Ces travaux de thèse portent sur la synthèse et la caractérisation de nanoparticules d’oxyde spinelle à base de cobalt, déposée à la surface de feuillets d’oxyde de graphène réduit. Ces nanocomposites ont pour but de servir de catalyseurs bifonctionnels intégrés à l’électrode à air des batteries lithium-air. La particularité des synthèses présentées repose sur le chauffage micro-onde des précurseurs en milieu aqueux entre 100 et 200 °C. Cette approche originale de chimie douce permet en outre la création de l’interface entre les nanoparticules d’oxyde et les feuillets de graphène directement pendant la synthèse des particules, au lieu de nécessiter une étape supplémentaire de greffage. L’oxyde de cobalt Co3O4 a servi de matériau modèle pour optimiser les différents paramètres de synthèse puis le protocole a été adapté à une série d’oxydes binaires en substituant une partie des atomes de cobalt par du nickel, du manganèse ou encore du fer. La co-précipitation des cations de métaux de transition au sein d’une même phase a été rendue possible grâce à la compréhension des diagrammes de Pourbaix pour ajuster les conditions redox et acido-basiques.Enfin, les propriétés électrocatalytiques des catalyseurs composites vis-à-vis des deux réactions inverses d’ORR et OER ont été testées. L’écart entre les potentiels d’OER et ORR a été diminué de manière significative grâce à la présence des nanoparticules de Co3O4 sur feuillets d’oxyde de graphène réduit, montrant ainsi la réversibilité du catalyseur.Des caractérisations structurales et morphologiques qui ont permis d’établir certains liens entre synthèse, nanostructure et activité électrocatalytique complètent ce travail. / This research work is focused on the design and characterisation of cobalt based oxides nanospinels anchored onto the surface of reduced graphene oxides (RGO) nanosheet, which will serve as bifunctional catalysts for the new generation lithium-air batteries. Whereas nanospinels are relatively simple to synthesize by conventional colloidal routes as nanoparticles dispersed into an aqueous solution, the synthesis we developed relies on a hydrothermal microwave treatment in the 100°C-200°C range. The main challenges of this nano-heterostructures synthesis was to create the interface between the nanoparticles and the RGO directly during the nanoparticles nucleation. RGO are very efficient microwave absorbers and could then convert microwave irradiation into heat in order to trigger precipitation of the spinel at the surface of the RGO sheet.Starting from Co3O4 as proof-of-concept material, the synthesis protocol has been successfully adapted to address binary oxides by substituting cobalt with first row transition metals such as nickel, manganese or iron. The precipitation of binary and ternary oxides was achievable thanks to a good understanding of the Pourbaix diagrams of all cations to adjust the acido-basic and redox conditions.Finally, the electrocatalytic activity of these supported spinel oxides was measured for both the oxygen reduction and oxygen evolution reactions (ORR and OER). The gap between the ORR and the OER potentials was significantly lowered by the presence of Co3O4 nanoparticles on the RGO, thus assuring the reversibility of this catalytic system, which is to be integrated in future scale-up test.

