Résumé confidentiel / Résumé confidentiel

Ces travaux de recherche portent sur la conception et la réalisation de commutateurs RF basées sur l’intégration de matériaux innovants fonctionnels tels que le dioxyde de vanadium (VO2) et les alliages de chalcogénures de types Ge2Sb2Te5 (GST) et GeTe. Le principe de fonctionnement de ces composants repose sur le changement de résistivité que présentent ces matériaux. Le VO2 possède une transition Isolant-Métal (MIT) autour de 68°C à travers laquelle le matériau passe d’un état isolant (forte résistivité) à un état métallique (faible résistivité). La transition MIT présente l’intérêt de pouvoir être initiée sous l’effet de plusieurs types de stimuli externes (thermique, électrique et optique) avec de faibles temps de commutation. Les alliages de types GST et GeTe ont la particularité de commuter réversiblement entre un état amorphe à forte résistivité à un état cristallin à faible résistivité suite à un traitement thermique spécifique. Les commutateurs à base de GST ou de GeTe présentent l'avantage de pouvoir opérer en mode bistable car le changement de résistivité présenté par ces matériaux est de type non volatile. Les composants réalisés ont de bonnes performances électriques (isolation et pertes d’insertion) sur une large bande. Nos travaux de recherche visent à proposer une solution alternative aux solutions classiques (semi-conducteurs et MEMS-RF) pour réaliser des commutateurs RF qui peuvent être par la suite utilisés dans la conception des dispositifs reconfigurables (filtres, Antennes). / This research work focuses on the design and realization of RF switches based on the integration of new materials such as vanadium dioxide (VO2), Ge2Sb2Te5 (GST) and GeTe chalcogenides alloys. The operating principle of these devices is based on the resistivity change presented by these materials. VO2 exhibits a Metal-Insulator transition (MIT) around 68°C for which the material changes from an insulating state (high resistivity) to a metallic one (low resistivity). The MIT transition can be triggered in different ways (thermally, electrically and optically) with low switching time. GST and GeTe alloys have the particularity to be reversibly switched between a high resistive-amorphous state to low resistive-crystalline state, under a specific heat treatment. Thanks to the non-volatile resistivity change presented by these materials, GST/GeTe-based switches are able to operate in bistable mode. The fabricated devices exhibit good electrical performances (insertion loss and isolation) over a broadband. The aim of our work is to propose an alternative solution to conventional technologies (semiconductors and RF-MEMS), to design RF switches that can be used afterward in the design of reconfigurable devices (filters, antennas).

La présence d'hétéroatomes et métaux dans des fractions lourdes de pétrole brut peuvent entraîner la désactivation des catalyseurs d’hydrotraitement et d’hydrocraquage. Les composés contenant ces éléments sont connus pour être inclus dans des agrégats macromoléculaires d’asphaltènes, qui sont considérées comme les composants les plus problématiques des produits pétroliers. Ces travaux ont pour objectif d’apporter une meilleure compréhension de l’environnement chimique de ces espèces et des phénomènes d’agrégation pour optimiser les processus de raffinage. Des techniques de séparation comme la chromatographie de perméation de gel ou Gel Permeation Chromatography (GPC), Advanced Polymer chromatographie (APC) et la chromatographie sur couche mince d’haute performance ou High Performance Thin Layer Chromatography (HPTLC) ont été combinées avec des techniques d’analyse élémentaire comme la spectrométrie de masse à plasma à couplage inductif ou Inductively Coupled Plasma Mass Spectrometry (ICP-MS) et la spectrométrie de masse moléculaire d’haute résolution pour la caractérisation des fractions pétrolières lourdes. Les profils de distribution en taille d’espèces qui contiennent du vanadium, du nickel et du soufre, les hétéroatomes et métaux les plus abondants dans les produits pétroliers, ont été déterminés par GPC couplé à une détection élémentaire par ICP MS. Les paramètres ayant le plus d’impact sur la distribution en taille et l’évolution des agrégats dans les solutions de différentes coupes pétrolières ont été optimisés. Cela nous a permis de faire différentes comparaisons, entre de nombreuses charges et effluents de procédés, ainsi que d’autres séries d’échantillons ou de mélanges provenant d’unités-pilotes d’hydrotraitement. Les résultats obtenus