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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
in passive lm and
the role of Cl
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
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
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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