Two relaxation mechanisms for rejuvenation of stable polymer glass

Abstract

We report on the rejuvenation of thin films of polystyrene (PS) as they are heated from stable glassy states - prepared either through vapour deposition or physical aging. For films with thickness $h \gtrsim 200$ nm, the rejuvenation of vapour deposited stable PS glass films follow behaviour well-documented for other stable glasses. For films with thickness $h \lesssim 160$nm the behaviour of the vapour deposited films becomes more complicated. This behaviour is characterized for different film thicknesses. The results are compared with vapour deposited films that are aged after rejuvenation or spincast and aged. Collectively, the results of these studies strongly suggest two distinct mechanisms that can result in rejuvenation, and hence two distinct relaxation processes that can couple to the material density. The two physical mechanisms can provide insight into poorly understood or apparently contradictory aspects of $T_g$ measurements in thin PS films.