Jlg. Ribelles et Mm. Pradas, STRUCTURAL RELAXATION OF GLASS-FORMING POLYMERS BASED ON AN EQUATION FOR CONFIGURATIONAL ENTROPY .1. DSC EXPERIMENTS ON POLYCARBONATE, Macromolecules, 28(17), 1995, pp. 5867-5877
A phenomenological model for the process of structural relaxation in g
lass-forming materials is discussed. The model is based on an expressi
on for the evolution of the configurational entropy of the material wh
en subjected to an arbitrary thermal history and contains four fitting
parameters. The prediction of the model is presented in terms of heat
capacity c(p)(T) curves, which are compared with the experimental DSC
heating scans. Experimental results on polycarbonate with a broad ser
ies of thermal histories are presented, and the routine employed to fi
t the parameters of the model is described. The procedure permits the
determination of material parameters (independent of thermal history)
of the polymer: a curve of calorimetric equilibrium relaxation times a
s a function of temperature and a value for the width parameter of the
Kohlrausch-Williams-Watts relaxation function. The possibility that t
he limit states of the structural relaxation process do not coincide w
ith the states obtained from the extrapolation of the experimentally d
etermined liquidus curve is also discussed.