Journal of Electroanalytical Chemistry 769 (2016) 5361

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Journal of Electroanalytical Chemistry

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

Olive leaf extract as natural corrosion inhibitor for pure copper

in 0.5 M NaCl solution: A study by voltammetry around OCP
Chahla Rahal a, Mohamed Masmoudi a, Ridha Abdelhedi a, Ren Sabot b, Marc Jeannin b,
Mohamed Bouaziz a, Philippe Refait b,
a
Laboratory of Electrochemistry and Environment (LEE), Sfax National Engineering School (ENIS) BPW, 3038 Sfax, University of Sfax, Tunisia
b
Laboratoire des Sciences de l'Ingnieur pour l'Environnement (LaSIE), UMR7356 CNRS Universit de La Rochelle, Bt. Marie Curie, Av. Michel Crpeau, 17042 La Rochelle cedex 01, France

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

Article history: The inhibiting action of olive leaf extract on corrosion of copper in 0.5 M NaCl solution was investigated via po-
Received 6 October 2015 tentiodynamic polarization and electrochemical impedance spectroscopy. For the highest inhibitor concentration
Received in revised form 9 March 2016 considered here the inhibition efciency reached 90% after 24 h of immersion. Polarization curves recorded
Accepted 12 March 2016
around OCP were computer tted with various kinetic laws to obtain detailed information on the inhibition pro-
Available online 16 March 2016
cess. This innovative procedure led to results consistent with those deduced from electrochemical impedance
Keywords:
spectroscopy and conrmed that the olive leaf extract act as a cathodic-type corrosion inhibitor mainly hindering
Olive leaf extract the transport and thus the reduction of dissolved O2. High performance liquid chromatography showed that
Oleuropein oleuropein was the major compound of the leaf extract and thus more likely the main inhibiting species.
Voltammetry 2016 Elsevier B.V. All rights reserved.
Copper
Corrosion
HPLC
EIS

1. Introduction
Corrosion inhibitors are commonly used in industry to reduce the
corrosion rate of metals and alloys. For copper protection in chloride-
containing media, various substances were considered [e.g. 18], and
it was shown that nitrogen, sulfur and aromatic containing organic
compounds reduced efciently the corrosion rate. The inhibiting action
of these organic compounds is usually attributed to their adsorption on
the metal surface, the polar functional groups playing the main role in
the adsorption process [5]. In general, this process depends on the
chemical structure of the inhibitor, the nature and surface charge of
the metal, the adsorption mode and the electrolyte [8].
However, most of these compounds are synthetic chemicals which
may be very expensive and hazardous to living creatures and environ-
ments. Because of economic and environmental factors, an inhibitor
must not only be efcient but also cheap, nontoxic and innocuous in
the environment. Various parts of plants proved to contain several
compounds that satisfy these criteria and plants thus constitute a
potential source of new corrosion inhibitors. Numerous studies were
recently achieved to determine the effects of some naturally occurring
substances on the corrosion of various metals, including copper, in
different corrosive media [e.g. 922].
Corresponding author.
E-mail address: prefait@univ-lr.fr (P. Refait).
In the Mediterranean coastal zone, olive leaves are one of the
by-products of farming of the olive grove; they exist in high amounts
in the olive oil industries (10% of the total weight of the olives). They
also accumulate during the pruning of the olive trees [23]. Olive leaves
are a cheap raw material that can however be the source of high-
added value products, e.g. phenolic compounds. This has recently raised
interest for their chemical composition and specic properties. It was
for instance shown that the olive leaf extract has anti-oxidative,
anti-inammatory and antimicrobial activities against bacteria and
fungi. It also exhibits anti-viral activities against several species like
haemorrhagic septicaemia rhabdo virus [24].
Following the same line, the present study aimed to determine the
efciency of a natural olive leaf extract as a corrosion inhibitor for
pure copper in 0.5 M NaCl solution. The organic species present in the
extract were characterized by high performance liquid chromatogra-
phy. Electrochemistry was used to study the evolution over time of
the inhibition efciency during 24 h experiments, the inuence of inhib-
itor concentration and the role of temperature. Results obtained with
electrochemical impedance spectroscopy (EIS) were compared to
those given by voltammetry. Polarization curves were recorded as
usual on a wide range of potential (from 0.55 V/SCE to +0.6 V/SCE)
at the end of the experiment. Additionally, other polarization curves
were recorded before each EIS analysis. They were acquired around
the open circuit potential (OCP) to limit modications of the electrode
surface. All these curves were analyzed via a computer tting procedure

