Applied Surface Science 152 Ž1999.

237–249
www.elsevier.nlrlocaterapsusc

A new triazole derivative as inhibitor of the acid corrosion of

mild steel: electrochemical studies, weight loss determination,
SEM and XPS
Fouad Bentiss a , Michel Traisnel b, Leon
´ Gengembre c , Michel Lagrenee
´ a,)

a
Laboratoire de Cristallochimie et Physicochimie du Solide, UPRES A 8012 ENSCL, BP.108, F-59652 VilleneuÕe d’Ascq Cedex, France
b
´ des Procedes
Laboratoire de Genie ´ ´ d’Interactions Fluides Reactifs-Materiaux,
´ ´ UPRES EA 2698 ENSCL, BP.108,
F-59652 VilleneuÕe d’Ascq Cedex, France
c
´ ´ ` et Homogene,
Laboratoire de Catalyse Heterogene ` USTL, URA-CNRS D04020, F-59655 VilleneuÕe d’Ascq Cedex, France
Received 7 June 1999; accepted 18 July 1999

Abstract

The effect of addition of 2w5-Ž2-pyridyl.-1,2,4-triazol-3-ylx phenol ŽPPT. on mild steel dissolution in 1 M hydrochloric
acid is studied through electrochemical impedance spectroscopy ŽEIS., potentiodynamic polarisation curves and gravimetric
measurements. The obtained results showed that PPT revealed a good corrosion inhibition. Potentiodynamic polarisation
studies indicate that PPT is a mixed-type inhibitor. The effect of temperature on the corrosion behaviour of mild steel in 1 M
HCl with addition of 80 mgrl of PPT was studied in the temperature range from 258C to 608C. The associated activation
corrosion and free adsorption energies have been determined. Scanning electron microscopy ŽSEM. and X-ray photoelectron
spectroscopy ŽXPS. of the mild steel revealed that PPT is absorbed on the steel surface. PPT appears to function through the
general adsorption mode following the Langmuir adsorption isotherm model. q 1999 Elsevier Science B.V. All rights
reserved.

Keywords: Corrosion; Steel; Triazole; Acid; Adsorption

1. Introduction aromatic rings. Generally, the tendency to form a

stronger coordination bond and, as consequence, in-
The applicability of organic compounds as corro-
hibition efficiency should increase in the order O -
sion inhibitors for metals in acidic media has been
N - S - P w8x. Nitrogen-containing heterocyclic
recognised for a long time w1–7x. The existing data
compounds are considered to be effective corrosion
show that most organic inhibitors act by adsorption
inhibitors. For example, benzotriazole has been used
on the metal surface. The adsorption of inhibitors
as an inhibitor for the corrosion of copper and its
takes place through heteroatoms such as nitrogen,
alloys w9–16x. It has also been used for the protection
oxygen, phosphorus and sulphur, triple bonds or
of aluminium, zinc and mild steel in acid and alka-
line media w17–19x. Substituted benzotriazoles and
)
Corresponding author. Tel.: q33-320-337-746; E-mail: other triazole compounds have also been extensively
michel.lagrenee@ensc-lille.fr studied w20–23x. A recent study has shown that the

