Corrosion Science 51 (2009) 2151–2157

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Effect of microcrystallization on pitting corrosion of pure aluminium

Guozhe Meng a,b,*, Liyan Wei a, Tao Zhang a,b, Yawei Shao a,b, Fuhui Wang a,b, Chaofang Dong c, Xiaogang Li b,c
a
Corrosion and Protection Laboratory, Key Laboratory of Superlight Materials and Surface Technology, Harbin Engineering University, Ministry of Education, Harbin 150001, China
b
State Key Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China
c
Corrosion and Protection Center, University of Science and Technology Beijing, Beijing 100083, China

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

Article history: A microcrystalline aluminium film with grain size of about 400 nm was prepared by magnetron sputtering
Received 9 January 2009 technique. Its corrosion behaviour was investigated in NaCl containing acidic solution by means of poten-
Accepted 29 May 2009 tiodynamic polarization curves and electrochemical noise (EN). The polarization results indicated that the
Available online 9 June 2009
corrosion potential of the sample shifted towards more positive direction, while its corrosion current
density decreased compared with that of pure coarse-grain Al. The EN analysis based on stochastic model
Keywords: demonstrated that there existed two kinds of effect of microcrystallization on the pitting behaviour of pure
A. Aluminium
aluminium: (1) the rate of pit initiation is accelerated, (2) the pit growth process was impeded. This leads to
B. Polarization
B. SEM
the enhancement of pitting resistance for the microcrystallized aluminium.
C. Pitting corrosion Ó 2009 Elsevier Ltd. All rights reserved.

1. Introduction Aluminium, as well as its alloys, has been extensively used in

The corrosion behaviour of metallic materials is determined not
only by their chemical compositions but also by their microstruc-
tures [1]. Nano- and microcrystalline materials have been the sub-
jects of intensive research in scientific and industrial communities
in recent years [2,3]. Their small grain size and the high volume
fraction of grain boundaries may result in their different corrosion
behaviour from that of the conventional polycrystalline materials.
It was reported that the corrosion resistance of nanocrystallized
304 stainless steel by sandblasting was obviously improved in
3.5% NaCl solution [4]. Thorpe et al. found that the corrosion resis-
tance of nanocrystalline Fe32–Ni36–Cr14–P12–B6 was signifi-
cantly greater than that of its amorphous counterpart because of
Cr enrichment in the surface film via rapid phase-boundary diffu-
sion [5]. The study on the corrosion behaviour of nano-alloys by
Zeiger et al. revealed an enhanced corrosion resistance of nano-
crystalline Fe–8 wt.% Al in Na2SO4 solution (pH = 6) [6]. Meng
et al. [7] investigated the corrosion behaviour of Fe–10Cr nanocrys-
talline coating with a grain size of 20–30 nm, indicating that the
pitting resistance of the Fe–10Cr nanocrystalline coating enhanced
greatly. The electrochemical corrosion behaviour of microcrystal-
line aluminium was investigated in acidic solution [1]. The results
revealed that the pitting resistance of microcrystalline aluminium
is improved due to the decreased isoelectric point.
* Corresponding author. Address: Corrosion and Protection Laboratory, Key
Laboratory of Superlight Materials and Surface Technology, Harbin Engineering
University, Ministry of Education, Nantong ST 145, Harbin 150001, China. Tel./fax:
+86 451 8251 9190.
E-mail address: mengguozhe@hrbeu.edu.cn (G. Meng).
industry because of its particular properties such as low density,
good appearance and corrosion resistance. However, experiences
demonstrate that Al and its alloys are susceptible to pitting corro-
sion when they are exposed to an aggressive environment such as
chloride media [8–17]. The review of the documents shows that
nanocrystallization or microcrystallization is in favor of the
enhancement of pitting resistance of metals or alloys. This is signif-
icant for preventing stress corrosion cracks because the corrosion
pits might be the most common sites for crack initiation. However,
the fundamental understanding about effect of the fine grain size
on the initiation and growth of pitting corrosion is still limited.
In this respect, our goal is to investigate the effect of microcrys-
tallization on the pitting corrosion of pure Al film in chloride-con-
taining acidic solutions. Conventional electrochemical techniques
including potentiodynamic polarization, electrochemical noise
were employed to investigate the pitting initiation and growth of
microcrystalline Al. It is anticipated that this research provides
an essential insight into the mechanisms of pitting corrosion of
microcrystalline Al.
2. Experimental details
A planar magnetron sputter machine (SBH 5115D) was used to
synthesize the microcrystalline aluminium film on quartz glass
substrate. The substrates were degreased for 10 min by ultrasonic
cleaning in acetone, then cleaned in distilled water and dried in air
before placing into the chamber for deposition. The target was a
380  128 cm sheet cut from commercial pure aluminium
(99.9 wt.%) ingot. The sputtering parameters were as follows: ar-
gon pressure 0.25 Pa; power 1.2 kW, substrate temperature

