Corrosion Science 45 (2003) 28932904 www.elsevier.

com/locate/corsci

Electrodeposition of solgel lms on Al for corrosion protection

Mari Sheer a, Alec Groysman b, Daniel Mandler
a

a,*

Department of Inorganic and Analytical Chemistry, The Hebrew University of Jerusalem, Givat Ram, Jerusalem 91904, Israel b Oil Reneries Ltd., R&D Lab, Haifa 31000, Israel Received 16 November 2002; accepted 6 March 2003

Abstract Solgel lms were electrodeposited on aluminum electrodes following the methodology we have developed and is based on applying negative potentials. This increases the pH at the surface, causing acceleration of the polymerization. Our process follows the two step method, in which the monomer is rst hydrolyzed in acidic solution (pH $ 4) and only then the negative potential is applied, which consumes protons and releases hydroxyl ions, thus enhancing the condensation. Films made of dierent monomers, i.e., tetraethoxysilane (TEOS), methyl trimethoxysilane and phenyl trimethoxysilane (PTMOS), were prepared, characterized and examined for their corrosion inhibition properties. Potentiodynamic polarization, electrochemical impedance spectroscopy, optical and scanning electron microscopy as well as atomic force microscopy have been used as a means of lm characterization. Hydrophobic and steric silanes, such as PTMOS showed a considerable corrosion inhibition capacity as compared to the capacity exhibited by less hydrophobic and steric derivatives such as TEOS. The dierence between the conventional dip-coating method and the electrodeposition approach for depositing solgel lms was also examined, indicating a clear advantage of the latter. 2003 Elsevier Ltd. All rights reserved.
Keywords: Corrosion inhibition; Solgel; Electrodeposition; Aluminum

Corresponding author. Tel.: +972-2-658-5831; fax: +972-2-658-5319. E-mail address: mandler@vms.huji.ac.il (D. Mandler).

0010-938X/$ - see front matter 2003 Elsevier Ltd. All rights reserved. doi:10.1016/S0010-938X(03)00106-9

2894

M. Sheer et al. / Corrosion Science 45 (2003) 28932904

1. Introduction Aluminum, due to its widespread applications [1] is an obvious substrate for corrosion studies. Its low cost, lightweight, high thermal and electrical conductivity grant aluminum a remarkable industrial and economical importance. Many of its applications are practicable due to its natural tendency to form a passivating oxide layer, which can articially be generated by anodizing the substrate. However, this passivating layer is deteriorated in aggressive media, such as chloride, which results in pitting corrosion [29]. Several methods have been applied for protecting aluminum and aluminum alloys against corrosion. Electrochemical passivation, inhibitions by soluble or adsorbed species as well as formation of a protecting coating on the surface are among the numerous available methods. These have recently been reviewed and therefore are only briey mentioned here [1014]. One of the relatively new approaches, which has been reported, however, only scarcely applied for corrosion inhibition, is solgel coating [1520]. A solgel lm is formed as a result of the hydrolysis and condensation of alkoxy-substituted transition metals, e.g., tetraalkoxysilanes [21] (Eqs. (1) and (2)). SiOCH3 4 ! SiOCH3 4n OHn nCH3 OH SiOCH3 4n OHn SiOCH3 4
OH =H nH2 O

