Au cours des dernières décennies, le contrôle de la corrosion des alliages exposés à des conditions sévères et complexes a été un grand défi pour les applications industrielles. Les coûts de la corrosion sont élevés et les stratégies de prévention sont devenues une demande industrielle importante. Le projet SCAPAC financé par l’ANR, a proposé d’étudier la corrosion lors de deux procédés industriels: le vapo-réformage du méthane et l’incinération des déchets ménagers. Bien que les conditions de fonctionnement de ces deux procédés soient différentes, les approches de modélisation peuvent être similaires. Dans le procédé de vapo-réformage du méthane, les composants métalliques sont soumis à la corrosion par « metal dusting », qui est une forme d’endommagement catastrophique qui affecte les alliages exposés à des températures élevées (400-800 °C) et des atmosphères sursaturées en carbone. De même, les composants métalliques des incinérateurs de déchets qui sont exposés à des atmosphères de combustion sont soumis à la corrosion à haute température sous dépôts de cendres. Le « metal dusting » est un phénomène critique qui a mené à des pertes matérielles importantes et à l’arrêt d’installations industrielles pendant les 50 dernières années. Les mécanismes de cette dégradation ont été identifiés et sont disponibles dans la littérature. Cependant, l'effet de certains paramètres des procédés ne sont pas encore bien compris et nécessitent des compléments d'études. En ce qui concerne la corrosion à haute température, les mécanismes sont bien documentés et une quantité considérable de travaux ont été publiés au cours des dernières décennies. De nombreux matériaux et revêtements ont été développés. Cependant, la performance des matériaux dans des environnements différents n'est pas assez bien comprise pour créer des modèles de prédiction de durée de vie. Une revue bibliographique de ces deux domaines a révélé qu’il existait des approches de modélisation. Néanmoins, il n'y a pas actuellement de modèle prédictifs fiables de durée de vie qui soit disponible dans la littérature pour les alliages commerciaux, et pour une gamme étendue de conditions expérimentales. La présente étude présente une méthodologie pour développer des modèles statistiques de prévision de durée de vie. Il s’agit d’évaluer la performance de matériaux soumis au « metal dusting » et à la corrosion à haute température sous dépôt. Deux bases de données ont été construites pour intégrer les résultats expérimentaux du projet SCAPAC, aussi bien que résultats de la littérature. Ceci afin d’avoir suffisant des données pour la modélisation. Ces bases de données ont permis d'analyser plus de 4000 vitesses de corrosion à l’aide de méthodes statistiques appliquées à différents scénarios. La méthodologie de l’Analyse des Composantes Principales (ACP) a été utilisée pour identifier les paramètres clés des mécanismes de corrosion, qui ont été ensuite utilisés pour construire des modèles de prédiction de durée de vie par Régression Linéaire Multiple (RLM). Pour la corrosion à haute température, trois modèles ont été obtenus dans le scénario de gradient thermique pour trois familles d'alliages: des aciers ferritiques, des alliages austénitiques à base de fer et nickel et des alliages à base de nickel, en montrant des résultats encourageants. Pour la corrosion par « metal dusting », deux modèles ont été obtenus pour expliquer le temps d'incubation et la cinétique croissance de profondeur de piqures, avec des résultats satisfaisants. Les modèles statistiques dans les deux cas ont été comparés avec deux résultats expérimentaux et théoriques montrant un bon accord, qui permet l'évaluation de la durée de vie des matériaux dans les conditions définies. / Over the last decades, the corrosion control of alloys exposed to severe and complex conditions in industrial applications has been a great challenge. Currently, corrosion costs are increasing and preventive strategies have become an important industrial demand. The SCAPAC project funded by the French National Research Agency has proposed to study the corrosion for two separate processes: Steam Methane Reforming (SMR) and Waste to Energy (WtE). Although the operating conditions of both processes are different, the modeling approaches can be similar. Metallic components in the SMR process are subjected to metal dusting corrosion, which is a catastrophic form of damage that affects alloys exposed to highly carburising gases (aC>1) at high temperatures (400–800 °C).