Corrosion Science 52 (2010) 788–793

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

Carbon steel corrosion inhibition in hydrochloric acid solution using a reduced

Schiff base of ethylenediamine
Adriana Barbosa da Silva a, Eliane D’Elia b, José Antonio da Cunha Ponciano Gomes a,*
a
Laboratório de Corrosão, Programa de Engenharia Metalúrgica e de Materiais, COPPE, Universidade Federal do Rio de Janeiro, Ilha do Fundão, Centro de Tecnologia,
Rio de Janeiro, RJ, Brazil
b
Departamento de Química Inorgânica, Instituto de Química, UFRJ, Avenida Athos da Silveira Ramos, 149, Centro de Tecnologia, Bloco A, Sala 634A,
21941-909 Cidade Universitária, Rio de Janeiro, RJ, Brazil

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

Article history: The behavior of the Schiff base N,N0 -bis(salicylidene)-1,2-ethylenediamine (Salen), its reduced form (N,N0 -
Received 8 July 2009 bis(2-hydroxybenzyl)-1,2-ethylenediamine) and a mixture of its preceding molecules, ethylenediamine
Accepted 30 October 2009 and salicylaldehyde, as carbon steel corrosion inhibitors in 1 mol L1 HCl solution was studied by corro-
Available online 10 November 2009
sion potential measurements, potentiodynamic polarization curves, electrochemical impedance spectros-
copy and spectrophotometry measurements. The experimental results showed that the reduced Salen
Keywords: presented the highest efficiency among the inhibitors studied. The results obtained in the presence of
A. Steel
Salen were similar to those obtained in the presence of the salicylaldehyde and ethylenediamine mixture,
A. Acid solutions
B. EIS
showing that in acid medium the Salen molecule undergoes hydrolysis, regenerating its precursor
B. Polarization molecules.
C. Acid inhibition Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction and a ketone or aldehyde, and have the general formula RC@NR [29].
Some works have revealed that the inhibition efficiency of these
Carbon steel corrosion has been the subject of many studies, compounds is much higher than the corresponding effect obtained
particularly in acid media commonly used in several industrial with amines and aldehydes. This phenomena is attributed to the
fields, such as acid pickling, industrial cleaning and oil-well acidiz- presence of the imine group (AC@NA) in the molecules [13].
ing [1,2]. In a recent work, Baddini et al. [3] analyzed 23 different Although the literature indicates that Schiff base compounds
compounds, including amines, alcohols, and thiourea and its deriv- are good corrosion inhibitors for carbon steel in acid media, the lit-
atives with respect to the corrosion of three different steels of erature also shows that, in some cases, the imine group is not sta-
interest to the petroleum industry. Inhibitors are needed to reduce ble, particularly in acid medium, where it undergoes hydrolysis,
the corrosion rate of metallic materials in the above mentioned regenerating an amine and an aldehyde [29–34]. Thus, in these
media. Most of the efficient inhibitors used in industry are organic cases, the efficiency measured is probably due to the presence of
compounds that contain mainly nitrogen, oxygen and sulphur these preceding compounds, which are already known as efficient
atoms, as well as multiple bonds, through which they are adsorbed corrosion inhibitors.
on the metal surface. A bond can be formed between the electron Emregül and Hayvali [13] compared the inhibitory action of a
pair of the donor atoms, and/or the electron cloud, and the metal Schiff base (4-[(4-hydroxy-3-hydroxymethyl-benzylidene)-ami-
surface, thereby reducing corrosive attack in acid medium. In spite no]-1,5-dimethyl-2-phenyl-1,2-dihydro-pyrazol-3-one) with that
of the large number of organic compounds found in the literature, of their preceding molecules, amine and aldehyde, but they proba-
the choice of an appropriate inhibitor for a particular system is dif- bly did not take into account the possible hydrolysis reaction of the
ficult due to the specificity of the inhibitor and the great variety of Schiff base. The authors presented the results obtained in the pres-
corrosion systems [4]. Thus, there is always a need to develop new ence of amine, aldehyde and Schiff base separately, and results ob-
corrosion inhibitors. tained from experiments using a mixture of aldehyde and amine
A wide range of studies have investigated the corrosion inhibi- were not included. In this way, the conclusion presented by the
tion of Schiff base compounds for mild steel, copper, zinc and alumi- authors, that the highest inhibition action is due to adsorption of
num [5–28]. Schiff bases are the condensation products of an amine the imine group, should be revised. The corrosion inhibition could
be due to the amine and aldehyde adsorptions occurring together,
with these molecules being regenerated by hydrolysis of the Schiff
* Corresponding author. Tel./fax: +55 21 22901544.
E-mail address: [email protected] (J.A. da Cunha Ponciano Gomes).
base.

