Orientador: Rubens Maciel Filho / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Química / Made available in DSpace on 2018-08-21T23:05:30Z (GMT). No. of bitstreams: 1 CelisAriza_OscarJavier_D.pdf: 10909211 bytes, checksum: 25518eb40de039638e4cc39a2cb6790e (MD5) Previous issue date: 2012 / Resumo: O potencial aproveitamento dos resíduos de petróleo obtido por destilação atmosférica ou a vácuo tem estimulado a procura de novos processos com a finalidade de transformar estas frações de baixo valor comercial, em derivados nobres de alto valor, tais como a gasolina e o GLP. O craqueamento térmico (viscorredução, coqueamento retardado) ou craqueamento catalítico (FCC, hidrocraqueamento) fazem parte deste grupo de processos amplamente utilizados em todo o mundo. Contudo, um dos desafios é procurar novas técnicas que facilitam a produção destas frações de alto valor, a partir de resíduos que atualmente não têm sido aproveitados para esta finalidade. Uma das desvantagens nos processos convencionais refere-se ao elevado consumo de energia para chegar à temperatura inicial das reações de quebra dos hidrocarbonetos. Porém, uma nova técnica rápida de craqueamento térmico destas frações foi desenvolvida e avaliada. A técnica proposta consistiu na utilização de sistema laser de CO2 e scanner óptico de varredura para focalização do feixe de laser diretamente no resíduo de petróleo com a finalidade de quebrar quimicamente os hidrocarbonetos por meio da energia térmica (aquecimento) gerada pela interação laser/petróleo. Sendo assim, nesta Tese, foi realizado um estudo experimental e de simulação para avaliar as melhores condições de operação do laser (potência, velocidade de varredura e número de varreduras) que permitam um melhor ganho na seletividade dos produtos. Testes experimentais foram desenvolvidos para um resíduo atmosférico chamado ETA e um de seus resíduos obtido pela destilação molecular. Particularmente, foram avaliadas as concentrações da fração gasosa (C1-C4, CO, CO2 e H2), fração líquida (gasóleo atmosférico, leve, pesado e super pesado) e a distribuição da massa molar dos produtos. Na avaliação da técnica foi feita uma prévia caracterização termofísica dos resíduos (por meio de dados experimentais ou modelos empíricos) para a simulação da melhor distribuição de temperatura do laser na superfície e no interior do material, desenvolvida na plataforma comercial computacional ANSYS CFX 13.0 ®. Finalmente, a partir dos dados de simulação e experimentais foi possível obter uma maximização da concentração do gasóleo atmosférico e leve (10 e 2 vezes a mais em comparação à amostra não-irradiada, respectivamente), além de uma minimização da fração de gasóleo pesado. Resultado obtido no ponto ótimo de operação do laser a uma potência de 41,5W, velocidade de varredura 0,6 m/s e número de varreduras de 8. A máxima conversão do resíduo molecular ETA obtido por craqueamento via laser de CO2 foi alcançada em 25%, mas em curtos instantes de tempo e pressão atmosférica. Segundo o grau de conversão, a nova técnica de craqueamento térmico de frações pesadas de petróleo por radiação laser pode ser classificada como uma técnica de craqueamento por viscorredução / Abstract: A better use of petroleum residues obtained by atmospheric or vacuum distillation has stimulated the research for new processes in order to transform these fractions of low commercial value into high value products, such as gasoline and LPG. The thermal cracking (viscobreaking, delayed coking) or fluid catalytic cracking (FCC, hydrocracking) has been part of kind of processes used world widely. However, the main challenge is to find new techniques that facilitate the production of these high-value fractions. One of the disadvantages in the above processes has been the high energy consumption to reach the initial temperature of the hydrocarbon reactions. For this reason, a new technique of rapid thermal cracking of these fractions was developed. The technique proposed consists in use a CO2 laser system with optical scanner to focus and driving the laser beam directly into the petroleum residue in order to crack the hydrocarbons through the thermal energy (heat), which is generated by the laser/petroleum interaction. Therefore, in this thesis, an experimental and simulation studies to evaluate the best laser operational conditions (laser power, scanning speed and number of scans) were proposed. Experimental tests have been