Corrosion Science 59 (2012) 186–197

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

Discussion of the CO2 corrosion mechanism between low partial pressure and
supercritical condition
Yucheng Zhang a, Xiaolu Pang a, Shaopeng Qu a, Xin Li b,c, Kewei Gao a,⇑
a
Department of Materials Physics and Chemistry, University of Science and Technology Beijing, Beijing 100083, China
b
China Petroleum Pipeline Coating Engineering Co., Ltd., Langfang 065000, Hebei, China
c
Department of Materials Science and Engineering, China University of Petroleum, Beijing 102249, China

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

Article history: The corrosion behaviour of X65 pipeline steel at various temperatures for different immersion time under
Received 16 September 2011 low CO2 partial pressure and supercritical CO2 condition were investigated by weight loss measurements
Accepted 1 March 2012 and surface analysis techniques. By comparing the characteristics of CO2 corrosion product scale formed
Available online 9 March 2012
under experimental conditions and the variation rule of corrosion rate with temperature, the CO2 corro-
sion mechanism under low partial pressure and supercritical condition was studied. To explain the big
Keywords: difference of corrosion rate between low CO2 partial pressure and supercritical CO2 condition, thermody-
A. Steel
namic calculation of the solubility of CO2 in H2O were discussed.
B. SEM
B. XRD
Ó 2012 Elsevier Ltd. All rights reserved.
B. Weight loss
C. Acid corrosion

1. Introduction 1710
log V corr ¼ 5:8  þ 0:67 logðpCO2 Þ ð1Þ
T
Low cost carbon steels are often used as construction material
where, Vcorr is the corrosion rate of carbon steels, mm/y; T is tem-
in oil producing and transportation pipelines, which are, however,
perature, K; pCO2 is the CO2 partial pressure, Pa.
very susceptible to corrosion in CO2 environments [1]. CO2 in an
This simple model which only includes CO2 partial pressure and
aqueous environment is a corrosive species that has caused several
temperature has been revised by de Waard and Milliams in 1991
failures related to the oil and gas pipelines as well as equipments
[15], 1993 [16] and 1995 [17] by introducing parameters such as
[2,3]. The presence of CO2 causes ‘‘sweet’’ corrosion due to the
pH, water chemistry, scaling tendency, total pressure, hydraulic
formation of corrosive carbonic acid, H2CO3, which significantly
diameter, fluid flow velocity, oil wetting, glycol concentration
increases the corrosion rates of carbon steels. Under suitable con-
and steel composition. According to de Waard–Milliams model,
ditions, corrosion products can form scales (FeCO3 or other iron
the corrosion rate of carbon steel increases with an increase of
compounds) on the corroded surface [4,5]. The corrosion rate of
CO2 partial pressure and the predicted corrosion rate is well accord
carbon steels in CO2 environments depends, to a great extent, on
with the laboratory and field data ranging from very low pressures
the environmental conditions involved, such as temperature, pres-
up to 1 MPa.
sure, pH, solution chemistry, water/oil ratio, flow, steel type, corro-
After de Waard–Milliams model, several oil companies and re-
sion inhibitor and the characteristics of the surface scales [6–12].
search institutions contributed with a great number of prediction
In order to describe the effect of these environmental conditions
models based either on empirical correlations with field and labo-
on the CO2 corrosion rate of carbon steels, a number of mathemat-
ratory data or on mathematical modeling considering chemical,
ical prediction models of CO2 corrosion related to experimental
electrochemical and transport processes. These models include
parameters were established. The first and most widely used mod-
NORSOK model, CORMED model, LIPUCOR model, HYDROCOR
el for predicting CO2 corrosion of carbon steels in wells and pipe-
model, KSC model, TULSA model, PREDICT model, SweetCor model,
lines was proposed by de Waard and Milliams in 1975 [13,14],
CORPOS model, OHIO model, ULL model, DREAM model, OLI model
shown as following [14]:
and FREECORP model, which have been described and discussed in
much detail in literature [18].
However, it should be noted that these models were developed
preferentially for service conditions in oil and gas production and
⇑ Corresponding author. Tel./fax: +86 10 62334909. pipeline transport, and therefore mainly focused on the corrosion
E-mail addresses: kwgao@yahoo.com, kwgao@mater.ustb.edu.cn (K. Gao). systems with CO2 partial pressures of 0–2 MPa. For high pressures,

