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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

The role of silicon alloying addition on the pitting corrosion resistance

of an Al-12 wt.%Si alloy
M.A. Pech-Canul a,∗ , M.I. Pech-Canul b , P. Bartolo-Pérez a , M. Echeverría a
a
Departmento de Física Aplicada, Cinvestav-Mérida, Km. 6 ant. carr. a Progreso, AP 73 Cordemex, Mérida Yuc., México, CP 97310
b
Cinvestav-Saltillo, Av. Industria Metalúrgica No. 1062 Parque Industrial Saltillo-Ramos Arizpe, Ramos Arizpe, Coahuila, México, CP 25900

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

Article history: The electrochemical behavior of Al-12 wt.%Si in neutral and slightly alkaline solutions was compared to
Received 15 December 2013 that of pure Al in order to explore the effect of Si on the properties of the passive film. The film growth
Received in revised form 10 May 2014 kinetics for the Al-Si alloy was slower than that corresponding to pure Al and XPS depth profile suggested
Accepted 10 May 2014
that the oxide film was thinner. Potentiodynamic polarization measurements in borate solution with
Available online xxx
addition of 0.01 M NaCl revealed that Si has a beneficial effect on the pitting resistance of the passive
film. The Mott-Schottky analysis indicated an n-type semiconductor behavior and that less noble flat-
band potential for the alloy corresponded with higher pitting potential. XPS results suggested that the
barrier layer on the alloy contains SiO2 particles distributed within the Al2 O3 /AlOOH film. The protectivity
of the Al-12%Si alloy was attributed in part to its ability to retard the adsorption of chloride ion, and also
because silicon oxide helps to block entry sites and restricts the transport of chloride ions through the
passive film.
© 2014 Elsevier Ltd. All rights reserved.

1. Introduction reveals different mechanisms to explain the role of alloying ele-

Alloying elements can have a substantial influence on the corro-
sion properties of aluminum. Due to the limited solubility of many
elements in aluminum, alloying elements are often distributed
not only in the Al solid solution, but also in fine precipitates and
coarse intermetallic particles. Early studies with Al-Cu solid solu-
tions showed that when copper is in solid solution, pitting corrosion
in sodium chloride solutions is inhibited due to a local acidifica-
tion mechanism [1,2]. Moshier and co-workers proposed that the
enrichment of oxidized alloying element caused by the preferen-
tial Al oxidation in passive films on supersaturated Al-transition
metal solid solutions (formed with small additions of Mo, Cr, Nb,
Ta and W) was responsible for increased pitting resistance [3–5].
McCafferty et al. produced binary aluminum surface alloys by ion-
implantation, showing that implanted elements with low pH of
zero charge of their oxides (Si, Cr, Zr, Nb, and Mo) rendered alloys
that had more positive pitting potentials than aluminum [6,7].
Frankel and co-workers studied pitting behavior on a range of sev-
eral sputter-deposited supersaturated Al alloy thin films (Al-Mo,
Al-Cr, Al-Mn, Al-W, Al-V, Al-Nb) and proposed that the increased
localized corrosion resistance is predominantly determined by the
effects on local dissolution kinetics [8]. So, the literature review
∗ Corresponding author.
E-mail address: max@mda.cinvestav.mx (M.A. Pech-Canul).
http://dx.doi.org/10.1016/j.electacta.2014.05.034
0013-4686/© 2014 Elsevier Ltd. All rights reserved.
ments on decreasing the susceptibility to pitting corrosion of binary
Al alloys. It seems that the process might be dependent on the kind
of alloying element [9].
The beneficial effect of Si in the pitting corrosion resistance of
bulk binary Al-Si alloys in neutral or slightly alkaline solutions has
been the subject of several studies in recent years. Amin et al. inves-
tigated the pitting corrosion of Al, Al-6%Si and Al-18%Si alloys in
neutral sulfate solutions in the absence and in the presence of
halide ions [10,11]. Their results showed that the pitting corro-
sion resistance decreased in the order: (Al-18%Si)> (Al-6%Si)> Al.
Although experimental evidence was not provided, such an affect
was attributed to the incorporation of Si atoms in the passive film,
arguing that such incorporation repairs the film defects and renders
it more stable. Investigation with pure Al and three Al-Si alloys (Al-
6%Si, Al-12%Si and Al-18%Si) in perchlorate solutions [12] and pure
Al vs Al-6%Si and Al-12%Si in KSCN solutions [13] revealed again
that Si enhances the pitting corrosion resistance of Al.
Recently, our research group reported the beneficial effect of sil-
icon in enhancing the pitting corrosion resistance of custom-made
Al-Si-Mg alloys in borate buffer solutions (pH 8.4) with additions of
0.01 M NaCl [14–16]. For instance, for the Al-10%Si-3%Mg alloy the
open circuit potential and the passive current density were very
similar to those for pure Al, but an ennoblement of 170 mV in the
pitting potential occurred.
The aim of this work is to study the role played by Si in enhancing
the protective properties of passive films formed on aluminum in

