Submitted by Aelson Maciera (aelsoncm@terra.com.br) on 2017-05-30T17:42:50Z No. of bitstreams: 1 DissBL.pdf: 8282671 bytes, checksum: 5dfca89e85bbea10d97a0617e91d1408 (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-06-01T17:47:56Z (GMT) No. of bitstreams: 1 DissBL.pdf: 8282671 bytes, checksum: 5dfca89e85bbea10d97a0617e91d1408 (MD5) / Approved for entry into archive by Ronildo Prado (ronisp@ufscar.br) on 2017-06-01T17:48:03Z (GMT) No. of bitstreams: 1 DissBL.pdf: 8282671 bytes, checksum: 5dfca89e85bbea10d97a0617e91d1408 (MD5) / Made available in DSpace on 2017-06-01T18:20:58Z (GMT). No. of bitstreams: 1 DissBL.pdf: 8282671 bytes, checksum: 5dfca89e85bbea10d97a0617e91d1408 (MD5) Previous issue date: 2017-02-13 / Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) / The study of ceramic composites assisted by computer simulation is well spread nowadays. It is an interest of the ceramic industry the development of materials models trustfully enough to reduce cost with prototypes and virtually explore an infinitude of materials compositions and thermomechanical loads. The mismatch of thermal and mechanical properties among the composite’s phases may induce decohesions or cracks after temperature variation. The computer modeling of this behavior could auxiliate the planning of the systems’ composition, as it becomes possible to evaluate the influence of the concentration of an specific constituent on the global behavior. The present dissertation aims to analyze the role of the geometrical feature, such as inclusion radius and volume fraction, in the composite behavior submitted to temperature variation. It was also analyzed the application of coesive elements to simulate the cracking phenomena in ceramic systems. The main results of this dissertation were not only the thermomechanical properties influence on the global behavior of ceramic systems, but also the construction of finite element models that might be usefull to others reseachers on the investigation of the thermomechancial behavior of distincts ceramic systems. / O estudo de compósitos cerâmicos assistido por simulação computacional encontra-se em plena expansão. É de grande interesse da indústria cerâmica o desenvolvimento de modelos confiáveis de materiais o suficiente para reduzir os custos com protótipos e explorar virtualmente uma infinidade de possibilidades de composições e solicitações termomecânicas. A diferença entre as propriedades termomecânicas dos constituintes de compósitos pode induzir o surgimento de defeitos quando estes são submetidos a variações de temperatura. A modelagem computacional adequada destes sistemas nestas condições pode auxiliar no planejamento da composição do sistema, uma vez que é possível avaliar a influência da concentração de determinado constituinte no comportamento global do compósito. O presente trabalho objetiva analisar desde a influência do raio e fração volumétrica de inclusões até o efeito das diferenças de propriedades termomecânicas entre as fases no comportamento de compósitos cerâmicos submetidos a variações de temperatura. Analisar também, a aplicação de elementos coesivos na simulação da fissuração de sistemas cerâmicos. Como resultados principais, apresenta-se não só a compreensão dos efeitos de determinadas propriedades termomecânicas, mas também a construção de modelos em elementos finitos que podem ser utilizados por terceiros na investigação do comportamento termomecânico de sistemas cerâmicos.

[pt] Corrosão sob tensão (SCC), que consiste na iniciação e propagação de trincas devido ao efeito combinado de tensões mecânicas e o ambiente corrosivo, é um dano potencial para estruturas e componentes. Além do mais, SCC pode ser explicado por diferentes mecanismos dependendo do par material ambiente corrosivo considerado, o que dificulta o uso de um modelo geral para predizer o comportamento de trincas em SCC. Sendo assim, projetos frequentemente utilizam um critério conservativo que desqualifica materiais susceptíveis à SCC sem analisar de maneira apropriada a influência dos campos de tensão que a induzem. O objetivo deste trabalho é avaliar o efeito de tensões elastoplásticas na corrosão sob tensão. Esta abordagem mecânica considera que todos os efeitos corrosivos envolvidos na corrosão sob tensão podem ser apropriadamente quantificados pelas tradicionais resistências do material à iniciação e propagação de trincas para um ambiente corrosivo específico. Corpos de prova de flexão em Alumínio fragilizados por Gálio líquido serão utilizados para prever o efeito de tensões residuais induzidas por deformações plásticas na iniciação de trincas por corrosão sob tensão. Além disso, uma análise quantitativa baseada no comportamento de trincas não propagantes a partir de entalhes será usada para estimar a tensão necessária para iniciar e propagar trincas em corpos de prova entalhados em aço AISI 4140 sujeitos à corrosão por sulfeto de hidrogênio em ambiente aquoso. O comportamento de trincas curtas e a carga máxima suportada pelos corpos de prova entalhados são analisadas considerando campos de tensões lineares elástico e elastoplásticos através do modelo proposto que será validado através de dados experimentais. / [en] Stress Corrosion Cracking (SCC), which consist in the initiation and propagation of cracks due to the combined attack of mechanical stresses and a corrosive environment is a potential danger for structures and components. Moreover, SCC can be explained by different mechanisms depending on the metal environmental pair, what makes difficult to create a generalized analytical approach to predict the crack behavior in SCC. Therefore, projects often use an over-conservative design criteria that disqualify a material susceptible to SCC without properly evaluate the influence of the stress fields that drive them. The aim of this work is to evaluate the effect of elastic-plastic stress in SCC. This mechanical approach assumes that all chemical effects involved in SCC problems can be appositely described and quantified by traditional material resistances to crack initiation and propagation at under specific environment. Aluminum bending specimens in Gallium environment are used to predict the effect of the residual stress induced by plastic deformation in the crack initiation under SCC conditions. Furthermore, a quantitative analysis based on the non-propagating crack behavior departing from notch tips are used to calculate the necessary stress to initiate and propagate SCC in AISI 4140 steel notched specimens under aqueous hydrogen sulfide environment. The non-propagating crack behavior and the maximum load supported by notched specimens are analyzed under linear elastic and elastic-plastic stress field through the proposed model that will be validated by experimental data.

