\

PERGAMON

Corrosion Science 30 "0888# 03360352

Pitting of aluminium in non!aqueous chloride

media
A[G[ Munoz\ J[B[ Bessone
Instituto de Ingenier(a Electroqu(mica y Corrosio n "INIEC#[ Dto de Qu(mica e Ingenier(a Qu(mica[
Universidad Nacional del Sur[ Av[ Alem 0142!7999 Bah(a Blanca Repu blica Argentina
Received 05 December 0886^ accepted 09 December 0887

Abstract
Pitting of Aluminium in non!aqueous chloride media was studied by means of potentiostatic\
low scan rate potentiodynamic polarisations and the ac!impedance method[ Initiation of pitting
was found to take place in a similar potential region as in aqueous media for the same chloride
concentration[ Ac!impedance studies performed at potentials close to pitting initiation suggest
adsorption and:or penetration of chloride ions occurring at the imperfection sites of surface
oxide layer[ Once pzc of Al is anodically exceeded\ pitting initiates and pit growth is ohmic
controlled by a salt _lm formed over the active surface which gives rise to an hemispherical
morphology at the early stages of the attack[ The presence of a salt _lm is found to be
responsible for the appearance of wide hysteresis cycle[ At potentials more negative than pzc\
pit growth is hindered and Al dissolution is controlled by ionic transport through the salt _lm
until equilibrium potential for the Al:AlCl2 system is reached[ 0888 Elsevier Science Ltd[
All rights reserved[
Keywords] aluminium^ pitting corrosion^ cyclic voltammetry^ EIS

0[ Introduction
Numerous theories have been proposed in order to explain pitting mechanism and
the in~uence of factors such as type of anion present\ pH and the characteristics of
surface passive layer on it 0[ In general\ the adsorption of aggressive anions on
surface oxide ~aws and their penetration and agglomeration at these imperfection
sites was considered as a possible explanation for pit nucleation 1[ It was also
suggested that pits can develop by means of an hydrolysis process giving rise to a

 Corresponding author] Fax] 943!80!411!431

E!mail address] jbessonecriba[edu[ar "J[ B[ Bessone#
9909!827X:88:, ! see front matter 0888 Elsevier Science Ltd[ All rights reserved[
PII] S 9 9 0 9 ! 8 2 7 X " 8 7 # 9 9 0 8 8 ! 0

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localised acidi_cation which avoid further repassivation 2\ 3[ Thus\ the role played
by chloride ions in the initiation of pitting is not totally clear[
Most studies of pitting of metals and alloys in non!aqueous media were performed
with small amounts of water\ to get in several cases an adequate solubility\ or with
the presence of acids 4[ Therefore\ these works are not of interest in attempting to
simplify the system under study\ so that valid conclusions on the in~uence of Cl on
pit nucleation may be drawn[ Relatively few studies of aluminium in anhydrous
non!aqueous media were carried out\ but these dealt mainly with the dissolution
mechanism or the activation of certain alloys 57[
The aim of this work is to analyse the speci_c in~uence of Cl on the initiation of
pitting and early stages of pit growth by approaching anhydrous conditions[ Thus\
the possibility of metal ion hydrolysis is eliminated or at least diminished to a great
extent[

