The effect of cooling rate on the glass transition of an amorphous polymer

Cooling down from the equilibrium state at different rates reveals the dynamic behavior of glass forming materials. In particular, the dependence of the glass transition region on the cooling rate, q is commonly agreed to contain information regarding the activation energy of the relaxation time, τ. In this work experimental and theoretical aspects of such a relationship have been highlighted. Experimentally, the glass transition zone of amorphous polystyrene films has been investigated over two decades of cooling rate (0.5–50 K/min) by using refractive index measurements. The shift of the glass transition temperature and the broadening of the transition zone at increased cooling rate have been characterized. Theoretically, the cooling experiments have been simulated within the integral formulation of the Kovacs–Aklonis–Hutchinson–Ramos (KAHR) model using the Vogel temperature dependence for the relaxation time. The Frenkel–Kobeko–Reiner equation, τq = constant, provided the needed relationship between the experiments and the theory, enabling the evaluation of the relevant parameter of the kinetic model, i.e. the Vogel activation energy and the zero configurational entropy temperature, from the shift of the glass transition temperature with cooling rate.