[en] The doping of sol-gel coatings with inhibitive species and more particularly with cerium salts provides a promising potential to replace hexavalent chromium treatments used in aeronautical industry. This study aims at evaluating the impact of cerium salts (cerium chloride and cerium ammonium nitrate) on the film formation and the ageing of the coating properties during immersion in aggressive solution or humidity fluctuations in atmospheric conditions. The effect of cerium oxidation state (Ce3 + or Ce4 +) and concentration in cerium salts (500 and 1000 ppm of cerium) was studied after incorporation in a sol-gel solution composed of TEOS (tetraethoxysilane) and GPMTS (3-glycidyloxypropyl)trimethoxysilane. The stability of sol-gel solutions was determined using rheological measurements. After application by dip-coating on 1050 aluminium alloy, barrier properties of the films were evaluated by Electrochemical Impedance Spectroscopy (EIS) versus immersion time in 0.1 M NaCl solution. The internal stresses generated inside the films were measured using cantilever methods during humidity and hygrothermal cycles. The cerium salts do not change the viscosity, the stability of the solutions and the film thickness. The film resistance decreases more strongly in presence of cerium salts during immersion. Films containing tetravalent cerium salts are more sensitive to humidity fluctuations in atmospheric conditions.
Research center :
CRIM - Ingénierie des matériaux
Disciplines :
Chemistry Education & instruction
Author, co-author :
Druart, Marie-Eve ; Université de Mons > Faculté Polytechnique > Science des Matériaux
[1] Twite, R.L., Bierwagen, G.P., Review of alternatives to chromate for corrosion protection of aluminum aerospace alloys. Prog. Org. Coat. 33 (1998), 91–100.
[2] Zheludkevich, M.L., Miranda Salvado, I., Ferreira, M.G.S., Sol–gel coatings for corrosion protection of metals. J. Mater. Chem. 15 (2005), 5099–5111.
[3] Joshua Du, Y., Damron, M., Tang, G., Zheng, H., Chu, C.J., Osborne, J.H., Inorganic/organic hybrid coatings for aircraft aluminum alloy substrates. Prog. Org. Coat. 41 (2001), 226–232.
[4] Figueira, R.B., Silva, C.J.R., Pereira, E.V., Organic–inorganic hybrid sol–gel coatings for metal corrosion protection: a review of recent progress. J. Coat. Technol. Res. 12 (2015), 1–35.
[5] Deflorian, F., Rossi, S., Fedrizzi, L., Silane pre-treatments on copper and aluminium. Electrochim. Acta 51 (2006), 6097–6103.
[6] Latella, B.A., Ignat, M., Barbé, C.J., Cassidy, D.J., Li, H., Cracking and decohesion of sol-gel hybrid coatings on metallic substrates. J. Sol-Gel Sci. Technol. 31 (2004), 143–149.
[7] Parkhill, R.L., Knobbe, E.T., Donley, M.S., Application and evaluation of environmentally compliant spray-coated ormosil films as corrosion resistant treatments for aluminum 2024-T3. Prog. Org. Coat. 41 (2001), 261–265.
[8] Wu, K.H., Chang, T.C., Yang, C.C., Wang, G.P., Dynamics and corrosion resistance of amine-cured organically modified silicate coatings on aluminum alloys. Thin Solid Films 513 (2006), 84–89.
[10] Quinet, M., Neveu, B., Moutarlier, V., Audebert, P., Ricq, L., Corrosion protection of sol–gel coatings doped with an organic corrosion inhibitor: chloranil. Prog. Org. Coat. 58 (2007), 46–53.
[11] Zheludkevich, M.L., Yasakau, K.A., Bastos, A.C., Karavai, O.V., Ferreira, M.G.S., On the application of electrochemical impedance spectroscopy to study the self-healing properties of protective coatings. Electrochem. Commun. 9 (2007), 2622–2628.
[12] Pepe, A., Aparicio, M., Durán, A., Ceré, S., Cerium hybrid silica coatings on stainless steel AISI 304 substrate. J. Sol-Gel Sci. Technol. 39 (2006), 131–138.
[13] Montemor, M.F., Ferreira, M.G.S., Cerium salt activated nanoparticles as fillers for silane films: evaluation of the corrosion inhibition performance on galvanised steel substrates. Electrochim. Acta 52 (2007), 6976–6987.
[14] Montemor, M.F., Pinto, R., Ferreira, M.G.S., Chemical composition and corrosion protection of silane films modified with CeO2 nanoparticles. Electrochim. Acta 54 (2009), 5179–5189.
[15] Paussa, L., Rosero-Navarro, N.C., Andreatta, F., Castro, Y., Duran, A., Aparicio, M., Fedrizzi, L., Inhibition effect of cerium in hybrid sol–gel films on aluminium alloy AA2024. Surf. Interface Anal. 42 (2010), 299–305.
[16] Raps, D., Hack, T., Wehr, J., Zheludkevich, M.L., Bastos, A.C., Ferreira, M.G.S., Nuyken, O., Electrochemical study of inhibitor-containing organic–inorganic hybrid coatings on AA2024. Corros. Sci. 51 (2009), 1012–1021.