1[ Experimental method
High purity polycrystalline aluminium rod "88[888)# in the form of rotating discs
axially embedded in a PTFE holder was used as a working electrode with 9[969 cm1
of apparent area[ Surface polishing was performed successively with 0999 grit SiC
paper and green felt polishing cloth embedded with 9[2 mm alumina[ Electrodes were
immersed in acetone and dried with hot air before performing each experiment[
Solutions were prepared with anhydrous dimethylformamide "DMF# of spec!
troscopic grade ") H1O9[90# and LiCl and LiClO3 of analytical grade[ Salts were
previously dried under vacuum at 039>C during 5 h[
The experiments were performed in a conventional three compartment cell sep!
arated from the atmosphere by means of glass joints and a tramp _lled with molecular
sieves[ Before each measurement\ dry N1 was bubbled through the solution for 34 min[
As counter electrode\ a large area platinum sheet was used[ As reference electrode\
the following system was utilised] Cd"Hg#:CdCl1"s#\ CdCl1[H1O"s#\ NaCl"s# "DMF# 8[
This latter presented a potential value of 9[65929[939 V vs sce\ it being measured
after each experiment\ since variation of the potential value was observed to occur
after several days[ All potentials in the text\ are referred to the Cd"Hg#:CdCl1 system
utilised[
Cyclic voltammetries performed with a Pt electrode in the working solutions showed
that an important increase of cathodic current takes place at potentials more negative
than 9[3 V\ this being due to the presence of water traces[ Solvent reduction was
reported not to occur until approximately 0[13 V 09[ At high positive potentials
"0[6 V#\ solvent oxidation begins[ Thus\ contributions given by secondary reactions
may be neglected within the potential region investigated[ Furthermore\ the presence
of free OH generated by H1O reduction does not seem to be probable[ Although
solubility data for LiOH in DMF were not reported\ a slight solubility\ if any\ is
expected since it was found to be insoluble in other organic solvents such as acetonitrile
and g!Butyrolactone 00\ 01[ Therefore\ an attack of the oxide _lm due to local
alkalisation is not expected[

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0338

Currentpotential responses were obtained using a linear voltage sweep generator

PAR Model 064\ a potentiostat!galvanostat PAR Model 062 and xy HP 3996 B
recorder[ Impedance measurements were carried out with a Solartron Electrochemical
Interface 0175 and a Solartron Frequency Response Analyser 0149 coupled to a
Hewlett Packard computer 8105[ A dual stage ISI DS 029 SEM and an EDAX 8599
quantitative energy dispersive analyser were used to examine the electrode attack[

2[ Experimental results
2[0[ Electrolytic conductance
Dimethylformamide was found to be an excellent solvent for LiCl\ which allow
solutions to be obtained with the presence of Cl[ Its dielectric constant of 26 allow
relatively high equivalent conductivities to be attained[ LiCl does not present a good
solubility in other commonly used solvents such as Acetonitrile and Dime!
thylsulfoxide[ Table 0 shows the speci_c conductivity of LiCl "DMF# solutions "k#
for di}erent concentration values[
In order to obtain a higher solution conductivity\ in particular for the lower
concentrated LiCl solutions\ LiClO3 was intended to be used as supporting solute[
However\ it was proved that ClO
3 can interact with aluminium\ so masking the e}ect
exerted by Cl[
2[1[ Voltammetric studies
Cyclic voltammetries at low anodic potential scan rate "9[990 V[s0# of Al in 9[4 M
LiCl "DMF# were performed starting from a potential value of 9[5 V with and

Table 0
Speci_c conductivities of the electrolytes used
at 10>C
CLiCl "M#

k "V0 cm0#

0
9[64
9[4
9[2
9[0
9[94
CLiCl "M# CLiClO3 "M#
9[09[8

7[93092
6[54092
5[44092
4[18092
1[65092
0[65092
19[0092

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Fig[ 0[ Cyclic voltammetries of Al at 9[990 V s0 with and without electrode rotation in 9[4 M LiCl solution[
"a# 9 rpm^ "b# 0799 rpm[ Es\c9[5 V\ Es\a9[014 V[

without electrode rotation "Figure 0#[ In both cases\ after an initial small leakage
current\ an anodic current raise at a potential near 9[9 V can be observed[ The
reverse scan shows a wide hysteresis cycle\ this being characteristic of pitting[ After a
maximum\ the current begins to decay without oscillations and following a linear
currentpotential relationship\ which suggests that an ohmic controlled process is
taking place[ Electrode rotation seems not to have a signi_cant in~uence on the
activation process as can be inferred by comparing both voltammetries "Figure 0*
curves a and b#[
The potential at which pitting initiates was observed to vary on repeating the same
experiment at the same conditions[ Thus\ the initial state of surface oxide seems to
exert a great in~uence on pitting mechanism in this medium[ On the other hand\
repassivation potential "Epp# was reproducible and independent of the sample used to
perform the experiment[
Decreasing anodic current can be observed with successive voltammetric cycles as
shown in Fig[ 1[ This fact may be related to the formation of increasing amounts of
corrosion product in the oxide defective sites where pitting was initiated\ that making
further metal dissolution di.cult[
Hysteresis cycle taking place at the reverse potential scan after pitting is attained\
was analysed[ Figure 2 shows the potentiostatic polarisation plot performed after
bringing the electrode to a potential value of 9[299 V at 9[990 V s0[ Current was
recorded at least for 09 min after the potential being applied[ The hysteresis cycle does
not disappear and the current values are much higher than those observed in the
cyclic voltammetries "Figures 01#\ it being a consequence of the increasing area of
growing pits[ After repassivation\ a new cyclic voltammetry shows that both pitting
and repassivation potentials remains at the same potential value as before "Figure
2*dashed curve#[
The same experiment but with electrode rotation was carried out "Figure 3#[ Also

