Corrosion Science 52 (2010) 3321–3330

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

Investigation of the inhibition effect of 5-((E)-4-phenylbuta-1,3-dienylideneamino)-

1,3,4-thiadiazole-2-thiol Schiff base on mild steel corrosion in hydrochloric acid
Ramazan Solmaz *
Bingöl University, Science and Letters Faculty, Chemistry Department, 12000 Bingöl, Turkey

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

Article history: The inhibition effect of 5-((E)-4-phenylbuta-1,3-dienylideneamino)-1,3,4-thiadiazole-2-thiol (PDTT)

Received 8 March 2010 Schiff base on mild steel corrosion in 0.5 M HCl was studied for both short and long immersion time.
Accepted 4 June 2010 For this purpose, potentiodynamic polarization, electrochemical impedance spectroscopy, linear polariza-
Available online 15 June 2010
tion resistance, hydrogen gas evolution, the change of open circuit potential as a function of immersion
time, SEM and AFM techniques were utilized. The PDTT Schiff base has shown remarkable inhibition on
Keywords: the corrosion of mild steel in 0.5 M HCl solution. The high inhibition efficiency was attributed to the block-
A. Mild steel
ing of active sites by adsorption of inhibitor molecules on the steel surface.
B. EIS
B. SEM
Ó 2010 Elsevier Ltd. All rights reserved.
C. Acid corrosion
C. Pitting corrosion

1. Introduction corresponding amines and aldehydes [11–18]. The presence of

Acid solutions are generally used for the pickling, industrial acid
cleaning, acid descaling, oil well acidizing, etc. [1–4]. Iron and its
alloys which are widely used in a lot of industrial processes could
corrode during these acidic applications particularly with the use
of hydrochloric acid and sulphuric acid. The corrosion prevention
of metals has always been an important subject to be dealt with.
The decreasing of corrosion rate of metals provides savings of re-
sources and economical benefits during the industrial applications.
The prevention of corrosion is vital not only for increasing the life-
time of equipments but also decreasing the dissolution of toxic
metals from the components into the environment. The use of
organic molecules as corrosion inhibitor is one of the most practi-
cal methods for protecting metals against the corrosion and it is
becoming increasingly popular. In recent years, a considerable
amount of effort is devoted to find novel, economical and efficient
corrosion inhibitors. Organic compounds bearing heteroatoms
with high electron density such as phosphor, sulphur, nitrogen,
oxygen or those containing multiple bonds which are considered
as adsorption centers, are effective as corrosion inhibitor [5–7].
The compounds contain both nitrogen and sulphur in their molec-
ular structure have exhibited greater inhibition compared with
those contain only one of these atoms [8–10].
Recently, Schiff base compounds have been of interest in order
to obtain efficient corrosion inhibitors since they provide much
greater inhibition by adsorption on metal surface compared with
* Tel.: +90 426 213 2550; fax: +90 426 213 2866.
E-mail addresses: rsolmaz01@gmail.com, rsolmaz@bingol.edu.tr
AC@NA group in Schiff base molecules enhances their adsorption
ability and corrosion inhibition efficiency [19,20]. Adsorption of
inhibitors on the metal surface involves formation of two types of
interaction (physical adsorption and chemical adsorption). Physical
adsorption requires the presence of both electrically charged sur-
face of the metal and charged species in the bulk solution. The sec-
ond one, chemisorption process involves charge sharing or charge
transfer from the inhibitor molecules to the metal surface to form
a co-ordinate type bond and takes place in the presence of hetero-
atoms (P, N, S, O, etc.) with lone pairs of electrons and/or aromatic
ring in the molecular structure [21,22].
Heterocyclic thiadiazole derivatives are friendly compounds
and find diverse applications in antibacterial activities [23]. 2-Ami-
no-5-mercapto-1,3,4-thiadiazoles (2A5MT) can be produced in
very high yields from thiosemicarbazides and carbon disulphide.
Such thiadiazoles are valuable intermediates for the synthesis of
corrosion inhibitors, pharmaceuticals, photography chemicals and
pesticides. 2A5MT derivatives were widely used for dispersed dyes
due to their brightness and good light fastness on hydrophobic fab-
rics [24]. 2A5MT has been extensively studied as corrosion inhibi-
tor for copper and bronze [25–27]. We have recently reported
2A5MT for the corrosion inhibition of mild steel [28]. Although
several methods synthetic exist, cinnamaldehyde (CA) occurs nat-
urally in the bark of cinnamon trees and other species of the genus
cinnamommum like camphor and cassia (about 90%). The predom-
inant application for cinnamaldehyde is in the agriculture, flavor
and fragrance industries. CA and its derivatives are also known
as corrosion inhibitors [29–35]. Considering the actual ecological
problems, the interest for this compound is also emphasized due

