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Corrosion Science 51 (2009) 21512157

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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 b c

Corrosion and Protection Laboratory, Key Laboratory of Superlight Materials and Surface Technology, Harbin Engineering University, Ministry of Education, Harbin 150001, China State Key Laboratory for Corrosion and Protection, Institute of Metal Research, Chinese Academy of Sciences, Shenyang 110016, China 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
A microcrystalline aluminium lm with grain size of about 400 nm was prepared by magnetron sputtering technique. Its corrosion behaviour was investigated in NaCl containing acidic solution by means of potentiodynamic polarization curves and electrochemical noise (EN). The polarization results indicated that the 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 demonstrated that there existed two kinds of effect of microcrystallization on the pitting behaviour of pure aluminium: (1) the rate of pit initiation is accelerated, (2) the pit growth process was impeded. This leads to the enhancement of pitting resistance for the microcrystallized aluminium. 2009 Elsevier Ltd. All rights reserved.

Article history: Received 9 January 2009 Accepted 29 May 2009 Available online 9 June 2009 Keywords: A. Aluminium B. Polarization B. SEM C. Pitting corrosion

1. Introduction The corrosion behaviour of metallic materials is determined not only by their chemical compositions but also by their microstructures [1]. Nano- and microcrystalline materials have been the subjects of intensive research in scientic 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 resistance of nanocrystalline Fe32Ni36Cr14P12B6 was signicantly greater than that of its amorphous counterpart because of Cr enrichment in the surface lm via rapid phase-boundary diffusion [5]. The study on the corrosion behaviour of nano-alloys by Zeiger et al. revealed an enhanced corrosion resistance of nanocrystalline Fe8 wt.% Al in Na2SO4 solution (pH = 6) [6]. Meng et al. [7] investigated the corrosion behaviour of Fe10Cr nanocrystalline coating with a grain size of 2030 nm, indicating that the pitting resistance of the Fe10Cr nanocrystalline coating enhanced greatly. The electrochemical corrosion behaviour of microcrystalline 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.

Aluminium, as well as its alloys, has been extensively used in 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 corrosion when they are exposed to an aggressive environment such as chloride media [817]. 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 significant 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 ne grain size on the initiation and growth of pitting corrosion is still limited. In this respect, our goal is to investigate the effect of microcrystallization on the pitting corrosion of pure Al lm in chloride-containing 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 lm 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: argon pressure 0.25 Pa; power 1.2 kW, substrate temperature

* 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). 0010-938X/$ - see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.corsci.2009.05.046

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100 C, the total sputtering time 4 h. Prior to depositing the lm, the target was sputtered for 10 min to remove the surface contaminants. TEM foil of the sputtered Al was prepared by ion milling and the microstructure was observed using a JEOL JEM-2010 transmission 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 reference 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 combining the anodic and cathodic curves in one gure. Electrochemical noise measurements were performed on Autolab 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 electrochemical current noise was measured between two identical working electrodes at the corrosion potential. EN data was instantaneously recorded with time for 48 h. Each set of EN records contains 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 dened 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 pitting 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 current Icorr is dened as:

where B is the SternGeary coefcient, Rn the noise resistance, rI the standard deviation of current, rE the standard deviation of potential and b the bandwidth of measurement. r2 E =b can be replaced by wE , so fn can be estimated from the following relations [19]:

fn B2 =wE

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 determined 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: rstly, 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 cumulative probability functions for predicting life time in reliability test because it can easily approximate the normal distribution, logarithmic 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:

F 1=fn 1 exp1=fn a =b

where a and b are the shape and scale parameters, respectively.From rearrangement of Eq. (6):

lnfln1=1 F 1=fn g a ln1=fn ln b

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 dened as:

a rt t a1 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 generated 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 multiple pits are considered [24,25]. To do this, the theoretical foundations 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

Icorr qfn

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 B=Rn BrI =rE q rI rE =Bb fn Icorr =q B2 b=r2 E

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smaller area (Si), the maximum pit depths (di) in each of the smaller areas will also follow a probability distribution. The probability (F) can be calculated according to Gumbel Type extreme value distribution by the following [27]:

   di l F exp exp

where l is the central parameter (the average value of the maximum pit depth) and a is the scale parameter, which denes 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 dened as follows:

F i=n 1

10

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 information on the stability criteria for pit growth [34]. Pure aluminium usually experiences low corrosion rates as its surface is covered with a protective oxide scale [35]. But the aws 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 stable 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 protective oxide scale is regenerated. 4. Results and discussion 4.1. Microstructure characterization of sputtered Al

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:

ln ln F

di

l a

11
Fig. 1 shows TEM images of the sputtered Al lm. Fig. 1a indicates that the sputtered Al consists of equiaxed crystals. The grain sized was approximately 400 nm. Moreover, the ne grain size is further demonstrated by the almost continuous ring character of the electron diffraction pattern in Fig. 1b. 4.2. Potentiodynamic polarization curves

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 indenitely, 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 subsequently the likelihood of growing into stable pits from metastable

Fig. 2 depicts the potentiodynamic polarization curves of both microcrystalline aluminium lm 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 tting the polarization curves using Corrview software, it was obtained that the corrosion current densities (icorr) of the microcrystalline aluminium lm and cast counterpart were about 1.83 108 A/cm2 and 1.32 106 A/cm2, respectively. And the corrosion potential (Ecorr) of microcrystalline

Fig. 1. (a) TEM image and (b) electron diffraction pattern of microcrystalline aluminium coating.

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0.0060 microcrystalline aluminium cast aluminium 0.0045
-2

microcrystalline aluminium cast aluminium

EAg/AgCl / V

-0.60 -0.75 -0.90 -1.05

R-1 / .cm n

0.0030

-1

0.0015 10
-8

10

-7

10

-6

10

-5

10
-2

-4

10

-3

10

-2

10

-1

i / A. cm

Fig. 2. Potentiodynamic curves for cast aluminium and microcrystalline aluminium in 0.5 mol/l NaCl acidic solution.

0.0000

10

20

30

40

50

Time / h
Fig. 4. Noise resistance Rn of cast aluminium and microcrystalline aluminium during 48 h immersion in 0.5 mol/l NaCl acidic solution.

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 uctuate greatly for cast aluminium throughout the experiment, while for microcrystalline aluminium sample, a bigger uctuations of EN is observed during the rst 10 h after the experiments began, and then the uctuations 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-

nomena [37]. Rn is dened 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 electrochemical noise data. Thus, 1/Rn was in direct proportion to instantaneous 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 rst 10 h after the experiments began, 1/Rn of microcrystalline aluminium was about one order of magnitude 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 microcrystalline aluminium changed slightly during the next time, which indicates that a protective scale was formed on the surface of microcrystalline aluminium. But 1/Rn of cast aluminium uctuated greatly and the uctuate amplitude during the next time, which indicated that cast aluminium surface was undertaking the competition 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 10
-5

10

-3

10

-1

10

10

10

Frequency of Event, fn( Hz)


Fig. 3. Electrochemical noise associated with pitting corrosion of cast aluminium (a) and microcrystalline aluminium (b) in 0.5 mol/l NaCl acidic solution. Fig. 5. Plots of the cumulative probability (F(fn)) vs. the frequency of events (fn) for cast aluminium and microcrystalline aluminium.

G. Meng et al. / Corrosion Science 51 (2009) 21512157


2 cast aluminium microcrystalline aluminium 0
-1

2155

10

microcrystalline aluminium

ln{ln[1/(1-F(1/fn))]}

r(t) / s

-1

-2

10

-2

cast aluminium -4 10
-3

-6 0
-12 -8 -4 0 4 8

10

15

20

25

30

Time / s
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.

ln(1/fn)
Fig. 6. Weibull probability plots for cast aluminium and microcrystalline aluminium in 0.5 mol/l NaCl acidic solution.

4.5. Pit growth probability cast aluminium, respectively. It indicated that the corrosion events frequency were distributed in a region of 101  103 Hz for microcrystalline 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 contrast, 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 microcrystalline aluminium, however localized corrosion or stable pits will occur on the cast counterpart. Weibull probability distribution was employed to further understand 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 microcrystalline 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 microcrystalline 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 tting 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 microcrystalline aluminium was about two orders of magnitude of that of cast aluminium at a given period of time t (30 s). It indicates that microcrystallization may accelerate the pit initiation rate of pure aluminium. 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 Faradays equation [28,36]. If the pits are assumed to be hemispherical [28,38], the pit radius/depth can be calculated, using Eq. (13).