A[G[ Munoz\ J[B[ Bessone : Corrosion Science 30 "0888# 03360352

0340

Fig[ 1[ Cyclic voltammetries of Al in 9[4 M LiCl solution at 9[990 V s0[ Es\c9[5 V\ Es\a9[17 V[ "a# 0st
cycle^ "b# 1nd cycle^ "c# 2rd cycle^ "d# 3th cycle[

Fig[ 2[ Potentiodynamic potential scan showing pitting of Al and reverse potentiostatic scan in 9[4 M
LiCl solution[ "***# initial potential scan at 9[990 V s0^ "! = !# potentiostatic reverse scan^ "*# cyclic
voltammetry at 9[990 V s0 performed after the potentiostatic scan[

in this case\ no appreciable e}ect of rotation was observed[ These results may indicate
that the hysteresis phenomenon is caused by a surface controlling process[
After bringing the electrode to a potential value of 9[299 V at 9[990 V s0\ current
vs time plots at di}erent potentials within the hysteresis region were recorded "Figure
4#[ A continuous current increase with the presence of small ~uctuations can be
observed at potential values higher than 9[9 V Fig[ 4"a#[ At more negative potentials\
the current tends to reach a steady state value which diminishes with decreasing
potential[ At a potential value of 9[244 V\ the current decays to zero\ indicating
that repassivation takes place Fig[ 4"b#[
It can be observed that pit growth can occur only at potential values more positive

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Fig[ 3[ Potentiodynamic potential scan showing pitting of Al and reverse potentiostatic scan in 9[4 M LiCl
solution with electrode rotation "rotation speed] 1999 rpm#[ "***# initial potential scan at 9[990 V s0^
"! = !# potentiostatic reverse scan[

Fig[ 4[ Potentiostatic current!time plots obtained at decreasing potential values starting from pitting state
of Al in 9[4 M LiCl solution at 9[2 V[ "a# above current maximum potential^ "b# below current maximum
potential of the hysteresis cycle[

than that corresponding to the current maximum of the hysteresis cycle[ It must be
also noted that this current maximum appears at a potential value close to that of
pitting initiation[ These experimental results may be explained considering that this
potential is the critical potential for speci_c adsorption of chloride ions\ which would
be close related to the potential of zero charge "pzc# of aluminium in this medium
Figure 5 shows the variation of the potential of current maximum with LiCl
concentration[ Corrections for ohmic drop were not made since it is not able to know
the actual current distribution function[ That means\ the current given by di}erent
pits with more or less active area is not known[ An approximately constant value of
9[914 V in the concentration range 9[2C0 M can be observed[ At concentrations
lower than 9[2 M\ a potential shift towards more positive values is also observed\ this
fact being mainly associated with the potential dependence of speci_c adsorption of
Cl[

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0342

Fig[ 5[ Potential of the current maximum for voltammetries performed at 9[990 V s0 in solutions of
di}erent LiCl concentrations[

Figure 6"a# shows a SEM picture of an aluminium sample after being at a potential
value of 9[09 V during 4 min in 9[4 M LiCl solution[ Numerous pits presenting a
size of 09 mm in average and covered with a _lm of corrosion product on the active
surface are observed[ Some of them present an hemispherical shape\ denoting an
attack controlled by the corrosion product Fig[ 6"b#[ A semiquantitative EDX
analysis performed on one of the pits indicates the presence of Al\ O and Cl in a
relationship of 29 at)\ 52 at) and 6 at) on average respectively "Figure 7#[ These
results allow to identify the corrosion product as AlCl2\ the high oxygen content being
explained in terms of an oxidation and:or hydration process on exposing the sample
to the atmosphere[
These results leads to relate the repassivation potential with the equilibrium poten!
tial for the reaction]
Al2Cl tAlCl2 "c#2e \