http://dx.doi.org/10.1016/j.jelechem.2016.03.010
1572-6657/ 2016 Elsevier B.V. All rights reserved.
54 C. Rahal et al. / Journal of Electroanalytical Chemistry 769 (2016) 5361
which provided information about the inuence of the inhibitor on the
cathodic process. This innovative approach proved a useful complemen-
tary method to EIS.
2. Experimental
2.1. Electrodes and electrolytes
The work electrodes were all made with the same pure copper
(99.99%) rod of 6 mm in diameter. The surfaces were prepared via an
abrading procedure with silicon carbide (from grade 240 to grade
1200), washed with distilled water and degreased with acetone. The
0.5 M NaCl solution used as aggressive medium was prepared with
98% min. purity NaCl and de-ionized water (resistivity 18.2 M cm).
The solutions were not stirred during the experiments. The inuence
of the olive leaf extract concentration was studied at room temperature
(RT) i.e. at 25 2 C when the experiments were performed (May
June). The effect of temperature on the inhibition efciency was studied
in the 2555 C range. A thermostat controlled the temperature with an
accuracy of 0.5 C. The evolution of the system was followed with
time during 24 h.
2.2. Extraction solution and extract preparation
The olive leaves were rst air-dried at room temperature (~25 C)
for one month in the absence of light. Then, 100 g of powdered leaves
were mixed with 1 L of de-ionized water under stirring for 1 h at
75 C. After cooling, the mixture was ltered through a lter paper
and the ltrate, stored in a freezer at 4 C, was used during the following
days. The pH of the ltrate was measured at 5.8 after preparation. The
obtained leaf extract was added to 0.5 M NaCl solutions in various
amounts (see Section 3.1).
2.3. Characterization of the olive leaf extract by HPLC
The quantitative analysis of olive leaf extract was carried out using
an Agilent Technologies series 1100 liquid chromatography system
(HPLC, Agilent Technologies, Karlsruhe, Germany) equipped with an
automatic injector, composed of a vacuum degasser, a quaternary
pump, a column oven and a diode array detector (DAD). An Eclipse
XDB-C18 column (250 4.6 mm, i.d., 5 m particle size; Waters Co.,
Milford, MA) was used at room temperature (25 C) with an injection
volume of 10 L. The mobile phase was composed of 0.25% acetic acid
in water (solvent A)/methanol (solvent B) at a ow rate of
0.6 mL min 1, with the following steps: 0 min, 5% B; 7 min, 35% B;
12 min, 45% B; 17 min, 50% B; 22 min, 60% B; 25 min, 95% B; 27 min,
5% B, and then a conditioning cycle of 5 min at the same conditions for
the subsequent analysis.
Detection and quantication were performed at 254 nm, near the
maximum absorption of most phenols [25]. Peaks were identied by
congruent retention times compared with available standards. Each
phenolic compound was quantied in comparison with its standard
when it was available while the other detected compounds were
quantied by other equivalent compounds.
2.4. Electrochemical measurements
Electrochemical measurements, including potentiodynamic
polarization and electrochemical impedance spectroscopy (EIS) were
performed in a classical three-electrode cell. Pure copper, platinum foil
and saturated calomel electrode (SCE: XR110, Radiometer-Analytical)
were used as working, counter and reference electrodes, respectively.
The open-circuit potential (OCP) was recorded as a function of time
except during the potentiodynamic polarization and EIS experiments.
The rst series of potentiodynamic polarization around OCP and EIS
experiments was performed after 1 h, a time necessary for the OCP to
reach a quasi-stationary value, and the other series after 6 and 24 h.
These polarization curves were acquired on a limited range of
potential around OCP to induce only a minor perturbation of the metal
surface. The potential was swept from the OCP to OCP + 70 mV, then
down to OCP-70 mV and back to OCP, at a scan rate dE/dt =
0.5 mV s1. Each curve was analyzed using a computer tting proce-
dure described in Section 2.5. The EIS measurements were carried out
in each case just after the acquisition of the polarization curve. Imped-
ance diagrams were obtained over a frequency range of 100 kHz to
10 mHz with ten points per decade using a 10 mV peak-to-peak sinusoi-
dal voltage. The linearity of the system was checked in varying the
amplitude of the ac signal applied to the sample. The impedance spectra
were tted using electrical equivalent circuits with EC-Lab software
(Bio-Logic).
Finally, after the last EIS experiment, i.e. approximately after 24 h of
immersion, a polarization curve was drawn from 0.55 V/SCE
to +0.6 V/SCE at a sweep rate dE/dt = 0.5 mV s1.
Each experiment was performed at least three times and the values
given for the various determined parameters are the average of the
various measurements.
2.5. Voltammetry around OCP (E = 70 mV): methodology
The determination of corrosion rates by electrochemical methods
generally implies to modify the potential of the metal electrode. The
range of this variation of potential has however to be kept small so as
to limit modications of the electrode/electrolyte interface and obtain
information on the processes really occurring at OCP. In a recent study
[26], it was for instance observed that after cathodic polarization, the
corrosion potential Ecorr of the metal could be decreased of 200 mV
because of O2 consumption and increase of interfacial pH, even if a rath-
er small scan rate of 0.2 mV/s was used (the variations of Ecorr should in-
crease with increasing scan rate). Moreover, if the potential range is
really important, the method must be considered as destructive because
the modications of the interface can be signicant and irreversible. For
such reasons, the measurement of the polarization resistance Rp per-
formed on a small potential range (typically 15 mV around OCP)
may be more adequate.
The method called here voltammetry around OCP involves a larger
range, for instance 70 mV as in the present study, but assumed to be
sufciently small to have a negligible impact on the metal/electrolyte
interface. The aim is not to determine Rp (in principle, the difference be-
tween the experimentally determined Rp and the true Rp value increases
with the potential range) but to obtain information on the kinetics of
the anodic and cathodic processes occurring at OCP. However, none of
the two processes can be neglected with respect to the other at the vi-
cinity of OCP. As a consequence, no linear part could be observed on
the log|j| vs. E curve acquired around OCP even if both reactions should
obey Tafel's law. For this reason, a tting procedure of the experimental
polarization curve is required, based on electrochemical kinetic laws.
The main advantage with respect to the so called Tafel method usually
used on polarization curves acquired on a wider potential range is that
various kinetic laws can be used, in particular for the cathodic reaction
(typically O2 reduction).
The experimental polarization curves j vs. E were computer tted as-
suming that the anodic reaction obeys Tafel's law and that the cathodic
reaction, i.e. the reduction of O2, was under mixed activationdiffusion
control. The expression of the anodic current ja is then:
ja jcorr :eaEEcorr 1
where a is the anodic Tafel coefcient, in V1.
 C. Rahal et al. / Journal of Electroanalytical Chemistry 769 (2016) 5361
The expression of the cathodic current jc, derived from the
KouteckyLevich equation, is:
1 Fig. 2 shows the polarization curves obtained on a large potential
jc

1 1 1 range at the end of the 24 h of immersion in the various olive leaf extract
ec EEcorr :
j lim jcorr j lim
where c is the cathodic Tafel coefcient, in V1, and jlim the limiting
current density.
The experimental function used for the mathematical modeling of
the potentiodynamic polarization curve j vs. E is then:
a EEcorr 1
j ja jc jcorr :e