0169-4332r99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 9 - 4 3 3 2 Ž 9 9 . 0 0 3 2 2 - 0
238 F. Bentiss et al.r Applied Surface Science 152 (1999) 237–249
inhibition efficiency of organic compounds contain-
ing heterocyclic nitrogen increases with the number
of aromatic systems and the availability of elec-
tronegative atoms in the molecule w24x.
In this work, we report on the new class of acid
corrosion inhibitors for mild steel, namely, 2w5-Ž2-
pyridyl.-1,2,4-triazol-3-ylx phenol ŽPPT.. The corro-
sion inhibition of mild steel by PPT in 1 M HCl has
been studied using various corrosion monitoring
techniques. Films on the surface were analysed by
scanning electron microscopy ŽSEM. and X-ray
photoelectron spectroscopy ŽXPS..
2. Experimental details
Fig. 1 shows the molecular formulae of the inves-
tigated compound PPT which was synthesised ac-
cording to previously reported experimental proce-
dure w25x.
A conventional three-electrode polymethyl-
methacrylate ŽPMMA. cell for the electrochemical
impedance spectroscopy and a glass cell for polarisa-
tion curves assembly were used in electrochemical
experiments. A mild steel disk was used as the
working electrode. The apparent surface of the work-
ing electrode was 1 cm2 . The counter electrode was
a Pt wire fitted into a glass holder and separated
from the working electrode compartment by a sin-
tered glass frit. The reference electrode was a satu-
rated calomel electrode ŽSCE. housing in a separated
compartment. The cell temperature was kept at 30 "
18C.
2.1. The electrochemical impedance spectroscopy
The electrochemical impedance spectroscopy
ŽEIS. measurements were carried out with the elec-
Fig. 1. Molecular formulae of triazole-type organic compound
studied ŽPPT..
trochemical system ŽTACUSSEL. which included a
digital potentiostat model Z COMPUTER at Ecor
after immersion in solution without bubbling. Square
sheets Ž5 cm = 5 cm = 0.05 cm. of mild steel expos-
ing a circular surface of 7.55 cm2 to the solution
were used as working electrodes. After the determi-
nation of steady-state current at a given potential,
sine wave voltages Ž10 mV. peak to peak, at fre-
quencies between 100 kHz and 10y2 Hz, were su-
perimposed on the rest potential. The measurements
performed at rest potentials after 20 h of exposure
were automatically controlled by computer pro-
grams.
2.2. Polarisation curÕes
The working electrode in the form of a disk was
introduced into a polytetrafluoroethylene holder ex-
posing a 1 cm2 surface to the solution. The working
electrode was immersed in a test solution for 30 min
until a steady-state open-circuit potential Ž EOCP . was
obtained. The cathodic polarisation curve was
recorded by polarising from the EOC P in a cathodic
direction under potentiodynamic conditions corre-
sponding to 30 mVrmin Žsweep rate. using a
TACUSSEL RADIOMETER PGZ 3O1 with contin-
uous stirring at 308C under nitrogen. After this scan,
the anodic polarisation curve was recorded by polari-
sation from the EOCP in the anodic direction.
Gravimetric experiments were carried out in a
double walled glass cell equipped with a ther-
mostated cooling condenser. The solution volume
was 100 cm2 . The weight loss of rectangular steel
specimens of size 5 cm = 2 cm = 0.05 cm in 1 M
HCl without and with addition of different concen-
trations of inhibitor was determined after 24 h of
immersion at 308C without bubbling. Three tests
were used to calculate the inhibition efficiency.
2.3. Scanning electron microscopy
The steel specimens coated by a film of 50 nm of
gold by sputtering before and after immersion were
investigated by using a JEOL 5300 scanning electron
microscope. The energy of the acceleration beam
employed was 20 kV.
 F. Bentiss et al.r Applied Surface Science 152 (1999) 237–249 239

