Neste trabalho, realizou-se o estudo que permitiu a otimização termodinâmica das seções binárias pertencentes ao diagrama de fase ternário do sistema LiF-GdF3-LuF3, para tanto o programa FactSage foi empregado na simulação computacional. Assim, o comportamento de fusão das misturas destes compostos foi elucidado, o que representa uma contribuição inovadora para o conhecimento das propriedades físicas e químicas destes materiais. Em particular, determinou-se a faixa de composições nas quais as soluções sólidas de LiGdxLu1-xF4 e GdxLu1-xF3 podem ser obtidas diretamente da fase líquida. Neste trabalho as três secções binárias, LiF-GdF3, LiF-LuF3 e GdF3-LuF3 foram reavaliadas experimentalmente utilizando a calorimetria exploratória diferencial para a obtenção de dados mais precisos de temperatura versus composição, uma vez que foi possível minimizar a contaminação das amostras com compostos de oxigênio. A capacidade calorífica e outros dados calorimétricos foram também determinados experimentalmente e comparados com os existentes na literatura. Os termos da energia livre de Gibbs de excesso para as fases representadas como soluções, os quais descrevem os efeitos de interação não ideal entre os dois fluoretos nestas fases, foram expressos com sucesso pela modelo polinomial Redlich-Kister. Finalmente, o caminho de solidificação no diagrama de fase ternário LiF-GdF3-LuF3 pôde ser extrapolado de acordo com o formalismo de Kohler-Toop. Assim, pela primeira vez, a interação ternária entre os compostos LiF, GdF3 e LuF3 foi determinada. / In this work, it was carried out the study that allowed the thermodynamic optimization of the binary sections belonging to the ternary phase diagram of the LiF-GdF3-LuF3 system, for this purpose the FactSage software was used in the computational simulation. Thus, the melting behavior of the mixture of these compounds has been elucidated, which represents an innovative contribution to the knowledge of the physical and chemical properties of these materials. In particular, it was determined the composition ranges in which the solid solutions of LiGdxLu1-xF4 and GdxLu1-xF3 can be obtained directly from the liquid phase. In this work the three binary sections, LiF-GdF3, LiF-LuF3 and GdF3-LuF3, were evaluated using differential scanning calorimetry to obtain more accurate data of temperature versus composition, since it was possible to minimize the contamination of the samples due to oxygen compounds. The heat capacity and other calorimetric data were experimentally determined and compared with those cited in the literature. The terms of the Gibbs free excess energy for the solution phases, which describe the non ideal interaction effects between the two fluorides at these phases, were expressed by the Redlich-Kister polynomial model. Finally, the solidification path in the ternary phase diagram LiF-GdF3-LuF3 could be extrapolated according to the Kohler-Toop formalism. Thus, for the first time, the interaction between the ternary compounds LiF, GdF3 and LuF3 was determined.

No presente trabalho são descritas as etapas de desenvolvimento e implantação das rotinas analíticas utilizando ICP-OES e ICP-MS para a determinação de elementos terras raras em materiais geológicos. A implantação inclui determinações comparativas de vários granitóides dos maciços ou complexos Ibiúna-Piedade, SP, e Cunhaporanga, PR, já previamente analisados por meio de ICP-MS e INAA (Universidade Kansas, em Lawrence, USA). Através de uma pequena modificação no método inicial, os limites de detecção para a análise dos ETR por ICP-OES foram melhorados para concentrações próximas à 10 vezes o condrito. Porém para a análise de ETR em materiais geológicos com valores inferiores a estes é necessária a utilização de uma técnica mais sensível como o ICP-MS. A técnica ICP-MS não é livre de problemas sendo necessárias correções de interferências moleculares e drift instrumental para a obtenção de resultados com precisão e exatidão adequados. Realizou-se a etapa de validação do método utilizando materiais de referência internacionais geológicos. A análise estatística dos resultados obtidos utilizando três métodos de abertura de amostra (ataque ácido em forno de microondas, em bombas tipo Parr e