Poly(methyl phenyl siloxane) in Random Nanoporous Glasses: Molecular Dynamics and Structure

ABSTRACTThe effect of a nanometer confinement on the molecular dynamics of poly(methyl phenyl siloxane) (PMPS) was studied by dielectric spectroscopy (DS), temperature modulated DSC (TMDSC) and neutron scattering (NS). DS and TMDSC experiments show that for PMPS in 7.5 nm pores the molecular dynamics is faster than in the bulk which originates from an inherent length scale of the underlying molecular motions. At a pore size of 5 nm the temperature dependence of the relaxation times changes from a Vogel / Fulcher / Tammann like behavior to an Arrhenius one. At the same pore size Δcp vanishes. These results give strong evidence that the glass transition has to be characterized by an inherent length scale of the relevant molecular motions. Quasielastic neutron scattering experiments reveal a strong change even in the microscopic dynamic.