Corrosion Science 43 (2001) 655±669

www.elsevier.com/locate/corsci

Electrochemical behaviour of Al, Al±Sn, Al±Zn

and Al±Zn±Sn alloys in chloride solutions
containing stannous ions
H.A. El Shayeb *, F.M. Abd El Wahab, S. Zein El Abedin
Electrochemistry and Corrosion Laboratory, National Research Centre, Dokki, Cairo 11212, Egypt
Received 3 September 1999; accepted 15 June 2000

Abstract

The electrochemical behaviours of AlI (99.999%), AlII (99.61%), Al±Sn, Al±Zn and Al±Zn±
Sn alloys were investigated in 0.6 M NaCl solutions containing Sn2‡ ions. The study was
carried out using polarization and potentiostatic current±time techniques complemented by
scanning electron microscope±energy dispersive X-ray analyzer investigations. It is found that
Sn2‡ ions have no activating in¯uence on the dissolution of AlI , AlII and Al±Sn alloy during I±
t measurements. This is attributed to the diculty of Sn di€usion into the surface layers, for
the activation process occurs only when the activator ions di€use into the bulk and create
defects in the oxide layers. On the contrary, the addition of Sn2‡ causes activation of Al±Zn
and Al±Zn±Sn alloys by varying degrees depending on Sn2‡ content. The presence of zinc as
an alloying component in the alloys facilitates the di€usion of the deposited Sn into the surface
layers revealing activation. XPS results con®rm the presence of both Sn4‡ and Sn2‡ oxidation
states in the oxide ®lm on the surface of Al±Zn alloy as well as Sn0 after treatment with 10ÿ3 M
Sn2‡ . The e€ect of simultaneous addition of Sn2‡ and Zn2‡ on the dissolution of Al in 0.6 M
NaCl was also studied. Ó 2001 Elsevier Science Ltd. All rights reserved.

Keywords: Aluminium; Aluminium alloys; Activation; Chloride; Stannous; Zinc; Tin

1. Introduction

The electrochemical behaviour of aluminium alloys is of interest because of their

applications in Al-batteries and as anode materials in cathodic protection systems.

*
Corresponding author. Fax: +202-337-0931.
E-mail address: sh_zein@hotmail.com (H.A. El Shayeb).

0010-938X/01/$ - see front matter Ó 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 1 0 - 9 3 8 X ( 0 0 ) 0 0 1 0 1 - 3
656 H.A. El Shayeb et al. / Corrosion Science 43 (2001) 655±669

The performance of Al anodes is a€ected by the nature of the alloying elements, the
thermal treatment as well as the purity of Al [1±3]. The most important factor for use
of aluminium in aqueous electrolyte is that complex oxide ®lms are formed irre-
versibly leading to the passivation of aluminium. Noticeable changes in the elect-
rochemical behaviour of aluminium have been reported when small amounts of Sn
[4±9], In [10±14], Zn [15,16], and Ga [17±20] are introduced to it as alloying activator
elements. Activation of aluminium can be achieved also by adding small quantities
of suitable metal cations, such as In3‡ , Ga3‡ , Hg2‡ or Sn4‡ , to the electrolyte [21±28].
It was found [29] that the activation of aluminium by In3‡ depends on the chloride
ion concentration, the surface ®nish of the samples and the purity of the metal.
Addition of In3‡ [30] produced activation of pure Al, Al±Zn and Al±Zn±Sn alloys in
0.6 M NaCl solution. The existence of Zn either as an alloying element or as a cation
in the electrolyte leads to an enhanced activity of aluminium in the presence of In3‡
ions [30].
The objective of the present work is to study, the e€ect of Sn2‡ ions on the
electrochemical behaviour of two grades of aluminium (AlI and AlII ), Al±Sn, Al±Zn
and Al±Zn±Sn alloys in chloride solutions using electrochemical and surface ana-
lytical techniques. The study is also extended to demonstrate the e€ect of the pres-
ence of Zn, either as an alloying element or as a cation in the electrolyte, on the
activation of aluminium by Sn2‡ ions.

