Materials Chemistry and Physics 105 (2007) 331–340

Evaluation of inhibition efficiency of an imidazoline derivative

in CO2-containing aqueous solution
Guoan Zhang a,∗ , Changfeng Chen a , Minxu Lu b ,
Chengwen Chai b , Yinshun Wu b
a Department of Materials Science and Engineering, China University of Petroleum,
18 Fuxue Road, Changping, Beijing 102249, PR China
b Corrosion and Protection Center, University of Science and Technology Beijing,

30 Xueyuan Road, Beijing 100083, PR China

Received 6 April 2006; received in revised form 8 April 2007; accepted 29 April 2007

Abstract
The inhibition efficiency of an imidazoline derivative for API X65 steel in CO2 -saturated 5% NaCl solution has been studied by using potentiody-
namic polarization and electrochemical impedance spectroscopy (EIS) measurements. This imidazoline derivative acts as a mixed-type inhibitor,
which suppresses both cathodic and anodic processes by its adsorption on the electrode surface according to Langmuir adsorption isotherm,
together with a slight positive shift in corrosion potential (Ecorr ). The adsorbed inhibitor on the surface of electrode affects the kinetic processes of
cathodic and anodic reactions and increases the reaction activation energy. Both potentiodynamic polarization and EIS measurements reveal that
this imidazoline derivative inhibits the corrosion of API X65 steel in CO2 -saturated 5% NaCl solution and that the inhibition efficiency increases
with increasing of the inhibitor concentration. The Nyquist plot of uninhibited electrode at Ecorr is characterized by a depressed semicircle from high
to medium frequencies and an inductive loop at low frequencies while the inhibited ones emerge “degradation” phenomena with simple depressed
capacitive loops. The semicircles representing the inhibitor film merge with the charge transfer loops. The inhibitor films form gradually and the
inhibition efficiency increases with increase of immersion time.
© 2007 Elsevier B.V. All rights reserved.

Keywords: Oil and gas fields; CO2 corrosion; Inhibitor; Potentiodynamic polarization; EIS

1. Introduction mechanisms have been proposed for the dissolution of carbon

steel in CO2 -containing aqueous solution. The main cathodic
Carbon steels are the most commonly used construction reactions can be summarized by four reactions [5,6]. At a lower
materials for pipelines in the oil and gas industry. They are, pH, H+ reduction is the dominant cathodic process because of the
however, very susceptible to corrosion in environment contain- high concentration of H+ (Eq. (1)). When pH increases to 4–6,
ing CO2 [1]. CO2 corrosion would give rise to the failure of the direct reductions of HCO3 − and H2 CO3 become important
pipelines and equipments and result in great economic loss and (Eqs. (2) and (3)). At a high overpotential, the dominant cathodic
calamitous accidents. Leakage of crude oil due to CO2 corrosion reaction changes to direct reduction of water (Eq. (4)):
would induce fire accident, water resource and environmental
2H+ + 2e → H2 (1)
pollution. CO2 corrosion has been one of the most common cor-
−
rosion problems in oil and gas industry because of both a high 2H2 CO3 + 2e → 2HCO3 + H2 (2)
general corrosion rate and severe localized corrosion [2–4].
When CO2 dissolves into water, carbonic acid will form, 2HCO3 − + 2e → 2CO3 2− + H2 (3)
which is more corrosive to carbon steel than a completely dis- 2H2 O + 2e → 2OH− + H2 (4)
sociated acid (such as HCl) at the same pH value. Several
Fe → Fe 2+
+ 2e (5)
∗ Corresponding author. Tel.: +86 10 62332458; fax: +86 10 62334410. The anodic reaction is mainly the dissolution of iron (Eq.
E-mail address: zhangguoan@gmail.com (G. Zhang). (5)) though it is maybe through several steps. During these cor-

