible to acidic
densities (10, 20, 50, 100 mA/cm2), and 3.5% NaCl with a pH of 6.5 was
TEL environment.
used as the atomizing solution. These values of current densities are

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W. Wu et al.
Fig. 4. Nyquist diagrams of different 2205 DSSs in TEL environment with a pH of 3.5, 6.5, and 7.5: (a) As-received, (b) normalized, and (c) quenched samples.
Fig. 5. Equivalent circuit for the Nyquist curves of different 2205 DSSs in TEL with a pH
of 3.5, 6.5, and 7.5.
Different models have been proposed for interpreting impedance
spectra on a passive metal surface. In this study, the equivalent circuit
given in Fig. 5 is adopted to fit the experimental data, where Rs corre-
sponds to the solution resistance, CPEdl represents the capacitance of the
double electrode layer, and Rct signifies the charge transfer resistance.
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Ocean Engineering 146 (2017) 311–323
CPEf and Rf are the capacitance and resistance of the passive film,
respectively. This model often corresponds to an inhomogeneous passive
film consisting of a porous outer layer and a compact inner layer (Boissy
et al., 2015; Chen et al., 2013; Cui et al., 2017). Meanwhile, the fitted Rct
and Rf values are shown in Fig. 6a and b, respectively. Both these values
decrease as pH decreases, implying that the acidification of moisture
results in the destruction of the passive film and deterioration of the
corrosion resistance. As compared to the as-received and normalized
microstructures, Rf of the quenched sample sharply drops at a pH of 6.5,
indicating that the passive film is badly damaged and it loses the capacity
of protecting the matrix after performing the quenching treatment.
3.1.2. Potentiodynamic polarization results
Potentiodynamic polarization curves of different 2205 DSSs in TEL
with a pH 3.5, 6.5, and 7.5 are shown in Fig. 7a, b, and 7c; meanwhile,
the relevant pitting potentials (Ep) and passive current densities (ipass) of
the three 2205 DSSs are plotted in Fig. 7d, e, and 7f. With a decrease in
pH, all curves shift toward right and hydrogen evolution reaction occurs
during the cathodic process. As is known, hydrogen permeation occurs in
TEL environment, hydrogen atoms could enter the passive film and un-
dermine its compactness. In spite of the appearance of the passive region,
the regions gradually shrink as pH decreases at all conditions. Further-
more, Ep decreases and ipass increases significantly, suggesting the sharp
W. Wu et al.
Fig. 6. Variations in (a) Rct and (b) Rf fitted with the equivalent circuit of different 2205 DSSs in TEL with a pH of 3.5, 6.5, and 7.5.
weakening of the resistance to pitting corrosion and significant promo-
tion of localized dissolution of the passive film with a decrease in pH.
3.2. SSRT behavior of 2205 DSS in TEL environment with various pH
values
The stress-strain curves of 2205 DSS were obtained by carrying out
SSRT experiments in air and moisture atmosphere with different pH
values (Fig. 8). Significantly, different curves were obtained for different
pH values and heat treatment conditions. Strain diminishes for all the
three samples in TEL as compared to that in air, especially for the
normalized and quenched samples, which indicates the susceptibility of
2205 DSS to SCC. The decrease in pH value causes a decrease in strain,
revealing an increased SCC susceptibility of 2205 DSS in TEL. The
elongation and reduction of area, as plotted in Fig. 9, decline as pH
changes from 7.5 to 3.0, which also confirms the increase in suscepti-
bility to SCC. Further, the reduction of area is more sensitive to the
increasing of acidity than the elongation of 2205 DSS. In addition, the
lowest elongation and reduction of area were achieved with the
quenched sample, which is in well accordance with the electro-
chemical behavior.
