Corrosion Science 118 (2017) 118128

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Corrosion behaviour of X65 carbon steel in supercritical-CO2

containing H2 O and O2 in carbon capture and storage (CCS) technology
Y. Tang, X.P. Guo, G.A. Zhang
Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Materials Chemistry and Service
Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Corrosion behaviour of X65 carbon steel in supercritical-CO2 (SC-CO2 ) containing H2 O and O2 was studied
Received 27 September 2016 by weight loss test, electrochemical measurements, and surface analysis. A setup was developed for in situ
Received in revised form 21 January 2017 electrochemical measurements in H2 O-saturated SC-CO2 phase by using Ag/AgCl reference electrode. It is
Accepted 29 January 2017
demonstrated that there is no essential difference in the electrochemical corrosion mechanism between
Available online 31 January 2017
SC-CO2 and non-SC-CO2 environments. The presence of small amount of O2 inhibits the formation of
protective FeCO3 lm and promotes the formation of non-protective Fe oxide, which leads to obvious
Keywords:
increase of corrosion rate in SC-CO2 phase.
A. Carbon steel
B. EIS 2017 Elsevier Ltd. All rights reserved.
B. SEM
B. XPS

1. Introduction
It is well known that greenhouse effect and global warming,
which is caused by the huge emissions of carbon dioxide (CO2 )
with increasing consumption of fossil energy, have become one
of the most concerned issues in the world. The climate change
and environmental issues caused by CO2 emissions would result
in extreme weather and natural disaster, which poses great threat
to the survival and development of human beings [1,2]. Therefore,
to reduce CO2 emissions is related to the sustainable development
of human society. Presently, to tackle the global climate change,
reduce CO2 emissions, has become one of the greatest challenges
that human beings are confronting with. Carbon capture and stor-
age (CCS) technology, which is the process of capturing CO2 from
the atmosphere, transporting the captured CO2 to a storage site,
and then injecting the captured CO2 into underground geological
formation, is considered by the International Energy Agency (IEA)
and the Intergovernmental Panel on Climate Change (IPCC) to be
an important and promising technology to reduce CO2 emissions
[36].
CCS involves three steps: capturing the CO2 produced by indus-
trial sources, compressing the captured CO2 for transportation, and
then injecting the captured CO2 into secure storage site for perma-
nent storage [7,8]. Pipelines transportation is the preferred method
Corresponding author.
E-mail address: zhangguoan@gmail.com (G.A. Zhang).
for large quantity and long distance transportation of CO2 in which
CO2 is usually compressed to supercritical state (SC-CO2 ) in order
to avoid two-phase ow regime and improve the transmission
efciency [9,10]. Currently, there are more than 6500 km of CO2
transport pipelines worldwide. In terms of economic consideration,
the usually adopted materials for CO2 transport pipelines are high
strength low carbon steels, such as X65 and X70 pipelines. These
carbon steels are susceptible to corrosion. It has been found that
dry CO2 is generally non-corrosive. However, the captured CO2 gas
from different industrial sources inevitably contains various impu-
rities. The most concerned impurity is H2 O, followed by O2 , NOx ,
H2 S, CO, SO2 , etc. [11,12]. Once H2 O separates from SC-CO2 stream
to form a free aqueous phase, SC-CO2 will dissolve in H2 O to form
H2 CO3 , and then cause internal corrosion of pipelines. Meanwhile,
impurities could further accelerate the corrosion of pipelines via
reducing the solubility of H2 O in SC-CO2 , decreasing the pH value
or changing the structure of corrosion products lm [1316]. In
brief, the corrosion of pipelines is a key problem that cannot be
ignored in the security implementation of CCS.
Previously, extensive studies on the corrosion issues of carbon
steel in the SC-CO2 environment were carried out in the bulk solu-
tion under the background of oil and gas elds [1722]. However,
the corrosion behaviour of carbon steel in bulk solution containing
SC-CO2 may be different from the corrosion behaviour in H2 O-
containing SC-CO2 phase. Quite a few works on the corrosion of
pipelines in H2 O-containing CO2 phase in CCS eld have been
reported in the past few years, and related studies are summa-
rized in Table 1 [14,15,2333]. Due to the difculty of implementing

http://dx.doi.org/10.1016/j.corsci.2017.01.028
0010-938X/ 2017 Elsevier Ltd. All rights reserved.
 Y. Tang et al. / Corrosion Science 118 (2017) 118128 119

Table 1
Summary of the research on the corrosion in SC-CO2 phase concerning impurities.

Materials T ( C) P(MPa) Impurities Methods Corrosion rate (mm/a) Refs.