Submitted by Lúcia Brandão (lucia.elaine@live.com) on 2015-07-15T16:05:00Z No. of bitstreams: 1 Tese - Cristiane Daliassi Ramos de Souza.pdf: 2429333 bytes, checksum: 3abea0012ee786e4320f226b2f591475 (MD5) / Approved for entry into archive by Divisão de Documentação/BC Biblioteca Central (ddbc@ufam.edu.br) on 2015-07-20T15:48:37Z (GMT) No. of bitstreams: 1 Tese - Cristiane Daliassi Ramos de Souza.pdf: 2429333 bytes, checksum: 3abea0012ee786e4320f226b2f591475 (MD5) / Approved for entry into archive by Divisão de Documentação/BC Biblioteca Central (ddbc@ufam.edu.br) on 2015-07-20T15:54:41Z (GMT) No. of bitstreams: 1 Tese - Cristiane Daliassi Ramos de Souza.pdf: 2429333 bytes, checksum: 3abea0012ee786e4320f226b2f591475 (MD5) / Made available in DSpace on 2015-07-20T15:54:42Z (GMT). No. of bitstreams: 1 Tese - Cristiane Daliassi Ramos de Souza.pdf: 2429333 bytes, checksum: 3abea0012ee786e4320f226b2f591475 (MD5) Previous issue date: 2012-11-10 / CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The Jatropha curcas L. is a vegetable species that supplies great amount of oil, but due to its toxicity cannot be used to feed human beings. It is a promising alternative for Biodiesel production. This Thesis had the purpose of perform analytic, thermal and energy studies for the oil extracted from oleaginous species Jatropha curcas L., cultivated in the State of Amazonas. The study was also done for byproducts such as fruit peels, seed peels and the cake originated by biofuel productive chain. To reach the proposed objective, the experimental activities were started with the sampling of the whole fruits in a plantation located in Itacoatiara city-Amazonas. Six independent samplings were done in different months and all the samples were submitted to physical characterization to evaluate size and weight for all parts of the fruit. The process to obtain the oil was done by two methods: mechanical extraction and chemical extraction (Soxhlet system). The chemical extraction was performed for all available samples and the best efficiency was the 50.21%, although all the extractions have presented good results (43-48%). The mechanical process was just performed for the 2010 crop presenting a satisfactory efficiency (33.14%). Then, the oil extracted by the two processes was characterized by several physical-chemical parameters. The oxidative stability by Rancimat was measured for the oils and the result was around 12 hours, this value is considered satisfactory when compared with other species. The fatty acid profile was analyzed by gas chromatography, which indicated the presence of higher concentrations of oleic and linoleic acids. The palmitic, stearic, arachidic and palmitoleic acids were also detected, however in smaller concentrations. The evaluation for thermal and energy potential was done for the oil and byproducts using TG/DTA, immediate analysis and superior heat power techniques. The results of thermal analysis for the oils obtained by chemical and mechanical extraction indicated thermal stability temperature about 180 and 217°C, respectively. Energy evaluation for byproducts was done by immediate analysis and high values for volatile materials were found (65-78%). These values characterize a fuel that can be easy and quickly burned during the combustion process. The results of PCS for the obtained oils presented high values (34-39 MJ/kg), which are close to the ones measured for diesel. For the byproducts, the results were between 17 and 21 MJ/kg, close and even superiors to the literature values for other agricultural residues showing, therefore, great applicability for use in energy generation processes. Finally, reactions with the Jatropha curcas L. oil were made to obtain biofuels through the methylic and ethylic transesterification and thermal cracking. The results for transesterification process were excellent, with efficiency above 90%, however, the physical-chemical evaluation showed that the methylic Biodiesel was the only one in conformity with the Resolution 14/2011 from ANP. A satisfactory efficiency of 75% was obtained for bio-oil. / O pinhão manso é uma espécie vegetal que fornece grande quantidade de óleo e por sua toxidade não pode ser usado na alimentação humana, podendo se transformar em uma alternativa promissora na produção de Biodiesel. Esta Tese teve a finalidade de realizar um estudo analítico, térmico e energético do óleo extraído da espécie oleaginosa pinhão manso (Jatropha curcas L.), cultivada no Estado do Amazonas, assim como dos co-produtos, tais como, cascas do fruto, cascas da semente e torta, presentes na cadeia produtiva de biocombustíveis. Para atingir o objetivo proposto, as atividades experimentais foram iniciadas com a coleta dos frutos na plantação localizada em Itacoatiara-AM. Foram feitas seis coletas em diferentes meses e todas as amostras foram submetidas à caracterização física avaliando o tamanho e a massa para todas as partes do fruto. Em seguida realizou-se o processo de obtenção do óleo, utilizando dois métodos, a extração mecânica e a extração com solvente (Método Soxhlet). A extração com solvente foi realizada para todas as amostras coletadas e o melhor rendimento obtido foi de 50,21%, apesar de ter obtido bons resultados em todas as extrações (43-48%). O processo mecânico foi realizado apenas com o lote da safra de 2010 apresentando um rendimento satisfatório (33,14%). Posteriormente, o óleo extraído foi caracterizado por diversos parâmetros físico-químicos. A estabilidade oxidativa por Rancimat foi realizada para o óleo do pinhão manso ficando em torno de 12 horas, um valor considerado satisfatório quando comparado com outras espécies. O perfil