Electrochimica Acta 55 (2010) 5253–5257

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

Fundamental studies of aluminum corrosion in acidic and basic environments:

Theoretical predictions and experimental observations
Mohsen Lashgari ∗ , Ali M. Malek
Department of Chemistry, Institute for Advanced Studies in Basic Sciences (IASBS), P.O. Box 45195-1159, Zanjan, Iran

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

Article history: Using quantum electrochemical approaches based on density functional theory and cluster/polarized
Received 12 December 2009 continuum model, we investigated the corrosion behavior of aluminum in HCl and NaOH media contain-
Received in revised form 13 April 2010 ing phenol inhibitor. In this regard, we determined the geometry and electronic structure of the species
Accepted 15 April 2010
at metal/solution interface. The investigations revealed that the interaction energies of hydroxide corro-
Available online 21 April 2010
sive agents with aluminum surface should be more negative than those of chloride ones. The inhibitor
adsorption in acid is more likely to have a physical nature while it appears as though to be chemical in
Keywords:
basic media. To verify these predictions, using Tafel plots, we studied the phenomena from experimental
Aluminum corrosion
Metal/solution interface
viewpoint. The studies confirmed that the rate of corrosion in alkaline solution is substantially greater
Cluster/polarized continuum model than in HCl media. Moreover, phenol is a potential-molecule having mixed-type inhibition mechanism.
Media effect The relationship between inhibitory action and molecular parameters was discussed and the activity in
Intrinsic cathodic protection alkaline media was also theoretically anticipated. This prediction was in accord with experiment.
© 2010 Elsevier Ltd. All rights reserved.

1. Introduction species optimized at meal/solution interface, rather than in vacuo.

Fundamental approaches to corrosion and corrosion inhibition
problems [1] are among interesting interdisciplinary topics in the
field of materials science in which their investigations are impor-
tant from both industrial and academic points of view, and have
attracted the attention of physical electrochemical scientists in
this area [2–4]. Although the validity of predictions in these stud-
ies should be ultimately approved by experiments, the empirical
approaches are often time-consuming, wearisome and expensive
[5]. Their investigations, particularly those with fundamental basis,
need some sophisticated instruments being capable of in situ ana-
lyzing the phenomena [6]. Thus, to minimize the experimental
efforts, theoretical investigations have been recently proposed as
an alternative to predict the phenomena before the direct observa-
tions by experiments [7].
The degradation of metals in aggressive environments can be
thought as a result of direct interactions of the corrosive agents
(e.g. Cl− , OH− , ..) with surface active sites in which the pres-
ence of inhibitor compounds can interfere and diminish the rate
of corrosion. In theoretical approaches, the adsorption of species
on metal surface can be investigated quantum electrochemically
through cluster/polarized continuum model [8], i.e. a modified ver-
sion of cluster model which applies the equilibrium structure of the
∗ Corresponding author. Tel.: +98 241 4153205; fax: +98 241 4249023.
E-mail address: Lashgari@iasbs.ac.ir (M. Lashgari).
Such theoretical investigations are obviously more useful if they
can predict the phenomenon before doing experiments.
By considering the remarks pointed above, we have in this work
attempted to evaluate the corrosion behavior of an amphoteric
metal like as aluminum in both acidic (HCl) and alkaline (NaOH)
media, firstly through theory and secondly by means of electro-
chemical approaches based on potentio-dynamic experiments [9].
It is also worthy to note that this non-transition metal has a wide
application in high-tech industries including aerospace, advanced
nuclear reactors, metal/air batteries, and ... [10]. This is mainly
because of light atomic-mass and capability of the metal to form
a protective oxide film on its surface. The passive film is unfortu-
nately degraded in hostile-corrosive environments and hence the
inhibitors should be applied. The molecule under consideration is
phenol inhibitor [11,12], introduced by Talati and Modi [13] as alu-
minum corrosion inhibitor in basic media. For the case of acid, we
are also interested here in examining the inhibition properties of
the molecule through current theory and experiment.
2. Theoretical
As implicitly mentioned above and the experimental reports
give extra support for that [14–16], the first step in aluminum cor-
rosion in aggressive solutions involves the contact adsorption of
corrosive agents on metal’s surface followed by chemical inter-
actions to form soluble products. Theoretically, the interaction of
species at metal/solution interface can be investigated by means of

0013-4686/$ – see front matter © 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2010.04.054
5254 M. Lashgari, A.M. Malek / Electrochimica Acta 55 (2010) 5253–5257

which are being used routinely for finding the equilibrium geom-
etry and electronic structure of the species, respectively [20]. For
aluminum atoms, however, we applied LANL2DZ basis set via Gen
keyword [19].

