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Terminal silanization of perfluoropolyether, polydimethylsiloxane, their block polymer and the self-assembled films on plasma-treated silicon surfaces

  • Qun Liu
  • Yi Sun
  • Zhanxiong Li
Original Paper
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Abstract

In this paper, terminal silanization of perfluoropolyether, polydimethylsiloxane and their block polymer was studied and N-(Triethoxysilylpropyl) urethano-perfluoropolyether (silanized-PFPE), N-(triethoxysilylpropyl) urethano-polydimethylsiloxane (silanized-PDMS), N-(Triethoxysilylpropyl) urethano-polydimethylsiloxane -block-perfluoropolyether (silanized-PSPF) were obtained, respectively. The self-assembled films of terminal silanized polymers were prepared on plasma-treated silicon surfaces via the liquid phase deposition method (LPD), and the surface structures and properties were investigated by contact angle (CA) measurements, X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDS) and atomic force microscopy (AFM). It was discovered that the hydrophilic plasma-treated silicon surfaces became hydrophobic and possessed lower surface-free energies after treating by all three silanized polymers. Among them, the self-assembled film of silanized-PFPE provided the lowest surface-free energy of 12.77 mN/m with the water contact angle being 118.2°. Self-assembled films with different deposition concentrations were prepared. Results showed that the higher the treating concentration, the higher water contact angle (WCA) obtained. The terminal silanized polymers were coated on the silicon substrates uniformly. This was identified by XPS and EDS measurements of chemical compositions on the surface of the films. AFM was used to analyze the surface morphologies of silanized PFPE-deposited films, which was found to be rough at all the different concentrations of treatment solution. A concentration of 5% could provide the completely covered film with the roughest surface and thus develop the surface with excellent hydrophobicity.

Keywords

Terminal silanization Perfluoropolyether Polydimethylsiloxane Self-assembled films Hydrophobicity 
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Notes

Acknowledgements

We gratefully acknowledge the financial supports by the National Natural Science Foundation of China (no. 51673137), Jiangsu Overseas Research and Training Program for University Prominent Young and Middle-aged Teachers and Presidents, and the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.

Supplementary material

11696_2018_547_MOESM1_ESM.docx (242 kb)
Supplementary material 1 (DOCX 242 kb)