0010-938X/$ - see front matter Ó 2009 Elsevier Ltd. All rights reserved.
doi:10.1016/j.corsci.2009.05.046
2152 G. Meng et al. / Corrosion Science 51 (2009) 2151–2157
100 °C, the total sputtering time 4 h. Prior to depositing the film,
the target was sputtered for 10 min to remove the surface contam-
inants. TEM foil of the sputtered Al was prepared by ion milling
and the microstructure was observed using a JEOL JEM-2010 trans-
mission electron microscope operated at 200 kV.
The specimens made of the same pure aluminium (99.9 wt.%)
ingot as the sputtering target were also employed as a comparison
in the following experiments. Prior to the experiments, the surfaces
of cast specimens were polished using SiC papers of successive
grades up to 2000, cleaned by distilled water, and then degreased
with acetone. All the cast and microcrystalline aluminium samples
were mounted in epoxy resin with an exposed area of 1 cm2.
The electrochemical measurements were performed in 0.5 mol/
l NaCl acidic (pH = 2) aqueous solutions. The pH value was adjusted
by diluting (0.05 mol/l) H2SO4 aqueous solution. All the reagents
used in this work were analytical pure. Distilled water was used
to prepare all aqueous solutions.
For potentiodynamic polarization measurements, a classical
three-electrode cell was employed, with a saturated Ag/AgCl refer-
ence electrode and a platinum sheet as counter electrode. Prior to
the potentiodynamic polarization measurements, the samples
were immersed for 1 h for stability in 0.5 mol/l NaCl acidic aqueous
solutions. Both the anodic polarized curve and the cathodic curve
were measured starting from the steady open circuit potential
using PAR 273 potentiostat (EG&G), with a scanning rate of
0.33 mV/s. The complete polarization curve was obtained by com-
bining the anodic and cathodic curves in one figure.
Electrochemical noise measurements were performed on Auto-
lab PGSTAT302 potentiostat by electrochemical noise (EN) mode.
Two identical specimens were used as the working electrode
(WE) and a saturated Ag/AgCl as the reference electrode. The elec-
trochemical current noise was measured between two identical
working electrodes at the corrosion potential. EN data was instan-
taneously recorded with time for 48 h. Each set of EN records con-
tains 1024 data points, and the data-sampling interval is 0.25 s.
All the electrochemical measurements were repeated three
times for better reproducibility. The temperature was kept at
25 ± 2 °C during all experiments.
3. Theoretical background
3.1. Shot noise theory
Shot noise theory is based on the assumption that the signals are
composed of packets of data departing from a base line. Shot noise
here can be defined as a signals caused by the fact that the current
is carried by the discrete charge carriers when an electrochemical
corrosion occurs. The number of charge carriers passing a given point
is a random variable. Provided that the individual events (such as pit-
ting initiation or growth) are independent of other events, the shot
noise analysis is applicable to the individual events [18,19].
If the shot noise is assumed to be caused by the breakdown of
an oxide scale, pit initiation and growth, the average corrosion cur-
rent Icorr is defined as:
Icorr ¼ qfn ð1Þ
where q is the average charge in each event and the fn frequency of
the occurrence of the events.
Since Icorr ;q and fn cannot be directly measured from the noise
data, each parameter should be estimated from the following
equations:
Icorr ¼ B=Rn ¼ BrI =rE ð2Þ
q ¼ rI rE =Bb ð3Þ
fn ¼ Icorr =q ¼ B2 b=r2E ð4Þ
