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Traitement des gaz d’échappement des groupes électrogènes alimentés par des gasoils, fuels marines ou bio-huiles : élimination des HAP en présence ou non de SOx / Treatment of exhaust gases from generators fueled with Diesel Marine diesel and bio-oils : removal of PAH in the presence or not of SOxSoufi, Jihène 10 July 2017 (has links)
Résumé confidentiel / Résumé confidentiel
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"Processamento, Caracterização Mecânica e Tribológica do Compósito Al2O3-NbC." / PROCESSING AND CHARACTERIZATION OF MECHANICAL AND TRIBOLOGICAL PROPERTIES OF Al2O3-NbC COMPOSITEVanderlei Ferreira 26 July 2001 (has links)
Neste trabalho foi investigado o processamento e propriedades mecânicas e tribológicas do compósito cerâmico Al2O3- NbC com o objetivo de desenvolver um compósito cerâmico com melhores propriedades do que a alumina pura. Como material para comparação foi utlizado a alumina que é uma cerâmica tradicionalmente aplicada onde é necessária elevada resistência mecânica e ao desgaste. A composição Al2O3-0,5%wtY2O3-20%wtNbC, que origina o compósito, passou por moagem e mistura em moinho tipo atrittor e secagem em evaporador rotativo. O pó obtido foi caracterizado quanto a distribuição granulométrica e morfologia. A alumina seguiu a rota tradicional de moagem e mistura em moinho de bolas, secagem em spray dryer; e mesma caracterização realizada para o compósito. Foi realizado estudo da sinterização em dilatômetro para os dois materiais com intuito de determinar as condições ideais de sinterização. Por meio de prensagem uniaxial seguida de prensagem isostática a frio foram confeccionadas amostras na forma de discos e pinos. Os materiais densos foram obtidos por sinterização normal sendo que a alumina ao ar e o compósito em atmosfera de argônio. As fases formadas no dois materiais foram determinadas por difração de raios X. As microestruturas foram estudas em microscópio eletrônico de varredura nas superfícies polidas e atacadas. Entre as propriedades mecânicas foram medidas o módulo elástico, a dureza e a tenacidade à fratura por meio de impressões Vickers. O compósito desenvolvido apresentou valores superiores em todas estas propriedades em relação a alumina. O estudo do comportamento tribológico foi realizado por meio do deslizamento de pinos, com extremidade cônica, de alumina e do compósito cerâmico sobre discos de alumina. Os ensaios foram realizados com a velocidade de 0,4m/s e com carregamento, por meio de peso morto, de 10N sob diferentes níveis de umidade relativa ( 26,8; 48 e 76,3%). O coeficiente de atrito cinético médio, assim como a taxa de desgaste, diminuiu em todos os ensaios com o aumento da umidade relativa, para os dois materiais. Este comportamento foi relacionado com a formação de uma camada na interface de contato entre as superfícies do pino e do disco de hidróxido de alumínio. O compósito demostrou maior resistência ao desgaste em todas as condições tribológicas estudadas. O compósito cerâmico desenvolvido claramente possui boas perspectivas como um novo material cerâmico em importantes aplicações técnicas. / In the present work processing, and mechanical and tribological properties of a ceramic composite Al2O3-NbC were investigated in order to develop a ceramic material with superior properties. Alumina was chosen as a reference since it is a traditional ceramic material for applications where elevated mechanical properties and wear resistance are required. The composition Al2O3 - 0.5 wt%Y2O3-20 wt%NbC was prepared by attrition milling followed by drying in a rotaevaporator. The resulting powder mixture was characterized for granulometry and powder particles morphology. Alumina was processed according to the traditional route of ball milling followed by passing through a spray drier, and the processed powder was then characterized the same way as the composite. Dilatometry was accomplished for both materials in order to define the ideal sintering conditions. Samples with the shape of discs and pins were compacted by uniaxial pressing followed by cold isostatic pressing. Densification was achieved by sintering in air and in argon for alumina and the composite, respectively. Phase composition of sintered materials was studied by X-ray diffraction (XRD). Microstructure was investigated by means of scanning electron microscopy (SEM) on polished and etched surfaces. Materials were also characterized for a number of mechanical properties, in particular for Young modulus, hardness, and fracture toughness by Vickers indentation method. The developed composite exhibited superior mechanical properties as compared to alumina. Tribological behavior was investigated by means of a sliding pin on disk test with pins of a conical shape prepared both from alumina and the composite, and an alumina disk. Tests were performed with the sliding speed of 0.4 m/s and 10N load under varying humidity conditions (26.8; 48, and 76.3%). Both the mean coefficient of friction and the wear rate diminished in all tests with the increase of humidity for both materials. Such behavior was attributed to a aluminum hydroxide layer formation between the pin and the disk surfaces. The developed composite exhibited better wear resistance under all tribologic conditions studied. The developed ceramic composite obviously has good perspectives as a new material for a variety of important technical applications.
