Adsorption of Oil onto API-X100 Pipeline Steel

in CO2-Saturated Solutions
FAYSAL FAYEZ ELIYAN and AKRAM ALFANTAZI

This research explores the validity of Langmuir adsorption theorem in analyzing the natural
corrosion inhibition by an aromatic C10H12 compound, in a hydrocarbon fuel, in 1-bar
CO2-saturated solutions. The adsorption isotherms were constructed from the efficiencies of
inhibition, by 10, 20, and 30 vol pct of the fuel, of the corrosion rates calculated from poten-
tiodynamic polarization measurements, in 2 NaCl g/L solutions at 293 K, 323 K, and 353 K
(20 °C, 50 °C, and 80 °C). The corrosion rates increased with temperature, and the hydrocarbon
fuel, seemingly showing cathodic-inhibition characteristics, acted less efficiently accordingly;
two main results the potentiodynamic polarization, electrochemical impedance spectroscopy
and open-circuit measurements, demonstrated agreement on with each other.

DOI: 10.1007/s11663-013-9912-y
Ó The Minerals, Metals & Materials Society and ASM International 2013

I. INTRODUCTION The emphasis in this article is to examine, on an

CO2 corrosion in oil and gas pipelines depends on
the types of the transported multiphase flows.[1] Consti-
tuted primarily of hydrocarbon oil, stratum water, and
entrapped CO2 and H2S gases, a number of flow regimes
can develop depending on the amounts and velocities of
the constituent phases, and on a number of intertwined
physicochemical factors.[2,3] The impacts of specific flow
regimes on the corrosion behavior have been investi-
gated in previous studies in flow loops in which the
amounts and velocities of the phases were varied and
controlled.[4–6] The findings—from a fundamental view-
point, regardless of a regime type, demonstrate the fact
that the corrosion rates increasingly become higher and
difficult to control when the amounts of water are more
than those of oil.
Transporting pipeline flows from newly explored
reservoirs does not conventionally pose a considerable
potential of corrosion damage[7] since oil, which is the
abundant constituent to transport, acts as a natural
barrier to cover the pipeline surfaces and inhibit the
corrosion reactions. The situation, however, becomes
critical as an oil reservoir ages to have less oil to need, as
a result, an enhanced recovery by pressurized fluids.
With time, water constitutes the majority of the trans-
ported flow within which CO2 has a greater capacity to
dissociate. The concentrations of the corrosive carbon-
carrying species, as a result, increase, and the pH
decreases in the water phase to whom increasing surface
areas are exposed.
FAYSAL FAYEZ ELIYAN, Research Assistant and AKRAM
ALFANTAZI, Professor, are with the Corrosion Group, Department
of Materials Engineering, The University of British Columbia, Vancou-
ver, BC, V6T 1Z4, Canada. Contact e-mail: faysal09@interchange.ubc.ca
Manuscript submitted March 12, 2012.
electrochemical basis, some basic thermodynamic
aspects that might govern the adsorption of oil in
association to its concentration and temperature. We
had previously reported that oil suppressed the corro-
sion rates of the API-X100 steel in 1-bar CO2-saturated
solutions[8–10] and bicarbonate solutions,[11] without
suggesting a mechanism or elucidating thermodynamic
reasons. In this research, oil adsorption is postulated to
be ascribed to an active aromatic constituent, tetrahy-
dronaphthalene (C10H12), in a test hydrocarbon fuel,
which was reported by Ayello et al.[12] as one of the
likeliest polar compounds to adsorb onto the corroding
surfaces and inhibit the reactions. We introduced, in
1-bar CO2-saturated solutions, low 10, 20, and
30 vol pct oil concentrations of which the concentra-
tions of C10H12 were calculated for which Langmuir
adsorption isotherms were postulated valid to construct.
This article is one of the first recent efforts devoted to
understand the thermodynamic interrelations of oil-
based inhibition with CO2 corrosion when investigated
by electrochemical methods. Suppression of corrosion
rates by oil was mostly evaluated by weight-loss
measurements and the possible active constituents that
drive inhibition, and the mechanisms of inhibition did
receive sufficient interest or specific examinations. Cui
et al.[13] reported an increase in the corrosion rates, of
three steels, from nearly 2 to 14 mm/year with increas-
ing water concentration from 50 to 100 vol pct in CO2-
saturated emulsions. Their findings were not compared/
complemented with other electrochemical findings, and
the significance of the oil type was not studied.
Similarly, Tang et al.[14] studied not, in a more detailed
study, relevant electrochemical corrosion aspects, but
the physical properties of four types of oil, such as
density and viscosity, were employed to explain the
transition of inhibition from of being stable-oil wetting
to intermittent wetting. In 72-psi CO2-pressurized,
3.5 wt pct NaCl autoclave emulsions at 353 K
(80 °C), a statistical analysis by Hernandez et al.[15]