de ácidos graxos foi analisado por cromatografia gasosa, o qual indicou a presença de altas concentrações dos ácidos oléico e linoléico. Os ácidos palmítico, esteárico, araquídico e palmitoléico também foram detectados, porém em concentrações menores. A avaliação do potencial térmico e energético foi realizada para o óleo e os co-produtos utilizando as técnicas de TG/DTA, análise imediata e PCS. Os resultados da análise térmica dos óleos, obtidos via extração química e mecânica, indicaram uma temperatura de estabilidade térmica em torno de 180C e 217C, respectivamente. Na avaliação energética dos co-produtos realizada pela análise imediata houve destaque para o teor de materiais voláteis, que apresentou valores elevados (65-78%), o que caracteriza um combustível mais fácil e rapidamente queimado durante o processo de combustão. Os resultados do PCS para os óleos obtidos apresentaram valores elevados (34-39 MJ/kg) e próximos ao diesel. Para os co-produtos, os resultados ficaram entre 17 e 21 MJ/kg, próximos e até superiores aos valores reportados na literatura para outros resíduos agrícolas mostrando, portanto grande aplicabilidade para utilização em processos de geração de energia. Por fim foram realizadas reações com o óleo de pinhão manso para obter biocombustíveis através da transesterificação metílica e etílica e do craqueamento térmico. Os resultados da transesterificação mostraram-se excelentes, com rendimentos acima de 90%, entretanto a avaliação físico-química mostrou que apenas o Biodiesel metílico ficou em conformidade com a Resolução 14/2011 da ANP. O Bio-óleo obteve um rendimento satisfatório (75%).

O objetivo deste trabalho é analisar e comparar o comportamento quanto à resistência à corrosão, permeabilidade de hidrogênio e sua relação com a susceptibilidade ao trincamento induzido por hidrogênio de aços ARBL, em ambientes contendo H2S, enfatizando a influência da microestrutura. Foram realizados tratamentos térmicos de normalização e têmpera (em água) de dois tipos de tubos API 5L X65 para aplicação sour service, obtendo-se três condições com diferentes microestruturas para cada tubo. Assim, as duas amostras tais como recebidas apresentavam microestruturas de: ferrita/perlita e, o outro, ferrita/ferrita acicular; após tratamento de normalização os dois tipos de amostras apresentaram microestrutura de ferrita/perlita; e, por último, os aços que passaram por têmpera constituíram-se de martensita. O eletrólito empregado foi a solução A (ácido acético contendo cloreto de sódio) da norma NACE TM0284-2011, saturado com H2S. Os materiais foram submetidos a: ensaios de polarização linear para determinação da Resistência de Polarização (Rp), ensaios de permeabilidade de hidrogênio - baseado na ASTM G148-2003 - e ensaios de resistência ao trincamento induzido por hidrogênio (HIC) segundo a norma NACE TM0284-2011; exames em microscópio óptico e eletrônico de varredura para caracterização microestrutural, da morfologia da corrosão e do trincamento. Após os ensaios de polarização linear, foi observada uma diferença pequena dos valores de Rp entre as diferentes amostras estudadas, entre 120 ?.cm2 e 210 ?.cm2; dentro desta faixa, as microestruturas de martensita (aços temperados) apresentaram a menor resistência à corrosão. Foi realizado o tratamento dos dados obtidos por polarização linear com a metodologia desenvolvida por Mansfeld (1973) para cálculo da taxa de corrosão, observando mudanças nos declives de Tafel evidenciando a formação de produtos de corrosão. Apesar da formação destes produtos a taxa de corrosão não foi afetada, já que estes produtos são dissolvidos na solução A, oferecendo uma baixa proteção contra à corrosão. Nos ensaios de permeabilidade de hidrogênio foi utilizada uma célula modificada tipo Devanathan-Stachurski, com a solução A, com injeção de H2S no lado de geração de hidrogênio e 0,2M NaOH no lado de detecção. Foi realizado o tratamento dos dados com o método tlag, calculando a difusividade aparente, concentração de hidrogênio no metal e quantidade de sítios de ancoramento de hidrogênio. Também foi utilizado um método de ajuste da curva experimental com a equação obtida a partir da segunda lei de Fick para calcular a difusividade aparente. Foram comparados os valores obtidos com os dois métodos, obtendo-se resultados similares de difusividade aparente. As amostras temperadas foram as que apresentaram menor difusividade aparente, maior concentração de hidrogênio e maior número de sítios de ancoramento. Após o ensaio de resistência ao trincamento induzido por hidrogênio os exames em microscópio óptico mostraram que as amostras de tubos API 5L X65 como recebidas e normalizadas não apresentaram trincamento, já as amostras que passaram por tratamento de têmpera apresentaram trincas. A realização dos ensaios e tratamento dos dados permitiram observar a relação entre a quantidade de interface e a taxa de corrosão: assim a microestrutura martensítica apresenta a maior taxa de corrosão devido a maior quantidade de interfaces. A difusividade de hidrogênio também é afetada por esta mesma microestrutura, por ter maior quantidade de interface e maior número de discordâncias, apresentando menor difusividade aparente, maior concentração de hidrogênio e maior quantidade de sítios de ancoramento, tem-se que a microestrutura de martensita apresenta maior susceptibilidade ao trincamento induzido por hidrogênio. A nucleação e propagação das trincas nesta microestrutura depende de vários mecanismos que atuam simultaneamente: (i) nucleação das microtrincas, (ii) formação de H2 nas microcavidades com aumento da pressão local e (iii) migração de átomos de hidrogênio até a ponta da