0010-938X/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2010.06.001
3322 R. Solmaz / Corrosion Science 52 (2010) 3321–3330
to its non-toxic character [32]. In this study, we have further im-
proved inhibition effect of 2A5MT by preparing its Schiff base with
CA. The synthesized Schiff base molecule has additional p bonds as
well as a phenyl group which are assumed to be active center of
adsorption and therefore the molecule is expected to show better
adsorption ability and corrosion inhibition efficiency. Because
comparison of the effect of molecular structure of aldehyde group
on compound’s inhibition action has not been aimed, Schiff base of
only one aldehyde group (cinnamaldehyde) was synthesized and
tested as corrosion inhibitor in this study. The aim of this study
is to investigate inhibition effect of PDTT on the mild steel corro-
sion in 0.5 M HCl solution for short and long immersion time and
also to clarify its inhibition mechanism.
2. Experimental
2.1. Preparation of electrodes
The working electrode was a cylindrical disc cut from a mild
steel specimen with following chemical composition (wt); C
(0.21%), Si (0.36%), Mn (1.25%), P (0.025%), S (0.046%), Cr (0.16%),
Ni (0.16%), Cu (0.41%), Mo (0.017%), Sn (0.017%), Al (0.003%), V
(0.081%) and Fe (remainder). The metal disc was coated with poly-
ester except its bottom surface with surface area of 0.50 cm2. The
surface of working electrode was mechanically abraded using dif-
ferent grades of sand papers, which ended with the 1000 grade,
prior to use. The disc was cleaned by washing with bidistilled
water, CCl4, bidistilled water, respectively, and finally dried with
a filter paper. For each test, a freshly abraded electrode was used.
2.2. Test solutions
The Schiff base was synthesized from the condensation reaction
of 2-amino-5-mercapto-1,3,4-thiadiazole with cinnamaldehyde in
ethanol according to the published method [36]. The molecular
structure of the synthesized Schiff base is given in Fig. 1. The cor-
rosion tests were performed in 0.5 M HCl solution in absence and
presence of various PDTT concentrations, respectively. The concen-
trations of the inhibitor employed were 1.0, 0.5, 0.1, 0.05, 0.01 mM.
The experiments were performed under air atmosphere without
stirring using freshly prepared solution at 298 K.
2.3. Electrochemical measurements
The potentiodynamic polarization curves, electrochemical
impedance spectroscopy (EIS) and linear polarization resistance
(LPR) measurements were carried out using a CHI 604 A.C. Electro-
chemical Analyzer (Serial Number 64721A) under computer con-
trol. A double-wall one-compartment cell with a three-electrode
configuration was used. The auxiliary electrode was a platinum
sheet with 2 cm2 surface area. The reference electrode was Ag/AgCl
(3 M KCl). All potential data given in this study were referred to
this electrode. The working electrode was immersed in test solu-
tion for 1 h to establish steady state open circuit potential (Eocp).
After measuring the Eocp, the electrochemical measurements were
S H
HS N C
N N
Fig. 1. Chemical structure of the studied Schiff base (5-((E)-4-phenylbuta-1,3-
dienylideneamino)-1,3,4-thiadiazole-2-thiol).
performed. The EIS experiments were conducted in the frequency
range of 100 kHz to 0.01 Hz at open circuit potential. The ampli-
tude was 0.005 V. In order to investigate the mechanism of inhibi-
tion, EIS experiments were also carried out at different anodic and
cathodic overpotentials which were previously determined from
polarization curves. LPR measurements were carried out by record-
ing the electrode potential ±0.010 V around open circuit potential
with 0.001 V s1 scan rate. The polarization resistance (Rp) was
determined from the slope of the obtained current–potential
curves.
The corrosion behavior of mild steel in 0.5 M HCl solution in the
presence and absence of 1.0 mM PDTT as a function of exposure
time was also performed over 120 h. For this purpose, the poten-
tiodynamic polarization, EIS, LPR, the hydrogen gas evolution
(VH2-t) and the change of open circuit potential with immersion
time (Eocp  t) were utilized. During the long-term tests, the work-
ing electrode was immersed in a beaker containing 200 mL test
solution. After different immersion time, electrochemical measure-
ments were performed under un-stirring conditions. In the hydro-
gen gas evolution measurements, a burette filled with 0.5 M HCl
solution was placed over the working electrode. The initial volume
of air in the burette was recorded and the volume of H2 gas evolved
from the corrosion reaction was monitored by the volume change
in the level of the solution as a function of time at 24 h intervals
over 120 h. Open circuit potential of working electrode was also re-
corded as a function of exposure time. The same experiments were
repeated in the presence of 1.0 mM PDTT. The long-term tests were
carried out at room temperature under un-stirring conditions.
2.4. Scanning electron microscopy and atomic force microscopy studies
The morphology of mild steel surface after its exposure to 0.5 M
HCl solution in the absence and presence of 1.0 mM PDTT for 120 h
was examined by SEM and AFM images. The SEM images were
taken using a Carl Ziess Evo 40 SEM instrument at high vacuum
and 10 kV EHT, AFM images were taken with Park SYSTEMS using
non-contact mode.
3. Results and discussion
3.1. Electrochemical impedance spectroscopy
The representative Nyquist and Bode plots of mild steel in 0.5 M
HCl solution in absence and presence of various concentrations of
Schiff base after 1 h exposure are given in Fig. 2a and b, respec-
tively. As it is seen from Fig. 2a, the Nyquist plot of mild steel in
0.5 M HCl solution does not yield perfect semicircle as expected
from the theory of EIS. The deviation from ideal semicircle is gen-
erally attributed to the frequency dispersion as well as to the inho-
mogeneities of surface and mass transport resistant [15,18,37–39].
A slightly depressed semi circular shape in Nyquist plot indicates
that the corrosion of mild steel in 0.5 M HCl solution is mainly con-
trolled by a charge transfer process [1,40,41]. The diameter of semi
circle increased after the addition of Schiff base to the aggressive
