Corrosion Science 50 (2008) 2705–2709

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

The inhibition activity of ascorbic acid towards corrosion of steel

in alkaline media containing chloride ions
L. Valek a,*, S. Martinez a, D. Mikulić b, I. Brnardić c
a
Department of Electrochemistry, Faculty of Chemical Engineering and Technology, Savska Cesta 16, 10000 Zagreb, Croatia
b
Department of Materials, Faculty of Civil Engineering, Kačićeva 26, 10000 Zagreb, Croatia
c
Department of Physical Chemistry, Faculty of Chemical Engineering and Technology, Marulićev Trg 20, 10000 Zagreb, Croatia

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

Article history: The activity of ascorbic acid towards steel corrosion in saturated Ca(OH)2 solution containing chloride
Received 8 April 2008 ions was investigated in this study. Concentration and time dependence of the protective properties of
Accepted 16 June 2008 the passive film were acquired by electrochemical impedance spectroscopy. The best inhibitive perfor-
Available online 24 June 2008
mance, i.e. the longest pitting initiation time was obtained in the presence of 103 M ascorbic acid, while
both lower and higher concentrations showed shortening of the pitting-free period. The overall behaviour
Keywords: of ascorbic acid was attributed to its ability to form chelates of various solubility having various metal/
A. Steel
ligand ratios and oxidation states of the chelated iron. The assumption of ascorbic acid assisted reductive
B. EIS
C. Pitting corrosion
dissolution of the passive layer at higher inhibitor concentrations was confirmed by cyclic voltammetry
C. Inhibition and ATR FTIR spectroscopy. It is proposed that the overall inhibitive effect at lower concentrations is due
to the formation of insoluble surface chelates and the effective blocking of the Cl adsorption at the sur-
face of passive film. A pronounced inhibitive effect observed after the pitting had initiated was ascribed to
the formation of a resistive film at the pitted area.
Ó 2008 Elsevier Ltd. All rights reserved.

1. Introduction effective inhibitors of chloride induced passive film breakdown at

The prevention of pitting corrosion is a question of high techno-
logical importance because the phenomenon of passivity is the
enabler for our current, metals-based civilization. In order to pre-
vent or postpone pitting, corrosion inhibitors may be applied. The-
oretically, the action of the organic corrosion inhibitors could be
aimed against each step of the pitting process. Thus, the inhibitors
could act by [1]: (i) blocking the adsorption of chloride ions on the
passive film by the competitive adsorption of an inhibitor and
screening the potential sites for the chloride ion adsorption, (ii)
preventing the chloride incorporation into the passive film, (iii)
repairing defects or pores in the film to prevent the pit nucleation,
(iv) inhibiting the pit growth. Since the adsorption of an aggressive
anion at a passive film surface is the initial step of passive film
breakdown, the suppression of chloride ion adsorption, by compet-
itive adsorption of organic molecules, is of particular interest.
Adsorption of organic molecules at the most active centres of a
passive electrode is believed to force chloride ions to interact with
less energetically favourable sites, therefore requiring greater acti-
vation energy for pitting to occur [2].
Compounds with functional groups containing oxygen, having
ability to form complexes with iron, have been reported to act as
* Corresponding author. Tel.: +385 14597116; fax: +385 14597139.
E-mail address: lvalek@fkit.hr (L. Valek).
the surface of steel by means of their competitive adsorption
through the surface complex formation [1–3]. For example, com-
pounds with carboxylic groups such as alkyl carboxylates, benzo-
ates and their substituted forms, have ability to form strong
chemical bond with surface Fe-ions, competing successfully with
Cl as a complexing agent for iron. Tannins are able to form che-
lates with iron [4] and mimosa tannin was shown to inhibit corro-
sion of steel in alkaline media containing chloride ions by sealing
the oxide film with sparingly soluble Fe(III) mono-chelates [2,5].
Ascorbic acid inhibitory properties towards steel corrosion were
investigated in acidic (pH 2–6) [6] and neutral media (pH 6–8) [7–
10]. In our previous investigation we compared the ascorbic acid
inhibitory action on steel in sat. Ca(OH)2 with the activity of eight
amino acids [11]. Rationalization of its superior performance was
supported by the molecular modelling results. The aim of the pres-
ent work is to assess the influence of the ascorbic acid concentra-
tion and the time of exposure to inhibitor solution on the
protective properties of the oxide film on steel.
2. Experimental
Investigation of non-alloyed special prestressing steel EN 10020
corrosion inhibition by ascorbic acid in saturated Ca(OH)2 solution
containing 0.14 M NaCl was performed using electrochemical
impedance spectroscopy (EIS) and cyclic voltammetry (CV). Mea-

