Corrosion Science 80 (2014) 442452

Contents lists available at ScienceDirect

Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Inhibitive properties of 2,5-bis(n-methylphenyl)-1,3,4-oxadiazole

and biocide on corrosion, biocorrosion and scaling controls of brass
in simulated cooling water
A. Rochdi a, O. Kassou a, N. Dkhireche a, R. Touir a,e, M. El Bakri a, M. Ebn Touhami a,, M. Sfaira c,
B. Mernari b, B. Hammouti d
a

Laboratoire des Matriaux, dElectrochimie et dEnvironnement, Facult des Sciences, Universit Ibn Tofal, Kenitra, Morocco
Laboratoire de Coordination et de Chimie Analytique, Universit Chouaib Doukkali, Facult des Sciences, El Jadida, Morocco
c
Laboratoire dIngnierie des Matriaux, de Modlisation et dEnvironnement, LIMME, Facult des Sciences Dhar El Mahraz, Universit Sidi Mohammed Ben Abdellah, Morocco
d
LCAE-URAC18, Faculty of Sciences, Mohammed the 1st University, BP 717 60000 Oujda, Morocco
e
Centre Rgional des Mtiers de lEducation et de Formation (CRMEF), Avenue Allal Al Fassi, Madinat Al Irfane, BP : 6210 Rabat, Morocco
b

a r t i c l e

i n f o

Article history:
Received 19 July 2013
Accepted 30 November 2013
Available online 12 December 2013
Keywords:
A. Brass
B. EIS
B. Biocide
C. corrosion inhibition
C. alkaline corrosion
C. Microbiological corrosion

a b s t r a c t
2,5-Bis(n-methylphenyl)-1,3,4-oxadiazole with (n = 2,3,4), denoted n-MPOX, have been investigated by
using potentiodynamic polarization (PP) and electrochemical impedance spectroscopy (EIS) methods,
to evaluate the electrochemical behavior of brass in simulated cooling water system. The PP study
revealed that oxadiazole inhibited both cathodic and anodic reactions, indicating a mixed type control
of inhibition. It was shown that, 3-MPOX as well as 4-MPOX, were the best inhibitors and the inhibition
efciency followed the sequence: 3-MPOX P 4-MPOX  2-MPOX. The interference between non-oxidizing biocide CTAB and 3-MPOX and 4-MPOX against corrosion and biocorrosion has also been studied.
2013 Elsevier Ltd. All rights reserved.

1. Introduction
Brasses are widely used in industry especially in heating cooling
systems because of their high thermal and electrical conductivities
[1,2]. However, as the zinc content of brass increases, the corrosion
rate of the alloy is observed to show a marked increase due to the
preferential dissolution of zinc from brass; such phenomenon is
termed as dezincication [3,4]. Recently many methods have been
developed aiming to reduce the rate of dezincication of brass
involving the use of some inhibitors; e.g., benzotriazole derivatives
[5,6] or development of novel brasses to resist dezincication [7].
Furthermore, the foremost problems in cooling systems are not
only corrosion but scaling or encrustation and biological fouling
phenomena as well. Since the rst involves deterioration of metallic surfaces by the aggressive medium, the second decreases thermal efciency exchange and can cause localized corrosion attack,
whereas the third leads to microbiologically inuenced corrosion
(MIC) called also biocorrosion. These processes, occurring simultaneously, greatly affect the normal industrial production and have
numerous economic impacts. Thus this issue has become a significant area of scientic and technological research.
Corresponding author. Tel.: +212 6 6158 63 00; fax: +212 5 37 32 94 33.
E-mail address: mebntouhami@yahoo.fr (M. Ebn Touhami).
0010-938X/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.corsci.2013.11.067

To overcome the above shortcomings, corrosion and scale inhibition of brasses constitute an important topic; i.e., in the presence
of an organic compound, the properties of an oxide protective layer
can be modied. Accordingly, the effectiveness of organic inhibitors, to prevent further metal dissolution, is related to the extent
to which they adsorb and cover the metal oxide surface. Many
azoles, as inhibitors, have been used to protect copper and brasses
against corrosion and encrustation. Indeed, triazole [811], triazole
phosphonate derivatives [12], tetrazole [13], and thiadiazole [14
16] gave good results in neutral media. The adsorption depends
on the structure of inhibitors, on the surface charge of the metal,
and on the type of the electrolyte. Moreover, data regarding the
use of N-heterocyclic compounds such as oxadiazole derivatives
are not so plentiful especially in neutral solution [17] when compared to the extensive studies in acidic media [1820].
On the other hand, literature reports pointed out that microorganisms tend to attach themselves onto surface, colonize, and proliferate to form a biolm. The biolm induces changes in the
electrochemical conditions at the metal/medium interface, and
thereby microorganisms can easily accelerate corrosion. The use
of quaternary ammonium compounds (surfactants) as non-oxidizing biocides has proven efcacy and performance in microbial control for various industrial applications [21]. The antimicrobial
effect is a function of the N-alkyl chain length, which conferred

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A. Rochdi et al. / Corrosion Science 80 (2014) 442452

lipophilicity [22]. Moreover, it is well known that the antimicrobial

activity involves an association between the positively charged
quaternary nitrogen of biocide and the negatively charged head
groups of acidic phospholipids in bacterial membranes [23]. These
biocides are effective at low concentration, stable, and fast-acting
in the inhibition of microbial growth and metabolism, aside being
capable from controlling biolm development.
To avoid corrosion, scale and bacterial fouling in the studied
corrosive medium whose composition represents the average concentration of salts presents in the water used in Moroccan cooling
water systems, many formulations with organic compounds,
including cetyltrimethylammonium bromide (CTAB) as non-oxidizing biocide (Table 1), have been developed in our laboratory.
For instance, sodium gluconate [24], monosaccharides [25],
TDMTAA [26], oxazoline [27], tetrazole [28] and phosphonate
[29,30].
In the present study, a comparative study was undertaken on
the inhibitive performance of 2,5-bis(n-methylphenyl)-1,3,4-oxadiazole (n = 2, 3, 4), denoted hereafter 2-MPOX, 3-MPOX, 4-MPOX,
respectively (Table 1). CTAB, with carbon chain of sixteen atoms,
was added to study the eventual interference effect on corrosion
process. The study was conducted by using potentiodynamic
polarization curves and electrochemical impedance spectroscopy
diagrams. Surface characterization studies were carried out to
establish the mechanism of corrosion inhibition of brass in the
corresponding aggressive medium.
2. Experimental procedure