1 1
ec EEcorr :
j lim jcorr
The corrosion potential (Ecorr) was directly read on the log| j| vs. E
curve while the corrosion current density (jcorr), the Tafel coefcients
a and c and limiting cathodic current density jlim were obtained via
the computer tting of the potentiodynamic polarization curves.
In some cases, the cathodic part of the log|j| vs. E curve was linear.
The computer tting of the j vs. E curve was then achieved using Tafel's
law for both anodic and cathodic currents. The experimental function
used for the mathematical modeling of the curve is in this case:
h i
j ja jc jcorr ea EEcorr ec EEcorr
In each case, only the part of the curve corresponding to the
negative-going scan from OCP + 70 mV down to OCP 70 mV was
computer tted.
3. Results and discussion
3.1. Phenolic compounds contents of the studied olive leaf extract
The determination of phenolic compounds contents of the olive leaf
extract was carried out by high performance liquid chromatography
(HPLC) using a solution obtained with 100 g of powdered leaves
mixed with 1 L of distilled water. The HPLC chromatogram (Fig. 1)
shows several peaks corresponding to phenolic compounds. Eight phe-
nolic compounds are identied in the olive leaf extract, namely, 1:
hydroxytyrosol, 2: tyrosol: 3: caffeic acid, 4: pcoumaric acid, 5: luteolin
7-glucoside, 6: apigenin 7-glucoside, 7: verbascoside and 8: oleuropein,
in agreement with previous works [25,2729]. The most abundant
compound was oleuropein, as it was also reported by several authors
[28,29].
The quantitative study led to an estimated concentration of
oleuropein of 2.42 mmol L1 (C1). For this study the solution C1 was di-
luted two and ve times which led to the solutions C2 (1.21 mmol L1)
and C3 (0.48 mmol L1).
Fig. 1. HPLC chromatogram at 254 nm of the obtained olive leaf extract. 1: hydroxytyrosol;
2: tyrosol; 3: caffeic acid; 4: pcoumaric acid; 5: luteolin 7-glucoside; 6: apigenin 7-
glucoside; 7: verbascoside; 8: oleuropein.
55
3.2. Effect of olive leaf extract concentration
3.2.1. Potentiodynamic polarization between 0.55 and +0.6 V/SCE
2
concentrations C1C3. They are compared to the curve obtained in
similar conditions in a 0.5 M NaCl solution without olive leaf extract,
solution referred to as blank.
In the potential range considered here, the cathodic reaction is
mainly the reduction of dissolved oxygen:
O2 2H2 O 4e 4OH 5
3
1 The anodic part of the curve shows three main regions of potential.
j lim In region (I) an apparent Tafel behavior is observed and the current
density increases up to jmax when the potential increases. The
dissolution process of copper in the presence of Cl ions proceeds via
a two-step reaction mechanism [30,31]. The rst step leads to the for-
mation of CuCl adsorbed on the metal surface according to the following
reaction:
Cu Cl CuCl e 6
Copper dissolution occurs in the second step via the formation of
CuCl
2 complex:
4
CuCl Cl CuCl2
7
In region (I), mixed charge transfer and mass transport controlling
kinetics are usually assumed and thus the Tafel behavior of the curve
is only apparent. In region (II), the current density decreases from
jmax to jmin due to the formation of a CuCl lm [30]. In region (III), the
potential increases again before to stabilize when it reaches a limiting
current density. The dissolution of the lm and/or metal is then
controlled by the diffusion of CuCl2 [31].
The presence of olive leaf extract results in a marked shift of the ca-
thodic branch of the polarization curve towards smaller current density
values, and to a lesser extent, of the anodic branch. This effect is in-
creased when the inhibitor concentration is increased and reaches a
maximum for the largest considered concentration C1. As a result, the
corrosion potentials shifted to more negative values in presence of
olive leaf extract, which conrms that this extract has a stronger inu-
ence on oxygen cathodic reduction than on copper oxidation reaction.
The Ecorr values measured for the blank, C3, C2 and C1 solutions are
Fig. 2. Polarization curves of copper obtained after 24 h in 0.5 M NaCl solution in the
absence (blank) and presence of different concentrations (C1C3) of olive leaf extract at
RT (~25 C).
56 C. Rahal et al. / Journal of Electroanalytical Chemistry 769 (2016) 5361
respectively equal to 210, 222, 278 and 295 mV/SCE. So the
Ecorr shift reaches 85 mV for the highest concentration (C1), a value
sufciently high to classify the olive leaf extract as a cathodic inhibitor
rather than a mixed inhibitor [32].
The benecial effect of the inhibitor on the substrate is also
illustrated by the shape of the curves in region (III). For the two largest
concentrations C1 and C2, the current density remains stable at j = jmin
when E increases. The adsorption of the inhibitor more likely hinders
the formation of the CuCl 2 adsorbed species (reaction 3) preventing
the dissolution of the CuCl lm and/or favoring its formation.
3.2.2. Voltammetry around OCP (E = 70 mV)
The polarization curves obtained after 24 h of immersion in the
various solutions on a limited potential range (E = 70 mV) were
computer tted as described in Section 2.5 to determine the corrosion
current density (jcorr), the corrosion rate (CR) and the inhibition ef-
ciency (). Fig. 3 shows as an example the experimental polarization
curve of copper obtained after 24 h in 0.5 M NaCl solution and the com-
puted curve.
The inhibition efciency () is then calculated according to the
following equation:
j0 corr jcorr
%  100
j0 corr
where j0corr and jcorr are the corrosion current densities in the absence
and presence of inhibitor, respectively.
The values obtained for the various determined parameters are
given in Table 1. First of all, it appears clearly that the corrosion rate de-
creases strongly with the increasing olive leaf extract concentration,
which denitively conrms that this extract contains at least one spe-
cies acting as a corrosion inhibitor, i.e. more likely oleuropein (OLE).
The inhibition efciency reaches 86 5% for the highest concentra-
tion considered here.
The anodic Tafel coefcient a is approximately constant around an
average value of 59 15 V1. This value corresponds to a Tafel slope
ba equal to 0.041 0.009 V decade 1, in agreement with the values
found for copper static electrodes in aerated neutral 3.03.5% g L 1
NaCl solutions that range between 0.045 and 0.060 V decade 1 [2].
The cathodic Tafel coefcient c was determined at 26 5 V 1 in
the blank solution but it decreases from 18 5 V1 to 33
2 V1 with the increase of the olive leaf extract concentration, which
may be related to the fact that the inhibitor mainly inuences the ca-
thodic reaction. It is also interesting to note that the curves obtained
in the blank solution and with the smallest inhibitor concentration C3
Fig. 3. Experimental polarization curve around OCP of copper obtained after 24 h in 0.5 M
NaCl solution (blank) and computed curve.
Table 1
Electrochemical kinetic parameters and inhibition efciency obtained from potentiody-
namic polarization curves (E = 70 mV, see Fig. 3) at RT (~25 C).
Solution jcorr a c jlim CR
(A cm2) (V1) (V1) (A cm2) (mm year1) (%)
Blank 4.3 1.3 38 13 26 5 a 0.05 1.3
C3 1.5 0.3 70 2 18 5 0.017 0.3 59 6
C2 1.8 0.3 65 14 24 7 6.1 0.02 0.3 60 8
C1 0.6 0.2 47 2 33 2 2.9 0.7 0.007 0.2 86 5
a
Four experiments were performed. In only 1 case the curve had to be tted with ca-
thodic reaction under mixed control. The obtained jlim value was 28 A cm2.
