Self‐Consistent Thermodynamics and Dynamics during Polymer Glass Transitions

Abstract

AbstractThe mechanisms behind the polymer glass transition, though not fully elucidated, have garnered significant attention. The Locally Correlated Lattice (LCL) theory [R. P. White, J. E. Lipson, Macromolecules 2016, 49, 3987] provides a novel perspective on free volume and establishes the relationship between polymer glass transition and free volume. In this study, we present a dynamic theoretical model based on the thermodynamic LCL theory, focusing on the kinetic evolution of free volume during polymer glass transition. Our analysis simultaneously examines the segmental diffusion coefficient, dynamic correlation length, free volume, and isobaric heat capacity. The results indicate that, upon reaching a critical temperature, heterogeneous dynamics and singular thermodynamics emerge concurrently. This study establishes a comprehensive correlation between thermodynamic singularities and dynamic inhomogeneities, offering valuable insights into the polymer glass transition process.