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).

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.

The need to inject treated seawater to enhance reservoir pressure and secondary oil recovery is increasing in the oil field, so also is the reservoir souring potential caused by the activities of Sulphate Reducing Bacteria (SRB) generating H2S in the reservoir. The total cost of SRB mediated corrosion in the United States alone is estimated to be 1-2 billion US dollars per year. In the last few years, a number of potential souring mitigation and prevention tools have been studied. These include: sulphate-reduction using membranes, biocide injection and nitrate injection. Out of all the various methods used for the mitigation and prevention of reservoir souring, the use of nitrate injection in conjunction with waterflood projects is becoming more popular because of its economic benefits and least environmental impact. However, nitrate injection is still widely considered as an emergent technology because there are still many unknowns. One of the major unknowns, of great concern is the susceptibility of subsea hardware components to nitrite, which is a by-product of nitrate anti-souring treatment. Any detrimental effect can compromise the technical integrity of subsea installations. The objective of this research is to study the corrosion susceptibility of CRA (13Cr- Martensitic, 22Cr, and 25Cr super duplex stainless steel) to pitting and stress corrosion cracking in the presence of nitrite. Research hitherto, has investigated corrosion susceptibility of carbon steel to nitrite and found out that nitrite causes pitting in carbon steel. This research work built on previous studies and extensively investigated the effect of nitrite on CRA materials in terms of pitting and stress corrosion cracking. Using electrochemistry techniques in conjunction with C-ring test and slow strain rate test, with variables such as temperature, and nitrite concentration all under anaerobic conditions. Metallographic examination and further evaluation using scanning electron microscopy confirmed pitting and intergranular stress corrosion cracking of 13Cr-L80 and 25Cr due to presence of nitrite.Test data confirmed that sodium nitrite is an anodic inhibitor; it shifts the corrosion potentials to more noble potential and also shifts the anodic curve to lower current, given a net reduction in corrosion rate. A critical concentration of 400ppm is required for inhibition to be effective on 13Cr-L80 and 25Cr. However, below the critical concentration, nitrite significantly increases the corrosion rate. The experimental data generated from this research work provides very valuable information that will tremendously assist the materials selection process for subsea and subsurface hardware components and also serve as a guide in the corrosion management process in existing systems.

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[pt] As tubulações de aços utilizadas pela indústria do petróleo estão constantemente expostas à ação do ácido sulfídrico (H2S) que é o veículo para a difusão do hidrogênio no aço, provocando o surgimento de trincas induzidas pela fragilização por hidrogênio e/ou trincas de corrosão sob tensão. A junta soldada, que é considerada a região crítica dos dutos, foi o objeto de avaliação neste trabalho mediante ensaios de tração sob baixa taxa de deformação (BTD) e através da norma NACE TM0177/96 - Método A (Standard Tensile Test), verificando o seu comportamento quanto à fragilização por hidrogênio e à corrosão sob tensão em aços da classe API grau X70 e X80. Uma solução de tiossulfato de sódio foi utilizada no ensaio BTD para avaliação da fragilização por hidrogênio e corrosão sob tensão, reduzindo custos e atendendo aos ítens de segurança. Os resultados mostraram que os aços API 5L X70 e X80 são susceptíveis à fragilização por hidrogênio e à corrosão sob tensão. / [en] The steel tubes used in the Oil Industry are constantly exposed to hydrogen sulphide (H2S) which leads to the diffusion of hydrogen into the steel, provoking hydrogen induced embrittlement cracks and/or stress corrosion cracking. Welded joints, generally considered to be the critical region in pipelines, were evaluated in this study, using slow strain rate tensile testing (SSRT) and NACE TMO177/96 - Method A (standard tensile test) norm, verifying the behaviour of joints in API X-70 and X-80 grade steels, with regard to hydrogen embrittlement and stress corrosion cracking. Sodium thiosulphate was used in the slow strain rate tests permit the evaluation of hydrogen embrittlement and stress corrosion cracking while reducing testing costs and maintaining safety standards. The results show that the API X-70 and X-80 grade steels are susceptible to hydrogen embrittlement and stress corrosion cracking.

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No description available.

The time reversal (TR) process manipulates a system's impulse response in order to focus a peak of acoustic energy at a specific location in space and time. This technique has been implemented in both fluid and solid media for purposes ranging from communications to source localization. This thesis will examine both the implementation and processing of TR for nondestructive evaluation in steel, specializing in nonlinear detection methods. A series of steel samples are inspected for stress corrosion cracking (SCC) using TR focusing to excite nonlinearities inherent in cracks. It is determined that SCC exists in the expected regions of the steel samples and that an induced increase in SCC corresponds to an increase in detected nonlinearity. In addition to this, a study is shown wherein TR signal processing is optimized for the detection of cracks. The TR impulse response is modified in a number of ways with the primary goal of increasing the amplitude of the TR focus. Each of these modifications is experimentally scrutinized for characteristics necessary for application to nondestructive evaluation, and ultimately one is chosen that amplifies TR focusing without increasing system nonlinearity. The optimized technique, decay compensation TR, is employed in the detection of SCC and is found to be as or perhaps even more successful than typical TR nondestructive evaluation methods.

Pitting corrosion is a prevalent form of corrosive damage that can weaken, damage, and initiate failure in corrosion-resistant metallic materials. For instance, 304 stainless steel is commonly utilized in various structures (e.g., miter gates, heat exchangers, and storage tanks), but is prone to failure through pitting corrosion and stress corrosion cracking under mechanical loading, regardless of its high corrosion resistance. In this study, to better understand the pitting corrosion damage development, controlled corrosion experiments were conducted to generate pits on 304 stainless steel specimens with and without mechanical loading. The pit development over time was characterized using a high-resolution laser scanner. In addition, to achieve scalable and automatic assessment of pitting corrosion conditions, two convolutional neural network-based computer vision algorithms were adopted and implemented to evaluate the efficacy of networks to identify existence of pitting damage. One was a newly trained convolutional neural network (CNN) using MATLAB software, while the other one was a retrained version of GoogLeNet. Overall, the experimental results showed that time is the dependent variable in predicting pit depth. Meanwhile, loading conditions significantly influence pit morphology. Under compression loading, pits form with larger surface opening areas, while under tension loading, pits have smaller surface opening areas. Deep pits of smaller areas are dangerous for structural members, as they can lead to high stress concentrations and early stress corrosion cracking (SCC). Furthermore, while the training library was limited and consisted of low-resolution images, the retrained GoogLeNet CNN showed promising potential for identifying pitting corrosion based on the evaluation of its performance parameters, including the accuracy, loss, recall, precision, and F1-measure.