Journal of Sol-Gel Science and Technology

, Volume 80, Issue 2, pp 567–578 | Cite as

Comparative anti-corrosion properties of alkylthiols SAMs and mercapto functional silica sol–gel coatings on copper surface in sodium chloride solution

  • Wenjie Sui
  • Wenjie Zhao
  • Xing Zhang
  • Shusen Peng
  • Zhixiang Zeng
  • Qunji Xue
Original Paper: Sol-gel, hybrids and solution chemistries


In this paper, we tried to fabricate a compact and thick mercapto functional silica sol–gel coating to achieve excellent corrosion resistance performance on copper. A detailed comparative study of alkylthiol self-assembled monolayers (SAMs) and mercapto functional silica sol–gel coating prepared by 1-octanethiol, n-dodecanethiol and (3-mercaptopropyl)trimethoxysilane (MPTMS) was carried out. The elements composition and chemical bonding of the protective coatings were characterized by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. In addition, the cross section morphologies of Cu–MPTMS sol–gel coating were investigated by field emission scanning electron microscopy. The wettability of various coatings was investigated by contact angle measurement instrument. Finally, the anti-corrosion ability of the coatings was characterized using an electrochemical workstation. Results demonstrated that compared to other alkylthiol SAMs, the Cu–MPTMS sol–gel coating showed the best anti-corrosion property in sodium chloride solution because it owned a multiple hierarchic Si–O–Si network structure, thus to achieve a higher range of thickness and lengthen the diffusion path way of corrosive medium. It was also found that compact and thick mercapto functional silica sol–gel coating shows better corrosion resistance performance than other SAMs of the same type.


Copper Self-assembled monolayer Sol–gel coating Alkylthiols Anti-corrosion 



This work was supported by the National Basic Research Program of China (2014CB643305), the National Natural Science Foundation of China (51202263), Zhejiang Province Key Technology Project (2015C01SA790002) and the Municipal Nature Science Foundation (2015A610060).


