Applied Surface Science 356 (2015) 63–72

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

The behavior of pre-corrosion effect on the performance of

imidazoline-based inhibitor in 3 wt.% NaCl solution saturated
with CO2
Huan-huan Zhang, Xiaolu Pang, Meng Zhou, Chao Liu, Liang Wei, Kewei Gao ∗
School of Materials Science and Engineering, University of Science and Technology Beijing, Beijing 100083, China

a r t i c l e i n f o a b s t r a c t

Article history: An imidazoline-based inhibitor was synthesized, characterized and tested as a corrosion inhibitor for
Received 29 March 2015 low alloy steel in CO2 -saturated 3 wt.% NaCl solution at 60 ◦ C. The influence of pre-corrosion on inhi-
Received in revised form 29 July 2015 bition efficiency of the inhibitor was evaluated. The results showed that the inhibitor had excellent
Accepted 1 August 2015
inhibition effectiveness on freshly abraded samples, with an inhibition efficiency of 98.7% in the pres-
Available online 5 August 2015
ence of 2.4390 × 10−5 mol/l inhibitor. The adsorption of the inhibitor on the steel surface was found
to obey Langmuir’s adsorption isotherm and chemisorption. Pre-corrosion had a detrimental effect on
Keywords:
the inhibitor performance, significant localized corrosion was observed on the pre-corroded samples
Corrosion inhibitor
CO2 corrosion
with 1.2195 × 10−5 mol/l inhibitor after 96 h immersion. The differences in inhibition efficiency of the
Pre-corrosion inhibitor for samples pre-corroded for different time were related to the different corrosion products
Corrosion products and the increase of surface area after pre-corrosion.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
CO2 corrosion is recognized as a major factor for the failure of
oil and gas pipelines, especially in the development of deep and
ultra-deep wells. CO2 corrosion has become a prominent problem
in plaguing petroleum industries [1–5]. At present, many pipelines
used in petroleum industry are made of low alloy steels due to
economic reasons [6]. However, they are very susceptible to CO2
corrosion [7]. There are many methods to restrain CO2 corrosion in
petroleum industry, the employ of corrosion inhibitor is considered
to be the most cost effective and simplest way to minimize the CO2
corrosion [8,9].
Imidazoline and its derivatives are considered to be one of the
most effective organic inhibitors [3,10], and have been widely used
to protect the pipelines from CO2 corrosion [1,10–14]. Because of
their biodegradability, imidazoline derivatives are considered as
“green” corrosion inhibitors [15]. The inhibition effectiveness of
imidazoline derivatives is mainly attributed to the adsorption of
the inhibitor on metallic surfaces. The inhibitor adsorbs on the
metal surface can suppress electrochemical reactions during the
corrosion processes [13,16,17].
∗ Corresponding author.
E-mail address: kwgao@yahoo.com (K. Gao).
It has been reported in the literature that the imidazoline deriva-
tives have excellent inhibition effectiveness on freshly abraded
samples in CO2 -saturated brine solutions [12,18,19]. However, in
practical applications, the pipelines might have been used for many
years before adding inhibitors. In this case, the metal surface might
be covered with different types of scale, such as iron carbonate
precipitates, un-corroded iron carbide [20]. The compounds on cor-
roded surfaces may have an important influence on the inhibitor
performance. Gulbrandsen et al. [20,21] studied the effect of pre-
corrosion on the inhibitor in CO2 corrosion environment, and the
results showed that the presence of laminar cementite (left on
the surface after the preferential dissolution of ferrite into Fe2+ )
has a negative effect on the inhibition efficiency. Paolinelli and his
co-workers [22] pointed out that pre-corrosion decreased the inhi-
bition efficiency of an imidazoline-based inhibitor for the tempered
martensite samples and ferrite-pearlitic samples. Kapusta et al. [23]
pointed out that one day pre-corrosion had a detrimental effect on
the inhibitor performance, while Hausler et al. [24,25] concluded
that four days pre-corrosion did not significantly affect the inhibitor
performance. From these above results, it is still not very clear how
the pre-corrosion affects the inhibitor performance.
The objective of the present study was to investigate the inhi-
bition performance of the synthesized imidazoline-based inhibitor
on low alloy steel in CO2 -saturated 3 wt.% NaCl solution, as well as
the influence of pre-corrosion on the inhibition efficiency of this
inhibitor. The adsorption behavior and inhibition performance of

http://dx.doi.org/10.1016/j.apsusc.2015.08.003
0169-4332/© 2015 Elsevier B.V. All rights reserved.
64 H.-h. Zhang et al. / Applied Surface Science 356 (2015) 63–72

Fig. 2. Molecular structure of the synthesized inhibitor.

