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Métodos de síntese que viabilizam a obtenção de compósitos contendo xerogéis de óxido de tungstênio e de pentóxido de vanádio pelo método sol-gel foram investigados, bem como a caracterização e propriedades catalíticas nas reações de epoxidação destes materiais. Brometo de cetiltrimetilamina e hexadecilamina foram intercalados nos xerogéis de óxidos vanádio e de tungstênio formando compostos híbridos orgânico-inorgânico ternários. Estas moléculas foram usadas com o objetivo de aumentar a distância interlamelar e conferir caráter hidrofóbico nos compostos híbridos para que facilitasse o acesso dos substratos orgânicos quando utilizados como catalisadores nas reações de epoxidação. Os parâmetros de difração de raios X comprovam a intercalação, com aumento da distância interplanar. Observa-se uma variação na posição da banda M=O para maiores valores de energia devido à interação eletrostática entre as cargas positivas das espécies convidadas com densidade de carga negativa das ligações M=O. O xerogel de óxido de tungstênio e o compósito com xerogel de óxido de vanádio com óxido tungstênio foram dispersos em matrizes de óxido hidróxido de alumínio e de xerogel de óxido de silício. Foi observado que os modos vibracionais no infravermelho não sofreram variações significativas, indicando que pequenas distorções ocorrem quando os xerogéis dos óxidos estão dispersos, ou seja, há interações fracas entre os componentes, corroborando com os padrões de difração de raios X que mostram a manutenção da estrutura inicial dos óxidos. No caso dos compósitos contendo óxido de vanádio em sílica empregando metiltrietóxissilano, houve a formação de partículas esféricas de sílica recobertas por filmes de óxido de vanádio. No entanto, ao utilizar o tetraelilortossilicato como precursor, houve a manutenção da estrutura lamelar dos óxidos, mas não se observou a formação das partículas esféricas de sílica. As propriedades catalíticas destes materiais foram testadas em reações de oxidação do cis-cicloocteno, estireno e ciclo-hexano usando peróxido de hidrogênio (H2O2), terc-butil hidroperóxido (t-BOOH) e ácido meta-cloroperbenzóico (m-CPBA) como agentes oxidantes. De modo geral, os resultados obtidos são satisfatórios e estão de acordo com os resultados apresentados na literatura para sistemas similares, sugerindo uma aplicação potencial destes materiais como catalisadores em reações de epoxidação e oxidação. / Synthetic procedures based on sol-gel process were developed aiming produce xerogel composites of mixed oxides such as tungsten oxide and vanadium oxide, as well as their characterization and catalytic properties in epoxidation reactions. Cetyltrimetylamine bromide and hexadecylamine were intercalated into vanadium oxide and tungsten oxide xerogels resulting in ternary hybrid inorganic-organic compounds. These molecules were used in order to increase the interlamelar distance and confer hydrophobic character facilitating the substrate access in catalyzes epoxidation reactions. X ray diffraction patterns demonstrate the intercalation. It was verified the shift of the M=O vibrational mode towards higher energy region due to electrostatic interaction between positive charges of guest species with negative character of M-O bonding. Tungsten oxide and vanadium and tungsten mixed oxide xerogels were dispersed in oxohydroxiy aluminum and silicon oxide matrices. No significant changes in the infrared vibrational modes were observed, suggesting that few distortions occur when xerogel materials are dispersed, due to weak interactions corroborating previous results. In the case of composites containing vanadium oxide and silica (methyltriethoxysilane as precursor), the final material is formed by sphere particles of silica covered with vanadium oxide film. However, when tetraethylorthosilicate was used as silica precursor, the lamelar structure of metal oxide is retained instead of spherical morphology. The catalytic properties of these materials were verified in oxidation of cis-cyclooctene, styrene, and cyclohexane using hydrogen peroxide (H2O2), terc-butyl hydroperoxide (t-BOOH), and cloroperoxybenzoic acid (m-CPBA) as oxygen donors. From a general point of view, the results are satisfactory and close with those found for similar systems, enabling them as catalysts for epoxidation and oxidation.