solution. This increase was more pronounced with increasing
inhibitor concentration which indicates adsorption of inhibitor
molecules on the metal surface. The difference in real impedance
at lower and higher frequencies is commonly considered as charge
transfer resistance. In this study, the difference in real impedance
at lower and higher frequencies was considered as the polarization
resistance (Rp) instead of charge transfer resistance (Rct), the rea-
son was previously discussed in detail [42–44].
The double layer can be represented by the electrical equivalent
circuit diagrams to model the metal/solution interface. EIS data
were fitted according to the electrical equivalent circuit diagrams
 R. Solmaz / Corrosion Science 52 (2010) 3321–3330
Fig. 2. The Nyquist plots (a) and Bode diagrams (b) of mild steel in 0.5 M HCl
solution without (s) and with the addition of 0.01 mM (N), 0.1 mM (h) and 1.0 mM
(d) PDTT (solid lines show fitted results).
suggested in Fig. 3a and b to model the mild steel/solution inter-
face in the absence and presence of inhibitor, respectively. The cal-
culated impedance parameters are given in Table 1. Where CPE is
constant phase element, n is the phase shift which can be ex-
plained as a degree of surface in homogeneity [45,46]. CPE was
used in place of a double layer capacitance (Cdl) in order to give a
more accurate fit to the experimental results [18]. Generally, the
(a) Rs CPE
Rp
(b) Rs CPE1
CPE2
R1
R2
Fig. 3. Electrical equivalent circuit diagrams generally used for modeling metal/
solution interface, in the absence of inhibitor (a), and presence of inhibitor (b).
Rp = Rct + Rd + Ra (for equivalent circuit diagram in (a)). Rp = Rf + Rpor (Rpor = Rct + Rd +
Ra) (for equivalent circuit diagram in (b)). Rs: solution resistance, Rct: charge transfer
resistance, Rd: diffuse layer resistance, Ra: resistance of accumulated species
(corrosion products, any existing molecules or ions, etc.), Rp: polarization resistance,
R1: film resistance (Rf), R2: pore resistance (Rpor, corresponds to uncovered regions
and pores), CPE1: film capacitance, CPE2: double layer capacitance.
3323
use of a CPE is required due to the distribution of the relaxation
times as a result of inhomogeneities present at a micro- or nano-le-
vel, such as the surface roughness/porosity, adsorption, or diffusion
[47]. The inhibition efficiency (I%) was calculated from the polari-
zation resistance using the following formula:
!
R0p  Rp
I% ¼  100 ð1Þ
R0p
where Rp and R0p are uninhibited and inhibited polarization resis-
tances, respectively.
As it is shown in Table 1, the CPE values decreased and polari-
zation resistance increased with increasing PDTT concentration.
The decrease in the CPE which can result from a decrease in local
dielectric constant and/or an increase in the thickness of double
layer was attributed to the gradual replacement of water mole-
cules and other ions originally adsorbed on the surface by adsorp-
tion of inhibitor molecules on the metal surface [11,13,37,38,48].
The adsorption of larger PDTT molecules also reduces the capaci-
tance through the increase in the double layer thickness [18].
The adsorption of inhibitor molecules at metal/solution interface
results in an increase of polarization resistance, which reduces cor-
rosion rate of mild steel.
The polarization resistance values were also determined from
the linear polarization resistance (LPR) technique. The Rp values
calculated from the LPR measurements are given in Table 1 with
corresponding inhibition efficiencies. As it is shown in Table 1,
polarization resistance increased with PDTT concentration sug-
gests enhancement of adsorption of Schiff base molecules on the
mild steel surface and blocking the active sites efficiently.
It is well known that, inhibiting ability of organic molecules
strictly depends on exposure time in aggressive solutions. In order
to examine effect of immersion time on the corrosion behavior of
mild steel in 0.5 M HCl solution without and with the addition of
1.0 mM PDTT, EIS and LPR techniques were used. Fig. 4a and b
shows the Nyquist diagrams of mild steel in uninhibited and inhib-
ited 0.5 M HCl solutions, respectively, after different exposure
time. The related electrochemical data are collected in Table 2.
As it is seen from Fig. 4 and Table 2, the polarization resistance
of mild steel in 0.5 M HCl solution reduced to 20 X cm2 after its
exposure for 4 h as a result of an increase in the roughness of the
surface upon exposure. However, the diameter of Nyquist plot of
steel in the presence of inhibitor slightly increased after 4 h expo-
sure when compared with that obtained after 1 h (Fig. 2). The in-
crease in diameter of Nyquist plot of mild steel in inhibitor
containing 0.5 M HCl solution was more pronounced after 24 h in
comparison with shorter immersion time indicates continuous
adsorption process. In contrary to the inhibited solution, the polar-
ization resistance of mild steel in blank solution was continued to
reduce. By increasing immersion time, two loops were more and
more distinguished and polarization resistance was slightly de-
creased. The first loop appearing at high frequencies was attributed
to the charge transfer resistance (Rct) and diffuse layer resistance
(Rd), the second loop at low frequencies was attributed to the film
resistance (Rf) and all other accumulated kinds (corrosion prod-
ucts, inhibitor molecules, etc.). As it can be clearly seen from
Fig. 4 and Table 2, the polarization resistance of mild steel is much
bigger in the presence of inhibitor in comparison with that
obtained in the absence of inhibitor. This indicates Schiff base is
a good corrosion inhibitor for mild steel in 0.5 M HCl solution.
The values of both polarization resistance and corrosion inhibi-
tion efficiency values (I%) corresponding to the LPR data as being
associated over 120 h immersion time are given in Table 2. The
I% values obtained from the LPR are comparable and run parallel
with those obtained from the EIS measurements. It is clear from
Table 2 that the Rp value in the inhibited solution increases up to
3324 R. Solmaz / Corrosion Science 52 (2010) 3321–3330

