Selective localization of nanohydroxyapatite in poly(3-hydroxybutyrate)/polycaprolactone blends composites and its effects on crystallization and molecular dynamics

This work deals with the thermodynamic selective localization of hydroxyapatite nanoparticles (Hap) and its effects on crystallization and molecular dynamics in immiscible polyester blend films based on poly(3-hydroxybutyrate) (PHB, 90 wt%) and polycaprolactone (PCL, 10 wt%). Polymer blend composite films were obtained through solution casting method and characterized by contact angle (surface energy measurements), ultraviolet–visible spectroscopy (UV–Vis), elemental mapping, X-ray diffraction (WAXD), differential scanning calorimetry (DSC), polarized optical microscopy (POM) and time domain nuclear magnetic resonance (TD-NMR) techniques. It was found that hydroxyapatite (Hap) is selectively localized in the PHB phase and consequently, nanoparticles strongly influenced the PHB crystallization behavior. DSC and POM results indicated that hydroxyapatite nanoparticles acted as a nucleating agent. However, no significant changes in crystallinity degree were observed by WAXD. Fractionated crystallization behavior was observed for PCL droplets and the increase in the Hap concentration promoted heterogeneous nucleation on the droplets surface due to the nanoparticles close to the interface. Molecular dynamics studies by TD-NMR suggested a disordered Hap nanoparticles distribution inside the polymer matrix, leading to slower dynamics in the semirigid fraction of the sample´s magnetization, typically attributed to restricted polymeric chains close to the particle’s surface.