0010-938X/$ - see front matter Ó 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2008.06.018
2706 L. Valek et al. / Corrosion Science 50 (2008) 2705–2709
surements were performed using PAR VMP2 potentiostat/galvano-
stat with VMP3/Z impedance option. Standard electrochemical cell
of volume 200 ml was used with three-electrode arrangement.
Counter electrode was a carbon rod and reference electrode was
saturated calomel electrode (SCE). All potentials reported, refer to
SCE. Working electrode was manually constructed from the steel
rod machined to give cross-sectional area of 0.1256 cm2
(d = 4 mm) and embedded into epoxy resin, with metal/epoxy
edges protected by an inert coating. Electrode was first mechani-
cally abraded by 600 and 1200 grade emery paper, then degreased
with ethanol and rinsed in redistilled water. Saturated
Ca(OH)2 + 0.14 M NaCl solution was prepared with p.a. grade
chemicals and doubly deionised water. P.a. grade L-ascorbic acid
(Riedel – de Haën) was added in concentration range of 104–
102 M. Measurements were performed after half an hour immer-
sion at the open circuit potential (OCP). EIS measurements were
performed in the frequency range between 100 kHz and 3 mHz
with ac potential perturbation of 10 mV amplitude. Time depen-
dence of the system behaviour was recorded by measuring the
impedance spectra at the OCP after different immersion times until
the appearance of the pitting corrosion at the electrode surface. CV
measurements were performed in saturated Ca(OH)2 solution
without NaCl, with addition of L-ascorbic acid (102, 103 M) in
the potential range between 1.2 V (SCE) and 0.6 V (SCE), with
scan rate 10 mV s1.
Attenuated total reflectance Fourier transform infrared spec-
troscopy (ATR FTIR) was performed at the steel samples
(A = 2  2 mm2) after the exposure to sat. Ca(OH)2 solution with
different ascorbic acid concentrations. Measurements were carried
out using Bruker Vertex 70 FTIR spectrometer. Spectra were col-
lected from 16 scans at the resolution of 4 cm1, between 400
and 4000 cm1. Samples were smoothed before immersion into
the solution to increase the optical quality of the prism/sample
interface. Then they were rinsed and dried in nitrogen stream
and pressed tightly against the prism. Measurements were carried
out after 20 h exposure of samples to the solution of sat.
Ca(OH)2 + 0.14 M NaCl with addition of different inhibitor concen-
trations (0, 103, 5  103 and 102 M).
3. Results and discussion
3.1. Influence of the ascorbic acid concentration on the properties of
the passive film on steel
In order to investigate the interfacial behaviour of steel in the
presence of ascorbic acid, EIS measurements in blank solution
and with addition of various ascorbic acid concentrations were
performed at the OCP after a half-hour immersion period.
As seen from our previous investigation [11], a single capacitive
semicircle is observed in the whole frequency range for steel in
ascorbic acid/sat. Ca(OH)2 + 0.14 M NaCl solution system, showing
that after short immersion times, corrosion process was mainly
dominated by a non-diffusional component, i.e. the interfacial
charge transfer [12]. The data (not shown) were fitted to a simple
equivalent electrical circuit (EEC) consisting of the solution resis-
tance Rs in series to a parallel combination of a resistance (R) and
a constant phase element CPE, which takes into account the inho-
mogeneity present at the solid/liquid interface. The impedance of
this circuit, ZðxÞ, at the angular frequency x is given by Eq. (1)
R
ZðxÞ ¼ Rs þ
1 þ RQðjxÞn
where the impedance of the CPE is given by
1 Fig. 1. Interfacial capacitance, Cif (d) and charge transfer resistance, Rct (s) of steel
Z CPE ¼
Q ðjxÞn
with 0 6 n 6 1, where n ¼ 1  2a=p, and a is the depression angle.
For n = 1, the CPE is an ideal capacitor and then Q is equal to a
capacitance, C.
The charge transfer resistances and the interfacial capacitances
obtained by the fitting procedure are shown in Fig. 1. Charge trans-
fer resistance attains maximum in the 103 M solution
(166.3 kX cm2) being almost three times higher compared to that
in the blank solution (58.1 kX cm2). A sharp decline in the charge
transfer resistance in the 102 M solution coincides with a signifi-
cant increase of the interfacial capacitance.
