Reconciling computational and experimental trends in the temperature dependence of the interfacial mobility of polymer films

Abstract

Many measurements have indicated that thin polymer films in their glass state exhibit a mobile interfacial layer that grows in thickness upon heating, while some measurements indicate the opposite trend. Moreover, simulations and limited measurements on glass-forming liquids at temperatures above the glass transition temperature Tg exhibit a growing interfacial mobility scale ζ upon cooling. To better understand these seemingly contradictory trends, we perform molecular dynamics simulations over a temperature regime for which our simulated polymer film enters a non-equilibrium glassy state and find that the relaxation time τα within the film interior, relative to the polymer-air interfacial layer, exhibits a maximum near the computational Tg. Correspondingly, we also observe that the interfacial mobility length scale exhibits a maximum near Tg, explaining the apparent reversal in the temperature dependence of this scale between the glass and liquid states. We show that the non-monotonic variation of ζ and the relative interfacial mobility to the film interior arise qualitatively from a non-monotonic variation of the gradient of the effective activation free energy of the film; we then obtain a quantitative description of this phenomenon by introducing a phenomenological model that describes the relaxation time layer-by-layer in the film for a temperature range both above and below Tg of the film as a whole. This analysis reveals that the non-monotonic trend in the relative interfacial mobility and ζ both arise primarily from the distinctive temperature dependence of relaxation in the interfacial layer, which apparently remains in local equilibrium over the whole temperature range investigated.