distillation, then obtained the imidazoline intermediate. After-

wards, added 7.4 g thiourea to the intermediate, accompanied with
octyl alcohol as solvent, and the reaction temperature was in the
range from 140 ◦ C to 160 ◦ C with stirring for 5 h. Finally, removed
Fig. 1. Microstructure of the low alloy steel. the redundant octyl alcohol by reduced pressure distillation, and
purified the product by alcohol. Molecular structure of the synthe-
sized inhibitor is depicted in Fig. 2.
the inhibitor were investigated by means of polarization curves,
weight loss method, electrochemical impedance spectroscopy (EIS)
2.3. Potentiodynamic polarization measurements
technique. The data obtained from the polarization curves of
the freshly abraded samples were used to define the adsorption
Electrochemical measurements were carried out using an elec-
isotherm. The influence of pre-corrosion on inhibition performance
trochemistry workstation (CS310, Wuhan Corrtest Instrument Co.
was explored on the samples pre-corroded for different time, by
Ltd., China) in a typical three-electrode setup under an atmospheric
means of weight loss method and electrochemical impedance spec-
pressure. Three-electrode jacketed test cell with a working volume
troscopy (EIS). The surface features of samples were studied by
of 250 ml was used as a container. The Ag/AgCl electrode was used
scanning electron microscope (SEM), X-ray diffraction (XRD) and
as the reference electrode, and a platinum electrode (1 cm2 ) was
surface profiler.
used as the counter electrode. Prior to each experiment, the sam-
ple with an exposed area of 1 cm2 was abraded with a series SiC
2. Materials and methods
papers ended with 800 grade, then used as the working electrode.
Before measurements, the freshly abraded specimens were
2.1. Specimen
immersed in the test solutions at open circuit potential (Eocp ) for
1 h to attain a stable state. The potentiodynamic polarization was
The chemical composition of the low alloy steel employed in this
acquired by scanning the potential range from cathodic potential of
study is (wt.%): 0.063 C, 0.18 Si, 0.50 Mn, 0.17 Mo, 0.019 Cr, 0.12
−0.3 V to +0.4 V (vs. Eocp ) with a sweep rate of 0.5 mV/s. The solution
Ni, 0.025 Nb, 0.016 Ti, 0.026 V, 0.11 Cu, <0.01 P, <0.01 S, Fe balance.
was bubbled by CO2 gas to ensure saturation throughout the exper-
The steel has a ferrite–pearlite microstructure, as shown in Fig. 1.
iment. Each test was repeated three times to ensure reproducibility
The samples used here were cut into 10 mm × 10 mm × 3 mm
of the results.
dimensions, abraded by a series SiC papers (up to grade 800),
washed with distilled water and rinsed with ethanol.
2.4. Immersion tests
2.2. Solution preparation
The immersion tests were conducted in a magnetic drive auto-
clave. Samples with an exposed area of 10 mm × 10 mm were fixed
The tests were conducted in a CO2 -saturated 3 wt.% NaCl
to a polytetrafluoroethylene holder, then, immersed in the test
solution without and with various concentrations of synthesized
solution. After sealed, the solution was de-aerated with CO2 for
inhibitor. Prior to test, the solutions were de-aerated by purging
120 min before the temperature and partial pressure of CO2 were
N2 for 2 h. It has been reported that CO2 corrosion rate is temper-
increased to 60 ◦ C and 1 MPa, respectively. Different immersion
ature dependent, and the corrosion rate has the largest value at
experiments were carried out to study the pre-corrosion effect on
60 ◦ C [26]. In addition, previous work pointed out that the imida-
the performance of imidazoline-based inhibitor in CO2 corrosion,
zoline derivative severely hydrolyzed at 85 ◦ C [27]. Therefore, in
as shown in Table 1. Each experiment was repeated twice to ensure
order to evaluate the inhibition effect of synthesized imidazoline-
reproducibility of the results.
based inhibitor on the steel in CO2 -saturated 3 wt.% solution, all the
The weight loss method was conducted to evaluate inhibition
experiments were performed at 60 ◦ C.
efficiency. Weighed the samples by a balance with a precision of
The employed inhibitor in this work was synthesized based
0.1 mg before and after immersion tests. After immersion for 96 h,
on stearic acid, diethylenetriamine and thiourea, according to the
the corrosion products on samples’ surface were removed using
methods reported in Refs. [28–31]. The synthesis was performed
the chemical cleanup method [32]. The corrosion rates can be cal-
in a 250 ml three-neck round-bottom flask. The flask was equipped
culated using the following equation [33]:
with a magnetic rotor, a thermometer and a condenser, in order to
collect water and xylene. The synthesis processes were flowing the 8.76 × 104 m
CR = (1)
procedure described below. St
All the synthesis processes were performed under the protec-
where CR is the general corrosion rate of the steel (mm/y), S is
tion of nitrogen. Firstly, 22.74 g stearic acid, 10.3 ml diethylenetri-
the electrode area (cm2 ), t is the immersion time (96 h), m is the
amine and 24 ml xylene were placed into the flask. Then heated
weight-loss (g), and  is the steel density (g/cm3 ).
the mixture solution to 155 ◦ C and stirred for 3 h with reflux at the
Inhibition efficiency (IE) is drawn from the corrosion rates [33]:
temperature in the range from 155 ◦ C to 165 ◦ C. Secondly, increased
the temperature to 195–220 ◦ C with stirring for 6 h. Subsequently, CR0 − CRinh
IE(%) = × 100 (2)
removed the redundant xylene and water by reduced pressure CR0
 H.-h. Zhang et al. / Applied Surface Science 356 (2015) 63–72 65

Table 1
The conditions of the immersion tests.