3.3. SSRT behavior of 2205 DSS in TEL environment with different
hydrogen charging current densities
3.3.1. Stress-strain curves
Fig. 10 displays the stress-strain curves of 2205 DSS obtained from the
SSRT experiments performed in moisture atmosphere with different
hydrogen charging current densities. Clearly, after being charged, the
specimens exhibit lower strain and higher sensitivity to SCC in marine
TEL environment. The strain of 2205 DSS sharply decreases with an in-
crease in current density irrespective of whether the heat treatment was
employed. Furthermore, as compared to the decrease in pH in moisture,
the increase in the amount of hydrogen atoms in steel causes more
distinct and clear effects on the SCC behavior. The elongation and
reduction of area are calculated and plotted in Fig. 11. The values
maintain a preferable level and reduce slowly for the as-received sample
as the hydrogen charging current density increases. While the normalized
and quenched samples are significantly affected by changes in the current
densities, resulting in extremely low elongation and reduction of area at
100 mA/cm2. Similarly, the reduction of area is more sensitive to the
increasing of hydrogen charging current density than the elongation of
2205 DSS.
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Ocean Engineering 146 (2017) 311–323
3.3.2. Fracture morphologies
The fracture morphologies of the three 2205 DSS samples were
examined using a scanning electron microscope (SEM). The results ob-
tained for the quenched 2205 DSS sample are shown in Fig. 12. Macro-
scopic fracture morphology examinations indicate the occurrence of
apparent necking on the samples without charging with hydrogen, while
the necking effect fades away and the SCC wall appears with an increase
in the hydrogen charging current density. The fracture morphology of the
2205 DSS in air corresponds to a dimple pattern with features of ductile
fracture. In contrast, obvious brittle fracture occurs on the 2205 DSS
samples in TEL, as evidenced by the predominant cleavage river pattern.
It is worth noting that anodic dissolution (AD) takes place in the SCC
process of 2205 DSS without charging with hydrogen and disappears
gradually with an increase in hydrogen charging current density, sug-
gesting that HE significantly aggravates and the relevant SCC mechanism
of 2205 DSS in TEL is changed from AD to HE.
3.3.3. Side morphologies
Similarly, the side surfaces of the quenched 2205 DSS were examined
using SEM, as shown in Fig. 13. The surface of the sample in air is smooth
without containing any pits and cracks, as shown in Fig. 13a, while in
TEL, pits and cracks appear on the quenched sample, implying the
appearance of susceptibility to SCC. Furthermore, the quantity, length,
and depth of the cracks on the side-surface of the samples constantly
increase as the hydrogen charging current density increases (Fig. 13b–f).
Thus, the SCC susceptibility quickly increases as soon as the sample is
charged, which is in well accordance with the variation tendency
observed with elongations and reductions of area as shown in Fig. 11.
Meanwhile, the occurrence of localized anodic dissolution on the side
surface is not obvious, and the profile cracks are not initiated from the
pits, indicating that the SCC mechanism of 2205 DSS in TEL mainly
corresponds to HE after charging with hydrogen.
4. Discussion
4.1. Electrochemical mechanism analysis of 2205 DSS in marine
atmosphere environment
Generally, 2205 DSS exhibits excellent resistance to corrosion in at-
mospheric environment. However, in marine atmosphere, aqueous vapor
is prone to congeal and covers the surface of 2205 DSS because of high
humidity and the special corrosive conditions accordingly formed,
namely, TEL. Corrosive ions accumulate in large quantities owing to the
low mobility of TEL. For example, Cl is one of the most dangerous ions
W. Wu et al. Ocean Engineering 146 (2017) 311–323

Fig. 7. Potentiodynamic polarization curves of different 2205 DSSs in TEL with a pH of 3.5, 6.5, and 7.5 (Fig. 7a–c show the polarization curves of the as-received, normalized, and
quenched samples, respectively; Fig. 7d–f show the corresponding pitting potentials and passive current densities).

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W. Wu et al. Ocean Engineering 146 (2017) 311–323

Fig. 8. Stress-strain curves of different of 2205 DSSs obtained from SSRT experiments performed in air and TEL with a pH of 3.5, 6.5, and 7.5: (a) As-received, (b) normalized, and (c)
quenched samples.

Fig. 9. Elongation and reduction of area of different 2205 DSSs in air and TEL with a pH of 3.5, 6.5, and 7.5: (a) Elongation and (b) reduction of area.

317
W. Wu et al. Ocean Engineering 146 (2017) 311–323

Fig. 10. Stress-strain curves of different 2205 DSSs obtained from SSRT experiments performed in TEL with different hydrogen charging current densities: (a) As received, (b) normalized,
and (c) quenched samples.