thoroughly with distilled water, degreasing by acetone, and nally

drying with compressed air. After abrasion with emery paper,
traces of SiC on the surface did not signicantly inuence the corrosion tests. Ultrasonic bath removal of SiC traces did not alter the
experimental corrosion rate. A saturated calomel electrode (SCE)
was used as a reference whose standard potential is 241 mVHNE
at 25 C. All potentials were given with reference to this electrode.
The potential was corrected from the Ohmic drop due to the solution resistance by using the high-frequency limit of the electrode
impedance as electrolyte resistance Rs. The reference electrode
was located far enough from the disc electrode to avoid distortions
in potential and velocity distributions [31]. The counter electrode
was a platinum plate of large surface area. The electrodes were
carefully positioned in the cell for reproducible geometry. The simulated cooling water solution, abbreviated as (SCW-solution), with
an electrical conductivity of 1678 lS cm1 measured at 299 K, was
previously used [28] and its composition is displayed in Table 2.
This composition represents the average amount of various ions
presents in waters used in Moroccan cooling water systems. Deionized water was used to prepare solutions. 2,5-Bis(2-methylphenyl)-1,3,4-oxadiazole (2-MPOX) 2,5-bis(3-methylphenyl)-1,3,
4-oxadiazole (3-MPOX), and 2,5-bis(4-methylphenyl)-1,3,4-oxadiazole (4-MPOX) were used as corrosion and scale inhibitors. The
cetyltrimethylammonium bromide (CTAB) was added as corrosion
and biolm inhibitor. The biocide was evaluated using the minimal
inhibitory concentration technique [32,33]. All assessments were
carried out at temperature and pH of 32 1 C and 7.35 0.02,
respectively; normal characteristic operating conditions for the
studied system.

2.1. Electrochemical cell and materials

2.2. Electrochemical methods
The electrolysis cell was Pyrex of cylinder (solution volume of
about 0.3 L) closed by cap containing ve openings. Three of them
were used for the electrodes. The working electrode (WE) was
brass and had a chemical composition of 58Cu40Zn2Pb with
cross-section of 1.32 cm2 which only was in contact with the
aggressive medium. The lateral part was covered with cataphoretic
paint to prevent any inltration of electrolyte. The disc electrode
thus prepared was mounted onto a rotation support to form a
rotating disc electrode (RDE). The rotating electrode used was an
INF-EL-EDI 101 type. The rotational speed adjustment was made
with an independent electronic amplier of CTV 101 type. Before
each experiment, the WE was wet-abraded by successive emery
paper treatments from 400 up to no. 1200 grade until a smooth
and planar surface was obtained. This was followed by washing

The working electrode was immersed in the test solution during

30 min until a steady state open circuit potential (Eocp) was obtained. For this study, the rotation speed of the disc electrode
was 1000 rpm. The steady-state polarization curves were recorded
potentiodynamically using a VoltaLab PGZ 100 and controlled by a
personal computer. The cathodic polarization curve was recorded
by polarization from Eocp to negative direction under potentiodynamic conditions corresponding to 1 mV s1 (sweep rate) and
under air atmosphere. After this scan, the anodic polarization curve
was recorded by polarization from Eocp to positive direction under
the same conditions as said before. To evaluate corrosion kinetic
parameters, a tting by SternGeary equation was used. To do
so, the overall current density values, i, were considered as the

Table 1
Molecular structures, names and abbreviations of the studied oxadiazole compounds and biocide.
Inhibitor formula

Name

Abbreviation

2,5-Bis(2-methylphenyl)-1,3,4-oxadiazole

2-MPOX

2,5-Bis(3-methylphenyl)-1,3,4-oxadiazole

3-MPOX

2,5-Bis(4-methylphenyl)-1,3,4-oxadiazole

4-MPOX

Cetyltrimethylammonium bromide

CTAB

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A. Rochdi et al. / Corrosion Science 80 (2014) 442452

Table 2
Composition of the studied simulated cooling water, SCW-solution.
Salts

MgCl2, 6H2O

CaCl2, 2H2O

Ca(NO3)2, 6H2O

MgSO4, 7H2O

NaHCO3

Concentration (mM)

2.85

3.64

0.566

1.56

3.77

sum of two contributions, anodic and cathodic current ia and ic,

respectively. For the potential domain not too far from the open
circuit potential, it may be considered that both processes followed
the Tafel law [34]. Thus, it can be derived from Eq. (1):

1
2

where icorr is the corrosion current density (A cm ), ba and bc are

the Tafel constants of anodic and cathodic reactions (V1), respectively. These constants are linked to the Tafel slopes b (V/dec) in
usual logarithmic scale given by the following equation::

2.3. Scanning electron microscopy (SEM)

Examination of brass specimens after exposure into the SCWsolution, without and with mixture 1 after a hold time immersion
of two days, was carried out using scanning electron microscopy
(SEM; JOEL JSM-5500).