X70 50 10 H2 O, O2 , SO2 Weight loss and surface analysis 0.150.9 [15]

X65 50 8 H2 O, O2 , SO2 <0.013.7 [23]
CS,1Cr, 3Cr 80 12 H2 O, H2 S <0.010.44 [24]
X65 50 8 H2 O 00.025 [25]
X65,13Cr 50 8 H2 O, O2 , SO2 <0.017 [26]
X65 50 10 H2 O, O2 , H2 S <0.010.34 [27]
X65 50 10 H2 O, O2 , H2 S, SO2 0.0151.439 [28]
X65 80 10 H2 O, H2 S 0.170.24 [29]
CS 50 15.2 H2 O Electrochemical measurement by two-electrode [30]
CS 50 10 H2 O Electrochemical measurement by using membrane coating 0.050.1 [31]
CS 31 7.93 H2 O Electrochemical measurement by dropping water 12 [32]
CS 45 7.58 H2 O, O2 , SO2 , NO2 112 [33]
CS 45 7.58 H2 O, MDEA, HCl, NaOH 0.15.6 [14]

Note: CS: carbon steel; MDEA: methyldiethanolamine.

in situ electrochemical measurements in H2 O-containing SC-CO2
phase, most previous studies were focused on weight loss mea-
surement combining with ex situ surface analysis. However, the
corrosion of carbon steel in H2 O-containing SC-CO2 phase is an
electrochemical process, and electrochemical kinetics information
is more conducive to understanding the corrosion mechanism. So
far, two research groups have performed in situ electrochemical
measurements in moist SC-CO2 phase. Thodla et al. [14,32,33] per-
formed electrochemical measurements by directly dripping a little
water on the electrode surface. However, the corrosion rate was
evidently higher than that measured in the H2 O-containing SC-CO2
environment without dripping water. Beck et al. [30,31] developed
electrochemical measurements in moist SC-CO2 phase by using
two-electrode system, i.e., carbon steel as working electrode and
stainless steel as counter/reference electrode. They also designed
a three-electrode probe covered by an ion conductive membrane
coating to provide electrolyte conductivity for electrochemical
measurements. However, the coated ion conductive membrane
may have impact on the electrochemical measurements, especially
in the mass transfer process of corrosive species. Additionally, it
is worth mentioning that the reference electrodes used in these
works were metal electrodes. It is not sure that the potentials of
these metal electrodes are stable and reliable enough to be used as
reference electrodes.
In this work, a self-designed setup was developed to study the
corrosion behaviour of X65 carbon steel in SC-CO2 phase contain-
ing H2 O and O2 impurities by in situ electrochemical measurements
(including electrochemical impedance spectroscopy (EIS), linear
polarization resistance (LPR), and polarization curve measure-
ments) using a Ag/AgCl reference electrode. The structure and
morphology of the corrosion products lm were also analysed by
surface characterization.
2. Experimental
2.1. Materials and method
In this experiment, API X65 pipeline steel, with a chemical com-
position (wt%): C 0.04%, Si 0.2%, Mn 1.5%, P 0.011%, S 0.003%, Mo
0.02%, and Fe balance, was used as experimental material. The size
of the specimen for weight loss test was 10 mm 10 mm 3 mm.
Before the weight loss test, all the specimens were abraded with
400 grit silicon carbide paper, and then degreased with acetone and
rinsed with deionized water. After pretreatment, the specimens
were mounted into a Teon (PTFE) mould, with an exposed sur-
face of 10 10 mm2 , and the rest surfaces were sealed with epoxy.
For in situ electrochemical measurements, a three-electrode system
was sealed with epoxy. X65 pipeline steel electrode was as work-
ing electrode (WE). A PTFE tube (with a porous ceramics cap at the
end) and a platinum sheet were embedded in the epoxy mould.
A Ag/AgCl electrode was inserted into the PTFE tube (lled with
0.1 M KCl) as reference electrode (RE), while the embedded plat-
inum sheet was as counter electrode (CE) for the electrochemical
measurements. The potential of Ag/AgCl electrode with 0.1 M KCl at
test temperature (50 C) is 0.286 V vs. SHE (standard hydrogen elec-
trode). All these electrode surfaces were ush with the epoxy mould
surface, and the distance between WE and CE/RE was 0.5 mm, as
shown in Fig. 1. The size of the specimen for electrochemical mea-
surements is 4 mm 5 mm 3 mm with an exposed area of 0.2 cm2 .
The pretreatment of the electrode was same as the specimen for
weight loss test.
Electrochemical and weight loss tests were conducted simulta-
neously in self-designed 3 L autoclave. Fig. 1 shows the schematic
diagram of the setup for electrochemical and weight loss measure-
ments. Before corrosion test, 100 mL deionized water, which was
deoxygenized by pure CO2 (99.99%) over 12 h, was added to the bot-
tom of the autoclave to ensure that the SC-CO2 was saturated with
H2 O throughout the test. The prepared specimens were mounted
inside the autoclave with its exposed face upwards, and placed
above the water. After closed the autoclave, CO2 or CO2 /O2 mixture
gas was injected into the autoclave with a booster pump so that the
autoclave was pressurized to the required pressure (8 MPa). All the
experiments were conducted at 50 C and lasted 96 h. After exper-
iment, the four specimens for weight loss test were cleaned with
distilled water. Three of them were for calculating the weight loss
corrosion rate and one of them was for surface analysis.
2.2. Electrochemical measurements
Electrochemical measurements were conducted with an elec-
trochemical work station. A three-electrode electrochemical cell