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Al-12 wt.%Si alloy, Electrochim. Acta (2014), http://dx.doi.org/10.1016/j.electacta.2014.05.034
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Fig. 1. a SEM image for Al-12% Si alloy and corresponding EDX mapping for (b) Al and (c) Si.

neutral and slightly alkaline solutions. The electrochemical behav- the counter electrode a Pt sheet. Potentiostatic polarization at a
ior of passive films formed on Al-12% Si is compared to that for a potential of 0.3 VSCE during 30 min was carried out in borate buffer
passive film in pure Al. solutions pH 8.4 (deareated with N2 bubbling before and during
the test) to compare the kinetics of passive film formation. Then,
2. Experimental potentiodynamic polarization at a sweep rate of 0.3 mV s−1 in the
anodic direction starting from the open circuit potential (Eoc ) was
2.1. Materials performed for Al and Al-12%Si in the same buffer solution but with
addition of 0.01 M NaCl.
Disc samples were cut from high purity (Goodfellow) aluminum
and Al-12 wt.% Si (temper as drawn) rods; a copper wire was 2.3. Mott-Schottky plots
attached to each disc for electrical connection and then they were
embedded in epoxy resin, leaving an exposed area of 0.283 cm2 The electronic behavior of passive films on aluminum and
and 1.77 cm2 for Al and Al-12% Si, respectively. Before each electro- the alloy was investigated in 0.1 M K2 SO4 solution pH 7.0
chemical experiment, the surface of specimens was abraded down (deareated with N2 bubbling) using the Mott-Schottky approach.
to a 1200 grit SiC paper, rinsed with distilled water and dried in hot
air. For surface characterization the samples were also polished to
mirror finish using aqueous slurries of 1 to 0.05 ␮m alumina, then
were cleaned ultrasonically for 3 min in distilled water and finally
dried with hot air. Fig. 1 show a SEM image (near the edge) of a
sample of Al-12%Si, acquired using a Jeol JSM-7600F field emission
SEM coupled with an energy-dispersive X-ray (EDX) detector. The
EDX mapping results clearly indicate that the light gray particles
correspond to silicon particles embedded in the aluminum matrix.
As shown with a photomicrograph obtained at 1000x magnifica-
tion (Fig. 2), such primary silicon particles occupy a large volume
fraction.

2.2. Electrochemical measurements in borate buffer solutions pH

8.4

All electrochemical measurements were performed with a

Gamry series G300 potentiostat-galvanostat in a conventional
three-electrode cell where the working electrode was Al or the Fig. 2. Optical micrograph at 1000x magnification of representative Al-12 wt.%Si
alloy, the reference was a saturated calomel electrode (SCE) and alloy.

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The electrodes were prepolarized at 0.7 VSCE for 2 h to attain steady-

state corresponding to a nearly constant thickness of the passive
layer. Capacitance versus potential results were then obtained by
electrochemical impedance measurements using a 10 mV sinu-
soidal signal at a single frequency of 1 kHz in potentials between
-0.6 and 0.7 V. The impedance measurements started at the more
negative limit and proceeded by steps of 20 mV to the upper limit.