0254-0584/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2007.04.076
332 G. Zhang et al. / Materials Chemistry and Physics 105 (2007) 331–340
rosion processes, a corrosion scale (FeCO3 ) would form on the
surface of the carbon steels (Eqs. (6)–(8)) [7]. The properties
and morphology of the scales would influence the corrosion rate
significantly:
Fe2+ + CO3 2− → FeCO3 (6)
Fe2+ + 2HCO3 − → Fe(HCO3 )2 (7)
Fe(HCO3 )2 → FeCO3 + CO2 + H2 O (8)
In order to reduce the corrosion of carbon steels in the oil
and gas industry, inhibitors are frequently added to the pro-
duced fluid to control corrosion as an economical and flexible
method. Inhibitors can adhere to metal surface to form a protec-
tive barrier against corrosive agents contacting with metal. The
efficiency of an inhibitor to provide corrosion protection depends
to a large extent upon the interactions between the inhibitor and
the metal surface [8,9]. The adsorbed inhibitors can affect the
corrosion reactions in two ways: the geometric blocking effect of
adsorbed inhibitive species on the metal surface and the electro-
catalytic effect of the inhibitor or its reaction products. For the
geometric blocking effect, the inhibition effect comes from the
reduction of reaction area on the surface of the corroding metal,
whereas for the electro-catalytic effect, the inhibition effect is
attributed to the change in the average activation energy barriers
of the anodic and cathodic reactions of the corrosion process
[10].
Organic inhibitors containing nitrogen are one of the most
effective means of protecting the severe internal corrosion of
carbon steel pipelines in oil and gas industry because of their
effectiveness and availability [11]. Since imidazoline-based
inhibitors have excellent inhibition ability in acidic media, they
are widely used for protecting oil well, gas well or pipelines
from CO2 corrosion in the oil and gas industry [1,4,12,13].
Wang et al. [14] had studied the electron configuration of sev-
eral imidazoline inhibitors by the quantum chemical calculation.
They found that electron donor group introduced, particularly,
the substituent group with conjugated system, to imidazoline
ring would improve corrosion inhibition efficiency of imidazo-
line derivatives. Schmitt et al. [15] reported the drag reducing
effect of inhibitors using a microelectrode array incorporated
flus into a surface impinged with a submerged jet. They revealed
that inhibitors reduced the wall shear stress dependent on their
chemical structure and concentration. Ramachandran et al. [16]
suggested inhibitors increased the Young’s modulus of the cor-
rosion product scale because inhibitors molecule replaced water
molecule in the pore of the corrosion scale. Inhibitors strength-
ened the corrosion scale, enhancing the protectiveness of this
corrosion scale.
In spite of the extensive use and its corresponding stud-
ies of imidazoline-based inhibitors in oil and gas fields, the
mechanism of inhibition remains unclear. In order to continue
to develop more effective and economic corrosion inhibitor
products, a better understanding of the mechanism of inhibi-
tion of current inhibitors would be helpful. Presently, the key
questions regarding the structure–performance relationships and
adsorption mechanism of imidazoline and corresponding amides
include: (a) role of hydrocarbon chain relative to imidazoline
head group and pendant amine group in film formation; (b)
thickness of the imidazoline film (monolayer or multilayer); (c)
stability and persistency of the imidazoline film; (d) solution
composition and hydrolysis of imidazoline [17].
Electrochemical impedance spectroscopy (EIS) is a power-
ful technique for the corrosion study in various corrosion and
protection fields such as organic coatings, passive films and
corrosion scales analysis. It can provide the information on cor-
rosion and protection mechanism, especially when an adsorbed
film or an applied organic coating is present. EIS had been widely
applied in the monitoring of inhibitor film persistency and in
the study of inhibitive mechanism of inhibitors. In this paper,
the inhibitive mechanism and inhibition efficiency of an imida-
zoline derivative for API X65 steel in CO2 -saturated 5% NaCl
solution were studied by means of potentiodynamic polarization
and EIS.
2. Experimental
API X65 pipeline steel, with a chemical composition (wt.%) C: 0.04%, Si:
0.2%, Mn: 1.5%, P: 0.011%, S: 0.003%, Mo: 0.02%, and Fe: balance, was