Ascorbic acid chelating properties could account for both, the
initial increase and the subsequent decrease of its inhibitive action.
Chang and Matijević [13] have proposed two mechanisms of iron
oxide behaviour in the presence of a chelating agent: (i) solution
coordination mechanism and (ii) surface complexation mecha-
nism. The first mechanism involves reaction of chelating agents
with Fe(II)-ions released from the bare oxide surface, accelerating
further release of the metal ions from the solids. The rate of disso-
lution will depend on the tendency of a metal ion to be released
from the solid oxide. The second mechanism assumes surface com-
plexation of metal ion with chelating species. In this case, after the
formation of surface complex, the relative bond strength of Fe-ion
with the lattice oxygen and with the chelating molecule will be of
outmost importance. If the lattice bond between the Fe-ion is suf-
ficiently weakened the entire complex will be released into the
solution. However, if the bond is stabile enough, the complex will
stay adsorbed at the surface, where the conformation of the chelat-
ing agent in its adsorbed form will play an essential role. It was
shown that this process is pH dependent and, in a higher pH envi-
ronment, iron release could be significantly reduced by formation
of Fe(III)-complex that results in progressive development of sur-
face insoluble film.
Ascorbic acid is known to form chelates through hydroxyl
groups of the lactone ring [14,15], hence it can be adsorbed at
the metal surface through formation of stable chelates with coord-
inatively unsaturated surface Fe-ions [7,11]. It has been reported in
literature that the increase in the concentration of a complexing
agent may change its activity towards iron dissolution from inhib-
itive to stimulative [2]. Solubility of a complex is to a large extent
determined by metal/ligand ratio, where for higher ratios sparingly
soluble mono or polynuclear complexes could be formed while for
lower ratios soluble complexes could be formed. It may be con-
cluded that the increase in ligand concentration and the resulting
decrease of the metal/ligand ratio in the near electrode layer create
favourable conditions for soluble complexes formation, while at
ð1Þ
ð2Þ in sat. Ca(OH)2 + 0.14 M NaCl, dependence on the ascorbic acid concentration
obtained from the EIS measurements.
 L. Valek et al. / Corrosion Science 50 (2008) 2705–2709
low concentration, insoluble chelates are formed. This could ac-
count for lower inhibitor efficiency observed at higher ascorbic
acid concentrations.
Furthermore, the pronounced capacitive behaviour, visible at
the highest ascorbic acid concentration, could be associated to
the oxidation/reduction of Fe(II)/Fe(III) species present at the metal
surface i.e. to the surface redox-type processes [5]. This would
implicate the existence of surface Fe atoms in a different valence
state at low and high ascorbate concentrations. High spin Fe(II)
species, probably attributable to the Fe(II)–ascorbate complex
were identified, by Mössbauer spectroscopy, at the mild steel sur-
face after exposure to ascorbate solution of concentrations higher
than 0.05 M [9]. Hence, another possible explanation for lower
inhibitor efficiency at higher concentrations is the occurrence of
reductive dissolution through the soluble Fe(II) chelate formation
[7,16] as opposed to the sparingly soluble Fe(III) chelate formation
at lower ascorbic acid concentrations. This is in concordance with
the known antioxidant activity of ascorbic acid and the fact that,
generally, the reducing power of the reducing agent solution in-
creases with the increase in concentration.
In order to compare redox behaviour of steel in the presence of
different ascorbate concentrations and to confirm the above
assumptions, cyclic voltammograms were recorded in 102 M
and 103 M solutions of ascorbic acid (Fig. 2). A detailed discussion
on the oxides formed during cyclic voltammetry of iron in alkaline
media is given in the study of Joiret et al. [17]. A two-layer film
consisting of an inner barrier layer of magnetite (Fe3O4) and an
outer layer of maghemite (c-Fe2O3) and/or its hydrated form lepi-
docrocite (c-FeOOH), has been proposed to be present on iron and
steel in neutral and alkaline media [18–21]. Three peaks present at