2. Experimental

Measurements were made on ultra-pure AlI (99.999%), AlII (99.61%), Al±Sn, Al±
Zn and Al±Zn±Sn alloys, the compositions of the alloys are given in Table 1. All
alloys were prepared from the aluminium of purity 99.61%, with high purity tin and
zinc as alloying additions and were used in the cast state. The electrodes were
abraded successively with metallographic emery paper of increasing ®neness up to
800 grit, then degreased with acetone and washed with running distilled water. The
electrodes were cathodically polarized at ÿ1900 mV(SCE) for 3 min in the electrolyte
(0.6 M NaCl) before polarization and potentiostatic current±time measurements.
The electrochemical cell was made of pyrex glass ®tted with a platinum auxiliary
electrode, separated from the electrolyte by a sintered glass diaphragm, and a sat-
urated calomel reference electrode (SCE). All solutions were prepared from analar
grade reagents and distilled water.

Table 1
The chemical composition of the alloys
Alloy Fe Si Cu Mn Mg Pb Zn Sn Al
AlII 0.225 0.109 0.012 0.005 0.0005 0.009 0.0009 0.0007 Rest
Al±Sn 0.402 0.067 0.062 0.005 0.011 0.009 0.0009 0.745 Rest
Al±Zn 0.155 0.041 0.005 0.126 0.0005 0.003 4.92 0.0007 Rest
Al±Zn±Sn 0.194 0.043 0.189 0.002 0.0005 0.004 5.59 0.685 Rest
 H.A. El Shayeb et al. / Corrosion Science 43 (2001) 655±669 657

Polarization measurements were made using a potentioscan (Wenking model POS

73). The electrode potential was changed in steps of 40 mV minÿ1 towards the
positive direction up to the breakdown potential. Potentiostatic current±time tests
were carried out using a potentiostat±galvanostat (Amel model 2053) with an X±Y
recorder (Kipp & Zonen). The treated electrodes were passivated in the electrolyte
for 20 min at ÿ1050, ÿ950 and ÿ980 mV in the case of AlI , AlII and Al±Sn alloy,
respectively, and at )1140 mV in the case of Al±Zn and Al±Zn±Sn alloys. These
potentials were chosen in the passive range. Appropriate amounts of dissolved SnCl2
or ZnCl2 salts were then added to the electrolyte maintaining the Clÿ ion concen-
tration constant. The SnCl2 solutions were freshly prepared for each experiment to
avoid hydrolysis and partial oxidation of Sn2‡ to Sn4‡ before the addition. The pH
after the addition of SnCl2 ranges from 2.3 to 4 depending on the concentration of
SnCl2 . The lower pH value is recorded at 10ÿ2 M SnCl2 . The solution was agitated
slowly by a magnetic stirrer to mix the additives with the electrolyte. A scanning
electron microscope (SEM: JSM T20 of JOEL Co. Ltd, Japan) and energy dispersive
X-ray analyzer (EDAX) were utilized to examine the electrode surface. XPS analysis
was carried out using a model 550 ESCA/SAM spectrometer (Physical Electronic,
USA). The system employed a magnesium X-ray anode (hm ˆ 1253:6 eV). Binding
energies were normalized to that of the atmospheric hydrocarbon at 284.6 eV. The
vacuum in the analysis chamber was better than 0.7 lPa.