Experiments Samples t (h) C (10−5 mol/l)

No. 1 a 96 0
No. 2 a 96 1.2195
No. 3 a 96 2.4390
No. 4 a 2 0
No. 5 p2 h 96 1.2195
No. 6 p2 h 96 2.4390
No. 7 a 24 0
No. 8 p24 h 96 1.2195
No. 9 p24 h 96 2.4390
No. 10 a 48 0
No. 11 p48 h 96 1.2195
No. 12 p48 h 96 2.4390
No. 13 b 96 1.2195
No. 14 p24 h 96 12.1950

Notes: a – freshly abraded samples; p2 h , p24 h , p48 h – samples pre-corroded for 2 h,
24 h, 48 h, respectively; b – samples with corrosion products removed after pre-
corroded for 24 h; t – corrosion time; C – inhibitor concentration.
where CR0 and CRinh are the corrosion rates (mm/y) of the samples
in the absence and presence of inhibitor, respectively.
2.5. EIS measurements
EIS measurements were performed using an electrochemistry
workstation in a typical three-electrode setup as mentioned above.
The samples pre-corroded for 2 h, 24 h, 48 h with an exposed area
of 1 cm2 were chosen as working electrode, respectively. After
immersed in the solution for 1 h to stabilize, the measurement of
EIS was carried out in a frequency range of 10,000–0.1 Hz. Ampli-
tude of 10 mV peak to peak was used for the ac signal for all EIS
measurements. The solution was bubbled by CO2 gas to ensure sat-
uration throughout the experiment. Each test was repeated three
times to ensure reproducibility of the results.
2.6. Surface analysis
The scanning electron microscope (SEM, model Zeiss Evo18,
Germany) equipped with energy dispersive spectroscopy (EDS)
was employed to examine the sample surface after immersion.
The corrosion products of samples were characterized with X-ray
diffraction (XRD) using the Rigaku D/max-rB diffractometer with
Cu Ka radiation. After the corrosion products were removed, the
sample surface was characterized by a surface profiler (Dektak 150),
and the corrosion depth was measured.
3. Results and discussions
Fig. 3. FT-IR spectra of the synthesized inhibitor.
respectively carried out on freshly abraded samples in CO2 -
saturated 3 wt.% NaCl solution in the absence and presence
of 0.4878 × 10−5 mol/l, 1.2195 × 10−5 mol/l, 1.9512 × 10−5 mol/l,
2.4390 × 10−5 mol/l and 4.8780 × 10−5 mol/l inhibitor. Fig. 4 shows
the polarization curves for the low alloy steel in CO2 -saturated
3 wt.% NaCl containing various concentrations of inhibitor.
The relevant electrochemical parameters obtained from the
polarization curves are presented in Table 2. The inhibition
efficiency (IE) and surface coverage () of the inhibitor were deter-
mined from the following equations [33,34]:
0
icorr − icorr
IE(%) = 0
× 100 (3)
icorr
icorr
 =1− 0
(4)
icorr
0
where icorr and icorr are the corrosion current densities in the
absence and presence of inhibitor, respectively.
The data listed in Table 2 exhibited that, the addition of the
inhibitor shifted the corrosion potential (Ecorr ) to positive direction,
indicating that the effect of the inhibitor on the anodic reaction was
more remarkable than that on the cathodic reaction. The difference
between Ecorr and Eocp might be related to the change of the surface
status of the working electrodes after cathodic polarization [29]. It
is noted from Table 2 that, with increasing the concentration of
the inhibitor, the corrosion current density (icorr ) decreased and
the inhibition efficiency (IE) increased. The high IE value suggested
a full coverage of the sample surface with inhibitor molecules. It
is also noted that the anodic and cathodic slopes changed with
inhibitor concentration, suggested that the addition of the inhibitor
not only reduced the anodic dissolution but also suppressed the

3.1. Characterization of the synthesized inhibitor

The structural characteristics of purified product were con-

firmed by FT-IR spectroscopy in the range 4000–500 cm−1 , as
shown in Fig. 3. FT-IR (KBr) : 3299 (N H), 2923 and 2853
( CH2 ), 1610 (C N), 1465 ( CH3 ), 1301 (C N), 1053 (C S), 721
( CH3 ). These peaks of the product are in accordance with the
reported characteristics [30,31]. The melting point of the synthe-
sized inhibitor is between 73 and 76 ◦ C. The synthesized inhibitor
has good solubility in water. The inhibitor was dissolved in alco-
hol in the ratio of 1:9 (wt.%, the former was inhibitor), in order to
facilitate to use.

