A fim de prever mecanismos para o controle dos danos impostos pela corrosão faz-se necessário deter ferramentas e conhecimento suficientes para entender os efeitos desta manifestação patológica sobre o comportamento mecânico do concreto armado. Nos últimos anos tornou-se crescente a utilização da modelagem numérica na simulação da degradação causados pela corrosão, graças ao baixo custo necessário à sua fomentação. Sabendo disso, nesta pesquisa foi desenvolvido um modelo numérico para a simulação em nível mesoscópico da expansão do concreto armado devido à formação de produtos de corrosão. O modelo desenvolvido é baseado no Método dos Elementos Finitos Posicional (MEFP) sob formulação Lagrangiana total, considerando material elástico isotrópico, com lei constitutiva de Saint-Venant-Kirchhoff e comportamento não linear geométrico. Para a representação das armaduras e dos produtos de corrosão, os quais estão inseridos na matriz de concreto, empregam-se elementos finitos lineares (fibras) ou planos (partículas) acoplados à malha de concreto por meio da técnica de embutimento. O comportamento dos produtos de corrosão é descrito por meio de formulações existentes na literatura, utilizando modelos analíticos relacionados a parâmetros intrínsecos ao fenômeno da corrosão e ao tempo de propagação. Os resultados encontrados neste trabalho apontam a eficiência do modelo desenvolvido e a sua aplicabilidade frente à simulação do comportamento mecânico de estruturas de concreto armado sujeitas à corrosão uniforme. / In order to provide the mechanisms for corrosion damage control, it is necessary to own sufficient software tools and knowledge for understanding the effects of this pathologic manifestation on the mechanic behavior of the reinforced concrete. In recent years it has become expanding the utilization of numeric modeling in the simulation of degradation arising from corrosion, thanks to low-cost of its fomentation. Knowing that in this research was designed a numeric model for a simulation at the mesoscopic level of the reinforced concrete because of the corrosion products. The designed model is based on the Finite Element Method (FEM) using the total Lagrange formulation, considering an elastic isotropic material, with a constitutive law of Saint-Venant-Kirchhoff and a behavior nongeometric linear. For a representation of the reinforcements and of the corrosion products (rust), which are inserted in the concrete matrix, it is used finite linear elements (fibers) or planes (particles) attached to the matrix of concrete through the technic embodiment. The products corrosion behavior is described by the formulations found in the literature, using analytical models related to parameters intrinsic to the corrosion phenomenon and to propagation time. The observed results in this work point out to the efficiency of this developed model and its applicability in view of the mechanical behavior of reinforced concrete structures liable to uniform corrosion.

En France, il est envisagé de stocker en formation géologique profonde les déchets radioactifs vitrifiés à haute activité et vie longue dans un conteneur en acier inoxydable chemisé par un surconteneur en acier non allié. Les principaux produits de corrosion attendus à la surface de ce dernier, i.e. la sidérite (FeIICO3) et la magnétite (FeIIFeIII2O4), jouent un rôle protecteur contre la corrosion en tant que couche passivante. Ce travail de thèse visait à étudier l’influence des groupes métaboliques bactériens réducteurs du fer ferrique (IRB) et des nitrates (NRB) sur les transformations de ces produits de corrosion en anoxie. Des souches modèles de NRB (Klebsiella mobilis) et IRB (Shewanella putrefaciens) ont, dans un premier temps, été incubées en présence de suspension de sidérite ou de magnétite, afin d’exacerber les processus de transformation du fer du fait d’une surface spécifique élevée, puis dans un second temps, en présence de films électrogénérés de ces produits pour se rapprocher des conditions d’un acier non allié corrodé en anoxie. Ces souches bactériennes sont capables de transformer la sidérite et la magnétite par des processus microbiens directs ou indirects et de conduire à la formation de rouille verte carbonatée (FeII4FeIII2(OH)12CO3). Ce composé occupe une place centrale dans le cycle biogéochimique du fer en anoxie en tant que transitoire commun à plusieurs réactions microbiennes mobilisant le fer sous deux états d’oxydation différents FeII et FeIII. L’originalité de ce travail de thèse est donc de montrer que des métabolismes bactériens inaccoutumés tels que les NRB ou les IRB sont susceptibles de