| Summary: | Sulfuric acid hydrolysis of native cellulose fibers produces stable suspensions of cellulose nanocrystals. Within a specific concentration range, the suspensions spontaneously form an anisotropic chiral nematic liquid crystal phase. This thesis examines the phase separation behaviour of these suspensions, alone and in the presence of added macromolecules. Initially, the effect of hydrolysis conditions on the nanocrystal and phase separation properties for hydrolyzed softwood pulp were investigated and compared to suspensions prepared from hardwood pulp. The macromolecules studied, blue dextrans of varying molecular weights and dye ligand densities, were synthesized and characterized with a number of techniques. The polyelectrolytic nature of these macromolecules was found to strongly influence their physico-chemical properties. Added blue dextran causes separation of an isotropic phase from highly concentrated, completely anisotropic suspensions. The observed phase separation was found to be associated with the charged dye molecules attached to the dextran. The partitioning behaviour of blue dextrans in biphasic aqueous suspensions of native cellulose nanocrystals was also studied with regard to the effect of total concentration of blue dextran, degree of dye substitution and dextran molecular weight on the blue dextran partition coefficient. Electrostatic and entropic contributions to the partition coefficient of blue dextran were discussed. Triphase isotropic-isotropic-nematic (I1--I 2--N) equilibria are observed in suspensions containing both neutral dextrans and polyelectrolytic blue dextrans of varying molecular weight. Based on these results, phase diagrams for cellulose nanocrystal suspensions with different combinations of dextran and blue dextran are presented.
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