No presente trabalho foi estudado o comportamento de um aço inoxidável austenítico do sistema Fe-Cr-Mn-N, nas condições como recebido, solubilizado e sensitizado, quando submetidos à meios contendo cloretos. Para analisar a suscetibilidade à corrosão sob tensão foram utilizados corpos de prova dos tipos DCB (\"Double Cantilever Beam\") e C(T) (\"Compact- Tension\"), pré-trincados em fadiga, com entalhes laterais e carregados com cunhas. Os meios empregados foram as soluções aquosas 45% em peso de MgCl2 na temperatura de ebulição de 154°C, água do mar sintética na temperatura ambiente e de ebulição de 100°C e 3,5% em peso de NaCI na temperatura ambiente. A suscetibilidade à corrosão sob tensão foi avaliada em termos do fator limite de intensidade de tensão, KISCC, e foram caracterizados os aspectos fractográficos dos corpos de prova em que ocorreram propagação de trinca por corrosão sob tensão. Foi verificado que apenas os corpos de prova do aço E3949 nas condições como recebido e sensitizado, foram suscetíveis à corrosão sob tensão em solução aquosa de 45% em peso de MgCl2 na temperatura de ebulição. Também foi determinado o comportamento eletroquímico do material nas condições citadas acima com relação aos meios empregados. Os resultados das curvas de polarização obtidas mostraram que o material apresenta baixa resistência à corrosão, principalmente em meios de MgCl2. / The present work studies the stress corrosion cracking behavior in austenitic Fe-Cr-Mn-N stainless steel, in as received, solubilized and sensitized conditions, when submited to several chlorides environments. To evalued the stress corrosion cracking susceptibility, DCB (\"Double Cantilcver Beam\") and C(T) (\"Compact- Tension\") specimens, fatigue precracked, side grooved and wedge loaded were used. The environments employed were boiling solution of 45 wt% of MgCl2 at 154ºC, synthetic sea water at room and 100°C temperatures, and a solution with 3,5 wt% of NaCI at room temperature. The susceptibility to stress corrosion cracking has been evaluated in terms of the threshold stress intensity factor, KISCC, and the fracture surface appearance of those specimens whose the crack propagation took place was characterized. The results showed that only the specimens in the as received and sensitized conditions, were suceptible to the stress corrosion cracking effect in the solution with 45 wt% of MgCl2 at the boilling temperature. Also, it has been verified the electrochemical behavior of this steel when submited in the above environments. The results of polarization curves showed that the material presents low corrosion strength, mainly in MgCl2 environments.

Afin de répondre aux besoins croissants en énergie primaire, le groupe Europlasma a développé le procédé CHO-Power permettant de valoriser énergétiquement un mélange de refus de tri d’ordures ménagères et de résidus de biomasse. L’une des particularités de ce procédé est l’utilisation d’un réacteur de dégradation thermique des goudrons et des particules solides fines par assistance plasma. L’objectif de cette étude de mieux appréhender les mécanismes réactionnels mis en jeu lors de l’épuration thermique du gaz. Dans cette optique, un réacteur pilote a été dimensionné puis construit sur la plate-forme de Recherche et Développement d’Europlasma. Il a été ensuite nécessaire de modifier le schéma réactionnel permettant la modélisation numérique de la dégradation des goudrons. Ce schéma réactionnel, couplé à l’utilisation d’un logiciel de mécanique des fluides numérique, permet de représenter les processus couplés (chimie, aéraulique, transferts thermiques) se déroulant au sein du réacteur. Deux modifications importantes ont été alors apportées au modèle cinétique simplifié jusque-là utilisé : la modélisation d’une phase discrète réactive permettant de prendre en compte la gazéification des particules de résidus carbonés et l’ajout de nouvelles voies réactionnelles afin de mieux modéliser la formation des particules de suie et de ses précurseurs. À terme, la comparaison des valeurs expérimentales à celle issues de la modélisation numérique permettra de valider ou non le schéma réactionnel dans sa globalité. / In order to contest to the high world demand for primary energy, the Europlasma group developed a new process, called CHO-Power, to enhance the thermochemical potential of a mixture of urban waste and biomass residues. One of the characteristics of this process is the use of a high temperature reactor assisted by a plasma torch for tar and soots thermal cracking. The aim of this study to improve the knowledge of the global reaction mechanism involved during the thermal treatment of gas. In this context, a pilot plant reactor was designed and built on the Europlasma Research and Development Center. During this work, the reaction pathway used to represent tars cracking at high temperature has been enhanced. Coupled to a computational fluid Dynamics Software, allow simulating the complex processes occurring within the reactor (aeraulics, reaction, and heat transfer). Two major changes were made to the simplified kinetic model previously used: the modeling of a discrete and reactive phase to take into account the possible particle gasification of carbonaceous residues and the addition of new reaction pathways to enhance the modeling of the formation of soot and its precursors. The comparison between the experimental and numerical values will validate or not the global reaction scheme and will give important information about the next evolution of the tar degradation scheme.

