Corros Rev 2016; aop

Original article

Dong Yang, Song Hui Liu, Yu Pei Shao, Shao Di Xu, Lu Lu Zhao, Qiang Qiang Liao*
and Hong Hua Ge

Electrochemical and XPS studies of alkyl

imidazoline on the corrosion inhibition of carbon
steel in citric acid solution
DOI 10.1515/corrrev-2016-0016 calcium carbonate/sulfate scales and/or ferric scales that
Received March 23, 2016; accepted August 1, 2016 emerge at the internal wall of thermodynamics equipments
after heat-engine plants operate for a long time, which will
Abstract: The corrosion inhibition behavior of an imida-
have a negative influence over the heat transfer of ther-
zoline derivative, namely, 2-undecyl-N-carboxymethyl-
modynamics equipments. Therefore, chemical scrubbing
N-hydroxyethyl imidazoline (UHCI) for carbon steel in
techniques with different acids tend to be inevitable meas-
4 wt.% citric acid solutions was characterized by weight
ures (Houben, 2003). However, acids will corrode carbon
loss method and electrochemical techniques in conjunc-
steel while they dissolve scale crust. Some “security clean-
tion with X-ray photoelectron spectrometer (XPS) tech-
ing agents” such as citric acid and amidosulphuric acid are
nique. The inhibitor has a good anti-corrosion effect on
employed to dissolve scale crust while they corrode carbon
the carbon steel in 4 wt.% citric acid solutions. The inhibi-
steel as little as possible (Zerfaoui et al., 2004). Moreover,
tion efficiency increases with UHCI concentrations from
“security cleaning agents” that have some advantages of
0 up to 0.4 wt.%, yet declines a bit at 0.6 wt.% per contra
low toxicity, non-volatility etc. comply with environmen-
with further augmentation of concentration. The inhibi-
tal requirements. Adding corrosion inhibitors to “security
tion efficiency declines with the rise of temperature from
cleaning agents” is still an indispensable step to be taken
20°C to 95°C, while it rises with the extension of soaking
in order to further reduce corrosion of carbon steel from
time from 2 h to 24 h. Two N1s peaks that appeared in XPS
“security cleaning agents” despite all those advantages.
spectra give proof of UHCI inhibitor adsorbed on the car-
Imidazoline derivatives are effective corrosion inhibi-
bon steel surface.
tors for mild steel in corrosive environments (­Ramachandran
Keywords: acid corrosion; carbon steel; EIS; modeling & Jovancicevic, 1999; Seal et al., 2000). Imidazoline mol-
studies; polarization. ecules are composed mainly of three different parts: a
nitrogenous azaheterocycle, a hydrocarbon longchain, and
a mutant side chain containing an active functional group.

1 Introduction There are many kinds of imidazoline compounds accord-

Carbon steel is one of the main metals that constitute ther-
modynamics equipments at heat-engine plants. There are
*Corresponding author: Qiang Qiang Liao, Shanghai Key Laboratory
of Materials Protection and Advanced Materials in Electric Power,
Shanghai Engineering Research Center of Energy-Saving in Heat
Exchange Systems, Shanghai University of Electric Power, Shanghai
200090, China, e-mail: 13371895959@163.com
Dong Yang, Song Hui Liu, Yu Pei Shao, Shao Di Xu, Lu Lu Zhao and
Hong Hua Ge: Shanghai Key Laboratory of Materials Protection
and Advanced Materials in Electric Power, Shanghai Engineering
Research Center of Energy-Saving in Heat Exchange Systems,
Shanghai University of Electric Power, Shanghai 200090, China
ing to the difference in size of hydrocarbon chains and in
the category of active functional groups. They are used for
anti-corrosion control in saltwater (Liu et al., 2009a,b),
carbon dioxide corrosion inhibition of mild steel (Okafor
et al., 2009; Ortega-Toledo et al., 2011; Wang et al., 2011),
high pressure H2S/CO2 anti-corrosion of mild steel (Zhang
et al., 2012), HCl corrosion inhibition of aluminum alloy (He
et al., 2014) and carbon steel (Zhang et al., 2011), H2SO4 cor-
rosion inhibition of mild steel (Okafor & Zheng, 2009), mild
steel corrosion inhibition in chloride solution saturated
with carbon dioxide (Jawich et al., 2012; Jevremović et al.,
2013; Zhao & Chen, 2012), copper corrosion inhibition in
NaCl solution (Liu et al., 2009a,b), and carbon steel corro-
sion inhibition in alkaline NaCl solution (Feng et al., 2011).

