Thickness Dependence of Segmental Dynamics in Free-Standing Thin Films Predicted by a Dynamically Correlated Network Model

Abstract

The anomalous dynamics and glass transition behaviors of supercooled liquids under nanoconfinement, such as ultrathin polymer films, have attracted much attention in recent decades. However, a complete elucidation of this mechanism has not yet been achieved. For the dynamics of bulk materials without confinement, we previously proposed a dynamically correlated network (DCN) model, which was found to agree well with the experimental data. The model assumes that segments with thermal fluctuations are dynamically correlated to their neighbors to form string-like clusters, which eventually grow into networks as temperature decreases. In this study, we applied the DCN model to nanoconfined free-standing films by using a simple cubic lattice sandwiched between two free surface layers consisting of virtual "uncorrelated" segments. The average size of DCNs at lower temperatures decreased with decreasing thickness because of confinement. This trend was associated with a decrease in the percolation temperature at which the size of DCN diverges. It was also revealed that the fractal dimension of the generated DCNs exhibits a peak with respect to temperature. The segmental relaxation time for free-standing polystyrene films was evaluated, and the predicted thickness dependence of the glass transition temperature qualitatively agreed with the experimental data. The results suggest that the concept of DCN is compatible with the dynamics of freestanding thin films.