jouer un rôle dans les processus de biocorrosion / Radioactive waste is one of the major problems facing the nuclear industry. To circumvent this issue France plans to store vitrified high-level nuclear waste in a stainless steel container, placed into a non-alloy steel overpack, at a depth of 500m in an argillaceous formation. The main iron corrosion products formed at the surface of the non-alloy steel are siderite (FeIICO3) and magnetite (FeIIFeIII2O4). These compounds are formed in the anoxic conditions present in the nuclear waste repository and play a protective role against corrosion as a passive layer. This work aims to investigate the activity of nitrate-reducing bacteria (NRB, Klebsiella mobilis) and iron-reducing bacteria (IRB, Shewanella putrefaciens) during the transformation of siderite and magnetite, especially those involved in anoxic iron biogeochemical cycle. Klebsiella mobilis and Shewanella putrefaciens were first incubated with siderite or magnetite suspensions (high surface specific area) in order to exacerbate the microbial iron transformation, subsequently incubated with a magnetite/siderite film synthesized by anodic polarization at applied current density. The transformation of siderite and magnetite by direct or indirect microbial processes led to the formation of carbonated green rust (FeII4FeIII2(OH)12CO3). As a transient phase shared by several bacterial reactions involving FeII and FeIII, this compound is the cornerstone of the anoxic iron biogeochemical cycle. The novelty of this thesis is the consideration of bacterial metabolisms of NRB and IRB often overlooked in biocorrosion processes

A fim de prever mecanismos para o controle dos danos impostos pela corrosão faz-se necessário deter ferramentas e conhecimento suficientes para entender os efeitos desta manifestação patológica sobre o comportamento mecânico do concreto armado. Nos últimos anos tornou-se crescente a utilização da modelagem numérica na simulação da degradação causados pela corrosão, graças ao baixo custo necessário à sua fomentação. Sabendo disso, nesta pesquisa foi desenvolvido um modelo numérico para a simulação em nível mesoscópico da expansão do concreto armado devido à formação de produtos de corrosão. O modelo desenvolvido é baseado no Método dos Elementos Finitos Posicional (MEFP) sob formulação Lagrangiana total, considerando material elástico isotrópico, com lei constitutiva de Saint-Venant-Kirchhoff e comportamento não linear geométrico. Para a representação das armaduras e dos produtos de corrosão, os quais estão inseridos na matriz de concreto, empregam-se elementos finitos lineares (fibras) ou planos (partículas) acoplados à malha de concreto por meio da técnica de embutimento. O comportamento dos produtos de corrosão é descrito por meio de formulações existentes na literatura, utilizando modelos analíticos relacionados a parâmetros intrínsecos ao fenômeno da corrosão e ao tempo de propagação. Os resultados encontrados neste trabalho apontam a eficiência do modelo desenvolvido e a sua aplicabilidade frente à simulação do comportamento mecânico de estruturas de concreto armado sujeitas à corrosão uniforme. / In order to provide the mechanisms for corrosion damage control, it is necessary to own sufficient software tools and knowledge for understanding the effects of this pathologic manifestation on the mechanic behavior of the reinforced concrete. In recent years it has become expanding the utilization of numeric modeling in the simulation of degradation arising from corrosion, thanks to low-cost of its fomentation. Knowing that in this research was designed a numeric model for a simulation at the mesoscopic level of the reinforced concrete because of the corrosion products. The designed model is based on the Finite Element Method (FEM) using the total Lagrange formulation, considering an elastic isotropic material, with a constitutive law of Saint-Venant-Kirchhoff and a behavior nongeometric linear. For a representation of the reinforcements and of the corrosion products (rust), which are inserted in the concrete matrix, it is used finite linear elements (fibers) or planes (particles) attached to the matrix of concrete through the technic embodiment. The products corrosion behavior is described by the formulations found in the literature, using analytical models related to parameters intrinsic to the corrosion phenomenon and to propagation time. The observed results in this work point out to the efficiency of this developed model and its applicability in view of the mechanical behavior of reinforced concrete structures liable to uniform corrosion.