fusão alcalina) mostrou a possibilidade de utilização do ataque ácido em forno de microondas e da fusão alcalina com posterior separação cromatográfica como alternativas eficientes para a determinação de ETR apesar da baixa eficiência nas recuperações dos elementos Zr e Hf em rochas ácidas e gnáissicas equivalentes. / The steps for the development of the analytical routines leading to the determination of the rare earth elements (REE) with the use of ICP-AES and ICP-MS techniques are discussed in this contribution. The set-up of these routines was also evaluated with determinations of REE in several granitoid rocks from the Piedade-Ibiuna (SP) and Cunhaporanga (PR) complexes, and the results compared with those obtained in other laboratories (University of Kansas, Lawrence) with ICP-MS and INAA. The work previously performed for the adaptation of REE determination with ICPAES was reviewed, allowing analyses to be realized with better results for concentrations close to 10 times the chondrite value. At lower concentrations, REE analysis have to be performed with ICP-MS. The ICP-MS technique shows much better accuracy and precision than ICPAES, but presents problems of its own. Instrumental drift corrections, as well as corrections due to molecular interferences, are mandatory. Evaluation of the successfully adapted routines was realized analyzing international reference materials several times and applying statistical tests. A comparison of results with three dissolution techniques (acid attack in microwave oven, use of Parr type bombs, and alkaline fusion with borates) showed that both acid attack and alkaline fusion with later chromatographic separation are rather efficient alternatives for the determination of REE, although Zr and Hf are not fully recovered in many acid igneous and equivalent gneissic rocks.

Submitted by Rosivalda Pereira (mrs.pereira@ufma.br) on 2017-05-05T19:36:02Z No. of bitstreams: 1 AnaQueirozSilva.pdf: 6863169 bytes, checksum: e47ae4d9bb4d9f8cffde413e5eecd620 (MD5) / Made available in DSpace on 2017-05-05T19:36:02Z (GMT). No. of bitstreams: 1 AnaQueirozSilva.pdf: 6863169 bytes, checksum: e47ae4d9bb4d9f8cffde413e5eecd620 (MD5) Previous issue date: 2016-07-19 / In recent years, research has increased in order to develop new materials processing methods have more advantages over conventional methods currently used which are quicker and cheaper. It has become common to use ceramics to obtain electronic devices, dielectric or piezoelectric. The CaTiO3 ceramic material has been widely used in electronic devices. The objective of this study was to synthesize and characterize perovskite ceramic-based CaTiO3 (Titanate Calcium) replaced with rare earths. The synthesis and replacement of perovskite were made from the starting materials Ca(OH)2, TiO2, Er2O3 and Yb2O3 by mechanical milling in a ball mill for 30 min at 250 rpm to homogenization and then was taken calcination in a muffle furnace. The obtained material powder showed perovskite phase to the orthorhombic space group Pbnm 62. The unit cell of the crystal lattice parameters showed a = 5.378 Å, b = 5.441 Å and c = 7.640 Å for the CaTiO3, which has four per unit cell formula. The number and type of modes provided for each frame can be given by the factor groups having a total of 24 vibrational modes Raman for CaTiO3 with said structure. The morphological characteristics were observed for the samples CTO (calcium titanate) prepared by solid state reaction, demonstrating the formation of small, round grain vacancies, which may be caused by distortions in the crystal lattice. The CTO replaced with Er2O3 and Yb2O3 showed typical bands of green light at 525 and 547 nm corresponding to the transition 4H11/2 → 4I15/2. The two smaller emission bands in the red, correspond to transition 4F9/2 to the ground state 4I15/2. The results obtained for the ceramic systems were satisfactory as the method used for synthesis, who presented with lower cost compared to existing processes. / Nos últimos anos, as pesquisas têm aumentado com o propósito de desenvolver novos métodos de processamento de materiais que apresentem mais vantagens em relação aos processos convencionais utilizados atualmente e que sejam mais rápidos e