Neste trabalho estudou-se a influência da substituição de TiO2 por Ta2O5 nas propriedades estruturais e eletrocatalíticas do sistema RuO2/Ta2O5. Uma investigação sistemática das propriedades estruturais, morfológicas, eletroquímicas e eletrocatalíticas para a produção de O2 em meio ácido foi conduzida usando ânodos de composição nominal Ti/(x)RuO2(1 – x)Ta2O5 (x = 0,1; 0,3; 0,5; 0,8), preparados por decomposição térmica (450 e 500 oC por 1h sob fluxo de 5 L min-1 de O2) das misturas precursoras preparadas em isopropanol (Aldrich). Os sais de cloretos precursores foram (RuCl3.xH2O e TaCl5 – Aldrich). Análises da composição e da morfologia da camada de óxidos foram feitas antes e após os testes acelerados de vida (TAV), através das técnicas de EDX (Energia dispersiva de raios-X) e MEV (Microscopia eletrônica de varredura) respectivamente. A microscopia mostrou estrutura de “barro-rachado" para a maioria dos filmes. As análises de EDX evidenciaram uma redução do conteúdo do Ru após o TAV. Os dados sobre a estrutura foram obtidos por DRX (Difração de raios-X) e mostraram forma rutílica para o RuO2 e ortorrômbica para Ta2O5. Os voltamogramas cíclicos deste sistema em meio ácido (0,5 mol dm-3 de H2SO4) apresentaram as bandas características da dupla Ru(III) / Ru(IV). Em baixos sobrepotenciais, o coeficiente de Tafel, b, apresenta valores entre 40 mV e 60 mV. Os valores de resistência ôhmica (0,5 – 2,0 W) sugerem que a queda ôhmica do sistema pode ser atribuída principalmente à resistência da solução. A atividade eletrocatalítica apresentou uma forte dependência em relação ao conteúdo de RuO2 no filme, aumentando conforme o aumento da quantidade de RuO2 na composição. A estabilidade do sistema foi avaliada pelo TAV, utilizando eletrólise a corrente constante (750 mA cm-2 e T = 80 oC em solução de H2SO4 0,5 mol dm-3). As análises dos resultados mostraram uma relação entre o tempo de operação do eletrodo e a quantidade do componente ativo (RuO2). A substituição de titânio por tântalo (x = 0,5) apresentou uma melhora considerável (54%) no tempo de operação destes óxidos. Estes resultados apontam o sistema Ru/Ta como um recobrimento bastante promissor para operação em condições drásticas. / In this work it was investigated the structural and electrochemical properties of the RuO2/Ta2O5 system. A systematic investigation of structural, morphologic, electrochemical and eletrocatalytic properties for O2 evolution from acidic solutions was conducted using anodes of nominal composition Ti/(x)RuO2(1 + x) Ta2O5 (x = 0.1; 0.3; 0.5; 0.8), prepared from appropriate mol ratio by thermal decomposition (450 and 500 oC for 1 h under O2-flux of 5 L min-1) from alcoholic (isopropanol – Aldrich) solutions of the precursors mixtures (RuCl3.xH2O and TaCl5 - Aldrich). Analyses of the composition and the morphology of the oxide layer were investigated before and after accelerated life tests (ALT), through EDX techniques (Energy Dispersive X-rays) and SEM (Scanning Electron Microscopy) respectively. SEM results showed typical mud-flat-cracking morphology for the majority of the films. EDX analyses even after total deactivation evidenced the reduction of the content of Ru in the coating. Structure data have been obtained by XRD (X-rays diffraction) and which showed the rutile-type struture for RuO2 and orthorhombic one for Ta2O5. Cyclic voltammograms of this system where registered in acidic solutions (0.5 mol dm-3 of H2SO4). The observed peak has been attributed to the solid-state redox transition of Ru(III)/Ru(IV). At low overpotentials, Tafel slope, b, ranges from 40 - 60 mV. The RW-values found (0.5 – 2.0 W), are in agreement with other RuO2-based oxide electrodes. This is a good evidence that the ohmic drop of the system can be attributed mainly to solution resistance. The eletrocatalytic activity shows a strong dependence with the RuO2 content in the film. The stability of the electrodes are evaluated by the ALT, performed at 0.5 mol dm-3 in aqueous H2SO4 (750 mA cm-2 and T = 80 oC). The results shows a straight relation between the ALT-values and the amount of active component (RuO2) presented in the coating. Changing TiO2 by Ta2O5 (x = 0.5) showed a considerable improvement (54%) in the ALT-values of these oxides. These results it is a good indication that Ru/Ta system might be a promising coating to operate under drastic conditions.