trinca diminuindo a força coesiva do reticulado facilitando a propagação. No entanto, esta relação entre microestrutura e HIC não pode ser generalizada, pois a susceptibilidade ao trincamento depende tanto da quantidade de sítios de ancoramento, como de sua energia de ligação, localização microestrutural e tamanho destes sítios. Outro fator importante é a presença de regiões de pouca ductilidade onde as trincas nucleadas tenham maior facilidade para sua propagação. Este trabalho contribuiu para o melhor entendimento dos mecanismos que levam à fragilização e danos provocados pelo hidrogênio, mostrando a relação entre microestrutura, corrosão, difusão e trincamento. Permitiu ampliar o conhecimento sobre os testes utilizados para avaliar o desempenho de aços microligados para aplicações em ambientes severos. / Pipelines produced from High Strength Low Alloy steels (HSLA) are a safe and cheap way to transport large quantities of petroleum and gas. HSLA steels offers mechanical and economic advantages. When HSLA steels are exposed to environments containing hydrogen sulphide (H2S), the steel can corrode and generate atomic hydrogen in the surface wich can diffuse and trapped, leading loss of mechanical properties and subsequent failures. The infrastructure to transport oil and gas represent a high cost investment, in adittion, they must be free from degradation processes that can causes severe health and environmental impacts. For this reason, the development of materials with high performance in aggressive environments is required. The aim of this study is to analyze and compare the corrosion behavior, hydrogen permeability and its relation with the susceptibility to Hydrogen Induced Cracking (HIC) of HSLA steels in environments containing H2S, with emphasis on the influence of microstructure. Normalizing and quenching heat treatments were applied in two different API 5L X65 pipelines for sour service. Three conditions were obtained (as received, normalized and quenched). The as received has a microstructure of ferrite / pearlite and ferrite / acicular ferrite, respectively; the microstructure of normalized specimens consist of ferrite / pearlite and finally quenched steels presented a microstructure of martensite. Solution A (acetic acid containing sodium chloride), according to NACE TM0284-2011 standard and saturated with H2S was used. The materials were tested by linear polarization technique, hydrogen permeability and Hydrogen Induced Cracking test (HIC). HIC tests were performed according to NACE TM0284-2011 standard. Optical microscope and scanning electron microscope were used for microstructural, corrosion and cracking characterization. Rp values show a slight difference between the different samples studied (120 ?.cm2 e 210 ?.cm2); the martensite microstructure (quenched) showed the lower corrosion resistance. Mansfeld (1973) method was used to calculate the corrosion rates from polarization curves. The Tafel slopes are differents between samples making evident the formation of corrosion products. Despite the growth of those corrosion products, the corrosion rate was not affected, since these products are dissolved in the solution A, providing a low corrosion protection. A modified Devanathan-Stachurski cell was used for the hydrogen permeability tests. It was used the solution A, with injection of H2S in the charging cell, and 0.1M NaOH solution on the oxidation cell. The hydrogen effective diffusivity, sub-surface concentration of atomic hydrogen at the charging side and number of hydrogen-trap sites were calculate by tlag method. Moreover, the experimental data were fitted using an equation derived from Fick\'s second law, in order to determinate the diffusion coefficient. The diffusion coefficient obtained from both methods were compare showing similar results. The quenching samples showed the lower diffusion coefficient, higher hydrogen concentration and number of trap sites. The steels in the as received and normalized conditins did not show cracks in Hydrogen Induced Cracking test; in the other hand, quenched samples presents cracks. The results shoed the relationship between the amount of interface and the corrosion rate. Being the martensitic microstructure the one with the higher corrosion rate. The diffusion coefficient in the martensitic microstructure, is a result of the high amount of interfaces and high dislocation density, leading to a lower diffusion coefficient, higher hydrogen concentration and number of trap sites. In the Hydrogen induced Cracking test the martensitic microstructure has shown the lower resistance to crack. The nucleation and propagation of the cracks in martensite depend of mechanisms that may act simultaneously: (i) nucleation of micro-cracks in preferential sites, (ii) formation of H2 in micro-cavities, with increase the local pressure, and (iii) hydrogen migration to the tip of the crack, decreasing the cohesive force in the lattice. However, the relationship between microstructure and Hydrogen Induced Cracking can not be generalized, since the susceptibility to cracking depends of several factors, like number of trap sites, binding trap energy, microstructural distribution and trap sizes. In addition, the presence of regions of low ductility can result in easy cracks nucleation and propagation. This thesis contributed to the understanding of the mechanisms that lead to hydrogen embrittlement and hydrogen damage, showing the relationship between microstructure, corrosion rate, diffusion and cracking, I ncreasing the scientific knowledge about the standard tests actually used to evaluate the performance of microalloyed steels in sour environments.

