Production routes to tune cellulose nanocrystal properties and their performance at high temperatures

Abstract

This thesis explores new and existing cellulose nanocrystal (CNC) production methods and evaluates their effects on CNC properties, with emphasis on their thermal performance. CNCs produced from industrial and lab-scale processes possess a wide range of surface chemistries, surface charge contents, as well as structural and morphological properties which affect their performance in CNC-based applications. Despite the broad range of available CNC properties, some challenges persist, particularly in the incorporation of CNCs into hydrophobic matrices, high brine liquid formulations, and high temperature applications. Herein, sulfated and carboxylated CNCs produced from large-scale processes were thoroughly characterized and key differences in their thermal performance and self-assembly and rheological behaviors were identified. Furthermore, an optimization study on phosphoric acid hydrolysis parameters and a novel surface modification method which deposits cellulose phosphate oligosaccharides onto CNC surfaces were proposed. The optimization study revealed that CNCs with high colloidal stability could not be produced with phosphoric acid alone; however, the weak acid hydrolysis allowed for precise control over CNC length. The deposition of oligosaccharides onto CNCs, however, resulted in highly colloidally stable CNCs possessing both phosphate and sulfate functional groups. Furthermore, this surface modification method altered CNC surface charge content, water interactions, and the viscosity of their aqueous suspensions. In these studies, however, changes in CNC thermal performance were difficult to elucidate. As such, to further understand the effects of CNC properties on both their dried and aqueous form thermal performance, a systematic comparison of sulfated, phosphated, and carboxylated CNCs was performed. CNCs were produced with new acid blend hydrolyses (i.e., combining sulfuric and phosphoric acid) as well as existing organic acid hydrolyses and oxidation routes. The combined effects of surface chemistry and counterion profoundly affected the thermal performance of dried CNCs, whereby sulfated and carboxylated CNCs were less thermally stable with proton and sodium counterions, respectively. Additionally, dried CNCs with more surface charge groups, shorter cellulose chains, and higher specific surface areas were found to be less resistant to high temperatures. As such, the new CNCs produced with acid blends exhibited superior thermal performance in their dried form due to their lower charge contents and longer cellulose chains. In their aqueous suspension form, carboxylated CNCs far outperformed both sulfated and phosphated CNCs at high temperatures; their suspensions remained colloidally stable at temperatures up to 150°C for extended time periods. Overall, this thesis equips CNC users and researchers with knowledge and tools to expand the usage of CNCs in commercial applications, particularly those which require high temperatures such as melt-processed polymer composites and oil and gas extraction fluids.