Materials Letters 60 (2006) 2633 2637 www.elsevier.

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Advanced nano-particles anti-corrosion ceria based sol gel coatings for aluminum alloys
Abdel Salam Hamdy
Department of Surface Treatment and Corrosion Control, Central Metallurgical R & D Institute, CMRDI, P.O. Box 87, Helwan, Cairo, Egypt Received 2 December 2005; accepted 18 January 2006 Available online 10 February 2006

Abstract Chromate conversion coatings can be successfully used for the corrosion protection of aluminum alloys. However, the environmental laws in many countries have imposed severe restrictions on chromate use due to its high toxicity and consequent environmental hazards. Many attempts have been made to find alternatives to chromating such as cerate. In this work, the effect of surface preparation prior to ceria treatment was studied. A series of specimens was prepared under the following conditions: (a) as polished, (b) directly treated, (c) etched, (d) oxide thickened, and (e) etching followed by oxide thickening. After surface preparation, the specimens dipped in ceria solutions prepared by solgel method. Electrochemical Impedance Spectroscopy (EIS) and polarization measurements have been used to evaluate the coating performance in 3.5% NaCl. The optimum conditions under which ceria treatments can provide good corrosion protection to the aluminum substrate were determined. Generally, ceria treatments improve the corrosion resistance due to the formation of protective oxide films which act as a barrier to oxygen diffusion to the metal surface. According to the EIS and polarization measurements, a combination between etching and oxide thickening has a vital role on the corrosion protection performance of AA6061-T6 in NaCl. 2006 Elsevier B.V. All rights reserved.
Keywords: Corrosion protection; Surface treatment; Aluminum alloys; Ceria; Solgel coatings

1. Introduction The advent of chromate replacements for aluminum alloys began in the late 1970s. As regulations became increasingly stricter, commercial, academic and government facilities have relied on a collaborative effort to come up with innovations for the corrosion protection of aluminum alloys [1]. Salts like cerate have been proposed as alternatives to chromate inhibitors, as have several other rare earth elements, because the rare earths behave as cathodic inhibitors in aluminum [2 14]. In previous work [2,8,9,1214] we found that cerate conversion coatings prepared by conventional method improve the corrosion resistance of aluminum due to formation of protective oxides, which act as a barrier to oxygen diffusion to the metal surface. However, most of the proposed alternative coatings formulations have failed to produce the level of protection that chromates provide. Advances in the
Tel.: +20 25010640; fax: +20 25010639. E-mail address: ashamdy@cmrdi.sci.eg. 0167-577X/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.matlet.2006.01.049

chemical tailorability of mixed alkoxide solgel coatings have led to attempts to create a long-lived, environmentally compliant, conversion coating for aluminum alloys [15]. It was shown that coating based on silica, ceria, vanadia and molybdenum can be tailored to produce a functionally gradient coating that will provide covalent bonding for strong coating adhesion and act as a barrier coating to limit the transport of water to the surface of the alloy [1620]. In this work, newly developed environmentally friendly surface treatments based on ceria prepared by solgel method were proposed as alternatives to toxic chromate-based systems. The effect of ceria solgel coatings on the corrosion behavior of Al6061 T6 in 3.5% NaCl solution will be studied using EIS and DC polarization techniques. A new surface preparation method consisted of pre-etching followed by oxide thickening before applying the solgel coating is proposed. Surface examination will be performed by scanning electron microscopy (SEM), Energy dispersive X-ray (EDS), X-ray Photoelectron Spectroscopy (XPS) and Atomic Force Microscopy (AFM).

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2. Experimental 2.1. Materials The specimens of AA6061 T6 alloy, in the form of 60 30 mm taken from a sheet 3 mm thick, were abraded to 800 finish with SiC grit papers, degreased in acetone, washed with distilled water, and dried in dry air. The nominal composition was as follows (wt.%): 0.35 Cu; 0.95 Mg; 0.70 Fe; 0.50 Si; 0.15 Mn; 0.15 Cr; 0.25 Zn; 0.15 Ti; remainder Al. 2.2. Sol synthesis and surface pre-treatment Ceria sol was prepared by dissolving 0.465 g (0.005 M) of CeCl37H2O and adding 0.48 g (0.01 M) citric acid and 250 ml C2H5OH. The solution was completed by distilled water to give a final concentration of 0.005 M cerium chloride. Four groups of specimens prepared under the following conditions: 1. 2. 3. 4. As-polished specimens (DT) Etching in 0.01 M KOH solution for 10 min (K) Oxide thickening in boiling distilled water for 1 h (B) Etching in 0.01 M KOH solution for 10 min followed by oxide thickening in boiling water for 1 h (KB).