3. Results and discussion

3.1. Polarization measurements

Polarization measurements for AlI , AlII , Al±Sn, Al±Zn, and Al±Zn±Sn alloys in
0.6 M NaCl solution free and containing di€erent concentrations of Sn2‡ ions were
carried out. Fig. 1 represents the polarization curves of AlI electrode as an example.
At lower concentrations of Sn2‡ , C 10ÿ3 M, a little e€ect on the cathodic branch of
the polarization curves of AlI electrode is noticed, while at higher concentrations, C
10ÿ3 M, the cathodic branch is strongly a€ected. There is a noticeable reduction step
increasing in height with increase in Sn2‡ content in the electrolyte. This step can be
attributed to the deposition of tin at the electrode surface. In the meantime, the
corrosion potential moves towards the positive direction with increase in Sn2‡
concentration. The ennoblement of Ecorr is ascribed to the fact that tin has a more
noble potential than aluminium. A reduction of the passive region is recorded and
the pitting potential moves slightly towards the negative direction with increase in
Sn2‡ content. These results indicate the activating e€ect of Sn2‡ on AlI electrode
during polarization measurements.
The polarization behaviour of AlII is almost similar to that of AlI electrode. The
pitting potential of Al±Sn electrode shifts slightly towards the negative direction by
increasing the concentration of Sn2‡ in the electrolyte and adopts values close to the
corrosion potential. The corrosion potential moves towards the positive direction
with increase in Sn2‡ content, due to the increased rate of deposition of Sn at the
658 H.A. El Shayeb et al. / Corrosion Science 43 (2001) 655±669

Fig. 1. Polarization curves of AlI electrode in 0.6 M NaCl and di€erent concentrations of Sn2‡ . Curves
(Ð) without Sn2‡ , (


) 10ÿ5 M Sn2‡ , (- - -) 10ÿ4 M Sn2‡ , (±
±) 10ÿ3 M Sn2‡ , (±

±) 2  10ÿ3 M Sn2‡ and
(±



±) 5  10ÿ3 M Sn2‡ .

electrode surface. Similar results were obtained in the case of Al±Zn and Al±Zn±Sn
alloys in 0.6 M NaCl solution containing Sn2‡ ions (no ®gures shown).

3.2. Current±time measurements

3.2.1. E€ect of Sn2‡ addition

The e€ect of Sn2‡ additions on the potentiostatic current±time curves of AlI , AlII ,
and the tested alloys in 0.6 M NaCl solution was investigated. Fig. 2 shows the I±t
curves of AlI electrode passivated at ÿ1050 mV (which is in the passive range) in 0.6
M NaCl solution to which di€erent concentrations of Sn2‡ were added after 20 min.
As shown from the curves, addition of lower concentrations of Sn2‡ (10ÿ4 M and
10ÿ3 M) causes instant shift in the current to the cathodic direction and then becomes
constant during the time of the experiment. At higher concentrations, the cathodic
current increases with the ¯uctuations of high frequency and magnitude. This is
attributed to the plating out of Sn at the electrode surface forming dendritic deposits.
This deposit is easily removed by running water because it is not tightly compact to
the surface. The formation of these dendritic deposits appears to be associated with
the deposition of Sn at an insulating aluminium oxide surface. The dendritic deposits
grow because of further deposition of metallic Sn and consequently a non-adherent
deposited layer is formed. Fig. 3 shows SEM±EDAX examination of AlI electrode
 H.A. El Shayeb et al. / Corrosion Science 43 (2001) 655±669 659

Fig. 2. Current±time curves of AlI electrode passivated at ÿ1050 mV in 0.6 M NaCl solution to which
di€erent concentrations of Sn2‡ were added after 20 min: (a) 10ÿ4 , (b) 10ÿ3 , (c) 3  10ÿ3 and (d) 10ÿ2 M
Sn2‡ .

after passivation at ÿ1050 mV in 0.6 M NaCl solution to which 10ÿ2 M Sn2‡ was
added after 20 min. As shown from the micrograph, Fig. 3(a), there is no attack to
the electrode surface and a Sn layer is plated out at the surface. A very small amount
of Sn was found to be deposited at the surface as revealed from the EDAX analysis,
Fig. 3(b).
AlII and Al±Sn alloy behave in the same manner as AlI electrode (no ®gures
shown). The electrodes were polarized at ÿ950 and ÿ980 mV for AlII and Al±Sn,
respectively, in 0.6 M NaCl solution to which di€erent concentrations of Sn2‡ were
added. The current surges rapidly and increases with ¯uctuations in the cathodic
direction after addition of Sn2‡ , due to the formation of dendritic deposit of Sn at
the electrode surface.
In contrast, Al±Zn and Al±Zn±Sn alloys show di€erent behaviour from AlI , AlII
and Al±Sn electrodes in Sn2‡ containing solution. The curves of Fig. 4 display the
660 H.A. El Shayeb et al. / Corrosion Science 43 (2001) 655±669