[1]. Likewise, metallic components in the Waste to Energy (WtE) process are subjected to high temperature corrosion under deposit that takes place in equipment exposed to atmospheres with high content of corrosive products of combustion. Metal dusting corrosion is considered as a critical phenomenon that has led to worldwide material loss for 50 years. A basic understanding of the degradation mechanisms is available. However, the effect of some process parameters is still not well understood in current literature and requires further study. Otherwise for high temperature corrosion, a considerable amount of literature has been published over the last few decades and the mechanisms are well documented. Also many materials and coatings have been developed. However, the material performance in different environments has not been sufficiently well understood to define suitable criteria for lifetime prediction models regarding operating conditions, due to the high complexity of the corrosion phenomena involved. Literature research in both fields revealed modeling approaches in different kinds of complex conditions and applications. Nevertheless, there are no lifetime models currently available in the open literature for commercial materials that consider a wide range of conditions and the relative weight of the variables involved in the corrosion processes. This dissertation presents a methodology to develop lifetime prediction models to evaluate materials performance under metal dusting and high-temperature corrosion conditions. Two databases were created to integrate experimental results from the SCAPAC project, as well as results from literature to enable sufficient amount of data for modeling. The databases allowed analyzing approximately 4000 corrosion rates by different statistical methods over different scenarios. The Principal Component Analysis (PCA) methodology was performed to identify the key parameters to create lifetime prediction models using Multiple Linear Regressions (MLR). For high-temperature corrosion, three models were obtained in the thermal gradient scenario for three families of alloys: low alloyed steels, Fe/Ni-based high temperature alloys and Ni-based alloys, showing agreeable results. For metal dusting corrosion, two models were obtained to explain the incubation times and the kinetic of pit depth growing, showing satisfactory results. The statistical models in both cases were compared with experimental and theoretical results showing good agreement with experimental findings, which allows performing the lifetime assessment of materials under defined conditions.

The aim of the thesis is a design of a grate steam boiler with capacity of 35 t/h and output steam parameters with temperature 430 °C and pressure 4,1 MPa. The first part of the thesis deals with stoichiometric calculations and boiler efficiency. The theses mainly focuses on the heat transfer calculation and the geometric design of individual heat transfer surfaces. The specifics of fuel are taken into consideration. The drawing of the basic boiler scheme is a part of the thesis.

The objective of this study is to investigate the eect of dierent fuels on two uidized bed boiler systemsat the energy company Soderenergi's site in Igelsta, called IKV and IGV P3. Today, recovered wastewood (RWW) is the major fuel share fed into the boilers. However, with an insecure fuel supply in thefuture, other fuel types must be considered. Based on knowledge from previous fuel usage in the boilers,an evaluation of how other potential fuel mixtures may eect the operation is conducted. The additionalfuels considered in the fuel blends are; stem wood chips, cutter shavings, solid recycled fuel (SRF) andrubber.With elemental analysis of the fuels and established key numbers, the previous fuel mixtures are evaluated.The indications by the guiding parameters are compared with experienced problems and the formercondition of the boilers, and the risk limits for the key numbers are adjusted to a suitable level. Thepotential mixtures are evaluated with the key numbers and the updated limits. In addition to the keynumbers, the heavy metal