La décrépitation (fracturation) des matériaux actifs de batteries associée à leur variation volumique lors des cycles de charge/décharge a pour effet d'accélérer leur corrosion par l'électrolyte et/ou d'induire une perte de connectivité électronique au sein de l'électrode ce qui réduit notablement leur durée de vie. C’est particulièrement le cas des hydrures métalliques utilisés dans les batteries Ni-MH. À ce jour, l'évaluation de leur fracturation se limite généralement à une observation post mortem des électrodes par microscopie ce qui ne permet pas une analyse détaillée du processus de décrépitation. À ce titre, un de nos principaux objectifs dans le cadre de ce travail de recherche a été de développer une méthode d'analyse novatrice et performante basée sur l'émission acoustique (EA) afin d'étudier in situ la fracturation d'électrodes négatives pour batteries Ni-MH. Dans une première étape, nous avons analysé en détail les signaux acoustiques produits lors de la charge (hydruration) d'un alliage commerciale à base de LaNi5 et d'un alliage MgNi obtenu par broyage mécanique. Nous avons ainsi pu séparer les signaux générés par la fracturation des particules d’hydrures métalliques de ceux associés à la formation de bulles de H2, ce qui a permis d’établir les mécanismes qui régissent leur fracturation. Par la suite, un montage expérimental, constitué d’une cellule électrochimique connectée à un capteur de force en compression et d’un équipement d’EA, a été mis point pour suivre in-situ la fracturation et la force générée par l’expansion/contraction lors du cyclage des électrodes MgNi et LaNi5. Nous avons ainsi pu confirmer que l’expansion/contraction volumique de l’alliage MgNi est plus progressif que pour l’alliage à base de LaNi5. Par la suite, l’étude comparée par EA des alliages MgNi, Mg0.9Ti0.1Ni et Mg0.9Ti0.1NiAl0.05 a permis de mettre en évidence l'influence de leur composition sur leur résistance à la pulvérisation. Finalement, nous avons étudié en détail l’influence de l’addition de palladium dans l’alliage Mg0.9Ti0.1NiAl0.05 sur son comportement électrochimique et sa résistance à la fracturation. / The pulverization (cracking) of active materials in batteries, induced by their volume change during charge/discharge cycles, accentuates their corrosion by the electrolyte and/or leads to a loss of electronic connectivity within the electrode, which notably reduces their cycle life. This particularly occurs for metallic hydrides used in Ni-MH batteries. To date, the evaluation of their cracking is generally limited to post mortem observations of the electrodes by microscopy, which does not allow for a detailed analysis of the decrepitation process. In this respect, one of our main research objectives was to develop an innovative and efficient analysis method based on acoustic emission (AE) for in situ monitoring of the cracking of negative electrodes for Ni-MH batteries. As a first step, a detailed analysis of the acoustic signals generated during the charge (hydriding) of a commercial LaNi5-based alloy and a MgNi alloy obtained by mechanical alloying was performed. This allowed separating the signals generated by the cracking of the metallic hydride particles from those induced by the formation of H2 bubbles. We have shown that the mechanism which governs the pulverization of the MgNi alloy remarkably differs from that of the LaNi5-based alloy. In a second step, an experimental set-up made of an electrochemical cell linked to a compression force cell and an AE equipment was elaborated, in order to monitor concomitantly the cracking and the force generated by the expansion/contraction of the MgNi and LaNi5 during cycling. We have thereby been able to confirm that the volume expansion/contraction of the MgNi alloy is more progressive than that of the LaNi5 alloy. The AE-based comparative study of MgNi, Mg0.9Ti0.1NiAl5 and Mg0.9Ti0.1NiAl0.05 alloys then allowed demonstrating the positive effect of the partial Mg substitution by Ti and adding of Al on the alloy decrepitation resistance. As a final step, we have studied the impact of palladium addition in the Mg0.9Ti0.1NiAl0.05 alloy on its electrochemical behaviour and cracking resistance.

