Resumo: O presente trabalho tem como objetivo a obtenção de óxidos de molibdênio e de tungstênio com propriedades texturais controladas, particularmente com elevadas áreas específicas. Tais óxidos serão posteriormente empregados como precursores nas sínteses de nitretos e carbetos de molibdênio e de tungstênio, materiais potencialmente promissores na decomposição catalítica da hidrazina em sistemas micropopulsivos de satélites. Sabe-se da literatura que uma rede inorgânica de óxidos pode ser proveniente de vários precursores. Visando alcançar o objetivo do trabalho proposto, procurou-se primeiramente obter os óxidos, via processo sol-gel, a partir da decomposição térmica dos alcóxidos de molibdênio e de tungstênio. No decorrer do desenvolvimento do projeto de pesquisa achou-se também conveniente testar a decomposição térmica de outros precursores. Estas novas rotas exigem as sínteses de complexos de molibdênio (VI) e de tungstênio (VI) com ácidos a-hidroxicarboxílicos, de ácidos molíbdico e túngstico e dos saia de amônio dos referidos metais. Os materiais sintetizados foram, sempre que possível, analisados por espectroscopia na região infravermelho, difração de raios X e medidas de adsorção de nitrogênio na sua temperatura de condensação. Algumas amostras foram submetidas à análise elementar para a determinação dos teores de C, N e H. Efetuou-se a decomposição térmica de todos os precursores, sendo os óxidos obtidos analisados pelas mesmas técnicas utilizadas anteriormente. Os óxidos de molibdênio apresentaram uma fase cristalina ortorrômbica, exceto em algumas amostras onde se observou além desta fase, a presença de uma pequena quantidade de material amorfo.Com relação ao óxido de molibdênio, o maior valor de área específica de um foi de 8m2/g para uma amostra proveniente da hidrólise controlada de um alcóxido metálico... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The present work hás a objective the obtaining of molibdenum and tungsten oxides with texturais controlled properties, particularly with high specific areas. Such oxides will be used later on as precursors in the nitrides and carbides synthesis of molibdenium and tungsten, materials potentially promissing in the catalytic decomposition of the hydrazine in micropopulsives system of satellites. It's known about the literature that an inorganic net of oxide can come from several precursors. Seeking to reach the objective of the proposed work, it was firstly tried to obtain the oxides through sol-gel process, starting from the thermal decomposition of the molybdenum and tungsten alcoxides. In elapsing of the development in the research project it was also convenient to test the thermal decomposition of others precursors. These new routes demand the syntheses of molibdenium(VI) and tungsten(VI) complexes with the a-hidroxycarboxylic acids, of molybdic and tungstic acids and of the ammonium salts of the referred metals.The synthesized materials were, whenever possible, analysed by spectroscopy in the infrared region, of X-rays diffraction and measures of adsorption of nitrogen in its condensation temperature. Some samples were submitted the elementary analysis for the determination of texts of C, N and H. The thermal decomposition of all precursors was made, being the obtained oxides analysed same techniques previously used. The molibdenium oxides presented crystalline orthorhombic phase, except in some samples where it was observed besides this phase, the presence of a small amount of amorphous material. With relationship to molibdenium oxide, the largest value of specific area went of 8m2/g to a coming sample of the controlled hydrolysis of a metallic alcoxide. It was also obtained of area around 8m2/g for the ocide, coming from a of molybdic acid sample... (Complete abstract, click electronic address below) / Orientador: Antonio Carlos Massabni / Coorientador: Sandra Helena Pulcinelli / Banca: Elizabeth Berwerth Stucchi / Banca: Carlos de Oliveira Paiva Santos / Banca: José Augusto Jorge Rodrigues / Banca: Ariovaldo de Oliveira Florentino / Doutor