No presente trabalho produziu-se amostras de flexão em três pontos, SENB, a partir de placas moldadas por compressão feitas de uma resina de Poli(metacrilato de metila) comercial. Dois conjuntos contendo 6 amostras cada foram então pré-trincados por meio de uma lamina afiada de aço adotando-se dois métodos diferentes propostos pela literatura técnica: através de batidinhas (gentle tapping) e através da inserção controlada a velocidade constante da lâmina, ambas usando um dispositivo especialmente desenhado para este fim. Estas amostras foram então submetidas ao ensaio de tenacidade à fratura em deformação plana, KIc, com o intuito de se testar a hipótese de que os diferentes métodos introduzem diferentes padrões de dano na matriz próxima à região da ponta da pré-trinca, o que, por sua vez, influência os resultados obtidos. Adotou-se a norma ASTM D 5045 como padrão do ensaio. Todas as amostras produziram resultados válidos para KIc, considerando-se os critérios da norma. Os resultados confirmam a hipótese inicial mostrando que os diferentes métodos de introdução da pré-trinca influenciam o valor medido de KIc a um nível de significância de 5% para a diferença das médias obtidas nos dois grupos, sendo que o valor mais conservador é obtido quando as pré-trincas são introduzidas pelo método das batidinhas (KIc = 1,15 ± 0,11 MPa m1/2). Com base nestes resultados novas amostras com geometria auto-similar às anteriores foram produzidas e usadas para a investigação do estado de tensão desenvolvido nas amostras pelo método da fotoelasticidade. Os resultados confirmam que os diferentes métodos de pré-trincamento produzem diferentes padrões de Moiré próximos à ponta da trinca, o que prova que os estados de tensão são efetivamente afetados e que o método da inserção controlada produz a maior perturbação no campo de tensão próximo à ponta da pré-trinca. / Single-Edge-Notch Bending samples produced out of compression-molded plates obtained from a commercial Poly(methyl metacrylate), PMMA, resin were investigated concerning the influence of the adopted pre-cracking methodology on plane strain fracture toughness results according to ASTM D 5045 standard. Two sets of 6 samples each were pre-cracked using a sharp-edge scalpel steel blade using two methodologies proposed in the technical literature: by gentle tapping on the blade and by controlled insertion at constant velocity, both using a device specially designed for these purposes. These sample were, then, submitted to the plane strain fracture toughness (KIc) test based on the hypothesis that different pre-cracking methods result in different damage levels of the matrix near the pre-crack tip and, hence, in different measured values for KIc. All samples produced valid results for KIc based on the geometric criteria adopted by the standard. The results confirm the original hypothesis showing that the two pre-cracking methods influence the measured value at a significance level of 5% for the comparison of the averages obtained in both sets. The most conservative value for plane strain fracture toughness of the investigated resin is obtained by pre-cracks introduced by gentle tapping on the blade (KIc = 1.15 ± 0.11 MPa m1/2). Based on these results new samples with a self-similar geometry were produced and submitted to photoelasticity tests to investigate the influence of the pre-cracking methods on the strain-field developed during three-point bending loading. The results confirm that the different methods produce different Moiré patterns close to the pre-crack tip, proving that the developed stress fields are different and that pre-cracks introduced by controlled insertion of the blade produce the largest perturbations of the strain field close to the pre-crack tip.

