Morphology and structure of oxide thin films obtained by the sol-gel method: a review

  • 1 Bulgarian Academy of Sciences, Institute of Metal Science, Equipment and Technologies with Hydro- and Aerodynamics Centre “Acad. Angel Balevski”, Bulgaria


One-component CeO2 coatings and bi-component CeO2/ZrO2 multilayer coatings were obtained by a sol gel process. The phase composition, surface morphology and roughness of the samples were studied by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), Atomic force microscopy (AFM) and X-ray scanning electron microscopy (XPS). The corrosion resistance and protective ability were characterized by using salty solution of 3.5% NaCl at 25 C. The multilayer configuration of CeO2 and ZrO2 ensure enhanced protection of the steel in comparison to the single CeO2 coatings and uncoated steel. The surface morphology and anticorrosion properties depend significantly on the treatment temperature of both CeO2 underlayer and ZrO2 top layer. At lower treatment temperatures, they are relatively dense and smooth. The corrosion resistance of the multilayers slows down, when ZrO2 coatings were heated above 500oC. This probably is due to the more pronounced crystallization of cubic zirconium dioxide, resulting in deeper boundaries between the individual grains. The protective properties of a CeO2/ZrO2 multilayers could be attributed to the low crystallized structure with very fine crystallites.



  1. G.P. Bierwagen, L. He, J. Li, L. Ellingson, D.E. Tallman, Studies of a new accelerated evaluation method for coating corrosion resistance thermal cycling testing, Prog. Org. Coat. (2000) 39 67-78.
  2. M. Sreemany, A. Bose, S. Sen, A study on structural, optical, electrical and microstructural properties of thin TiOx films upon thermal oxidation: Effect of substrate temperature and oxidation temperature, Physica B: Condensed Matter (2010) 405 / 1 85-93.
  3. E. Setare, K. Raeissi, M.A. Golozar, M.H. Fathi, J. Corros. Sci. (2009) 51 1802.
  4. G.A. Battiston, R. Gerbasi, A. Gregori, M. Porchia, S. Cattarin, G.A. Rizzi, PECVD of amorphous TiO2 thin films: Effect of growth temperature and plasma gas composition, Thin Solid Films (2000) 371 126-131.
  5. Y. Wang, W. Tiana, T. Zhang, Y. Yang, Corros. Sci. (2009) 51 2924.
  6. A. Perez, A. Billard, C. Rébéré, C. Berziou, S. Touzain, J. Creus, Corros. Sci. (2013) 74 240.
  7. P. Eiamchai, P. Chindaudom, A. Pokaipisit, P. Limsuwan, A spectroscopic ellipsometry study of TiO2 thin films prepared by ion-assisted electron-beam evaporation, Curr. Appl. Phys. (2009) 9 707- 712.
  8. E. György, G. Socol, E. Axente, I.N. Mihailescu, C. Ducu, S. Ciuca, Anatase phase TiO2 thin films obtained by pulsed laser deposition for gas sensing applications, Appl. Surf. Sci. (2005) 247/1 429-433.
  9. S. M. Waita, B. O. Aduda, J. M. Mwabora, C. G. Granqvist, S. Lindquist, G. A. Niklasson, A. Hagfeldt, G. Boschloo, Electron transport and recombination in dye sensitized solar cells fabricated from obliquely sputter deposited and thermally annealed TiO2 films, J. Electroanal. Chem. (2007) 605 151-156.
  10. J. Aarik, A. Aidla, A.-A. Kiisler, T. Uustare, V. Sammelselg, Effect of crystal structure on optical properties of TiO2 films grown by atomic layer deposition, Thin Solid Films (1997) 305/1 270-273.
  11. P. Shinde, S.B. Sadale, P.S. Patil, P.N.Bhosale, A. Brüger, M. Neumann-Spallart, C.H. Bhosale, Properties of spray deposited titanium dioxide thin films and their application in photoelectrocatalysis, Solar Energy Materials and Solar Cells (2008) 92/3 283-290.
  12. B. Wafula, J. Simiyu, S. Waita, B. Aduda, J. Mwabora, Effect of nitration on pressed TiO2 Photoelectrodes for Dye-Sensitized solar cells, African J. Sci. Technol. (AJST), Science and Engineering Series (2007) 8/2 63-71.
