J Appl Electrochem (2012) 42:233–248

DOI 10.1007/s10800-012-0389-1

ORIGINAL PAPER

Electrochemical investigations on the corrosion behavior

and corrosion natural inhibition of API-X100 pipeline steel
in acetic acid and chloride-containing CO2-saturated media
Faysal Fayez Eliyan • Akram Alfantazi

Received: 28 November 2011 / Accepted: 6 February 2012 / Published online: 2 March 2012
Ó Springer Science+Business Media B.V. 2012

Abstract The purpose of this experimental work was to energy resources, the associated time-dependent problems
investigate selected electrochemical aspects of the corro- remain unresolved [1]. One of these problems is the
sion behavior of API-X100 in CO2-saturated, multivari- chemical degradation caused by carbon dioxide accompa-
able-controlled corrosion media. Utilizing potentiodynamic nying the formation water which is intermixed with oil in
polarization and electrochemical impedance spectroscopy the transported emulsions. Gaseous carbon dioxide dis-
(EIS), the corrosion rates, anodic dissolution, cathodic solves in the formation water to produce the corrosive
regimes, and free interfacial interactions were discussed. carbon-carrying species H2CO3 and HCO 3 by which the
The tests were performed with respect to the environmental corrosion reactions are driven. The severity of the corrosion
factors of 10, 20, 30, 40, 50, and 60 g L-1 chloride and of attack, most commonly governed by the cathodic reactions
10, 20, 30, 40, 50, and 60 mL L-1 acetic acid at 20 and [2] is dependent on the environmental factors, such as
90 °C in the absence and presence of 10 vol% crude oil. partial pressure of carbon dioxide (PCO2 ), temperature, pH,
The corrosion rates exhibited a peak value with respect to chloride content, and acetic acid [3]. In fact, the complexity
the chloride content while they increased continuously with of this type of corrosion arises from the inadequate under-
the acetic acid content irrespectively from temperature. standing of the interrelation between these factors and on
The corrosion behavior was nearly independent from their consequent effect on the corrosion behavior, rate, and
chloride in the presence of acetic acid and oil demonstrated surface. Clover et al. [4] performed a high CO2 pressure
an effective inhibition in all conditions. EIS results showed testing at 50 °C correlating the rate of localized and general
an agreement with the polarization findings and indicated corrosion attacks to the microstructures of several pipeline
adsorption-controlled mechanisms. steels. The cathodic reactions were found proportional to
the unassociated acetic acid and temperature in CO2-satu-
Keywords Low alloy steel  EIS  Polarization  rated conditions of adjusted pH values of 4 showing cor-
Kinetic parameters  API-X100  Oil rosion penetration rates reaching 15 mm year-1 [5]. In the
context of the chemically multivariable-controlled corro-
sion, the acetic acid effect on the corrosion type was found
1 Introduction temperature dependent and its ‘‘inhibitive’’ effect on the
anodic reactions were limited by the chloride content [6].
High strength low alloy (HSLA) pipeline steels have been Carbon dioxide corrosion in the multiphase environments
recently considered for oil and gas transportation facilities can become a function of water content and/or dispersion in
by which an enhanced integrity is achieved. Although the relation to the oil phase and, depending on the transporta-
extended allowance with respect to higher operation pres- tion velocity, corrosion rates can be effectively suppressed.
sures and flow rates is then met with greater demand for Ajmera et al. [7] reported significant reductions in the
corrosion rates in the CO2-saturated solutions with respect
to the effective chemical constituents in the crude oils
F. F. Eliyan (&)  A. Alfantazi
The University of British Columbia, Vancouver, BC, Canada correlating that to the wettability and hydrophilic and/or
e-mail: faysal09@[Link] hydrophobic properties of the emulsified interfaces.

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234 J Appl Electrochem (2012) 42:233–248

Paraffin-based crude oils were indicated as effective natural The three electrodes were connected to a Princeton
inhibitors decreasing the corrosion rates by as much as Applied Research (PAR) Versastat 4 potentiostat/galva-
50–70% at 42 °C during flow conditions attributing that to nostat whose functions are correlated to VersaStudio
the polar nature of the adsorbed layers [8]. In the open v1.50.3712 software program. Open circuit potentials
literature, CO2 corrosion did not receive a wide interest with (OCP), potentiodynamic polarization, and electrochemical
respect to chemically multivariable-controlled mechanisms impedance spectroscopy (EIS) test results were processed,
and the effect of natural inhibition in these conditions analyzed, and presented to perform the electrochemical
was not clearly elucidated from an electrochemical investigation with respect to the environmental factors.
perspective.
In our work, a detailed electrochemical investigation 2.2 Test material
was performed in unbuffered 1-bar-CO2-saturated condi-
tions with an extended range of chloride and acetic acid at The test samples were cut out of a pipeline segment made
20 and 90 °C in the absence and presence of 10 vol% oil. from API-X100 steel. They were machined into proper disks
Potentiodynamic polarization was utilized to study the of nominal dimensions of a 15 mm diameter and 5 mm
effects of those two chemical factors in separate schemes thickness and were soldered to copper wires by a conductive
and in an intermixed matrix of incremental amounts on the silver paste. Afterwards, they were mounted in special hard
corrosion behavior. EIS was also employed to elucidate the cold-curing epoxy resins. Prior to each corrosion test, they
electrochemical interactions at the interface considering were sequentially wet ground by silicon carbide emery
the same environmental conditions. The electrochemical papers of 120, 320, and 600 grit. Afterwards, they were
evaluations were carried out in a regular glass test cell degreased ultrasonically with ethyl alcohol for 10 min and
setup to provide an understanding on corrosion and inhi- then rinsed with distilled water and dried in a cool air stream.
bition of a new generation pipeline steel API-X100. The chemical composition analysis of the test material was
made by inductive coupled plasma (ICP) and LECO carbon
analysis techniques. The chemical composition on a weight
2 Experimental details percent basis is shown in Table 1. The optical microstructure
of as-received steel is shown in Fig. 1. For the microstruc-
2.1 Corrosion test setup tural analysis, a sample was wet ground to 1,200 grit silicon
carbide finish and then polished sequentially with 6 and 1 lm
The tests were performed in a standard three-electrode glass diamond suspensions. Afterwards, the sample was etched
jacket cell of a total volume of 1 L. The working electrode with 2% nital (2 mL acid ? 98 mL ethyl alcohol) and then
was made out of API-X100 pipeline steel, the counter elec- treated with alcohol swapping and dried in a cool air stream.
trode was a graphite rod, and the reference electrode was a The microstructure of the as-received sample showed a
saturated calomel electrode (SCE) of ?0.241 VSHE isolated mixture of acicular ferrite and dispersed bainite colonies with
at the laboratory ambient temperature. The electrochemical micro-variations in color, possibly due to micro-variations in
contact between the reference electrode and the working the alloying content.
electrode was achieved by a Luggin capillary tube with a
Vycor frit. The cell was connected to a Cole-Parmer heater 2.3 Test solutions
controlled by a digital setup.
A gas bubbler was inserted into the cell to purge nitro- The corrosion tests were performed in unbuffered 1-bar-
gen gas for 120 min to deoxygenate the test solutions and CO2-saturated media of sodium chloride with concentra-
then carbon dioxide was continuously purged throughout tions of 10, 20, 30, 40, 50 and 80 g L-1 and acetic acid
the test time periods. A gas mass-flow controller was used of 10, 20, 30, 40, 50 and 80 mL L-1 prepared as oil-free
to control the flow rate of the purged gas to achieve an solutions and 10 vol% oil-containing emulsions. The
effective positive pressure inside the cell. The test solutions experiments were performed in unbuffered media with pH
were continuously stirred by a magnetic stirrer to achieve values between 4.2 and 4.8 in the acetic acid-free solutions
an effective homogenous mixing when oil was introduced. and from 3.3 to 4 in the acetic acid-containing solutions