Made available in DSpace on 2014-12-17T15:41:53Z (GMT). No. of bitstreams: 1 RicardoMO_DISSERT.pdf: 2015893 bytes, checksum: dea62cb9390752fd7430293c73c9a1dd (MD5) Previous issue date: 2011-12-06 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / The catalytic cracking of triglycerides presents itself as a possible alternative to the production of biofuels with low emission of pollutants. In this work were synthesized the SAPO-5, the catalysts for the cracking reaction of soybean oil is presented. The solids were powder X-ray diffraction (XRD), thermogravimetric analysis (TG/DTG) and infrared spectroscopy (FTIR). The analyses indicated that the synthesis method has employed to obtain materials with high surface area and high acid. The soybean oil thermal and thermal catalytic cracking, realized from the room temperature to 450 ?C in a simple distillation system, has allowed obtaining two liquid fractions, each consisting of two phases, one aqueous and another organic, organic liquid (OL). The OL obtained from first fractions has shown high acid index, even in the thermal catalytic process. The products obtained in the cracking of soybean oil were analyzed by distillation, acid number, infra-red spectroscopy, density, viscosity, carbon residue, cetane number determination and characterization. The analysis of the products obtained in the presence and in the absence of the SAPO-5 permitted to conclude that all the solids tested presented catalytic activity in the deoxygenation of final products only at the second step of the cracking process / O craqueamento catal?tico de triacilglicer?deos se apresenta como uma alternativa vi?vel para a produ??o de biocombust?veis com baixa emiss?o de poluentes. Neste trabalho foi sintetizado o SAPO-5, o catalisador foi utilizado na rea??o de craqueamento do ?leo de Girassol. O s?lido foi caracterizado por difra??o de raios -X, an?lise termogravim?trica, espectroscopia no infravermelho. As an?lises indicaram que atrav?s do m?todo de s?ntese empregado foram obtidos materiais com elevada ?rea espec?fica e alta acidez. A partir do craqueamento t?rmico e termocatal?tico do ?leo de girassol, realizado desde a temperatura ambiente at? 450 oC em um sistema de destila??o simples, foram obtidas duas fra??es l?quidas, cada uma contendo duas fases, uma aquosa e outra org?nica. A primeira fra??o do l?quido org?nico obtido apresentou alto ?ndice de acidez, no processo de craqueamento t?rmico. Os produtos obtidos no craqueamento de ?leo de Girassol foram analisados por destila??o, ?ndice de acidez, espectroscopia no infravermelho, densidade, viscosidade e determina??o do ?ndice de cetano. A an?lise dos produtos obtidos na presen?a e na aus?ncia do SAPO-5, sintetizados permitiu concluir que todos os s?lidos testados apresentaram atividade catal?tica para a desoxigena??o dos produtos finais apenas na segunda etapa do processo de craqueamento

Made available in DSpace on 2014-12-17T15:42:09Z (GMT). No. of bitstreams: 1 SolangeAQ_TESE.pdf: 2741616 bytes, checksum: ad21da6882b166123a02d610e3d096ef (MD5) Previous issue date: 2009-08-06 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The nanostructured molecular sieve SBA-15 was synthesized by the hydrothermal method, and modified with lanthanum with Si/La molar ratios of 25, 50, 75 and 100. The materials were evaluated as catalysts for the cracking of n-hexane model reaction. Type SBA- 15 and LaSBA-15 mesoporous materials were synthesized using tetraetilortosilicato as a source of silica, hydrochloric acid, heptahydrate lanthanum chloride and distilled water. Pluronic P123 triblock. polymer was used as structure template. The syntheses were carried out by 72 hours. The obtained SBA-15 samples were previously analyzed by thermogravimetry, in order to check the conditions of calcination for removal of organic template. Then, the calcined materials were characterized by X-ray diffraction, infrared spectroscopy, adsorption and desorption of nitrogen, scanning electron microscopy and X-ray microanalysis by dispersive energy. The acidity of the samples was determined using adsorption of n-bulinamina and desorption followed by thermogravimetry. It was found that the