Table 1
Fitting results of EIS data for mild steel in 0.5 M HCl solution without and with various concentrations of PDTT after 1 h exposure.

Cinh (mM) EIS LPR

2 2 2
CPE1 (lF cm 2
) n1 R1 (X cm ) CPE2 (lF cm 2
) n2 R2 (X cm ) Rp (X cm ) I (%) Rp (X cm2) I (%)
Blank 1594.7 0.77 22.5 22.5 22
0.01 122.2 0.91 3.4 194.5 0.85 121 124 81.9 108 79.6
0.05 99.2 0.91 4.7 178.9 0.87 335 340 87.1 157 85.9
0.1 165.3 0.86 41.4 66.4 0.85 347 388 94.2 355 93.8
0.5 92.8 0.89 36.0 99.9 0.80 649 685 96.7 732 97.0
1.0 45.9 0.92 96.4 80.7 0.71 951 1047 97.9 1046 97.9

3.2. Potentiodynamic polarization measurements

Fig. 5 shows the representative potentiodynamic polarization

curves of mild steel in 0.5 M HCl solution in the absence and
presence of various concentrations of PDTT. The corresponding
electrochemical parameters, i.e., corrosion potential (Ecorr), corro-
sion current density (icorr), weight loss (W) and inhibition efficiency
(I%) values were calculated from these curves and are given in
Table 3. The I% was calculated from polarization measurements
according to the relation;
 0 
icorr  icorr
I% ¼  100 ð2Þ
icorr
0
where icorr and icorr are the uninhibited and the inhibited corrosion
current densities, respectively. Corrosion current densities were ob-
tained by the extrapolation of the current–potential lines to the cor-
responding corrosion potentials. The weight loss was calculated
theoretically with the help of corrosion current densities.
It can be clearly seen from Fig. 5 that, as would be expected,
both anodic metal dissolution of iron and cathodic hydrogen evo-
lution reactions were inhibited after the addition of Schiff base to
the aggressive solution. This result is indicative of the adsorption

Fig. 4. Nyquist plots of mild steel in 0.5 M HCl solution in the absence (a) and
presence of 1.0 mM PDTT (b) after 4 h (d), 24 h (h), 72 h and (N) 120 h (s)
exposure time (solid lines show fitted results).

Table 2
Polarization resistance and inhibition efficiencies of mild steel in 0.5 M HCl solution in
the absence and presence of 1.0 mM PDTT after different immersion time.
Fig. 5. Polarization curves of mild steel in 0.5 M HCl solution without (s) and with
t (h) Blank PDTT
the addition of 0.01 mM (N), 0.1 mM (h) and 1.0 mM (d) PDTT.
EIS LPR EIS LPR
Rp (X cm2) Rp (X cm2) Rp (X cm2) I (%) Rp (X cm2) I (%)
Table 3
4 20 16.4 1165 93.3 1169 98.6
Electrochemical parameters for mild steel determined from polarization measure-
24 15 12.1 1600 99.1 1489 99.2
ments in 0.5 M HCl solution without and with various concentrations of PDTT after
72 5.8 8.3 925 99.4 914 99.1
1 h exposure.
120 3.3 3.5 700 99.5 637 99.5
Cinh (mM) Ecorr (V(Ag/AgCl)) icorr (lA cm2) W (g m2 h1) I (%)
Blank 0.460 715.0 7.45
0.01 0.479 146.6 1.53 79.5
24 h, and then tends to decrease. Because of a strong decrease in 0.05 0.468 121.4 1.27 83.0
the Rp value for uninhibited 0.5 M HCl solution compared to the 0.1 0.481 40.2 0.42 94.4
0.5 0.467 18.8 0.20 97.4
inhibited one, a high I% value was calculated after 120 h of expo-
1.0 0.469 13.0 0.14 98.2
sure time.
 R. Solmaz / Corrosion Science 52 (2010) 3321–3330 3325