Polidutos, tanques de armazenamento de combustíveis e outras estruturas metálicas estão em constante contato com diferentes tipos de solos, diversos horizontes ou camadas, expostos à ação corrosiva nessa interação. Isso possibilita a ocorrência de danos de conseqüências expressivas ao ambiente e à expectativa de trabalho, podendo implicar em contaminações derivadas por vazamento dos produtos de estocagem, derramamento durante transporte, acidentes causados por tubulações sem adequada manutenção além das perdas financeiras associadas. Conhecer a dinâmica de interações entre as superfícies metálicas e o entorno é fundamental a fim de prever comportamentos e desenvolver materiais melhor aplicados. Os aços classe API são utilizados em tubulações de alta e baixa pressão mantendo características de elevada resistência mecânica e à corrosão e, ainda assim, são suscetíveis de ocorrências do processo corrosivo, dado que, estão em contanto com diferentes ambientes desde regiões de mangue até atmosferas industriais. No presente caso, avaliou-se como se comportam aços API 5L X70 em contato com diferentes horizontes de alguns solos no Brasil. O estudo correlacionou a presença de espécies químicas como íons formados em solução, minerais primários e secundários. Além disso, foram avaliadas as características físicas e químicas como pH, condutividade elétrica, sólidos totais dissolvidos, entre outras, com as respostas quanto à resistência e formas de corrosão. Para tanto, foram utilizadas técnicas como difratometria de raios X, microscopia eletrônica de varredura, fluorescência por raios X por reflexão total, análise de injeção de fluxo além de análises de granulometria e gravimetria, dentre outras. Isto foi feito com a finalidade de obter a caracterização dos solos, a identificação dos produtos de corrosão, a análise da solução dos solos, a avaliação dos metais ensaiados e a classificação das formas e tipos de corrosão. Os resultados demonstraram que diferentes horizontes dos solos, assim como os diversos tipos de solos analisados, produzem um ataque diferenciado na estrutura metálica evidenciando essa seletividade. Também, o estudo demonstrou que tais respostas podem ser rapidamente obtidas com o emprego da solução do solo como meio analítico em comparação às avaliações usuais. / Pipelines, fuel storage tanks and other metallic structures are in permanent contact and exposed to different types of soils, of horizons or layers, or of soil aggressiveness. This interaction may cause expressive damages to the environment and to the planned work. Contamination may occur due to leakage of stored products, splitting during transportation, accidents caused by pipelines without extensive maintenance. The result of these accidents could be, among others, some financial losses. In order to recognize the dynamic interactions between metallic surfaces and the environment it is crucial to have preventive actions and to develop better-applied materials. API steel 5L X70 has been used in structures of low and high pressure with high mechanical strength and corrosion and, even so, it is susceptible to etching corrosion since it is in contact with different environments from mangrove regions to industrial environments. The present case evaluated the role of 5L X70 API steel in contact with different soil horizons representative of the Brazilian soil. This investigation correlated chemical species with solute ions in soil solution, secondary and primary phase minerals besides physical and chemical characteristics as pH, electric conductivity, total dissolved solids, among others, to the results of corrosion resistance and ways of corrosion. The evaluation was carried out using x-ray diffractometry, scanning electron microscopy, total reflection x-ray fluorescence, fuel injection flow besides texture and gravimetric analyses to soil characterization and mineralogy, identification of corrosion products, soil solution analyses, evaluation of tested materials and classification of ways and types of corrosion. This was an attempt to integrate the data to a better understanding of the process involving reagents and products. The results showed that different soil horizons such as different types of analyzed soils produce specific etching in metallic structures showing this selectivity. The study also shows that these results can be readily obtained with soil solution as an analytical means in comparison with nowadays evaluations.

