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Corrosion inhibition of mild steel in acidic

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ARTICLE in MATERIALS CHEMISTRY AND PHYSICS MARCH 2009
Impact Factor: 2.26 DOI: 10.1016/j.matchemphys.2008.09.019

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Materials Chemistry and Physics 114 (2009) 267271

Contents lists available at ScienceDirect

Materials Chemistry and Physics

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

Corrosion inhibition of mild steel in acidic media by [BMIm]Br Ionic liquid

H. Ashassi-Sorkhabi , M. Eshaghi
Electrochemical Research Laboratory, Department of Physical Chemistry, Center of Excellence for New Materials and Clean Chemistry, Faculty of Chemistry, University of Tabriz,
29 Bahman Boulevard, Tabriz 5166614766, Iran

a r t i c l e

i n f o

Article history:
Received 26 December 2007
Received in revised form
10 September 2008
Accepted 13 September 2008
Keywords:
Corrosion inhibitor
Electrochemical techniques
Adsorption

a b s t r a c t
The inhibiting behavior of 1-butyl-3-methylimidazolium bromide [BMIM]Br on mild steel corrosion in
1.0 M HCl as corroding solution at 25 C was evaluated by various corrosion monitoring techniques. The
obtained results showed that [BMIM]Br is a good inhibitor for mild steel in 1.0 M HCl solution. Potentiodynamic polarization data indicated that the [BMIM]Br acts essentially as a mixed-type inhibitor. The effect
of inhibitor concentration on zero charge potential (ZCP) of the mild steel in 1.0 M HCl was studied and its
comparison with OCP has been made for evaluation of the mechanism of adsorption of [BMIm]+ cation.
The effect of temperature on corrosion behavior of mild steel in 1.0 M HCl with addition of [BMIM]Br
was studied in the temperature range of 2545 C. The inhibition efciency decreases with the rise of
temperature.
2008 Elsevier B.V. All rights reserved.

1. Introduction

2. Experimental

Acid solutions are commonly used in the chemical industry

to remove the scales from the metallic surfaces. The addition of
inhibitors secures the metal against an acid attack effectively. The
applicability of organic compounds as corrosion inhibitors for metals in acidic media has been recognized for a long time [16]. The
existing data show that most organic inhibitors act by adsorption
on the metal surface. The adsorption of inhibitors occurs through
heteroatoms such as nitrogen, oxygen, phosphorus and sulphur,
triple bonds or aromatic rings. These compounds are adsorbed on
the metallic surface block the active corrosion sites. Adsorption
behavior of organic molecules on the surface of metals depends
on molecular structure of the organic compounds, surface charge
density and zero charge potential of metals [7].
Ionic liquids have attracted considerable attention in recent
years. They have been identied as media for green synthesis which
are used in a wide range of chemical processes. One of the most
important properties of ionic liquids is that of negligible vapor
pressure [8].
The aim of this work is to investigate the inhibiting inuence
of [BMIm]Br on mild steel corrosion in 1.0 M hydrochloric acid
solution. This has been studied by weight loss, potentiodynamic
polarization and electrochemical impedance spectroscopy (EIS)
techniques.

Prior to all measurements the mild steel specimens (0.027% P; 2.08% Si; 0.034%
Cr; 0.014% W; 0.018% Mo; 0.260% Mn; 0.008% C; 0.005% S; 0.016% Ni; 0.353% Al and
the remainder Fe) were ground with different emery papers (grade 400, 600, 800,
1000 and 1200), rinsed with double-distilled water, degreased in absolute ethanol
and dried by compressed air at room temperature. The aggressive solutions made of
AR grade 37% HCl. Appropriate concentrations of acid were prepared using doubledistilled water. The concentration range of inhibitor employed was 220 mM in acid
solutions. Required [BMIm]Br 99% was purchased from Soluent Innouation without
further purication. Fig. 1 shows the structure of [BMIm]Br. All experiments were
performed under the atmospheric ambient and the temperature of the solutions
was controlled by thermostat (Memert).
Weight loss experiments were performed according to the method described
previously [9]. Tests were conducted in 1.0 M HCl solution with different concentrations of inhibitor. At the end of the tests the specimens were carefully washed in
absolute ethanol, and then were reweighed. Duplicate experiments were performed
in each case and the mean value of the weight loss was reported. Electrochemical experiments were carried out using an Autolab (PGSTAT 30). A three-electrode
arrangement was used for electrochemical studies. Working electrode was prepared
from a mild steel sheet, mounted in polyester so that the area exposed to corrosive
solution was 1 cm2 . A saturated calomel electrode (SCE) and a 1 cm 1 cm platinum electrode were used as the reference and counter electrodes, respectively. For
potentiodynamic polarization measurements the potential sweep rate was 1 mV s1 .
The immersion time before each measurement was 60 min to access an equilibrium
potential. The impedance measurements were carried out in the frequency range of
30 kHz to 0.1 Hz at the open circuit potential (OCP), by applying 10 mV sine wave ac
voltage.

