Please read the abstract in the section 00front of this document / Dissertation (MSc (Chemistry))--University of Pretoria, 2003. / Chemistry / unrestricted

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M.Sc. / Polymerization of a-olefins by metallocene-based catalysts, is an ever expanding field with current scientific research continuing in an endeavor to develop chiral catalysts with greater stereospecificity and activities. However, the application of metallocene catalysts in oligomerization reactions of a-olefins has been somewhat neglected. This is despite the fact that metallocene catalysis can offer a convenient route to the synthesis of higher a-olefin oligomers. Furthermore, by utilizing an assortment of functional group transformations, a-olefin oligomers can serve as intermediates for a variety of specialty chemicals. Notwithstanding the possibility of employing alternative ligands in catalysis, the use of non-cyclopentadienyl-based complexes is a topic that has only recently been considered. Comparative studies of a series of analogous complexes is lacking in this field and thus a pertinent study of a number of known metallocene complexes was executed in this project. Furthermore, an industrially applicable process for oligomerization was sought after. This was in fact achieved by subjecting the a-olefins 1-pentene, 1- hexene and 1-octene, to oligomerization conditions with a previously unreported and lowered methylaluminoxane ratio. This reaction proved to be highly selective to dimer formation of the three aforementioned higher a-olefins. In order to gain more insight into the oligomerization process, the progress of the reaction was also followed. Only zirconium complexes were synthesized and furthermore, the induction of oligomerization as opposed to polymerization (using compounds known to be active solely as polymerization catalysts), was attempted by increasing the reaction temperature. The second part of this project entailed the synthesis and subsequent testing of zirconium catalysts containing non-cyclopenatadienyl-based ligands. These complexes have frameworks with chelating phenolate or naphtholate ligands. These complexes were tested for oligomerization, but results proved to be negative.

The widespread use of high temperature superconductors through improved understanding of their underlying physics is in part dependent on the synthesis of large, high quality single crystals for physical research. Crucible corrosion is an important factor hindering the routine synthesis of large, high purity rare-earth barium cuprate superconductor single crystals. Molten BaCuO2-CuO fluxes required for the growth of such crystals are highly corrosive to substrate materials, and corrosion products may lead to chemical contamination of crystals and other practical difficulties. BaZrO3 is known to be inert to BaCuO2-CuO melts, but its use has remained restricted to a very small number of laboratories worldwide because it is very sensitive to the effects of off- stoichiometric or residual secondary phases which degrade its performance. BaZrO3 suitable for sustained melt containment is difficult to produce due to kinetic limitations of phase purity, difficulty in sintering to adequate density, and very narrow stoichiometry tolerances of finished ceramics. The existing literature provided a guide to the production of high quality BaZrO3, but was not sufficiently complete to readily allow production of crucibles suitable for this application. The two basic aims of this project were: To provide a comprehensive and quantitative description of the necessary attributes of crucibles for barium cuprate melt processing and to expand the knowledge of solid-state BaZrO3 processing to encourage its widespread application to crucible manufacture; To explore the application of solution chemical processes whose potential benefits could lead to routine application of BaZrO3 through improved ceramic quality and processing properties. / Based primarily on solid-state processing research, the optimal stoichiometry for corrosion resistant crucibles was observed over the narrow range of 1.003±0.003 Ba : (Zr + Ht) mole ratio. Residual ZrO2 must be strictly avoided even at very low levels because severe localized expansion of Z a grains during reaction with the melt severely reduces corrosion resistance. Although the effect of Ba-rich phases are less severe, their abundance must be suppressed as much as allowed by the production process. Solid-state derived crucibles with a large barium excess were unstable and readily attacked by water. TEM analysis clearly showed residual Zr02 was present as discrete grains and not as grain boundary films, and also the prevalence of intragranular defects in Ba-rich ceramics. Quantitative knowledge of the narrow range of required stoichiometry is critical for developing successful solid-state and solution chemical processes. Reliably achieving the required stoichiometry and phase purity is experimentally challenging and beyond the capability of many processing systems. Systematic investigation revealed sharp changes in physical properties of processed powders across the phase boundary. The resistance of BaZrO3, of the desired stoichiometry to grain growth during powder processing has not previously been reported in the available literature. At the desired stoichiometry for corrosion resistance, powder grain growth resistance combined with very precise control over stoichiometry makes the solid-state process more competitive with solution-based processes than previously acknowledged in the literature. The development of solution processes for BaZr03 precursors is complicated by aqueous chemistry of zirconium compounds. / This project developed the first chemically derived precursor process demonstrated to produce a ceramic of adequate quality for sustained barium cuprate melt containment. The barium acetate / zirconium oxychloride / ammonium oxalate system provided control over stoichiometry without requiring elevated solution temperatures, a large excess of barium reagents, or reagents containing alkalis. Despite showing the capability to supersede the solid-state process, the oxalate process still requires further refinement to more reliably achieve high sintered densities. Although the attributes required for sustained barium cuprate melt containment are now clear, its routine mass production remains reliant on further development of solution chemical techniques or improvements to the kinetics of solid-state processing. This project advanced ceramic design and processing technology in the BaZrO3 system and provided new approaches in meeting the challenging analytical needs of research and process control for high quality production of this compound.

The metal hydride used as hydrogen storage material has come into public notice. It is very important to understand the crystal structure and the permutation of hydrogen and the metal crystal structure of hydride for developing industrial hydrogen storage material. The tetrahedral formation of the atom intervals of titanium/zirconium alloys benefits the absorbing of hydrogen atoms. Especially under high temperature, the titanium/zirconium alloys have high affinity on hydrogen, and hydrogen atoms help to absorb within the titanium/zirconium alloys can spread and enter materials fast on the surface, this way will get uniform saturation solid solution. Therefore, we use hydrogen gas in the high-temperature gaseous phase to melt the titanium/zirconium alloys and observe the crystal structure and morphology of hydride precipitates with transmission electron microscopy. The research contents are as follows: (1) In Ti-H system, ageing of quenched specimens which contained the hydrides are found to have a face-centered tetragonal structure (£^-titanium hydride). Ageing of furnace-cooled specimens which contained the hydrides are found to have a face-centered cubic structure (£_-titanium hydride). (2) In Zr-H system, ageing of quenched specimens which contained the hydrides are found to have a face-centered tetragonal structure (£^-zirconium hydride). Ageing of furnace-cooled specimens which contained the grain-boundary hydrides are found to have a face-centered cubic structure (£_-zirconium hydride).