Fuel for nuclear reactors with an increased thermal conductivity offers the potential for lower fuel operating temperatures and reduced fission gas release rates. Uranium dioxide (UO2) based composites offer a method of achieving a higher thermal conductivity. Silicon carbide (SiC) and molybdenum (Mo) have been identified as potential candidates for use in a composite fuel material. Uranium dioxide composites were manufactured with the inclusion of whiskers and granules of SiC up to a 30 vol% loading. The manufacturing route used was based on the current process employed to commercially manufacture UO2 fuel, by reductive sintering. Composites containing Mo were manufactured via spark plasma sintering and included loadings of up to 10 vol% Mo. The composites were characterised on their microstructural properties and where appropriate the thermal conductivity was determined by laser flash analysis. The composites containing SiC achieved low densities, 95%TD. The microstructure contained channel like structures of Mo, due to the use of an agglomerated UO2 precursor powder. An increased thermal conductivity was determined for the molybdenum composites. At the maximum measurement temperature of 800°C the increase was found to be 68% in the 10 vol% composites compared to UO2.

Dans le domaine des piles SOFC, un des principaux objectifs actuels est la réduction de latempérature de fonctionnement des cellules en deçà de 700°C, afin de garantir une plusgrande durabilité des systèmes électrochimiques et des matériaux de cellules. En outre, leprocédé d’élaboration d’une cellule complète comprend actuellement deux voire trois étapesde frittage; une seule opération de frittage pourrait conduire à une diminution conséquente ducoût de production de la cellule. Le but de ce travail de thèse est d’apporter une contribution àces deux problématiques en proposant un procédé d’élaboration d’une cellule de pile àcombustible SOFC en une seule opération dite de cofrittage et avec une sélection dematériaux à hautes performances électrochimiques.Cette thèse a été abordée selon trois thématiques principales : mécanique, microstructurale etélectrochimique.Après la caractérisation du comportement en frittage des matériaux retenus pour l’étude, uncycle de frittage conduisant à une microstructure d’électrolyte acceptable (porosité fermée) aété sélectionné. Le cofrittage a ensuite été étudié selon un aspect mécanique. Les phénomènesde courbure engendrés par le cofrittage ont été expliquées à l’aide d’une modélisationanalytique et confrontées à des observations in situ. Le travail s’est ensuite orienté dans uneapproche microstructurale avec l’optimisation de la microstructure de la cathode en utilisantune modélisation numérique basée sur la méthode des éléments discrets. Les composants de lacellule complète ont finalement été caractérisés par spectroscopie d’impédanceélectrochimique afin d’optimiser leurs performances. Enfin, une cellule complète exempt defissure a été réalisée par cofrittage et ses performances électrochimiques ont été estimées. / In the field of SOFCs, a major objective is the reduction of the cell operating temperaturebelow 700°C, in order to ensure greater durability of electrochemical systems and cellmaterials. In addition, the fabrication process of a complete cell currently includes two orthree stages of sintering. Thus one sintering process could lead to a consequent decrease in theproduction cost of the cell. The purpose of this thesis is to contribute to these two issues byproposing a method for manufacturing a SOFC fuel cell in a single operation called cofiringand with a selection of high electrochemical performance materials.This thesis is addressed in three main areas: mechanical, microstructural and electrochemical.After sintering behavior characterization of the selected materials, a sintering cycle leading toan acceptable electrolyte microstructure (closed porosity) was selected. The cofiring was thenapproached by a mechanical aspect. The curvature Phenomena caused by of cofiring wereexplained using an analytical model and compared with in situ observations. The work is thencontinued with a microstructural approach. The optimization of the cathode microstructurewas done using a numerical modeling based on the discrete element method. Cell componentswere finally characterized by electrochemical impedance spectroscopy to optimize theirperformances. Finally, a free crack complete cell was obtained by co-sintering process and herelectrochemical performance was estimated.