"0#

which has a standard reversible potential of 0[97 V vs sce in aqueous media 02[
Figure 8 shows repassivation potential values obtained in di}erent LiCl con!
centration solutions[ A relatively good agreement was observed when experimental
data were adjusted by the Nernst expression for eq[ "0#\ where activity coe.cients
were neglected]
E0 E 09 9[9480 logCLiCl [

"1#
9
0

A potential value of 9[264 V was obtained for E \ this value being close to that
corresponding for aqueous media "9[21 V0[97 V sce#[
The in~uence of LiCl concentration on pitting in the range 9[94 MC0 M was
also investigated by performing cyclic voltammetries at 9[990 V s0[ Pitting potential
was observed to vary on repeating the experiment at the same anion concentration
and potential scan rate used[ Therefore\ this fact might be attributed to the initial
state of surface oxide[

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Fig[ 6[ "a# and "b# SEM micrographs obtained at di}erent magni_cations of an Al sample after attack for
4 min at 9[0 V in 9[4 M LiCl solution[

3[ Ac!impedance studies
Ac!impedance spectra were obtained at di}erent potential values in 9[4 M LiCl
solution following the behaviour observed in Fig[ 0[ The _rst study embraces the
forward potential scan\ going from the passive "9[164 V# to the active state
"9[164 V#[ The second study followed the reverse scan\ starting at 9[364 V after
stabilising the pitting process[
Previous to the _rst study\ the electrode was left to stabilise for approximately
29 min at 9[164 V[ During this period of time\ the current was observed to evolve

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0344

Fig[ 7[ EDX analysis of corrosion product observed within pits[

Fig[ 8[ Repassivation potential "Epp# for di}erent LiCl concentration solutions[ "# Experimental data^
"*# Epp9[2649[9480 log CLiCl[

quickly from a small initial cathodic value to a constant one[ This fact may be
attributed to the reduction of traces of water present in solution[ Afterwards\ suc!
cessive ac!impedance spectra at increasing potentials were performed[
Figure 09"a# shows the Bode plots obtained below pitting potential in a frequency
range 9[94 Hzf09[999 Hz[ A typical capacitiveresistive behaviour without sig!
ni_cative changes within the potential region investigated is observed[ Experimental
data were adjusted according to the electric equivalent circuit depicted in Fig[ 00"a#[
Then\ the complex impedance is given by]a
Z"jv#Rs Rox :0"jvCox Rox #a

"2#

where Cox is the capacitance of metal:oxide:electrolyte system and a is the factor

v1pf[

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Fig[ 09[ Bode plots for Al at di}erent potential values[ "a#] 9[4 M LiCl^ "# 9[164 V^ "# 9[064 V^ "e#
9[964 V^ DE19 mV[ "b#] 9[4 M LiClO3^ "# 9[964 V^ "r# 9[064 V^ "# 9[214 V^ DE03 mV[
"*!# Simulated curves[

Fig[ 00[ Electric equivalent circuits for total electrode impedance[ "a# passive behaviour^ "b# active behav!
iour[

introduced by Kendig and Mansfeld 03 to account for deviations from ideal behav!
iour caused by inhomogenities in the electrochemical system[ By means of a non!
linear _tting computer program\ the following mean parameters values within the
potential region investigated were obtained] Rox5[9095 V\ Rs199 V\
Cox9[06 mF and a9[81[
The high resistance value accounting for the very low electronic conductivity of the
barrier aluminium oxide _lm must be noted[ Then\ deviations of ideal behaviour
observed at the higher frequencies are related with e}ects of dielectric relaxation of
the oxide _lm 04\ 05[
In order to study the in~uence of Cl on the passive behaviour in non!aqueous
media\ ac!impedance spectra were performed in 9[4 M LiClO3 solution in a potential
region where aluminium was observed to be still passive Fig[ 09"b#[ At _rst sight\
the same general features as in chloride solution without signi_cative changes with
potential are observed[ Then\ a _tting procedure according to the circuit shown in Fig[
00"a#\ results in the following mean parameters values] Rox8[1095 V\ Rs199 V\
Cox9[924 mF and a9[81[ The increased resistance value compared with that in
chloride solution\ may be related to a stabilisation e}ect caused by the presence of

