Communication: Surface-facilitated softening of ordinary and vapor-deposited glasses

Abstract

A common distinction between the ordinary glasses formed by melt cooling and the stable amorphous films formed by vapor deposition is the apparent mechanism of their devitrification. Using quasi-adiabatic, fast scanning calorimetry that is capable of heating rates in excess of 105 K s-1, we have investigated the softening kinetics of micrometer-scale, ordinary glass films of methylbenzene and 2-propanol. At the limit of high heating rates, the transformation mechanism of ordinary glasses is identical to that of their stable vapor-deposited counterparts. In both cases, softening is likely to begin at the sample surface and progress into its bulk via a transformation front. Furthermore, such a surface-facilitated mechanism complies with zero-order, Arrhenius rate law. The activation energy barriers for the softening transformation imply that the kinetics must be defined, at least in part, by the initial thermodynamic and structural state of the samples.