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Produção, caracterização e determinação de propriedades físico-químicas de catalisadores e suportes utilizados em processos de hidrotratamentoChagas, Luciano Honorato 22 November 2013 (has links)
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Previous issue date: 2013-11-22 / O grande interesse na hidrodessulfurização (HDS) de gasolina é realizar remoção profunda de enxofre e, ao mesmo tempo, reduzir a perda do numero de octanos que ocorre no processo de HDS minimizando a hidrogenação (HID) de olefinas, as quais são benéficas para a octanagem. Além do componente ativo e do promotor, o suporte deve ser considerado uma parte integral do catalisador. Nesse sentido, diversos suportes (incluindo aluminas e óxidos mistos) foram preparados a partir da calcinação de diferentes precursores. Uma amostra de Boehmita comercial foi usada como precursora de polimorfos de alumina. Para comparação, três outros precursores foram sintetizados a partir de diferentes métodos. Particularmente, o uso de excesso de ureia promoveu uma forma muito cristalina de carbonato básico de alumínio. Cada precursor foi calcinado em várias temperaturas gerando polimorfos de alumina, os quais foram analisados estruturalmente por DRX e RMN de 27Al. Devido ao interesse em suportes para catalisador, atenção especial foi dada à fase γ-Al2O3, a qual em adição a investigação estrutural foi submetida à análise textural. Essas quatro amostras de γ-Al2O3 foram utilizadas como suportes para catalisadores do tipo CoMo, que foram testados em reações de HDS de tiofeno e HID de cicloexeno. Os testes catalíticos mostraram que as atividades catalíticas crescem com o aumento do diâmetro médio de poros das fases CoMo/γ-Al2O3, e estão diretamente relacionados à dispersão do molibdênio sobre o suporte. Os resultados mostraram que a partir de diferentes rotas de síntese, e usando uma rota comum de calcinação, podem-se obter materiais com a mesma composição, mas com diferentes propriedades estruturais e texturais. Além disso, catalisadores do tipo CoMo suportados, contendo 20 % de MoO3 e 3 % de CoO, foram preparados por impregnação ao ponto úmido com soluções aquosas de molibdênio e cobalto sobre óxidos mistos obtidos a partir de hidrotalcitas. Os precursores contendo variadas quantidades de Mg, Co e Al ou Ni, Co e Al foram sintetizados pelo método de hidrólise de ureia. A calcinação leva a óxidos mistos cujas características estruturais dependem da composição. A caracterização dos suportes foi feita pelas técnicas de BET, DRX, RMN, IV, UV-vis/DRS e TPR. As amostras sulfetadas foram usadas como catalisadores em reações simultâneas de HDS de tiofeno e HID de cicloexeno. Os resultados foram comparados com catalisadores convencionais CoMo/γ-Al2O3, indicando que as atividades catalíticas dependem dos métodos de preparação dos precursores e suportes. Na série Mg-Co-Al o catalisador com maior quantidade de magnésio mostrou as maiores atividades de HDS e HID, sugerindo que a basicidade está associada com a performance catalítica. Adicionalmente, a amostra sem magnésio e contendo alta quantidade de cobalto exibiu as menores atividades e a maior seletividade (HDS/HID = 3,86). Os resultados indicam que o excesso de cobalto diminui a atividade enquanto a presença de magnésio contribui para aumentá-la. Por outro lado, a série Ni-Co-Al exibiu as menores razões HDS/HID. Nesse caso, as altas atividades para hidrogenação são atribuídas às altas quantidades de níquel. Adicionalmente, uma comparação entre catalisadores contendo 10 % de MoO3 e 3 % de CoO, suportados em óxidos mistos derivados de HDL e um catalisador suportado em alumina, revela que o suporte mais ácido tem maior influência sobre a capacidade de hidrogenação do catalisador. Entretanto, apesar da composição e das características estruturais dos suportes, o método de preparação pode influenciar significativamente no desempenho de um catalisador suportado. / The great interest in hydrodesulfurization (HDS) of gasoline is to perform a deep sulfur removal and, at the same time, to reduce the loss of the octane number occurring in the HDS process, by minimizing the hydrogenation of olefins which are beneficial to this property. Besides the active component and the promoter, the support has to be considered an integral part of the catalyst. In this sense, several supports (enclosing aluminas and mixed oxides) were prepared from calcination of different precursors. A commercial sample of Boehmite was used as precursor of alumina polymorphs. For comparison, three other precursors were synthesized from different methods. Particularly, the use of excess of urea promoted a very crystalline form of basic aluminum carbonate. Each precursor of alumina was calcined at various temperatures generating alumina polymorphs, which were structurally analyzed by XRD and 27Al MAS NMR. Due to interest in catalysis supports, special attention was given to the γ-Al2O3 phase, which in addition to structural investigation was subjected to textural analysis. These four γ-Al2O3 samples were used as catalyst supports like CoMo, which were tested in reactions of HDS of thiophene and HID of cyclohexene. The