METALLURGICAL AND MATERIALS TRANSACTIONS B

on the inhibition by asphaltenic and paraffinic oils, of
different concentrations, were linked to certain polar
functional groups.
In a conventional glass-jacketed cell, we carried out
potentiodynamic polarization and electrochemical
impedance spectroscopy (EIS) measurements in contin-
uously stirred, 1-bar CO2-saturated, 2 g/L NaCl brines.
The corrosion kinetics and the basic thermodynamics of
adsorption are investigated in association to low oil
concentrations at 293 K, 323 K, and 353 K (20 °C,
50 °C, and 80 °C).
The results contribute to meeting the need for the
better understanding of the natural corrosion inhibition,
its mechanisms, and the roles of the possible responsible
species that constitute the inhibitive interfacial layers.
The corrosion rates can then be better predicted for the
in-field and new-generation pipeline steels, and the
corrosive multiphase flows can be more effectively
controlled to ultimately achieve the long-term, reliable
integrity and safety of the oil and gas pipelines.
water and dried in a cool air stream. The chemical
composition, which is shown in Table I, was analyzed
by inductive coupled plasma (ICP) and LECO carbon
analysis. The microstructure of the test material, as
shown in Figure 1, was mainly acicular-ferritic and
bainitic.
C. Test Solutions
The tests were carried out in 1-bar CO2-saturated
solutions synthesized from double-distilled, deionized
water of 2 g/L NaCl concentration, and of 10, 20, and
30 vol pct ShellÓ diesel fuel whose properties are shown
in Table II. The pH of the solutions was unbuffered of
between 4.2 and 5.4. The low amount of chloride
considered in the investigations is within a typical range
of concentrations in the desalted flows.[16] 293 K, 323 K,
and 353 K (20 °C, 50 °C, and 80 °C) were the test
temperatures, maintained at ±1 K.
D. Electrochemical Tests

II. EXPERIMENTAL DETAILS The test samples were cathodically conditioned at

2 V vs SCE for nearly 2000 s right after immersion in
A. Corrosion Test Setup
The corrosion tests were carried out in a standard,
three-electrode, 600-mL, glass-jacketed cell. The poten-
tials were measured against the saturated calomel
electrode (SCE) of +0.241 V vs SHE, which was
isolated in a capillary bridge tube at room temperatures.
A gas bubbler was fitted into the cell to purge N2 for
60 minutes to deoxygenate the solutions before CO2 was
continuously purged during the tests. The jacketed part
of the cell was a part of a loop that carried water flows at
high temperatures from a Cole-Parmer heater to per-
form the 323 K and 353 K (50 °C and 80 °C) experi-
ments. The cell was placed over a magnetic plate by
which a stirring bar rotating at a constant speed was
used to mix and homogenize water and oil. A PAR
Versastat 4 potentiostat was used to perform the
experiments, and by synchronizing it to VersaStudio
software, the experiments were controlled, and the Fig. 1—The optical micrograph of the test API-X100 microstructure.
results were analyzed.

Table II. Selected Chemical and Physical Properties of the

B. Test Material Emulsified Hydrocarbon
Rectangular samples machined out of API-X100
pipeline segment were soldered to copper wires and Property Details
mounted in hard epoxy resins reliable at high temper- Appearance dark green
ature. The samples were wet-ground sequentially with Carbon Number C3 to C12
120, 320, and 600 grit emery papers, and ultrasonically Initial Boiling Point 298 K (25 °C)
degreased with ethyl alcohol and rinsed with distilled Boiling Range 298 K (25 °C) to 443 K
(170 °C)
Flash Point (°C) >10
Lower/Upper 1 to 6
Table I. Chemical Composition and Carbon Equivalent of the
Flammability (pct V)
Test API-X100 Steel
Auto-ignition >250
Temperature (°C)
Composition (Weight Percent)
Vapor Pressure (kPa) <38 at 293 K (20 °C)
C Mn Mo Ni Al Cu Ti Nb Cr V C.E. Density (g/cm3) 0.63 at 398 K (15 °C)
Kinematic Viscosity (mm2/s) 0.5 to 0.75 at 313 K
0.1 1.66 0.19 0.13 0.02 0.25 0.02 0.043 0.016 0.003 0.45 (40 °C)