Fig. 3. (a) Scanning electron micrograph of AlI electrode obtained after potentiostatic polarization at
ÿ1050 mV in 0.6 M NaCl ‡ 10ÿ2 M Sn2‡ and (b) EDAX analysis of the area shown in the micrograph.

current±time measurements of Al±Zn electrode polarized at ÿ1140 mV in 0.6 M

NaCl solution to which di€erent concentrations of Sn2‡ were added after 20 min. As
it clear from the curves of Fig. 4, that addition of Sn2‡ causes activation by varying
degrees is depending on Sn2‡ concentration. Addition of a lower concentration of
Sn2‡ (10ÿ4 M) to the electrolyte has no activating in¯uence on the Al±Zn alloy, while
at a Sn2‡ concentration of 7  10ÿ4 M, the current increases in the anodic direction
after an induction period indicating the activating e€ect of Sn2‡ . As the concen-
tration increases, the induction period decreases and the anodic current increases
smoothly till reaching a maximum value and after that the current begins to decrease
and attains a constant value. This behaviour is due to the deposition of Sn on the
 H.A. El Shayeb et al. / Corrosion Science 43 (2001) 655±669 661

Fig. 4. Current±time curves of Al±Zn electrode passivated at ÿ1140 mV in 0.6 M NaCl solution to which
di€erent concentrations of Sn2‡ were added after 20 min: (a) 10ÿ2 , (b) 10ÿ3 , (c) 3  10ÿ3 , (d) 8  10ÿ4 , (e)
7  10ÿ4 and (f) 10ÿ4 M Sn2‡ .

electrode surface, where in the beginning, the concentration of Sn on the surface is

enough to change the nature of oxide ®lm and play its role as an activator, hence, the
anodic current increases forming the ascending part of the curve. After that, a fur-
ther deposition of Sn leads to the formation of a Sn coating, which acts as a barrier
coating. Therefore, the current decreases till attaining a constant value. At Sn2‡
concentration of 10ÿ2 M, the anodic current increases swiftly without the induction
period, indicating the larger activating e€ect of Sn2‡ ion and by the time the current
decreases with ¯uctuations moving towards the cathodic direction. Such behaviour is
ascribed to the deposition of a large amount of Sn at the electrode surface, which in
turn, suppresses the electrode activity. This situation is con®rmed by SEM±EDAX
examination of the surface of Al±Zn electrode polarized at ÿ1140 mV in 0.6 NaCl
and 10ÿ2 M Sn2‡ , (Fig. 5). As seen from the scanning electron micrograph, Fig. 5(a),
the attack appears to be severe but the presence of Sn on the electrode surface, as
detected by the corresponding EDAX pro®le (Fig. 5(b)), retards to some extent the
activation process. On the other hand, a very small amount of Sn is found on the
662 H.A. El Shayeb et al. / Corrosion Science 43 (2001) 655±669

Fig. 5. (a) Scanning electron micrograph of Al±Zn electrode obtained after potentiostatic polarization at
ÿ1140 mV in 0.6 M NaCl ‡ 10ÿ2 M Sn2‡ and (b) EDAX analysis of the area shown in the micrograph.

electrode surface at 10ÿ3 M Sn2‡ concentration, Fig. 6(a), hence the electrode is
attacked severely as seen from the micrograph of Fig. 6(b).
The current±time curves of Al±Zn±Sn electrode, polarized at ÿ1140 mV in 0.6 M
NaCl solution to which di€erent concentrations of Sn2‡ were added after 20 min, are
displayed in Fig. 7. There is resemblance between the obtained curves and those of
Al±Zn, alloy whereas the activating e€ect of Sn2‡ on the dissolution of Al±Zn±Sn
alloy is lower than its e€ect on Al±Zn alloy. The lower activating action of Sn2‡ may
be due to the presence of Sn as an alloying component in Al±Zn±Sn alloy.
 H.A. El Shayeb et al. / Corrosion Science 43 (2001) 655±669 663

Fig. 6. (a) EDAX analysis of the area shown in the micrograph and (b) scanning electron micrograph of
Al±Zn electrode obtained after potentiostatic polarization at ÿ1140 mV in 0.6 M NaCl ‡ 10ÿ3 M Sn2‡ .