No presente trabalho, peças com gradiente funcional de Al2O3 com reforço de NbC foram planejadas com o intuito de obter um MGF (material com gradiente funcional) com uma alta dureza e boa tenacidade à fratura a partir de diferentes técnicas de sinterização. Os MGFs apresentam-se como uma excelente alternativa quando é necessária a união de materiais com propriedades térmicas ou mecânicas muito diferentes, já que possuem uma transição suave de propriedades ao longo do corpo, como consequência de uma mudança gradual do teor das fases. No planejamento dos MGFs foram utilizadas análises dilatométricas para compatibilizar o comportamento durante a sinterização de cada camada e assim minimizar as tensões que ocorrem durante a retração, responsáveis por trincas e delaminações. Nos ensaios de dilatometria observou-se que a diferença máxima de retração entre os compósitos de teor de NbC variando de 5 a 30 %p é de 4,85%, assim, foram projetados MGFs com um passo de 5% de NbC, reduzindo esta diferença para 2,73%. Compósitos monolíticos de Al2O3 com diferentes teores de NbC foram sinterizadas a 1500ºC num forno convencional sob atmosfera de grafite. As densidades das peças sinterizadas foram inferiores a 90% da densidade teórica (DT), o que comprometeu a dureza dos compósitos (10 a 14 GPa), inferiores que as durezas dos materiais originais. Uma das maiores dificuldades no processamento destes compósitos foi sua densificação, prejudicada devido à presença de partículas de alta refratariedade na matriz de alumina, pelo que foi realizado um estudo do efeito da nióbia (Nb2O5) como auxiliar de sinterização nos compósitos Al2O3-NbC. Utilizando 0,5 %mol deste aditivo foi possível melhorar as densidades dos compósitos que, segundo os resultados da microscopia eletrônica de varredura (MEV), devido a uma densificação em presença de fase líquida. No entanto, a melhora na densidade é efetiva para temperaturas inferiores a 1450°C devido provavelmente à sobrequeima. Devido às dificuldades para obter peças densas a partir desses compósitos, foi utilizado o processo de Spark Plasma Sintering (SPS), o qual foi bem sucedido para obter peças com gradiente funcional com boa densidade (> 98 %TD) e livres de trincas. O gradiente projetado foi mantido com sucesso após a sinterização e, graças à alta densidade das peças, foi possível atingir altas durezas (até 24,3 GPa) e tenacidade à fratura ~5 MPa.m1/2, fazendo com que estes materiais apresentem potencial de aplicação como ferramentas de corte. / In the present work, Al2O3/ NbC graded composites were designed in order to obtain a FGM with a high hardness and good fracture toughness from different sintering techniques. Functionally graded materials (FGM) present enormous potential on matching materials that have different mechanical and thermal properties via a gradual transition throughout the body, as a consequence of a gradual transition of the phase content. For designing of FGMs, a dilatometric analysis was used for matching the sintering behavior of each layer in order to minimize the thermal strains occurring during shrinkage and that are responsible for cracking and delamination. It was observed that the maximum difference in shrinkage between these composites is 4.85%, which could be reduced to 2.73% if a FGM with step of 5% NbC is produced. Monolithic composites of Al2O3 with different amounts of NbC were sintered at 1500°C in a conventional oven under an atmosphere of graphite, the density of the sintered pieces were less than 90 %TD, compromising the hardness of the composites (10 to 14 GPa) that were lower than the hardness of the original materials. Due to the fact that one of the greatest difficulties in processing these composites is a densification, which is impaired due to the presence of high refractory particles in the alumina matrix, a study of the effect of the niobia (Nb2O5) as a sintering aid in the composite Al2O3-NbC was conducted, with addition of 0.5 mol% was possible to improve the density of the composites, due to the liquid state sintering according to the SEM results. However, this effect is only effective until a temperature of 1450°C probably due to the overfiring. In order to obtain dense bodies from these composites, Spark plasma sintering (SPS) was used. This process was successful for producing functional graded bodies with good density (> 98% TD) and crack free. The designed gradient was successfully maintained after sintering and due to the high density of FGMs, it was possible to attain high hardness (up to 24.3 GPa) and a fracture toughness of ~ 5 MPa.m1/2, showing that these materials have a good potential application as cutting tools.