SiOCH3 4n OHn1 OSiOCH3 3 CH3 OH

Such a lm can provide protection against corrosion of metals by creating a physical and chemical barrier between the metal and its environment. Taking into account that a solgel lm can bear dierent organic groups (using monomers with non-hydrolizable moieties) makes it a very appealing approach for designing lms with superior protection capabilities. Moreover, procedures for incorporating inorganic, organic and biological substances in the course of the condensation process, have been developed and can be used for increasing corrosion inhibition [2227]. However, the conventional methods for depositing solgel lms on metals, i.e., dip-coating, spin-coating and spraying, are suitable to at surfaces only, produce relatively thick coating and do not distinguish between the Al and other non-metallic parts that need not be covered and protected. We have recently developed a novel approach for the electrochemical deposition of solgel lms, based on electrochemically accelerating the condensation step by altering the pH on the surface [22]. It is well known that the hydrolysis of alkoxy metals is catalyzed by acid, while the condensation step is base-catalyzed. Our approach is derived from the two-step method, where the hydrolysis of the alkoxide metal monomer is carried out under acidic conditions followed by condensation at high pH levels. According to the methodology we have developed, application of negative potentials to the substrate to be coated consumes protons at the metal surface, causing a local increase of the pH. This allows the deposition of the solgel lm on the conducting parts only and controlling the thickness of the deposited lm by the potential of the substrate.

M. Sheer et al. / Corrosion Science 45 (2003) 28932904

2895

Here we report on the application of our approach for depositing well controlled thin silica based lms [22]. We examine the corrosion inhibition of such lms prepared from dierent alkoxy silane monomers, namely, tetraethoxysilane (TEOS), methyl trimethoxysilane (MTMOS) and phenyl trimethoxysilane (PTMOS). We nd that the corrosion inhibition increases with the hydrophobicity of the lm. The capability of the lms to inhibit corrosion was studied by potentiodynamic polarization, scanning electron microscopy (SEM), atomic force microscopy (AFM) and electrochemical impedance spectroscopy (EIS).

2. Experimental Electrochemical experiments were performed using a VersaStat potentiostat (EG&G). The impedance measurements were carried out using an AutoLab system (PGSTAT 10, EcoChemie). Electron probe X-ray microanalysis (EPXMA) measurements were performed with a JEOL JSM-6400 SEM. AFM images were acquired with a NanoScope II (Digital Instruments, CA) operated in the contact mode using a 0.58 N m1 cantilever. The thickness of the deposited lms was measured with a prolometer (Alpha Step 100, Tencor) and the contact angles were measured with a Ramet-Hart 100 contact angle goniometer. Dip coating of the solgel lms was carried out with a homemade lifter with a constant withdrawal speed of 50 lm s1 . Tetraethyl orthosilicate (TEOS, 99.999%), methyltrimethoxysilane (MTMOS, 98%) and phenyl trimethoxysilane (PTMOS, 97%) were purchased from Aldrich and used as received. Absolute ethanol (A.R. Frutarom), HCl (Merck), sodium chloride (Merck), tetrabutylammonium tetrauoroborate (Merck) and high purity water (EasyPure U.V. Barnstead) were used for the preparation of the dierent solutions. In order to match the sample geometry to the specic experiment requirements, three types of aluminum samples were applied. Aluminum rods (99.999%, 6.35 mm diameter, Aldrich) embedded in a Teon sheath were used for the electrochemical measurements, maintaining a constant exposed area throughout the experiments. Aluminum plates (5050-H24, 99.5%) and thin Al lms (1.2 lm, 99.999%) sputtered on Si (generously given by Intel, Israel) were used for SEM and AFM imaging, respectively. The plates and rods were polished prior to lm deposition using rst emery papers (400, 600 and 2000 grits, Buehler) followed by alumina paste (1 and 0.05 lm). Finally, all samples were sonicated in ethanol, clean water and dried at room temperature for 12 h prior to their use. The deposition solution consisted of approximately 2 M of silane monomer and a 4:4:1 ethanol:monomer:water molar ratio and 0.1 M tetrabutylammonium tetrauoroborate as an electrolyte. Typically, after preparing the solution it was left under continuous stirring for 1 h at 40 C, which was needed for hydrolysis. Then a constant negative potential ()1.8 V vs. Hg/Hg2 SO4 ) was applied for 30 min while the solution was gently stirred with a small magnetic bar. The rod samples were carefully withdrawn from the solution manually, while the plates and the sputtered samples were withdrawn out of the solution using a lifter with a constant