3. Results and discussion

3.1. Weight loss studies

Corresponding author. Tel.: +98 411 3393136; fax: +98 411 3340191.
E-mail addresses: habib ashassi@yahoo.com, ashassi@tabrizu.ac.ir
(H. Ashassi-Sorkhabi).
0254-0584/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2008.09.019

The weight loss of the mild steel in 1.0 M HCl with and without of various concentrations of [BMIm]Br is determined after 6 h

268

H. Ashassi-Sorkhabi, M. Eshaghi / Materials Chemistry and Physics 114 (2009) 267271

Table 3
Electrochemical impedance measurement of mild steel in 1.0 M HCl for various
concentration of [BMIm]Br.

Fig. 1. Structure of 1-butyl-3-methylimidazolium bromide inhibitor used in this

study.
Table 1
Weight loss data of mild steel in 1.0 M HCl for various concentration of [BMIm]Br.
Inhibitor conc. (mM)

rcorr (mg cm2 h1 )

w (%)

Blank
2
4
10
20

3.43
1.28
1.01
0.71
0.32

63
70
79
90

Inhibitor conc. (mM)

Rs ( cm2 )

Rt ( cm2 )

Blank
2
4
10
20

1.0
1.1
1.1
1.2
1.2

6.5
18.4
24
31.7
78

Cdl (F)
331
155
140
94
41

z

0.875
0.879
0.882
0.888
0.897

64
72
80
92

collected in Table 2. Eq. (2) was used to calculate the inhibition

efciency (p ) where I0 and Icorr are the corrosion current density
values without and with inhibitor, respectively:
p =

Fig. 2. Potentiodynamic polarization curves for mild steel in 1.0 M HCl containing
different concentrations of [BMIm]Br.

I0 Icorr
100
I0

(2)

The addition of the studied inhibitor decreases the cathodic

and anodic current densities. As it is shown in Fig. 2, cathodic
polarization curves rise parallel, indicating that the hydrogen evolution reaction is activation controlled [10]. Thus, the presence of
[BMIm]Br does not affect the mechanism of this process. The values of the corrosion potential (Ecorr ) do not change with inhibitor
concentration. These results demonstrate that [BMIm]Br exhibits
both cathodic and anodic inhibition effects and acts as a mixed-type
inhibitor in 1 M HCl.
In potentials higher than 400 mV/SCE, the presence of inhibitor
did not change the values of current vs. potential. This potential can
be dened as the desorption potential. The same results have been
reported with other organic compounds [11,12]. This fact means
that the inhibition mode of [BMIm]Br depends on electrode potential. However, [BMIm]Br inuences the anodic reaction at potentials
more negative than 400 mV/SCE.
3.3. Electrochemical impedance measurements

of immersion at 25 C. Eq. (1) determines the inhibition efciency

where W0 and Wcorr are the corrosion rates of mild steel with and
without the inhibitor, respectively. Values of the inhibition efciency obtained are given in Table 1:
w =

W0 Wcorr
100
W0

(1)

Corrosion rate values of mild steel decrease when the inhibitor

concentration increases. The inhibition efciency increases with
increasing inhibitor concentration, reaching a maximum value
(90%) of 20 mM of [BMIm]Br. Gravimetric measurements conrm
the protection property of [BMIm]Br in 1.0 M HCl. The inhibition
may be due to adsorption of [BMIm]+ on the mild steel surface.
3.2. Potentiodynamic polarization curves
Fig. 2 shows the inuence of [BMIm]Br on the cathodic and
anodic potentiodynamic polarization curves of mild steel in 1.0 M
HCl. Electrochemical corrosion parameters such as corrosion potential (Ecorr ), cathodic and anodic Tafel slops (ba , bc ) and corrosion
current density (Icorr ), obtained by extrapolation of Tafel lines, are