Submitted by ANA KARLA PEREIRA RODRIGUES (anakarla_@hotmail.com) on 2017-08-07T12:48:06Z No. of bitstreams: 1 arquivototal.pdf: 4672568 bytes, checksum: 30655ee26e612b43221335d08bddc500 (MD5) / Made available in DSpace on 2017-08-07T12:48:06Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 4672568 bytes, checksum: 30655ee26e612b43221335d08bddc500 (MD5) Previous issue date: 2016-02-29 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Magnesium stannate (Mg2SnO4) and titanate (Mg2TiO4) are inverse spinel-type oxides, applied as humidity sensors, hot resistor, dieletric, temperature compensation capacitor, electronic ceramic and refractory material. In the present work, these two materials were combined in order to obtain a solid solution, Mg2(Ti1-xSnx)O4, (x = 0; 0,25; 0,50; 0,75; 1,0) by the modified-Pechini method, in order to investigate the influence of Sn4+ substitution for Ti4+ in the spinel lattice for application as photocatalyst for discoloration of Gold yellow remazol and to avoid micro-organism adhesion into surfaces. The synthesis of the spinels was optimized. Catalysts were characterized by X-ray diffraction, UV-visibe spectroscopy, Raman spectroscopy, infrared spectroscopy, surface area measurement using BET method. Mg2TiO4 is a metastable compound, which decomposes into ilmenite (MgTiO3) above 800 °C. On the other hand, reaches long-range order at lower temperatures, while single phase Mg2SnO4 is only obtained from 900 °C. For these reasons, different temperatures are necessary to obtain the single phase materials. Infrared and Raman spectra confirmed the presence of [MgO6]-10, [TiO6]-8, [SnO6]-8 octahedra and (MgO4)-6 tetrahedra. The photocatalytic tests were carried out in a reactor comprising of UVC lamp (λ = 254 nm). Mg2SnO4 presented the best photocatalytic result, with 79% of discoloration at pH 6 and 87% at pH 3, while Mg2TiO4 showed 7% of conversion at pH 6, without increasing efficiency at pH 3. The obtained spinels were effective in inhibiting bacterial and fungal growth as indicated by fluorescence analysis for Gram positive bacteria (S. aureus and S. mutans), Gram negative bacteria (P. aeruginosa and E. coli) and fungus (Candida albicans) showing the potential for microbial anti-adhesion material. Tests with higher titanium content showed the best results except for E. coli. / O estanato (Mg2SnO4) e o titanato de magnésio (Mg2TiO4) são óxidos do tipo espinélio inverso, aplicados como sensores de umidade, resistor de calor, dielétrico, capacitor para compensação de temperatura, cerâmica eletrônica e material refratário. Nesse trabalho, os dois materiais foram combinados com a finalidade de obter uma solução sólida, Mg2(Ti1-xSnx)O4, (x = 0; 0,25; 0,50; 0,75; 1,0), utilizando o método Pechini modificado, de modo a investigar a influência da substituição dos íons Sn4+ por íons Ti4+ na rede do espinélio para aplicação como catalisadores na descoloração do corante remazol amarelo ouro e na antiadesão microbiana. A síntese dos espinélios foi otimizada. Os catalisadores foram caracterizados pelas técnicas de difração de raios-X, espectroscopia na região do ultravioleta e do visível, e espectroscopia Raman, espectroscopia na região do infravermelho e medida de área superficial por BET. O Mg2TiO4 é um composto metaestável, se decompondo em ilmenita (MgTiO3) acima de 800 °C. Por outro lado, o Mg2TiO4 se organiza a longo alcance em temperaturas mais baixas enquanto que o Mg2SnO4 monofásico é obtido apenas a partir de 900°C. Com isso, observa-se que diferentes temperaturas são necessárias para se obter os materiais monofásicos. Os espectros de IV e Raman confirmaram a presença dos octaedros [MgO6]-10, [TiO6]-8, [SnO6]-8 e tetraedro (MgO4)-6. Os testes fotocatalíticos foram realizados em um reator composto por lâmpadas UVC (λ = 254 nm). O Mg2SnO4 apresentou o melhor resultado, com descoloração de 79 % em pH 6 e 87 % em pH 3, enquanto o Mg2TiO4 apresentou conversão de 7 % em pH 6, sem aumento de eficiência em pH 3. Os espinélios obtidos mostraram-se eficazes na inibição do crescimento bacteriano e fúngico como indicado pela análise de fluorescência para bactérias Gram positivas (S. aureus e S. mutans), Gram negativas (P. aeruginosa e E. coli) e para o fungo (Candida albicans) mostrando o potencial de antiadesão microbiana dos materiais. Os testes com maior teor de titânio apresentaram os melhores resultados exceto para a E. coli.