O estudo do eletrorrevestimento de tântalo sobre aço e sobre cobre foi realizado na mistura eutética FLINAK (29,2% LiF - 11,7% NaF - 59,1% KF - % em massa) contendo 15% em massa de K2TaF7. Foram estudadas as influências da densidade de corrente catódica, do tempo de eletrólise, da temperatura e da natureza do substrato sobre as eficiências de correntes catódicas e a morfologia dos revestúnentos. Depósitos de tântalo lisos, brilhantes, aderentes e uniformes foram obtidos com alta eficiência de corrente catódica usando os seguintes parâmetros: densidade de corrente catódica de 23 mA/cm2 a 50 mA/cm2, temperatura de 750°C e tempo de eletrólise de 30 minutos a 120 minutos. Os revestimentos obtidos nestas condições possuem espessuras de 18 µm a 41 µm. Os depósitos de tântalo sobre aço e sobre cobre são constituídos de tântalo puro, sem formação de camada de difusão. Ensaios de eletrodeposição de camadas delgadas de tântalo em catodos de formas e geometrias complexas mostraram o bom poder de cobertura do tântalo. Curvas potencial de circuito aberto x tempo, feitas à temperatura ambiente em soluções de ácido nítrico a 40%, a 50% e a 60% em massa, ácido clorídrico a 3,6% em massa e ácido sulfúrico a 80% em massa, mostraram ótima concordância entre o potencial de circuito aberto estacionário do tântalo maciço comercial e dos revestimentos de tântalo sobre cobre nestes meios. Curvas potencial de circuito aberto x tempo feitas à temperatura ambiente em meio de ácido clorídrico a 3,6% em massa, para revestimentos sobre aço mostraram que a semelhança com o tântalo maciço só é observada em depósitos recentes, o que foi atribuído à difusão do ferro do substrato para a superficie do revestimento. Ensaios gravimétricos mostraram que a velocidade de corrosão dos revestimentos é comparável com a do tântalo comercial, em meios de ácido nítrico a 40% e a 50% em massa, à temperatura de ebulição. / The study of tantalum electroplating on copper and carbon steel has been carried out in FLINAK eutectic (29.2% LiF -11.7% NaF -59.1% KF - wt%) containing 15wt% K2TaF7. The effects of current cathodic density, time of electrolysis, temperature and substrate kind have been studied in relation to the cathodic current efficiencies and the coating morphology. Tantalum deposits, with good smoothness, brightness, adherence and uniformity were obtained with high cathodic efficiency, using the following conditions: 23 mA/cm2 to 50 mA/cm2 cathodic current densities, 30 minutes to 120 minutes electrolysis time interval and 750°C temperature. Under these conditions the coatings are about 18 µm to 41 µm thick. The deposits obtained on carbon steel and copper are both constituted of pure tantalum without formation of interdiffusion layer. The results of tantalum thin coatings electrodeposition on cathodes of complex geometrics and shapes showed the good throwing power of tantalum. Open circuit potential x time curves have been recorded for massive tantalum and for tantalum coatings on copper in 40 wt%, 50 wt% and 60 wt% nitric acid, 3.6 wt% hydrochloric acid and 80 wt% sulfurie acid at room temperature. They showed similar stationary open-circuit poteutial values for both the massive tantalum and the tantalum coatings. Open circuit potential x time curves for tantalum coatings on carbon steel performed in 3.6%wt hydrochloric acid at room temperature showed that the similarity with massive tantalum exists only with recent deposits, because of iron diffusion from substrate to coating surface. Gravimetric tests showed comparable corrosion rate values for massive tantalum and tantalum coatings in boiling 40wt% and 50wt% nitric acid.