0010-938X/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.corsci.2012.03.006
 Y. Zhang et al. / Corrosion Science 59 (2012) 186–197
these models are not applicable. For example, at 40 °C and 7.5–
9 MPa, the corrosion rates of X65 and 0.5Cr carbon steels in aque-
ous CO2 conditions ranged in the order 1–6 mm/y [19], however
the corrosion rates of both steels under these conditions predicted
by KSC model [20] and NORSOK model [21] were 10 and 17 mm/y,
respectively. Thus, the corrosion rates measured in the experi-
ments at high pressures were generally much lower than those
predicted by the CO2 corrosion models.
Possible explanations to the big difference between measured
and predicted corrosion rates of carbon steels could ascribe to a
change in CO2 solubility with pressure and that liquid or supercrit-
ical CO2 interacts differently from gaseous CO2 with water [22]. In
general, in the case of scale-free CO2 corrosion, an increase of CO2
partial pressure typically leads to an increase in the corrosion rate,
which has been verified by many predicted models. The commonly
accepted explanation is that with an increase of pressure the
concentration of H2CO3 increases and accelerates the cathodic
reactions, and ultimately enhances the corrosion rate [2]. Surpris-
ingly, when the CO2 partial pressure continues to increase up to
supercritical condition while the temperature and the pressure
are over 31.1 °C and 7.38 MPa, respectively, severe corrosion was
encountered at carbon steels as well as corrosion resistant alloys
(more than 10 mm/y for carbon steels [23–26] and even
0.8 mm/y for 13Cr stainless steel [23]). This is due to the high
corrosiveness of aqueous phases coexisting with supercritical
CO2, which has already been observed by many researchers
[23–28].
It is common knowledge that supercritical CO2 corrosion exists
in tertiary oil and gas recovery like EOR (Enhanced Oil Recovery)
[29] or EGR (Enhanced Gas Recovery) [30] where injection of CO2
is applied to extend the life of oil and gas reserves. Furthermore,
the upcoming CCS (Carbon Capture and Storage) technologies
[31] raises even more frequently the question of materials integrity
under high temperature and high pressure CO2 conditions up and
into the supercritical region [32]. So, in the implement of EOR,
EGR and CCS, supercritical CO2 corrosion problem has to be solved
urgently and more researches need to be carried out on supercrit-
ical CO2 corrosion.
The question arose is that why the present CO2 prediction mod-
els were widely accord with laboratory and field data at low pres-
sures (usually below 1 MPa) but were not applicable at high
pressures? Also, why the supercritical CO2 corrosion caused more
severe corrosion to carbon steels than that at low pressures? This
may imply different CO2 corrosion mechanism between low CO2
partial pressure and supercritical CO2 conditions. Although the
CO2 corrosion mechanisms at CO2 partial pressures relevant for
the oil and gas transport (usually below 1 MPa) have been widely
studied [2,4,5,13,33–38], however, very few investigations so far
have been performed on the CO2 corrosion mechanism under high
pressures, especially supercritical CO2 conditions.
Thus, the objective in this work is to find the difference of CO2
corrosion mechanism between low partial pressure and supercrit-
ical conditions by comparing the CO2 corrosion behaviour of X65
pipeline steel at various temperatures and with different immer-
sion time under low CO2 partial pressure and supercritical CO2
conditions.
2. Experimental procedure
The material used in this study was X65 pipeline steel and its
chemical composition (wt.%) is 0.04 C, 1.5 Mn, 0.2 Si, 0.02 Mo
and Fe balance. The test specimens were machined to a size of
10  10  3 mm3. Prior to the experiments, the surface of the spec-
imen was ground with silicon carbide (SiC) paper progressively up
to 800 grit. After drying in hot air, the specimen was weighed
187
(precision 0.1 mg) and then stored in a desiccator until use. Before
the specimens were put into autoclave, they were fixed in a spec-
imen holder (made by polytetrafluoroethene (PTFE)), only one sur-
face (10  10 mm2) was exposed to corrosion medium and the
other surfaces were sealed by silicone rubber.
All corrosion experiments were carried out in a high tempera-
ture and high pressure autoclave and the schematic experimental
setup is shown in Fig. 1. The corrosion medium was distilled water
together with high purity (99.99%) CO2. Prior to the experiments,
the water was deaerated by N2 bubbling for 4 h and then intro-
duced into the autoclave. The autoclave was deoxygenated again
by purging with CO2 gas with a purity of 99.99% for 2 h and then
heated to the required temperatures. After that, the autoclave
was pressed to the required pressures and statically kept for cer-
tain immersion time. In this study, the experiments under low
CO2 partial pressure and supercritical CO2 condition are constant
at 1 and 9.5 MPa, respectively. For constant immersion time exper-
iments, the immersion time was 168 h and the temperatures were
50, 80, 110 and 130 °C, respectively. For the tests with different
immersion time, the temperature was kept at 80 °C and the
immersion time was 0.5, 2, 7, 23, 48, 96 and 168 h, respectively.
All the experimental conditions in this study are listed in Table 1.
After the experiments, all specimens were taken out and imme-
diately cleaned by deionized water and acetone. To remove the CO2
corrosion product scale, the specimen was pickled in 10% hydro-
chloric acid (HCl) inhibited with 10 g/L hexamethylenetetramine
(urotropine), rinsed subsequently in deionized water and acetone
and dried. Then, the weight loss of the specimen was measured
to calculate the corrosion rate by the following equation [39]:
8:76  104 Dm
V corr ¼ ð2Þ
S qt
where Vcorr is the corrosion rate, mm/y; Dm is the weight loss, g; S is
the surface area of specimen, cm2; q is the density of test steels, g/
cm3; t is the immersion time, h. The final value of the corrosion rate
in this study was averaged of three specimens.
After the experiments, the chemical composition and morphol-
ogy of CO2 corrosion product scale were analyzed by means of
Scanning Electron Microscopy (SEM), X-ray diffraction (XRD) and
Energy Dispersive X-ray Spectroscopy (EDS). As the CO2 corrosion
product scale is not electricity-conductive and also contains the
Fig. 1. Experimental setup used in this study 1: specimen; 2: specimen holder; 3:
insulation jacket; 4: autoclave body; 5: heating jacket; 6: gas valve; 7: pressure
gauge; 8: addition of brine and additives; 9: stirring motor; 10: thermocouple; 11:
gas valve; 12: medium.
188 Y. Zhang et al. / Corrosion Science 59 (2012) 186–197