ClO
3 [ The presence of ClO 3 gives rise to an inhibition of pitting in this medium as
can be noted comparing the voltammetries performed with and without the presence

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0346

Fig[ 01[ Cyclic voltammetries at 9[990 V s0 for Al with and without the presence of ClO
3 [ "a# 9[0 M LiCl^
"b# 9[0 M LiCl 9[8 M LiClO3[

Fig[ 02[ Nyquist plots for Al in 9[4 M LiCl solution at di}erent potential values above pitting initiation[ "a#
9[014 V^ "b# 9[064 V^ "c# 9[114 V^ "d# 9[164 V[ 9[94 Hzf09999 Hz[ DE19 mV[ "*# Simulated
curves] "a# Rs0915 V\ Rox0[72094 V\ Cox9[09 mF^ "b# Rs362 V\ Rox5[15093 V\ Cox9[987 mF^
"c# Rs083 V\ R00[96092 V\ R1351 V\ C9[975 mF\ L0[66 H^ "d# Rs100 V\ R0442 V\
R1064 V\ C9[987 mF\ L0[14 H[

of those anions "Figure 01#[ Then\ the higher capacitance value obtained in the
presence of Cl may be explained in terms of an interaction of these anions with the
surface oxide layer[
Figure 02 shows the Nyquist plots obtained at various potentials once the pitting
potential is exceeded[ At _rst\ a capacitiveresistive behaviour is maintained with an
important decrease of oxide _lm resistance with increasing potential "plots a and b#^
then\ the appearance of an inductive loop is observed "plots c and d#\ that being
associated with the formation of a salt _lm[ In this later case\ impedance data were
interpreted in terms of the equivalent circuit shown in Fig[ 00"b#[ According to this
model\ the total impedance is given by]
Z" jv#Rs"0:C#:jv"0:CZf#

"3#

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Fig[ 03[ Nyquist plots for Al in 9[4 M LiCl at di}erent potential values after stabilisation of a salt _lm at
9[364 V[ "# 9[215 V^ "r# 9[114 V^ "# 9[014 V[ "*# simulated curves obtained by data _tting
with eq[ "4#[ Frequencies in Hz[ DE5 mV[

Fig[ 04[ Potential dependence of parameters obtained by adjusting equivalent circuit proposed for salt _lm
formed in 9[4 M LiCl solution[ "a# total capacitance "C# and inductance "L#^ "b# R0\ R1 and Rt[

Zf " jv#R0 "LR1 #jv:jvLR1 \

"4#

where C may be related as a _rst approximation to a series connection between

double layer and oxide layer capacity and the other circuit elements are associated
with the salt _lm:metal interface[
The second study was performed after a stabilisation of pitting process during
approximately 1 h at the most positive potential investigated "9[364 V#[ In this way\
more information on the properties of the salt _lm formed during pitting could be
obtained[
Figure 03 shows Nyquist plots obtained at di}erent potentials within the pitting
potential region "E9[09 V# following the potentiostatic reverse scan shown in Fig[
2[ Values of R0\ R1\ L and C were obtained by adjusting the experimental data to eq[
"4# using a non!linear _tting computer program[ Figure 04"a# shows capacitance "C#
and inductance "L# vs potential plots[ Capacitance was observed to increase towards
the pitting potential following a linear relationship while an important increase of

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0348

Fig[ 05[ Nyquist plots for Al in 9[4 M LiCl solution at di}erent potential values close to pitting initiation
after salt _lm formation[ "a# 9[014 V^ "b# 9[964 V^ "c# 9[914 V[ Frequencies in Hz[ DE5 mV[

inductance takes place at potential values lower than 9[29 V[ This fact may be
explained in terms of a _lm stabilisation process occurring inside the salt _lm[ Then\
according to the adopted model\ the sum of R0 and R1 may be identify as the charge
transfer resistance de_ned by]
Rt limv: Re"Zf #[

