A liga Incoloy 800 é usada em tubulações do gerador de vapor (GV) nos reatores de água pressurizada (PWR). Nestes, os tubos são suportados por placas. A literatura tem reportado a ocorrência de falhas por corrosão por frestas na região onde os tubos entram em contato com as placas de suporte, atribuída ao acúmulo conjunto de cloreto (Cl-) e tiossulfato (S2O32-). Para minimizar este problema inibidores de corrosão são adicionados à água de alimentação. Apesar da corrosão por frestas ser o foco principal da literatura, os mecanismos por trás do efeito conjunto de ambos os íons agressivos sobre a resistência à corrosão localizada das superligas em conjunto com o efeito da presença de inibidores têm sido pouco abordados. Desse modo, o presente estudo utilizou técnicas eletroquímicas e de caracterização superficial para estudar o efeito da presença de S2O32- em diferentes concentrações e da adição de 10-6M do inibidor de corrosão etanolamina (ETA) sobre a resistência à corrosão por pite da superliga Incoloy 800 em meio 0,3M de Cl-. Os ensaios de espectroscopia de impedância eletroquímica (EIS) realizados no potencial de circuito aberto (OCP) mostraram que, para todas as condições utilizadas, a liga se mantém passiva, e que o comportamento melhora com a diminuição da razão [Cl-/S2O32-] e com o tempo de imersão. Para esta condição, as análises por XPS mostraram que a interação do Cl- com a camada passiva é fraca quando este íon se encontra isolado no meio e que o tiossulfato apresenta condições para a redução sobre a película passiva do Incoloy 800, ambos os fatores podendo ser responsáveis pela melhora da resposta de impedância com o tempo de imersão. O ajuste dos diagramas de impedância com circuitos equivalentes (CEE) evidenciou a adsorção de S2O32-, indicando que este íon controla a resposta de impedância em altas frequências quando adicionado em concentrações equivalentes à concentração de cloretos. Os ensaios de polarização anódica mostraram que o Incoloy 800 não é suscetível à corrosão localizada na presença apenas de tiossulfato, porém apresenta corrosão por pites em 0,3M de NaCl, exibindo, no entanto, propriedades de repassivação. Por sua vez, na solução contendo os dois ânions o comportamento eletroquímico é controlado pela razão [Cl-/S2O32-]. Assim para uma alta razão, a quebra da película se dá pela ação do cloreto com o tiossulfato atuando de modo a estabilizar os pites metaestáveis, diminuindo o potencial de quebra e impedindo a repassivação do eletrodo. Por sua vez, para uma baixa razão, o oxiânion atua de modo inibitivo, impedindo o efeito prejudicial do Cl- sobre a camada passiva. A caracterização por MEV mostrou que, sempre que ocorreu, a corrosão por pites teve início nas proximidades das partículas de segunda fase de TiN, e que a presença do tiossulfato aumenta a agressividade do ataque localizado, formando pites maiores e mais profundos, embora em menor número, provavelmente devido à formação de sulfetos metálicos nas regiões submetidas ao ataque localizado. No OCP, a adição de 10-6M de ETA ao meio contendo 0,3M de NaCl sem e com 0,075M de S2O32- provocou mudanças no potencial de corrosão e diminuiu o módulo de impedância da liga. As análises por XPS mostraram a adsorção da ETA à superfície do eletrodo e que este aumenta à adsorção do íon tiossulfato à superfície do eletrodo. Por sua vez, o ajuste dos diagramas de impedância com CEE indicou a ocorrência de processos controlados por difusão na camada passiva. Em concordância com os ensaios de impedância, as curvas de polarização anódica apresentaram maiores valores de corrente passiva na presença do inibidor. No que concerne à corrosão por pites, a adição de 10-6M de ETA não inibiu a quebra da película protetora para a solução contendo apenas íons cloreto e impediu a repassivação, levando à formação de pites maiores a mais profundos. Porém na presença de Cl- e S2O32- (em baixa concentração) houve inibição da quebra da película passiva, indicando um possível efeito sinergético entre a amina e o oxiânion no sentido de dificultar a adsorção dos íons cloreto. / Alloy 800 is used for tubing in the steam generator (SG) at Pressurized Water Reactors (PWR). These pipes are supported by plates. The literature reports the occurrence of crevice corrosion failures on the tubes in the regions where they are in contact to the supporting plates, which has been attributed to the accumulation of chloride (Cl-) and thiosulfate (S2O32-). In order to minimize this problem, corrosion inhibitors are added to the feed water. Despite crevice corrosion be the main focus of the literature, the mechanisms behind the joint effect of both aggressive ions on the localized corrosion resistance of superalloys in the presence of inhibitors have been scarcely investigated. Therefore, the present study used electrochemical and surface characterization techniques in order to study the effect of S2O32- presence in different concentrations and the addition of 10-6M of ethanolamine (ETA) corrosion inhibitor on the pitting corrosion resistance of Alloy 800 in 0.3M NaCl solution. The electrochemical impedance spectroscopy (EIS) tests performed at open circuit potential (OCP) showed, for all conditions applied, that the alloy maintains its passivity, which is enhanced as the [Cl-/S2O32-] ratio decreases as well as the immersion time. For this condition, the XPS analyses showed that Cl- ions interact weakly with the passive layer when they are the sole aggressive species in the medium and that thiosulfate may be reduced on the passive film of Alloy 800, both factors may explain the improvement of impedance response with the immersion time. EIS diagrams fitting with electrical equivalent circuits (EEC) pointed to S2O32- adsorption at the alloy surface, and indicated that these ions may control the high frequency impedance response when added at concentrations equivalent to that of chloride ions. Anodic polarization experiments showed that Alloy 800 is not susceptible to localized corrosion in the presence of only S2O32-, but exhibits pitting corrosion in 0.3M NaCl, showing, although, repassivation properties. On the other hand, in the medium containing both anions the electrochemical behavior is controlled by [Cl-/S2O32-] ratio. Thus, for a high ratio, chlorides breakdown the film and thiosulfate stabilize the metastable pits, reducing the breakdown potential and preventing the repassivation of the electrode. However, for a low ratio, the oxyanion acts as inhibitors, preventing the detrimental effect of Cl- on the passive layer. SEM characterization showed that, whenever it occurred, pitting corrosion starts at TiN second phase particles, and that the presence of thiosulfate enhances the aggressiveness of the localized attack, forming larger and deeper pits, but in a lesser quantity, probably due to the formation of metallic sulphides in regions submitted to the localized attack. On the OCP, the addition of 10-6M of ETA to the medium containing 0.3M NaCl with and without 0.075M S2O32- caused shifts on the corrosion potential and decreased the alloy impedance modulus. The XPS analyses showed the adsorption of ETA on the electrode surface and that it also enhances the thiosulfate adsorption. On the other hand, fitting of the EIS diagrams with EEC indicated the occurrence of diffusion-controlled processes within the passive layer. In agreement with the impedance experiments, the anodic polarization curves showed higher passive current values in the presence of inhibitor. With regard to pitting corrosion, the addition of 10-6M of ETA did not inhibit the breakdown of the passive film in the solution containing only chloride ions and also prevented the repassivation process, leading to the formation of larger and deeper pits. However, in the presence of Cl- and S2O32- (low concentration) the inhibition of the passive layer breakdown occurred, indicating a possible synergistic effect between the amine and the oxyanion in order to hindering the adsorption of chloride ions.