Au cours des dernières années, la synthèse ciblée du butadiène en utilisant le bioéthanol a suscité une attention sans précédent en raison de l'intérêt croissant aux matières premières biosourcées ainsi que de la demande croissante en butadiène.Un processus pertinent dans ce contexte est le processus d'Ostromyslensky, qui s’effectue en deux étapes, comprenant la déshydrogénation de l'éthanol en acétaldéhyde en une étape séparée , suivie de la production de butadiène dans la deuxième étape par réaction d'acétaldéhyde avec de l'éthanol supplémentaire. Bien que la viabilité économique et la faisabilité de ce procédé d’éthanol en butadiène (ETB) soient bien établies, il reste de la place pour de meilleures performances catalytiques et une meilleure sélectivité. Dans cet effort, notre objectif était de développer une famille de catalyseurs sur silice à base de silice bien définis, basés sur la chimie organométallique de surface (SOMC) et de les tester lors de la conversion d'EtOH / AA en BD. Le premier ensemble de pré-catalyseurs a été synthétisé en traitant le [(=SiO)2TaHx] précédemment connu avec du N2O en tant qu'oxydant doux. La deuxième famille de catalyseurs a été préparée par calcination de l'espèce alkyl de tantale à 500°C. Les pré-catalyseurs ont été caractérisés par FTIR, RMN SS, UV-vis-DRS, DRX, EXAFS et HR-STEM. On a découvert que les pré-catalyseurs SOMC oxydés au N2O avaient principalement isolé des espèces [(SiO)2Ta (OH)x] peuplant la surface, tandis que la famille des pré-catalyseurs synthétisés par calcination mettait en évidence un mélange d’espèces de surface, y compris des agrégations de type cordes. Les tests catalytiques sur ces catalyseurs ont donné des résultats prometteurs, présentant une catalyse supérieure dans la transformation d'EtOH / AA en BD en termes de sélectivité en BD et de rendement par rapport à l'état de la technique. Outre l'excellente sélectivité, une gamme étroite de distribution du produit et une formation négligeable de coke ont été observées. Les espèces de TaOx isolées sur le pré-catalyseur oxydé au N2O ont montré une activité nettement meilleure et se sont révélées être les sites actifs de cette conversion par rapport à l'agrégation en chaîne de centres de tantale sur le matériau calciné. Sur la base de ces études DRIFT et in situ sur les catalyseurs, un mécanisme préliminaire pour cette conversion a été proposé / In the recent years on-purpose synthesis of butadiene using bioethanol has gained unprecedented attention owing to rise in interest for bio-based feedstock along with the steeply increasing demand for butadiene (BD). In this regard a relevant process is the Ostromyslensky’s two-step process, involving dehydrogenation of ethanol to acetaldehyde in a separate step, followed by butadiene production in the second stage by co-feeding ethanol and acetaldehyde. Although the economic viability and feasibility of this ethanol to butadiene (ETB) process is well established, there is a room for better catalytic performances and selectivity. In this endeavour our aim was to develop a family of well-defined Ta-based silica-supported catalysts through Surface Organometallic Chemistry (SOMC) and test them in the conversion of EtOH/AA to BD. The first set of pre-catalysts was synthesized by treating the previously known [(=SiO)2TaHx] with N2O as mild oxidant. The second family of catalysts was prepared by calcination of the tantalum alkyl species at 500°C. The pre-catalysts were characterized by FTIR, SS NMR, UV-vis-DRS, XRD, EXAFS and HR-STEM. The N2O oxidized SOMC pre-catalysts were found to have mostly isolated [(=SiO)2Ta(OH)x] species populating the surface whereas the family of pre-catalysts synthesized via calcination evidenced a mixture of surface species, including string-like aggregations.Catalytic tests over these catalysts generated promising results exhibiting superior catalysis in the transformation of EtOH/AA to BD in terms of both BD selectivity and yield compared to the state of the art. In addition to the excellent selectivity a narrow range of product distribution and negligible coke formation was observed. Isolated TaOx species on the N2O oxidized pre-catalyst showed markedly better activity and were found to be the active sites in this conversion compared to the string-like aggregation of tantalum centres on the calcined material. Based on this and in-situ DRIFT studies over the catalysts a preliminary mechanism for this conversion was proposed