The corrosion behavior of mild steel in acidic solution in the

presence of [BMIm]Br was investigated by the EIS at 25 C. The
Nyquist and Bode plots of mild steel in inhibited and uninhibited acidic solutions containing various concentrations of [BMIm]Br
are shown in Fig. 3. Table 3 collects various parameters such as
charge-transfer resistance (Rt ), double layer capacitance (Cdl ) and
percentage inhibition efciency (z ) calculated from Eq. (3) where
Rt(inh) and Rt are the charge-transfer resistance values with and
without inhibitor, respectively:
z =

Rt(inh) Rt
Rt(inh)

100

(3)

The impedance spectra were analyzed by tting to the equivalent circuit model shown in Fig. 3. It is apparent from this gure
that the charge-transfer resistance value of mild steel in uninhibited
HCl solution signicantly changes after the addition of [BMIm]Br.
The Rt values were calculated from the difference in impedance at
lower and higher frequencies as suggested by Tsuru et al. [13]. The
values of Cdl are obtained at the frequency fmax , at which the imaginary component of the impedance is maximal (Z max ), using the

Table 2
Potentiodynamic polarizations parameters of mild steel in 1.0 M HCl for various concentration of [BMIm]Br.
Inhibitor conc. (mM)

Ecorr (mV/SCE)

ba (mV dec1 )

bc (mV dec1 )

Icorr (mA cm2 )

rcorr (mm y1 )

p (%)

Blank
2
4
10
20

554
556
557
556
557

88
71
71
66
62

109
102
92
90
96

3.46
1.25
0.98
0.61
0.21

40.1
14.5
11.3
7.0
2.5

64
72
82
94

0.64
0.72
0.82
0.94

H. Ashassi-Sorkhabi, M. Eshaghi / Materials Chemistry and Physics 114 (2009) 267271

269

Table 4
Effect of temperature on the inhibition efciency of 20 mM [BMIm]Br in 1.0 M HCl
with (Icorr ) and without (I0 ) of inhibitor.
Temp. ( C)

I0 (mA cm2 )

Icorr (mA cm2 )

p (%)

25
35
45

3.46
6.40
12.35

0.21
1.34
2.48

94
79
78

tion indicating a charge-transfer process mainly controlling the

corrosion of mild steel.
3.4. Effect of temperature
Temperature can modify the interaction between the mild
steel electrode and the acidic media. Generally the corrosion rate
increases with the rise of the temperature [15]. The values of inhibition efciency obtained from polarization curves (are not shown) in
1.0 M HCl in the absence and presence of 20 mM of [BMIm]Br at the
temperature range of 2545 C are given in Table 4. These results
indicate that the corrosion current density increases more rapidly
with temperature in the absence of inhibitor. Therefore, [BMIm]Br
acts as an efcient inhibitor in the range of temperature studied.
The efciency of the tested inhibitor depends on the temperature
and decreases with the rise of temperature, which could be caused
by desorption of the inhibitor from the mild steel surface.
The apparent activation energy for the corrosion process is
calculated from Arrhenius type plot according to the following
equation:

 E 
a

Icorr = A exp

RT

(5)

where Ea is the apparent activation corrosion energy, R is the universal gas constant, A is the Arrhenius pre-exponential constant and T
is the absolute temperature. Arrhenius plots for the corrosion current density of mild steel are given in Fig. 4. The obtained values
for Ea in 1.0 M HCl in the absence and presence of [BMIm]Br are
50.1 and 97.6 kJ mol1 , respectively. It can be found that the energy
barrier of corrosion reaction increases with the inhibitor concentration. This phenomenon may be attributed to the change in the
mechanism of the corrosion process in the presence of adsorbed
inhibitor molecules. It is often interpreted by physical adsorption
lead to the formation of an adsorptive lm of electrostatic character
[16,17].
Fig. 3. Nyquist and Bode plots for mild steel in 1.0 M HCl containing different concentrations of [BMIm]Br and the corresponding equivalent circuit.

following equation:
Cdl =

1
2fmax Rt

(4)

It is found that the Rt values increase with increasing [BMIm]Br

concentration while the Cdl values tend to decrease. The decrease
in Cdl values is due to the adsorption of [BMIm]Br on the metal
surface [14]. The greatest inhibition is observed at a concentration of 20 mM. The parameter n is generally accepted to be
a measure of surface inhomogeneity, and its increase in the
inhibited solution compared to the pure acid is connected with
a decrease in heterogeneity resulting from inhibitor adsorption.
The inhibition efciencies, calculated from impedance results,
show the same trend as those obtained from polarization and
weight loss measurements. In fact, the presence of [BMIm]Br is
accompanied by the increase of the value of Rt in an acidic solu-

Fig. 4. Arrhenius slopes calculated from corrosion current density for mild steel in:
(a) 1.0 M HCl and (b) 1.0 M HCl + 20 mM of [BMIm]Br.