  1. 1.
    Fan Y, Li C, Chen Z, Chen H (2012) Study on fabrication of the superhydrophobic sol–gel films based on copper wafer and its anti-corrosive properties. Appl Surf Sci 258:6531–6536CrossRefGoogle Scholar
  2. 2.
    Biswas BN, Mollah MYA, Susan MA (2012) Potentiodynamic studies on corrosion of copper by chloride ions and its inhibition by inorganic and organic ions in aqueous buffer solution. Ionics 18:189–195CrossRefGoogle Scholar
  3. 3.
    Liang C, Wang P, Wu B, Huang N (2010) Inhibition of copper corrosion by self-assembled monolayers of triazole derivative in chloride-containing solution. J Solid State Electrochem 14:1391–1399CrossRefGoogle Scholar
  4. 4.
    Sorensen PA, Kiil S, Dam-Johansen K, Weinell CE (2009) Anticorrosive coatings: a review. J Coat Technol Res 6:135–176CrossRefGoogle Scholar
  5. 5.
    Laibinis PE, Whitesides GM, Allara DL, Tao YT, Parikh AN, Nuzzo RG (1991) Comparison of the structures and wetting properties of self-assembled monolayers of normal-alkanethiols on the coinage metal-surfaces, Cu, Ag, Au. J Am Chem Soc 113:7152–7167CrossRefGoogle Scholar
  6. 6.
    Caprioli F, Martinelli A, Gazzoli D, Di Castro V, Decker F (2012) Enhanced protective properties and structural order of self-assembled monolayers of aromatic thiols on copper in contact with acidic aqueous solution. J Phys Chem C 116:4628–4636CrossRefGoogle Scholar
  7. 7.
    Chen Z, Huang L, Huang L, Li L (2012) Study on behavior of docecanethiol sams on pure copper surface. Surf Technol 41:1–4CrossRefGoogle Scholar
  8. 8.
    Wan L, Du W, Li J, Ding Y, Chen B (2013) Inhibition effects of odtadecanethiol self-assembled monolayers for bronze–silver galvanic corrosion. J Chin Soc Corros Prot 33:245–250Google Scholar
  9. 9.
    Fan H, Li S, Zhao Z, Wang H, Shi Z, Zhang L (2011) Inhibition of brass corrosion in sodium chloride solutions by self-assembled silane films. Corros Sci 53:4273–4281CrossRefGoogle Scholar
  10. 10.
    Zucchi F, Frignani A, Grassi V, Trabanelli G, DalColle M (2007) The formation of a protective layer of 3-mercapto-propyl-trimethoxy-silane on copper. Corros Sci 49:1570–1583CrossRefGoogle Scholar
  11. 11.
    Huang L, Lin K, Yang F, Xu S, Zhou S (2005) Corrosion resistance of copper surface modified with (3-mercaptopropyl)trimethoxysilane in NAOH solution. J Mater Prot 38:10–13Google Scholar
  12. 12.
    Huang L, Lin K, Yang F, Xu S, Zhou C (2005) Structure and corrosion electrochemical properties of self-assembled (3-mercaptopropyl) trimethoxysilane films on copper electrode. Electrochem 11:188–192Google Scholar
  13. 13.
    Zucchi F, Grassi V, Frignani A, Trabanelli G (2004) Inhibition of copper corrosion by silane coatings. Corros Sci 46:2853–2865CrossRefGoogle Scholar
  14. 14.
    Tremont RJ, Blasini DR, Cabrera CR (2003) Controlled self-assembly of mercapto and silane terminated molecules at Cu surfaces. J Electroanal Chem 556:147–158CrossRefGoogle Scholar
  15. 15.
    Zhang L, Qian J, Yu Z (2011) Characterization and corrosion inhibition ability of self-assembled γ-mercaptopropyltrimethoxysilane. J Bohai Univ (Nat Sci Ed) 4:340–343Google Scholar
  16. 16.
    Du W, Li J, Wan L, Chen B, Ding Y (2012) Corrosion inhibition of bronze by self-assembled monolayers of octadecanethiol. Chin J Nonferrous Met 22:3249–3254Google Scholar
  17. 17.
    Ou J, Wang J, Zhou J, Liu S, Yu Y, Pang X, Yang S (2010) Construction and study on corrosion protective property of polydopamine-based 3-layer organic coatings on aluminum substrate. Prog Org Coat 68:244–247CrossRefGoogle Scholar
  18. 18.
    Peng S, Han J, Zhao W, Zeng Z, Chen J, Wu X (2015) The protection and degradation behaviors of mercapto functional sol–gel coating on copper surface. J Electrochem Soc 162:C128–C134CrossRefGoogle Scholar
  19. 19.
    Peng S, Zeng Z, Zhao W, Chen J, Han J, Wu X (2014) Performance evaluation of mercapto functional hybrid silica sol–gel coating on copper surface. Surf Coat Technol 251:135–142CrossRefGoogle Scholar
  20. 20.
    Chiavari C, Balbo A, Bernardi E, Martini C, Zanotto F, Vassura I, Bignozzi MC, Monticelli C (2015) Organosilane coatings applied on bronze: influence of UV radiation and thermal cycles on the protectiveness. Prog Org Coat 82:91–100CrossRefGoogle Scholar
  21. 21.