Neste trabalho foram realizados experimentos de soldagem de chapas de Tântalo e Monel 400 com 100 m de espessura. Foram realizadas soldas em um laser de Nd:YAG operando em modo pulsado e em um Laser de Fibra operando em modo contínuo. Em seguida a microestrutura das amostras foram analisadas através de microscopia ótica e foram realizados ensaio de microdureza Vickers. As amostras que apresentaram melhores resultados foram submetidas a ensaios de tração e a ensaios de corrosão. Após análise dos resultados observou-se que a soldagem a laser apresenta muitos benefícios em relação a outros processos convencionais para chapas finas. A soldagem no modo pulsado apresentou maior relação de aspecto se comparado a soldagem em modo contínuo. A soldagem em modo contínuo apresentou uma velocidade de soldagem muito superior ao modo pulsado. Os resultados indicaram que a soldagem no modo pulsado apresenta maior aplicabilidade para chapas finas, devido à necessidade um controle preciso sobre a intensidade aplicada. / This work carried out welding experiments of Tantalum and Monel 400 plates with 100 mm thickness. Welds were made with an Nd: YAG laser operating in a pulsed mode and in a fiber laser operating in continuous mode. Then the microstructure of the samples were analyzed by optical microscopy and were performed Vickers microhardness test. Samples that showed better results were subjected to tensile tests and the corrosion tests. After analysis of the results showed that the laser welding offers many benefits over other conventional processes for thin sheets. The welding in pulsed mode presented in superior aspect ratio compared to welding in continuous mode. The welding in continuous mode showed a much higher welding speed to pulsed mode. The results indicated that the welding in pulsed mode shows more applicability for sheet metal, due the need of a precise control of applied intensity.

This Thesis describes the synthesis and reactivity of Group 5 imido and hydrazido complexes with tridentate, trianionic ligands. Various synthetic routes towards these hydrazido compounds were explored and in which several intermediates were synthesised and their chemistry was explored. The reactivity of the imido and hydrazido complexes with unsaturated and other small molecules was also studied. <b>Chapter One</b> provides a general introduction to tridentate pincer and tripodal ligands. The structure, synthesis and reactivity of Group 4 and 5 imido and hydrazido complexes is also reviewed. <b>Chapter Two</b> describes three different synthetic routes towards tantalum hydrazido complexes with tridentate, trianionic ligands. Synthesis, characterization and bonding analysis of the precursor dichloride species Ta(NN₂^SiMe3)Cl₂, which is used as starting material for two of the synthetic routes, is also described. The synthesis, characterization and bonding analysis of the tantalum dialkyl and alkyl-amido precursors prepared in the multistep route is also explored. <b>Chapter Three</b> describes the synthesis and characterisation of Group 5 imido complexes with tridentate, trianionic ligands of the type Li₃(NN₂^R) and Li₃(NNN^SiMe3). Reactivity studies of the imido complex Nb(NN₂iPr)(N^tBu)(py)₂ with unsaturated and other small molecules are also explored. <b>Chapter Four</b> describes the synthesis and characterisation of Group 5 hydrazido complexes with tridentate, trianionic ligands by two different synthetic routes, alongside a bonding analysis of the imido compounds M(NN₂^R)(N^tBu)(py)₂ and their hydrazido analogues M(NN₂^R)(NNPh₂)(L)_x. Reactivity studies of the hydrazido complex Nb(NN₂^iPr)(NNPh₂)(py)₂ with unsaturated and other small substrates are also described. <b>Chapter Five</b> presents full experimental procedures and characterising data for the new methodologies and complexes reported in this Thesis.