Fig. 11. Elongation and reduction of area of different 2205 DSSs in TEL with different hydrogen charging current densities: (a) Elongation and (b) reduction of area.

318
W. Wu et al.
Fig. 12. Fracture morphologies of the quenched 2205 DSS sample obtained from SSRT experiments performed (a) in air and in TEL with different hydrogen charging current densities: (b)
0 mA/cm2; (c) 10 mA/cm2; (d) 20 mA/cm2; (e) 50 mA/cm2; and (f) 100 mA/cm2.
for passive films (Meng et al., 2014; Souza et al., 2010), and increase in
the Cl content would result in easy destruction of the passive film,
causing localized anodic dissolution to occur as below:
Fe  2e→Fe2þ
On the other hand, the oxygen content in TEL is relatively high since
TEL exhibits a high specific surface area, and a fast relevant diffusion rate
is achieved due to the short distance (Zhong et al., 2013). Thus, the
electrochemical cathodic reaction is primarily the reduction of oxygen,
Ocean Engineering 146 (2017) 311–323
which occurs more violently than that occurs in aqueous solution:
O2 þ 2H2 O þ 4e→4OH  (4)
þ
When pH decreases, the content of H in TEL increases, resulting in
(3)
significant promotion of both the anodic and cathodic processes. A pre-
vious study (Wang et al., 2015a,b) suggested that the localized dissolu-
tion of iron could be accelerated under acidic environments containing
Cl, as Cl combines with Fe2þ to form an adsorption complex as the
intermediate product in the process of AD. The reactions can be described
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W. Wu et al.
Fig. 12 (continued).
as follows:
Fe þ HCl→ðFeClÞads þ H þ þ e (5)
ðFeClÞads →FeClþ þ e (6)
FeClþ þ H þ →Fe2þ þ HCl (7)
Meanwhile, the cathodic reaction rapidly changes due to the presence
of abundant Hþ in TEL. Thus, hydrogen evolution occurs as the main
cathodic reaction, thereby facilitating the electrochemical pro-
cess further.
H þ þ e→Hads (8)
2Hads →H2 (9)
The electrochemical curves (Figs. 4 and 7) obtained in our study
indicate that the impedance arc radius of 2205 DSS decreases as pH
decreases. More importantly, both the anodic and cathodic curves are
shifted toward right and hydrogen evolution occurs in the cathodic part.
Ep decreases and ipass increases distinctly as the pH of TEL decreases, thus
proving the above-mentioned analysis.
4.2. Effect of hydrogen in marine TEL environment on the SCC behavior of
2205 DSS
The effect of hydrogen on the SCC behavior of 2205 DSS in marine
atmosphere was studied by changing the content of hydrogen ions in TEL
and hydrogen atoms in steel, which is achieved by altering the pH of TEL
and charging hydrogen to the 2205 DSS, respectively. A comparison of
the analysis results of the side surfaces of quenched samples after per-
forming SSRT is shown in Fig. 14. Fig. 14a and b show the results ob-
tained for the 2205 DSS samples measured in TEL with a pH of 6.5 and
3.0 without charging with hydrogen, and Fig. 14c represents the sample
charged under 10 mA/cm2 and measured in TEL with a pH of 6.5.
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Ocean Engineering 146 (2017) 311–323
Clearly, for the first way, i.e., changing the pH of TEL, the pitting
potential of 2205 DSS gradually drops as pH decreases (Fig. 7). Localized
anodic dissolution is significantly promoted under acidic TEL environ-
ment containing Cl, as stated in Eqs. (5)–(7). Thus, pits are naturally
formed and motivates the initiation of microcrack under stress concen-
tration (Ramamurthy and Atrens, 2010; Zhu et al., 2013), accelerating
the SCC process in TEL, as shown in Fig. 14a and b. Besides, the increase
of hydrogen ion concentration in TEL induces hydrogen evolution and
further produces the cathodic charging hydrogen current. Though the
current density is weak, hydrogen permeation can still occur under the
conditions of TEL (Zheng et al., 2007), causing an improvement in the
hydrogen content in the matrix. Subsequently, hydrogen atoms combine
to form molecular hydrogen, resulting in the occurrence of HE during the
process of SCC and enhancement of the SCC susceptibility. Therefore, the
SCC behavior of 2205 DSS in marine TEL environment with a pH of 7.5,
6.5, and 3.0 is attributed to the combined effect of AD and HE.
