Hydrophobic, organic–inorganic hybrid sol–gel coatings containing boehmite nanoparticles for metal corrosion protection

  • Ömer KesmezEmail author
Original Paper


In this study, fluoro-functionalized hydrophobic/oleophobic hybrid nanocomposite coatings, which are highly resistant and transparent, long-lasting and mechanically stable, have been deposited on metal substrate surfaces by the sol–gel method. Organic–inorganic hybrid matrix was prepared using tetraethoxysilane and organically modified silicon alkoxide, namely 3-(glycidyloxypropyl) trimethoxysilane. Additionally, to increase hydrophobic behavior, a fluorinated silica-alkoxide precursor and AlO(OH) NPs were added to the hybrid matrix. Water and n-hexadecane contact angle, surface morphologies, thicknesses and surface roughness of the films were determined. Additionally, optical characterizations and mechanical properties of the films such as light transmittance, haze, clarity, gloss were investigated. A salt spray corrosion test and electrochemical corrosion measurements were also performed. Optimum properties were acquired in the hydrophobic hybrid nanocomposite coating containing 15 wt% of 3 nm AlO(OH) NPs.

Graphical abstract


Functional coatings Hybrid sol–gel matrix AlO(OH) NPs Hydrophobicity Corrosion protection 



I gratefully acknowledge financial support of the Akdeniz University Research Found. Help of Dr. Edip Bayram (Akdeniz University) for electrochemical analysis is gratefully acknowledged.

Compliance with ethical standards

Conflict of interest

The author declares that they have no conflict of interest.