Les composants du circuit primaire des réacteurs nucléaires à eau sous pression (REP) subissent une corrosion généralisée entraînant le relâchement d'espèces solubles dans le fluide primaire (principalement Fe, Ni, Cr, Mn, Co). Sous l'effet de la convection du fluide, ces espèces sont entraînées dans le circuit primaire. Une partie de ces espèces peut précipiter sur les surfaces du combustible et être activée sous l'effet du flux neutronique régnant dans cette région. Ce dépôt de produits de corrosion peut, sous l'effet des forces hydrodynamiques du fluide primaire, être érodé (ou bien dissous si les conditions thermo-chimiques le permettent). Ces espèces activées (principalement du 58Co, 60Co, 51Cr et 54Mn), sous l'effet de la convection vont se retrouver disséminées dans l'ensemble du circuit primaire où elles pourront se redéposer (ou bien précipiter) sur les différents composants et ainsi contaminer l'ensemble du circuit primaire. Au cours d'un cycle de fonctionnement normal dans un REP EDF, l'activité du fluide dans le circuit primaire est relativement constante (généralement de l'ordre de 10-20 MBq.m-3 en 58Co). Cependant, lors de certains cycles de fonctionnement (en fonction de la gestion de combustible), notamment on observe des montées d'activités volumiques importantes en 58Co et en 51Cr pouvant atteindre une centaine de fois celles observées habituellement. Ces montées d'activités volumiques sont dues à l'établissement dans les régions les plus "chaudes" des assemblages de combustible d'un régime d'ébullition nucléée. L'ébullition peut dans certains cas multiplier par un facteur 10 à 100 l'épaisseur de dépôt formé sur le combustible conduisant ainsi à un transfert de masse plus important sous forme particulaire entre le dépôt et le fluide primaire du fait de l'érosion. Une modélisation des mécanismes de transfert de masse entre le fluide primaire et le dépôt sur ces régions "chaudes" du combustible en régime d'ébullition nucléée et les impacts sur la contamination du circuit primaire sont décrits dans ce mémoire. L'ébullition à la surface du dépôt ou bien dans le dépôt lui-même provoque un enrichissement à la paroi en espèces ioniques pouvant entraîner une précipitation plus importante ou bien modifier le comportement d'une espèce d'un régime de dissolution à un régime de précipitation ; le dépôt de particules turbulent et inertiel est lui aussi favorisé. La vaporisation du fluide à la paroi ainsi que la formation des bulles elles-mêmes entraînent aussi un dépôt et une précipitation plus importants. La prise en compte de ces mécanismes de transfert de masse dans le code OSCAR (Outil de Simulation de la ContAmination en Réacteur), développé au sein du Laboratoire de Modélisation des interactions et Transferts en Réacteur au CEA, conduit à une bonne reproduction des résultats expérimentaux issus du retour d'expérience des centrales françaises tant au niveau des dépôts formés dans les régions avec ébullition que des activités volumiques. / The Pressurized Water Reactors (PWRs) primary circuit materials are subject to general corrosion leading to soluble metallic element (mainly Fe, Ni, Cr, Mn, Co) transfer and subsequent ion precipitation processes on the primary circuit surfaces. When deposited on fuel rods, these species are activated by neutron flux. Thus, crud erosion and dissolution processes induce to primary coolant activity. During a normal operating cycle in a EDF PWR, the volume activity in the coolant is relativly stable (usually about 10-20 MBq.m−3 in 58Co). In some cycles (depending on fuel management), significant increases in 58Co and 51Cr volume activities are observed (10 to 100 times the ordinary volume activities). These increases of volume activities are due to local sub-cooled nucleate boiling on the "hot" parts of fuel assemblies. As presented in this thesis, boiling at the top of some fuel assemblies may lead to much higher amount of metallic elements than usual (some micrometers). Indeed, boiling that can locally occurs under PWR conditions concentrates species and to increase significantly the quantity of deposited and precipitated material. Erosion flux is higher in these regions due to thicker crud thickness, involving a greater mass transfer of activated isotopes to the primary coolant. The OSCAR calculation code, developed by the "Laboratoire de Modélisation des interactions et Transferts en Réacteur" in CEA, with these new mass transfer models can now well estimate the amount of deposit and the volume activities in the primary coolant in case of boiling in accordance with french PWR measurements.

The thesis deal with applying low-pressure low-temperature plasma to corrosion products layers on bronze. Layers of corrosion products on samples were artificially prepared. As a result, they had the same composition and could be irreversibly destroyed during experiments, which would not be possible with real archeological artifacts. Bronze, copper and tin alloy, samples were cut with respect to the size of the plasma-chemical device. XRF was used to determine the bronze composition. Before being corroded by the active medium, each sample was washed with ethanol and dried with a hot air stream. Until now, the procedure was the same for all samples. During formation of corrosion products layers, two factors have to be taken into account: the time consumption and the corrosiveness of the active environment. By focusing on one or the other factor, several groups of samples with differently degraded surfaces were created. The fastest way was to place samples in a corrosion chamber where sodium chloride solution was applied at the elevated temperature. The samples were corroded within a few days there. Longer, but in terms of corrosion products layers compactness better way proved procedure where the samples were sealed in the desiccator. At the desiccator bottom the Petri dish with an inorganic acid was placed, in our case, with hydrochloric acid inside. This method corroded the samples within one month. The longest but the most closed to the real live method was the burial of samples into soil or compost. However, this method corroded the samples within two years. Final step after the samples were removed from any corrosive environment, were dried under low pressure and were placed in a barrier film made bag together with moisture and oxygen absorbers. So prepared samples with layers of corrosion products have been treated in a low-pressure low-temperature plasma. Treatment was carried out in the apparatus which is based on the reactor: cylinder of quartz glass having a diameter of 100 mm and a length of 900 mm. The reactor was supplied with a working gas or a mixture of working gases with a total flow rate of 50 sccm. In our case, one is pure hydrogen or a combination with argon. A rotary oil pump was used to provide vacuum. The reactor base pressure was 10 Pa before treatment, while during the treatment it was 150 Pa. High-frequency generator (13.54 MHz) was used for supply the system with energy through two copper electrodes located outside the reactor. According to the energy delivery method, the treatment was carried out in a continuous or pulse mode. The sample temperature was monitored during the experiment and were evaluated the emission spectra from OES. The sample temperature was one of the key factors. The measurement was first done with a thermocouple, later switched to a thermocouple with optical data transmission. A safe temperature was set and then the whole process was controlled through it. In addition, the effect of the energy delivery method, value of the delivered power, sample size, presence of incrusted layers and composition of working gas were studied. After application of plasma, samples were analyzed by SEM – EDX and XRD. After the evaluation of the acquired knowledge and experience, a real artifact - a bronze chisel from the site of Boskovice - was treated. This documentation lacked the artifact, so it could be used to verify the lessons learned about plasma chemical reduction.