catalytic tests show that catalytic activities increase with pore diameters of CoMo/γ-Al2O3 phases and are directly related to dispersion of molybdenum on the support. The results showed that, from different synthesis procedures and common route of calcination, one can obtain materials with the same composition but with different structural and textural properties. Furthermore, supported CoMo catalysts containing 20 % of MoO3 and 3 % of CoO were prepared by incipient wetness impregnation of molybdenum and cobalt aqueous solutions over mixed oxides obtained from hydrotalcite precursors. The precursors, containing varying amounts of Mg, Co and Al or Ni, Co and Al cátions, were synthesized by urea hydrolysis method. The calcination led to mixed oxides whose structural characteristics depend on the composition. Characterization of the supports by BET, XRD, NMR, FTIR, UV-vis/DRS and TPR techniques was carried out. The sulfided samples were used as catalysts in simultaneous hydrodesulfurization of thiophene and hydrogenation of cyclohexene. The results were compared with conventional CoMo/γ-Al2O3 catalysts, which indicate that the catalytic activities depend on the preparation method of the precursors and supports. In the Mg-Co-Al series, the high magnesium content catalyst show higher HDS and HYD activities, suggesting that the support basicity is associated with catalytic performance. Furthermore, the free magnesium and high cobalt content catalyst show lower activities and higher selectivity (HDS/HYD = 3.86). The results indicate that the excess of cobalt decreases the activities while the presence of magnesium contributes to improve them. Otherwise, the Ni-Co-Al series show the smaller HDS/HYD ratios. In this case, the higher hydrogenation activities are assigned to high nickel content. Additionally, a comparison between catalysts containing 10 % of MoO3 and 3 % of CoO, supported on mixed oxides derived of LDH and a catalyst supported on alumina reveals that the most acidic support (alumina) has great influence over hydrogenation capacity of the catalyst. However, besides the composition and structural characteristics of the supports, the preparation method can to influence significantly the performance of a supported catalyst.
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Etude diélectrique des isolants plats anodisés pour la conception de machines électriques / Dielectric study of flat anodized insulations for electrical machine designBabicz, Sylvain 06 December 2016 (has links)
L’augmentation de la classe de température des machines électriques tournantes atteint son maximum avec des vernis organiques spéciaux pouvant supporter jusqu’à 280 °C. La rupture technologique se trouve alors dans la substitution d’un vernis organique par une matière inorganique. La famille des céramiques répond aux critères. Ces céramiques sont de bons diélectriques et résistent à de fortes températures. Dans ces travaux, le conducteur étudié se présente sous la forme d’un ruban et se compose d’une âme conductrice en aluminium, dont la couche isolante a été obtenue par le processus électrochimique d’anodisation. Ce processus permet de faire croître sur l’aluminium une couche d’alumine de quelques micromètres. L’objectif de ces travaux de thèse est de caractériser ce type de conducteur pour démontrer la possibilité ou non de l’utiliser comme conducteur pour la réalisation de bobinages pour des machines dites « hautes températures », pouvant fonctionner jusqu’à des températures ambiantes de 400 °C. Des mesures de TADP, TEDP, tensions de claquage sont effectuées sous des conditions environnementales variables (hautes températures, températures négatives, humidité variable). Les actionneurs réalisés avec ce type de conducteur seront alimentés par un convertisseur provoquant des fronts raides et des surtensions. Un modèle théorique de bobine est donc proposé, basé sur l’étude du spectre d’impédance de celle-ci, et permettant de prédire l’amplitude du premier dépassement suite à un front raide. L’amélioration de l’isolation des bobines se fait par une imprégnation à l’oxyde de bore, après confection des bobines, renforçant la couche d’alumine sur les bords du ruban. / The use of state of the art organic enamels, capable to withstand 280 °C, makes the temperature class increase of electrical machine reaching its maximum. A technological breakthrough can be found by the substitution of organic enamel by a ceramic based insulation. Those materials are good dielectrics and their temperature resistance is very high compared to a classical technology. In this work, the studied conductor is an aluminum tape which insulation is obtained by an anodisation, an electrochemical process. This surface treatment makes the aluminum oxidizing: a thin layer of a few micrometres is obtained, thus representing the insulation layer of the conductor. The objectives of those PhD works is to identify and characterize this particular type of conductor so as to demonstrate the ability of using an anodized aluminum tape to makeelectrical machine running up to 400 °C. Measurements of PDIV, PDEV, and breakdown voltage are carried under various environmental conditions (temperatures varying from -70 °C up to 650 °C, variable humidity level). The use of an inverter to supply this high temperature machine induces steep fronts and over voltages. As a consequence, a theoretical model of a coil, made with this kind of conductor, is then proposed and based upon the impedance spectrum of the coil. The aim of this model is to help the designer to predict the first over voltage amplitude and to make the insulation of the first coil according to that. At least, a coil insulation improvement is depicted, using boron oxide: an impregnation is held to reinforce the alumina layer on the edge of the tape
