Influence of the 3-Hydroxyvalerate Content on the Processability, Nucleating and Blending Ability of Poly(3-Hydroxybutyrate-co-3-hydroxyvalerate)-Based Materials.

Poly(3-hydroxybutyrate-co-3-hydroxyvalerate (P(3HB-co-3HV) copolymers are an attractive class of biopolymers whose properties can be tailored by changing the 3-hydroxyvalerate monomer (3HV) concentration, offering the possibility of counteracting problems related to high crystallinity, brittleness, and processability. However, there are few studies about the effects of 3HV content on the processability of copolymers. The present study aims to provide new insights into the effect of 3HV content on the processing step including common practices like compounding, addition of nucleation agents and/or amorphous polymers as plasticizers. P(3HB-co-3HV)-based films containing 3, 18, and 28 mol % 3HV were processed into films by extrusion and subsequent molding. The characterization results confirmed that increasing the 3HV content from 3 to 28 mol % resulted in a decrease in the melting point (from 175 to 100 °C) and an improvement in mechanical properties (i.e., elongation at break from 7 ± 1% to 120 ± 3%). The behavior of P(3HB-co-3HV) in the presence of additives was also investigated. It was shown that an increase in the 3HV content leads to better miscibility with amorphous polymers.

Physical-Chemical and Structural Stability of Poly(3HB-co-3HV)/(ligno-)cellulosic Fibre-Based Biocomposites over Successive Dishwashing Cycles.

In order to lengthen the life cycle of packaging materials, it is essential to study their potential for reuse. This has been never carried out for emerging bio-based and biodegradable materials such as PHBV/(ligno-)cellulosic fibre-based biocomposite materials. This work therefore highlights the impact of successive dishwashing cycles on the physical-chemical and structural stability of such materials. Several parameters were considered to assess this stability, such as the visual aspect and colour, the microstructure, the thermal and tensile properties, and the overall migration in food liquid simulants. The effect of fibre composition, morphology, and content was investigated by selecting three types of commercial (ligno-)cellulosic fibres and two filler contents (20 and 40 wt%). A great potential for reuse of PHBV films was highlighted by their high stability after up to at least 50 dishwashing cycles. However, the addition of (ligno-)cellulosic fillers negatively impacts the stability of PHBV-based materials, especially due to the hygroscopic behaviour of (ligno-)cellulosic fillers and the heterogenous microstructure of biocomposites, with at best up to 10 possible dishwashing cycles for ultra-pure cellulose. In conclusion, reuse including dishwashing steps can be considered for neat PHBV materials, while this should be prohibited for PHBV/(ligno-)cellulosic fibre-based biocomposite materials.

Development of Bio-Inspired Hierarchical Fibres to Tailor the Fibre/Matrix Interphase in (Bio)composites.

Several naturally occurring biological systems, such as bones, nacre or wood, display hierarchical architectures with a central role of the nanostructuration that allows reaching amazing properties such as high strength and toughness. Developing such architectures in man-made materials is highly challenging, and recent research relies on this concept of hierarchical structures to design high-performance composite materials. This review deals more specifically with the development of hierarchical fibres by the deposition of nano-objects at their surface to tailor the fibre/matrix interphase in (bio)composites. Fully synthetic hierarchical fibre reinforced composites are described, and the potential of hierarchical fibres is discussed for the development of sustainable biocomposite materials with enhanced structural performance. Based on various surface, microstructural and mechanical characterizations, this review highlights that nano-objects coated on natural fibres (carbon nanotubes, ZnO nanowires, nanocelluloses) can improve the load transfer and interfacial adhesion between the matrix and the fibres, and the resulting mechanical performances of biocomposites. Indeed, the surface topography of the fibres is modified with higher roughness and specific surface area, implying increased mechanical interlocking with the matrix. As a result, the interfacial shear strength (IFSS) between fibres and polymer matrices is enhanced, and failure mechanisms can be modified with a crack propagation occurring through a zig-zag path along interphases.

Hierarchical thermoplastic biocomposites reinforced with flax fibres modified by xyloglucan and cellulose nanocrystals.

This work is focused on the modification of the interphase zone in short flax fibres / polypropylene (PP) composites by a bio-inspired modification of fibres called "nanostructuration" that uses the adsorption of biomass by-products, i.e. cellulose nanocrystals (CNC) and xyloglucan (XG), to create hierarchical flax fibres. The wettability and interfacial adhesion study reveals a strong decrease in the polar character of CNC modified flax fibres, hence increasing the work of adhesion with PP. Moreover, combining XG/CNC modified interphases with MAPP coupling agent enhances the ultimate mechanical properties of biocomposites with higher tensile strength and work of rupture, and modifies failure mechanisms as revealed by in situ micro-mechanical tensile SEM experiments. Bio-based hierarchical composites inspired by naturally occurring nanostructures open a new path for the development of sustainable composites with enhanced structural properties.

Adsorption of xyloglucan and cellulose nanocrystals on natural fibres for the creation of hierarchically structured fibres.

Green treatment of natural fibres is a major issue in paper, textile and biocomposites industries to design innovative and eco-friendly products. In this work, hierarchical structuring of flax woven fabrics by the adsorption of xyloglucan (XG) and cellulose nanocrystals (CNC) is studied. Indeed, CNC have high mechanical properties, high specific surface area and great potential for functionalization. The adsorption of XG and CNC has been investigated in terms of localization by confocal and scanning electron microscopy (SEM) and quantification through adsorption isotherms. Adhesion force measurements have also been performed by Atomic Force Microscopy (AFM). XG and CNC are homogeneously adsorbed on flax fabric and adsorption isotherms reach plateau values around 20 mg /gfibres for both. The pre-adsorption of XG on flax fabric influences the amount of adsorbed CNC in the high concentrations and also creates entanglements and strong interactions between XG and CNC with the formation of an extensible network.