the anodic and cathodic scan of the steel cyclic voltammogram in
blank solution correspond to the successive oxidation of steel to
the higher oxidation states (Fe(OH)2 ? Fe3O4 ? aFe2O3 and/or c-
Fe2O3) and subsequent reduction to the lower oxidation states
(aFe2O3 and/or c-Fe2O3 ? Fe3O4 ? Fe(OH)2). Formation of Fe(III)
containing species c-Fe2O3 and/or c-FeOOH through partial oxida-
tion and hydrolysis of Fe3O4 in the external part of the passive
layer is visible at potentials above 0.6 V (SCE).
It has been reported previously that the addition of ascorbic
acid to sat. Ca(OH)2 significantly alters the redox behaviour of steel
leading to almost complete suppression of all oxidation and reduc-
tion peaks [11]. As seen from Fig. 2, the difference in the behaviour
of steel in 103 M and 102 M solutions is particularly obvious at
potentials more positive than 0.2 V (SCE) where for 102 M solu-
tion a new anodic current peak appears. Absence of the corre-
sponding reduction peak may indicate the lack of accumulation
of reaction products due to the dissolution of steel caused by for-
Fig. 2. Cyclic voltammograms of steel in sat. Ca(OH)2 and with addition of 103 M
and 102 M ascorbic acid, scan rate 10 mV s1 (2nd cycle).
2707
mation of soluble Fe(II) chelate [5,22], resulting in oxide film dete-
rioration. In confirmation, anodic linear polarization in 102 M
solution containing chlorides [23] has led to a visible deterioration
of anodic film and the appearance of numerous small pits at the
electrode surface almost giving the impression of general corro-
sion, while for lower concentrations of ascorbic acid, characteristi-
cally, only one pit has been observed beyond the pitting potential.
3.2. EIS measurements of the time dependant system behaviour
In order to determine a long term behaviour of the reinforcing
steel exposed to the solution with and without the ascorbic acid,
EIS spectra were measured after different exposure times at the
OCP (data not shown). Time dependence of the system behaviour
could be divided into two phases.
The first period, before the pitting appearance, is characterised
by the EIS response having one time constant. The data were fitted
to a simple EEC, described in the previous section, and the repre-
sentative results of the time dependence of the resistance are
shown in Fig. 3. The second period, after the pitting appearance,
is characterised by the EIS spectra having two time constants.
The data were fitted to the Armstrong’s EEC. Total resistance as a
function of time is also shown in Fig. 3.
The initial rise of resistance observed in all systems may be as-
cribed to the passive film growth at the electrode surface. Apart
from the first few hours of exposure, for the rest of the time up
to the pitting initiation, resistances obtained in the presence of
ascorbic acid were lower than those without the ascorbic acid.
In concordance with the previously described model of Chang
and Matijević it may be concluded that at concentrations below
5  103 M, ascorbic acid inhibits corrosion by forming stable sur-
face chelates while, at the same time, supporting iron dissolution
through chelating iron cations ejected from the oxide layer. During
the first few hours of exposure, the former effect dominates, and
the inhibitory activity is visible. It is reasonable to assume that
the latter effect becomes important after the oxide layer has grown
to a certain extent, and the dissolution current through the oxide
layer has become sufficiently small. The final thickness and protec-
tive properties of the oxide layer would depend upon relative influ-
ences of the two processes. After a certain period of growth, the
oxide layer in the absence of chelating agent becomes thicker
and more protective as the dissolution of metal through the oxide
layer decreases without being counterbalanced by chelation.
However, the pitting initiation period itself is considerably
longer in 103 M (200 h) and 2.5  103 M (140 h) solutions than
in the blank solution (60 h) and in 5  103 M (30 h) solution. This
is concordant with the results of our previous investigation where
Fig. 3. Time dependence of total resistance of steel in sat. Ca(OH)2 + 0.14 M NaCl
and with addition of different ascorbic acid concentrations, obtained by EIS
measurements.
2708 L. Valek et al. / Corrosion Science 50 (2008) 2705–2709