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Preparation of activated kaolin for bleaching rice bran oil and synthetic kaolinites to assess sorption properties of these particles in relation to their morphology / Préparation de kaolins activés pour le blanchiment de l'huile de riz et estimation des propriétés d'adsorption de kaolinites de synthèses en relation avec leur morphologieAung, Lei Lei 02 May 2014 (has links)
Cette étude a fait l'objet de deux parties. L'une porte sur l'effet de différents types d'activation (chimique, thermique, mécanique) de kaolins (géo-matériaux riches en kaolinite) sur leurs propriétés de décoloration vis-à-vis de l'huile de riz. L'autre traite de l'effet de la taille et de la morphologie de kaolinites de synthèse sur leurs propriétés d'adsorption.Cette étude a montré que lorsque le kaolin était chauffé à plus de 100°C avant de subir une activation acide en milieu sulfurique, citrique ou oxalique, la capacité de décoloration vis-à-vis de l'huile de riz était fortement réduite. Cet effet a été directement mis en relation avec la destruction partielle ou totale de la structure de la kaolinite, associée à une forte lixiviation de l'aluminium de l'échantillon et à la précipitation de silice amorphe. Il s'est donc avéré que la préservation des sites aluminols présents sur les surfaces externes des particules de kaolinites semblait être un critère primordial à conserver en vue d'obtenir de bonne capacité de décoloration. Dans ce contexte, les meilleures capacités de décoloration (82% environ) ont été obtenues en utilisant conjointement un traitement thermique modéré (<100°C), un broyage mécanique de l'échantillon avant l'étape d'activation acide, une concentration en acide de l'ordre de 0.3 à 0.5 mol/L et un rapport (argile)/(solution acide) de l'ordre de 1/50. Notons que les plus fortes valeurs de surfaces spécifiques n'ont pas forcément été associées aux échantillons présentant les meilleures capacités de décoloration en raison de la présence de silice amorphe et de la non-préservation des sites aluminols de la kaolinite ; sites responsables de l'adsorption des pigments de molécules de chlorophylle-a.Par ailleurs, aucune étude à notre connaissance ne reliait directement les morphologies de particules de phyllosilicates à leurs propriétés d'adsorption vis-à-vis de deux cations inorganiques. Dans le cas des kaolinites naturelles, une charge permanente souvent significative et attribuable à des impuretés minéralogiques empêche toute tentative de relier directement la forme des particules à un coefficient de sélectivité entre deux cations pour des sites latéraux donnés. Des kaolinites ont donc été synthétisées par voie hydrothermale en considérant différentes conditions physico-chimiques, afin d'obtenir des morphologies variées (hexagones plus ou moins anisotropes). Pour ces échantillons synthétiques pour lesquels aucune impureté minéralogique et charge permanente n'a été détectée, des isothermes expérimentales d'adsorption entre Na+ et H+ ont été mesurées. Ces cations ont été choisis étant donné leur présence ubiquiste dans les eaux naturelles et leur fort pouvoir compétiteur par rapport aux cations traces métalliques. Grâce aux surfaces spécifiques des sites latéraux et des densités de site issues de la cristallographie des différentes faces présentes dans nos échantillons ((010), (110), (1-10)), un coefficient de sélectivité entre Na+ et H+ sur l'ensemble des sites latéraux d'une morphologie donnée a pu être estimé à l'aide d'un modèle de complexation de surface. Les résultats ont montré que le coefficient de sélectivité Na+/H+ dépendait très fortement de la morphologie de la particule, et que par conséquent les propriétés d'adsorption des kaolinites ne pouvaient pas être obtenues avec précision sans une connaissance fine de la morphologie des particules. / The dissertation consists of two main parts; the first part is devoted to the effect of physical/thermal and chemical activation of kaolin on bleaching of rice bran oil. In this study, samples were prepared from natural Ranong kaolin. This study focused on the effects of both thermal treatment (from 100 to 900°C) and chemical activation (sulfuric acid, hydrochloric acid, citric acid and oxalic acid using different acid concentrations or different clay/acid ratio) on the capacity of kaolins to bleach rice bran oil. When kaolin was treated with high temperature (>100°C) prior to reflux and with a high acid concentration during reflux, the kaolinite structure was partially or completely destroyed associated to a