ont pu être mis en regard de caractéristiques macroscopiques comme la viscosité. Le couplage du nouveau système APC avec l’ICP MS a été mis au point avec succès. Cette technique a permis de réaliser des cartographies d’échantillons pétroliers plus rapides qu’en GPC tout en consommant moins de solvant. Cependant, les différences des chromatogrammes APC obtenus par rapport aux profils GPC suggèrent des interactions indésirables avec la phase stationnaire, qui ont été l’objet d’une évaluation approfondie.Enfin, un dernier type de séparation a été évaluée. L’HPTLC, qui utilise des plaques à usage unique, peut être appliquée à la séparation de produits lourds par polarité, et ce sans étapes de déasphaltage préalable, contrairement aux colonnes de chromatographie liquide qui peuvent être détériorées à cause de l'adsorption irréversible et de la précipitation des asphaltènes. Différents types de plaques et éluants ont été testés afin de développer une méthode simple pour la séparation des fractions SAR (Saturés, Aromatiques et Résines) des échantillons de distillat sous vide ou Vacuum Gas Oil (VGO). Ce travail avait pour but des migrations en une seule étape et analyse UV qui pourrait être mis en œuvre pour l’analyse de routine dans les laboratoires de contrôle avec une adsorption irréversible réduite. Des résultats très prometteurs ont été obtenus avec l’utilisation de plaques de cellulose pour la séparation des familles de polarité différentes au sein des agrégats d’asphaltènes. Des tests sur l'analyse directe des plaques par Désorption-Ionisation par Électronébulisation (DESI) MS, l'analyse directe en temps réel ou Direct Analysis in Real Time (DART) MS et Ablation Laser (LA) ICP MS ont été effectués. / The presence of heteroatoms and metals in heavy fractions of crude oil can cause the deactivation of hydrotreatment and hydrocracking catalysts. Compounds containing these elements are known to be included in macromolecular asphaltene aggregates, which are considered the most problematic components of heavy oil. This thesis aimed for a better understanding of the chemical environment of these species and on the aggregation phenomenon to optimize refining processes. Separation techniques such as Gel Permeation Chromatography (GPC), Advanced Polymer Chromatography (APC) and High Performance Thin Layer Chromatography (HPTLC) were combined with elementary analysis techniques such as Inductively Coupled Plasma Mass Spectrometry (ICP MS) or high-resolution molecular mass spectrometry for the characterization of heavy fractions of crude oil. Here, the size profiles of species that contain vanadium, nickel and sulfur, the most abundant heteroatoms and metals present in petroleum products, were determined by GPC online with elemental detection by ICP MS. The parameters having the most significant impact on size distribution and the evolution over time of aggregates from solutions of different petroleum cuts were optimized. This allowed the comparison between various feeds and effluents and other series of samples and mixtures from pilot units of refining processes by GPC ICP MS. Results obtained could be related to macroscopic characteristics such as viscosity. Hyphenation of the new APC System to ICP MS has been successfully completed. It allowed the mapping of petroleum samples faster than GPC, therefore with less solvent consumption. However, the differences of the APC chromatograms obtained with respect to the GPC profiles suggested significant unwanted interactions of the highly polar compounds of the petroleum samples with the stationary phase, which have been thoroughly studied. Finally, another type of separation was evaluated. HPTLC, of single-use plates, can be applied to the analysis of heavy petroleum products by polarity without prior deasphalting steps while chromatography columns can be deteriorated because of the irreversible adsorption and asphaltene precipitation. To this end, various types of plates and eluents were tested to develop straightforward SAR (Saturates, Aromatics and Resins) separations of Vacuum Gas Oil (VGO) samples. This method, based on single-step migrations with reduced irreversible adsorption and UV monitoring, could be implemented for routine analysis in control laboratories. Very promising results were obtained by the use of cellulose plates for the separation of different families within asphaltene aggregates. Tests on Desorption ElectroSpray Ionization (DESI) MS, Direct Analysis in Real Time (DART) MS and Laser Ablation (LA) ICP MS analyses of the plates have been performed.

