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Electrochimica Acta 54 (2009) 41554163

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Electrochimica Acta
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Electronic structure and pitting behavior of 3003 aluminum
alloy passivated under various conditions
Y. Liu
a
, G.Z. Meng
a,b
, Y.F. Cheng
a,
a
Dept. of Mechanical & Manufacturing Engineering, University of Calgary, Calgary, AB T2N 1N4, Canada
b
College of Materials Science and Chemical Engineering, Harbin Engineering University, Harbin 150001, China
a r t i c l e i n f o
Article history:
Received 5 December 2008
Received in revised form 19 February 2009
Accepted 20 February 2009
Available online 3 March 2009
Keywords:
Aluminum alloy
Passivity
Pitting corrosion
Chloride ions
Electrochemical measurements
a b s t r a c t
Passivity of aluminum (Al) alloy 3003 in air and in aqueous solutions without and with chloride
ions was characterized by electrochemical measurements, including cyclic polarization, electrochemi-
cal impedance spectroscopy (EIS), localized EIS and potential of zero charge, MottSchottky analysis and
secondary ion mass spectroscopy (SIMS) technique. Stability, pitting susceptibility and repassivation abil-
ity of Al alloy 3003 under various lm-forming conditions were determined. Results demonstrated that
passive lms formed on 3003 Al alloy in air and in Na
2
SO
4
solution without and with NaCl addition show
an n-type semiconductor in nature. The passive lm formed in chloride-free solution is most stable, and
that formed in chloride-containing solution is most unstable, with the lm formed in air in between.
Pitting of Al alloy 3003 passivated both in air and in aqueous solutions is inevitable in the presence of
chloride ions. There is the strongest capability for the air-passivated Al alloy 3003 to repassivate, and
the weakest repassivating capability for Al alloy 3003 passivated in chloride-containing solution. The
resistance of the passivated Al alloy 3003 to pitting corrosion is dependent on the competitive effects
of pitting (breakdown of passive lm) and repassivation (repair of passive lm). According to the dif-
ferences between corrosion potential and potential of zero charge, passive lm formed in air has the
strongest capability to adsorb chloride ions, while the lm formed in chloride-containing solution the
least. Chloride ions causing pitting of passivated Al alloy 3003 in air and in chloride-free solution come
from the test solution, while those resulting in pitting of passivated Al alloy 3003 in chloride-containing
solution mainly exist in the lm during lm-forming stage.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
Aluminum (Al) alloys of 3xxx series, due to their favorable
strength-to-weight property, high thermal conductivity, excellent
formability, as well as good corrosion resistance, have been widely
used in automobile heat exchange systems, replacing more tra-
ditional materials like stainless steels and copper alloys [1,2].
However, Al alloys are prone to experience pitting corrosion dur-
ing service in cooling system[35]. It has been acknowledged [6,7]
that corrosion resistance of aluminum(Al) alloy depends on forma-
tion of a layer of passive lm on its surface. However, halide ions,
especially chloride ions (Cl

), show a strong attack to passive lm,


resulting in pitting corrosion of Al alloy. It was reported [8,9] that
3xxx series Al alloys containing 11.5% manganese (Mn) and Al/Mn
intermatellic compounds might undergo the attack of chloride ions
at vulnerable defect sites. The role of Cl

in pitting processes and


its interaction with passive lmhave been studied extensively, and

Corresponding author. Tel.: +1 403 220 3693; fax: +1 403 282 8406.
E-mail address: fcheng@ucalgary.ca (Y.F. Cheng).
models have been developed to illustrate pitting corrosion [1013].
Inparticular, point defect model (PDM) is a relatively mature model
to describe the growth mechanism and kinetics of passive lm as
well as pit initiation and growth in the presence of Cl