dramatic leaching of alumina, and amorphous silica dominated the samples. The measured maximum bleaching capacity obtained was not consistent with the highest specific surface area and pore volume; rather, it depended on the alumina contents in the samples. Thus, the partial preservation of the kaolinite structure is crucial to obtain an appropriate bleaching capacity of kaolin. This is directly related to the preservation of the aluminol sites present at the kaolinite surface. XRF analysis showed that the alumina contents of 28-34% were values to reach in order to obtain optimum bleaching capacities of kaolin, independently of the different acid used. Finally, optimum bleaching of ~83%, ~82% and ~81% were achieved by grinding the kaolin prior to reflux with low acid concentration of hydrochloric acid (0.5 M), sulfuric acid (0.3 M) and citric acid (0.5 M), respectively with clay/acid ratio of 1:50.The second part of the thesis aims to elucidate the influence of morphology of kaolinites on their sorption properties. For that, Na+/H+ sorption isotherms in water saturated conditions of synthetic kaolinites and natural well crystallized kaolinite, called KGa--1b commercialized by the Clay Mineral Society, were performed and interpreted. Kaolinites used in this study were hydrothermally synthesized from partially crystallized kaolinite as a function of different final pH (pHF) ranging from 0.8 to 8.3. Results obtained for KGa--1b were compared with data obtained in literature for this mineral, in order to fully validate this approach. This study found that cation exchange capacity, due to both isomorphic substitutions in the crystals (permanent charge), and silanol and aluminol edge sites were highly variable. Typically, CEC at pH=9 varied from ~0.8 cmolc/kg for well crystallized kaolinite (pHF 0.8) to ~33 cmolc/kg for disordered lath-shaped kaolinite (pHF 8.3). Na+/H+ sorption isotherms were obtained for all synthetic kaolinites as a function of pH ranging from pH 3 to 11. Results showed that sorption of Na+ increases dramatically with pH. Typically for all kaolinite samples except for the one synthesized at pHF=8.3, Na+ sorption is rigorously equal to zero when pH<7, indicating no permanent charge in the samples (in contrast to natural KGa--1b kaolinite), and increases when pH>7 due to sorption on edge sites. The amount of dissolved silica measured during Na+/H+ isotherm is higher for experiments performed with kaolinites synthesized in basic conditions (for pHF 7.4 and pHF 8.3) than for kaolinites synthesized in acid conditions (for pHF 0.8 and pHF 3.3). These latter results lead to conclude that sorption site density can be considered constant when pH is between 4 and 10, independently of the morphologies of particles. In this context, a thermodynamic modeling procedure using a complexation model was applied to interpret the data obtained with hexagonal- and lath-shaped particles. During this procedure, selectivity coefficient between Na+ and H+ cations were obtained considering the total edge site densities calculated from lateral specific surfaces estimated for synthetic kaolinites and crystallography data.
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Valorisation de polyols en phase aqueuse sur catalyseurs bimétalliques supportés pour la production d'hydrocarbures / Polyols valorization in aqueous phase on bimetallic supported catalysts for hydrocarbons productionMessou, Davina Gnamien-Bla 09 December 2016 (has links)
La biomasse végétale (source de carbone renouvelable) peut être utilisée pour fabriquer des carburants liquides et produits de base pour la chimie. Ainsi depuis environ une dizaine d'années, se développe le procédé APHDO (Aqueous Phase HydroDeOxygenation) de transformation directe en phase aqueuse de polyols d'origine lignocellulosique (comme le sorbitol) en alcanes valorisables (C5-C6). Ce procédé repose sur une catalyse hétérogène bifonctionnelle métal/acide et fait intervenir des ruptures compétitives de liaisons C-C et C-O. L'objectif de la thèse est de mettre au point des systèmes bimétalliques supportés actifs et sélectifs pour la transformation du sorbitol en hexane. La modification d'un catalyseur de référence Pt/SiO2-Al2O3 par ajout de Re, Ir, Pd, Rh et Ru est effectuée par trois techniques de synthèse : co-imprégnation, imprégnations successives et dépôt par réduction catalytique. Les performances des catalyseurs bimétalliques sont comparées à isoconversion de sorbitol à celles des catalyseurs monométalliques parents pour un test catalytique réalisé en autoclave, avec une solution aqueuse à 10% massique de sorbitol, à 240°C et 60 bar de pression totale sous H2. Les produits se répartissent en phase gaz (CO2, alcanes en C1-C6) et liquide (composés oxygénés). Le sorbitane et l'isosorbide sont majoritairement formés en phase liquide, le dernier étant un intermédiaire clé de la transformation du sorbitol dans cette étude. Les catalyseurs Pt-Ru/SiO2-Al2O3 s'avèrent les plus sélectifs pour la réaction, celui préparé par imprégnations successives conduisant à une plus forte proportion de C6 en phase gaz comparé aux deux monométalliques Pt/SiO2-Al2O3 et Ru/SiO2-Al2O3. / Plant Biomass (renewable