3. Experimental

The electrochemical measurements were conducted on a

Fig. 1. Schematic representation of Al31 (19,12) with its sub-clusters; namely,
Al10 (7,3), Al5 (4,1), Al9 (6,3) and Al7(6,1); the letters O, B and H (1 and 2) denote
to on-top, bridge and hollow adsorption sites, respectively.
high-purity (99.999) Al rod of 3 mm diameter, purchased from
Sigma–Aldrich® , mounted in epoxy resin to expose the cross-
sectional area of 7 mm2 to the electrolytes. Before each experiment,
the surface of Al electrode was wet ground with successive emery
(SiC) papers # 220, 400, 600, 800 and 1000, washed in distilled
water and acetone to remove dust and grease. Thereafter, Al
electrode was immersed in the alkaline-etching solution (1.5 g
tri-sodium phosphate + 1.5 g sodium carbonate in 100 ml distilled
water [21]) for 30 s at 353 K, rinsed again and finally followed by
drying.
The corrosive solutions applied in this study were 0.5 M HCl and
NaOH, and the inhibitory action was examined at a relatively high,
0.01 M, inhibitor concentration. All chemicals were AnalaR grade,
purchased from Sigma–Aldrich® or Merck KGaA companies.
For electrochemical studies, a three-electrode T-controlling
setup (Metrohm USA Inc.) was used. Here, the reference and
counter electrodes were Ag/AgCl (3 M) and Pt-foil (3 cm2 ), respec-
tively. The corrosion tests were potentio-dynamically carried out
using an AUTOLAB/PGSTAT30 instrument with GPES software (ECO
CHEMIE). The scan rate was 1 mV s−1 and the tests ran after 10 min
[22,23]. Each experiment was repeated at least three times and the
mean value was reported as the final result.

cluster model and applying quantum chemical calculations based

4. Results and discussion
on density functional theory (DFT) [17].
In cluster approach to corrosion and corrosion inhibition prob-
The interaction of corrosive agents and solvent molecule with
lems [17], it is generally assumed that the adsorption of species on
aluminum surface was studied. The results are given in Table 1 and
metal surface has a local nature. Therefore, the interactions will be
depicted in Fig. 2. As it can be seen from the table, the hydrox-
limited to those portions of the surface atoms, which are under-
ide anions in comparison with chloride ones adsorb more strongly
lying directly beneath the adsorbed species. Furthermore, since
in less distances. Because of this tenacious attack of the hydrox-
the adsorption of species is already taken place in solution part
ide corrosive agents (strongly adsorption at short distances), there
of the interface, the characteristic of media in this region should
is no doubt the aluminum corrosion to be more severe in NaOH
be accounted for. This can be done through polarized continuum
as compared with that measured in HCl media. This prediction is
model (PCM) with dielectric constant of six as reported in our pre-
vious works [4,9].
The cluster applied here is a relatively large set of aluminum Table 1
Adsorption of aggressive agents and water molecule with Al31 (19,12) surface
atoms taken from face centered cubic Al 1 1 1 surface [5] and
through various sites; for geometrical information please see Fig. 2.
commonly abbreviated with Al31 (19,12) in cluster terminology, as
shown in Fig. 1. Four different adsorbing sites are recognized here. Species Equilibrium Adsorption energy Induced (Mülliken)
The sites are on-top (O), bridge (B), hollow 1 and 2 (H1 and H2 ), distance (Å) (kcal/mol)a charges on metal
surface (a.u.)
depicted separately via Al10 (7,3), Al5 (4,1), Al9 (6,3) and Al7 (6,1) sub-
clusters, which are imaginable within the main Al31 (19,12) cluster. Cl− 2.32b −55.1 −0.56408
2.12c −45.7 −0.61408
As it can be seen from Fig. 1, the selection of clusters has been
2.09d −43.2 −0.62202
made with symmetric considerations. This is because of reducing 2.03e −39.9 −0.64045
the computational costs so that the calculations can be feasible
OH− 1.84b −133.9 −0.56000
on a personal computer. The procedure for systematic construc- 1.27c −141.9 −0.49398
tion of such symmetric clusters has been reported by us elsewhere 1.12d −145.8 −0.52320
[17]. In order to give bulk properties to these artificial clusters, we 1.18e −144.6 −0.49549
fixed the locus of each metallic atom in space using experimental H2 O 2.06b −15.9 −0.16911
crystallographic data [18] available in literature. 2.15c 4.0 −0.49398
To compare the results of different adsorbing sites, all single 2.78d −4.1 −0.11816
point energy calculations were carried out on the same Al31 (19,12) 2.26e 2.9 −0.14925

cluster after the optimization task was completed for each site
using its own sub-cluster. All quantum chemical calculations pre-
sented in this work were on the base of density functional theory
(DFT; B3LYP version), performed by Gaussian 03 suite of computer
codes [19] via a dual core 2.13 GHz processor. The basis sets applied
in these calculations were standard 3-21G** and 6-311G** basis sets
a
Defined as Eint = Especies-cluster − (Especies + Ecluster ) [17]. In these energies, the cor-
rections of basis set superposition error (BSSE) were also taken into account via
counterpoise method (Boys–Bernardi scheme) [24].
b
Adsorption on metal surface through on-top site.
c
Adsorption on metal surface through bridge site.
d
Adsorption on metal surface through hollow 1 site.
e
Adsorption on metal surface through hollow 2 site.
 M. Lashgari, A.M. Malek / Electrochimica Acta 55 (2010) 5253–5257 5255