[1416].
Passive lms formed on Al alloy under various conditions are
associated with different structures. For example, a thin layer of Al
oxide lmformed immediately in air is observed to be amorphous,
while the passive lmformed in aqueous solution is usually dense,
coherent and compact [6]. It is expected that there are signicant
effects of the structure of passive lm on its electrochemical and
semiconducting properties, and thus the pitting corrosion resis-
tance. To date, there has been limited work to investigate and
compare mechanistically the electrochemical and semiconducting
properties andpittingsusceptibilities of passive lms formedunder
the various conditions [1720]. For example, Bockris and Kang [17]
measured MottSchottky plots of the passive-lm-covered pure Al
and its alloys to categorize the passive lm on Al and Al alloys are
n-type semiconductors. Fernandes et al. [18] investigated the elec-
tronic properties of oxide lm formed on 99.5% Al and 2024-T3 Al
alloy in a sulphuric-boric bath. The results indicated that the lm
shows an n-type semiconductive behavior, with bandgap energies
0013-4686/$ see front matter 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.electacta.2009.02.058
4156 Y. Liu et al. / Electrochimica Acta 54 (2009) 41554163
and semiconducting characteristics depending on the environmen-
tal conditions. Levinea et al. [19] employed MottSchottky analysis
to study the properties of oxide lm of Al alloy 2024-T3, and deter-
mined that it is a p-type semiconductor, with non-stoichiometric
defects or substitutions existing in the ultra-thin layer. Koboti-
atis et al. [20] studied the electronic properties of passive layer
grown anodically on Al 70775 in chromate and oxalate solutions
using electrochemical impedance spectroscopy. It was found that
the oxide developed in the presence of chromate (good inhibitor)
exhibits aless-nobleat-bandpotential andalower averagedensity
of state.
It has been acknowledged [1416] that the electronic struc-
ture and properties of passive lms were responsible for the lm
breakdown and the initiation of pitting. A high pit density occur-
ring on the metal surface was generally associated with an n-type
oxide. However, the actual correlation between the semiconduc-
tive behavior of passive lms and the pitting susceptibility was
nonexistent. Furthermore, passive lms formed under different
conditions are expected to show different semiconducting prop-
erties and have distinct electronic structures, which would result
in different pitting susceptibilities. In this work, passive lms
formed on Al alloy 3003 either in air or in aqueous solutions
without and with Cl

were characterized by various electro-


chemical techniques, including cyclic polarization, electrochemical
impedance spectroscopy (EIS), localized EIS (LEIS) and potential
of zero charge (PZC), MottSchottky analysis, and secondary ion
mass spectroscopy (SIMS). Electrochemical corrosion behavior of
the passivated 3003 Al alloy electrode was determined, and the
composition and electronic structure of the lm was studied. The
adsorption, penetration and distribution of Cl