used in this experiment. Coupons were machined into 10 mm diameter rods,
cut and mounted with epoxy resin with an exposed area of 0.78 cm2 . Electrical
contact was made by attaching a copper wire. Coupons were polished up to
800 grit silicon carbide paper, rinsed with deionized water and degreased in
acetone.
Testing solution was 5% NaCl making up from analytical grade reagents and
deionized water with a working volume of 1 L. The inhibitor used in this study
was an imidazoline derivative which synthesized from oleic acid, diethylene-
trianmine and thiourea, as shown in Eqs. (9)–(11). A detailed synthesization
process of inhibitor has been described elsewhere [18]. Testing solution was
deaerated by purging CO2 (99.95%) for 4 h prior to experiment. Then, coupons
were quickly mounted on the holder and the inhibitor was added to the solu-
tion. One more hour CO2 purge was carried out to deaerate oxygen entering
in the mounting process. CO2 gas was allowed to bubble into the solution at a
low flow rate to ensure entire saturation throughout the testing and gas exit was
sealed with water. A positive pressure of deoxygenated CO2 was maintained in
the cell during the experiment to minimize the possibility of air ingress. All the
electrochemical experiments were performed at atmospheric pressure.
Fig. 1. Polarization curves of API X65 steel exposed in CO2 -saturated 5% NaCl
solution without or with different concentration inhibitor: (a) blank, (b) 10 ppm,
(c) 50 ppm, (d) 100 ppm, and (e) 200 ppm.
 G. Zhang et al. / Materials Chemistry and Physics 105 (2007) 331–340
A PARSTAT® 2273 electrochemical synthesis measure unit was used for
electrochemical measurement in a bath. A three-electrode test cell was used
with a platinum plane as counter electrode. A saturated calomel electrode (SCE)
was chosen as reference electrode. API X65 steel coupons (Ø 10 mm × 5 mm)
were employed as working electrode. Potentiodynamic scans were carried out by
changing the electrode potential automatically from −400 mV to +300 m versus
open circuit potential with a scan rate of 1 mV/s. Impedance was measured at
open circuit potential with a sinusoidal potential excitation of 10 mV amplitude
in the frequency range from 100 kHz to 5 mHz. The impedance data were fitted
with ZsimpWin software using equivalent circuit.
3. Results and discussions
3.1. Potentiodynamic polarization
The corrosion behaviors of API X65 steel exposed to
CO2 -saturated 5% NaCl solution without or with different
concentration inhibitor were studied by potentialdynamic polar-
ization at ambient temperature. Typical polarization curves were
shown in Fig. 1. It is observed that this imidazoline deriva-
tive inhibits both anodic and cathodic reactions by decreasing
polarization current density. The values of corresponding kinetic
parameters such as corrosion potential (Ecorr ), corrosion current
density (icorr ), anodic and cathodic Tafel slope (ba , bc ) are listed
in Table 1. These kinetic parameters are obtained by perform-
ing a least square fit of the measured data in feeble polarization
333
(9)
(10)
(11)
zone with a self-compiled program. It can be seen that the cor-
rosion potentials (Ecorr ) of inhibited electrodes marginally shift
towards positive region and the shifts are found to be depen-
dent on inhibitor concentration. The potentials (Ei=0 ) at which
current density equate to zero shift to negative region. This dif-
ference between Ecorr and Ei=0 may be attributed to the change
of the surface status of the electrodes after cathodic polarization.
The decrease in corrosion rate associating with a shift of both
cathodic and anodic branches of the polarization curves towards
lower current densities, together with a slight positive shift in
corrosion potential, indicates that this imidazoline derivative
acts as a mixed-type inhibitor. The inhibition efficiency (IE)
is calculated as follows:
i0corr − icorr
IE(%) = × 100 (12)
i0corr
where i0corr , icorr are the uninhibited and inhibited corrosion
current densities, respectively. The inhibition efficiencies of dif-
ferent inhibitor concentration are also listed in Table 1. It can
be seen that the inhibitor inhibits greatly the corrosion of API
X65 steel and the inhibition efficiency increases with inhibitor
concentration.
It is also observed that anodic polarization curves in the
presence of inhibitor emerge an abrupt increase of current den-
334 G. Zhang et al. / Materials Chemistry and Physics 105 (2007) 331–340