Neste trabalho estudou-se a influência da substituição de TiO2 por Ta2O5 nas propriedades estruturais e eletrocatalíticas do sistema RuO2/Ta2O5. Uma investigação sistemática das propriedades estruturais, morfológicas, eletroquímicas e eletrocatalíticas para a produção de O2 em meio ácido foi conduzida usando ânodos de composição nominal Ti/(x)RuO2(1 – x)Ta2O5 (x = 0,1; 0,3; 0,5; 0,8), preparados por decomposição térmica (450 e 500 oC por 1h sob fluxo de 5 L min-1 de O2) das misturas precursoras preparadas em isopropanol (Aldrich). Os sais de cloretos precursores foram (RuCl3.xH2O e TaCl5 – Aldrich). Análises da composição e da morfologia da camada de óxidos foram feitas antes e após os testes acelerados de vida (TAV), através das técnicas de EDX (Energia dispersiva de raios-X) e MEV (Microscopia eletrônica de varredura) respectivamente. A microscopia mostrou estrutura de “barro-rachado” para a maioria dos filmes. As análises de EDX evidenciaram uma redução do conteúdo do Ru após o TAV. Os dados sobre a estrutura foram obtidos por DRX (Difração de raios-X) e mostraram forma rutílica para o RuO2 e ortorrômbica para Ta2O5. Os voltamogramas cíclicos deste sistema em meio ácido (0,5 mol dm-3 de H2SO4) apresentaram as bandas características da dupla Ru(III) / Ru(IV). Em baixos sobrepotenciais, o coeficiente de Tafel, b, apresenta valores entre 40 mV e 60 mV. Os valores de resistência ôhmica (0,5 – 2,0 W) sugerem que a queda ôhmica do sistema pode ser atribuída principalmente à resistência da solução. A atividade eletrocatalítica apresentou uma forte dependência em relação ao conteúdo de RuO2 no filme, aumentando conforme o aumento da quantidade de RuO2 na composição. A estabilidade do sistema foi avaliada pelo TAV, utilizando eletrólise a corrente constante (750 mA cm-2 e T = 80 oC em solução de H2SO4 0,5 mol dm-3). As análises dos resultados mostraram uma relação entre o tempo de operação do eletrodo e a quantidade do componente ativo (RuO2). A substituição de titânio por tântalo (x = 0,5) apresentou uma melhora considerável (54%) no tempo de operação destes óxidos. Estes resultados apontam o sistema Ru/Ta como um recobrimento bastante promissor para operação em condições drásticas. / In this work it was investigated the structural and electrochemical properties of the RuO2/Ta2O5 system. A systematic investigation of structural, morphologic, electrochemical and eletrocatalytic properties for O2 evolution from acidic solutions was conducted using anodes of nominal composition Ti/(x)RuO2(1 + x) Ta2O5 (x = 0.1; 0.3; 0.5; 0.8), prepared from appropriate mol ratio by thermal decomposition (450 and 500 oC for 1 h under O2-flux of 5 L min-1) from alcoholic (isopropanol – Aldrich) solutions of the precursors mixtures (RuCl3.xH2O and TaCl5 - Aldrich). Analyses of the composition and the morphology of the oxide layer were investigated before and after accelerated life tests (ALT), through EDX techniques (Energy Dispersive X-rays) and SEM (Scanning Electron Microscopy) respectively. SEM results showed typical mud-flat-cracking morphology for the majority of the films. EDX analyses even after total deactivation evidenced the reduction of the content of Ru in the coating. Structure data have been obtained by XRD (X-rays diffraction) and which showed the rutile-type struture for RuO2 and orthorhombic one for Ta2O5. Cyclic voltammograms of this system where registered in acidic solutions (0.5 mol dm-3 of H2SO4). The observed peak has been attributed to the solid-state redox transition of Ru(III)/Ru(IV). At low overpotentials, Tafel slope, b, ranges from 40 - 60 mV. The RW-values found (0.5 – 2.0 W), are in agreement with other RuO2-based oxide electrodes. This is a good evidence that the ohmic drop of the system can be attributed mainly to solution resistance. The eletrocatalytic activity shows a strong dependence with the RuO2 content in the film. The stability of the electrodes are evaluated by the ALT, performed at 0.5 mol dm-3 in aqueous H2SO4 (750 mA cm-2 and T = 80 oC). The results shows a straight relation between the ALT-values and the amount of active component (RuO2) presented in the coating. Changing TiO2 by Ta2O5 (x = 0.5) showed a considerable improvement (54%) in the ALT-values of these oxides. These results it is a good indication that Ru/Ta system might be a promising coating to operate under drastic conditions.

