Thesis (PhD)--University of South Australia, 1998

Thesis (PhD)--University of South Australia, 1998

Thesis (PhD)--University of South Australia, 1995

Abstract Understanding the phase transformations/developments that result due to varying the production parameter of engineering materials is vital to development of new materials. The effects of yttria and niobium oxide on the phase changes and mechanical properties of mullite fiber reinforced zircon-zirconia ceramic composites produced by in-situ sintering of raw materials was investigated. Varied amounts of powder zirconia, yttria and niobium oxide were mixed in a turbula mixer with a fixed composition of clay (70% volume) of known mineralogical composition and mechanically milled in a planetary ball mill. The blended powders/clay were compacted into standard sample dimensions, and finally fired at 1400°C and held at varied time of one, two and three hours. The fired samples were characterized using ultra-high resolution field emission scanning electron microscope (UHR-FEGSEM) equipped with energy dispersive spectroscopy (EDX), and X-ray diffractometry (XRD). Various mechanical properties of the sintered samples were also investigated. It was observed that the investigated mechanical properties (with the exception of shrinkages) improved with the amount of raw zirconia initially used in the samples. It was also observed that addition of niobium oxide favours the formation polymignite phase, while the presence of both yttria and niobium oxide in the raw materials resulted in the formation of fergusonite phase in the samples. Both additives favour the phase transformation of zirconia from monoclinic to tetragonal and cubic phases even at temperature as low as 1400°C. It was concluded that the improved mechanical properties of the samples was due to strengthening by both mullite fibers reinforcement and phase transformation strengthening.

Preserving the anatase phase of TiO2 is of interest due to the photocatalytic activity of this phase, which is generally considered superior to rutile Ti02 due to a higher surface area. The retardation of the anatase to rutile transition through the use of low cost dopants, zircon and bauxite, was investigated. Pressed powder compacts of anatase TiO2 doped with varying levels of bauxite and zircon powders were fired at 1025??C for durations of 2, 3 and 4 hours. X-ray diffraction analysis, Scanning electron microscopy, Energy dispersive X-ray spectroscopy and Raman spectroscopy were used to evaluate the effect these dopants have on the transition to rutile. It was found that both zircon and bauxite retard the transition to rutile in the solid state. Increasing the level of bauxite dopant consistently increases the preservation of the anatase phase. It was found that at levels of bauxite doping over 5 wt%, over 90% of the anatase phase is retained through 2 hour firing cycles. Using EDS, zircon particles were observed to nucleate elongated prismatic rutile grains. Whilst XRD analysis showed that the addition of zircon has a marked effect on retarding the overall transition of anatase to rutile, increasing levels of this dopant over 2.5% brings about a reduction in preserved anatase, probably due to increased rutile nucleation. Findings showed Samples doped with 2.5% ZrSi04 retained approximately 95% anatase through 2 hour firing cycles.

Thesis (Ph. D.)--University of Wisconsin--Madison, 1941. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves [108]-[116]).

Thesis (M.S. in geology)--Washington State University, December 2008. / Title from PDF title page (viewed on Mar. 4, 2009). "School of Earth and Environmental Sciences." Includes bibliographical references (p. 77-83).

This dissertation focuses on the microstructural and analytical characterization of plasma dissociated zircon (PDZ) which was produced by the South African Nuclear Energy Corporation (NECSA). The techniques used in the analysis of the material include scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy and wavelength dispersive X-ray spectrometry (EDS and WDS), infrared spectroscopy, Raman spectroscopy and X-ray diffraction (XRD). The differences in morphology of the zirconia (ZrO2) crystals observed in the PDZ are related to the thermal history of the material. Large zirconia crystals grow in a spherulitic manner and have the monoclinic crystal structure. Some smaller crystals formed via a rapid cooling process appear to retain the tetragonal or cubic crystal structures rather than relaxing to the monoclinic structure, and this may be because such nanocrystals are stabilised by small surface area or constraints from surrounding materials. Impurity distribution analysis of the PDZ showed that majority of the impurities present in zircon segregates to the silica phase during the dissociation process. The infrared and Raman spectroscopy analysis of the PDZ material indicated that the zirconia is present in the monoclinic and tetragonal polymorphs. X-ray diffraction revealed the presence of monoclinic, tetragonal and cubic zirconia phases. Rietveld refinement of the XRD patterns revealed zirconia to be predominantly found in the monoclinic polymorph followed by the tetragonal and cubic polymorphs. A Fourier transform infrared (FTIR) spectrometer equipped with an attenuated total reflectance (ATR) cell proved to be a viable method for determining the percentage dissociated zircon in PDZ.