0010-938X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.10.038
 A.B. da Silva et al. / Corrosion Science 52 (2010) 788–793 789

The results of the present work attempt to clarify the interpre- The chemical structures of the investigated compounds are
tation of the behavior of these compounds on the corrosion process shown in Fig. 1.
of carbon steel in acid solutions.
Schiff bases can be reduced to the corresponding amine deriva- 2.2. Electrolyte
tives, which have a higher stability because they do not undergo
the hydrolytic processes encountered in the Schiff bases. In this The electrolyte was a 1 mol L1 HCl solution prepared using
case, the imine group (AC@NA) is reduced to an amine group double distilled water. All chemicals were analytical grade re-
(ACANH) by reaction with sodium borohydride [32]. agents. The experiments were carried out under non-stirred and
In the literature, only Emregül and Atakol [23] compare the naturally aerated conditions at 25 °C. Comparative analysis of the
Schiff base with its reduced form on iron corrosion in 1 mol L1 inhibitors was carried out using 5  103 mol L1 of Schiff base
HCl solution. The results of electrochemical impedance obtained and 5  103 mol L1 of its reduced form. In order to compare
in that work at the corrosion potential, and the cathodic and anodic the effect of the reduced Schiff base on carbon steel corrosion with
polarization curves, showed that the reduced form presents the its hydrolysis products, experiments were also performed in the
highest inhibition efficiency. This fact surprised the authors, who presence of 5  103 mol L1 of ethylenediamine, 102 mol L1 of
expected that the p-electrons of the imine group were the deter- salicylaldehyde and presence mixture of both compounds while
mining factor in the process of adsorption. However, the ultraviolet maintaining this concentration range, to which 1% ethanol was
analysis (data not presented by the authors) showed that the Schiff added for solubility reasons.
bases underwent hydrolysis in the acid solutions with an overall
change of 40% after 5 days for one of the compounds studied, with 2.3. Electrochemical measurements
the major change being observed in the first 2 h.
The objective of the present work is to investigate the inhibitor All of the electrochemical experiments were carried out using a
effects of N,N0 -bis(salicylidene)-1,2-ethylenediamine (Salen), its re- conventional three-electrode cell consisting of a carbon steel work-
duced form (N,N0 -bis(2-hydroxybenzyl)-1,2-ethylenediamine) and ing electrode, a saturated calomel electrode (SCE) as reference and
a mixture of the preceding molecules, ethylenediamine and salicyl- a platinum wire as a counter-electrode. The working electrode was
aldehyde in a ratio of 1:2, on carbon steel corrosion in 1 mol L1 a carbon steel specimen with the following composition (in wt%):
HCl solution using electrochemical techniques: corrosion potential C 0.17–0.24, P max 0.04, S max 0.05, Mn 0.3–0.6, Fe balance. These
measurements, anodic and cathodic polarization curves, electro- electrodes were prepared by embedding the carbon steel plate in
chemical impedance measurements (EIS), and spectrophotometry epoxy resin and exposing a flat surface of approximately 1 cm2 to
