The structure of extruded films based on blends of polyvinyl alcohol and poly(3-hydroxybutyrate) (PHB) was studied for various compositions. The methods of DSC and X-ray analysis were used. As the phase-sensitive characteristics of the composite films, diffusion and water vapor permeability were also investigated. In addition, the tensile modulus and relative elongation-at-break were measured. Changes in the glass transition temperature of the blends and constant melting points of the components show their partial compatibility in intercrystallite regions. At the content of PHB in the composite films equal to 20–30 wt % their mechanical characteristics and water diffusion coefficients are dramatically changed. This fact, along with the analysis of the X-ray diffractograms, indicates a phase inversion in the above narrow concentration interval. The complex pattern of the kinetic curves of water vapor permeability is likely to be related to additional crystallization, which is induced in the composite films in the presence of water
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