Solvent and temperature effects on diffusion in polymer–solvent systems



The temperature dependence of the mutual diffusion coefficient at zero solvent concentration for a number of polystyrene–solvent systems is satisfactorily represented by an equation derived from a new version of the free-volume theory of molecular transport. The free-volume parameter which governs the temperature dependence of the diffusion rate is linearly related to the size of the solvent as estimated by its molar volume at OK. Data taken on various polystyrene–solvent systems are used to deduce information on the mechanism of solvent transfer in polymeric systems.