linear polarization measurements have shown that ascorbic acid,
present in concentration of 103 M, has the ability to retard pitting
nucleation with a shift of Epit  Ecor value by almost 300 mV com-
pared to that in the blank solution [23]. It may be concluded that
the adsorbed inhibitor molecules effectively block the adsorption
of Cl at the surface of passive film thereby extending the pitting
initiation time.
It is worth mentioning that similar behaviour has been assumed
for the passive layer on steel in the presence of EDTA chelating
agent [24,25]. In the case of EDTA, it has been suggested that: (i)
EDTA supported dissolution of the barrier layer and hindered for-
mation of the outer layer because of its ability to chelate Fe(II) cat-
ions ejected from the oxide layer and (ii) EDTA adsorbed strongly
in the oxygen vacancies at the barrier layer/solution interface,
thereby effectively blocking the adsorption of Cl at the surface
of passive film.
In all systems, the pitting appearance is accompanied by a sig-
nificant decrease in the interfacial resistance. The resistance for all
the ascorbic acid solutions (P2.55 kX cm2) in the postpitting per-
iod is higher than the resistance of the blank solution (0.7 kX cm2).
It is known that once the pitting corrosion is ongoing, the inhibitor
can delay or prevent pit growth [1]. However, the pit growth pro-
cess is more difficult to control by the use of inhibitors than the
prior stages of aggressive anion adsorption and pit initiation. The
reason for this is the fact that the electrolyte within the pits has
lower pH and a higher aggressive anion concentration than the
bulk electrolyte. Higher concentration of metal anion at the pit
area could result in the enhanced metal/ligand ratio and formation
of insoluble complexes at the pit surface, forming a layer that influ-
ences the mechanism of pit growth. The Bode plots of the imped-
ance spectra after the pitting formation at the electrode surface
are shown in Fig. 4.
The results of the EIS measurements after the pitting corrosion
appearance were successfully fitted to Armstrong’s EEC. The
impedance of this circuit, ZðxÞ, at the angular frequency, x, is gi-
ven by Eqs. (3) and (4) [17].
R1
ZðxÞ ¼ ð3Þ
1
1þZ 2 ðxÞ=R1
þ R1 Q 1 ðjxÞn1
being
R2
Z 2 ð xÞ ¼ ð4Þ
1 þ R2 Q 2 ðjxÞn2
Since data obtained in inhibitor free solution exhibited only a
straight line in the first time constant frequency range, in order to
obtain good fit, the EEC was modified by omitting the R1 The EEC
consisted of CPE1 placed in series between the Rs and parallel com-
bination of CPE2 and R2. Parameters obtained by fitting the experi-
mental data are shown in Table 1.
Appearance of the first time constant could be the result of the
formation of resistive film consisting of corrosion products at the
pit surface. In the presence of the inhibitor, the resistance of such
layer is significantly higher compared to the one formed without
the inhibitor presence. Under the given circumstances, it could
be concluded that the inhibitor presence influences the pitting pro-
cess by forming resistive film at the pit surface [26].
The second time constant could be ascribed to the sum of pro-
cesses appearing at the pitted and passive area. The impedance re-
sponse of such interface could be interpreted within the model of
localized corrosion [26], where the impedance is given by Eq. (5)