Ermoluminescência (TL), Ressonância Paramagnética Eletrônica (EPR) e absorção Óptica (AO) de duas amostras de zirconita ou zircão (de cor marrom), de Minas Gerais, de origem exata e desconhecida. As duas curvas de emissão TL mostraram a presença de 4 picos TL visíveis em 140, 215, 270 e 350 ºC, bastante superpostos. Por deconvolução, outros picos foram revelados. A intensidade dos picos TL em 140, 215 ºC em função da dose apresenta um comportamento linear seguido de sublinear. O espectro de emissão TL é composto de duas bandas em 480 e 580 nm, que são devidas à presença do Dy na nossa amostra. Além de Dy muitos outros elementos são encontrados na amostra, porém, não têm influência na emissão TL. Os espectros de EPR da amostra em pó irradiada mostraram a presença de um sinal central em g=2,000, devido ao centro SiO45- que é isotrópico, o que é facilmente observado na amostra policristalina (em pó). Na amostra monocristalina pode-se observar que existem outros centros EPR não isotrópicos, produzidos durante a irradiação da amostra, e que são devidos à perda ou ganho de um elétron por parte do grupo SiO44-. Os estudos de decaimento isócrono do sinal SiO45 e dos picos TL mostraram que existe correlação entre o centro EPR e os centros TL, o que nos levou a um possível mecanismo TL, segundo o qual o Dy3+ perde um elétron passando para Dy4+ durante a irradiação. O elétron liberado é capturado por SiO44- formando o centro EPR, SiO45-. Quando se aquece a amostra para a leitura TL o processo inverso acontece, deixando Dy3+ em estados excitados, e na transição ao estado fundamental duas emissões de luz, uma em 480nm e outra em 580nm são observados. As bandas de AO são devido ao Urânio (1100), H2O (1900nm) e o radical OH (1400nm). Estas bandas não são afetadas pela irradiação gama utilizada neste trabalho. / In the present work the investigation of some properties of Thermoluminescence (TL), Electronic Paramagnetic Resonance (EPR) and Optical Absorption (OA) of two samples of zircon (of brown color) from Minas Gerais, but the unknown exact origin, were carried out. The glow curves of thermoluminescence emission have shown the presence of 4 TL peaks at 140, 215, 270 and 350 ºC although strongly overlaped. By deconvolution more peaks were revealed. The intensity of the TL peaks at 140 and 215 ºC as function of the radiation dose presents linear and sublinear behavior. The TL emission spectrum has shown two bands at 480 and 580 nm, which are due to the Dy content in our sample. Appart from Dy many other elements are found in the sample, however, they do not participate in the TL emission. The EPR spectra of the irradiated powder sample showed a central signal whith g=2,000 that is due to the SiO45- center. This signal is isotropic and easily observed in the polycrystalline sample (in powder). In the monocrystalline sample non-isotropic signals can be observed due to EPR centers produced by irradiation. They are due to the loss or gain of one electron from the SiO44- group. The isocronal decay curves of the SiO45- signal and that of TL peaks are similar indicating a correlation between the EPR and TL centers suggesting us a possible TL mechanism: the Dy3+ looses one electron and converts into Dy4+ during irradiation. The electron liberated is then captured by SiO44- forming the SiO45- EPR center. When the sample is heated in order to read out TL the inverse process takesplace leaving the Dy3+ in excited states. In the transition to the ground state two light emissions are observed, one in 480nm and other in 580nm. In the OA spectrum measuremment two bands due to the Uranium (1100 and 1503nm), one to H2O(1900nm) and one due to the radical OH (1400nm) are observed. These bands are not afected by the irradiation used in this work.