Table 1 The chemical composition and carbon equivalent of the steel used in this study
Composition (wt%) CE
C Mn Mo Ni Al Cu Ti Nb Cr V

0.1 1.67 0.21 0.13 0.02 0.25 0.01 0.043 0.016 0.003 0.47

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J Appl Electrochem (2012) 42:233–248 235

were immersed into the cell. Potentiodynamic polarization

measurements were performed at a scan rate of 0.5 mV s-1
within a potential range at which the characteristic features
of the anodic and cathodic regimes were fairly revealed with
respect to the environmental factors. Electrochemical
impedance spectroscopy (EIS) tests were performed to study
the interfacial interactions during the open circuit potential.
The frequency range was from 0.01 to 10,000 Hz with a
sampling rate of 10 points per decade. The polarization tests
were performed three times and the corrosion parameters of
rate and potential exhibited a good reproducibility. EIS tests
were performed at least three times showing reproducible
impedance profiles of similar sizes and characteristics.
Fig. 1 Optical micrograph of API-X100 steel showing martensite
(dark), bainite and ferrite (light) colonies

3 Results and discussion

with respect to the chloride content and temperature. The
relatively few amount of oil of 10 vol% was found not to 3.1 Potentiodynamic polarization tests
affect the pH values. To achieve effective homogeneity
between the aqueous brines and oil, dioctyl sulfosuccinate Potentiodynamic polarization tests were performed to
sodium (C20H37NaO7S) salt, an anionic surfactant, was study the corrosion behavior in oil-free and oil-containing
added with 0.2 wt% to the oil-containing emulsions. conditions as illustrated in Figs. 2, 3, 4, 5, 6, 7, 8, 9, and 10
Table 2 shows selected properties of the emulsified in which the amounts of acetic acid and chloride were
hydrocarbon and, according to the crude oil classification varied from 10 to 60 mL L-1 and 10 to 60 g L-1,
based on the carbon number and density in [9], the test respectively at 20 and 90 °C. The polarization behavior
hydrocarbon represents a typical medium-weight crude oil. seemed to be governed by the cathodic capabilities of
Double distilled deionized water was utilized for the test CH3COOH, H2CO3, H?, and H2O, in which chloride also
solutions and the salinity, and the acetic acid content ranges introduced significant changes in the cathodic regimes.
were extended to simulate some extremely corrosive saline
stratum water cuts accompanying the decreasing oil content 3.1.1 Oil-free test conditions
extracted from depleted oil wells [10]. The effect of tem-
perature was set to be 20 and 90 °C within ±1 °C. The corrosion behavior was first investigated in chloride-free
conditions to reveal the cathodic effect on the accelerated
2.4 Electrochemical tests corrosion reactions. The influence of the electroactive spe-
cies involved in the polarization performance was segregated
After full deoxygenation and consequent CO2 saturation in acetic acid-free and acetic acid-containing, CO2-saturated
were achieved at the required temperatures, the samples and N2-saturated media, in four profiles shown in Fig. 2a.
The least corrosion potential and rate resulted when the total
reduction was exclusively dominated by H2O and H?.
Table 2 Selected chemical and physical properties of the crude oil
However, upon CO2 saturation, the cathodic current densi-
considered
ties were about an order of magnitude greater, revealing the
Property Details substantially enhanced cathodic processes by H2CO3. This
Appearance Pale yellow carbon-carrying agent is a consequence of CO2 dissolution in
Initial boiling point (°C) 170 water governed by dissociation equilibrium constants in low
Boiling range (°C) 170–390 pH conditions of approximately 4. Therefore, the corrosion
Flash point (°C) 63 rate was higher accompanied by an expected more noble
Lower/upper flammability (%V) 1–6
corrosion potential (Ecorr) by as much as 45 mV. Interest-
Auto-ignition temperature (°C) [220
ingly, the anodic dissolution showed a continuous acceler-
Vapor pressure (Pa) \100 at 20 °C
ation in comparison to that of N2-saturated medium. This
supports already proposed views on the possible direct
Density (g cm-3) 0.84 at 15 °C
involvement of H2CO3 and HCO 3 in the dissolution mech-
Kinematic viscosity (mm2 s-1) 2–4.5 at 40 °C
anisms [11, 12] as follows:

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236 J Appl Electrochem (2012) 42:233–248

a 0.0
N2 purged - Acetic Acid free a 0.0

CO2 purged - Acetic Acid free

-0.2 CO2 purged - With Acetic Acid -0.2
N2 purged - With Acetic Acid
-0.4 -0.4

Potential/V vs. SCE

Potential/V vs. SCE

-0.6 -0.6

-0.8 -0.8
Increased chloride content

-1.0 -1.0

-1.2 -1.2

-1.4 -1.4
-8 -7 -6 -5 -4 -3 -2 -1 -8 -7 -6 -5 -4 -3 -2 -1
-2 -2
log (i/A cm ) log (i/A cm )
0.0
b 0.0
N2 purged - Acetic Acid free b
CO2 purged - Acetic Acid free
-0.2 CO2 purged - With Acetic Acid b -0.2

N2 purged - With Acetic Acid

-0.4

Potential/V vs. SCE

-0.4
Potential/V vs. SCE

-0.6 -0.6

-0.8 -0.8
Increased chloride content

-1.0 -1.0

-1.2 -1.2

-1.4 -1.4
-8 -7 -6 -5 -4 -3 -2 -1 -8 -7 -6 -5 -4 -3 -2 -1

log (i/A cm-2) log (i/A cm-2)

Fig. 2 Potentiodynamic polarization in CO2-saturated and N2-satu-

rated conditions, free of and containing 10 mL L-1 acetic acid in Fig. 3 Potentiodynamic polarization in oil-free, CO2-saturated,
a chloride-free and in b 10 g L-1 chloride-containing conditions chloride-free, and containing 10, 30, and 60 g L-1 chloride-contain-
ing conditions at a 20 and b 90 °C

Fe þ H2 CO3 ! FeCO3 þ 2Hþ þ 2e ð1Þ

 
In addition FeHCOþ 3 ads becomes involved in the
dissolution mechanism as follows:
0.0

Fe þ HCO þ
3 ! FeHCO3 þ 2e

ð2Þ
-0.2

FeHCOþ
3 $ Fe
2þ
þ HCO
3 ð3Þ
-0.4
Potential/V vs. SCE

The introduction of 10 mL L-1 of CH3COOH nearly

multiplied the cathodic regime covering that already -0.6 Increased acetic acid

resulted in the acetic acid-free-CO2 saturated medium.

-0.8
The corrosion rate consequently increased accompanied
by enhanced CH3COOH-influenced hydrogen evolution. -1.0
Interestingly, the highest current densities were attained in
the acetic acid-containing N2-saturated medium, making -1.2

the two extreme, maximum and minimum, corrosion rates

-1.4
and potentials in the N2-saturated media. -8 -7 -6 -5 -4 -3 -2 -1

There was a similar respect of corrosion exhibited in log (i/A cm-2)

acetic acid-containing CO2-saturated medium. However,
Fig. 4 Potentiodynamic polarization in oil-free, CO2-saturated, ace-
the considerable deceleration in both anodic and cathodic tic acid-free, and containing 10, 30, and 60 mL L-1 acetic acid-
branches in that condition suggests the ability of the active containing conditions at 20 °C

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J Appl Electrochem (2012) 42:233–248 237

decelerating manner, on these interfacial barriers or

through impeded diffusion of the reducible species in
possible mechanisms with respect to the salinity and acetic
acid [13].
As shown in Fig. 2b, the same four cases were considered
in the presence of 10 g L-1 chloride. In the case of acetic
acid-free, N2-saturated medium, the anodic reactions were
greatly accelerated and Ecorr was more negative accompa-
nied by enhanced kinetics of water reduction. In addition, the
active anodic polarization exhibited a multi-slope behavior
corresponding possibly to an early formation of hydroxide-
based films [14] before a continuous dissolution and/or
transformation to stable oxide films as follows:
Fe þ OH $ FeOH
ads ð4Þ
FeOH
ads ! FeOHads þ e

ð5Þ
FeOHads ! FeOHþ
ads þe 
ð6Þ
FeOHþ 
ads þ OH ! Fe(OH)2 ! Hydrous ½Fe(OH)2  ð7Þ
However, in the CO2-saturated medium, two distinct
cathodic regimes were revealed. The corrosion behavior
was anodically sensitive to chloride where the accelerated
anodic polarization intersected the combined mass-limited
cathodic reduction of H2CO3 and H?. The active reduc-
tions of water in the acetic acid-free conditions were within
nearly the same orders of magnitude and the corrosion rates
were higher in comparison to the chloride-free conditions.
The greatest cathodic current densities, with a modified
Fig. 5 a Corrosion current density and b corrosion potential variation
with respect to chloride and acetic acid contents at 20 and 90 °C mixed charge–mass transfer shoulder, were exhibited in
N2-saturated medium with the valid justifications proposed
0.0
for the chloride-free conditions.
The investigations on the polarization behavior were
-0.2 further carried out to study the effect of chloride and acetic
acid at separate schemes with specific ranges between 20 and
-0.4
90 °C. As shown in Fig. 3a, comparative to the chloride-free
Potential/V vs. SCE

-0.6
condition at 20 °C, the behavior appeared to be anodically
Increased sensitive to the small dose of chloride of 10 g L-1 where the
chloride content
-0.8 corrosion rate was as much as seven times higher and the
corrosion potential was approximately 90 mV lower.
-1.0
The cathodic regime exhibited the mass transfer limited
-1.2
reduction of H2CO3, and H? upon chloride-influenced
kinetics of hydrogen evolution in the more conductive con-
-1.4
-8 -7 -6 -5 -4 -3 -2 -1
ditions of greater ionic strengths [15] similar to the obser-
log (i/A cm-2) vations reported in [16]. In addition, the reduction regime
was finally dominated by purely charge-transfer reduction of
Fig. 6 Potentiodynamic polarization in oil-free, CO2-saturated, ace- water at similar potentials around –1 VSCE, regardless of the
tic acid-free, and containing 10, 30, and 60 g L-1 in the presence of
chloride content. Corrosion current densities exhibited a
10 mL L-1 acetic acid at 20 °C
‘‘bow’’ on the Evan’s map where the anodic sensitivity was
restricted by decelerated cathodic reactions. The corrosion
carbon-carrying species in facilitating effective passivation current densities showed a peak value before it decreased
even with the presence of acetic acid. Moreover, this might with the greater chloride content along with the steady
indicate that the cathodic reactions occurred, although in a decrease in the corrosion potentials. It seemed that the