Z 1 1 1
2 ðxÞ ¼ ð1  FÞZ p ðxÞ þ FZ pit ðxÞ ð5Þ

where Z p is related to the passive area, Z pit is related to the pitted

area and F is the area fraction on which pitting occurs. The resulting
resistance is given by Eq. (6):

R1 1 1
2 ¼ ð1  FÞRp þ FRpit ð6Þ

and capacitance by Eq. (7)

Fig. 4. Bode plots of the impedance spectra of steel in sat. Ca(OH)2 + 0.14 M NaCl
and with addition of different ascorbic acid concentrations, after the pitting
formation at the electrode surface.
C 2 ¼ ð1  FÞC p þ FC pit ð7Þ
Since the exact pitted area (F) could not be determined, one cannot
distinguish the fraction of resistance related to the pitting and pas-
sivity processes, hence the exact value of Rpit and Cpit could not be
determined. According to Mansfeld [26], Rp is significantly higher
than Rpit and in spite of the very low F the resistance of the pitted
area mostly contributes to R2 value. Also Cpit is significantly higher

Table 1
EIS parameters obtained by fitting data presented in Fig. 4

Exp. time – AA conc. n1 C1/F cm2 R1/X cm2 n2 C2/F cm2 R2/X cm2
3
170 h – 0M 0.184 – – 0.851 5.127  10 703
265 h – 103 M 0.744 1.028  104 227 0.906 3.728  104 2751
235 h – 2.5  103 M 0.608 4.052  104 748 0.674 1.511  103 3618
114 h – 5  103 M 0.774 4.373  105 410 0.674 2.831  104 2552
 L. Valek et al. / Corrosion Science 50 (2008) 2705–2709
Fig. 5. ATR FTIR spectra of the crystalline ascorbic acid and steel surface after 20 h
exposure to the sat. Ca(OH)2 + 0.14 M NaCl and with addition of different ascorbic
acid concentrations.
than Cp and contributes mostly to C2 value. Considering R2 values
presented in Table 1. it could be concluded that the corrosion at
the pitted area is significantly suppressed by the presence of the
inhibitor.
3.3. ATR FTIR spectra of the steel surface exposed to ascorbic acid
solutions
ATR FTIR spectra of the steel surface were measured in order to
determine the presence of the inhibitor molecules at the metal sur-
face after exposure to the inhibitor solutions of various concentra-
tions. The spectra were recorded after 20 h of exposure as
according to Fig. 3. At that moment, a relatively stable surface state
had been achieved for all systems and pitting had not yet occurred.
The resulting spectra as well as spectra of crystalline L-ascorbic
acid are presented in Fig. 5.
No bands were detected in blank solution. Although being less
well defined, the majority of the bands observed in the spectra of
the steel samples exposed to ascorbic acid solutions of concentra-
tion up to 5  103 M, closely resemble those appearing in the
crystalline L-ascorbic acid spectra. Also, the intensity of the system
response increases up to 5  103 M with the increase in concen-
tration. The identical spectrum of very low intensity is obtained
for a sample exposed to 102 M ascorbic acid solution, indicating
significantly smaller amount of adsorbed species at the steel sur-
face [7].
However, there are two distinctive differences between the ad-
sorbed inhibitor spectra and that of the crystalline ascorbic acid: (i)
The band of medium intensity at 1750 cm1 in the crystalline L-
ascorbic acid spectrum, assigned to the C(1)@O stretching vibra-
tion [27–29], was not observed in the spectra of the inhibitor ad-
sorbed at the steel surface. This band has been previously
reported to shift to the lower wave numbers upon metal ion bind-
ing [28,29] and has probably overlapped by neighbouring more
intensive broad band centred at 1615 cm1. (ii) Several bands at
1135, 1111, 1070, 1043, 1020 and 985 cm1 observed in the crys-
talline L-ascorbic acid spectrum, assigned to the C–O and C–C
stretching vibrations, suffered the major loss in intensities in the
spectra of the adsorbed inhibitor. This could be related to the
ascorbate C–O group participation in the surface chelate forma-
2709
tion [28,29]. In conclusion, the results of ATR FTIR measurement
corroborate the assumption of sparingly soluble ascorbic acid che-
late formation at lower concentrations and its assistance in oxide
layer dissolution at higher concentrations.
4. Conclusions
Ascorbic acid was found to act as a pitting corrosion inhibitor on
steel in chloride containing sat. Ca(OH)2 solution.
The oxide film protective properties were assumed to depend
upon: (i) the inhibitive action of ascorbic acid through insoluble
surface chelate formation, (ii) the stimulative action of ascorbic
acid through soluble surface chelate formation and (iii) the stimu-
lative action of ascorbic acid through chelation of the iron cations
ejected from the oxide layer.
At concentrations above 5  103 M, reductive dissolution of
steel through soluble Fe(II) chelate formation was assumed to yield
low charge transfer resistance and short pitting initiation time.
Cyclic voltammetry and ATR FTIR spectroscopy results obtained
were in support of this assumption.
Presence of ascorbic acid at optimal concentration of 103 M
suppressed iron dissolution in the first few hours of exposure, pro-
longed the pitting initiation phase and, after pitting had occurred,
influenced the localized corrosion process by slowing down the
pitting propagation process through the formation of the resistive
film at the pit surface.
Acknowledgement
The financial support from the Ministry of Science Education
and Sport of the Republic of Croatia, provided under project 125-
0822161-2982, is gratefully acknowledged.
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