employed for an atmospheric residue called ETA and for one of its residues obtained by molecular distillation. Specifically, the gas fraction yield (C1-C4, CO, CO2 and H2), liquid fraction yield (atmospheric, light, heavy and super heavy gas oils) and molar mass distribution of the products were determinated. In order to improve the research, a thermophysical characterization of the residues (by experimental data or empirical models) was developed. This part was an important topic to simulate the temperature distribution within the petroleum residue and it was performed by the commercial computational tool ANSYS CFX 13.0®. It was shown by both simulation and experimental data that a maximization of atmospheric and light gas oil yields (respectively, 10 and 2 times more in comparison with the not irradiated sample) was obtained and further a minimization of heavy gas oil yield. These results have been obtained at the best operational condition of laser of CO2, such as: power beam 41,5W, scanning speed of 0,6 m/s and number of scans of 8. A maximum conversion of 25% was obtained for the molecular residue ETA but with short time instant atmospheric pressure. Moreover, according to the conversion degree, the new thermal cracking technique of heavy petroleum fractions by laser radiation can be classified near to the viscobreaking technique / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química

This thesis addresses the issues surrounding the application of the finite element method to analyse composite structure repairs with an emphasis on aircraft applications. A comprehensive literature survey has been carried out for this purpose and the results are presented. A preliminary study and a comparative study of different modelling approaches have been completed. These studies aim to explore and identify the problems in modelling repairso n simplec ompositep anelsw ith speciala ttention given to adhesivem odelling. Three modelling approaches have been considered: Siener's model which is an extension of the traditional plane strain 2D model used for adhesively bonded joints, Bait's model which is a promising new approach and a full 3D model. These studies have shown that these methods are complementary providing a different insight into bonded repairs. They have also highlighted the need for a new modelling approach which will provide an overall view of bonded repairs. Improved modelling approachesh ave been developedf or externallyb onded patch and flush repairs. These models enable the study of adhesive failure as well as composite adherendf ailures.T hesea pproachesh aveb eena ppliedt o real repairs and the predicted results compared to experimental data. Four case studies have been conducted: external bonded patch repairs to composite plates, a scarf joint for bonded repairs, a flat panel repaired with a scarfed patch and a repaired curved panel. These case studies have shown that bonded repairs to composite structures can be analyseds uccessfullyu sing PC-basedc ommercialf inite elementc odes.

Heat of hydration is a property of Portland cement and a direct result of the chemical reaction between cement and water. The amount of heat released is dependent upon the cement mineralogical composition, curing temperature, water to cement ratio, and cement fineness. High temperature resulting from heat of hydration (thereon referred to as HOH) of cement can affect the hydration process, and consequently the kinetics of development of the mechanical properties of concrete. One of the main reasons triggering the interest in HOH of cement is its implication in thermal cracking of concrete. The high temperature gradient between the inner core and the outer surface of a concrete element is known to result in large tensile stresses that may exceed tensile strength, thus leading to early–age thermal cracking in mass concrete. This dissertation initially addresses accurately predicting the heat of HOH of Portland cement at seven days based on the heat flow data collected from isothermal calorimetry for a time interval of 0-84 h. This approach drastically reduces the time required to identify the seven day HOH of Portland cement. The second part of this study focuses on cement fineness and its critical role on the heat generated by Portland cement during hydration. Using a matrix of four commercially available Portland cements, representing a wide range of mineralogical composition, and