3.2. Potentiodynamic polarization curves

In order to evaluate the inhibition effect of synthesized Fig. 4. Polarization curves for the steel in CO2 -saturated 3 wt.% NaCl solution con-
inhibitor on the employed steel, polarization measurements were taining various concentrations of inhibitor at 60 ◦ C.
66 H.-h. Zhang et al. / Applied Surface Science 356 (2015) 63–72

Table 2
Polarization parameters for the steel in CO2 -saturated 3 wt.% NaCl solution with different concentrations of inhibitor.

T (◦ C) C (10−5 mol/l) Ecorr (mV) Eocp (mV) icorr (␮A/cm2 ) ba (mV/dec) bc (mV/dec) IE (%) 

0 −643 −651 277.48 138 −520 –

0.4878 −630 −644 147.43 129 −350 46.87 0.4687
60 1.2195 −610 −626 12.37 64 −253 95.54 0.9554
1.9512 −606 −604 11.60 58 −230 95.82 0.9582
2.4390 −616 −595 9.48 61 −220 96.58 0.9685
4.8780 −610 −591 5.42 47 −195 98.05 0.9805

Note: C – the inhibitor concentration.

◦
hydrogen evolution reaction [35]. The above results indicated that The calculated value of Gads was −45.97 kJ/mol. The negative
the inhibitor acted as a mix-type inhibitor, and the retardation value indicated that the inhibitor spontaneously adsorbed on the
◦
of the samples corrosion processes at anodic and cathodic reac- samples’ surface. In general, when the absolute value of Gads is
tion sites took place, and it was attributed to the adsorption of the 40 kJ/mol or larger, the adsorption of the inhibitor on the sample
inhibitor molecules [36,37]. The results revealed that the inhibitor surface is related to chemisorption [41]. The result revealed that
had good inhibition effectiveness on the studied steel in 3% NaCl the adsorption mechanism of inhibitor on the steel was chemical
solution saturated with CO2 at 60 ◦ C. adsorption at 60 ◦ C.
The inhibitor molecular structure is composed of a five-member
3.3. Adsorption isotherm ring containing nitrogen elements (the headgroup), a hydropho-
bic C17 H35 group, and a hydrophilic C2 H4 NHC SNH2 group,
The  values (obtained from polarization curves) and the as shown in Fig. 2. The chemisorption of the imidazoline-based
inhibitor concentration (C, mol/l) were used to determine the best- inhibitor onto the steel surface involves charge-sharing or charge-
fitting adsorption isotherm, in order to explain the adsorption transfer from the inhibitor molecules to the steel surface to form
process for the inhibitor on the freshly abraded samples surfaces. coordinate type of bond [36]. The imidazoline ring and S atom
Attempts were made to choose the best fitting model from the were the active sites of the synthesized inhibitor, and they could
different adsorption isotherms, namely [38]: form polycentric chemical adsorption. Then the imidazoline ring
and S atom could adsorb onto the freshly abraded sample sur-
Termkin isotherm : KC = ea (5) face by donating ␲-electron to Fe atoms and accepting electrons
 from 3d orbits of the Fe atoms [6]. In addition, a protonation of
Langmuir isotherm : = KC (6) the inhibitor would take place at S atom, and then, the protonated
1−
inhibitor molecule could also adsorb onto the negatively charged
 steel surface [29,36].
Frumkin isotherm : KC = × e−2a (7)
1−
Freundlich isotherm :  = KC a (8) 3.4. Corrosion rates

where K is the equilibrium constant of the inhibitor adsorption pro- Fig. 6 shows the corrosion rates of the samples in 3 wt.% NaCl
cess, a is the parameter of interaction between inhibitor molecules solution at various concentrations of inhibitor after 96 h immersion.
adsorbed on the steel surface. The value of correlation coefficient Three trends are evident in Fig. 6. Firstly, the corrosion rate sig-
(R2 ) was used to choose the best-fitting isotherm equation, and nificantly decreased with adding 1.2195 × 10−5 mol/l inhibitor for
the R2 values were listed in Table 3. The results revealed that the freshly abraded samples (No. 2). However, the corrosion rates sub-
Langmuir isotherm provided best fitting for the adsorption of the stantially increased for the pre-corroded samples in the presence
inhibitor from the CO2 -saturated 3 wt.% NaCl solution onto the steel of 1.2195 × 10−5 mol/l inhibitor, respectively, as experiments No.
surface at 60 ◦ C. 5, No. 8, No. 11 shown. Furthermore, the corrosion rates of samples
The plot of C/ versus C gave straight line, as shown in Fig. 5. The pre-corroded for 24 h (No. 8), 48 h (No. 11) were larger than that of
derivation of the slope (0.9340) from unity could be attributed to samples pre-corroded for 2 h (No. 5), and the samples pre-corroded
the interactions between the adsorbed species on the steel surface for 24 h (No. 8) had the highest corrosion rate. On the other hand,
and the change of the adsorption heat with the increase of surface
coverage [39]. The K value was determined from the intercept of
the line in Fig. 5, and the result was 291,247 l/mol.
K value is related to the standard free energy of adsorption by
the following equation [40]:
◦
1 (−Gads )
K= exp (9)
55.5 RT
where 55.5 is the concentration of water in solution expressed in
mole, R is molar gas constant, and T is 60 ◦ C.

