Thesis ((MSc. (Physics)) -- University of Limpopo, 2018 / The mechano-chemical technique was employed to synthesise the undoped, cobalt and indium single and double doped ZnO nanoparticles powder samples. The x-ray diffraction (XRD), scanning electron microscopy (SEM), raman spectroscopy (RS), ultraviolet-visible spectroscopy (UV-vis), and photoluminescence (PL) spectroscopy were employed to characterise the prepared samples. The XRD and energy dispersive spectroscopy (EDS) results confirmed that the prepared samples were of hexagonal wurzite form. In addition, it was found that the diffraction pattern for In-ZnO nanoparticles display an additional peak which was associated with In3+ dopant. The peak suggest that In3+ ions prefer the interstitial site in the hexagonal ZnO structure. Doping the ZnO nanoparticles with Co and In did not significantly affect the lattice parameters but the average grain sizes of the nanoparticles were found to be reduced. The morphology of the samples revealed by the SEM images appear to be more spherical. The Raman modes obtained from the excitations wavelength of 514.532 nm further indicated that the prepared samples were of hexagonal ZnO structures. The energy band gap of the prepared samples were calculated from the UV-vis data which showed that the doped ZnO nanoparticles had smaller energy band gap compared to the undoped ZnO nanoparticles. The excitation wavelength of 350 nm were used in the PL study where various defects related emissions were observed for the doped and undoped ZnO nanoparticles. The kenosistec station equipment was used to investigate the prepared samples for gas sensing application. Ammonia (NH3), methane (CH4) and hydrogen sulphide (H2S) gases were probed. In all the response curves observed, the undoped and double doped ZnO nanoparticles are being favoured at a temperature range 200 – 350oC. In addition, the double doped ZnO nanoparticles was found to be more sensitive to CH4 at low temperatures and low v concentrations. / National Research Foundation (NRF) and Council for Scientific and Industrial Research (CSIR)

Thesis (Ph. D.)--University of Canterbury, 2010. / Typescript (photocopy). "February 2010." Includes bibliographical references (p. 168-181). Also available via the World Wide Web.

Structural and electronic effects in hydrocarbon reactions over metal oxides have been examined by comparing the reactions of methyl (-CH₃) and methylene (=CH₂) fragments on three different oxide single crystal surfaces: α-Cr₂O₃(101̅2), α-Cr₂O₃(0001), and α-Fe₂O₃(101̅2). The intermediates have been generated through the decomposition of halogenated hydrocarbons. The primary reactions of methyl and methylene over α-Cr₂O₃ are methyl dehydrogenation to methylene, and methylene coupling (C-C bond formation) to ethylene (CH₂=CH₂). The different surface geometric structures of α-Cr₂O₃(101̅2) and (0001) lead to an increase in the activation barrier for methylene surface migration, a critical step in the coupling reaction, of 5.9 kcal/mol over the (0001) surface. For methyl dehydrogenation, differences in the local site pair (cation/anion) geometry and the proximity of surface lattice oxygen to the methyl group do not result in a significant difference in the barrier for dehydrogenation, suggesting that the surface anions play a minor role in the dehydrogenation of methyl on these surfaces. Electronic differences in the Fe³⁺ (𝑑⁵) and Cr³⁺ (𝑑³) cations on structurally-similar α-Cr₂O₃(101̅2) and α-Fe₂O₃(101̅2) surfaces lead to major differences in reaction selectivity. α-Cr₂O₃(101̅2) is nonreducible under the reaction conditions of this study, but α-Fe₂O₃(101̅2) is highly reducible due to the difference in the d electron configuration. Hydrocarbons are formed over α-Cr₂O₃(101̅2), but nonselective oxidation products (CO₂, CO, H₂O) are formed over the stoichiometric α-Fe₂O₃(101̅2) surface along with surface reduction. Reduction of the α-Fe₂O₃(101̅2) leads to a shift in the product selectivity towards formaldehyde (CH₂O) and ethylene. For the limited number of systems examined in this study, examples of geometric structure sensitive (methylene coupling) and structure insensitive (methyl dehydrogenation) reactions have been found on α-Cr₂O₃, and electronic effects are observed for the reactions on α-Cr₂O₃(101̅2) and α-Fe₂O₃. For the structure sensitive reaction, the differences in surface geometry impact the reactions kinetics over Cr₂O₃ but not the types of products formed, while the electronic differences give rise to dramatic changes in the selectivity associated with the very different products formed over α-Cr₂O₃(101̅2) and α-Fe₂O₃(101̅2). / Ph. D.

