Advanced biomaterials from renewable resources: An investigation on cellulose nanocrystal composites and carbon dioxide extraction of rendered materials.

摘要

The annual global consumption of petroleum-based plastics is approximately 280 million tons and is impacting the sustainability of our planet and prosperity of future generations. One solution is the development of bio-based polymer materials with advanced properties for commercial applications. Therefore, the ultimate goal of this dissertation is to investigate the properties of new bio-based materials for broader applications. This dissertation includes two research areas: cellulose nanocomposites, and CO2 extractions of rendered fat. In the first half, cellulose nanocrystals (CNCs), which exhibit excellent mechanical and optical properties, were investigated for the reinforcement of a biodegradable polymer. The properties of these nanocomposites were studied to intellectually contribute to the understanding of the reinforcement mechanisms of CNC nanocomposites. In the second half, a more efficient and greener extraction of fat from rendered materials (RMs) was explored to broaden their potential applications, which include protein-based polymers and biofuels.;Since CNCs are hydrophilic, surface modification with various surfactants was first accomplished in this research, increasing the dispersion stability in non-polar solvents by at least a month. Only 1 wt.% of surfactant with respect to CNCs was needed to afford a significant increase in the CNC stability, representing a much lower percentage than the values reported in the literature. Moreover, these CNCs showed the ability to self-assemble into local liquid crystal structures, a potential advantage for polymer reinforcement. CNCs were subsequently investigated as an additive for polylactic acid (PLA), which is the most widely used synthetic biopolymer in the market. CNC addition yielded a 61% increase in toughness at 1 wt.% CNC load. The tensile strength and modulus were not affected by the CNC addition, addressing one of the most frequent issues in the toughening of polymers. In addition, polarized microscopy revealed self-assembly formation of the enhanced composites indicating that the reinforcement was influenced by the CNC nanoscale structure on the matrix. These structures were found to be distributed in different directions along the extrusion line, suggesting that an angled CNC orientation favored a higher toughness as observed in natural cellulose fibers. PLA was also modified by grafting polyacrylic acid (PAA), which provided a stiffer and more hydrophilic surface for the addition of unmodified CNCs. In this case, the toughness of the PLA copolymer decreased with CNC concentration, while the tensile modulus increased. This effect was attributed to an increase of polymer crystallinity upon addition of CNCs, probably due to an enhanced compatibility provided by the PAA chains.;For the purpose of obtaining a more efficient separation of proteins and fats from RMs, liquid and supercritical CO2 (LCO2 and SCCO2) were explored as solvents for the extraction, demonstrating the ability to extract up to 97% of the fat in the RMs. Higher fat solubilities in LCO2 were obtained compared to SCCO2, a result attributed to a retrograde phenomenon. These results are advantageous for the separation of rendered fats at relatively low temperatures and pressures, obtaining higher yields than screw pressing currently used in the industry. However, this extraction requires high amounts of CO2 due to low fat solubilities. This issue was addressed using CO2-assisted mechanical extraction, resulting in yields up to 81%, representing a 98% increase compared to conventional extraction, and significantly reducing the amount of CO2 for the extraction.