Dans le cadre du développement durable, les procédés rapides, propres et peu énergivores sont très recherchés particulièrement en chimie pour les réactions d’oxydation. A part les solutions de génie des procédés, la catalyse est l’un des meilleurs atouts pour améliorer le processus. Le vanadium étant l’un des meilleurs métaux catalytiques pour de tels réactions, nous avions à nous attaquer son problème de relargage dans le milieu réactionnel en vue d’applications acceptables pour l’environnement. Nous proposons donc dans cette thèse des catalyseurs au vanadium fixé à l’intérieur des nano pores de silices mésoporeuses hexagonales de type MCM-41. La grande dispersion et la rétention du vanadium sont promues grâce à la présence d’ion d’ancrage : Al(III), Ti(IV), Zr(IV) and Ce(IV). Une grande variété de catalyseurs de type V-(Al/Ti/Zr/Ce)-MCM-41 ont été préparés à partir de trois méthodes de synthèse: l’une, ultra-rapide en une étape assistée par micro-onde, la seconde à étapes séquentielles multiples mettant en œuvre une technique de pochoir moléculaire et la troisième à nombre d’étapes réduites utilisant un traitement thermique partiel d’une surface préalablement organosilylée avant le greffage des métaux. Un large panel de techniques physicochimiques fut appliqué à la caractérisation de ces solides avec une attention particulière portée à l’analyse de la bande de transfert de charge ligand-métal du vanadium au degré d’oxydation +5 dont le décalage vers le bleu est corrélé à la taille des clusters d’oxyde de ces ions. La rétention du vanadium dans le méthanol a été corrélée à la dispersion du vanadium comme la dégradation à l’air du 1,2-diphényle-2-méthoxyéthanol. Ce substrat fut choisi comme modèle pour étudier la dégradation de la lignine par clivage C-C ou C-O. Notons que ce bio-polymère produit du phénoxypropanol methylé bio-sourcé utilisé dans les bio-carburants et comme précurseur en chimie fine. Dans le cas présent, un balayage à haut débit de la dégradation de cette molécule mettant en œuvre 96 mini-réacteurs en parallèle a permis de sélectionner le solvant, le métal d’ancrage et la teneure des deux métaux donnant la plus haute conversion. Contrairement aux catalyseurs homogènes, nos catalyseurs présentent une très haute sélectivité en clivage C-C. / The search for practical large-scale, fast, clean and energy saving chemical processes are highly regarded in the frame of a sustainable development, particularly for the most problematic oxidation reactions. Apart from chemical engineering solutions, improving the process using heterogeneous catalysis is one of the most adapted solution. Vanadium being considered the best metal for such kind of reactions, one had to tackle the problem of its high dispersion on a support to minimize its high propensity for leaching and to optimize its stability for practicable, safe and clean uses. In the present thesis, vanadium is supported inside the nanopores of a mesoporous silica of MCM-41 type where the high dispersion is assisted by the presence of anchoring ions such as Al(III), Ti(IV), Zr(IV) and Ce(IV) ions. A large set of V-(Al/Ti/Zr/Ce)-MCM-41 catalysts was prepared according to three different methods of preparation: i) ultra-fast one-pot synthesis protocol using the assistance of microwave, ii) post-synthesis modification using molecular stencil patterning (MSP) technique and iii) partial thermal treatment (PTT) of the organo-silylated support. The catalysts were characterized thoroughly using a panel of physical techniques and, particularly, the blue shift of the optical gap measured from the vanadium charge transfer band known to correlated with the dispersion of the metal. In complement, the stability was tested from metal leaching using methanol as a corrosive solvent while their catalytic reactivity was estimated in the aerobic oxidation of 1,2-diphenyl-2-methoxyethanol. This is a model reaction that simulates the oxidative C-C bond cleavage in lignin, the most difficult and crucial step in the degradation of this biopolymer, then producing in a clean way valuable methoxylated phenoxy propanol units useful for biomass fuels or bio-sourced precursors for fine chemistry. A high throughput screening approach was applied to test this aerobic oxidation reaction running over 96 reactors in parallel at the same temperature and sorting out the best catalysts with the most suitable anchoring ions and metal loading for the highest catalytic efficiency. / 在可持续发展的背景下，对于清洁高效节能可行的大规模化工过程尤其是存在诸多问题的氧化反应过程的探索倍受瞩目。