After the surface pretreatment, the specimens were dipped into ceria sols for 10 min, dried at 110 C for 30 min and heat treated at 500 C for 30 min. A comparison will be made between the corrosion resistances obtained from the four groups after applying the ceria sol and as-polished samples without any surface treatment (WT) after 30 days of immersion in 3.5% NaCl solution. 2.3. Methods The corrosion behavior of the previous groups was monitored using electrochemical impedance spectroscopy (EIS) and DC polarization techniques during immersion in

3.5% NaCl solution open to air and at room temperature for up to 30 days. A three-electrode set-up described elsewhere [12] was used with impedance spectra being recorded at the corrosion potential Ecorr. A saturated calomel electrode (SCE) was used as the reference electrode. It was coupled capacitively to a Pt wire to reduce the phase shift at high frequencies. EIS was performed between 0.01 Hz and 65 kHz frequency range using a frequency response analyzer (Autolab PGSTAT 30, EcoCheime, The Netherlands). The amplitude of the sinusoidal voltage signal was 10 mV. DC polarization tests of specimens previously immersed for 30 days in 3.5% NaCl solution were made at a scan rate of 0.07 mV/s in the applied potential range from 0.15 to 0.7 VSCE with respect to Ecorr using an Autolab PGSTAT 30 galvanostat/ potentiostat, EcoCheime, The Netherlands. The exposed surface area was 2.54 cm2. All curves were normalized to 1 cm2. SEM images were obtained using a digital scanning electron microscope Model JEOL JSM 5410, Oxford Instruments, Japan. Microprobe analysis was performed using energy dispersive spectrometry, EDS, Model 6587, Pentafet Link, Oxford microanalysis group, UK. XRD analysis was performed using Bruker axs, Model D8 ADVANCE, Germany. AFM analysis was performed using Scanning Probe Microscope/Atomic Force Microscope SPM/AFM Dimension 3100. XPS analysis was performed using XPS/ESCA PerkinElmer PHI 5100 ESCA System.
3. Results and discussion A thick layer of Al-oxide was formed after immersion of the aspolished samples without any surface treatment (WT) after 30 days of immersion in 3.5% NaCl solution. This layer increased the insulating power of the passive film in addition to hindering the ion diffusion through the surface. This layer cannot protect the surface completely and hence severe localized corrosion will take place in the presence of Cl ions. According to EIS measurements (Fig. 1), cerium sol gel coatings improve the surface resistance of aluminum to localized corrosion. The specimens etched and oxide thickened prior to ceria treatment showed

Fig. 1. Nyquist plots after 30 days of immersion in NaCl. Blank WT (), as-polished (without treatment). Group 1 DT (), directly treated in ceria (without surface pre-treatments). Group 2 K (), etching followed by ceria treatment. Group 3 B ( ), boiling water for 1 h followed by ceria treatment. Group 4 KB () etching followed by boiling water for 1 h followed by ceria treatment.

A.S. Hamdy / Materials Letters 60 (2006) 26332637 Table 1 Polarization data after 30 days in NaCl solution Sample As-polished Ceria (KB) Ecorr (mV) 778 738 Passive current (A) 3 10 6 0.5 10 6 Epit (mV) 740 683 Perfect passivity domain Not present 8 mV