subjecting each of the as-received cements to several grinding increments, a linear relationship was established between cement fineness and heat of hydration. The effect of cement fineness and mineralogical composition on HOH of Portland cement was then related through a mathematical expression to predict the HOH of Portland cement based on its mineralogical composition and fineness. Three expressions were proposed for the 1, 3 and 7 day HOH. The findings indicate that the equations developed, based on cement main phase composition and fineness, can be used to identify cements with high heat of HOH that may cause thermal cracking in mass concrete elements. Also, the equations can be used to correlate the HOH with the other properties of Portland cement for quality control and prediction of chemical and physical properties of manufactured Portland cement and concrete. Restrained shrinkage experiments results on mortar specimens prepared with cements of variable phase composition and fineness indicate that interaction of C3A and sulfate source is the prime phenomenon followed by cement fineness as the second main factor influencing concrete cracking. In order to minimize this effect, the third part of this study focused on studying alternatives that can lower the heat generated by concrete on hydration through the incorporation of nanomaterials; namely, graphene nanoparticles. The results indicate that incorporation of graphene a as replacement for Portland cement improves thermal diffusivity and electrical conductivity of the cement paste. Consequently, the use of graphene can trigger improvement of the thermal conductivity of concrete elements thus reducing the cracking potential of concrete. Measurements of HOH of graphene-cement paste, at w/c=0.5, using isothermal conduction calorimetry, indicate that incorporation of graphene up to 10% increases the length of the induction period while reduces the magnitude of the alite main hydration peak due to the filler effect. Furthermore, increasing the w/c ratio from 0.5 to 0.6 and graphene content from 1 % to 10% (as a partial replacement of cement) increases the 7 day HOH of Portland cement by 50 J/g. Isothermal conduction calorimetry heat flow curves show that incorporation of graphene particles up to 10% does not have significant effect on interaction of aluminates and sulfates sources since the time of occurrence of the C3A sulfate depletion peak is not affected by graphene substitution up to 10%. Full factorial statistical design and analysis conducted on compressive strength data of mortar specimens prepared at two w/c ratios, using cements of different finenesses and graphene content indicates that the quantity of graphene and the physical interaction due to variable w/c, graphene and cement fineness, have the smallest P-value among all the samples, representing the most significant impact on compressive strength of mortar samples. It appears that in graphene cement paste composites, addition of 1% graphene results in 21% reduction of Young’s modulus. Increasing the graphene content from 1% to 5% and/or 10% does not show significant effect on Young’s modulus. Similar trends can be observed in the hardness of graphene cement paste samples. In conclusion, partial replacement of Portland cement with graphene nanoparticles in concrete mixtures is a good alternative to lower the cracking potential in mass concrete elements.

I vår nutid har människan möjlighet att genom cracking och fildelning hämta ett datorprogram utan att köpa det. Studenter under utbildning, där verktyg används i form av mjukvara, visar sig utnytja möjligheten att lätt få tag i dessa verktyg genom att fildela. Syftet med uppsatsen är att undersöka studenters tankar och resonemang gällande fildelning av mjukvara avsedd för medieproduktion. Undersökningen genomfördes med två olika metoder. En där studenter innom media fick svara på en enkät med frågor rörande deras köp av media-teknik och mjukvara. Samt frågor om deras fildelningsvanor. En metod där respondenter under intervju fick svara på frågor angående vilken väg de tog mot att börja studera som mediatekniker och vilka tankar de hade kring fildelning. Resultatet visar att studenter främst fildelar för att kunna testa och avgöra om det är värt att betala för mjukvaran de testat. Resultatet visar också att det är större changs att studenter köper den kreativa mjukvaran om de tidigare prövat denna genom fildelning.