was used with X65 carbon steel as working electrode (WE), plat-
inum as counter electrode (CE), and Ag/AgCl electrode (0.1 M KCl)
as reference electrode (RE). EIS measurements were performed
at open circuit potential (OCP) with a 5 mV AC perturbations in
the frequency from 104 Hz to 102 Hz. Linear polarization resis-
tance measurements were performed from 0.005 V to 0.005 V vs.
OCP with a scan rate of 0.1 mV/s. Polarization curve measurements
were performed from 0.25 V to 0.25 V vs. OCP with a scan rate of
0.5 mV/s.
2.3. Surface characterization
After corrosion test, the surface and cross-section morpholo-
gies of corroded specimens were observed by scanning electron
microscope (SEM).The composition of corrosion products on the
specimens surface was analyzed by energy dispersive spectrometer
120 Y. Tang et al. / Corrosion Science 118 (2017) 118128
Fig. 1. Schematic diagram of the setup for in situ electrochemical measurements in H2 O-saturated SC-CO2 environment.
Fig. 2. Weight loss corrosion rate of X65 carbon steel in H2 O-saturated SC-CO2 phase
without and with O2 for 96 h.
(EDS), X-ray diffraction (XRD), and X-ray photoelectron spec-
troscopy (XPS).
3. Results
3.1. Weight loss corrosion rate measurements
Fig. 2 shows the weight loss corrosion rate of X65 carbon steel
after corrosion in H2 O-saturated SC-CO2 phase without and with O2
for 96 h. It can be seen that the corrosion rate in the absence of O2
was about 0.25 mm/a. In the presence of O2 , the corrosion rates with
95 mg/L O2 and 475 mg/L O2 were about 0.91 mm/a and 1.52 mm/a,
respectively, which indicates that the presence of small amount of
O2 promotes the corrosion of X65 carbon steel. Furthermore, the
corrosion rate increases with the increase of O2 concentration. The
obtained corrosion rate is close to Chois results with the similar
experimental conditions [26]. Compared to the results in Table 1,
there is difference in the corrosion rate, but in the same range. It
should be noted that the experimental conditions, such as water
content, impurity species and their contents, and corrosion period,
were so different.
3.2. Open circuit potential and linear polarization measurements
Fig. 3(a) shows the time dependence of open circuit potential
(OCP) of X65 carbon steel in H2 O-saturated SC-CO2 phase without
and with O2 . It is seen that the OCP at the beginning was much
more positive than the normal potential of carbon steel in CO2 -
H2 O system. After more than ten hours, the OCP shifted to negative
direction suddenly. This situation means that no continuous water
lm was formed on the electrode surface at the beginning. Then,
the measured OCP was not the real value at that time. After more
than ten hours, continuous water lm was formed on the electrode
surface as the condensation of water. Then, the electrochemical
measurements were possible and the measured OCP was the real
value. The OCP without O2 was around 0.68 V vs. Ag/AgCl (0.1 M
KCl) while the OCPs with O2 were around 0.72 V vs. Ag/AgCl (0.1 M
KCl), i.e., a more negative potential in the presence of O2 .
Fig. 3(b) shows the time dependence of the polarization resis-
tance (Rp , obtained by linear polarization measurement) of X65
carbon steel in H2 O-saturated SC-CO2 phase without and with O2 .
Since the water lm started to form after about more than 10 h,
only the data after 20 h were presented. It is seen that the Rp in the
absence of O2 is in the range of four orders of magnitude, which is
much larger than that in the presence of O2 (less than three orders
of magnitude). Moreover, when O2 concentration increases from
95 mg/L to 375 mg/L, the RP decreases further, which suggests that
the corrosion rate increases with the increase of O2 concentration.
3.3. Polarization curve measurements
Fig. 4 shows the polarization curves of X65 carbon steel after
corrosion in H2 O-saturated SC-CO2 phase without and with O2
for 96 h. It is seen that both the cathodic and anodic process are
primarily under activation control regardless the presence of O2
or not [34,35]. The anodic current density increases prominently
while cathodic current density increases slightly after adding small
amount of O2 , which leads to a negative shift of corrosion potential
and an increase in corrosion current density. It is well known that
O2 is a strong depolarization agent. Ferrous ions could be oxidized
to ferric iron ion by O2 , leading to the signicant increase of anodic
current density in the presence of O2 . However, for cathodic reduc-
tion reactions, the reduction of H+ still plays a dominant role in the
presence of small amount of O2 . Therefore, the increase in cathodic
reaction rate is slight. Therefore, the increase in cathodic reaction
rate is slight. Furthermore, when protective FeCO3 lm is formed
on the electrode surface in CO2 -containing environment, the cor-
rosion potential of steel usually shifts in positive direction [36].
This situation indicates that the protective FeCO3 lm usually has
more inhibitive effect on anodic reaction than cathodic reaction.
The presence of O2 inhibits the formation of protective FeCO3 lm.
 Y. Tang et al. / Corrosion Science 118 (2017) 118128 121

Fig. 3. Time dependence of OCP (a) and polarization resistance (b) of X65 carbon steel in H2 O-saturated SC-CO2 phase without and with O2.

