Nitride fuels have always been considered a good candidate for GENIV reactors, as well as space reactors, due to their high fissile density, highthermal conductivity and high melting point. In these concepts, not beingcompatible with water is not a significant problem. However, in recent years,nitride fuels started to raise an interest for application in thermal reactors,as accident tolerant or high performance fuels. However, oxide fuels havebenefited from decades of intensive research, and thousands of reactor-years.As such, a large effort has to be made on qualifying the fuel and developingtools to help assess their performances.In this thesis, the modeling side of this task is chosen. The effort istwo-fold: determining fundamental properties using atomistic models andputting together all the properties to predict the performances under irradi-ation using a fuel performance code. The first part is done combining manyframeworks. The density functional theory is the basis to compute the elec-tronic structure of the materials, to which a Hubbard correction is added tohandle the strong correlation effects. Negative side effects of the Hubbardcorrection are tackled using the so-called occupation matrix control method.This combined framework is first tested, and then used to find electronic andmechanic properties of the bulk material as well as the thermomechanicalbehavior of foreign atoms. Then, another method, the self-consistent meanfield (SCMF) one, is used to reach the dynamics properties of these foreignatoms. In the SCMF theory, the data that were obtained performing the abinitio simulations are treated to provide diffusion and kinetic flux couplingproperties.In the second step of the work, the fuel performance code TRANSURA-NUS is used to model complete fuel pins. An athermal fission gas releasemodel based on the open porosity is developed and tested on oxide fuels.A model for nitride fuels is introduced, and some correlations are bench-marked. Major issues remaining are pointed out and recommendations asto how to solve them are made. / <p>QC 20170227</p>

With respect to nitrides being considered as potential fast reactor fuels, research is conducted on the out-of-pile thermophysical properties, sintering and fabrication processes, gas migration mechanisms, self-diffusion and point defect behaviour of actinide nitrides, their surrogate materials, and the inert matrix material ZrN . The experimental research, carried out in the framework of qualifying fuel for the European Lead Cooled Training Reactor (ELECTRA), shows that sintered ZrN and (Dy,Zr)N pellet densities are influenced by the oxygen concentration in the material. The effect is confirmed in sintered (Pu,Zr)N pellets. Oxygen concentration also plays a role in the thermophysical properties of inert matrix nitride fuels, but does not have an impact on the electrical properties of these materials. With the fuel fabrication methods applied here, clean nitride powders can be synthesized. However, the subsequent fabrication phases, including milling and solid solution formation, increases the impurity levels significantly. Research of equal importance is performed on materials free of fabrication-induced impurities, whose properties are studied by employing first-principles methods. ZrN, UN and (U,Zr)N are studied, whereas the results from ZrN are expected to be applicable for actinide nitrides as a first approximation. The migration of noble gases in ZrN, on the atomic scale, confirms the experimentally observed tendency for noble gases with higher atomic number to be retained in the fuel matrix, while the majority of He is released to the fuel pin. Materials modelling implies that self-diffusion of nitrogen and metal atoms in inert matrix nitride fuels is accelerated under irradiation, since noble gas retention reduces migration barriers which govern self-diffusion. Unlike Kr and Xe, He has the capacity to be released into the fuel matrix, after having been trapped in a vacancy. The results are expected to aid in providing an explanation to the macroscopic diffusion phenomena in nitride fuels, as the diffusion behaviour of noble gases is sparsely studied. In addition, a study on the miscibility of ZrN and UN in a narrow composition range suggests solubility, based on the negative mixing energies. The results obtained from research on inert matrix nitride fuel underline several beneficial properties which are desirable in a fast reactor fuel. The relevance of these results is analyzed and contextualized in the thesis, from the perspective of current research and development in the field. / <p>QC 20130611</p>

Depuis plusieurs années, le laboratoire SPCTS de Limoges a focalisé son attention sur l’étude des matériaux tellurates (à base de cations Te6+), dont les propriétés optiques non-linéaires du troisième ordre (χ(3)) doivent être encore supérieures à celles des matériaux tellurites (à base de cations Te4+) traditionnellement considérés. En effet, les calculs ab initio montrent que les propriétés non-linéaires d’ordre trois du composé tellurate TeO3-β sont environ 10 fois plus élevées que celles du composé tellurite TeO2-α. A ce titre, une étude théorique du système (1-x)TeO2+ xTeO3 a été entreprise afin de comprendre l’origine structurale de cette importante différence de propriétés. Les résultats de cette étude ont montré que cette différence était liée à l’augmentation du « degré de polymérisation » et à la diminution du gap énergétique associées à chacune des phases de ce système et ce, avec le taux croissant en cations Te6+. Ces conclusions ont ensuite été généralisées à travers une étude plus globale menée sur un grand nombre de composés oxydes de type MnOm et MnTepOm. Une attention particulière a été portée aux propriétés non-linéaires du composé TeO3-β. Une étude expérimentale puis théorique a permis de mettre en évidence que ses exceptionnelles propriétés non-linéaires étaient directement corrélées aux propriétés des liaisons chimiques le constituant. Compte tenu de l’ensemble de ces résultats, la synthèse de verres tellurates a été envisagée à travers l’étude du système TeO2-Mg3TeO6. Outre leurs forts intérêts pour l’optique, les matériaux tellurates sont aussi de bons candidats en vue d’une intégration dans des dispositifs de type « Low Temperature Cofired Ceramics ». C’est pourquoi, l’étude du composé Bi6Te2O15 a été entreprise. A cet égard, son protocole de frittage a été optimisé au moyen de la technologie « Spark Plasma Sintering » (SPS), et ses propriétés diélectriques mesurées se sont révélées prometteuses. / For several years, SPCTS laboratory of Limoges has focalized his attention to the study of tellurate materials (Te6+ cations-based compounds), whose third order non-linear optical properties (χ(3)) must be superior to those of tellurite materials (Te4+ cations-based compounds) traditionally considered. Indeed, ab initio calculations show those the third order non-linear optical properties of the TeO3-β tellurate compound are about 10 time higher than that of TeO2-α tellurite phase. In this connection, the theoretical study of the (1-x)TeO2+ xTeO3 system was undertaken in order to understand the structural origins of these properties. Results have shown that the increasing of the “polymerization degree” and the decreasing of the energetical gap associated to each structure of this system, with the increasing ratio of Te6+ cations were at the origin of this change of properties. These conclusions were generalized through the study of many oxide compounds such as MnOm and MnTepOm. A special attention was paid to the non-linear properties of the TeO3-β compound. Experimental and theoretical studies allowed highlighting that its exceptional properties were correlated to its chemical bonding properties. Taking into account all these results, the synthesis of tellurate glasses was investigated, through the study of the TeO2-Mg3TeO6 binary system. Besides their great interest for optical applications, tellurate materials are also good candidates for LTCC applications. Therefore the study of the Bi6Te2O15 compound was also managed in this work. Its sintering process was optimized using the “Spark Plasma Sintering” technology, and its dielectric properties measurements have evidenced very promising values.