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2 D. Yang et al.: Corrosion inhibition behavior of UHCI on carbon steel in citric acid solution

There are some reports about corrosion and protection CH2

of carbon steel in citric acid media in the open literature. N CH2
Gouda et al. (1980) found that the corrosion behavior of +
steel in static O2-free citric acid solutions depended on the C11H23 C N CH2CH2OH

acid concentration and the pH value. Chu and Wan (1993)

also believed that the corrosion rate of iron increases with
the concentration of citric acid because of an efficient
chelating effect of citrate ions with ferrous ions. Li et al.
(2014) extracted the efficient ingredients of Phyllostachys
nigra Munro leaves as the corrosion inhibitor of cold rolled
steel against 0.2 mol l−1 citric acid solution, and its inhibi-
tion efficiency is 81.2% at the inhibitor concentration of
0.2 wt.% according to weight loss data. Katariya et al. (2013)
employed a zeolite coating as the inhibitor of mild steel cor-
rosion in citric acid solutions, and its inhibition efficiency
achieved up to 97% in a 20 vol.% citric acid solution.
In this work, the inhibition mechanism and adsorption
behaviors of 2-undecyl-N-carboxymethyl-N-hydroxyethyl
imidazoline (UHCI) for 20# carbon steel in 4 wt.% citric
acid solution have been investigated by means of the weight
loss, electrochemistry, and surface analysis techniques.
CH2COONa
Figure 1: The molecular structure of UHCI.
The elemental composition of 20# carbon steel speci-
mens is given in Table 1.
Rectangular carbon steel coupons with exposed area
of 28.0 cm2 (5.0 cm × 2.5 cm × 0.2 cm) were used for weight
loss measurements. Cylindrical carbon steel rods with
effective area of 0.79 cm2 (∅1.0 cm) were used for surface
analysis and electrochemical measurements. In advance
of experiments, all specimens were carefully ground with
silicon carbide abrasive paper from 180 up to 1200 grit,
subsequently rinsed with deionized water, degreased with
acetone, and then blow-dried with cool air.

2.2 Weight loss measurements

2 Materials and methods
2.1 Solutions and materials
In this work, the inhibitor investigated was a sort of imida-
zoline compound, namely, UHCI, which was from Shang-
hai Fakai Chemical Industry Co. Ltd., Shanghai, China.
The molecular structure of UHCI is shown in Figure 1.
UHCI specimen bought is amber liquid whose concen-
tration of UHCI is 40 wt.%. It was regarded as the liquid
whose nominal concentration of UHCI is 100 wt.% when
different nominal concentrations were prepared. So the
actual concentration of UHCI in the paper is the nominal
concentration multiplied by 40%. Citric acid is an ana-
lytically pure agent, which was from Shanghai Qiangshun
Chemical Industry Co. Ltd., Shanghai, China. All testing
solutions were prepared using deionized water. A 4 wt.%
citric acid solution was employed on the basis of Guide-
line for chemical cleaning of fossil plants (DL/T 794-2012,
China) (Cao et al., 2012). The test solutions whose volumes
were 0.5 l were obtained through dissolving UHCI of dif-
ferent concentrations into the 4 wt.% citric acid solution.
The carbon steel blocks were hung in the testing solutions
after weighing (m1). The blocks were taken out of the test
solution after an immersion period of 4 h, removing rust by
soft rubber, flushed with deionized water, degreased with
acetone, and then weighed again (m2). Parallel weight loss
measurements were taken three times, and the weight loss
was reckoned by averaging these values. The mean cor-
rosion rate (ν) is calculated from the following equation:
m1 − m2
ν= (1)
S ⋅t

where S is the exposed area of a block, and t is immer-
sion time (4 h). The corrosion inhibiting efficiency (ηWL) is
evaluated by
ν0 − ν
ηWL = × 100% (2)
ν0

where ν0 and ν are the mean corrosion rates of 20# carbon
steel blocks in 4 wt.% citric acid solutions without and
with the accession of UHCI, respectively.