where B is the Stern–Geary coefficient, Rn the noise resistance, rI the
standard deviation of current, rE the standard deviation of potential
and b the bandwidth of measurement. r2E =b can be replaced by wE ,
so fn can be estimated from the following relations [19]:
fn ¼ B2 =wE ð5Þ
where wE is the low frequency limit (0.01 Hz) of power spectral
density of potential.
3.2. Stochastic model for pit initiation
The cumulative probability F(fn) at each fn is numerically deter-
mined from the set of fn data previously calculated by using Eq. (5).
The procedure for determining the cumulative probability F(fn)
from fn data is described as follows: firstly, all calculated fn data
are arranged in order from the low to the high value; secondly,
the cumulative probability F(fn) is calculated as i/(n + 1), where i
is the rank in the ordered fn data (i = 1, 2, 3, . . ., n) and n the total
number of fn data.
Weibull distribution function is one of the widely used cumula-
tive probability functions for predicting life time in reliability test
because it can easily approximate the normal distribution, loga-
rithmic normal distribution and exponential distribution functions
[20]. In addition, it is also possible to analyze data even when two
or more failure modes are present at the same time [21]. The
cumulative probability F(1/fn) of a failure system can be introduced
just as Weibull distribution function based upon a ‘‘weakest-link”
model [22,23], which is expressed as:
Fð1=fn Þ ¼ 1  exp½ð1=fn Þa =b ð6Þ
where a and b are the shape and scale parameters, respec-
tively.From rearrangement of Eq. (6):
lnfln½1=ð1  Fð1=fn ÞÞg ¼ a lnð1=fn Þ  ln b ð7Þ
Therefore, the parameters a and b can be obtained from the
slope of the linear ln{ln[1/(1-F(1/fn))]} vs. ln (1/fn) plots (Weibull
probability plots) and from the intercept on the ln{ln[1/(1-F(1/
fn))]} axis, respectively. The conditional event generation rate r(t)
is employed as a kind of failure rate in reliability engineering,
which is defined as:
a
rðtÞ ¼ t a1 ð8Þ
b
Here, t denoted time (s).
Based upon Weibull distribution function, the value of r(t)Dt
represents the generation probability of events in the next unit
time Dt for the specimens in which events have not been gener-
ated when t has elapsed. This condition is well corresponding to
the pit embryo formation rate of the pitting corrosion [22,23].
3.3. Stochastic model for pit growth
Pit depth growth is modeled using a nonhomogeneous Markov
process, which links the initiation and growth stages when multi-
ple pits are considered [24,25]. To do this, the theoretical founda-
tions of extreme value statistics have been employed. It is shown
that the solution of the Kolmogorov forward equations, governing
the growth of an individual pit, is in the domain of attraction of the
Gumbel distribution. And the Gumbel extreme value distribution
has often been used to model the deepest pits behaviour [26]. In
these applications, the Gumbel Type distribution has been claimed
to account for the statistical nature in the observed behaviour of
pitting corrosion systems [22,20].
For a pitting corrosion, a large number of corrosion pits with
various depths (d), which follow a probability distribution, will
appear on the total area (S) of the sample. If S is divided into n
 G. Meng et al. / Corrosion Science 51 (2009) 2151–2157
smaller area (Si), the maximum pit depths (di) in each of the smal-
ler areas will also follow a probability distribution. The probability
(F) can be calculated according to Gumbel Type extreme value dis-
tribution by the following [27]:
  
