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.

The objective of this Thesis is to devise a system for the "rheology-based design" of non-settling (homogeneous) slurry pipelines that is more conducive to application by practicing engineers without impairing its accuracy or utility for research purposes. The cornerstone is the development of a new rheological model and constitutive equation for homogeneous slurry based on the aggregation/deaggregation of the suspended mineral particles. This “yield plastic” model is shown to describe a family of models that includes the Newtonian, Bingham plastic and Casson models as special cases. It also closely approximates the results of many consistency models, including power law, yield power law, Cross and Carreau-Yasuda. The yield plastic model is then used to develop design equations to determine the pressure-gradient of laminar and turbulent pipe flow. A relative energy dissipation criterion is proposed for the laminar-turbulent transition and shown to be consistent with currently used transition models for Newtonian and Bingham fluids. Finally, a new dimensionless group (the “stress number”) is proposed that is directly proportional to the pressure-gradient and independent of the velocity. When the design equations are presented graphically in terms of the stress number and the plastic Reynolds number, the resulting “design curve diagram” is shown to be a dimensionless (pressure-gradient vs. velocity) pipe flow curve. The net result is that the hydraulic design of homogeneous slurry systems only requires the use of a single constitutive equation and three engineering design equations. The results are presented in a conceptually easy form that will foster an intuitive understanding of non-Newtonian pipe flow. This will assist engineers to understand the impact of slurry rheology when designing, operating and troubleshooting slurry pipelines and, in the future, other slurry related processes.

Polymorphism can influence every aspect of the properties of a solid including the shelf life, dissolution rate, solubility, formulation properties and processing properties of a solid drug. A deeper understanding of polymorphism and related solid state properties would ensure an improved quality of the materials used throughout drug preparation, dosage form formulation and clinical trials. Therefore, determination of the existence of polymorphs and pseudopolymorphs, characterization of different solid state forms and their respective properties, and controlling the existing form in the resulting formulation all form part of a rapidly growing field within pharmaceutical research and industry. Carbamazepine (CBZ) was the model drug used in this study. FT-Raman spectroscopy was chosen as a main investigative technique in this study to evaluate its potential in monitoring (pseudo)polymorphic conversions in aqueous suspensions in the absence or presence of various pharmaceutical excipients. Partial least squares analysis (PLS) was used for quantitative analysis of the spectral data. Earlier it has been found that CBZ converts rapidly to the dihydrate (DH) when exposed to humidity or water, and this has been reported to be the main reason for the sometimes observed greatly decreased bioavailability of marketed CBZ tablets. In this study, the conversion kinetics of CBZ (forms I, II and III) to DH in aqueous suspension were found to be first order kinetics with an unconverted portion (R� [greater than or equal to] 0.95), where the crystal morphology appeared to play a more important role in its conversion kinetics than the polymorphic form. The influence of pharmaceutical excipients on the conversion of CBZ in aqueous suspension was also explored. For excipients such as methylcellulose (MC), hydroxypropyl methylcellulose (HPMC) and hydroxypropyl cellulose (HPC) which have both a low solubility parameter (< 27.0 MPa[1/2]) and strong hydrogen bonding groups, complete inhibition of the conversion of CBZ was possible even at a very low concentration (0.1 % w/v). Raman spectroscopy showed its high applicability in investigating CBZ conversion kinetics and screening of excipient effects in aqueous environment. It was demonstrated that Raman has a robust nature in quantitative analysis since problems such as different particle size, morphology, and spatial distribution of the two solid state forms of the drug seemed not to have significant influence on Raman scattering. This study has also clarified the relative importance of many contributing factors (type of crystalline form (CBZ or DH), crystal morphology, surface area, and excipient interactions with drug particles) influencing the in vitro dissolution of CBZ. The solid state characterization approach taken in this study will provide a deeper insight into the dissolution performance of drugs and should thus lead to a better understanding of in vitro/in vivo behavior of drugs.

Thesis (Ph.D.) -- McMaster University, 1999. / Includes bibliographical references (leaves 179-187). Also available via World Wide Web.

Thesis (M.S.)--Virginia Polytechnic Institute and State University, 1993. / Vita. Abstract. Includes bibliographical references (leaf 210). Also available via the Internet.

Thesis (MTech (Electrical Engineering))--Cape Peninsula University of Technology, 2007. / Includes bibliographical references. Also available online.

Thesis (Ph. D.)--Michigan State University. Dept. of Chemical Engineering and Materials Science, 2006. / Title from PDF t.p. (viewed on June 19, 2009) Includes bibliographical references (p. 199-212). Also issued in print.

Thesis (Ph. D.)--University of Washington, 1999. / Vita. Includes bibliographical references (leaves 71-75).

Thesis (Ph.D.)--University of Delaware, 2009. / Principal faculty advisor: John W. Gillespie, Dept. of Materials Science. Includes bibliographical references.

Thesis (M.S.)--University of Missouri-Columbia, 2006. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed Aug. 29, 2007). Includes bibliographical references.