Les propriétés idéales d’un matériau de blindage sont la combinaison d’une extrême dureté pour casserles noyaux des projectiles et d’une grande ductilité pour résister à l’impact et arrêter les fragments du projectile. Or cettecombinaison de propriétés est incompatible avec un matériau unique. Pour pallier ce problème, les concepteurs de blindageassocient un matériau dur (céramique) à un matériau ductile (métal). Une autre solution serait de réaliser un matériauprésentant un gradient de propriétés mécaniques : dans le cas présent, d’une très grande dureté de la face avant à une grandeductilité de la face arrière. Les technologies non conventionnelles de frittage telles que le Spark Plasma Sintering (SPS)permettent d’assembler ou de fritter/assembler des matériaux aux caractéristiques aussi différentes et complémentaires. Ils’agit donc d’étudier les conditions d’assemblage ou de cofrittage de tels matériaux (dans le cas présent, Al2O3 et Ti) ainsique l’influence de la microstructure résultante de l’ensemble sur sa performance balistique.La première partie de ce travail a porté sur la caractérisation de l’alumine et du titane. Cinq poudres d’alumines ontété étudiées d’un point de vue comportement au frittage. Trois d’entre elles sont retenues en raison de leurs microstructuresintéressantes, proches en termes de densité et de taille de grains. Ces alumines ont été caractérisées mécaniquement (dureté,ténacité, résistance à la rupture) et balistiquement pour n’en garder qu’une dans la deuxième partie du travail. Le titane, frittédans les mêmes conditions que l’alumine, a montré qu’il n’avait malheureusement pas les propriétés attendues (absence deductilité).La seconde partie du travail a montré que l’obtention de MGFs sains à partir de Al2O3 et Ti uniquement est délicate,que ce soit avec un intercalaire sous forme de monocouche ou de multicouche. La forte affinité du titane avec l’oxygène(formation d’oxyde ou en insertion) et le carbone (formant des carbures), ainsi que sa réactivité avec l’alumine (produisantdes intermétalliques) rend le MGF fragile et incapable d’accommoder les contraintes résiduelles d’élaboration. L’insertiond’une faible proportion de nickel (plus ductile et moins réactif vis-à-vis de l’oxygène que le titane) dans les composites apermis d’obtenir des MGFs sains, dont le comportement balistique a pu être évalué. / The objective is to improve ballistic performance of armors. A perfect armor combines ductility to resistto the impact and high hardness to stop projectile’s fragments. However, such an association of properties is inconsistent witha single material. The solution is to perform a functionally graded material (FGM) with a ductile metal at the back side of thesample and a hard ceramic on the top side. Non-conventional technologies like Spark Plasma Sintering allow joining orsintering all types of materials with different and additional properties. Furthermore, with this technique, high heating ratescan be achieved, limiting grain growth and resulting in a fine microstructure. The goal is to study joining conditions or cosinteringof such materials (in this case, Al2O3 and Ti), as well as the resulting microstructure on the ballistic efficiency.The first part of the study focused on the characterization of alumina and titanium. Five powders of alumina werestudied from a sintering point of view. Three of which were selected because of their interesting microstructures, close indensities and grain sizes. These ceramics have been characterized mechanically (hardness, toughness and strength) andballistically. One of them is adopted to realize FGM. Titanium, sintered with the same conditions, unfortunately, doesn’t haveexpected properties (absence of ductility).The second part of the work showed that the preparation of FGM without cracks from Al2O3 and Ti only ischallenging, with an interlayer with one or more layers. The strong affinity of Ti with oxygen (formation of oxides orinsertion) with C (forming carbides) and its reactivity with alumina (forming intermetallics) make the FGM brittle and enablethe release of residual stresses during the process. By adding a low amount of nickel (more ductile and less reactive withoxygen and titanium) in composites, FGMs almost without cracks were obtained. The latter were evaluated ballistically.

L'utilisation de la thermoélectricité passe par une amélioration du rendement du module thermoélectrique à travers l'optimisation de ses dimensions et l'augmentation du facteur de mérite des matériaux thermoélectriques, mais aussi par une réduction des coûts de synthèse et de mise en forme. Dans le cadre de cette thèse nous nous sommes intéressés à la synthèse de β–Zn4Sb3 nanométrique par une méthode de chimie douce à faible dépense énergétique. Nous avons étudié la mise en forme de ce matériau par des technologies d'impression qui permettent d'atteindre les dimensions optimales et présentent un coût réduit. β-Zn4Sb3 est obtenu en deux étapes : une synthèse à reflux suivie d'un traitement thermique à 400°C sous vide secondaire. La composition chimique (DRX, affinement Rietveld), la morphologie (MEB, TEM) et la stabilité en température (spectroscopie Raman) de la poudre sont étudiées. β-Zn4Sb3 ainsi obtenu est densifié par SPS et ses propriétés thermoélectriques sont mesurées montrant une augmentation du facteur de mérite pour des températures inférieures à 100°C. Au dessus de cette température, la présence de porosité et de zinc augmente la résistivité électrique et la conductivité thermique et les échantillons ont un facteur de mérite de 0,6 à 400°C. Enfin, la poudre est mise en forme par sérigraphie et atomisation sur substrat en verre et en Kapton. Le β-Zn4Sb3 montre une forte résistivité électrique juste après impression mais l'application de traitement mécanique et thermique permet de la diminuer. Le facteur de mérite estimé des dépôts est de 0,06 à 400°C. Cependant le faible coût de mise en forme et la possibilité d'automatisation rendent ces techniques viables. / Use of thermoelectricy involves an increase of the module efficiency. In this purpose we need to optimize the dimension of the module and to increase the figure of merit of thermoelectric materials. But we also need to reduce the synthesis and shaping cost. Within the framework of this thesis, we focused on the synthesis of β-Zn4Sb3 nanoparticles by a low energy technique: wet chemistry. We also studied the shaping of this material by printing technologies. These cost-effective technologies allow reaching optimized dimensions. β-Zn4Sb3 is synthesized in two steps: a reflux synthesis flowed by a thermal treatment at 400 °C under vacuum. Chemical composition (XRD, Rietveld refinement), morphology (SEM, TEM) and thermal stability of the powder are studied. The as product β-Zn4Sb3 is densified by SPS and we measured its properties. They show an increase of the figure of merit for temperatures below 100 °C. However above this temperature the presence of zinc and porosity increase electric resistivity and thermal conductivity, leading to a figure of merit of 0.6 at 400 °C. Finally the powder is shaped by two printing technologies: screenprinting and atomization on glass and Kapton substrate. Just after printing the samples show a high electrical resistivity but a decrease is observed after mechanical and thermal treatment. The estimate figure of merit of printing β-Zn4Sb3 is 0.06 at 400 °C. However the printing techniques are cost-effective and allow mass production, which make them still interesting.