Dans le contexte énergétique actuel, la thermoélectricité, basée sur la conversion directe de l'énergie thermique en énergie électrique, est en plein essor. Cette technologie, qui permet de récupérer l'énergie perdue sous forme de chaleur au cours de processus industriels, est basée sur l'utilisation de modules thermoélectriques. Ces modules sont constitués de la juxtaposition de branches thermoélectriques, constituées de semi-conducteurs n et p, reliées par des jonctions électriques. Dans la gamme de températures de 300 à 600°C, les matériaux de type skutterudite RM4X12 (R : terre rare, M : métal de transition, X : pnictogène) présentent des propriétés thermoélectriques intéressantes. Cependant, les propriétés aux interfaces entre les jonctions électriques et le matériau thermoélectrique jouent un rôle très important dans la performance des modules thermoélectriques. Il est nécessaire de minimiser les pertes électriques et thermiques au niveau de ces interfaces. De même, en zone chaude principalement, il est impératif de limiter l'inter-diffusion entre les éléments constituant le matériau thermoélectrique et le matériau utilisé pour les connexions électriques. La formation de composés aux interfaces peut, en effet, être à l'origine de la dégradation des propriétés du matériau thermoélectrique. Ces contraintes conduisent à introduire des barrières de diffusion entre le matériau thermoélectrique et les connexions électriques. C'est dans ce contexte que ce situe la présente étude, l'objectif étant d'étudier la potentialité de matériaux à base de nitrure de tantale en tant que barrières de diffusion. Ainsi, des couches minces à base de nitrure de tantale ont été déposées, par le procédé de pulvérisation cathodique, sur les substrats de type skutterudite, CeFe4Sb12, les connexions électriques étant en cuivre. L'efficacité de barrières monocouches, TaN, et tri-couches, TaN/Ta/TaN, a été étudiée, ces couches présentant une épaisseur totale de 1 ou 1,5 µm. La première étape de ce travail a consisté en l'étude de la stabilité thermique du matériau skutterudite afin de déterminer le domaine d'utilisation en température de ce matériau. Dans une seconde étape, la potentialité de monocouches, TaN, et multicouches, TaN/Ta/TaN, en tant que barrières de diffusion a été déterminée à partir d'une étude microstructurale. Les assemblages CeFe4Sb12/barrière/Cu ont été préalablement soumis à des traitements thermiques sous vide à des températures variant de 400 à 600°C. Enfin dans une dernière étape, l'étude théorique des mécanismes de migration a été menée à partir des calculs d'énergies d'incorporation et de migration des atomes étrangers, tels que le cuivre et l'antimoine, dans le nitrure de tantale massif. / Due to the current energy context, thermoelectricity based on the direct conversion of thermal energy into electrical energy is of great interest. Direct conversion of thermal energy to electrical energy requires the use of thermoelectric devices made of n- and p-type semiconductor couples connected by electrical junctions. RM4X12 (R: rare earth, M: transition metal, X: pnictogen) skutterudite compounds have been reported to be promising for thermoelectric applications in the [400-600]°C intermediate temperature range. However the performance of thermoelectric devices is strongly dependent on the joining of thermoelectric couples with metal electrodes as the conversion efficiency is greatly influenced by the contact resistance. High electrical and thermal conductivities are required associated with a high interfacial mechanical strength. Moreover the joining material has to be selected to avoid any interfacial reaction occurring during the device fabrication and use. Diffusion barriers are also needed to limit these interfacial reactions which may be detrimental to the thermoelectric device performance. The aim of this work is to study the efficiency of tantalum nitride based materials as diffusion barriers. TaN single layer and TaN/Ta/TaN multilayers barriers were deposited by sputtering between the CeFe4Sb12 skutterudite substrate and the Cu electrical junction. The inter-diffusion of elements was studied through these mono- and multi-layers, of 1 μm or 1.5 μm in thickness. In a first step, the thermal stability of the skutterudite has been investigated to determine the use temperature range of this material. In a second step the efficiency of TaN and TaN/Ta/TaN layers as diffusion barriers has been determined from a microstructural study. CeFe4Sb12/barrier/Cu stackings were previously annealed under vacuum in the [400-600]°C temperature range. Finally a theoretical study of the migration mechanisms was carried out from the calculations of the incorporation and migration energies of species, more specifically Sb and Cu, in the bulk tantalum nitride.

The topic of this thesis is the design of an automatic preanodizer to be used to preadjust precision tantalum resistors by anodizing their surfaces. The purpose of the preanodizer is to generate a controllable voltage ramp to be applied to a set of tantalum resistors which are immersed in a suitable electrolyte. The slope and maximum value of the voltage ramp are set to produce the current required for proper anodization of the resistors. The rate of anodization determines the rate of change of the resistor value. This thesis covers the design of an electronic device to meet a set of requirements specified by the Western Electric Company. The primary tasks the device has to perform are the generation of a linear voltage ramp of adjustable slope and maximum voltage and the supply of a given maximum current. Metering circuits are provided to measure, store and display the current and the maximum value reached by the ramp voltage.

