Chao-Ching Chang1,2, Zi-Min Lin1 , Shu-Hui Huang1 and Liao-Ping Cheng This email address is being protected from spambots. You need JavaScript enabled to view it.1,2

1Department of Chemical and Materials Engineering, Tamkang University, Tamsui, Taiwan 251, R.O.C.
2Energy and Opto-Electronic Materials Research Center, Tamkang University, Tamsui, Taiwan 251, R.O.C.


Received: April 17, 2015
Accepted: September 12, 2015
Publication Date: December 1, 2015

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Silica nanoparticles synthesized from tetraethoxysiliane (TEOS) via a solgel process were surface-modified by using 3-(trimethoxysilyl)propyl methacrylate (MSMA) and 1H, 1H, 2H, 2Hperfluorooctyltriethoxysilane (13F). MSMA acted as a coupling agent and a C=C provider, whereas 13F was employed to enhance hydrophobicity. The surface-modified silica particles together with a multi-functional monomer were UV-cured to yield highly transparent thin films (~7 μm) on plastic substrates. Both FE-SEM imaging and UVvisible spectroscopy confirmed uniform dispersion of nano-silica in the hybrid thin films. The coating surfaces were extremely smooth, with average roughness over the range 1.02.3 nm based on profilometric measurements. X-ray photoelectron spectroscopy indicated that surface-modified silica particles have migrated to the top surface to reduce the surface energy. Therefore, only a small dosage of 1 mol% (vs. TEOS) was enough to engender surface hydrophobicity with water contact angle of 100. Furthermore, all of the prepared coatings were hard with pencil hardness reached 6H, and they adhered strongly to the poly(methyl methacrylate) substrate according to the peel test.

Keywords: Colloidal Silica, Hard Coating, UV-curing, Plastic Substrate, Hydrophobic