For another way, namely, charging hydrogen, both the fracture and
side surfaces are relatively smooth without obvious AD or pit, even with a
low hydrogen charging current density of 10 mA/cm2 (Figs. 12c, 13c and
14c). Thus, it can be concluded that the effect of AD is negligible in the
process of SCC. Simultaneously, the sample shows a higher susceptibility
to SCC in TEL accompanied by the formation of plenty of microcracks,
and the cracks are almost straight and propagate in transgranular mode,
indicating that a large number of hydrogen atoms can be permeated into
the steel during charging and induce abundant microcracks. Thus, the
SCC behavior of 2205 DSS with different hydrogen charging current
densities is mainly controlled by the mechanism of HE or HIC.
4.3. Effect of microstructures of 2205 DSS on the SCC behavior in marine
TEL environment
Irrespective of whether pH decreases or the hydrogen charging cur-
rent density increases, the normalized and quenched 2205 DSSs show a
higher susceptibility to SCC than the as-received 2205 DSS in TEL (Figs. 9
and 11), which suggests the resistance of the 2205 DSS weld joint to
W. Wu et al.
Fig. 13. Side morphologies of the quenched 2205 DSS sample obtained from SSRT experiments performed (a) in air and in TEL with different hydrogen charging current densities: (b)
0 mA/cm2; (c) 10 mA/cm2; (d) 20 mA/cm2; (e) 50 mA/cm2; and (f) 100 mA/cm2.
stress corrosion is sharply weakened. Thus, the SCC behavior is signifi-
cantly affected by the microstructure of 2205 DSS. In this paper, after
heating at 1,350
C for 10 min, the microstructure of the samples is
almost entirely transformed into α-ferrite, and a solid-state phase change
occurs as temperature decreases. However, due to the fast cooling rate
employed, the time obtained for achieving phase transformation is
extremely low. Hence, the microstructure of quenched 2205 DSS is
characterized by coarser grain size, higher ferrite contents, and more
extensive precipitation of chromium nitride as compared to the
normalized 2205 DSS sample (Chen and Yang, 2001; He et al., 2010;
Hsieh et al., 2001). Abundant defects remain during the normalizing and
quenching processes, which mainly includes dislocations, vacancies, and
precipitated phases. According to previous studies (Geng et al., 2015; Ha
and Kwon, 2007), the resistance of 2205 DSS to corrosion would be
worsened due to the presence of the above-mentioned microstructure
features in the duplex stainless steel. Thus, in the marine TEL environ-
ment, the corrosion behavior occurs quickly on the surface of normalized
and quenched 2205 DSS samples in the marine TEL condition. Further-
more, as pH declines, the relevant passive film resistance (Rf in Fig. 6b)
and pitting potential (Ep in Fig. 7) of the 2205 DSS sharply decrease in
TEL. Pit is prone to develop and subsequently microcracks initiate under
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Ocean Engineering 146 (2017) 311–323
stress. At the same time, a large amount of hydrogen atoms permeates
into the matrix due to the presence of various defects, thereby leading to
the local distortion of stress, degradation of mechanical properties of the
steel, and facilitation of the initiation and propagation of microcracks
(Akiyama and Li, 2016; Popov, 2015; Yan et al., 2015). Finally, the
susceptibilities of the normalized and quenched 2205 DSSs to SCC are
substantially improved, and the SCC mechanism in the TEL is controlled
by the synergistic effect of AD and HE at different pH values and the
effect of HE at different hydrogen charging current densities.
5. Conclusions
As the pH declines, 2205 DSS exhibits a lower pitting potential and
passive film resistance, indicating the deterioration of resistance to
corrosion, and pitting corrosion is prone to occur in a marine TEL envi-
ronment. Localized anodic dissolution is significantly promoted and
hydrogen evolution occurs fiercely under acidic conditions, and even-
tually results in the SCC mechanism to be the synergistic effect of AD
and HE.