Table 2
Fitted electrochemical parameters of the polarization curves of X65 carbon steel after corrosion in H2 O-saturated SC-CO2 phase without and with O2 for 96 h.

Conditions Ecorr (V vs. Ag/ACl (0.1 M KCl)) Icorr (A/cm2 ) ba (mV/dec) bc (mV/dec)
5
8 MPa CO2 0.679 3.24 10 242 222
8 MPa CO2 + 95 mg/L O2 0.713 1.03 104 83 211
8 MPa CO2 + 475 mg/L O2 0.719 1.09 104 173 268

Fig. 4. Polarization curves of X65 carbon steel after corrosion in H2 O-saturated SC-
CO2 phase without and with O2 for 96 h.

Therefore, in the presence of O2 , the increase of anodic current den-

sity due to inhibiting the formation of protective FeCO3 lm is more
obvious than that of cathodic current density. The corresponding
values of electrochemical parameters, including corrosion poten-
tial (Ecorr ), corrosion current density (Icorr ), and anodic and cathodic
Tafel slopes (ba , bc ), are listed in Table 2. It is seen that the corrosion
current density increases obviously in the presence of O2 .

3.4. Electrochemical impedance spectroscopy measurements

Fig. 5 shows the EIS of X65 carbon steel in H2 O-saturated SC-

CO2 phase without and with O2 in the initial period (32 h). It is seen
that all the impedance spectra exhibit three time constants, i.e., a
capacitive loop in high frequency, an inductive loop in intermedi-
ate frequency, and another capacitive loop in low frequency. The
capacitive loop in high frequency may be attributed to the double
layer capacitance and charge transfer resistance, while the induc-
tive loop in intermediate frequency is likely due to the formation
of adsorbed intermediate products ((FeOH)ads ) during the anodic
dissolution of bare steel, and the capacitive loop in low frequency
may be associated with the corrosion products lm [37,38]. Fur-
thermore, the impedance without O2 is far larger than those with
O2 , which indicates that the presence of O2 promotes the corro-
sion of steel. The inductive loop in intermediate frequency in the
Fig. 5. EIS Nyquist (a) and Bode (b) plots (measured at open circuit potential) of X65
carbon steel in H2 O-saturated SC-CO2 phase without and with O2 in the initial stage.
presence of O2 gradually shrinks while the capacitive loop in low
frequency region enlarges.
Fig. 6 shows the EIS of X65 carbon steel in H2 O-saturated SC-
CO2 phase without and with O2 in the late period (72 h96 h). It is
seen that the inductive loop in intermediate frequency disappears
entirely and all the impedance spectra are characterized by dou-
ble capacitive loops in the late period. Similarly, the impedance
without O2 is far more than those with O2 . In the absence of O2 ,
compared to the impedance in the initial period, the impedance
122 Y. Tang et al. / Corrosion Science 118 (2017) 118128

Fig. 6. EIS Nyquist (a, c, e) and Bode (b, d, f) plots (measured at open circuit potential) of X65 carbon steel in H2 O-saturated SC-CO2 phase without and with O2 in the late
stage: (a and b) 8 MPa CO2 , (c and d) 8 MPa CO2 + 95 mg/L O2 , (e and f) 8 MPa CO2 + 475 mg/L O2.

in the late period increases obviously, which may be attributed to

the formation of protective corrosion products on the specimen
surface. However, in the presence of O2 , no obvious increase in
the impedance is observed in the late period. There is no essential
difference in the electrochemical corrosion mechanism between
SC-CO2 and non-SC-CO2 environments [37,38].
To obtain the electrochemical parameters, an equivalent circuit
shown in Fig. 7(a) is used to t the EIS data in the initial stage (three
time constants), while the equivalent circuit shown in Fig. 7(b) is
used for the EIS data in the late stage (double capacitive loops).
In the equivalent circuits, Rs is solution resistance; Qdl is constant
phase element representing the double layer capacitance; Rct is
charge transfer resistance; Qf is constant phase element represent-
ing the capacitance of corrosion products lm; Rf is the resistance
of corrosion products lm; RL is the resistance of inductance; L
Fig. 7. Equivalent circuits for tting the EIS of X65 carbon steel in H2 O-saturated
is inductance. Tables 3 and 4 list the tted parameters obtained
SC-CO2 phase without and with O2 : (a) for the EIS in the initial stage, (b) for the EIS
through EIS data tting with the equivalent circuits. It is seen that in the late stage.
in the absence of O2 , the impedance (Rct + Rf ) increases with time,
which indicates that the corrosion rate of steel decreases due to
the formation of protective corrosion products lm. In addition,
the impedance in the absence of O2 is more than four orders of the presence of O2 is less than three orders of magnitude, which
magnitude, revealing a low corrosion rate, while the impedance in indicates that the presence of O2 leads to a signicant increase in
corrosion rate. Furthermore, with the increase of O2 concentration
 Y. Tang et al. / Corrosion Science 118 (2017) 118128 123

