Relationship between free volume properties and structure of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) membranes via various crystallization conditions

The relationship between the crystalline structure and the free volume properties within the amorphous phase of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) membranes, which were prepared via isothermal crystallization processes at various crystallization temperatures, was investigated. From the data of positron annihilation lifetime (PAL) spectroscopy over a temperature range of 25-90 °C, the temperature dependence of free volume size, amount, distribution, and relative fractional free volume and thermal expansion behaviors of free volume were discussed. The existence of a rigid-amorphous fraction (RAF) which constrained long-range motions in the semi-crystalline polymer was demonstrated by DSC trace and considered to interpret the temperature dependence of those free volume properties. Based on the crystallization conditions, the effect of the crystallization rate of PHBV polymer was proposed to explain the thermal expansion coefficients of free volume size. The membranes crystallized at faster crystallization rate would accompany higher thermal expansion coefficients of free volume size and the larger free volume size at higher temperatures. Larger distribution of the free volume size and higher thermal expansivity of o-Ps lifetime dispersion (dσ/dt) of isothermally melt-crystallized membranes were observed as a result of the bimodal distribution of the lamellar periodicity, which was obtained by small-angle X-ray scattering (SAXS), and less amount of RAF than that of a cold-crystallized membrane. Conclusively, free volume size and thermal expansion of the free volume in PHBV membranes were affected by the kinetics of crystallization; comparatively, the total amount of free volume and fractional free volume were determined by the final crystallinity. The size distribution of free volume was associated with the crystalline lamellar structure which was dominated by the crystallization conditions.