Ce travail s’inscrit dans le contexte d’une meilleure prédiction de la durée de vie de structures soumises au risque d’amorçage et de propagation de fissures multiples de corrosion sous contrainte (CSC). Ainsi, en développant une méthodologie expérimentale originale basée sur des mesures conjointes de corrélation d’images numériques (DIC), d’émission acoustique (EA) et de bruit électrochimique (EN), et leur analyse, ce travail vise à contribuer à l’amélioration de la compréhension des mécanismes impliqués dans le développement de colonies de fissures courtes de CSC qui interagissent entre elles, et à la simulation du comportement de cette colonie. Le choix de conditions optimales de traitement thermique d’un alliage base-Ni et de pH d’une solution de polythionate, a permis la maitrise des paramètres géométriques et morphologiques de colonies de fissures intergranulaires, qui ont été investiguées par DIC grâce à l’optimisation d’une préparation de surface adaptée. Les différentes phases de propagation d’une fissure unique et d’une colonie de fissures ont été identifiées, de même que les mécanismes associés, par des expérimentations et analyses réalisées en 2D et en 3D. Cette approche expérimentale innovante a permis de poser les bases d’une approche numérique puis de la valider. Un focus particulier a été porté sur l’EN au travers d’une analyse critique des perturbations engendrées par le bruit de l’instrumentation et par l’asymétrie du système d’étude. Les limitations de la technique pour son application à l’étude quantitative de la corrosion sous contrainte ont été évaluées sur la base des résultats de l’étude. Une transposition de la démarche expérimentale à hautes pressions et températures est proposée comme perspective à court terme de ce travail, qui permet également d’envisager la prise en compte de différents modes de propagation des fissures en lien avec la microstructure du matériau dans l’approche numérique. / This work concerns with the current needs of enhancing the tools used for predicting the remnant lifetime of structures subjected to the risk of initiation and propagation of multiple stress corrosion cracks (SCC). The approach consists in developing an original experimental methodology based on joint measurements of digital image correlation (DIC), acoustic emission (EA) and electrochemical noise (EN). The final objective is to contribute to both the understanding of the mechanisms involved in the development of interacting short stress corrosion cracks and to the modeling of the colony behavior. The choice of optimal conditions for the heat treatment of a Nickel-base alloy and for the pH of a polythionate solution allowed controlling the morphological parameters of intergranular cracks colonies, which were investigated by DIC owning to an optimized suitable surface treatment. The different propagation stages of a single crack and some colonies were identified, together with the involved mechanisms, through experiments and analyses performed in 2D and 3D. This innovative experimental approach allowed settling the basements of the numerical modeling and validating it. A particular attention was focused on EN measurements through a critical analysis of the perturbations generated by the instrumental noise and the asymmetry of the studied system. The limitations of the technique for its application to the quantitative study of SCC were evaluated on the basis of the present results. A transposal of the experimental approach towards high temperature and pressure conditions of test was finally proposed as a short-term prospect of this work, also allowing considering other modes of crack propagation linked to the material microstructure in the numerical approach.

Em nível microscópico, as rochas apresentam microdefeitos que agem como concentradores locais de tensão, favorecendo a ocorrência de ruptura frágil. O entendimento desse processo requer análises experimentais em rochas submetidas a tensões de tração. O ensaio de compressão diametral é uma alternativa apropriada, pois não apresenta as dificuldades envolvidas no ensaio de tração direta. A propagação de microfissuramento em materiais frágeis produz liberação de energia na forma de ondas elásticas chamadas de emissões acústicas (EA). O monitoramento com EA permite acompanhar a propagação de dano no corpo de prova (CP), sem perturbá-lo. Nesta pesquisa, CPs de mármore e monzogranito são submetidos a ensaios de compressão diametral com deslocamentos monotônicos e cíclicos, com controle de deslocamento. Aplica-se a técnica de EA, em conjunto com análises petrográficas, análises das curvas de força versus deslocamento e exame visual, para caracterizar o seu processo de microfissuramento. A localização tridimensional das fontes de EA foi realizada inicialmente utilizando-se o software AEwin® da PASA. Foi desenvolvido um programa de localização aprimorado que incorpora o cálculo da velocidade de propagação das ondas (vp) média para cada instante em que uma fonte é localizada. O novo programa (Crack Location by Acoustic emission with P Wave Velocity determination, CLAPWaVe) mostra um claro decréscimo da velocidade de propagação com o aumento do dano. O programa desenvolvido (CLAPWaVe) mostrou melhor ajuste e maior coerência com a literatura e com a condição final rompida dos CPs do que o software AEwin. Em mármore e monzogranito o microfissuramento se inicia a 25-30% e 75-85% do carregamento de pico, respectivamente, e localiza-se na vizinhança do centro do CP. Em ambas as rochas se acumulou, também, dano na região dos apoios do CP, associado à transferência de carregamento do berço ao CP. Antes do pico de carregamento, o microfissuramento tornou-se mais denso e localizado no centro e nos apoios do CP, embora a região central ainda concentre a maior parte. Após o pico, o microfissuramento acumulou-se em uma das faces do CP, progredindo até a outra face. O monzogranito apresentou ruptura progressiva do CP, enquanto que no mármore a maior parte da superfície de ruptura já está desenvolvida imediatamente após o pico. Durante o ensaio em ambas as rochas, no núcleo central foram registradas as menores velocidades vp do CP. Na região dos apoios, embora tenha havido microfissuramento, registraram-se as maiores velocidades vp no CP, pois o confinamento produzido pelo contato com o berço aumentou localmente a rigidez do CP. A distribuição não homogênea de vp no CP revelou que a consideração desse parâmetro como constante e igual à condição intacta ao longo do ensaio, como comumente encontrado na literatura, não