in passive lm and
the role of Cl

in pitting of Al alloy 3003 were discussed. It is


anticipated that this research provides an essential insight into the
mechanistic understanding of passive lm formation and break-
down as well as pitting corrosion of Al alloy 3003 under various
conditions.
2. Experimental
2.1. Electrodes and solutions
Specimens for electrochemical tests were cut from a round bar
of 3003 Al alloy supplied by DANA Canada Corporation, with the
chemical composition (wt%): Cu 0.20, Fe 0.70, Si 0.60, Mn 1.50,
Mg 0.05, Cr 0.05, Zn 0.10, Ti 0.05 and Al balance. Specimens were
machined and embedded in epoxy resin manufactured by LECO,
leaving a circular working area of 0.4cm
2
. The working surface was
ground with emery papers up to 1200 grit, cleaned by deionized
water and degreased in acetone.
2.2. Formation of passive lms on 3003 Al alloy
Three types of passive lm were formed on Al alloy 3003 under
controlled conditions. The rst type was formed in air naturally
when 3003 Al alloy electrode was exposed in air. The second and
third types were formed in 0.25M Na
2
SO
4
solution, without and
with 0.5M NaCl, respectively. Preparation of oxide lm in solution
was not simply to immerse the air-exposed 3003 Al alloy electrode
to the aqueous solution. The electrode surface was groundrst with
a 1200-grit emery paper that is installed inside the lm-forming
solution in order to remove completely the air-formed lm before
the new lm was generated in the solution. The ground electrode
continued to stay in solution for 2h, and there was external poten-
tial applied at this stage. After then the lm-covered electrode was
transferred rapidly to the test solution for electrochemical charac-
terization.
Fig. 1. Cyclic polarization curves of the passivated 3003 Al alloy electrode in 0.25M
Na
2
SO
4
+0.5M NaCl solution (potential scanning rate: 0.333mV/s).
All solutions were made up from analytical grade reagents and
ultra-pure deionized water (18Mcm in resistivity).
2.3. Electrochemical measurements
Electrochemical measurements were performed through a
Gamry Reference 600 electrochemical system by using a three-
electrode cell, with 3003 Al alloy as working electrode (WE), a
saturated calomel electrode (SCE) as reference electrode (RE) and
a Pt wire as counter electrode (CE). All electrochemical tests were
conducted in 0.25M Na
2
SO
4
+0.5M NaCl solution.
Prior to cyclic polarization measurement, 3003 Al alloy WE was
immersedintest solutionat least 1huntil corrosionpotential (E
corr
)
reached a steady-state value. Anodic polarization scan was per-
formed at a potential sweep rate of 0.333mV/s, with a reverse in
scan direction when anodic current density reached 0.1mA/cm
2
.
Pitting potential (E
pit
) was determined when anodic current den-
sity deviated abruptly from the stable passive current density, as
indicated in Fig. 1.
The conventional EIS measurements were conducted on the
macroscopic Al alloy 3003 WE at E
corr
or E
pit
, with the measur-
ing frequency ranging from 20kHz to 0.001Hz and an applied AC
disturbance signal of 10mV.
LEISmeasurements wereperformedonWEthroughaPARModel
370 scanning electrochemical workstation, which was comprised
of a scanning Pt microprobe with a 10m tip, a 370 scanning con-
trol unit, an M236A potentiostat, an M5210 lock-in amplier and a
video camera system. For LEIS mapping, the Pt microprobe, which
was set above the electrode surface at 50m, was stepped over a
designated area of the electrode. The probe scanning took the form
of a raster in xy plane. The step size during LEIS scanning was con-
trolled to obtain a plot of 32 lines 24 lines with a scanning area of
1000m750m. An AC disturbance signal of 10mV was applied
to WE that was at E
corr
. The measurement frequency was xed at
10Hz.
Inmeasurements of PZCof 3003Al alloyelectrode, afrequencyof
18Hz and an AC disturbance signal of 10mV were applied. Double-
charge layer capacitance was obtained from the measured EIS.
All the tests were performed at ambient temperature (22

C)
and open to air.
2.4. SIMS characterization
Negative and positive SIMS characterizations were performed
through a ToF-SIMS IV instrument manufactured by IonTOF GmbH.
Y. Liu et al. / Electrochimica Acta 54 (2009) 41554163 4157
A chopped 15keV Ga
+
ion beam of about 200nm in diameter was
used to generate secondary ions, which were then separated by
the time-of-ight mass analyzer. In the imaging mode, maps of the
lateral distribution of elements across the target surface were col-
lected from an area of 40m80m. For the depth proling, a
dual ion beam technique was used, where the Ga analytical ion
gun was scanned over an area of 30m30m near the centre
of a crater of 200m200m, created by another, sputter ion
gun. The sputter guns used either Cs
+
or O

ion beams of 80nA at


1keV initial energy for negative and positive secondary ion proles
correspondingly.
In order to characterize the permeation and diffusion of chlo-
ride ions in passive lms formed under various conditions, i.e., in
air and in aqueous solutions without and with chloride ions, the
lms were polarized at an anodic potential of 0.65V (SCE) in
0.25M Na
2
SO
4
+0.5M NaCl solution for 3h, and then character-
ized by SIMS. For comparison, a blank specimen that was lmed
in 0.25M Na
2
SO
4
solution without further anodic polarization in
chloride-containing solution was also under SIMS characteriza-
tion.
3. Results
3.1. Cyclic polarization measurements
Fig. 1 shows the cyclic polarization curves measured on Al alloy
3003 with passive lms formed in air and aqueous solutions with-
out and with chloride ions in 0.25M Na
2
SO
4
+0.5M NaCl solution,
where the solid arrows indicated the potential scan direction. It is
seen that all passivated electrodes showed a stable passive region
where the low passive current density was independent of poten-
tial. Current density then increased abruptly at E
pit
, followed with a
positive hysteresis loop during reverse potential scanning. The val-
ues of E
pit
were 0.60V, 0.53V and 0.50V (SCE) for electrodes
withpassivelms formedinair, inNa
2
SO
4
solution, andinchloride-
containing Na
2
SO
4
solution, respectively. There was similar E
rp
of
about 0.70V (SCE) for all electrodes. Furthermore, although the
current density was set at 0.1mA/cm
2
for scan reversion, it did not
decrease immediately after the potential was reversely scanned,
but continued to increase. The different current densities resulted
in different sizes of the hysteresis loop for the three types of passive
lm, which were correspondent with different repassivation abili-
ties of the lm. There was the biggest loop for passive lm formed
in chloride-containing solution, while the smallest loop for the lm
formed in air.
3.2. Conventional EIS measurements on the macroscopic electrode
Fig. 2 shows the Nyquist diagrams measured on Al alloy 3003
electrodes with passive lms formed in air and in solutions with-
out and Cl