In light of the above results, it can be noticed that the Al±Zn and Al±Zn±Sn alloys
display an active behaviour on addition of Sn2‡ to the electrolyte due to the presence
of Zn as an alloying component in the alloy. The presence of Zn at the electrode
surface facilitates the incorporation of the deposited Sn into the surface layers
showing activation. As stated before, according to Breslin et al. [13,31], the presence
of Zn as an alloying element promotes the nucleation of ZnAl2 O4 spinel, which gives
rise to increased defects and cracking of the protective layer. Therefore, the incor-
poration of Sn into the bulk of the alloy is more easier than its incorporation into the
Al surface. Moreover, considering the radii of Sn2‡ , Zn2‡ and Al3‡ , 0.93, 0.74, and
 respectively [32], Sn2‡ has better solubility in ZnAl2 O4 (on the alloy surface)
0.51 A,
than in Al2 O3 (on the Al surface).
664 H.A. El Shayeb et al. / Corrosion Science 43 (2001) 655±669

Fig. 7. Current±time curves of Al±Zn±Sn electrode passivated at ÿ1140 mV in 0.6 M NaCl solution to
which di€erent concentrations of Sn2‡ were added after 20 min: (a) 10ÿ2 , (b) 3  10ÿ3 , (c) 5  10ÿ3 , (d)
10ÿ3 , and (e) 10ÿ4 M Sn2‡ .

Analysis of the surface layers of Al±Zn alloy after treatment by Sn2‡ ions, can
give additional information about the mechanism of activation by Sn2‡ . XPS
analysis was performed after potentiostatic I±t measurements, at ÿ1140 mV, in 0.6
M NaCl and 10ÿ3 M Sn2‡ . The Al (2p), Zn (2p), Sn (3d), and O (1s) spectra are
shown in Figs. 8 and 9. The spectrum of Fig. 8(a) revealed three peaks at 72.8, 74.2,
and 74.9 eV arising from Al in the substrate, ZnAl2 O4 and Al2 O3 , respectively
[33,34]. This con®rms the presence of ZnAl2 O4 spinel in the surface layers of the
electrode. Two peaks for zinc species were detected according to the spectrum of Fig.
8(b), one of them was observed at 264.4 eV, suggesting the presence of ZnO on the
surface. The second peak was recorded at 268 eV, indicating the formation of
HZnOÿ 2 soluble complex to which the general formula ZnOX is ascribed [35]. Also,
this peak may be associated with the formation of ZnAl2 O4 .
Fig. 9(a) corresponds to the Sn (3d) spectrum of the Al±Zn alloy, which clearly
showed the existence of 3d3=2 and 3d5=2 energy levels. Three peaks were present at
484.2, 486.2 and 487.6 eV corresponding to the Sn 3d5=2 energy level. These peaks
belonged to Sn, Sn2‡ and Sn4‡ , respectively [36±40]. These results con®rm the ex-
istence of the two species of Sn (Sn4‡ and Sn2‡ ) in the Al2 O3 oxide layer. It is clearly
seen, from the intensity of the three peaks, that the major constituents present is Sn4‡
 H.A. El Shayeb et al. / Corrosion Science 43 (2001) 655±669 665

Fig. 8. XPS spectrum of (a) Al (2p) and (b) Zn (2p) measured for Al±Zn alloy after potentiostatic current
time measurement at ÿ1140 mV in 0.6 M NaCl and 10ÿ3 M Sn2‡ .