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238 J Appl Electrochem (2012) 42:233–248

Fig. 7 3-D representation of

corrosion current density
variations with respect to
chloride and acetic acid contents
at a 20 and b 90 °C

corrosion behavior in chloride-containing CO2-saturated It seemed that the corrosion behavior in chloride-con-
media was associated with the physical changes at the taining CO2-saturated media was associated with the phys-
corroding interfaces where the enhanced dissolution led to ical changes at the corroding interfaces where the enhanced
more effective supersaturation with the increased chloride dissolution led to more effective supersaturation with the
content. increased chloride content. Chloride ions contributed in a

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J Appl Electrochem (2012) 42:233–248 239

0.0
a 0.0
Chloride-free
–1
10 g L
-0.2 –1 -0.2
30 g L
–1
60 g L
-0.4 -0.4
Potential/V vs. SCE

Potential/V vs. SCE

-0.6 -0.6
Increased
chloride content
-0.8 -0.8
Increased chloride content
-1.0 -1.0

-1.2 -1.2

-1.4 -1.4
-8 -7 -6 -5 -4 -3 -2 -1 -8 -7 -6 -5 -4 -3 -2 -1
-2
log(i/A cm ) log (i/A cm-2)

b 0.0 Fig. 10 Potentiodynamic polarization in oil-containing, CO2-satu-

Chloride-free
10 g L
–1 rated, chloride-free, and containing 10, 30, and 60 g L-1 chloride in
-0.2 30 g L
–1
the presence of 10 mL L-1 acetic acid at 20 °C
–1
60 g L
Potential/V vs. SCE

-0.4
(FeC3) through which carbon-carrying species accumulated
-0.6 to combine with the increasing concentrations of Fe2?. Iron
carbonate (FeCO3) precipitated over the FeC3 leading to a
-0.8
deceleration in the cathodic reactions that confirms with the
-1.0
Increased chloride content visual observations when the surfaces were more blackened
during the cathodic phase right below the corrosion poten-
-1.2 tials when the amount of chloride was greater. At 90 °C,
similarities to 20 °C conditions were exhibited, as shown in
-1.4
-8 -7 -6 -5 -4 -3 -2 -1 Fig. 3b, but with apparent accelerations in both anodic and
log(i/A cm-2) cathodic branches. The cathodic reductions showed an
extended kinetic regime making the total reduction of H?
Fig. 8 Potentiodynamic polarization in oil-containing, CO2-satu- and/or H2CO3, existing with different speciation [18], more
rated, chloride-free, and containing 10, 30, and 60 g L-1 chloride at mixed charge–mass transfer controlled. The anodic disso-
a 20 and b 90 °C
lution in 50 and 60 g L-1 chloride conditions exhibited
0.0 considerable retardations corresponding possibly to facili-
tated formation of more adherent corrosion products that
-0.2 could contribute to the active behavior.
The effect of acetic acid content from 10 to 60 mL L-1
-0.4
Potential/V vs. SCE

was investigated at 20 °C from the polarization perspective

-0.6 Increased acetic acid
in chloride-free conditions, which is shown in Fig. 4.
Acetic acid reduction, described in Eq. 8 [19] prevailed the
-0.8 cathodic regime in these CO2-saturated media, making the
current densities multiplied by as much as five times
-1.0
higher.
-1.2 2CH3 COOHðaqÞ þ 2e ! 2CH3 COO
ðaqÞ þ H2ðgÞ ð8Þ
-1.4
-8 -7 -6 -5 -4 -3 -2 -1
Introduction of acetic acid increased the corrosion rates
log (i/A cm )-2 markedly, making the corrosion potentials as noble as
110 mV than that of acetic acid-free. 20 °C condition and the
Fig. 9 Potentiodynamic polarization in oil containing, CO2-satu- polarization behaviors at 90 °C were also similar. Corrosion
rated, acetic acid-free, and containing 10, 30, and 60 mL L-1 acetic
acid at 20 °C current densities and corrosion potentials are collectively
presented in Fig. 5a, b for acetic acid and chloride-containing
proportional manner in establishing pH gradients decreasing conditions at 20 and 90 °C. The corrosion rates were signifi-
towards the corroding interfaces [17]. Ferrous ions (Fe2?) cantly higher at 90 °C by as much as 17–20 times in chloride-
consequently escaped from the conductive iron carbide containing solutions and by nearly 8 times in acetic acid-

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240 J Appl Electrochem (2012) 42:233–248

a 120
10 g L
-1
c 10 g L
-1
-1
30 g L 30 g L
-1

100 60 g L
-1
30 60 g L
-1

80
20

ZIM /Ω cm2
ZIM /Ω cm2

60

40 10

20
0
0

-20 -10
-20 0 20 40 60 80 100 120 -10 0 10 20 30 40
ZRE /Ω cm2 ZRE /Ω cm2

b 120 10 g L-1
60
35 60
30 g L-1
d
100 60 g L-1 50 30 50
10 g L-1
25

Phase angle/deg
80 40 30 g L-1

Phase angle/deg
40
60 g L-1
IZI/Ω cm2

20

IZI/Ω cm2
60 30 30
15
40 20 20
10
20 10 10
5

0 0
0 0

-3 -2 -1 0 1 2 3 4 5
-3 -2 -1 0 1 2 3 4 5
log (f/Hz) log (f/Hz)

Fig. 11 Impedance of oil-free conditions with respect to the chloride content of 10, 30, and 60 g L-1 at 20 °C in a Nyquist and b bode; and at
90 °C in c Nyquist and d bode plots

Fig. 12 Equivalent circuit

proposed for the oil-free Qdl
conditions at 20 and 90 °C

RS

Qa

Rct

Ra

containing solutions. For the reasons discussed previously in temperature-accelerated anodic reactions made the corrosion
this context, the corrosion rates were increasingly sensitive potentials in both conditions lower.
towards the few amounts of chloride before they showed The multi-variable-governed corrosion behavior was
peaks and consequently decreasing due to the decelerated investigated on the basis of the effect of acetic acid on the
cathodics. However, the corrosion rates were continuously variability of the corrosion rates with the increased chloride
proportional to the increased acetic acid content. It seemed content. As shown in Fig. 6, the reduction of acetic acid,
also that the effect of chloride in increasing the corrosion introduced with the amount of 10 mL L-1 prevailed the total
rates was more significant than that of acetic acid at 90 °C. cathodic reduction regimes along with the full range of
The corrosion potentials, as illustrated previously, increased chloride. The initial anodic sensitivity towards the chloride
with the acetic acid content and decreased with that of content was preserved, but the corrosion potentials were
chloride in a steady manner. Interestingly, the higher considerably higher than those in acetic acid-free conditions.

