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

International audiencePoly(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)

Chloramphenicol Loaded Sponges Based on PVA/Nanocellulose Nanocomposites for Topical Wound Delivery

In the present study, polymer sponges based on poly(vinyl alcohol) (PVA) were prepared for the topical wound administration of chloramphenicol (CHL), an antibiotic widely used to treat bacterial infections. Nanocellulose fibrils (CNF) were homogenously dispersed in PVA sponges in three different ratios (2.5, 5, and 10 wt %) to improve the mechanical properties of neat PVA sponges. Infrared spectroscopy showed hydrogen bond formation between CNF and PVA, while scanning electron microscopy photos verified the successful dispersion of CNF to PVA sponges. The addition of CNF successfully enhanced the mechanical properties of PVA sponges, exhibiting higher compressive strength as the content of CNF increased. The PVA sponge containing 10 wt % CNF, due to its higher compression strength, was further studied as a matrix for CHL delivery in 10, 20, and 30 wt % concentration of the drug. X-ray diffraction showed that CHL was encapsulated in an amorphous state in the 10 and 20 wt % samples, while some crystallinity was observed in the 30 wt % ratio. In vitro dissolution studies showed enhanced CHL solubility after its incorporation in PVA/10 wt % CNF sponges. Release profiles showed a controlled release lasting three days for the sample containing 10 wt % CHL and 1.5 days for the other two samples. According to modelling, the release is driven by a pseudo-Fickian diffusion

Effect of Monomer Type on the Synthesis and Properties of Poly(Ethylene Furanoate)

This work aimed to produce bio-based poly(ethylene furanoate) (PEF) with a high molecular weight using 2,5-furan dicarboxylic acid (FDCA) or its derivative dimethyl 2,5-furan dicarboxylate (DMFD), targeting food packaging applications. The effect of monomer type, molar ratios, catalyst, polycondensation time, and temperature on synthesized samples’ intrinsic viscosities and color intensity was evaluated. It was found that FDCA is more effective than DMFD in producing PEF with higher molecular weight. A sum of complementary techniques was employed to study the structure–properties relationships of the prepared PEF samples, both in amorphous and semicrystalline states. The amorphous samples exhibited an increase in glass transition temperature of 82–87 °C, and annealed samples displayed a decrease in crystallinity with increasing intrinsic viscosity, as analyzed by differential scanning calorimetry and X-ray diffraction. Dielectric spectroscopy showed moderate local and segmental dynamics and high ionic conductivity for the 2,5-FDCA-based samples. The spherulite size and nuclei density of samples improved with increased melt crystallization and viscosity, respectively. The hydrophilicity and oxygen permeability of the samples were reduced with increased rigidity and molecular weight. The nanoindentation test showed that the hardness and elastic modulus of amorphous and annealed samples is higher at low viscosities due to high intermolecular interactions and degree of crystallinity