Table 1
Fitting results of the electrochemical parameters of API X65 steel exposed in CO2 -saturated 5% NaCl solution without and with imidazoline derivative inhibitor
Testing conditions Ecorr (mV vs. SCE) Ei=0 (mV vs. SCE) icorr (␮A cm−2 ) ba (mV/dec) bc (mV/dec) IE (%)a

Temperature (◦ C) Concentration (ppm)

25 0 −714.0 −698.5 161.3 55.66 132.98

25 10 −643.3 −727.2 11.2 65.91 96.93 93.06
25 50 −630.2 −687.5 2.7 67.64 127.98 98.33
25 100 −622.1 −721.3 1.8 50.51 175.75 98.88
25 200 −620.2 −727.2 1.7 56.34 129.20 98.95
25 0 −714.0 −689.5 161.3 55.66 132.98
45 0 −713.5 −707.9 229.9 51.54 164.36
60 0 −712.9 −702.1 329.9 61.77 107.54
75 0 −708.4 −704.8 355.1 64.01 101.38
25 50 −630.2 −687.5 2.7 67.64 127.98 98.33
45 50 −630.0 −700.3 3.8 75.56 162.29 98.35
60 50 −630.5 −688.6 8.7 67.24 123.25 97.36
75 50 −650.5 −714.3 17.6 60.84 110.48 95.04
a Calculating with Eq. (12).

sity when polarization potential attains a relatively positive The effects of temperature on the corrosion rate and polar-
value. This indicates an anodic desorption process of inhibitor ization curves are shown in Fig. 2. The corresponding kinetic
takes place [19]. The surface coverage Θ of adsorbed inhibitive parameters, which are obtained by fitting the measured data in
species usually decreases with the increase of potential in anodic feeble polarization zone, are listed in Table 1. It can be seen
branch, i.e. (dΘ/dE) < 0. The increase of polarization potential that the corrosion rates in the presence of inhibitor are always
accelerates the dissolution of metal not only on the surface with- much less than that of without inhibitor. This indicates that the
out adsorbed species but also the surface with adsorbed inhibitive inhibitor is efficient at the temperature studied. The corrosion
species because the adsorbed species becomes instable at a high rates increase with temperature in both uninhibited and inhibited
polarization potential. The adsorbed inhibitor species will depart solutions due to the acceleration of transfer process of reactive
metal surface quickly due to an acceleration of heat migra- ion and the increase of reactive rate coefficient. The activation
tion process and the anodic dissolution of metal. The original energy of cathodic and anodic reactions can be calculated as
adsorption–desorption equilibrium is broken as the adsorption follows:
rate less than desorption rate, and the surface coverage decreases
abruptly. The decrease of surface coverage, in turn, acceler-  
ates the dissolution of metal. This repeated process will result E0
i0corr = k exp − (13)
in the surface coverage decrease to zero ultimately and metal RT
becomes “naked” to solution as the case of the solution without
inhibitor. Therefore, it is observed that at a potential higher than  
−350 mV the polarization curves in absence and presence of E
icorr = k exp − (14)
inhibitor almost coincide (are not shown in the figure). RT

Fig. 2. Polarization curves of API X65 steel exposed in CO2 -saturated 5% NaCl solution at different temperature: (a) blank, 25 ◦ C, (b) blank, 45 ◦ C, (c) blank, 60 ◦ C,
(d) blank, 75 ◦ C, (e) 50 ppm, 25 ◦ C, (f) 50 ppm, 45 ◦ C, (g) 50 ppm, 60 ◦ C, and (h) 50 ppm, 75 ◦ C.
 G. Zhang et al. / Materials Chemistry and Physics 105 (2007) 331–340 335

Fig. 3. The relationship between R ln icorr and 1/T in the absence and presence Fig. 5. EIS Bode plots of API X65 steel exposed in CO2 -saturated 5% solution
of inhibitor. without inhibitor: log|Z|: , experimental points; , fitting points. Phase angle:
, experimental points and , fitting points.