Volumecm

Charge passed Molecular mass Faraday constant n Density 3 r! 3 volume cm3 10000 2 2p

12

Pit diameter lm

13

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 t the plots in Fig. 8. The scale parameter a and location parameter l for microcrystalline aluminium and cast aluminium were obtained by the linear tting (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 aluminium, two linear regions were observed and the largest depth of the

-ln[-ln(F)], F = i/(n+1)

microcrystalline aluminium

Table 1 The values of the shape parameter a and the scale parameter b for the localized corrosion of microcrystalline aluminium and cast aluminium by linear tting of the plots in Fig. 6. Sample Microcrystalline aluminium Cast aluminium a (shape parameter) 0.60 0.29 0.83 b (scale parameter) 0.85 0.91 318.08

cast aluminium

-2 0 5 10 15 20 25 30

Depth of pit / m
Fig. 8. Gumbel probability plots for cast aluminium and microcrystalline aluminium.

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Table 2 Gumbel distribution parameters for microcrystalline aluminium and cast aluminium in 0.5 mol/l NaCl acidic solution. Sample Microcrystalline aluminium Cast aluminium

a
0.25 5.58 1.72

l (lm)
0.75 15.88 7.24

0.0016 cast aluminium microcrystalline aluminium

0.0012

0.0008

0.0004

0.0000 Metastable pits -0.0004 Stable pits

10

15

20

25

30

35

Depth of pit /m
Fig. 9. Distribution of depth of pits on cast aluminium and microcrystalline aluminium in 0.5 mol/l NaCl acidic solution.

greatly with the increase of the depth of pits for microcrystalline aluminium, while it decreased gradually for cast counterpart. This indicated that a deeper stable pits (>10 lm) was very hard to form on microcrystalline Al, and the cast aluminium was prone to form deeper stable pits in such solutions. This may be attributed to the microstructure difference between microcrystalline and cast Al. It is known that the chemical activity of materials greatly increases when the grain size was ned. Therefore, the enhanced chemical activity of microcrystalline Al increased the active sites on the surface, thereby the concentration of passive lm formation chemicals (such as OH) in the vicinity of the surface, which led to the enhancement of the repassivation when the metastable pits initiated. On the other hand, the microcrystallization greatly increased grain boundaries, which may decrease the chloride concentration per grain boundary [2]. For the metastable pits are always covered by a layer that is a remnant of the passive lm which can be removed by cleaning in ultrasonic water [39], after immersion in 0.5 mol/l NaCl acidic solution for 48 h, the microcrystalline Al sample was quickly moved into the ultrasonic water for 1 min and then dried for scanning electron microscopy examination. Fig. 11 shows the corrosion morphologies of cast aluminium (Fig. 11a) and microcrystalline aluminium (Fig. 11b) after the immersion for 48 h in 0.5 mol/l NaCl acidic solution. It was observed that a few pits with large depths

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 microcrystlline 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

Probability / s.cm

10

-5

Pit probability (1-F)

10

-9

cast aluminium
-13

10

10

-17

microcrystalline aluminium

10

15

20

25

30

Depth of pit / m
Fig. 10. Probabilities of various depths of pits on cast aluminium and microcrystalline aluminium (predicted by statistical analysis). Fig. 11. SEM images of corrosion morphology of (a) cast aluminium and (b) microcrystalline aluminium after the immersion of 48 h in 0.5 mol/l acidic NaCl.

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(>10 lm) occurred on the surface of cast Al (Fig. 11a), while many small metastable pits (approximately 13 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 lm exhibits clearly a passivation 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 counterpart 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 nancial support from Harbin Engineering University (Start-up Foundation for Innovation, No.HEUFT07046), the nancial support from the Ministry of Science and Technology of China (No. 2005DKA10400) and the nancial 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 modication of English. References
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