2.4. X-ray photoelectron spectroscopy charge-transfer resistance Ž R t . values were calcu-

lated from the difference in impedance at lower and
The steel disk was immersed in the 1 M HCl higher frequencies as suggested by Tsuru et al. w28x.
containing 80 mgrl of PPT at 308C for 24 h without To obtain the double layer capacitance Ž Cdl . the
bubbling. After removal from the glass cell the disk frequency at which the imaginary component of the
was rinsed with ethanol and dried in air at room impedance is maximal ŽyZmax Y
. is found and intro-
temperature. Surface analyses were performed with duced in Eq. Ž1.:
an ESCALAB 220 XL spectrometer from vacuum
1
Generators. The monochromatised Al K a X-ray Cdl s Ž 1.
source Ž1486.6 eV. was operated in the CAE Žcon- v Rt
stant analyser energy. mode ŽCAE s 150 eV for The inhibition efficiency of corrosion of steel is
survey spectra and CAE s 30 eV for high resolution calculated from Eq. Ž2. by using charge transfer
spectra., using the electromagnetic lens mode. A resistance:
flood gun source Ž6 eV. was applied to the poly-
meric samples to compensate the sample charging Ry1 y1
tcor y R tcorŽinh .
h Ž %. s = 100 Ž 2.
effect. The polymeric samples were frozen down to Ry1
tcor
173 K before XPS measurements to avoid a degrada-
tion under X-ray radiation and vacuum. The binding where R tcor and R tcorŽinh. are the charge transfer-re-
energy scale was initially calibrated using the sistance values without and with inhibitor, respec-
Cu2p 3r2 Ž932.7 eV., Ag3d 5r2 Ž368.2 eV. and tively. The impedance parameters derived from these
Au4f 7r2 Ž84 eV. peak positions and internal calibra- investigation are given in Table 1.
tion was referenced to the C1s energy at 285 eV for The Nyquist plots of mild steel in inhibited and
aliphatic species. Quantification of outer layers uninhibited acidic solutions containing various con-
atomic composition and spectral simulation of the centrations of PPT are shown in Fig. 2. It is apparent
experimental peaks were achieved using the software from this figure that the charge transfer-resistance
provided by VG Scientific. value of mild steel in uninhibited HCl solution sig-
Mild steel strips containing 0.09% P, 0.38% Si, nificantly changes after the addition of PPT. It is
0.01% Al, 0.05% Mn, 0.21% C, 0.05% S and the found ŽTable 1. that the R t values increase with
remainder iron were used for the gravimetric and increasing PPT concentration while the Cdl values
electrochemical measurements. Before use, the strips tend to decrease. The decrease in Cdl values is due
were mechanically polished on wet SiC paper Žgrade to the adsorption of PPT on the metal surface w21x.
120-600-1200., rinsed with bidistilled water, de- The greatest inhibition is observed at a concentration
greased ultrasonically in ethanol and dried in air at of 80 mgrl.
room temperature.
3.2. Potentiodynamic polarisation curÕes
The 1 M HCl solutions used were prepared from
37% HCl ŽAR grade. and doubly distilled water. The
Fig. 3 shows polarisation curves of mild steel in 1
concentration range of inhibitor employed was 20 to
M HCl in the absence and in the presence of differ-
80 mgrl.
Table 1
Impedance measurements and inhibition efficiency for mild steel
3. Results in 1 M HCl containing different concentrations of PPT
Concentration Rt Cdl Erest potential h
3.1. The electrochemical impedance spectroscopy Žmgrl. Ž V cm2 . ŽmFrcm2 . ŽmVrSCE. Ž%.

The corrosion behaviour of mild steel in acidic 0 16 517 y520 –

solution in the presence of PPT was investigated by 20 254 141 y491 93.7
40 374 109 y469 95.7
the EIS at 308C after 20 h of immersion. The equiva- 60 618 73 y470 97.4
lent circuit models employed for this system were 80 698 67 y442 97.7
identical to those reported previously w26,27x. The
240 F. Bentiss et al.r Applied Surface Science 152 (1999) 237–249
Fig. 2. Nyquist diagrams for mild steel in 1 M HCl containing different concentrations of PPT.
ent concentrations of PPT. The corrosion kinetic
parameters derived from these curves are shown in
Table 2. The values of the corrosion current density
Ž Icor . of mild steel in the inhibited solutions were
smaller than those for the inhibitor-free solution. The
inhibition efficiency of PPT for the corrosion of mild
steel is calculated by using corrosion current density
as follows:
Icor y IcorŽinh .
h Ž %. s = 100
Icor
where Icor and IcorŽinh. are the corrosion current
density values without and with inhibitor, respec-
tively. They are determined by extrapolation of ca-
thodic Tafel lines to the corrosion potential.
As can be seen from Fig. 3 and Table 2, cathodic
current-potential curves gave rise to parallel Tafel
lines indicating that the hydrogen evolution reaction
is activation-controlled. The addition of PPT does
not change the values of corrosion potential Ž Ecor .
and cathodic Tafel slope Ž bc .. These results demon-
strated that the hydrogen evolution reaction is inhib-
ited and that the inhibition efficiency is increased
with inhibitor concentration, reaching a maximum
value of 80 mgrl of PPT.
For an overvoltage higher than y200 mVrSCE,
the presence of PPT did not change the current-vs.-
potential characteristics ŽFig. 3.. This potential can
be defined as the desorption potential. The same
results have been reported with other organic com-
pounds w29,30x. This fact means that the inhibition
Ž 3. mode of PPT depends on electrode potential. How-
ever, PPT influences the anodic reactions at poten-
tials more negative than y200 mVrSCE. This result
indicates that PPT exhibits both cathodic and anodic
inhibition effects. This suggests a mixed-type con-
trol. PPT mainly acts as a mixed-type inhibitor in 1
M HCl.
3.3. Corrosion weight loss test
The weight loss of the mild steel in 1 M HCl
without and in the presence of various concentrations
of PPT is determined after 24 h of immersion.
 F. Bentiss et al.r Applied Surface Science 152 (1999) 237–249 241

Fig. 3. Potentiodynamic polarisation curves for mild steel in 1 M HCl containing different concentrations of PPT.