ðdi  lÞ
F ¼ exp  exp 
a surface is covered with a protective oxide scale [35]. But the flaws
where l is the central parameter (the average value of the maximum
pit depth) and a is the scale parameter, which defines the width of the
distribution. Here, we suppose the total area S = 1 cm2.
On the other hand, the extreme value statistics analysis will be
employed according to the following procedure: (1) all calculated
extreme value data are arranged in order from the smallest to
the largest value; (2) the probability F is defined as follows:
F ¼ i=ðn þ 1Þ
where i is the rank in the ordered extreme value (i = 1, 2, 3, . . ., n)
and n the total number of extreme value data [27].
Combined Eq. (9) with Eq. (10) and (11) is obtained as follows:
1 l
 lnð ln FÞ ¼ di 
a a
l and a can be obtained in terms of the line relationship between
ln(lnF) and di. Furthermore, the probability (1-F) of the pits with
the depth d P di can be obtained according to Eq. (9).
3.4. Pitting corrosion process of pure aluminium
It has been shown that a large numbers of pits are formed on
aluminium alloys when exposed to a chloride media [8,9].
However, the vast majority of these pits which nucleate do not
propagate indefinitely, but repassivate after a very short period
of growth [28,29]. These pits are described as metastable pits
[30,31]. The other pits, however, continue growing for a longer
time to form stable pits with greater depth [32,33]. These stable
pits are fatal when considering the effects of corrosion damage.
Metastable pits and stable pits are thought to be initiated in the
same manner, and stable pits are considered a subset of metastable
pits [2,22,28]. In order to predict when stable pits will develop, it is
important to determine when metastable pits occur, and subse-
quently the likelihood of growing into stable pits from metastable
Fig. 1. (a) TEM image and (b) electron diffraction pattern of microcrystalline aluminium coating.
2153
pits [32]. The study of metastable pits is therefore an important
issue in the prediction of the development of pitting corrosion. It
provides unique opportunities for understanding pitting corrosion.
Especially, the repassivation of metastable pits provides informa-
tion on the stability criteria for pit growth [34].
ð9Þ Pure aluminium usually experiences low corrosion rates as its
in the oxide scale are unable to be repaired immediately when
exposed to a chloride media. These ‘‘pit promoting” ions interfere
with the oxide formation chemicals preventing local repassivation
of the metal. Then the pits at these locations will develop into sta-
ble pits. Unlike stable pits, metastable pits only grow to a very
small size (less than 10 lm in diameter) at which stage their
growth is arrested [36]. The only possible reason for these pits to
cease growing in light of the reactivity of the metal is that the pro-
ð10Þ tective oxide scale is regenerated.
4. Results and discussion
4.1. Microstructure characterization of sputtered Al
ð11Þ
Fig. 1 shows TEM images of the sputtered Al film. Fig. 1a indi-
cates that the sputtered Al consists of equiaxed crystals. The grain
sized was approximately 400 nm. Moreover, the fine grain size is
further demonstrated by the almost continuous ring character of
the electron diffraction pattern in Fig. 1b.
4.2. Potentiodynamic polarization curves
Fig. 2 depicts the potentiodynamic polarization curves of both
microcrystalline aluminium film and cast pure aluminium in
0.5 mol/l NaCl (pH = 2.5) acidic aqueous solution. It shows that
the polarization behaviour of the anodic polarization curve of
microcrystalline aluminium is distinctly different from that of
the cast counterpart. Microcrystalline aluminium shows obvious
self passivation characteristics, while cast aluminium presents
active dissolution in the solution. By fitting the polarization curves
using Corrview software, it was obtained that the corrosion current
densities (icorr) of the microcrystalline aluminium film and cast
counterpart were about 1.83  108 A/cm2 and 1.32  106 A/cm2,
respectively. And the corrosion potential (Ecorr) of microcrystalline
2154 G. Meng et al. / Corrosion Science 51 (2009) 2151–2157

