View More View Less
  • 1 Department of Physics, National Technical University of Athens, Zografou Campus, 157 80, Athens, Greece
  • | 2 Department of Experimental Physics, University des Saarlandes, Saarbrücken, Germany
  • | 3 Department of Physics, Tokai University, Hiratsuka, Kanagawa, 259–1292, Japan
  • | 4 Center for Biomaterials, Universidad Politécnica de Valencia, Valencia, Spain
Restricted access

Abstract

Hydrogels based on nanocomposites of statistical poly(hydroxyethyl acrylate-co-ethyl acrylate) and silica, prepared by simultaneous copolymerization and generation of silica nanoparticles by sol–gel process at various copolymer compositions and silica contents, characterized by a fine dispersion of filler, were investigated with respect to glass transition and polymer dynamics by dielectric techniques. These include thermally stimulated depolarization currents and dielectric relaxation spectroscopy, covering together broad ranges of frequency and temperature. In addition, equilibrium water sorption isotherms were recorded at room temperature (25 °C). Special attention was paid to the investigation of effects of silica on glass transition, polymer dynamics (secondary γ and βsw relaxations and segmental α relaxation), and electrical conductivity in the dry systems (xerogels) and in the hydrogels at various levels of relative humidity/water content. An overall reduction of molecular mobility is observed in the nanocomposite xerogels, in particular at high silica contents. Analysis of the results and comparison with previous work on similar systems enable to discuss this reduction of molecular mobility in terms of constraints to polymeric motion imposed by interfacial polymer–filler interactions and by the formation of a continuous silica network interpenetrated with the polymer network at filler contents higher than about 15 wt%.

  • 1. NA Peppas eds. 1986 Hydrogels in medicine and pharmacy I CRC Press Boca Raton, FL.

  • 2. Stoy, V, Kliment, C 1996 Hydrogels: speciality plastics for biomedical and pharmaceutical applications Technomic Basel.

  • 3. Kyritsis, A, Pissis, P, Gomez Ribelles, JL, Monleon Pradas, M 1994 Depolarization thermocurrent studies in poly(hydroxyethyl acrylate)/water hydrogels. J Polym Sci Part B Polym Phys 32:10011008 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 4. Kyritsis, A, Pissis, P, Grammatikakis, J 1995 Dielectric relaxation spectroscopy in poly(hydroxyethyl acrylate)/water hydrogels. J Polym Sci Part B Polym Phys 33:17371750 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 5. Kyritsis, A, Pissis, P, Gomez Ribelles, JL, Monleon Pradas, M 1995 Polymer-water interactions in poly(hydroxyethyl acrylate) hydrogels studied by dielectric, calorimetric and sorption isotherm measurements. Polym Gels Netw 3:445469 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 6. Gallego Ferrer, G, Monleon Pradas, M, Gomez Ribelles, JL, Pissis, P 1998 Swelling and thermally stimulated depolarization currents in hydrogels formed by interpenetrating polymer networks. J Non-Cryst Solids 235–237:692696 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 7. Gomez Ribelles, JL, Monleon Pradas, M, Gallego Ferrer, G, Peidro Torres, N, Perez Gimenez, V, Pissis, P, Kyritsis, A 1999 Poly(methyl acrylate)/poly(hydroxyethyl acrylate) sequential interpenetrating polymer networks. Miscibility and wáter sorption behavior. J Polym Sci Part B Polym Phys 37:15871599 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 8. Campillo-Fernandez, AJ, Salmeron Sanchez, M, Sabater i Serra, R, Meseguer Duenas, JM, Monleon Pradas, M, Gomez Ribelles, JL 2008 Water-induced (nano) organization in poly(ethyl acrylate-co-hydroxyethyl acrylate) networks. Eur Polym J 44:19962004 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 9. Kyritsis, A, Spanoudaki, A, Pandis, C, Hartmann, L, Pelster, R, Shinyashiki, N, Rodríguez Hernández, JC, Gómez Ribelles, JL, Monleón Pradas, M, Pissis, P 2011 Water and polymer dynamics in poly(hydroxyl ethyl acrylate-co-ethyl acrylate) copolymer hydrogels. Eur Polym J 47:23912402 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 10. Haraguchi, K 2007 Nanocomposite hydrogels. Curr Opin Solid State Mater Sci 11:4754 .