References

  1. Al-Khaldi TA, Lyon SB (2012) The effect of interfacial chemistry on coating adhesion and performance: a mechanistic study using aminobutylphosphonic acid. Prog Org Coat 75:449–455.  https://doi.org/10.1016/j.porgcoat.2012.06.011 CrossRefGoogle Scholar
  2. Bielawska M, Jańczuk B, Zdziennicka A (2013) Adhesion work and wettability of polytetrafluorethylene and poly(methyl methacrylate) by aqueous solutions of cetyltrimethylammonium bromide and Triton X-100 mixture with ethanol. J Colloid Interface Sci 404:201–206.  https://doi.org/10.1016/j.jcis.2013.05.002 CrossRefPubMedGoogle Scholar
  3. Brzoska JB, Shahidzadeh N, Rondelez F (1992) Evidence of a transition temperature for the optimum deposition of grafted monolayer coatings. Nature 360:719–721.  https://doi.org/10.1038/360719a0 CrossRefGoogle Scholar
  4. Chattopadhyay S, Chakraborty SP, Laha D, Baral R, Pramanik P, Roy S (2012) Surface-modified cobalt oxide nanoparticles: new opportunities for anti-cancer drug development. Cancer Nano 3:13–23.  https://doi.org/10.1007/s12645-012-0026-z CrossRefGoogle Scholar
  5. Cheng DF, Masheder B, Urata C, Hozumi A (2013) Smooth perfluorinated surfaces with different chemical and physical natures: their unusual dynamic dewetting behavior toward polar and nonpolar liquids. Langmuir 29:11322–11329.  https://doi.org/10.1021/la402398y CrossRefPubMedGoogle Scholar
  6. Cichomski M, Kośla K, Grobelny J, Kozłowski W, Kowalczyk PJ, Busiakiewicz A, Szmaja W, Balcerski J (2010a) Nano- and microtribological characterization of silanes deposited on cobalt substrate. J Alloy Compd 507:273–278.  https://doi.org/10.1016/j.jallcom.2010.07.176 CrossRefGoogle Scholar
  7. Cichomski M, Kośla K, Grobelny J, Szmaja W, Balcerski J (2010b) Tribological and magnetic characterization of fluorosilanes on cobalt surface. J Alloy Compd 501:362–365.  https://doi.org/10.1016/j.jallcom.2010.04.106 CrossRefGoogle Scholar
  8. Cichomski M, Kośla K, Kozłowski W, Szmaja W, Balcerski J, Rogowski J, Grobelny J (2012) Investigation of the structure of fluoroalkyl silanes deposited on alumina surface. Appl Surf Sci 258:9849–9855.  https://doi.org/10.1016/j.apsusc.2012.06.040 CrossRefGoogle Scholar
  9. Cichomski M, Kosla K, Grobelny J, Kozłowski W, Szmaja W (2013) Tribological and stability investigations of alkylphosphonic acids on alumina surface. Appl Surf Sci 273:570–577.  https://doi.org/10.1016/j.apsusc.2013.02.081 CrossRefGoogle Scholar
  10. Devaprakasam D, Sampath S, Biswas SK (2004) Thermal stability of perfluoroalkyl silane self-assembled on a polycrystalline aluminum surface. Langmuir 20:1329–1334.  https://doi.org/10.1021/la0359676 CrossRefPubMedGoogle Scholar
  11. Döbbelin M, Tena-Zaera R, Marcilla R, Iturri J, Moya S, Pomposo JA, Mecerreyes D (2010) Multiresponsive pedot-ionic liquid materials for the design of surfaces with switchable wettability. Adv Funct Mater 19:3326–3333.  https://doi.org/10.1002/adfm.200900863 CrossRefGoogle Scholar
  12. Dolmaire N, Méchin F, Espuche E, Pascault JP (2006) Modification of a hydrophilic linear polyurethane by crosslinking with a polydimethylsiloxane. Influence of the crosslink density and of the hydrophobic/hydrophilic balance on the water transport properties. J. Polym. Sci Pol Phys 44:48–61.  https://doi.org/10.1002/polb.20675 CrossRefGoogle Scholar
  13. Dong JP, Wang AF, Ng KYS, Mao GZ (2006) Self-assembly of octadecyltrichlorosilane monolayers on silicon-based substrates by chemical vapor deposition. Thin Solid Films 515:2116–2122.  https://doi.org/10.1016/j.tsf.2006.07.041 CrossRefGoogle Scholar
  14. Ellinas K, Pujari SP, Dragatogiannis DA, Charitidis CA, Tserepi A, Zuilhof H, Gogolides E (2014) Plasma micro-nanotextured, scratch, water and hexadecane resistant, superhydrophobic, and superamphiphobic polymeric surfaces with perfluorinated monolayers. ACS Appl Mater Interface 6:6510–6524.  https://doi.org/10.1021/am5000432 CrossRefGoogle Scholar
  15. Fadeev AY, McCarthy TJ (1999) Trialkylsilane monolayers covalently attached to silicon surfaces: wettability studies indicating that molecular topography contributes to contact angle hysteresis. Langmuir 15:3759–3766.  https://doi.org/10.1021/la981486o CrossRefGoogle Scholar