This thesis presents three different approaches to model corrosion-induced crack propagation in reinforced concrete structures. The first approach is solved numerically using finite differences to model the softening behaviour of concrete in tension. The second approach idealizes the concrete cover as either a brittle elastic or an elastoplastic material so that it may be solved using a closed-form solution. Both approaches are based on a thick-walled cylinder (TWC) analogy and consider rust compressibility and rust diffusion into cracks. The third approach uses finite element modelling to validate the application of the TWC and perform a parametric study. The results obtained using each approach are compared against each other as well as against experimental results. The TWC was found to be an appropriate analogy for the geometries and reinforcement configurations considered. Analytical models were found to provide upper and lower limits to the results based on the numerical model. The experimental data found in the literature showed reasonable agreement with predictions from the numerical and elastoplastic models.

Fatigue in concrete is a complex phenomenon involving formation of microcracks, their coalescence into major crack and simultaneous formation of the fracture process zone ahead of the crack tip. Complex phenomena are best dealt through an energy approach and hence it is reasonable to use the theory of thermodynamics. Fracture mechanics and damage mechanics are two theories that are based on physically sound principles and are used to describe failure processes in materials. The former deals with the study of macroscopic cracks, whereas the latter defines the state of microcracking. In this study, the concepts from these theories are utilized to improve our understanding and modeling of fatigue process in concrete. In this thesis, a closed form expression for the thermodynamic function entropy is proposed and examined for its size independency and its use as a material property to characterize failure of concrete under fatigue. In the thermodynamic formalism, dissipative phenomena are described by a dissipation potential or its dual, from which evolution laws for internal variables could be defined. In this work, closed form expressions for dual of dissipation potential are derived using concepts of dimensional analysis and self-similarity within the framework of fracture mechanics and damage mechanics. Consequently, a fatigue crack propagation law and a fatigue damage evolution law are proposed respectively. A method is proposed in this study to correlate fracture mechanics and damage mechanics theories by equating the potentials obtained in each theory. Through this equivalence, a crack could be transformed into an equivalent damage zone and vice versa. Also, damage state corresponding to a given crack in a member can be quantified in terms of a damage index. An analytical way of computing size independent S-N curves is proposed, using a nonlocal damage theory by including aggregate size and specimen size in the formulation. It is realized from this study that fracture mechanics and damage mechanics theories should be used in a unified manner in order to accurately model the process of fatigue in concrete. Furthermore, based on the models developed in this study, several damage indicators for fatigue of concrete are proposed. The advantages and limitations of each of these indices are presented such that, the relevant damage index could be used, based on available parameters. Additionally, deterministic sensitivity studies are carried out to determine the most important parameters influencing fatigue life of a concrete member.