    Sinapi F, Lejeune I, Delhalle J, Mekhalif Z (2007) Comparative protective abilities of organothiols sam coatings applied to copper dissolution in aqueous environments. Electrochim Acta 52:5182–5190CrossRefGoogle Scholar
  22. 22.
    Sinapi F, Julien S, Auguste D, Hevesi L, Delhalle J, Mekhalif Z (2008) Monolayers and mixed-layers on copper towards corrosion protection. Electrochim Acta 53:4228–4238CrossRefGoogle Scholar
  23. 23.
    Sinapi F, Deroubaix S, Pirlot C, Delhalle J, Mekhalif Z (2004) electrochemical evaluation of the corrosion protection of bi-dimensional organic films self-assembled onto brass. Electrochim Acta 49:2987–2996CrossRefGoogle Scholar
  24. 24.
    Yang SR, Kolbesen BO (2008) A comparative study of the growth of octadecyltrichlorosilane and 3-mercaptopropyltrimethoxysilane self-assembled monolayers on hydrophilic silicon surfaces. Appl Surf Sci 255:1726–1735CrossRefGoogle Scholar
  25. 25.
    Abdureyim A, Okudaira K, Harada Y, Masuda S, Aoki M, Seki K, Ito E, Ueno N (2001) Characterization of 4-mercaptohydrocynnamic acid self-assembled film on au (111) by means of X-ray photoelectron spectroscopy. J Electron Spectrosc Relat Phenom 114:371–374CrossRefGoogle Scholar
  26. 26.
    Bindu V, Pradeep T (1998) Characterisation of alkanethiol (Cnh2n + 1sh, N = 3, 4, 6, 8, 10, 12 and 18) self assembled monolayers by X-ray photoelectron spectroscopy. Vacuum 49:63–66CrossRefGoogle Scholar
  27. 27.
    Inoue R, Kitagawa M, Nishigaki T, Morita D, Ichino K, Kusano H, Kobayashi H (1999) Xps study of Zn X Mg 1 − X S: Mn ternary compound thin films. Appl Surf Sci 142:341–345CrossRefGoogle Scholar
  28. 28.
    Li Y, Lu W, Wang Y, Tran T (2009) Studies of (3-mercaptopropyl) trimethoxylsilane and bis (trimethoxysilyl) ethane sol–gel coating on copper and aluminum. Spectrochim Acta Part A 73:922–928CrossRefGoogle Scholar
  29. 29.
    Wang X, Xing WY, Song L, Yang HY, Hu Y, Yeoh GH (2012) Fabrication and characterization of graphene-reinforced waterborne polyurethane nanocomposite coatings by the sol–gel method. Surf Coat Technol 206:4778–4784CrossRefGoogle Scholar
  30. 30.
    Lu X, Guo Z, Huang R, Chen M (2011) Preparation of a (3-mercaptopropyl) triethoxylsilane film on copper and its corrosion protective performance. Acta Phys Chim Sin 27:108–112Google Scholar
  31. 31.
    Weng C, Chang C, Peng C, Chen S, Yeh JM, Hsu CL, Wei Y (2011) Advanced anticorrosive coatings prepared from the mimicked xanthosoma sagittifolium-leaf-like electroactive epoxy with synergistic effects of superhydrophobicity and redox catalytic capability. Chem Mater 23:2075–2083CrossRefGoogle Scholar
  32. 32.
    Qin L, Zhao W, Hou H, Jin Y, Zeng Z, Wu X, Xue Q (2014) Achieving excellent anti-corrosion and tribological performance by tailoring the surface morphology and chemical composition of aluminum alloys. RSC Adv 4:60307–60315CrossRefGoogle Scholar
  33. 33.
    Chen M, Lu X, Guo Z, Huang R (2011) Influence of hydrolysis time on the structure and corrosion protective performance of (3-mercaptopropyl) triethoxysilane film on copper. Corros Sci 53:2793–2802CrossRefGoogle Scholar
  34. 34.
    Kear G, Barker B, Walsh F (2004) Electrochemical corrosion of unalloyed copper in chloride media—a critical review. Corros Sci 46:109–135CrossRefGoogle Scholar
  35. 35.
    Peng S, Zeng Z, Zhao W, Li H, Xue Q, Wu X (2012) Synergistic effect of thiourea in epoxy functionalized silica sol–gel coating for copper protection. Surf Coat Technol 213:175–182CrossRefGoogle Scholar
  36. 36.
    Wang P, Liang C, Wu B, Huang N, Li J (2010) Protection of copper corrosion by modification of dodecanethiol self-assembled monolayers prepared in aqueous micellar solution. Electrochim Acta 55:878–883CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media New York 2016

Authors and Affiliations

  • Wenjie Sui
    • 1
    • 2
  • Wenjie Zhao
    • 1
  • Xing Zhang
    • 2
  • Shusen Peng
    • 1
  • Zhixiang Zeng
    • 1
  • Qunji Xue
    • 1
  1. 1.Key Laboratory of Marine Materials and Related Technologies, Zhejiang Key Laboratory of Marine Materials and Protective Technologies, Ningbo Institute of Materials Technology and EngineeringChinese Academy of SciencesNingboChina
  2. 2.School of Materials Science and EngineeringNorth University of ChinaTaiyuanChina

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