2896

M. Sheer et al. / Corrosion Science 45 (2003) 28932904

withdrawing speed of 50 lm s1 . Finally, the samples were dried for 24 h at room temperature. In order to measure the lms thickness with a prolometer; a notch was made in the semi-dried lms (using a thin wood stick, which did not scratch the substrate). This was necessary as the high vapor pressure of the solgel solution caused lms edges to be undened, making the measurement at these places impossible. Potentiodynamic polarization measurements were carried out in a conventional three-electrode cell using an Hg/Hg2 SO4 (saturated K2 SO4 ) as reference electrode whereas a 6 mm diameter graphite rod served as a counter electrode. The electrodes were immersed in solution for 30 min before applying potential. For the impedance measurements, a three-electrode electrochemical cell was used consisting of Teon coated aluminum rod as the working electrode, a large surface area platinum wire as the counter electrode and an Ag/AgCl wire was the reference electrode, for simplication, potentials are quoted vs. Hg/Hg2 SO4 (E0 (Hg/ Hg2 SO4 ) 0.640 V vs. SHE and E0 (Ag/AgCl) 0.197 V vs. SHE). The electrodes were left in a 0.1 M NaCl solution under open circuit potential for at least 30 min before each spectrum. Spectra were recorded at potentials close and positive to open circuit potential: )1.34 V, )1.14 V, )0.94 V and )0.74 V (vs. Hg/Hg2 SO4 ) and in the frequency range of 1 Hz to 50 kHz using a 5 mV rms perturbation.

3. Results and discussion The electrochemical deposition of a solgel lm [23] is driven by applying either negative or positive potentials that induce signicant pH changes at the electrode surface due to the reduction or oxidation of water (Eqs. (3) and (4)). 2H2 O 2e ! H2 2OH 2H2 O ! O2 4H 4e 3 4

The pH changes accelerate the condensation process, i.e., the polymerization, resulting in the deposition of an insoluble lm on the electrode surface. We have been motivated by the large variety of available derivatives of trimethoxysilanes that should result in lms with dierent and tunable properties. Hence, we chose initially three monomers, TEOS, MTMOS and PTMOS, which dier signicantly in the hydrophobicity of the deposited lm. 3.1. Characterization of the deposited lms Dierent surface techniques, such as microscopy, that probe the interfacial properties of the surface were applied for studying the deposition of the solgel lms. Fig. 1 shows the atomic force microscope (AFM) images of solgel lms of the three dierent monomers, electrochemically deposited on sputtered Al. These lms, due to their atness, were used for AFM imaging. For comparison, the image of a bare Al surface is also shown (Fig. 1A). It can be seen that the bare Al surface exhibits

M. Sheer et al. / Corrosion Science 45 (2003) 28932904

2897

Fig. 1. 7 7 lm AFM images of sputtered aluminum: (A) bare surface (roughness rms value: 11.9 nm) and electrochemically coated ()1.8 V for 30 min) with: (B) TEOS (roughness rms value: 10.9 nm), (C) MTMOS (roughness rms value: 9.5 nm) and (D) PTMOS (roughness rms value: 8.7 nm). The height scale in all images is 100 nm.

relatively large grains (of the order of a few square microns) separated by distinct grain boundaries. While the grain boundaries can still be seen after depositing a sol gel lm made of TEOS, they are hardly observable with a MTMOS and are completely hindered as a result of depositing a PTMOS lm. This might be due to either an increase in the lm thickness with its hydrophobicity or to repulsive interactions between the AFM tip and the surface as the hydrophobicity of the latter increases. The dierence in the hydrophobicity of the lms can easily be determined by measuring the water static contact angle (Table 1). While a TEOS coated Al surface yields a contact angle of 88, a MTMOS and a PTMOS give 93 and 96, respectively. The clear trend of increasing the contact angle with the hydrophobicity of the monomer can be seen, in spite of the fact that the changes are not very large.