Table 1
Experimental conditions.

No. Pressure (MPa) Temperature (°C) Immersion time (h)

1 9.5 50 80 110 130 168 (0.5, 2, 7, 23, 48, 96)
a a a
1
a a a
2
a a a
3
a a a
4
a a a
5
a a a
6
a a a
7
a a a
8
a a
9–14 (a)
a a
15–20 (a)
a
For each immersion time, one experiment was carried out.

carbon element, a spray gold processing was made on the speci-
men before SEM observations. After that, the specimen was sealed
by epoxy, and then cut along the cross-section. The cross-sectional
analysis was carried out to examine the cross-section morphology
and the thickness of the CO2 corrosion product scale.
3. Results
3.1. CO2 corrosion behaviour of X65 steel at 80 °C with different
immersion time
Fig. 2(a) and (b) shows the XRD spectra on the corroded surface
of X65 pipeline steel immersed in water saturated with CO2 under
low partial pressure and supercritical condition at 80 °C for various
immersion time, respectively. There is no obvious difference ob-
served between these two conditions. In the first 2 h, only pure
iron was detected, while the diffraction peaks of FeCO3 appeared
and substituted for that of pure iron after 48 h. It is noticed that
after 7 h immersion, only iron peaks from the substrate were de-
tected at low CO2 partial pressure, while the specimen had been
covered by FeCO3 scale under supercritical CO2 condition.
The surface and cross-section morphologies of the corroded
specimens at 80 °C under low CO2 partial pressure and supercriti-
cal CO2 condition for different immersion time are shown in Figs. 3
and 4, respectively. By comparing the appearance of CO2 corrosion
product scale (shown in Figs. 3 and 4) with the XRD analysis
(shown in Fig. 2), it can be seen that the surface coverage by iron
carbonate scale increased with the increase of immersion time.
In both conditions, there was no scale formed before 2 h, as shown
in Figs. 3(a) and (b) and 4(a) and (b). However, during 2–7 h, the
scale formed under supercritical CO2 condition, while no scale
was found at low CO2 partial pressure, as shown in Figs. 3(c) and
4(c), which indicates that increasing pressure is more benefit to

Fig. 2. XRD analysis of CO2 corrosion product scales formed at 80 °C for various immersion time under low CO2 partial pressure (a) and supercritical CO2 condition (b).
 Y. Zhang et al. / Corrosion Science 59 (2012) 186–197 189

a1 b1 c1 d1

20 µm 20 µm 20 µm 20 µm

a2 b2 c2 d2
A
A A
A B
C C
20 µm 20 µm C 20 µm C 20 µm

e1 f1 g1

20 µm 20 µm 20 µm

A e2 A f2 A g2
B
B B
C 20 µm C 40 µm 40 µm
C
Fig. 3. The surface and cross-section morphologies of CO2 corrosion product scales formed at low CO2 partial pressure at 80 °C for various immersion time (a: 0.5 h; b: 2 h; c:
7 h; d: 23 h; e: 48 h; f: 96 h; g: 168 h) (1: surface morphology; 2: cross-section morphology; A: epoxy; B: scale; C: steel substrate).