could be tted in most cases with activation controlled cathodic
reaction (i.e. using Eq.4). In contrast, O2 reduction was under mixed
activationdiffusion control for the larger C2 and C1 concentrations
and Eq.3 had to be used. Moreover, it appears that the limiting cathodic
current jlim decreases (in absolute value) when the inhibitor concentra-
tion increases. This clearly shows that the inhibitor hinders oxygen
reduction, i.e. decreases the cathodic reaction rate.
Looking back to the polarization curves acquired on a large range of
potential (Fig. 2), it can be seen that O2 reduction is completely con-
trolled by diffusion in any solution (even in blank) for the more cathodic
potentials (around 0.5 V/SCE). In contrast, the computer tting of the
8
polarization curves acquired around OCP showed that the kinetic of ox-
ygen reduction was whether partially controlled by diffusion or mainly
controlled by charge transfer but was never totally controlled by diffu-
sion (in this last case jcorr = jlim). However, one must recall that the re-
sults obtained by voltammetry around OCP relate to the kinetics at OCP,
which are those of main interest. The kinetic of the cathodic reaction
may be partially controlled by charge transfer at OCP and totally con-
trolled by diffusion at more cathodic potentials. Actually, in the case of
a mixed activationdiffusion control, the limiting effects of diffusion
are increasing when the potential decreases, until jlim is nally reached
for strongly cathodic potentials. So the observation of a plateau (j = jlim)
at 0.5 V/SCE does not necessarily means that the kinetic is mainly
controlled by diffusion at OCP (i.e. 0.2 V/SCE); it may be partially
controlled by charge transfer. This gives another example of the
relevance of voltammetry around OCP.
Some computer ttings of the polarization curves obtained in the
blank required the use of a mixed activationdiffusion controlled kinetic
for oxygen reduction while others were achieved using Tafel's law for
the cathodic process. It is probable that the impact of diffusion was
too small to be detected by voltammetry around OCP while EIS revealed
the diffusional process. The method may not be sufciently accurate in
some cases.
3.2.3. Electrochemical impedance spectroscopy (EIS)
Fig. 4 shows the Nyquist diagrams obtained after 24 h of immersion
in 0.5 M NaCl solution without and with various concentrations of olive
leaf extract at 25 C. The Nyquist diagrams obtained without inhibitor
(blank) and with the small inhibitor concentration C3 shows a
depressed semicircle in the high frequency region. This high frequency
semicircle is mainly due to the charge transfer and double-layer
capacitance [33]. For concentrations C2 and C1, and more particularly
for C1, the shape of the diagram in the high frequency region differs
and appears to involve two overlapping semi-circles. The second
semi-circle may correspond to the lm of corrosion products. For con-
centration C3, a slight inductive behavior is observed at low frequency.
It could be linked to a non-stationarity of the system. However, the
evolution of OCP was followed with time (results not shown) and it
was observed that in any case, the OCP was stable after less than
15 min. So even after 1 h it seems that the system has reached stationary
conditions. Consequently, such a behavior may rather be due to adsorp-
tion phenomena and thus may point out the adsorption of the inhibitor
on the copper surface. This inductive behavior was neglected, i.e. the
data corresponding to the lowest frequencies of this peculiar impedance
 C. Rahal et al. / Journal of Electroanalytical Chemistry 769 (2016) 5361
Fig. 4. Nyquist plots for copper electrode immersion in 0.5 M HCl solutions without
(blank) and with various concentrations (C1C3) of olive leaf extract at RT (~25 C) for
24 h.
diagram were excluded for the modeling. Actually it is masked by a
stronger effect at the higher concentrations C1 and C2. For these two
concentrations and for the blank as well, the curves deviate from their
semicircular shape at low frequency, which may be related to a
diffusion phenomenon, more likely that of dissolved O2. From the
analysis of the potentiodynamic polarization curves obtained with
E = 70 mV, it was deduced that O2 reduction was under mixed ac-
tivationdiffusion control for the larger C1 and C2 concentrations and
mainly under activation control at concentration C3. The EIS results
are therefore clearly consistent with those given by voltammetry. In
the case of the blank solution, both situations were met and the Nyquist
plot shown here corresponds to a case where the cathodic reaction was
partially controlled by diffusion.
Finally, it is clearly visible that the diameter of the curve grows with
increasing olive leaf extract concentration. This indicates that the corro-
sion rate decreases due to the inhibitor in agreement with voltammetry
experiments.
Fig. 5. Equivalent circuits used to t the EIS experimental data.
57
In accordance with this preliminary description of the EIS results, the
analysis of impedance data were performed with the various equivalent
circuits presented in Fig. 5. These models were used in various studies to
describe the behavior of copper or copper alloys in chloride containing
solutions, with or without adsorption inhibitors [30,3336]. That of
Fig. 5a proved suitable for the Nyquist plot of copper in the blank solu-
tion. In this model, Rs is the solution resistance, Rct is the charge transfer
resistance, Q dl corresponds to the capacitance of the double layer and W
is the Warburg impedance related to the diffusion processes in the low
frequency region. This shows that the contribution of the lm of corro-
sion products formed on the metal surface is negligible. In contrast, the
equivalent circuits used for copper in solutions containing olive leaf
extract include a contribution of the lm of corrosion products via the
resistance Rf and the element Qf (Figs. 5b and c). Actually, Q dl and Qf
represent constant phase elements (CPE) used in place of capacitors to
compensate for deviations from ideal dielectric behavior. These
deviations arise from the inhomogeneous nature of the electrode due
to surface roughness, inhibitor adsorption, porous layer formation, etc.
that leads to a distribution of time constants on the electrode surface.
The equivalent circuit of Fig. 5b does not include Warburg impedance
and was used for concentration C3. The equivalent circuit of Fig. 5c in-
cludes Warburg impedance and was used for concentrations C2 and
C1. A typical example of the results given by the computer ttings is
presented in Fig. 6. The model shows a good agreement with the
experimental results for both Nyquist and Bode plots.
The values obtained after the computer tting of the Nyquist
diagrams are listed in Table 2. The parameters n1 and n2, associated
with Q f and Q dl respectively, are fractional parameters describing the
departure of the electrode from an ideal surface: for n = 1 the CPE
describes an ideal capacitor. The inhibition efciency was computed
according to:
Rp R0p
%  100 9
Rp
where R0p and Rp are total polarization resistance of copper in the
solution in the absence and presence of inhibitor, respectively. In each
case, Rp is the sum of Rf and Rct.
Fig. 6. Experimental Bode and Nyquist plots and their mathematical tting: Example of
