Afin de remplacer les électrodes de carbone consommables dans le procédé d'électrolyse Hall-Héroult, le développement d'anodes inertes résistantes à l'oxydation est un défi technique pour les principaux leaders de la production d'aluminium. Certaines recherches actuelles se focalisent sur des cermets prometteurs et originaux constitués d'une matrice céramique biphasée et de particules métalliques dispersées, ayant une conductivité électrique et une résistance à la corrosion suffisantes à haute température. Jusqu'à présent, les études n'ont pas réellement pris en compte l'aspect thermomécanique qui est d'une importance primordiale pour les céramiques, en raison de leur comportement fragile et de leur sensibilité aux chocs thermiques. Supervisé par le groupe Rio Tinto Alcan et son Centre de recherche de Voreppe, le travail de thèse est axé sur le développement d'outils numériques intégrant le comportement mécanique du matériau pour le calcul des probabilités de rupture d'anodes. Le travail se base sur une étude expérimentale des propriétés mécaniques de la température ambiante à la température de l'électrolyse : paramètres statistiques de Weibull, module d'élasticité, conductivité thermique, coefficient de dilatation thermique, résistance au fluage... Les calculs par éléments finis tiennent également compte de l'oxydation progressive du matériau et des chargements thermomécaniques induits par l'environnement.

Cette étude est dédiée au développement d'une anode pour une pile à combustible SOFC monochambre. Ce dispositif ne présente pas de séparation physique entre les compartiments anodique et cathodique, contrairement à une pile conventionnelle. Un mélange contenant de l'oxygène et un hydrocarbure est directement injecté sur l'ensemble du dispositif comprenant électrolyte, anode et cathode. La cathode doit être sélective à la réduction de l'oxygène et l'anode à l'oxydation de l'hydrocarbure. Ce dispositif permet donc de s'affranchir des problèmes d'étanchéité des dispositifs conventionnels mais les matériaux d'électrode doivent répondre à des critères catalytiques restrictifs. L'étude a été réalisée avec une anode de type cermet composée de nickel et d'oxyde de cérium gadolinié (CGO). L'hydrocarbure choisi est le propane. L'objectif du travail est de comprendre les phénomènes physico-chimiques se produisant à l'anode afin d'optimiser les conditions de fonctionnement de la pile monochambre, sous mélange O2 / C3H8. Pour cela, les propriétés catalytiques des poudres de nickel et de CGO ont été déterminées en fonction de la température et du rapport O2 / C3H8. Après avoir optimisé les paramètres de préparation des anodes par sérigraphie sur électrolyte support (CGO), des mesures de conductivité électrique par méthode Van der Pauw ont été réalisées également sous différents mélanges O2 / C3H8 en fonction de la température. La confrontation des résultats (propriétés catalytiques et électriques) a permis de mettre en évidence l'existence d'une température limite de fonctionnement, qui dépend du rapport O2 / C3H8. En-dessous de cette température limite, le nickel s'oxyde et l'anode catalyse principalement l'oxydation totale du propane. Au-dessus de cette température limite, le nickel reste sous la forme métallique et catalyse préférentiellement l'oxydation partielle du propane. Ces résultats sont également corroborés à des calculs thermodynamiques, qui mettent en évidence que la réaction préférentielle à basse température est l'oxydation du nickel. Des phénomènes d'oscillations de la conductivité électrique et de la température ont permis de proposer un mécanisme réactionnel basé sur le dépôt et l'oxydation de carbone. Enfin, des dispositifs complets monochambre ont été élaborés en utilisant une cathode BSCF (Ba0,5Sr0.5Co0,8Fe0,2O3) et testés.

Recent nuclear proliferation concerns and disarmament agreements have encouraged the U.S. to decrease the excess amount of weapons-grade and reactor-grade plutonium. Continued use of nuclear power without a permanent solution for waste disposition has also led to the need for a reliable method by which the waste products, specifically plutonium, can be utilized or destroyed. One possible solution to plutonium destruction is achieved by manufacturing it into small microspheres and embedding it within an inert metal matrix, then placing it inside a conventional nuclear reactor. This process would burn some of the plutonium while producing electricity. PuO2Zr dispersion fuel has been proposed for such a purpose. Prior to its use, however, this non-fertile metal matrix dispersion fuel must be shown to be mechanically stable in the reactor environment. The internal mechanical interactions of dispersion fuel were modeled using finite element analysis. The results were used to assess the stability of PuO2Zr dispersion fuel inside a reactor. Several parameters, including fuel particle size, volumetric loading, temperature, and burnup, were varied to determine the maximum amount of plutonium that can be burned while maintaining fuel integrity. Earlier experiments using UO2 stainless steel dispersion fuels were used to validate the model and establish a failure criterion. The validated model was then used to determine the parameter space over which PuO2Zr dispersion fuel can be successfully used. These results show that PuO2Zr dispersion fuel is robust and may offer a reliable method for plutonium disposal in current reactors.