Table 1: Chemical composition of 20# carbon steel samples.

Element C Si Mn P S Cr Ni Cu Fe
Composition (wt.%) 0.18 0.25 0.42 0.02 0.02 0.18 0.22 0.21 The balance

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 D. Yang et al.: Corrosion inhibition behavior of UHCI on carbon steel in citric acid solution 3

2.3 Surface analysis perturbation in amplitude at OCP. The ZSimpWin software

(EChem Software, USA) was applied to impedance analy-
The cylindrical carbon steel specimens were immersed ses, and appropriate equivalent circuits were for fitting
in testing solutions for 4 h and then taken out and dried impedance data. The inhibition efficiency (ηELS) is counted
with cool air for scanning electron microscope (SEM) and by the following formula (Epelboin et al., 1972; Feng et al.,
X-ray photoelectron spectrometer (XPS) measurements, 2011):
respectively.
Rct − Rct ,0
A SU-1500 scanning electron microscope (Hitachi, ηEIS = × 100% (4)
Rct
Japan) was employed to examine the morphologies on the 
surfaces of the specimens without and with the inhibitor
under the acceleration voltage of 15 kV. where Rct,0 and Rct are the charge transfer resistance values
The XPS spectra were obtained with a PHI-5000C ESCA in the 4 wt.% citric acid solution without and with UHCI,
photoelectron spectrometer (Perkin-Elmer, USA) using Mg respectively.
Kα radiation (hν = 1253.6 eV) as excitation sources. All the
analyses were performed at a pressure < 1 × 10−8 mm Hg.
The take-off angle from the surface was 45°. The C1s line of
284.6 eV was a reference to adjust the binding energy shift
3 Results and discussion
due to electrostatic charging, and the sputter profiles were
analyzed using the XPS Peak-Fit 4.1 software package. 3.1 Weight loss measurements

Table 2 shows the values of the corrosion rates and the­

2.4 Electrochemical measurements
All electrochemical experiments were done in a common
three-electrode bath with a platinum electrode as the aux-
iliary electrode and a saturated calomel electrode (SCE)
as the reference electrode using a Versa STAT 3 electro-
chemical workstation (Ametek, USA). The carbon steel
electrodes embedded in epoxy resin were soaked in the
testing solution at the open circuit potential (OCP) for 4 h
such that a stable OCP could be observed for all electrodes
before electrochemical measurements were taken. The
parallel measurements of the electrodes were taken on the
trot to ensure reproducibility.
The differential capacity curves were measured at
various potentials from −0.9 VSCE to −0.1 VSCE at a fre-
quency of 1000 Hz with a CHI 660 electrochemical work-
station (Shanghai Chenhua Instruments Co. Ltd., China).
The voltage range of polarization curves was from −0.9
VSCE to −0.2 VSCE at a scanning speed of 1 mV s−1. The inhi-
bition efficiency (ηp) is counted by the following formula:
­inhibition efficiency, obtained from weight loss measure-
ments at various concentrations of UHCI in 4 wt.% citric
acid solution. The inhibition efficiency increases with UHCI
concentrations from 0 up to 0.4 wt.% yet declines a bit at
0.6 wt.% per contra with further augmentation of concen-
tration. The highest inhibition efficiency of the carbon steel
sample is 89.28% in the presence of 0.4 wt.% UHCI after 4 h
immersion. The extremum phenomenon of inhibitor con-
centration is probably the reason that anodic desorption of
an inhibitor occurs when inhibitor concentration increases
up to a certain value, bringing about the decrease of inhibi-
tion efficiency instead of the rise (Cao, 1996).
3.2 Surface analysis
Figure 2 presents the SEM images of the carbon steel
surface in 4 wt.% citric acid solution without and with
0.4 wt.% inhibitor after 4 h immersion. As it is shown

icorr
0
− icorr Table 2: Corrosion rate and inhibition efficiency data obtained from
ηp (%) = × 100 (3) weight loss measurements for 20# carbon steel samples in 4 wt.%
icorr
0
 citric acid solutions without and with various concentrations of
UHCI.
where icorr and icorr
0
are the corrosion current densities
of carbon steel with and without the inhibitor in 4 wt.% Concentration (wt.%) ν (g m−2 h−1) ηWL (%) ση (%)

citric acid solution, respectively. 0 1.5380 – –

The electrochemical impedance spectroscopy (EIS) 0.05 0.2697 82.5 5.25
measurements were implemented at a frequency range 0.4 0.1649 89.3 4.84
0.6 0.1707 88.9 3.96
from 100 kHz to 0.05 Hz with a 5 mV sinusoidal potential