concentration, the heating value, the moisture content and the ash content ofthe fuel blends are included in the evaluation. The considered damages in the boilers caused by the fuelblends are corrosion, sintering and fouling.The damage level from the current fuel usage for IKV and IGV P3 is fairly low. The results from theanalyzed fuel mixtures show an increased damage risk in the boilers. Additionally, adjustments of theboiler systems are required by some of the analyzed fuel mixtures. In general, the corrosion risk andthe heavy metal content will increase in comparison with today's fuel. The fouling and slagging are aswell expected to increase for the assessed fuel mixtures. Moreover, the result illustrates an increased ashgeneration, which demands a reconstruction of the ash cooling system for IKV. Furthermore, the increaseof LHV in the assessed fuel mixtures to IGV P3, is likely to require an increased capacity of the ue gasrecirculation pump.In the analysis of the potential fuel mixtures it is found that the corrosion risk expressed by the keynumbers is reduced with a higher share of rubber. The heavy metal content is, however, increased,leading to e.g. an enhanced risk for formation of eutectic salts, which as well are corrosive. On thecontrary, the fuel mixtures with a high risk expressed by the key numbers, have the lowest concentrationsof heavy metals. Due to the results are con icting, a balance between the risk indicated by the keynumbers and the heavy metal concentration must be considered in the evaluation. The fuel mixturesconsidered causing least damage to IKV are a mixture of 42% RWW, 48% wood fuel and 15% SRF, and amixture of 70% wood fuel, 20% SRF and 10% rubber. The fuel mixtures considered causing least damageto IGV P3 are a mixture of 85% RWW and 15% rubber and a mixture of 70% RWW and 30% SRF. / Syftet med studien var att undersoka branslets paverkan pa tva uidbaddpannor, IKV och IGV P3, hos energiforetaget Soderenergi. Idag ar det huvudsakliga branslet i dessa pannor returtra (RT). Med en standigtrorlig branslemarknad kravs kunskap av alternativa branslen. Baserat pa tidigare bransleanvandning,har paverkan fran potentiella bransleblandningar pa pannan undersokts. Utover returtra ar stamveds is,span, papper-plast-tra (SRF) och gummi med i de analyserade blandningarna.Med elementaranalyser pa branslen och etablerade nyckeltal utvarderades de tidigare anvanda branslena.Indikationen fran nyckeltalen ar jamford med upplevda problem och risknivaerna for nyckeltalen arandrade till passande nivaer. De framtida bransleblandningarna analyserades med hjalp av nyckeltalenoch de uppdaterade risknivaerna. Utover nyckeltalen analyserades tungmetallhalten, varmevardet, fukthaltenoch askhalten i bransleblandningarna. De pannskador orsakade av bransleblandningarna somundersokts ar korrosion, sintring och paslag.Det nuvarande branslet till IKV och IGV P3 ger en relativt lag skadeniva. Resultaten fran de analyseradebransleblandningarna visar att skaderisken i pannorna kommer att oka och forandringar av pannan kankomma att kravas. Generellt kommer korrosionsrisken och tungmetallinnehallet att oka i jamforelse meddagens bransle. Okat paslag och slaggning ar ocksa forvantat. Vidare visar resultatet att askproduktionenkommer att oka, vilket gor att IKVs kylsystem for bottenaskan kommer behovas byggas ut. LHV for deanalyserade bransleblandningarna for IGV P3 okar, vilket innebar att kapaciteten for returgas aktarnatroligen maste okas.I jamforelsen av de olika bransleblandningarna visas att korrosionsrisken, forutspadd av nyckeltalen,minskar med en hogre andel gummi. Daremot okar tungmetallinnehallet, vilket leder till en okad riskfor bildning av eutektiska salter, vilka ocksa ar korrosiva. Bransleblandningarna med en indikerad hogrisk av nyckeltalen, har tvartemot den lagsta koncentrationen av tungmetaller. Eftersom resultatenar motsagande, kravs en avvagning mellan riskerna indikerade av nyckeltalen och tungmetallshalten.De bransleblandningar som ar ansedda att vara minst skadliga for IKV ar en blandning av 42% RT,48% tradbransle och 15% SRF, och en blandning av 70% tradbransle, 20% SRF och 10% gummi. Debransleblandning som ar ansedda att vara minst skadliga for IGV P3 ar en blandning av 85% RT och15% gummi, och en blandning av 70% RT och 30% SRF.

No description available.