Low cost silicates with apatite-structure (general formula of apatite A10-xM6O26±δ, where A = rare earth or alkaline earth and M= Si, Ge, P, V..) have been proposed recently as promising solid electrolyte materials (oxygen ion conductors) for use at intermediate temperature solid oxide fuel cells (SOFCs). These materials exhibit sufficiently high ionic conductivity (e.g. ~ 0.01 S cm-1 at 700 oC), which is dominated by the interstitial site mechanism and can exceed that of yttria-stabilized-zirconia (YSZ), the solid electrolyte used in state-of-the-art SOFCs. The apatite structure is tolerant to extensive aliovalent doping, which has been applied for improving ionic conductivity. In this work are presented results concerning synthesis, conductivity and catalytic characterization of Fe- and/or Al-doped apatite type lanthanum silicates (ATLS) of the general formula La10-zSi6-x-yAlxFeyO26±δ as well as electrochemical characterization of interfaces of ATLS pellets with perovskite and Ni-based electrodes. The aim was to investigate the properties of these ATLS material, in particular as it concerns their potential use as SOFC components or as catalysts in oxidation reactions. The conductivity of pellets prepared from ATLS powders synthesized via four different methods and having different grain size was measured under air and at different temperatures in the range 600 -850 oC, aiming to identification of the effect of composition (doping), method of synthesis, grain size and pellet sintering conditions. For electrolytes of the same composition, those prepared via mechanochemical activation exhibited the highest conductivity, which was improved with increasing Al- and decreasing Fe-content. In state-of-the-art SOFCs perovskite electrodes are used as cathodes and Ni-based electrodes as anodes, thus electrochemical characterization of perovskite and Ni-based/ATLS interfaces was carried out. As it concerns perovskite/ATLS interfaces, the characterization focused on the study of the open circuit AC impedance characteristics of a La0.8Sr0.2Ni0.4Fe0.6O3-δ/La9.83Si5Al0.75Fe0.25O26±δ interface, at temperatures 600 to 800 oC and oxygen partial pressures ranging from 0.1 to 20 kPa. Under the aforementioned conditions, it was observed that the impedance characteristics of the interface were determined by at least two different processes, corresponding to two partially overlapping depressed arcs in the Nyquist plots. The polarization conductance of the interface was found to increase with increasing temperature as well as with increasing oxygen partial pressure, following a power law dependence. The electrochemical characterization of Ni-based electrodes/ATLS interfaces involved study of the electrochemical characteristics of NiO-apatite cermet electrodes as well as a Ni sputtered electrode interfaced with Al- or Fe-doped apatite electrolytes, under hydrogen atmospheres. The impedance characteristics of these electrodes were found to be determined by up to three different processes, their relative contribution depending on the electrode microstructure, Ni content (as it concerns the cermet electrodes), temperature, hydrogen partial pressure and applied overpotential. Aiming to investigation of potential catalytic properties of ATLS materials the catalytic activity for CO combustion of a series of ATLS powders was studied. For this purpose, two series of apatite-type lanthanum silicates La10-xSi6-y-zAlyFezO27-3x/2-(y+z)/2 (ATLS), undoped or doped with Al and/or Fe, were synthesized via sol-gel and modified dry sol-gel methods and tested as catalysts for CO combustion. The experiments revealed that the ATLS powders were catalytically active for CO combustion above approximately 300 oC, with light-off temperatures T50 (50% conversion of CO) ranging from 505 to 629 oC. The study focused on the effect on catalytic activity of the synthesis method and doping with Al and/or Fe. Non-doped ATLS with stoichiometric structure, namely La10Si6O27 prepared via the sol-gel method, exhibited the highest catalytic activity for CO oxidation among all tested compositions, the comparison being based on the measured catalytic rate (expressed per surface area of the catalyst) under practically differential conditions. Compared to La-Sr-Mn-O and La-Sr-Co-Fe-O perovskite powders, the tested ATLS powders exhibited lower catalytic activity for CO oxidation. / -