measurements. the electrolyte. Prior to each measurement, the electrode surface
was mechanically abraded with a series of emery paper (200,
320, 400, 500 and 600), rinsed with ethanol and acetone and finally
2. Experimental dried in hot air.
Electrochemical experiments were carried out using an Autolab
2.1. Synthesis of the Schiff base and the reduced form digital potentiostat model PGSTAT 302. In order to obtain a steady
state open circuit potential, the working electrode was immersed
2.1.1. Salen into the test solution for 1 h before the measurements. The electro-
The Schiff base N,N0 -bis(salicylidene)-1,2-ethylenediamine chemical impedance spectroscopy measurements were performed
(Salen) was prepared as described in [33] according to the following at open corrosion potential, Ecorr, using a frequency range within
procedure. A stirred solution containing 4.0 mmol of salicylalde- the limits 100 kHz and 10 mHz with a sinusoidal signal amplitude
hyde in ethanol (50 mL) was added dropwise to an ethanolic equal to 10 mV. Potentiodynamic anodic and cathodic polarization
solution containing 2.0 mmol of ethylenediamine (10 mL). Precipi- curves were performed using a scan rate equal to 20 mV min1
tation of Salen as brilliant yellow flakes in the solution started al- from the corrosion potential to 300 mV of anodic or cathodic over-
most immediately. This mixture was then stirred for 1 h in order potential, respectively. All experiments were performed at least
to promote complete reaction. The solid was filtered and washed three times to ensure reproducibility.
with cold ethanol. The ligand was recrystallized in ethanol, dried
over silica and then characterized by FTIR spectroscopy. IR data 2.4. Spectrophotometry measurements
(KBr, cm1): 1636 (tC@N), 1610 (tC@C), 1284 (tCAO), 750 (dCHaromatic);
m.p. = 127 °C. The UV/vis spectra in the 380–500 nm range were obtained on a
Varian Cary 1E UV/Vis spectrophotometer using quartz cells of
light pass length 1.00 cm, and 5  104 mol L1 solutions in abso-
2.1.2. Reduced Salen lute ethanol in order to verify hydrolysis of the Schiff base.
In order to reduce the imine bond the following procedure was
done according to previously described methods [33]. Schiff base
Salen (1 mmol) was dissolved in absolute ethanol and 3 mmol of
sodium borohydride (NaBH4) were added in small portions over
1 h. The resulting mixture was stirred for 2 h, and during this per-
iod its yellow color disappeared and a colorless solution was ob-
tained. The solvent was removed under vacuum and 50 mL of
distilled water was added to the resulting oil. The inhibitor was
then extracted with small portions of CHCl3. The organic fractions
were collected, dried with MgSO4 and filtered. The solvent was
again removed under vacuum and the resulting white crystals
were washed with cold isopropyl alcohol. The reduced Salen
(N,N0 -bis(2-hydroxybenzyl)-1,2-ethylenediamine) was character-
ized by FTIR spectroscopy. IR data (KBr, cm1): 3288 (tNAH), Fig. 1. Molecular structure of the organic compounds studied as corrosion
1606 (tC@C), 1284 (tCAO), 753 (dCHaromatic); m.p. = 121 °C. inhibitors (1) salicylaldehyde (2) ethylenediamine (3) Salen (4) reduced Salen.
790 A.B. da Silva et al. / Corrosion Science 52 (2010) 788–793