  13. S. Schiller, G. Beister, W. Sieber, G. Schirmer, E. Hacke, Influence of deposition parameters on the optical and structural properties of TiO2 films produced by reactive dc plasmatron sputtering, Thin Solid Films (1981) 83 239-245.
  14. A. Trinchi, Y.X. Li, W. Wlodarski, S. Kaciulis, L. Pandolfi, E. Comini, G. Sberveglieri, Investigation of sol–gel prepared CeO2- TiO2 thin films for oxygen gas sensing, Sensors and Actuators B (2003) 95/1 145-150.
  15. R. B. Figueira, C. J. R. Silva, Hybrid sol-gel coatings for surface protection, In world scientific reference of hybrid materials, World scientific series in nanoscience and nanotechnology, World scientific: Singapore (2019) 145–192.
  16. A. P. Periyasamy, M. Venkataraman, D. Kremenakova, J. Militky, Y. Zhou, Progress in sol-gel technology for the coatings of fabrics, Review, Materials (2020) 13 1838, 1-34.
  17. Y. Ohko, Sh. Saitoh, T.Tatsuma and A. Fujishima, Photoelectrochemical Anticorrosion and Self-Cleaning Effects of a TiO2 Coating for Type 304 Stainless Steel, J. Electrochem. Soc. (2001) 148 B24-B28.
  18. E. Ghali, V. S. Sastri, M. Elboujdaini, Corrosion Prevention and Protection: Practical Solutions”, New York, John Wiley & Sons, USA (2007).
  19. A Ghasemi, T Shahrabi, A A Oskuie, H Hassannehad and S Sanjabi, Effect of heat treatment on corrosion properties of sol-gel titania–ceria nanocomposite coating, J. Alloys Comp. (2010) 504 237-242.
  20. L. Curkovic, H.O. Curkovic, S. Salopek, M.M. Renjo, S. Šegota. Enhancement of corrosion protection of AISI 304 stainless steel by nanostructured sol–gel TiO2 films, Corrosion Science (2013) 77 176-184.
  21. D. Guergova, E. Stoyanova, D. Stoychev, I. Avramova, P. Stefanov, Self-healing effect of ceria electrodeposited thin films on stainless steel in aggressive 0.5 mol/L NaCl aqueous solution, J. Rare Earths (2015) 33, 1212.
  22. W. Cheng, C. Li, X Ma, L. Yu and G. Liu, Effect of SiO2- doping on photogenerated cathodic protection of nano-TiO2 films on 304 stainless steel, Mater. & Design (2017) 126 155-161.
  23. M. R. Majdi, I. Danaee, S. S. S. Afghahi, Preparation and anti-corrosive properties of cerium oxide conversion coatings on steel X52. Mat. Res. (2017) 20 445–451.
  24. K. A. Yasakau, A. Kuznetsova, S. Kallip, M. Starykevich, J. Tedim et al., A novel bilayer system comprising LDH conversion layer and sol-gel coating for active corrosion protection of AA2024. Corros. Sci. (2018) 143 299–313.
  25. U. Tiringer, I. Milošev, A. Durán, Y. Castro, Hybrid sol–gel coatings based on GPTMS/TEOS containing colloidal SiO2 and cerium nitrate for increasing corrosion protection of aluminium alloy 7075-T6. J. Sol-Gel Sci. Technol. (2018) 85 546–557.
  26. V. Petkov, R. Valov, Effects of diamond nanoparticles on the microstructure, hardness and corrosion resistance of chromium coatings, American Journal of Chemical Engineering (2020) 8 6, 125-130.
  27. S. Yordanov, I. Stambolova, V. Blaskov, B. Jivov, S. Simeonova, S. Vassilev, L. Lakov, V. Dyakova, Corrosion Resistance of Samarium Doped TiO2 Sol-Gel Coatings, International Journal “NDT Days” (2020) III/3, pp. 164-168.
  28. S. Yordanov, B. Jivov, S. Simeonova, L. Lakov, V. Dyakova, M. Aleksandrova, M.Gacheva, I. Stambolova, Corrosion Resistance of TiO2 Films Grown on Stainless Steel, International Journal “NDT Days” (2021), IV/4, pp. 243-247.