Submitted by Automa??o e Estat?stica (sst@bczm.ufrn.br) on 2017-03-20T19:29:07Z No. of bitstreams: 1 WendelAndersonDantasTeixeira_DISSERT.pdf: 3957759 bytes, checksum: cc4a46d4569b9607cedd8a5a5758b525 (MD5) / Approved for entry into archive by Arlan Eloi Leite Silva (eloihistoriador@yahoo.com.br) on 2017-03-21T22:40:07Z (GMT) No. of bitstreams: 1 WendelAndersonDantasTeixeira_DISSERT.pdf: 3957759 bytes, checksum: cc4a46d4569b9607cedd8a5a5758b525 (MD5) / Made available in DSpace on 2017-03-21T22:40:07Z (GMT). No. of bitstreams: 1 WendelAndersonDantasTeixeira_DISSERT.pdf: 3957759 bytes, checksum: cc4a46d4569b9607cedd8a5a5758b525 (MD5) Previous issue date: 2016-11-30 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES) / Interfaces Metal-WC-Co est?o presentes em opera??es de perfura??o de po?os de petr?leo, onde se utilizam brocas tric?nicas de insertos cer?micos duros. A a??o combinada de corte, esmagamento e desagrega??o de rochas causa a degrada??o das brocas de perfura??o. A degrada??o est? relacionada com o desgaste, fratura total ou parcial do corpo da broca ou dos insertos, choque t?rmico e corros?o. Tamb?m o deficiente encaixe mec?nico dos insertos cer?micos nos cones da broca pode originar o seu destacamento provocando uma s?rie de danos ? broca. O aprimoramento no processo de produ??o de interfaces metal-cer?mica pode eliminar ou minimizar algumas das falhas acima mencionadas nas brocas tric?nicas, otimizando o seu tempo de vida ?til, e portanto, reduzindo o custo m?trico de perfura??o. A brasagem ? uma t?cnica extensivamente utilizada para uni?o de metais e cer?micos, podendo ser uma excelente alternativa ao processo comum de encaixe mec?nico de ?pressfitting? dos insertos cer?micos no corpo de a?o da broca. A metaliza??o das superf?cies WC-Co ? utilizada para melhorar a molhabilidade e ades?o de sistemas M/C. Neste trabalho, pretendeu-se avaliar o efeito da temperatura de brasagem em uni?es de insertos WC-6Co com a?o H13 utilizando ligas de adi??o com base no eut?tico 72Ag28Cu, em um forno com uma condi??o de alto v?cuo. A caracteriza??o mec?nica, microestrutural e morfol?gica das uni?es geradas foi avaliada em ensaios de flex?o de 3 pontos, MEV-EDS e DRX. Os melhores resultados de resist?ncia mec?nica foram encontrados para os sistemas brasados a 880?C com liga de adi??o eut?tica AgCu. / Metal-WC-Co interfaces are present in oil well drilling operations, where tricone drill bits with hard ceramic inserts play an important role. The combination of cutting, crushing and breaking up of rocks results in the degradation of tricone drill bits by wear, total or partial rupture of the drill bit body or the ceramic inserts, thermal shock and corrosion. In addition, the improper pressfitting of the ceramic inserts on the bit body may cause its total detachment, and promote serious damages to the drill bit. The improvement on the production process of metal-ceramic interfaces can eliminate or minimize some of above-mentioned failures presented in tricone drill bits, optimizing their lifetime and so reducing drilling metric cost. Brazing is a widely established technique to join metal-ceramic materials, and may be an excellent alternative to the common mechanical press fitting process of hard ceramic inserts on the steel bit body for tricone drill bit. The metallization of WC-Co surfaces is used to improve the wetting and adhesion of the M/C system, when a liquid phase is present during the brazing process. In this work, the effect of brazing temperature was studied on WC-6Co and H13 steel couples, using 72Ag28Cu eutectic based brazing alloys inside a furnace under high vacuum. Mechanical and microstructure caracterization of the interfaces produced was analysed by 3 point flexural tests, SEM-EDX and XRD techinques.d, and the interfaces produced were analysed by SEM-EDX. Better results for mechanical strenght were found for the systems brazed at 880?C using AgCu eutectic braze alloy.