Ermoluminescência (TL), Ressonância Paramagnética Eletrônica (EPR) e absorção Óptica (AO) de duas amostras de zirconita ou zircão (de cor marrom), de Minas Gerais, de origem exata e desconhecida. As duas curvas de emissão TL mostraram a presença de 4 picos TL visíveis em 140, 215, 270 e 350 ºC, bastante superpostos. Por deconvolução, outros picos foram revelados. A intensidade dos picos TL em 140, 215 ºC em função da dose apresenta um comportamento linear seguido de sublinear. O espectro de emissão TL é composto de duas bandas em 480 e 580 nm, que são devidas à presença do Dy na nossa amostra. Além de Dy muitos outros elementos são encontrados na amostra, porém, não têm influência na emissão TL. Os espectros de EPR da amostra em pó irradiada mostraram a presença de um sinal central em g=2,000, devido ao centro SiO45- que é isotrópico, o que é facilmente observado na amostra policristalina (em pó). Na amostra monocristalina pode-se observar que existem outros centros EPR não isotrópicos, produzidos durante a irradiação da amostra, e que são devidos à perda ou ganho de um elétron por parte do grupo SiO44-. Os estudos de decaimento isócrono do sinal SiO45 e dos picos TL mostraram que existe correlação entre o centro EPR e os centros TL, o que nos levou a um possível mecanismo TL, segundo o qual o Dy3+ perde um elétron passando para Dy4+ durante a irradiação. O elétron liberado é capturado por SiO44- formando o centro EPR, SiO45-. Quando se aquece a amostra para a leitura TL o processo inverso acontece, deixando Dy3+ em estados excitados, e na transição ao estado fundamental duas emissões de luz, uma em 480nm e outra em 580nm são observados. As bandas de AO são devido ao Urânio (1100), H2O (1900nm) e o radical OH (1400nm). Estas bandas não são afetadas pela irradiação gama utilizada neste trabalho. / In the present work the investigation of some properties of Thermoluminescence (TL), Electronic Paramagnetic Resonance (EPR) and Optical Absorption (OA) of two samples of zircon (of brown color) from Minas Gerais, but the unknown exact origin, were carried out. The glow curves of thermoluminescence emission have shown the presence of 4 TL peaks at 140, 215, 270 and 350 ºC although strongly overlaped. By deconvolution more peaks were revealed. The intensity of the TL peaks at 140 and 215 ºC as function of the radiation dose presents linear and sublinear behavior. The TL emission spectrum has shown two bands at 480 and 580 nm, which are due to the Dy content in our sample. Appart from Dy many other elements are found in the sample, however, they do not participate in the TL emission. The EPR spectra of the irradiated powder sample showed a central signal whith g=2,000 that is due to the SiO45- center. This signal is isotropic and easily observed in the polycrystalline sample (in powder). In the monocrystalline sample non-isotropic signals can be observed due to EPR centers produced by irradiation. They are due to the loss or gain of one electron from the SiO44- group. The isocronal decay curves of the SiO45- signal and that of TL peaks are similar indicating a correlation between the EPR and TL centers suggesting us a possible TL mechanism: the Dy3+ looses one electron and converts into Dy4+ during irradiation. The electron liberated is then captured by SiO44- forming the SiO45- EPR center. When the sample is heated in order to read out TL the inverse process takesplace leaving the Dy3+ in excited states. In the transition to the ground state two light emissions are observed, one in 480nm and other in 580nm. In the OA spectrum measuremment two bands due to the Uranium (1100 and 1503nm), one to H2O(1900nm) and one due to the radical OH (1400nm) are observed. These bands are not afected by the irradiation used in this work.