Non-equilibrium glassy properties and their relevance in Case II transport kinetics

Abstract

Some relevant non-equilibrium properties, frozen into the glassy matrix, have been considered, and related expressions for the excess chemical potential have been proposed. Both isotropic and anisotropic cases have been analysed. In the isotropic case, the out-of-equilibrium has been related to the excess volume over the value of the equilibrium liquid; the calculation of the energy related with the excess volume has been performed by using a liquid lattice constitutive equation. In the anisotropic case, use has been made of the entropy decrease due to the existing orientations. It is shown that, in both cases, the driving force for swelling is heavily influenced by the out-of-equilibrium which is frozen in the glass under the usual operating conditions; in particular, the out-of-equilibrium term becomes the dominant term in the anisotropic case at high orientations. In the isotropic case, the introduction of the excess over-equilibrium results in an improvement of a recently proposed kinetic model.