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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci
a r t i c l e i n f o a b s t r a c t
Article history: This research argues that the corrosion rate for high strength steel in CO2-saturated solutions reaches a
Received 13 February 2012 maximum at a threshold chloride content. At 20 °C, the corrosion rates increased from 60 lA/cm2 in 5 g/L
Accepted 23 June 2012 solutions to a maximum of 185 lA/cm2 in 15 g/L solutions, and then became less in the more concen-
Available online 10 July 2012
trated solutions. The anodic dissolution accelerated at 90 °C and the cathodic reactions decelerated with
adding 10 vol.% oil where the chloride content effect remained relatively the same. Some EIS experiments
Keywords: demonstrated an agreement with the polarization results without confirming that threshold effect of
A. API-X100
chloride on charge transfer.
A. CO2
A. Oil
Ó 2012 Elsevier Ltd. All rights reserved.
B. Polarization
B. EIS
A. Chloride
0010-938X/$ - see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.corsci.2012.06.032
38 F.F. Eliyan et al. / Corrosion Science 64 (2012) 37–43
Property Details
The test solutions were made with double-distilled deionized
water with different amounts of chloride, continuously purged Appearance Green
Carbon number C4–C12
Initial boiling point (°C) 25
Table 1 Boiling range (°C) 25–170
Chemical composition of the test material. Flash point (°C) >10
Lower/upper flammability (%V) 1–6
Composition (wt.%) C.E. Auto-ignition temperature (°C) >250
Vapor pressure (kPa) <38 at 20 °C
C Mn Mo Ni Al Cu Ti Nb Cr V
Density (g/cm3) 0.63 at 15 °C
0.1 1.67 0.21 0.13 0.02 0.25 0.01 0.043 0.016 0.003 0.47 Kinematic viscosity (mm2/s) 0.5–0.75 at 40 °C
F.F. Eliyan et al. / Corrosion Science 64 (2012) 37–43 39
and
3.1. OCP and potentiodynamic polarization tests
Fe þ 2H2 CO3 ! FeðHCO3 Þ2 þ H2 ; ð2aÞ
The OCPs were almost between 640 and 720 mV vs. SCE,
tending to be less with higher chloride content and at 90 °C. Oil,
FeðHCO3 Þ2 ! Fe2þ þ 2HCO3 ; ð2bÞ
more effective in the dilute solutions, made the OCPs in many of
the repeated experiments less than these in oil-free conditions.
Our high-temperature OCPs were closely within the range of the HCO3 ! Hþ þ CO2
3 ; ð2cÞ
longer-time OCP tests performed by Moiseeva et al. in similar con-
ditions [17]. We found, on all samples, intact gray–black layers Fe2þ þ CO2
3 ! FeCO3 ð2dÞ
whose formation could be well consistent with the valuable mech-
The potentiodynamic experiments were performed on fresh
anistic information Moiseeva et al. introduced in the beginning of
samples after being conditioned at 2 V vs. SCE for a period of
their paper. They believed that during the free conditions the pro-
time. Within a proper potential range and scan, some key charac-
portions between the oxide, hydroxide, and carbonate components
teristics of the anodic and cathodic kinetics appeared useful to
of the black layer undergo critical changes, probably responsible
handle our case. In Fig. 2, selected polarization profiles from
for the OCP changes over a long period of time. Since the pH in
20 °C conditions are shown together with the full corrosion poten-
our cases was well below 6, we cannot regard bicarbonate a key
tial and current data. The polarization behavior in the chloride-
oxidizer during the free conditions. But rather, as mentioned in
containing solutions was similar except that the corrosion rates
many CO2 corrosion studies [18–20], we generally regard the ano-
were chloride-dependent. Yet we do not know, in comparison to
dic dissolution and film formation being governed by the two
the chloride-free conditions whose rates were the lowest, how
simultaneous processes:
chloride exposed the cathodic regimes as being driven by at least
two reduced species, H2CO3 and H2O.
Fig. 2. Potentiodynamic polarization, and corrosion rates and potentials at 20 °C. Fig. 3. Potentiodynamic polarization, and corrosion rates and potentials at 90 °C.