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J Appl Electrochem (2012) 42:233–248 241

Table 3 Electrical component values of the equivalent circuit proposed for the oil-free conditions with respect to the chloride content at 20 and
90 °C
Temperature Chloride content Electric components
-1
(°C) (g L ) Rs (X cm2) Qdl (lF cm-2) ndl Rct (X cm2) Qads (lF cm-2) nads Rads (X cm2) v2

20 10 6.73 18.4 0.621 87.46 26.7 0.987 12.56 2.4E-05

30 3.63 31.2 0.842 10.00 25.0 0.818 62.63 1.5E-05
60 1.00 48.2 0.916 4.63 20.7 0.627 70.28 4.5E-05
90 10 0.68 10.0 0.962 1.18 45.0 0.744 30.77 6.1E-05
30 0.04 58.5 0.946 2.90 10.8 0.842 35.09 1.7E-05
60 1.20 83.2 0.923 0.04 62.1 0.767 34.37 1.8E-05

variations of Ecorr–icorr were attributed to, when effective

a 80
10 ml L-1
passivation had a strong tendency to form.
30 ml L-1
60 ml L-1
3-D comprehensive representations of the corrosion
current density with respect to the chloride and acetic acid
60
contents are shown for 20 and 90 °C, respectively in Fig. 7a,
b. The corrosion rates were proportional to the acetic acid
ZIM /Ω cm2

content in all chloride-containing solutions as if the ele-

40 mentary profile of acetic acid-free condition is exaggerated
along with the acetic acid contents. Interestingly, the initial
sensitivity towards the smallest chloride content producing a
20 peak value was preserved and was increasing, as expected,
with the greater acetic acid content. Acetic acid, introduced
in different amounts, made the corrosion rates relatively
0 independent from the greater chloride content. The corrosion
0 20 40 60 80
rates seemed to be acetic acid controlled while in the most
ZRE /Ω cm2
concentrated acetic acid-containing solutions, they showed
elevated, yet fairly flat 3-D strip of corrosion rates. It is
b 100 35
10 ml L
-1 interesting that although there are similar trends that the
-1 30
30 ml L
-1
corrosion rates exhibited with respect to acetic acid at the two
60 ml L
25 chloride extremes, chloride-free and the most concentrated
brines, the corrosion rates were nearly four times greater with
20
the presence of chloride.
2
IZI /Ω cm

15 The corrosion rates at 90 °C were significantly greater and

although the trends were appreciably similar with respect to
10
the simultaneous effects of chloride and acetic acid, however,
5 these effects seemed to be more identified. Except with the
0
acetic acid-free, 10 and 20 mL L-1 containing conditions,
the corrosion rates were proportional to the chloride content
10
-3 -2 -1 0 1 2 3 4 5 without exhibiting a significant peak. It appeared that there
log (f/Hz) was a temperature-dependent acetic acid allowance for
Fig. 13 Impedance of oil-free conditions with respect to acetic acid
increased chloride contents to induce their full anodic effect
content of 10, 30, and 60 mL L-1 at 20 °C in a Nyquist and b bode where the corrosion rates increased without the retardation
plots exhibited at 20 °C. In addition, the corrosion rates were pro-
gressively greater with the increased chloride and acetic acid
contents in a manner not very discernable at 20 °C.
It seemed also that acetic acid, although it had greater corro-
sion rates in comparison to those of acetic acid-free condi- 3.1.2 Oil-containing test conditions
tions, made the corrosion rates independent from the chloride
content. This could be due to the ability of acetic acid in The polarization behavior was investigated in 10 vol%
interrupting the interfacial physical significance by which the oil-containing conditions considering the effect of chloride

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242 J Appl Electrochem (2012) 42:233–248

Table 4 Electrical component values of the equivalent circuit proposed for the oil-free conditions with respect to acetic acid content at 20 and
90 °C
Temperature HAc content Electric components
(°C) (mL L-1)
Rs Qdl ndl Rct Qads nads Rads v2
(X cm2) (lF cm-2) (X cm2) (lF cm-2) (X cm2)

20 10 16.04 43.4 0.947 26.56 63.2 0.985 21.58 1.43E-05

30 16.23 38.6 0.921 26.02 58.3 0.980 28.13 1.23E-05
60 15.97 38.9 0.976 28.34 19.4 0.964 13.29 2.27E-05
90 10 0.89 60.3 0.613 0.02 76.8 0.982 1.55 2.32E-05
30 0.46 67.0 0.645 0.41 19.6 0.988 0.55 6.39E-05
60 0.92 72.3 0.688 0.25 50.9 0.971 2.80 6.99E-05

a 25
b 3.0
10 g L-1 10 g L-1
30 g L-1 30 g L-1
60 g L-1 60 g L-1
20 2.5

2.0
15

1.5
ZIM /Ω cm2

ZIM /Ω cm2

10

1.0

0.5

0
0.0

-5 -0.5
-5 0 5 10 15 20 25
-0.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
2
ZRE /Ω cm
ZRE /Ω cm2