Then, it can be deduced: 3.2. EIS measurement

1 Figs. 4 and 5 show the Nyquist and Bode plots for API X65
R ln i0corr = R ln k − E0 (15)
T steel exposed to CO2 -saturated 5% NaCl solution for 2 h at room
temperature without inhibitor. The Nyquist plot, as shown in
1 Fig. 4, is characterized by a depressed semicircle from high to
R ln icorr = R ln k − E (16)
T medium frequencies and an inductive loop at low frequencies.
It is suggested that the dissolution of iron in CO2 -saturated 5%
where E0 and E are the activation energy in absence and NaCl solution follows the consecutive mechanism with adsorbed
presence of inhibitor, respectively, which can be obtained by the intermediate product. The mechanism can be written as follows
line slops of R ln icorr ∼ 1/T. k is constant and R is gas constant. [20]:
The plots of R ln icorr ∼ 1/T in the absence and presence of
inhibitor are shown in Fig. 3. E0 and E, which attained from Fe + H2 O  FeOHads + H+ + e (17)
the slops of the lines, are 14.39 and 48.24 kJ mol−1 , respec-
tively. This indicates that the adsorbed species affects the kinetic FeOHads → FeOH+ + e (18)
process of anodic and cathodic reactions simultaneously and
FeOH+ + H+  Fe2+ + H2 O (19)
increases the reaction activation energy.
The appearance of capacitive semicircle can be attributed
to the double layer capacitance and transfer resistance. The
inductive loop arises from the adsorbed intermediate product
(FeOHads ) in the absence of inhibitor. An equivalent circuit for
simulating this process is shown in Fig. 6(a) and the fitting val-
ues of impedance parameters are listed in Table 2. It can be seen
from Fig. 4 that the impedance spectra have a form of a depress
semicircle in the complex plane with the center under the real
axis. Such behavior is typical for the solid electrodes. It is usu-
ally refer to as frequency dispersion of impedance data different
from the pure capacitance. Although it has been attributed to
roughness and inhomogeneities of the solid surfaces [21–23],
the reason that this phenomenon takes place is still not clear. A
constant phase element (CPE), which has a non-integer power
dependence on the frequency, is employed to describe the dou-
ble layer capacitance [24]. Its impedance is described by the
expression:
1
Fig. 4. EIS Nyquist plots of API X65 steel exposed in CO2 -saturated 5% NaCl ZCPE = (jω)−n (20)
solution without inhibitor: , experimental points and , fitting points. Y0
336 G. Zhang et al. / Materials Chemistry and Physics 105 (2007) 331–340

