4.6 Article

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

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JOURNAL OF MATERIALS SCIENCE
卷 56, 期 5, 页码 3692-3712

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SPRINGER
DOI: 10.1007/s10853-020-05492-8

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  1. Coordenacao de Aperfeicoamento de Pessoal de Nivel Superior-Brasil (CAPES) [001]
  2. Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPq) [159648/2017-3]

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This study investigates the selective localization of hydroxyapatite nanoparticles in polymer composite materials, and its effects on crystallization and molecular dynamics. The nanoparticles act as nucleating agents and influence the crystallization behavior of the polymer matrix, leading to changes in molecular dynamics within the sample.
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.

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