baratos. Tem se tornado comum utilizar cerâmicas para a obtenção de dispositivos eletrônicos, dielétricos ou piezoelétricos. O material cerâmico CaTiO3 tem sido amplamente utilizado em dispositivos eletrônicos. O objetivo deste trabalho foi sintetizar e caracterizar cerâmicas perovskitas à base de CaTiO3 (Titanato de Cálcio) substituída com terras raras. A síntese e a substituição da perovskita foram feitas à partir dos materiais de partida Ca(OH)2, TiO2, Er2O3 e Yb2O3 por moagem mecânica em um moinho de bolas por 30 min, a 250 rpm para homogeneização e em seguida, foi feita calcinação em um forno tipo mufla. O pó obtido do material apresentou fase de perovskita com grupo espacial ortorrômbica Pbnm 62. A célula unitária da rede cristalina apresentou os parâmetros a=5,378 Å, b=5,441 Å e c=7,640 Å para o CaTiO3, a qual possui quatro fórmulas por célula unitária. O número e tipo de modos previstos para cada estrutura pode ser dado pelo fator de grupos, havendo um total de 24 modos vibracionais Raman para o CaTiO3 com a estrutura citada. Foram observadas as características morfológicas para as amostras de CTO (Titanato de Cálcio), preparadas por reação no estado sólido, demonstrando a formação de grãos pequenos e redondos com vacâncias, que podem ser causadas por distorções na rede cristalina. O CTO substituído com Er2O3 e Yb2O3 apresentou bandas típicas da luz verde em 525 e 547 nm que correspondem à transição 4H11/2→4I15/2. As duas bandas menores de emissão no vermelho, correspondem à transição 4F9/2 para o estado fundamental 4I15/2. Os resultados obtidos para os sistemas cerâmicos mostraram-se satisfatórios quanto ao método utilizado para síntese, que, apresentou-se com menor custo comparado aos processos existentes.

Les interactions fluide-roche intervenant dans les systèmes hydrothermaux océaniques ont été étudiées expérimentalement en surveillant les isotopes du Mg et Sr. Les résultats suggèrent que les réactions rapides à températures moyennes pourraient expliquer en partie les divergences identifiées précédemment dans le bilan marin du Sr. De plus, la ré-dissolution de l'anhydrite dans les stades avancés peut expliquer les faibles quantités d'anhydrite trouvée dans les échantillons de basalte océanique altérés. L'évolution du δ26/24Mg dans les fluides indique que le Mg isotopiquement lourd a été incorporé préférentiellement dans les minéraux des argiles.Le fractionnement entre les terres rares et le Ca pendant la précipitation de calcite a été étudié expérimentalement. Ces données suggèrent que l'incorporation du REE3+ dans la structure de la calcite est probablement équilibrée par l'incorporation de Na+ et que les coefficients de partage déduits pour les conditions marines peuvent varier considérablement selon la composition du fluide. Enfin, l'étude de la solubilité de l'hydroxylbastnasite (REE(CO3)(OH)), conduite au cours de ce travail, indique que cette phase est moins soluble que les autres carbonates des terres rares connus. / The fluid-rock interactions occurring in hydrothermal systems at or near mid-oceanic ridges (MOR) were studied experimentally while monitoring the Mg and Sr isotopic evolution. The results suggest that fast intermediate-temperature reactions could partly explain previously identified discrepancies in the marine 87Sr/86Sr budget. Furthermore, late-stage anhydrite re-dissolution caused by fluid reduction and temperature decreases in our experiments represent a potential explanation for the low amounts of anhydrite found in altered oceanic basalt samples. The fluid δ26/24Mg indicate that isotopically heavy Mg was preferentially incorporated into the clays. Towards the interpretation of rare earth element (REE) patterns in marine calcite, the fractionation between the REEs and Ca during the precipitation of calcite was studied experimentally. These data suggest that the incorporation of REE3+ ions into the calcite structure was likely charge balanced by incorporation of Na+, and that inferred partition coefficients for marine conditions can vary substantially depending on the fluid composition. Furthermore, the solubility of hydroxylbastnasite (REE(CO3)(OH)) was determined, indicating that this phase is less soluble than other known REE carbonates.