Fig. 14 Impedance of oil-free conditions with respect to chloride content of 10, 30, and 60 g L-1 in the presence of 20 mL L-1 acetic acid
represented by Nyquist plots a 20 and b 90 °C

and that of acetic acid from preliminary perspectives without likely associated with the agglomerative interference of
considering the extended simultaneous multi-variable effect. hydrogen evolution with the adsorbed hydrocarbon. Oil
In the carbonated conditions, considering the variance of seemed also to modify the mass-limit reduction of H? and/or
chloride, the corrosion rates decreased upon the addition of H2CO3 at potentials above -1 VSCE to be mixed controlled
oil accompanied by a decrease in the corrosion potentials. with the charge transfer. This behavior could be subject for
In addition, although the trend exhibited in the polarization further investigations on the organic inhibitors effect on the
profiles in the oil-free conditions were persevered, however, reduction mechanisms with respect to chloride and/or carbon
the addition of oil made the chloride effect more pronounced; dioxide partial pressure. In the anodic regime, oil adsorption
that is, the increased chloride content to the inhibited inter- seemed involved in the pre-passivation phase to the extent
faces resulted in an enhanced cathodic effect and the corro- that the effective, electrochemical-based, adsorption impe-
sion potentials were more spaced, as shown in Fig. 8a at ded the passivation process. This is suggested from the
20 °C. The relationship between oil miscibility and its comparison with the oil-free conditions where the dissolu-
adsorption capabilities for effective inhibition seemed to be tion process seemed less retarded and, with respect to chlo-
apparent in the chloride-free and low chloride-containing ride, the anodic current densities were higher. At 90 °C,
conditions. As shown, the mass-limited cathodic regime in the current densities were nearly an order of magnitude
the chloride-free condition exhibited noise current spikes greater and the dissolution kinetics was noticeably enhanced.

123
J Appl Electrochem (2012) 42:233–248 243

The corrosion potentials were kept within the same potential factors [22, 23]: kinetics and adsorption. In CO2-saturated
range of oil-free conditions although there was a slight media, the cathodic reactions govern the corrosion problem
decrease in corrosion rates and appreciable current noises in [24] where the hydrogen generation is driven by the car-
the cathodic regimes, as shown in Fig. 8b. In these condi- bon-carrying species being dominantly reduced in charge-
tions, oil was much less miscible resulting in compromised transfer fashion. Over time, adsorption of the electroactive
inhibition efficiency, but the nature of the cathodic inhibition species becomes the rate determining step [25]. Therefore,
seemed temperature independent. in our case during the free conditions, adsorption resulted
The effect of oil on the corrosion behavior with respect in depressed semicircles extending in some cases to reveal
to the increased acetic acid content was also investigated at a relative overlapping between the medium and low fre-
20 °C, as shown in Fig. 9. The corrosion rates were con- quency regions. The increased amount of chloride activated
siderably less, but the influence of acetic acid reduction in the corroding ferrite colonies, and, in turn, became less
elevating the corrosion potentials was preserved. In addi- polarization resistant, which confirms with polarization
tion, the cathodic shoulders were modified with lower results. The capacitive nature exhibited, regardless of
current densities and with appreciable noise in more the environmental factors of chloride and temperature, is
separated mass-limited reduction profiles. The decelerated associated with the presence of the enhanced cathodic
anodic current densities seemed to show earlier retarda- platform of iron carbide (FeC3) [26]. This layer possibly
tions, but still reflected the effect of increased acetic acid became an active conductive part of the microstructure of
content. The behavior at 90 °C showed a similar behavior our high strength steel of 0.47 wt% C. The cathodic reac-
to that at 20 °C but with accelerated current densities. tions accelerated by the chloride-sensitive localized pH
Oil seemed to enhance the effect of acetic acid in making gradients across the porous FeC3 lead to increased, kinet-
the electrochemical response more independent from the ically dependent, dissolution and resulted in single bode
chloride content, as shown in Fig. 10. Although there was a phase peaks within almost the same order of magnitude. At
decrease in the corrosion rates, the presence of 10 mL L-1 20 °C, phase peaks exhibited a gradual increase with the
acetic acid resulted in similar corrosion behaviors with chloride content reflecting the enhanced electrochemical
respect to the absence and/or presence of chloride. role of processes outside the double layer. In 60 g L-1
chloride-containing condition, the peak was broader and
3.2 Electrochemical impedance spectroscopy (EIS) the bode behavior changed in the medium to low frequency
region, suggesting a possible onset change in the governing
The electrochemical interactions were studied by electro- mechanism. This could be attributed to an initiated for-
chemical impedance spectroscopy (EIS) to elucidate the mation of a mixed layer of FeCO3 and FeC3 where the
possible mechanism(s) and the interrelated chemical supersaturation possibly increased with the already plenti-
contributions of acetic acid and chloride at the corroding ful amounts of the reducible species. At 90 °C, the Nyquist
interfaces. Within a specific range of frequency at open plots decreased in size as adsorption became more signif-
circuit potentials (OCP) and potentiostatic conditions, the icant and the phase peaks showed a shift to higher fre-
impedance response was characterized with equivalent quencies, but were comparable. The proposed equivalent
circuits of proper electrical elements [20]. The same range circuit of the configuration {R(Q(R(QR)))} achieved a
of acetic acid and chloride in the polarization tests were perfect fitting with the experimental data and is shown in
considered at 20 and 90 °C in oil-free and oil-containing Fig. 12. Solution resistance and resistances at the double
CO2-saturated emulsions. layer and across the adsorption fields are represented by
Rs, Rct, and Rads respectively. Although the capacitance
3.2.1 Oil-free test solutions and/or pseudo capacitance was exhibited, a constant phase
element (CPE) was considered to account for the surface
Nyquist plots representing the oil-free conditions with heterogeneities at the double layer (Qdl) and the adsorption
respect to the chloride content at 20 and 90 °C are shown in field (Qads). The CPE impedance (ZCPE) is described by
Fig. 11. Nyquist profiles depicted similar mechanisms as Eq. 9 as follows [27]:
the complex plane features across the frequency range at
ZCPE ¼ 1=QðjxÞn ð9Þ
both temperatures showed a similarity. Partially depressed pffiffiffiffiffiffiffi
semicircles were exhibited proportionally decreasing x is 2pf, j equals 1, and n is a factor which has a value
with the chloride content with variations at low frequency between 0 and 1. As shown in Table 3, Rs decreased with
where the significance of possibly cathodic charge-transfer the increased chloride content and higher temperature and,
processes appears [21]. At the interface, the corrosion is as a result of the enhanced dissolution charge transfer,
governed by two simultaneous processes interchangeably showed a continuous decrease. Interestingly, Qdl showed
influencing dissolution and other physically developed an opposite trend as it seemed proportional with the

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244 J Appl Electrochem (2012) 42:233–248