40 F.F. Eliyan et al. / Corrosion Science 64 (2012) 37–43
Between 1.2 and 1 V vs. SCE, water is reduced in a charge- chloride effect on the anodic and cathodic reactions. In other
transfer-limited fashion below H2CO3 and H+ were reduced at al- words, that trend, which was actually reproducible, supports two
most between 140 and 300 lA/cm2 limiting current densities. assumptions that the chloride, if introduced with few amounts, in-
The anodic dissolution currents accelerated with the overpotential creases the anodic sensitivity to result in an increase in the corro-
before showing, in the chloride-containing solutions, a decelera- sion rates. Moreover, increasing the chloride content above a
tion at about 0.5 V vs. SCE. A black intact film was found at the threshold value makes the corrosion rates less in a manner the cor-
end of the polarization on all samples. The corrosion current den- rosion polarization becomes governed by the cathodic reactions.
sities (icorr) were iteratively calculated by Butler–Erdey–Grúz–Vol- The notion that CO2 corrosion is originally governed by the catho-
mer equation [21] (Eq. (3)), fitted with the ± 20 mV polarization dic reactions is uncontroversial and becoming more valid in many
from the corrosion potentials. mechanistic studies. We therefore believe the decrease of the cor-
rosion rates in our case is attributed to the deceleration of the
2:3gs 2:3gs
i ¼ icorr exp exp½ ð3Þ cathodic reactions for reasons difficult to determine. However that
ba bc
encourages us, in future studies, to link the electrochemical results
The corrosion rates, higher by about 40 lA/cm2 in the chloride- to the main physical and compositional characteristics of corroding
free conditions, increased from about 60 lA/cm2 in 5 g/L, to interfaces. Deploying a good method to investigate some interfa-
150 lA/cm2 in 10 g/L, and to 185 lA/cm2 in 15 g/L solutions in cial aspects, with precise electrochemical measures, could help
which the corrosion rates were the maximum. The corrosion rates understand the dependence of the cathodic reactions on the chlo-
were always less with the higher chloride content up to about 40 g/ ride content. That could be pursued together with benefiting from
L, and becoming finally almost insensitive of about 120 lA/cm2 in the information on the cathodic dependence on the microstructure
the more concentrated solutions. The corrosion potentials being and composition in similar conditions [22–24]. We also stress on
less – from about 650 to 750 mV vs. SCE – with the increased the need for special studies on the chloride effect on the polariza-
chloride content was of a good kinetic value in analyzing the tion right above 1 V vs. SCE to CO2 corrosion potentials. Such
studies could lead to better understanding on the effects of the
solution conductivities and the interactions between chloride ions,
H+ and H2CO3 on CO2 corrosion.
The polarization behavior at 90 °C was similar to that at 20 °C,
but the anodic reactions accelerated. As a result, the corrosion rates
were higher – by almost three times – and the corrosion potentials
were lower – by almost 30–40 mV. We did not handle the high-
temperature cases with the same incremental chloride contents,
but despite of some discrepancy, the corrosion rates reached max-
ima in the dilute solutions of 5–20 g/L. The cathodic polarization,
as shown in Fig. 3, seemed to be more governed by mixed
charge-and-mass-transfer-limited reduction in the region above
1 V vs. SCE. Regardless of temperature, there was an interesting
short upright anodic overpotential exclusively in the highly con-
centrated solutions. That behavior, which is dependent on the high
chloride content, requires to be explained by a special physical
investigation.
We performed some experiments in N2-saturated solutions at in a manner relatively similar to that in oil-free solutions. Regard-
20 °C and, as shown in Fig. 4, the corrosion rates and potentials less of the chloride content and temperature, the corrosion poten-
were notably lower than these in CO2 solutions. As being princi- tials were lower than these in the oil-free solutions suggesting oil
pally governed by the water reduction in higher-pH solutions, is a cathodic inhibitor. The difference was however much less at
the cathodic current densities were less than in the CO2-solutions 90 °C and in the concentrated solutions. As shown in Fig. 5 for
and the corrosion rates appeared proportional with the chloride 90 °C conditions, oil caused some fluctuations in the cathodic
content. That was contrary to what was found in the CO2 solutions currents and, as was appreciably the case at 20 °C, the cathodic
suggesting that the deceleration of the cathodic reactions, and con- shoulders extended to be more under a mixed-reduction control.
