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[Summary] Some properties of zirconium compounds in aqueous solution have been determined using physico-chemical techniques. Zirconium oxychloride was used as the source of zirconium in all detailed investigations; zirconium sulphate was used in a few cases for comparative purposes. The Stokes diaphragm cell method has been used to determine the diffusion coefficient of zirconium in hydrochloric acid solution. It was found that the diffusion coefficient fell progressively with time, a limiting value being reached 4 to 5 weeks after dissolving the salt, and it was demonstrated that particles in the aged solutions were more homogeneous than in freshly prepared solutions. The limiting values were concentration dependent; dilute solutions had a lower diffusion coefficient than the more concentrated solutions when measured at the natural pH. In the presence of added acid the rate of diffusion was increased until a limiting value was reached in 0.5 M acid. The addition of alkali or complexing acids reduced the rate of diffusion.

Various oxygen- and nitrogen-donor ligands were investigated as potential zirconium masking agents in zirconium tanning. α-Hydroxycarboxylic acid ligands were identified as effective zirconium(IV) chelators in acidic aqueous solution. Glycolic acid, lactic acid, mandelic acid, 4-hydroxymandelic acid, 4-chloromandelic acid and 4-bromomandelic acid complexes were synthesised, isolated and characterised using a range of analytical techniques. Linear Free Energy Relationships were examined to optimise the stability of the zirconium complexes. Hammett [sigma] plots and Yukawa-Tsuno modified σ plots of the mandelate ligand and zirconium complex series indicated that inductive effects dominate within the benzene ring, however, mesomeric effects are significant outside the ring. Zirconium 4-hydroxymandelate complex solutions were identified as the most effective tanning agents and achieved shrinkage temperatures of 80 and 97ºC for hide powder and goatskin, respectively. The zirconium and 4-hydroxymandelic acid interact synergistically to yield leather equivalent to combination tanned leather in one step. Tanning was performed similarly to vegetable tanning processes with a pickle pH of approximately 5 and fixation was achieved upon acidification. Pilot-scale tanning of goatskin produced white tanned leathers and crust leathers which were physically and aesthetically comparable to matched chromium tanned material.

ZrN has been identified as a candidate material for use as an inert matrix fuel host for the transmutation of plutonium and minor actinides. These materials will be subjected to large amounts of different types of radiation within the nuclear reactor core. The types of radiation include fission fragments and alpha-particles amongst others. Recent studies suggest that nanocrystalline material may have a higher radiation tolerance than their polycrystalline and bulk counterparts. Some studies have shown that swift heavy ion irradiation may also significantly modulate hydrogen and helium behaviour in materials. This phenomenon is also of considerable practical interest for inert matrix fuel hosts, since these materials accumulate helium via (n,) reactions and will also be subjected to irradiation by fission fragments. The aim of this investigation is therefore to study the effects of fission fragment and alpha particle irradiation on nanocrystalline ZrN. In an effort to simulate the effects of fission fragments on nanocrystalline zirconium nitride different layers (on a Si substrate) of various thicknesses (0.1, 3, 10 and 20 μm) were irradiated with 167 MeV Xe, 250 MeV Kr and 695 MeV Bi ions to fluences in the range from 31012 to 2.61015 cm-2 for Xe, 1×1013 to 7.06×1013 cm-2 for Kr and 1012 to 1013 cm-2 for Bi. The purpose of this irradiation is to simulate the effects of fission fragments on nanocrystalline ZrN. In order to simulate the effects of alpha particles and the combined effects of alpha particles and fission fragments on nanocrystalline ZrN it was irradiated with 30 keV He to fluences between 1016 and 5×1016 cm-2, 167 MeV Xe to fluences between 5×1013 and 1014 cm-2 and also 695 MeV Bi to a fluence of 1.5×1013 cm-2. He/Bi and He/Xe irradiated samples were annealed at temperatures between 600 and 1000 °C. The different irradiated layers were subsequently analysed via X-ray diffraction (XRD), μ-Raman, transmission electron microscopy (TEM) and nano indentation hardness testing (NIH) techniques. XRD, TEM, μ-Raman and NIH results indicate that ZrN has a very high tolerance to the effects of high energy irradiation. The microstructure of nanocrystalline ZrN remains unaffected by electronic excitation effects even at a very high stopping power. TEM and SEM results indicated that post irradiation heat treatment induces exfoliation at a depth that corresponds to the end-of-range of 30 keV He ions. Results from He/Xe irradiated samples revealed that electronic excitation effects, due to Xe ions, suppress helium blister formation and consequently the exfoliation processes. He/Bi samples however do not show the same effects, but this is possibly due to the lower fluence of Bi ions. This suggests that nanocrystalline ZrN is prone to the formation of He blisters which may ultimately lead material failure. These effects may however be mitigated by electronic excitation effects from certain SHIs.

An investigation of the zirconium-rich corner of the zirconium-titanium-niobium constitutional diagram is described. X-ray techniques and metallography were used. A high-temperature x-ray goniometer attachment was employed to construct ternary isopleths. Isothermal sections and lattice parameter measurements are also outlined. The occurrence of a transitional ω -phase identified tentatively as tetragonal, is noted. The ternary constitutional data presented represent essentially a survey of the zirconium-rich corner and more detailed results must await further work. / Applied Science, Faculty of / Materials Engineering, Department of / Graduate

The tetra-halides of zirconium and hafnium were reacted with one equivalent of the potentially tridentate hybrid ligand, N(SiMe₂CH₂PR₂)2-, (R = Me, i-Pr, t-Bu) to generate the corresponding mono-ligand complexes MCl₃{N(SiMe₂CH₂PR₂)₂), (M = Zr, Hf). Based on the results obtained from the solution spectroscopic data and the single crystal X-ray diffraction analyses of HfCI₃{N(SiMe₂CH₂PMe₂)₂> and ZrCl₃{N(SiMe₂CH₂P(i-Pr)₂)₂) the stereochemistries of all the MCI ₃{N(SiMe ₂CH₂PR₂) ₂) complexes were found to be meridional in solution, but both facial and meridional geometries were displayed in the solid state dependent on the ligand. The mono-ligand derivatives served as useful starting materials for the generation of zirconium- and hafnium-carbon bonds. Thus the addition of three equivalents of MeMgCl to one equivalent of MCl₃{N(SiMe₂CH₂PR₂)₂} generated the trimethyl complexes M(CH₃)₃{N(SiMe₂CH₂PR₂)₂}. When two equivalents of MeMgCl was added to the mono-ligand complexes, an inseparable mixture of the monomethyl and dimethyl derivatives was obtained. The stereochemistry of Hf(CH₃)₃{N(SiMe₂CH₂PMe₂)₂} is facial in the solid state but displays unusual fluxional behaviour in solution. This behaviour is observed for all the trimethyl derivatives as a consequence of the dissociative nature of the phosphine donors. Several possible rearrangement pathways for these compounds are discussed in an attempt to interpret this behaviour in solution. / Science, Faculty of / Chemistry, Department of / Graduate

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N/A / Thesis / Master of Engineering (ME)

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