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Biobased and biocompatible polymers, such as polyhydroxyalkanoates (PHAs), are of great interest for a large range of applications in the spirit of green chemistry and upcoming reuse and recycling strategies. Polyhydroxybutyrate (PHB), as a promising biocompatible polymer belonging to PHAs, is subject to increased research concern regarding the high degree of crystallinity and brittle behavior of the resulting materials. Therefore, the improvement of PHB's physico-mechanical properties aims to decrease the Young's modulus values and to increase the ductility of samples. Here, we proposed an ambitious approach to develop melt-processed materials, while combining PHB characteristics with the ductile properties of poly(ε-caprolactone) (PCL). In order to compatibilize the poorly miscible PHB/PCL blends, dicumyl peroxide (DCP) was used as a free-radical promotor of polyester interchain reactions via the reaction extrusion process. The resulting PHB/PCL-DCP materials revealed a slight increase in the elongation at break, and significant improvement in the impact resistance (7.2 kJ.m−2) as compared to PHB. Additional decrease in the Young's modulus values was achieved by incorporating low molecular polyethylene glycol (PEG) as a plasticizer, leading to an important improvement in the impact resistance (15 kJ.m−2). Successful 3D printing using fused deposition melting (FDM) of the resulting PHB/PCL-based blends for the design of a prosthetic finger demonstrated the great potential of the proposed approach for the development of next-generation biomaterials. [ABSTRACT FROM AUTHOR]

In the category of biopolymers, polylactide or polylactic acid (PLA) is one of the most promising candidates considered for future developments, as it is not only biodegradable under industrial composting conditions, but it is produced from renewable natural resources. The modification of PLA through the addition of nanofillers is considered as a modern approach to improve its main characteristic features (mechanical, thermal, barrier, etc.) and to obtain specific end-use properties. Iron oxide nanoparticles (NPs) of low dimension (10–20 nm) such as magnetite (Fe3O4), exhibit strong magnetization in magnetic field, are biocompatible and show low toxicity, and can be considered in the production of polymer nanocomposites requiring superparamagnetic properties. Accordingly, PLA was mixed by melt-compounding with 4–16 wt.% magnetite NPs. Surface treatment of NPs with a reactive polymethylhydrogensiloxane (MHX) was investigated to render the nanofiller water repellent, less sensitive to moisture and to reduce the catalytic effects at high temperature of iron (from magnetite) on PLA macromolecular chains. The characterization of nanocomposites was focused on the differences of the rheology and morphology, modification, and improvements in the thermal properties using surface treated NPs, while the superparamagnetic behavior was confirmed by VSM (vibrating sample magnetometer) measurements. The PLA−magnetite nanocomposites had strong magnetization properties at low magnetic field (values close to 70% of Mmax at H = 0.2 T), while the maximum magnetic signal (Mmax) was mainly determined by the loading of the nanofiller, without any significant differences linked to the surface treatment of MNPs. These bionanocomposites showing superparamagnetic properties, close to zero magnetic remanence, and coercivity, can be further produced at a larger scale by melt-compounding and can be designed for special end-use applications, going from biomedical to technical areas. [ABSTRACT FROM AUTHOR]

Due to the added value conferred by zinc oxide (ZnO) nanofiller, e.g., UV protection, antibacterial action, gas-barrier properties, poly(lactic acid) (PLA)–ZnO nanocomposites show increased interest for utilization as films, textile fibers, and injection molding items. The study highlights the beneficial effects of premixing ZnO in PLA under given conditions and its use as masterbatch (MB), a very promising alternative manufacturing technique. This approach allows reducing the residence time at high processing temperature of the thermo-sensitive PLA matrix in contact of ZnO nanoparticles known for their aptitude to promote degradation effects onto the polyester chains. Various PLA–ZnO MBs containing high contents of silane-treated ZnO nanoparticles (up to 40 wt.% nanofiller specifically treated with triethoxycaprylylsilane) were produced by melt-compounding using twin-screw extruders. Subsequently, the selected MBs were melt blended with pristine PLA to produce nanocomposite films containing 1–3 wt.% ZnO. By comparison to the more traditional multi-step process, the MB approach allowed the production of nanocomposites (films) having improved processing and enhanced properties: PLA chains displaying higher molecular weights, improved thermal stability, fine nanofiller distribution, and thermo-mechanical characteristic features, while the UV protection was confirmed by UV-vis spectroscopy measurements. The MB alternative is viewed as a promising flexible technique able to open new perspectives to produce more competitive multifunctional PLA–ZnO nanocomposites. [ABSTRACT FROM AUTHOR]