hydrothermal synthesis method was suitable for the synthesis of the SBA-15 mesoporous materials, with an excellent degree of hexagonal ordering. The reactions of catalytic cracking of n-hexane were carried out using a fixed bed continuous flow microreactor, coupled on-line to a gas chromatograph. From the catalytic evaluation, it was observed that the mesoporous materials containing lanthanum showed different results for the reaction of cracking of nhexane compared to the unmodified mesoporous material SBA-15. As a result of cracking was obtained as main products hydrocarbons in the range of C1 to C5. The catalyst that showed better properties in relation to the acidity and catalytic activity was LaSBA-15 with the ratio Si/La = 50 / A peneira molecular nanoestruturada SBA-15 foi sintetizada pelo m?todo hidrot?rmico, e modificada com lant?nio com raz?es molares Si/La de 25, 50, 75 e 100. Os materiais obtidos foram avaliados como catalisador para a rea??o modelo de craqueamento de n-hexano. Os materiais mesoporosos tipo SBA-15 e LaSBA-15 foram sintetizados utilizando tetraetilortosilicato, como fonte de s?lica, ?cido clor?drico, cloreto de lant?nio heptahidratado e ?gua destilada. Como direcionador estrutural foi utilizado copol?mero tribloco Pluronic P123. As s?nteses foram realizadas durante 72 horas. As amostras de SBA-15 modificadas foram avaliadas por termogravimetria para verificar as condi??es de calcina??o para remo??o do direcionador org?nico. Ap?s a retirada do direcionador as amostras de SBA-15 modificadas com diversas raz?es Si/La (25, 50, 75 e 100) foram caracterizadas por an?lises por difra??o de raios-X, espectroscopia na regi?o do infravermelho, adsor??o e dessor??o de nitrog?nio, microscopia eletr?nica de varredura e microan?lise de raios X por energia dispersiva. A acidez das amostras foi determinada utilizando adsor??o de n-bulinamina seguido de dessor?ao por termogravimetria. Verificou-se que o m?todo de s?ntese hidrot?rmica foi adequado ? s?ntese dos materiais mesoporosos modificados com excelente grau de ordena??o hexagonal. As rea??es de craqueamento catal?tico do n-hexano foram realizadas em um microreator catal?tico de leito fixo com fluxo cont?nuo acoplado em linha com um cromat?grafo a g?s. A partir da avalia??o catal?tica, foi observado que os materiais mesoporosos contendo lant?nio foram mais ativos que o SBA-15, para a rea??o de craqueamento do n-hexano, obtendo-se como produto hidrocarbonetos na faixa de C1 a C5. O catalisador que apresentou melhores propriedades, em rela??o ? acidez e a atividade catal?tica foi o sintetizado com a raz?o Si/La=50

Made available in DSpace on 2014-12-17T15:42:28Z (GMT). No. of bitstreams: 1 ViniciusPSC_TESE.pdf: 2718372 bytes, checksum: e1cb932e65d078fa3eeb0af3e2b2ce2a (MD5) Previous issue date: 2013-11-29 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / A catalyst of great interest to the scientific community tries to unite the structure of ordered pore diameter from mesoporous materials with the properties of stability and acid activity to microporous zeolites. Thus a large number of materials was developed in the past decades, which although being reported as zeolites intrinsically they fail to comply with some relevant characteristics to zeolites, and recently were named zeolitic materials of high accessibility. Among the various synthesis strategies employed, the present research approaches the synthesis methods of crystallization of silanized protozeolitic units and the method of protozeolitic units molded around surfactant micelles, in order for get materials defined as hierarchical zeolites and micro-mesoporous hybrid materials, respectively. As goal BEA/MCM-41 hybrid catalysts with bimodal pore structure formed by nuclei of zeolite Beta and cationic surfactant cetyltrimethylammonium were developed. As also was successfully synthesized the hierarchical Beta zeolite having a secondary porosity, in addition to the typical and uniform zeolite micropores. Both catalysts were applied in reactions of catalytic cracking of high density polyethylene (HDPE), to evaluate its properties in catalytic activity, aiming at the recycling of waste plastics to obtain high value-added