Fluid diffusion in glassy polymers proceeds in ways that are not explained by the standard diffusion model. Although the reasons for the anomalous effects are not known, much of the observed behavior is attributed to the long times that polymers below their glass transition temperature take to adjust to changes in their condition. The slow internal relaxations of the polymer chains ensure that the material properties are history-dependent, and also allow both local inhomogeneities and differential swelling to occur. Two models are developed in this thesis with the intent of accounting for these effects in the diffusion process.
In Part I, a model is developed to account for both the history dependence of the glassy polymer, and the dual sorption which occurs when gas molecules are immobilized by the local heterogeneities. A preliminary study of a special case of this model is conducted, showing the existence of travelling wave solutions and using perturbation techniques to investigate the effect of generalized diffusion mechanisms on their form. An integral averaging method is used to estimate the penetrant front position.
In Part II, a model is developed for particle diffusion along with displacements in isotropic viscoelastic materials. The nonlinear dependence of the materials on the fluid concentration is taken into account, while pure displacements are assumed to remain in the range of linear viscoelasticity. A fairly general model is obtained for three-dimensional irrotational movements, with the development of the model being based on the assumptions of irreversible thermodynamics. With the help of some dimensional analysis, this model is simplified to a version which is proposed to be studied for Case II behavior.