La Corrosion Sous Contrainte (CSC) est un des principaux modes de dégradation des composants assemblés par soudage dans Réacteurs à Eau Pressurisée (REP). Le retour d’expérience de 2007 sur les soudures en alliage à base de nickel a présenté 3 cas de fissuration par CSC sur l’Alliage 82 sur les 300 cas recensés dans le circuit primaire. L’objectif de cette étude est alors d’identifier des paramètres microstructuraux et mécaniques à l’échelle de la microstructure impliqués dans l’amorçage de fissures. Les caractérisations du matériau pour identifier ces paramètres sont composées d’une part, d’analyses de la composition chimique et d’analyses EBSD (Electron Back-Scattered Diffraction) pour la morphologie et les orientations cristallographiques des grains pour la microstructure et, d’autre part, de mesures expérimentales de déformation en surface et de calculs numériques de champs de contrainte autour des joints de grains par éléments finis pour le comportement mécanique. La corrélation de ces informations avec les sites d’amorçage de fissures de CSC obtenus avec les essais d’amorçage entrepris sur des éprouvettes U-bend en milieu vapeur d’eau hydrogénée à 400°C, 188 bar a confirmé la sensibilité de l’Alliage 82 en CSC avec une fissuration intergranulaire des joints de grains dont la particularité première est d’être perpendiculaire à la sollicitation (mode I). Les autres paramètres concernent celui de la chimie locale au niveau des joints de grains, de leur nature (généraux ou spéciaux) et du chargement mécanique appliqué à ces derniers (contrainte et différence de déformation). Cette méthodologie, applicable à d’autre matériau, a permis de mieux comprendre quels sont les paramètres microscopiques sensibilisent la cohésion du joint de grains et à quels degré d’importance doivent-il être pris en compte dans le mécanisme d’amorçage de fissures de CSC. / In Pressurize Water Reactors (PWR), Stress Corrosion Cracking (SCC) is the mean degradation mode of components pieced together by welding. Nickel based alloys are, among others, used in dissimilar metal welding (DMW). International report showed only 3 cracking cases in Alloy 82 out of 300 cracking cases concerned on nickel based alloys DMW in primary water circuit. The aim of this study is to identify which microstructural and local mechanism parameters at microstructure scale provide the initiation of SCC cracks. Characterizations performed on specimen surface to identify those parameters are composed ofchemical composition analysis and EBSD analysis (Electron Back-Scattered Diffraction) to know the morphology and the crystallography of grains for microstructure features on one hand, and experimental strain fields measured by Digital Imaging Correlation (DIC) of gold microgrids deposed by electronic lithography on U-bend specimen surface and stress fields calculated along grains boundaries by finite element for local mechanical features on the other hand. The correlation between those characterizations and localization of initiation sites of SCC cracks, obtained on U-bend specimens tested in autoclave in hydrogen steam water at 400°C and 188 bar for 3500 hours, confirmed the susceptibility of the Alloy 82 in SCC conditions with intergranular SCC cracks. The perpendicular position to the loading direction (mode I) is the worst conditions for grains boundary in SCC. The others points concern the chemical composition (precipitation, impurities) around grain boundary and the grain boundary type which is more susceptible when it is a High Angle Grain Boundary. It is following by the mechanical characterization (stress and strain gradient) along grain boundary. This methodology can be used to other material and helped to define which microstructural and mechanical parameter can be define the initiation of SCC cracks.

