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Materiais empregados em polos petroquímicos têm sofrido exigências cada vez mais criteriosas em relação as suas condições de trabalho e desempenho em campo e, atualmente, a liga metálica mais utilizada para a confecção de tubos centrifugados para aplicação nesses locais de trabalho é a liga de aço inoxidável HP modificada com microadições (HPNb-MA). Esses materiais, cuja microestrutura na condição bruta de fundição é composta por uma matriz austenítica com carbonetos de cromo e nióbio nos contornos dos grãos e que apresentam propriedades paramagnéticas em temperatura ambiente, são empregados em polos petroquímicos por apresentarem excelentes propriedades mecânicas em temperaturas elevadas, além de considerável resistência a carburização e perda de massa por oxidação. Visando melhores desempenhos e maiores durabilidades, as microadições são realizadas de maneira intencional e controlada durante o processo de centrifugação. Entre elas, os elementos pertencentes as terras raras têm apresentado resultados satisfatórios em relação a melhorias em propriedades mecânicas em temperatura ambiente e em temperaturas elevadas. O presente trabalho busca padronizar a microadição de ítrio e titânio na liga em estudo, realizando comparações com um material similar cuja composição química se diferencia apenas pela não adição de terras raras durante a confecção dos tubos. Análises comparativas e estatísticas foram realizadas com o intuito de se determinar qual amostra obteria o melhor desempenho em campo. Como parâmetros, foram adotados ensaios de análise química, propriedades mecânicas em temperatura ambiente e temperaturas elevadas, ruptura por fluência, macrografia, microscopia eletrônica de varredura, raios-X, MET, carburização e oxidação. Em paralelo, foi desenvolvido um equipamento capaz de quantificar o nível de carburização dos materiais em estudo em função de alterações das propriedades ferromagnéticas dessas ligas metálicas quando expostas a ambientes carburizantes e com elevadas temperaturas, utilizando para isso, resultados obtidos a partir de simulações laboratoriais e amostras obtidas diretamente de fornos de pirólise. / Materials used in petrochemical poles have undergone increasingly demanding requirements regarding their working conditions and performance in the field. Today, the most used metal alloy for the manufacture of centrifugally cast tubes applied in these work places is the HP stainless steel alloy, modified with micro-addition (HPNb-MA). These materials, which microstructure in as-cast condition is made of an austenitic array of chromium and niobium carbides contouring the grains, exhibit paramagnetic properties at room temperature. They are employed in the petrochemical poles because of its excellent mechanical properties at elevated temperatures, in addition to considerable resistance to carburization and mass loss by oxidation. Aiming for a better performance and longer durability, the micro-addition is carried out in an intentional and controlled way during the centrifugation process. Between them, the elements belonging to rare earths have presented satisfactory results regarding to improvements in its mechanical properties at room temperature and at elevated temperatures. The present work seeks to standardize the micro-addition process of yttrium and titanium in the alloy under study, making comparisons with a similar material which chemical composition differs only by not adding rare earths during the tubes manufacture. Comparative and statistics analysis were carried out with the intent of determining which sample would attain the best performance in the field. Chemical analysis tests, mechanical properties at room temperature and at elevated temperatures, creep rupture, macrography, scanning electron microscopy, X-ray, TEM, carburization and oxidation were adopted as parameters. In parallel, an equipment capable of quantifying the carburization level of the materials under study was developed. These levels are measured in function of changes in the ferromagnetic properties of these metallic alloys when exposed to carburizing and high temperature environments. The equipment makes use of results obtained from laboratory simulations and samples obtained directly from pyrolysis furnaces.