Table 3
Fitted electrochemical parameters of the EIS of X65 carbon steel in H2 O-saturated SC-CO2 phase without and with O2 in initial period of experiment (32 h).

Conditions Qdl (1 cm2 sn1 ) n1 Rct ( cm2 ) RL ( cm2 ) L (H/cm2 ) Qf (1 cm2 sn2 ) n2 Rf ( cm2 )
8 5
8 MPa CO2 2.52 10 0.96 812.8 2565 2.328 9.88 10 0.75 3145
8 MPa CO2 + 95 mg/L O2 3.938 108 0.92 357.8 2236 0.131 2.68 104 0.85 136.5
8 MPa CO2 + 475 mg/L O2 1.808 108 0.98 258.1 1526 0.032 4.64 104 0.83 225

Table 4
Fitted electrochemical parameters of the EIS of X65 carbon steel in H2 O-saturated SC-CO2 phase without and with O2 in the late period of experiment.

Conditions Time (h) Qdl (1 cm2 sn1 ) n1 Rct ( cm2 ) Qf (1 cm2 sn2 ) n2 Rf ( cm2 )

8 MPa 74 3.558 105 0.55 8347 0.000566 0.92 3896

CO2 85 8.749 105 0.53 11350 0.000213 0.98 16220
96 1.334 104 0.58 6630 0.000827 0.98 19340

8 MPa 72 7.229 108 0.87 79 0.001057 0.56 222

CO2 + 95 mg/L 84 9.195 108 0.85 104 0.000721 0.54 290
O2 96 2.888 107 0.77 132 0.000629 0.52 389

8 MPa 72 3.51 107 0.78 121 0.001081 0.84 217

CO2 + 475 mg/L 84 1.576 106 0.70 133 0.001382 0.80 208
O2 96 8.789 107 0.75 144 0.001497 0.86 170

