Partially crosslinked poly(β‐hydroxybutyrate‐co‐β‐hydroxyvalerate)/poly(butylene succinate) (PHBV/PBS) and poly(β‐hydroxybutyrate)/poly(butylene succinate) (PHB/PBS) blends were prepared by melt compounding with dicumyl peroxide. The effect of partial crosslinking on crystallization of the PHBV/PBS and PHB/PBS blends was investigated systematically. Differential scanning calorimetry results showed that the overall crystallization rates of both PHBV and PBS in their blends were enhanced considerably by the partial crosslinking. Similar results were also detected in the PHB/PBS blends. The polarized optical microscope observation displayed that the nuclei density of PHBV was increased while the spherulitic morphology did not change much. Conversely, the PBS spherulites turned into cloud‐like morphology after the partial crosslinking which is a result of the decrease in spherulite size, the reduction in interspherulite distance and the interconnection of fine PBS domains. Wide angle X‐ray diffraction patterns confirmed the enhancement in crystallization of the PHBV/PBS blends after the partial crosslinking without modification on crystalline forms of the PHBV and PBS components. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014, 131, 41020.
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