Due to climate changes and an increasing global temperature, the maritime transport sector has taken upon a mission to reduce their share of greenhouse gas emissions by 50% until 2050. Combustion engines used in ships mainly run on carbon-based fuels, but to achieve the reduction of emissions it is crucial to investigate the possibility of alternative fuels. Ammonia is an alternative fuel with a carbon free chemical composition that shows big potential, with several initiatives to put ammonia driven ship engines on the market in the near future. For ships to be able to run on ammonia fuel, the engine materials have to withstand the corrosive effect of ammonia whilst still ensuring that the motor runs properly. In this study, two piston ring materials are investigated with regards to long-term effects of exposure to ammonia solution. The piston ring materials investigated were comprised of a cast iron substrate covered with either a chromium ceramic coating or a with a cermet coating, the latter also coated with an aluminium-bronze based running in layer on top. The materials were submerged in 25% ammonia solution for different time intervals up to 12 weeks, with a solution change every fourth week. After exposure to ammonia, the materials were tribologically tested in a reciprocal sliding test rig. The surfaces, both inside and outside of the wear tracks, were analysed with SEM and EDS, as well as with CSI. The chromium ceramic coating did not seem to get affected by, or interact chemically, with the ammonia solution. Exposing the material to ammonia did not seemingly affect the tribological properties. However, two different behaviours were observed when analysing the cermet coated samples with a running-in layer of aluminium-bronze. These samples reacted with the ammonia solution in two different ways, resulting in the series being split into two. In both cases precipitates were formed, but the colour changes of the solutions differed for the series. The coatings were also worn differently, as in one case a flattening effect was observed throughout all time intervals, whereas in the other case the worn volume and track depth seemed to increase with exposure to ammonia solution.

Les cermets, nommés M(p)-CMC(s), « Ceramic Matrix Composite dispersed with Metallic Particles », sont prometteurs dans les applications à haute température. Un cermet modèle (304L-YSZ) constitué de 40 % vol. de particules d'acier inoxydable 304L dispersées dans une matrice de zircone partiellement stabilisée à l’yttrium a été préparé par métallurgie des poudres. Les cermets sont homogènes et possèdent une densité voisine de 97 % par rapport à la densité théorique. Une étude cinétique basée sur l’hypothèse de l’étape limitante, a été réalisée afin de proposer un mécanisme et un modèle d’oxydation du cermet. Dans un premier temps, l’oxydation de la poudre d’acier inoxydable a été étudiée sous oxygène à 800 °C. Les expériences d'oxydation sous He (80 %)-O2 (20 %) ont été conduites par thermogravimétrie. Conformément à la littérature, la cinétique d’oxydation de la poudre suit un régime de diffusion. Une couche d’oxyde à base de chrome à croissance externe est observée.En revanche, la cinétique d’oxydation du cermet modèle est différente de celle de la poudre de 304L. Un fort gain de masse est observé dès l’introduction de l’oxygène au début du palier isotherme. Pendant le palier isobare, la prise de masse est lente et n’est pas régie par la diffusion. La caractérisation des cermets oxydés montre que des nodules riches en chrome apparaissent tout d’abord à l’intérieur du métal. Puis une couche d’oxyde à base de chrome et de fer se forme par croissance externe. La matrice de zircone ne limite pas la diffusion de l’oxygène vers le métal. Elle se fissure sous l’action des contraintes mécaniques induites par le changement de volume des particules de 304L pendant l’oxydation. / Ceramic matrix composite dispersed with metallic particles, called M(p)-CMC(s), are being developed for optimizing several functions of industrial components in severe atmospheres at high temperature.The corrosion of a model M(p)-CMC(s), based on 304L stainless steel and yttrium doped zirconia (304L(p)-ZrO2(s); 40%/60% in volume) is studied and compared with the oxidation behaviour of the stainless steel powders. The oxidation behaviour of the model 304L(p)-ZrO2(s) composite produced by powder metallurgy, studied by means of the thermogravimetry under 20 % O2 in helium at 800 °C, is presented. Oxidation curves show a fast increase in mass gain followed by slow one for the composite material. SEM observations and Auger spectroscopy measurements of the oxidized composite indicate an outward complex Cr and Fe rich oxide layer whereas Cr2O3 nodules are observed to nucleate and develop inward. For 304L stainless steel powder, the shape of the mass gain curve is parabolic, in agreement with a diffusion controlled oxidation. SEM observations of oxidised powder and in situ XRD measurements at 800 °C under oxygen show an external growth of Cr2O3 oxide layer.The low resistance to oxidation of the composite (compared to the powder) in the initial period seems to be due to the properties of the zirconia/metallic particles interface obtained after the sintering process. Under reducing conditions, the initial Cr2O3 layer reacts with zirconia matrix. TEM observation of the “as sintered” interface between the metallic particles and the ceramic shows no chromia layer. Sudden changes in oxygen partial pressure during experiments reveal an accelerating effect of the oxygen pressure.