[17] Shi, H., Liu, F., Han, E., Corrosion behaviour of sol–gel coatings doped with cerium salts on 2024-T3 aluminum alloy. Mater. Chem. Phys. 124 (2010), 291–297.
[18] Trabelsi, W., Triki, E., Dhouibi, L., Ferreira, M.G.S., Zheludkevich, M.L., Montemor, M.F., The use of pre-treatments based on doped silane solutions for improved corrosion resistance of galvanised steel substrates. Surf. Coat. Technol. 200 (2006), 4240–4250.
[19] Haley, T.J., Pharmacology and toxicology of the rare earth elements. J. Pharm. Sci., 54, 1965.
[20] Greenwood, N.N., Earnshaw, A., Chemistry of the Elements. 1984, Pergamon Press.
[21] Bethencourt, M., Botana, F.J., Calvino, J.J., Marcos, M., RodrÍguez-Chacón, M.A., Lanthanide compounds as environmentally-friendly corrosion inhibitors of aluminium alloys: a review. Corros. Sci. 40 (1998), 1803–1819.
[22] Arenas, M.A., Bethencourt, M., Botana, F.J., de Damborenea, J., Marcos, M., Inhibition of 5083 aluminium alloy and galvanised steel by lanthanide salts. Corros. Sci. 43 (2001), 157–170.
[23] Li, F.-B., Newman, R.C., Thompson, G.E., In situ atomic force microscopy studies of electrodeposition mechanism of cerium oxide films: nucleation and growth out of a gel mass precursor. Electrochim. Acta 42 (1997), 2455–2464.
[24] Andreatta, F., Druart, M.E., Lanzutti, A., Lekka, M., Cossement, D., Olivier, M.G., Fedrizzi, L., Localized corrosion inhibition by cerium species on clad AA2024 aluminium alloy investigated by means of electrochemical micro-cell. Corros. Sci. 65 (2012), 376–386.
[25] Cabral, A.M., Trabelsi, W., Serra, R., Montemor, M.F., Zheludkevich, M.L., Ferreira, M.G.S., The corrosion resistance of hot dip galvanised steel and AA2024-T3 pre-treated with bis-[triethoxysilylpropyl] tetrasulfide solutions doped with Ce(NO3)3. Corros. Sci. 48 (2006), 3740–3758.
[26] Sugama, T., Cerium acetate-modified aminopropylsilane triol: a precursor of corrosion-preventing coating for aluminum-finned condensers. J. Coat. Technol. Res. 2 (2005), 649–659.
[27] Trabelsi, W., Cecílio, P., Ferreira, M.G.S., Yasakau, K., Zheludkevich, M.L., Montemor, M.F., Surface evaluation and electrochemical behaviour of doped silane pre-treatments on galvanised steel substrates. Prog. Org. Coat. 59 (2007), 214–223.
[28] Ansart, F., Bleta, R., Bonino, J.-P., Esteban, J., Jaubert, O., Gressier, M., Lenormand, P., Menu, M.-J., Xuereb, E., Bares, P., Process for the Anticorrosion Treatment of a Solid Metal Substrate and Treated Solid Metal Substrate Capable of Being Obtained by Such a Process. (Google Patents), 2012.
[29] Malfatti, C.F., Menezes, T.L., Radtke, C., Esteban, J., Ansart, F., Bonino, J.P., The influence of cerium ion concentrations on the characteristics of hybrid films obtained on AA2024-T3 aluminum alloy. Mater. Corros. 63 (2012), 819–827.
[30] Cambon, J.-B., Esteban, J., Ansart, F., Bonino, J.-P., Turq, V., Santagneli, S.H., Santilli, C.V., Pulcinelli, S.H., Effect of cerium on structure modifications of a hybrid sol–gel coating, its mechanical properties and anti-corrosion behavior. Mater. Res. Bull. 47 (2012), 3170–3176.
[31] Cambon, J.-B., Ansart, F., Bonino, J.-P., Turq, V., Effect of cerium concentration on corrosion resistance and polymerization of hybrid sol–gel coating on martensitic stainless steel. Prog. Org. Coat. 75 (2012), 486–493.
[32] Zhong, X., Li, Q., Hu, J., Yang, X., Luo, F., Dai, Y., Effect of cerium concentration on microstructure, morphology and corrosion resistance of cerium–silica hybrid coatings on magnesium alloy AZ91D. Prog. Org. Coat. 69 (2010), 52–56.
[33] Trabelsi, W., Cecilio, P., Ferreira, M.G.S., Montemor, M.F., Electrochemical assessment of the self-healing properties of Ce-doped silane solutions for the pre-treatment of galvanised steel substrates. Prog. Org. Coat. 54 (2005), 276–284.
[34] Suegama, P.H., de Melo, H.G., Benedetti, A.V., Aoki, I.V., Influence of cerium (IV) ions on the mechanism of organosilane polymerization and on the improvement of its barrier properties. Electrochim. Acta 54 (2009), 2655–2662.