  1. Altinbalik MT, Mutlu S (2014) A comparative cost analysis between conventional and progressive draw die. Int J Mod Manuf Technol VI(1).
  2. Arukalam IO, Oguzie EE, Li Y (2018) Nanostructured superhydrophobic polysiloxane coating for high barrier and anticorrosion applications in marine environment. J Colloid Interface Sci 512:674–685. CrossRefGoogle Scholar
  3. ASTM D523–14 (2014) Standard test method for specular gloss. ASTM Int. Google Scholar
  4. Ates M, Dolapdere A (2015) Electrochemical polymerization of thiophene and poly(3-hexyl)thiophene, nanocomposites with TiO2, and corrosion protection behaviors. Polym Plast Technol Eng 54(17):1780–1786. CrossRefGoogle Scholar
  5. Baghery P, Farzam M, Mousavi AB, Hosseini M (2010) Ni–TiO2 nanocomposite coating with high resistance to corrosion and wear. Surf Coat Technol 204(23):3804–3810. CrossRefGoogle Scholar
  6. Basu BJ, Hariprakash V, Aruna ST, Lakshmi RV, Manasa J, Shruthi BS (2010) Effect of microstructure and surface roughness on the wettability of superhydrophobic sol–gel nanocomposite coatings. J Sol Gel Sci Technol 56(3):278–286. CrossRefGoogle Scholar
  7. Corcione CE, Frigione M (2012) UV-cured polymer-boehmite nanocomposite as protective coating for wood elements. Prog Org Coat 74(4):781–787. CrossRefGoogle Scholar
  8. ČSN ISO 9227 (2007) Corrosion tests in artificial atmospheres—salt spray tests. European Standard EN ISO 9227:2006Google Scholar
  9. D3359-09 (2013) Standard test methods for measuring adhesion by tape test. ASTM. Google Scholar
  10. Decker C, Keller L, Zahouily K, Benfarhi S (2005) Synthesis of nanocomposite polymers by UV-radiation curing. Polymer 46(17):6640–6648. CrossRefGoogle Scholar
  11. García SJ, Fischer HR, Van Der Zwaag S (2011) A critical appraisal of the potential of self healing polymeric coatings. Prog Org Coat 72(3):211–221. CrossRefGoogle Scholar
  12. Gerhardus K, Jeff V, Thopson N, Moghissi O, Gould M, Payer J (2016) International measures of prevention, application, and economics of corrosion technologies study. pp 1–216.
  13. Guo Z, Zhou F, Hao J, Liu W (2006) Effects of system parameters on making aluminum alloy lotus. J Colloid Interface Sci 303(1):298–305. CrossRefGoogle Scholar
  14. Haas KH, Wolter H (1999) Synthesis, properties and applications of inorganic–organic copolymers (ORMOCER®s). Curr Opin Solid State Mater Sci 4(6):571–580. CrossRefGoogle Scholar
  15. Haas KH, Amberg-Schwab S, Rose K, Schottner G (1999) Functionalized coatings based on inorganic–organic polymers (ORMOCER®s) and their combination with vapor deposited inorganic thin films. Surf Coat Technol 111(1):72–79. CrossRefGoogle Scholar
  16. Hornberger H, Virtanen S, Boccaccini AR (2012) Biomedical coatings on magnesium alloys—a review. Acta Biomater 8(7):2442–2455. CrossRefGoogle Scholar
  17. ISO 1518-2:2011 (2011) Paints and varnishes—Determination of scratch resistance—part 2: variable-loading method.
  18. ISO 15184:2012 (2012) Paints and varnishes—determination of film hardness by pencil test.
  19. Jeong HJ, Kim DK, Lee SB, Kwon SH, Kadono K (2001) Preparation of water-repellent glass by sol–gel process using perfluoroalkylsilane and tetraethoxysilane. J Colloid Interface Sci 235(1):130–134. CrossRefGoogle Scholar
  20. Kesmez Ö (2019) Preparation of UV-curable hybrid films via sol–gel synthesis for hydrophobic surface applications. J Sol Gel Sci Technol 91(1):1–10. CrossRefGoogle Scholar
  21. Kesmez Ö, Akarsu E (2017) Corrosion-resistant hybrid coatings for copper surfaces substrates by sol–gel chemistry. J Turk Chem Soc Sect A Chem 4(Sp. is. 1):1. Google Scholar
  22. Kesmez Ö, Erdem Çamurlu H, Burunkaya E, Arpaç E (2009) Sol–gel preparation and characterization of anti-reflective and self-cleaning SiO2–TiO2 double-layer nanometric films. Sol Energy Mater Sol Cells 93(10):1833–1839. CrossRefGoogle Scholar
  23. Kesmez Ö, Kiraz N, Burunkaya E, Çamurlu HE, Asiltürk M, Arpaç E (2010) Effect of amine catalysts on preparation of nanometric SiO2 particles and antireflective films via sol–gel method. J Sol Gel Sci Technol. Google Scholar
  24. Kesmez Ö, Akarsu E, Çamurlu HE, Yavuz E, Akarsu M, Arpaç E (2017) Preparation and characterization of multilayer anti-reflective coatings via sol–gel process. Ceram Int. Google Scholar