In this investigation, the cation distribution in ferrites of spinel-type structure is spectroscopically investigated with respect to the observed magnetic behavior. The ferrite thin films were fabricated by pulsed laser deposition and consequently annealed at different temperatures as well as atmospheres. Structural properties were determined with various methods and the crystalline quality was examined. The dielectric function line-shape was parametrized based on empirical evidence and was found to be dominated by electronic transitions between d orbitals of Fe2+ cations as well as transitions from O 2p to 3d and 4s orbitals of iron and zinc cations. The strongest magneto-optical response was observed for transitions involving cations, which correspond to lattice disorder and inversion within the normal spinel structure. With the decrease in the substrate temperature during fabrication, a decrease in the magnetic response was observed. The diminishing ferrimagnetic order was directly correlated to the decrease in strength of the transitions, involving Fe3+ on tetrahedral lattice sites. After thermal treatment in argon atmosphere and at a temperature below the deposition temperature, the increase in the magnetic response was explained through the facilitation of oxygen vacancies. With the increase in treatment temperature, a decrease in ferrimagnetic order was related to the recrystallization of the disordered spinel structure toward a more stable normal configuration, evident in the dielectric function spectra. The cationic configuration distribution in the surface as well as the bulk region, as a function of Zn concentration, was determined from approximation of the XPS and the dielectric function spectra, respectively. The difference in the cation configuration distribution, in films of predominantly inverse configuration, was related to the weak magnetic response, as opposed to films of predominantly normal spinel configuration. Our results demonstrate that a defect-rich surface region could serve as a possible explanation for the ferrimagnetic order in a nominally non-magnetic normal spinel ZnFe2O4. In combination with structural property determination, the net magnetic behavior is explained through the local cationic disorder, determined from the parametrization of the dielectric function spectra in a wide spectral range.:1 Introduction 2 Theoretical background and fundamental considerations 2.1 Spinel ferrite crystal structure 2.2 Crystal field stabilization energy 2.3 Band structure description 2.4 Verwey transition 2.5 Magnetic exchange interactions 3 Sample preparation and modification 3.1 Macroscopic spinel film formation 3.2 Pulsed laser deposition 3.3 Thermal treatment 3.4 Sample overview 4 Methods and general properties 4.1 Structure characterization techniques 4.1.1 X-ray diffraction 4.1.2 X-ray reflectivity 4.1.3 Energy dispersive X-ray spectroscopy 4.1.4 Focused ion beam and scanning electron microscopy 4.1.5 Raman spectroscopy 4.2 Surface properties 4.2.1 Atomic force microscopy 4.2.2 X-ray photoelectron spectroscopy 4.3 Dielectric tensor properties 4.4 Spectroscopic ellipsometry 4.5 Magneto-optical Kerr effect 4.6 Magneto-static properties 5 Results and discussion 5.1 Magnetic and optical properties of Fe3O4 thin film and single crystal 5.2 Magneto-optical properties of ZnxFe3−xO4 thin films 5.3 Fabrication temperature dependent ferrimagnetic order 5.4 Thermally induced structural stabilization 5.5 Cation configuration in dependence on the Zn concentration 5.5.1 Structural property determination 5.5.2 Composition characterization 5.5.3 Magneto-static behavior 5.5.4 Section summary and discussion 6 Summary and outlook Bibliography List of article contributions Selbstständigkeitserklärung Acknowledgments

