Abstract
The diffusion, solubility, and permeability behavior of oxygen and carbon dioxide were studied in amorphous and semicrystalline syndiotactic polystyrene (s‐PS). The crystallinity was induced in s‐PS by crystallization from the melt and cold crystallization. Crystalline s‐PS exhibited very different gas permeation behavior depending on the crystallization conditions. The behavior was attributed to the formation of different isomorphic crystalline forms in the solid‐state structure of this polymer. The β crystalline form was virtually impermeable for the transport of oxygen and carbon dioxide. In contrast, the α crystalline form was highly permeable for the transport of oxygen and carbon dioxide. High gas permeability of the α crystals was attributed to the loose crystalline structure of this crystalline form containing nanochannels oriented parallel to the polymer chain direction. A model describing the diffusion and permeability of gas molecules in the composite permeation medium, consisting of the amorphous matrix and the dispersed crystalline phase with nanochannels, was proposed. Cold crystallization of s‐PS led to the formation of a complex ordered phase and resulted in complex permeation behavior. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2519–2538, 2001