-2

10

-3

10

Blank solution
-4

410 M 2-MPOX
-4
810 M 2-MPOX
-4
1010 M 2-MPOX
-4
1210 M 2-MPOX

-4

The corrosion parameters were then evaluated by means of

nonlinear least square method by applying Eq. (1) using Origin
software. However, for this calculation, the potential range applied
was limited to 0.100 V around Ecorr, else a signicant systematic
divergence was sometimes observed for both anodic and cathodic
branches.
The electrochemical impedance spectroscopy measurements
were carried out using a transfer function analyzer (VoltaLab PGZ
100), with a small amplitude a.c. signal (10 mV rms), over a frequency domain from 100 kHz to 10 mHz with ve points per decade. The EIS diagrams were done in the Nyquist representation.
The results were then analyzed in terms of an equivalent electrical
circuit using Bouckamp program [35].

-1

10

10

-5

10

-1,0

-0,8

-0,6

-0,4

0,0

0,2

0,4

0,6

(b)

10

-1

10

-2

10

-3

10

Blank solution
-4

-4

10

-5

410 M 3-MPOX
-4
810 M 3-MPOX
-4
1010 M 3-MPOX
-4
1210 M 3-MPOX

10

-1,2

-1,0

-0,8

-0,6

3. Results and discussion

-0,4

-0,2

0,0

0,2

0,4

0,6

Potential, E / VSCE

3.1. Inhibitive effect of oxadiazole derivatives

(c)

Current density, i / mA cm -2

10

3.1.1. Potentiodynamic polarization, PP curves

Fig. 1 exemplies the potentiodynamic polarization (PP) curves
for brass, in SCW-solution, in the absence and presence of different
concentrations of n-MPOX (n = 2, 3, 4). The anodic current density
of brass in the presence of each inhibitor has been signicantly reduced with respect to that of the free solution. It is to be noted that,
in the presence of 2-MPOX, the decrease of the anodic branch remains concentration-independent. These results suggest that in
the presence of oxadiazole molecules, a protective lm gets adsorbed onto the brass substrate bafing the dissolution of brass
in anodic sites. On the other hand, similar results are registered
on the cathodic reactions since the cathodic current branches decrease at a xed potential. Indeed, the fact that the cathodic process slows down can be due to the covering of the surface with
oxadiazole monolayer which means that the oxygen diffusion is arrested with the barrier created at the brass/solution interface. So,
both anodic and cathodic processes are inhibited in the presence
of oxadiazole derivatives indicating that these last act as mixedtype inhibitors.

-0,2

Potential, E / V SCE

Current density, i / mA cm -2

ln 10 2:303
b

b
b

Current density, i / mA cm -2

i ia ic icorr  fexpba  E  Ecorr  expbc  E  Ecorr g

(a)

10

-1

10

-2

10

-3

10

Blank solution
-4

-4

10

410 M 4-MPOX
-4
810 M 4-MPOX
-4
1010 M 4-MPOX
-4
1210 M 4-MPOX

-5

10

-1,2

-1,0

-0,8

-0,6

-0,4

-0,2

0,0

0,2

0,4

0,6

Potential, E / V SCE
Fig. 1. Polarization curves for brass electrode in SCW-solution at different
concentrations of the studied molecules (a) 2-MPOX, (b) 3-MPOX and (c) 4-MPOX.

A. Rochdi et al. / Corrosion Science 80 (2014) 442452

To yield quantitative approach, icorr, and Ecorr are evaluated from

the experimental results using a dened function of Non-linear
least squares curve t (Eq. (1)) of graphic software (Origin, OriginLab). In all cases, the correlation factor R2 is greater than 0.999
indicating a reliable result. Fig. 2 shows, as for an example, the results of regressions calculation for the cathodic and anodic
branches for brass electrode in SCW-solution at different concentrations of 2-MPOX. In this calculation, the potential domain is limited in the vicinity of corrosion potential; Ecorr 100 mV. A good
agreement between the calculated and the experimental polarization data was obtained as is trusted in Fig. 2.
The obtained values of some kinetic parameters such as corrosion potential, Ecorr, corrosion current density, icorr, anodic and
cathodic Tafel slopes, ba, bc, and inhibiting efciency, gPP, are given
in Table 3. The corrosion inhibition efciency is evaluated from the
corrosion current densities values using the relationship (3):
0

gPP

icorr  icorr
0

icorr

 100

where icorr and icorr are the corrosion current densities values without and with inhibitor, respectively.
When compared to the uninhibited solution, the corrosion potential does not change so much, unless a slight decrease, in the
presence of 2-MPOX, whereas a distinguished shift in more cathodic direction is observed with 3-MPOX and 4-MPOX. The corrosion
current density, extracted using the SternGeary equation by Tafel
extrapolation method, at 103 M, is more than eleven and ten
times lower in the presence of 3-MPOX and 4-MPOX, respectively
compared to the blank solution, whereas it is only two times lower
in the presence of 2-MPOX. It is noted that in presence of inhibitors, the slope of the polarization curve becomes gentler corresponding to an increase of the polarization resistance. In
addition, it is noted that in this electrolyte, the IR drop is likely
to be large at higher currents, which are observed in the blank
solution. This can be explained by the formation of corrosion product at the surface copper.
In turn, the inhibition efciency is found to increase appreciably
with rise of inhibitor concentration. The obtained optimum concentration is 103 M for all inhibitors after which gPP decreases.
These results indicate that the increase of inhibitor concentration
might be attributed to the formation of barrier lm which prevents
the natural water from attacking the metal surface with adsorption
of oxadiazole molecules on the brass surface involving interactions
between the p-electrons of the heterocyclic structure of the
-2

Current density, i / mA cm

-2

10

-3

10

-4

Blank solution
-4
410 M 2-MPOX
-4
810 M 2-MPOX
-4
1010 M 2-MPOX
-4
1210 M 2-MPOX

10

-5

10

-0,24

-0,20

-0,16

-0,12

-0,08

-0,04

Potential, E / VSCE
Fig. 2. Comparison of experimental (scatter) and tting (red line) data using a nonlinear tting with SternGeary equation for brass electrode in SCW-solution at
different concentrations of 2-MPOX. (For interpretation of the references to color in
this gure legend, the reader is referred to the web version of this article.)