Les générateurs de vapeur sont d'imposants échangeurs de chaleur qui alimentent les turbines des centrales nucléaires à eau pressurisée. Au cours de leur exploitation, des dépôts d'oxydes s'y accumulent et obstruent progressivement des trous prévus pour le passage du fluide. Ce phénomène, appelé colmatage, pose des problèmes de sûreté. Une méthode de diagnostic est nécessaire pour optimiser la stratégie de maintenance permettant de s'en prémunir. La piste explorée dans cette thèse est l'analyse de la réponse dynamique des générateurs de vapeur lors de transitoire de puissance, à l'aide d'un modèle physique monodimensionnel. Deux améliorations ont été apportées au modèle existant au cours de la thèse : la prise en compte des débits perpendiculaires à l'axe du générateur de vapeur et la modélisation du déséquilibre cinématique entre la phase liquide et la phase vapeur. Ces éléments ont ajouté des degrés de liberté permettant de mieux reproduire le comportement réel des générateurs de vapeur. Une nouvelle méthodologie de calage et de validation a alors été proposée afin de garantir la robustesse du modèle.Le problème inverse initial était mal posé car plusieurs configurations spatiales de colmatage peuvent donner des réponses identiques. La magnitude relative de l'effet des dépôts suivant leur localisation a été évaluée par analyse de sensibilité avec la méthode de Sobol'. La dimension de la sortie fonctionnelle du modèle a au préalable été réduite par une analyse en composantes principales.Enfin, une méthode de réduction de dimension appelée régression inverse par tranches a été mise en œuvre pour déterminer dessous-espaces de projection optimaux pour le diagnostic. Une méthode de diagnostic plus robuste et mieux maitrisée que celle existante a pu être proposée grâce à cette nouvelle formulation. / Steam generators are massive heat exchangers feeding the turbines of pressurised water nuclear power plants. Internal parts of steam generators foul up with iron oxides which gradually close some holes aimed for the passing of the fluid. This phenomenon called clogging causes safety issues and means to assess it are needed to optimise the maintenance strategy. The approach investigated in this thesis is the analysis of steam generators dynamic behaviour during power transients with a monodimensional physical model. Two improvements to the model have been implemented. One was taking into account flows orthogonal to the modelling axis, the other was introducing a slip between phases accounting for velocity difference between liquid water and steam. These two elements increased the model's degrees of freedom and improved the adequacy of the simulati onto plant data. A new calibration and validation methodology has been proposed to assess the robustness of the model. The initial inverse problem was ill posed: different clogging spatial configurations can produce identical responses. The relative importance of clogging, depending on its localisation, has been estimated by sensitivity analysis with the Sobol' method. The dimension of the model functional output had been previously reduced by principal components analysis. Finally, the input dimension has been reduced by a technique called sliced inverse regression. Based on this new framework, a new diagnosis methodology, more robust and better understood than the existing one, has been proposed.