3. Results and discussion Table 1

Corrosion potential values obtained for a carbon steel specimen in 1 mol L1 HCl in
the absence and presence of Salen, salicylaldehyde, ethylenediamine and reduced
Fig. 2 shows the open circuit potential vs. time curves obtained Salen.
to carbon steel in 1 mol L1 HCl solution in the absence and pres-
Solution E (mVSCE)
ence of ethylenediamine, a 1:2 mixture of ethylenediamine and
salicylaldehyde and reduced Salen. It can be seen in this figure that 1 mol L1 HCl (blank) 497
5  103 mol L1 ethylenediamine 503
the potentials recorded after 1 h of immersion of the electrode in
102 mol L1 salicylaldehyde 511
the solution reached a steady state condition. The curves obtained 5  103 mol L1 ethylenediamine + 102 mol L1 salicylaldehyde 512
in the presence of the others inhibitors present the same behav- 5  103 mol L1 Salen 511
iour. The carbon steel corrosion potential values obtained in the 5  103 mol L1 reduced Salen 499
absence and presence of the inhibitors are shown in Table 1. There
was no significant variation of the potential, and in all conditions,
the open corrosion potential was within the limits of 497 and
512 mV vs. SCE.
Fig. 3 presents the electrochemical impedance diagrams ob-
tained at the corrosion potential in the absence and presence of
the inhibitors. Only one capacitive loop can be observed in the fre-
quency range adopted. The polarization resistance value obtained
in the presence of 5  103 mol L1 Salen (55 X cm2) was quite
similar to the value obtained in the presence of the
5  103 mol L1 ethylenediamine and 102 mol L1 salicylalde-
hyde mixture (48 X cm2). However, the polarization resistance ob-
tained in the presence of the reduced Salen, approximately
308 X cm2, was higher than the polarization resistance obtained
with the other inhibitors. This result is in accordance with the re-
sults of the electrochemical impedance and cathodic and anodic
polarization curves obtained by Emeregül and Atakol [23], who
showed that the reduced Schiff base presents higher inhibition effi-
ciency than the Schiff base itself.
Table 2 shows the inhibition efficiency values calculated from
polarization resistance values obtained from the electrochemical
impedance diagrams presented in Fig. 3 as follows:

RP  R0P
IE ¼  100 ð1Þ
RP

where Rp and R0p are the polarization resistance of carbon steel with
Fig. 3. Electrochemical impedance diagrams obtained at the corrosion potential for
and without inhibitor molecules, respectively. The IE obtained in carbon steel in 1 mol L1 HCl in the absence (j) and presence of 5  103 mol L1 of
the presence of 5  103 mol L1 Salen (69%) is quite similar to ethylenediamine (+), 1  102 mol L1 of salicylaldehyde (N), a mixture containing
the value obtained in the presence of the 5  103 mol L1 ethy- 5  103 mol L1 of ethylenediamine and 1  102 mol L1 of salicylaldehyde (),
lenediamine and 102 mol L1 salicylaldehyde mixture (65%). This 5  103 mol L1 of Salen (d), 5  103 mol L1 reduced Salen (h). (A) Full scale and
(B) zoom.
result suggests that the inhibition effect obtained is due to the
conjoint action of the amine and aldehyde molecules produced by
Salen hydrolysis. These results also suggest that the inhibition ac-
tion cannot be attributed to the imine group adsorption as reported Table 2
Polarization resistance values obtained from the electrochemical impedance dia-
grams and corresponding inhibition efficiency for the corrosion of carbon steel in
1 mol L1 HCl in the absence and presence of Salen, salicylaldehyde, ethylenediamine
and reduced Salen.

Solution Rp (X cm2) IE (%)

1
1 mol L HCl (blank) 17 –
5  103 mol L1 ethylenediamine 19 11
102 mol L1 salicylaldehyde 40 58
5  103 mol L1 ethylenediamine 48 65
+ 102 mol L1 salicylaldehyde
5  103 mol L1 Salen 55 69
5  103 mol L1 reduced Salen 308 94

in the literature [9,21,27]. This assumption is supported by the IE of

94% obtained in the presence of 5  103 mol L1 reduced Salen, as
indicated in Table 2.
The anodic and cathodic polarization curves of carbon steel in
1 mol L1 HCl solution in the absence and presence of the inhibi-
Fig. 2. Open circuit potential vs. time curves of carbon steel in 1 mol L1 HCl in the
absence (j) and presence of 5  103 mol L1 of ethylenediamine (+), a mixture
tors are presented in Fig. 4. A decrease of the anodic and cathodic
containing 5  103 mol L1 of ethylenediamine and 1  102 mol L1 of salicylal- current density, indicating the presence of the inhibitors blocking
dehyde () and 5  103 mol L1 of reduced Salen (h). both processes, can be observed. Additionally, the polarization
 A.B. da Silva et al. / Corrosion Science 52 (2010) 788–793 791