Dans un contexte normatif toujours plus sévère concernant les rejets automobiles polluants, la substitution des aciers par des alliages d’aluminium dans les structures des véhicules est en plein essor. Ce projet de thèse, qui s’inscrit dans un programme de développement de la société Constellium, cible plus précisément les alliages d’aluminium de la série 7xxx (Al-Zn-Mg) qui, malgré leurs propriétés mécaniques élevées, peuvent présenter une sensibilité à la corrosion sous contrainte (CSC) liée au phénomène de fragilisation par l’hydrogène (FPH). La compréhension des mécanismes mis en jeu dans ce type d’endommagement constitue donc une première étape vers une optimisation métallurgique en vue d’une industrialisation future de ces alliages dans le secteur automobile. La première partie de ces travaux est consacrée à l’étude de l’influence de l’état métallurgique de l’alliage 7046 sur son comportement en CSC et à l’identification des mécanismes de dégradation. Un lien direct a pu être mis en évidence entre l’abattement des propriétés mécaniques et les modes de rupture actifs et la quantité d’hydrogène dans l’alliage. Les deux modes d’endommagement observés, intergranulaire-fragile et transgranulaire-fragile, ont respectivement été attribués à un enrichissement en hydrogène aux joints de grains et au piégeage de l’hydrogène au niveau des précipités intragranulaires. Les interactions entre l’hydrogène et les précipités fins d’une part et les dislocations d’autre part, identifiés comme deux hétérogénéités microstructurales critiques vis-à-vis de la FPH, ont été étudiées à une échelle plus locale dans la seconde partie du travail de thèse. Les essais ont été réalisés sur des échantillons modèles, chargés en hydrogène en milieu H2SO4 sous polarisation cathodique et la profondeur de pénétration de l’hydrogène a été évaluée par SKPFM (Scanning Kelvin Probe Force Microscopy). L’ensemble des résultats obtenus met en évidence : 1/ un effet « barrière » des précipités fins et des dislocations sur la diffusion de l’hydrogène en relation avec un abattement des propriétés mécaniques moins important, 2/ un transport possible de l’hydrogène par les dislocations et 3/ l’efficacité du SKPFM pour déterminer précisément des coefficients de diffusion apparents de l’hydrogène. Ces résultats ouvrent ainsi de nouvelles pistes vers la compréhension des mécanismes de CSC dans les alliages Al-Zn-Mg. / Automotive industry is increasingly affected by standards requiring a major cut of polluting emissions, leading R&D policies to focus on replacing steel by aluminum alloys. This thesis project, initiated by the manufacturer Constellium, focuses on 7xxx (Al-Zn-Mg) aluminum alloys known to have high mechanical properties but also to be susceptible to stress corrosion cracking (SCC) partly attributed to hydrogen embrittlement (HE). Understanding the mechanisms involved would be a first step towards a metallurgical optimization and a future industrialization of these alloys. The first part focuses on the SCC behavior of the 7046 aluminum alloy, related to its microstructure, and the identification of degradation mechanisms involved. A hydrogen amount – loss of mechanical properties relationship was highlighted. The damage observed was explained by the presence of hydrogen in the grain boundaries and by a trapping effect of the intragranular hardening precipitates, limiting the hydrogen diffusion to the grain boundaries. Interactions between hydrogen and hardening precipitates and dislocations, both identified as critical microstructural heterogeneities for HE, are studied at a local scale in a second part. The hydrogen effect was characterized by penetration depth measurements made by SKPFM (Scanning Kelvin Probe Force Microscopy) on “model” samples cathodically charged in H2SO4. The whole results finally highlight: 1/ a “shielding” effect of fine precipitates and dislocations on hydrogen diffusivity related to a lower susceptibility to HE, 2/ hydrogen transport by dislocations and 3/ the efficiency of SKPFM to precisely measure effective diffusion coefficients of hydrogen. These results lead to new opportunities to understand SCC mechanisms in Al-Zn-Mg alloys.

La corrosion sous contrainte (CSC) est un phénomène synergique d'endommagement qui résulte d'un processus de corrosion (dissolution, adsorption) et d'une rupture mécanique (fissuration). Les mécanismes de couplage mécano-électrochimique en pointe de fissure nécessaires à la compréhension du phénomène sont encore mal connus puisqu'ils dépendent du système d'étude (métal/milieu agressif) et font intervenir de nombreux facteurs mécaniques et électrochimiques. Dans cette thèse, nous nous proposons d'étudier les interactions réciproques entre la dissolution et l'état de contrainte mécanique en pointe de fissure (facteurs d'intensité des contraintes) pour le cas du Zircaloy-4 en milieu aqueux halogéné. Les éprouvettes sont d’abord pré-fissurées par fatigue à l’air avec la technique du Load-Shedding, ce qui permet alors de maîtriser le facteur d’intensité des contraintes résiduel de pré-fissuration par fatigue. Ensuite, une pré-oxydation thermique est réalisée pour produire une couche de film passif sur les surfaces de l’éprouvette. Les réactions électrochimiques sont alors concentrées en pointe de fissure qui induit également une concentration des effets mécaniques. Des techniques de corrélation d'images sont développées dans le but d'identifier les facteurs d'intensité des contraintes et d'estimer la longueur de fissure en temps réel. Ainsi des essais originaux de CSC, permettant d'imposer les facteurs d'intensité en pointe de fissure, sont conduits et les résultats montrent alors clairement les effets synergiques entre l'évolution des mesures mécaniques et des courants de dissolution. D'autre part, l'existence d'un facteur d'intensité des contraintes seuil de propagation en CSC, présentant une forte dépendance à l'histoire de chargement et à la variation de l'état de contrainte locale en pointe de fissure (variation des facteurs d'intensité des contraintes), est mise en évidence. Ceci montre alors que la plasticité doit évoluer pour que la dissolution se produise. Ainsi, le temps caractéristique d'arriver de nouvelles dislocations en pointe de fissure ne doit pas dépasser la durée caractéristique des réactions de passivation. Enfin sur la base des résultats expérimentaux, un modèle de loi de propagation phénoménologique de fissure en CSC est proposé et ses paramètres sont identifiés et validés à partir de différents essais de CSC. / Stress corrosion cracking (SCC) is a damage phenomenon which results from the synergy between corrosion process (dissolution, adsorption) and mechanical fracture (crack propagation). Although this phenomenon is well known, its modelling is still a challenging issue, especially concerning mechano-electrochemical coupling mechanisms