Les alliages légers (Al, Mg) sont aujourd’hui majoritairement utilisés dans les industries aéronautique, électronique, automobile. Toutefois, la faible résistance à la corrosion et à l’abrasion de ces alliages restreint leur développement à grande échelle. Les nouveaux concepts de protection contre la corrosion des alliages légers se basent non seulement sur un effet barrière par une couche épaisse d'oxyde (PEO) ou peindre, mais surtout sur une protection active à l’aide d’inhibiteurs de corrosion spécifiques. Ces inhibiteurs de corrosion pourraient être libérés "sur demande" et génèrent un phénomène ‘d’auto guérison’. L’utilisation des méthodes d’analyse in situ and ex situ modernes spectroscopiques pourraient permettre de mettre en lumière l’évolution de systèmes aussi complexe et aider à mieux définir les facteurs régulant ces processus. / Nowadays light alloys (Al, Mg) are widely used in a number of areas such as electronics, aeronautic, automotive and construction industries. However, the low corrosion and wear resistance of these alloys hinders application of Al and Mg alloys on a larger scale. The new concepts for corrosion protection of light alloys should include not only barrier protection by a thick oxide layer (PEO) or by paint but also an active protection by specific corrosion inhibitors which can be released “on request” and ensure so-called “self-healing”. Use of in situ and ex situ spectroscopic methods could bring a new view to the evolution of such a complicated system and help to define factors controlling these processes.

Объектом исследования является идея осуществления производства антикоррозийных продуктов. Целью работы является обоснование экономической целесообразности реализации проекта по производству антикоррозийных продуктов. В процессе выполнения работы были получены следующие результаты. В рамках изучения методических подходов к оценке экономических перспектив были даны определения экономического и маркетингового анализа, определены их основные методы и задачи. А также составлена авторская классификация антикоррозионных продуктов, учитывающая их ключевые признаки. Результаты анализа рыночных и перспектив позволили выявить основных потребителей и конкурентов интересующего отраслевого рынка, а также позволили определить оптимальный объем выпуска антикоррозийного продукта и его среднерыночную стоимость. Таким образом, оптимальный объем выпуска, не нарушающий сложившегося рыночного равновесия, составляет порядка 30 тонн, а среднерыночная стоимость 1 тонны продукта составляет 100-110 тыс. рублей. Результаты патентного исследования, проведенного в рамках оценки научно-технических перспектив, позволили определить динамику патентования и выявить аналогичные технические решения. На основе результатов проведенного патентного исследования пределен средний срок жизни проекта по производству железооксидного пигмента с противокоррозионными свойствами – 4 года. Научно-практическим результатом, полученным автором в процессе выполнения работы, является создание модели производства, учитывающей более эффективные инструменты реализации идеи по производству антикоррозийных продуктов. В рамках этой модели, с учетом выводов, сделанных в аналитической части работы, рассчитаны показатели экономической эффективности трех вариантов трансфера технологии. / The object of the study is the idea of the production of anti-corrosion products. The purpose of the work is to justify the economic feasibility of the project for the production of anti-corrosion products. The following results were obtained in the course of the work. As part of the study of methodological approaches to the assessment of economic prospects, the definitions of economic and marketing analysis were given, their main methods and tasks were determined. And also the author's classification of anticorrosion products, taking into account their key features. The results of market and prospects analysis allowed to identify the main consumers and competitors of the industry market of interest, as well as to determine the optimal volume of production of anti-corrosion product and its average market value. Thus, the optimal volume of output that does not violate the existing market balance is about 30 tons, and the average market value of 1 ton of product is 100-110 thousand rubles. The results of the patent research conducted in the framework of the assessment of scientific and technical prospects allowed to determine the dynamics of patenting and to identify similar technical solutions. Based on the results of the patent research, the average life of the project for the production of iron oxide pigment with anti – corrosive properties is limited to 4 years. The scientific and practical result obtained by the author in the process of the work is the creation of a production model that takes into account more effective tools for the implementation of the idea for the production of anti-corrosion products. Within the framework of this model, taking into account the conclusions made in the analytical part of the work, the indicators of economic efficiency of the three options for technology transfer are calculated.