445

inhibitors and the vacant d-orbitals of brass surface atoms. Similar

explanation has been sought to explain the discrepancy in the order of inhibition efciency by triazole phosphonate derivatives
[12]. The highest inhibiting effect is observed with 3-MPOX. The
sequence of the undertaken oxadiazole inhibitors is then, 3MPOX P 4-MPOX  2-MPOX. The scarcely protective lm obtained with 2-MPOX by a simple surface blocking mechanism
maybe demonstrates a sterically hindered from adhering onto
the brass surface through oxygen and/or nitrogen atom of the oxadiazole ring due to the presence of two methyl groups in the ortho
position. Further quantum chemical investigations, in the inhibiting mechanism, of these oxadiazole derivatives are under progress.
Meanwhile, Ebenso et al. [36] have reported a comparative study of
quinoline molecule QL and its derivatives, namely quinaldine QLD
(with a methyl group in the ortho position of pyridine). It was
found two orientations of QLD and none of them did not cover
the metal surface desirably and therefore would not result in effective corrosion inhibition.
3.1.2. Electrochemical impedance spectroscopy, EIS diagrams
Electrochemical impedance spectroscopy constitutes a powerful tool to understand, in more details, the mechanism taking place
at the brass/electrolyte interface. The Nyquist diagrams, in SCWsolution, in the presence and absence of oxadiazole derivatives,
are shown in Fig. 3. The impedance measurements are performed
under potentiostatic conditions, at 32 C and pH = 7.35. Before each
experiment, the electrode is left at the open circuit conditions during half an hour at a rotation speed of the disc electrode WE equal
to 1000 rpm. The electrode does not evolve signicantly during the
impedance measurements. All impedance spectra exhibit large
capacitive loop throughout the explored frequency range from
100 kHz to 10 mHz. The shape of which is signicantly changed,
in size, with respect to the inhibitors addition into the SCW-solution; i.e., the impedance of the inhibited system increased with
inhibitor concentrations until the optimum one of 103 M. In the
presence of 2-MPOX, the impedance module is smaller in the
whole frequency range compared to those observed in the presence of 4-MPOX and 3-MPOX, respectively.
Besides in Fig. 3, on can see a part of capacitive loop at high frequency side (f > 1 kHz). The small semi-circle at the high frequency
side, which appeared in all solutions, might be related to the electric double layer. This loop has depressed semicircular appearance,
which is often referred to frequency dispersion as a result of non
homogeneity or roughness of the solid surface [37]. Below 1 kHz,
a markedly depressed capacitive loop can be observed. This second
loop can be split into two capacitive contributions; although badly
separated. Because of this poor separation and in terms of researches reported in Refs. [24,25,38], which show similar diagrams,
2RC-ZW electrical circuit design, as shown in Fig. 4, is used to describe the brass/electrolyte interface model. ZW represents, at low
frequency, the Warburg impedance. Indeed, this last is introduced
because it reects the diffusion process of dissolved oxygen from
the bulk solution to the electrode surface and/or the diffusion process of soluble zinc or copper species in the reverse sense; i.e., from
the electrode surface to the bulk solution. In the middle frequency,
though not clearly observed, with all oxadiazole derivatives addition, the adsorption would occur, in these samples, if the time
was so sufcient to create an adsorption layer on the metal surface
or probably the process of adsorption might be overlaid by the
relaxation process of the electric double layer.
Fig. 5a reports, as an example of relative t, the Nyquist diagram for 3-MPOX at 103 M, in SCW-solution, obtained with the
suggested circuit model. The measured and simulated data t well
enough. Clearly, the measured impedance diagram is in accordance
with that calculated using the equivalent circuit model. This result
indicates that the proposed electrical circuit could reasonably

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A. Rochdi et al. / Corrosion Science 80 (2014) 442452

Table 3
Data obtained from the polarization curves of brass in SCW-solution in the absence and presence of various concentrations of 2-MPOX 3-MPOX, and 4-MPOX.
Inhibitor

Concentration M

Ecorr (mVSCE)

icorr (lA cm2)

ba (mV dec1)

bc (mV dec1)

gPP (%)

Blank solution
2-MPOX

00
4  104
8  104
10  104
12  104

141
150
154
157
160

1.7
1.3
1.02
0.85
1.02

665
489
456
558
174

1264
233
199
305
586

23
40
50
40

3-MPOX

4  104
8  104
10  104
12  104

152
178
190
219

0.52
0.18
0.15
0.42

283
317
245
295

483
271
219
305

69
89
91
75

4-MPOX

4  104
8  104
10  104
12  104

156
180
170
176

0.71
0.25
0.17
0.47

276
535
251
261

388
553
267
556

58
85
90
72

model the corrosion process occurring at the studied brass/electrolyte interface. Moreover, the results of tting, according to a simplex procedure, minimize the values of chi-squared v2 (not given
here), which corresponds therefore to the sum of quadratic deviations between experimental and calculated data, and exhibit the
goodness of the t [38,39].
The most important parameters derived from EIS measurements, as extracted from the 2RC-ZW equivalent circuit, are collected in Table 4. In this study, Rs refers to the resistance
solution, Rct is the charge transfer resistance, Rf denotes the adsorption lm resistance. Cdl and Cf represent the double layer capacitance and adsorption lm capacitance, respectively. It is
important to mention that the last two studied capacitances are
affected by imperfections of the surface, and this effect is
simulated via a constant phase element; i.e., CPE. Therefore, the
introduction of a CPE rather than an ideal capacitor, to the equivalent circuit, is of great importance in tting impedance spectra
[40]. Considering the roughness and in-homogeneities of solid
electrode surface, here, the constant phase elements CPEf and CPEdl
are used to replace the lm capacitance and the double layer
capacitance, respectively, and their values can be assessed by the
following equation [40,41]:

Z CPE x Y 1 jx

n

where Y is the CPE constant, x is the sine wave modulation angular

frequency (in rad s1), j2 = 1 is the imaginary number and n is the
CPE exponent. Depending on n, CPE can represent resistance
[ZCPE = R, n = 0], capacitance [ZCPE = C, n = 1], inductance [ZCPE = L,
n = 1] or Warburg impedance for (n = 0.5) [42].
The inhibiting efciency derived from EIS, gEIS% is also added in
Table 4 and calculated using the following equation:

gEIS %

Rct  R0ct
 100
Rct

where R0ct and Rct are the charge transfer resistance values in the absence and in the presence of inhibitor, respectively. In fact, the
choice of such parameter to evaluate the performance of an inhibitor is dictated by the fact that Rct is reciprocally proportional to the
corrosion rate [43]. The presented data in Table 4 show that, the
inhibiting efciency increases, with n-MPOX concentration reaching 90% and 91% for 4-MPOX and 3-MPOX, respectively. The inhibiting efciency values got from EIS data are comparable and run
parallel with those obtained from the potentiodynamic polarization
measurements.
The electrolytic resistance, Rs, increases with the increase of
each inhibitor concentration until the optimum and decreases
thereafter. Such results were observed by some researchers and
no explanation was proposed [17]. The authors suggest that the

evolution of such parameter maybe imputed to the fact that a larger value of the electrolyte resistance decreases the galvanic coupling between the anodic and cathodic local cells when more and
more oxadiazole molecules will adsorb on the active sites of brass
surface and form a denser lm gradually leading to smaller corrosion rate and consequently to larger inhibiting efciency.
The values of charge transfer resistance Rct increase with rise of
concentration which indicates the insulated adsorption layers formation. Moreover, the optimum the concentration of oxadiazole,
the larger is the amount of Rct. The highest values of Rct observed
for 3-MPOX and 4-MPOX followed by 2-MPOX, suggest their enhanced inhibitor performance. The increase in Rct observed, as
the concentration of oxadiazole molecules increases, indicates that
the charge transfer process is impeded from the time when the
uncovered area available for this process is diminishing due to
the adsorption of more and more molecules at the brass/electrolyte
interface.
The double layer capacitance Cdl is too high for all solutions. Indeed, the corrosion/scale products increase the real interface area
of the electrode, and then Cdl becomes much larger; in agreement
with other studies reported elsewhere in Refs. [24,38]. The decrease in Cdl is due to the gradual replacement of water molecules
by the adsorption of oxadiazole molecules at the brass/electrolyte
interface, which is leading to a protective lm on the brass surface
which prevents mass and charge transfers; accordingly it is
decreasing the extent of the dissolution reaction [44]. This nding
explains the role played by the additive oxadiazole molecules as
corrosion/scale inhibitors.
The phase shift ndl which remains almost constant; ca. 0.5 is not
fully understood and seems in contradiction with the well known
evolution of this parameter. Indeed, as often observed in similar
studies [17], the ndl value increases after the addition of inhibitor
molecules explained by some decrease of the initial surface heterogeneity due to the adsorption of inhibitor molecules on the most
active adsorption sites of the electrode surface. However, the CPEf,
with its nf values close to 0.5 in all solutions, appears to have
Warburg characters suggesting that the mass transport may take
place through the lm. The presence of Warburg impedance in
the proposed circuit conrms also that the mass transport is limited by the surface passive lm. The same behavior was shown
by Sherif and Park [45], in the corrosion inhibition of some thiadiazole derivatives previously described in 3% NaCl solution.
Rf and Cf indicate the characteristic of a lm formation on the
metal surface illustrating the creation of adsorption layer in the
presence of oxadiazole derivatives. The Cf values are not reasonable
for a thin surface lm formed by oxadiazole compounds on the
brass and/or the brass oxide surface. The former is corroborated
by the fact that the surface roughness is not to be neglected as
can be justied by the values of the phase shift nf equal ca. 0.5 in

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A. Rochdi et al. / Corrosion Science 80 (2014) 442452

- Imaginary Part, - Z'' / k cm2

20

Blank solution
-4
410 M 2-MPOX
-4
810 M 2-MPOX
-4
1010 M 2-MPOX
-4
1210 M 2-MPOX

15

(a)

10

Fig. 4. 2RC-ZW equivalent circuit proposed for tting the impedance spectra
obtained on brass surface in SCW-solution both with and without 2-MPOX, 3-MPOX
and 4-MPOX.

0.012
0,398
0.012

0.012

80

Experimental data
Fitting data

0.012
0.01

10

15

20

Real Part, Z' / k cm

25

30

- Imaginary Part, - Z'' / k cm2

80

Blank solution
-4
410 M 3-MPOX
-4
810 M 3-MPOX
-4
1010 M 3-MPOX
-4
1210 M 3-MPOX

60

(b)

- Imaginary Part, -Z/ k cm2

0,398

60

0,0141

40

0,1

20
0,891

0.014

(a)

40

20

40

60

80

Real Part, Z/ k cm

100

100
0.012

20

Experimental data
Fitting data

0.398

0,794

0.01

0
0

20

40

60

Real Part, Z' / k cm

- Imaginary Part, - Z'' / k cm2

80

80

Blank solution
-4
410 M 4-MPOX
-4
810 M 4-MPOX
-4
1010 M 4-MPOX
-4
1210 M 4-MPOX

60

100

(c)

- Imaginary Part, - Z/ k cm 2

0.012

80

60

5,011

40

20

25,118

(b)

0
0

20

40

60

80

Real Part, Z/ k cm

40

120

Fig. 5. Comparison between the measured and simulation data for impedance
diagrams of brass in SCW-solution (a) in the presence of 3-DTOX at 103 M, (b) in
the presence of mixture 1 at Ecorr (T = 32 C, X = 1000 rpm). Mixture 1: 103 M 3MPOX + 20 ppm CTAB.