at crack tip, because it depends on model system (metal/aggressive media) and large number of mechanical and electrochemical factors. In this thesis, mutual interactions between dissolution and the stress state around the crack tip (stress intensity factor) are studied in the case of Zircaloy-4 in aqueous halide solution. Samples are first pre-cracked in air by using fatigue load-shedding procedure to control the stress intensity factor. Then, pre-oxidization is used to produce a thin protective passive layer on their surface. The electro-chemical reactions are thus concentrated at the crack tip which also induces a concentration of the mechanical effect. During the test, digital images of the sample surface are acquired. Digital Image Correlation is performed a posteriori in order to obtain the evolution of the crack length and the stress intensity factors. Further, a specific procedure is developed in order to perform the DIC analysis while the test is running. This allows to control the load so that a given value of the stress intensity factor is prescribed. With this innovative experimental technique, we perform experimental tests that allow to discriminate the effects between different stress corrosion cracking mechanisms. It is suggested that once a critical anodic polarization is exceeded, the crack growth rate depends on the stress intensity factor but also on its time derivative. Indeed, a threshold effect is obtained on the stress intensity factor, meaning that plasticity must increase for the dissolution reaction to occur, but also on its rate meaning that time for plasticity to produce new dislocations must not exceed the characteristic duration of the passivation reaction. A phenomenological crack propagation model is proposed and its parameters are then identified and validated from the experimental measurements during SCC tests.

L'industrie se tourne de plus en plus vers les matériaux composites. A l'échelle de la microstructure leur comportement est fortement hétérogène mais à l'échelle de la structure ceux-ci peuvent être considérés homogène. Les méthodes multi-échelles ont été développées pour résoudre les problèmes de structure avec un temps de calcul raisonnable. Ces méthodes sont validées par comparaison avec un calcul numérique où les hétérogénéités sont entièrement maillées. Dans ce travail de thèse, une structure architecturée modèle a été créée au centre d'une plaque (homogène) mince en acier inoxydable (304L). La cellule unitaire du matériau architecturé est constitué d'un carré avec un trou au centre. L'utilisation d'une caméra à très haute résolution (270 millions de pixels) permet de suivre simultanément l'évolution des déformations aux échelles microscopique et macroscopique. La variation de l'orientation de la structure architecturée modifie les sollicitations appliquées aux cellules unitaires. Les expériences réalisées ont pour but d'analyser les cinématiques de déformation des cellules unitaires sous un chargement multi-axial. La recherche des cellules ayant une cinématique périodique est réalisée. Il est ainsi montré que les cellules avec une cinématique non périodique correspondent à la zone de transition entre le matériau architecturé et le matériau homogène. La connaissance des cinématiques des cellules permet d'investiguer les changements d'échelles dans le domaine linéaire et non-linéaire. Le passage de l'échelle macroscopique à l'échelle microscopique est particulièrement étudié avec le choix des conditions aux limites. Le remplacement des cellules ayant une cinématique périodique par un milieu homogène équivalent (MHE) est traité. La géométrie de la cellule unitaire introduit des symétries dans le comportement du MHE, celui-ci devient cubique. Les caractéristiques élastiques du MHE sont obtenus par homogénéisation à partir des résultats expérimentaux. Un critère de Tsaï-Hill est identifié dans le domaine non-linéaire. Le dernier chapitre s'intéresse à la fissuration de la zone architecturée et à l'initiation de la localisation des déformations dans les cellules. Le support de la localisation est calculé à partir du champ des déformations mesuré par CIN. La cinématique de la cellule est enrichie avec une discontinuité et le saut de déplacement normal à la localisation est identifié. Une comparaison avec le saut de déplacement calculé par corrélation d'images étendue à l'échelle macroscopique est menée afin de valider la stratégie d'identification à l'échelle microscopique. / Industry employ more and more composite materials in structures todecrease the weight. At the microstructure scale behavior is strongly heterogeneous but at the structure scale behaviour may be considered homogeneous. Multiscale methods have been developed to solve the structural problems with a reasonable calculation time. These methods are validated by comparison with a numerical calculation where heterogeneities are fully meshed. In this thesis work, an ideal architectural material was created in the center of a (homogeneous) stainless steel (304L) thin plate. The unit cell architecture material consists of a square with a hole in the center. The use of a high resolution camera (270 million pixels) allows to follow simultaneously the evolution of deformation at microscopic and macroscopic scales. The orientation of the heterogeneous structure modifies the sollicitations applied to the unit cells. The experiments are designed to analyze the kinematics of deformation of the unit cells in a multi-axial loading. Unit cells with periodic kinematics are searched. It is thus shown that the cells with a non-periodic kinematic correspond to the transition zone between the homogeneous material and the architectured material. Knowledge of the kinematic cells allows to investigate the scale changings in the linear and nonlinear range. The downscaling from the macroscopic to the microscopic scale is particularly studied with the choice of boundary conditions. An equivalent homogeneous medium (MHE) is determined as a remplacement for the cells having a periodic kinematic. The geometry of the unit cell introduced symmetries in the behavior of MHE, it becomes cubic (orthotropic with material parameters). The elastic characteristics of the MHE are obtained by homogenization from the experimental results. A criterion of Tsai-Hill is identified in the non-linear domain. The last chapter is interested in cracking of the architected zone and the initiation of strain localization in cells. The support of location is calculated from the strain field measured by correlation. The kinematics of the cell is enriched with a discontinuity and the displacement jump normal to the localization is identified. A comparison with the displacement jump calculated by extended digital image correlation at the macroscopic scale is conducted to validate the identification strategy at the microscopic level.