raw materials and fuels. The BEA/MCM-41 hybrid materials with 0 days of pre-crystallization did not show enough properties for use in catalytic cracking reactions, but they showed superior catalytic properties compared to those ordered mesoporous materials of Al-MCM-41 type. The structure of Beta zeolite with hierarchical porosity leads the accessibility of HDPE bulky molecules to active centers, due to high external area. And provides higher conversion to hydrocarbons in the gasoline range, especially olefins which have great interest in the petrochemical industry / Um catalisador de grande interesse na comunidade cient?fica tenta unir a estrutura de di?metro de poros ordenados dos materiais mesoporosos e as propriedades de estabilidade e atividade ?cida similares ?s ze?litas microporosas. Assim um grande n?mero de materiais foi desenvolvido nas d?cadas passadas, onde embora sendo intrinsecamente relatadas como ze?litas deixam de cumprir com algumas caracter?sticas pertinentes ?s ze?litas, e recentemente foram nomeados de materiais zeol?ticos de elevada acessibilidade. Dentre as diversas estrat?gias de s?ntese empregadas, o presente trabalho de pesquisa abordou os m?todos de s?ntese da cristaliza??o de unidades protozeol?ticas silanizadas e o m?todo de unidades protozeol?ticas moldadas ao redor de micelas de surfactantes, para obter materiais definidos como ze?litas hierarquizadas e materiais h?bridos micro-mesoporoso, respectivamente. Como meta foram desenvolvidos catalisadores h?bridos BEA/MCM-41 com estrutura porosa bimodal formada por n?cleos da ze?lita Beta e surfactante cati?nico cetiltrimetilam?nio. Como tamb?m, sintetizados com sucesso a ze?lita Beta hierarquizada que possui uma porosidade secund?ria, em adi??o aos t?picos e uniformes microporos zeol?ticos. Ambos os catalisadores foram aplicados em rea??es de craqueamento catal?tico de polietileno de alta densidade, para avalia??o de suas propriedades na atividade catal?tica, visando a reciclagem de pl?sticos residuais para obten??o de mat?rias-primas de elevado valor agregado e combust?veis. Os materiais h?bridos BEA/MCM-41 com 0 dias de pr?-cristaliza??o n?o demonstraram propriedades suficientes para aplica??o em rea??es de craqueamento catal?tico, por?m evidenciaram propriedades catal?ticas superiores comparados aos materiais mesoporosos ordenados do tipo Al-MCM-41. A estrutura da ze?lita Beta de porosidade hierarquizada favorece a acessibilidade das mol?culas volumosas do PEAD aos centros ativos, devido ? elevada ?rea externa. E proporciona maior convers?o a hidrocarbonetos na faixa da gasolina, principalmente olefinas que possuem grande interesse na ind?stria petroqu?mica

No processo de craqueamento catalítico fluidizado do petróleo (FCC) ocorre o envenenamento do catalisador pelo V presente sob a forma de complexos, que se decompõem na etapa de regeneração resultando espécies que atacam estruturalmente a zeólita - o principal componente do sistema catalítico. O emprego de terras raras (TR) como passivadores do efeito deletério provocado pelo V neste processo é estudado no presente trabalho. Sob condições similares àquelas encontradas no processo de regeneração, tris-acetilacetonatos TR foram adicionados ao catalisador para craqueamento na presença de V em proporções estabelecidas. Os resultados da interação entre os componentes deste sistema foram analisados e observou-se que as TR têm razoável capacidade de inibir o ataque do V ao catalisador desativado, preservando parcialmente a conversão catalítica do material. Análises de propriedades texturais, luminescência e DRX indicaram que a inserção de TR por meio de complexos é mais efetiva que por meio de óxidos no método empregado, além de não influenciarem as propriedades originais do catalisador na ausência de V. Os resultados dos ensaios realizados por RPE, EFX, RMN 51>/sup>V e MEV-EED revelaram que a capacidade demonstrada pelas TR em neutralizar o V está associada à formação de TRVO4 termo-quimicamente estáveis nas condições estudadas. Em virtude da reduzida capacidade de permeação das TR através das partículas do catalisador, a interação ocorre preferencialmente na superficie das micro-esferas. Todas as TR foram