Stringlike Cooperative Motion Explains the Influence of Pressure on Relaxation in a Model Glass-Forming Polymer Melt.

Numerous experiments reveal that the dynamics of glass-forming polymer melts are profoundly influenced by the application of pressure, but a fundamental microscopic understanding of these observations remains incomplete. We explore the structural relaxation of a model glass-forming polymer melt over a wide range of pressures ( P ) by molecular dynamics simulation. In accord with experiments for nonassociating polymer melts and the generalized entropy theory, we find that the P dependence of the structural relaxation time (τ α ) can be described by a pressure analog of the Vogel-Fulcher-Tammann equation and that the characteristic temperatures of glass formation increase with P , while the fragility decreases with P . Further, we demonstrate that τ α for various P can quantitatively be described by the string model of glass formation, where the enthalpy and entropy of activation are found to be proportional, an effect that is expected to apply to polymeric materials under various applied fields.