1.2
a 10 ml L-1 b 10 ml L-1
30 ml L-1 30 ml L-1
60 60 ml L-1 1.0 60 ml L-1

0.8

40

ZIM /Ω cm2
ZIM /Ω cm2

0.6

0.4
20

0.2

0 0.0

-0.2
0 20 40 60 -0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
ZRE / Ω cm2 ZRE / Ω cm2

Fig. 15 Impedance of oil-free conditions with respect to acetic acid content of 10, 30, and 60 mL L-1 in the presence of 30 g L-1 chloride
represented by Nyquist plots a 20 and b 90 °C

conductive platform developed for hydrogen evolution acetic acid content at both temperatures. Charge transfer
[28]. Adsorption resistance at 20 °C was proportional to resistance, as well as that of adsorption, were almost
the chloride content where adsorption became more pro- independent from the content, but showed a great depen-
nounced on active areas possibly covered by more inter- dence on temperature across the more capacitive regions
mediate species [29]. v2 values are included in the same characterized. The compliance of the proposed mechanism
table and indicate the perfect fitting with orders of 10-5. for acetic acid-containing conditions were achieved,
At 90 °C, charge transfer was significantly less across regardless of both content and temperature, which is
capacitive fields and adsorption resistance showed a rela- different from the results indicated for the low frequency
tive independence from chloride content. loops in [30]. This could be attributed to the chemical
Introduction of acetic acid enhanced the cathodic power factors induced by the presence of approximately 80 g L-1
of the already corrosive CO2-saturated media which is NaCl and other varying amounts of CaCl2 and
indicated by Eq. 8 where dissolution was accelerated. MgCl26H2O considered in the simulated oil field forma-
As shown in Fig. 13, for 20 °C conditions, the Nyquist tion water in the study.
loops were more capacitive, decreasing in proportion with Introduction of acetic acid with an amount of 20 mL L-1
acetic acid amount. The almost perfect semicircles were changed the interfacial influence of by-amount chloride.
smaller than those exhibited with respect to the chloride As shown in Fig. 14, the Nyquist plots representing the
content confirming with the polarization tests results as less interrelated interaction of chloride and acetic acid at 20 and
polarization resistance is depicted. Therefore, the acceler- 90 °C resulted in depressed capacitive high-frequency
ated cathodic kinetics resulted in single peaks at compa- semicircles and inductive low frequency loops. Acetic acid
rable phase angles and low frequencies. Impedance moduli made the adsorption process slower as it was more favorable
jZj were relatively close to each other at both the high and on the conductive FeC3 in the acetic acid-free conditions.
low frequency regions. The impedance response at 90 °C As a result, chloride preserved its proportional role in
was similar, reflecting a temperature-independent charge- decreasing the polarization resistance in conditions where
transfer dominated mechanism, but with enhanced disso- the cathodic reactions became accelerated and dominantly
lution of smaller semicircles. The equivalent circuit controlled by charge transfer, similar to the results in [30]. At
proposed for the chloride-containing conditions achieved 90 °C, the mechanism was similar with respect to the chlo-
a reliable fitting to the impedance data of acetic acid ride content but the complex impedance was nearly an order
conditions, and the electric components are shown in of magnitude smaller than at 20 °C.
Table 4. Solution resistance values were higher than those The interaction between chloride and acetic acid was
in chloride-containing conditions and were comparable in studied from a different perspective where the interfacial

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J Appl Electrochem (2012) 42:233–248 245

effect of acetic acid is considered in the presence of the active interfaces more significantly in lower chloride-
30 g L-1 chloride as shown in Figs 15a, b at 20 and 90 °C, containing emulsions. The high-frequency semicircles
respectively. Although the basic adsorption-governed were substantially depressed followed by inductive loops
mechanism did not show a change in comparison to the resulting from the adsorbed oil layers similar to the results
chloride-free conditions, the increased acetic acid content reported in [33]. The significance of increased chloride
induced an adverse effect on the polarization resistance content on decreasing the polarization resistance was
[31]. The overlapped low frequency loop increased in size exhibited in the low frequency regions. Oil induced inter-
accordingly where the enhanced cathodic reactions seemed facial changes throughout the frequency range were com-
to be counterpart by effective precipitation of FeCO3. At parative with the oil-free conditions, as revealed from the
the interface, FeCO3 became incorporated with the porous bode plots. The broader phase peaks showed a slight shift
iron carbide blocking the active sites as already indicated to higher frequencies and showed a valley within compa-
in [32] where the introduction of acetic acid caused a rable low frequencies as a signature of effective induction.
temporary increase in the corrosion rates, but FeCO3 Different from the results in [34] on the imidazoline-based
showed morphological changes and remained protective. inhibition performance, the bode profiles did not show
multi slopes at low frequencies, excluding the hypothesis
3.2.2 Oil-containing test solutions of multitime-constant inhibition impedance.
At 90 °C, the significance of oil adsorption was
Nyquist and bode impedance representations for oil-con- less confirming with the visual observation of less oil
taining conditions at 20 and 90 °C are shown collectively miscibility at higher temperatures. Nevertheless, inductive
in Fig. 16 with respect to the chloride content. Oil inhibited impedance was exhibited in the concentrated chloride

a c
1400 10 g L
-1
100
-1
-1 30 g L
30 g L 30 -1
80 -1 60 g L
1200 60 g L
-1
10 g L
ZIM /Ω.cm2

60

1000
40

20
ZIM /Ω cm2

ZIM /Ω cm2

800
20

600 0

0 20 40 60 80 100

ZRE /Ω cm2 10
400

200

0 0

0 200 400 600 800 1000 1200 1400

0 10 20 30
ZRE /Ω cm2 ZRE /Ω cm2

b10000 10 g/L
80 d 100 10 g/L
80

ZRE (Ω.cm2) 30 g/L

ZRE (Ω.cm2) 30 g/L
60 g/L 60 g/L
1000 60 60
Phase angle/deg

Phase angle/deg

10
IZI /Ω cm2

40
IZI /Ω cm2

100 40

10 20 20
1

1 0 0

0.1 -20 0.1 -20

-3 -2 -1 0 1 2 3 4 5 -3 -2 -1 0 1 2 3 4 5

log (f/Hz) log (f/Hz)