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4 D. Yang et al.: Corrosion inhibition behavior of UHCI on carbon steel in citric acid solution

Figure 2: SEM images of the carbon steel surface in 4 wt.% citric acid solution without (A) and with inhibitor (B) after 4 h immersion.

presented since these elements are the components of the

compound structure. The deconvolution of the C1s signal
of the steel sample treated by UHCI may be fitted into two
peaks located at 285.7 and 288.7 eV (Figure 4A). The first
Intensity (a.u.)

component has the greatest contribution and is mainly

ascribed to the C-N in the imidazole ring (Beguin et al.,
Fe2p

O1s

1998) and C-H in the alkyl chain (Mancia et al., 1989).

C1s

The second component is attributed to C = O bond in the

carboxylic group (Jones & Sammann, 1990). In the N1s
N1s

spectrum (Figure 4B), two peaks that appeared at 400.7

1000 800 600 400 200 0 and 402.4 eV are attributed to the quaternary nitrogen and
Binding energy (eV) C-N = C bond at the imidazole ring, respectively (Schmiers
et al., 1999). In the O1s spectrum (Figure 4C), a single
Figure 3: Wide-scan XPS spectra of carbon steel specimen
peak that appeared at 532.7 eV is attributed to the C = O for
immersed in a 4 wt.% citric acid solution containing 0.4 wt.% UHCI
for 4 h immersion. the carboxyl group (Barr, 1978; Mangolini et al., 2011). In
the Fe2p spectrum (Figure 4D), there are four peaks that
appeared at 711.87, 715.77, 719.51, and 725.45 eV ascribed
Table 3: XPS survey scan composition (at.%) of the carbon steel to FeOOH (Barr, 1978), Fe3O4 and Fe(II) satellite (Clayton
surface in 4 wt.% citric acid solution with 0.4 wt.% inhibitor after & Lu, 1986), Fe(III) satellite (Castro & Ciampi, 1995), and
4 h immersion. ghost structure (Chevalier et al., 2014), respectively. Two
N1s peaks that appeared in XPS spectra give proof of UHCI
Element C N O Fe Mn Si inhibitor adsorbed on the carbon steel surface.
Composition (at.%) 59.85 2.42 31.01 6.28 0.16 0.27

3.3 OCP measurements

in Figure 2A, the specimen surface was dramatically
damaged in the lack of the inhibitor. However, the speci-
men surface is smooth and intact in the existence of the
inhibitor (Figure 2B). It indicates that the corrosion of the
carbon steel surface is mitigated to a great extent by UHCI
compared with the blank carbon steel. Therefore, the SEM
results visually display the good inhibition effect of UHCI.
XPS spectra of the carbon steel specimen immersed
in 4 wt.% citric acid solution with 0.4 wt.% inhibitor
(Figure 3) were recorded to obtain more details about the
metal-solution interface. The surface atomic compositions
are given in Table 3. The peaks of C and N from UHCI are
In order to make sure enough immersion time before
other electrochemical experiments were conducted under
steady state, Figure 5 depicts Eocp-t curves for the carbon
steel electrodes in 4 wt.% citric acid solution with and
without UHCI at 298 K. It is obvious that the Eocp values
after immersion are very negative for the electrodes with
and without UHCI. The blank electrode has a steady OCP
of −0.55 VSCE after about 1 h immersion, while the elec-
trode with 0.4 wt.% UHCI shifts to a more positive poten-
tial and gradually reaches a constant OCP of −0.49 VSCE
after approximately 2.2 h immersion. The anodic shift of

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 D. Yang et al.: Corrosion inhibition behavior of UHCI on carbon steel in citric acid solution 5

A B
C1s N1s
Intensity (a.u.)

Intensity (a.u.)
290 285 410 405 400
Binding energy (eV) Binding energy (eV)

C D
O1s Fe2p
Intensity (a.u.)