  29. E. Nouria, M. Shahmiria, H. Reza Rezaiea, F. Talayianb, Surf. Coat. Technol. (2011) 205 5109.
  30. E. Nouri, M. Shahmiri, H. Reza Rezaie, F. Talayian, Surf. Coat. Technol. (2012) 206 3809.
  31. C. M. Malengreauxa, G. M.-L. Léonarda, S. L. Pirarda, I. Cimierib, S.D. Lamberta, J.R. Bartlettc, B. Heinrichsa, Chem. Eng. J. (2014) 243 537.
  32. S. R. Meher, L. Balakrishnan, Mater. Sci. Semicond. Process. (2014) 26 251.
  33. P. E. Johnson, P. Muttil, D. MacKenzie, E. C. Carnes, J. Pelowitz, N. A. Mara, W. M. Mook, S. D. Jett, D. R. Dunphy, G. S. Timmins, C. J. Brinker, ACS Nano (2015) 9 (7) 6961-6977.
  34. C. J. Brinker, G. W. Scherer, Sol–gel science. The physic and chemistry of sol–gel processing Academic Press, San Diego (1990).
  35. J. D. Wright, N. A. J. Sommerdijk, Sol-Gel Materials: Chemistry and Applications, Gordon and Breach Science Publishers (2001).
  36. R. X. Che, H. Gao, H. B. Zhao, J. X. Fang, Developing history and present situation of sol-gel science, Journal of Yunnan University (2005) 27(3A) 378-383.
  37. Gazala Ruhi, O. P. Modi, I. B. Singh, “Hot Corrosion Behavior of sol-gel Nano Structured Zirconia Coated 9Cr1Mo Ferritic Steel in Alkali Metal Chlorides and Sulphates Deposit Systems at High Temperatures, Journal of Surface Engineered Materials and Advanced Technology (2013) 3 55-60.
  38. W. Liu, Y. Chen, C. Ye, P. Zhang, Preparation and characterization of doped sol-gel zirconia films, Ceramics International (2002) 28/4 349-354.
  39. A. J. Lopez, J. Rams, and A. Urena, Sol-gel coatings of low sintering temperature for corrosion protection of ZE41 magnesium alloy, Surface and Coatings Technology (2011) 205/17-18 4183- 4191.
  40. A. R. Phani, F. J. Gammel, T. Hack, H. Haefke, Enhanced corrosion resistance by sol-gel-based ZrO2-CeO2 coatings on magnesium alloys, Mater. Corros. (2005) 56 (2) 77-82.
  41. V. Kozhukharov, S. Kozhukharov, G. Tsaneva, J. Gerwann, M. Schem, T. Schmidt, M. Veith, Investigation on the corrosion protection ability of nanocomposite hybrid coatings, Bulgarian Chemical Communications (2008) 40/3 310–317.
  42. G. Tsaneva, V. Kozhukharov, S. Kozhukharov, M. Ivanova, J. Gerwann, M. Schem, T. Schmidt, Functional nanocomposite coatings for corrosion protection of aluminum alloy and steel, Journal of Chemical Technology and Metallurgy (2008) 43/2 231- 238.
  43. I. Strawberige, P.F. James, The factors affecting the thickness of sol–gel derived silica coating prepared by dipping, J. Non-Cryst. Solids (1986) 86 381-393.
  44. C.J. Brinker, A.J. Hund, P.R. Shunk, G.C. Frye, C.S. Ashley, Review of sol–gel thin film formation, J. Non-Cryst. Solids (1992) 147/148 424-436.
  45. H. Kouzuka, S. Takenaka, S. Kimura, Nanoscale radiative striations of sol–gel-derived spin-coating films, Scripta Mater. (2001) 44 1807-1811.
  46. T. L.Metroke, R. L. Parhhill, E. T. Knobbe, Prog. Org. Coat. (2001) 41 233.
  47. S.K.Tiwari, M. Tripathi, R. Singh, Corros. Sci. (2012) 63 334.
  48. X.Q. Cao, R. Vassen, D. Stoever, Ceramic materials for thermal barrier coatings, J. Eur. Ceram. Soc. (2004) 24 1-10.
  49. K. W. Tenze, K. Valle, L. Bianchi, P. Belleville and N. Caron, Nanostructured Zirconia Coatings Processed by PROSOL Deposition, Surface and Coatings Technology (2008) 202/18 4349- 4354.