Plusieurs composants présents dans les réacteurs à eau sous pression (REP) ont été fabriqués en alliage 600, un alliage base nickel contenant environ 16% de chrome. Le retour d’expérience, comme les études de laboratoire, montrent une sensibilité à la corrosion sous contrainte (CSC) de cet alliage en milieu primaire.Des études antérieures ont permis de développer un modèle d’amorçage basé sur une approche macroscopique et dépendant de différents paramètres tels que : la température, la contrainte et la microstructure du matériau. Cependant, ce modèle manque de robustesse car l’effet de la teneur en hydrogène dissous et l’effet de l’histoire de chargement mécanique ne sont pas considérés et les effets microstructuraux ne le sont que partiellement.Ces travaux de thèse ont comme objectif principal de développer un modèle local prévoyant le temps d’amorçage des fissures de CSC en fonction de paramètres locaux liés à la microstructure du matériau (précipitation intergranulaire), à l'environnement (température, et teneur en hydrogène dissous) et aux contraintes locales aux joints des grains. Cette étude comprend donc la caractérisation des matériaux (analyse chimique, microstructure et comportement mécanique) et la réalisation des essais d’oxydation et de corrosion sous contrainte, ainsi que leur interprétation.Le modèle local développé est basé sur des grandeurs physiques et enchaine les différentes étapes de CSC à savoir l’incubation, l’amorçage et la propagation des fissures. Pour construire ce modèle, nous avons considéré la formation de pénétrations d’oxyde aux joints de grains comme une étape-clé dans l’amorçage des fissures de CSC. Pour cela, une cinétique d’oxydation intergranulaire pour l’alliage 600 a été identifiée. De plus, un critère d’amorçage des fissures de CSC a été déterminé en couplant contrainte locale et profondeur d’oxydation intergranulaire critique. Enfin, l’étape de propagation des fissures a été modélisée à partir d’une base de données rassemblant les profondeurs de fissure atteintes en fonction du temps d’essai pour différentes conditions expérimentales. / Several components present in the primary circuit of Pressurized Water Reactors (PWR) of nuclear power plants were manufactured with Alloy 600, a nickel base alloy containing 16 wt.% chromium. Operating experience of PWRs and laboratory tests showed that Alloy 600 is susceptible to stress corrosion cracking (SCC).Previous studies have allowed developing an initiation model based on a macroscopic approach and depending on several parameters such as temperature, applied stress and material microstructure. However, this model suffers from a lack of accuracy: dissolved hydrogen content and mechanical loading history effects are not considered and the microstructure effects (such as intergranular precipitation) are only partially taken into account.The aim of this study is to develop a ‘local’ model predicting stress corrosion cracking initiation time, based on physical mechanisms and local parameters related to the material microstructure (intergranular precipitation), the environment chemistry (temperature and dissolved hydrogen content) and stress concentration at grain boundaries. The local model relies on a cracking scenario with three main steps: incubation, initiation and crack extension.The formation of intergranular oxide penetration was assumed to be a key step in SCC initiation. For this purpose, oxidation tests were performed in simulated primary water. The intergranular oxidation kinetics of Alloy 600 was studied and the effects of intergranular carbide precipitation, dissolved hydrogen content and temperature were investigated. In addition, a cracking criterion coupling a critical local stress and a critical intergranular oxide depth was estimated. Finally, a sigmoid crack growth law was used to simulate both the slow and fast propagation steps. The local model was validated using a database built from the results of SCC tests performed on Alloy 600 and gathering the crack depths reached as a function of test duration for different experimental conditions (material microstructure, loading conditions).

Ce travail porte sur la prévision du risque de fissuration en fretting fatigue des contacts Teta/Frette des conduites flexibles servant à l’acheminement du pétrole et du gaz. Les mouvements de la houle produisent des micros déplacements typiques du fretting entre les fils de Teta et de Frette. Le problème des conduites flexibles est particulièrement complexe puisqu’il implique de prendre en compte des forts niveaux de pressions induisant de la plasticité et des sollicitations variables. Pour répondre à ce problème, des études expérimentales et numériques ont été menés en parallèle. L’étude de fissuration est divisée entre prévision du risque d’amorçage des fissures et étude des conditions de propagation. L’amorçage est étudié avec le critère de fatigue multiaxial de Crossland appliqué à distance critique pour prendre en compte les gradients de contrainte spécifiques au fretting. Cette distance critique est optimisée pour être représentative du large spectre de gradient des contraintes étudié. Il est montré que si la distance critique est constante quelle que soit le gradient des contraintes, elle est associée à une longueur de fissure amorcée dépendante du gradient (couple ℓopt-bopt). Cette approche optimisée, combinée à une loi élastoplastique représentative permet des estimations très précises des conditions d’amorçage des fissures. [...] / This work concerns the prediction of fretting fatigue cracking risk in the Teta/Frette contacts of flexible pipes used for oil&gaz transportation. Swell movements produce micro-displacements between Teta wires and Frette wires, which are typical of fretting. Fretting problem in flexible pipes is particularly complex as it involves taking account of high pressure levels inducing plasticity and variable loadings. To answer this problem, experimental and numerical studies have been carried out. Cracking study is divided between crack nucleation risk prediction and the study of crack propagation conditions. Crack nucleation is studied using Crossland multiaxial fatigue criterion applied at a critical distance to address fretting stress gradient effect. This critical distance is optimized to be representative of the wide spectrum of stress gradient studied. It is shown that if the critical distance is constant whatever the stress gradient, it is combined with a crack nucleation length which depends on the stress gradient (ℓopt-bopt couple). This optimized approach, combined with a representative elastic-plastic material law, allows very precise estimates of crack nucleation conditions. [...]