Table 3
Correlation coefficient (R2 ) and values of the constants in the adsorption isotherm of
Termkin, Langmuir, Frumkin and Freundlich with inhibitor in CO2 -saturated 3 wt.%
NaCl solution.

T Termkin Langmuir Frumkin Freundlich

(◦ C) (R2 , a) (R2 ) (R2 , a) (R2 , a)

60 0.5985, 3.2202 0.9825 0.9094, 1.9310 0.5834, 0.3131 Fig. 5. Langmuir isotherm adsorption model of the inhibitor on the surface of stud-
ied steel in CO2 -saturated 3 wt.% NaCl solution at 60 ◦ C.
 H.-h. Zhang et al. / Applied Surface Science 356 (2015) 63–72 67

Table 4
Circuit parameters from the modeling of the impedance spectra for the samples performed under different conditions.

Experiments Rs ( cm2 ) YCPE (−1 cm2 sn 10−6 ) nCPE Rct ( cm2 ) IE (%)

No. 1 5.43 ± 0.92 879 ± 53 0.85 ± 0.04 106 ± 7 –

No. 2 3.63 ± 0.43 446 ± 38 0.87 ± 0.03 224 ± 12 52.7
No. 3 4.82 ± 0.81 652 ± 32 0.84 ± 0.03 333 ± 13 68.2
No. 4 5.57 ± 0.75 114 ± 11 0.86 ± 0.04 1908 ± 23 94.8
No. 5 4.22 ± 0.53 2047 ± 102 0.82 ± 0.02 84 ± 8 –
No. 6 3.83 ± 0.92 2326 ± 143 0.82 ± 0.02 99 ± 5 15.2
No. 7 5.13 ± 0.35 2029 ± 51 0.80 ± 0.02 109 ± 9 23.0
No. 8 5.79 ± 0.64 107 ± 13 0.83 ± 0.03 1599 ± 43 93.4
No. 9 5.41 ± 0.58 842 ± 56 0.85 ± 0.03 106 ± 6 –
No. 10 4.04 ± 0.69 1002 ± 87 0.86 ± 0.02 142 ± 11 25.4
No. 11 4.57 ± 0.52 919 ± 44 0.82 ± 0.01 193 ± 14 45.1
No. 12 6.23 ± 0.77 106 ± 9 0.87 ± 0.03 1417 ± 35 92.5

Notes: No. 1, No. 5, No. 9 – samples p2 h , p24 h and p48 h without inhibitor, respectively; No. 2, No. 6, No. 10 – samples p2 h , p24 h and p48 h with 1.2195 × 10−5 mol/l inhibitor,
respectively; No. 3, No. 7, No. 11 – samples p2 h , p24 h and p48 h with 2.4390 × 10−5 mol/l inhibitor, respectively; No. 4, No. 8, No. 12 – samples p2 h , p24 h and p48 h removed
corrosion products and then immersed with 1.2195 × 10−5 mol/l inhibitor, respectively.

