Journal of Sol-Gel Science and Technology

, Volume 70, Issue 1, pp 90–103 | Cite as

A hybrid organic–inorganic sol–gel coating for protecting aluminium alloy 7075-T6 against corrosion in Harrison’s solution

  • Peter Rodič
  • Jernej Iskra
  • Ingrid Milošev
Original Paper


A two-step procedure for synthesizing a new type of hybrid coating is presented. Coatings were synthesized from tetraethyl orthosilicate, 3-(trimethoxysilyl)propyl methacrylate and zirconium(IV) propoxide (ZTP). Zirconium(IV) propoxide was chelated with methacrylic acid. The synthesis, which proceeded at room temperature, was optimized using in situ Fourier transform infrared spectroscopy (FTIR). The effects of ZTP content, ageing and Zr/Si ratio were investigated. The viscosity of the sols increased with the ratio of Zr to Si. The terminal stability of the hybrid coatings was determined by thermogravimetric analysis and their composition and morphology analyzed by FTIR and scanning electron microscopy combined with energy dispersive X-ray spectroscopy. Sols were deposited on the aluminium AA7075-T6 substrate by spin-coating. The corrosion properties in dilute Harrison’s solution of samples coated by hybrid coatings were determined by electrochemical polarization methods. The coatings substantially improved the corrosion resistance of the substrate, as shown by a broad range of passivity extending up to high electrode potentials. The degree of protection was dependent on the content of zirconium and the time of ageing. The strong corrosion protection was ascribed to the bonding between silicon, oxygen and zirconium (Si–O–Si, Si–O–Zr), as proved by the FTIR analysis.


AA7075-T6 aluminium alloy Hybrid sol–gel coating FTIR Zirconium(IV) propoxide Harrison’s solution 



The authors thank Barbara Kapun, BSc, for valuable technical help and Prof. Barbara Malič for fruitful discussions regarding the FTIR analysis of solid samples and viscosity measurements. The financial support by the Slovenian Research Agency is acknowledged.