METALLURGICAL AND MATERIALS TRANSACTIONS B

the solutions, and the experiments were repeated three
times to insure reproducibility. The open-circuit poten-
tial (OCP) tests were first carried out to explore some of
the effects of the environmental factors on the corrosion
behavior during a short time of immersion of 3600 s. On
newly prepared fresh specimens, the potentiodynamic
polarization was carried out at 0.5 mV/s from 0.8 to
0.5 V vs SCE. It was also scanned from 2 V vs SCE
to the corrosion potentials to study the cathodic
reactions. The EIS tests were carried out at the OCPs
with a frequency range of from 10,000 to 0.01 Hz, with a
sampling rate of 10 points per decade. The experimental
setup and procedures were validated by ASTM Stan-
dard G 1-03.[17]
III. RESULTS AND DISCUSSION
A. The OCP and Potentiodynamic Polarization Tests
The OCPs in the oil-free solutions were higher from
nearly 710 to 700, and 680 mV vs SCE at 293 K,
323 K, and 353 K (20 °C, 50 °C, and 80 °C), respec-
tively. Over time, as shown in Figure 2, they showed a
slight increase after a period ranging from 1000 to
1500 s at 323 K and 353 K (50 °C and 80 °C). The
ranges of the OCPs, both in oil-free and oil-containing
solutions, were within those reported in a previous
research in which different concentrations of chloride
were considered.[8] In that research we had reported
that, guided by findings by Moiseeva et al.,[18] the
proportions of the oxide and carbonate products,
interchangeably, might change over time. For the cases
in this research, the corrosion products probably
became thicker over time, especially with the increase
of the OCPs at high temperatures, to result in
deceleration of the dissolution reactions. The increase
of the OCPs with temperature can also be partially
attributed to the increase of the rates of the cathodic
reactions—by which the CO2 corrosion is con-
trolled,[19] although the extent of dissociation of CO2
could substantially decrease at high temperatures. Oil,
as shown in Figure 2, caused the OCPs to be lower,
indicating that oil could act as a cathodic inhibitor.
Adding 10 vol pct oil resulted for the OCPs to be
nearly 700, 707, and 735 mV vs SCE at 293 K,
323 K, and 353 K (20 °C, 50 °C, and 80 °C), respec-
apparently at 20 °C (293 K) where oil was most
miscible.
Only at 323 K and 353 K (50 °C and 80 °C), the
anodic current densities appeared higher in the presence
of oil, showing also some fluctuations. At the end of the
anodic polarization, the specimens were covered by
intact black scales. The cathodic polarization profiles
show two main regions of influence of the cathodic
reductions of H2O, and of H2CO3, and H+. Below 1 V
vs SCE, from 20 to 40 mV, the total cathodic reduction
was dominated by the charge-transfer-controlled reduc-
tion of H2O. The currents at 2 V vs SCE in oil-free
solutions were nearly 25, 35, and 56 mA/cm2 at 293 K,
323 K, and 353 K (20 °C, 50 °C, and 80 °C), respec-
tively.
Above 1 V vs SCE, where the total cathodic
currents were dominated by the reductions of H2CO3
and H+, the inhibitive effect of oil was well noticeable,
and the shape of the profiles changed. The corrosion
current densities (icorr), which are shown in Figure 4
along with the corrosion potentials, were iteratively
calculated by Butler–Erdey–Grúz–Volmer equation,[20]
which was fitted along with nearly ±20 mV from the
corrosion potentials:
    
2:3gs 2:3gs
i ¼ icorr exp  exp : ½1
ba bc
The current density and corrosion current density are
represented as (i) and (icorr); the anodic and cathodic
Tafel slopes are represented as (ba) and (bc); and the
activation overpotential is (gs). The corrosion rates were
higher with temperature being nearly from 40, 83, and
170 lA/cm2 in the oil-free solutions, and from 25, 76,
and 130 lA/cm2 in the presence of 10 vol pct oil. The
corrosion potentials did not show a clear trend of
variation with temperature, but they were lower in the
presence of oil.
-0.66
-0.68
OCP (V vs. SCE)