除化学工程解决方案之外，通过多相催化来改进反应过程也是最可行的途径之一。钒被认为是最适合于催化此类反应的金属之一，其亟待解决的问题是实现钒在载体上的高度分散，并最大限度地降低其浸出倾向，改善其稳定性，从而实现对其安全清洁有效的利用。本文提出将钒负载于MCM-41型六方介孔二氧化硅的纳米孔道中，通过锚定离子如Al(III)、 Ti(IV)、Zr(IV)、Ce(IV)离子的存在促进钒的高度分散和固载。采用三种不同的方法制备了一系列V-(Al/Ti/Zr/Ce)-MCM-41催化剂：1、超快微波一步合成法，2、使用分子复刻版技术改性的后嫁接法，3、对有机硅烷化载体进行部分热处理改性的后嫁接法。通过一系列物理化学技术对合成的催化剂进行了充分表征，特别是对与金属分散度相关的钒的电荷跃迁带的测量和与其对应的光谱带隙蓝移进行了分析。随后，以甲醇作为腐蚀溶剂对合成的钒催化剂进行了金属析出的稳定性测试。通过一种木质素模型化合物1,2-diphenyl-2-methoxyethanol的需氧氧化反应测试了所合成负载型钒催化剂的催化活性。在相同温度及反应条件下，用96通道高通量微反应器技术评价了所制催化剂对该反应的催化性能，筛选出具有最高催化效率的负载型钒催化剂及其最适合的锚定离子。该反应中的碳-碳键裂解反应是木质素降解的最关键也是最困难的步骤之一，可通过这类生物聚合物的降解以清洁的方式生产有用的生物质燃料或生物来源高附加值精细化学品前驱体。

Le travail de thèse présenté dans ce manuscrit traite du développement de dispositifs à base de dioxyde de vanadium VO₂ et de méta-surfaces dans le moyen infrarouge pour des applications passives et une intégration sur des lasers à cascade quantique (QCL). Ce travail a permis l'élaboration de nouvelles conditions de dépôt du matériau à changement de phase VO₂ par ablation laser pulsé à des températures compatibles avec les hétérostructures de III-V utilisées en optoélectronique. Les caractérisations des couches minces déposées montrent un changement de la réflectivité et de la conductivité électrique entre l'état isolant à basse température et l'état métallique à haute température autour de 68°C (341 K). Des développements ont ensuite été menés sur l'emploi d'un réseau de méta-surfaces permettant d'obtenir une couche homogène d'indice de réfraction effectif résonnant. Ces méta-surfaces sont constituées de résonateurs à anneau fendu dont la fréquence de résonance peut être ajustée par le choix de leurs paramètres géométriques et des matériaux les constituant. Une modulation optique de plus de 100cm-1 du pic de la résonance a été obtenue lors de la transition de phase avec des méta-surfaces déposées sur un film de VO₂. Ce résultat est très prometteur pour la conception de dispositifs monolithiques, robustes, compacts, accordables en fréquence et dont les propriétés optiques ne dépendent que de la température de la couche de VO₂.Enfin, ce travail étudie la fonctionnalisation des QCL dans le moyen infrarouge (7-8 µm) par des couches de VO₂ et de méta-surfaces. Il vise à comprendre l’influence des couches intégrées sur les propriétés d’émission. Afin de garantir une bonne interaction entre ces couches et le mode guidé du laser tout en ayant des pertes optiques faibles, des nouveaux guides d'onde ont été modélisés, puis les premiers QCL à base de VO₂ ont été démontrés et une température maximale de fonctionnement de 334 K a été mesurée. / The thesis work presented in this manuscript deals with the development of vanadium dioxide VO₂ and meta-surfaces based devices in the mid-infrared for passive applications and an integration on quantum cascade lasers (QCL).This work enabled the elaboration of new deposition conditions for the VO₂ phase change material by pulsed laser ablation at temperatures compatible with III-V heterostructures used in optoelectronics. The characterizations of the VO₂ coated thin films show a change in reflectivity and in electric conductivity between the insulating state at low temperature and the metallic state at high temperature around 68°C (341 K).Developments were then carried out on the use of a meta-surfaces array in order to obtain an homogeneous layer of resonant effective refractive index. These meta-surfaces are constituted by split-ring resonators, whose resonance frequency can be adjusted by choosing their geometric parameters and the materials they are made of. An optical modulation of more than 100cm-1 of the resonance peak has been obtained during the phase transition with meta-surfaces deposited on a VO₂ layer. This result is very promising for the conception of monolithic, robust, compact, frequency tunable devices and whose optical properties only depend on the VO₂ layer temperature.Finally, this work studies the functionalization of mid-infrared QCL (7-8 µm) with VO₂ and meta-surfaces layers. It aims at understanding the influence of the integrated layers on the emission properties. In order to ensure a good interaction between these layers and the laser guided mode while having low optical losses, new waveguides were modeled, then the first VO₂ based QCL have been demonstrated and a maximum operating temperature of 334 K has been measured.

