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Chitin nanofibers of unique structure and properties can be obtained from crustacean and fishery waste. These chitin nanofibers have roughly 4 nm diameters, aspect ratios between 25–250, a high degree of acetylation and preserved crystallinity, and can be potentially applied in hydrogels. Hydrogels with a chitin nanofiber content of 0.4, 0.6, 0.8, 1.0, 2.0, and 3.0 wt % were successfully prepared. The methodology for preparation is new, environmentally friendly, and simple as gelation is induced by neutralization of the charged colloidal mixture, inducing precipitation and secondary bond interaction between nanofibers. Pore structure and pore size distributions of corresponding aerogels are characterized using auto‐porosimetry, revealing a substantial fraction of nanoscale pores. To the best of our knowledge, the values for storage (13 kPa at 3 wt %) and compression modulus (309 kPa at 2 wt %) are the highest reported for chitin nanofibers hydrogels.

Bio-based polymers are of increasing interest in packaging applications as alternatives to petroleum-based polymers. Xyloglucan (XG) derived from tamarind seed waste was recently explored as a high performance biopolymer for packaging applications. Xyloglucan films have high strength, stiffness and oxygen barrier performance, but suffer from limitations in properties under high humidity conditions. This aspect is addressed in the present work using XG modification by enzymatic removal of side chain galactose residues. The modified XG was characterized using carbohydrate analysis and MALDI-TOF MS analysis for sugar and oligosaccharide compositions respectively. The consequence of galactose removal for XG chain packing was theoretically predicted using a group contribution method and the estimation of Hansen's solubility parameters. The properties of films made from modified XG in terms of tensile, oxygen transmission rate, and thermo-mechanical behaviour were measured and related to the structure of modified XGs. Modified XG films preserved the Young's modulus at high humidity at a level of 4.3 GPa at 92% relative humidity. Moreover, the oxygen permeability of modified XG samples was very low and was about 1.5 cc μm [m2 day]−1 kPa−1 at 80% relative humidity, more than 80% lower than that for native XG. The main reason is that modified XG absorbs less moisture, due to a decreased solubility. Decreased free volume may also contribute, as galactose residues are removed and XG branches become shorter.

Nacre-mimetic clay/polymer nanocomposites with clay platelet orientation parallel to the film surface show interesting gas barrier and mechanical properties. In moist conditions, interfacial adhesion is lowered and mechanical properties are reduced. Molecular dynamic simulations (MD) have been performed to investigate the effects of counterions on molecular adhesion at montmorillonite clay (Mnt)-xyloglucan (XG) interfaces. We focus on the role of monovalent cations K(+), Na(+), and Li(+) and the divalent cation Ca(2+) for mediating and stabilizing the Mnt/XG complex formation. The conformation of adsorbed XG is strongly influenced by the choice of counterion and so is the simulated work of adhesion. Free energy profiles that are used to estimate molecular adhesion show stronger interaction between XG and clay in the monovalent cation system than in divalent cation system, following a decreasing order of K-Mnt, Na-Mnt, Li-Mnt, and Ca-Mnt. The Mnt clay hydrates differently in the presence of different counterions, leading to a chemical potential of water that is highest in the case of K-Mnt, followed by Na-Mnt and Li-Mnt, and lowest in the case of Ca-Mnt. This means that water is most easily displaced from the interface in the case of K-Mnt, which contributes to the relatively high work of adhesion. In all systems, the penalty of replacing polymer with water at the interface gives a positive contribution to the work of adhesion of between 19 and 35%. Our work confirms the important role of counterions in mediating the adsorption of biopolymer XG to Mnt clays and predicts potassium or sodium as the best choice of counterions for a Mnt-based biocomposite design.

Polysaccharide biopolymers from renewable resources are of great interest as replacements for petroleum-based polymers since they have lower cradle-to-grave non-renewable energy use and greenhouse gas emissions. Starch is widely used as a packaging material but is based on food resources such as potato or corn, and suffers from high sensitivity to water vapor even under ambient conditions. For the first time, xyloglucan (XG) from tamarind seed waste is explored as an alternative high-performance biopolymer from non-food feedstock. XG is purified, and dissolved in water to cast films. Moisture sorption isotherms, tensile tests and dynamic mechanical thermal analysis are performed. Glycerol plasticization toughening and enzymatic modification (partial removal of galactose in side chains of XG) are attempted as means of modification. XG films show much lower moisture sorption than the amylose component in starches. Stiffness and strength are very high, with considerable ductility and toughness. The thermal stability is exceptionally high and is approaching 250 °C. Glycerol plasticization is effective already at 10% glycerol. These observations point towards the potential of XG as a “new” biopolymer from renewable non-food plant resources for replacement of petroleum-based polymers.