p2 h , p24 h and p48 h , in the presence of 1.2195 × 10−5 mol/l inhibitor,

Fig. 6. Corrosion rates of samples corroded for 96 h: No. 1, No. 2 and No. 3 – freshly
abraded samples; No. 5 and No. 6-samples pre-corroded for 2 h, respectively; No.
8, No. 9 and No. 14 – samples pre-corroded for 24 h, respectively; No. 11 and No.
12 – samples pre-corroded for 48 h, respectively; No. 13 – samples with corrosion
products removed after pre-corroded for 24 h.
the corrosion rate decreased after the removal of corrosion prod-
ucts on the samples pre-corroded for 24 h (No. 13) in the presence
of 1.2195 × 10−5 mol/l inhibitor.
Similar trend of corrosion rates of samples in the solution with
2.4390 × 10−5 mol/l inhibitor was observed, such as experiments
No. 3, No. 6, No. 9 and No. 12 shown in Fig. 6. When the inhibitor
concentration increased to 1.2195 × 10−4 mol/l, the corrosion rates
of samples pre-corroded for 24 h decreased sharply (No. 14).
The inhibition efficiencies (IEs) for different samples are shown
in Fig. 7. It is noted that the IE for freshly abraded samples was 97.5%
in the presence of 1.2195 × 10−5 mol/l. While the IEs for the samples
were 79.1%, 4.8% and 19.1%, respectively. However, the IE value
significantly increased after the removal of corrosion products on
the samples pre-corroded for 24 h. The results indicated that pre-
corrosion had a detrimental effect on the inhibitor performance.
In the presence of 2.4390 × 10−5 mol/l inhibitor, the IEs for freshly
abraded samples, samples p2 h , p24 h and p48 h were 98.7%, 96.4%,
81.5% and 84.8%, respectively.
With increasing the inhibitor concentration to 1.2195 ×
10−4 mol/l, the IE for sample p24 h was 98.9%, as shown in Fig. 7.
From the above results, the pre-corrosion effect on the inhibitor
performance may be mainly related to the formation of corrosion
products on the corroded surfaces.
3.5. EIS tests
Fig. 8 shows experimental and simulated impedance plots for
pre-corroded samples immersed in CO2 -saturated 3 wt.% NaCl solu-
tion in the absence and presence of inhibitor.
For pre-corroded samples, only one peak was observed in the
phase angle and frequency plot in the absence and presence of
inhibitor. The result indicated that there was only one time con-
stant, and the system could be described by one-time constant
model which consists of electrolyte resistance (Rs ), charge trans-
fer resistance (Rct ), and double layer capacitance, as shown in
Fig. 9.
Table 4 lists the circuit parameters which were obtained from
the analysis of impedance spectra in Fig. 8. The fitting errors were
controlled within 10%. The inhibition efficiency (IE) was calculated
by the following equation [33]:
Rct,inh − Rct,0
IE(%) = × 100 (10)
Rct,inh

Fig. 7. Inhibition efficiencies for samples after 96 h immersion: No. 2 and No. 3-
freshly abraded samples, respectively; No. 5 and No. 6-samples pre-corroded for 2 h,
respectively; No. 8, No. 9 and No. 14-samples pre-corroded for 24 h, respectively;
No. 11 and No. 12-samples pre-corroded for 48 h, respectively; No. 13-samples with
corrosion products removed after pre-corroded for 24 h.
where Rct,inh and Rct,0 are the charge transfer resistance values with
and without inhibitor, respectively.
In this research, the increase of Rct value indicated that the reac-
tions of CO2 corrosion were inhibited [42]. As listed in Table 4,
the Rct values of pre-corroded samples respectively increased with
adding inhibitor into the electrolyte, and the results indicated
that some inhibitor molecules were adsorbed on the sample sur-
face. Furthermore, the Rct values were significantly increased after
removing the corrosion products from the samples in the presence
of 1.2195 × 10−5 mol/l inhibitor. The results were found to corre-
spond to the immersion tests results, and further confirmed that the
corrosion products had a detrimental effect on the performance of
the corrosion inhibitor.
From Table 4, in the presence of inhibitor, it is noted that
sample p2 h had the highest Rct , sample p24 h showed the lowest
68 H.-h. Zhang et al. / Applied Surface Science 356 (2015) 63–72

Fig. 8. Nyquist and Bode plots of pre-corroded samples exposed in CO2 -saturated 3 wt.% NaCl solution containing various concentrations of inhibitor: p2 h , p24 h , p48 h -samples
pre-corroded for 2 h, 24 h, 48 h, respectively; (a–c) without inhibitor; (d–f) with 1.2195 × 10−5 mol/l inhibitor; (g–i) with 2.4390 × 10−5 mol/l inhibitor; (j–l) samples with
corrosion products removed after pre-corrosion with 1.2195 × 10−5 mol/l inhibitor.

Rct . The results indicated that the dissolution of the base metal
was the easiest for sample p24 h and the most difficult for sam-
ple p2 h . The inhibition efficiencies for samples p2 h , p24 h and p48 h
had the same trend with weight-loss results in the presence of
1.2195 × 10−5 mol/l and 2.4390 × 10−5 mol/l inhibitor.
Fig. 9. Equivalent circuit model used in the fitting of impedance data for the studied
inhibitor.
3.6. Surface analysis
Fig. 10 shows the surface micrographs of freshly abraded sam-
ples after 96 h immersion without and with 1.2195 × 10−5 mol/l
and 2.4390 × 10−5 mol/l inhibitor, respectively. The sample sur-
face was totally covered by corrosion products in the absence
of inhibitor, as shown in Fig. 10(a), it should be due to the
dissolution of metal and the formation of corrosion products. How-
ever, in the case of respectively adding 1.2195 × 10−5 mol/l and
2.4390 × 10−5 mol/l inhibitor into the electrolyte, the samples sur-
faces were well protected. The original grinding scratches were
clearly observed, as shown in Fig. 10(b) and (c), and it could be
attributed to the formation of a protective layer between raw mate-
rial and corrosive medium [43]. Therefore, it could be concluded
 H.-h. Zhang et al. / Applied Surface Science 356 (2015) 63–72 69

