Nonisothermal melt-crystallization kinetics of hydroxyapatite-filled poly(3-hydroxybutyrate) composites

The knowledge of biomedical implants ranging from drug delivery devices to tissue engineering and based on bioresorbable polymer composites is increasing, but the study of the crystallization kinetics of these kinds of composites is seldom a concern. The focus of our experimental research was the nonisothermal-crystallization behavior of poly(3-hydroxybutyrate) (PHB)/hydroxyapatite (HA) composites, which was monitored by means of differential scanning calorimetry at different cooling rates. Various macrokinetic models were applied to describe the process of nonisothermal crystallization. The results showed that the modified Avrami model and Mo's approach could describe the nonisothermal crystallization of the composites very well, but the Ozawa analysis alone was thought to be rather inapplicable. The values of the half-time and kinetic crystallizability showed that the crystallization rate increased with increasing cooling rates for both PHB and the composites. The HA particles served as additional nucleation sites, and low levels of HA resulted in dramatic increases in the crystallization rate with respect to pure PHB; however, high HA contents (> 20 wt %) clearly retarded the growth process. The activation energy for nonisothermal crystallization was evaluated with the Kissinger method and was found to vary with the incorporation of HA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5388–5395, 2006