Table 5 that in the absence of O2 , a single compact layer of FeCO3 lm is

EDS analysis of X65 carbon steel after corrosion in H2 O-saturated SC-CO2 phase
without and with O2 for 96 h.
Element
Conditions Fe (wt%) C (wt%)
8 MPa CO2 Site A 57.89 16.14
8 MPa CO2 + 95 mg/L O2 Site B 62.31 11.21
Site C 64.74 14.34
8 MPa CO2 + 475 mg/L O2 Site D 70.11 7.91
Site E 68.01 14.52
from 95 mg/L to 475 mg/L, the impedance further decreases, which
means the further increase of corrosion rate.
3.5. SEM morphology and EDS surface analysis
Fig. 8 shows the SEM surface morphologies of X65 carbon steel
after corrosion in H2 O-saturated SC-CO2 phase without and with O2
for 96 h. In the absence of O2 , heterogeneous FeCO3 polygonal crys-
tals lm, which is typical corrosion products in CO2 environment
[38,39], is observed on the specimen surface. The heterogeneous
FeCO3 corrosion products lm may be attributed to the heteroge-
neous water lm formed on the specimen surface. The stacking
FeCO3 polygonal crystals were compact. The area without FeCO3
polygonal crystals lm may be associated with the position with-
out water lm formed. In the presence of O2 , the corrosion products
lm were relatively loose. Apart from the FeCO3 polygonal crystals
lm, some loose globular corrosion products are also observed on
the FeCO3 lm, as shown in Fig. 8(d and f). These globular corrosion
products dispersed on the specimen surface and could not provide
effective protection for the corrosion of substrate. Furthermore, the
corrosion products in the presence of O2 are much looser than those
without O2 , especially in the case with 475 mg/L O2 . Therefore, the
corrosion products in the presence of O2 have less protection for
the corrosion of steel substrate.
EDS analysis of the corrosion products was performed at differ-
ent sites (marked in Fig. 8(b, d, f)) and the corresponding element
contents are listed in Table 5. The corrosion products consist of
Fe, C, and O elements. Combined with SEM surface morphology
images, EDS analysis demonstrates the presence of FeCO3 lm in
the absence of O2 . In the presence of O2 , the globular corrosion
products on the FeCO3 crystal lm should be Fe oxide.
Fig. 9 shows the SEM cross-section morphologies of the corro-
sion products lm and the corresponding EDS linear scan. It is seen
observed, while in the presence of O2 , two layer corrosion prod-
ucts are observed, i.e., a relatively compact inner layer of FeCO3
lm and a loose outer layer of Fe oxide lm. The thickness of cor-
O (wt%) rosion products lm increases in the presence of O2 because two
layer corrosion product lms are formed. However, the thickness of
25.97
26.48 corrosion products lm decreases with the increase of O2 concen-
20.92 tration, which may be attributed to the inhibition of the formation
of FeCO3 lm by higher O2 concentration. Moreover, it should be
21.98
17.47 noted that the thickness of corrosion products lm is also deter-
mined by the thickness of the formed water lm at the site which
cross section observation is performed. The EDS linear scan shows
higher Fe content in the outer layer. Furthermore, the corrosion
products lm in the presence of O2 is much thicker than that with-
out O2 , indicating more severe corrosion in the presence of O2 .
The SEM cross-section morphologies and EDS linear analysis reveal
that the addition of O2 would oxidize Fe2+ to Fe3+ , and to some
extent inhibit the formation of protective FeCO3 lms, thus leading
to the increase of corrosion rate. However, the inner layer FeCO3
lm still exists and has protective performance for the steel sub-
strate. Therefore, it could be concluded that CO2 corrosion plays a
dominant role in SC-CO2 phase containing small amount of O2 .
3.6. XRD analysis
Fig. 10 shows the XRD of X65 carbon steel after corrosion in
H2 O-saturated SC-CO2 phase without and with O2 for 96 h. It is
evident that FeCO3 and Fe were primarily detected in the absence
or presence of O2 . It is well known that FeCO3 is the typical cor-
rosion product in CO2 environment. The presence of Fe peak may
be attributed to incomplete coverage of corrosion products on the
electrode surface, as shown in Fig. 8. Furthermore, the corrosion
products lm is thin in the absence of O2 . Therefore, Fe substrate
was also detected by XRD. With the increase of O2 concentration,
the intensity of Fe peak decreases gradually, and almost no Fe peaks
is observed in the presence of 475 mg/L O2 , probably owing to the
relatively thick corrosion products lm in the presence of O2 . In
addition, its worth noting that there were no iron oxides detected
by XRD in the CO2 -O2 environment. This may be attributed that the
iron oxide formed under this condition was amorphous.
3.7. XPS analysis
To further determine the composition of the corrosion products,
XPS was used to analyse the elemental composition and valence
124 Y. Tang et al. / Corrosion Science 118 (2017) 118128

Fig. 8. SEM surface morphologies of X65 carbon steel after corrosion (without electrochemical measurement) in H2 O-saturated SC-CO2 phase without and with O2 for 96 h:
(a and b) 8 MPa CO2 , (c and d) 8 MPa CO2 + 95 mg/L O2 , (e and f) 8 MPa CO2 + 475 mg/L O2.

state of elements. Fig. 11 shows the XPS of X65 carbon steel after Table 6
Binding energy and specication for the elements by XPS analysis of X65 carbon
corrosion in H2 O-saturated SC-CO2 phase without and with O2 for
steel after corrosion in H2 O-saturated SC-CO2 phase without and with O2 for 96 h.
96 h. Table 6 lists the corresponding binding energy and specica-
tion for the elements. It is seen that C, O, Fe elements are present Elements Binding energy (eV) Peak At.%
on the electrode surface. The peak of each element was tted to 8 MPa CO2
obtain the information about the valence state of elements. In the C1s 282.2 SiC 64.43
absence of O2 , the C1s peaks at 284.6 eV, 289.3 eV could be assigned 284.6 Adventitious C
289.4 FeCO3
to adventitious carbon and carbonate, respectively. Meanwhile, the
O1s 531.6 FeCO3 30.17
peak of O1 s at 531.6 eV is associated with the oxygen in the carbon- Fe 709.3 Fe 5.40
ate. The tting of Fe 2p3/2 peak indicates that the peaks at 710.7 eV 2p3/2 710.7 FeCO3
and 713.9 eV correspond to FeCO3 and the satellite peak, respec- 713.9 Satellite peak
tively [40]. Therefore, there is only FeCO3 lm in the absence of O2 . 8 MPa CO2 + 475 mg/L O2
In the presence of O2 , the C1 s peaks are also assigned to adventi- C1s 284.6 Adventitious C 32.47
tious carbon and carbonate. For O1s, apart from the peak assigned to 289.2 FeCO3
O1s 529.7 Fe2 O3 55.59
carbonate (531.4 eV), a new peak appears at 529.8 eV, which could
531.4 FeCO3
be attributed to Fe oxide. The Fe 2p3/2 peaks at 710.4 eV, 711.6 eV, Fe 709.0 Fe 11.94
and 713.7 eV could be assigned to FeCO3 , Fe2 O3 , and the satel- 2p3/2 710.3 FeCO3
lite peak, respectively. This indicates that FeCO3 and Fe2 O3 lms 711.6 Fe2 O3
713.7 Satellite peak
simultaneously exist in the presence of O2 .
 Y. Tang et al. / Corrosion Science 118 (2017) 118128 125