copper in 0.5 M NaCl solution with inhibitor concentration C2 after 24 h at room
temperature. Circles and squares (phase): experimental curves, lines: computed curves.
58 C. Rahal et al. / Journal of Electroanalytical Chemistry 769 (2016) 5361
Table 2
Electrochemical impedance parameters for copper electrodes after 24 h in 0.5 M NaCl solutions with or without olive leaf extract at RT (~25 C).
Solution
Blank
Rs ( cm2) 8.5 3
Rct ( cm2) 2500 800
Qdl 103 (1 cm2 sn1) 0.15 0.12
n1 0.74 0.07
Rf ( cm2)
Qf 106 (1 cm2 sn2)
n2
W (1 cm2 s0.5) 216 18
% 47 2
As it was already visible from the Nyquist plots, Rct increases with
the inhibitor concentration from 2500 to 22,000 cm2. The resistance
Rf of the lm of corrosion products also increases with the inhibitor con-
centration up to 3000 cm2, which explains why the shape of the
curves changes with the inhibitor concentration. However, the increase
of Rp is mainly due to the increase of Rct with the inhibitor concentra-
tion. The inhibitor, by adsorbing on the metal surface, blocks the cathod-
ic sites so that only the small proportion of the surface not covered by
the inhibitor remains active. Schematically, if only 10% of the surface is
not blocked, then Icorr is divided by 10. The current density is still
expressed using the overall surface S, and therefore jcorr (and also jlim)
is then also divided by 10. In contrast Rct, expressed in cm2, is
multiplied by 10: Rct = Rmes ct S = 10 (Rmes
ct S / 10), where Rmes
ct is
the measured charge-transfer resistance in , and Rmes ct S / 10 is in
rst approximate equal to the Rct value measured without inhibitor,
i.e. describes the behavior of the metal surface not covered by the inhib-
itor. As shown by the increase of Rf, the inhibitor also adsorbs on the lm
of corrosion products, favoring its stability and increasing its protective
ability. This result is consistent with what was observed on the polariza-
tion curves acquired in a large potential range (Fig. 2): the adsorption of
the inhibitor on the CuCl lm limits its dissolution at strongly anodic po-
tentials. So, even if the 90% efciency of olive leaf extract is mainly due
to the adsorption of organic molecules directly on the metal surface
there is also a slight contribution (i.e. Rf / (Rf + Rct) = 12% of the
inhibiting effect) coming from the adsorption of the molecules on corro-
sion products that have formed on parts of the metal not protected by
the inhibitor.
Finally, it can be seen that the values of determined from EIS spec-
tra (Table 2) are very similar to those determined from the mathemat-
ical modeling of the potentiodynamic polarization curves recorded
around OCP (Table 1).
3.3. Effect of immersion time
3.3.1. Voltammetry around OCP (E = 70 mV)
Fig. 7 shows the potentiodynamic polarization curves of copper in
0.5 M NaCl solution without and with olive leaf extract obtained after
(a) 1 h, (b) 6 h and (c) 24 h of immersion. Only the larger inhibitor
concentration C1 was considered here. The kinetic parameters were ob-
tained from these curves as explained in Section 3.2.2 by computer
tting of the curves using Eq.(6) or Eq.(7). They are gathered in
Table 3. It can be seen that in any case the corrosion current density of
copper in the presence of olive leaf extract is lower than that of the
copper electrode in NaCl solution. More precisely, the values of are
all higher than 70%. The value of (86 5%) reached after 24 h of
immersion is higher than the others. The anodic coefcient a is not
changed by the inhibitor, which indicates that the mechanism of the
anodic process is not modied. Actually, it is also clear from the curves
of Fig. 7 that only the cathodic reaction is inhibited. This once again con-
rms that the inhibitor behaves as a barrier hindering the access of O2 to
the cathodic sites of the copper surface.
C3 C2 C1
7.607 0.011 83 61
4465 100 6250 1000 22,000 5000
0.09 0.01 0.09 0.03 0.07 0.01
0.73 0.02 0.73 0.03 0.55 0.01
275 125 1150 200 3000 500
39 5 23 3 13.5 2.5
0.89 0.01 0.87 0.01 0.90 0.02
378 100 334 100
65 4 90 4
The curves obtained in the blank solution for this series of
experiment were tted in any case with O2 reduction under mixed
activationdiffusion control. It can however be seen in Table 3 that the
values computed for jlim are signicantly higher (in absolute value)
than those determined with inhibitor concentration C1, e.g.
19 A cm2 vs. 5.1 A cm 2 after 1 h. Actually, the inhibition
efciency could also be computed using |jlim | instead of jcorr in Eq.(8).
The values of are then 73 10%, 62 10% and 90 4%, i.e. values
similar to those computed from jcorr. This shows once again that the
inhibitor inuences the rate of O2 reduction.
Note nally that all the experiments were performed once again, but
with voltammetry around OCP applied only at the end of the 24 h of im-
mersion. The results obtained proved consistent with those of the main
series of experiments, where voltammetry around OCP was applied
after 1 h, 6 h and 24 h. This shows that the method did not lead to
signicant changes of the electrode surface; it can then be used as a
non-destructive technique to follow the evolution of a system over time.
3.3.2. Electrochemical impedance spectroscopy
Fig. 8 shows the Nyquist plots obtained for copper in 0.5 M NaCl so-
lution without (a) and with (b) inhibitor concentration C1 at different
immersion times (1, 6 and 24 h). In both solutions, the shape of the
Nyquist diagram does not change with increasing time. Only its diame-
ter varies. Actually, it clearly increases with time in the presence of the
inhibitor. In contrast, there is no clear trend in the blank solution. As
already noted in Section 3.2, the impedance diagrams of copper in the
blank solution show only one capacitive attened loop at high
frequency. This loop relates to the charge-transfer process of copper dis-
solution occurring at the metal/electrolyte interface. The growing lm
of corrosion products has not a signicant inuence on the corrosion
process for such small immersion times. In contrast, the Nyquist dia-
grams obtained with inhibitor concentration C1 clearly reveal the pres-
ence of two overlapping capacitive loops, one corresponding to charge
transfer, the other to the contribution of the lm formed on the surface.
Another time constant appears in the low-frequency region related to
mass transport, i.e. more likely O2 diffusion. SIE indicates that the pro-
cess is partially controlled by diffusion in both solutions, in agreement
with the results given by voltammetry for this series of experiments.
The impedance data could be modeled using equivalent circuits 5a
for the blank solution and 5c for inhibitor concentration C1 (see
Fig. 5). The determined values of the various parameters are given in
Table 4. It can be noted rst that the Rct value obtained for the blank so-
lution does not vary signicantly over time (taking into account the dis-
persion of the measurements). This is consistent with the assumption
that the lm of corrosion products does not inuence the corrosion pro-
cess, i.e. that it has a poor protective ability. In agreement, the corrosion
rate determined by voltammetry around OCP (Table 3) remains approx-
imately constant. In contrast, Rct clearly increases over time for the
inhibitor concentration C1. Note that Qdl decreases while Rct increases.
Moreover, Rf also increases, which shows that both benecial effects
 C. Rahal et al. / Journal of Electroanalytical Chemistry 769 (2016) 5361 59