Charging hydrogen has a tremendous influence on the SCC behavior
of 2205 DSS, which causes extremely low elongation and reduction of
W. Wu et al.
Fig. 14. Comparison analysis of side morphologies of quenched 2205 DSS after performing SSRT experiments at (a) pH 6.5, no charging; (b) pH 3.0, no charging; and (c) pH 6.5, hydrogen
charging under 10 mA/cm2.
area, smooth fracture appearance, and abundant side cracks. The sus-
ceptibility to SCC sharply improves as the current density increases, and
the SCC mechanism is mainly controlled by HE.
The normalized and quenched 2205 DSSs reveal a lower pitting po-
tential and a higher SCC susceptibility than the as-received 2205 DSS
sample irrespective of the decrease in pH or increase in the hydrogen
charging current density, which could be attributed to the coarser grain
size, higher ferrite contents, and more extensive precipitation of chro-
mium nitride in the microstructure.
Acknowledgement
The authors would like to acknowledge the financial support from the
National Basic Research Program of China (973 Program) (Grant No.
2014CB643300), National Nature Science Foundation of China
(No.51471034) and China Scholarship Council (CSC)
(No.201606465051).
References
Akiyama, E.J., Li, S.J., 2016. Electrochemical hydrogen permeation tests under
galvanostatic hydrogen charging conditions conventionally used for hydrogen
embrittlement study. Corros. Rev. 34, 103–112.
Boissy, C., Ter-Ovanessian, B., Mary, N., Normand, B., 2015. Correlation between
predictive and descriptive models to characterize the passive film–Study of pure
chromium by electrochemical impedance spectroscopy. Electrochim. Acta 174,
430–437.
Chen, T., John, H., Xu, J., Lu, Q., Hawk, J., Liu, X., 2013. Influence of surface
modifications on pitting corrosion behavior of nickel-base alloy 718. Part 1: effect of
machine hammer peening. Corros. Sci. 77, 230–245.
Chen, T.H., Yang, J.R., 2001. Effects of solution treatment and continuous cooling on
σ-phase precipitation in a 2205 duplex stainless steel. Mater. Sci. Eng. A 311, 28–41.
Chen, X., Gao, F.J., Wang, Y.L., He, C., 2016. Transient numerical model for crevice
corrosion of pipelines under disbonded coating with cathodic protection. Mater. Des.
89, 196–204.
322
Ocean Engineering 146 (2017) 311–323
Cheng, Y.L., Zhang, Z., Cao, F.H., Li, J.F., Zhang, J.Q., Wang, J.M., Cao, C.N., 2004.
A study of the corrosion of aluminum alloy 2024-T3 under thin electrolyte layers.
Corros. Sci. 46, 1649–1667.
Cui, Z.Y., Wang, L.W., Ni, H.T., Hao, W.K., Man, C., Chen, H.S., Wang, X., Liu, Z.Y.,
Li, X.G., 2017. Influence of temperature on the electrochemical and passivation
behavior of 2507 super duplex stainless steel in simulated desulfurized flue gas
condensates. Corros. Sci. 118, 31–48.
Dunne, D.P., Hejazi, D., Saleh, A.A., Haq, A.J., Calka, A., Pereloma, E.V., 2016.
Investigation of the effect of electrolytic hydrogen charging of X70 steel: I. The effect
of microstructure on hydrogen-induced cold cracking and blistering. Int. J. Hydrogen
Energy 41, 12411–12423.
Geng, S.N., Sun, J.S., Guo, L.Y., Wang, H.Q., 2015. Evolution of microstructure and
corrosion behavior in 2205 duplex stainless steel GTA-welding joint. J. Manuf.
Process. 19, 32–37.
Gholami, M., Hoseinpoor, M., Moayed, M.H., 2015. A statistical study on the effect of
annealing temperature on pitting corrosion resistance of 2205 duplex stainless steel.
Corros. Sci. 94, 156–164.
Ha, H., Kwon, H., 2007. Effects of Cr2N on the pitting corrosion of high nitrogen stainless
steels. Electrochim Acta 52, 2175–2180.