Intensity (a.u.)

540 535 530 735 730 725 720 715 710 705
Binding energy (eV) Binding energy (eV)

Figure 4: High-resolution XPS spectra for detected elements of C1s (A), N1s (B), O1s (C) and Fe2p (D), respectively.

–0.40 60
Blank Blank
0.4 wt.% 0.4 wt.%
50
–0.45
Eopc (VSCE)

40
C (µF cm–2)

–0.50
30

–0.55
20

–0.60 10
0.0 0.5 1.0 1.5 2.0 2.5
t (h)
0
–0.9 –0.8 –0.7 –0.6 –0.5 –0.4 –0.3 –0.2 –0.1
E (VSCE)
Figure 5: Eocp-t curves for the carbon steel electrodes in 4 wt.% citric
acid solution with and without UHCI at 298 K.
Figure 6: Differential capacity curves of carbon steel electrodes
after being immersed in 4 wt.% citric acid solution with and without
0.4 wt.% UHCI for 4 h.
potential can be ascribed to the spontaneous adsorption
of UHCI on carbon steel surface, suggesting that the inhi-
bition may be an anodic inhibition mechanism.
from −0.9 VSCE to −0.1 VSCE (Figure 6). It can be found
out that the electric double-layer capacitance (EDLC)
3.4 D
 ifferential capacity and polarization reaches the lowest value of 35.17 μF cm−2 at about −0.55
measurements VSCE related to the potential of zero charge for the blank
electrode, while the EDLC value keeps a small constant
The differential capacity curves of carbon steel elec- value of 4.36 μF cm−2 at the potential lower than −0.55 VSCE
trodes after being immersed in 4 wt.% citric acid solution for the electrode with 0.4 wt.% UHCI because UHCI sub-
without and with 0.4 wt.% UHCI for 4 h were obtained stitutes for citrate and H2O adsorbed on the carbon steel

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6 D. Yang et al.: Corrosion inhibition behavior of UHCI on carbon steel in citric acid solution

–2 The corrosion current density of iron in citric acid

solutions is mainly dominated by the anodic oxidation
–3 reaction of iron. The vicarious adsorption course would
occur between the inhibitor molecules in the solution and
–4
water or citric acid molecules on the anodic reactive sites
log/(A cm–2)

of the carbon steel surface and subsequently diminishes

–5 Blank
0.05 wt.% the solubility of Fe surface, giving rise to the improvement
–6
0.2 wt.% of metal corrosion inhibition.
0.4 wt.%
Table 4 shows electrochemical parameters of the carbon
0.6 wt.%
–7 steel electrodes in 4 wt.% citric acid solution with different
–0.9 –0.8 –0.7 –0.6 –0.5 –0.4 –0.3 –0.2 –0.1
concentrations of inhibitor after 4 h immersion at 298 K.
E (VSCE)
It can be seen that the corrosion current density icorr of the
Figure 7: Partly representative polarization curves for carbon steel carbon steel electrode with UHCI decreases greatly, while
in 4 wt.%. the corrosion potential Ecorr has a shift to positive potential
compared with those of the electrode without UHCI, indicat-
surface. The EDLC value of the electrode with 0.4 wt.% ing that the protection of UHCI against carbon steel corro-
UHCI has an obvious increase after the potential is more sion has improved significantly. Moreover, their inhibition
than −0.41 VSCE, suggesting that the desorption of UHCI on efficiency (ηp1) decreases with the increase of UHCI concen-
the carbon steel surface occurs. tration from 0 to 0.4 wt.% and then declines a bit at 0.5 and
Potentiodynamic polarization curves of 20# carbon 0.6 wt.%. The inhibition efficiency at the concentration of
steel immersed in 4 wt.% citric acid solutions for 4 h at 0.4 wt.% is 87.2% based on the polarization data.
298 K with and without UHCI at various concentrations The influence of temperature and soaking time on
are displayed in Figure 7. On the basis of the mechanism inhibition efficiency was investigated by polarization
for the anodic dissolution of iron in citric acid solutions
recommended by Chu and Wan (1993), possible electro- Table 4: Electrochemical parameters of the carbon steel electrodes
dissolution reactions of iron in citric acid solutions are in 4 wt.% citric acid solution with different concentrations of inhibi-
expressed as follows: tor after 4 h immersion at 298 K.