Fig. 9. SEM cross-section morphologies (a, c, e) and EDS linear scans (b, d, f) of X65 carbon steel after corrosion (without electrochemical measurement) in H2 O-saturated
SC-CO2 phase without and with O2 for 96 h: (a and b) 8 MPa CO2 , (c and d) 8 MPa CO2 + 95 mg/L O2 , (e and f) 8 MPa CO2 + 475 mg/L O2.

4. Discussion system [27]:

The corrosion mechanism of X65 carbon steel in H2 O-containing 2H+ + 2e H2 (2)

SC-CO2 phase is similar to that of atmospheric corrosion under thin
2H2 CO3 + 2e 2HCO
3 + H2 (3)
liquid lm [41,42]. During the corrosion of carbon steel in H2 O-
containing SC-CO2 phase, water rst adsorbed on the steel surface
2HCO 2
3 + 2e 2CO3 + H2 (4)
to form a thin layer of water lm. Then, SC-CO2 and other impuri-
ties (for example O2 ) would immediately dissolve into H2 O to form The proton reduction (Reaction (2)) is the dominant reaction
acidic electrolyte solution. Based on the calculation of solubility due to the low pH. Anodic reaction is the dissolution of steel:
model, the pH of free water phase exposed to 8 MPa CO2 is approx-
imately 3.1 [43], and it has been found that it is more corrosive than Fe Fe2+ + 2e (5)
hydrochloric acid at the same pH.
The corrosion of carbon steel in H2 O-containing SC-CO2 phase is As the corrosion of steel proceeds, when the product of
an electrochemical process, and the electrochemical reactions can [Fe2+ ] [CO3 2 ] exceeds the solubility product of FeCO3 , FeCO3 lm
be summarized as follows: would be formed on the steel surface [28].
Initially, SC-CO2 dissolves into water:
Fe2+ + CO2
3 FeCO3 (6)
CO2 (g) + H2 O (l) H2 CO3 (aq) (1)
Fe2+ + 2HCO
3 Fe(HCO3 )2 (7)
The cathodic reactions may include the reduction of reduc- decompose
ing species (H+ , H2 CO3 , HCO3 ) in H2 O-containing SC-CO2 Fe(HCO3 )2 FeCO3 + CO2 + H2 O (8)
126 Y. Tang et al. / Corrosion Science 118 (2017) 118128
Fig. 10. XRD of X65 carbon steel after corrosion (without electrochemical measure-
ment) in H2 O-saturated SC-CO2 phase with and without O2 for 96 h.
The overall reaction in the corrosion of X65 carbon steel in H2 O-
containing SC-CO2 phase is:
Fe + CO2 + H2 O FeCO3 + H2
FeCO3 will increasingly precipitate in the area where H2 O con-
denses during the corrosion process, and nally the electrode
surface is covered by a compact layer of FeCO3 lm, preventing the
substrate from further corrosion. A schematic diagram of the cor-
rosion mechanism of X65 carbon steel in H2 O-containing SC-CO2
phase is shown in Fig. 12(a). In the initial stage, the adsorbed water
lm is not continuous. Dissolution of steel and cathodic reduction
reactions occur on the steel surface where water lm is formed.
As corrosion proceeds, Fe2+ concentration is high in the water lm
in the late stage due to the dissolution of steel, and then compact
and thick FeCO3 lm is formed on the steel surface, which provides
protection for the corrosion of steel. Since some specimen surface
areas is not covered by the water lm, no FeCO3 lm is observed in
these areas, as shown in Fig. 8(a).
Fig. 11. XPS of X65 carbon steel after corrosion (without electrochemical measurement) in H2 O-saturated SC-CO2 phase with and without O2 for 96 h: (a) 8 MPa CO2 , (b)
8 MPa CO2 + 475 mg/L O2.
However, in the presence of O2 , both the weight loss and
electrochemical measurements indicate that the corrosion rate dra-
matically increases after adding small amount of O2 . Moreover, the
corrosion rate increases with the increase of O2 concentration. It is
well know that O2 is a strong depolarization agent. The addition of
O2 would result in additional cathodic reduction of O2 [26,40]:
O2 + 4H+ + 4e 2H2 O (10)
Meanwhile, the formed Fe2+ after corrosion of steel would be
further oxidized to Fe3+ :
Fe2+ + 2H2 O Fe(OH)2 + 2H+ (11)
4Fe(OH)2 + 2H2 O + O2 4Fe(OH)3 (12)
2Fe(OH)3 + nH2 O Fe2 O3 nH2 O + 3H2 O (13)
In CO2 -H2 O-O2 system, it is believed that the cathodic process
includes hydrogen evolution induced by CO2 and oxygen reduc-
tion induced by O2 at the same time. Corrosion products include
FeCO3 , Fe2 O3 .nH2 O. In the presence of O2 , Fe2+ can be oxidized
into Fe3+ , which leads to the decrease of Fe2+ concentration at
the anodic zone. Then, the presence of O2 inhibits the formation
of protective FeCO3 (Reaction (6)) and accelerates the dissolution
(9) of steel (Reaction (5)). Therefore, the addition of O2 leads to the
increase of corrosion rate. The presence of O2 inhibits the formation
of protective FeCO3 lms, and promotes the formation of non-
protective Fe oxide. Electrochemical measurements and surface
analysis demonstrate the high corrosion rate and less protective
performance of corrosion products lm after adding small amount
of O2 . Furthermore, surface and cross-section SEM images indicate
that a two-layer corrosion products lm is observed in the presence
of O2 . The inner layer is the compact FeCO3 lm while the outer
layer is the loose iron oxide. The relevant corrosion mechanism of
carbon steel in the presence of O2 is presented in Fig. 12(b). In the
initial stage, after water adsorbed on the specimen surface, both
CO2 and O2 dissolved into water. The corrosion of steel occurred
with the cathodic reactions of hydrogen evolution and reduction of
O2 . As the corrosion of steel, both FeCO3 and Fe2 O3 were formed
on the steel surface as mentioned above. However, the FeCO3 was
 Y. Tang et al. / Corrosion Science 118 (2017) 118128 127