"5#

Rt shows an initial decrease and a further increase towards lower potentials Fig[
04"b#\ this fact being probably related to an initial decrease of thickness and further
stabilisation of the _lm[ At potentials close to 9[9 V\ ac!impedance data present a
large scattering at relatively low frequencies "f0 Hz# and denote the presence of a
high inductive e}ect and a markedly increase of charge transfer resistance "Rt# "Figure
05#[ Then\ this behaviour evolves to that observed in the passive region[

4[ Discussion
Voltammetric results suggest that pitting of aluminium takes place in non!aqueous
solutions with the presence of only traces of water Fig[ 0"a# and Fig[ 0"b#[ The
induction time for pit initiation is closely related to the initial state of the surface
oxide\ viz[\ _lm thickness\ structure and the presence of defective sites[ Therefore\
variation of pitting potential observed for several experiments performed at the same
experimental conditions is to be expected if potential scan rate is not low enough[
However\ it was observed that pitting always takes place in the neighbourhood of
9[9 V for the same Cl concentration[ This potential is close to the pzc reported for
aluminium in aqueous 9[90 N KCl solution 06 "9[990 V or 9[650 V vs sce#[
Once the pzc is exceeded\ the electric _eld established through the oxide induces the
migration of aggressive anions towards the metal:oxide interface\ this process being
favoured at imperfection sites[
The wide hysteresis cycle observed in voltammetries cannot be attributed to an

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e}ect caused by the potential scan rate used since this e}ect was also observed
performing the reversal scan in a potentiostatic way Fig[ 2[ On the other hand\ the
independence on electrode rotation showed by the voltammograms in the reverse
potential scan demonstrates that the hysteresis e}ect is related to a surface controlled
process "Figure 0"b# and Fig[ 3#[ Hence\ the appearance of an hysteresis cycle seems
to be related with the formation of a salt _lm giving rise to mass transport limiting
conditions for anodic aluminium dissolution[
Inspection of SEM pictures Fig[ 6"b# con_rms the presence of a salt _lm\ which
bring about a characteristic attack of hemispherical type\ in a similar way as occurs
in aqueous media at high anodic current densities 07\ 08[ Studies carried out on
aluminium in aqueous 9[0 M HCl solution gave evidence of a dissolution process
controlled by a salt barrier layer once a potential value of 9[6 V vs sce is exceeded
for a potential sweep in positive sense 19[
The anodic current decrease observed with successive voltammetric cycles Fig[ 1
can be explained in terms of a sealing of the oxide defective sites where pitting was
initiated by the salt _lm formed[ This e}ect also suggests that an ageing process occurs
in the salt _lm\ which increases its resistivity[
The potential of the current maximum observed in the hysteresis cycle "Figures 0
3# is close related to the pzc[ Then\ two di}erent states of pitting process can be
distinguished at both sides of this potential]
"i# at more positive potentials\ an enrichment of aggressive anions inside the pit
give rise to a continuous pit growth re~ected by a steady increase of anodic
current with small ~uctuations Fig[ 4"a#^
"ii# at more negative potentials\ adsorption of Cl is not favoured\ pit growth is
arrested and metal dissolution is controlled by the rate of ionic migration
through the salt _lm formed over the active surface of pits[
Therefore\ this ohmic control bring about the observed linear currentpotential
relationship Fig[ 2 and the appearance of a limiting current in the potentiostatic
currenttime transients Fig[ 4"b# in this potential region[
These observations are in accordance to studies carried out on AlCl2 _lm in aqueous
media[ In this medium\ a dual salt layer on corroding aluminium is formed] an outer
hydrated layer with ohmic conduction and an anhydrous layer with sinh conduction
next to the metal 08[ This latter type of conduction corresponds to a solid!state ionic
transport across the _lm\ which results in the Ohm|s law in the case of low!_eld
approximation[ In our conditions\ only an anhydrous layer is possible to be formed[
Towards more cathodic potentials\ the current decays to zero once the equilibrium
potential for eq[ "0# is reached[ If a new cycle is intended Fig[ 1\ metal dissolution is
hindered until the pzc is reached\ in a similar manner as when the oxide _lm is present[
The higher capacitance values obtained in the ac!impedance studies performed
below pitting potential in chloride compared to those in perchlorate solution reveal
an interaction of Cl with the aluminium surface oxide Fig[ 09"a\b#[ This interaction
may be considered similar to that taking place in aqueous media\ where chloride ions
are chemically bonded to the oxide surface to form chlorocomplexes to be then
transported to the solution 11[ Taking into account that the surface oxide consists