  • 11. Janovák, L, Varga, J, Kemény, L, Dékány, I 2009 Swelling properties of copolymer hydrogels in the presence of montmorillonite and alkylammonium montmorillonite. Appl Clay Sci 43:260270 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 12. Janovák, L, Varga, J, Kemény, L, Dékány, I 2009 The effect of surface modification of layer silicates on the thermoanalytical properties of poly(NIPAAm-co-AAm) based composite hydrogels. J Therm Anal Calorim 98:485493 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 13. Rodriguez Hernandez, JC, Salmeron Sanchez, M, Gomez Ribelles, JL, Monleon Pradas, M 2007 Polymer-silica nanocomposites prepared by sol–gel technique: nanoindentation and tapping mode AFM studies. Eur Polym J 43:27752783 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 14. Rodriguez Hernandez, JC, Monleon Pradas, M, Gomez Ribelles, JL 2008 Properties of poly(2-hydroxyethyl acrylate)-silica nanocomposites obtained by the sol–gel process. J Non-Cryst Solids 354:19001908 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 15. Pandis, C, Spanoudaki, A, Kyritsis, A, Pissis, P, Rodriguez Hernandez, JC, Gomez Ribelles, JL, Monleon Pradas, M 2011 Water sorption characteristics of poly(2-hydroxyethyl acrylate)/silica nanocomposite hydrogels. J Polym Sci Part B Polym Phys 49:657668 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 16. Stathopoulos, A, Klonos, P, Kyritsis, A, Pissis, P, Christodoulides, C, Rodriguez Hernandez, JC, Monleon Pradas, M, Gomez Ribelles, JL 2010 Water sorption and polymer dynamics in hybrid poly(hydroxyethyl-co-ethyl acrylate)/silica hydrogels. Eur Polym J 46:101111 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 17. F Kremer A Schoenhals eds. 2002 Broadband dielectric spectroscopy Springer Berlin.

  • 18. Donth, E 2001 The glass transition: relaxation dynamics in liquids and disordered materials Springer Berlin.

  • 19. S Havriliak Jr Havriliak, SJ 1997 Dielectric and mechanical relaxation in materials Hanser Munich.

  • 20. Kripotou, S, Pissis, P, Savelyev, YV, Robota, LP, Travinskaya, TV 2010 Polymer dynamics in polyurethane/clay nanocomposites studied by dielectric and thermal techniques. J Macromol Sci Phys 49:86110 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 21. Pelster, R, Spanoudaki, A, Kruse, T 2004 Microstructure and effective properties of nanocomposites: ferrofluids as tunable model systems. J Phys D Appl Phys 37:307317 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 22. Pissis, P, Kyritsis, A 1997 Electrical conductivity studies in hydrogels. Solid State Ionics 97:105113 .

  • 23. Angell, CA 1991 Relaxation in liquids, polymers and plastic crystals—strong/fragile patterns and problems. J Non-Cryst Solids 131–133:1331 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 24. Fragiadakis, D, Pissis, P 2007 Glass transition and segmental dynamics in poly(dimethylsiloxane)/silica nanocomposites studied by various techniques. J Non-Cryst Solids 353:43444352 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 25. Kourkoutsaki, Th, Logakis, E, Kroutilova, I, Matejka, L, Nedbal, J, Pissis, P 2009 Polymer dynamics in rubbery epoxy networks/polyhedral oligomeric silsequioxanes nanocomposites. J Appl Polym Sci 113:25692582 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 26. Fragiadakis, D, Bokobza, L, Pissis, P 2011 Dynamics near the particle surface in natural rubber–silica nanocomposites. Polymer 52:31753182 .

    • Crossref
    • Search Google Scholar
    • Export Citation
  • 27. Klonos, P, Panagopoulou, A, Bokobza, L, Kyritsis, A, Peoglos, V, Pissis, P 2010 Comparative studies on effects of silica and titania nanoparticles on crystallization and complex segmental dynamics in poly(dimethylsiloxane). Polymer 51:54905499.

    • Search Google Scholar
    • Export Citation
  • 28. Napolitano S , Wuebbenhorst M. The lifetime of the deviations from bulk behavior in polymers confined at the nanoscale. Nat Commun. 2011;2: 260. doi: .

    • Crossref
    • Search Google Scholar
    • Export Citation

Monthly Content Usage

Abstract Views Full Text Views PDF Downloads
Jan 2021 0 0 0
Feb 2021 1 0 0
Mar 2021 2 0 0
Apr 2021 0 0 0
May 2021 2 0 0
Jun 2021 1 0 0
Jul 2021 0 0 0