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Tungsten is considered the prime candidate material for plasma facing components within fusion reactors. However, exposure of tungsten to neutron flux brings about transmutation of tungsten into by-products: Re, Os and Ta. Under increasing levels of radiation damage, irradiation induced clustering/precipitation takes place that embrittles and thus reduces lifetime of such tungsten components. This thesis was undertaken to explore this subject on a deeper level. There are three components to this study. The first part considers the effect of Re content on irradiation induced clustering. Lab-made plate W-xRe (x: 2, 5, 10 and 25at.%) alloys were exposed to 1.2, 3.9 and 33dpa, self-ion irradiated at 773K. Analysis of cluster number density and volume fraction found they increase with damage level and bulk Re content. Based on these trends and existing literature data, a hypothesis was proposed suggesting clusters originate from vacancy clusters. Also, at 33dpa, rod shaped clusters form in W-25Re alloys while spherical clusters are present in other alloys. The clusters show close correspondence with irradiation induced precipitates and appear to be precursor phase. In the second part of this thesis, the effect of Os and Ta on cluster formation and alloy mechanical properties is examined. Lab-made plate W-1Re-1Os and W-2Re-1Ta alloys were irradiated at 33dpa at 573 and 773K and compared against control W-2Re alloy. At 33dpa and 573K, the Os and Ta presence suppresses cluster formation. Both ternary alloys contain smaller cluster diameter, composition, number density and volume fraction than the W-2Re alloy. However, at 33dpa and 773K, Os and Ta have opposing effects on cluster behaviour. Os increases the cluster nucleation rate and raises irradiation hardening (compared to W-2Re). Meanwhile, Ta presence decreased cluster number density and reduced the irradiation hardening (compared to W-2Re alloy). As well, Ta showed no evidence of clustering, only Re clusters form in the W-2Re-1Ta alloy. The final aspect of the thesis analyzes the effect of material microstructure and external variables on cluster formation in W-Re alloys. Commercial wire form W-25Re alloy was irradiated at 1.2dpa at 573 and 773K as atom probe needles and bulk sample. The larger free surface on atom probe needle samples appears to act as a sink for self-interstitials and vacancies at both temperatures. The effect of grain size and dislocation density was examined by irradiating commercial W-5Re wire (0.5-1μm diameter) and plate (1-3mm diameter) samples (annealed and unannealed) to 33dpa and 573K. It was found grain boundaries and dislocations act as defect sinks at 573K. Additionally, radiation enhanced Re grain boundary enrichment was observed for first time. The effect of grain size on cluster behaviour at 773K was also analysed. Commercial wire and lab-made plate W-3Re, W-5Re and W-25Re alloys were irradiated to 33dpa at 773K. The larger grain boundary area in wire samples is suspected of acting as a sink for self-interstitials leaving more vacancies for promoting cluster formation compared to lab-made samples. The discoveries made in this thesis broaden our current understanding of irradiation induced phase formation in tungsten. Their implications on plasma facing component design are discussed as well as recommendations for improvements. Further, areas requiring further research in this field are also highlighted.

Orientador: José Arana Varela / Co-orientador: Sergio Mazurek Tebcherani / Banca: Evaldo Toniolo Kubaski / Banca: Máximo Siu Li / Banca: Sônia Maria Zanetti / Banca: Anderson André Felix / Resumo:Este trabalho é referente ao estudo investigativo da influência de um tratamento térmico assistido por pressão nas respostas de propriedade elétrica, como sensor de gás e propriedade ótica de fotoluminescência de nanopartículas de trióxido de tungstênio (WO3), obtidas por processo hidrotermal assistido com micro-ondas adaptado. As condições de tratamento foram de 180 ºC sob pressão de 2 MPa durante 32 horas. Os óxidos obtidos foram previamente caracterizados por difração de raios X (DRX), volumetria de adsorção de nitrogênio (BET), espectroscopia de fotoelétrons excitados por raios X (XPS), microscopia eletrônica de varredura por emissão de campo (FEG-SEM) e espectroscopia micro Raman. Pelas técnicas combinadas foi possível caracterizar detalhadamente os materiais sintetizados, como sua estrutura, forma, tamanho e composição química. Foi possível comparar a respostas do material quando o óxido é submetido ao tratamento térmico assistido por pressão com o óxido obtido somente com tratamento térmico convencional. A originalidade do trabalho está em compreender como o tratamento térmico assistido por pressão está alterando as respostas do trióxido de tungstênio, sem a necessidade da adição de dopantes. Quando analisado a propriedade ótica após esse tratamento com pressão, o trióxido de tungstênio apresentou um aumento na intensidade de emissão, passando da emissão de maior contribuição em 460 nm (azul) para a emissão em 549 nm (verde). O espectro ainda apresenta um deslocamento para o