The morphology of crystallisation of PHBV/PHBV copolymer blends

The crystallisation of a range of as-produced poly(3-hydroxybutyrate-co-3-hydroxyvalerate) copolymer blends from a mixed culture polyhydroxyalkanoate production process, with low (15%), high (82%) and intermediate (62% and 50%) average 3-hydroxyvalerate (3HV) contents, was studied at different temperatures using polarised optical microscopy, differential scanning calorimetry and X-ray crystallography. The low-3HV content material had narrow compositional distribution and crystallised in the typical highly regular banded spherulite morphology, while the other materials displayed varying degrees of interpenetrating crystallisation of separate crystal phases comprising either the 3HV or 3-hydroxybutyrate (3HB) crystal lattice structure. Because of the differing and competing crystallisation kinetics of these phases coupled with diffusion effects, there was a very strong influence of crystallisation temperature on the resulting morphology. Thus manipulation of the final material properties of such copolymeric materials is dependent on understanding these effects and controlling their processing and crystallisation temperatures and conditions.