Table 2
Electrochemical parameters of the aluminum corrosion in HCl and NaOH solu-
tions (0.5 M); obtained from Tafel (potentio-dynamic) experiments at different
temperatures.

T −Ecorr ˇa −ˇc Rp icorr

(K) (V vs Ag/AgCl) (V/decade) (V/decade) ( cm2 ) (mA/cm2 )

298 1.535a 0.513 0.207 260 3.468

0.969b 0.416 0.184 691 0.008

308 1.566a 7.715 0.331 116 16.700

1.042b 0.292 0.200 558 0.092

318 1.589a 12.376 0.004 92 24.940

1.032b 0.224 0.196 434 0.104
a
NaOH solution.
b
HCl solution.

for less corrosion tendency observed in hydrochloric acid media

Fig. 2. Adsorptions of hydroxide anion and water molecule on Al(1 1 1) surface
through on-top (O), bridge (B) and hollow (H1 and H2 ) sites (see Fig. 1).
totally supported by experimental data as illustrated in Fig. 3 and
quantified in Table 2; namely, the rate of corrosion (icorr ) in the
case of NaOH is firmly greater than that of HCl, and the rate ratio
OH− /iCl− ) is about 400 at room temperature.
(icorr corr
Besides the relatively loose attachments of chloride anions on
aluminum surface, Table 1 provides additional data to justify the
less corrosion tendency of aluminum metal in HCl media. As it can
be seen here (Table 1), for the case of chloride adsorption, extra neg-
ative charges are induced on metal surface. The induced electrons
may cause partial neutralization of the positive charges, appear-
ing naturally on aluminum surface in non-basic environments [25].
Therefore, this partial pumping of electrons to the metal surface
(electron induction) may be considered as an alternative reasoning
and the effect may be furthermore declared as an intrinsic cathodic
protection arising from anion/metal interactions.
The other result deducible from Table 1 is related to the most
probable adsorbing sites which is on-top for adsorption of Cl− and
H2 O, and hollow for the case of hydroxide anions. These preferential
adsorptions seem to be in direct relation with the size of species. In
the case of OH− with a relatively small size, the anions can penetrate
more deeply to the voids of surface and consequently interact with
more metallic atoms in comparison with H2 O or Cl− .
Concerning the inhibitor species adsorbing on metal surface, it
is worthwhile to notify that the phenol is among chemical com-
pounds being de-protonated in alkaline solutions and appears in
the form of anionic species, so-called phenoxide or phenolate. By
contrast, the phenol molecule is less likely protonated in acid solu-
tions. Even thought this process (protonation) could be possible
under harsh circumstances, the interaction of the cationic species
with metal surface should be negligible because of hindrance effect
[4] as well as electrostatic repulsion resulting in acidic environ-
ments [25]. In the latter case, we believe that the interaction of
cationic species with metal surface is gradually enhanced by simul-
taneous deprotonation of the species at metal/solution interface
[5]. Thus, in the present work, we have only considered the inter-
actions of neutral and anionic forms of the inhibitor molecule with
metal surface. The results of these investigations are summarized
in Table 3 and demonstrated in Fig. 4. In this regard, the following
results are justifiable:
(1) Because of the lack of proton in phenoxide and the availability
of extra lone pairs on oxygen center, it is reasonable that the

Table 3
Interaction of inhibitor species with Al31 (19, 12) surface through different sites; for
geometrical information please see Fig. 4.

Species Equilibrium Adsorption energy Induced (Mülliken)

distance (Å) (kcal/mol)a charges on metal
surface (a.u.)

Phenol 2.52b −8.6 0.60918

3.05c −1.6 0.64441
3.19d −3.1 0.67167
3.51e −3.7 0.58711

Phenoxide 1.86b −69.6 −0.45402

1.41c −68.0 −0.53294
1.29d −67.8 −0.60469
1.33e −62.4 −0.58627
a
Defined as Eint = Especies-cluster − (Especies + Ecluster ) [17]. In these energies, the cor-
rections of basis set superposition error (BSSE) were also taken into account via
counterpoise method (Boys–Bernardi scheme) [24].
b
Adsorption on metal surface through on-top site.
c
Adsorption on metal surface through bridge site.
d
Fig. 3. Potentio-dynamic polarization curves (Tafel plots) observed for pure alu- Adsorption on metal surface through hollow 1 site.
e
minum in HCl and NaOH solutions (0.5 M) at room temperature. Adsorption on metal surface through hollow 2 site.
5256 M. Lashgari, A.M. Malek / Electrochimica Acta 55 (2010) 5253–5257

Table 4
Electrochemical parameters of the aluminum corrosion inhibition in presence of
phenol molecules (0.01 M) in HCl media (0.5 M); obtained from Tafel (potentio-
dynamic) experiments at different temperatures.