  25. Kiraz N, Burunkaya E, Kesmez Ö, Asiltürk M, Çamurlu HE, Arpaç E (2010) Sol–gel synthesis of 3-(triethoxysilyl)propylsuccinicanhydride containing fluorinated silane for hydrophobic surface applications. J Sol Gel Sci Technol. Google Scholar
  26. Koene BE, Martin R, Goff A, Hay J (2016) Durable hydrophobic coatings for corrosion protection. Adv Mater TechConnect Briefs 2016(1):229–232Google Scholar
  27. Lakshmi RV, Bharathidasan T, Basu BJ (2011) Superhydrophobic sol–gel nanocomposite coatings with enhanced hardness. Appl Surf Sci 257(24):10421–10426. CrossRefGoogle Scholar
  28. Lakshmi RV, Bharathidasan T, Bera P, Basu BJ (2012) Fabrication of superhydrophobic and oleophobic sol–gel nanocomposite coating. Surf Coat Technol 206(19–20):3888–3894. CrossRefGoogle Scholar
  29. Lakshmi RV, Bera P, Anandan C, Basu BJ (2014) Effect of the size of silica nanoparticles on wettability and surface chemistry of sol–gel superhydrophobic and oleophobic nanocomposite coatings. Appl Surf Sci 320:780–786. CrossRefGoogle Scholar
  30. Larena A, Millán F, Verdú M, Pinto G (2001) Surface roughness characterisation of multilayer polymer films for graphic arts applications. Appl Surf Sci 174(3–4):217–224. CrossRefGoogle Scholar
  31. Liu J, Silveira J, Groarke R, Parab S, Singh H, McCarthy E, Brabazon D (2019) Effect of powder metallurgy synthesis parameters for pure aluminium on resultant mechanical properties. Int J Mater Form 12(1):79–87. CrossRefGoogle Scholar
  32. Maeztu JD, Rivero PJ, Berlanga C, Bastidas DM, Palacio JF, Rodriguez R (2017) Effect of graphene oxide and fluorinated polymeric chains incorporated in a multilayered sol–gel nanocoating for the design of corrosion resistant and hydrophobic surfaces. Appl Surf Sci 419:138–149. CrossRefGoogle Scholar
  33. Milošev I, Kapun B, Rodič P, Iskra J (2015) Hybrid sol–gel coating agents based on zirconium(IV) propoxide and epoxysilane. J Sol Gel Sci Technol 74(2):447–459. CrossRefGoogle Scholar
  34. Ming W, Melis F, Van de Grampel RD, Van Ravenstein L, Tian M, Van der Linde R (2003) Low surface energy films based on partially fluorinated isocyanates: the effects of curing temperature. Prog Org Coat 48(2–4):316–321. CrossRefGoogle Scholar
  35. Mishra T, Mohanty AK, Tiwari SK (2013) Recent development in clay based functional coating for corrosion protection. Key Eng Mater 571(July):93–109. CrossRefGoogle Scholar
  36. Mohamed AMA, Abdullah AM, Younan NA (2015) Corrosion behavior of superhydrophobic surfaces: a review. Arabian J Chem 8(6):749–765. CrossRefGoogle Scholar
  37. Montemor MF (2014) Functional and smart coatings for corrosion protection: a review of recent advances. Surf Coat Technol 258:17–37. CrossRefGoogle Scholar
  38. Phani AR, Santucci S (2006) Evaluation of structural and mechanical properties of aluminum oxide thin films deposited by a sol–gel process: comparison of microwave to conventional anneal. J Noncryst Solids 352(38–39):4093–4100. CrossRefGoogle Scholar
  39. Plueddemann EP (1983) Silane adhesion promoters in coatings. Prog Org Coat 11(3):297–308. CrossRefGoogle Scholar
  40. Purcar V, Stamatin I, Cinteza O, Petcu C, Raditoiu V, Ghiurea M, Andronie A (2012) Fabrication of hydrophobic and antireflective coatings based on hybrid silica films by sol–gel process. Surf Coat Technol 206(21):4449–4454. CrossRefGoogle Scholar
  41. Rivero P, Maeztu J, Berlanga C, Miguel A, Palacio J, Rodriguez R (2018) Hydrophobic and corrosion behavior of sol–gel hybrid coatings based on the combination of TiO2 NPs and fluorinated chains for aluminum alloys protection. Metals 8(12):1076. CrossRefGoogle Scholar
  42. Schmidt H, Karnieli A (2000) Remote sensing of the seasonal variability of vegetation in a semi-arid environment. J Arid Environ 45(1):43–59. CrossRefGoogle Scholar
  43. Seok SI, Kim JH, Choi KH, Hwang YY (2006) Preparation of corrosion protective coatings on galvanized iron from aqueous inorganic–organic hybrid sols by sol–gel method. Surf Coat Technol 200(11):3468–3472. CrossRefGoogle Scholar
  44. Sheen YC, Huang YC, Liao CS, Chou HY, Chang FC (2008) New approach to fabricate an extremely super-amphiphobic surface based on fluorinated silica nanoparticles. J Polym Sci Part B Polym Phys. Google Scholar