  50. P. Kiruthika, R. Subasri, A. Jyothirmayi, K. Sarvani, N. Y. Hebalkar, Effect of plasma surface treatment on mechanical and corrosion protection properties of UV-curable sol-gel based GPTS-ZrO2 coatings on mild steel, Surface and Coatings Technology (2010) 204/8 270-1276.
  51. S.K. Tiwari, M. Tripathi, R. Singh, Electrochemical behavior of zirconia based coatings on mild steel prepared by sol–gel method, Corros. Sci. 63 (2012) 334–341.
  52. W. K. Tan, H. Muto, G. Kawamura, Z. Lockman, A. Matsuda, (2021), Nanomaterial Fabrication through the Modification of Sol– Gel Derived Coatings, Review, Nanomaterials.
  53. Y. Gao, L. Zhao, X. Yao, R. Xiangyu and Zh. Tang, Surface Coat. Technol. 434 (2018) 2349.
  54. Bukhari S B, Imran M, Bashir M, Riaz S and Naseem Sh, J. Alloys and Compounds (2018) 767 1238.
  55. Chang Sue-min, Doong Ruey-an, Thin Solid Films (2005) 489 17
  56. E. Alat, A.T. Motta, R.J. Comstock, J.M. Partenzana, Multilayer (TiN, TiAlN) ceramic coatings for nuclear fuel cladding, J. Nucl. Mater. (2016) 478 236-244.
  57. Z. Lei, Q. Zhang, X. Zhu, D. Ma, F. Ma, Z. Song, Y.Q. Fu, Corrosion performance of ZrN/ZrO2 multilayer coatings deposited on 304 stainless steel using multi-arc ion plating, Appl. Surf. Sci. (2018) 431 170-176.
  58. E. Marin, L. Guzman, A. Lanzutti, W. Ensinger, L. Fedrizzi, Multilayer Al2O3/TiO2 Atomic Layer Deposition coatings for the corrosion protection of stainless steel, Thin Solid Films (2012) 522 283-288.
  59. G.R. Salazar-Band, S.R. Morae, A.J. Motheo, S.A.S. Machado, Anticorrosive cerium-based coatings prepared by the solegel method, J. Sol. Gel Sci. Technol. (2009) 52 415-423.
  60. M.L. Zheludkevich, R. Serra, M.F. Montemor, K.A. Yasakau, I.M.M. Salvado and M.G.S. Ferreira, Nanostructured sol–gel coatings doped with cerium nitrate as pre-treatments for AA2024- T3: corrosion protection performance, Electrochimica Acta (2005) 51 208-217.
  61. M.F. Montemor, M.G.S. Ferreira, Cerium salt activated nanoparticles as fillers for silane films: Evaluation of the corrosion inhibition performance on galvanised steel substrates, Electrochimica Acta (2007) 52 6976- 6987.
  62. M. F. Montemor, W. Trabelsi, S. V. Lamaka, K. A. Yasakau, M. L. Zheludkevich, Bastos A. C., Ferreira M. G. S., The synergistic combination of bis-silane and CeO2-ZrO2 nanoparticles on the electrochemical behaviour of galvanised steel in NaCl solutions, Electrochimica Acta (2008) 53(20) 5913-5922.
  63. Roohangiz Zandi Zand, Victoria Flexer, Michel De Keersmaecker, Kim Verbeken, Annemie Adriaens, Effects of Activated Ceria and Zirconia Nanoparticles on the Protective Behaviour of Si lane Coatings in Chloride Solutions, J. Electrochem. Sci., (2015) 10 997-1014.
  64. M.F. Montemor, A.M. Simões, M.G.S. Ferreira, M.J. Carmezim, Composition and Corrosion resistance of cerium conversion films on the AZ31 magnesium alloy and its relation to the salt anion, App. Surf. Sci. (2008), 254 1806-1814.
  65. C. Motte, N. Maury, M.-G. Olivier, J.-P. Petitjean, J.-F. Willem, Cerium treatments for temporary protection of electroplated steel, Surf. Coat. Technol. (2005) 200 2366-2375.
  66. A. Conde, M.A. Arenas, A. de Frutos, J. de Damborenea, Effective corrosion Protection of 8090 alloy by cerium conversion coatings, Electrochimica Acta (2008) 53 7760-7768.
  67. N.C. Rosero-Navarro, S.A. Pellice, A. Duran, M. Aparicio, Effects of Ce containing sol–gel coatings reinforced with SiO2 nanoparticles on the protection of AA2024, Corros. Sci. (2008) 50 1283-1291.