  1. 1.
    Davis JR (1999) Corrosion of aluminum and aluminum alloys. ASM International, USAGoogle Scholar
  2. 2.
    Chou T, Chandrasekaran C, Cao G (2003) J Sol-Gel Sci Technol 26:321–327CrossRefGoogle Scholar
  3. 3.
    Kendig MW, Buchheit RG (2003) Corrosion 59:379–400CrossRefGoogle Scholar
  4. 4.
    Dimitriev Y, Ivanova Y, Iordanova R (2008) J Univ Chem Technol Metall 43:181–192Google Scholar
  5. 5.
    Twite RL, Bierwagen GP (1998) Prog Org Coat 33:91–100CrossRefGoogle Scholar
  6. 6.
    Bierwagen G, Brown R, Battocchi D, Hayes S (2010) Prog Org Coat 68:48–61CrossRefGoogle Scholar
  7. 7.
    Restriction of Hazardous Substance Directive (ROHS) 2002/95/EC,
  8. 8.
    Zheng SX, Li JH (2010) J Sol-Gel Sci Technol 54:174–187CrossRefGoogle Scholar
  9. 9.
    Wen J, Wilkes GL (1996) Chem Mater 8:1667–1681CrossRefGoogle Scholar
  10. 10.
    Han Y-H, Taylor A, Mante MD, Knowles KM (2007) J Non-Cryst Solids 353:313–320CrossRefGoogle Scholar
  11. 11.
    Guglielmi M (1997) J Sol-Gel Sci Technol 8:443–449Google Scholar
  12. 12.
    Metroke TL, Parkhill LR, Knobbe TE (2001) Prog Org Coat 41:233–238CrossRefGoogle Scholar
  13. 13.
    Zheludkevich ML, Salvado IM, Ferreira MGS (2005) J Mater Chem 15:5099–5111CrossRefGoogle Scholar
  14. 14.
    Oubaha M, Etienne P, Calas S, Sempere R, Nedelec JM, Moreau Y (2005) J Non-Cryst Solids 351:2122–2128CrossRefGoogle Scholar
  15. 15.
    Pirhady Tavandashti N, Sanjabi S, Shahrabi T (2009) Prog Org Coat 65:182–186CrossRefGoogle Scholar
  16. 16.
    Du Joshua Y, Damron M, Tang G, Zheng H, Chu C-J, Osborne JH (2001) Prog Org Coat 41:226–232CrossRefGoogle Scholar
  17. 17.
    Voevodin NN, Grebasch NT, Soto WS, Kasten LS, Grant JT, Arnold FE, Donley MS (2001) Prog Org Coat 41:287–293CrossRefGoogle Scholar
  18. 18.
    Rajath Varma PC, Colreavy J, Cassidy J, Oubaha M, McDonagh C, Duffy B (2010) Thin Solid Films 518:5753–5761CrossRefGoogle Scholar
  19. 19.
    Andreatta F, Paussa L, Lanzutti A, Rosero Navaro NC, Aparicio M, Castro Y, Duran A, Ondratschek D, Fedrizzi L (2011) Prog Org Coat 72:3–14CrossRefGoogle Scholar
  20. 20.
    Zheludkevich ML, Serra R, Montemor MF, Miranda Salvado IM, Ferreira MGS (2006) Surf Coat Technol 200:3084–3094CrossRefGoogle Scholar
  21. 21.
    Girardi F, Graziola F, Aldighieri P, Fedrizzi L, Gross S, Di Maggio R (2008) Prog Org Coat 62:376–381CrossRefGoogle Scholar
  22. 22.
    Hosseini SMA, Jafari AH, Jamalizedah E (2009) Electrochim Acta 54:7207–7213CrossRefGoogle Scholar
  23. 23.
    Voevodin NN, Grebasch NT, Soto WS, Arnold FE, Donley MS (2001) Surf Coat Technol 140:24–28CrossRefGoogle Scholar
  24. 24.
    Zheludkevich ML, Serra R, Montemor MF, Yasakau KA, Miranda Salvado IM, Ferreira MGS (2005) Electrochim Acta 51:208–217CrossRefGoogle Scholar
  25. 25.
    Schem M, Schmidt T, Gerwann J, Mittmar M, Veith M, Thompson GE, Molchan IS, Hashimoto T, Skeldon P, Phani AR, Santucci S, Zheludkevich ML (2009) Corrosion Sci 51:2304–2315CrossRefGoogle Scholar
  26. 26.
    Montemor MF, Trabelsi W, Lamaka SV, Yasakau KA, Zheludkevich ML, Bastos AC, Ferreira MGS (2008) Electrochim Acta 53:5913–5922CrossRefGoogle Scholar
  27. 27.
    Gonzales E, Pavez J, Azocar I, Zagal JH, Zhou X, Melo F, Thompson GE, Páez MA (2011) Electrochim Acta 56:7586–7595CrossRefGoogle Scholar
  28. 28.
    Nass R, Schmidt H, Arpac E (1990) SPIE 1328:258–263CrossRefGoogle Scholar
  29. 29.
    Datchary W, Mehner A, Zong HW, Lucca DA, Klopfstein MJ, Ghisleni R, Grimme D, Brinksmeier E (2005) J Sol-Gel Sci Technol 35:245–251CrossRefGoogle Scholar
  30. 30.
    Del Monte F, Cheben P, Grover CP, Mackenzie JD (1999) J Sol-Gel Sci Technol 15:73–85CrossRefGoogle Scholar
  31. 31.
    Oubaha M, Smaili M, Etinne P, Coudray P, Moreau Y (2003) J Non-Cryst Sol 318:305–313CrossRefGoogle Scholar
  32. 32.
    Twite R, Balbyshev S, Bierwagen G (1997) In: Taylor SR, Isaacs HG, Drooman EW (eds) Proceedings of symposium on environmentally acceptable inhibitors and coatings, special publication of the electrochemical society, vol 95–16, p 202Google Scholar
  33. 33.
    Brinker CJ, Scherer GW (1990) Sol-gel science. The physics and chemistry of sol-gel processing. Academic Press, San Diego, p 358Google Scholar
  34. 34.
    Pellice SA, Williams RJJ, Sobrados I, Sanz J, Castro Y, Aparicio M, Duran A (2006) J Mater Chem 16:3318–3325CrossRefGoogle Scholar
  35. 35.
    Chmel A, Mazurina EK, Shashkin VS (1990) J Non-Cryst Solids 122:285–290CrossRefGoogle Scholar
  36. 36.
    Chan C-K, Peng S-L, Chu I-M, Ni S-C (2001) Polymer 42:4189–4196CrossRefGoogle Scholar
  37. 37.
    Graziola F, Girardi F, Bauer M, di Maggio R, Rovezzi M, Bertagnolli H, Sada C, Rossetto G, Gross S (2008) Polymer 49:4332–4343CrossRefGoogle Scholar
  38. 38.
    Khaled SM, Sui R, Charpentier PA, Rizkalla AS (2007) Langmuir 23:3988–3995CrossRefGoogle Scholar
  39. 39.
    Rajath Varma PC, Colreavy J, Cassidy J, Oubaha M, Duffy B, McDonagh C (2009) Prog Org Coat 66:406–411CrossRefGoogle Scholar
  40. 40.
    Sorek Y, Zevin M, Reisfeld R, Hurvist T, Ruschin S (1997) Chem Mater 9:670–676CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2014

Authors and Affiliations

  1. 1.Department of Physical and Organic ChemistryJožef Stefan InstituteLjubljanaSlovenia
  2. 2.Centre of Excellence for Integrated Approaches in Chemistry and Biology of ProteinsCIPKeBiPLjubljanaSlovenia

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