He, Y., Zhu, N., Lu, X., Li, L., 2010. Experimental and computational study on
microstructural evolution in 2205 duplex stainless steel during high temperature
aging. Mater. Sci. Eng. A 528721–528729.
Hsieh, R., Liou, H., Pan, Y., 2001. Effects of cooling time and alloying elements on the
microstructure of the gleeble-simulated heat-affected zone of 22% Cr duplex stainless
steels. J. Mater. Eng. Perform. 10, 526–536.
Hu, Y.B., Dong, C.F., Sun, M., Xiao, K., Zhong, P., Li, X.G., 2011. Effects of solution pH and
Cl on electrochemical behavior of an Aermet100 ultra-high strength steel in acidic
environments. Corros. Sci. 53, 4159–4165.
Izquierdo, J., Nagy, L., Gonzalez, S., Santana, J.J., Nagy, G., Sou, R.M., 2013. Resolution
of the apparent experimental discrepancies observed between SVET and SECM for the
characterization of galvanic corrosion reactions. Electrochem. Commun. 27, 50–53.
Li, D.G., Wang, J.D., Chen, D.R., Liang, P., 2014. Influences of pH value, temperature,
chloride ions and sulfide ions on the corrosion behaviors of 316L stainless steel in the
simulated cathodic environment of proton exchange membrane fuel cell. J. Power
Sources 272, 448–456.
Li, X.G., Zhang, D.W., Liu, Z.Y., Li, Z., Du, C.W., Dong, C.F., 2015. Materials science: share
corrosion data. Nature 527, 441–442.
Liao, X.N., Cao, F.H., Zheng, L.Y., Liu, W.J., Chen, A.N., Zhang, J.Q., Cao, C.N., 2011.
Corrosion behaviour of copper under chloride-containing thin electrolyte layer.
Corros. Sci. 53, 3289–3298.
W. Wu et al.
Luo, H., Dong, C.F., Li, X.G., 2012. The electrochemical behavior of 2205 duplex stainless
steel in alkaline solutions with different pH in the presence of chloride. Electrochim.
Acta 64, 211–220.
Luo, H., Dong, C.F., Xiao, K., Li, X.G., 2011. Characterization of passive film on 2205
duplex stainless steel in sodium thiosulphate solution. Appl. Surf. Sci. 258 (1),
631–639.
Lv, J.L., Liang, T.X., Wang, C., Dong, L.M., 2016. Effect of ultrafine grain on tensile
behaviour and corrosion resistance of the duplex stainless steel. Mater. Sci. Eng. C 62,
558–563.
Meng, G.Z., Li, Y., Shao, Y.W., Zhang, T., Wang, Y.Q., Wang, F.H., 2014. Effect of Cl- on
the properties of the passive films formed on 316L stainless steel in acidic solution.
J. Mater. Sci. Technol. 30 (3), 253–258.
Mohtadi-Bonab, M.A., Szpunar, J.A., Basu, R., Eskandari, M., 2015. The mechanism of
failure by hydrogen induced cracking in an acidic environment for API 5L X70
pipeline steel. Int. J. Hydrogen Energy 40, 1096–1107.
Popov, B.N., 2015. Hydrogen permeation and hydrogen-induced cracking. Corros. Eng.
327–364.
Ramamurthy, S., Atrens, A., 2010. The influence of applied stress rate on the stress
corrosion cracking of 4340 and 3.5NiCrMoV steels indistilled water at 30
C. Corros.
Sci. 52 (3), 1042–1051.
Raman, R.K., Siew, W.H., 2010. Role of nitrite addition in chloride stress corrosion
cracking of a super duplex stainless steel. Corros. Sci. 52, 113–117.
Refait, Ph., Jeannin, M., Sabot, R., Antony, H., Pineau, S., 2013. Electrochemical
formation and transformation of corrosion products on carbon steel under cathodic
protection in seawater. Corros. Sci. 71, 32–36.
Saleh, A.A., Hejazi, D., Gazder, A.A., Dunne, D.P., Pereloma, E.V., 2016. Investigation of
the effect of electrolytic hydrogen charging of X70 steel: II. Microstructural and
crystallographic analyses of the formation of hydrogen induced cracks and blisters.