  68. A. Kartsonakis, A.C. Balaskas, E.P. Koumoulos, C.A. Charitidis, G.C. Kordas, Incorporation of ceramic nanocontainers into epoxy coatings for the corrosion protection of hot dip galvanized steel, Corros. Sci. (2012) 57 30-41.
  69. S.M.A. Shibli, F. Chacko, Development of nano CeO2- incorporated high performance hot-dip zinc coating, Surf. Coat. Technol. (2008) 202 4971-4975.
  70. G.R. Salazar-Banda, S.R. Moraes, A.J. Motheo, S.A.S. Machado, Anticorrosive cerium-based coatings prepared by the sol– gel method, J. Sol-Gel Sci. Technol. (2009) 52 415–423.
  71. Michele Fedel, Emanuela Callone, Matias Fabbian, Flavio Deflorian, Sandra Dirè, “Influence of Ce3+ doping on molecular organization of Si-based organic/inorganic sol-gel layers for corrosion protection”, Applied Surface Science (2017) 414 82–91.
  72. S. Yordanov, I. Stambolova, L. Lakov, B. Jivov, V. Blaskov, S. Vasilev, Effect of CeO2 dopant on the structure and protection properties of TiO2 sprayed coatings deposited on carbon steel, Journal of Chemical Technology and Metallurgy (2018) 53 (6) 1179-1185.
  73. S. Yordanov, I. Stambolova, V. Blaskov , L. Lakov, S. Vassilev, Y. Kostova, B. Jivov, Effect of treatment temperature of TiO2/SiO2 and ZrO2/SiO2 coatings on their corrosion stability, International Scientific Journal “Machines. Technologies. Materials” (2018) XII/5 222-224.
  74. S. Yordanov, I. Stambolova, V. Blaskov, L. Lakov, S. Vassilev, B. Jivov, Al. Elyas, Vl. Petkov, Anticorrosion sol-gel coatings of CeO2, ZrO2 and TiO2 deposited on SiO2 underlayer, International Journal “NDT Days” (2018) 1/3 308-313.
  75. S. Yordanov, I. Stambolova, L. Lakov, S. Vassilev, B. Jivov, Sol-gel CeO2 and ZrO2 coatings on CeO2: study of the phase composition, morphology and corrosion resistance, Comptes rendus de l’Acade'mie bulgare des Sciences (2019) 72 (1) 55-61.
  76. S. Yordanov, I. Stambolova, L. Lakov, S. Vassilev, B. Jivov, A. Nedelcheva-Bachvarova, Corrosion stability in salt medium of stainless steel and carbon steel, using different oxide sol gel coatings, International Scientific Journal - Materials Science. Non- Equilibrium Phase Transformations (2019), V / 1, 16-18.
  77. I. Stambolova, O. Dimitrov, S. Yordanov, L. Lakov, B. Jivov, S. Vassilev, V. Blaskov, M. Shipochka, Application of ZrO2 and ZrO2-TiO2 Coatings as Corrosion Barriers: Surface Composition and Structure, International Journal “NDT Days” (2019) II/2 160- 164, 2019.
  78. S. Yordanov, I. Stambolova, M. Shipochka, S. Simeonova, N. Grozev, L. Lakov, M. Aleksandrova, B. Jivov, V. Blaskov, Investigation of anticorrosive behavior of zirconia-titanium coatings in NaCl medium, International Scientific Journal "Machines. Technologies. Materials" (2020), XIV/1 34-36.
  79. S. Yordanov, I. Stambolova, L. Lakov, M. Aleksandrova, B. Jivov, V. Blaskov, N. Boshkov, Enhancement of corrosion resistance of steel, coated with various coatings on the base of SiO2, TiO2, ZrO2 and CeO2, International Scientific Journal "Materials Science. Non-equilibrium Phase Transformations" (2020) VI/1 15- 16.
  80. I. Stambolova, O. Dimitrov, M. Shipochka, S. Yordanov, V. Blaskov, S. Vassilev, B. Jivov, S. Simeonova, K. Balashev, N. Grozev, L. Lakov, Corrosion resistance of sol-gel ZrO2 coatings deposited on stainless steel, Journal of Physics: Conference Series (2020) 1492 (1) 012025.

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