[pt] A crescente demanda mundial por energia e a necessidade do controle de emissão de gás carbônico (CO2), principal gás responsável pelo aquecimento global, exigem o desenvolvimento de novas tecnologias para a produção de energia com menor emissão de CO2. O uso de fontes alternativas na produção energética está aumentando, mas não é suficiente para suprir a demanda, portanto o uso de combustíveis fósseis ainda é necessário. Neste contexto, o uso da oxicombustão em usinas a carvão em conjunto com a captura e sequestro de carbono (CCS) surge como uma alternativa às usinas convencionais a carvão, pois não emite CO2 na produção de energia. O processo de oxicombustão difere basicamente do convencional pela queima de O2 puro e gás reciclado ao invés de ar. Com isso uma atmosfera rica em CO2 e H2O é formada no boiler, podendo aumentar a corrosão dos materiais em contato com o gás. Este trabalho teve como objetivo investigar o comportamento em corrosão em alta temperatura de ligas de ferro submetidas a condições simples e duplas em atmosferas ricas em CO2. Ligas experimentais e comerciais de ferro com diferentes teores de cromo, cobalto e carbono foram expostas a atmosferas contendo CO2, H2O e SO2 a 600 graus Celsius durante 1000 horas. As amostras foram analisadas em condição simples, onde a amostra é exposta a um mesmo gás em todas as faces e em condição dupla onde a amostra é exposta a vapor d água de um lado e um gás do outro, criando um gradiente de hidrogênio na amostra. As amostras foram caracterizadas por MEV, MET, EDS e microscópio ótico. Os resultados demonstraram que há maior corrosão em condição dual que em condição simples. A maioria das ligas experimentais apresentaram menor oxidação que o aço comercial VM12 em atmosferas ricas em CO2. Entretanto o aço VM12 apresentou melhores resultados quando exposto ao vapor d água. / [en] The world s increasing demand for energy and the need to control carbon dioxide (CO2) emissions, the main gas responsible for global warming, requires development of new technologies to produce energy with lower CO2 emission. Use of alternative renewable sources in energy production is increasing, but not enough to meet the demand. Thus, fossil fuel is still necessary. In this context, oxyfuel together with carbon capture and sequestration (CCS) arises as an alternative to conventional coal-fired power plants, because it does not emit CO2 during energy production. The oxyfuel process differs from the conventional process by burning pure O2 and recycled fuel gas instead of air. Therefore, a CO2-H2O-rich atmosphere is formed in the boiler, increasing the materials corrosion in contact with this atmosphere. The objective of this work was to investigate the high temperature corrosion behavior of iron alloys subjected to single and dual conditions in CO2-rich atmospheres. Model and commercial iron alloys with different chromium, cobalt and carbon content were exposed to atmospheres containing CO2, H2O and SO2 at 600 Celsius degrees for 1000 hours. The samples were analyzed in single atmosphere condition, when all sample faces were exposed to the same gas, and in dual atmosphere condition where the samples were exposed to water vapor on one side, to a gas on the other, creating an hydrogen gradient in the sample. The samples were characterized using TEM, SEM, EDS and light microscope. Results showed different corrosion rates according to chemical composition and microstructure of the samples and gases. Results showed that corrosion is higher in dual condition than in single condition. Most of the model alloys presented less corrosion than commercial steel VM12 in CO2-rich atmospheres. However, steel VM12 presented better results when exposed to water vapor.

The primary intention with this Doctoral thesis is to fillin the knowledge gaps and raise the level of understandingregarding the different metal dusting mechanisms in general andexplain the process in detail for high alloyed materials.Considerable effort is put into identifying the driving forcesand elucidating the diffusional processes in metal dusting. The results are based on a series of long-term laboratory exposures of stainless steels and high-performance commercial alumina-forming Fe- and Ni-base alloys in synthesis gasmixtures, plus a separate shorter study on ultra pure iron. ANi-base alloy was also investigated after a two years field exposure in a methanol plant. Post exposure metallographic examinations and analysis aswell as thermodynamic calculations were made in order toidentify and describe the operating metal dusting mechanisms.Two main mechanisms were previously used to explain metaldusting, one on the basis of decomposition of metastable carbides (Type I) the other on graphite formation (TypeII). A new metal dusting mechanism has been identified in this Thesis which appears on high alloyed steels and Ni-base alloys,an active corrosion induced by carbon and oxygen, denoted TypeIII. Both the mechanisms and the type of corrosion products were consistent with the thermodynamic conditions of the material under the influence of a carbon and oxygen gradient.It was shown that this mechanism not only accelerates the metaldusting process, in fact, it determines the overall metaldusting kinetics on stainless steels and Ni-base alloys. Another feature, which may occur at temperatures where metalbulk and even static grain boundary diffusion is too slow forexplaining the metal dusting corrosion process, was identifiedon a Ni-base alloy. It involves a fast growing cellular structure with discontinuous precipitated carbides whichprovides fast metal dusting kinetics by the Type IIImechanism. A Type IV metal dusting mechanism, continued fragmentationby graphitization until nano-sized particles are formed andcatalyse carbon nanotube formation is also described. Thesteady state process and the driving force for metal dusting onpure iron was identified and described. With these additional processes it is now possible to extendour understanding of the metal dusting processes to a widerange of engineering alloys. / QC 20100825