O xerogel de pentóxido de vanádio possui estrutura bi-dimensional que viabiliza a intercalação de diferentes espécies como íons, compostos orgânicos e espécies poliméricas. E, quando associeado a outros óxidos de metais transição, tais como, WO3 e MoO3 apresenta uma importância em reações de catálise, pois estes óxidos atuam como promotores em reações como, por exemplo, a redução catalítica seletiva do NOx a NH3 e a oxidação de hidrocarbonetos. Além disso, estes óxidos melhoram as propriedades eletroquímicas e eletrocrômicas, favorecendo assim sua utilização em células fotoquímicas, células para conversão de energia solar e cátodos de baterias e lítio. Dentre estes óxidos, o óxido de tungstênio hidratado foi escolhido não somente por favorecer a dissociação ácida das moléculas, mas também por apresentar uma estrutura lamelar que favorece reações de intercalação sem afetar significativamente sua estrutura original. Neste contexto, o xerogel de óxido misto V2O5/WO3 foi sintetizado e suas propriedades eletroquímicas bem como sua capacidade de intercalação foi investigada. em relação ao comportamento eletroquímico, a melhor resposta foi obtida para o óxido misto com menor concentração de WO3, ao passo que para os óxidos com alta quantidade de óxido de tungstênio, a intercalação dos íons Li+ não foi eficiente. Estudos de voltametria cíclica revelaram que a resposta eletroquímica do óxido misto é similar à encontrada para o xerogel de pentóxido de vanádio. Em adição, outros resultados revelaram a dependência da resposta eletroquímica com a natureza do eletrólito suporte. Também foi verificado que é possível intercalar anilina e agentes tensoativos (Brometo de Cetiltrimetilamônio - CTAB), mantendo o caráter bi-dimensional. Neste trabalho, o compósito V2O5/WO3/SiO2 foi preparado pelo método sol-gel. A metodologia usada possibilitou a preparação de microesferas de sílica cobertas por xerogel de V2O5/WO3, conservando não somente a estrutura, mas também as propriedades eletroquímicas. A atividade catalítica avaliou a oxidação do estireno em fase líquida. / Vanadium pentoxide xerogel has a bi-dimensional structure which is suitable for intercalation of a variety of ions, organic compounds, and even polymeric species. In addition, when associated with other metal oxides such as WO3 and MoO3, it presents an important role in catalysis, since the resulting oxides act as promoters in catalytic reduction of the NOx to NH3 and hydrocarbons oxidation. Besides, these oxides improve electrochemical and electrochromic properties, leading to their use in photochemical cells, cathodes and in solar energy cells. Among several metal oxides, hydrated tungsten oxide was chosen not only because of favor the acid dissociation of molecles but also because of its lamellar structure that allows intercalation reactions without affect significantly the original structure. In this context, V2O5/WO3 xerogel mixed oxides were synthesized and electrochemical properties as well as intercalation capacity were investigated. Concerning the electrochemical behavior, the best response was obtained for the mixed oxides with low concentration of WO3, whereas for the oxides with high amount of tungsten oxide, the lithium ions intercalation was not efficient. Cyclic voltammetric studies revealed that the electrochemical response of mixed oxide is similar to that found for the vanadium pentoxide xerogel. In addition, our results reveal the dependence of the electrochemical response on the nature of the supporting electrolyte. It was also verified that it is possible to intercalate aniline and surfactant molecules (N-cetyl-N,N,N,-trimethyl-ammonium bromide - CTAB), maintaining the bi-dimensional character. In this work, V2O5/WO3/SiO2 composite was prepared by sol-gel method. The methodology used enables the preparation of silica microspheres covered by V2O5/WO3 xerogel mixed oxides, retaining not only its structure but also the electrochemical properties. the catalytic activity evaluated in the oxidation of the styrene in liquidphase.