and solution, respectively, in 0.25M Na


2
SO
4
+0.5M
NaCl solution (at E
corr
). There was a common characteristic for all
curves, i.e., a capacitive semicircle in the high-frequency range and
a diffusive tail in the low-frequency range. There was the biggest
semicircle for passive lm formed in solution without chloride
ions, and the smallest semicircle for the lm formed in chloride-
containing solution.
Fig. 3 shows the Nyquist diagrams of the passivated 3003 Al
alloy electrodes at E
pit
. It is seen that, at E
pit
, there was a sig-
nicant decrease of the semicircle size. Moreover, an inductive
loop was observed in low-frequency range in all diagrams. Fur-
thermore, there was the biggest diameter of the semicircle for
passive lm formed in chloride-free solution (1300), and the
smallest one for passive lm formed in chloride-containing solu-
tion(12only). Observationof electrode morphologies after LEIS
Fig. 2. Nyquist diagrams measured on 3003 Al alloy with passive lms formed
in air (a), chloride-free solution (b) and chloride-containing solution (c) in 0.25M
Na
2
SO
4
+0.5M NaCl solution at individual corrosion potential.
measurements in Fig. 4 showed that the electrode passivated in
chloride-containing solution suffered severe pitting corrosion with
deep pits (Fig. 4c), while the passivated electrode in air and in
chloride-free solutionhad slight pitting withsmall and shallowpits
(Fig. 4a and b).
The EIS measurements were performed in aerated solutions and
thus described the sum of cathodic and anodic processes proceed-
ing on heterogenous surface of oxide and pits. However, at E
pit
,
anodic reaction including pitting corrosion dominated the elec-
trode behavior, and the cathodic response was too small to be
ignored.
3.3. LEIS measurements
Fig. 5 shows the LEIS maps measured over 3003 Al alloy
electrodes with passive lms formed in air and the solutions
without and with chloride ions, respectively, at E
corr
in 0.25M
Na
2
SO
4
+0.5MNaCl solution. Inthexyz three-dimensional space,
|Z| represents the measured impedance amplitude, which usually
refers to the resistance of electrode to localized corrosion at indi-
vidual measuring point. Thus, the uctuating plane in the 3Dgure
represents the distribution of local impedance over the scanned
surface of the electrode. The 3D impedance distribution was also
projected on xy plane, where the impedance amplitude of indi-
vidual point was represented with different colors. It is seen that
there were frequent uctuations of impedance value measured on
passive lmformed in air (Fig. 5a). The impedance distribution was
the most uniform on electrode passivated in chloride-free solution
(Fig. 5b).
3.4. PZC measurements
Fig. 6shows the double-charge layer capacitance of passive lms
formed in air, 0.25MNa
2
SO
4
, and 0.25MNa
2
SO
4
+0.5MNaCl solu-
tions, respectively, as a function of applied potential. It is seen
that there is a common feature for the three curves, i.e., a mini-
mum of double-charge layer capacitance that is considered as PZC
of the electrode was observed. In addition, steady-state corrosion
potential (E
corr
) of the passivated 3003 Al alloy electrode was also
included in each diagram. Generally, PZC ware more negative than
E
corr
for all passivated electrodes. The differences between E
corr
and
PZC (E=E
corr
PZC) for passive lms formed in air, Na
2
SO
4
solu-
tion and Na
2
SO
4
+NaCl solution were 0.119V, 0.093V and 0.036V,
4158 Y. Liu et al. / Electrochimica Acta 54 (2009) 41554163
Fig. 3. Nyquist diagrams of 3003 Al alloy with passive lms formed in air (a),
chloride-free solution (b), and chloride-containing solution (c) at individual E
pit
.
respectively. Thus, there was a smaller potential difference, E, for
passive lm formed in aqueous solutions than that formed in air,
and further, passive lm formed in chloride-containing solution
had a smaller potential difference than that formed in chloride-free
solution.
Fig. 4. Surface morphology of 3003 Al alloy with passive lms formed in air (a),
chloride-free solution (b), and chloride-containing solution (c) at individual E
pit
.
3.5. Capacitance measurements and MottSchottky analysis
Potential dependence of the capacitance of space-charge layer
(C
sc
) is expressed by MottSchottky relationship [21]:
for n-type semiconductor
1
C
2
SC
=
2
e
r