A neutron activation analysis procedure for the simultaneous determination of Au, Pd and Ir, and separate determination of Os is described and applied to the determination of these metals in the Mount Albert ultramafic pluton, Quebec. The Mount Albert is an alpine-type ultramafic body whose petrography, geology and geochemistry has been discussed in some detail by MacGregor (1962, 1964). It consists mainly of serpentinized dunite and peridotite. However, it is distinguished by the presence of an eastern lobe which is essentially unserpentinized. In addition to ferromagnesians, two varieties of spinel including disseminated accessory chrome spinel and massive, discordant chromite veins or schlieren are important mineralogical constituents. Twenty samples were analyzed including 5 fresh dunites and peridotites, 8 serpentinized equivalents, 4 disseminated chrome spinels, 1 clinopyroxenite, and 2 massive chromite. The concentrations (in p. p. b.) of average fresh ultramafics and their serpentinized equivalents are:-------------------------------------- ---------------------Pd----Os----Ir----Au------------------------------------------- Fresh rocks------------7.7----7.2--2.5--0.99------------------------------------------- Serpentinized rocks---10----6.6--2.2---2.4-------------------------------------------- The piuton was intruded as a nearly solid mass of olivine and some orthopyroxene with about 15 weight per cent melt. A small concentration of the precious metals, a factor of 2 to 3, in the melt relative to crystalline phases appears to have occurred. The disseminated chrome spinel and massive chromite appear to concentrate the precious metals. In particular, Os and Ir content of the massive chromite is approximately 10 times that of fresh or serpentinized whole rocks. There is little change in average precious metal content with serpentinization. Pd shows a slight increase, and Ir and Os slight decreases in concentration with degree of serpentinization. Only Au appears significant to be enriched in serpentinized rocks where a twofold increase occurs. The variation in precious metal content of all four metals increase when the rocks are serpentinized: When normalized to chondrite meteorites, the precious metal data give fractionation trends similar to that of average chondrite. These trends are compatible with a model in which alpine ultramafics are regarded as residua from the partial melting of parental material of approximately chondritic composition. / Thesis / Master of Science (MSc)

The self-assembly of magnesium aluminate spinel as a result of dewetting an overlaid thin film of (chiefly) gold was investigated. Thin films of gold were deposited on single-crystalline spinel substrates and were heat-treated to dewet gold film which led to self-assembly of intricate structures consisting of faceted spherical particles atop of frustums. The current work was conducted in continuation of previous studies which reported formation of such intricate structures. The most recent studies had evidently overruled a pure gold self-assembly scenario as was pointed out in preliminary investigations. It was in fact proven that these structures consist of three distinct parts: (i) a single or polycrystalline gold faceted sphere, (ii) quasi-phase interfacial bilayer, and (iii) a crystalline MgAl2O4 necking structure spontaneously risen from spinel substrate. In the current work, samples were produced through different film deposition methods of sputter, thermal evaporation, and e-beam evaporation coating which underwent thermal annealing to induce dewetting of gold film and subsequent self-assembly of intricate structures. Several characterization methods such as electron microscopy, X-ray energy dispersive spectroscopy, electron energy loss spectroscopy, and atom probe tomography were utilized to survey the different features of the intricate structures with focus on chemical analysis of the gold-spinel interface. The results rejected the previous findings about formation of interface complexion at the boundary of gold-spinel. It was found out that gold-spinel interface is in fact an ordinary metal-oxide boundary with sharp atomic distinction and no inter-diffusion or formation of interfacial complexion. It was further discovered that dewetting pure gold thin films does not result in formation of spinel self-assembly and existence of elemental impurities of copper (Cu) in the initial film is vital in development of such structures. Finally, it was concluded that chemical composition of metallic overlayer and the heat treatment parameters most fundamentally influence formation and physical characteristics of those self-assembled structures. / Thesis / Master of Applied Science (MASc)

