Free-volume study of ethylene-vinyl alcohol copolymer evaluated through positronium lifetime measurement

The free-volume, of size ranging from 0.2 to 0.4 nm in radius, in an ethylene-vinyl alcohol copolymer was estimated using positronium lifetime measurement to elucidate the dependence of oxygen permeability on the free-volume size and fraction, on the ethylene content and on the crystallinity. The permeability and the free-volume fraction with varying the ethylene content were well related and the relation was interpreted based on the free-volume theory near below and above the glass transition temperature. On the other hand, the crystallinity significantly influenced the fraction of the amorphous region, where the free-volume hole exists, along with a slight change of the free-volume size. The variation of the permeability with the crystalline degree cannot be explained from the averaged free-volume fraction estimated by the whole volume of the polymer, but the permeability correlated with the free-volume size apparently.