Int. J. Hydrogen Energy 41, 12424–12435.
Skrifvars, B.J., Backman, R., Hupa, M., Salmenoja, K., Vakkilainen, E., 2008. Corrosion of
superheater steel materials under alkali salt deposits Part 1: the effect of salt deposit
composition and temperature. Corros. Sci. 50, 1274–1282.
Souza, E.C., Rossitti, S.M., Rollo, J., 2010. Influence of chloride ion concentration and
temperature on the electrochemical properties of passive films formed on a super
duplex stainless steel. Mater. Character. 61, 240–244.
Sun, S.Q., Zheng, Q.F., Li, D.F., Wen, J.G., 2009. Long-term atmospheric corrosion
behaviour of aluminium alloys 2024 and 7075 in urban, coastal and industrial
environments. Corros. Sci. 51, 719–727.
323
Ocean Engineering 146 (2017) 311–323
Vera, R., Villarroel, M., Carvajal, A.M., Vera, E., Ortiz, C., 2009. Corrosion products of
reinforcement in concrete in marine and industrial environments. Mater. Chem. Phys.
114, 467–474.
Wan, H.X., Du, C.W., Liu, Z.Y., Song, D.D., Li, X.G., 2016. The effect of hydrogen on stress
corrosion behavior of X65 steel welded joint in simulated deep sea environment.
Ocean. Eng. 114, 216–223.
Wang, W.H., Wang, Q.S., Wang, C.Y., Yi, J., 2014. Experimental studies of crevice
corrosion for buried pipeline with disbonded coatings under cathodic protection.
J. Loss Prev. Proc. 29, 163–169.
Wang, Y., Cheng, X.Q., Li, X.G., 2015a. Electrochemical behavior and compositions of
passive films formed on the constituent phases of duplex stainless steel without
coupling. Electrochem. Commun. 57, 56–60.
Wang, Y.F., Cheng, G.X., Wu, W., 2015b. Effect of pH and chloride on the micro-
mechanism of pitting corrosion for high strength pipeline steel in aerated NaCl
solutions. Appl. Surf. Sci. 349, 746–756.
Wu, W., Hao, W.K., Liu, Z.Y., Li, X.G., Du, C.W., Liao, W.J., 2015. Corrosion behavior of
E690 high-strength steel in alternating wet-dry marine environment with different
pH values. JMEPEG 24, 4636–4646.
Yan, Y.J., Yan, Y., He, Y., 2015. Hydrogen-induced cracking mechanism of precipitation
strengthened austenitic stainless steel weldment. Int. J. Hydrogen Energy 40,
2404–2414.
Zanotto, F., Grassi, V., Balbo, A., 2014. Stress corrosion cracking of LDX 2101 duplex
stainless steel in chloride solutions in the presence of thiosulphate. Corros. Sci. 80,
205–212.
Zhang, T., Chen, C., Shao, Y., Meng, G., Wang, F., Li, X., Dong, C., 2008. Corrosion of pure
magnesium under thin electrolyte layers. Electrochim. Acta 53, 7921–7931.
Zheng, C.B., Huang, Y.L., Yu, Q., Zhu, Y.Y., 2007. Hydrogen permeation behavior and
corrosion monitoring of steel in cyclic wet-dry atmospheric environment. Mater.
Corros. 58 (9), 716–720.
Zhong, X.K., Zhang, G.A., Qiu, Y.B., Chen, Z.Y., Guo, X.P., Fu, C.Y., 2013. The corrosion of
tin under thin electrolyte layers containing chloride. Corros. Sci. 66, 14–25.
Zhou, H.R., Li, X.G., Ma, J., Dong, C.F., Huang, Y.Z., 2009. Dependence of the corrosion
behavior of aluminum alloy 7075 on the thin electrolyte layers. Mater. Sci. Eng. B
162, 1–8.
Zhu, L.K., Yan, Y., Qiao, L.J., 2013. Stainless steel pitting and early-stage stress corrosion
cracking under ultra-low elastic load. Corros. Sci. 77, 360–368.
Zvirko, О.І., 2017. Electrochemical methods for the evaluation of the degradation of
structural steels intended for long-term operation. Mater. Sci. 52 (4), 588–594.