2.4. Determination of pzc

It is well known that the adsorption of chloride ions is correlated

to the surface charge at the metal/electrolyte interface. To describe
this phenomenon, one experimental parameter that is commonly
used is the potential of zero charge (Epzc ) determined by the capac-
itance method. Assuming that the interfacial capacitance is the
double layer capacitance (Cdl ), the position of the minimum of the
capacitance versus potential curve defines Epzc . Considering that in
acid electrolytes complications by adsorption are minimized [17] a Fig. 3. Decay of anodic current with time in borate buffer solution pH 8.4 after
stepping the Al and Al-12%Si electrodes to 0.3 VSCE .
solution of 0.1 M HCl (prepared with reagent grade HCl and deion-
ized water) was selected to determine and compare the Epzc for
Al and Al-12%Si. Differential capacitances were measured through pH 6.9. Considering that it is generally accepted that the oxide film
single-frequency EIS in the corresponding potential range with a on aluminum is an n-type semiconductor [24–27] a schematic of
potential step of 5 mV on freshly polished surfaces. A frequency of the physicochemical processes that occur within a passive film on
2 Hz and an ac disturbance signal of 10 mV were used. aluminum is presented in Fig. 5, where the n-type doping is rep-
resented by oxygen vacancies and metal interstitials. Reaction (1)
describes the injection of Ali 3+ into the barrier layer as an intersti-
2.5. XPS
tial, which is then ejected into the solution (reaction 3). Reaction (2)
results in the growth of the barrier layer into the bulk of aluminum,
X-ray photoelectron spectroscopy (XPS) was used to analyze the
while reaction (5) leads to the destruction of the barrier layer by
chemical composition of the potentiostatically formed oxide layer
dissolution. The oxygen vacancies produced by reaction (2) are con-
on the aluminum and Al-12%Si surface. Passive films were formed
sumed at the film/solution interface by reaction (4). As established
in 0.1 M K2 SO4 solution pH 7.0 (deareated with N2 bubbling) at a
in the PDM the transient in film growth current density depends
potential of 0.7 VSCE during 45 min. XPS measurements were car-
mainly on the generation of oxygen vacancies at the metal/film
ried out on a Thermo Scientific K-Alpha XPS spectrophotometer.
interface and the dissolution of the film at the film/solution inter-
A monochromatic Al K␣ X-ray source was used, with a spot area
face. So, the results in Fig. 3 suggest that for the Al-12%Si alloy
of 400 ␮m. Core level spectra for C1s, Al2p, Si2p and O1s were
the balance between these two processes leads to a slower film
acquired in the depth profile mode using a 1 kV argon ion (Ar+ )
growth kinetics and also to a thinner film compared to that for
beam.
pure aluminum.
Fig. 6 shows anodic polarization curves for Al and Al-12%Si
3. Results and discussion in deaerated borate solutions containing 0.01 M NaCl. The pitting
potential (Epit ) is clearly defined by a sharp increase in the current
3.1. Potentiostatic and potentiodynamic polarization density, which in the case of pure Al occurs around -0.585 VSCE . For
measurements the Al-Si alloy there is a shift of about 85 mV in the positive direc-
tion. This is an indication that the passive film on Al-12Si is more
The typical current transients corresponding to potentiostatic resistant to pitting corrosion that pure Al, although the effect is
growth of passive films at 0.3 VSCE in borate buffer solution pH only modest since there is also a shift in Eoc . Our research group has
8.4 exhibited the characteristic decrease of current with anodiz-
ing time associated to nucleation and growth of the passive film.
Results corresponding to the initial period of 3 min are shown in
Fig. 3. It is evident that at a given time, less current is required for
passive film growth on the Al-Si alloy than on pure Al. The inter-
pretation of current-time transients describing anodic oxide film
growth on metals is often based on two theories, the high field
conduction model (HFM) [18,19] and the point defect model (PDM)
[20–22]. Zhang et al. [20] suggested the following diagnostic rela-
tionshipto discriminate between the two models (HFM and PDM):
f (j) = −j /j =  ln j, where j is the current density and j is the
differential dj/dt. The HFM predicts that a plot of f(j) vs ln j should
give a value of ␴ greater than 0, and the PDM predicts that ␴=0 (f(j)
constant). The diagnostic plots obtained from the data in Fig. 3 are
presented in Fig. 4, and show that f(j) is essentially independent of
the current density in both cases. In other words, it suggests that
the growth of the barrier layer in aluminum and Al-12%Si in the
borate solution pH 8.4 is consistent with the PDM. Such result for
aluminum is in agreement with the observations of Aligizaki and 
Macdonald [23] for barrier layers grown in a borate buffer solution Fig. 4. Diagnostic plot [20] of f (j) = −j /j VS ln j, using the data in Fig. 3.