M.Sc. / This study comprises the preparation and characterisation of new azolinylidene- and divinylcarbene complexes of chromium, molybdenum and tungsten, from 1- phenylpyrawle, 1-methylimidazole and 4,4-dimethyl-2,2-thienyloxazoline precursors. The reaction of 1-phenylpyrazolyllithium with (C0) 6M (M Cr, Mo or W) yields after alkylation with CH3S03CF3 in THE the two products (C0)5M[C(OCH3X(ONPhNCHC(H)] and (C0)5M[C(0{CH2}40C113)(aNPhNCH6H)]. A 'H NMR study indicates the existence of two isomers for each of the two tungsten CO'cli•lexes. 1-Methylimidazolyllithiura reacts with (CO)6M (M = Cr, Mo or W) to give the carbene complexes (C0)5MK'N(CH3)CHCH14(C I i 3)] after alkylation with CH3S03CF3, and the imine complexes (C0)5MOCHN(CH3)CH6H] after protonation with SO3CF3. Reaction of 1-methylimidazolyllithium with the anionic salt (C0)5 Cl = Cr or W), followed by alkylation with CH3S03CF3 affords both the mono- and bis(carbene) complexes, (CO)5M[CN(CH3)CHCHN(CH3)] and (C0)41v1[6N(CH3)CHCIRA(CH3)]2. The complex (C0)5W[C(0 {CH2 } 40C113)(t‘NPhNaldH)] reacts with phenylethynthiolate to furnish an anionic organometallic synthon that can either be alkylated or protonated. Protonation leads to two isomeric forms of the metal-coordinated thioaldehyde, (C0)5W4—SHC(Ph)=C(OCH3)(oNPhNCHell), whilst alkylation with various electrophilic reagents produces the metal coordinated dithio-esther (C0)5 W4--S=C [ SCH3] [C(Ph)=C(OCH3)(tNPhNaldH)]. The neutral divinylcarbene complexes (C0)5Cr{cC(a0CH2CMe2N)SC CH} (a) and (C0)5W{cC(COCH2CMe214)SCH9H} (19) are prepared by reaction of (C0)5MCr with the 3-lithiated thienyloxazoline, followed by alkylation with CH3S03CF3 . These complexes are the first examples of coordinated 'divinylcarbenes utilizing the group 6 transition metals, where the carbene carbon shows carbene character. They are also in another sense unique since the nucleopbutlic heteroatom where alkylation occurs, is situated outside the coordinated ring-system, and, therefore, more than two bonds removed fro the carbene carbon atom.

Le tungstène est le matériau choisi pour le divertor d'ITER en raison de ses propriétés thermiques et physiques. Les densités de flux et les énergies des particules, et la température de surface pourront varier de plusieurs ordres de grandeur le long de la surface du divertor, soit respectivement 1020-1024 m2s-1, 0.1-100 eV, et 370-1370K. Exposé à de telles conditions, le tungstène peut subir de l'érosion, des fissurations et d'autres modifications de surface affectant ses propriétés thermomécaniques. Une autre préoccupation est la rétention des atomes de tritium implantés dans la surface et leur diffusion dans l'épaisseur du matériau. Nombre d'études ont porté sur la rétention et les modifications de surface induite par le plasma, mais se concentraient principalement sur l'effet de l'énergie des ions, leur fluence et la température de surface, mais très peu portaient sur l'influence du flux de plasma, avec des résultats erratiques et peu cohérents entre eux. L'objectif de cette thèse est de fournir une image cohérente du comportement du tungstène exposé à des conditions pertinentes pour les futurs réacteurs de fusion. Une investigation systématique évaluant l'impact de la densité de flux de plasma et de la température de l'exposition sur les modifications de surface et l'accumulation d'hydrogène dans tungstène a été effectuée au moyen d'expériences menées dans les dispositifs plasma linéaires, PSI-2 à Jülich, Pilot-PSI et Magnum-PSI à DIFFER, et PISCES-A à UCSD. La corrélation entre densité de flux de particules, température d'exposition, modifications de surface et rétention de l'hydrogène dans le tungstène a été étudiée pour différentes microstructures de matériau. Des échantillons de trois types de tungstène poly-cristallin (traité thermiquement à 1273 et 2273 K) et monocristallin (orientation 110) ont été exposés à des plasmas de deutérium et des températures de surface de 530 à 1170 K à deux gammes différentes de flux d'ions deutérium (~1022 et ~1024 m2s-1). Toutes les expositions ont été effectuées à la même énergie d'ions incidents de 40 eV et une fluence de particules de 1026 m2. Les échantillons ont été analysés post mortem en utilisant diverses techniques d'imagerie et d'analyse de surface (microscopie, spectroscopie de désorption thermique (TDS) et analyse par faisceau d'ions). L'augmentation du flux de particules de deux ordres de grandeur a provoqué la formation de bulles au-dessus de 700 K, températures pour lesquelles elles sont généralement absentes à faible flux. De petites cloques de respectivement quelques dizaines de nm et jusqu'à une taille latérale de 1 micron ont été détectées sur des échantillons de