vermelho, em comprimentos de onda maiores. Este deslocamento e mudança na intensidade podem estar correlacionados a diminuição de vacâncias de oxigênio após o tratamento térmico assistido por pressão. Também foram estudadas as propriedades elétricas como sensor de gás do tipo-n para gases redutores e oxidantes (H2 e NO2, respectivamente). As amostras tratadas... / Abstract: The aim of this work is to study the influence of a pressure-assisted heat treatment on the electrical and optical properties of nanoparticulate tungsten trioxide (WO3) obtained by microwave assisted hydrothermal method. The behavior of WO3 as gas sensor and its pholominescence emission were used to evaluate the electrical and optical properties, respectively. Samples were heat-treated under an air pressure of 2 MPa at 180ºC for 32 h. The oxides obtained were previously characterized by X-ray diffraction (XRD), nitrogen adsorption volumetric (BET), X-ray Photoelectron Spectroscopy (XPS), and field emission scanning electron microscopy (FEG-SEM) and micro Raman Spectroscopy. Using combined techniques, the structure, morphology, size and chemical composition of the synthetized materials were characterized in details. A comparison between samples that underwent the pressure-assisted heat treatment and samples that underwent a conventional heat treatment was established. The originality of the work is to understand how the pressure-assisted heat treatment chames the tungsten trioxide behavior without the addition of dopants. The photoluminescence emission intensity increased after the pressure treatment, and the maximum emission changed from 460 nm (blue) to 549 nm (green). The spectrum exhibited a red shift at higher wavelengths. This displacement and change in intensity can be correlated to a decrease in oxygen vacancies after the pressure-assisted heat treatment. In addition, the electrical properties were investigated as a n-type gas sensor for NO2 and H2 that are reducing and oxidizing gases, respectively. Samples became more resistive to electric current impeding the investigation of the sensing properties of the oxide under study. / Doutor

abstract: Sensitivity is a fundamental challenge for in vivo molecular magnetic resonance imaging (MRI). Here, I improve the sensitivity of metal nanoparticle contrast agents by strategically incorporating pure and doped metal oxides in the nanoparticle core, forming a soluble, monodisperse, contrast agent with adjustable T2 or T1 relaxivity (r2 or r1). I first developed a simplified technique to incorporate iron oxides in apoferritin to form "magnetoferritin" for nM-level detection with T2- and T2* weighting. I then explored whether the crystal could be chemically modified to form a particle with high r1. I first adsorbed Mn2+ ions to metal binding sites in the apoferritin pores. The strategic placement of metal ions near sites of water exchange and within the crystal oxide enhance r1, suggesting a mechanism for increasing relaxivity in porous nanoparticle agents. However, the Mn2+ addition was only possible when the particle was simultaneously filled with an iron oxide, resulting in a particle with a high r1 but also a high r2 and making them undetectable with conventional T1-weighting techniques. To solve this problem and decrease the particle r2 for more sensitive detection, I chemically doped the nanoparticles with tungsten to form a disordered W-Fe oxide composite in the apoferritin core. This configuration formed a particle with a r1 of 4,870mM-1s-1 and r2 of 9,076mM-1s-1. These relaxivities allowed the detection of concentrations ranging from 20nM - 400nM in vivo, both passively injected and targeted to the kidney glomerulus. I further developed an MRI acquisition technique to distinguish particles based on r2/r1, and show that three nanoparticles of similar size can be distinguished in vitro and in vivo with MRI. This work forms the basis for a new, highly flexible inorganic approach to design nanoparticle contrast agents for molecular MRI. / Dissertation/Thesis / Ph.D. Bioengineering 2012