L’utilisation des alliages de titane dans de nombreuses applications (transport, énergie, chimie,...) permet des gains de masse importants en tirant profit du rapport propriétés mécaniques/masse volumique qui est avantageux pour ce type de matériaux. L’utilisation de ces alliages dans des environnements à hautes températures (T>500°C) nécessite de se préoccuper de leur comportement et de comprendre les mécanismes de dégradation dans ces conditions sévères. Certains facteurs peuvent influencer le comportement des alliages de titane en oxydation, comme l’application de cycles de chauffage/refroidissement, la présence de vapeur d’eau ou la présence de sels, selon les conditions d’utilisation.Ce travail de thèse s’est attaché à comprendre les mécanismes d’oxydation d’un alliage de titane utilisé dans l’aéronautique : l’alliage Ti6242S. Il a été étudié à 560°C sous air, sous air humide et en présence de dépôts solides de sel(s) de type NaCl et/ou Na2SO4. Pour cela, des oxydations de longues durées avec et sans dépôts solides de sels ont été réalisées. Les résultats obtenus montrent que la présence de NaCl provoque une dégradation importante du comportement en oxydation des échantillons. La dissolution d’oxygène dans le métal observée sous air ne se produit plus en présence de dépôts de sels. En revanche, une oxydation interne de l’alliage a lieu et des fissures apparaissent dans la profondeur du substrat métallique. La dégradation du matériau est attribuée à la présence de dichlore et à la formation de chlorures métalliques volatiles. Un mécanisme réactionnel a été proposé afin d’expliquer l’effet néfaste des dépôts de NaCl. L’effet d’un dépôt de sels mixte NaCl/Na2SO4 sur l’oxydation de l’alliage Ti6242S est cependant moins marqué.L’évolution des propriétés mécaniques de l’alliage Ti6242S a également été étudiée après oxydation. Une simple oxydation de 100 h sous air provoque une diminution importante de la ductilité du matériau à cause de la zone de dissolution d’oxygène formée pendant l’oxydation. En présence d’un dépôt de NaCl et après 100h d’oxydation à 560°C, la perte de ductilité est encore plus importante et la rupture de l’éprouvette intervient dès la fin du domaine élastique. Dans ces conditions, la pièce perd une partie de sa section porteuse et la limite élastique et le module élastique du matériau restant sont fortement impactés. La présence d’un dépôt mixte NaCl/Na2SO4 pendant l’oxydation a un effet moins marqué sur les propriétés mécaniques du matériau, en accord avec la plus faible réactivité de l’alliage Ti6242S avec ce type de dépôt. Les mécanismes inhérents au changement de propriétés mécaniques sont expliqués dans le travail de thèse. / The use of titanium alloys in many applications (transport, energy, chemistry,...) allows significant weight savings in relation to the good mechanical properties/density ratio of these materials. Since titanium alloys are employed at high temperatures (T>500°C), their behavior in such conditions has to be studied in severe conditions in order to understand degradation mechanisms. Moreover, some specific conditions can be met during application, like thermal cycling, water vapour or presence of salts. These parameters are known to influence oxidation behavior of titanium alloys.In this thesis work, oxidation behavior of an aeronautics titanium alloy (Ti6242S) has been studied in air and moist air at 560°C. The effect of solid salt deposits (NaCl and/or Na2SO4) on the oxidation behavior of Ti6242S alloy has also been taken into account. Ti6242S samples were oxidized at 560°C for oxidation times up to 19 000 hours with or without solid salt deposits. NaCl deposit resulted in an important deterioration of Ti6242S alloy behavior at this temperature. Oxygen dissolution in the metal was no longer observed compared to ageing in air, but internal oxidation of the alloy could be evidenced, and cracks were observed deeply into the metallic substrate after oxidation. The corrosion resistance decrease in such conditions was attributed to the presence of chlorine and formation of volatile metallic chlorides due to the presence of NaCl. A degradation mechanism based on active oxidation of Ti6242S alloy exposed to NaCl salt was proposed. The second salt deposit tested consisted in a mixed NaCl/Na2SO4 salt deposit. The harmful effect of this salt deposit on the oxidation behavior of Ti6242S alloy was lower than that of a simple NaCl deposit.Mechanical properties of Ti6242S alloy exposed to solid salt deposits at 560°C were then studied. A simple oxidation in air for 100 hours without salt deposit resulted in an important loss of ductility of the tested samples due to the presence of oxygen solid solution into the metal. The same oxidation time caused an even more important loss of ductility for the samples covered by NaCl deposits. In this case, sample failure occurred at the end of the elastic deformation domain. Elastic modulus and yield strength were also strongly decreased. Mixed NaCl/Na2SO4 deposit exhibited a lower impact on the mechanical properties of the oxidized Ti6242S sample, in accordance with the lower reactivity of Ti6242S alloy with this type of salt deposit. Mechanisms explaining Ti6242S alloy mechanical behavior in such conditions were explained in this thesis work.