La desquamation en plaque est une forme de dégradation de la pierre monumentale fréquemment observée. Cette morphologie spécifique résulte de l’initiation et la propagation d’une fissure subparallèle à la surface, qui subit diverses sollicitations en conditions naturelles d’exposition. L’objectif de cette recherche est de mieux comprendre ces mécanismes d’altération et d’appréhender les paramètres déterminants dans l’initiation de la fissuration au sein des pierres mises en œuvre. Une approche en mécanique de la rupture a ainsi été proposée. L’influence des minéraux argileux, mis en cause dans ce phénomène, est étudiée et discutée. Trois pierres ont été sélectionnées, une molasse, un grès et une kersantite, présentant de nombreux exemples de desquamation lorsqu’elles sont exposées. Leur comportement hydromécanique est caractérisé en tenant compte de leur anisotropie naturelle. Les propriétés élastiques, la résistance à la traction et la ténacité sont mesurées après saturation, pour plusieurs humidités relatives en phase d’humidification et de séchage, et après plusieurs cycles de variations d’humidité relative. Un couplage de mesure des dilatations et des vitesses d’ondes acoustiques a permis un suivi précis de l’endommagement au fil des cycles. L’influence des minéraux argileux dans les processus d’altération a pu être vérifiée. Ces phases ont été identifiées comme des facteurs essentiels de la dégradation, car elles constituent des plans de fragilité favorisant l’endommagement et la fissuration du matériau, et ce d’autant plus qu’elles se dilatent lors des sollicitations naturelles. / Flaking is a deterioration pattern widely observed on monumental stone heritage. This pattern is due to the initiation and propagation of a crack subparallel to the surface of the stone exposed to natural weathering. This research aims to better understand the alteration mechanisms and to determine the parameters involved in such crack initiation within monumental stones. A fracture mechanics approach is proposed and the influence of clay minerals on this detachment alteration is discussed. The research is carried out on three stones, a molasse, a sandstone and a kersantite, showing scaling effect when submitted to natural conditions. Their hydromechanical behaviour is studied with respect to their natural anisotropy. Elastic properties, tensile strength and toughness are measured after saturation, at various RH values during humidification and drying, and after several cycles. Wave propagation combined with dilatation measurements is used to follow damage during the RH variations cycles. The influence of clay minerals on alteration processes is verified. These phases are critical factors of stone degradation as they are weakness planes leading to damage and cracking, especially generated by their swelling.