No description available.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24107号 / 工博第5029号 / 新制||工||1785(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 作花 哲夫, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Ce travail traite de l’étude des propriétés structurales et magnétiques de Co2MnO4, une spinelle à symétrie cubique inversée et de groupe spatial Fd3m. Co2MnO4 est un composé multiferroïque dont les propriétés électriques et magnétiques sont dues à la présence des éléments Co et Mn, à valence mixte, distribués sur les sites tétraédriques et octaédriques de la structure AB2O4. La présence des états d’oxydation du Co et du Mn, Co2+/Co3+ et Mn2+/Mn3+/Mn4+, est en étroite relation avec les conditions de synthèse et traitements thermiques. La substitution partielle des cations par un élément non-magnétique, le Bi, dans la série BixCo2-xMnO4 (0.0 ≤ x ≤ 0.3) permet également de modifier les propriétés physiques de la spinelle. Les composés ont été synthétisés par une variante de la méthode de précurseurs polymériques, MPPM, et calcinés à 1100 °C pendant 24 h. La diffraction des rayons-X (DRX), associée à l’affinement structural par la méthode Rietveld, ont montré pour ces matériaux cristallisés, une même structure cristallographique dont les paramètres de maille augmentent avec la quantité de Bi. Les observations par microscopie électronique à balayage (MEB) ont permis d’observer une variation de la forme et de la taille des grains, cette dernière variant entre 1 et 10 µm. L’insertion du bismuth atteint une limite de solubilité due à la différence notable entre les rayons ioniques du Co (0,65Å) et du Bi (1,17Å), conduisant alors à la formation d’une phase secondaire riche en Bi. Afin d’éviter la formation des phases secondaires, deux stratégies de synthèse ont été mises en place : l’une, substituer le Bi par du Co dans le système CoxBi2‑xMnO4 (0.0 ≤ x ≤ 1.7) et l’autre, utiliser une méthode originale de synthèse, la mécanoactivation MS, pour la série CoxBi2‑xMnO4 (0.0 ≤ x ≤ 1.7). Le comportement ferrimagnétique du composé initial non-substitué est maintenu après substitution partielle du Co par le Bi, avec une irréversibilité marquée entre les courbes ZFC et FC et une transition ferromagnétique très bien définie à TC. Plusieurs paramètres magnétiques tels que TC, Tmax, MFC (extrapolation de la courbe FC à T=0), température de Curie-Weiss ΘCW et moment effectif eff, sont modifiés d’une façon significative en fonction du contenu en Bi et confirment le phénomène de saturation dû à la non-solubilité du bismuth dans la structure cristalline cubique. A partir des données structurales et magnétiques, une équation d’équilibre de charges du type (Co2+)[Co2+x(Bi3+,CoIII)1-xMn3+1-xMn4+x]O4 est proposée, où l’ion Co2+, responsable des interactions antiferromagnétiques, se situe en position tétraédrique « (..) » et tous les autres cations, responsables des interactions ferromagnétiques, en positions octaédriques « [..] ». Les cations CoIII, de configuration bas-spin (S = 0) et non-magnétique, sont substitués par le Bi, également non-magnétique, ce qui résulte en un moment effectif μeff de 8.2µB, presque invariant avec la substitution du Co par le Bi. / Structural and magnetic properties of Co2MnO4, an inverse spinel structure with spatial group Fd3m and cubic symmetry, were investigated by X-Ray Diffraction (DRX) and using a SQUID magnetometer. Co2MnO4 is a multiferroic compound presenting electrical and magnetic properties due to the presence of the Co and Mn elements, which are distributed on tetrahedral and octahedral sites of the AB2O4 structure. Valence fluctuations of Co and Mn (Co2+/Co3+ and Mn2+/Mn3+/Mn4+) can easily occur and depend on the synthesis procedures and thermal processes, which can change the oxidation states of the metallic cations. In this work, samples of BixCo2-xMnO4 (0.0 ≤ x ≤ 0.3) were synthesized, partially replacing Co by Bi, a non magnetic element. A soft chemical route, the modified polymeric precursors method (MPPM) was used. All samples were heat-treated in similar conditions, under a temperature of 1100 ºC (24h). DRX results, associated with Rietveld refinements, showed crystalline materials with similar crystallographic data. The cell parameter of the cubic structure increased with the Bi content. SEM images showed that Bi presence altered the grains sizes (~1 - 10 µm). A spurious phase, rich in Bi, was formed due to both the solubility limit of Bi and the ionic radii of Co (0,65Å) and Bi (1,17Å). In order to solve these questions, synthesis of a new solid solution, the CoxBi2-xMnO4 (0.0 ≤ x ≤ 1.7), by the MPPM route was