Magnesium hydroxide, a stable flame retardant, can be obtained by mining or by the hydration of magnesium oxide. In this study, the effect of different hydrating agents on the pH of the hydrating solution, rate of hydration of MgO to Mg(OH)2 and product surface area were studied as a function of the temperature of hydration. Ammonium chloride, magnesium acetate, magnesium nitrate, nitric acid, acetic acid, water, magnesium chloride, sodium acetate and hydrochloric acid were used as hydrating agents. The hydration experiments were carried out in a water bath between 30 - 80 oC for 30 minutes. Dried MgO samples were introduced to the hydrating solution and the slurry was stirred at a constant speed. At the end of each experiment, the slurry was vacuum filtered, washed with water, dried at 200 oC and hand ground. The products were then characterized by TGA, XRF, XRD and BET surface area analyses. There was not a significant difference in the hydration behaviour of the hydrating agents up to 50 oC, where less than 10 % of magnesium hydroxide was formed. When compared to the hydration in water, all the hydrating agents with the exception of sodium acetate showed a significant increase in the degree of hydration. Sodium acetate formed the lowest amount of magnesium hydroxide, ranging between 1.2 and 12.2 % magnesium hydroxide. Hydrations performed in hydrochloric acid and magnesium nitrate formed the largest percentage (11.8 %) of magnesium hydroxide at 60 oC. Magnesium acetate, magnesium nitrate, magnesium chloride and hydrochloric acid seemed to be the most effective hydrating agents at 70 oC with the percentage magnesium hydroxide being formed ranging between 20.0 and 23.9 %. The amount of hydroxide formed doubled at 80 oC, with the largest percentage (56.7 %) formed from the hydration in magnesium acetate. The hydration reaction seemed to be dependent upon the presence of Mg2+ and acetate ions. It seemed that magnesium oxide hydration is a dissolution-precipitation process controlled by the dissolution of magnesium oxide. The results have also indicated that the pH and temperature of the hydrating solution strongly influence the degree of hydration. / Chemistry / M.Sc. (Chemistry)

The separation of oxidation-reduction reactions into individual half-cells with a resulting "mixed potential" is well known as a dissolution mechanism for metals; however, the mechanism by which non-conducting crystals lose ions to the solution has been studied only slightly.

Master of Science / Department of Kinesiology / Brett J. Wong / Nitrate supplementation in the form of beetroot juice (BRJ) has been shown to increase nitric oxide (NO), where nitrate can be reduced to nitrite and NO through both nitric oxide synthase (NOS) independent and dependent pathways. We tested the hypothesis that BRJ would augment the NO component of cutaneous thermal hyperemia. Dietary intervention consisted of one shot of BRJ for three days. Six subjects were equipped with two microdialysis fibers on the ventral forearm and randomly assigned to lactated Ringer’s (control) or continuous infusion of 20mM L-NAME (NOS inhibitor). The control site was subsequently perfused with L-NAME once a plateau in the local heating response was achieved to quantify NOS-dependent cutaneous vasodilation. Skin blood flow via laser-Doppler flowmetry (LDF) and mean arterial pressure (MAP) were measured; cutaneous vascular conductance (CVC) was calculated as LDF/MAP and normalized to %CVCmax. Maximal vasodilation was achieved via local heating to 43°C and 54mM sodium nitroprusside infusion. There was a significant decrease in DBP after BRJ (Pre-BRJ:74 ± 1 mmHg vs. Post-BRJ: 61 ± 2 mmHg; p < 0.05) and significant reduction in MAP after BRJ (Pre-BRJ: 90 ± 1 mmHg vs. Post-BRJ: 80 ± 2 mmHg; p < 0.05). The initial peak and secondary plateau phase of cutaneous thermal hyperemia were attenuated at sites with continuous LNAME; however, there was no effect of BRJ on either the initial peak at control sites (Pre-BRJ: 76 ± 3%CVCmax vs. Post-BRJ: 75 ± 4%CVCmax) or L-NAME sites (Pre-BRJ: 60 ± 4%CVCmax vs. Post-BRJ: 59 ± 5%CVCmax) or the secondary plateau phaseat control sites (Pre-BRJ: 88 ± 4%CVCmax vs. Post-BRJ: 90 ± 4%CVCmax) or L-NAME sites (Pre-BRJ: 45 ± 5%CVCmax vs. Post-BRJ: 51 ± 3%CVCmax). The decrease in %CVCmax to L-NAME infusion during the plateau of local heating (i.e. post-L-NAME drop) was greater after BRJ (Pre-BRJ: 36 ± 2%CVCmax vs. Post-BRJ: 28 ± 1%CVCmax; p < 0.05). This resulted in a greater contribution of NOS to the plateau phase of local heating (Pre-BRJ: 57±3%CVCmax vs. Post-BRJ: 64±2%CVCmax; p < 0.05). These data suggest BRJ modestly improves NOS-dependent vasodilation to local heating in the cutaneous vasculature of healthy humans.

No description available.