API X65 steel in CO2 -containing solutions with inhibitor con-

Fig. 6. Equivalent circuit models used for fitting the experimental impedance
data: (a) uninhibited electrode; (b) inhibited electrodes. Rs , solution resistance;
CPE, constant phase element; Rt , charge transfer resistance; RL , inductance
resistance; L, inductance; Cfilm , capacitance of inhibitior film; Rpore , solution
resistance in pore.
√
where Y0 is a proportional factor, j = −1, ω = 2πf, n is a phase
shift. For n = 0, it represents a resistance with R = Y0−1 ; for n = 1,
it represents a capacitance with C = Y0 . The phase angle θ versus
log f in Bode plot appears a peak in high frequency and a valley in
low frequency, which represent the capacitive loop and inductive
loop, respectively.
The fitting Nyquist and Bode plots of experimental
data obtained for uninhibited electrode are also shown in
Figs. 4 and 5. It can be seen that the fitting results match the
experimental data very well.
The Nyquist and Bode plots for API X65 steel exposed to
CO2 -saturated 5% NaCl solution for 2 h at room temperature
with the inhibitor of different concentration are shown in Fig. 7.
The continuous increase in the diameter of the Nyquist semicir-
cle with the increasing of inhibitor concentration suggests that
the inhibition efficiency increases with inhibitor concentration.
Most of the impedance spectra obtained for the corrosion of
sist of a depressed capacitive loop. It can be considered that
the resistance of inhibitor film is much smaller than the charge
transfer resistance. The semicircle representing the inhibitor film
merging with the charge transfer loop result in that the Nyquist
plots emerge a “degradation” phenomenon. In the Bode θ versus
log f plots, it can be seen that there are two-time constants. One
time constant emerges at a frequency about 10 Hz. This can be
attributed to the double layer capacitance and charge transfer
resistance. Another at about 1000 Hz can be corresponding to
the relaxation process of an adsorbed inhibitor film as a surface
dielectric film normally has a small time constant and so has
a phase angle shift in the high frequency range. This inhibitor
film changes the electrode interfacial structure and results in an
additional time constant.
For analysis of the impedance spectra, as shown in Fig. 7, a
simple equivalent circuit (EC) given in Fig. 6(b) was used. The
values of impedance parameters, which obtained by fitting the
impedance data with ZsimpWin software using an equivalent
circuit, are listed in Table 2. The inhibition efficiency got from
the charge transfer resistance is calculated by
Rt − R0t
IE(%) = × 100 (21)
Rt
where R0t , Rt are the charge transfer resistances without and
with inhibitor, respectively. As higher value of charge transfer
resistance corresponds to lower corrosion rate, the difference
between R0t and Rt is dependent on the inhibitor’s effective-
ness in corrosion control. The values of inhibition efficiency
increase with increasing concentration of inhibitor, indicating
that a higher surface coverage is obtained in a solution with the
optimum concentration of inhibitor.
It is found that the Rt values increases in the presence of
inhibitors, whereas the values of Y0 (represents double layer
capacitance) are found to decrease. The changes in Rt and Y0
values are due to the gradual change of electrode interface struc-
ture. The increase of Rt indicates that the adsorbed inhibitor

Table 2
Electrochemical impedance data of API X65 steel exposed in CO2 -saturated 5% NaCl solution without and with imidazoline derivative inhibitor
Rs ( cm2 ) Cfilm (␮F cm−2 ) Rpore ( cm−2 ) Y0 (×10−4 −1 cm−2 s−n ) n Rt ( cm2 ) RL ( cm2 ) L (H cm−2 ) IE (%)a

Concentration (ppm)
0 3.8 3.501 0.87 337 936 1823
10 3.8 16.27 24.39 2.492 0.81 1764 80.90
50 3.8 8.33 8.57 2.357 0.76 2618 87.13
100 3.8 4.52 5.79 1.459 0.65 3900 91.36
200 3.8 3.92 6.34 1.488 0.70 5234 93.65
Immersion time (h)
4 3.8 4.21 7.81 2.501 0.67 2989 88.73
8 3.8 4.55 9.39 2.462 0.68 3458 90.25
12 3.8 4.84 10.17 2.378 0.69 3716 90.93
24 3.8 5.64 11.74 2.235 0.72 4060 91.70
36 3.8 6.47 13.23 2.220 0.72 4569 92.62
48 3.8 6.99 13.89 2.245 0.73 5122 93.42
60 3.8 7.20 13.78 2.276 0.73 5396 93.75
72 3.8 7.59 13.79 2.325 0.72 5519 93.89
a Calculating with Eq. (21).
 G. Zhang et al. / Materials Chemistry and Physics 105 (2007) 331–340 337

Fig. 7. . Nyquist and Bode plots of API X65 steel exposed in CO2 -saturated 5% NaCl solution with the inhibitor of different concentration: , blank, , 10 ppm,
, 50 ppm, , 100 ppm, , 200 ppm.