indicating imine bond cleavage due to Salen hydrolysis. Conse-

quently, the formation of ethylenediamine and salicylaldehyde
occurs.
Thus, both electrochemical and UV/vis absorption spectra
results confirm Salen hydrolysis. Moreover, these results are
according to Correia et al. [33] that showed that similar Schiff
bases are more susceptible to hydrolysis than the corresponding
reduced form. The corrosion inhibition efficiency of this compound
mentioned in many reports has been interpreted as an effect of the
imine group [9,21,27]. However, the results obtained in the present
work support the assumption that inhibition is related to the effect
of the aldehyde and amine molecules, which are already known for
their corrosion-inhibiting properties.
Therefore, on the basis of the presented results, it is reasonable
to claim that the corrosion inhibiting effects of Salen in acid media
should be reconsidered. When in acidic medium, the Salen mole-
cule is unstable and undergoes hydrolysis to regenerate its precur-
sor molecules, salicylaldehyde and ethylenediamine. The inhibitor
Fig. 4. Polarization curves of carbon steel in 1 mol L1 HCl in the absence (j) and effect can be associated with the presence of these molecules in
presence of 5  103 mol L1 of ethylenediamine (+), 1  102 mol L1 of salicylal- solution. Another point to be stressed is the higher IE obtained
dehyde (N), a mixture containing 5  103 mol L1 of ethylenediamine and
1  102 mol L1 of salicylaldehyde (), 5  103 mol L1 of Salen (d) and
with reduced Salen. This behavior demonstrates that the use of this
5  103 mol L1 of reduced Salen (h). more stable compound can produce much better results with re-
spect to the corrosion control of carbon steel in acid environments.
Since the reduced Salen molecule presented the best inhibition
result obtained with Salen is quite similar to that obtained in the efficiency, we decided to study its protective effects at other
presence of the amine and aldehyde mixture. Again, these results concentrations. Table 3 presents the corrosion potential values
suggest that the Salen molecule is hydrolyzed to its precursor mol- obtained for carbon steel in 1 mol L1 HCl solution in the absence
ecules, ethylenediamine and salicylaldehyde, in acidic medium. It and presence of reduced Salen in the concentration range of
is very important to remark that the decrease of the anodic and 5  105 mol L1 to 102 mol L1. The open circuit potential vs.
cathodic current density is much more expressive in the presence time curves obtained to this concentration range of reduced Salen
of the reduced Salen molecule. These results are in agreement with are not shown but the curves presented the same behaviour as
the electrochemical impedance diagrams that presented the high- showed in Fig. 2. All the open circuit potentials have a reliable sta-
est IE in the presence of this inhibitor. ble value after 1 h immersion of the electrode in the solution. The
These results suggest that the reduced form of Salen is more results show that the open corrosion potential does not depend on
stable in acidic medium when compared to the Schiff. The inhibitor the reduced Salen concentration.
effect of Salen can be associated to the presence of the amine and Fig. 6 presents the corresponding electrochemical impedance
aldehyde in solution. In order to confirm Salen hydrolysis, its diagrams for carbon steel in 1 mol L1 HCl solution in the absence
UV/vis absorption spectra were obtained in ethanol and acidic and presence of reduced Salen in the same concentration range.
ethanolic solution by the addition of hydrochloric acid until the The polarization resistance increases with the reduced Salen
pH reached zero. The UV/vis data are presented in Fig. 5. The re- concentration, showing a maximum value at 102 mol L1
sults obtained in ethanol showed a strong absorption in the visible (321 X cm2). Table 4 shows the IE values calculated from the polar-
region at around 405 nm. This absorption is due to the imine group ization resistance values extracted from the electrochemical
present in this molecule [35]. In acidic ethanolic solution, the band impedance diagrams. An IE of 95% was the maximum value ob-
associated with this absorption disappeared after few minutes, tained at 102 mol L1. This concentration is above the saturation
limit, since with a lower concentration (at 5  103 mol L1), the
IE was almost the same, 94%.
Fig. 7 presents the polarization curves of carbon steel in
1 mol L1 HCl solution in the absence and presence of reduced
Salen in the concentration range of 5  105 mol L1 to
102 mol L1. These curves show that the presence of the inhibitor
decreases both the anodic and cathodic current density. This effect
increases with increasing the reduced Salen concentration.
All of the results suggest an adsorption mechanism of the mol-
ecule on the metal surface, decreasing both anodic and cathodic

Table 3
Corrosion potential values obtained for a carbon steel specimen in 1 mol L1 HCl in
the absence and presence of different concentrations of reduced Salen.