Thesis (M.Sc. (Physics)) -- University of Limpopo, 2015 / While the effect of sulphur on c-ZrO2 is often considered in application of advanced solid oxide fuel cells and biomass gasification cleanup, there has been little study on the effect of sulphur on general structure of c-ZrO2. In this work a study of the structural, energetic, electronic and elastic properties of doped c-ZrO2-xSx, t-ZrO2xSx and m-ZrO2-xSx solid solutions has been carried out using ab-initio total energy calculation of the density functional theory under plane wave pseudopotential method within generalized gradient approximation using the self-consistent virtual crystal approximation (VCA). It has been shown that all the calculated properties obtained after relaxation are in good agreement with available experimental and other calculated values, particularly at x=0. Furthermore, the formation and cohesive energies were calculated to determine the relative stability of all three non-sulphated and sulphated polymorphs of ZrO2. The density of states and band structures have been computed for x = 0.0 - 0.5, and the actual size of the band gap of ZrO2 compounds narrowed with partial replacement of oxygen by sulphur, while peaks above Fermi level move towards the Fermi level. The material changes its insulating properties to semiconductor material as a function of sulphur concentration, which might be useful for potential application. We also investigated and calculated, for the first time, the effect composition variation on mechanical stability, the independent elastic constants and other elastic parameters of the sulphated compounds. The polycrystalline bulk moduli, shear moduli, Young and Poisson’s ratio have been deduced by using Voight-Reuss-Hill (VRH) approximation. In addition we also show the geometric and electronic structure of pure ZrOS and ZrS2 and compare them with the obtained geometric and electronic structures of ZrO2-xSx.

In order to achieve a better understanding of the processes that occur during formation and sintering of zirconia, various chemical and physical techniques were used. Along with Perturbation Angular Correlation spectroscopy, that allowed us to investigate microscopic properties inside the nanometer-size zirconia grains, such techniques as Scanning Electron Microscopy and X-ray diffraction were used for determining the size of particles before and after sintering, and Neutron Activation Analysis was employed for measuring the impurity levels in zirconia powders. By controlling the initial conditions and heat treatment of the powders, we investigated the dependence of formation of the charged defects on the existing molecular structure and morphology of zirconia particles. During the study, it was discovered that at low temperature the PAC frequencies of tetragonal zirconia behave very similarly for all materials that were used in this study. If stabilization is achieved by heavy doping, there are shifts and line-broadening due to the presence of dopants but no obvious differences in the essential physics. One material included in this group is Nb-doped zirconia that has no oxygen vacancies. It was concluded that there are no detectable oxygen vacancies in our pure or lightly doped tetragonal zirconia powders before they are heated into the temperature region where sintering occurs. Vacancies are incorporated as the samples are heated above 1050��C, the temperature at which sintering becomes important. The oxygen vacancies in samples that have been heated to 1200��C remain when cooled. We see no vacancy concentration dependence on the atmosphere for samples not doped with +5 valent elements in order to reduce the vacancy density at 1200��C. In several instances, samples that had been heated to a maximum temperature of 1050��C or 1100��C contained a vacancy density that was small (<100 ppm) but measurable. A reduced oxygen pressure increased the oxygen vacancy density by a measurable amount in these samples. Samples that are tetragonal at 800��C are well-sintered after being heated to 1200��C. Samples that are monoclinic below 1170��C are very poorly sintered at 1200��C and contain few vacancies. Flowing Cl in the system as the samples are sintering retards the densification of the grains. These samples had the smallest density of oxygen vacancies. / Graduation date: 1998

In order to understand better the defect structure and dynamics associated with lower valent dopants complexed with native defects in group IV oxides, In/Cd perturbed angular correlation spectroscopy was performed in ceria and zirconia. Examining the orientation symmetry axis of defects in ceria single crystals at low temperature has allowed the identification of a cadmium with a bound near-neighbor oxygen-vacancy complex as well as a complex involving a cadmium with two opposing, near-neighbor oxygen vacancies. The orientation of the symmetry axis of a third complex is reported; however, this information is not sufficient to identify it. Complementing these low temperature studies, the dynamics of the cadmium/oxygen-vacancy interaction in zirconia at high temperatures was studied. The motion of the oxygen vacancy at high temperatures results in a damping of the PAC signal. This damping is not well characterized by the heuristic Marshall-Meares PAC fitting function, and a model is proposed to fit the data in terms of three physical parameters associated with the vacancy's motion. These parameters are the rate at which a bound oxygen vacancy hops among equivalent sites about the probe, the rate at which a bound vacancy detraps, and the rate at which a vacancy is trapped by cadmium. Fits of individual spectra using this model give respective activation energies of 0.3-0.6 eV, 0.9-1.6 eV, and 0.4-0.6 eV. The uncertainty in these energies can most likely be reduced by fitting spectra from multiple temperatures simultaneously. Despite the large uncertainty in the fitted energies, the values are physically reasonable and indicate that the model adequately describes the motion of the oxygen vacancy about cadmium. / Graduation date: 1997