Table 1 Contact angle, thickness (sputtered aluminum) and OCP (aluminum rod) of bare and electrodeposited Al surfaces Sample Water static contact angle ()  Thickness (A) Open circuit potential (mV, vs. Hg/Hg2 SO4 ) Al 83 (1) )1103 (5) Al/TEOS 88 (1) 1600 (200) )1100 (50) Al/MTMOS 93 (1) 1810 (110) )930 (90) Al/PTMOS 96 (1) 1700 (100) )900 (20)

2898

M. Sheer et al. / Corrosion Science 45 (2003) 28932904

Table 2 Element analysis of bare and PTMOS electrodeposited Al surfaces Bare aluminum Element C O Si Al At.% 1.49 14.90 0.64 82.26 (0.40) (0.23) (0.08) (0.36) Aluminum coated with PTMOS Element C O Si Al At.% 68.79 20.78 10.35 0.08 (0.65) (0.54) (0.15) (0.03)

The relatively high contact angle of bare Al is somewhat surprising, although in agreement with previous reports [28,29]. The thickness of the lms, measured with a prolometer, is summarized in Table 1. These results indicate that the changes in the thickness of the dierent lms can be neglected, taking into account the precision of the results. It is possible that making a notch across the lm caused some imprecision in the measurements by either incomplete removal of the wet lm from the substrate or through scratching the substrate itself. Therefore, we can only assume that the thickness of the dierent lms obtained from the dierent monomers is practically the same, which implies that the dierences in the AFM images are presumably due to the tipsurface interactions. The element analysis measured by EPXMA of a PTMOS lm (Table 2) indicates that the silicon/carbon ratio is ca. 1:6.6, which is close to that expected (1:6) in the case that the PTMOS is completely hydrolyzed and the phenyl ring is the only source of carbon in the lm. Moreover, the ratio of Si:O is indeed 1:2 as in SiO2 . These results conrm that the deposited PTMOS lms are made of completely hydrolyzed and polymerized solgel lms, whose physical properties dier from each other due to the non-hydrolyzable moiety. Since the PTMOS exhibits the slowest hydrolysis rate among the monomers used, it is evident that the other lms are made of completely hydrolyzed monomers as well [21]. 3.2. Characterization of the deposited lms under corrosive conditions The open circuit potentials (OCP, referred also as Ecorr ) measured in a 0.15 M NaCl solution are summarized in Table 1. It can be seen that while a TEOS lm has no inuence on the OCP, the other more hydrophobic lms, MTMOS and PTMOS shift the OCP by ca. 0.17 V to more positive values indicating passive properties exhibited by these coatings. Comparing the corrosion inhibition of the dierent layers can be best evaluated by performing cyclic potentiodynamic polarization measurements (Fig. 2). The measurements were carried out in a 0.15 M NaCl solution and the potential applied was scanned at 1 mV s1 in the potential window of )1.1 to 0.6 V and back to )1.0 V (vs. Hg/Hg2 SO4 ). Samples were made of rods with a constant exposed area. As dissolved O2 was present in the solution, the OCPs correspond to the pitting potential. The bare Al shows a typical behavior of anodic dissolution. The pitting

M. Sheer et al. / Corrosion Science 45 (2003) 28932904

1

2899

0.5

E/V vs. Hg/Hg2SO4

A B C D E

-0.5

-1

-1.5 -14 10

10

-12

10

-10

10

-8

10

-6

10

-4

10

-2

I/Area (A/cm2)
Fig. 2. Potentiodynamic polarization curves recorded in 0.15 M NaCl of: ABare aluminum, and electrochemically coated ()1.8 V vs. Hg/Hg2 SO4 for 30 min) with: BTEOS, CMTMOS, DPTMOS and EAluminum coated with PTMOS using the dip-coating method. The electrodes were left for 30 min under OCP before scanned at 1 mV s1 .