-0.30 0.0060
microcrystalline aluminium microcrystalline aluminium
cast aluminium
cast aluminium
-0.45

0.0045
-0.60
EAg/AgCl / V

-2
R-1n / Ω .cm
-0.75
0.0030

-1
-0.90

-1.05
0.0015
-8 -7 -6 -5 -4 -3 -2 -1
10 10 10 10 10 10 10 10
-2
i / A. cm

Fig. 2. Potentiodynamic curves for cast aluminium and microcrystalline aluminium 0.0000
0 10 20 30 40 50
in 0.5 mol/l NaCl acidic solution. Time / h

Fig. 4. Noise resistance Rn of cast aluminium and microcrystalline aluminium

aluminium increases 50 mV as compared with that of the cast
counterpart. This indicated that microcrystallization remarkably
improved the passivation behaviour with decreasing corrosion rate
for pure aluminium in the acid chloride media.
4.3. Evolution of corrosion rate
Fig. 3 presents the electrochemical noise signals measured on
cast aluminium (Fig. 3a) and microcrystalline aluminium (Fig. 3b)
samples in 0.5 mol/l NaCl acidic solutions. It shows that the potential
noise and current noise both fluctuate greatly for cast aluminium
throughout the experiment, while for microcrystalline aluminium
sample, a bigger fluctuations of EN is observed during the first 10 h
after the experiments began, and then the fluctuations gradually
decrease to a small value. This indicates that microcrystalline
aluminium is more stable than cast aluminium in such solutions.
Recently, the electrochemical noise impedance Rn is often found
to be equivalent to the polarization resistance of corrosion phe-
during 48 h immersion in 0.5 mol/l NaCl acidic solution.
nomena [37]. Rn is defined as the ratio of the standard deviations
of the potential noise to the current noise between two identical
working electrodes and is often obtained by analyzing the electro-
chemical noise data. Thus, 1/Rn was in direct proportion to instan-
taneous corrosion rate. 1/Rn of microcrystalline and cast Al can be
obtained from the electrochemical noise data. Fig. 4 shows the 1/Rn
changed with time for microcrystalline and cast Al, respectively. It
indicated that, during the first 10 h after the experiments began,
1/Rn of microcrystalline aluminium was about one order of magni-
tude higher than that of the cast counterpart. However, it
decreased from 1.5  103 to 6.5  104 X1 cm2, while 1/Rn of
cast aluminium increased from 1.3  104 to 4.5  103 X1 cm2
during the next time of the experiment. Then, 1/Rn of microcrystal-
line aluminium changed slightly during the next time, which indi-
cates that a protective scale was formed on the surface of
microcrystalline aluminium. But 1/Rn of cast aluminium fluctuated
greatly and the fluctuate amplitude during the next time, which
indicated that cast aluminium surface was undertaking the compe-
tition process between pit initiation and repassivation, and then
the surface of cast aluminium was being destroyed.

4.4. Pit initiation rate

Fig. 5 shows the plots between the cumulative probability F(fn)

and the frequency of events fn for microcrystalline aluminium and

1.0
Cumulative Probability of Events F(fn)

cast aluminium

0.8

0.6

0.4

microcrystalline aluminium

0.2

0.0
-5 -3 -1 1 3 5
10 10 10 10 10 10
Frequency of Event, fn( Hz)

Fig. 3. Electrochemical noise associated with pitting corrosion of cast aluminium Fig. 5. Plots of the cumulative probability (F(fn)) vs. the frequency of events (fn) for
(a) and microcrystalline aluminium (b) in 0.5 mol/l NaCl acidic solution. cast aluminium and microcrystalline aluminium.
 G. Meng et al. / Corrosion Science 51 (2009) 2151–2157 2155

2
cast aluminium
microcrystalline aluminium
-1 microcrystalline aluminium
10
0
ln{ln[1/(1-F(1/fn))]}