  16. Faucheux N, Schweiss R, Lutzow K, Werner C, Groth T (2004) Self-assembled monolayers with different terminating groups as model substrates for cell adhesion studies. Biomaterials 25:2721–2730.  https://doi.org/10.1016/j.biomaterials.2003.09.069 CrossRefPubMedGoogle Scholar
  17. Fiorilli S, Rivolo P, Descrovi E, Ricciardi C, Pasquardini L, Lunelli L, Vanzetti L, Pederzolli C, Onida B, Garrone E (2008) Vapor-phase self-assembled monolayers of aminosilane on plasma-activated silicon substrates. J Colloid Interface Sci 321:235–241.  https://doi.org/10.1016/j.jcis.2007.12.041 CrossRefPubMedGoogle Scholar
  18. Foisner J, Glaser A, Attner J, Hoffmann H, Friedbacher G (2003) Atomic force microscopy investigation of the growth of different alkylsiloxane monolayers from highly concentrated solutions. Langmuir 19:3741–3746.  https://doi.org/10.1021/la026646h CrossRefGoogle Scholar
  19. Furukawa Y, Kotera M (2010) Water and oil repellency of polysiloxanes with highly fluorinated alkyl side chains. J Appl Polym Sci 87:1085–1091.  https://doi.org/10.1002/app.11505 CrossRefGoogle Scholar
  20. Ghosh AK, Bertels E, Goderis B, Smet M, Hemelrijck DV, Mele BV (2015) Optimisation of wet chemical silane deposition to improve the interfacial strength of stainless steel/epoxy. Appl Surf Sci 324:134–142.  https://doi.org/10.1016/j.apsusc.2014.10.075 CrossRefGoogle Scholar
  21. Gong YY, Wang MCP, Zhang X, Ng HW, Gates BD (2012) Optimizing the quality of monoreactive perfluoroalkylsilane-based self-assembled monolayers. Langmuir 28:11790–11801.  https://doi.org/10.1021/la301742s CrossRefPubMedGoogle Scholar
  22. Guimont A, Beyou E, Alcouffe P, Martin G, Sonntag P, Cassagnau P (2013) Synthesis and characterization of PDMS-grafted graphite oxide sheets. Polymer 54(18):4830–4837.  https://doi.org/10.1016/j.polymer.2013.06.060 CrossRefGoogle Scholar
  23. Hoque E, DeRose JA, Houriet R, Hoffmann P, Mathieu HJ (2007) Stable perfluorosilane self-assembled monolayers on copper oxide surfaces: evidence of siloxy–copper bond formation. Chem Mater 19:798–804.  https://doi.org/10.1021/cm062318h CrossRefGoogle Scholar
  24. Jradi K, Laour D, Daneault C, Chabot B (2011) Control of the chemical and physical behaviour of silicon surfaces for enhancing the transition from hydrophilic to superhydrophobic surfaces. Colloid Surface A 374:33–41.  https://doi.org/10.1016/j.colsurfa.2010.10.050 CrossRefGoogle Scholar
  25. Kawasaki M, Sato T, Tanaka T, Takao K (2010) Rapid self-assembly of alkanethiol monolayers on sputter-grown Au(111). Langmuir 16:1719–1728.  https://doi.org/10.1021/la990310z CrossRefGoogle Scholar
  26. Kessman AJ, Cairns DR (2011) Template-assisted encapsulation of fluorinated silanes in silica films for sustained hydrophobic-oleophobic functionality. J Colloid Interface Sci 360:785–792.  https://doi.org/10.1016/j.jcis.2011.05.026 CrossRefPubMedGoogle Scholar
  27. Khorasani MT, Mirzadeh H, Kermani Z (2005) Wettability of porous polydimethylsiloxane surface: morphology study. Appl Surf Sci 242:339–345.  https://doi.org/10.1016/j.apsusc.2004.08.035 CrossRefGoogle Scholar
  28. Krawczyk J, Szymczyk K, Zdziennicka A, Jańczuk B (2013) Wettability of polymers by aqueous solution of binary surfactants mixture with regard to adhesion in polymer–solution system II. Critical surface tension of polymers wetting and work of adhesion. Int J Adhes Adhes 45:106–111.  https://doi.org/10.1016/j.ijadhadh.2013.05.002 CrossRefGoogle Scholar
  29. Kujawa J, Cerneaux S, Kujawski W (2014) Investigation of the stability of metal oxide powders and ceramic membranes grafted by perfluoroalkylsilanes. Colloid Surface A 443:109–117.  https://doi.org/10.1016/j.colsurfa.2013.10.059 CrossRefGoogle Scholar
  30. 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 n-alkanethiols on the coinage metal surfaces, copper, silver, and gold. J Am Chem Soc 113:7152–7167.  https://doi.org/10.1021/ja00019a011 CrossRefGoogle Scholar
  31. Lei WW, Li H, Shi LY, Diao YF, Zhang YL, Ran R, Ni W (2017) Achieving enhanced hydrophobicity of graphene membranes by covalent modification with polydimethylsiloxane. Appl Surf Sci 404:230–237.  https://doi.org/10.1016/j.apsusc.2017.01.292 CrossRefGoogle Scholar
  32. Liu GZ, Gooding JJ (2006) An interface comprising molecular wires and poly(ethylene glycol) spacer units self-assembled on carbon electrodes for studies of protein electrochemistry. Langmuir 22:7421–7430.  https://doi.org/10.1021/la0607510 CrossRefPubMedGoogle Scholar