source of carbon) can be used to make liquid fuels and basic products of chemistry. So, from about ten years, the APHDO (Aqueous Phase HydroDeOxygenation) process is developed for the direct transformation in aqueous phase of polyols from Biomass (such as sorbitol) into renewable alkanes (C5-C6). This process involves a metal/acid bifunctional heterogeneous catalysis and competitive C-O and C-C bond cleavages. The aim of the PhD work is to develop supported bimetallic systems active and selective for the transformation of sorbitol into hexane. The modification of a reference Pt/SiO2-Al2O3 catalyst by addition of Re, Ir, Pd, Rh and Ru is carried out by three synthesis methods: co-impregnation, successive impregnations and deposit by catalytic reduction. The performances of bimetallic catalysts are compared at sorbitol isoconversion to those of the parent monometallic catalysts for a catalytic test carried out in an autoclave with an aqueous solution of sorbitol (10 wt%) at 240°C and 60 bar total pressure under dihydrogen. The products are distributed in the gas phase (CO2, C1-C6 alkanes) and in the liquid phase (oxygenated compounds). Sorbitan and isosorbide are predominantly formed in the liquid phase, the latter being a key intermediate of sorbitol transformation in this study. Pt-Ru/SiO2-Al2O3 catalysts are the most selective for the reaction, the one prepared by successive impregnations leads to a higher proportion of C6 in gaseous phase compared to both monometallic Pt/SiO2-Al2O3 and Ru/SiO2-Al2O3 catalysts.
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Influence de l'eau (vapeur, liquide) et du régime d'oxydation sur la dégradation de revêtements alumino-formeurs sur superalliage à base nickel / Influence of water (vapour, liquid) and of the oxidation regime on the high temperature degradation of alumina-forming coatings on Ni-based superalloysBrossard, Maxime 29 September 2014 (has links)
En service, les matériaux constituant les aubes de turbine aéronautique (superalliages à base nickel) sont soumis à des environnements agressifs susceptibles d’altérer leurs propriétés structurales. Les atmosphères oxydantes impliquées sont en général complexes (O2, H2O, CO2, SO2, NOx…), la quantité d’eau présente pouvant en particulier varier selon le régime moteur et les conditions environnantes (nuages, précipitations, humidité de l’air). Pour apporter une protection contre l’oxydation à haute température, on met en œuvre des revêtements alumino-formeurs sur lesquels une barrière thermique peut, de plus, être déposée. Le présent travail se proposait donc d’étudier l’influence de l’eau, sous forme vapeur et/ou liquide, sur le comportement de revêtements alumino-formeurs de référence, ou développés au LaSIE (barbotine d’aluminium, électrodéposition de CeO2), selon différents régimes d’oxydation (isotherme et cyclique). Afin de se rapprocher des conditions en service, une démarche scientifique originale a été proposée avec la mise en œuvre de conditions de vieillissement et post-vieillissement variées, à haute température, lors des phases de refroidissement, ou encore à température ambiante. Les expériences menées ont montré qu’une introduction de vapeur d’eau n’a que peu d’effet en régime isotherme à 1100°C, notamment lorsqu’une couche d’alumine alpha s’est développée en surface. L’ajout d’eau à froid (humidité relative,gouttes d’eau) accroît l’écaillage des couches d’oxydes, au-delà d’un temps d’oxydation critique, alors que l’apport d’eau lors de la phase de refroidissement des cycles thermiques conduit à une dégradation catastrophique des aluminures de nickel par un mécanisme combinant fatigue thermique et piqûration. / Upon service, aero-turbine blades (nickel-based superalloys) are submitted to high temperature degradation that may alter their structural properties. The oxidizing atmospheres are particularly complex (O2, H2O, CO2, SO2, NOx…) with variable water vapour contents as function of the engine regime and the atmospheric conditions (clouds, rain, relative humidity of air). These substrate materials are protected by alumina-forming coatings to improve their oxidation resistance, while additional thermal barrier coatings insulate the hottest parts. This PhD project aims at studying the effect of water (vapour, liquid) on the degradation of conventional and new coatings (Al slurry, electrodeposited CeO2) developed at the LaSIE laboratory under different oxidation regimes (isothermal and cyclic). An approximation to service conditions was proposed through an original methodology in which several oxidation and post-ageing conditions for different oxidation ranges (hot, upon cooling, at room temperature) were performed. The experiments showed little effect of water vapour mixed with air at 1100°C in isothermal conditions, in particular when the alumina scale grew over the surface. In contrast, water-containing environments at room temperature (relative humidity, water drops) increased the spallation of the oxide scales above a critical threshold time. Cyclic oxidation with water cooling provoked in turn, a catastrophic failure of the aluminide coatings by a mechanism involving thermal fatigue and pitting corrosion.