0.01

20

100

0.398
0.015
0.01
0.01

0
0

20

40

60

Real Part, Z' / k cm

80

100

Fig. 3. Nyquist diagrams for brass in SCW-solution at different concentrations of

the studied molecules (a) 2-MPOX, (b) 3-MPOX and (c) 4-MPOX obtained at Ecorr.

all cases (Table 4). It can be seen that Rf values increased while Cf
values decreased for all inhibitors until the optimum concentration. That is, the ionic conductivity of surface lm decreases with
rise of inhibitor concentrations. Assuming that the ionic conduction through the lm is ensured by pores crossing the lm and taking into account the increase of lm thickness, the total surface of
pores should then be dramatically reduced with addition of

oxadiazole molecules. It is noteworthy that the values of Rct, in

the most cases, are circa two orders of magnitude higher than that
of Rf. This nding can be explained by the fact that the inner barrier
layer plays the most important role in the corrosion process of
brass protection in the studied cooling water.
Likewise, the value of the relaxation time constant, sdl = Rct  Cdl, increases globally with oxadiazole concentration, especially
with 3-MPOX and 4-MPOX, until the optimum one; i.e., the time
of adsorption process becomes therefore much higher which
means a slow adsorption process. This result is in agreement between the amount of charge that can be stored (that is capacitance)
and discharge velocity in the interface, sdl [46]. However, in the
case of 2-MPOX, the time constant sdl remains almost the same
equal to 5 s even if the rise of concentration. This result explains

448

A. Rochdi et al. / Corrosion Science 80 (2014) 442452

Table 4
Electrochemical impedance parameters for brass in SCW-solution at different concentrations of 2-MPOX 3-MPOX, and 4-MPOX oxadiazole derivatives.
Rsa

Inhibitor/M

Rcta

Cdl

Rf

CPEf
Cfb

nf

64

0.63

ndl

sfb

sct/sf

gEIS (%)

Blank solution
2-MPOX
4  104
8  104
10  104
12  104

112

10

264

0.54

262
297
300
200

20
22
25
18

253
234
216
250

0.53
0.52
0.55
0.54

5
5.1
5.4
4.5

5
7
10
4

107
83
40
88

0.55
0.61
0.59
0.57

0.5
0.5
0.4
0.4

10
10.2
13.5
11.2

50
54
60
44

3-MPOX
4  104
8  104
10  104
12  104

209
228
249
252

40
60
115
50

160
120
100
125

0.54
0.56
0.59
0.58

6.4
7.2
11.5
6.3

20
40
60
25

105
85
63
86

0.57
0.62
0.63
0.61

2.1
3.4
3.8
2.2

3.05
2.12
3.03
2.86

75
83
91
80

4-MPOX
4  104
8  104
10  104
12  104

263
285
288
269

30
50
100
60

162
125
111
130

0.55
0.57
0.62
0.59

4.9
6.3
11.1
7.8

15
32
52
32

107
83
67
88

0.56
0.63
0.64
0.60

1.6
2.6
3.5
2.8

3.1
2.4
3.1
2.8

67
80
90
83

Rct and Rf are expressed in kX cm2 while Rs is expressed in X cm2.

Cdl, Cf are given in lF cm2, sdl, sf are given in seconds.

Current density, i / mA cm-2

10

10

-1

10

-2

10

-3

10

-4

10

-5

-1,2

(a)

10

Current density, i / mA cm-2

a
b

sdlb

CPEdl

Blank solution
20 ppm CTAB
-3
10 M 3-MPOX
Mixture 1
-1,0

-0,8

-0,6

-0,4

-0,2

0,0

0,2

0,4

0,6

0,8

10

-1

10

-2

10

-3

10

-4

10

-5

(b)

-1,2

1,0

Blank solution
20 ppm CTAB
-3
10 M 4-MPOX
Mixture 2
-0,9

-0,6

-0,3

0,0

0,3

0,6

0,9

Potential, E / VSCE

Potential, E / VSCE

Fig. 6. Polarization curves for brass electrode in SCW-solution containing (a) 103 M of 3-MPOX, 20 ppm of CTAB and their mixture (b) 103 M of 4-MPOX, 20 ppm of CTAB
and their mixture at T = 32 C and X = 1000 rpm.

Table 5
Data obtained from polarization curves for brass in SCW-solution containing 103 M of 3-MPOX and 4-MPOX with and without 20 ppm of CTAB (T = 32 C, X = 1000 rpm).
Formulation

Ecorr (mVSCE)

icorr (lA cm2)

ba (mV dec1)

bc (mV dec1)

iP (lA cm2)

gpp (%)

Blank solution
20 ppm CTAB
103 M 3-MPOX
103 M 4-MPOX
Mixture 1
Mixture 2

141
118
190
181
241
143

1.7
0.37
0.15
0.17
0.09
0.1

665
471
245
251
225
491

1264
551
219
267
392
234

5
5

78
91
90
95
94

Mixture 1: 103 M 3-MPOX + 20 ppm CTAB.