Fig. 12. Schematic diagram of corrosion mechanism of X65 carbon steel in H2 O-saturated SC-CO2 phase without and with O2 : (a) without O2 , (b) with O2.

relatively compact while Fe2 O3 was loose, as shown in the SEM sur-
face and cross-section images. Then, at the area where FeCO3 lm
was formed, O2 was not easy to pass through the relatively compact
FeCO3 lm. Therefore, the oxidation of Fe2+ to Fe3+ by O2 was just
carried out on FeCO3 lm surface, i.e., Fe2 O3 was formed on FeCO3
lm. However, at the area where Fe2 O3 was formed, the reducing
species (such as H+ , H2 CO3 , HCO3 ) could pass through the loose
Fe2 O3 lm, which leads to the formation of FeCO3 lm under the
loose Fe2 O3 . Therefore, in the late stage, relatively compact FeCO3
was formed in the inner layer, while the loose Fe2 O3 was formed
in the outer layer. A similar bilayer structure corrosion products
lm was also reported in the CO2 -H2 O-H2 S environment [24]. The
protective performance of the corrosion products lm formed in
the presence of O2 is less than that formed without O2 . Moreover,
there is no obvious change in the protective performance of the
corrosion products lm with the increase of O2 concentration due
to the formation of loose Fe2 O3 lm with both O2 concentrations.
5. Conclusions
In this work, a setup was developed for in situ electrochemi-
cal measurement in H2 O-saturated SC-CO2 phase by using Ag/AgCl
reference electrode. It is demonstrated that there is no essential
difference in the electrochemical corrosion mechanism between
SC-CO2 and non-SC-CO2 environment. The impedance spectra
exhibit three time constants, i.e., a capacitive loop in high frequency,
an inductive loop in intermediate frequency, and another capaci-
tive loop in low frequency in the initial stage. The inductive loop in
intermediate frequency disappears entirely and all the impedance
spectra are characterized by double capacitive loops in the late
period.
The weight loss measurement shows that the corrosion rate of
carbon steel in H2 O-saturated SC-CO2 phase is about 0.25 mm/a. In
the presence of O2 , the corrosion rates with 95 mg/L and 475 mg/L
O2 are about 0.91 mm/a and 1.52 mm/a, respectively, which indi-
128 Y. Tang et al. / Corrosion Science 118 (2017) 118128
cates that the presence of small amount of O2 promotes the
corrosion of X65 carbon steel. The obtained corrosion rate is close
to Chois results with the similar experimental conditions. Com-
pared to the results in Table 1, there is difference in the corrosion
rate (but in the same range) due to the difference in experimental
conditions.
In H2 O-saturated SC-CO2 phase, a single compact layer of FeCO3
lm is formed, while in the presence of O2 , two layer of corro-
sion products are observed, i.e., a relatively compact inner layer
of FeCO3 lm and a loose outer layer of Fe oxide lm. The presence
of O2 inhibits the formation of protective FeCO3 lms and promotes
the formation of non-protective Fe oxide, which results in obvious
increase of corrosion rate.
Acknowledgments
The authors thank the support of National Natural Science Foun-
dation of China (Nos. 51371086, 51571097). The authors also thank
the support of analytical and testing center of Huazhong University
of Science and Technology.
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