[pt] A redução na emissão de CO2 na atmosfera é um dos desafios atuais mais importantes enfrentados por diferentes indústrias no mundo. A geração de energia através da queima de combustíveis fósseis utilizando oxigênio puro [1], também chamada de tecnologia de oxicombustão, é uma opção utilizada pelas indústrias de geração de energia para minimizar os índices de concentração de CO2 até emissão ZERO [1,2]. Inevitavelmente, as tubulações dos trocadores de calor que conformam aquelas plantas de energia, sofrem corrosão em contato com os gases de combustão (H2O-CO2) em altas temperaturas. Estas tubulações, fabricadas com aço ou com ligas ferro-cromo vem sendo utilizadas no intuito de reduzir a corrosão. Tubulações com revestimentos/recobrimentos protetores tem sido também considerados para aumentar a resistência a processos corrosivos sem requerer o emprego de ligas de alto custo. Um revestimento adequado deve ser inerte e estável em altas temperaturas como é o caso dos materiais cerâmicos. A alumina, sendo um material estável em ambientes característicos do processo de oxicombustão apresenta características favoráveis para esta proteção [3]. Amostras de Fe-Cr foram oxidadas sob condições que simularam processos de Oxicombustão nos laboratórios do Bundesanstalt Für Materialforschung Und-Prüfung (BAM) Berlim-Alemanha. O processo ocorreu a 650 graus Celsius durante 2000 h, em atmosfera contendo 60 por cento CO2,30 por cento H2O, 7 por cento N2, 2 por cento O2 e 1 por cento SO2. A caracterização microestrutural das amostras oxidadas foi realizada nos laboratórios do instituto Nacional de Tecnologia (INT), utilizando técnicas de Microscopia Eletrônica de Varredura (MEV) e Espectroscopia por Dispersão de Energia de Raios-X (EDS). Foram produzidos riscos na superfície do revestimento de Al2O3, previamente aos testes de oxidação, para simular falhas no revestimento; além da eficácia do revestimento de alumina, foi também avaliado o papel do cromo como meio protetor contra a corrosão e de outros elementos de liga no processo de oxidação do aço P92, buscando identificar o mecanismo de oxidação. Como resultado do fluxo dos gases de oxicombustão há formação de camadas de Fe3O4, Fe2O3 e cromo-espinélio nas ligas sem revestimento. As amostras que possuíam o revestimento de alumina apresentaram ótima proteção, com resultados de uma alta eficácia, enquanto as amostras que tinham riscos apresentaram uma oxidação interna de oxidação cromo-espinélio protetor na matriz logo abaixo da região afetada. / [en] The reduction in the emission of CO2 in the atmosphere is one of the most important problems faced by different industries in the world. The generation of energy from oxyfuel oxygen, [1], also called Oxyfuel technology, is a matter of CO2 emission for ZERO [1,2]. Inevitably, as pipes of the heat exchangers that make up these power plants, they suffer corrosion in contact with the flue gases (H2O-CO2) at high temperatures. These pipes, made of steel or iron-chromium alloys, are not used instead of reducing corrosion. Pipes with protective coatings have already been submitted to increase resistance to corrosive processes without requiring the use of high cost alloys. One which must be inert and static at high temperatures is the case of ceramic materials. An alumina, being a suitable material to the environments characteristic of the Oxyfuel process, presents characteristics favorable to the protection [3]. Fe-9Cr samples were oxidized under conditions that simulated Oxyfuel processes in the laboratories of the Bundesanstalt Für Materialforschung Und-Prüfung (BAM) Berlin-Germany. The process occurred at 650 degree Celsius for 2000 h, in an atmosphere containing 60 percent CO2, 30 percent H2O, 7 percent N2, 2 percent O2 and 1 percent SO2. The microstructural characterization of the oxidized samples was performed in the laboratories of the National Institute of Technology (INT), using Scanning Electron Microscopy (SEM) and X-ray Energy Dispersion Spectroscopy (EDS) techniques. Risks were produced on the Al2O3 coating surface, prior to the oxidation tests, to simulate coating failures; besides the effectiveness of the alumina coating, the role of chromium as a protective medium against corrosion and other alloying elements in the oxidation process of P92 steel was also evaluated, in order to identify the oxidation mechanism. As a result of the flow of oxyfuel gases, Fe3O4, Fe2O3 and chromium-spinel layers are formed in the alloys without coating. The samples that had the alumina coating presented optimum protection, with results of a high efficiency, while the samples that had scratches presented an internal oxidation of protective chromium-spinel oxidation in the matrix just below the affected region.