  1. [1] Schmidt, H., “Nanoparticles by Chemical Synthesis, Processing to Materials and Innovative Applications,” Applied Organometallic Chemistry, Vol. 15, No. 5, pp. 331343 (2001). doi: 10.1002/aoc.169
  2. [2] Daoud, W. A., Xin, J. H. and Tao, X., “Superhydrophobic Silica Nanocomposite Coating by a Low-Temperature Process,” Journal of the American Ceramic Society, Vol. 87, No. 9, pp. 17821784 (2004). doi: 10.1111/j.1551-2916.2004.01782.x
  3. [3] Dodiuk, H., Rios, P. F., Dotan, A. and Kenig, S., “Hydrophobic and Self-Cleaning Coatings,” Polymers for Advanced Technologies, Vol. 18, No. 9, pp. 746750 (2007). doi: 10.1002/pat.957
  4. [4] Rios, P. F., Dodiuk, H., Kenig, S., McCarthy, S. and Dotan, A., “Durable Ultra-Hydrophobic Surfaces for Self-Cleaning Applications,” Polymers for Advanced Technologies, Vol. 19, No. 11, pp. 16841691 (2008). doi: 10.1002/pat.1208
  5. [5] Budunoglu, H., Yildirim, A., Guler, M. O. and Bayindir, M., “Highly Transparent, Flexible and Thermally Stable Superhydrophobic ORMOSIL Aerogel Thin Films,” ACS Applied Materials and Interfaces, Vol. 3, No. 2, pp. 539545 (2011). doi: 10.1021/am10 1116b
  6. [6] Ebert, D. and Bhushan, B., “Transparent, Superhydrophobic and Wear-Resistant Coatings on Glass and Polymer Substrates Using SiO2, ZnO, and ITO Nanoparticles,” Langmuir, Vol. 28, No. 31, pp. 1139111399 (2012). doi: 10.1021/la301479c
  7. [7] De, S., Jana, D., Medda, S. K. and De, G., “Wavelength Selective Antireflective Coatings on Plastics with Hydrophobic Surfaces,” Industrial and Engineering Chemistry Research, Vol. 52, No. 23, pp. 7737 7745 (2013). doi: 10.1021/ie400395c
  8. [8] Boudot, M., Gaud, V., Louarn, M., Selmane, M. and Grosso, D., “SolGel Based Hydrophobic Antireflective Coatings on Organic Substrates: a Detailed Investigation of Ammonia Vapor Treatment (AVT),” Chemistry of Materials, Vol. 26, No. 5, pp. 18221833 (2014). doi: 10.1021/cm403787v
  9. [9] Li, H., Jiang, M., Hu, D., Yan, Y., Li, Q., Dong, L. and Xiong, C., “Solvent-Free Zirconia Nanofluids/Silica Single-Layer Multifunctional Hybrid Coatings,” Colloids and Surfaces A: Physicochemical and Engineering Aspects, A, Vol. 464, No. 5, pp. 2632 (2015). doi: 10.1016/j.colsurfa.2014.10.014
  10. [10] Chang, C. C., Oyang, T. Y., Hwang, F. H., Chen, C. C. and Cheng, L. P., “Preparation of Polymer/Silica Hybrid Hard Coatings with Enhanced Hydrophobicity on Plastic Substrates,” Journal of Non-Crystalline Solids, Vol. 358, No. 1, pp. 7276 (2012). doi: 10.1016/j. jnoncrysol.2011.08.024
  11. [11] Chang, C. C., Oyang, T. Y., Chen, Y. C., Hwang, F. H. and Cheng, L. P., “Preparation of Hydrophobic Nanosilica-Filled Polyacrylate Hard Coatings on Plastic Substrates,” Journal of Coatings Technology Research, Vol. 11, No. 3, pp. 381386 (2014). doi: 10.1007/s11 998-013-9540-0
  12. [12] Gilberts, J., Tinnemans, A. H. A., Hogerheide, M. P. and Koster, T. P. M., “UV Curable Hard Transparent Hybrid Coating Materials on Polycarbonate Prepared by the SolGel Method,” Journal of Sol-Gel Science and Technology, Vol. 11, No. 2, pp. 153159 (1998). doi: 10.1023/A:1008693413965
  13. [13] Chang, C. C., Wang, S. H., Chen, Y. C. and Cheng, L. P., “Preparation and Characterization of Spironaphthooxazine/polyacrylate Photochromic Hard Coatings on Plastic Substrates,” Journal of Applied Science and Engineering, Vol. 17, No. 2, pp. 167174 (2014). doi: 10.6180/jase.2014.17.2.07
  14. [14] Chou, T. P. and Cao, G., “Adhesion of Sol-Gel-Derived OrganicInorganic Hybrid Coatings on Polyester,” Journal of Sol-Gel Science and Technology, Vol. 27, No. 1, pp. 3141 (2003). doi: 10.1023/A:1022675 809404
  15. [15] Schottner, G., Rose, K. and Posset, U., “Scratch and Abrasion Resistant Coatings on Plastic LensesState of the Art, Current Developments and Perspectives,” Journal of Sol-Gel Science and Technology, Vol. 27, No. 1, pp. 7179 (2003). doi: 10.1023/A:1022684011 222
  16. [16] Almaral-Sanchez, J. L., Rubio, E., Mendoza-Galvan, A. and Ramirez-Bon, R., “Red Colored Transparent PMMASiO2 Hybrid Films,” Journal of Physics and Chemistry of Solids, Vol. 66, No. 10, pp. 16601667 (2005). doi: 10.1016/j.jpcs.2005.06.006
  17. [17] Blanc, D., Last, A., Franc, J., Pavan, S. and Loubet, J. L., “Hard UV-Curable Organo-Mineral Coatings for Optical Applications,” Thin Solid Films, Vol. 515, No. 3, pp. 942946 (2006). doi: 10.1016/j.tsf.2006. 07.177
  18. [18] Toselli, M., Marini, M., Fabbri, P., Messori, M. and Pilati, F., “SolGel Derived Hybrid Coatings for the Improvement of Scratch Resistance of Polyethylene,” Journal of Sol-Gel Science and Technolog, Vol. 43, No. 1, pp. 7383 (2007). doi: 10.1007/s10971-007- 1560-8
  19. [19] Jeon, S. J., Lee, J. J., Kim, W., Chang, T. S. and Koo, S. M., “Hard Coating Films Based on OrganosilaneModified Boehmite Nanoparticles under UV/Thermal Dual Curing,” Thin Solid Films, Vol. 516, No. 12, pp. 39043909 (2008). doi: 10.1016/j.tsf.2007.07. 165
  20. [20] Wu, L. Y. L., Boon, L., Chen, Z. and Zeng, X. T., “Adhesion Enhancement of SolGel Coating on Polycarbonate by Heated Impregnation Treatment,” Thin Solid Films, Vol. 517, No. 17, pp. 48504856 (2009). doi: 10.1016/j.tsf.2009.03.086
  21. [21] Chen, C. C., Lin, D. J., Don, T. M., Huang, F. H. and Cheng, L. P., “Preparation of OrganicInorganic Nano-Composites for Antireflection Coatings,” Journal of Non-Crystalline Solids, Vol. 354, No. 32, pp. 38283835 (2008). doi: 10.1016/j.jnoncrysol.2008. 04.010
  22. [22] Lee, C. K., Don, T. M., Lai, W. C., Chen, C. C., Lin, D. J. and Cheng, L. P., “Preparation and Properties of Nano-Silica Modified Negative Acrylate Photoresist,” Thin Solid Films, Vol. 516, No. 23, pp. 83998407 (2008). doi: 10.1016/j.tsf.2008.04.051
  23. [23] Huang, F. H., Chang, C. C., Oyang, T. Y., Chen, C. C. and Cheng, L. P., “Preparation of Almost DispersantFree Colloidal Silica with Superb Dispersiblility in Organic Solvents and Monomers,” Journal of Nanoparticle Research, Vol. 13, No. 9, pp. 38853897 (2011). doi: 10.1007/s11051-011-0342-y
  24. [24] Chang, C. C., Huang, F. H., Chang, H. H., Don, T. M., Chen, C. C. and Cheng, L. P., “Preparation of WaterResistant Antifog Hard Coatings on Plastic Substrate,” Langmuir, Vol. 28, No. 49, pp. 1719317201 (2012). doi: 10.1021/la304176k
  25. [25] Lin, D. J., Chen, C. C., Su, Y. C., Huang, S. H. and Cheng, L. P., “Preparation of Silica Filled Poly(2-hydroxymethyl methacrylate) Nanocomposites Cured by Photoirradiation during the SolGel Process,” Journal of Applied Polymer Science, Vol. 94, No. 5, pp. 1927 1935 (2004). doi: 10.1002/app.21097
  26. [26] Lin, D. J., Don, T. M., Chen, C. C., Lin, B. Y., Lee, C. K. and Cheng, L. P., “Preparation of a NanosilicaModified Negative-Type Acrylate Photoresist,” Journal of Applied Polymer Science, Vol. 107, No. 2, pp. 11791181 (2008). doi: 10.1002/app.27151