a1 b1 c1 d1

20 µm 20 µm 20 µm 20 µm

a2 b2 c2 d2
A A
A A
B
B
C C
20 µm 20 µm C 20 µm C 20 µm

e1 f1 g1

20 µm 20 µm 20 µm

A e2 A f2 A g2
B B
B
C
C 40 µm C 80 µm 80 µm

Fig. 4. The surface and cross-section morphologies of CO2 corrosion product scales formed under supercritical CO2 condition at 80 °C for various immersion time (a: 0.5 h; b:
2 h; c: 7 h; d: 23 h; e: 48 h; f: 96 h; g: 168 h) (1: surface morphology; 2: cross-section morphology; A: epoxy; B: scale; C: steel substrate).
190 Y. Zhang et al. / Corrosion Science 59 (2012) 186–197
forming scale [40,41]. From the cross-section morphologies shown
in Figs. 3(d) and (e) and 4(d) and (e), it can be seen that although in
both cases steel surface was covered with corrosion product scale
for immersion time from 23 to 48 h, the corrosion product scale
was not dense and had some local defects. When the immersion
time was 96 h or longer, the iron carbonate scales formed in both
cases obviously became denser, as can be seen from Figs. 3(f)
and (g) and 4(f) and (g).
The fact that the formation of iron carbonate scale with immer-
sion time was earlier appeared under supercritical CO2 condition
(see Fig. 4(c)) than that at low CO2 partial pressure (see Fig. 3(c))
could ascribe to the iron carbonate precipitation and growth kinet-
ics. It is no doubt that the prerequisite for the scale formation is a
super saturated solution. In the case of CO2 corrosion, when the
concentrations of Fe2+ and CO32 ions exceed the solubility product
of iron carbonate, solid iron carbonate precipitates on the steel sur-
face [33,42]:
Fe2þ þ CO2
3 ! FeCO3
According to the models proposed by Johnson and Tomson in
1991 [43] and van Hunnik and Hendriksen in 1996 [44], two fol-
lowing equations (Eq. (5) [44] is a revised version of Eq. (4) [43]
for the use in a wide range of supersaturation) are used to describe
the kinetics of iron carbonate precipitation in CO2 corrosion:
RP ¼ f ðTÞfðSS Þ0:5  1g2
RP ¼ f ðTÞðSS  1Þð1  S1
S Þ
where, RP is the precipitation rate of iron carbonate, kmol m s1;3
SS is the supersaturation of iron carbonate; and f(T) (kmol m3 s1)
is the temperature impact factor that can be obtained by the kinetic
constant kr (kg2 mol1 m2 s1) which obeys Arrhenius law.
Iron carbonate supersaturation SS is defined as follows [34,40]:
½Fe2þ ½CO2
3 
SS ¼
K sp
where [Fe2+] represents the equilibrium ferrous ion concentration,
mol/L; [CO32] represents the equilibrium concentration of carbon-
ate ion, mol/L; Ksp is the solubility product of iron carbonate.
In the experiments with different immersion time, the temper-
ature was constant, thus Ksp could be approximately considered as
a constant. However, with increasing pressure, the concentration
of H2CO3 increases, which accelerates the cathodic reactions to
generate more CO32 in the solution [24,25]. To keep the electric
charge balance, the anodic reaction accordingly accelerates to
release more Fe2+ into the solution. With an increase of the concen-
trations of Fe2+ and CO32 ions, the supersaturation of iron carbon-
ate correspondingly increases according to Eq. (6). In this case,
according to Eqs. (4) and (5), the precipitation rate of iron carbon-
ate increases with an increase of supersaturation. In general, rapid
precipitation of iron carbonate can promote the scale to form. This
is the reason why the CO2 corrosion product scale under supercrit-
ical CO2 condition was formed during 2–7 h while it can be only
formed after 23 h at low CO2 partial pressure, as can be seen from
Figs. 4(c) and 3(c) and (d).
Fig. 5 shows the corrosion rates of X65 pipeline steel exposed in
water saturated with CO2 under low partial pressure and supercrit-
ical condition at 80 °C for 0.5, 2, 7, 23, 48, 96 and 168 h, respec-
tively. In general, the corrosion rates of X65 pipeline steel
decreased with an increase of the immersion time, no matter under
low CO2 partial pressure or supercritical CO2 condition. In the first
2 h immersion when there was no scale formed on the steel
surface, the corrosion rates only decreased slightly and kept a high
level, e.g. about 17 mm/y at low CO2 partial pressure and about
28 mm/y under supercritical CO2 condition. It is known that in
35
30 28.3 9.5 MPa
Corrosion rate, mm/y
27.5 1 MPa
25
20.56
20 17.2
15 16.5 12.87
16.2
10 8.5
7.35 7.26
5
8.36
4.03
0 1.75 1.64
0 20 40 60 80 100 120 140 160 180
Immersion time, h
Fig. 5. The corrosion rates of X65 steel exposed in water saturated with CO2 under
low partial pressure and supercritical condition at 80 °C for various immersion
time.
ð3Þ
the case of scale-free CO2 corrosion, an increase of CO2 partial pres-
sure typically leads to an increase in the corrosion rate, as the con-
centration of H2CO3 increases with an increase of pressure, which
consequently accelerates the cathodic reaction, and ultimately en-
hances the corrosion rate [2,16,45]. That is why the corrosion rate
at low CO2 partial pressure (17 mm/y) was much lower than that
ð4Þ under supercritical CO2 condition (28 mm/y).
Furthermore, as shown in Fig. 5, in the immersion time range of
ð5Þ 2–7 h, the corrosion rate under supercritical CO2 condition de-
creased sharply while it only slightly decreased at low CO2 partial
pressure, which ascribes to the formation of corrosion product
scale, as can be seen from the morphologies in Figs. 3(c) and 4(c)
and XRD analysis in Fig. 2. In general, the decrease of CO2 corrosion
rates was mainly due to the passivation of the surface by CO2 cor-
rosion product scales formed on the surfaces of steels.
In addition, in both conditions the corrosion rates decreased
ð6Þ sharply in the immersion time range of 7–48 h while the corrosion
rates decreased more smoothly with the immersion time from 48
to 96 h. When the immersion time increased up to 96 h or longer,
the corrosion rates decreased very slightly and nearly kept con-
stant. It could be explained that with an increase of the immersion
time, the surface coverage percentage by iron carbonate increased,
at the same time, the iron carbonate scales became denser and
more protective, as shown in Figs. 3(c)–(g) and 4(c)–(g). This is
in good agreement with the experimental results of Cui et al. [46].
The error bars shown in the plots of Fig. 5 were used for the
experimental uncertainty analysis of corrosion rate measurement.
It could be seen that after certain immersion time (96 h in this
study, as shown in Fig. 5), the corrosion rate changed very slightly
and nearly kept constant. Therefore, the following investigations
were carried out at longer and constant immersion time (168 h).
3.2. CO2 corrosion behaviour of X65 steel at various temperatures with
constant immersion time
The chemical composition of CO2 corrosion product scale
formed at various temperatures for 168 h immersion was analyzed
by means of EDS, as shown in Fig. 6. These results revealed that
both under low CO2 partial pressure and supercritical CO2 condi-
tion, the element compositions of the scales formed at various
temperatures were the same and consisted of Fe, O and C.
In Fig. 7, for both conditions, the XRD spectra of the scales
formed at various temperatures were similar. All the diffraction
peaks of the scales were corresponding to FeCO3 crystal and only
the relative intensities of FeCO3 peaks at various temperatures
were different. No iron crystal peaks were detected. This indicated
 Y. Zhang et al. / Corrosion Science 59 (2012) 186–197 191