T −Ecorr ˇa −ˇc Rp icorr IE

(K) (V vs Ag/AgCl) (V/decade) (V/decade) ( cm2 ) (␮A/cm2 ) (%)

298 1.010 0.244 0.162 1657 26.2 71

308 1.010 0.241 0.304 1127 51.6 44
318 1.051 0.230 0.196 504 90.7 13

natively accountable by means of activation energy criteria [27]

suggested for inhibitor investigations through the following
pseudo-Arrhenius equation:

icorr = A × e−Ea /RT (2)

In this formula, A is a concentration-dependent pre-

exponential factor and Ea is standing for activation energy
(apparent value) of the corrosion process. The values calculated
here for Ea in presence and absence of the inhibitor compound
are 48.9 and 10.4 kJ/mol, respectively. It indirectly reconfirms
the physisorption [26,28].
(3) The strongest interaction for both neutral and anionic species
is resulting from on-top mode of adsorption in which the max-
imum orbital overlapping is taken place between pz electron
of the aluminum atom (oriented normally outwards the metal
surface) and lone pairs of the oxygen center.
(4) The inhibitor adsorption on metal surface is almost perpendic-
ular for the case of alkaline solution while it will be inclined in
acidic medium (the balance of hindrance effect and maximum
overlapping).

5. Conclusion

On the basis of present quantum electrochemical approaches,

we can conclude that:

(1) Hydroxide corrosive agents in comparison with chloride ones

Fig. 4. Adsorptions of phenoxide anion and phenol molecule on Al(1 1 1) surface
through on-top (O), bridge (B) and hollow (H1 and H2 ) sites (see Fig. 1).
anionic species adsorb more strongly in short distances. Thus
it is predicted that the inhibitor adsorption in alkaline solution
is chemical compared to that in acidic media. This prediction is
experimentally confirmable since there is no claim to observe
any marked effect on inhibitory performance with increas-
ing the media’ temperature [13]; in the case of physisorption,
however, the inhibitory action should be decreased because
of de-attachment of the inhibitor species weakly adsorbed on
metal surface as a result of thermal motion acceleration.
(2) The adsorption energy of the neutral molecule with metal sur-
face is relatively low so it is expectable the inhibitor species
in acid solution being most likely physisorbed. This theoreti-
cal expectation is quite in agreement with experimental data
presented in Table 4; namely, the decreasing of inhibition effi-
ciency (Eq. (1)) with increasing of temperature indicates the
physisorption [26].
 
icorr
IE(%) = 1− 0
× 100 (1)
icorr
0
Here, icorr and icorr denote to the corrosion current density mea-
sured in presence and absence of the inhibitor, respectively. The
physisorption of phenol molecule in acid solution is also alter-
adsorb more strongly. This tenacious attack of the hydroxide
anions causes the aluminum corrosion in alkaline media to be
more severe as compared with that measured in HCl solution.
(2) The inhibitor adsorption on aluminum surface has a physical
nature in acidic environment. This physical interaction is also
in line with inhibitory behavior determined at different tem-
peratures.
(3) Potentio-dynamic polarization investigations indicated that
phenol molecule is among good mixed-type inhibitors, influ-
encing on both anodic and cathodic reactions (changes ˇa and
ˇc ) of the aluminum corrosion in HCl solution.
(4) The inhibitor adsorption in alkaline solution is taken place most
likely perpendicular to the metal surface while it becomes tilted
as the species being neutral, particularly in acidic environ-
ments.
(5) The strongest interaction between aluminum surface and
species Cl− , H2 O, phenol and phenoxide, is resulting through
on-top mode of adsorption. For the case of OH− , however, the
adsorption is via the hollow site.
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compounds remains unchanged or shows a slight tendency to decrease as com-
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it is remarkable to notify that the increasing of activation barrier is generally
accountable, because of corrosion rate decreasing in presence of inhibitor com-
pounds, regardless the adsorption being physical or chemical. But, it should be
justified for those situations in which the energy does not increase! This is
because the energy referring here as the activation energy is not exactly the
energy barrier, but includes the heat of inhibitor adsorption (Hads ) as well.
The latter quantity is significant for the case of chemical interactions (being
highly negative) so that it can counterbalance the energy increasing.