Le design de complexes luminescents hétérobimétalliques a suscité un intérêt croissant ces dernières années en raison de leurs propriétés photophysiques uniques. Dans ces complexes de Nd (III) ou Yb (III) associés à des chromophores du bloc d, la forte émission du métal de transition dans le visible est utilisée pour sensibiliser de façon efficace les niveaux f-f du lanthanide(III) qui émet à son tour dans le visible ou l'IR selon la terre rare. Plus spécifiquement l'attention s'est focalisée sur le développement de complexes hétérobimétalliques d-f pour l'émission dans le proche infrarouge (NIR). En effet le proche infrarouge, comparé à l'UV, pénètre plus facilement les tissus biologiques humains notamment la peau. Bien que de telles propriétés confèrent à ces complexes bimétalliques un fort potentiel pour le diagnostic médical, aucun complexe hétérobimétallique d-f greffé de façon covalente à une matrice de silice n'a été décrit. Dans ce travail de nouveaux complexes hétérobimétalliques d-f contenant des ligands silylés ont été préparés et greffés sur la silice. Les complexes monomères [Ru(bpy)2(bpmd)]Cl2 (noté Ru), [Ru(bpy)(bpy-Si)(bpmd)]Cl2 (noté RuL) et [Ln(TTA-Si)3] (noté LnL3) et les complexes hétérobimétalliques d-f Ru-LnL3 et Ln-RuL (Ln = Nd3+, Yb3+) ont été préparés. La caractérisation des complexes a été effectuée par spectroscopie Raman, RMN 1H et 13C RMN. Les spectres RMN 1D 1H et 13C NMR ainsi que 2D de corrélation HSQC confirment les structures proposées. L'étude des propriétés photophysiques met en évidence l'émission de l'élément lanthanide dans le proche infrarouge ainsi que l'efficacité du processus de transfert d'énergie Ru-Ln qui est facilité par le ligand (2,2'-bipyrimidine). Les mesures de durée de vie et de rendement quantique (ΦET) pour le transfert d'énergie indiquent des valeurs remarquables comprises entre 30 et 84 %. La valeur du rendement quantique (ΦET) du complexe d'Yb-RuL, 73,4 %, est à ce jour la plus grande valeur rapportée pour un complexe hétérobimétallique Ru (II)-Yb (III). Le greffage sur différentes matrices de silice, mésoporeuse SiO2 ou dense SiO2 d, a été réalisé. Les nanohybrides SiO2-RuL, SiO2-NdL3 et SiO2-YbL3 ont été obtenus avec des taux de greffage allant de 0,08 à 0,18 mmol de complexe par gramme de silice. [...] / The design of heterobimetallic luminescent complexes has gained growing interest in recent years due to their unique photophysical properties. More specifically, the development of heterobimetallic complexes using d-block chromophores to sensitize the near-infrared (NIR) emission of lanthanide complexes (such as Nd(III) and Yb(III)) has received significant attention taking into account their longer emission wavelengths and the interest of the NIR emission which penetrates human tissue more effectively than UV light. These properties give them potential applications in medical diagnostics or biomedical assays. Transitions to excited state levels of transition metal complexes occurring in the visible and characterized by large absorption coefficients, could efficiently sensitize f-f levels of Ln(III) ions. In this work new d-f heterobimetallic complexes containing silylated ligands were prepared supported on silica materials. [Ru(bpy)2(bpmd)]Cl2 (labeled Ru), [Ru(bpy)(bpy-Si)(bpmd)]Cl2 (labeled RuL) and [Ln(TTA-Si)3] (labeled LnL3) and d-f heterobimetallic complexes, Ru-LnL3 and Ln-RuL (Ln = Nd3+, Yb3+) were prepared. Structural characterization was carried out by Raman Scattering, 1H and 13C NMR spectroscopies. Results obtained from 1H-13C HMBC and HSQC correlation NMR spectra confirm the formation of proposed complexes. Photophysical properties studies highlight the efficiency of Ru-Ln energy transfer processes in NIR-emitting lanthanide complexes mediated by conjugated bridging ligand (2,2'-bipyrimidine). Lifetime measurements were carried out and values of quantum yield for energy transfer (?ET) between 30 and 84 % could be evaluated. ?ET of 73.4 % obtained for the Yb-RuL complex is the largest value reported for Ru(II)-Yb(III) heterobimetallic complexes so far. Grafting on different silica matrix was also demonstrated. SiO2-Ru, SiO2-NdL3 and SiO2-YbL3 nanohybrids were obtained with grafting efficiencies from 0.08 to 0.18 mmol g-1 of silica.[...]