species of ionic radius 0.71 A,  which is almost equal to that of Zn2‡ (0.74 A). 
4‡
Therefore, it is expected that the incorporation of Sn into the surface layers of Al±
Zn alloy is more easier and the substitution of Sn4‡ in place of Zn2‡ in the surface
layers may occur, creating defects in the oxide layers and leading to active dissolu-
tion of the alloy.
XPS determination of the atomic surface concentration of Al, Zn and Sn can give
additional information about the dissolution process (Table 2). The high surface
concentration of Zn, 13%, compared to its concentration in the bulk, 4.92%, indi-
cates the di€usion of zinc to the outermost surface layer. This gives rise to an in-
creased possibility of dissolution of ZnO as HZnOÿ 2 and consequently replacement
of Zn2‡ by Sn4‡ .
The oxygen peak obtained from the electron spectroscopy chemical analysis, Fig.
9(b), has a width of 3.5 eV, indicating that it is caused by a sum of several over-
lapping peaks and con®rming the presence of oxygen in di€erent forms. This con-
clusion is supported by the XPS peaks in Figs. 8 and 9(a), which indicate that the
most probable chemical forms of oxygen are Al2 O3 , ZnO, ZnOX, SnO and SnO2 .
666 H.A. El Shayeb et al. / Corrosion Science 43 (2001) 655±669

Fig. 9. XPS spectrum of (a) Sn (3d) and (b) O (1s) measured for Al±Zn alloy after potentiostatic current
time measurement at ÿ1140 mV in 0.6 M NaCl and 10ÿ3 M Sn2‡ .
 H.A. El Shayeb et al. / Corrosion Science 43 (2001) 655±669 667

Table 2
XPS analysis of the Al±Zn surface
Species Concentration (at %)
Al 76
Zn 13
Sn 11

3.2.2. E€ect of simultaneous Sn2‡ and Zn2‡ addition on AlI

It seemed of importance to study the e€ect of simultaneous addition of Sn2‡ and
Zn2‡ on the I±t curves of ultrapure AlI electrode passivated at )1050 mV in 0.6 M
NaCl solution. As manifested in Fig. 10, addition of l0ÿ2 M Zn2‡ with two Sn2‡ ion
concentrations, 10ÿ3 and 10ÿ2 M, gives the same results when adding Sn2‡ alone.
This is ascribed to the plating out of Sn at the electrode surface, where the deposition
of Sn is more thermodynamically favoured than Zn. It is well known that, the de-
position of activator metals depends on the driving force in the cell for the reduction
of the activator species which, in turn, is governed by the standard electrode po-
tentials of the Sn2‡ =Sn and Zn2‡ =Zn couple; ÿ0.136 and ÿ0.76 V, respectively, such
values indicate that the deposition of zinc is less thermodynamically favoured.

Fig. 10. Current±time curves of AlI electrode passivated at ÿ1050 mV in 0.6 M NaCl solution to which (a)
10ÿ2 M Zn2‡ ‡ 10ÿ3 M Sn2‡ and (b) 10ÿ2 M Zn2‡ ‡ 10ÿ2 M Sn2‡ were added after 20 min.
668 H.A. El Shayeb et al. / Corrosion Science 43 (2001) 655±669

4. Conclusions

(1) Sn2‡ has no activating in¯uence on the dissolution of AlI , AlII and Al±Sn
electrodes during I±t measurements. This is attributed to the diculty of Sn di€usion
into the surface layers, for the activation process occurs only when the activator ions
di€use into the bulk and create defects in the oxide layers.
(2) Addition of Sn2‡ causes activation of Al±Zn and Al±Zn±Sn alloys by varying
degrees depending on Sn2‡ concentration. However, the presence of zinc as an al-
loying component in the alloys facilitates the di€usion of the deposited Sn into the
surface layers revealing activation. The existence of zinc promotes the nucleation of
ZnAl2 O4 spinel, which gives rise to increased defects and cracking of the protective
layer. Therefore, the di€usion of Sn into the bulk of the alloy is more easier than its
di€usion into Al surface.
(3) XPS results con®rm the presence of both Sn4‡ and Sn2‡ oxidation states in the
oxide ®lm on the surface of Al±Zn alloy as well as Sn0 after treatment with 10ÿ3 M
Sn2‡ .

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