270

H. Ashassi-Sorkhabi, M. Eshaghi / Materials Chemistry and Physics 114 (2009) 267271

Table 5
Values of () for the mild steel electrode in 1.0 M HCl for various concentration of
[BMIm]Br at 25 C.
Electrolyte

Ecorr (mV/SCE)

PZC (mV/SCE)

= Ecorr PZC (mV/SCE)

Cs (F)

Blank
2
4
10
20

556
556
557
556
557

536
546
547
567
578

20
10
10
11
21

610
271
151
97
69

Fig. 5. Langmuir adsorption plot for mild steel in 1.0 M HCl containing different
concentration of [BMIm]Br.

3.5. Adsorption isotherm

Basic information on the interaction between the inhibitors and
the steel surface is provided by the adsorption isotherm. The degree
of surface coverage, , at different inhibitor concentrations in 1.0 M
HCl was evaluated from polarization measurements ( = p /100) at
25 C (Table 2). The plot of Cinh / against inhibitor concentration
(Cinh ) displayed a straight line for tested inhibitor (Fig. 5). The linear
plot with high correlation coefcient (0.998) and slope of 1.003
clearly revealed that the surface adsorption process of [BMIm]Br
on the mild steel surface obeys the Langmuir isotherm. Likewise,
it suggests that an adsorption process occurs [18], which can be
expressed as follows [19]:
1
Cinh
=
+ Cinh
Kads


(6)

where Kads is the adsorption equilibrium constant. Free energy of

adsorption (Gads ) can be calculated by Eq. (7). The numeral of 55.5
is the molar concentration of water in the solution:
Kads

1
Gads
=
exp
55.5
RT

(7)

The value of Gads for adsorption of [BMIm]Br was found to be

8.9 kJ mol1 . The negative value of Gads suggests that [BMIm]Br
is spontaneously adsorbed on the mild steel surface. Literature
survey reveals that the values of Gads around 20 kJ mol1 or
lower are consistent with the electrostatic interaction between the
charged molecules and the charged metal (physical adsorption)
[20].
3.6. Determination of the zero charge potential
The potential of zero charge, PZC, may help in determining the
type of adsorption that occurs at the electrode surface [21]. The
determined PZC values in the absences and presence of the investigated inhibitors and their comparison with the corresponding Ecorr
values reveal that the surface of the steel electrode is negatively
charged at the OCP in the blank solution. The values of Ecorr , PZC
and the difference between them, , are presented in Table 5. These
results conrm the electrostatic adsorption of [BMIm]+ cations on
the negatively charged mild steel surface in HCl solution, thus negative excess charge on the mild steel surface is decreased. This may
explain the negative shift of PZC upon adding [BMIm]Br. This negative shift in PZC increases with increasing [BMIm]Br concentration,
since more [BMIm]+ cations will electrostatically adsorb on the
electrode surface (Fig. 6).

Fig. 6. Capacitance vs. voltage plots recorded for mild steel in 1.0 M HCl containing
different concentrations of [BMIm]Br.

Ai et al. [7] obtained the same results using imidazoline derivative (quaternary ammonium salt) as a cationic inhibitor for carbon
steel corrosion in NaCl solution by electrochemical, weight loss and
some other methods and revealed that in NaCl solution, the organic
inhibitor can easily adsorb on the carbon steel surface; therefore
they presented the similar interpretation for adsorption behavior
of inhibitor on carbon steel.
4. Conclusions
From the overall experimental results and discussion the following conclusions can be deduced:
The [BMIm]Br is a good inhibitor for mild steel in 1.0 M HCl. The
inhibition efciency increases with an increase of inhibitive concentration to attain a maximum value of 94% at 20 mM.
[BMIm]Br acts as mixed-type inhibitor without modifying the
mechanism of hydrogen evolution.
There are good agreements between the inhibition efciencies,
obtained from gravimetric method and electrochemical measurements.
The adsorption of inhibitor on the mild steel is found to follow
the Langmuir adsorption isotherm.
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