Fig. 9. EIS Bode plots of API X65 steel exposed in CO2 -saturated 5% NaCl
Fig. 8. EIS Nyquist plots of API X65 steel exposed in CO2 -saturated 5% NaCl solution with 50 ppm inhibitor: log|Z|: , experimental points and , fitting
solution with 50 ppm inhibitor: , experimental points and , fitting points. points. Phase angle: , experimental points and , fitting points.

species increase the resistance of the dissolution reaction of adsorbs on the surface of electrode, it must eliminate the water
metal. The decrease in Y0 is attributed to the adsorption of molecule originally adsorbing on the surface of electrode. There-
this inhibitor compound on the metal surface leading to the fore, water molecules on electrode interface are largely replaced
formation of film from acidic solution. When inhibitor species by inhibitor molecules which have a lower dielectric constant.

Fig. 10. Nyquist and Bode plots of API X65 steel exposed in CO2 -saturated 5% NaCl solution with 50 ppm inhibitor for different time: , 4 h; , 8 h; , 12 h;
, 24 h; , 36 h; , 48 h; , 60 h; , 72 h.
338 G. Zhang et al. / Materials Chemistry and Physics 105 (2007) 331–340

Fig. 11. Bilayer schematic model for imidazoline derivative adsorption on metal surface.

