Configurational entropy in thermoset polymers

The configurational entropy describes the atomic structure in a material and controls several material properties. Often the configurational entropy is determined through dielectric or calorimetric measurements where the difference between the entropies of the crystalline state and the amorphous state is determined. Many amorphous materials such as thermoset polymers have a high crystallization barrier, greatly limiting the applicability of the existing methods for determining the configurational entropy. In this work, a novel differential scanning calorimetry (DSC) method, based on measurement of the glass transition temperature at different heating rates, for determination of the configurational entropy is introduced. The theory behind the method has a universal character for amorphous materials, as it solely involves measurement of the glass transition temperature. The temperature dependency of the configurational entropy is determined for epoxy resins and PMMA (poly(methyl methacrylate)) to demonstrate the versatility of the method. On the basis of the findings of the introduced method, the influence of the degree of cross-linking and the chemical structure of the network is discussed.