encontradas no catalisador desativado no estado de oxidação (III) e o V no estado de oxidação (V). As TR estudadas apresentaram desempenhos ligeiramente diferentes, no que conceme à neutralização do V no sistema e o Y apresenta o melhor desempenho. Propôs-se, para este sistema um mecanismo que relaciona a capacidade de passivação da TR às propriedades termodinâmicas da reação com V. / In the fluidized catalytic cracking process (FCC process) of petroleum, vanadium complexes present in the FCC feed cause catalyst poisoning. The decomposition of these complexes in the regeneration step produces species that attack the zeolite structure - the main active component in the catalytic system. This work evaluates the employment of rare earths (RE) as passivators to mitigate the deleterious effects ofthe V in the FCC feed. Controlled amounts of tris-acethylacetonate of RE were added to cracking catalyst containing V, under similar conditions to those of the regeneration process. The results of the interaction among the components of this system were analyzed and it was observed that RE have reasonable capacity to inhibit the V attack to the disabled catalyst, partially preserving the material catalytic conversion. Analyses of textural properties, luminescence and XRD indicated that the insertion of RE as complexes is more effective than as oxides in the methods employed. Also, they do not influence the catalyst original properties in the absence of V. The results of the experiments accomplished by EPR, XPS, 51V NMR and SEM-EDS revealed that the capacity demonstrated by RE to neutralize the V is associated with the formation of thermo chemically stable REVO4 at the test conditions. Due to the reduced capacity of RE penetration into the catalyst particles, the interaction happens preferentially in the surface of the micro spheres. All RE found in the catalyst were at the oxidation state (III) and the V at the oxidation state (V). The RE studied presented approximately the same performance in terms of V immobilization on the system and Y presents the best performance. For this system, a mechanism that relates the passivation capacity of RE to the thermodynamic properties of the reaction with V is proposed.

Les catalyseurs d’hydrocraquage et d’hydroisomérization sont bifonctionnels, avec une fonction hydro-déshydrogénante et une fonction acide, une zéolithe protonée, pour isomériser et craquer les alcènes. Par dynamique moléculaire ab initio avancée, et avec prise en compte explicite des effets thermiques (300 – 500 K), nous avons étudié les mécanismes d’isomérisation et de craquage d’alcènes C7 dans la zéolithe chabazite dans le but d’obtenir des constantes de vitesse fiables et d’interpréter la distribution des produits.Par la méthode blue moon, nous avons établi les premiers profils d’énergie libre d’isomérisations d’alcènes C7, avec des carbocations intermédiaires (et des états de transition cyclopropanes protonés, PCP), reliant des isomères di- à tri- et mono- à di-branchés (Sections III et IV). Nos simulations démontrent que les effets dynamiques et l’échantillonnage correct des rotamères jouent un rôle crucial sur la stabilité des intermédiaires et des états de transition. Ces effets ne pouvaient pas être décrits par les précédentes études de DFT statiques. Les barrières bien plus basses pour l’isomérisation de type A sont ainsi retrouvées, et expliquées par un état de transition mou, alors que l’état de transition de l’isomérisation de type B est contraint, à cause de la formation d’un edge PCP. L’étude des réactions de craquage avec les mêmes méthodes (Section V) éclaircit le rôle des cations secondaires. Pour la première fois, nous identifions les états de transitions des β-scissions. Nous déduisons de cette analyse des constantes de vitesse ab initio qui pourront être utilisées dans un modèle cinétique pour prédire l’activité et la sélectivité du catalyseur. / Hydrocracking and hydroisomerization catalysts are bifunctional, with a hydro-dehydrogenation function and an acidic function, typically an acid zeolite, to isomerize and crack alkenes. With advanced ab initio molecular dynamics approach, and explicit simulation of the effects of