0
N
D

E
fb

T
e

(1)
Y. Liu et al. / Electrochimica Acta 54 (2009) 41554163 4159
Fig. 5. LEIS maps measured on 3003 Al alloy electrodes with passive lms formed in
air (a), chloride-free solution (b), and chloride-containing solution (c) at individual
Ecorr in 0.25M Na
2
SO
4
+0.5M NaCl solution.
for p-type semiconductor
1
C
2
SC
=
2
e
r

0
N
A

E
fb

T
e

(2)
where e is electron charge (1.610
19
C),
r
is dielectric con-
stant of Al oxide, taken as 10 [22],
0
is the vacuum permittivity
(8.8510
14
F cm
1
), N
D
is the donor density, N
A
is the acceptor
Fig. 6. Relationship between double-charge layer capacitance vs. applied potential
for 3003 Al alloy with passive lms formed in air (a), chloride-free solution (b) and
chloride-containing solution (c).
density, E is the applied potential,
fb
is at-band potential, is
Boltzmann constant (1.3810
23
J K
1
) and T is absolute temper-
ature. N
D
and N
A
can be determined from the slope of the linear
relationship between C
2
SC
and E, while
fb
is obtained from the
extrapolation to C
2
SC
= 0.
4160 Y. Liu et al. / Electrochimica Acta 54 (2009) 41554163
Fig. 7. MottSchottky curves for three types of passive lmformed on 3003 Al alloy
measured at 1000Hz in 0.25M Na
2
SO
4
+0.5M NaCl solution.
Fig. 7 shows the MottSchottky curves for the three types of
passive lm measured at 1000Hz in 0.25M Na
2
SO
4
+0.5M NaCl
solution. To demonstrate the consistence of capacitances measured
by EIS and MottSchottky at E
corr
, the lm formed in chloride-
containing solution was used as an example. The capacitances were
0.36F m
2
and0.5F m
2
, respectively, indicating that the measured
capacitance corresponded to the capacitance of passive lm. It is
seen Fig. 7 that all passive lms behaved like an n-type semicon-
ductor, with a positive slope of the linear C
2
SC
E. The curved form
of the lines indicated the highly disordered nature of passive lm
where highly localized states existed between the valence and the
conduction bands [23,24]. The tted values of at-band potential
and donor density for three passive lms are shown in Table 1. It is
clear that passive lm formed in air had a more negative
fb
and a
higher N
D
, and there were similar values of
fb
and N
D
for passive
lms formed in aqueous solutions.
3.6. SIMS characterization
Fig. 8 shows the chloride concentration proles of the three
passive lms formed under various conditions and a blank 3003
Al alloy specimen measured by SIMS. It is seen that the concen-
tration of chloride ions decreased continuously with the sputter
depth in the electrode. As expected, there was the lowest or even
zero chloride concentrationfor passive lmformed inNa
2
SO
4
solu-
tion without a further anodic polarization in chloride-containing
solution. The permeation depth of chloride ions into passive lm
followed the order: lm formed in chloride-free solution<lm
formed in air <lmformed in chloride-containing solution. Despite
theslight irregularityof chlorideconcentrationdeterminedbySIMS
for passive lmformed in chloride-free solution, generally, the con-
centrationof permeatedchloride ions was rankedas: lmformedin
air <lmformedinchloride-free solution<lmformedinchloride-
containing solution.
Table 1
Flat-band potential,
fb
, and donor density, ND, for passive lms formed under vari-
ous conditions.
Film formation medium
fb
vs. SCE (V) ND (10
27
m
3
)
In-air 1.509 32.39
In 0.25M Na
2
SO
4
solution 0.833 7.73
In 0.25M Na
2
SO
4
+0.5M NaCl solution 0.815 7.48
Fig. 8. Depth proles of chloride ions on passive lms measured by SIMS.
4. Discussion
4.1. Passive lms formed on 3003 Al alloy in air and in aqueous
