Calorimetric and Dielectric Study of Renewable Poly(hexylene 2,5-furan-dicarboxylate)-Based Nanocomposites In Situ Filled with Small Amounts of Graphene Platelets and Silica Nanoparticles.

Poly(hexylene 2,5 furan-dicarboxylate) (PHF) is a relatively new biobased polyester prepared from renewable resources, which is targeted for use in food packaging applications, owing to its great mechanical and gas barrier performance. Since both properties are strongly connected to crystallinity, the latter is enhanced here by the in situ introduction in PHF of graphene nanoplatelets and fumed silica nanoparticles, as well as mixtures of both, at low amounts. For this investigation, we employed Fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and dielectric spectroscopy (BDS). The fillers were found to improve crystallization in both the rate (increasing Tc) and fraction (CF), which was rationalized via the concept of fillers acting as crystallization agents. This action was found stronger in the case of graphene as compared to silica. BDS allowed the detection of local and segmental dynamics, in particular in PHF for the first time. The glass transition dynamics in both BDS (α relaxation) and DSC (Tg) are mainly dominated by the relatively high CF, whereas in the PHF filled uniquely with silica strong spatial confinement effects due to crystals were revealed. Finally, all samples demonstrated the segmental-like dynamics above Tg, which screens the global chain dynamics (normal mode).