353 K (80°C), oil-free

tively. The OCP profiles of the oil-containing solutions
at high temperature were relatively of intense fluctu-
ations. It is difficult to ascribe that to special interac- -0.70
323 K (50°C), oil-free
293 K (20°C), with oil
tions, given that oil was observed significantly less 323 K (50°C), with oil
miscible at high temperatures. 293 K (20°C), oil-free

The potentiodynamic polarization profiles in oil-free

and 10 vol pct oil solutions are shown in Figure 3. -0.72

They were generally similar but well indicative of the

effects of temperature and oil. Both the anodic and 353 K (80°C), with oil
cathodic current densities increased with higher tem- -0.74
perature. Oil decelerated the corrosion rates in propor- 0 1000 2000 3000 4000
tion with its amount, and lowered the corrosion Time (s)
potentials. It decelerated the cathodic current densities
to up to almost two times at above 0.8 V vs SCE. It Fig. 2—The open-circuit potentials in oil-free and 10 vol pct oil
decelerated the anodic current densities, but most solutions.

METALLURGICAL AND MATERIALS TRANSACTIONS B

 -0.50 Temperature (K)
290 300 310 320 330 340 350 360
200

-0.55 293 K (20°C), with oil

180
293 K (20°C), oil-free -710
323 K (50°C), oil-free 160
323 K (50°C), with oil
Potential (V vs. SCE)

-0.60 140
353 K (80°C), oil-free

Ecorr (V vs. SCE)

-715
353 K (80°C), with oil
120

icorr (A/cm )
2
-0.65
100
-720
80
-0.70
60 icorr, oil-free
icorr, with oil -725
40
Ecorr, oil-free
-0.75 Ecorr, with oil
20

0 -730
10 20 30 40 50 60 70 80 90
-0.80
10-6 10-5 10-4 10-3 10-2 Temperature (°C)
Current density (A/cm2)
Fig. 4—The corrosion rates and potentials in oil-free and 10 vol pct
oil solutions.
293 K (20°C), with oil
-0.8 323 K (50°C), oil-free
353 K (80°C), with oil

293 K (20°C), oil-free 353 K (80°C), oil-free to adsorb onto the surface as a homogenous monolayer
saturated with molecules of limited interactions, satis-
-1.0
fying Langmuir adsorption theorem.[22] Its mathemati-
323 K (50°C), with oil cal expression incorporates concentration (C) and an
Potential (V vs. SCE)

-1.2
energetic coefficient of proportionality (b) as
h
¼ bC: ½3
-1.4 1h

-1.6
The Langmuir isotherms representing C10H12 adsorp-
tion at 293 K, 323 K, and 353 K (20 °C, 50 °C, and
80 °C) are shown in Figure 6. The energy coefficients
-1.8 were extracted by linear fitting whose intercepts were set
to zero. Their linear regressions (R2) were high (>0.9). b
decreased with temperature and, from its relation with
-2.0
10-5 10-4 10-3 10-2
free energy of adsorption [Eq. 4],[22] DGads was calcu-
2 lated.
Current density (A/cm )  
DGads
Fig. 3—The potentiodynamic polarization in oil-free and 10 vol pct b ¼ exp : ½4
RT
oil solutions.

The corrosion rates, and efficiency of inhibition (g)
which is related to the degree of surface coverage (h) in
Eq. [2], are presented in Table III.
icorr;free  icorr;oil
h¼g¼
icorr;free
icorr,free and icorr,oil denote corrosion current density in
the oil-free and oil-containing solutions. As mentioned
in the introduction, C10H12, whose chemical structure is
shown in Figure 5, is a polar aromatic compound
considered most responsible for adsorption by sharing
its p-electron density. Its molecular weight is 132.2 g/
mol,[12] and its concentration was calculated from the
concentrations of the hydrocarbon fuel of a molecular
weight of approximately 231 g/mol.[21] C10H12 is postulated
As shown in Table III, the free energy of adsorption
was of a negative value at 293 K (20 °C)—the temper-
ature at which the inhibition was the most effec-
tive—indicating the spontaneous and strong nature of
adsorption. Enthalpy (DHads ) and entropy (DSads ) of
: ½2
adsorption, shown in Table IV, were calculated as
functions of C10H12 concentration by considering an
alternative expression of Eq. [4] as
 
h DHads  TDSads
¼ C exp  : ½5
1h RT
The relation was transformed to be linear and was
plotted in Figure 7, from which enthalpy and entropy
were extracted. The enthalpy was negative, and it
increased with the oil concentration indicating that

