Influence of chitosan protonation degree in nanofibrillated cellulose/chitosan composite films and their morphological, mechanical, and surface properties.

Composite films of nanofibrillated cellulose (NFC) and chitosan (CS) were prepared by spray deposition method, and the influence of polymers ratio and protonation degree (α) of chitosan was evaluated. Films were characterized using morphological, mechanical, and surface techniques. Higher NFC content increased Young's modulus of film composites and reduced air permeability, while higher CS content increased water contact angle. Variations in the degree of protonation of chitosan from non-protonated (α = 0) to fully protonated (α = 1) in the NFC/CS composite film with a fixed composition allowed to modulate surface, mechanical, and structural properties, such as water contact angle (31.3-109.2°), Young's modulus (1.7-5.3 GPa), elongation at break (3.1-1.2 %), oxygen transmission rate (9.0-5.5 cm3/m2day) and air permeability (2074-426 s). Highly protonated chitosan composite films showed similar contact angles to pure chitosan films, while low protonated chitosan composite films presented contact angles similar to pure NFC films, suggesting a possible coating effect of NFC by CS through electrostatic interactions, evidenced by microscopy and spectroscopy analysis. By mixing both polymers and adjusting composition and protonation degree it was possible to enhance their properties, making pH adjustment a useful tool for NFC/CS composite films formation.

Recent developments in short- and medium-chain- length Polyhydroxyalkanoates: Production, properties, and applications.

Developing renewable resource-based plastics with complete biodegradability and a minimal carbon footprint can open new opportunities to effectively manage the end-of-life plastics waste and achieve a low carbon society. Polyhydroxyalkanoates (PHAs) are biobased and biodegradable thermoplastic polyesters that accumulate in microorganisms (e.g., bacterial, microalgal, and fungal species) as insoluble and inert intracellular inclusion. The PHAs recovery from microorganisms, which typically involves cell lysis, extraction, and purification, provides high molecular weight and purified polyesters that can be compounded and processed using conventional plastics converting equipment. The physio-chemical, thermal, and mechanical properties of the PHAs are comparable to traditional synthetic polymers such as polypropylene and polyethylene. As a result, it has attracted substantial applications interest in packaging, personal care, coatings, agricultural and biomedical uses. However, PHAs have certain performance limitations (e.g. slow crystallization), and substantially more expensive than many other polymers. As such, more research and development is required to enable them for extensive use. This review provides a critical review of the recent progress achieved in PHAs production using different microorganisms, downstream processing, material properties, processing avenues, recycling, aerobic and anaerobic biodegradation, and applications.

In Situ Cellulose Nanocrystal-Reinforced Glycerol-Based Biopolyester for Enhancing Poly(lactic acid) Biocomposites.

Biobased, elastomeric polymer poly(glycerol succinate-co-maleate) (PGSMA) was produced using a "green" synthesis with added cellulose nanocrystals (CNCs) to create a novel PGSMA-CNC material. PGSMA-CNC was synthesized with the aim of developing a new strategy for successfully dispersing CNCs within a poly(lactic acid) (PLA) matrix for optimal reinforcement of tensile strength and modulus while having the added benefit of the proven toughness enhancements of PLA/PGSMA blends. Optical microscopy and fractionation in tetrahydrofuran showed that CNCs agglomerated during PGSMA-CNC synthesis and remained in agglomerates during PLA/PGSMA-CNC reactive blending. Fourier transform infrared, differential scanning calorimetry, and dynamic mechanical analyses also showed that PGSMA-CNC inhibited the formation of PGSMA crosslinks and PLA-g-PGSMA during reactive blending. These two effects resulted in loss of impact strength and only a 4% increase in tensile modulus over PLA/PGSMA at the highest CNC content. Further work in preventing CNC aggregation could help improve mechanical properties of the final blend.

Synthesis of Glycerol-Based Biopolyesters as Toughness Enhancers for Polylactic Acid Bioplastic through Reactive Extrusion.

The synthesis of polyesters based on glycerol, succinic acid [poly(glycerol succinate), PGS] and/or maleic anhydride [poly(glycerol succinate-co-maleate), PGSMA] was investigated aiming to produce a green product suitable for toughening of polylactic acid (PLA) using melt blending technologies. The molar ratio of reactants and the synthesis temperature were screened to find optimum synthesis conditions leading to the highest toughness enhancement of PLA. It was found that a molar ratio of reactants of 1:1 glycerol/succinic acid increases the effectiveness of PGS as a toughening agent for PLA, which correlates with the achievement of a higher molecular weight on the synthesis of PGS. The introduction of maleic anhydride as a comonomer for the synthesis of the partial replacement of succinic acid was advantageous for making PGS suitable for reactive extrusion (REX) mediated by free radical initiators. The tensile toughness of the REX PLA/PGSMA blends was improved by 392% compared with that of neat PLA, which was caused by the simultaneous cross-linking of PGSMA within the PLA matrix, and the in situ formation of PLA-g-PGSMA graft copolymers acting as interfacial compatibilizers. Two-dimensional nuclear magnetic resonance and Fourier transform infrared analysis confirmed the formation of PLA-g-PGSMA species on REX experiments. This in turn caused a decrease in the diameter of the PGS particles dispersed within the PLA matrix from >10 µm to approximately 2 µm as observed using scanning electron microscopy. A further increase of 1600% in the toughness of the blends was achieved by lowering the synthesis temperature of PGSMA from 180 to 150 °C. The optimum synthesis conditions for PGSMA leading to the highest increase in the toughness of 80/20 PLA/PGSMA blends were found to be 1:0.5:0.5 mol glycerol/succinic acid/maleic anhydride synthesized at a temperature of 150 °C for 5 h.