pCO2=1MPa o
pCO2=9.5MPa
130 C O Fe
Fe Au o
130 C
O Au C Fe
C Fe
Au Fe
O
C OFe
o
110 C Au Fe o
110 C
C Fe

CPS
CPS

o
Au Fe 80 C O
COFe
o
C Fe Au Fe 80 C

O
O Fe o Au Fe
50 C C Fe o
Au 50 C
C Fe

0 2 4 6 8 0 2 4 6 8
E, keV E, keV
(a) (b)
Fig. 6. EDS analysis of CO2 corrosion product scale formed at various temperatures for 168 h immersion under low CO2 partial pressure (a) and supercritical CO2 condition (b).

basically identical with that under supercritical CO2 condition (see

Fig. 9), both of which were a crystalline layer, which has already
been identified as FeCO3 in the previous EDS and XRD analysis
shown in Figs. 7 and 8.
At 50 and 80 °C, the scale composed of crystal grains with het-
erogeneous size in both conditions, as shown in Figs. 8(a) and (b)
and 9(a) and (b). However, with increasing temperatures up to
110 and 130 °C, the grain size decreased significantly and the scale
became more compact, as can be seen from Figs. 8(c) and (d) and
9(c) and (d). This phenomenon was especially obvious under
supercritical CO2 condition. Smaller grains could closely accumu-
late together and form a compact FeCO3 scale, which can also be
identified by the cross-section morphologies shown in Figs. 10
and 11.
The phenomenon that CO2 corrosion product scale formed at
high temperatures looks more compact than that at low tempera-
tures could be still ascribed to the iron carbonate precipitation and
growth kinetics at various temperatures. According to Eqs. (4)–(6),
the precipitation rate depends on the iron carbonate solubility
product. A number of researches [47–52] revealed that the solubil-
ity product of iron carbonate Ksp is a function of temperature (Tk),
expressed in the following Eqs. (7) [50], (8) [51] and (9) [52]:

1365:17
log K sp ¼ 14:66 þ ð7Þ
Tk

2:1963
log K sp ¼ 59:2385  0:041377T k 
Tk
þ 24:5724 log ðT k Þ ð8Þ

 
DH 0 1 1 1
log K sp ¼ log K 298:15   
2:303R T k 298:15 2:303RT k
Z Tk Z Tk
Fig. 7. XRD spectra of CO2 corrosion product scales formed at various temperatures
1
 DC dT k þ DC d ln T k ð9Þ
for 168 h immersion under low CO2 partial pressure (a) and supercritical CO2 298:15 2:303RT k 298:15
condition (b).
where Ksp is the solubility product of iron carbonate; Tk is the tem-
perature, K; R is the gas constant, 8.3145 J mol1 K1; DH0 is the
that the scales formed under these conditions were very thick and standard enthalpy of reaction, J/mol; DC is the standard heat capac-
compact. Combining the EDS analysis and XRD results shown in ity of reaction, J mol1 K1. According to Eqs. (7)–(9), the solubility
Figs. 6 and 7, it could be concluded that the composition of CO2 product of iron carbonate decreases with an increase of tempera-
corrosion product scale formed under these conditions was only ture, which has been verified by experiments [47,48,51].
FeCO3, without other corrosion phases such as Fe3O4, a-FeOOH As the solubility product of iron carbonate Ksp decreases with an
and so on. increase of temperature, the iron carbonate supersaturation SS
The surface morphologies of CO2 corrosion product scales accordingly increases according to Eq. (6) and consequently iron
formed at various temperatures are shown in Figs. 8 and 9. It carbonate precipitation rate RP increases from the precipitation
was obvious that the surface morphologies of the CO2 corrosion kinetics shown in Eqs. (4) and (5). The higher the temperature,
product scale formed at low CO2 partial pressure (see Fig. 8) were the bigger the supersaturation SS and the higher the iron carbonate
192 Y. Zhang et al. / Corrosion Science 59 (2012) 186–197

Fig. 8. Surface morphologies of CO2 corrosion scales formed at low CO2 partial pressure for 168 h immersion at 50 °C (a), 80 °C (b), 110 °C (c) and 130 °C (d).