METALLURGICAL AND MATERIALS TRANSACTIONS B

 Table III. Corrosion Inhibition and free Energy of Adsorption

Oil Content
Temperature (Volume Percent) C10H12 (M) icorr,oil (lA/cm2) g (Percent) h/(1  h) b (M1) DGads (kJ/mol)
293 K (20 °C) 10 0.477 24.7 41.88 0.721 1.050 0.119
20 0.953 20.2 52.5 1.105
30 1.430 18 57.6 1.358
323 K (50 °C) 10 0.477 75.8 8.23 0.090 0.353 2.800
20 0.953 66.3 20 0.250
30 1.430 52.4 37 0.587
353 K (80 °C) 10 0.477 160.7 5.88 0.062 0.127 6.05
20 0.953 150 11.8 0.134
30 1.430 143.2 14.7 0.172

0.5

10 vol% oil
20 vol% oil
0.0 30 vol% oil

-0.5

-1.0

Fig. 5—The chemical structure of tetrahydronaphthalene (C10H12).

-1.5

1.4 293 K (20oC)

323 K (50oC)
-2.0
353 K (80oC)
1.2
-2.5

1.0
-3.0
2.8x10-3 2.9x10-3 3.0x10-3 3.1x10-3 3.2x10-3 3.3x10-3 3.4x10-3
0.8 1/T (1/K)

0.6
Fig. 7—Plots of ln(h/(1  h)) vs 1/T for 10, 20, and 30 vol pct oil
solutions.

0.4
of capacitive depressed arcs and inductive loops at the
high- and low-frequency regions, respectively. Similar to
0.2 previously reported EIS findings,[24,25] the shapes of the
spectra, which were smaller at higher temperatures,
suggest that adsorption—governed by intermediate
0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 adsorbents such as FeHCOþ 
3 and FeOH , which drive
C10H12 concentration (M) dissolution—dominated the interfacial processes. The
magnitude and frequency of the single phase peaks of
Fig. 6—Langmuir adsorption isotherms for C10H12 concentrations at between 5 and 10 Hz indicate the charge-transfer-based
293 K, 323 K, and 353 K (20 °C, 50 °C, and 80 °C). processes, and as the temperature is less, the significance
of adsorption is less, and the cathodic reactions are
C10H12, as a natural inhibitor, adsorbs onto the surface slower—to become the controlling reactions.[26] The
in an exothermic process.[23] The entropy was negative Bode IZI plots reveal clearly the influence of temperature
and showed a slight increase with oil concentration on and outside the double layer where the charge-
showing evidence that the gradual desorption of water transfer resistance decreased, and so did the solution
molecules by the adsorbing C10H12 molecules depends resistance. The measured EIS data were fitted with an
considerably on oil concentration. equivalent circuit, shown in Figure 9, which accounts
for the intermediate species adsorption with inductance
B. The Electrochemical Impedance Spectroscopy (EIS) (L) and inductive resistance (RL). The constant phase
Tests element (CPE) accounts for the interfacial heterogene-
ities[27] and its admittance (Y) is expressed as[28]
The interfacial corrosion interactions at the OCPs np np
were investigated by EIS. As shown in Figure 8 for the Y ¼ YQ xn cos þ jYQ xn sin ; ½6
oil-free solutions, the similar Nyquist spectra consisted 2 2