[35] Suegama, P.H., Sarmento, V.H.V., Montemor, M.F., Benedetti, A.V., de Melo, H.G., Aoki, I.V., Santilli, C.V., Effect of cerium (IV) ions on the anticorrosion properties of siloxane-poly(methyl methacrylate) based film applied on tin coated steel. Electrochim. Acta 55 (2010), 5100–5109.
[36] Hammer, P., Schiavetto, M.G., dos Santos, F.C., Benedetti, A.V., Pulcinelli, S.H., Santilli, C.V., Improvement of the corrosion resistance of polysiloxane hybrid coatings by cerium doping. J. Non-Cryst. Solids 356 (2010), 2606–2612.
[37] Pepe, A., Aparicio, M., Ceré, S., Durán, A., Preparation and characterization of cerium doped silica sol–gel coatings on glass and aluminum substrates. J. Non-Cryst. Solids 348 (2004), 162–171.
[38] Montemor, M.F., Ferreira, M.G.S., Electrochemical study of modified bis-[triethoxysilylpropyl] tetrasulfide silane films applied on the AZ31 Mg alloy. Electrochim. Acta 52 (2007), 7486–7495.
[39] Garcia-Heras, M., Jimenez-Morales, A., Casal, B., Galvan, J.C., Radzki, S., Villegas, M.A., Preparation and electrochemical study of cerium–silica sol–gel thin films. J. Alloys Compd. 380 (2004), 219–224.
[40] Olivier, M.-G., Romano, A.-P., Vandermiers, C., Mathieu, X., Poelman, M., Influence of the stress generated during an ageing cycle on the barrier properties of cataphoretic coatings. Prog. Org. Coat. 63 (2008), 323–329.
[41] Perera, D., Oosterbroek, M., Hygrothermal stress evolution during weathering in organic coatings. J. Coatings Technol. 66 (1994), 83–88.
[42] Perera, D.Y., On adhesion and stress in organic coatings. Prog. Org. Coat. 28 (1996), 21–23.
[43] Perera, D.Y., Effect of thermal and hygroscopic history on physical ageing of organic coatings. Prog. Org. Coat. 44 (2002), 55–62.
[44] Romano, A.P., Olivier, M.G., Vandermiers, C., Poelman, M., Influence of the curing temperature of a cataphoretic coating on the development of filiform corrosion of aluminium. Prog. Org. Coat. 57 (2006), 400–407.
[45] Druart, M.-E., Richir, J.-B., Poirier, C., Maseri, F., Godeau, N., Langer, L., Olivier, M., Influence of sol-gel application conditions on metallic substrate for optical applications corrosion engineering. Sci. Technol. 46 (2011), 677–684.
[46] Jurgens, E., Mager, M., Ittera, U., Wenkin, M., Piens, M., Internal stesses in inorganic-organic hybrid coatings for plastics. Pitture e vernici 84 (2008), 23–32.
[47] Capelossi, V.R., Poelman, M., Recloux, I., Hernandez, R.P.B., de Melo, H.G., Olivier, M.G., Corrosion protection of clad 2024 aluminum alloy anodized in tartaric-sulfuric acid bath and protected with hybrid sol–gel coating. Electrochim. Acta 124 (2014), 69–79.
[48] Zheludkevich, M.L., Serra, R., Montemor, M.F., Yasakau, K.A., Salvado, I.M.M., Ferreira, M.G.S., Nanostructured sol–gel coatings doped with cerium nitrate as pre-treatments for AA2024-T3: corrosion protection performance. Electrochim. Acta 51 (2005), 208–217.
[50] Franquet, A., Le Pen, C., Terryn, H., Vereecken, J., Effect of bath concentration and curing time on the structure of non-functional thin organosilane layers on aluminium. Electrochim. Acta 48 (2003), 1245–1255.
[51] Brinker, C.J., Scherer, G.W., Sol-Gel Science: The Physics and Chemistry of Sol-Gel Processing Academic Press. 1990.
[52] J.G., K., Properties of Aluminum Alloys: Tensile, Creep, and Fatigue Data at High and Low temperatures. 1999.
[53] Perera, D.Y., Effect of pigmentation on organic coating characteristics. Prog. Org. Coat. 50 (2004), 247–262.
[54] Landau, L.D., Levich, B.G., Dragging of liquid by a plate. Acta Physicochim. 17 (1942), 42–54.
[55] Kasten, L.S., Grant, J.T., Grebasch, N., Voevodin, N., Arnold, F.E., Donley, M.S., An XPS study of cerium dopants in sol–gel coatings for aluminum 2024-T3. Surf. Coat. Technol. 140 (2001), 11–15.
[56] Olivier, M.G., Fedel, M., Sciamanna, V., Vandermiers, C., Motte, C., Poelman, M., Deflorian, F., Study of the effect of nanoclay incorporation on the rheological properties and corrosion protection by a silane layer. Prog. Org. Coat. 72 (2011), 15–20.
[57] Perera, D.Y., Nguyen, T., Hygroscopic stress and failure of coating/metal systems. Double Liaison 43 (1996), 66–71.