-1
r(t) / s
-2
-2 10

cast aluminium

-4
-3
10

-6
-12 -8 -4 0 4
ln(1/fn)
Fig. 6. Weibull probability plots for cast aluminium and microcrystalline
aluminium in 0.5 mol/l NaCl acidic solution.
cast aluminium, respectively. It indicated that the corrosion events
frequency were distributed in a region of 101  103 Hz for micro-
crystalline aluminium and 103  101 Hz for the cast counterpart.
The frequency region of the distribution of fn of microcrystalline
aluminium is wider and higher than that of the cast aluminium.
Considering that high frequency of initiation of metastable pits
will tend to occur all over the aluminium surface, the corrosion of
pure aluminium will be preferentially uniform corrosion. In con-
trast, the corrosion will localize over the surface when low
frequency of initiation of pits is dominant. Therefore, fn provided
a relatively good discrimination between localized corrosion and
uniform corrosion. Al-Mazeedi and Cottis [19] has reported that
the type of corrosion changed from uniform corrosion to localized
corrosion when the distribution of fn shifted from higher frequency
to lower frequency region for steel. In this respect, macro-uniform
corrosion or metastable pits will preferentially occur on microcrys-
talline aluminium, however localized corrosion or stable pits will
occur on the cast counterpart.
Weibull probability distribution was employed to further under-
stand the process of pitting initiation. Fig. 6 depicts the Weibull
probability plots (ln{ln[1/(1-F(1/fn)))]} vs. ln(1/fn) plots) for micro-
crystalline and cast aluminium, respectively. Two linear regions
were observed for microcrystalline aluminium but only one for cast
aluminium. This indicated that two failure modes existed for micro-
crystalline Al and only one did for the cast counterpart.
According to Eq. (7), the values of the shape parameter a and
scale parameter b were determined (summarized in Table 1) by
linear fitting of the plots in Fig. 6. Then the pitting initiation rate
of microcrystalline and cast Al can be obtained based on Eq. (8).
Fig. 7 showed the plots of r(t) vs. t for microcrystalline and cast
Al, respectively. It was observed that the value of r(t) of microcrys-
talline aluminium was about two orders of magnitude of that of
0 5 10 15 20 25 30
Time / s
8
Fig. 7. Plots of the conditional event generation rate r(t) vs. time (t) for cast
aluminium and microcrystalline aluminium in 0.5 mol/l NaCl acidic solution.
4.5. Pit growth probability
The integration of current transient with time could be used to
determine the charge passed for each current transient spike. This
charge is the result of the formation of a pit and can be related to
the physical volume of the pit (Eq. (12)) by using Faraday’s equa-
tion [28,36]. If the pits are assumed to be hemispherical [28,38],
the pit radius/depth can be calculated, using Eq. (13).
3 Charge passed  Molecular mass
Volumeðcm Þ ¼ ð12Þ
Faraday constant  n  Density
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi!
3  volume ðcm3 Þ
Pit diameter ðlmÞ ¼ 3  10000  2 ð13Þ
2p
where molecular mass of aluminium is 27 g/mol, Faraday constant
is 96,500, and density of aluminium is 2.70 g/cm3. The largest pit
sizes (diameter) within each of the EN segments were calculated
and the values were subjected to extreme value statistics analysis.
Fig. 8 shows the relationship between ln(lnF) and depth of pit
d. Gumbel distribution Eq. (11) was used to fit the plots in Fig. 8.
The scale parameter a and location parameter l for microcrystalline
aluminium and cast aluminium were obtained by the linear fitting
(summarized in Table 2). For microcrystalline aluminium, only one
linear region was observed and the largest depth of the pits was
approximately 5 lm, which indicated that only metastable pit
(diameters <10 lm) might occur on the surface. But for cast alumin-
ium, two linear regions were observed and the largest depth of the
6
-ln[-ln(F)], F = i/(n+1)

cast aluminium at a given period of time t (30 s). It indicates that 4 microcrystalline aluminium
microcrystallization may accelerate the pit initiation rate of pure
aluminium.
2

Table 1
The values of the shape parameter a and the scale parameter b for the localized 0 cast aluminium
corrosion of microcrystalline aluminium and cast aluminium by linear fitting of the
plots in Fig. 6.

Sample a (shape parameter) b (scale parameter) -2

0 5 10 15 20 25 30
Microcrystalline aluminium 0.60 0.85
0.29 0.91
Depth of pit / μm
Cast aluminium 0.83 318.08
Fig. 8. Gumbel probability plots for cast aluminium and microcrystalline aluminium.
2156 G. Meng et al. / Corrosion Science 51 (2009) 2151–2157

Table 2 greatly with the increase of the depth of pits for microcrystalline
Gumbel distribution parameters for microcrystalline aluminium and cast aluminium aluminium, while it decreased gradually for cast counterpart. This
in 0.5 mol/l NaCl acidic solution.
indicated that a deeper stable pits (>10 lm) was very hard to form
Sample a l (lm) on microcrystalline Al, and the cast aluminium was prone to form
Microcrystalline aluminium 0.25 0.75 deeper stable pits in such solutions.
Cast aluminium 5.58 15.88 This may be attributed to the microstructure difference between
1.72 7.24 microcrystalline and cast Al. It is known that the chemical activity of
materials greatly increases when the grain size was fined. Therefore,
the enhanced chemical activity of microcrystalline Al increased the
active sites on the surface, thereby the concentration of passive film
0.0016
formation chemicals (such as OH) in the vicinity of the surface,
cast aluminium
which led to the enhancement of the repassivation when the meta-
microcrystalline aluminium
0.0012 stable pits initiated. On the other hand, the microcrystallization
2

greatly increased grain boundaries, which may decrease the chloride

Probability / s.cm

concentration per grain boundary [2].