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the best corrosion protection after 30 days of immersion in NaCl. The surface resistance of such specimens was about 7.4 104 cm2 compared with 0.43 104 cm2 for the as-polished specimens without ceria treatment. Directly treated (DT) samples as well as the samples which were etched (K) or oxide thickened (B) prior to ceria treatment showed surface resistance of 2.8 104, 5.0 104 and 3.5 104 cm2, respectively. Cyclic potentiodynamic tests (Table 1) confirmed these results where the pitting potential, Epit, of ceria treated specimens is 57 mV more nobel than the as-polished specimens. The corrosion potential, Ecorr, of ceria treated specimens is also 40 mV more nobel than the as polished specimens. These results confirm the previous observations that cerium behave as cathodic inhibitors in aluminum [2 7,1214]. The pitting area under the loop of ceria is too small to that obtained from as-polished specimens. An onset perfect passivity domain of about 8 mV was detected in the ceria treated specimens. Conversely, as-polished specimens did not show any perfect passivity domain. SEM (Fig. 2) showed that the specimens which were etched and oxide thickened prior to ceria treatment had a more smooth appearance than the directly treated (DT) specimens. The film formed in the first case is more compact and distributed uniformly over the surface. This is may be due to formation of a compact Si-rich oxide film distributed uniformly over the surface of aluminum substrate. Conversely, the samples which were directly treated with ceria without any surface modification showed non-uniform surface distribution which suggests the distribution depends on the substrate microstructure [7] resulting in pitting and crevice corrosion as well as micro-cracking. SEM image at corroded area of the specimens which were etched and oxide thickened prior to ceria treatment (Fig. 3) revealed presence of Al2O3 agglomerates and micro-cracked film. EDS and XRD

Fig. 3. SEM of the sample etched and oxide thickened prior to ceria treatment after 30 days in 3.5% NaCl (micro-cracking and agglomeration at a corroded area).

analyses of the above did not detect the presence of cerium indicating that cerium may be present as a very thin film [2]. This result was evidenced by AFM surface topography (Fig. 4) which revealed compact surface film of smooth appearance for the etched specimens while the non-etched ones showed agglomerated layer. Consequently; etched specimens are more effective in reducing the number of pits. This observation could be answered why the pitting area under the loop of the etched samples is too small to that obtained from as polished specimens (Table 1). These results confirm the importance of the etching process to improve the localized corrosion resistance by formation of a protective Al-oxide film incorporated with cerium which acts as a barrier to oxygen diffusion to the metal surface in addition to the cathodic inhibitive effect. XPS analysis (Fig. 5) revealed presence of relatively higher amount of Al 2s and Al 2p for the samples etched followed by oxide thickening compared with the non-etched samples. The amount of cerium detected in all cases was too small to be accounted. Based on the results of SEM, AFM and XPS, we suggest that the corrosion protection is mainly due to the surface distribution of the Al-oxide film. If this film will distribute uniformly over the surface, the resistance to localized corrosion will

Fig. 2. SEM of the samples etched and oxide thickened followed by ceria treatment and directly treated samples after 30 days in 3.5% NaCl (surface distribution at non corroded area).

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Fig. 4. AFM surface topography image of etched and non-etched oxide thickened samples before corrosion.

increase and vice versa. Since the etching process was the only factor changed between two treatments, we can conclude that the etching process prior to oxide thickening has a dual effect. The first is to enhance the distribution of Al-oxide uniformly. The second is to prevent agglomeration of the surface Al-oxide film and consequently, enhances formation of uniformly distributed compact oxide film of smooth appearance. Therefore, the pitting corrosion resistance was improved.

4. Conclusions 1. Direct treatment with ceria sol gel coatings (without surface modification) cannot offer good corrosion protection in NaCl. 2. Cerium treatments improve the localized corrosion resistance of aluminum in NaCl and behave as cathodic inhibitors in aluminum.

3. A combination between etching and oxide thickening processes prior to ceria coatings plays a vital role in the mechanism of corrosion protection of Al-alloys. The best corrosion resistance was observed for the specimens that passed with etching together with oxide thickening processes prior to ceria sol gel coatings. 4. XPS analysis revealed presence of higher amount of Aloxide for the samples etched followed by oxide thickening compared with the non-etched samples. AFM showed that film formed in the samples etched followed by oxide thickening is more compact and has smoother appearance than the oxide thickening samples without etching. 5. Etching process prior to oxide thickening plays an important role to enhance the distribution of Al-oxide uniformly and to prevent agglomeration of the surface Al-

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Fig. 5. Al 2s and Al 2p ratios of corroded KB and B.

