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TMP 87 D5
TMP 87 D5
DOI 10.1007/s10800-012-0389-1
ORIGINAL PAPER
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@interchange.ubc.ca 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
123
236 J Appl Electrochem (2012) 42:233–248
a 0.0
N2 purged - Acetic Acid free a 0.0
-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
-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
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
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J Appl Electrochem (2012) 42:233–248 237
-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
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
-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)
-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
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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
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
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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)
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.
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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
b10000 10 g/L
80 d 100 10 g/L
80
Phase angle/deg
10
IZI /Ω cm2
40
IZI /Ω cm2
100 40
10 20 20
1
1 0 0
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)
RL (X cm2)
Qads (lF cm-2)
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
Rct (X cm2)
6.937
6.176
0.845
0.833
Rs (X cm2)
4 Conclusion
Elements
Rs (X cm2)
Elements
6.74
2.55
0.83
0.402
0.704
3.550
0.546
summarized as follows:
1. The lowest corrosion current densities and corrosion
Temperature (°C)
Temperature (°C)
Temperature (°C)
90
90
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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
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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