No description available.

The demand for rare earth elements (REEs) has increased over the last decade due to applications in high technology devices including those in the defense industry. The recovery of REEs from primary sources such as rare earth minerals are viable using physical separations followed by chemical processing. However, weak market values and environmental concerns have limited the viability of such operations. On the other hand, REE recovery from secondary sources such as apatite ore, bauxite waste, and waste recycling, provides an opportunity to take advantage of a resource that does not require mining costs as well as other associated costs given that these expenses are covered by the revenue generated from the production of the primary material. Coal-based materials represent a potential source for REEs which may be extracted and concentrated by the use of physical and/or chemical processes. The current study focused on developing a leaching process to extract REEs from the pre-combustion coal sources including coarse and fine refuse and low-valued material obtained from coal preparation plants. Materials collected for leaching characteristic studies were found to have average total REE concentrations in the range of 200-350 ppm on a whole sample basis. Mineralogy studies performed on Fire Clay seam coal refuse using SEM-EDS detected micro-dispersed rare earth phosphate mineral particles which are generally difficult to dissolve in strong acid solutions. On the other hand, XRD analysis results from a high REE content segment of the West Kentucky No. 13 coal seam indicated the presence of fluorapatite which is soluble in weak acid solutions. The mineral associations of REEs were studied by extracting REEs using different types of acids under various pH conditions. Differential extraction of the REEs was examined along with the associated impurity elements such as iron, aluminum, and calcium among others. The findings showed that the light REEs were primarily associated in a phosphate mineral form, whereas the heavy REEs were mostly present in an ion substitution form associated with clay minerals. Relatively high concentrations of REEs were discovered in mixed-phase particles consisting of both coal and mineral matter. By reducing the particle size, more leachable forms of REEs were liberated and recovered along with the associated mineral matter embedded in the coal structure. The type of lixiviant played an important role during the initial stage of leaching but was found to be insignificant as the system reached equilibrium. Solids concentration in the leaching medium has an important role in establishing the throughput capacity of the leaching system. Test results found that an increase in solids concentration had a significant negative effect on rare earth recovery. This finding may be explained by higher concentrations of soluble calcium-based minerals such as calcite which provided localized pH increases near and within the pores of the solids. The result was precipitation of CaSO4 within the pores which blocked access for the lixiviants. This hypothesis was supported by the findings from BET and XPS analyses which found lower pore volume in high solid concentration systems and the existence of CaSO4 on the surface of the solids. Leaching test results obtained using sulfuric acid over a range of temperatures showed that the leaching process was mainly driven by a diffusion control process. The activation energy determined for an Illinois No. 6 coal source was 14.6 kJ/mol at the beginning of the reaction and 35.9 kJ/mol for the rest of the leaching process up to 2 hours. For material collected from the Fire Clay coal seam, the apparent activation energy was 36 kJ/mol at the start of the leaching reaction and decreased to 27 kJ/mol over the remaining period of the test. The activation energy values were nearly equivalent to the upper-level values that generally define a diffusion control process and the lower values of a chemical reaction control process. The lack of clarity in defining a clear control mechanism is likely associated with the variability in associated mineralogy, various modes of occurrence of the REEs and the interfacial transfer of product through the porous structure of the coal-based particles which requires relatively high activation energy. As such, both diffusion control and chemical reaction control mechanisms are likely occurring simultaneously during the leaching process with diffusion control being more dominant.

