Dynamic properties of solvent confined in silica gels studied by broadband dielectric spectroscopy

We report the results of a broadband (10−2–107 Hz) dielectric spectroscopy study on a solvent system (glycerol–water solution) confined in a porous silica matrix. The dielectric relaxation of the system is studied as a function of both temperature (120–280 K) and solvent composition (0–36 glycerol molar percentage), at constant matrix composition. Our data show that glycerol–water systems confined inside silica gel are characterized by a very complex dynamics quite different from that observed in solution, thus indicating that confinement may deeply modify solvent dynamics. Indeed in addition to the relaxation processes similar to those occurring in bulk samples, new dielectric relaxations are detected: two non-collective relaxations, attributed to water molecules strongly interacting with pore surfaces and to the glycerol trapped within the matrix structure, respectively; a relaxation in the glycerol free sample (and in samples at very low glycerol content) almost coincident with that observed in other different confinement conditions and governed by geometrical confinement per se. Moreover, at high glycerol content we observe two non-Arrhenius processes at least 4 order of magnitude slower than solution-like main relaxation; at low glycerol content the two above relaxations merge and show a fragile to strong transition at about 200 K.