Fe + HCit 2− ⇔ Fe(HCit)2ads
−
(5) Concentration (wt.%) Ecorr (V vs. SCE) icorr (μA cm−2) ηp1 (%)

0 −0.5727 58.93 –
Fe(HCit)2ads
−
⇔ Fe(Cit)2ads
−
+ H+ + e− (6) 0.05 −0.4838 13.41 77.2
0.1 −0.4638 9.527 83.8
Fe(Cit)2ads
−
→ Fe(Cit)− + e− (rate-determining step) (7) 0.2 −0.4688 8.927 84.9
0.3 −0.4779 8.314 85.9
0.4 −0.4550 7.530 87.2
Fe(Cit)− + H+ ⇔ Fe2+ + HCit 2− (8) 0.5 −0.4554 7.864 86.7
0.6 −0.4567 7.941 86.5
The cathodic hydrogen evolution is a result of the fol-
lowing steps:
Table 5: Electrochemical parameters obtained from polarization
Fe + H + e ⇔ FeHads (9)
+ − measurements for 20# carbon steel electrodes in 4 wt.% citric acid
solution without and with 0.4 wt.% inhibitor after 4 h immersion
under different temperatures.
FeHads + H+ + e − ⇔ Fe + H 2 (10)
Temperature Concentration Ecorr icorr ηP2
The ferrous iron is further oxidized into ferric iron (°C) (wt.%) (V vs. SCE) (μA cm−2) (%)
compounds for the effect of oxygen dissolved in the test
20 0 −0.5456 79.12 –
solution with UHCI as follows (Hu et al., 2012):
0.4% −0.4813 8.577 89.2
40 0 −0.5231 93.06 –
Fe2+ + H2O ⇔ FeOH+ + H+ (11) 0.4% −0.4896 12.53 86.5
70 0 −0.5405 100.8 –
2FeOH+ + O2 + 2e − ⇔ 2FeOOH (12) 0.4% −0.4923 15.31 84.8
95 0 −0.5377 101.52 –
0.4% −0.4809 15.92 84.3
3FeOOH + H + e ⇔ Fe3O4 + 2H2O (13)
+ −

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 D. Yang et al.: Corrosion inhibition behavior of UHCI on carbon steel in citric acid solution 7

Table 6: Electrochemical parameters obtained from polarization icorr without and with 0.4 wt.% UHCI all increase with the
measurements for 20# carbon steel electrodes in 4 wt.% citric acid extension of soaking time from 2 h to 24 h, but icorr values
solution without and with 0.4 wt.% inhibitor at different soaking time.
without UHCI increase more quickly. Therefore, the inhi-
bition efficiency rises from 87.8% to 95.4% with the exten-
Soaking Concentration Ecorr icorr ηP3
time (h) (wt.%) (V vs. SCE) (μA cm−2) (%) sion of soaking time from 2 h to 24 h.

2 0 −0.5604 54.55 –
0.4% −0.4580 6.679 87.8
4 0 −0.5727 58.93 – 3.5 Electrochemical impedance spectra
0.4% −0.4550 7.530 87.2
6 0 −0.5762 67.98 –
0.4% −0.4570 7.674 88.7 The impedance plots for 20# carbon steel after 4 h
8 0 −0.5719 83.76 – soaking in 4 wt.% citric acid solutions with and without
0.4% −0.4619 8.268 90.1 UHCI are depicted in Figure 8 as Nyquist and Bode dia-
12 0 −0.5734 141.1 – grams. One capacitive loop which was observed on the
0.4% −0.4642 9.295 93.4
impedance representation of the blank electrode implies
24 0 −0.5918 245.9 –
that the corrosion of carbon steel is greatly dominated
0.4% −0.4781 11.19 95.4
by the charge transfer process and generally correlated
with the charge transfer of the corrosion process and
measurements. The results are shown in Tables 5 and 6, double electric layer behavior (Bard & Faulkner, 2000;
respectively. Corrosion current densities icorr without and Bockris & Khan, 1993). The impedance plots of the
with 0.4 wt.% UHCI increase with the rise of temperature electrodes with UHCI take on three time constants cor-
from 20°C to 95°C, and the inhibition efficiency declines responding to two capacitive impedances and one induc-
from 89.2% to 84.3% in Table 5. Corrosion current densities tive resistance, respectively. The impedance loops of the