of inhibitor molecules on the active sites of mild steel surface. The
inhibition of both anodic and cathodic reactions is more pro-
nounced with the increasing inhibitor concentration. However,
there is no an absolute shift in corrosion potential to more anodic
or more cathodic potentials in comparison with corrosion potential
observed in blank solution. These results suggest that PDTT can be
classified as mixed type corrosion inhibitor [18].
The cathodic current–potential curves (Fig. 5) giving rise to par-
allel lines indicates that the addition of PDTT to the 0.5 M HCl solu-
tion does not modify the hydrogen evolution mechanism and the
reduction of H+ ions at mild steel surface takes place mainly
through a charge transfer mechanism [49–51]. However, in the
anodic part of current–potential curves a different behavior was
observed in comparison with cathodic part. It can be seen from
Fig. 5 that Schiff base molecules act as corrosion inhibitor only at
low potentials. However, corrosion rate increased in the presence
of inhibitor at more positive potentials than 0.300 V(Ag/AgCl)
and the mechanism of anodic dissolution reaction was seen to be
changed. This behavior may be the result of a significant dissolu-
tion of iron, leading to desorption of inhibitor film from the metal
surface [41,52]. In this case, desorption rate of inhibitor should be
higher than its adsorption rate [53]. The observed phenomenon is
generally described as the corrosion inhibition of the metal with
the formation of a protective layer of adsorbed species at the metal
surface [41,54]. These results indicate that the inhibition mode of
inhibitor depends on the electrode potential.

Fig. 6. Nyquist plots of the mild steel at 0.100 and 0.200 V cathodic overpotentials (a and a0 ), +0.100 anodic overpotential (b and b0 ) and +0.300 anodic overpotential (c and
c0 ) obtained in 0.5 M HCl solution in the absence (s) and presence of 1.0 mM PDTT (d).
3326 R. Solmaz / Corrosion Science 52 (2010) 3321–3330
In order to discuss the mechanism of anodic and cathodic reac-
tions in more detail, EIS experiments were carried out at different
anodic and cathodic overpotentials (g) which were previously
determined from the current–potential curves (Fig. 5). The ob-
tained data are presented in Nyquist representation and given in
Fig. 6. It can be seen from Fig. 6 that, in the cathodic potential
range, only one capacitive loop was obtained in blank solution at
0.100 and 0.200 V cathodic overpotentials suggests that at this
potential range the reduction of H+ ions is completely charge trans-
fer controlled. The same behavior was observed in the presence of
inhibitor indicates that the addition of Schiff base to the aggressive
solution does not change the mechanism of hydrogen evolution
reaction. The inhibitor molecules are first adsorbed onto mild steel
surface and, therefore, impedes by merely blocking the reaction
sites of the mild steel surface. In this way, the surface area avail-
able for H+ ions is decreased while the actual reaction mechanism
remains unaffected [18,28,44,55,56]. The polarization resistance
values of mild steel in the blank solution at 0.100 and 0.200 V
cathodic overpotentials are 7.1 and 2.8 X cm2, respectively. How-
ever, the polarization resistance of mild steel at the same overpo-
tentials was considerably increased after the addition of Schiff
base. In the presence of PDTT, the calculated polarization resis-
tance values at 0.100 and 0.200 V cathodic overpotentials were
600 and 110 X cm2, respectively. These results show that the
inhibitor molecules adsorb on cathodic sites and diminish the
reduction of H+ ions efficiently.
In anodic range, a different behavior was observed as it is
clearly seen from Fig. 6. At +0.100 V anodic overpotential, Nyquist
plot of mild steel contains two time constants in blank solution.
The first capacitive loop appeared at high frequencies was attrib-
uted to the charge transfer resistance, and a straight line at low fre-
quencies may be due to accumulated corrosion products at metal
surface, which hinders the diffusion of ions [44]. The Nyquist plots
of mild steel contains only one capacitive loop in inhibited solution
shows that the anodic dissolution of mild steel is charge transfer
controlled. The resistance value of mild steel in the presence of
Schiff base at +0.100 V anodic overpotential was higher than that
calculated in the absence of inhibitor indicate that the adsorption
of inhibitor molecules considerably reduced dissolution of mild
steel at low anodic overpotentials. The appearance of Nyquist plots
