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On the amount of free volume in gas–polymer mixtures

Using sorption and dilatation data, the molar volumes of CO 2 and CH 4 that are inaccessible for diffusion were determined for silicone rubber. These values were used to calculate the mobile gas concentration for CO 2 and CH 4 in glassy polycarbonate assuming that an iso-free-volume state exists below the T g . The analysis presented here suggests an alternative view of the concept of partial immobilization that is independent of the dual mode sorption model. Those molecules that contribute to maintaining the iso-free-volume glassy state are mobile while those that do not are completely immobile