Dielectric investigations of the dynamic glass transition in nanopores

Broadband dielectric spectroscopy (${10}^{\mathrm{-}2}$ Hz–${10}^9$ Hz) is employed to study the dynamic glass transition of low-molecular-weight glass-forming liquids being confined to nanoporous sol-gel glasses with pore sizes of 2.5, 5.0, and 7.5 nm. As glass-forming liquids, salol (one hydroxy group), pentylene glycol (two hydroxy groups), and glycerol (three hydroxy groups) were chosen. We interpret the dielectric spectra in terms of a two-state model with dynamic exchange between a bulklike phase in the pore volume and an interfacial phase close to the pore wall. This enables one to analyze in detail the interplay between the molecular dynamics in the two subsystems (bulklike and interfacial), its dynamic exchange, and hence their growth and decline in dependence on temperature and strength of the molecular interactions. For glycerol it is shown that a bulklike dynamic glass transition takes place in subvolumes as small as about 1 nm. © 1996 The American Physical Society.