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0350

of a composite type of Al1O2\ Al"OH#2 and AlO"OH# 12\ so the following reactions
may be occurring at the oxide:electrolyte interface]
AlO"OH#Cl :AlOClOH \

"6#

Al"OH#2 Cl :Al"OH#1 ClOH [

"7#

The presence of ClO

3 gives rise to a stabilisation of the oxide _lm and a pitting
inhibition as may be deduced by comparing the voltammetries performed with and
without the presence of that anion for the same Cl concentration Fig[ 01[ This
e}ect was also observed by others 7[ In addition\ XPS studies have shown that
ClO
3 can be reduced inside the oxide _lm through the following reaction 13]
2
ClO
7e :3:2Al1 O2 Cl [
3 7:2Al

"8#

Thus\ a sealing of defective sites of the oxide may take place leading to a decrease of
electronic conductivity[
Unlike in aqueous media\ generation of charge species at oxide:electrolyte interface
seems not to be possible and ionic conduction is hindered 1\ 14[ The reaction
products generated by eqs[ "67# may further react with Cl to form AlCl2[ However\
whatever compound is formed\ this would remain at the surface due to the poor
solubility of salts in this medium[
The marked increase of oxide conductivity observed during pitting initiation Fig[
02"a# may be explained in terms of migration of Cl through the oxide _lm[ Studies
carried out by the Rutheford backscattering spectroscopy method give evidence of a
penetration of Cl during galvanostatic anodisation of aluminium bringing about an
oxide region containing certain Cl concentration 15[ It was also suggested that the
transport mechanism possibly involve a structural rearrangement and liquid!like
behaviour under the electric _eld\ this process being favoured at imperfection regions
of the oxide[
The chloride ions would penetrate into the oxide lattice\ followed by substitution
of O 1[ This substitution does not create only additional charge carriers but also
aluminium ion vacancies in the cation lattice\ so reducing the _lm resistance for ionic
charge transfer[
The appearance of a pseudo!inductive loop at low frequency values Fig[ 02"c#
may be attributed to salt _lm properties modulations such as its density\ ionic con!
ductivity or thickness[ Relaxation of adsorbed species may be another explanation
14[ Similar results were obtained in ac!impedance studies carried out on aluminium
oxide _lms\ obtained by the plasma!enhanced chemical vapour deposition method
16[
A stabilisation process taking place inside the salt _lm formed may be the cause
for the observed increase of the capacitance and inductance on approaching to pitting
potential Fig[ 04"a#[ Thus\ as the electrode potential decreases\ the concentration of
Cl inside it diminishes\ the _lm consolidates and the ions mobility is reduced[ This
fact would bring about an increase of not only the _lm resistivity Fig[ 04"b# but also
the mean relaxation time[ However\ another aspects on the nature of the _lm must

0351

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be further analysed\ viz[\ the possibility of complex species as AlCl

3 or AlCl1 and
addition reactions taking place between AlCl2 and the solvent[
Then\ the increase of charge transfer resistance taking place close to pitting potential
Fig[ 05 can be explained in terms of aluminium dissolution through localised regions
where a high resistive salt _lm controls further dissolution[

5[ Conclusions
According to the results obtained\ the following conclusions can be drawn]
"i# A localised attack takes place on aluminium in non!aqueous chloride media
near the potential of zero charge of aluminium[ Once the pzc is anodically
exceeded\ migration and accumulation of Cl at imperfection sites of the
oxide\ are the main factor for pitting initiation[
"ii# During pitting initiation\ adsorption and penetration of Cl into the oxide
structure give rise to an increase of the conductivity and the relaxation phenom!
ena\ this process being favoured at imperfection sites of the oxide[
"iii# A salt _lm formed at the initial stages of pit formation\ gives rise to an ohmic
control for further metal dissolution and its presence is responsible for the
appearance of a wide hysteresis cycle and an hemispherical attack[ At poten!
tials more positive than pzc\ pit growth can occur[ At more negative potentials\
pit growth is arrested and dissolution of aluminium is controlled by ionic
transport through the salt _lm formed[ This behaviour is maintained until
potential is brought to cathodic values respective to equilibrium potential for
the system Al:AlCl2 in this medium[