attempted. In parallel, a novel elaboration method, the mechanochemical route (MS), was used to synthesize the BixCo2-xMnO4 (0.0 ≤ x ≤ 0.3) series. The magnetic results, MxT (Zero‑Field–Cooled / Field–Cooled) cycles, 1/χ-versus-T curves and MxH hysteresis loops, revealed important information about the magnetic nature and oxidation states of the Co and Mn cations. The ferrimagnetic behavior of Co2MnO4 was preserved, with the ZFC/FC curves exhibiting well-defined magnetic transitions and strong irreversibility below TC. Several magnetic parameters, such as TC, Tmax, MFC (extrapolation of the FC curve to T=0), the coercive field HC and MS (saturation magnetization to H= 50 kOe) changed significantly with the Bi content. According to the structural and magnetic results, a charge balance is proposed, (Co2+)[Co2+x(Bi3+,CoIII)1-xMn3+1-xMn4+x]O4, where Co2+ occupies the tetrahedral positions “(  )” and is responsible of the antiferromagnetic interactions, all others cations occupying the octahedral sites “[  ]” and are responsible of ferromagnetism. The CoIII cations at the octahedral sites are on a low-spin non-magnetic configuration (S = 0) and they are partially substituted by Bi, also a non-magnetic ion, resulting on an effective moment μeff  ~ 8,2 µB, with no change as a function of the Bi content. / As propriedades estruturais e magnéticas do composto Co2MnO4, uma estrutura espinélio inversa de grupo espacial Fd3m e simetria cúbica, foram investigadas por difração de raios X e usando um magnetômetro SQUID. Co2MnO4 é um composto multiferróico, exibindo propriedades elétricas e magnéticas devido à presença dos elementos Co e Mn, distribuídos nos sítios tetraédricos e octaédricos da estrutura AB2O4. A flutuação das valências Co2+/Co3+ e Mn2+/Mn3+/Mn4+ podem ocorrer facilmente e estão sujeitas aos processos de síntese e efeitos térmicos, podendo ser associados a estes variações nos estados de oxidação de Co e Mn devido à substituições parciais destes elementos. Neste trabalho foram sintetizadas amostras BixCo2-xMnO4 (0,0 ≤ x ≤ 0,3), sendo o Bi um elemento não magnético. Para tal, uma rota de síntese química, o método MPPM, foi utilizada. Todas as amostras foram submetidas a tratamentos térmicos em condições idênticas, na temperatura de estabilização da fase BixCo2-xMnO4 igual a 1100ºC (24h). Os resultados de DRX e refinamentos de Rietveld mostraram que o método MPPM produziu amostras cristalinas com informações cristalográficas idênticas, exceto no caso do parâmetro de rede que aumentou em dependência ao percentual de Bi. As imagens morfológicas destes materiais mostraram que o Bi alterou a forma e o tamanho dos grãos variando entre (~0,5 – 1,7 µm). Devido ao limite de solubilidade do Bi dentro da rede espinélio e à diferença entre os raios iônicos do Co (0,65Å) e Bi (1,17Å), a formação de uma fase espúria rica em Bi ocorreu. No sentido de solucionar questões como esta, a síntese do sistema CoxBi2-xMnO4 (0,0 ≤ x ≤ 1,7) pela rota MPPM e de BixCo2-xMnO4 (0,0 ≤ x ≤ 0,3) por método de mecanosíntese foram realizadas. Os resultados magnéticos, curvas MxT (Zero Field – Cooled ZFC e Field – Cooled FC); 1/χ versus T e MxH, revelaram informações importantes sobre a disposição dos cátions presentes. O comportamento ferrimagnético de Co2MnO4 foi mantido, com as curvas ZFC e FC mostrando irreversibilidade e transições bem definidas abaixo de TC. No entanto, os valores de TC, Tmáx e MFC (extrapolação da curva FC para T = 0) obtidos por MxT, assim como ΘCW obtidos por 1/χ versus T, e HC e MS (magnetização de saturação para H= 50 kOe) obtidos por MxH sofreram mudanças significativas, as quais foram associadas ao Bi que alterou o ambiente magnético dos materiais. De acordo com os resultados estruturais e magnéticos, um balanço de cargas foi proposto para BixCo2-xMnO4: (Co2+)[Co2+x(Bi3+, CoIII)1-xMn3+1-xMn4+x]O4, sendo os cátions Co2+ nas posições ( ), responsáveis pelas interações AFM e todos os cátions posicionados em [ ] na relação acima, responsáveis pelo caráter FM destes materiais. Os valores de μef = ~ 8,2µB, para todas as amostras BixCo2-xMnO4 (0,0 ≤ x ≤ 0,3), não sofreram alterações. Os cátions CoIII, presentes nos sítios octaédricos, possuem uma configuração de baixo spin (S = 0), o que não implicou em qualquer mudança na soma total dos μef quando da substituição de Co por Bi, uma vez que ambos não são elementos co momentos magnéticos.