  45. Shi Z, Jia JX, Atrens A (2012) Galvanostatic anodic polarisation curves and galvanic corrosion of high purity Mg in 3.5% NaCl saturated with Mg(OH) 2. Corros Sci 60:296–308. CrossRefGoogle Scholar
  46. Shi X, Yu K, Jiang L, Li C, Li Z, Zhou X (2018) Microstructural characterization of Ni-201 weld cladding onto 304 stainless steel. Surf Coat Technol 334(November 2017):19–28. CrossRefGoogle Scholar
  47. Tang C, Liu W, Ma S, Wang Z, Hu C (2010) Synthesis of UV-curable polysiloxanes containing methacryloxy/fluorinated side groups and the performances of their cured composite coatings. Prog Org Coat 69(4):359–365. CrossRefGoogle Scholar
  48. Tatar P, Kiraz N, Asiltürk M, Sayilkan F, Sayilkan H, Arpaç E (2007) Antibacterial thin films on glass substrate by sol–gel process. J Inorg Organomet Polym Mater 17(3):525–533. CrossRefGoogle Scholar
  49. Tavandashti NP, Sanjabi S (2010) Corrosion study of hybrid sol–gel coatings containing boehmite nanoparticles loaded with cerium nitrate corrosion inhibitor. Prog Org Coat 69(4):384–391. CrossRefGoogle Scholar
  50. Thomas S, Birbilis N, Venkatraman MS, Cole IS (2013) Self-repairing oxides to protect zinc: review, discussion and prospects. Corros Sci 69:11–22. CrossRefGoogle Scholar
  51. Scratch Hardness Tester acc. to Model 291 Description, Technical Instructions, Operating (2019).
  52. Umoren SA, Solomon MM (2019) Protective polymeric films for industrial substrates: a critical review on past and recent applications with conducting polymers and polymer composites/nanocomposites. Prog Mater Sci 104(March):380–450. CrossRefGoogle Scholar
  53. Valipour Motlagh N, Birjandi FC, Sargolzaei J, Shahtahmassebi N (2013) Durable, superhydrophobic, superoleophobic and corrosion resistant coating on the stainless steel surface using a scalable method. Appl Surf Sci 283:636–647. CrossRefGoogle Scholar
  54. Vazirinasab E, Jafari R, Momen G (2018) Application of superhydrophobic coatings as a corrosion barrier: a review. Surf Coat Technol 341(November 2017):40–56. CrossRefGoogle Scholar
  55. Vivar Mora L, Taylor A, Paul S, Dawson R, Wang C, Taleb W, Barker R (2018) Impact of silica nanoparticles on the morphology and mechanical properties of sol–gel derived coatings. Surf Coat Technol 342(August 2017):48–56. CrossRefGoogle Scholar
  56. Wankhede RG, Morey S, Khanna AS, Birbilis N (2013) Development of water-repellent organic–inorganic hybrid sol–gel coatings on aluminum using short chain perfluoro polymer emulsion. Appl Surf Sci 283:1051–1059. CrossRefGoogle Scholar
  57. Yeganeh M, Nguyen TA (2019) Methods for corrosion protection of metals at the nanoscale. Kenk Nanotec Nanosci 5:37–44. Google Scholar
  58. Yu Q, Xu J (2012) Structure and surface properties of fluorinated organic–inorganic hybrid films. J Sol Gel Sci Technol 61(1):243–248. CrossRefGoogle Scholar
  59. Zhang Z, Zhu X, Yang J, Xu X, Men X, Zhou X (2012) Facile fabrication of superoleophobic surfaces with enhanced corrosion resistance and easy repairability. Appl Phys A Mater Sci Process 108(3):601–606. CrossRefGoogle Scholar
  60. Zhang Y, Ge D, Yang S (2014) Spray-coating of superhydrophobic aluminum alloys with enhanced mechanical robustness. J Colloid Interface Sci 423:101–107. CrossRefGoogle Scholar
  61. Zheludkevich ML, Serra R, Montemor MF, Yasakau KA, Salvado IMM, Ferreira MGS (2005a) Nanostructured sol–gel coatings doped with cerium nitrate as pre-treatments for AA2024-T3 Corrosion protection performance. Electrochim Acta 51(2):208–217. CrossRefGoogle Scholar
  62. Zheludkevich ML, Serra R, Montemor MF, Ferreira MGS (2005b) Oxide nanoparticle reservoirs for storage and prolonged release of the corrosion inhibitors. Electrochem Commun 7(8):836–840. CrossRefGoogle Scholar
  63. Zheludkevich ML, Serra R, Montemor MF, Miranda Salvado IM, Ferreira MGS (2006) Corrosion protective properties of nanostructured sol–gel hybrid coatings to AA2024-T3. Surf Coat Technol 200(9):3084–3094. CrossRefGoogle Scholar
  64. Zheng S, Li J (2010) Inorganic–organic sol gel hybrid coatings for corrosion protection of metals. J Sol Gel Sci Technol 54(2):174–187. CrossRefGoogle Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2019

Authors and Affiliations

  1. 1.Department of Chemistry, Faculty of ScienceAkdeniz UniversityAntalyaTurkey

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