Acknowledgements
Financial support from Consejo Nacional de Investigaciones Ciet(_cas y Tecnicas
"CONICET\ PID No 227589981# and Ciencia y Tecnica U[N[S[ "UNS!CU!9918:84#
are acknowledged[ Also\ one of us "A[G[M[# thanks CONICET for the grant received[

References
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1
2
3
4
5
6
7
8

Z[ Szklarska!Smialowska\ Pitting Corrosion of Metals\ Chap[ 08[ NACE\ Houston\ Texas\ 0875[
J[B[ Bessone\ D[R[ Salinas\ C[E[ Mayer\ M[ Ebert\ W[J[ Lorenz\ Electrochim[ Acta 26 "0881# 1172[
J[R[ Galvele\ J[ Electrochem[ Soc[ 012 "0865# 353[
J[R[ Galvele\ J[B[ Lumsden\ R[W[ Stahele\ J[ Electrochem[ Soc[ 014 "0867# 0193[
G[C[ Palit\ K[ Elayaperumal\ Corros[ Sci[ 07 "0867# 058[
L[ Bai\ B[E[ Conway\ J[ Electrochem[ Soc[ 026 "0889# 2626[
N[M[ Gontmakher\ O[N[ Nechaeva\ V[P[ Grigoriev\ L[N[ Nekrasov\ Elektrokhimiya 02 "0866# 0637[
L[ Bai\ B[E[ Conway\ J[ Appl[ Electrochem[ 11 "0881# 020[
L[W[ Marple\ Anal[ Chem[ 28 "0856# 734[

A[G[ Munoz\ J[B[ Bessone : Corrosion Science 30 "0888# 03360352

0352

09 J[N[ Butler\ in] P[ Delahay\ C[W[ Tobias "Eds[#\ Advances in Electrochemistry and Electrochemical
Engineering\ vol[ 6[ John Wiley + Sons\ New York\ 0869\ pp[ 049[
00 S[ Pons\ S[B[ Khoo\ Electrochim[ Acta 16 "0871# 0050[
01 D[ Aurbach\ J[ Electrochem[ Soc[ 025 "0878# 895[
02 W[M[ Latimer\ The Oxidation States of Elements and Their Potentials in Aqueous Solutions[ Prentice!
Hall\ Englewood Cli}s\ N[J[\ 0841[
03 F[ Mansfeld\ M[W[ Kendig\ W[J[ Lorenz\ J[ Electrochem[ Soc[ 021 "0874# 189[
04 S[ Ru)e\ M[M[ Lohrengel\ J[W[ Schultze\ Solid State Ionics 61 "0883# 18[
05 A[W[ Hassel\ M[M[ Lohrengel\ Electrochim[ Acta 39 "0884# 322[
06 S[ Trasatti\ J[ Electroanal[ Chem[ 22 "0860# 240[
07 H[ Kaesche\ Werksto}e Korros[ 28 "0877# 041[
08 T[R[ Beck\ Electrochim[ Acta 18 "0873# 374[
19 C[M[A[ Brett\ Corros[ Sci[ 22 "0881# 192[
10 T[ Beck\ Electrochim[ Acta 29 "0874# 614[
11 L[ Tomcsanyi\ K[ Varga\ I[ Bartik\ G[ Horanyi\ E[ Maleczki\ Electrochim[ Acta 23 "0878# 744[
12 W[C[ Moshier\ G[D[ Davis\ J[S[ Ahearn\ Corros[ Sci[ 16 "0876# 674[
13 J[ Painot\ J[ Augustynsky\ Electrochim[ Acta 19 "0864# 636[
14 J[B[ Bessone\ C[ Mayer\ K[ Juttner\ W[J[ Lorenz\ Electrochim[ Acta 17 "0872# 060[
15 M[ Skeldon\ K[ Shimizu\ P[ Skeldon\ G[E[ Thompson\ G[C[ Wood\ Corros[ Sci[ 26 "0884# 0362[
16 E[J[ Lee\ S[I[ Pyun\ Corros[ Sci[ 26 "0884# 046[