The Impact of the Molecular Weight on the Nonequilibrium Glass Transition Dynamics of Poly(Phenylmethyl Siloxane) in Cylindrical Nanopores

Changes in the glass transition dynamics caused by nanoconfinement reveal pronounced out-of-equilibrium features. Therefore, the confinement effects weaken with time. Using dielectric spectroscopy, we have investigated the impact of molecular weight on the equilibration kinetics of the studied polymer embedded within anodic aluminum oxide nanoporous templates. For our research, we have used poly(phenylmethyl siloxane) (PMPS) with low (M-w = 2530 g/mol) and high (M-w = 27,800 g/mol) molecular weight. We have found that the observed faster dynamics of the nanoporeconfined systems weakens with time, and ultimately it is possible to regain the bulk-like mobility. The equilibration time increases by reducing the pore size and lowering the annealing temperature much below the glass transition temperature of the interfacial layer, T-g_interface. The experimental data analysis has also revealed that the molecular weight of the nanopore-confined polymer influences the recovery of the bulk segmental relaxation time, tau(alpha). Low-molecular-weight PMPS rearrange and reach denser packing of the polymer chains with greater ease than the high-molecular-weight one. Finally, we have also demonstrated that the molecular weight affects the relationship between the time constant characterizing the equilibration kinetics and the characteristic time of viscous flow in cylindrical channels of nanometer size.