Meanwhile, the thickness of adsorbed inhibitor molecule layer et al. [25] and Tan et al. [13]. This inhibitor film changes the
is usually more than that of water molecule. Therefore, the elec- electrode interfacial structure and results in an additional time
trode interface adsorbed inhibitor molecule has a lower double constant.
layer capacitance.
The fitting results for the impedance spectra measured in 3.3. Adsorption isotherm
50 ppm inhibitor concentration with an equivalent circuit given
in Fig. 6(b), as a representative example, were shown in The information on the interaction between this imidizoline
Figs. 8 and 9. It can be seen that the fitted and measured results derivative and electrode surface can be provided by the adsorp-
match quite well in Nyquist and Bode plots. tion isotherm. In order to obtain the adsorption isotherm, the
The Nyquist and Bode plots of the electrode after exposed relation between the surface coverage Θ, which is equivalent
to CO2 -containing 5% NaCl solution with 50 ppm inhibitor to the inhibition efficiency (IE) obtained by EIS, and inhibitor
for different immersion times are shown in Fig. 10 and the concentration (Cinh ) was studied. The plot of Θ/(1 − Θ) ∼ Cinh
impedance parameters are listed in Table 2. The continuous emerges a straight line, as shown in Fig. 12, which indicates that
increase in the diameter of Nyquist semicircles with the immer- the adsorption of this inhibitor can be fitted to Langmuir adsorp-
sion times indicates that the presence of inhibitor distinctly but tion. This result demonstrates that the inhibition of electrode by
gradually changes the corrosion kinetics on the electrode sur-
face. This is maybe corresponding to the surface coverage of the
inhibitor.
In the Bode impedance plots, the module at low frequency
region increases with time, which indicates that the corrosion
rate decreases with immersion time. The Bode θ versus log f
plots emerge two-time constants before 24 h. One time con-
stant at a frequency about 1 Hz can be attributed to the double
layer capacitance and the other at about 1800 Hz can be cor-
responding to relaxation process of an adsorbed inhibitor film.
Besides this two-time constant, a new phase angle shift at higher
frequency range (about 34 Hz) forms gradually in the Bode θ ver-
sus log f plots after 24 h and a continuous increase in the phase
angle shift with exposure time. The emergence of this new phase
shift suggests that a new inhibitor film gradually forms in the
electrode surface with increase of exposure time. This suggests
that the inhibitor is a bilayer structure and molecular result-
ing from the interaction among the long hydrocarbon chain, as Fig. 12. Langmuir adsorption isotherm plot of API X65 exposed in the CO2 -
shown in Fig. 11. A similar result was also obtained by Lopez satuated 5% NaCl solution with an imidazoline derivative inhibitor.
 G. Zhang et al. / Materials Chemistry and Physics 105 (2007) 331–340
Fig. 13. Polarization curves (a) and Nyquist plot (b) of API X65 steel exposed in CO2 -saturated 5% NaCl solution with 50 ppm imidazoline and derivative.
this inhibitor is attributed to adsorption of this compound on the
electrode surface.
Imidazoline-based inhibitor may adsorb on the electrode
surface in the form of a neutral molecule via chemisorption
mechanism involving the sharing of electrons between the nitro-
gen atom and iron. The N–C–N bond in imidazoline molecule
is of p–␲ conjugation property and the carbon atom has some
sp2 hybrid orbital geometry. Introduction of electron releasing
substiuent or conjugation system on the C atom remarkably
strengthen the chemical adsorption of the N atom on the metal
surface. Owing to the conjugation system, ␲-electron is easily
translated to d-orbital of Fe atom along to ␲-system. Adsorp-
tion can also occur in the cationic form with positively charges
part of the molecule (ammonium –NH3 + ) oriented toward neg-
atively charges of iron surface as chloride ions are adsorbed on
electrode surface.
By introducing the thiourea, in addition to the adsorption of
the azoles, a protonation of imidizoline derivative will take place
at S atom as following:
(22)
The adsorption of this imidazoline derivative at metal solu-
tion interface can be represented as a substitutional adsorption
process between the inhibitor molecules in the aqueous solution
and the water molecules on the metallic surface. By adsorbing
on the metal surface inhibitor molecule control the anodic and/or
cathodic reactions during corrosion process. The protonated
inhibitor molecules can also adsorb electrostatically onto the
negatively charged metal surfaces through their cationic forms.
Thus the imidizoline derivative has higher inhibition efficiency.
To study the difference of inhibition efficiency of the imidizo-
line and its derivative, Fig. 13 shows the polarization curves and
339
Nyquist plots of the API X65 steel in 5% CO2 -saturated solu-
tion with 50 ppm imidizoline and its derivative. It can be seen
that the polarization curve with imidizoline derivative emerges
a small corrosion current and a large charge transfer resistance
is observed in EIS measure, which suggests that the imidizoline
derivative has higher inhibition efficiency.
4. Conclusions
The results of potentiodynamic polarization indicate that this
imidazoline derivative, as a mixed-type inhibitor, inhibits both
cathodic and anodic processes, together with a slight positive
shift in corrosion potential (Ecorr ). The adsorbed inhibitor on
the surface of electrode affects the kinetic process of anodic and
cathodic reactions and increases the reaction activation energy.
Nyquist plot of uninhibited electrode at Ecorr is characterized
by a depressed semicircle from high to medium frequencies
range and an inductive loop at low frequency range, while
the inhibited ones emerge simple depressed capacitive loops
because the semicircle representing the inhibitor film merges
with the charge transfer loop. The inhibition efficiencies increase
with the increasing of inhibitor concentration and immersion
times.
This imidazoline derivative has higher inhibition efficiency
than that of imidazoline by introducing thiourea. The adsorp-
tion of this imidazoline derivative inhibitor is fitted to Langmuir
adsorption. These results demonstrate that the inhibition of API-
X65 steel by this inhibitor is attributed to adsorption of this
compound on the iron surface.
Acknowledgements
The authors acknowledge National Natural Science Foun-
dation of China Key Program “Research on Corrosion of
Metallic Materials in Multiphase Media Environment under
High Temperature and High Pressure Conditions” (50231020)
and National Natural Science Foundation of China “Study of
Correlativity Between High Temperature High Pressure CO2
Corrosion Behavior and Ions Transport in Corrosion Scale”
(50601029) for the financial support of this research.
340 G. Zhang et al. / Materials Chemistry and Physics 105 (2007) 331–340
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