Investigation of Crystallization Kinetics in Polyhydroxyalkanoates through Hyperthermal Cycles

Polyhydroxyalkanoates (PHAs) are emerging, promising sustainable biobased, biodegradable polymers with strong potential to replace conventional plastics in packaging, agricultural, cosmetics, and biomedical applications. In this study, we investigate the crystallization behavior of two key PHA typespolyhydroxybutyrate (PHB) and poly-(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV)under both isothermal and nonisothermal conditions using controlled hyperthermal cycles. Isothermal analyses were performed following rapid hypercooling at 500 °C/min to isolate crystallization kinetics, effectively minimizing interference from the cooling stage. The isothermal data revealed activation energies of 91 kJ/mol for PHB and 139 kJ/mol for PHBV. Hypercooling cycles were also employed to examine nonisothermal crystallization kinetics at cooling rates up to 500 °C/min, mimicking industrial processing speeds. The nonisothermal analysis of PHB and PHBV showed a pronounced decrease in crystallinity with increasing cooling rates. Specifically, PHB's crystallinity dropped from 48.6 to 10.9%, while that of PHBV fell from 45.9% to near zero, accompanied by the disappearance of exothermic peaks. The isothermal and nonisothermal crystallization behaviors were analyzed using the commonly used modeling, revealing the limited capability of these models in terms of the prediction of the nonisothermal crystallization kinetics from isothermal crystallization data. This study provides novel insights into the thermally driven crystallization mechanisms of PHAs and underscores their sensitivity to processing conditionscritical knowledge for optimizing manufacturing techniques in sustainable polymer applications.