The domestic sector will play an important role in the decarbonisation and decentralisation of the energy sector in the future. Installation numbers of building-integrated small-scale energy systems such as photovoltaics (PV), wind turbines and micro-combined heat and power (CHP) have significantly increased. However, the power output of PV and wind turbines is inherently linked to weather conditions; thus, the injected power into the public grid can be highly intermittent. With the increasing share of renewable energy at all voltage levels challenges arise in terms of power stability and quality. To overcome the volatility of such energy sources, storage technologies can be applied to temporarily decouple power generation from power consumption. Two emerging storage technologies which can be applied at residential level are hydrogen systems and vanadium-redox-flow-batteries (VRFB). In addition, the building-integrated energy sources and storage system can be combined to form a hybrid renewable energy system (HRES) to manage the energy flow more efficiently. The main focus of this thesis is to investigate the dynamic performance of two emerging energy storage technologies, a hydrogen loop composed of alkaline electrolyser, gas storage and proton exchange membrane (PEM) fuel cell, and a VRFB. In addition, the application of building-integrated HRES at customer level to increase the self-consumption of the onsite generated electricity and to lower the grid interaction of the building has been analysed. The first part deals with the development of a research test-bed known as the Hybrid Renewable Energy Park (HREP). The HREP is a residential-scale distributed energy system that comprises photovoltaic, wind turbine, CHP, lead acid batteries, PEM fuel cell, alkaline electrolyser and VRFB. In addition, it is equipped with programmable electronic loads to emulate different energy consumption patterns and a charging point for electric vehicles. Because of its modular structure different combinations of energy systems can be investigated and it can be easily extended. A unified communication channel based on the local operating network (LON) has been established to coordinate and control the HREP. Information from the energy systems is gathered with a temporal resolution of one second. Integration issues encountered during the integration process have been addressed. The second part presents an experimental methodology to assess the steady state and dynamic performance of the electrolyser, the fuel cell and the VRFB. Operational constrains such as minimum input/output power or start-up times were extracted from the experiments. The response of the energy systems to single and multiple dynamic events was analysed, too. The results show that there are temporal limits for each energy system, which affect its response to a sudden load change or the ability to follow a load profile. Obstacles arise in terms of temporal delays mainly caused by the distributed communication system and should be considered when operating or simulating a HRES at system level. The third part shows how improved system models of each component can be developed using the findings from the experiments. System models presented in the literature have the shortcoming that operational aspects are not adequately addressed. For example, it is commonly assumed that energy systems at system level can respond to load variations almost instantaneously. Thus, component models were developed in an integrated manner to combine theoretical and operational aspects. A generic model layout was defined containing several subsystems, which enables an easy implementation into an overall simulation model in MATLAB®/Simulink®. Experimental methods were explained to extract the new parameters of the semi-empirical models and discrete operational aspects were modelled using Stateflow®, a graphical tool to formulate statechart diagrams. All system models