Fig. 16 Impedance of oil-containing conditions with respect to the chloride content of 10, 30, and 60 g L-1 at 20 °C in a Nyquist and b bode;
and at 90 °C in c Nyquist and d bode plots

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246 J Appl Electrochem (2012) 42:233–248

4.1E-05
5.3E-05
5.5E-05

3.4 E–05
3.6 E–05
Qdl

v2

v2
RS

4.4E-05
3.8E-05
Rct

v2
Rads (X cm2)
L (H cm-2)

RL L

1.542
18.990
68.4
15.2
377.6

L (H cm-2)
Fig. 17 Equivalent circuit proposed for the oil-containing conditions
Table 5 Electrical component values of the equivalent circuit proposed for the oil-containing conditions with respect to the chloride content at 20 and 90 °C

at 20 and 90 °C

2.38
3.09
0.776
0.668
nads
RL (X cm2)

emulsions of 50 and 60 g L-1 at which the extent of

6.716
21.61

interaction between oil and the adsorbed electroactive

458.8

RL (X cm2)
Qads (lF cm-2)

species was not clear. As shown in Table 5, charge-transfer

2.378
3.497
resistance was nearly an order of magnitude greater than
that of oil-free conditions at 20 °C as Qdl showed an
21.18
48.1

opposite trend with a capacitive character with respect to

Rct (X cm2)

the chloride content. As expected, the significance of oil

76.78
33.32
900.21

Rct (X cm2)

adsorption was less with the increased chloride content, as

depicted from trends of the induction parameters RL and
Rct (X cm2)

6.937
6.176

L. The equivalent circuit proposed for the oil-influenced

25.96
3.46

induction is shown in Fig. 17 and achieved a perfect fitting

0.677
0.753
0.833

with the experimental data. The Nyquist profiles with

ndl

0.845
0.833

respect to acetic acid in oil-containing conditions are

ndl

shown in Fig. 18, showing the similar significance of oil

0.776
0.971
ndl

inhibition exhibited in chloride-containing conditions.

Qdl (lF cm-2)

However, oil did not cause a significant reduction in the

Qdl (lF cm-2)

charge transfer, as indicated by the trends of Rct and RL that

Qdl (lF cm-2)

are shown in Table 6 where the enhanced cathodic gener-

71.4
92.6
99.4

ation of hydrogen destabilized the oil layers.

10.71
12.69
11.6
25.5
Rs (X cm2)
Elements

Rs (X cm2)

4 Conclusion
Elements
Rs (X cm2)
Elements
6.74
2.55
0.83

0.402
0.704
3.550
0.546

In this experimental work, the electrochemical evaluation

of API-X100 pipeline steel revealed important information
about the multichemical effects on the corrosion behavior
Chloride content (g L-1)

Chloride content (g L-1)

in CO2-saturated media. It was useful to study the inter-

Chloride content (g L-1)

actions between chloride and acetic acid when introduced

with different amounts and it was confirmed that acetic
acid effect prevailed that of chloride. Acetic acid made the
corrosion behavior almost independent from the chloride
content in a manner proportional with its content and when
10
30
60

the temperature was higher. The basic findings can be

50
60
10
40

summarized as follows:
1. The lowest corrosion current densities and corrosion
Temperature (°C)

Temperature (°C)

Temperature (°C)

potentials were in the acetic acid-free, N2-saturated

conditions regardless of chloride content. The intro-
duction of acetic acid enhanced the cathodic reactions,
but chloride enhanced the kinetics of water reduction.
20

90

90

In addition, it was evident that there was a direct

123
J Appl Electrochem (2012) 42:233–248 247

a 10 ml L-1 b 4
10 ml L-1
30 ml L-1 20 ml L-1
60 60 ml L-1 60 ml L-1

40
ZIM /Ω cm2

ZIM /Ω cm2
20
1

0
0

0 20 40 60 0 1 2 3 4
ZRE /Ω cm2 ZRE /Ω cm2

Fig. 18 Impedance of oil-containing conditions with respect to acetic acid content of 10, 30, and 60 mL L-1 represented by Nyquist plots a 20
and b 90 °C

Table 6 Electrical component values of the equivalent circuit proposed for the oil-containing conditions with respect to acetic acid content at 20
and 90 °C
Temperature (°C) Chloride content (g L-1) Electric components
Rs (X cm2) Qdl (lF cm-2) ndl Rct (X cm2) RL (X cm2) L (H cm-2) v2

20 10 14.54 83.1 0.697 45.40 10.07 5.43 3.6E-05

30 7.54 78.6 0.763 35.94 11.31 4.81 1.4E-05
60 8.83 88.1 0.801 31.13 5.59 2.35 1.6E-05
90 10 1.40 14.8 0.864 1.62 5.31 0.0074 2.3E-05
30 1.42 65.6 0.509 1.25 0.97 0.0116 1.3E-05
60 1.44 71.4 0.961 0.45 0.178 0.0063 2.9E-05

involvement of carbon-carrying species in the anodic 5. EIS results showed an agreement with the polarization
dissolution mechanisms. data reflecting the significance of adsorption of the
2. Anodic sensitivity towards chloride was limited by intermediate species in both chloride-containing and
decelerated cathodic reactions while the corrosion acetic acid-containing conditions. However, the inter-
rates were proportional to the acetic acid content with facial interactions became inductive with respect to
more noble corrosion potentials. The corrosion poten- the chloride content in the presence of acetic acid and
tials decreased with the chloride content and at higher the effect of acetic acid on the polarization resistance
temperatures. changed in the presence of chloride.
3. The corrosion rates increased with increased chloride 6. Regardless of temperature, oil adsorption made the
and acetic acid content while the corrosion behaviors Nyquist profiles larger exhibiting induction loops.
became nearly independent from the chloride content The profiles varied in the same respect towards the
in the presence of acetic acid at both temperatures. environmental factors in the oil-free conditions.
4. Oil caused a significant deceleration in current densi-
ties but with a greater effectiveness at low tempera- Acknowledgments The authors would like to thank Qatar National
tures and in the acetic acid-free conditions. Research Fund (QNRF) for providing the financial support for this work.

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248 J Appl Electrochem (2012) 42:233–248

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