Le phénomène de relâchement de nickel des tubes de générateur de vapeur des centrales R.E.P. est responsable d'une grande partie de la contamination radioactive du circuit primaire. Une solution envisagée pour limiter ce relâchement est l'application d'un revêtement anticorrosion, côté interne des tubes. Ce travail vise à étudier la faisabilité et l'efficacité de ce type de traitement de surface dans les conditions du circuit primaire (320°C, 150 bars). L'étude a permis d'établir un procédé de synthèse par voie sol-gel compatible avec des substrats métalliques, conduisant à des films denses et mésoporeux à partir d'alcoxydes de métaux de transition, dont la réactivité est contrôlée par l'ajout de l'acétylacétone. La température de traitement thermique conditionne la cristallisation des films, la formation d'une couche enrichie en chrome contribuant à l'effet anticorrosion et la diffusion de nickel et de fer dans le film. Les films denses de ZrO2 présentent un meilleur effet barrière à la diffusion cationique et constitue une barrière anticorrosion. L'applicabilité des films de ZrO2 sur les tubes de générateur de vapeur à l'état de réception a été réalisée en adaptant l'épaisseur du film. Des essais de vieillissement dans les conditions du milieu primaire en autoclave et dans une boucle à recirculation ont été réalisés. Ces essais ont montré un phénomène de dissolution et reprécipitation des films de TiO2 tandis que les films de ZrO2 conservent davantage leur structure, malgré la formation de porosités en surface. Les films de ZrO2 vieillis pendant 500 h semblent conserver leurs propriétés de barrière à la diffusion de nickel. / Steam generator nickel release represents a major contribution to the radioactive contamination of the Pressurized Water Reactor primary circuit. One of the considered solutions is the deposition of a protective coating on the internal side of the alloy 690 tubes. The goal of this work is to study these coatings and their feasibility and efficiency in the primary circuit conditions (320°C, 150 bars). Firstly, a sol-gel thin film synthesis, leading to dense and mesoporous films, from transition metals alcoxides (butoxide titanium and propoxide zirconium) has been studied. Their reactivity is controlled by acetylacetone, which plays the role of complexing agent. The thermal treatment temperature appears to be a key parameter of the process, as it determines the oxide crystallization, the formation of a rich chromium layer below the film (which reinforces anticorrosion properties) and the nickel and iron diffusion in the film. ZrO2 coatings behave as cationic diffusion barriers and limit the corrosion. The applicability of ZrO2 coatings on industrial substrates, namely steam generators internal side with a 200 nm roughness, has been carried out by adapting the film thickness. Ageing tests in the primary circuit conditions have been conducted in an autoclave and a circulation loop. These tests have shown a dissolution – reprecipitation behavior of TiO2 coatings whereas ZrO2 coatings keep their structure despite the formation of surfacic porosities. ZrO2 dense coatings seem to keep limiting the nickel diffusion after 500 h of ageing in the primary circuit conditions.

No description available.