Le vaporeformage du méthane (SMR) est encore aujourd’hui la méthode industrielle de synthèse d’hydrogène la plus rentable. L’efficacité globale de ce procédé est cependant limitée par les contraintes techniques intrinsèques au design des unités de production actuelles. Dans un souci constant d’intensification des procédés, des échangeurs-réacteurs intensifiés sont à l’étude chez AIR LIQUIDE. Les progrès dans le domaine des techniques de fabrication additive métallique ont permis d’envisager des unités de production sous formes d’équipements compacts, présentant des canaux millimétriques, qui optimisent les transferts de masse et de chaleur. Pour atteindre des taux de conversion élevés, et ce malgré des temps de contacts réduits, ces structures obligent à développer de nouvelles architectures de catalyseurs. Des phases actives supportées stables et très actives pour la réaction SMR à base de rhodium ont été préparés à partir de supports MgAl2O4 commerciaux. L’étude de l’impact du taux de métal noble, des propriétés des supports, ainsi que des traitements thermiques a permis de comprendre les interactions existantes entre les phases actives et les supports oxydes. Les propriétés catalytiques en condition de reformage ont pu être reliées aux morphologies des phases actives synthétisées. La fonctionnalisation des canaux des échangeurs-réacteurs millistructurés par une méthode proche du dip-coating est détaillée dans cette thèse. Des formulations de suspensions adaptées, aux comportements rhéologiques maîtrisés, ont permis avec des protocoles de dépôt adéquats, de rendre fonctionnel des échangeurs-réacteurs de taille semi-industrielle qui ont été testés avec succès durant plusieurs centaines d’heures. / The Steam Methane Reforming (SMR) process is still today the most profitable industrial synthesis process of hydrogen. The efficiency of this technique is however facing intrinsically technical limitations due to the design of production units. In order to intensify the global process, exchangers-reactors are under investigation at AIR LIQUIDE. Thanks to recent progresses in metallic additive manufacturing, new compact equipment can be designed. Structures made of millimetric channels allow optimizing heat and mass transfers. New catalyst architecture design needs to be developed to reach high conversion rates despite extreme low contact times in such devices. Stable and highly active rhodium-based catalysts supported on spinel MgAl2O4 have been prepared in this aim. The impact of rhodium loading, properties of supports, as well as thermal treatments have allowed us understanding active phase and support interactions. Catalyst properties under SMR conditions have been linked to active phase morphologies. Functionalization of exchangers-reactors channels through a dip-coating technique has been detailed in this thesis. The formulations of suspensions of washcoat have been optimized thanks to rheological behavior characterizations to achieve very low viscosities. A procedure to deposit homogeneous coatings with controlled thicknesses on the internal channels has been validated on a pilot structure. These new intensified exchangers-reactors have been successfully tested for methane conversion during several hundred of hours.