commences at potentials near the OCP and develops extremely fast. The hydrophilic layer of TEOS has a very minor eect, however, stabilizes, to some extend pitting as evidenced by the small hysteresis (depolarized pitting kinetics). On the other hand, the MTMOS and in particular the PTMOS show a quite dramatic eect in suppressing the anodic currents by three or four orders of magnitude as compared with the bare surface. These layers further stabilize pitting. In addition and as mentioned above the Ecorr of both these lms are shifted to values that are more positive. Nonetheless, the hydrophobic solgel coatings get corrupted as the potential exceeds approximately 0.3 V. Namely, on scanning back the anodic currents increase substantially resulting in large hysteresis (polarized pitting kinetics). The polarization curve of a lm prepared by dip coating is also shown in Fig. 2. PTMOS monomer was used for preparing the dip-coated sample. The large hysteresis, the shift to a lower current region and the Ecorr value indicate that electrodeposition of the lm is preferable, with respect to corrosion protection, over the dip-coating method. The SEM images shown in Fig. 3 provide an explanation for the phenomena. It is clear that the edges of the dip-coated plate are not covered with solgel lm as the electrodeposited, where the plate is uniformly covered with the protecting lm. The bare area is exposed to corrosion attack, an attack that can be prevented by the electrodeposition procedure, which assures the coverage of the whole conducting areas. This highlights one of the major advantages of the electrodeposited approach, which allows depositing lms onto complex geometries. Fig. 4 shows SEM images of the four Al surfaces after running the polarization curves. The images speak for themselves and provide an excellent proof of the

2900

M. Sheer et al. / Corrosion Science 45 (2003) 28932904

Fig. 3. SEM images of Al coated with PTMOS by: (A) dip-coating, (B) electrodeposition method.

Fig. 4. SEM images of Al samples after subjected to a cycle of potentiodynamic polarization in 0.15 M NaCl. (A) Bare Al, and electrochemically coated ()1.8 V for 30 min) with: (B) TEOS, (C) MTMOS, and (D) PTMOS.

dierent behavior detected by the polarization curves. The conclusion that the best corrosion inhibition is achieved by the PTMOS monomer is reinforced. All the samples were prepared by application of the same negative potential and employing a dierent monomer. In the TEOS coated Al plate the corrosion pits are easily recognized, large sized and very dense almost as in the bare surface. It is clear that this solgel coating provides almost no protection to the aluminum substrate. The PTMOS, on the contrary, provided a substantial corrosion protection; there are actually no pits visible in the image corresponding to that lm. From these images, it is also clear that the MTMOS-based lm exhibited a better protection than the TEOS lm. The pits in the MTMOS lm are smaller and more scattered than those

M. Sheer et al. / Corrosion Science 45 (2003) 28932904

2901

in the TEOS lm. Hence, the SEM images show clearly and successfully the increase of the corrosion protection with increased hydrophobicity of the solgel lm. The electrochemical impedance spectra, recorded in 0.1 M NaCl solution, are shown in Figs. 5 and 6. EIS has been widely applied for studying corrosion and corrosion inhibition of Al in chloride media [4,12,30,31]. Fig. 5A shows the Bode plots recorded at )1.14 V vs. Hg/Hg2 SO4 , which is close to the open circuit potential, where the rate of corrosion is minimal. Bode plots are the preferred presentation for analyzing corrosion of metals coated by polymers as was discussed by Mansfeld [32]. The spectra shown correspond to the bare Al surface and to Al coated with PTMOS deposited electrochemically and by dip coating. As expected, the curve of the electrochemically coated PTMOS electrode is shifted towards the high impedance region compared to the curves of the dip-coated and the bare electrodes. The impedance of the electrochemically deposited sample is signicantly higher, throughout the whole frequency range, than the other samples. The dierence in the impedance becomes even more pronounced as the potential is made more positive, as shown in Fig. 5B.