Mixture 2: 103 M 4-MPOX + 20 ppm CTAB.

that the performance of 2-MPOX is therefore achieved at low concentration and any more inhibitor addition does not, or very
slightly, affect the brass/electrolyte interface.
Meanwhile, the proposed equivalent circuit related to
oxadiazole presence contains three relaxation time constants
among them the formation of adsorption layer on the brass surface; however this layer is not clearly observed or distinguishable

when oxadiazole are used as inhibitors. In fact, if the adsorption of

oxadiazole molecules had a considerable impact on the studied
interface, the ratio of both time constants sdl/sf with (sf = Rf  Cf)
would change, and the adsorption process could be identied
[47]. As results, this ratio is circa 10 for 2-MPOX, whereas it is only
3 for both 3-MPOX and 4-MPOX. The constant ratio justies, rst,
the poor separation of the two processes; adsorption and double

A. Rochdi et al. / Corrosion Science 80 (2014) 442452

100

- Imaginary Part, - Z'' / k cm2

(a)

Blank solution
20 ppm CTAB
-3
10 3-MPOX
Mixture 1

80

449

0.01

60

0.01

40

0,1258

20
0.01

0.01

0
0

20

40

60

80

100

120

Real Part, Z' / k cm

- Imaginary Part, - Z'' / k cm2

100

(b)

Blank solution
20 ppm CTAB
-3
10 M 4-MPOX
Mixture 2

80

0.014

60

0,125

40
0.01

20
0.01

0.01

0
0

20

40

60

80

100

120

140

160

Real Part, Z' / k cm

Fig. 7. Nyquist diagrams for brass in SCW-solution containing (a) 103 M of 3MPOX, 20 ppm of CTAB and mixture 1 (b) 103 M of 4-MPOX, 20 ppm of CTAB and
mixture 2 at Ecorr and T = 32 C, X = 1000 rpm. Mixture 1: 103 M 3-MPOX + 20 ppm
CTAB, Mixture 2: 103 M 4-MPOX + 20 ppm CTAB.
Fig. 8. SEM pictures of brass electrode surface after 48 h immersion in SCWsolution: (a) the blank solution and (b) in the presence of mixture 1: 103 M 3MPOX + 20 ppm CTAB.
Table 6
Electrochemical impedance parameters for brass in SCW-solution containing 103 M
of 3-MPOX and 4-MPOX with and without 20 ppm of CTAB (T = 32 C, X = 1000 rpm).
Inhibitor/M

Blank solution
20 ppm CTAB
103 M 3-MPOX
103 M 4-MPOX
Mixture 1
Mixture 2

Rsa

112
95
249
285
277
305

Rcta

10
30
115
100
300
230

CPEdl

Rf

Cdlb

ndl

264
165
100
111
11
37

0.54
0.56
0.59
0.62
0.91
0.75

5
40
60
52
30
32

CPEf

Cfb

nf

64
52
63
67
30
15

0.63
0.66
0.63
0.64
0.65
0.74

gEIS
(%)

0.59
0.50

78
91
90
97
96

Mixture 1: 103 M 3-MPOX + 20 ppm CTAB.

Mixture 2: 103 M 4-MPOX + 20 ppm CTAB.
a
Rct and Rf are expressed in kX cm2 while Rs is expressed in X cm2.
b
Cdl, Cf are given in lF cm2.

layer relaxations. On the other hand, the double layer process is ten
times faster than the adsorption process for 2-MPOX, at what time
it is only three times faster for 3-MPOX and 4-MPOX. These ndings can also explain the best inhibiting efciencies obtained with
3-MPOX and 4-MPOX when compared to 2-MPOX.

3.2. Effect of CTAB addition on oxadiazole inhibition performance

In contrast to fresh water, circulating cooling water system contains abundant organic substances among inorganic ions which are
responsible of fouling by microorganisms in addition to corrosion
as well as scale formation. In order to mitigate these three main
problems; corrosion, scaling and biofouling, simultaneously in circulating cooling water, biocide are usually injected at the same
point with corrosion and scale inhibitor compounds in such
aggressive media. CTAB, as non-oxidizing biocide, has proven efcacy and performance in microbial control for various industrial
applications. It is not only surfactant, commercially available, but
is also a quaternary ammonium salt which along with a long
hydrocarbon chain of sixteen carbon atoms, whose homologues
have been largely used as biocide and inhibitors [48-50]. Indeed,
CTAB acts as effective biocide by disturbing the arrangements of
phospholipid molecules in the bacterial cell. For this purpose, the
combined effect of the optimum concentration of the best undertaken oxadiazole derivatives, is studied with 20 ppm of CTAB, as

450

A. Rochdi et al. / Corrosion Science 80 (2014) 442452

reported in our earlier papers [27,29], in order to examine their

eventual synergistic inhibition efciency on the corrosion of brass
in SCW-solution.
3.2.1. PP data
Fig. 6 brings out the currentvoltage characteristics of 3-MPOX,
4-MPOX, CTAB and mixtures of them (mixture 1: 103 M 3MPOX + 20 ppm CTAB) and (mixture 2: 103 M 4-MPOX + 20 ppm
CTAB) added simultaneously and separately to evaluate the corrosion inhibiting efciency and the eventual interference between
them. It is clear from Fig. 6 that CTAB and the two mixtures exhibit
cathodic and anodic inhibition effects. Therefore, CTAB and mixtures can be classied as inhibitors of mixed-type in SCW-solution.
Moreover, both anodic and cathodic processes are drastically
inhibited in the presence of mixtures when compared to oxadiazole derivatives taken solely.

The electrochemical parameters obtained from the polarization measurements are listed in Table 5. The corrosion potential
shifts to more anodic potentials with 20 ppm of CTAB while it
remains almost constant and markedly decreases in the presence of mixture 2 and mixture 1, respectively. The corrosion
current density is more than eighteen and seventeen times lower in the presence of mixture 1 and mixture 2, respectively
when compared to the blank solution. In the light of this
information, CTAB exerts a synergetic effect with both products.
Indeed, the addition of CTAB increases the inhibiting efciency
from 91 to 95 in the case of 3-MPOX and 90 to 94 in the case
of 4-MPOX.
The biocide CTAB is incorporated into the system, kills bacteria,
stops the production of hydrogenase enzyme and nally prevents
more and more the cathodic depolarization on metal surface
[43]; therefore cathodic reaction is markedly shifts toward lower

(a)

Elements
Wt. %

Si

Pb

Ca

Cu

Zn

5.13 6.34 0.15 0.57 2.89 1.92 44.86 38.15

(b)
Elements
Wt. %

7.18 2.75

Al

Si

Pb

0.2

0.32

1.99

Ca

Cu

Zn

0.00 52.07 35.50

Fig. 9. Qualitative and quantitative EDX analyses of brass electrode surface after two days of immersion in SCW-solution: (a) blank solution and, (b) in the presence of
mixture 1 (103 M 3-MPOX + 20 ppm CTAB).