Values of the inhibition efficiency obtained are given inhibitor, respectively. PPT inhibits the corrosion of
in Table 3. In the case of the weight loss method the mild steel. Corrosion rate values of mild steel de-
inhibition efficiency is determined by the relation crease when the inhibitor concentration increases.
W y Winh The inhibition efficiency increases with increasing
h Ž %. s = 100 Ž 4. inhibitor concentration reaching a maximum value
W Ž95.2%. of 80 mgrl of PPT ŽTable 3.. Gravimetric
where W and Winh are the values of weight loss of measurements confirm the protection of PPT in 1 M
steel after immersion in solutions without and with HCl.

Table 2
Potentiodynamic polarisation parameters of the mild steel in 1 M
HCl, in 1 M HCl containing different concentrations of PPT at Table 3
308C and the corresponding corrosion efficiency values deter- Corrosion rates of mild steel and inhibition efficiencies for various
mined from extrapolation of the Tafel lines concentrations of PPT in 1 M HCl
Concentration Ecor Icor bc h Concentration of Corrosion rate Inhibition efficiency h
Žmgrl. ŽmVrSCE. ŽmArcmy2 . ŽmVrdec. Ž%. PPT Žmgrl. Žmg cmy2 hy1 . Ž%.
0 y474 574 150 – 0 3.019 –
20 y470 104 152 81.9 20 0.260 91.4
40 y477 90 151 84.3 40 0.205 93.2
60 y477 81 152 85.9 60 0.133 95.6
80 y476 64 150 88.9 80 0.112 96.3
242 F. Bentiss et al.r Applied Surface Science 152 (1999) 237–249
From Fig. 4, it can be seen that inhibition effi-
ciency obtained from electrochemical measurements
and weight loss are in reasonably good agreement.
3.4. Effect of temperature
Temperature can modify the interaction between
the steel electrode and the acidic media without and
with PPT inhibitor. Polarisation curves for mild steel
in 1 M HCl in the absence and presence of 80 mgrl
of PPT in the temperature range 25–608C are shown
in Figs. 5 and 6. Corresponding data are given in
Tables 4 and 5. The current corrosion density in-
creased with increasing temperature both in uninhib-
ited and inhibited solutions and the values of inhibi-
tion efficiency of PPT are nearly constant in the
temperature range studied ŽTables 4 and 5..
The corrosion current density for steel increases
more rapidly with temperature in the absence of
Fig. 4. Inhibition efficiency for mild steel in 1 M HCl containing different concentrations of PPT: Ža. polarisation curves, Žb. EIS and Žc.
weight loss measurements.
inhibitor Žblank.. These results confirm that PPT acts
as an efficient inhibitor in the range of temperature
studied. PPT inhibitor efficiency is temperature-inde-
pendent.
Arrhenius plots for the corrosion current density
of mild steel are given in Fig. 7. The activation
energies can be calculated from the following rela-
tionships:
Ea
Icor s k exp y žRT
X
/ Ž 5a .
Ea
X
Icor s k exp y žRT / Ž 5b .
where Ea and EaX are the apparent activation corro-
sion energies in the absence and presence of the
inhibitor, respectively, k s constant. The calculated
values of Ea and EaX are 84 and 51 kJrmol, corre-
spondingly. The reduction of the activation energy in
the presence of PPT may be attributed to the
 F. Bentiss et al.r Applied Surface Science 152 (1999) 237–249 243

Fig. 5. Effect of temperature on the cathodic and anodic responses for mild steel in deaerated 1 M HCl.