Tridentate "pincer" ligands provide a unique balance of stability and reactivity in organometallic chemistry. The development of diarylamido-based PNP pincer ligands has led to many applications in catalysis, including the potential to facilitate unique chemical transformations at transition metal centers. The main objective of this thesis was to explore transition metal chemistry supported by the PNP pincer framework for both early and late transition metals. In Chapter I, the history behind the design and synthesis of pincer complexes is described. The advantages and disadvantages of various pincer ligands are reviewed to show the reasoning behind the synthesis of the PNP pincer framework. Chapter II discusses the synthesis of novel Hf and Ta complexes involving the PNP ligand. Reactions of (PNP)HfCl3 with large alkyl Grignards led to double alkylation and triple alkylation was achieved with methyl Grignard. (PNP)HfMe3 and (PNP)Hf(CH2SiMe3)2Cl displayed remarkably irregular coordination environments about hafnium, in contrast to the approximately octahedral structure of (PNP)HfCl3. (PNP)HfMe3 was found to be thermally stable at 75 degrees C, whereas thermolysis of (PNP)Hf(CH2SiMe3)2Cl under similar conditions led to a mixture of products. The major decomposition product is believed to be a Hf alkylidene complex on the basis of in situ NMR spectroscopic observations (e.g., delta 248.2 ppm in the 13C{1H} NMR spectrum). The reaction of (PNP)TaF4 with an excess of ethyl Grignard led primarily to the double alkylation product, (PNP)Ta(CH2CH3)2F2. Repeating this reaction in the presence of excess ethyl Grignard and dioxane resulted in the formation of an ethylene complex, (PNP)Ta(=CHCH3)(C2H4). In Chapter III, a C-C reductive elimination study is described comparing two pincer ligand scaffolds: Me(PNP) ligand and TH(PNP) ligand. The tied ligand has previously been found to be more sterically demanding than the untied ligand, which has allowed for faster N-C cleavage, faster oxidative addition and a more selective alkyne dimerization catalyst. This study reveals that the tied ligand complex, TH(PNP)Rh(C6H4CF3)(Ph), undergoes slower reductive elimination of p-Ph-C6H4CF3 (< 4% after 7 h at 38 degrees C; t1/2 = 7.7 h at 64 degrees C; t1/2 = 2.13 h at 75 degrees C) than Me(PNP)Rh(C6H4CF3)(Ph) (t1/2 = 15.6 min at 38 degrees C).

<p>Digital microfluidics as implemented in electrowetting-on-dielectric (EWD) technology has been widely used as a platform for miniaturizing the biomedical or biochemical laboratory on a chip in recent years. DNA pyrosequencing, one of the DNA sequencing-by-synthesis methods, has been successfully integrated on EWD devices. However, this platform requires microliters of reagents and 200~300V of applied voltages, which contributes to higher costs and limits the feasibility of a portable system. This dissertation proposes a low voltage EWD device using multi-layer insulators that can manipulate picoliter droplets on chip. A 300pl droplet was dispensed and actuated at voltages as low as 11.4Vrms and 7.2Vrms respectively on a 95um electrode a EWD device with a 20um SU8 gasket. The stacked insulators in the actuator consisted of 135nm tantalum pentoxide (Ta2O5) and 180nm parylene C films deposited and coated with 70 nm of CYTOP. The physical scaling of electrodes was further demonstrated for 33um and 21um electrode devices, resulting in droplets of 12pl and 5pl respectively in conjunction with 3um gaskets. Manipulation of magnetic beads during dispensing, droplet splitting and merging, and droplet transport were also demonstrated on the scaled EWD devices. The chemiluminescent light produced by the on-chip reaction of 100pl ATP-luciferin and luciferase could be detected with an external cooled CCD camera, but detecting this reaction with smaller-scale droplet reactions was limited by the external detector's sensitivity. Based on fundamental theories and experiments, the actuation voltage and dimensional scaling of EWD devices have been demonstrated, but the use of picoliter droplets in biochemical applications will required improved sensing methods.</p> / Dissertation