were changed at higher anodic overpotentials, both in the absence
and presence of Schiff base. A capacitive loop was observed at the
high frequencies and followed an inductive loop was appeared at
low frequencies in the absence of inhibitor at +0.300 V anodic
overpotential. Such inductive loops at low frequencies were com-
monly attributed to the relaxation process [4]. As it is seen from
Fig. 6, a small inductive loop at low frequencies was also appeared
in the presence of inhibitor. This observation shows that a relaxa-
tion of the surface inhibitor film takes place at more positive
potentials which may be the result of significant dissolution of iron
leading to desorption of the inhibitor from the metal surface [44].
We have previously studied inhibition efficiency of 2A5MT for
mild steel corrosion in 0.5 M HCl solution. According to our previ-
ous report [28] inhibition efficiency of 2A5MT at 1.0 mM inhibitor
concentration was found to be 80.3%. The present results showed
that inhibition efficiency of corresponding Schiff base at the same
inhibitor concentration increased to 98.2%. The greater inhibitive
power of the PDTT can be related to the presence of more p elec-
trons in it’s molecular structure because of presence of extra dou-
ble bonds, a phenyl group as well as an iminic (AC@NA) group. The
other point of view for greater inhibition efficiency of PDTT lines in
the large size of Schiff base molecules [20].
The corrosion inhibition efficiency of 2A5MT and/or its deriva-
tives have been studied for different metals. 2A5MT reported to
perform good inhibition efficiency for copper in saturated ethanol
solution (9 g/L) [25]. The efficiency of 2A5MT and 2-methyl-5-mer-
capto-1,3,4-thiadiazole as copper corrosion inhibitors in neutral
chloride environments was theoretically and experimentally
investigated [26]. The obtained estimates of the total dc path resis-
tance showed that the studied thiadiazole derivatives were excel-
lent copper corrosion inhibitors. The corrosion behavior of bronze
in the presence of 2A5MT has been investigated in 5% citric acid at
60 °C using electrochemical measurements [27]. It was reported
that the presence of 2A5MT cause a remarkably decrease in corro-
sion rate which was attributed mainly to the protective film
formed by 2A5MT. The corrosion behavior of carbon steel has been
studied in the absence and presence of different concentrations of
CA in citric acid for different immersion times (6 and 24 h) at 30 °C
using weight loss, potentiodynamic polarization and impedance
measurements [35]. CA has given good inhibition efficiency, but
it was decreased when duration of immersion increased from 6
to 24 h. The high inhibition efficiency of CA was explained by for-
mation of the adsorbed protective inhibitor film.
3.3. Hydrogen gas evolution measurements
During the corrosion of iron in strong acid solution, the cathodic
reaction is reduction of H+ ions to molecular hydrogen according to
reaction mechanism given below [1,44]:
Fe þ Hþ $ ðFeHþ Þads ð3Þ
ðFeHþ Þads þ e ! ðFeHÞads ð4Þ
ðFeHÞads þ Hþ þ e ! Fe þ H2 ð5Þ
Because the rate of hydrogen gas evolution is directly propor-
tional to the rate of corrosion, the measuring of hydrogen gas
evolved at cathodic sites as a function of reaction time can give
valuable information about starting and continuity of the corro-
sion. The relative speed and effectiveness of the gasometric tech-
niques as well as their suitability for in situ monitoring, any
perturbation by an inhibitor with respect to gas evolution in
metal/solution systems has been established in the literature
[57–61]. In order to measure hydrogen gas volume during the
corrosion, a burette was filled with the test solution and placed
over the working electrode. The change of the volume of H2 gas
evolved from the corrosion reaction in 0.5 M HCl solution without
and with the addition of 1.0 mM PDTT as a function of exposure
time was graphically shown in Fig. 7. It can be seen from Fig. 7,
the rate of H2 evolution is small at the beginning of the reaction
in blank solution. It increases remarkably, after a certain time
most probably due to the increased surface area of mild steel as
a result of excess dissolution of iron. However, the rate of H2 evo-
lution was considerably reduced after the addition of Schiff base
160
140 blank
120 PDTT
-2
100
VH2 / mL cm
80
60
40
20
0
-20
0 24 48 72 96 120 144
t/h
Fig. 7. Hydrogen gas volume evolved on mild steel electrode as a function of
exposure time in 0.5 M HCl (s) and containing 1.0 mM PDTT (d) solutions.
 R. Solmaz / Corrosion Science 52 (2010) 3321–3330 3327