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Fig. 5. Physicochemical processes occurring in the barrier layer, according to the
PDM [22]. AlAl : aluminum cation in a normal cation position. Ali3+ : interstitial alu-
minum cation, OO : oxygen ion in anion site, VO•• : oxygen vacancy, VAl : aluminum
vacancy at metal phase.
reported similar polarization curves in the same solution for several
Al-Si-Mg alloys [14,15]. For comparison purposes, the polarization
curves for two representative Al-Si-Mg alloys are also plotted in
Fig. 6. The microstructural characterization of these ternary alloys
[14,15] showed that Mg2 Si is the predominant intermetallic phase.
Fig. 6 shows that for the ternary alloys the pitting potential is clearly
defined and the passive current densities are in the order of the one
observed in pure Al; however, the current densities in the active
region are significantly higher compared to the observed for Al and
Al-12%Si. Such high anodic activity is attributed to selective disso-
lution of Mg from the intermetallic particles of Mg2 Si. For the alloy
with 10%Si and 9.5%Mg Epit is about 170 mV more positive than that
for Al, and for the alloy with 12.5%Si and 10%Mg it is about 250 mV
more positive. This leaves no doubt that Si as an alloying element
has a beneficial effect on the pitting corrosion resistance.
3.2. Mott-Schottky analysis
It is generally accepted that passive films on metals behave
as semiconductors and that there is a close relationship between
Fig. 6. Anodic polarization curves for Al and Al-12Si in deareated borate solutions
pH 8.4 containing additions of 0.01 M NaCl. The polarization curves for two Al-Si-Mg
alloys is included for comparison.
Please cite this article in press as: M.A. Pech-Canul, et al., The role of silicon alloying addition on the pitting corrosion resistance of an
Al-12 wt.%Si alloy, Electrochim. Acta (2014), http://dx.doi.org/10.1016/j.electacta.2014.05.034
Fig. 7. Mott-Schottky plot for Al and Al-12Si after the passive film was grown during
2 h at E = 0.7 VSCE in a 0.1 M K2 SO4 solution.
solid-state properties of the films with its corrosion resistance.
The analysis of capacitance versus potential data based on the
Mott-Schottky theory is the most common method for probing the
electronic properties of passive films. According to this theory, the
space charge capacitance (Csc ) for an n-type semiconductor oxide
follows the Mott-Shottky equation
1 2
 kT