Les superalliages à base nickel des turbines aéronautiques sont susceptibles de subir des phénomènes de corrosion et/ou d’oxydation à haute température par les environnements agressifs rencontrés en service. Aussi, des revêtements d’aluminure sont appliqués par dépôt chimique afin d’assurer la protection des pièces contre ces phénomènes. La dégradation progressive de ces revêtements mène à la nécessité de les enlever afin d’en appliquer des nouveaux. Les bains chimiques industriels pour enlever les revêtements et les oxydes sont très toxiques, polluants et plutôt empiriques. Ainsi, ce travail de thèse se proposait d’étudier une méthode alternative et originale, par voie électrochimique permettant de contrer les limitations des approches chimiques. La voie électrochimique par application d’un potentiel (mode potentiostatique) a été étudiée afin de procurer la sélectivité entre le substrat et le revêtement lors de la dissolution, ainsi que le contrôle in-situ du procédé à l’aide d’une cellule à 3 électrodes. La faisabilité de la méthode a d’abord été démontrée, puis différentes procédures (par cycles cathodique/anodique, en continu et, parfois, avec modification du potentiel imposé) ont été développées. Nous avons pu mettre en relation les états métallurgiques des systèmes revêtement/substrat avec leur comportement électrochimique et avons mis également en lumière que le taux de dissolution est principalement gouverné par la concentration d’aluminium dans le revêtement alors que lorsque le platine est incorporé à ce même revêtement, le taux de dissolution est homogène. De même, nous avons démontré par XPS et par MET que la teneur en chrome modifie de manière significative l’homogénéité du décapage lors des phases de polarisation cathodique par un mécanisme de passivation de la surface, qui bloque l’activité électrochimique. Cependant, la tenue en oxydation cyclique des revêtements décapés par voies chimique et électrochimique n’a pas pu véritablement être démontrée car les revêtements avaient une microstructure différente. Enfin, des essais sur pièces de turbine ont montré le haut degré de sélectivité de l’approche ici étudiée. / Nickel based superalloys of aeronautical turbines are subjected to high temperature oxidation and/or corrosion in service conditions. Thus, protective aluminide coatings are applied onto the parts by chemical vapor deposition. The degradation of the coatings with time requires them to be removed prior to recoating the parts. The chemical baths industrially employed are toxic, polluting and quite empirical. Therefore, this thesis aimed at studying an alternative and original electrochemical method to circumvent the drawbacks of the chemical approach. Fixed potentials (potentiostatic mode) were thus applied to provide selectivity between the coating and the substrate upon the dissolution process, as well as to ensure in-situ control through a 3-electrode cell. The feasibility of the method was first demonstrated, then different procedures (cathodic/anodic cycles; continuous anodic and sometimes with modification of the potential) were investigated. The correlations between the metallurgical phases of the coating/substrate systems were elucidated. It also appeared that dissolution is mainly governed by the concentration of aluminium in the coating whereas the incorporation of platinum to the coating brought about the homogeneous dissolution. In addition, XPS and MET confirmed the hypothesis by which the chromium content drastically change the stripping homogeneity upon the cathodic polarization step by passivation of the surface and the subsequent electrochemical blocking. However, the results on the cyclic oxidation behaviour of the coatings priorly stripped chemically or electrochemically were not conclusive enough as the microstructure of the original coatings was different. Finally, quite a few stripping trials were carried out onto real turbine parts that confirmed the high selectivity of the electrochemical approach studied.