The reductions of WO₃ with hydrogen, with CO, and with carbon, as well as the reduction of WO₃/graphite mixtures with hydrogen, were studied using thermogravimetry, evolved gas analysis, X-ray powder diffraction, and scanning electron microscopy. The intermediate phases W₂₀O₅₈, W₁₈O₄₉ and WO₂, were observed in the reductions. The final product of the reductions with hydrogen and carbon was tungsten, and we was formed in the reduction with CO. The reaction paths in the overall processes were determined. The reactant/product gas ratio had a considerable influence on which reactions took place. The morphology of the sample was characterised at different stages of the reduction. The shape of the WO₃ particles was retained during the reduction. Particle growth was observed in the reduction with hydrogen and was attributed to the formation of WO₂(OH)₂(g). The kinetics of the reductions were investigated , and the reaction mechanisms determined. The reduction of WO₃ with CO was studied from 650 to 900°C, and occurred at a phase boundary with an activation energy of 40 kJ mol⁻¹ . The reduction of WO₂, was studied under the same conditions. The reaction also occurred at a phase boundary and had an activation energy of 62 kJ mol⁻¹. The reduction of WO₃ with carbon was studied from 935 to 1100°C and took place via CO and CO₂. Two stages were observed in the reduction . The first stage, which corresponded approximately to the formation of WO₂ had an activation energy of 66 kJ mol⁻¹ and was limited by diffusion through the porous reacting particles. The second stage was first order and had an activation energy of 40 kJ mol⁻¹. The reduction of WO₃ and WO₃ graphite mixtures with hydrogen were studied from 575 to 975 °C. The reactions were controlled by mass-transfer under the conditions investigated. The addition of carbon increased the rate of the reduction process , but did not affect the phases formed in the system. CO₂ was evolved mainly at the start, and CO mainly at the end of the process.

Fundamental research on the growth of porous anodic alumina (PAA) films has been undertaken for many years because of the complexity of the processes involved and the wide range of commercial applications. In this study, a tungsten tracer approach has been used to determine the influences of current density and electrolyte temperature on the incorporation of the tracer and its distribution and consequently, the growth mechanisms of PAA films. The efficiencies of growth of PAA films, formed during anodizing at 5 mA cm-2 in the three major forming acids at 25°C, are ~60%, due to loss of outwardly migrating Al3+ ions at the film/electrolyte interface. Thus, only the inwardly migrating O2- ions contribute to formation of the anodic oxide at the film/metal interface. The pores are developed due to flow of alumina from beneath the pore base regions toward the cell walls, which is indicated by distortion of the incorporated Al-W alloy layers and retention of the tungsten species within the anodic films. PAA films formed at a low range of current densities (<2 mA cm-2) develop by a field-assisted dissolution mode, with significant losses of aluminium and tungsten species to the electrolyte, and low expansion factors of less than 1.2. Conversely, films formed at current densities ≥2 mA cm-2 grow by a flow mechanism: flow of film material transports the alumina oxide, including the incorporated tungsten tracers, from the barrier layer regions to the cell walls, resulting in relatively thicker films at higher current densities and retention of the tungsten within the films. The tungsten remains mainly within the inner cell region of the films, with a tungsten-free region present next to the pore wall. The efficiency of film growth increases from ~0.29 to ~0.73 with increase of current density from 0.5 to 30 mA cm-2, and from ~0.26 to ~0.88 with increasing current density between 0.5 and 50 mA cm-2 for anodizing in sulphuric and oxalic acids respectively.Comparatively, for PAA films formed at 15 mA cm-2 in oxalic acid, reduction of electrolyte temperature from 20 to 1°C gives rise to a slight increase of the anodizing efficiency from ~0.67 to ~0.74; the film expansion factor also increases from ~1.32 to ~1.43. The previous arises from reduced field-assisted ejection of Al3+ ions at the decreased electrolyte temperature.Anodizing of the aluminium substrates in phosphoric acid or neutral phosphate solution generates barrier anodic alumina films and the barrier layers of porous films respectively, which comprise phosphorus-containing outer regions and a phosphorus-free inner regions. The phosphorus-containing outer region accounts for ~0.67 of the barrier films and the ~0.80 of the barrier layer of the porous films. Further, the distributions of phosphorus species are not significantly affected by the incorporation of the tungsten tracer nanolayer into the films; the influence of the phosphorus species on the outward migration of the tungsten species is also negligible.This tungsten tracer study suggests a significant influence of the flow of alumina oxide, under the high electric field, on the formation of PAA films at current densities ≥2 mA cm-2.