were validated using measured data from the experimental analysis. The results show a low mean-absolute-percentage-error (<3%). Furthermore, an advanced energy management strategy has been developed to coordinate and to control the energy systems by combining three mechanisms; statechart diagrams, double exponential smoothing and frequency decoupling. The last part deals with the evaluation, operation and control of HRES in the light of the improved system models and the energy management strategy. Various simulated case studies were defined to assess a building-integrated HRES on an annual basis. Results show that the overall performance of the hydrogen loop can be improved by limiting the operational window and by reducing the dynamic operation. The capability to capture the waste heat from the electrolyser to supply hot water to the residence as a means of increasing the overall system efficiency was also determined. Finally, the energy management strategy was demonstrated by real-time experiments with the HREP and the dynamic performance of the combined operation has been evaluated. The presented results of the detailed experimental study to characterise the hydrogen loop and the VRFB as well as the developed system models revealed valuable information about their dynamic operation at system level. These findings have relevance to the future application and for simulation studies of building-integrated HRES. There are still integration aspects which need to be addressed in the future to overcome the proprietary problem of the control systems. The innovations in the HREP provide an advanced platform for future investigations such as electric-vehicles as decentralised mobile storage and the development of more advanced control approaches.

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Thèse numérisée par la Direction des bibliothèques de l'Université de Montréal.

Uma série de amostras do sistema catalítico V2O5/TiO2 foi preparada pelo método sol-gel com diferentes teores da fase ativa (de 0 a 9% em massa de V2O5) e calcinada em diferentes temperaturas (de 250 a 6000C). Sistema similar foi obtido pelo método de impregnação para a comparação. Os catalisadores foram caracterizados quanto suas propriedades texturais e estruturais pelas técnicas de Adsorção de N2 a 77K, Difratometria de Raios-X (DRX), Espectroscopia Raman, Ressonância Paramagnética Eletrônica (EPR), Espectroscopia de Fotoelétrons Excitados por Raios-X (XPS) e Espectroscopia de Absorção de Raios-X (XAS). Testes catalíticos para a verificação da atividade e seletividade foram realizados frente à reação de conversão do metanol. O sistema obtido pelo método sol-gel apresentou elevada área superficial e porosidade, as quais foram ampliadas com o aumento do teor de vanádio e reduzidos com o aumento da temperatura de calcinação. O sistema preparado por impregnação apresentou as mesmas propriedades texturais do suporte comercial. A análise de DRX identificou a existência de TiO2 nas formas cristalográficas anatásio e rutilo, não foi identificada a presença de V2O5 na forma cristalina. No sistema preparado por impregnação a estrutura cristalográfica do suporte se mantém, independente do teor de vanádio, porém a partir de 6% de V2O5 foi identificado à presença de V2O5 cristalino. Os espectros de Raman mostraram a presença de dois grupos superficiais de vanádio, os vanadilos monoméricos e os vanadatos poliméricos mesmo em elevados teores de vanádio, nos sistemas preparados pelo processo sol-gel. Nos catalisadores obtidos por impregnação foram identificados modos vibracionais referentes ao V2O5 cristalino.Os resultados obtidos por XAS confirmaram os obtidos por DRX e indicaram a presença de vanádio V4+ e V5+, porém com simetria diferente da forma cristalina V2O5. A determinação da razão entre os átomos V/Ti superficiais feita por XPS mostrou ser crescente com o aumento do teor de vanádio. Os espectros de EPR indicaram a presença de pelo menos três famílias de íons V4+ em diferentes simetrias, duas delas inseridas na matriz da titânia na fase rutilo e a outra dispersa na superfície. O sistema obtido por impregnação apresentou poucos íons V4+. Os testes catalíticos revelaram que a atividade e seletividade catalítica foram praticamente as mesmas para os