Dans les systèmes d’Electrolyse Haute Température (EHT), le matériau choisi comme interconnecteur doit avoir une bonne résistance à la corrosion sous air et sous mélange H2/H2O à 800 °C, et maintenir une bonne conductivité sur de longues durées. Dans ce cadre, l’objectif de ce travail était, d’une part, d’évaluer un alliage ferritique commercial (l’alliage K41X) comme matériau d’interconnecteur pour l’application EHT. Dans ce but, ont été mis en place des essais d’oxydation en four et en thermoblance pour accéder aux cinétiques d’oxydation, et des mesures de résistivité pour évaluer le paramètre ASR (Area Specific Resistance) à 800°C. D’autre part, l’étude a permis d’apporter des éléments de compréhension plus fondamentaux sur les mécanismes d’oxydation des alliages chromino-formeurs, en particulier sous mélange H2-H2O, par le biais d’essais et de caractérisations spécifiques (Photoélectrochimie, traçage isotopique, essais de longues durées). Cette double stratégie est également appliquée pour l’étude d’une solution de revêtement (obtenu à l’aide de la MOCVD) basée sur l’oxyde pérovskite LaCrO3 qui présente des propriétés de conductivité élevée particulièrement intéressante en vue de l’application EHT. Ainsi, cette étude amène également des éléments de compréhension sur le rôle du lanthane comme élément réactif dont l’effet est souvent discuté dans la littérature. Pour les deux milieux, à 800°C, la couche d’oxyde formée est une couche duplexe Cr2O3/(Mn,Cr)3O4 , recouverte dans le cas du mélange H2-H2O par une fine couche d’oxyde spinelle Mn2TiO4 . Sous air, le mécanisme de croissance déterminé ici est cationique, en accord avec la littérature. La présence d’un revêtement LaCrO3 ne modifie pas ce mécanisme mais ralentit la cinétique de croissance de la couche sur les premières centaines d’heure. De plus, le revêtement améliore l’adhérence et la conductivité de la couche d’oxyde. Sous mélange H2-H2O, le mécanisme de croissance se révèle anionique. La présence de revêtement ralentit la cinétique d’oxydation. Bien que .d’épaisseurs similaires, les couches d’oxyde présentent sous air une résistivité d’un ordre de grandeur inférieure à celle mesurée sous H2-H2O. Il est mis en évidence que la forte résistivité de l’alliage en milieu H2-H2O est liée à la présence de protons issus de la vapeur d’eau présents dans la couche d’oxyde. Le revêtement ne permet néanmoins pas d améliorer la conductivité sous H2-H2O. / In High Temperature Vapor Electrolysis (HTVE) system, the materials chosen for the interconnectors should have a good corrosion behaviour in air and in H2-H2O mixtures at 800°C, and keep a high electronic conductivity over long durations as well. In this context, the first goal of this study was to evaluate a commercial ferritic alloy (the K41X alloy) as interconnect for HTVE application. Oxidation tests in furnace and in microbalance have therefore been carried out in order to determine oxidation kinetics. Meanwhile, the Area Specific Resistance (ASR) was evaluated by Contact Resistance measurements performed at 800°C. The second objective was to improve our comprehension of chromia-forming alloys oxidation mechanism, in particular in H2/H2O mixtures. For that purpose, some specific tests have been conducted: tracer experiments, coupled with the characterization of the oxide scale by PEC (PhotoElectroChemistry). This approach has also been applied to the study of a LaCrO3 perovskite oxide coating on the K41X alloy. This phase is indeed of high interest for HTVE applications due to its high conductivity properties. This latter study leads to further understanding on the role of lanthanum as reactive element, which effect is still under discussion in literature.In both media at 800°C, the scale is composed of a Cr2O3/(Mn,Cr)3O4 duplex scale, covered in the case of H2-H2O mixture by a thin scale made of Mn2TiO4 spinel. In air, the growth mechanism is found to be cationic, in agreement with literature. The LaCrO3 coating does not modify the direction of scale growth but lowers the growth kinetics during the first hundreds hours. Moreover, with the coating, the scale adherence is favored and the conductivity appears to be slightly higher. In the H2-H2O mixture, the growth mechanism is found to be anionic. The LaCrO3 coating diminishes the oxidation kinetics. Although the scale thickness is about the same in both media, the ASR parameter is one order of magnitude higher in H2/H2O than in air. Specific contact resistance tests show that the higher resistivity in the H2/H2O mixture is closely linked to the presence of protons in the scale. Moreover, tracer experiments show that these protons come from the water molecule dissociation, and not from the H2 molecule. In H2/H2O, the LaCrO3 coating does not increase the conductivity