Basalt outcrops in Curlew Valley consist of vii several flow remnants and eruptive centers situated along the valley margins. Basalt is also found in association with salic rocks that erupted in the central portion of The basalts are of probable Pliocene age and the valley. were erupted during a period of active extensional tectonics. Since their emplacement, and downfaulted. the basalts have been extensively eroded The present morphology reflects the erosional and depositional processes of prehistoric Lake Bonneville. Twelve samples were analyzed chemically for major oxides, trace elements, and rare-earth elements. The basalts form a hypersthene normative series ranging from olivine tholeiite to tholeiite. Based on chemical data, the basalts form three distinct groups. Comparison of the major oxides shows two of the groups forming a differentiation sequence separate from the third group. Trace element and rare-earth element data indicate that the three chemical groups are related to a common source but that two batches of magma probably emanated from this source. Pyrolite, spinel lherzolite, and garnet lherzolite were evaluated as hypothetical mantle materials from which a parent magma might be derived through partial melting. Based on rare-earth element profiles, garnet lherzolite appears to be the most likely source material for deriving the basalts. The trace element and rare-earth element data do not show any anomalies that would suggest contamination from crustal material. Comparison of chemical data shows that the Curlew Valley basalts are genetically similar to basalts from the Kelton and Rozel Point-Black Mountain areas, southwest and southeast of the study area, respectively. The Curlew Valley basalts are chemically similar to olivine tholeiites from the Snake River Plain and Blackfoot Reservoir areas in Idaho, but they do not show much similarity to basalts near Snowville, Utah, northeast of the study area. The Curlew Valley basalts are generally more iron rich and less alkalic than other basaltic rocks from the eastern Basin and Range Province.

Abstract not available

A great deal of theoretical activity has resulted from blending the fields of computer science and quantum mechanics. Out of this work has come the concept of a quantum computer, which promises to solve problems currently intractable for classical computers. This promise has, in turn, generated a large amount of effort directed toward investigating quantum computing experimentally. ¶ Quantum computing is difficult because fragile quantum superposition states of the computer’s register must be protected from the environment. This is made more difficult by the need to manipulate and measure these states. ¶ This thesis describes work that was carried out both to investigate and to demonstrate the utility of rare earth ion dopants for quantum computation. Dopants in solids are seen by many as a potential means of achieving scalable quantum computing. Rare earth ion dopants are an obvious choice for investigating such quantum computation. Long coherence times for both optical and nuclear spin transitions have been observed as well as optical manipulation of the spin states. The advantage that the scheme developed here has over nearly all of its competitors is that no complex nanofabrication is required. The advantages of avoiding nano-fabrication are two fold. Firstly, coherence times are likely to be adversely effected by the “damage” to the crystal structure that this manufacture represents. Secondly, the nano-fabrication presents a very serious difficulty in itself. ¶ Because of these advantages it was possible to perform two-qubit operations between independent qubits. This is the first time that such operations have been performed and presents a milestone in quantum computation using dopants in solids. It is only the second time two-qubit operations have been demonstrated in a solid. ¶ The experiments performed in this thesis were in two main areas: The first was the characterisation of hyperfine interactions in rare earth ion dopants; the second, simple demonstrations directly related to quantum computation. ¶ The first experiments that were carried out were to characterise the hyperfine interactions in Pr[superscript 3]+:Y[subscript 2]SiO[subscript 5]. The characterisation was the first carried out for the dopants in a site of such low symmetry. The resulting information about oscillator strengths and transition frequencies should prove indispensable when using such a system for quantum computation. It has already enabled an increase in the coherence times of nuclear spin transitions by two orders of magnitudes. ¶ The experiments directly related to the demonstration of quantum computation were all carried out using ensembles. The presence of a significant distribution of resonant frequencies, or inhomogeneous broadening, meant that many different sub-ensembles could be addressed, based on their resonant frequencies. Furthermore, the properties of the sub-ensembles could be engineered by optically pumping unwanted members to different hyperfine states away from resonance with the laser. ¶ A previously demonstrated technique for realising ensembles that could be used as single qubits was investigated and improved. Also, experiments were carried out to demonstrate the resulting ensembles’ utility as qubits. Further to this, ions from one of the ensembles were selected out, based on their interaction with the ions of another. Elementary two qubit operations were then demonstrated using these ensembles.