Poly(3−hydroxybutyrate−co−3−hydroxyhexanoate) (PHBH) films were prepared using a cast film technique. Dioxane was chosen over other polymer solvents as it resulted in homogenous films with better morphology. Several plasticizers with different molecular weights and concentrations were added to the biopolymer solution prior to casting. Thermal, crystalline, and permeability properties were analyzed by thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), X−ray diffraction (XRD), and both water vapor and oxygen transmission rate analysis. In general, the addition of plasticizers decreased the glass transition temperature (T_g), cold crystallization temperatures (T_cc), melting temperatures, as well as crystallinity degrees and increased the crystallite sizes and water vapor and oxygen transmission rates. The use of isosorbide and low-molecular-weight poly(ethylene glycol) (PEG) lowered the Tg around 30 °C at the highest used concentration, also being the most effective in increasing the crystallite size. When considering isosorbide and low-molecular-weight poly(ethylene glycol) (PEG) as very good plasticizers for PHBH, the question of which plasticizer to use strongly relies on the desired PHBH application.

In this work, physically crosslinked injectable hydrogels based on carrageenan, locust bean gum, and gelatin, and mechanically nano-reinforced with green graphene oxide (GO), were developed to address the challenge of finding materials with a good balance between injectability and mechanical properties. The effect of GO content on the rheological and mechanical properties, injectability, swelling behavior, and biocompatibility of the nanocomposite hydrogels was studied. The hydrogels’ morphology, assessed by FE-SEM, showed a homogeneous porous architecture separated by thin walls for all the GO loadings investigated. The rheology measurements evidence that G′ > G″ over the whole frequency range, indicating the dominant elastic nature of the hydrogels and the difference between G′ over G″ depends on the GO content. The GO incorporation into the biopolymer network enhanced the mechanical properties (ca. 20%) without appreciable change in the injectability of the nanocomposite hydrogels, demonstrating the success of the approach described in this work. In addition, the injectable hydrogels with GO loadings ≤0.05% w/v exhibit negligible toxicity for 3T3-L1 fibroblasts. However, it is noted that loadings over 0.25% w/v may affect the cell proliferation rate. Therefore, the nano-reinforced injectable hybrid hydrogels reported here, developed with a fully sustainable approach, have a promising future as potential materials for use in tissue repair.

The production of self-reinforced composites allows for a targeted tailoring of the property profile for specific applications and offers the physical-mechanical advantages of a synergistic combination of the two components with a high value in terms of their end-of-life scenarios. This study deals with the preparation and evaluation of self-reinforced biocomposites of poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV) with PHBV microparticles produced for the first time by industry-oriented melt processing. First, microparticles with a size of 4 μm were prepared and characterized by using the miniemulsion/evaporation technique. These microparticles were then incorporated into the PHBV matrix by extrusion and injection molding. Electron microscopy revealed particles in biocomposites. The results indicate heterogeneous nucleation, leading to higher crystallinity at higher melting temperatures. This leads to a slight embrittlement and an improvement of the barrier properties against oxygen and water vapor. These industrially produced biocomposites benefit from particles by showing, among other things, higher barrier properties while retaining their green character, making them promising and easily accessible candidates for future packaging applications.