Dynamic phase transitions in freestanding polymer thin films

After more than two decades of study, many fundamental questions remain unanswered about the dynamics of glass-forming materials confined to thin films. Experiments and simulations indicate that free interfaces enhance dynamics over length scales larger than molecular sizes, and this effect strengthens at lower temperatures. The nature of the influence of interfaces, however, remains a point of significant debate. In this work, we explore the properties of the nonequilibrium phase transition in dynamics that occurs in trajectory space between high- and low-mobility basins in a set of model polymer freestanding films. In thick films, the film-averaged mobility transition is broader than the bulk mobility transition, while in thin films it is a variant of the bulk result shifted toward a higher bias. Plotting this transition’s local coexistence points against the distance from the films’ surface shows thick films have surface and film-center transitions, while thin films practically have a single transition throughout the film. These observations are reminiscent of thermodynamic capillary condensation of a vapor–liquid phase between parallel plates, suggesting they constitute a demonstration of such an effect in a trajectory phase transition in the dynamics of a structural glass former. Moreover, this transition bears similarities to several experiments exhibiting anomalous behavior in the glass transition upon reducing film thickness below a material-dependent onset, including the broadening of the glass transition and the homogenization of surface and bulk glass transition temperatures.