sistemas preparados pelos dois métodos. Entretanto, a estabilidade catalítica do sistema obtido via sol-gel foi superior ao sistema preparado por impregnação. / A series of samples of the catalytic system V2O5/TiO2 was prepared by the sol-gel method with different proportions of the active phase (from 0 to 9% in mass of V2O5) and calcined in different temperatures (from 250 to 6000C). A similar system was obtained by the impregnation method for comparison. The catalyst were characterized by their textural and structural properties by Adsorption of N2 at 77K, X-Ray Diffraction (XRD), Raman Spectroscopy, Electronic Paramagnetic Resonance (EPR), X-Ray Photoelectron Spectroscopy (XPS) and X-Ray Absorption Spectroscopy (XAS). Catalytic tests for the verification of the activity and selectivity were performed by the conversion reaction of the methanol. The system obtained by the sol-gel method presented a high superficial area and porosity, which were enlarged by the increase of vanadium proportion and reduced with increase of the calcinations temperature. The system prepared by impregnation presented the same textural proprieties of the commercial support. XRD analysis identified the existence of TiO2 in two crystallographic forms, anatase and rutile. It was not identified the presence of V2O5 in the crystalline form. In the system prepared by impregnation the crystallographic structure of the support keeps, independent of the vanadium content, however starting from 6% of the vanadia was identified crystalline V2O5. Raman spectra showed the presence of two superficial groups of vanadium, the monomeric vanadyls and the polymeric vanadates even for elevated contents of vanadium, in the system prepared by the impregnation method vibrational modes were identified referring to V2O5 crystalline. The results obtained by XAS confirmed the obtained by XRD and indicated the presence of V4+ and V5+, however with different symmetry from the V2O5 in a crystalline form. The determination of the proportion between the surface V/Ti atoms determined by XPS showed to be increased with the increase of the vanadium content. EPR spectra indicated the presence of at least three V4+ion families in different symmetries; two of them inserted in the matrix of titania in the rutile phase and to other dispersed on the surface. The system obtained by impregnation presented few V4+ ions. The catalytic tests reveled that the catalytic activity and selectivity were practically the same for the systems prepared by both methods. However, the catalytic stability of the system obtained via sol-gel was superior to the system prepared by impregnation.

Medidas de atenuação ultrassônica e constante elástica em ligas de Cr-V, utilizando técnicas de pulso eco foram realizadas e as transições na temperatura de Neel, TN, estudadas. Um modelo teórico é proposto para descrever os comportamentos da atenuação e constante elástica perto da transição em TN. De acordo com o modelo proposto a adição de vanádio diminui drasticamente o coeficiente de difusão, modificando a natureza da transição. Foram utilizadas amostras de cromo contendo 0,2%V; 0,5%V; 0,67%V; 1,0%V e 1,5%V. A partir da dependência aproximadamente linear de TN com a concentração de vanádio conclui-se que 3,3% V corresponderá à TN= 0K. O efeito do campo magnético até 4,5T revelou-se insuficientemente para a obtenção de monodomínio magnético e não causa nenhuma variação mensurável em TN / Measurements of ultrasonic attenuation and elastic Constant in Cr-V alloys, using pulse echo techniques were realized and the transitions at the Neel temperature, TN, were studied. We propose a theoretical model which describe the behavior of the ultrasonic attenuation and elastic Constant near the transition in TN. According to the theoretical model the addition of Vanadium to chromium, drastically diminishes the diffusion coefficient thus changing the nature of the transition. It was used samples of chromium containing 0,2%V; 0,5%V; 0,67%V; 1,0%V and 1,5%V. From the approximately linear dependence of TN with the vanadium concentration it was concluded that 3,3%V corresponds to TN= 0. The effect of magnetic fields up to 4,5T was insufficient to produce single-Q samples, and did not cause any mensurable variation in TN