Multiple melting behaviour of poly(3-hydroxybutyrate-co-hydroxyvalerate) using step-scan DSC

Melting behaviour and crystal morphology of poly(3-hydroxybutyrate) (PHB) and its copolymer of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) with various hydroxyvalerate (HV) contents [5 wt.% (PHB5V), 8 wt.% (PHB8V) and 12 wt.% (PHB12V)] have been investigated by conventional DSC, step-scan differential scanning calorimetry (SDSC), wide angle X-ray diffraction (WAXRD) and hot stage polarised optical microscopy (HSPOM). Crystallisation behaviour of PHB and its copolymers were investigated by isothermal crystallisation kinetics. Thermal properties were investigated after isothermal crystallisation treatment. Multiple melting peak behaviour was observed for all polymers. SDSC data revealed that PHB and its copolymers undergo melting–recrystallisation–remelting during heating, as evidenced by exothermic peaks in the IsoK baseline (Cp,IsoK, non-reversing signal). An increase in degree of crystallinity due to significant melt–recrystallisation was observed for isothermally crystallised polymers. SDSC proved a convenient and precise method for measurement of the apparent thermodynamic specific heat (Cp,ATD, reversing signal). PHB and PHBV showed different crystal morphologies for similar crystallisation condition. HSPOM results showed that the crystallisation rates reduced and sizes of spherulites were significantly increased as HV content increased.