= E − Efb − (1)
2
Csc eεεo ND e
where ND is the donor concentration, ␧ is the dielectric con-
stant of the semiconductor, ␧0 is the vacuum permittivity, e is
the elementary charge, k is the Boltzmann constant and T the
temperature. This equation suggests that a plot of 1/Csc 2 versus
E gives a straight line. The point of intersection with the poten-
tial axis gives the flat band potential (Efb ) and the slope gives the
carrier density. In this work, values of the space charge capaci-
tance were obtained from the experimentally determined electrode
capacitance (C) and the relationship corresponding to the series
connection between Csc and the Helmholtz layer capacitance CH
1/C = 1/Csc + 1/CH . A typical value of CH = 50 ␮F cm−2 was used
in the calculations. Fig. 7 shows the Mott-Schottky plots for alu-
minum and Al-12%Si obtained in a 0.1 M K2 SO4 solution. Linear
relations with positive slopes indicate that for both materials the
passive films are n-type semiconductors. Since the passive film on
aluminum is often hydrated, a value of ␧=10 was used [28] for
estimation of the donor concentration from the slope of the Mott-
Schottky plot. Considering that the Al-12%Si alloy contains a large
volume fraction of primary Si particles, it is likely that the pas-
sive film consists of a mixed oxide. Thus, the dielectric constant
in this case can be estimated by the use of an ideal mixing equa-
tion: εalloy = (1 − f ) εAl2 O3 + fεSiO2 , where f is the mole fraction of
the alloying oxide. Taking the value ␧SiO2 = 3.9 [29] and assuming
as a first approximation that the f is equal to the composition of Si in
the base alloy, we obtain ␧alloy = 9.2. Values of Efb and ND obtained
from the Mott-Schottky analysis are presented in Table 1. The cor-
responding values for pure aluminum are in good agreement with
those obtained by Bockris and Kang [25] in the same type of solu-
tion. For the Al-12%Si alloy Efb is more negative and ND is higher,
Table 1
Results of Mott-Schottky analysis.
sample Efb /VSCE ND /cm−3
Al -1.15 1.05 × 1020
Al-12% Si -1.31 2.50 × 1020
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Fig. 8. Relationship between double-layer capacitance and applied potential for Al
and Al-12Si freshly polished electrodes immersed in 0.1 M HCl.
compared to the values obtained for pure Al. The relevance of these
results will be discussed below.
It is generally accepted that the electronic properties of the pas-
sive films may play an important role in the susceptibility to local
breakdown. In particular for passive films on Al and Al alloys, a cor-
relation between flat band potential and pitting potential has been
observed by different authors [30,31]: less noble flat band poten-
tials correspond to higher pitting potentials. Results in Table 1 show
that Efb for the alloy is 160 mV more negative compared to that for
pure Al and Fig. 6 shows that Al-12%Si has a lower passive current
density and a more positive pitting potential. Thus, our results are
consistent with the literature, and confirm that the passive film on
the Al-12%Si alloy is more protective than the one on pure Al.
The diagnostic plot in Fig. 4 suggests that the growth of passive
films on both the Al and Al-12%Si electrodes can be described by the
PDM and Fig. 7 confirms that both films behave as n-type semicon-
ductors. In pure Al the donors are mainly oxygen vacancies (and
possible aluminum interstitials). In the Al-12%Si alloy, silicon is
present in two forms, in solid solution and as primary particles. Sil-
icon in solid solution might enter into the Al2 O3 lattice as a dopant,
and thus it would affect the defect chemistry of thepassive oxide
layer. For instance, if it enters as substitutional Si• 3+ a decrease in
Al
the donor concentration by charge compensation would occur. On
the other hand, primary Si particles get oxidized during the anodic
polarization (see XPS results below), thus, the appearance of the
Si/SiO2 and SiO2 /Al2 O3 interfaces within the passive film might
introduce more defects. So, the result in Table 1 showing that ND
is higher for the alloy compared to pure Al seems to be reasonable
and is an indication of the highly disordered nature of the passive
film. It is interesting to observe that for aluminum alloys contain-
ing Cu, Ta Mo or W Bockris and Kang [25] also observed a decrease
in the slope of the Mott-Schottky plot compared to that for Al (i.e.,
they also obtained an increase in the donor density for the alu-
minum alloys). Now, within the framework of the PDM, a passive
film with high donor density is associated with a small film thick-
ness. Such observation has been confirmed, for instance, for iron
[32] and stainless steel [33,34] in neutral and slightly alkaline solu-
tions. Therefore the ND values in Table 1 suggest that the passive
film on the Al-12%Si alloy is thinner than that formed on pure Al,
in agreement with results of film growth kinetics in Fig. 3.
3.3. Potential of zero charge
Fig. 8 shows the double layer capacitance as a function of
potential in 0.1 M HCl for native oxide films on Al and Al-12%Si.
Both curves exhibit a minimum, which defines the Epzc . The
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Al-12 wt.%Si alloy, Electrochim. Acta (2014), http://dx.doi.org/10.1016/j.electacta.2014.05.034
5
Fig. 9. Selective spectra at 4 representative etching times for Al 2p of passive film
grown on pure Al during 45 min at 0.7 VSCE in neutral sulfate solution.
corresponding value for pure Al (-1.03 VSCE ) is consistent with the -
0.84 VNHE value (-1.08 VSCE ) reported by Trassati [35]. A significant
effect of silicon on surface charge is observed, since the Epzc for
Al-12Si is 217 mV more positive compared to that for Al. The sign
and the value of the difference E between Eoc and Epzc provides
information about the adsorption process. If E > 0 the surface is
positively charged and chloride ions are easily adsorbed. If E < 0
the surface is negatively charged and chloride ion adsorption is
avoided. The E values for Al and Al-12Si are 10 mV and -61 mV,
respectively. This shows that Al-12Si is less susceptible to pitting
than Al since the adsorption of chloride ions is not favorable.
The breakdown of the passive film in chloride containing envi-
ronments involves several steps [36–39] (adsorption of the chloride
ion at the passive film-solution interface, penetration of Cl− into
the passive film, etc.). Results in Fig. 8 suggest that adsorption of
chloride ion would be retarded due to the presence of SiO2 in the
passive film. However, the modification of the acid-base properties
of the surface may not be the only reason for higher protectivity
of the Al-12%Si alloy. A significant volume fraction is occupied by
primary silicon particles, so we would expect the rate of passivity
breakdown to be affected not only by the adsorption of chloride
but also by other steps in the pitting mechanism which are related
to the structure of the passive film. The passive film on aluminum
contains high energy “entry sites” [25] at which the chloride can
be more strongly adsorbed and can substantially penetrate into the
passive film. In the Al-12%Si alloy–Si-O-Si- chains are likely to form
[40] which tend to block the entry sites and restrict the transport
of chloride ions through the passive film. So, the protectivity of the
Al-12%Si alloy seems to be similar to that proposed by Bockris and
Kang [25]; i.e., the adsorption of the chloride ion on the surface of
the passive film as well as its penetration into the film are greatly
retarded by the presence of the alloying element.
3.4. XPS analysis
Figs. 9 and 10 show the results of XPS measurements for a
passive film grown on pure Al at 0.7 VSCE in neutral sulfate solu-
tion during 45 min. Fig. 9 shows the XPS spectra evolution of Al
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Fig. 10. Comparison of high resolution spectra at the beginning and after 3 min Fig. 12. Comparison of high resolution spectra at the beginning and after 3 min
etching for O 1s of a passive film grown on pure Al as indicated in the caption of etching for O 1s of a passive film grown on Al-12%Si as indicated in the caption of
Fig. 9. Fig. 11.

