Understanding the lignin effect and related structural parameters relevant to the recalcitrance of the plant cell wall and the individual and cooperative effects on enzymatic saccharification are vital for improving current processing and conversion methods for cellulosic biofuels. Data were collected from several pretreatment technologies (Hot-water, organo-solv, lime, lime-oxidant, dilute acid, and dilute acid-oxidant pretreatments) on cellulose ultrastructure, partial delignification followed by dilute acid pretreatment, dilute acid pretreatment of enzymatic isolated lignin, and melt rheology test of organo-solv lignin. Results showed minimal cellulose ultrastructural changes occurred due to lime and lime-oxidant pretreatments, which however especially at short residence time displayed relatively high enzymatic glucose yield. Dilute acid and dilute acid-oxidant pretreatments resulted in the largest increase in cellulose crystallinity, para-crystalline, and cellulose-Iβ allomorph content as well as the largest increase in cellulose microfibril or crystallite size. Organo-solv pretreatment generated the highest glucose yield, which was accompanied by the most significant increase in cellulose microfibril or crystallite size and decrease in relatively lignin contents. Lignin acted as a barrier which restricted cellulose crystallinity increase and cellulose crystallite growth during dilute acid pretreatment, and that partial delignification instead of complete lignin removal during DAP would benefit the increase of sugar yield. Furthermore, a deeper understanding of the structural change of lignin in the absence of cellulose-hemicellulose matrix during dilute acid pretreatment confirmed that delignification had the most beneficial effect in poplar, but for switchgrass was the xylan removal. In addition, investigation on the structural change of organo-solv lignin during melt rheology test indicated that high purity lignin isolated from plant biomass with the lowest S/G (syringyl/guaiacyl) ratios will exhibit superior processing performance characteristics to produce high-quality carbon fibers. These findings can aid both in the development of improved enzymes that contain activities to decompose recalcitrant structures and in the design of various processing conditions that efficiently convert specific biomass feedstock into sugars. They can also help in the design of new chemical modifications on lignin and innovative biosynthesis strategies for producing linear-fiber-forming lignin with high-performance.

A novel photocrosslinkable and melt processible terpolymer precursor for carbon fibers has been successfully synthesized and characterized. The terpolymer was synthesized by an efficient emulsion polymerization route and has a typical composition of acrylonitrile/ methyl acrylate/acryloyl benzophenone in the molar ratio of 85/14/1. This thesis describes a systematic variation of the polymerization variables in the emulsion polymerization which may further enhance the system. In particular, the effects of chain transfer agent, initiator, and surfactant concentration on the polymer properties were studied. / Master of Science