Fig. 9. Surface morphologies of CO2 corrosion scales formed under supercritical CO2 condition for 168 h immersion at 50 °C (a), 80 °C (b), 110 °C (c) and 130 °C (d).

precipitation rate RP are. As the precipitation rate increases with
the increase of temperature, the scale forms more rapid and
becomes more compact and protective at higher temperatures.
Similar trend was also found in the experimental results provided
by Sun and Nesic [34] and Cui et al. [46].
The variation of the thickness of CO2 corrosion product scale
with temperature is shown in Fig. 12. No matter under low CO2
partial pressure or supercritical CO2 condition, the thickness of
the scale decreased with an increase in the scale forming temper-
ature. However, at a given temperature, the thickness of the scale
formed under supercritical condition was bigger than that under
low CO2 partial pressure, which suggests that increasing pressure
is more benefit to forming scale, because higher CO2 partial
pressure leads to an increase in bicarbonate and carbonate ion con-
centration and a higher supersaturation (Eq. (6)), which accelerates
the precipitation of FeCO3 and the formation of scale [40,41].
The corrosion rates of X65 pipeline steel immersed in water sat-
urated with CO2 under low partial pressure and supercritical con-
dition for 168 h at different temperatures are shown in Fig. 13. In
both conditions, the corrosion rate increased with an increase of
temperature from 50 to 80 °C and then decreased from 80 to
130 °C. The maximum corrosion rate was observed at 80 °C. The
variation rule of corrosion rate with temperature is in agreement
with our previous studies [23] and the results from Ikeda et al.
[53]. However, it should be noted that although the variation of
corrosion rate with temperature was the same, the corrosion rate
 Y. Zhang et al. / Corrosion Science 59 (2012) 186–197
Fig. 10. Cross-section morphologies of CO2 corrosion product scales formed under low CO2 partial pressure for 168 h immersion at 50 °C (a), 80 °C (b), 110 °C (c) and 130 °C
(d) (A: epoxy, B: scale, C: steel substrate).
under supercritical CO2 condition was much higher than that at
low CO2 partial pressure at all temperatures.
It is known that the temperature accelerates all the processes
(electrochemical, chemical, transport, etc.) involved in corrosion.
One would expect then that the corrosion rate steadily increases
with temperature, and this is the case when precipitation of iron
carbonate or other protective scales does not occur. However, the
situation changes markedly once the concentrations of Fe2+ and
CO32 ions exceed the solubility product of iron carbonate. In that
case, increasing temperature accelerates the kinetics of precipita-
tion and the formation of the protective scale. Since iron carbonate
scales formed faster and were more protective at higher tempera-
tures, thereby the corrosion rate decreased more with the increase
of temperature. That is why the corrosion rates at 110 and 130 °C
were lower compared with 50 and 80 °C.
By comparing the thickness of CO2 corrosion product scale (see
Fig. 12) and the corrosion rates at various temperatures (see
Fig. 13), it could be found that although the thicknesses of CO2 cor-
rosion product scale formed at low temperatures (50 and 80 °C)
were bigger than that at high temperatures (110 and 130 °C), the
corrosion product scale had some local defects and failures, as
shown in Figs. 10(a) and (b) and 11(a) and (b). In this case, the
193
solution can still approach to the steel surface through the defects
such as pore in the scale and therefore the scale showed poor pro-
tectiveness. Due to the poor protectiveness of the corrosion prod-
uct scale at lower temperatures, the corrosion rates were still
much higher than that at higher temperatures, which indicates
that the compactness of CO2 corrosion product scale plays domi-
nant role in decreasing the corrosion rate while the thickness of
CO2 corrosion product scale had little effect on the corrosion rate.
4. Discussion
4.1. CO2 corrosion mechanism
In the absence of water, no water molecules are available to hy-
drate Men+ metal ions. Hence, no electrochemical corrosion can
take place in dry CO2 both under low pressures and supercritical
conditions [23,27].
In the presence of water, CO2 dissolves into water to form car-
bonic acid (H2CO3). The initial step is presented by the following
reaction:
CO2 þ H2 O ! H2 CO3 ð10Þ
194 Y. Zhang et al. / Corrosion Science 59 (2012) 186–197

Fig. 11. Cross-section morphologies of CO2 corrosion product scales formed under supercritical CO2 condition for 168 h immersion at 50 °C (a), 80 °C (b), 110 °C (c) and 130 °C
(d) (A: epoxy, B: scale, C: steel substrate).
Thickness of CO2 product scale,µm