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Surface modification of oxide nanoparticles using phosphonic acids : characterization, surface dynamics, and dispersion in sols and nanocomposites / Modification de surface de nanoparticules d’oxyde par des acides phosphoniques : caractérisation, dynamique de surface et dispersion dans des sols et des nanocompositesSchmitt, Céline 30 November 2015 (has links)
Les dispersions colloïdales de nanoparticules (NPs) sont très répandues dans l'industrie, et permettent d'éviter l'utilisation de NPs sèches, controversée pour des raisons de toxicité. Le contrôle des interactions entre les NPs et le milieu dispersant reste le point clé de ces systèmes. La modulation de ces interactions permet de contrôler l'état de dispersion des NPs dans les sols. De plus, les nanocomposites NPs-polymère se sont avérés prometteurs pour une large gamme d'applications, ainsi l'utilisation de sols pourrait présenter une voie avantageuse d'incorporation des NPs dans le polymère, tout en offrant la possibilité de contrôler leur état de dispersion, et in fine les propriétés du matériau, celles-ci étant liées à l'état de dispersion des NPs. L'objectif de ce travail de thèse est le développement de méthodes de modification de surface de NPs d'oxyde en dispersion colloïdale, tout en contrôlant la dispersion des NPs dans les sols et dans les nanocomposites issus de ces sols. Puis, l'évaluation de cet état de dispersion par SAXS. Deux méthodes de modification de surface ont ainsi été développées : la première implique le greffage d'acides phosphoniques sur des NPs de silice recouvertes d'alumine en dispersion dans l'eau, et la seconde met en jeu le greffage d'acides phosphoniques sur des NPs de TiO2 et leur transfert d'une phase aqueuse à une phase CHCl3. Les NPs modifiées ont été caractérisées par diverses méthodes. Leur état de dispersion a été étudié par DLS et SAS. De plus, pour les NPs de silice-amine, l'impact de la densité de greffage du C8PA sur la structure des NPs (à l'état sec) a été mis en évidence par SAXS et différents processus de relaxation ont été étudiés par BDS pour les NPs nues et modifiées. Enfin, ces NPs ont été incorporées dans un polymère de PEA par voie aqueuse via des latex et leur état de dispersion dans les composites a été mesuré par SANS. / Colloidal nanoparticles (NPs) dispersions are largely used in the industry, and avoid the use of dried NPs, which is controversial due to safety concerns. The key point in such systems remains the control of the interactions with the dispersed medium and between the NPs. Mastering these interactions allows controlling the NPs' state of dispersion. Moreover, as polymer-NPs nanocomposites have been found promising for a wide variety of applications, the use of colloidal sols could thus be an advantageous way of NPs' incorporation in the polymer, with a possible control of the NPs state of dispersion, and finally on the properties of the material, as they are linked to the NPs' dispersion. The purpose of this PhD work is to develop surface-functionalization methods of oxide NPs in colloidal sols in order to control the dispersion of NPs in the sols and in polymer nanocomposites derived from these sols, and to evaluate this dispersion using SAXS. Two surface modification methods have been developed to obtain aqueous or organic sols of functionalized NPs. The first one concerns the reaction in water of alumina-coated silica NPs with phosphonic acids (PAs), and the second one involves the simultaneous grafting and phase transfer of TiO2 NPs from an aqueous to a CHCl3 phase using PAs. The resulting NPs were characterized and their state of dispersion was monitored by DLS and SAS measurements. The impact of the C8PA grafting density on the structure of modified alumina-coated silica NPs in the dried state was evidenced by SAXS. The different relaxation processes of bare and grafted NPs were studied by BDS. These NPs were then incorporated in a PEA polymer by an aqueous latex route, and their structure in the nanocomposites was investigated by SANS.