Ce travail marque le départ d'une nouvelle thématique au sein du laboratoire dans le domaine des piles à combustible à oxydes solides planaires. Fort de son expérience dans le domaine des capteurs, l'objectif a été de réaliser des prototypes avec des technologies "bas coûts" comme la sérigraphie à partir de matériaux classiques pour les piles, plutôt que de rechercher des nouveaux matériaux avec des propriétés optimales, mais qui peuvent être amoindries lors de la réalisation d'un dispositif complet. Ces matériaux sont la zircone yttriée (YSZ) pour l'électrolyte, un manganite de lanthane dopé au strontium (LSM) pour la cathode et d'un cermet à base d'oxyde de nickel et de zircone yttriée (Nio-YSZ) pour l'anode.<br />la première partie des travaux a consisté à caractériser les propriétés physico-chimiques et électriques des matériaux choisis, sur des frittés d'abord et ensuite sur des couches sérigraphiées de YSZ, LSM ou NiO-YSZ. Ces caractérisations ont montré une bonne adaptabilité de nos matériaux pour une application pile à combustible.<br />La seconde partie a consisté à tester les prototypes réalisés sur l'électrolyte support, et sur anode support avec les électrodes et l'électrolyte déposé par sérigraphie. Les faibles performances obtenues sont surtout dues à la faible température de fonctionnement (800°C), à l'épaisseur de l'électrolyte support (environ 1mm)ou à la porosité des couches de YSZ par sérigraphie. Enfin, nous avons en même temps testé un dispositif original qui consiste à exposer les deux électrodes à un mélange de combustible et du comburant. Ce dispositif mono-chambre prometteur inspiré de l'expérience des capteurs potentiométriques développés au laboratoire par Nicolas Guillet (2001), permet de s'affranchir des problèmes d'étanchéité des deux compartiments gazeux. De plus, les performances obtenues ne sont que deux fois moindres par rapport à celles obtenues avec une pile conventionnelel à deux chambres gazeuses.

<p>The aim of this thesis is to investigate how material surfaces are affected by various surface treatments and how this relates to the adhesion of the coating. The materials that were studied were WC-Co and Cermets and the surface treatments used were polishing, grinding with coarser and finer abrasive grains, and finally wet blasting and dry blasting. Focus was on deformations and residual stresses in the surface, surface roughness and cracks. The test methods used for examining the samples included surface roughness measurements, residual stress measurements, adhesion tests using Rockwell indentation and SEM images of the surface and the cross section.<br /><br />The results concluded that polishing gives very good adhesion. Additionally, the adhesion for ground surfaces was good for WC-Co but very poor for Cermets. Furthermore, it was observed that finer abrasive grains did not result in better adhesion. In fact, the coarser grains gave slightly better results. Finally, it was concluded that wet blasting has a clear advantage over dry blasting and results in much better adhesion, especially for the Cermets. The results for the WC-Co were a bit inconsistent and so further research is required.</p>

The aim of this thesis is to investigate how material surfaces are affected by various surface treatments and how this relates to the adhesion of the coating. The materials that were studied were WC-Co and Cermets and the surface treatments used were polishing, grinding with coarser and finer abrasive grains, and finally wet blasting and dry blasting. Focus was on deformations and residual stresses in the surface, surface roughness and cracks. The test methods used for examining the samples included surface roughness measurements, residual stress measurements, adhesion tests using Rockwell indentation and SEM images of the surface and the cross section.<br /><br />The results concluded that polishing gives very good adhesion. Additionally, the adhesion for ground surfaces was good for WC-Co but very poor for Cermets. Furthermore, it was observed that finer abrasive grains did not result in better adhesion. In fact, the coarser grains gave slightly better results. Finally, it was concluded that wet blasting has a clear advantage over dry blasting and results in much better adhesion, especially for the Cermets. The results for the WC-Co were a bit inconsistent and so further research is required.