Glass transition of polymers confined to nanoporous glasses

The glassy dynamics of poly(propylene glycol) (PPG) and poly(methyl phenyl siloxane) (PMPS) confined to nanoporous glasses (pore sizes 2.5-20 nm) investigated by dielectric spectroscopy, temperature modulated DSC and neutron scattering is compared. For both systems the relaxation rates estimated from dielectric spectroscopy and temperature modulated DSC agree quantitatively indicating that both experiments sense the glass transition. For PPG the glassy dynamics in nanopores is determined by a counterbalance of an adsorption and a confinement effect where the temperature dependence of the relaxation times obeys the Vogel/Fulcher/Tammann (VFT-) equation. The former effect results from an interaction of the confined macromolecules with the internal surfaces which in general slows down the molecular dynamics. A confinement effect leads to an acceleration of the segmental dynamics compared to the bulk state and points to an inherent length scale on which the glassy dynamics takes place. The step of the specific heat capacity Deltac(p) at the glass transition vanishes at a finite length scale of 1.8 nm. This result supports further the conception that a characteristic length scale is relevant for glassy dynamics. For PMPS down to a pore size of 7.5 nm the temperature dependence of the relaxation times follows the VFT-dependence and a confinement effect is observed like for PPG. At a pore size of 5 nm this changes to an Arrhenius-like behavior with a low activation energy. At the same pore size Deltac(p) vanishes for PMPS. This points to a dramatic change in the character of molecular motions responsible for glassy dynamics and supports further the relevance of a characteristic length scale on which it takes place. Quasielastic neutron scattering experiments on PMPS reveal that the microscopic dynamics characterized by the mean square displacement depends on confinement above the glass transition. The diffusive character of the relevant molecular motions seems to disappear at a length scale of about 1.6 nm.