Although hydrides of metal carbonyls are widely known, the number of hydrides in the related family of metal nitrosyls is extremely small. The preparation of a series of nitrosyl hydrides from the treatment of [CpW(NO)I₂]₂ (Cp=ƞ⁵-C₅H₅) with Na[H₂Al(OCH₂CH₂OCH₃)₂] is described. The addition of one or two equivalents of the aluminum reagent results in the formation of [CpW(NO)IH]₂ or [CpW(NO)H₂]₂ respectively. The reaction of [CpW(NO)IH]₂ with a Lewis base (L=P(OPh)₃, P(OMe)₃, PPh₃ or PMe₃) gives the monometallic CpW(NO)IHL, while [CpW(NO)H₂]₂ reacts with P(OPh)₃ or P(OMe)₃ to yield [CpW(NO)HL]₂ which undergoes further reaction to give CpW(NO)H₂L. Proton NMR spectroscopy shows that all bimetallic species contain bridging hydride ligands and are therefore best, formulated as [CpW(NO)1]₂(µ-H)₂, [CpW(NO)H]₂(µ-H)₂ and [CpW(NO)L]₂(µ-H)₂. The ¹H NMR spectrum of [CpW(NO)H]₂(µ-H)₂ shows that there is no hydride ligand exchange on the NMR time scale and that ¹jH(terminal)W ≃ ¹jH(bridging)w > ²jHW. From this finding, it is possible to develop new criteria for assessing the static or fluxional nature of hydride ligands for several families of organotungsten hydrides (Cp₂W, CpW(CO)₃, W(CO)₃ and CpW(NO)x (x=l or 2)). Within each family, the magnitude of ¹JHW strongly reflects the type of metal hydride bonding, i.e. [Formula Omitted] and suggests that bridge bonding involves all the atoms in the bridge and therefore the "fused" notation is introduced. Treatment of CpW(NO)(CH₂SiMe₃)₂ with low pressures of H₂ (60-80 psig) in the presence of Lewis bases (L=P(0Ph)₃, PMePh₂) gives the unusually stable alkyl hydride compounds CpW(NO)(H)(CH₂SiMe₃)L. This chemistry is then extended to the Cp* (Cp*=ƞ⁵ -C₅Me₅) analogues, including the preparation of the appropriate starting materials. Upon thermolysis of Cp*W(NO)(H)(CH₂SiMe₃)(PMe₃) in C₆H₆, the intermolecular C-H activation product Cp*W(N0)(H)(C₆H₅)(PMe₃) is cleanly formed. However, intermolecular activation of CH₄, C₆H₁₂ or n-C₆H₁₄ does not occur under similar experimental conditions. Hydrogenolysis of Cp*W(NO)(CH₂SiMe₃)₂ at high pressures (≃920 psig) with no Lewis base present results in the formation of isolable [Cp*W(NO)H]₂(µ-H)₂ and [Cp*W(N0)H](µ-H)₂[Cp*W(N0)(CH₂SiMe₃)]. The latter is a new example of the rare class of dinuclear alkyl hydride complexes. Proton NMR spin tickling experiments on this compound allow the complete assignment of all couplings in the spectrum and show that ¹jH(terminal)W' ¹JH(bridging)W and ²jHW have the same sign. / Science, Faculty of / Chemistry, Department of / Graduate

Tungsten is listed on the European Commission list of critical raw materials that are crucial to Europe’s economy. By raising awareness of tungsten as a critical raw material the EU can prioritise to enhance exploration, mining and recycling of tungsten. In this thesis the structural relationship between wall rock and veins, in a greisen-tungsten vein deposit, were analysed with the intention to interpret how tectonic deformation events control the emplacement of tungsten-bearing veins. The objective of this thesis is to investigate if and how structures controlled hydrothermal fluid flow and ore formation in the Peña del Seo tungsten-greisen vein deposit. Greisen systems are associated with tin and tungsten-bearing minerals and are related to intrusive magmatic bodies of granitic composition. Greisen-related granites (leucogranites), form at shallow depths in the crust (1.5-4 km) generally in intracontinental tectonic settings such as orogenic belts. The study site is located in the West Asturian-Leonese Zone in northwest Spain. This zone marks the transition between the foreland and the hinterland and is recognized as being part of a continental margin, where Palaeozoic rocks were deposited unconformably. These rocks were subsequently subjected to folding during the Variscan orogeny (370-290 Ma). Three main types of structures were generated due to three deformational phases (D1, D2 and D3) during