The influence of Two-Step Sintering (TSS) process on the final microstructure of oxide ceramics materials with two different crystal structures was studied. Tetragonal zirconia (stabilized with 3mol%Y2O3, particle size 90nm and 140nm ) and cubic zirconia (8mol%Y2O3, 70nm) powders were cold isostatically pressed and pressure less sintered with different heating schedules. The microstructures achieved with TSS method were compared with microstructures achieved with conventional Single-Step Sintering schedule (SSS). The results showed that the efficiency of the TSS of these oxide ceramics was more dependent on their crystal structure than on their particle size and green body microstructure. The method of TSS brought only negligible improvement of the microstructure of tetragonal zirconia ceramics. On the other hand, TSS was successful in the sintering of cubic zirconia ceramics; it led to a decrease in grain size by a factor of 2.

V předložené diplomové práci bylo studováno slinování hexagonálního Al2O3 a kubického MgAl2O4 pomocí slinovacích cyklů složených z beztlakého předslinutí metodou dvojstupňového slinování s následným doslinutím s využitím tlaku (HIPováním). Cílem bylo pokusit se snížit (při zachování vysoké dosažené hustoty) střední velikost zrn a tím zvýšit tvrdost keramiky popř. optickou transparenci. Hlavní úsilí bylo věnováno optimalizaci předslinutí pomocí různých slinovacích cyklů. Přestože bylo vyzkoušeno velké množství různých kombinací teplot a prodlev dvojstupňového slinování, nepodařilo se výrazným způsobem zvýšit výslednou tvrdost vzorků. V případě kubického MgAl2O4 bylo dosaženo hustot blížících se teoretické hustotě, což se projevilo v optické transparentnosti vzorků.

Aim: The aim of the present study was to evaluate how the material KATANA ™ Zirconia YML is affected in strength depending on two different sintering programs. The evaluation of the strength was made by means of a biaxial flexural strength test.   Material and method: A total of 48 test specimens, 32 specimens were produced by KATANA ™ Zirconia YML and 16 specimen cups that formed the control group, by KATANA ™. Zirconia UTML. The specimens were designed as circular disks and were placed in two different layers in the disk, between Enamel-Body 1 and Body 2-Body 3. The specimens were divided into two subgroups of which 24 specimens were quickly sintered and the remaining (n = 24) specimens were conventionally sintered and the strength was evaluated with a biaxial flexural strength test.   Results: The highest mean value for the biaxial flexural strength test was shown by the test group which was high-speed sintered, with placement in Body 2 - Body 3. This was significant in comparison with other groups (p> 0.001) in addition to conventional sintered with the same placement in the disk. Both control groups showed low mean values ​​in comparison with the test groups, control group K (414 MPa) as the lowest in comparison with all other groups. When comparing the two control groups S and K, no significant difference was shown.   Conclusion: The bending strength varies depending on which layers are loaded regardless of fast and conventional sintering. The sintering parameters are significant for the bending strength. / Syfte: Syftet med föreliggande studie var att utvärdera hur materialet KATANA™ Zirconia YML påverkas i hållfasthet beroende av två olika sintringsprogram. Utvärderingen av hållfastheten gjordes med hjälp av ett biaxialt böjhållfasthetstest.   Material och metod: Totalt framställdes 48 provkroppar, 32 stycken framställdes av KATANA™ Zirconia YML och 16 provkoppar som utgjorde kontrollgrupp, av KATANA™. Zirconia UTML. Provkropparna var utformade som cirkulära diskar och dem placerades i två olika skikt i disken, mellan Enamel-Body 1 och Body 2-Body 3. Provkropparna delades in i två undergrupper varav 24 provkroppar snabbsintrades och resterande (n=24) provkroppar sintrades konventionellt och hållfastheten utvärderades med ett biaxialt böjhållfasthetstest.   Resultat: Högst medelvärde för det biaxiala böjhållfasthetstestet uppvisade testgruppen som snabbsintrats, med placering i Body 2 – Body 3. Detta var signifikant i jämförelse med övriga grupper (p > 0,001) förutom konventionellt sintrat med samma placering i disken. Båda kontrollgrupperna uppvisade låga medelvärden i jämförelse med testgrupperna, kontrollgrupp K (414 MPa) som lägst i jämförelse med alla övriga grupper. Vid jämförelse mellan de två kontrollgrupperna S och K uppvisades inte någon signifikant skillnad.   Slutsats: Böjhållfastheten varierar beroende på vilka skikt som belastas oavsett snabb- respektive konventionell sintring. Sintringsparametrarna är betydande för böjhållfastheten.

