published_or_final_version / abstract / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / abstract / Physics / Doctoral / Doctor of Philosophy

Fundamental solvent extraction studies on the separation of the lanthanides were carried out by investigating both the hydroxamic acid and phosphinic acid reagent families. In general, the lanthanides were found to extract as self-adducts. It was found that the separation of the individual lanthanides with both of these reagent families was adversely affected by steric hindrance.

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In the Mojave Pegmatite district, located in northwestern AZ, numerous pegmatites intrude syn- to post-collisional Paleoproterozoic granitic rocks. The slightly older Cerbat plutons are associated with the suturing of the Mojave and Yavapai terranes whereas Aquarius granites were emplaced during the Yavapai Orogeny as the sutured terranes docked with North America. A detailed study of 5 pegmatites shows that they are zoned with composite cores and contain REE minerals characteristic of NYF pegmatites. However, they exhibit characteristics atypical for NYF pegmatites including F depletion, white microcline, an absence of columbite and, in the Rare Metals pegmatite, have muscovite and beryl. With the exception of the Kingman pegmatite, they exhibit normal LREE-HREE distributions. The Kingman pegmatite is extremely LREE enriched, HREE depleted and exhibits an unusual Nd enrichment which, in some cases, is sufficiently high that allanite is Nd dominant, thus a new mineral species, allanite-Nd.

A dissertation submitted to the Faculty of Science, University of the Witwatersrand, Johannesburg, in fulfillment of the academic requirements for the degree of Master of Science. Johannesburg, March 2016. / Zinc oxide (ZnO) continues to receive widespread attention due to its excellent optical and electronic properties; it demonstrates the combined characteristics of high transmittance and electrical conductivity. Despite the tremendous drive for its application in optoelectronic devices, the full nature of the point defects and defect complexes have not been characterised comprehensively. In this work, luminescence characteristics of the intrinsic defects in ZnO thin films and the rare-earth ions Eu3+ and Tb3+ in ZnO powders are investigated under blue-laser excitation. The thin films used in this study were deposited using the radio-frequency magnetron sputtering method over a 2 hour duration under varied power and substrate bias conditions. The powders were synthesized by the chemical bath deposition method with dopant concentrations of 1.0 mol%. Grazing incidence X-ray diffraction (XRD) was used to determine the lattice properties of the samples. Photoluminescence studies were primarily conducted at room temperature (300 K) with the 457.9 nm, 476.5 nm and 488.0 nm laser lines as excitation sources. For the ZnO thin films, XRD patterns of a hexagonal wurtzite structure with a c/a ratio of about 1.60 and a u-parameter of 0.38 were obtained. Photoluminescence measurements show a broad emission band in the 500.0-900.0 nm range, centred at 656.0 nm. Annealed films yielded relatively more intense photoluminescence spectra than the as-prepared films. The intrinsic point defects and defect level transitions responsible for the broad emission are discussed. For the ZnO powders, the XRD patterns of the annealed samples of pristine ZnO, ZnO:Eu3+ and ZnO:Tb3+ are similarly consistent with a hexagonal wurtzite ZnO phase. Energy dispersive spectroscopy (EDS) confirmed the presence of the Eu3+ and Tb3+ dopants in the respective ZnO host while scanning electron microscopy (SEM) measurements showed the morphology of the sample powders. Photoluminescence spectra of pelletized samples, obtained in the 460.0-900.0 nm range, exhibit relatively intense Eu3+ and Tb3+ emission bands superimposed on a broad emission background. The RE3+ emission bands are attributed to the 5D0 → 7FJ (J = 0, 1, 2, 3, 4) and the 5D4 → 7FJ (J = 0, 1, 2, 3, 4, 5, 6) electronic transitions of Eu3+ and Tb3+, respectively, while the background emission is attributed to intrinsic defects. Crystal-field energy levels for the Eu3+ ion and the Tb3+ ion occupying a C3v symmetry site were deduced from fitting Gaussian curves to the RE3+ emission bands. Possible channels for transfer of energy from the intrinsic defects to Eu3+ and Tb3+ are discussed. / LG2017