Orientador: João Andrade de Carvalho / Resumo: Caldeiras de produção de vapor são utilizadas no setor siderúrgico para produzir e disponibilizar vapor para o processo de geração de energia e para os vários setores que necessitam de aquecimento durante a fabricação de seus produtos, como por exemplo, a vaporização de criogênicos para distribuição na planta. Portanto, caldeiras são equipamentos que necessitam ter confiabilidade. Atualmente, a CSN (siderúrgica brasileira de grande porte) possui duas caldeiras do início da década de 80 que somente partem e operam com uma chama piloto utilizando gás de coqueria, um gás que é subproduto da produção de coque em uma planta siderúrgica. Assim, para alcançar o objetivo de mais confiabilidade e flexibilidade na operação destas caldeiras, utilizou-se os métodos de índice Wobbe, corrigido pela pressão, e o método dos múltiplos índices de Weaver para avaliar a substituição do gás de coqueria pelo gás natural de modo que estas caldeiras possam operar com gás natural em caso de indisponibilidade de gás de coqueria. Mesmo que o aporte energético entre os gases seja diferente, este pode ser ajustado pela pressão do gás. A temperatura de chama adiabática não tem variação significativa, reduzindo-se apenas 1,4%. As emissões de fumaças e CO2 aumentam com a substituição, porém as emissões de NOx tem redução. A utilização do método dos múltiplos índices de Weaver para análise de intercambiabilidade demonstra que o gás natural não é um substituo para um queimador projetado para queimar gás de co... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: Steam generators are used in the steel industry to produce and supply steam process for power generation and for other sectors that need heat to manufacture their products, such as the cryogenics vaporization for distribution in the facilities. Therefore, steam generators are equipment that need to have reliability. Currently, CSN (large Brazilian steelmaker) has two steam generators from the early 1980s that only startup and operate with a pilot flame using coke oven gas, a gas that is a byproduct of coke production at a steel plant. Thus, in order to achieve the working objective, reliability and flexibility in the operation of these steam generators, the Wobbe index method, with pressure-corrected, and the Weaver's multiple index method were used to verify the coke oven replacement for natural gas, and then, these steam generators can operate with natural gas in case of coke oven gas unavailability. Results shown in the same way that the energy increase between the gases are different can be adjusted in the pressure reduction. The flame temperature has insignificant variation, only 1.4%. Off gas and CO2 emissions increase with interchangeability. However, NOx emissions are reduced. The Weaver multiple index method for interchangeability analysis demonstrates that natural gas is not a gas to replace coke oven gas in a burner designed to burn coke oven gas, but if the burner is designed to natural gas, coke oven gas may be the substitute gas. Regarding the heat input and pri... (Complete abstract click electronic access below) / Mestre

The goal of this thesis is to simulate the course of events during Dukovany Nuclear Power Plant blackout and to determine the optimal process of cooling down the cold branches of the primary circuit loops to secure the maximum amount of the primary fuel needed for the residual heat outlet so that the operating staff has as much time as possible for renewing the electric power supply. The first part of the thesis describes nuclear power plants built in the Czech Republic and in the world as well as reactor blocks whose construction is being considered. The detailed description of Dukovany’s steam generator is shared in chapter three. Following chapter summarizes blackouts that occurred at power plants around the world, events that might have led to blackouts in the Czech Republic, and it also describes current approach to blackout problematics at Dukovany Nuclear Power Plant. Chapters six and seven contain the core of the thesis. That includes detailed description of a mathematical model explaining the behaviour of a reactor block during blackout as well as the analysis of the results found.

The thesis deals with a project of a steam generator heated with liquid sodium. The first section describes some types of steam generators at nuclear power plants which have been projected or put into use. The next part presents a draft concept of the steam generator, solved by this work. The implementation of the steam generator module has been selected from several options, based on the thermal, hydraulic and stress calculations and on the chosen criteria. The conclusion of this thesis deals with the evaluation of the final solution in terms of nuclear safety and technical solutions, and compares this solution to similar projects following various criteria.

This thesis deals with thermal calculation and design of proportions and layout of calorific components of a heat recovery steam generator according to given output parameters of steam and input parameters of flue gas. Furthermore, the proportions of boiler drums and irrigation and transfer pipes are designed and draught losses are calculated.

This master‘s thesis describes thermal calculation and design of proportions of calorific components of a heat recovery steam generator (HRSG) for given input parameters of flue gas and output parameters of steam. Part of the thesis is design proportions of boiler drums, irrigation and transfer pipes. On the end of the thesis is counting draught losses and design drawning of steam generator.

This master´s thesis deals with two pressure heat recovery steam generator behind gas turbine. From the entered parameters steam and gas were designed heating surfaces, specifically their size and configuration. The overall design is then proposed in the drawing.