10 10 10 10

9 8 7 6 5 4

|Z|/

10 10

1000 100 10 1 10 100 1000 10

4

10

f/Hz
10 10 10
9 8 7 6 5 4

|Z|/

10 10 10

1000 100 10 1 10 100 1000 10

4

10

f/Hz
Fig. 5. Bode plots of (( ) bare, (.) electrodeposited PTMOS and (r) dip-coated PTMOS) Al samples recorded at: (A) )1.14 V and (B) )0.74 V vs. Hg/Hg2 SO4 .

2902

M. Sheer et al. / Corrosion Science 45 (2003) 28932904

700

A
600 500

-Z/

400 300 200 100 0.00 0 100 200 300 400 500 600 700

Z/
1200

B
1000 800

-Z/

600 400 200 0 0 70 200 400 600 800 1000 1200

Z/
C
60 50 40

-Z/M

30 20 10 0 0 10 20 30 40 50 60 70

Z/M
Fig. 6. Complex plane plots of: (A) bare Al (Rp 4:0 107 X, C 1:9 109 F), (B) dip-coated PTMOS (Rp 2:6 107 X, C 9:1 1011 F) and (C) electrodeposited PTMOS (Rp 1:2 108 X, C 1:5 1012 F) recorded at )0.74 V vs. Hg/Hg2 SO4 . The samples where immersed in the solution for 30 min before spectra were recorded.

The data shown here were acquired at )0.74 V vs. Hg/Hg2 SO4 where the rate of corrosion is fairly high at the bare and dip-coated surfaces. Fig. 6, where the complex plane plots of the same samples at )0.74 V are shown, supports our ndings. It should be noticed that while the real and imaginary components of the bare

M. Sheer et al. / Corrosion Science 45 (2003) 28932904

2903

(Fig. 6A) and dip-coated (Fig. 6B) Al surfaces are of the order of 102 103 X, those of the electrochemically deposited lm is four orders of magnitude higher. Equivalent circuit analysis was performed on the impedance data, based on a simple circuit, made of a resistor connected in series to a parallel-connected resistor and capacitor. The values are given in the gure caption of Fig. 6. In essence, EIS results clearly indicate that the electrochemically deposited lms exhibit a superior corrosion resistance.

4. Conclusions Solgel lms have been electrochemically deposited on aluminum and tested as corrosion inhibitors. The deposition is based on altering the pH on the Al surface, which is driven by a cathodic reaction of water reduction. Three dierent monomers that dier primarily by their hydrophobicity have been used and showed remarkable dierences in their protection. The more hydrophobic lm, which was based on phenyl trimethoxysilane showed the best corrosion protection, while that made of tetraethoxysilane had only a minor protection on the Al underneath. Our study clearly shows the great potential of solgel lms for corrosion protection. The fact that numerous monomers are available, that can be used to tune the properties of the deposited solgel lm, opens the ability to design lms with much better and selective corrosion protection. Moreover, we have clearly shown that our method of electrochemically depositing the lms is superior as compared with the conventional dip or spin coating methods for corrosion inhibition as it enables to coat structures with complex geometries. We are currently examining the eect of mixed solgel lms in which inorganic anions are electrostatically incorporated for enhancing the corrosion protection further.

Acknowledgement This work was supported by the Ministry of Science, Culture and Sports under the strategic research (contract 1095).

References
[1] A. Despic, V. Parkhutik, in: J.O. Bockris, R.E. White, B.E. Conway (Eds.), Modern Aspects of Electrochemistry, vol. 20, Plenum, New York, 1989. [2] P.L. Cabot, F.A. Centellas, J.A. Garrido, E. Perez, H. Vidal, Electrochim. Acta 36 (1) (1990) 179. [3] Z. Szklarska-Smialowska, Corros. Sci. 41 (1998) 1743. [4] A. Kuznetsova, T.D. Burleigh, V. Zhukov, J. Blachere, J.T. Yates, Langmuir 14 (1998) 2502. [5] M. Elboujdaini, E. Ghali, R.G. Barradas, M. Girgis, J. Appl. Electrochem. 25 (1995) 412. [6] J.B. Bessone, D.R. Salinas, C.E. Mayer, M. Ebert, W.J. Lorenz, Electrochim. Acta 37 (1992) 2283.