the Variscan orogeny. D1 resulted in east-verging recumbent folding and formation of a related axial-planar parallel cleavage (S1), D2 resulted in displacement along large thrust sheets and D3 produced upright folding and refolding of F1 folds. Geological mapping with a focus on structural geology was carried out in March 2019, covering an area of approximately 0.25 km2. Structural measurements and oriented rock samples for microstructural study in thin sections were collected in the field. Additionally, photogrammetric mapping of structures was performed on a 3D photogrammetry model derived from a UAS survey. The geometry of the Peña del Seo tungsten-greisen vein deposit is interpreted to result from two major deformation events. The axial planar foliation (S1) at Peña del Seo is correlated to the regional fabric that developed during D1 of the Variscan orogeny. The related F1 folds are caused by buckling accompanied by flexural slip folding mechanism during D1. Forceful intrusion of the granite underlying the Peña del Seo deposit caused bending of the overlying rocks layers during D2. Layer-parallel stretching is likely to have caused tension fractures perpendicular to bedding in the outer arc of the F2 fold hinge. The formation of local crenulation and related spaced cleavage can be explained by layer-parallel shortening in the inner arc of the F2-fold. Local transposition of S1-foliation occurred during emplacement of quartz veins and explains the different orientation of strike of foliation between the northern and southern parts of the area. Fractures forming during formation of F2-fold are likely to have worked as conduits for ascending hydrothermal, ore-bearing fluids forming the Peña del Seo tungsten-greisen vein deposit.

abstract: This thesis explores the potential application of the phase change material tungsten trioxide (WO3) in optical force modulation for spacecraft and satellites. It starts with a literature review of past space optical force applications as well as potential phase change materials for optical force modulation. This is followed by the theoretical model and discussions of the optical properties of a variety of materials used in the structures explored thereafter. Four planar structures were analyzed in detail. Two of the structures were opaque and the other two were semi-transparent. The first of the opaque structures was a tungsten trioxide film on aluminum substrate (WO3/Al). It was found to have a 26% relative change in radiation pressure with WO3 thickness of 200 nm. The second opaque structure was a tungsten trioxide film on silicon spacer on aluminum substrate (WO3/Si/Al). This structure was found to have a 25% relative change in radiation pressure with 180 nm WO3 and 20 nm Si. The semitransparent structures were tungsten trioxide film on undoped silicone substrate (WO3/Si), and a tungsten trioxide film on a silicone spacer on tungsten trioxide (WO3/Si/WO3). The WO3/Si structure was found to have an 8% relative change in radiation pressure with 200 nm WO3 and 50 nm Si. The WO3/Si/WO3 structure had a relative change in radiation pressure of 20% with 85 nm WO3 and 90 nm Si. These structures show promise for attitude control in future solar sailing space missions. The IKAROS mission proved the functionality of using phase change material in order to steer a space craft. This was accomplished with a 7.8% relative change in radiation pressure. However, this only occurred at a pressure change of 0.11 µN/m2 over a range of 0.4 to 1.0 µm which is approximately 77.1% of the solar spectrum energy. The proposed structure (WO3/Al) with a 26% relative change in radiation pressure with a pressure change of 1.4 µN/m2 over a range 0.4 to 1.6 µm which is approximately 80% of the solar spectrum energy. The magnitude of radiation pressure variation in this study exceeds that used on the IKAROS, showing applicability for future mission. / Dissertation/Thesis / Masters Thesis Aerospace Engineering 2020