solutions
The present work shows clearly (Fig. 2) that there are quite
different stabilities of passive lms formed on 3003 Al alloy
electrode under various conditions. The measured EIS plots at cor-
rosion potential, i.e., a high-frequency capacitive semicircle and
a low-frequency diffusive tail, are tted with an electrochemi-
cal equivalent circuit shown in Fig. 9a [25], where R
s
is solution
resistance, CPE is constant phase element, R
f
is charge-transfer
resistance of passivated 3003 Al alloy electrode, and W is Warburg
diffusive impedance. The high-frequency capacitive semicircle rep-
resents the charge-transfer reaction of passivated 3003 Al alloy,
while the low-frequency diffusive impedance is associated with
the oxygen diffusion. Under stable passivation, the lm formation
achieves an equilibriumstate. Thus, the lmformation rate is equal
to the dissolution rate of 3003 Al alloy. Electrochemical parameters
tted from EIS data are listed in Table 2. Apparently, there is the
largest resistance (thus the most stable) for passive lm formed in
Fig. 9. Electrochemical equivalent circuits used for tting EIS data measured at
individual Ecorr (a) and at E
pit
(b).
Y. Liu et al. / Electrochimica Acta 54 (2009) 41554163 4161
Table 2
Electrochemical parameters tted from EIS data measured at individual Ecorr.
Film-forming condition Rs () CPE-Y
0
(S s
n
) n R
f
(10
5
) W (S s
0.5
)
In air 7.4 7.14 0.93 1.91 226
In 0.25M Na
2
SO
4
solution 9.6 7.48 0.80 5.71 24.9
In 0.25M Na
2
SO
4
+0.5M NaCl solution 9 1.58 0.91 1.03 247
chloride-free solution, the smallest resistance (most unstable) for
passivelmformedinchloride-containingsolution, andthepassive
lm formed in air in between.
In general, passive lm formed in aqueous solution is usually
associated with a compact, uniformstructure because of hydration
process occurring on 3003 Al alloy electrode. It is acknowledged
[26,27] that the hydrated passive lm always shows a higher sta-
bility than that without hydration. For passive lm formed in air,
the lm structure is usually non-uniform, with different thickness
and compositional distribution. The LEIS mapping on air-formed
passive lm shows signicant uctuations of local impedance on
the lm (Fig. 5a), demonstrating the structural non-uniformity.
As a comparison, the LEIS mapping on passive lms formed in
aqueous solutions (Fig. 5b and c) is quite uniform. LEIS has been
demonstrated as a unique alternative to characterize the localized
corrosion behavior of metal at a microscopic scale [2831]. While
the conventional EIS reects an averaged impedance response of
a macroscopic electrode, LEIS provides information specic to the
individual microscopic site. Therefore, a LEIS mapping is capable of
detect local active spots where a low impedance is usually iden-
tied. It is thus concluded from Fig. 5 that passive lms formed in
aqueous solutions are muchmore uniform, withfewer local defects,
than that formed in air.
For passive lm formed in chloride-containing solution, it is
expected that chloride ions get involved in the lm formation pro-
cess, as demonstrated by SIMS characterization results (Fig. 8) that
there is the deepest chloride sputter depth and the highest chlo-
ride concentrationat individual depth. It is generally acknowledged
[6,7] that Cl

plays an important role in initiation and propagation


of pitting corrosion. The high concentration of Cl

existing in the
passive lm formed in chloride-containing solution results in the
difculty of lm to be repassivated, as seen in cyclic polarization
measurement in Fig. 1. Upon initiation of the corrosion pit, Cl