2904

M. Sheer et al. / Corrosion Science 45 (2003) 28932904

[7] M.G. Fontana, Corrosion Engineering, Third ed., McGraw-Hill International, New York, 1987, pp. 278315. [8] B.J. Wiersma, K.R. Hebert, J. Elec. Chem. Soc. 138 (1) (1991) 48. [9] W.A. Badawy, F.M. Al-Khara, Corros. Sci. 39 (4) (1997) 681. [10] A.Y. El-Etre, Corros. Sci. 43 (4) (2000) 1031. [11] S. Pyun, S. Moon, J. Solid-State Electrochem. 3 (6) (1999) 331. [12] C.M.A. Brett, I.A.R. Gomes, J.P.S. Martins, J. Appl. Electrochem. 24 (1994) 1158. [13] C. Mary, C. Whitten, L. Chiu-Tsu, Prog. Org. Chem. 38 (2000) 151. [14] R.L. Twite, G.P. Bierwagen, Prog. Org. Coat. 33 (1998) 91. [15] X.F. Yang, D.E. Tallman, V.J. Gelling, G.P. Bierwagen, L.S. Kasten, J. Berg, Surf. Coat. Technol. 140 (2001) 44. [16] M. Guglielmi, J. SolGel Sci. Technol. 8 (1997) 443. [17] T.L. Metroke, R.L. Parkhill, E.T. Knobbe, Prog. Org. Coat. 41 (2001) 233. [18] M. Mennig, C. Shelle, A. Duran, J.J. Damborenea, M. Guglielmi, G. Brusatin, J. SolGel Sci. Technol. 13 (13) (1998) 717. [19] M. Atik, P.D. Neto, L.A. Avaca, M.A. Aegerter, Ceram. Int. 21 (6) (1995) 403. [20] M. Atik, P.D. Neto, L.A. Avaca, M.A. Aegerter, J. Appl. Electrochem. 23 (1995) 142. [21] C.J. Brinker, Solgel Science, Academic Press, New York, 1990. [22] R. Shacham, D. Avnir, D. Mandler, Adv. Mater. 11 (5) (1999) 384. [23] D. Avnir, J. Am. Chem. Soc. 28 (1994) 328. [24] G. Thim, M. Oliveira, E. Oliveira, F. Melo, Non-Cryst. Sol. 273 (2000) 124. [25] M. Khobaib, L.B. Reynolds, M.S. Donley, Surf. Coat. Technol. 140 (2001) 16. [26] N. Voevodin, C. Jecoate, L. Simon, M. Khobaib, M. Donley, Surf. Coat. Technol. 140 (2001) 29. [27] Y.J. Du, M. Damron, G. Tang, H.X. Zheng, C.J. Chu, J.H. Osborne, Prog. Org. Coat. 41 (2001) 226. [28] J.D. Bernardin, I. Mudawar, C.B. Walsh, E.I. Franses, Int. J. Heat Mass Transfer 40 (1997) 1017. [29] K. Watanabe, M. Sakairi, H. Takahashi, S. Hirai, S. Yamaguchi, J. Electroanal. Chem. 473 (1999) 250. [30] S.S. Sayed, A.E. Rehim, H.H. Hassan, M.A. Amin, Mater. Chem. Phys. 70 (2001) 64. [31] F.S. Bovard, T.D. Burleigh, A.T. Smith, Electrochim. Acta 40 (2) (1995) 201. [32] F. Mansfeld, J. Appl. Electrochem. 25 (1995) 187.