Fig. 10. Surface micrographs of freshly abraded samples after 96 h immersion: (a) without inhibitor; (b) with 1.2195 × 10−5 mol/l inhibitor; (c) with 2.4390 × 10−5 mol/l
inhibitor.

that the inhibitor had an excellent inhibition effect on freshly
abraded samples in studied conditions.
Fig. 11 shows the surfaces morphologies and corresponding EDS
results of samples p2 h , p24 h and p48 h .
Fig. 12 shows the cross sections morphologies of the samples
pre-corroded for different time.
As shown in Figs. 11(a) and 12(a), there was little corrosion
products on the surface of sample p2 h , and some steel alloying ele-
ments were detected on the surface (Fig. 11(b)). In fact, cementite
(part of the original steel) was left on the surface after the prefer-
ential dissolution of ferrite [22]. However, as shown in Fig. 13(a),
almost no Fe3 C was observed on the surface of sample p2 h , due

Fig. 11. SEM surface micrographs and EDS results of pre-corroded samples: (a) (1) – samples pre-corroded for 2 h, respectively; (b) (2) – samples pre-corroded for 24 h,
respectively; (c) (3) – samples pre-corroded for 48 h, respectively.
70 H.-h. Zhang et al. / Applied Surface Science 356 (2015) 63–72
Fig. 12. SEM cross section micrographs of the samples pre-corroded for 2 h (a), 24 h (b) and 48 h (c), respectively.
to the short corrosion time. With the increase of corrosion time,
significant differences were observed on sample p24 h , as shown
in Fig. 12(b), the cross section showed a ‘skeleton’ on the sample
surface. The ‘skeleton’ should be related to un-corroded cementite
residues [44], and XRD result (Fig. 13(b)) showed that there were
mainly Fe3 C and iron matrix on the sample p24 h surface. Moreover,
EDS results (Fig. 11(1–3)) exhibited that the copper element had
an accumulation tendency on the surface of sample p24 h compared
with sample p2 h . Cubic particles were observed on the surface of
sample p48 h (Fig. 11(c)), and XRD result (Fig. 13(c)) revealed that
they were FeCO3 . As it is seen in Fig. 12(c), the film of FeCO3 on
the sample was porous and non-protective. These results indicated
that the corrosion products on samples pre-corroded for 2 h, 24 h
and 48 h were different.
Previous works have pointed out that the detrimental effect of
pre-corrosion on the inhibition efficiency were related to the accu-
mulation of cementite on the corroded surface. The cementite could
provide a larger cathodic area or prevent the inhibitor interacting
with ferrite. Therefore, the inhibition efficiency decreased as the
cementite area increased [20–22,44]. The accumulation of copper
on the surface also had a negative effect on the inhibitor perfor-
mance [21]. In this study, in the presence of 1.2195 × 10−5 mol/l and
2.4390 × 10−5 mol/l inhibitor, the surfaces of samples p2 h and p24 h
had much more cementite than freshly abraded samples, and led to
the inhibition efficiencies lower than that for freshly abraded sam-
ples, respectively. Therefore, the different inhibition efficiencies for
samples p2 h and p24 h should be due to the different amounts of
cementite and copper on the surfaces.
Fig. 12(c) indicated that the corrosion product layer formed on
sample p48 h was porous. The inhibitor would be more strongly
adsorbed with the external FeCO3 through Lewis acid-base inter-
actions, compared with metallic iron [22]. Then electrolyte would
migrate to raw metal via the loose corrosion product layer. Con-
sequently, the raw metal was dissolved, and the samples p48 h
endured a higher corrosion rate than the freshly abraded sam-
ples in the presence of 1.2195 × 10−5 mol/l and 2.4390 × 10−5 mol/l
inhibitor, respectively.
It has been reported that the formation of inhibitor layer on
pre-corroded sample is slower than that on freshly abraded sam-
ple [20–22]. EIS results shown in Table 4 revealed that samples p2 h
Fig. 13. XRD results of the samples pre-corroded for 2 h (a), 24 h (b) and 48 h (c), respectively.
and p24 h , respectively had the smallest and largest Rct in the pres-
ence of inhibitor. Rct value represented the amount of ferrous ions
diffused into the electrolyte. Inhibitor molecules are more strongly
adsorbed onto the exposed Fe3 C, FeCO3 and ferrous ions through
Lewis acid-interactions, compared to metallic irons [22]. Then, the
inhibitor molecules interacted with Fe3 C, FeCO3 on the samples
surfaces and ferrous ions in the solution, enhanced the raw metal
to have a more severe dissolution. In this case, more ferrous ions
diffused into the electrolyte to interact with the inhibitor, finally
a vicious circle formed. Therefore, the inhibition efficiencies for
samples p2 h , p24 h and p48 h were different, as shown in Fig. 7 and
Table 4.
Moreover, with the dissolution of base metal, no protec-
tive corrosion product layer formed on the sample surface due
to the inhibitor action [22,45]. With the increase of immer-