Table 3
Electrochemical kinetic parameters and inhibition efciency at RT (~25 C) obtained from
potentiodynamic polarization curves (E = 70 mV) for concentration C1 compared to
those obtained without inhibitor (blank) at different times.

Solution Ecorr jcorr a c jlim

(h) (mV) (A cm2) (V1) (V1) (A cm2) (%)

Immersion time = 1 h
Blank 245 35 3.4 0.6 50 10 28 8 19
C1 238 6 0.85 0.15 65 2 48 8 5.1 1.3 75 4

Immersion time = 6 h
Blank 221 25 3.35 0.55 75 5 35 5 9.3 1.7
C1 233 15 0.9 0.3 64 3 52 18 3.5 0.3 73 9

Immersion time = 24 h
Blank 263 50 4.3 1.3 38 13 26 5 28
C1 258 8 0.6 0.2 47 2 33 2 2.9 0.7 86 5

was still moderate, which explains why the organic molecules nally
adsorb on this lm.

3.4. Effect of temperature

The effect of temperature on the inhibition efciency was investigat-

ed by voltammetry around OCP (E = 70 mV) in the temperature
range 298328 K. The results obtained in 0.5 M NaCl solution with
inhibitor concentration C1 are shown in Fig. 9. The kinetic parameters
determined by computer tting are listed in Table 5.
It can be noted rst that, once again, the cathodic reaction could only
be modeled by the kinetic law corresponding to a mixed activation

Fig. 7. Polarization curves around OCP of copper in 0.5 M NaCl solution without inhibitor
(blank) or with the largest inhibitor concentration in C1 at different times: (a) 1 h; (b) 6 h
and (c) 24 h.

of the inhibitor increase over time. Accordingly, the highest inhibition

efciency is observed after 24 h.
In conclusion, the inhibition efciency increases with time and is
only around 6070% at the beginning of the corrosion process (at least
during 6 h). It reaches 90% only after a longer immersion time (but be-
fore 24 h). This is in fact consistent with the observed effect of the inhib-
Fig. 8. Nyquist plots for copper at different times (a) in 0.5 M NaCl solution without
itor on the corrosion products. The lm of corrosion product was mainly inhibitor (blank) at different times and (b) in 0.5 M NaCl solution with inhibitor
formed on some parts of the steel surface while the inhibition efciency concentration C1, at RT (~25 C).
60 C. Rahal et al. / Journal of Electroanalytical Chemistry 769 (2016) 5361

Table 4
Electrochemical impedance parameters at RT (~25 C) obtained for concentration C1 after various times compared to those obtained without inhibitor.

Time Rs Rct Qdl 103 n1 Rf Qf 106 n2 W

(h) ( cm2) ( cm2) (1 cm2 sn1) ( cm2) (1 cm2 sn2) (1 cm2 s0.5) (%)

Blank
1 6.9 0.3 2600 600 0.12 0.05 0.61 0.05 478 47
6 9.5 3.5 3300 300 0.27 0.13 0.60 0.05 230 80
24 8.5 3 2500 800 0.15 0.12 0.74 0.07 216 18

With inhibitor concentration C1

1 8.4 0.2 8940 30 0.14 0.02 0.6 1 1000 500 16 4 0.88 0.02 434 50 73 2
6 7.8 1.2 13,300 2400 0.11 0.02 0.53 0.03 650 500 9.7 3 0.94 0.03 110 50 72 8
24 61 22,000 5000 0.07 0.01 0.55 0.01 3000 500 13.5 2.5 0.90 0.02 334 100 90 4

diffusion control. Secondly, it can be seen from Fig. 9 that increasing the
temperature increased the current density of the potentiodynamic po-
larization curves. This is more clearly illustrated in Table 5 by the
variations of jcorr with temperature. Similarly, the limiting current jlim
increases (in absolute value) signicantly with temperature, from
2.9 A cm2 at 298 K to 127 A cm2 at 328 K. This is due to the
fact that diffusion is a thermally activated process with a higher effect
on the reaction rate than the decrease of O2 concentration linked to
the increase of temperature.
The dependence of the corrosion rate on temperature can be
expressed by the Arrhenius equation:


Ea
jcorr A exp
RT
where jcorr is the corrosion current density, A is the frequency factor, Ea
is the activation energy of the copper corrosion reaction, T is the
absolute temperature and R the universal gas constant
(8.314 J mol 1 K 1). The obtained Arrhenius plot Ln jcorr vs. 1/T is
given in Fig. 10. It is compared to that of copper in 0.5 M NaCl solution
without inhibitor, drawn using the Ea value of 17.9 kJ mol1 given in
previous work [37] and the corrosion current density obtained at
25 C in our experimental conditions (i.e. 4.3 A cm2, see Table 1).
The experimental curve obtained with the olive leaf extract corresponds
approximately to a straight line and the Ea value can be determined
from the slope of this line. The tting of this curve with a straight line
gave a value of 47 6 kJ mol 1 for the activation energy Ea of the
corrosion process with inhibitor.
This value is signicantly higher than that of 17.9 kJ mol1 obtained
previously for copper without inhibitor (and used for drawing the
corresponding line in Fig. 9) [37], which explains why the variations
of jcorr are more pronounced in the presence of the inhibitor. This effect
can be quantied by computing the inhibition efciency at each
temperature. The results, given in Table 5, show that decreases
when the temperature increases, from 86% at 298 K to 63% at 328 K.
An increase of the corrosion activation energy in the presence of inhib-
itor, associated with a decrease in inhibition efciency with increasing
temperature, is frequently interpreted as due to the formation of an ad-
sorption lm of physical nature, i.e. involving electrostatic interactions
with the metal surface [36,38]. Conversely, a chemisorption mechanism
corresponds to an increase in inhibition efciency with temperature
and a lower activation energy in the presence of the inhibitor [3940].
Our results suggest a predominant physisorption of the inhibiting
species. Actually, it has been proposed that physisorbed molecules are
bound to the metal at cathodic sites and mainly inhibit the corrosion
11
process by hindering the cathodic reaction. This is consistent with the
voltammetry analysis that shows that the decrease of the corrosion
current density was mainly due to a decrease of the cathodic reaction
rate (see Figs. 2 and 7).
4. Conclusions
The olive leaf extract was found to be an effective green inhibitor of
copper in 0.5 M NaCl. The inhibition efciency was found to increase
with time during the 24 h experiments performed in this study, and
reached 90% for the largest considered inhibitor concentration. Experi-
ments over longer times are to be performed to specify if the efciency
can further increase. Two electrochemical methods were used, EIS and
voltammetry around OCP (E = 70 mV). In this last case, the
polarization curves were computer tted using various kinetic laws
for the cathodic reaction, which provided information on the inhibition
process. Both methods led to consistent results, for instance the values
of = 90 4% (EIS) and 86 5% (voltammetry) after 24 h for the
largest inhibitor concentration considered in this study. From an applied
point of view, this means that could be increased using a larger
inhibitor concentration.
The inhibiting species present in the olive leaf extract act as a
cathodic inhibitor adsorbed on the metal surface. The decrease of the
inhibition efciency with the temperature and the value obtained for
the apparent activation energy of the corrosion process indicate a
predominant physisorption mechanism. Such type of inhibitors is
efcient at ambient temperature, but is characterized by a loss in
inhibition efciency at elevated temperatures.

Table 5
Electrochemical kinetic parameters and inhibition efciency obtained from potentiody-
namic polarization curves (E = 70 mV) for concentration C1 at different temperatures.

T Ecorr jcorr a c jlim

(K) (mV) (A cm2) (V1) (V1) (A cm2) (%)