0.0008
For the metastable pits are always covered by a layer that is a
remnant of the passive film which can be removed by cleaning in
0.0004 ultrasonic water [39], after immersion in 0.5 mol/l NaCl acidic
solution for 48 h, the microcrystalline Al sample was quickly
0.0000
moved into the ultrasonic water for 1 min and then dried for scan-
Metastable pits Stable pits ning electron microscopy examination. Fig. 11 shows the corrosion
morphologies of cast aluminium (Fig. 11a) and microcrystalline
-0.0004 aluminium (Fig. 11b) after the immersion for 48 h in 0.5 mol/l NaCl
0 5 10 15 20 25 30 35
Depth of pit /μm acidic solution. It was observed that a few pits with large depths

Fig. 9. Distribution of depth of pits on cast aluminium and microcrystalline

aluminium in 0.5 mol/l NaCl acidic solution.

pits was about 30 lm, which indicated that both metastable pit
(diameters <10 lm) and stable pit (diameters >10 lm) might occur
on the surface.
Fig. 9 showed the statistical probabilities of various pit depth. It
demonstrated that for microcrystalline aluminium, the pits with
depth of 1.5 lm have the maximum probability indicating the
occurrence of metastable pits on the surface. However, the pits
with depth of 15 lm have the maximum probability (>10 lm)
for cast aluminium indicating that the metastable pits may grow
into stable pits.
The probabilities of a series of given depth of pits was calculated
using Eq. (10) in terms of obtained a and l values for microcrystl-
line aluminium and cast aluminium, respectively (Fig. 10). From
Fig. 10, it can be seen that the smaller the depth of pits, the bigger
the probabilities. The possibilities of smaller metastable pits
(<2 lm) were higher for microcrystalline than for cast aluminium.
However, one notable character was that the probability decreased

-5
10
Pit probability (1-F)

-9
10
cast aluminium

-13
10

-17
10
microcrystalline aluminium

0 5 10 15 20 25 30
Depth of pit / μm

Fig. 10. Probabilities of various depths of pits on cast aluminium and microcrys- Fig. 11. SEM images of corrosion morphology of (a) cast aluminium and (b) micro-
talline aluminium (predicted by statistical analysis). crystalline aluminium after the immersion of 48 h in 0.5 mol/l acidic NaCl.
 G. Meng et al. / Corrosion Science 51 (2009) 2151–2157
(>10 lm) occurred on the surface of cast Al (Fig. 11a), while many
small metastable pits (approximately 1–3 lm in diameter)
occurred on the surface of microcrystalline Al (Fig. 11b). It is well
corresponding to the results obtained by statistical method.
5. Conclusion
The microcrystalline aluminium film exhibits clearly a passiv-
ation behaviour in 0.5 mol/l NaCl acidic solution with much positive
corrosion potential and lower corrosion current in comparison with
the cast aluminium.
Metastable pits can occur on the microcrystalline aluminium
surface, which are hard to develop into stable pits with deeper
depth (>10 lm). However, the metastable pits on the cast counter-
part exhibit higher probability to grow into stable pits.
To sum up, microcrystallization can enhance the repassivation
of pure aluminium and therewith decrease its pitting susceptivity.
Acknowledgments
The authors acknowledge the financial support from Harbin
Engineering University (Start-up Foundation for Innovation,
No.HEUFT07046), the financial support from the Ministry of
Science and Technology of China (No. 2005DKA10400) and the
financial support from Key Laboratory of Superlight Materials
and Surface Technology (Harbin Engineering University), Ministry
of Education. The authors are also grateful to Professor Weitao
Wu for suggestion and modification of English.
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