Reaching the ideal glass transition by aging polymer films

Abstract

Searching for the ideal glass transition, we exploit the ability of glassy polymer films to explore low energy states in remarkably short time scales. We use 30 nm thick polystyrene (PS) films, which in the supercooled state basically display the bulk polymer equilibrium thermodynamics and dynamics. We show that in the glassy state, this system exhibits two mechanisms of equilibrium recovery. The faster one, active well below the kinetic glass transition temperature (T_g), allows massive enthalpy recovery. This implies that the ‘fictive’ temperature (T_f) reaches values as low as the predicted Kauzmann temperature (T_K) for PS. Once the thermodynamic state corresponding to T_f = T_K is reached, no further decrease of enthalpy is observed. This is interpreted as a signature of the ideal glass transition.