Cellulose nanocrystals-starch nanocomposites produced by extrusion: Structure and behavior in physiological conditions.

Different amounts of cellulose nanocrystals (CNCs) were added to glycerol-plasticized thermoplastic starch (TPS) to obtain bio-based nanocomposites. First, nanocomposites are prepared by extrusion and their structure is studied at different scales using WAXS (Wide Angle X-ray Scattering) and solid-state NMR (Nuclear Magnetic Resonance) for local/crystalline organization, AF4 (Asymmetrical Flow Field-Flow Fractionation) for molecular weight and chain length, and SEM (Scanning Electron Microscopy) for the morphology at a larger scale. Then, relevant mechanical properties and behavior in physiological conditions (swelling, enzymatic degradation) are characterized. The results show that the incorporation of cellulose nanocrystals up to 2.5 wt% causes a mechanical reinforcement as determined by DMTA (Dynamic Mechanical Thermal Analysis) and reduces the swelling and the enzymatic degradation of the materials compared to reference TPS. This could be linked to the formation of starch-cellulose hydrogen and hydroxyl bonds. Conversely, above 5 wt% CNC content nanocrystals seem to aggregate which in turn worsens the behavior in physiological conditions.

All-natural bio-plastics using starch-betaglucan composites.

Grain polysaccharides represent potential valuable raw materials for next-generation advanced and environmentally friendly plastics. Thermoplastic starch (TPS) is processed using conventional plastic technology, such as casting, extrusion, and molding. However, to adapt the starch to specific functionalities chemical modifications or blending with synthetic polymers, such as polycaprolactone are required (e.g. Mater-Bi). As an alternative, all-natural and compostable bio-plastics can be produced by blending starch with other polysaccharides. In this study, we used a maize starch (ST) and an oat ß-glucan (BG) composite system to produce bio-plastic prototype films. To optimize performing conditions, we investigated the full range of ST:BG ratios for the casting (100:0, 75:25, 50:50, 25:75 and 0:100 BG). The plasticizer used was glycerol. Electron Paramagnetic Resonance (EPR), using TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) as a spin probe, showed that the composite films with high BG content had a flexible chemical environment. They showed decreased brittleness and improved cohesiveness with high stress and strain values at the break. Wide-angle X-ray diffraction displayed a decrease in crystallinity at high BG content. Our data show that the blending of starch with other natural polysaccharides is a noteworthy path to improve the functionality of all-natural polysaccharide bio-plastics systems.

Plant-crafted starches for bioplastics production.

Transgenically-produced amylose-only (AO) starch was used to manufacture bioplastic prototypes. Extruded starch samples were tested for crystal residues, elasticity, glass transition temperature, mechanical properties, molecular mass and microstructure. The AO starch granule crystallinity was both of the B- and Vh-type, while the isogenic control starch was mainly A-type. The first of three endothermic transitions was attributed to gelatinization at about 60°C. The second and third peaks were identified as melting of the starch and amylose-lipid complexes, respectively. After extrusion, the AO samples displayed Vh- and B-type crystalline structures, the B-type polymorph being the dominant one. The AO prototypes demonstrated a 6-fold higher mechanical stress at break and 2.5-fold higher strain at break compared to control starch. Dynamic mechanical analysis showed a significant increase in the storage modulus (E') for AO samples compared to the control. The data support the use of pure starch-based bioplastics devoid of non-polysaccharide fillers.

Shape memory starch-clay bionanocomposites.

1-10% starch/clay bionanocomposites with shape memory properties were obtained by melt processing. X-ray diffraction (XRD) and TEM evidenced the presence of a major fraction of clay tactoids, consisting of 4-5 stacked crystalline layers, with a thickness of 6.8 nm. A significant orientation of the nanoparticles induced by extrusion was also observed. Tensile tests performed above the glass transition of the materials showed that the presence of clay nanoparticles leads to higher elastic modulus and maximum stress, without significant loss in elongation at break which typically reached 100%. Samples submitted to a 50% elongation and cooled below the glass transition showed shape memory behavior. Like unreinforced starch, the bionanocomposites showed complete shape recovery in unconstrained conditions. In mechanically constrained conditions, the maximum recovered stress was significantly improved for the bionanocomposites compared to unreinforced starch, opening promising perspectives for the design of sensors and actuators.

Effect of crystallinity and plasticizer on mechanical properties and tissue integration of starch-based materials from two botanical origins.

The application of starch-based materials for biomedical purposes has attracted significant interest due to their biocompatibility. The physical properties and crystal structure of materials based on potato starch (PS) and amylomaize starch (AMS) were studied under physiological conditions. PS plasticized with 20% glycerol presented the best mechanical properties with an elastic modulus of 1.6MPa and a weak swelling, remaining stable for 30 days. The in vitro cell viability of 3T3 cells after contact with extracts from PS and AMS with 20% glycerol is 72% and 80%, respectively. PS presented good tissue integration and no significant inflammation or foreign body response after 30 days intra-muscular implantation in a rat model, contrary to AMS. It was shown that glycerol plasticization favors a fast B-type crystallization of PS materials, enhancing their mechanical strength and durability, and making them a good candidate for bioresorbable and biocompatible materials for implantable medical devices.