also
contributes to the rapid propagation of pitting.
4.2. Pitting susceptibility of 3003 Al alloy electrodes passivated in
air and in aqueous solutions
Electrochemical cyclic polarization measurement is capable of
predicting the susceptibility of passivated metal to pitting corro-
sion [6,32]. Generally, if the reverse anodic curve is shifted to lower
currents, i.e., negative hysteresis, or if the reverse curve essentially
retraces the ascending curve, i.e., neutral hysteresis, no pitting cor-
rosion will occur on the target metal or alloy. In contrast, if the
reverse anodic curve is shifted to higher currents than the for-
ward curve, i.e., positive hysteresis, pitting corrosion will occur. It
is apparent from Fig. 1 that positive hysteresis loops are measured
on 3003 Al alloy passivated under various conditions, suggesting
that pitting of 3003 Al alloy passivated in air and in aqueous solu-
tions is inevitable in the test system. The values of E
pit
show that
it is earliest for 3003 Al allow passivated in air to occur pitting,
while it is relatively most difcult for 3003 Al alloy passivated in
chloride-containing solutiontoinitiate pitting, withthat passivated
in sulfate solution in between. Thus, in accordance with the mea-
sured E
pit
, The pitting susceptibility of passivated 3003 Al alloy is
ranked as: in air >in chloride-free solution>in chloride solution.
Furthermore, the area of the measured positive hysteresis loop
indicates the repassivity capability of the metal or alloy, and a
smaller area indicates a stronger ability for metal or alloy to
repassivate. Therefore, there is the strongest capability for the
air-passivated3003Al alloy torepassivate, andthe weakest repassi-
vating capability for 3003Al alloy passivatedinchloride-containing
solution.
The resistance of a passivated metal or alloy to pitting is depen-
dent on the competitive effects of pitting (breakdown of passive
lm) and repassivation (repair of passive lm). Although the air-
formed passive lm is easy to initiate pitting in chloride solution
(the lowest E
pit
), it has the strongest capability to repassivate, i.e., to
self-repair after pitting initiation. Thus, the overall ability of passi-
vated 3003 Al alloy to pitting is in moderate state. The passive lm
formed in chloride-containing solution has the relatively most pos-
itive E
pit
, but the weakest repassive ability. Consequently, it shows
the most active state. The passive lmformed in chloride-free solu-
tion is the most stable, which is attributed to the moderate E
pit
and
repassivating ability. The relative stability of passive lms formed
under various conditions is demonstrated by EIS measurements on
passivated 3003 Al alloy electrodes at their individual E
pit
(Fig. 3).
Upon pitting, the roughness of the electrode surface increases, and
the electrode state thus becomes more non-uniform. As a conse-
quence, an inductive loop is observed in the low-frequency range,
which is one of the typical features indicating pitting corrosion or
electrode roughening [33,34]. The EIS feature is tted withthe elec-
trochemical equivalent circuit in Fig. 9b, where L is inductance and
R
L
is inductive resistance. The ttedelectrochemical parameters are
shown in Table 3. It is seen that there is the highest charge-transfer
resistance for passive lmformedinchloride-free solution(Fig. 3a),
and the lowest charge-transfer resistance for the lm formed in
chloride-containing solution (Fig. 3b).
4.3. Pitting mechanism of passivated 3003 Al alloy electrodes
The present work demonstrates that passive lms formed in air
and in aqueous solutions behave like an n-type semiconductor, as
indicated by a positive slope of MottSchottky relationship inFig. 6.
According to point defect model [35], the main electron donors
in an n-type semiconductor are oxygen vacancies. Chloride ions
would occupy the positions of oxygen vacancies to generate cation
vacancies at solution/lm interface, which transport towards the
lm/metal interface to produce cation vacancy condensate, result-
ing in local depart of passive lm and thus pitting. A complete
Table 3
Electrochemical parameters tted from EIS data measured at E
pit
.
Passivation condition Rs () CPE-Y
0
(10
5
S s
n
) n R
f
() RL () L (H)
In air 39 126 0.80 970.1 687 106
In 0.25M Na
2
SO
4
solution 35 1.93 0.71 1573 821 123K
In 0.25M Na
2
SO
4
+0.5M NaCl solution 2.9 1.64 1 10.15 0.97 2.22
4162 Y. Liu et al. / Electrochimica Acta 54 (2009) 41554163
Fig. 10. Schematic diagrams of electric eld distributions at the electrode/solution
interface when electrode is at Ecorr (a) and PZC (b).
description about the interfacial electrode reactions and mass-
transport processes are proposedby MacdonaldbasedonPDM[35].
Therefore, adsorption and permeation of chloride ions into passive
lm is usually the rst step to cause pitting.
To understand fundamentally the sources of chloride ions to
result in pitting in passive lm under different forming conditions,
the potential of zero charge is measured and shown in Fig. 6. The
potential of zero charge at which the excess charge at the elec-
trode/electrolyte interface could be eliminated usually acts as a
reference in determining the type and amount of ions adsorbed
on the electrode surface [36]. If an electrode under its open-circuit
potential is positively charged and thus adsorbed with anions, the
PZC is a more negative potential applied to counteract the excess
charges at the interface, as schematically represented in Fig. 10. The
potential differences between E
corr
and PZC, E, for Al passive lms
formed under various conditions show positive values, suggesting
that the electrode surfaces are positively charged at E
corr
for all
types of passive lms. Consequently, chloride ions are expected to
adsorb onelectrode surface. Furthermore, fromthe value of E, it is
deduced that passive lmformed in air has the largest capability to
adsorb chloride ions, while the lm formed in chloride-containing
solution the least. Thus, passive lm formed in aqueous solution,
especially the chloride-containing solution, has a weak capability
in anions adsorption, which is attributed to the mutual repulsion
among anions. It is expected that a high concentration of chloride
ions exists in passive lm formed in chloride-containing solution,
and a further adsorption of chloride ions from the solution will be
repulsed. Therefore, chloride ions causing pitting of passive lm
formed in air and in chloride-free solution come fromthe test solu-
tion, while chloride ions resulting in pitting of passive lm formed
inchloride-containing solutionare mainly those existing inthe lm
during lm-forming stage.
It has been demonstrated [20,37,38] that passive lm with a
higher donor density is always associated with a lower resistance
to pitting corrosion. The present work shows that there is the high-
est donor density in passive lm formed in air, as seen in Table 1,
providing potential sites for chloride ions to occupy. Moreover, it
is determined that there is the strongest capability for chloride ion
adsorption on passive lm formed in air, it is expected that the
passive lm formed in air has the lowest resistance to pitting, as
demonstrated by a lowest E
pit
.
It is realizedthat the size, shape anddistributionof secondphase
intermetallic particles inuence the pitting corrosion behavior. For
example, it was found [39] that the adsorption of Cl