tungstène poly-cristallin recuit et monocristallin. Au contraire, les cloques sont absentes sur les échantillons recristallisés, sauf à faible flux et basse température où des vésicules d'environ 10 micron et des cavités sont apparues le long des joints de grains. La rétention totale de deutérium a été mesurée par TDS. A faible température d'exposition la fraction retenue était un à deux ordres de grandeur plus élevée après l'exposition à faible flux qu'à haut flux. Au contraire, une tendance opposée de la rétention totale à des températures d'exposition élevées a été observée. Par conséquent, le maximum de la rétention de deutérium totale a été observé pour une température supérieure dans le cas du flux incident de particules élevée (~850 K) comparée à l'exposition de faible flux (~650 K). Globalement les résultats sur la rétention de deutérium étaient similaires pour toutes les microstructures de tungstène étudiées. La rétention diminue à haute température et son maximum est plus bas pour des expositions à haut flux. Or, en raison du décalage de la rétention maximale vers des températures plus élevées, la quantité de deutérium piégée pour des températures supérieures à 800 K était plus élevée à haut flux qu'à faible flux, soit ~ un ordre de grandeur inférieur à la rétention maximum à faible flux / Tungsten is the selected material to be used in the ITER divertor due to its favorable thermal and physical properties. Particle flux densities and energies, and surface temperature will vary by several orders of magnitude along the divertor surface, with values in the range 1020-1024 m2s-1, 0.1-100 eV and 370-1370 K, respectively. Exposed to such conditions, tungsten may undergo erosion, cracking and other surface modifications affecting its thermal and mechanical properties. Another concern is the retention of implanted radioactive fuel atoms (tritium) in the material surface and their diffusion through the bulk. A considerable amount of studies have addressed retention and plasma induced surface modifications, focusing mainly on the effect of ion energy, ion fluence and surface temperature while very little knowledge exists on the influence of the plasma flux. These results are largely scattered and occasionally bear a lack of consistency. The aim of this thesis is to provide a coherent picture of the behavior of tungsten exposed to plasma conditions relevant for future fusion reactors. A systematic investigation assessing the impact of the plasma flux density and exposure temperature on surface modifications and hydrogen accumulation in tungsten was performed by means of experiments carried out in the linear plasma devices PSI2 at Forschungszentrum Juelich, Pilot-PSI and Magnum-PSI at DIFFER, and PISCES-A at UCSD. The correlation between the particle flux density, exposure temperature, surface modifications and hydrogen retention in tungsten was investigated for different material microstructures. Three types of polycrystalline tungsten (thermally treated at 1273 and 2273 K) and single crystal tungsten samples (110 crystal orientation) were exposed to deuterium plasmas at surface temperatures of 530-1170 K to two different ranges of deuterium ion fluxes (low and high flux: ~1022 and ~1024 m2s-1). All the exposures were performed at the same incident ion energy of 40 eV and particle fluence of ~1026 m2. The exposed samples were analyzed postmortem utilizing various surface imaging and analyses techniques (microscopy, thermal desorption spectroscopy and ion beam analysis). Increasing the particle flux by two orders of magnitude caused blister formation at temperatures above 700 K for which blistering is usually absent under low flux exposure conditions. Small blisters of several tens of nanometers and up to 1 micrometer of lateral size were detected on the annealed polycrystalline and in single crystal tungsten samples, respectively. On the contrary, blisters were absent on the recrystallized samples except for the low flux and low temperature case where large blisters of about 10 micrometer and cavities along the grain boundaries appeared. The total deuterium retention was measured by means of thermal desorption spectroscopy (TDS). In the cases with low exposure temperatures, the retained fraction of deuterium was one to two orders of magnitude higher after exposure to the low flux compared to the high flux. On the contrary, an opposite tendency of the total deuterium retention at high exposure temperatures was observed. Hence, the maximum of the total deuterium retention was observed to occur at a higher temperature in the case of high incident particle flux (~850 K) compared to low flux exposures (~650 K). Overall, experimental results on deuterium retention were similar for all the investigated tungsten microstructures. Deuterium retention decreased at high temperatures and the maximal retention was lower for high flux exposures. However, due to the shift of the maximal retention to higher temperatures, the amount of deuterium retained at temperatures above 800 K was higher at high flux rather than at low flux, being still about one order of magnitude lower than the maximal retention at low flux