Fig. 6. Effect of temperature on the cathodic and anodic responses for mild steel in deaerated 1 M HClq 80 mgrl of PPT.
244 F. Bentiss et al.r Applied Surface Science 152 (1999) 237–249

Table 4 The carefully deconvoluted N1s spectrum of the

The influence of temperature on the electrochemical parameters steel surface exposed to 80 mgrl of PPT in 1 M HCl
for mild steel electrode immersed in 1 M HCl
ŽFig. 9b. is consistent with the presence of 5N–
Temperature Ecor Icor
Ž8C. ŽmVrSCE. ŽmA cmy2 .
structure and –NH– structure Ž400.0 eV. and proto-
nated nitrogen at 401.7 eV. A new peak becomes
25 y480 398
visible at 397.6 eV showing that there has been a
30 y474 574
40 y460 957 reduction.
50 y450 1626 The XPS spectrum ŽFig. 11. shows also that the
60 y455 3506 substrate covered with PPT exhibits a peak for Fe2p
at BE of 711.0 eV characteristic of Fe 3q showing
the subsequent oxidation of the steel surface w35x.

chemisorption of PPT inhibitor on steel surface 3.7. Adsorption isotherm

w31,32x.
If one supposes that the adsorption of this in-
3.5. Scanning electron microscopy hibitor follows the Langmuir adsorption isotherm,
the degree of surface coverage Ž u . is given by:
To establish whether inhibition is due to the bCinh
formation of a film on the metal surface via adsorp- us Ž 6.
tion scanning electron photograph were taken ŽFig. 1 q bCinh
8.. It was found that an adsorbed layer is formed on where b designates the adsorption coefficient. The
mild steel, which inhibits corrosion. The protection degree of surface coverage Ž u . for different concen-
provided by PPT to mild steel in 1 M HCl solutions trations of the inhibitor in acidic media has been
was retained, when specimens dipped in acids con- evaluated from electrochemical measurements using
taining the organic molecules were transferred into the equations w36x,
fresh acid without inhibitor. This observation clearly
CdlŽ us0. y Cdl u
proves that the inhibition is due to the formation of us Ž 7a .
an insoluble stable film through the process of ad- CdlŽ us0. y CdlŽ us1.
sorption of the organic molecules on the metal sur- and
face.
IcorŽ us0. y Icoru
us Ž 7b .
3.6. X-ray photoelectron spectroscopy IcorŽ us0. y IcorŽ us1.

The presence of PPT on the mild steel was moni- The surface coverage values Ž u . were tested
tored using the characteristic N1s signal. The XPS graphically to fit a suitable adsorption isotherm. In
studies show that PPT is adsorbed on the steel both cases, the plots of Cinh P uy1 vs. Cinh yielded a
surface. The XPS spectrum of PPT exhibits two straight line indicating that the adsorption of PPT
peaks ŽFig. 9a. at a binding energy ŽBE. of about
399.7 eV and 401.3 eV, which can be attributed to Table 5
5N– or –NH– and 5NqH – structures, respectively The influence of temperature on the electrochemical parameters
w33,34x. However, the molecular conformation of for mild steel electrode immersed in 1 M HClq80 mgrl of PPT
PPT can yield intramolecular hydrogen bonding Temperature Ecor Icor h
Ž8C. ŽmVrSCE. ŽmA cmy2 . Ž%.
which leads to a positive polarisation of the nitrogen
atom and, therefore, an increased binding energy 25 y471 47 88.2
w35x. Thus, the presence of the positively charged 30 y476 64 88.9
40 y467 141 85.3
nitrogens Ž5Nq H– structure. can be explained by 50 y460 220 86.5
hydrogen bonding between the hydroxyl and the 60 y447 428 87.8
nitrogen atom of the heterocycle as shown in Fig. 10.
 F. Bentiss et al.r Applied Surface Science 152 (1999) 237–249 245

Fig. 7. Arrhenius slopes calculated from corrosion current density for mild steel in: Ža. 1 M HCl and Žb. 1 M HClq 80 mgrl of PPT.

from 1 M HCl solutions on the mild steel surface sation curves for mild steel in the presence of PPT is
obeyed the Langmuir adsorption isotherm ŽFig. 12.. calculated to be 0.22 l mgy1 and 0.16 l mgy1 in 1 M
The value of the adsorption coefficient Ž b . from HCl, respectively. This is in good agreement with
electrochemical impedance spectroscopy and polari- the values of inhibition efficiency obtained from the

Fig. 8. SEM photograph of the surface for mild steel: Ža. before immersion and Žb. after 24 h of immersion at 308C in 80 mgrl PPT q 1 M
HCl.
246 F. Bentiss et al.r Applied Surface Science 152 (1999) 237–249

Fig. 9. N1s XPS core-level spectra of Ža. pure PPT and Žb. steel surface exposed to a Ž80 mgrl PPT q 1 M HCl. solution for 24 h at 308C.