298 258 0.6 47 33 2.9 86

308 234 1 75 42 6 82
318 286 2.4 34 41 14 65
Fig. 9. Effect of temperature on the polarization curves around OCP of copper in 0.5 M NaCl
328 344 3.1 20 21 127 63
solutions with inhibitor concentration C1, after 24 h.
 C. Rahal et al. / Journal of Electroanalytical Chemistry 769 (2016) 5361
Fig. 10. Ln jcorr vs. 1/T plot used to calculate the Arrhenius slopes for copper in 0.5 M NaCl
solution with inhibitor concentration C1, compared with that computed from [38] for
copper in 0.5 M NaCl solution without inhibitor (blank).
The inhibiting effect is due to the adsorption of the various phenolic
compounds, present in the olive leaf extract onto the copper surface.
HPLC analysis showed that oleuropein was the most abundant of
these compounds in the leaf extract and thus more likely the main
inhibiting species. Additional work is however required to detail the
mechanisms of the inhibition process and the role of various substances
present in the olive leaf extract.
References
[1] H. Otmacic Curkovic, E.S. Lisac, H. Takenouti, The inuence of pH value on the
efciency of imidazole based corrosion inhibitors of copper, Corros. Sci. 52 (2010)
398405.
[2] R.F.V. Villamil, P. Corio, J.C. Rubim, S.M.L. Agostinho, Sodium dodecylsulfate/benzo-
triazole synergistic effect as an inhibitor of processes on copper/chloridric acid
interfaces, J. Electroanal. Chem. 535 (2002) 7583.
[3] D.Q. Zhang, L.X. Gao, G.D. Zhou, Inhibition of copper corrosion by bis-(1-
benzotriazolymethylene)-(2,5-thiadiazoly)-disulde in chloride media, Appl. Surf.
Sci. 225 (2004) 287293.
[4] B. Duran, G. Bereket, Cyclic voltammetric synthesis of poly(N-methylpyrrole) on
copper and effects of polymerization parameters on corrosion performance, Ind.
Eng. Chem. Res. 51 (2012) 52465255.
[5] M. Scendo, D. Poddebniak, J. Malyszko, Indole and 5-chloroindole as inhibitors of
anodic dissolution and cathodic deposition of copper in acidic solutions, J. Appl.
Electrochem. 33 (2003) 287293.
[6] S. Kuma, T.S. Narayanan, M.S. Kumar, A. Manimaran, Dezincication of brass in
sulde polluted sodium chloride medium: evaluation of the effectiveness of 2-
mercaptobenzothiazole, Int. J. Electrochem. Sci. 1 (2006) 456469.
[7] Guo-Ding Zhou, Hua Shao, B.H. Loo, A study of the copper electrode behavior in
borax buffer solutions containing chloride ions and benzotriazole-type inhibitors
by voltammetry and the photocurrent response method, J. Electroanal. Chem. 421
(1997) 129135.
[8] H. Ma, S. Chen, L. Niu, S. Zhao, S. Li, D. Li, Inhibition of copper corrosion by several
Schiff bases in aerated halide solutions, J. Appl. Electrochem. 32 (2002) 6572.
[9] C. Rahal, M. Masmoudi, M. Abdelmouleh, R. Abdelhedi, An environmentally friendly
lm formed on copper: characterization and corrosion protection, Prog. Org. Coat.
78 (2015) 9095.
[10] A.Y. El-Etre, Natural honey as corrosion inhibitor for metals and alloys. I. Copper in
neutral aqueous solution, Corros. Sci. 40 (1998) 18451850.
[11] M.K. Awad, Eco friendly corrosion inhibitors: inhibitive action of quinine for
corrosion of low carbon steel in 1 M HCl, J. Appl. Electrochem. 36 (2006)
11631168.
[12] K. Krishnaveni, J. Ravichandran, Inuence of aqueous extract of leaves of Morinda
tinctoria on copper corrosion in HCl medium, J. Electroanal. Chem. 735 (2014)
2431.
61
[13] A. Bouyanzer, B. Hammouti, L. Majidi, Pennyroyal oil from Mentha pulegium as
corrosion inhibitor for steel in 1 M HCl, Mater. Lett. 60 (2006) 28402843.
[14] M. Benabdellah, M. Benkaddour, B. Hammouti, M. Bendahhou, A. Aouniti, Inhibition
of steel corrosion in 2 M H3PO4 by artemisia oil, Appl. Surf. Sci. 252 (2006)
62126217.
[15] E. Chaieb, A. Bouyanzer, B. Hammouti, M. Benkaddour, Inhibition of the corrosion of
steel in 1 M HCl by eugenol derivatives, Appl. Surf. Sci. 246 (2005) 199206.
[16] B. Mller, Inhibition of the corrosion of steel in 1 M HCl by eugenol derivatives,
Corros. Sci. 44 (2002) 15831591.
[17] Y. Li, P. Zhao, Q. Liang, B. Hou, Berberine as a natural source inhibitor for mild steel in
1 M H2SO4, Appl. Surf. Sci. 252 (2005) 12451253.
[18] A.Y. El-Etre, M. Abdallah, Z.E. El-Tantawy, Corrosion inhibition of some metals using
lawsonia extract, Corros. Sci. 47 (2005) 385395.
[19] A.Y. El-Etre, Inhibition of aluminum corrosion using Opuntia extract, Corros. Sci. 45
(2003) 24852495.
[20] A.Y. El-Etre, M. Abdallah, Natural honey as corrosion inhibitor for metals and alloys.
II. C-steel in high saline water, Corros. Sci. 42 (2000) 731738.
[21] Sh. Shen, X.Y. Guo, P. Song, Y.C. Pan, H.Q. Wang, Y. Wen, H.F. Yang, Phytic acid
adsorption on the copper surface: observation of electrochemistry and Raman
spectroscopy, Appl. Surf. Sci. 276 (2013) 167173.
[22] M.N. El-Haddad, Chitosan as a green inhibitor for copper corrosion in acidic
medium, Int. J. Biol. Macromol. 55 (2013) 142149.
[23] J. Tabera, A. Guinda, A. Ruiz-Rodriguez, F.J. Senorans, E. Ibanez, Countercurrent
supercritical uid extraction and fractionation of high-added-value compounds
from a hexane extract of olive leaves, J. Agric. Food Chem. 52 (2004) 47744779.
[24] R. Briante, M. Patumi, S. Terenziani, E. Bismuto, F. Febbraio, Olea europaea L. leaf ex-
tract and derivatives: antioxidant properties, J. Agric. Food Chem. 50 (2002)
49344940.
[25] M. Bouaziz, R.J. Grayer, M.S.J. Simmonds, M. Damak, S. Sayadi, Identication and
antioxidant potential of avonoids and low molecular weight phenols in olive
cultivar chemlali growing in Tunisia, J. Agric. Food Chem. 53 (2005) 236241.
[26] D. Nguyen Dang, L. Lanarde, M. Jeannin, R. Sabot, Ph. Refait, Inuence of soil
moisture on the residual corrosion rates of buried carbon steel structures under
cathodic protection, Electrochim. Acta 176 (2015) 14101419.
[27] R. Briante, F. La Care, F. Febbraio, M. Patumi, R. Nucci, Bioactive derivatives from
oleuropein by a biotransformation on Olea europaea leaf extracts, J. Biotechnol. 93
(2002) 109119.
[28] S. Lee-Huang, L. Zhang, P.L. Huang, Y. Tae Chang, L.H. Paul, Anti-HIV activity of olive
leaf extract (OLE) and modulation of host cell gene expression by HIV1 infection
and OLE treatment, J. Biophys. Res. Commun. 307 (2003) 10291037.
[29] M. Bouaziz, S. Sayadi, Isolation and evaluation of antioxidants from leaves of a
Tunisian cultivar olive tree, Eur. J. Lipid Sci. Technol. 107 (2005) 497504.
[30] G. Kear, B.D. Barker, F.C. Walsh, Electrochemical corrosion of unalloyed copper in
chloride media a critical review, Corros. Sci. 46 (2004) 109135.
[31] C. Deslouis, B. Tribollet, G. Mengoli, M. Musiani, Electrochemical behavior of copper
in neutral aerated chloride solution. I. Steady-state investigation, J. Appl.
Electrochem. 18 (1988) 374383.
[32] W.H. Li, Q. He, S.T. Zhang, C.L. Pei, B.R. Hou, Some new triazole derivatives as
inhibitors for mild steel corrosion in acidic medium, J. Appl. Electrochem. 38
(2008) 289295.
[33] H. Hassaira, L. Bousselmi, S. Khosrof, E. Triki, Evaluation of the inhibitive effect of
benzotriazole on archeological bronze in acidic medium, Appl. Phys. 113 (2013)
923931.
[34] S. Hong, W. Chen, H.Q. Luo, N. Bing Li, Investigation of the inhibition effect of
trithiocyanuric acid on corrosion of copper in 3.0 wt.% NaCl, Corros. Sci. 66 (2013)
308314.
[35] K.F. Khaled, Experimental and atomistic simulation studies of corrosion inhibition of
copper by a new benzotriazole derivative in acid medium, Electrochim. Acta 54
(2009) 43454352.
[36] F. Caprioli, A. Martinelli, V. Di Castro, F. Decker, Effect of various terminal groups on
long-term protective properties of aromatic SAMs on copper in acidic environment,
J. Electroanal. Chem. 693 (2013) 8694.
[37] S. Hong, W. Chen, H.Q. Lao, N.B. Li, Inhibition effect of 4-amino-antipyrine on the
corrosion of copper in 3 wt.% NaCl solution, Corros. Sci. 57 (2012) 270278.
[38] A. Popova, E. Sokolova, S. Raicheva, M. Christov, AC and DC study of the temperature
effect on mild steel corrosion in acid media in the presence of benzimidazole
derivatives, Corros. Sci. 45 (2003) 3358.
[39] E.E. Oguzie, Evaluation of the inhibitive effect of some plant extracts on the acid
corrosion of mild steel, Corros. Sci. 50 (2008) 29932998.
[40] E.E. Oguzie, G.N. Onuoha, A.L. Onuchukwu, Inhibitory mechanism of mild steel
corrosion in 2 M sulphuric acid solution by methylene blue dye, Mater. Chem.
Phys. 89 (2005) 305311.