100 8
9.5 MPa
9.5 MPa 1 MPa
80 1 MPa
Corrosion Rate, mm/y

60
4
40

2
20

0 0
40 60 80 100 120 140 40 60 80 100 120 140
Temperature,°C Temperature,°C

Fig. 12. Variation of the thickness of CO2 corrosion product scale formed under low Fig. 13. The corrosion rates of X65 pipeline steel immersed in water saturated with
CO2 partial pressure and supercritical CO2 condition for 168 h immersion as a CO2 under low partial pressure and supercritical condition for 168 h at different
function of scale forming temperature. temperatures.
 Y. Zhang et al. / Corrosion Science 59 (2012) 186–197 195

A typical CO2 corrosion system composes of three cathodic reac-
tions and one anodic reaction. The cathodic reactions include the
reduction of carbonic acid into bicarbonated ions (Eq. (11)), the
reduction of bicarbonate into carbonated ions (Eq. (12)) and the
reduction of hydrogen ions (Eq. (13)):
2H2 CO3 þ 2e ! H2 þ 2HCO3
HCO3 ! Hþ þ CO2
3 ð12Þ
supercritical condition with increasing pressure, it will lead to dif-
ferent interaction with water, i.e. CO2 solubility in water will not
follow Henry’s law in liquid or supercritical CO2 conditions, which
leads CO2 solubility in water to increase significantly with increas-
ing pressure to supercritical region [25], as shown in the following
discussion.
ð11Þ
4.2. The reason why the corrosion rates of steels under low CO2 partial
pressure and supercritical CO2 condition show so big difference?

2Hþ þ 2e ! H2 ð13Þ It is known that Henry’s law can be applied in order to calculate
the vapor–liquid equilibrium of CO2 at low pressures [55]. How-
The anodic reaction is the dissolution of iron shown in Eq. (14):
ever, at high pressures, Henry’s law cannot be used to calculate
Fe ! Fe2þ þ 2e ð14Þ the concentration of CO2 in the solution [24]. Thus, under super-
critical CO2 conditions, the mutual solubility of CO2 and H2O could
So, the whole CO2 corrosion reaction can be written as follows: be obtained from the following equations provided by Spycher
et al. [56] and Choi et al. [24,25]:
CO2 þ H2 O þ Fe ! FeCO3 þ H2 ð15Þ
1B
These electrochemical reactions of CO2 corrosion shown in Eqs. yH2 O ¼ ð16Þ
1=A  B
(10)–(15) are often accompanied by the formation of FeCO3 scales
(and/or other iron compounds such as Fe3O4), which can be protec-
xCO2 ¼ Bð1  yH2 O Þ ð17Þ
tive or non-protective depending on the experimental conditions
under which they are formed. The effect of environmental condi- where xCO2 is the solubility of CO2 in water (molar fraction) and yH2 O
tions (such as temperature, pressure, pH, solution chemistry, flow is the solubility of H2O in CO2 (molar fraction).
and metallurgy of the steel) on the CO2 corrosion rate of steels Parameters A and B in Eqs. (16) and (17) are defined as follows:
mainly depends on their effect on the formation and morphological !
characteristics of corrosion product scale [6–12]. This type of CO2 K 0H2 O ðP  P 0 ÞV
H O
A¼ exp 2
ð18Þ
corrosion mechanism at CO2 partial pressures relevant for the oil /H2 O Ptot RT
and gas transport (usually below 1 MPa) have been widely studied
!
and accepted by the researchers, as shown in many literatures /CO2 Ptot ðP  P0 ÞV CO2
[2,4,5,13,33–38]. B¼ exp  ð19Þ
In this study, under both low CO2 partial pressure and supercrit- 55:508K 0CO2 ðgÞ RT
ical CO2 condition, the characteristics of CO2 corrosion product where Vi is the average partial molar volume of the pure condensed
scale formed under experimental conditions (at various tempera- component i over the pressure interval P0 to P, cm3/mol; K is the
tures and different immersion time) were basically identical. true equilibrium constant; /i is the fugacity coefficient; Ptot is the
Moreover, although the corrosion rates of X65 pipeline steel under total pressure, bar; P is the partial pressure, bar; P0 is the reference
experimental conditions had quantitative difference between low pressure, 1 bar; R is the gas constant, 8.3145 J mol1 K1; T is the
CO2 partial pressure and supercritical CO2 condition, it showed temperature, K.
the same variation trend with temperature – increased first and As an example, the solubility of CO2 in water at 50 °C and pres-
then decreased, with a maximum corrosion rate at 80 °C. These re- sures to 600 bar calculated using Eq. (17) in terms of mole fractions
sults imply that supercritical CO2 corrosion is basically identical are shown in Fig. 14 [56]. The CO2 solubility in water increases
with the commonly known typical CO2 corrosion patterns at low sharply with pressure up to the critical point and smoothly after
partial pressure shown in Eqs. (10)–(15). this point. The CO2 solubility trend with pressure reflected two sol-
In addition, Wang et al. [54] studied the effect of CO2 partial ubility curves for two distinct phases: supercritical CO2 above crit-
pressures on the Nyquist impedance plots and found that the ical pressure and gaseous CO2 below this pressure. This resulted in
CO2 partial pressure obviously changed the ‘‘size’’ of the semicircle a sharp change in slope on the overall solubility trends, as shown in
but it imparted little change in the shape of the impedance plot.
This implies that with a change of CO2 partial pressure, the corro-
sion rates were altered while the corrosion mechanism was not
0.03
changed, because the ‘‘size’’ of the semicircle corresponds to the
scale resistance and the corrosion rate while the shape of the
CO2 Mole Fraction in H2O