METALLURGICAL AND MATERIALS TRANSACTIONS B

where x is the angular frequency, and n is the CPE (n was between 0.70 and 0.85). The solution resistance
exponent. The charge-transfer resistance (Rct) decreased (Rs) decreased from nearly 22 to 16 X cm2, and RL,
from nearly 75 X cm2 at 293 K (20 °C) to about which is proportional to the surface coverage of reaction
X cm2 at 353 K (80 °C), and the double layers were intermediates, decreased from 20 to 2.5 X cm2, at 293 K
pseudo-capacitive and the admittance (Ydl) seemed and 353 K (20 °C and 80 °C), respectively.
accordingly unaffected of nearly 22 9 104 S sn/cm2 Oil made the Nyquist spectra highly characteristic of
interfaces covered by corrosion-inhibiting stable lay-
ers.[29] As shown in Figure 10 for the 10 vol pct oil-
100 containing solutions, they were larger than those of the
oil-free solutions and so were, more specifically, the
inductive loops at the lower frequencies. Both the
80 Nyquist and Bode plots showed changes with temper-
ature similar to those of the oil-free solutions. The Bode
phase profiles showed low-frequency valleys and single
Zim (Ω.cm )
2

60
peaks that appeared at higher frequencies ranging
between 20 and 160 Hz. The equivalent circuit proposed
40
for the oil-free solutions was applicable to fit the EIS
response of the oil-containing solutions. Rct, which was
293 K (20°C)
20
323 K (50°C) 1000

353 K (80°C)

0
800
0 20 40 60 80 100
Zre (Ω.cm2)
Zim (Ω.cm )
600
(a)
2

30 400 293 K (20°C)

293 K (20°C)
100 293 K (20°C)

323 K (50°C)
200
323 K (50°C)
20 353 K (80°C)
353 K (80°C)
Phase angle (deg)

323 K (50°C)
0
IZI (Ω.cm )
2

353 K (80°C) 0 200 400 600 800 1000

10
Zre (Ω.cm2)
(a)
0 60
1000 293 K (20°C)

293 K (20°C)
323 K (50°C)
353 K (80°C)
353 K (80°C) 323 K (50°C)
10 -10
10 -3 10 -2 10 -1 10 0 10 1 10 2 10 3 10 4 10 5 40
Phase angle (deg)

Frequency (Hz)
IZI (Ω.cm )
2

(b)
Fig. 8—The EIS spectra in oil-free solutions represented by 20
100
(a) Nyquist and (b) Bode plots.

CPEdl

0
RS

R ct
10 -3 10 -2 10 -1 10 0 10 1 10 2 10 3 10 4 10 5
Frequency (Hz)
RL L
(b)
Fig. 9—The equivalent circuit fitting the EIS response in the oil-free Fig. 10—The EIS spectra in 10 vol pct oil solutions represented by
and oil-containing solutions. (a) Nyquist and (b) Bode plots.

METALLURGICAL AND MATERIALS TRANSACTIONS B

 Table IV. Enthalpy and Entropy of Adsorption

Oil (Volume 1/T (1/K)

Percent) (1 9 103) Ln(h/(1  h)) Slope Intercept DHads (kJ/mol) DSads (J/mol K)
10 3.413 0.328 4294.8 15.2 35.71 120.3
3.096 2.411
2.833 2.773
20 3.413 0.100 3584.5 11.9 29.8 99.2
3.096 0.532
2.833 2.012
30 3.413 0.306 3619.2 12.2 30.09 104.5
3.096 1.386
2.833 1.758

higher in the oil-free solutions, decreased from 1000 to
400 X cm2 at 293 K and 353 K (20 °C and 80 °C),
respectively, but RL was 280 X cm2, relatively the same
regardless of temperature.
IV. CONCLUSIONS
An electrochemical corrosion investigation and a brief
thermodynamic analysis of the adsorption of an inhibit-
ing hydrocarbon fuel in 1-bar CO2-saturated emulsions
are outlined in this research. The corrosion rates, calcu-
lated from potentiodynamic measurements, were inhib-
ited in proportion with the hydrocarbon fuel amount, but
with less efficiency at high temperatures. Ascribing the
inhibition to an active aromatic C10H12 compound,
Langmuir adsorption isotherms were constructed to
calculate the free energy, enthalpy, and entropy of
inhibition. The main kinetic findings on the cathodic
reactions and dissolution in oil-free and oil-containing
solutions were interlinked from the potentiodynamic
polarization, EIS, and OCP measurements.
ACKNOWLEDGMENT
This research was made possible by NPRP Grant
#09-211-2-089 from the Qatar National Research
Fund (a member of Qatar Foundation).
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METALLURGICAL AND MATERIALS TRANSACTIONS B