to the aggressive media. After 120 h, the total measured H2 gas

volume is 146 and 0.4 mL cm2 in uninhibited and inhibited
0.5 M HCl solutions, respectively. A considerably decrease in H2
volume in the presence of Schiff base can be attributed to the
adsorption of Schiff base molecules on the mild steel surface
and prevention of adsorption of H+ ions onto the metal surface
as illustrated in reaction (3) thereby, consequently slowing down
of the cathodic reaction [44].

3.4. Change of open circuit potential with immersion time

The variation of open circuit potential of mild steel as a function

of exposure time (Eocp  t) in 0.5 M HCl in the absence and pres-
ence of 1.0 mM PDTT was graphically presented in Fig. 8. It is clear
from Fig. 8, the Eocp value of mild steel in 0.5 M HCl solution shifts
towards more positive potentials continuously up to 24 h and after
this time period it is nearly stable around 0.460 V(Ag/AgCl). How-
ever, the addition of Schiff base produces a considerably nobler Eocp
value and tends to posses more cathodic values with the increasing
immersion time.

3.5. Scanning electron microscopy and atomic force microscopy studies

The surface morphology of mild steel specimens exposed to

0.5 M HCl solution in the absence and presence of Schiff base for
120 h were examined by high resolution SEM and AFM techniques.
Fig. 9 shows SEM images of mild steel surface which immersed in
0.5 M HCl solution without and with the addition of 1.0 mM PDTT.
It can be clearly seen from Fig 9a that, the specimen surface was
strongly damaged in the absence of inhibitor due to metal dissolu-
tion in aggressive solution. A large number of pits with large size
and high depth distributed over the surface are seen. However, Fig. 9. SEM images of mild steel surface after exposed to 0.5 M HCl solution without
(a) and with the addition of 1.0 mM PDTT (b) after 120 h (Mag: 5K).
no pits and cracks except polishing lines were observed in the
micrograph after the addition of Schiff base to the aggressive solu- are wide and deep pits on the surface, which indicate the main
tion (Fig. 9b). Inhibitor molecules adsorbed on active sites of mild characteristic of pitting corrosion. However, the surface is more
steel and a smoother surface was observed when compared to the uniform in the inhibited solution than the surface in the absence
surface treated with uninhibited 0.5 M HCl solution. of the inhibitor except some hallows structures, which most prob-
AFM is a powerful technique to investigative the surface mor- ably due to polishing lines (Fig. 10b). The inhibitor molecules are
phology at nano- to micro-scale and has become a new choice to adsorbed on the active sites and protected the metal against
study the influence of inhibitors on the generation and the pro- corrosion.
gress of corrosion at the metal/solution interface [44]. The three-
dimensional AFM images of mild steel surface exposed to 0.5 M
3.6. Adsorption isotherm
HCl solution in the absence and presence of 1.0 mM PDTT for
120 h are shown in Fig. 10a and b, respectively. The obtained
The efficiency of Schiff base molecules as a successful corrosion
AFM results are in very good agreement with the SEM results. As
inhibitor mainly depends on their adsorption ability on the metal
it is seen from Fig. 10a, mild steel has a very porous structure after
surface. The adsorption process consists of the replacement of
exposing to 0.5 M HCl solution in the absence of inhibitor. There
water molecules at a corroding interface according to following
process [62].
-0.350 OrgðsolÞ þ nH2 OðadsÞ ! OrgðadsÞ þ nH2 OðsolÞ ð6Þ
blank
where Org(sol) and Org(ads) are the organic molecules in the solution
PDTT
Eocp / V(Ag/AgCl)

-0.400 and adsorbed on the metal surface, respectively, and n is the num-
ber of water molecules replaced by the organic molecules. It is
essential to know the mode of adsorption and the adsorption iso-
-0.450 therm that can give important information on the interaction of
inhibitor and metal surface. The surface coverage value, h (h = I/
100) for different concentrations of Schiff base was used to explain
-0.500 the best adsorption isotherm. Attempts were made to fit surface
coverage values determined from LPR measurements into different
adsorption isotherm models. The linear regression coefficient val-
-0.550
ues (R2) determined from the plotted curves were found to be
0 24 48 72 96 120 144
0.99996 for Langmuir, 0.90048 for Temkin, 0.9154 for Bockris–
t/h
Swinkels (x = 1), 0.9594 for Flory–Huggins and 0.9881 for Frumkin
Fig. 8. The change of open circuit potential as a function of exposure time in 0.5 M adsorption isotherms. According to these results, it can be con-
HCl (s) and containing 1.0 mM PDTT (d) solutions. cluded that the best description of the adsorption behavior of PDTT
3328 R. Solmaz / Corrosion Science 52 (2010) 3321–3330

DGads ¼ RT lnð55:5K ads Þ ð8Þ

5
The average value of equilibrium constant was 1.97  10 M1
reflects the high adsorption ability of PDTT on mild steel surface
[63]. (Thermodynamic parameters were determined from the EIS,
the potentiodynamic polarization measurements and the LPR
techniques and average values were given.) The negative value of
standard free energy of adsorption (40.16 kJ mol1) indicates
spontaneous adsorption of Schiff base on mild steel surface and
also the strong interaction and stability of the adsorbed layer with
the steel surface [64–66].
Generally the standard free energy of adsorption values of
20 kJ mol1 or less negative are associated with an electrostatic
interaction between charged molecules and charged metal surface
(physical adsorption); those of 40 kJ mol1 or more negative in-
volves charge sharing or transfer from the inhibitor molecules to
the metal surface to form a co-ordinate covalent bond (chemical
adsorption) [67,68]. The calculated standard free energy of adsorp-
tion value is closer to 40 kJ mol1. Therefore, it can be concluded
that the adsorption of Schiff base on the mild steel surface is more
chemical than physical one [69,70].