sion time, the localized corrosion appeared. In the presence of
1.2195 × 10−5 mol/l inhibitor for 96 h immersion, sample p24 h
underwent the most severe localized corrosion, and sample p2 h
exhibited the least serious localized corrosion, respectively, as
shown in Fig. 14.
After the corrosion products were removed, the samples sur-
faces were examined by a surface profiler. The corrosion depth was
measured, five pits with the highest corrosion depth were detected
and their average value was calculated [46]. The localized corrosion
rate was calculated by the following equation [47]:
365 × 24 × h
Vcorr = (11)
t
where Vcorr (mm/y) is the localized corrosion rate of the samples, h
is the average depth of deepest depth (mm), and t is the immersion
time (h).
Fig. 15 shows the localized corrosion rates of the pre-corroded
samples in the presence of 1.2195 × 10−5 mol/l inhibitor. Samples
pre-corroded for 24 h had the highest localized corrosion rate about
8.67 ± 0.85 mm/y (No. 5), the localized corrosion rates of the sam-
ples pre-corroded for 2 h and 48 h were 4.08 ± 0.73 mm/y (No. 8)
and 7.93 ± 1.34 mm/y (No. 11), respectively.
In the presence of 1.2195 × 10−5 mol/l inhibitor, the IE value for
samples p24 h increased after corrosion products removed, how-
ever, it was still lower than that for freshly abraded samples. The
 H.-h. Zhang et al. / Applied Surface Science 356 (2015) 63–72
Fig. 14. Cross section micrographs of the samples pre-corroded for 2 h (a), 24 h (b) and 48 h (c) with 1.2195 × 10−5 mol/l inhibitor after 96 h immersion, respectively.
result might be due to the significant change in the surface of the
sample during pre-corrosion. After pre-corrosion, the samples had
a larger surface area, and then a higher inhibitor concentration was
required to obtain excellent inhibition effect [48]. On the other
hand, the inhibitor would formed a relative non-protective film on
the samples with larger surface roughness [49].
The results in Fig. 7 exhibited that, with increasing the inhibitor
concentration from 1.2195 × 10−5 mol/l, 2.4390 × 10−5 mol/l
to 1.2195 × 10−4 mol/l, inhibition efficiencies were gradually
increased to 99% for samples p24 h . This indicated that the
employed inhibitor could also be used to inhibit the CO2 corro-
sion of pre-corroded samples. However, compared to the freshly
abraded samples, the effective inhibition concentration of the
inhibitor employed to suppress the corrosion of pre-corroded
samples increased. The concentrations of 1.2195 × 10−5 mol/l and
2.4390 × 10−5 mol/l inhibitor were proven too low for pre-corroded
samples, and a higher concentration inhibitor was required to
obtain the same inhibition effect, this should be attributed to the
increased area after pre-corrosion and the formation of corrosion
products.
Previous works [20] have pointed out that, compared to freshly
abraded samples, the detrimental effect of pre-corrosion on the
inhibitor performance might be related to the presence of a cemen-
tite layer on the sample surface, while other types of scale on
the surface (such as rust layers and carbonate layers) did not
impair the inhibitor performance. In this work, for the different
corrosion products on the pre-corroded samples surfaces, such
as few cementite, thick cementite film and ferrous carbonate
film, they all had negative effectiveness on the inhibitor perfor-
mance. Furthermore, the surface area significantly changed after
pre-corrosion, while few literatures have taken the factor into
account.
Fig. 15. Localized corrosion rates of the samples pre-corroded for 2 h (No. 5), 24 h
(No. 8) and 48 h (No. 11) with 1.2195 × 10−5 mol/l inhibitor after 96 h immersion,
respectively.
71
4. Conclusions
1. The adsorption process of the synthesized inhibitor on freshly
abraded samples was chemisorption and followed Langmuir
isotherm.
2. The inhibitor exhibited good inhibition efficiency for freshly
abraded samples about 98.7%. However, the pre-corrosion would
decrease the inhibition efficiency, and led to localized corrosion.
3. In the presence of 1.2195 × 10−5 mol/l inhibitor, the inhibition
efficiencies for samples pre-corroded for 2 h, 24 h and 48 h were
71.9%, 4.8% and 19.1%, respectively, while these values were
respectively increased to 96.4%, 81.5%, 84.8%, when the inhibitor
concentration increased to 2.4390 × 10−5 mol/l.
4. The decrease in inhibition efficiency for the pre-corroded sam-
ples should be attributed to the residual amounts of cementite,
element Cu and the formation of FeCO3 on the pre-corroded
sample surface.
5. The increase surface area of the pre-corroded sample had a neg-
ative effect on the inhibitor performance.
Acknowledgements
This work was supported by the Beijing Natural Science Foun-
dation (No. 2131004) and National Natural Science Foundation of
China (No. 51271024).
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