Pour les réacteurs de génération IV, les carbures mixtes (U,Pu)C, avec leur grande densité en atomes fissiles et leurs excellentes propriétés thermiques, sont potentiellement des combustibles à la fois économiques (coeurs plus compacts et plus efficaces) et sûrs (marge à la fusion élevée). Un bon simulant de l’(U,Pu)C pour des études R&D sur son comportement est l’UC, puisqu’ils possèdent des structures très similaires. La synthèse par carbothermie a été utilisée car elle est la plus étudiée et celle actuellement envisagée industriellement. Cependant, elle implique la manipulation de poudres : sous air, le carbure peut réagir très violemment à température ambiante, et sous atmosphère contrôlée il est susceptible d’absorber les impuretés. Une installation inertée sous Ar, BàGCARA, a donc été utilisée. Les améliorations du procédé de fabrication ont notamment portés sur l’atmosphère de frittage afin d’évaluer l’impact sur la pureté des échantillons (vis-à-vis des quantités d’oxygène). La méthode originale d’analyse par faisceau d’ions a permis de déterminer la composition de surface (profils d’oxygène en profondeur dans les premiers 1 μm et stoechiométrie moyenne). Elle a pour la première fois été mise en oeuvre pour l’analyse de l’oxygène dans les matériaux carbonés. Les analyses DRX ont montré le passage par un intermédiaire réactionnel lors de la carbothermie et une meilleure cristallisation des échantillons fabriqués dans BàGCARA. Ils possèdent aussi une meilleure microstructure, densité et aspect visuel que ceux fabriqués par le procédé de référence. Un frittage sous vide mène à un UC plus dense avec moins de secondes phases que les frittages sous Ar, Ar/H2 ou sous contrôle de PC. Cependant, il n’a pas été possible d’analyser les carbures sans passage sous air ce qui peut impacter leur paramètre de maille et mener à leur détérioration. Lorsque l’UC est initialement exempt d’oxygène, il s’oxyde plus vite et plus intensément, de manière hétérogène. Les contraintes mécaniques induites entre les grains mènent à la fracturation du matériau et à une corrosion fissurante, puis à la décohésion du matériau. Une étude des mécanismes d’oxydation serait intéressante afin de valider et de comprendre l’évolution du matériau lorsqu’il est en contact avec l’oxygène. Une étude des mécanismes mis en jeu pourrait être envisagée par couplage des techniques d’EBSD et d’analyse par faisceau d’ions afin de vérifier s’il existe un lien entre une oxydation préférentielle des grains et leur orientation cristallographique. / Mixed carbides (U, Pu)C, are good fuel candidate for IVth generation reactors because of their high fissile atoms density and excellent thermal properties for economical (more compact and efficient cores) and safety reasons (high melting margin). UC can be imagine as a surrogate material ror R&D studies on (U,Pu)C fuel behavior, because of their similar structures. The carbothermic reaction was used because it is the most studied and now consider for industrial process. However, it involves powders manipulation : in air, carbide can strongly react at room temperature and under controlled atmosphere it can absorb impurities. An inerted installation under Ar, BàGCARA, was therefore used. Process improvements were carried out, including the sintering atmosphere in order to evaluate the impact on the sample purity (about oxygen content). The original method by ion bearn analysis was used to determine the surface composition (oxygen in-depth profiles in the first microns and stoichiometry). This oxygen analysis was set for the first time in carbonaceous materials. XRD analysis showed the formation of an intermediate compound during the carbothermic reaction and a better crystallization of the samples fabricated in BàGCARA. They also have a better microstructure, density, and visual appearance if compared to former samples. Vacuum sintering leads to a denser UC with fewer second phases if compared to Ar, Ar/H2 or controlled PC atmospheres. However, it was not possible to analyze carbides without air contact which may impact their lattice parameter and lead to their deterioration. When the carbide is initially free of oxygen, it oxidizes faster, more intensely and heterogeneously. The mechanical stress induced between the grains lead to fracturing the material, to corrosion cracking and then a debonding of the material. A study of oxidation mechanisms would be interesting to validate and understand the evolution of the material in contact with oxygen. A study of the mechanisms involved could be considered by coupling EBSD technique and ion beam analysis to check whether there is a link between a preferential oxidation of the grains and their crystallographic orientation.