sequently the corrosion rates, with the chloride content is a special We like to mention that we saw, at low potentials, the intense
case with CO2 corrosion. In the anodic branch, the current densities high-temperature hydrogen evolution passing through metastable
showed a considerable upright deceleration for a wide potential oil films by which we can relate that to cathodic fluctuations. We
range corresponding possibly to the formation of hydroxide-based found at the end of the polarization some oil well adsorbent on
films. The currents showed, regardless of the chloride content, an the black layers, encouraging future investigations on the effect
acceleration at almost the same 0.72 V vs. SCE. of oil on the filming process probably could be best understood
The current densities decelerated at the presence of 10 vol.% oil. by slower potentiodynamic polarization.
Being more effective at 20 °C and in the dilute solutions, oil re-
duced the corrosion rates by as much as 30–60% at 20 °C and by
not more than 10% at 90 °C. It should be noted that both corrosion
potentials and current densities changed with the chloride content
Fig. 6. EIS spectra at 20 °C at open circuit potentials. Fig. 7. EIS spectra at 20 and 90 °C, at (a) 0.8 V and (b) 1.2 V vs. SCE.
42 F.F. Eliyan et al. / Corrosion Science 64 (2012) 37–43
3.2. EIS tests content as were the interesting potentiodynamic trends. Abiding
to the assumption that adsorption in our case drove the interac-
Some EIS tests were performed to study the chloride effect on tions; it appears difficult to propose how chloride affects the pro-
the double layer and charge transfer, and to find any consistency cess or what the mechanistic aspects are ready to change with
with the polarization results. The tests were performed after a respect to the chloride content. However, the EIS results were use-
short time of immersion after the cathodic conditioning in the ful in knowing charge transfer resistance decreased generally with
open circuit potentials and in 0.8 and 1.2 V vs. SCE. The capac- the chloride content and as clearly did the solution resistance. The
itive, relatively overlapped Nyquist spectra, shown in Fig. 6 for EIS was fitted with a nested {R(Q(R(QR)))} equivalent circuit. It was
20 °C, suggest the interactions were mainly governed by adsorp- applicable to fit the experimental data and it showed both the dou-
tion. Supported by similar EIS measurements reported by Chen ble layer and adsorption were highly capacitive. At 90 °C, the spec-
et al. [25], we believe adsorption was sustained by iron intermedi- tra were similar, but smaller than these in 20 °C solutions. The
ates originated from multi-step dissolution. Our understanding, charge transfer resistance was also three times less and the phase
based actually on the chloride content effect, would be better to al- peak location and intensity were more related to the chloride con-
low articulate on the hydrogen evolution –normally driven by tent. Recognizing the importance of the cathodic reduction, some
charge transfer and affected by the physical transitions [26]– EIS tests were performed at 0.8 and 1.2 V vs. SCE during which
should we have performed successive experiments over a specified the mass-transfer-limited reduction of H2CO3 and H+, and charge-
long period of time. Rather, we now regard the chloride content – a transfer-limited reduction of H2O occur, respectively. The spectra,
research keyword– as being not the strong factor with which the shown in Fig. 7, depicted clear evidence the course of the cathodic
mechanism of dissolution or reduction would change. The Nyquist reactions, at least from the electrochemical perspective at these
amplitudes – which actually reflect the charge transfer resistance low potentials, is independent from the chloride content. It would
[27] – were not as reproducible with respect to a given chloride be interesting that EIS of 0.8 V vs. SCE was under diffusion control
while that of 1.2 V vs. SCE was clearly under adsorption control as
water was reduced at high rates. The spectra of both potentials at
90 °C were apparently smaller. Oil, as shown in Fig. 8, made EIS
inductive at the low-frequency regions, and increased markedly
the charge transfer resistance. The charge transfer resistance de-
creased with the chloride content and was lower at 90 °C. The
phase peaks appeared at about 10 Hz and some little valleys ap-
peared at the low-frequency regions.
4. Conclusion
Acknowledgment
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