Reduced Salen E (mVSCE)

Blank 497
5  105 495
5  104 497
103 498
2.5  103 496
5  103 499
Fig. 5. The UV/vis spectra of Salen (d) in ethanol and (s) in acidic ethanolic 102 497
solution (pH zero) by the addition of HCl.
792 A.B. da Silva et al. / Corrosion Science 52 (2010) 788–793

Fig. 6. Electrochemical impedance diagrams obtained at the corrosion potential for

carbon steel in 1 mol L1 HCl in the absence (j) and presence of reduced Salen at
different concentrations: 5  105 mol L1 (), 5  104 mol L1 (4), 103 mol L1
(N), 2.5  103 mol L1 (5), 5  103 mol L1 (h), 102 mol L1 (d).

Fig. 8. Langmuir isotherm for adsorption of reduced Salen on the carbon steel
Table 4 surface in 1 mol L1 HCl.
Polarization resistance values obtained from the electrochemical impedance dia-
grams and corresponding inhibition efficiency for the corrosion of carbon steel in
1 mol L1 HCl in the absence and presence of different concentrations of reduced The best fit was obtained using the Langmuir isotherm, ex-
Salen.
pressed as:
Reduced Salen Rp (X cm2) IE (%)
C 1
Blank 17 ¼ þC ð3Þ
5  105 20 15
h K ads
5  104 39 56
where Kads is the adsorption constant.
103 54 69
2.5  103 130 87 Fig. 8 presents a straight line obtained by plot of C/h against
5  103 308 94 concentration with a linear correlation coefficient and a slope near
102 321 95 to unity (0.9998 and 1.014, respectively), showing that the adsorp-
tion behavior of the inhibitor obeys this isotherm. The adsorption
constant is related to the standard free energy of adsorption
processes and, as a consequence, the carbon steel corrosion rate. (D0ads ) by Eq. (4):
The establishment of isotherms that describe the adsorption
behavior of this inhibitor on the metal surface can provide valuable
1 DG0ads
ln K ads ¼ ln  ð4Þ
indications of the nature of the interaction. In the present research, 55:5 RT
the Langmuir, Frumkin, and Temkin isotherms were tested. The de- where 55.5 is the molar concentration of water in the solution ex-
gree of surface coverage (h) was evaluated from polarization resis- pressed in molarity units (mol L1).
tance values obtained from the electrochemical impedance The values obtained for Kads and D0ads were 2.9  103 and
diagrams as follows: 30 kJ mol1, respectively. The negative values of D0ads indicate that
the adsorption of the inhibitor molecule on the metal surface is a
RP  R0P
h¼ ð2Þ spontaneous process.
RP

4. Conclusion

1. The results obtained in the presence of Salen are similar to

those obtained in the presence of a 2:1 salicylaldehyde and eth-
ylenediamine mixture;
2. In acidic medium, the Salen molecule undergoes hydrolysis,
regenerating its precursor molecules of salicylaldehyde and
ethylenediamine;
3. The reduced Salen molecule presented the best IE when com-
pared with Salen and its precursor molecules ethylenediamine
and salicylaldehyde;
4. Reduced Salen behaves as an adsorption inhibitor by blocking
the active sites, decreasing both anodic dissolution and cathodic
processes, and consequently the carbon steel corrosion rate;
5. The reduced Salen molecule adsorption follows the Langmuir
isotherm.

Fig. 7. Polarization curves of carbon steel in 1 mol L1 HCl in the absence (j) and
presence of reduced Salen at different concentrations: 5  105 mol L1 (),
Acknowledgement
5  104 mol L1 (4), 103 mol L1 (N), 2.5  103 mol L1 (5), 5  103 mol L1
(h), 102 mol L1 (d). The authors thank CNPq for a research fellowship.
 A.B. da Silva et al. / Corrosion Science 52 (2010) 788–793 793

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