in passive
lmprefers at or around inclusions and second phase particles due
to weaker oxide lm on these sites. This relevant subject will be
explored in more detail in the further work.
5. Conclusions
Passive lm formed on 3003 Al alloy in air and in Na
2
SO
4
solu-
tion without and with NaCl addition shown-type semiconductor in
nature. Passive lmformed in chloride-free solution is most stable,
and that formed in chloride-containing solution is most unstable,
with the lm formed in air in between. Passive lm formed in air
is associated with a non-uniform structure/composition and the
highest donor density in electronic structure, resulting in a reduced
stability than those formed in aqueous solution. However, incorpo-
ration of chloride ions in passive lm would decrease signicantly
the resistance of the lm to pitting when it is formed in a chloride-
containing solution.
Pitting of 3003Al alloy passivatedinair andinaqueous solutions
is inevitable in the presence of chloride ions in the test solution.
There is the strongest capability for the air-passivated 3003 Al alloy
to repassivate, and the weakest repassivating capability for Al alloy
passivated in chloride-containing solution. The resistance of the
passivated 3003 Al alloy to pitting is dependent on the competi-
tive effects of pitting (breakdown of passive lm) and repassivation
(repair of passive lm).
The positive potential differences between E
corr
and potential of
zero charge for Al passive lms formed under various conditions
suggest that the electrode surfaces are positively charged at E
corr
.
Consequently, chloride ions are expected to adsorb on electrodes.
Passive lm formed in air has the strongest capability to adsorb
chloride ions, while the lm formed in chloride-containing solu-
tion the least. Chloride ions causing pitting of passive lm formed
in air and in chloride-free solution come from the test solution,
while those resulting in pitting of passive lm formed in chloride-
containing solution exist in the lm during lm-forming stage.
Acknowledgements
This work was supported by Canada Research Chairs Pro-
gram, Natural Science and Engineering Research Council of Canada
(NSERC) and Dana Canada Corporation.
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