temperature (300 – 500 K), we investigate the mechanisms of isomerization and cracking reactions of C7 alkenes within the chabazite zeolite in order to provide reliable rate constants and explain the observed products distribution. By blue moon sampling, we established for the first time, the free energy profiles for the isomerization of C7 alkenes in zeolites, with carbenium ions as intermediates (and protonated cyclopropane (PCP) as transition states), connecting di- to tri-branched, and mono- to di-branched alkene isomers (Sections III and IV). We demonstrate that the dynamic effects with the correct sampling of rotational conformers play an important role to quantify the stability of the key intermediates and transition states. These effects could not be captured by previous static DFT simulations. The much lower barriers for type A isomerization mechanisms are thus recovered, and assigned to a loose transition state, while the transition state of type B isomerization is tighter, due to the formation of an edge PCP. The study of cracking reactions (Section V) with the same methods, unravel the role of secondary cations. For the first time, we identify the structures of transition states involved in the β-scission mechanisms. From this analysis, we deduce the ab initio- rate constants that could be used in future kinetic modeling to predict activity and selectivity of the catalyst.

Cette thèse a été réalisée en cotutelle entre l'Université Technique Nationale Ivan Pul'uj de Ternopil (TNTU, Ukraine) et l’Université Blaise Pascal (Clermont Ferrand, France). Les travaux ont été effectués au sein de l'Institut Pascal de l’Université Blaise Pascal - Clermont II, de l’IFMA et du CNRS, dans le thème scientifique Matériaux actifs et intelligents, modélisation multi-échelle de l'axe Mécanique, Matériaux et Structures, et au sein de l'Institut Français de Mécanique Avancée. Les travaux réalisés sont inscrits dans l'action transversale « Matériaux et Modélisations Multi-Echelles » de l'Institut Pascal et, en partie, dans l'action MAIM du Laboratoire d'Excellence Labex IMobS3. La thèse présentée appartient au domaine scientifique de la mécanique de la rupture et la science des matériaux.Le but de ce travail est l’étude de l'effet du temps de fonctionnement sur les dommages de la structure, les propriétés mécaniques et la ténacité d'acier de collecteur de surchauffe dans les centrales thermiques et de développer les méthodes qui sont basées sur l'évaluation de la résistance résiduelle du collecteur en tenant compte des dispersions des propriétés mécaniques, du chargement opérationnel et des défauts de taille. La thèse étudie l'influence de l'hydrogénation sur le comportement mécanique, la ténacité et les micro-mécanismes de rupture dans le matériau du collecteur de surchauffe à déformation lente. / This thesis has been performed under the cotutelle agreement between Ternopil Ivan Pul’uj National Technical University (TNTU, Ukraine) and Blaise Pascal University (Clermont Ferrand, France). The thesis has been carried out within Pascal Institute of the Blaise Pascal University - Clermont II, the IFMA and the CNRS, in the Scientific Theme “Active and Smart Materials and Multiscale Modeling” of the Mechanics, Materials and Structures Department, and within the French Institute for Advanced Mechanics. The work is included in the Transversal Action "Materials and Multi-scale Modelling" of the Pascal Institute and in the Action MAIM of the Excellence Laboratory Labex IMobS3. The presented thesis belongs to the scientific field of fracture mechanics and material science. The aim of the thesis is to study the effect of operating time on damage of structure, mechanical properties and fracture toughness of superheater collector steel at thermal power plants (TPPs) and to develop the methods that are based on the assessment of the residual strength of collector taking into account the mechanical properties scatter, operational loading and defect sizes. The thesis studies the influence of hydrogenation on mechanical behavior, fracture toughness and fracture micromechanisms in the material of superheater collector at slow deformation.

Abstract not available