3.7. Inhibition mechanism

Thermodynamic parameters showed that the adsorption of

PDTT on the mild steel surface 0.5 M HCl solution is chemical than
physical one. Chemical adsorption of PDTT arises from the donor
acceptor interactions between free electron pairs of hetero atoms
and p electrons of multiple bonds as well as phenyl group and va-
cant d orbitals of iron [20,69]. It has been reported that the adsorp-
tion of heterocyclic compounds occurs with the aromatic rings
some times parallel but mostly normal to the metal surface. The
Fig. 10. Three-dimensional AFM images of mild steel surface after exposed to 0.5 M orientation of molecules could be dependent on the pH and/or
HCl solution without (a) and with the addition of 1.0 mM PDTT (b) for 120 h.
electrode potential. However, more work should be completed to
confirm the above arguments [71]. In the case of parallel adsorp-
can be explained by Langmuir adsorption isotherm which is given tion of inhibitor molecules, the steric factors also must be taken
by Eq. (7). A representative Langmuir adsorption isotherm using into consideration.
the LPR data is given in Fig. 11. The adsorption of organic molecules on the solid surfaces can-
Langmuir adsorption isotherm can be expressed by the follow- not be considered only as purely physical or as purely chemical
ing equation: adsorption phenomenon. In addition to the chemical adsorption,
inhibitor molecules can also be adsorbed on the steel surface via
C ðinhÞ 1 electrostatic interaction between the charged metal surface and
¼ þ C ðinhÞ ð7Þ
h K ðadsÞ charged inhibitor molecule if it is possible. The free energy of
adsorption value is not very greater than 40 kJ mol1 should indi-
where Cinh is inhibitor concentration and Kads is the equilibrium cate contribution of physical adsorption. If the contribution of elec-
constant for the adsorption–desorption process. The standard free trostatic interactions takes place, the following adsorption process
energy of adsorption of inhibitor (DGads ) on mild steel surface can can additionally be discussed.
be evaluated with the following equation: The surface charge of metals can be determined by the compar-
ison of open circuit potential with the respective potential of zero
charge (PZC). EIS measurements were carried out at different over-
1.2 potentials and a plot of Rp vs. applied potential was obtained
(Fig. 12) according the methods used in literature [72,73]. As it is
1.0 seen from Fig. 12, the obtained curves show a parabola with a max-
imum at 0.484 V(Ag/AgCl), which can be called the PZC of mild
0.8
C / θ (mM)

steel in 0.5 M HCl solution containing 1.0 mM PDTT. The open cir-
cuit potential of mild steel (0.469 V(Ag/AgCl)) is more positive than
0.6
the potential of zero charge shows that the surface of mild steel is
0.4 positively charged in inhibited 0.5 M HCl solution.
The anodic dissolution of iron follows the steps [1]:
0.2
 
Fe þ Cl $ ðFeCl Þads ð9Þ
0.0
  
0.0 0.2 0.4 0.6 0.8 1.0 1.2 ðFeCl Þads $ ðFeCl Þads þ e ð10Þ
C (mM) 
ðFeCl Þads $ ðFeCl Þ þ e
þ 
ð11Þ
Fig. 11. Langmiur adsorption plot of mild steel in 0.5 M HCl solution containing þ 
ðFeCl Þ $ Fe2þ þ Cl ð12Þ
different concentrations of PDTT.
 R. Solmaz / Corrosion Science 52 (2010) 3321–3330
Fig. 12. The plot of Rp vs. electrode potential in 0.5 M HCl containing 1.0 mM PDTT
solution.
Schiff bases have basic character and expected to be protonated
in equilibrium with the corresponding neutral form in strong acid
solutions.
PDTT þ Hþ $ PDTTHþ ð13Þ

Because mild steel surface carried positive charge, Cl ions
should be first adsorbed onto the positively charged metal surface
according to reaction (9). Then the inhibitor molecules adsorb
through electrostatic interactions between the negatively charged
metal surface and positively charged Schiff base molecule (PDTT+)
and form a protective (FeClPDTT+)ad layer. In this way, the oxida-
tion reaction of (FeCl)ads as shown by reaction steps from (10) to
(12) can be prevented [63,44]. The protonated Schiff base mole-
cules are also adsorbed at cathodic sites of metal in competition
with hydrogen ions according to Eq. (3). The adsorption of proton-
ated Schiff base molecules reduces the rate of hydrogen evolution
reaction [1,28,69]. Finally, it should also be emphasized that, the
large size and high molecular weight of Schiff base molecule can
also contribute the greater inhibition efficiency of PDTT [20].
4. Conclusions
The PDTT Schiff base was synthesized and investigated as corro-
sion inhibitor for mild steel in 0.5 M HCl solution for both short and
long immersion time using a series of techniques. The following
points can be emphasized:
1. PDTT has an excellent inhibition effect for the corrosion of mild
steel in 0.5 M HCl solution. Its inhibition efficiency is both con-
centration and immersion time dependent. The high inhibition
efficiency of Schiff base was attributed to the adherent adsorp-
tion of the inhibitor molecules on the metal surface.
2. The potentiodynamic polarization curves indicated that PDTT
behaved as mixed type corrosion inhibitor by inhibiting both
anodic metal dissolution and cathodic hydrogen evolution
reactions.
3. The adsorption of PDTT molecules on mild steel surface has
been described Langmuir adsorption isotherm. The high value
of adsorption equilibrium constant and negative value of stan-
dard free energy of adsorption suggested that, PDTT was
strongly adsorbed on mild steel surface and this adsorption
took place spontaneously.
4. The calculated standard free energy of adsorption has been
found close to 40 kJ mol1 which can be explained as chemical
rather than physical adsorption.
5. The high resolution AFM and SEM micrographs were showed
that the corrosion of mild steel in 0.5 M HCl solution was
3329
described by existing pitting and the addition of inhibitor to
the aggressive solutions diminished the corrosion of mild steel.
Acknowledgements
The experimental measurements were carried out in Çukurova
University, Science and Letters Faculty, Chemistry Department,
Physicochemistry Research Laboratory. The author is greatly
thankful to Çukurova University for experimental measurements
in Physicochemistry Research Laboratory. The author is greatly
thankful to Assoc. Prof. Mustafa Çulha for SEM and AFM analysis.
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