A 2000 B 3.5
Blank Blank
0.05 wt.% 0.05 wt.%
0.1 wt.% 0.1 wt.%
1500 0.2 wt.% 0.2 wt.%
0.3 wt.% 3.0 0.3 wt.%
0.4 wt.% 0.4 wt.%
–Zim (Ω cm2)

log (Z /Ω cm2)

1000 0.5 wt.% 0.5 wt.%

1 Hz 0.6 wt.%
0.6 wt.%
Fitted 2.5 Fitted
500 0.1 Hz

0.1 Hz
1 Hz
0 0.1 Hz 2.0
0 500 1000 1500 2000 –2 0 1 2 3 4 5 6
–1
Zre (Ω cm2) log (f/Hz)

C 50
Blank
0.05 wt.%
40 0.1 wt.%
0.2 wt.%
30 0.3 wt.%
0.4 wt.%
−θ ( °)

0.5 wt.%
20 0.6 wt.%
Fitted
10

–10
–2 –1 0 1 2 3 4 5 6
log (f/Hz)

Figure 8: Nyquist (A) and Bode (B and C) diagrams for carbon steel in 4 wt.% citric acid solution with different concentrations of UHCI at
298 K after 4 h immersion.

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8 D. Yang et al.: Corrosion inhibition behavior of UHCI on carbon steel in citric acid solution

A B CPEf YCPE = Y0 (iω)n  (14)

CPEdl

Rs CPEdl
Rs where Y0 represents the proportional factor, ω the angular
Rf Rct frequency, i imaginary root, and n the phase shift. The
Rct
L RL equivalent circuit in Figure 9 is well fitted with our imped-
ance data. A reasonable accuracy of the fitting is as evi-
Figure 9: Equivalent circuit models of the carbon steel electrodes in denced by χ2 in the order of between 10−4 and 10−5 for all
citric acid solution: (A) blank and (B) UHCI. impedance data.
At the corrosion potential, the faradaic admittance of
the metal electrode immersed in the solution with corro-
carbon steel are flattened semicircles whose centers are sion inhibitors can be depicted as follows (Cao & Zhang,
below the real axis. It is well known as the dispersing 2002):
effect (Cao & Zhang, 2002; Khaled & Hackerman, 2004).
1 B
Figure 8 obviously illustrates that the diameter of the YF = + (15)
Rct iω
semicircle of carbon steel in blank acid solution was 1+
a 
greatly augmented after the accession of UHCI in the
acid media. Moreover, the impedance response of carbon where
steel increases with the concentration of UHCI from 0 up
 ∂I ∂ | I c |  ∂θ 
to 0.4 wt.%. However, the diameters of the semicircle B= a −  ⋅  (16)
 ∂θ ∂θ  s  ∂E  s
with 0.5 wt.% and 0.6 wt.% UHCI are both smaller than 
that of 0.4 wt.% UHCI. The EIS results are consistent with
the weight loss data.  ∂ζ 
a = −  (17)
The equivalent circuit (Figure 9A) employed for the  ∂θ  s

blank electrode consists of a constant phase element
(CPE) in parallel with a charge transfer resistance (Rct), dθ
connecting in series with solution resistance (Rs). Con- ζ= (18)
dt 
sidering the characteristic of three time constants, the
equivalent circuit in Figure 9B is used to fit the imped-
The subscript “s” signifies the steady state, Ia anodic
ance data of the electrodes with UHCI. In Figure 9B, Rs,
current densities, Ic cathodic current densities, and θ cov-
Rf, Rct, and RL represent the solution resistance, film
erage of adsorbed inhibitor on the surface of electrode.
resistance, charge transfer resistance, and inductive
 ∂I ∂ | I c |
resistance, respectively; CPEf and CPEdl are the constant Based on Cao’s viewpoint (Cao, 2008),  a −  <0
 ∂θ ∂θ  s
phase elements substituted for the film capacitance and
for an anodic corrosion inhibitor and B > 0 when an
the EDLC, respectively; L is the inductance, which is inti-
inductive arc appears in the low-frequency region,
mately associated with the desorption of UHCI on the
 ∂θ 
surface of carbon steel. which denotes that   < 0 according to formula (18),
 ∂E  s
The admittance of a CPE is defined as

Table 7: The fitting impedance data for carbon steel electrodes in 4 wt.% citric acid solutions without and with various concentrations of
UHCI at 298 K.