Please read the abstract in the section 00front of this document / Dissertation (MSc (Chemistry))--University of Pretoria, 2006. / Chemistry / unrestricted

A study of the reactions between molybdenum and tungsten disilicide (MoSi2 and WSi2) with anhydrous hydrogen fluoride and fluorine was carried out to investigate the chemical behaviour of the materials. These two compounds were used as alternatives that resemble the chemical behaviour of uranium silicide (U3Si2). An extensive literature survey of U3Si2 processing techniques is included, which guided the process selection for this work. The thermogravimetric results of a study into the dry fluorination of molybdenum and tungsten disicilides using both anhydrous hydrogen fluoride and dilute fluorine gas as fluorinating agents are reported. For both solids the observed reactions with fluorine follow the thermodynamically predicted routes, in which the formation of the volatile metal hexafluorides, along with gaseous silicon tetrafluoride was observed. The disilicides get fully converted at roughly 300 to 400 °C respectively. The expected products for the reactions of both solids with hydrogen fluoride are solid tungsten metal, solid molybdenum metal, hydrogen gas, and gaseous silicon tetrafluoride. The metal fluorides (WF4 and MoF3) were not obtained because they form at low temperatures only. Therefore the metals of molybdenum and tungsten were obtained as final products respectively from both reactions; and were verified with the aid of XRF and XRD analyses. Mass-transfer phenomena are shown to play a role in the reactions between hydrogen fluoride and both disilicides, preventing unrestrained complete fluorination of the two solids. Kinetic parameters are reported and the rate limiting mechanisms identified. Copyright / Dissertation (MSc)--University of Pretoria, 2012. / Chemical Engineering / unrestricted

The Peña del Seo tungsten deposit in northwestern Spain is situated in the tin (Sn)-tungsten (W) metallogenic province of Europe − one of the richest tin-tungsten (tantalum-lithium) mineral provinces in the world. The European Union’s current goal is to become self-sufficient of these commodities in the near future and the iTARG3T project was launched in order to improve the understanding and provide innovative exploration methods of these types of deposits. This master thesis will contribute to the iTARG3T project. The aim was to determine which physico-chemical conditions (temperature, pressure, salinity) that prevailed during the emplacement of the Peña del Seo deposit. A geochemical study was done consisting of a fluid inclusion study on the quartz veins from the deposit, and a whole-rock geochemistry analyse of the granitic rock. Homogenisation temperatures ranged between 97,6° C to 325,6° C and salinities (NaCl % equiv.) between 0,2% to 21,3%. The fluid was determined to consist of a two-component system of H2O and NaCl based on eutectic temperature. Based on its geochemical classification the granitic rock was considered to be an alkali granite, strongly peraluminous with S-type characteristics. At least two different types of fluids were present during the emplacement of the Peña del Seo deposit, one that was hot and with a moderate salinity, and one that had a lower temperature than the other fluid and a lower salinity, possibly meteoric water. The depositional mechanism of tungsten is thought to be caused by a combination between mixing between two fluids and cooling of the fluids, with the main depositional mechanism being cooling since the change in salinity was not of such magnitude that it would change the fluid chemical composition, while the decrease in temperature was. It is uncertain whether the granitic rock found at Peña del Seo is part of the granitic cupola of the greisen system. The granitic rock has similar characteristics as the leucogranites of the West Asturian-Leonese Zone and based on quartz vein morphology, which cut the D2 foliation, time of emplacement of the deposit could be linked to the syntectonic event at 320-310 Ma. If the relation between the granitic rock and the greisen system can be determined the time of emplacement would be possible.

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