Les bétons autoplaçants (BAP), développés depuis plusieurs années sont encore à l'heure actuelle qualifiés de « nouveaux bétons » car leur utilisation reste modeste bien qu'ils possèdent un fort potentiel de développement. Ce frein peut être expliqué par leur coût plus élevé, leur sensibilité à la ségrégation et à la fissuration due à leur fort retrait ainsi que par le manque de connaissances sur leur durabilité. Les BAP se distinguent des bétons ordinaires principalement par un dosage en éléments fins plus important. Ainsi, l'utilisation de fines additions minérales plus économiques et/ou plus écologiques dans ces bétons parait judicieuse sous certaines conditions. La présente thèse s'inscrit dans ce contexte et a pour objectifs de contribuer au développement de BAP plus écologiques et à l'étude de leur durabilité. Notre choix s'est porté sur deux ciments industriels à forte teneur en additions, le ciment CEM Ill à base de laitier de haut fourneau et le ciment CEM V à base de cendres volantes et de laitier de haut fourneau ainsi que sur deux additions minérales encore peu étudiées dans la littéraire : le métakaolin et un sédiment de dragage calciné. Différentes formulations dérivées d'une formulation de BAP de parement de référence à base de CEM 1 ont été mises au point. Les résultats des essais mécaniques et physico-chimiques menés sur les différentes formulations montrent un effet plus ou moins important des additions sur le comportement mécanique au jeune âge et un effet positif certain à plus long terme. Les résultats des mesures de retrait endogène et de dessiccation de l'état frais (plastique) à l'état durci bien hydraté montrent que certaines additions augmentent le retrait de dessiccation des BAP (laitier et sédiment calciné) alors que d'autres le réduisent considérablement (le métakaolin). L'effet indéniable des additions sur l'amélioration de certains indicateurs de durabilité (diffusion des chlorures et perméabilité au gaz) et sur l'augmentation de leur sensibilité à la carbonatation a été quantifié. L'influence assez complexe des différentes additions est étudiée à la lumière des analyses physico-chimiques et microscopique. Enfin, une modélisation mésoscopique est développée et appliquée aux BAP en vue d'une une étude paramétrique. L'effet de la forme des granulats et de leur concentration sur le comportement global en compression et traction d'éprouvette de SAP ainsi que l'effet de l'endommagement mécanique sur l'évolution de la perméabilité sont étudiés. / Self-compacting concretes (SCC), developed several years ago are still considered as “•novel concrete" as their use remains modest although they have a strong development potential. This is mainly due to their higher cos, their sensitivity to segregation and cracking due to their high shrinkage and also due to the lack of information about their durability. SCCs are distinguished from ordinary concrete mainly by their high content of paste. The use of supplementary cementitious materials (SCM), grow increasingly for economic and environmental reasons. This thesis falls within this context and aims to contribute to the development of greener SCCs and to the study of their durability.Two industrial blended cements containing high amounts of SCM, slag cement CEM Ill and CEM V cement containing slag and fly ash as well as two mineral additions still little studied in the literature: metakaolin and calcined dredged sediment are used. Various SCC mixtures derived from a reference SCC based on CEM 1 cement were developed. The results of the mechanical, physical and chemical testing on the different formulations show a greater or lesser effect of SCM on the mechanical behavior at early age and some positive effect over the long term. The results of measurements of the autogenous and drying shrinkage from fresh state (plastic) to well hydrated state show that some SCMs increase the drying shrinkage of SCCs (slag and calcined sediment) while ethers significantly reduce its amplitude (metakaolin).The undeniable effect of SCMs on improving some durability indicators (chloride diffusion and gas permeability) and on increasing the sensitivity to carbonation was quantified. The rather complex influence of the different SCMs is studied in the light of physicochemical and microscopie analyzes. Finally, mesoscopic modeling is developed and applied to SCCs for a parametric investigation. The effect of the shape of aggregates and their concentration on the overall behavior in compression and tensile SCC specimen as well as the effect of the mechanical damage on the evolution of permeability are studied.