2p at 4 selective sputter etching times during the beam depth
profiling. Each spectrum consists of two peaks, corresponding to
aluminum metal (Al0 ) and oxidized aluminum (Al3+ ). Such assign-
ment has been made based on the value of binding energy for
oxidized aluminum and the chemical shift between the two peaks
(approximately 3 eV) [41,42]. The evolution of the relative inten-
sities of the component peaks agrees well with the presence of an
oxide/oxyhydroxide layer. After 3 min etching the Al3+ peak is still
present, but very small. Fig. 10 shows a comparison of the spectra
for O 1s corresponding to 0 and 3 min etching. Deconvolution of
each spectrum with the XPSPEAK software [43] suggests that it
consists of two peaks, corresponding to the Al-O-Al and Al-O-H fea-
tures [41,42], in agreement with the commonly accepted structure
of barrier-type anodic films on aluminum: a hydrated outer layer
on top of a dense inner layer mainly composed of Al2 O3 [25,44].
Fig. 11 shows the XPS spectra evolution of Al 2p at 4 selec-
tive sputter etching times during the beam depth profiling for the
passive film grown on Al-12%Si. Similarly to the observed for the

Fig. 11. Selective spectra at 4 representative etching times for Al 2p of passive film Fig. 13. Selective spectra at 4 representative etching times for Si 2p of passive film
grown on Al-12%Si during 45 min at 0.7 VSCE in neutral sulfate solution. grown on Al-12%Si as indicated in the caption of Fig. 11.