impedance spectroscopy, polarisation curves and ciency increases with increasing adsorption coeffi-
weight loss measurements. Thus, inhibition effi- cient.
 F. Bentiss et al.r Applied Surface Science 152 (1999) 237–249 247

4. Discussion adsorbed chloride or sulfate ions w37x. The better

The adsorption of triazole on the metal surface
can occur either directly via donor–acceptor interac-
tions between the p-electrons of the heterocyclic
compound and the vacant d-orbitals of surface iron
atoms or via interaction of triazole with already
Fig. 10. Intramolecular hydrogen bonding of PPT.
performance of PPT in 1 M HCl can be explained in
the following way. In aqueous acidic solutions, the
triazole exists either as neutral molecules or in the
form of cations. The triazole may be adsorbed on the
metal surface in the form of neutral molecules in-
volving the deplacement of water molecules from the
metal surface and sharing of electrons between the
nitrogen atoms and the metal surface w38x. These
heterocyclic nitrogen compounds may also be ad-
sorbed through electrostatic interactions between the
positively charged nitrogen atom and the negatively
charged metal surface w39x. It has been observed that
the adsorption of the inhibitor can be influenced by
the nature of anions in acidic solution w40,41x. The
specific adsorption of anions having a smaller degree
of hydration, such as chloride ions, is expected to be

Fig. 11. Fe2p spectrum of oxidised steel surface exposed to a Ž80 mgrl PPT q 1 M HCl. solution for 24 h at 308C.
248 F. Bentiss et al.r Applied Surface Science 152 (1999) 237–249
Fig. 12. Langmuir adsorption plots for mild steel in 1 M HCl containing different concentrations of PPT from: Ža. the double layer
capacitance and Žb. the current corrosion density.
more pronounced. Being specifically adsorbed, they
create a layer of excess negative charge directed
towards the solution and favour more adsorption of
the cations w42x. Strong adsorption of organic
molecules is not always a direct binding of the
molecule with the metal surface. In some cases, the
adsorption can occur through the already adsorbed
chloride ions which interact with the subsequently
adsorbed organic molecules. The molecular structure
of the organic compound is important in synergistic
inhibition. The greatest synergistic inhibition is to be
expected for an anion–cation pair in which both ions
have appreciable tendencies toward covalent binding
w28x.
It should be mentioned that PPT does not show a
corrosion inhibition effect at mild steel electrode
potentials higher than y200 mVrSCE ŽFig. 3.. This
potential can be defined as the desorption potential.
The same results have been reported with other
organic compounds w29,30x. In cases where the cor-
rosion inhibition depends on the potential of the
electrode, the observed inhibition phenomenon is
generally described as corrosion inhibition of the
interface associated with the formation of a bidimen-
sional layer of adsorbed inhibitor species at the
electrode surface w43x. The behaviour of the triazole
at potentials higher than y200 mVrSCE may be the
result of significant steel dissolution leading to a
desorption of the adsorbed film of the triazole in-
hibitor from the electrode surface in 1 M HCl. In this
case, the desorption rate of PPT is higher than its
adsorption rate.
5. Conclusions
We can conclude that
Ø PPT inhibits the corrosion of mild steel in 1 M
HCl medium.
Ø The steady state measurements have shown that
the addition of triazole-type organic compound
does not change the proton reduction mechanism.
 F. Bentiss et al.r Applied Surface Science 152 (1999) 237–249
Ø PPT is found to affect both the anodic and ca-
thodic process, i.e., PPT is a mixed type inhibitor.
Ø The results obtained from electrochemical
impedance spectroscopy, polarisation curves and
the weight loss are in reasonably good agreement.
Ø The inhibition efficiency of PPT is temperature-
independent and its addition leads to a decrease
of activation corrosion energy.
Ø SEM and XPS have shown that inhibition of
corrosion by DHT is due to the formation of a
chemisorbed film on the metal surface.
Ø The adsorption of PPT from 1 M HCl on the mild
steel surface obeys a Langmuir adsorption
isotherm.
Acknowledgements
The authors would like to thank the FEDER, the
CNRS, the ‘‘region Nord-Pas de Calais’’ and the
` de l’Enseignement Superieur
‘‘Ministere ´ et de la
Recherche Scientifique’’ for their financial support
for the acquisition of the XPS spectrometer.
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