oxide film and consequently the pitting corrosion resistance was improved. References
[1] R.L. Twite, G.P. Bierwagen, Progress in Organic Coatings 33 (1998) 91. [2] A.S. Hamdy, A.M. Beccaria, P. Traverso, Journal of Applied Electrochemistry 35 (2005) 473. [3] B.R.W. Hinton, D.R. Arnott, N.E. Ryan, Materials Performance 8 (1987) 42. [4] B.R.W. Hinton, D.R. Arnott, N.E. Ryan, Materials Forum 9 (1986) 162. [5] A.E. Hughes, B.R.W. Hinton, R. Taylor, M. Henderson, K. Nelson, L. Wilson, S.A. Nugent, International Patent application No. PCT/AU94/ 00539, International Patent No.WO95/08008. [6] S. Lin, H. Shih, F. Mansfeld, Corrosion Science 33 (1992) 1331. [7] M. Dabal, L. Armelao, A. Buchberger, L. Calliari, 2nd International Symposium on Aluminum Surface Science and Technology, 2125 May, UMIST, Manchester, England, 2000, Paper No. 97. [8] A.S. Hamdy, Corrosion Protection of Aluminum Composites by Silicate/ Cerate Conversion Coatings, Surface Coatings and Technology, in press (Available online). [9] A.S. Hamdy, Ph.D. dissertation, Faculty of Science, University of Cairo, Feb. 2003. [10] K. Aramaki, Corrosion Science 43 (2001) 591. [11] A.R. Trueman, A.E. Hughes, G. McAdam, B.R.W. Hinton, 2nd International Symposium on Aluminum Surface Science and Technology, 2125 May, UMIST, Manchester, England, 2000, p. 270. [12] A.S. Hamdy, A.M. Beccaria, R. Spiniello, Corrosion Prevention and Control 48 (2001) 101. [13] A.S. Hamdy, A.M. Beccaria, Corrosion protection of aluminum metal matrix composites by cerium conversion coatings, Surface and Interface Analysis 34 (2002) 171175. [14] A.S. Hamdy, A.M. Beccaria, Cerium conversion coatings: a new era of chrome-free pretreatments, 21st Annual Conference Corrosion Problems

[15] [16]

[17]

[18]

[19]

[20]

in Industry, Dec. 1720, Egyptian Corrosion Society, Sharm El-Sheikh, Red Sea City, Egypt, 2002. L.S. Kasten, J.T. Grant, N. Grebasch, N. Voevodin, F.E. Arnold, M.S. Donley, Surface and Coatings Technology 140 (2001) 11. A.S. Hamdy, A.A. Ismail, A.K. Ismail, D.P. Butt, Novel anti-corrosion nano-sized vanadia-based thin films prepared by solgel method for aluminum alloys, 4th Japanese-Mediterranean Workshop on Applied Electromagnetic Engineering for Magnetic, Superconducting and Nano Materials, (JAPMED'4), Sheraton Cairo Hotel, Egypt, September 1720, 2005. A.S. Hamdy, A.K. Ismail, D.P. Butt, A.A. Ismail, Comparative Studies on Anticorrosion Nano-Particle Silica-, Ceria-and Molybdate Based Thin Films Adsorbed on Aluminum Alloys, Presented at the International Symposium on the Role of Adsorbed Films and Particulate Systems in Nano and Biotechnologies, August 24-26, 2005, Gainesville, Florida. Coorganized by the Particle Engineering Research Center (PERC) and the Center for Surface Science and Engineering, University of Florida, USA. A.S. Hamdy, Review: corrosion protection via solgel derived nano-sized thin films, 22nd Annual Conference Corrosion Problems In Industry, Dec. 811, Egyptian Corrosion Society, Ain El-Sukhna beach, Red Sea Resort, Egypt, 2003. A. S. Hamdy, A.K. Ismail, D.P. Butt, A.A. Ismail, Sol-gel Prepared AntiCorrosion Vanadia-Based Ceramic Coatings for 6061-T6 Aluminum Alloy, Presented at the International Symposium on the Role of Adsorbed Films and Particulate Systems in Nano and Biotechnologies, August 2426, 2005, Gainesville, Florida. Co-organized by the Particle Engineering Research Center (PERC) and the Center for Surface Science and Engineering, University of Florida, USA. A.S. Hamdy, A.A. Ismail, A.K. Ismail, Newly developed silica-based ceramic coatings prepared by solgel technology for aluminum alloys, Presented at the 23rd Annual Conference Corrosion Problems in Industry, Dec. 69, Egyptian Corrosion Society, Nozha Beach Resort Red Sea, Egypt, 2004.