Les stratifiés composites sont de plus en plus utilisés dans les pièces de structures des aéronefs ce qui fait émerger de nouvelles problématiques comme celle des Impacts de Faible Energie (IFE). En effet, bien qu’ils possèdent des propriétés rapportées à leur masse très intéressantes ces matériaux peuvent être vulnérables aux petits chocs. Or, compte tenu des nombreux paramètres influents lors d’un tel impact (énergie, vitesse, stratification...), les essais actuellement majoritairement privilégiés à l’échelle industrielle sont long et coûteux. Ainsi, l’apport de la simulation numérique pourrait être d’une grande aide pour les constructeurs. La pratique du « virtual testing », en particulier, permettrait d’aller dans cette direction ce qui aurait pour effet de rationaliser les campagnes d’essais et les coûts financier qui en découlent. Cependant, elle peine à être mise en place ici car le temps CPU nécessaire pour la simulation fine des ndommagements induits par les IFE est trop important avec les méthodes actuelles. Partant de ce constat, ce travail a consisté à tirer avantageusement partie de la localisation spatiale et temporelle des délaminages, fissurations matricielles et ruptures de fibres qui peuvent apparaître pendant l’impact pour diminuer le coût de calcul. Ainsi une méthode multiéchelle en espace et en temps a été mise en place. Elle consiste à découper la structure impactée en deux zones. L’une est située autour du point d’impact, elle contient l’ensemble des non-régularités du problème (contact, loi adoucissante, modèle de zone cohésive). Elle est traitée avec le code de dynamique explicite Europlexus. L’autre correspond à la partie complémentaire. Le problème mécanique y est beaucoup plus régulier et il est traité avec le code de dynamique implicite Zset/Zébulon. Un couplage peu intrusif basé sur la méthode GC est donc réalisé entre ces deux codes. Il permet d’utiliser une modélisation adaptée dans chacune des deux régions ce qui permet en particulier d’utiliser des pas de temps différents. Un rapport supérieur à 1000 peut ainsi être obtenu entre celui du code explicite fixé par la condition de stabilité et celui utilisé dans la partie complémentaire. Un gain de temps CPU significatif confirmé par la simulation d’un impact réalisé sur un panneau composite raidi est ainsi obtenu. Il est également montré que la répartition implicite/explicite peut évoluer au cours du calcul. Pour cela un mécanisme de bascule a été mis en place. Il permet ainsi de faire transiter la résolution d’une partie de la structure initialement traitée dans le code Zebulon dans Europlexus. Un gain de temps supplémentaire est alors obtenu grâce à cette méthode sur le même cas d’application. / The composite laminates are increasingly used in aircraft structural parts which lead to new issues such as the Low Energy Impacts (LEI). Indeed, although they have well mechanical properties relative to their mass, small shocks may be very harmfull for laminates. Controlling such situations is essential for manufacturers that why lot of testing campaigns are currently performed. Yet, they are time consuming and expensive considering the many influential parameters (energy, speed, layup...). Numerical simulations of this phenomenon by practicing the so called “virtual testing” process could be really helpfull to rationalize testing campaigns in order to save money. Yet, this practice remain currently hard to do at the industrial scale due to the excessive CPU time required for fine simulation of damages induced by the LEI. Based on this observation, this work has consisted in taking advantage of the spatial and temporal location of delamination, matrix cracking and fiber breakage that can occur during impact in order to reduce the computational cost. Thus, a space and time multiscale method has been put in place. The impacted structure is split into two areas. One is located around the impacted point, it contains all the non-regularities of the problem (contact, softening law, cohesive zone model). This domain is treated with the explicit dynamics code Europlexus. The other one corresponds to the complementary part. The mechanical problem is much more regular and it is treated with the implicit dynamics code Zset / Zebulon. A low intrusive coupling based on the GC method is carried out between these two codes. It allows to use an adapted model in both regions different time step are in particular used. A time step ratio upper to 1000 can be reach between the one of the explicit code set by the stability condition and the one used in the complementary part. As a results, significant CPU time is saved. This is confirmed by the simulation of a stiffened composite panel impacted. It is also shown that the implicit / explicit allocation can change over the calculation. To do that, a switch mechanism has been established. It thus makes it possible to transit the resolution of a portion of the structure initially solved in the code Zebulon to Europlexus. As a results, further gain is obtained.