Magnetic measurements are useful tools for quality control of cemented carbides. Previous work at Sandvik Mining and Rock Technology has shown that the coercivity increases with increased cooling rate during sintering for a specific grade.  This study aims to investigate why the coercivity changes with the cooling rate and if this is true for other cemented carbide grades as well. Three different cemented carbide grades were sintered with different cooling rates and evaluated with coercivity, Cobalt-magnetic saturation and hardness measurements, and with microscopy and Electron Backscatter Diffraction analysis. It was found that the coercivity increased with increasing cooling rates for the previously studied grade, but not for the two other grades. It was expected that the increased coercivity would indicate a decrease in WC grain size, but the results showed that the WC grain size of the fastest and slowest cooling rate were the same. However, a change in size of the Co areas between the WC grains was found. The fast cooled sample showed smaller Co areas than the slow cooled sample. These Co/WC grain boundaries increase the coercivity. An increased fraction of hcp-Co/fcc-Co was also found for the fast cooled material which also increases the coercivity. No relationship between the hardness and the coercivity or the cooling rate was found.   The contiguity for the different grades was also calculated.  No significant difference in contiguity between the different cooling rates of each material was found but the contiguity values between the different materials differed.  This is probably mainly dependent on the different binder contents of the materials. / Magnetiska egenskaper är en viktig del av kvalitetskontrollen av hårdmetaller.  Tidigare forskning hos Sandvik Mining and Rock Technology har visat att koerciviteten hos en hårdmetallsort ökar med ökad kylhastighet vid sintring.  Målet med den här studien är att undersöka varför koerciviteten ökar med kylhastigheten och om detta även gäller andra hårdmetallsorter.  Tre olika hårdmetallsorter sintrades med olika kylhastigheter undersöktes med mätningar av koercivitet, magnetisk mättnat i koboltfasen och hårdhet,  samt med mikroskopi och Electron Backscatter Diffraction analys. Det  visade  sig  att  koerciviteten  ökade  med  ökad  kylhastighet  för  hårdmetallsorten  som  studerats tidigare, men inte för de andra två sorterna.  En ökad koercivitet förväntas visa på en minskad WC-kornstorlek, men resultaten visar att det långsamt kylda och snabbkylda provet hade samma WC-kornstorlek.  Däremot upptäcktes en ändring av storleken på Co-områdena mellan WC-kornen.  Det snabbkylda provet visade en mindre storlek av Co-områdena jämfört med det långsamt kylda provet. Fler Co/WC-korngränser i det snabbkylda provet leder till en ökad koercivitet.  Fraktionen av hcp-Co/fcc-Co-korngränser ökade också för det snabbkylda provet vilket också ökar koerciviteten. Inget samband mellan hårdheten och koerciviteten eller kylhastigheten upptäcktes.  Beräkning av kontiguiteten för de olika sorterna genomfördes också. Ingen signifikant skillnad i koercivitet mellan de olika kylhastigheterna för the olika sorterna hittades,  men kontiguiteten mellan de olika sorterna varierade. Det beror mest troligt på att dom olika sorterna har olika mängd matrismaterial.

In this work, the thermal behavior of a DBC substrate with a multi-die array using an inductively generated temperature input is investigated. Through a combination of iterative modeling and numerical simulations, the study analyzes the temperature distribution and the resulting temperature profiles within the entire setup. These results provide valuable insights into the practical impact of an alternative temperature generation by induction heating in the field of multi-die attach and power packaging.:1. Introduction 2. Problem description 3. Preliminary results 4. Conclusions 5. References 6. Authors