Concentration Rs Rf CPEf n1 Rct CPEdl N2 RL L ηEIS χ2

(wt.%) (Ω cm2) (Ω cm2) (μΩ−1 cm−2 sn) (Ω cm2) (μΩ−1 cm−2 sn) (Ω cm2) (H cm2) (%)

0 114.9 – – – 254.7 230.5 0.7958 – – – 6.56 × 10−4

0.05 108.0 170.6 29.72 0.7177 968.6 207.7 0.6971 5533 6583 73.70 8.24 × 10−5
0.1 105.1 162.2 32.91 0.7267 1228 132.6 0.7022 3001 12,510 79.26 3.60 × 10−5
0.2 130.3 97.73 84.34 0.6463 1458 190.4 0.7046 3071 14,142 82.53 4.64 × 10−5
0.3 93.74 98.36 52.36 0.7166 1591 76.50 0.7150 3850 16,802 83.99 4.56 × 10−5
0.4 103.2 195.6 73.42 0.6641 1840 42.34 0.6846 7394 20,341 86.16 7.65 × 10−5
0.5 98.06 158.5 91.93 0.6563 1630 40.15 0.7673 5828 10,532 84.37 3.32 × 10−5
0.6 97.68 162.9 94.21 0.6550 1588 37.70 0.7694 3913 15,641 83.96 3.45 × 10−5

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 D. Yang et al.: Corrosion inhibition behavior of UHCI on carbon steel in citric acid solution
suggesting that the coverage of UHCI on the electrode
surface declines with the positive shift of potential. It is
related to the desorption phenomenon of UHCI adsorbed
on the iron surface.
Data from Table 7 show that the Rct values with UHCI
increase greatly, while the Cdl values decrease in com-
parison with those of the bare carbon steel electrode.
Moreover, the Rct values increase with the UHCI concen-
tration from 0.05 wt.% up to 0.4 wt.% in 4 wt.% citric
acid solution, then decrease with the further increment of
UHCI concentration. The supreme inhibition efficiency is
86.16% at the UHCI concentration of 0.4 wt.% according
to Eq. (4).
4 Conclusions
This study has the following conclusions:
1. UHCI has displayed a good inhibitive ability for car-
bon steel corrosion in citric acid solution.
2. The inhibition efficiency increases with UHCI con-
centrations from 0 up to 0.4 wt.% yet declines a bit at
0.6 wt.% per contra with the further augmentation of
concentration. The inhibition efficiency declines with
the rise of temperature from 20°C to 95°C, while it rises
with the extension of soaking time from 2 h to 24 h.
3. Two N1s peaks that appeared in XPS spectra give proof
of UHCI inhibitor adsorbed on the carbon steel surface.
Acknowledgments: This work was supported by Innova-
tion Program of Shanghai Municipal Science and Tech-
nology Commission (11DZ2210500, 12DZ2280300, and
14DZ2261000) and Innovation Program of Shanghai
Municipal Education Commission (12ZT13), China.
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Graphical abstract
Dong Yang, Song Hui Liu, Yu Pei
Shao, Shao Di Xu, Lu Lu Zhao, Qiang
Qiang Liao and Hong Hua Ge
Electrochemical and XPS studies of
alkyl imidazoline on the corrosion
inhibition of carbon steel in citric
acid solution
DOI 10.1515/corrrev-2016-0016
Corros Rev 2016; xx(x-x): xxx–xxx
Corros Rev 2016 | Volume x | Issue x
Original article: The inhibition mech-
anism and adsorption behaviors
of 2-undecyl-N-carboxymethyl-N-
hydroxyethyl imidazoline (UHCI) for
20# carbon steel in 4 wt.% citric acid
solution were investigated by means
of weight loss, electrochemistry, and
surface analysis techniques.
Keywords: acid corrosion; carbon
steel; EIS; modeling studies;
polarization.
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