Pour un réacteur à eau pressurisée, la contamination radioactive du circuit primaire constitue un problème majeur pour les opérations de maintenance. La principale source de cette contamination est le relâchement des produits de corrosion des tubes GV en alliages base nickel représentant environ les trois quarts de la surface totale du circuit primaire. L’oxydation des alliages base nickel en milieu primaire, à l’origine du relâchement, a fait l’objet de nombreuses études. Certaines pistes d’amélioration ont d’ailleurs d’ores et déjà été explorées comme la métallurgie des tubes et plus précisément leur état de surface, la pré-oxydation, l’addition de zinc au sein du milieu primaire. Cependant, la compréhension du phénomène demeure lacunaire. La nature et la structure de la couche d’oxyde formée sur les alliages base nickel est relativement bien connue, mais pas sa cinétique de formation et de relâchement ou de façon bien moins précise. L’objet principal de cette étude est donc le développement et la mise en œuvre d’un dispositif expérimental innovant permettant de suivre l’épaisseur d’oxyde formée par une mesure optique de réflectométrie in situ, ainsi que le relâchement en ligne par mesure de concentration par ICP – MS. Les échantillons utilisés lors des différents essais expérimentaux ont également été analysés par diverses techniques notamment l’XPS et le MET afin d’apporter de nouveaux éléments sur la nature ou la structure des couches d’oxyde. En outre, ces analyses, permettant également d’évaluer les épaisseurs d’oxyde ont contribué à valider les résultats d’oxydation obtenus par réflectométrie. L’utilisation de ce moyen expérimental a permis d’obtenir des résultats, certes peu nombreux mais aux perspectives prometteuses. / The radioactive contamination is a significant issue for the maintenance of the primary loop of a water pressurized reactor. The corrosion products released by steam generators tubes made of nickel base alloys, which represent seventy five percent of the whole primary loop surfaces, are highly responsible for this pollution. The oxidation of nickel base alloys in primary water is thus a widely studied subject. Besides, some mitigation means have already been performed like the control of tube manufacturing and of their surface state in particular, a pre-oxidation process, the injection of zinc into primary water. However, the phenomenon remains deficiently understood. The oxide layer nature and structure, formed on nickel base alloys is relatively well known, but this knowledge is far less precise about the layer formation and release kinetics. The main subject of this study is thus to develop an innovative experimental facility which permits to obtain the layer thickness by in situ optical reflectometry measurements, and the corrosion products release by concentration ICP – MS in line measurements. The implementation of these two techniques has needed lots of theoretical and technical adjustments, especially in situ way of using the reflectometry. Some analyses, XPS and MET in particular, have been performed on the different used samples to bring new facts about the nature and structure of oxide layers. Moreover, these analyses have contributed to validate the oxidation results, by measuring the oxide layer thickness and comparing it to the reflectometric results. The different tests realized with this new experimental device are quite promising and should be used and improved to perform others valuable tests.