A. Rochdi et al. / Corrosion Science 80 (2014) 442452

current densities in the presence of CTAB. In addition, in the two

mixtures, the anodic curve highlights a level of anodic current density over a wide potential range (300 mV). This result argues favorably to the fact that these new formulations signicantly enlarge
the eld of passive material. In fact, the inhibitor molecules passivate the metal, acting as a barrier between the metal and corrosive
medium. The corresponding current density of passivity is ca.
5 lA cm2. This passivation enhances also the brass electrode
resistance from pitting corrosion [40].

3.2.2. EIS data

Fig. 7 shows the Nyquist diagrams of 103 M 3-MPOX, 103 M
4-MPOX, 20 ppm CTAB, mixture 1 and mixture 2 obtained after
30 min of hold time immersion at Ecorr and for a rotation speed
of 1000 rpm at T = 32 C. The Nyquist diagrams display a attened semi-circle with a deformation in the high frequency
domain as observed in the absence of CTAB. Thus, the experimental data are achieved with the same electrical equivalent circuit
of Fig. 4. A comparison between the measured and simulation
data for the impedance spectrum of brass in simulated cooling water containing the mixture 1 is shown in Fig. 5b. The
non-linear regression calculation is close to the experimental result. The tted data extracted from the circuit model are given in
Table 6.
It reveals that the addition of mixtures in the SCW-solution increases the charge transfer resistance and decreases the double
layer capacitance; due to the formation of protective layer on brass
surface, and does not change other aspects of corrosion behavior. A
higher charge transfer resistance is associated with a slower corroding system. The inhibiting efciency goes from 91 to 97 and
from 90 to 96 when 20 ppm of CTAB is added to 103 M 3-MPOX
and 103 M 4-MPOX, respectively. Together, these ndings show
a synergistic effect between oxadiazole compounds 3-MPOX or
4-MPOX and CTAB, possibly due to the formation of a higher
homogeneous resistive layer that causes a greater decrease of the
corrosion process.
Aramaki et al. [51,52] have proposed two types of joint
adsorption mechanisms, namely competitive and cooperative,
to explain the synergism observed when two inhibitors are
simultaneously added in solution. In competitive adsorption,
the two compounds are adsorbed at different sites on the metal
surface, while in cooperative adsorption; one is chemisorbed on
the surface when the other comes to physisorbe thereon. The
synergism parameter, S is calculated from the impedance data
using the following relationships (6)(8), with h = g/100:

1  h12
1  h012

h12 h1 h2  h1  h2

h012

1=Rct12
1
1=Rct0

h1+2 and h012 are the calculated and measured surface coverage of
mixture, respectively.
h1 and h2 are the surface coverage of n-MPOX and CTAB, respectively calculated from Rct. Rct1+2 is the charge transfer resistance in
the presence of mixture and Rct0 is the charge transfer resistance in
the absence of both compounds. The S values derived from the two
studied mixtures are lower than unity (Table 6). According to Aramaki criterion [51], a competitive adsorption explains the synergy
observed between the two compounds (oxadiazole inhibitor and
biocide CTAB).

451

3.3. SEM and EDX results

Fig. 8 shows the scanning electronic microscopy (SEM) images
of brass surface that have been exposed to the SCW-solution during two days in the absence and presence of mixture 1. The image
of the surface exposed to the inhibitor-free aggressive solution
(Fig. 8a), shows heterogeneous layer of corrosion/scale products
(appearance white clusters). Indeed, an EDX qualitative analysis
(Fig. 9a) and quantitative (inserted table) further identied characteristic scale products elements (Ca, O and C) on this layer. Moreover, the SEM image, in the presence of mixture 1 (Fig. 8b), shows a
large area free of corrosion/scale products (appearance of stripe
polishes) and reveals the formation of a protective layer. This protection ability is probably due to the formation of copper and zinc
complexes of 3-MPOX/CTAB over the brass surface against corrosion/scale phenomena. In this case, EDX analysis (Fig. 9b) shows
a disappearance of Ca peak and its quantity (inserted table) as well
as a height decreasing of C and O picks indicating that mixture 1 is
adsorbed on the metal surface and also justies that this formulation plays scale and corrosion inhibitor.

4. Conclusion
Electrochemical measurements (dc currentvoltage and ac
impedance) were coupled with SEM and EDX techniques to investigate corrosion, scaling and biofouling inhibition of brass in simulated cooling water system. To do so, three oxadiazole derivatives
were undertaken solely and added with a non-oxidizing biocide
CTAB (mixtures). The main conclusions can be drawn:
Potentiodynamic polarization (PP) studies have shown that the
oxadiazole derivatives slowed down both cathodic and anodic processes and thus act as mixed-type inhibitors. Good performances
were obtained with 3-MPOX and 4-MPOX when compared to 2MPOX. The inhibiting efciency followed the sequence: 3-MPOX
(91%) P 4-MPOX (90%)  2-MPOX (50%). The addition of 20 ppm
of biocide showed better inhibition (mixture 1 (95%) P mixture 2
(94%). Such results were regarded as synergism effect between
oxadiazole molecules and CTAB to protect brass surface against
corrosion and biocorrosion. Additionally, a large passivity current
plateau of circa 300 mV was registered in the mixture solutions
which reinforced the brass resistance against pitting corrosion.
EIS measurements, in agreement with PP data, proved the
inhibitive properties of oxadiazole molecules corroborating once
the sequence of oxadiazole inhibitors obtained with polarization
curves and on the other hand the synergism action with CTAB.
The SEM images and EDX analyses conrmed the formation of
insoluble stable lm thus the corrosion/scale inhibitor character
of mixture 1.
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