Neste trabalho foram estudadas duas composições vítreas, a saber: 30PbF2 - 15InF3 - 20GaF3 - 15ZnF2 - 20CaF2, chamada fluoroindogalato e 41,5Al2O3 - 47,4CaO - 7SiO2 - 4,1MgO, chamada LSCA ( do inglês Low Silica content Calcium Aluminate). A matriz de fluoroindogalato foi dopada com dois conjuntos de íons terras-raras: Tm3+ + Ho3+ e Er3++Yb3+, enquanto que a matriz LSCA foi dopada apenas com os íons Er3+:Yb3+. O objetivo do trabalho foi a caracterização destas matrizes como possíveis meios ativos para laser de estado sólido nas regiões de 2,0 µm (Ho3+) e 2,8µm (Er3+). Neste sentido, foram realizados os experimentos de absorção óptica, fotoluminescência e tempo de vida. A partir dos dados obtidos, foram calculados os parâmetros de intensidade de Judd-Ofelt, os microparâmetros de transferência de energia e o coeficiente de ganho óptico das transições eletrônicas 5I7→ 5I8 (Ho3+) e 4I11/2→ 4I13/2 (Er3+). A contribuição deste trabalho a espectroscopia de terras-raras em vidros está na caracterização destes íons em termos dos parâmetros de transferência de energia via os modelos de Dexter e Yokota e Tanimoto. Haja vista que tais dados não se encontram disponíveis na literatura especializada. Os resultados mostraram que ocorrem processos de transferência de energia de ordem mais alta que dipolo-dipolo nas interações Tm3+→ Tm3+ e Tm3+→ Ho3+. A transição 5I7 → 5I8 do Ho3+ apresenta coeficiente de ganho óptico positivo a partir da densidade de excitação de 1,2 kW/cm2. Os processos de transferência de energia Er3+→ Er3+ e Er3+→ Yb3+ ocorrem via mecanismo de dipolo-dipolo e a transição 4I11/2→ 4I13/2 do Er3+ não é auto-terminada na matriz de fluoroindogalato. O coeficiente de ganho óptico para esta transição é sempre positivo para qualquer densidade de excitação. . A matriz LSCA apresenta auto-terminação da transição 4I11/2→ 4I13/2 do Er3+, sendo portanto, necessária a inserção dos mecanismos de upconversion para a observação de ganho óptico nesta transição eletrônica / In this work two vitreous compositions were studied, that are: fluoroindogalate (30PbF2 - 15InF3 - 20GaF3 - 15ZnF2 - 20CaF22) and LSCA (41,5Al2O3 - 47,4CaO - 7SiO2 - 4,1MgO) - Low Silica Content Calcium Aluminates. The fluoroindogalate host was doped with two sets of rare earth ions: Tm3+ + Ho3+ and Er3++Yb3+, whereas the LSCA host was only doped with Er3+ and Yb3+ ions. The aim of the work was the characterization of these hosts as possible active media for solid state lasers in the spectral regions of 2,0 µm (Ho3+) and 2,8µm (Er3+). In this sense, optical absorption, photoluminescence and lifetime experiments were performed. From the resulting data, Judd-Ofelt intensity parameters, energy transfer microparameters and the electronic transitions 5I7→ 5I8 (Ho3+) and 4I11/2→ 4I13/2 (Er3+) optical gain coefficients were calculated. This work\'s contribution to the rare earth spectroscopy lies in the characterization of such ions in terms of the energy transfer parameters using the Dexter, and Yokota and Tanimoto models considering that these data are not available in the specialized literature. The results have shown that higher than dipole-dipole order processes occur in the interactions Tm3+→ Tm3+ and Tm3+→ Ho3+. The Ho3+ 5I7→ 5I8 transition presents positive optical gain coefficient starting from the excitation density of 1.2 kW/cm2. The energy transfer processes Er3+→ Er3+ and Er3+→ Yb3+ occur via dipole-dipole mechanism and the Er3+ 4I11/2→ 4I13/2 transition is not auto terminated in the fluoroindogalate host. The optical gain coefficient for this transition is always positive for any excitation density. The LSCA host presents auto termination of the Er3+ 4I11/2→ 4I13/2 making it necessary the insertion of upconversion mechanisms for the observation of the optical gain in this electronic transition