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Fig. 14. Schematic representation of alloy-solution interphase, considering the oxi-
dation of primary Si particles.
passive film on pure Al (Fig. 9), each spectrum consists of two peaks,
corresponding to aluminum metal (Al0 ) and oxidized aluminum
(Al3+ ). The evolution of the relative intensities of the component
peaks is also similar to that for a passive film on pure Al. After 3 min
etching there is still a contribution (although small) of oxidized
Al. The comparison of the spectra for O 1s corresponding to 0 and
3 min etching is presented in Fig. 12. A deconvolution of each spec-
trum suggests that it consists of two peaks. The one with the lower
binding energy corresponds to the Al-O-Al feature. The other, with
higher BE can be attributed to Al-O-H and to the Si-O bond [45,46].
Fig. 13 shows the XPS spectra evolution of Si 2p at the 4 selective
sputtering times. Two peaks can be identified, attributed to elemen-
tal silicon and the Si4+ component, corresponding to SiO2 [45,46].
It is interesting to observe that intensities for Si0 are roughly uni-
form throughout the film, while that for oxidized silicon decreases
slightly. These results are consistent with the hypothesis put for-
ward above that the passive film on the Al-12%Si alloy might consist
of a mixed oxide and that–Si-O-Si- chains might be present. Tak-
ing into account the microstructure of the alloy (Figs. 1 and 2) a
schematic representation of the cross section for the passivated
alloy is proposed in Fig. 14. Primary Si particles inside the passive
film are expected to be fully oxidized. However the nearly uniform
concentration of Si0 throughout the film might be an indication
Fig. 15. Comparison of XPS depth profiles for passive films formed under potentio-
static conditions (45 min at 0.7 VSCE in sulfate solution) on a) Al and b) Al-12%Si.
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7
that some particles are partly oxidized. As a final indication of the
effect of silicon on the properties of the passive film, the XPS depth-
concentration profiles for the passive films on Al and Al-12%Si are
compared in Fig. 15. Even after 180 s sputtering, the concentration
of Al in Fig. 15(a) has not reached a constant value. On the other
hand, the profile in Fig. 15(b) shows that the concentration of Al
has leveled off after 140 s sputtering. The fact that a shorter time
is required to reach a constant concentration of Al for the passive
film on the Al-12%Si alloy gives a qualitative indication that the
film is thinner than the one formed on pure Al. Such result is in
agreement with the observation that lower currents are required
to grow the passive film on the alloy (Fig. 3) and indications from
the Mott-Schottky analysis that a higher donor density is related to
a lower oxide film thickness.
4. Conclusions
Results of potentiostatic growth of passive films on Al and Al-
12%Si in borate buffer solution pH 8.4 showed that less charge is
required to grow the passive film on the alloy, and gave indica-
tion that the growth of barrier layer is consistent with the PDM in
both cases. Anodic polarization curves in the borate solutions in
the presence of chloride ions showed that the passive film on the
alloy exhibited a modest increase in pitting resistance compared
to that for Al, but the beneficial effect was remarkably supported
by results with custom-made Al-Mg-Si alloys containing roughly
the same concentration of Si. The Mott-Schottky analysis for pas-
sive films formed under potentiostatic conditions in neutral sulfate
solutions showed that they behave as n-type semiconductor in both
cases. Pitting susceptibility (measured by the pitting potential) was
correlated with electronic properties of the passive films; less noble
flat-band potential for the alloy corresponded with higher pitting
potential. The barrier layer on the alloy had a higher donor density
and was thinner (as indicated by XPS depth profile analysis) com-
pared to that on pure Al, in agreement with predictions from the
PDM. The XPS spectra for Si 2p at different depths showed com-
ponent peaks for elemental Si and SiO2 . Considering that the alloy
contains a large volume fraction of primary silicon particles and
results of XPS analysis, it is suggested that the passive film contains
SiO2 particles distributed within the Al2 O3 /AlOOH film. Measure-
ments of the potential of zero charge by the capacitance method
showed that a modification in the acid-base properties of the sur-
face occurred due to the presence of SiO2 . The protectivity of the
passive film on the Al-12%Si alloy has been explained in part due to
its ability to retard the adsorption of chloride ion, and also because
silicon oxide helps to block entry sites and restricts the transport
of chloride ions through the passive film.
Acknowledgements
The authors are grateful to Conacyt (National Council of Science
and Technology, México) for financial support under grants FOMIX-
Yucatán 2008-108160 and CONACYT LAB-2009-01 No. 123913. The
authors are grateful to E.E. Coral-Escobar and A.D. Zapata-Loria
for technical assistance with electrochemical measurements, D.
Huerta with SEM/EDAX analysis and to W. Cauich Ruiz with the
XPS analysis.
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