Les barres de commande du futur démonstrateur de réacteur à neutrons rapides refroidi au sodium (RNR – Na) nommé ASTRID sont constituées de pastilles de B4C enfermées dans une gaine en acier inoxydable AIM1 (15Cr-15Ni-0,4Ti). En service, les pastilles de B4C sont plongées dans le sodium liquide à une température allant de 500 à 600 °C. Les retours d’expérience des RNR - Na ont mis en évidence que la durée de vie des barres de commande était limitée par leur cinétique de carburation. Cependant, un phénomène de boruration des gaines a été observé lors d’essais réalisés « hors réacteur / hors irradiation ». Afin de maîtriser la durabilité des barres de commandes, il est donc nécessaire d’évaluer précisément la nature de l’interaction entre les gaines en acier et le B4C dans le sodium liquide. Ainsi, deux campagnes d’essai ont été menées : 1. Trois aciers inoxydables (AIM1, 316L et EM10) ont été exposés dans du sodium liquide fortement carburant (ac > 1) à 500, 600 et 650 °C. 2. Les mêmes nuances d’aciers ont été exposées dans du sodium liquide contenant de la poudre de B4C en excès à 500 et 600 °C. La première campagne a été réalisée pour avoir une meilleure compréhension des mécanismes et des cinétiques de carburation des barres de commande. Tout d’abord, l’état de carburation a été caractérisé finement au moyen de différentes techniques d’analyse (microsonde de Castaing, diffraction des rayons X du rayonnement synchrotron, microscopie électronique en transmission). Ensuite, la cinétique de carburation a été simulée à l’aide d’un modèle analytique simplifié de la carburation puis grâce à un outil commercial plus complet de simulation numérique de la diffusion à l’équilibre thermodynamique (DICTRA). Des écarts ont été observés entre les simulations des états de carburation réalisées avec DICTRA et les mesures expérimentales (profil de concentration en carbone et population de carbures). Afin de prédire au mieux l’état de carburation des aciers rencontré à 500 et 600 °C, il a notamment été démontré qu’il est probablement nécessaire de prendre en compte la diffusion du carbone dans les joints de grains et un écart à l’équilibre thermodynamique entre le carbone piégé dans les carbures et le carbone dissout dans la matrice. La deuxième campagne expérimentale a concerné l’étude du système : acier – B4C – Na. Des caractérisations couplées à des études thermodynamique et cinétique ont permis de proposer un mécanisme de carburation et de boruration des aciers. Après la dissolution du B4C dans le sodium, deux phénomènes ont été observés. Le bore réagit avec les aciers pour former une couche duplexe de borures à la surface (MB, M2B) et des borures dans les joints de grains du substrat. La cinétique de formation de la couche de borures dans les aciers suit une loi parabolique. Le carbone entraine une légère carburation des aciers plus en profondeur et le degré de carburation des aciers s’est avéré constant entre 250 et 3000 h d’exposition, ce qui suggère que le phénomène de carburation s’opère probablement avant la formation d’une couche continue de borures. / Pellets of boron carbide, B4C, enclosed in AIM1 (15Cr-15Ni-0.4Ti) stainless steel tubes are constitutive materials of the control rods in the future French Advanced Sodium Technological Reactor for Industrial Demonstration (ASTRID). During reactor operation, the B4C pellets are immersed in liquid sodium in the temperature range 773-873 K. Based on the feedback from operation of former Sodium Fast Reactors (SFR), the lifetime of the control rods has been shown to be limited by their carburization kinetics. Although, boriding of the steels was observed in out-ofpile studies. In order to increase the lifetime prediction of the aforementioned components in service, detailed information on the chemical interaction between the steel and B4C in liquid sodium is required. As a result, two sets of out-of-pile experiments were conducted: 1. Three stainless steels (AIM1, 316L, EM10) were exposed to highly carburizing sodium (ac > 1) at 773, 873 and 923 K. 2. The same grades were exposed to high purity B4C powder in liquid sodium at 773 and 873 K. The first campaign was performed in order to have a better understanding of the carburization phenomenology and kinetics of the control rods. The extent of carburization was evaluated. A good description of the carburization kinetics was obtained by means of two models and a simulation tool (DICTRA). The limits of the simulation tools were exposed. It was shown that the grain boundary diffusion of carbon had to be taken into account. The second set of experiments was carried out in order to study the system: steel – B4C – Na. A thorough examination of the nature of the chemical interaction was performed. The characterizations were combined with a thermodynamic and kinetic study to propose a carburization and boriding mechanism. The B4C powder dissolved in liquid sodium and reacted with the steels to form a boride layer (MB and M2B) at the surface, borides in the grain boundaries and a carburized zone underneath. The growth kinetics of the boron affected zone was shown to be parabolic. The carburization depth did not evolve between 250 and 3000 h and suggested that this phenomenon occurred during a transient stage.