impedance plot determines the corrosion mechanism. Therefore,

it could be concluded that the corrosion mechanism under super-
0.02
critical CO2 conditions is identical with a known typical CO2 corro- Ref. 58
sion system at low pressures. Ref. 59
However, it should be noted that in this study the corrosion Ref. 60
rates of X65 pipeline steel under supercritical CO2 conditions were Ref. 61
0.01
much higher (about 3–4 times) compared with low CO2 partial Ref. 62
pressure, as shown in Fig. 13. A similar high corrosion rate
(>10 mm/y) was also reported for carbon steels by Choi and Nesic
[24,25] and Cui et al. [26]. The question arose is that now that the 0.00
corrosion mechanism under supercritical CO2 conditions is similar 0 100 200 300 400 500 600
with the typical CO2 corrosion, which factor causes so big differ- Pressure, bar
ence in corrosion rate between low CO2 partial pressure and super- Fig. 14. The solubility of CO2 in H2O at 50 °C and pressures to 600 bar in terms of
critical CO2 condition? A commonly accepted view for this big mole fractions [56]. Experimental data are shown as symbols, with sources given in
difference is that since CO2 changes from gaseous to liquid or Figures. Solubilities calculated using Eq. (17) are shown as solid lines.
196 Y. Zhang et al. / Corrosion Science 59 (2012) 186–197
Fig. 14. The CO2 critical pressure is recognized as a turning point for
the concentrations of H2CO3 and HCO3. This is because after the
critical point, the gas CO2 will be changed into supercritical CO2
which exhibits special physicochemical properties of both a liquid
and a gas CO2-filling its container like a gas but with a density like
that of a liquid. At the critical point (31.1 °C, 7.38 MPa), the density
of the CO2 can increase drastically up to 0.4–0.5 g cm3 [57]. That
is why the solubility of CO2 in water under supercritical CO2 con-
ditions is much higher than that at low pressures.
A comparison between the calculated solubility of CO2 in H2O at
50 °C according to Eq. (17) and the experimental data available in
the literatures [58–62] is also represented in Fig. 14. The results
presented in Fig. 14 show a good agreement between the calcu-
lated data and the experimental data at various pressures. There-
fore, it is suitable to use Eq. (17) to calculate the solubility of CO2
in water under supercritical CO2 conditions.
As shown in Fig. 14, when the CO2 partial pressure increases,
the solubility of CO2 in water phase increases, which consequently
enhances the concentrations of carbonic species (H2CO3, HCO3
and CO32) in the solution. Based on the studies by Choi and Nesic
[24,25], with an increase of pressure, the concentrations of H2CO3
and HCO3 increases. For example, in the experimental pressures
of this study, the H2CO3 concentration under supercritical CO2 con-
dition (9.5 MPa, 206 ppm) is 5.4 times than at low pressure (1 MPa,
38 ppm).
With an increase of the concentrations of H2CO3 and HCO3, the
processes of the electrochemical corrosion reactions shown by Eqs.
(11)–(15) will be accelerated accordingly and ultimately the corro-
sion rate was increased [2]. Consequently, the corrosion rate of X65
pipeline steel under supercritical CO2 condition was much higher
than that at low CO2 partial pressure.
5. Conclusion
In this study, the CO2 corrosion behaviour of X65 pipeline steel
at various temperatures for different immersion time under low
CO2 partial pressure and supercritical CO2 condition were investi-
gated by weight loss measurements and surface analysis tech-
niques. The following conclusions can be drawn:
1. Under both low CO2 partial pressure and supercritical CO2 con-
dition, the corrosion behaviour of X65 pipeline steel, including
characteristics of CO2 corrosion product scale and the variation
rule of corrosion rate with temperature, were similar.
2. The change in CO2 partial pressure does not change the corro-
sion mechanism. Supercritical CO2 corrosion was basically iden-
tical with the typical CO2 corrosion patterns at low pressures.
3. However, due to the significantly higher concentration of corro-
sive carbonic acid under supercritical CO2 condition, the corro-
sion rates of X65 pipeline steel under supercritical CO2
condition were much higher than that at low CO2 partial
pressure.
Acknowledgment
The authors would like to express their thanks to Prof. Changf-
eng Chen (Department of Materials Science and Engineering, China
University of Petroleum, Beijing, China) for his help in supercritical
CO2 corrosion experiments.
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