  33. Liu J, Wu S, Zou M, Zheng X, Cai Z (2012) Surface modification of silica and its compounding with polydimethylsiloxane matrix: interaction of modified silica filler with PDMS. Iran Polym J 21:583–589.  https://doi.org/10.1007/s13726-012-0062-x CrossRefGoogle Scholar
  34. Lu X, Zhou J, Zhao Y, Qiu Y, Li J (2008) Room temperature ionic liquid based polystyrene nanofibers with superhydrophobicity and conductivity produced by electrospinning. Chem Mater 20:3420–3424.  https://doi.org/10.1021/cm800045h CrossRefGoogle Scholar
  35. Owens DK, Wendt RC (1969) Estimation of the surface free energy of polymers. J Appl Polym Sci 13:1741–1747.  https://doi.org/10.1002/app.1969.070130815 CrossRefGoogle Scholar
  36. Pan LN, Dong HR, Bi PY (2010) Facile preparation of superhydrophobic copper surface by HNO3, etching technique with the assistance of CTAB and ultrasonication. Appl Surf Sci 257:1707–1711.  https://doi.org/10.1016/j.apsusc.2010.09.001 CrossRefGoogle Scholar
  37. Park JH, Yun TH, Kim KY, Song YK, Park JM (2012) The improvement of anticorrosion properties of zinc-rich organic coating by incorporating surface-modified zinc particle. Prog Org Coat 74:25–35.  https://doi.org/10.1016/j.porgcoat.2011.09.012 CrossRefGoogle Scholar
  38. Schreiber F (2000) Structure and growth of self-assembling monolayers. Prog Surf Sci 65:151–257.  https://doi.org/10.1016/S0079-6816(00)00024-1 CrossRefGoogle Scholar
  39. Shen Y, Zhang Y, Zhang Q, Niu L, You T, Ivaska A (2005) Immobilization of ionic liquid with polyelectrolyte as carrier. Chem Commun 33:4193–4195.  https://doi.org/10.1039/b507688a CrossRefGoogle Scholar
  40. Sun PL, Horton JH (2013) Perfluorinated poly(dimethylsiloxane) via the covalent attachment of perfluoroalkylsilanes on the oxidized surface: effects on zeta-potential values. Appl Surf Sci 271:344–351.  https://doi.org/10.1016/j.apsusc.2013.01.199 CrossRefGoogle Scholar
  41. Ulman A (1996) Formation and structure of self-assembled monolayers. Chem Rev 96:1533.  https://doi.org/10.1021/cr9502357 CrossRefPubMedGoogle Scholar
  42. Vitale A, Pollicino A, Bernardi E, Bongiovanni R (2015) Ultrathin perfluoropolyether coatings for silicon wafers: a XPS study. Prog Org Coat 78:480–487.  https://doi.org/10.1016/j.porgcoat.2014.06.014 CrossRefGoogle Scholar
  43. Weinstein RD, Moriarty J, Cushnie E, Colorado R Jr, Lee TR, Patel M, Alesi WR, Jennings GK (2003) Structure, wettability, and electrochemical barrier properties of self-assembled monolayers prepared from partially fluorinated hexadecanethiols. J phys chem B 107:11626–11632.  https://doi.org/10.1021/jp035067y CrossRefGoogle Scholar
  44. Wen K, Maoz R, Cohen H, Sagiv J, Gibaud A, Desert A, Ocko BM (2008) Postassembly chemical modification of a highly ordered organosilane multilayer: new insights into the structure, bonding, and dynamics of self-assembling silane monolayers. ACS Nano 2:579–599.  https://doi.org/10.1021/nn800011t CrossRefPubMedGoogle Scholar
  45. Wong KY, Krull UJ (2005) Surface characterization of 3-glycidoxypropyltrimethoxysilane films on silicon-based substrates. Anal Bioanal Chem 383:187–200.  https://doi.org/10.1007/s00216-005-3414-y CrossRefPubMedGoogle Scholar
  46. Wu L, Cai L, Liu AQ, Wang W, Yuan YH, Li ZX (2015) Self-assembled monolayers of perfluoroalkylsilane on plasma-hydroxylated silicon substrates. Appl Surf Sci 349:683–694.  https://doi.org/10.1016/j.apsusc.2015.05.073 CrossRefGoogle Scholar
  47. Xie XJ, Qu LT, Zhou C, Li Y, Zhu J, Bai H, Shi GQ, Dai LM (2010) An asymmetrically surface-modified graphene film electrochemical actuator. ACS Nano 4:6050–6054.  https://doi.org/10.1021/nn101563x CrossRefPubMedGoogle Scholar
  48. Zhao ZL, Ni HG, Han ZY, Jiang TF, Xu YJ, Lu XL, Ye P (2013) Effect of surface compositional heterogeneities and microphase segregation of fluorinated amphiphilic copolymers on antifouling performance. ACS Appl Mater Interf 5:7808–7818.  https://doi.org/10.1021/am401568b CrossRefGoogle Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2018

Authors and Affiliations

  1. 1.College of Textile and Clothing EngineeringSoochow UniversitySuzhouChina
  2. 2.National Engineering Laboratory for Modern SilkSuzhouChina

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