INFLUENCE OF RHEOLOGICAL PROPERTIES IN MASS TRANSFER PHENOMENA: SUPER CASE II SORPTION IN GLASSY POLYMERS

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Abstract
The sorption rate of swelling penetrants in glassy polymers has been considered as controlled both by the swelling kinetics and the penetrant diffusion through the swollen layer. The stress exerted on the glassy core at the moving boundary is the driving force for the swelling, and results from an osmotic stress and a differential swelling stress contribution. During the sorption process, the osmotic stress at the moving boundary decreases, due to the increasing diffusion resistance; the differential swelling stress, on the contrary, increases giving rise to an acceleration of the front velocity (Super Case II). The particular case of negligible diffusion resistance in the swollen region is here considered in more detail. It is shown that the rheological properties of both swollen and glassy phases crucially enter the mass transport problem; thestress relaxation in the swollen region must be taken into account in order to obtain a thickness dependent Super Case 11 effect