Sharp Fronts Due to Diffusion and Viscoelastic Relaxation in Polymers

A model for sharp fronts in glassy polymers is derived and analyzed. The major erect of a diffusing penetrant on the polymer entanglement network is taken to be the inducement of a differential viscoelastic stress. This couples diffusive and mechanical processes through a viscoelastic response where the strain depends upon the amount of penetrant present. Analytically, the major effect is to produce explicit delay terms via a relaxation parameter. This accounts for the fundamental difference between a polymer in its rubbery state and the polymer in its glassy state, namely the finite relaxation time in the glassy state due to slow response to changing conditions. Both numerical and analytical perturbation studies of a boundary value problem for a dry glass polymer exposed to a penetrant solvent are completed. Concentration profiles in good agreement with observations are obtained.