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A Palaeoproterozoic high-sulphidation epithermal gold deposit at Orivesi, southern FinlandKinnunen, A. (Aulis) 06 May 2008 (has links)
Abstract
The metamorphosed Palaeoproterozoic Orivesi gold deposit in southern Finland is located within the Tampere Schist Belt, which belongs to the Svecofennian domain. The Orivesi mine, run by Outokumpu Mining Oy, was in production from 1994 to 2003, during which time a total of approximately 1.7 million tons of ore was extracted, with an Au content of 9.31 g/t, implying a total output 13.115 tons of gold in concentrate.
The hydrothermal alteration halo can be divided successively into chlorite-dominant, sericite-dominant and quartz-dominant rocks from the outer zone inwards. The host rocks of the ore are quartz rocks with andalusite-rich quartz rocks. Topaz-bearing rocks also occur in the inner part of the alteration halo. In addition to Au, the elements Ag, Te, Bi, Sb, S, As, Se, Cu, Zn, Pb, Sn and Mo are enriched to varying degrees within the alteration halo.
The main ore minerals include base metal sulphides, sulphosalts and tellurides. Pyrite is the most common sulphide. The sulphosalts are represented by tetrahedrite, bournonite, boulangerite and meneghinite. The most common gold, gold-silver and silver tellurides are calaverite, montbrayite, petzite, kostovite, sylvanite and hessite. Other known tellurides include tellurobismuthite, altaite, melonite, frohbergite, tsumoite, tetradymite and rucklidgeite.
Gold occurs mostly in fine-grained native grains containing an average of 5% Ag. The native gold is usually of very small grain size, generally < 20 µm. Most of the gold grains in the deposit occur as intergrowths with tellurides.
The adjacent hypabyssal intrusion is an obvious source of both hydrothermal fluids and metals. A comb quartz layering has been discovered in the transition zone between the intrusion and the alteration halo.
The Orivesi deposit is thought to belong to the high-sulphidation epithermal type. Soon after its formation the deposit encountered deformation and metamorphism that amounted to lower amphibolite facies conditions. The subsequent retrograde metamorphism caused the reappearance of some hydrothermal minerals typical of high-sulphidation epithermal deposits.
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Structuration et mise en forme de matériaux moléculaires poreux au sein de membranes d'alumine / Growth of porous molecular materials in thepores of alumina membranesGualino-Tamonino, Marion 21 September 2015 (has links)
Cette thèse concerne la mise en forme et la structuration de polymères de coordination poreux (PCP, ou MOFs pour Metal-Organic Frameworks) au sein de membranes d'alumine macroporeuses (Øpores ˜ 200 nm), dont le rôle est double. Obtenus sous forme de cristaux, les MOFs sont fragiles. La membrane constitue d'une part une coque protectrice pour le polymère de coordination impliqué dans le matériau composite. D'autre part, elle fait office de matrice, permettant la fabrication de nanostructures unidimensionnelles (1D), obtenues après élimination sélective de la dite matrice. La fonctionnalisation préalable de la membrane, ainsi que les paramètres opératoires (concentration en réactifs, nombre de cycle de filtration, étape de lavage intermédiaire...) ont été largement étudiés, ce qui a permis d'élaborer avec succès plusieurs composites PCP/membrane. Ainsi, des composites incluant des PCP tels que HKUST-1, ZIF-8, et un matériau à transition de spin Fe(pz)[Ni(CN)4] ont été préparés. Pour le polymère de coordination ZIF-8, des nanofibres 1D ont été isolées avec succès après dissolution de la membrane. Tous les composites et les nano-objets résultants ont été amplement caractérisés en termes de morphologie (MEB, MET, AFM), de composition chimique (Raman, DRX, IR), et de propriétés (magnétiques ou d'adsorption/désorption de gaz). / This thesis aimed at the construction of porous coordination polymer (PCP, or MOFs Metal-Organic Frameworks for) within macroporous alumina membranes (Øpores ˜ 200 nm), whose role is twofold. Obtained as crystals, MOFs are fragile. The membrane firstly provides a protective shell for the coordination polymer embedded in the composite material. Moreover, the membrane acts as a matrix, enabling the elaboration of one-dimensional nanostructures (1D), obtained after selective elimination of the matrix. The functionalization of the membrane, and the experimental parameters (reagents concentration, number of cycles, intermediate washing-step...) have been widely studied. They allowed accessing various PCP/membrane composites. Composites involving HKUST-1, ZIF-8 and Fe(pz)[Ni(CN)4] spin transition MOFs have been prepared. For the coordination polymer ZIF-8, 1D nanofibers have been successfully isolated after dissolution of the membrane. These composites and the resulting nano-objects have been extensively characterized in terms of morphology (SEM, TEM, AFM), chemical composition (Raman, XRD, IR), and properties (magnetic or gas adsorption / desorption).
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