Cette thèse s’inscrit dans le contexte de la durabilité des structures en acier au carbone envisagées pour le stockage des déchets radioactifs à haute activité et à vie longue. Ce travail porte plus particulièrement sur la simulation numérique de la corrosion généralisée (et de son évolution), principale forme de corrosion susceptible d’affecter ces aciers en phase aqueuse et en condition désaérée.Le processus de corrosion des aciers au carbone est grandement influencé par la formation de couches de produits de corrosion (CPC) dont le rôle sur l’évolution de la vitesse de corrosion a été mis en évidence dans de nombreuses études. Le caractère plus ou moins protecteur d’une CPC dépend de plusieurs paramètres physiques (porosité, épaisseur et propriétés électriques de CPC) et chimiques (pH, PCO2, formations de complexes,…). Le principal objectif de ce travail de thèse est l’étude du rôle d’une CPC de sidérite sur la vitesse de corrosion des aciers au carbone en condition désaérée. Le régime de corrosion est ainsi simulé sur la base de modèles mécanistes en faisant appel à une résolution par la méthode des éléments finis de l’équation de transport réactif en milieu poreux et en potentiel libre.Dans un premier temps, l’étude de la stabilité d’une CPC par expérience numérique est présentée et constitue une étape importante dans la mesure où elle permet de sélectionner les paramètres influençant cette stabilité et par conséquent le processus de corrosion. Cette expérience numérique confirme des résultats expérimentaux obtenus sur des coupons dans un environnement représentatif des conditions de stockage mais sur des durées beaucoup plus courtes (de l’ordre de quelques années). Ces calculs montrent qu’en fonction des conditions chimiques (pH, complexants,…), morphologiques (épaisseur, distribution de porosité dans la CPC, …) et des propriétés électriques de la couche, on obtient soit un dépôt stable pouvant potentiellement entraîner une diminution de la vitesse de corrosion, ou soit un dépôt instable mettant à nu la surface du métal et qui se traduit par une vitesse de corrosion élevée.De manière complémentaire, le transitoire de croissance d’une CPC est également étudié en prenant en compte numériquement le déplacement de l’interface métal – CPC correspondant à la création de vide par la dissolution du métal. Deux approches, la première dite « implicite » et la seconde dite « explicite », de mouvement de cette interface sont présentées. Tous ces modèles numériques sont comparés à différents retours d’expérience. A cet égard, une loi de précipitation de la sidérite, discutée et confrontée aux différentes lois de la littérature, est proposée. Les résultats de simulation d’un transitoire de croissance d’une CPC conductrice sont conformes à certains retours d’expériences, montrant d’abord une phase active de corrosion suivie d’une phase pseudo-passive où la vitesse de corrosion est ralentie par le recouvrement de la surface métallique par la CPC. / This thesis is related to the issue of the sustainability of carbon steel structures intended for the storage of high-level long-lived radioactive waste. This work focuses on the numerical simulation of the uniform corrosion (and on its evolution), representing the main form of corrosion likely to affect these steel components in aqueous and deaerated conditions.The corrosion process of carbon steels is greatly influenced by the formation of corrosion product layers (CPL) whose role on the evolution of the corrosion rate has been demonstrated in numerous studies. The more or less protective nature of a CPL depends on several physical (porosity, thickness and electrical properties of CPL) and chemical parameters (pH, PCO2, complex formations, ...). The main objective of this thesis is the study of the role of a siderite CPL on the corrosion rate of carbon steels in deaerated conditions. The corrosion regime is simulated on the basis of mechanistic models using a finite element method to resolve the reactive transport equation in porous media and in free potential conditions.Firstly, the stability of a CPL is studied by numerical experiment and constitutes an important step that permits to select the key parameters influencing this stability and consequently the corrosion process. This numerical experiment confirms experimental results obtained on coupons in an environment representative of the storage conditions but on much shorter durations (few years). These calculations show that depending on the chemical conditions (pH, complexing medium, ...), morphological (thickness, distribution of porosity in the CPC, ...) and the electrical properties of the layer, we obtain either a stable deposit that could potentially lead to a decrease of the corrosion rate, or an unstable deposit exposing the metal surface and resulting in a high corrosion rate.In a second time, the transient step i.e. the formation and growth process of a CPL, is also studied numerically considering the displacement of the metal-CPC interface corresponding to the creation of voids caused by the dissolution of the metal. Two approaches, the first one called "implicit" and the second "explicit", of the movement of this interface are presented. All these numerical models are compared with different experimental feedbacks. Thus, a kinetics law of precipitation of siderite, discussed and compared with different laws proposed in the literature, is implemented in these models. The results obtained by simulating the growth of a conductive CPL are consistent with some experimental feedbacks, showing firstly a period of active corrosion followed by a pseudo-passive period during which the corrosion rate is significantly decreased resulting from the coverage of the metal surface by the CPL.