Made available in DSpace on 2014-12-17T15:41:43Z (GMT). No. of bitstreams: 1 AlyssonEGM.pdf: 4274696 bytes, checksum: 0f940193275b15ce59b4b1f45e3dc11c (MD5) Previous issue date: 2008-09-24 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / Were synthesized different ferrites NixZn1-xFe2O4 (0,4 ≤ x ≤ 0,6) compositions by using citrate precursor method. Initially, the precursors citrates of iron, nickel and zinc were mixed and homogenized. The stoichiometric compositions were calcined at 350?C without atmosphere control and the calcined powders were pressed in pellets and toroids. The pressed material was sintered from 1100? up to 1200?C in argon atmosphere. The calcined powders were characterized by XRD, TGA/DTG, FTIR, SEM and vibrating sample magnetometer (VSM). All sintered samples were characterized using XRD, SEM, VSM and measurements of magnetic permeability and loss factor were obtained. It was formed pure ferromagnetic phase at all used temperatures. The Rietveld analyses allowed to calculate the cations level occupation and the crystallite size. The analyses obtained nanometric crystals (12-20 nm) to the calcined powder. By SEM, the sintered samples shows grains sizes from 1 to 10 μm. Sintered densities (ρ) were measured by the Archimedes method and with increasing Zn content, the bulk density decrease. The better magnetization results (105-110 emu/g) were obtained for x=0,6 at all sintering temperatures. The hysteresis shows characteristics of soft magnetic material. Two magnetization processes were considered, superparamagnetism at low temperature and the magnetic domains formation at high temperatures. The sintered toroids presents relative magnetic permeability (μr) from 7 to 32 and loss factor (tanδ) of about 1. The frequency response of toroids range from 0,3 kHz to 0,2 GHz. The composition x=0,5 presents both greater μr and tanδ values and x=0,6 the most broad range of frequency response. Various microstructural factors show influence on the behavior of μr and tanδ, such as: grain size, porosity across grain boundary and inside the grain, grain boundary content and domain walls movement during the process of magnetization at high frequency studies (0,3kKz 0,2 GHz) / Foram sintetizadas diferentes composi??es da ferrita Ni1-xZnxFe2O4 com 0,4 ≤ x ≤ 0,6 pelo uso do m?todo dos citratos precursores. Para se obter a fase estequiom?trica do sistema Ni1-xZnxFe2O4 foram misturados e homogeneizados os citratos precursores de ferro, n?quel e zinco. As composi??es estequiom?tricas foram calcinadas em atmosfera ambiente na temperatura de 350?C e depois prensadas em pastilhas e tor?ides. As amostras prensadas foram sinterizadas nas temperaturas de 1100?, 1150? e 1200?C em atmosfera de arg?nio. Os p?s calcinados foram caracterizados por DRX, TGA/DTG, FTIR, MEV e magnetometria de amostra vibrante (MAV) e as amostras sinterizadas por DRX, MEV, MAV, massa espec?fica e medidas de permeabilidade e perdas magn?ticas. Observou-se a forma??o de fase pura ferrimagn?tica em todas as temperaturas aplicadas. A an?lise pelo m?todo de Rietveld calculou o n?vel de ocupa??o dos c?tions e o tamanho de cristalito. Foram obtidos tamanhos de cristais nanom?tricos, de 12 a 20 nm para os p?s calcinados. Por MEV, as amostras sinterizadas apresentam tamanhos de gr?os na faixa de 1 a 10 μm. A massa espec?fica (ρ) do material sinterizado apresenta uma tend?ncia de diminui??o com a adi??o de Zn. Os melhores resultados de magnetiza??o foram obtidos para x=0,6 nas tr?s temperaturas de sinteriza??o, variando de 105 a 110 emu/g. As histereses mostram um perfil de materiais magn?ticos moles. Dois processos de magnetiza??o foram considerados, o superparamagnetismo a baixa temperatura (350?C) e a forma??o de dom?nios magn?ticos em altas temperaturas. Os materiais sinterizados apresentam permeabilidade (μ) de algumas unidades, de 7 a 30, e perdas magn?ticas (tanδ) por volta de 1. A resposta em freq??ncia dos n?cleos toroidais est? na faixa de 0,3 kHz a 0,2 GHz. Os maiores valores de μ e tanδ s?o para x=0,5 e a maior faixa de resposta em freq??ncia ? para x=0,6. V?rios fatores da microestrutura contribuem para o comportamento das grandezas μ e tanδ, tais como: os tamanhos dos gr?os, porosidade inter e intragranular, quantidade de contornos de gr?os e os aspectos da din?mica das paredes de dom?nios quando excitadas magneticamente sob alta freq??ncia