representa a condição real do CP danificado. O microfissuramento no monzogranito se propaga principalmente através dos cristais de quartzo, seguindo um caminho tortuoso subparalelo à direção de carregamento e liberando altos níveis de energia absoluta. No mármore, a propagação segue os planos de clivagem da calcita, liberando níveis baixos de energia absoluta. Os histogramas da distribuição espacial da resistência em ambas as rochas mostraram bom ajuste a uma distribuição de Weibull, porém o monzogranito mostrou melhor ajuste e menor variabilidade que o mármore. As análises dos sinais no domínio das frequências mostraram que o microfissuramento é caracterizado por emissões de banda larga. / At microscopic level, rocks exhibit microflaws, which act as local stress concentrators, favoring the occurrence of brittle failure. The understanding of this process requires experimental analyses of rock specimens under tensile stresses. The diametral compression test is an adequate alternative for such a studies, because it does not present the difficulties of direct tension tests. Crack propagation in brittle materials releases energy as transient elastic waves known as acoustic emission (AE). Monitoring with AE enables an insight into the cracking process without affecting the integrity of the sample. In this work, marble and monzogranite specimens were subjected to monotonic and cyclic displacementcontrolled diametral compression tests. The AE monitoring technique was applied in conjunction with petrographic analyses, interpretation of the load versus displacement curves and visual examination of the samples for the characterization of their cracking process. The three-dimensional localization of the AE sources was initially carried out by using the software AEwin® from PASA. An improved localization software, which considers the P-wave velocity variation along the damage process (vp) for each AE source was developed. The developed software (Crack Location by Acoustic emission with P Wave Velocity determination, CLAPWaVe) has shown greater consistency with literature and the final cracked samples and better accuracy than AEwin. Microcracking in monzogranite and marble initiated at 25-30% and 75-80% of the peak load, respectively, and is located at the center of the specimen. In addition, both rocks showed concentrated microcracking close to the region of contact between the specimen and the loading platens, related to the loading transference along the loading edge. Before peak load, microcracking becomes denser and localized at the center and the contact region of the specimen, although, the central region still concentrates the main portion of the damage. After the peak load, new microcracks were first concentrated on one of the faces at the center of the specimen and then propagated through its thickness all the way to the other face. The progressive failure in monzogranite extended through to the end of the test, while in marble the main portion of the failure surface of the specimen developed just after peak. During the whole test in both rocks, the lowest velocities (vp) of the specimen were recorded in the central core. Although microcracking was induced at the contact region, the highest velocities vp of the specimen were registered there, because of the confinement effect produced by the platens, which lead to a local increase in the stiffness of the specimen. The non-homogeneous distribution of vp in the specimen has revealed that the utilization of this parameter as a constant and equal to the value measured in the specimen before testing (as usually adopted in the literature), does not represent the real condition of the damaged specimen. In monzogranite, microcracks propagate mainly through quartz crystals, following a tortuous path subparallel to the loading direction, by releasing high-level of absolute energy, while in marble the propagation of microcracks follows the cleavage planes of calcite, by releasing low-level of absolute energy. The histograms of spatial strength distribution in both rocks have shown good adjustment to a Weibull distribution, but monzogranite exhibited a more accurate adjustment with lower variability than marble. The analysis of signals in the frequency domain showed that the microcracking is characterized by wide band emissions.

La fissuration d’éléments minces en béton dès le jeune âge correspond à une réalité observée sur des ouvrages en construction. Cette fissuration concerne des bétons courants de bâtiments, pour lesquels les matériaux de qualité optimale ne sont pas toujours disponibles, en particulier au niveau des granulats. Le but de cette thèse est de définir une approche expérimentale d’étude de ces phénomènes et de proposer des interprétations pour les sensibilités relatives à la fissuration en fonction de la nature des granulats et de leurs taux de saturation initiaux. La sensibilité des moyens de mesures existants conçus pour des bétons spéciaux (BAP et BHP) a d’abord dû être<p>vérifiée. Un nouveau dispositif expérimental a été développé dans le but de mieux décrire l’évolution de la résistance et de la capacité de<p>déformation en traction du béton jeune. Les indicateurs globaux (macroscopiques) apparaissent plus sensibles que les indicateurs de la microstructure pour rendre compte des différences de comportement observées. L’évolution du module élastique, du retrait plastique et endogène corrélées à l’évolution de la capacité de déformation et de la résistance en traction permettent de mieux caractériser le risque<p>potentiel de fissuration par retrait empêché. La fin de prise correspond à une phase critique. L’influence de la saturation des granulats est<p>indirecte, et résulte des variations du rapport Eau d’ajout/Ciment, à rapport Eau efficace/Ciment constant. La nature des granulats intervient au niveau des évolutions relatives de la résistance en traction et du module élastique. La méthodologie peut être appliquée à l’étude d’autres types de bétons et d’autres paramètres de formulation. / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

Alloy 617 displays a ductility dip during straining at exactly 1000˚C, leading to brittle fracture. A sudden decrease in ductility appearing during Gleeble hot ductility tests of Ni-based superalloys is a well-known phenomenon, while its cause is unknown. Many mechanisms have been established as possible contributors to the issue, and in later years not one, but the simultaneous presence of several of these mechanisms were confirmed as the cause. The ductility dip leads to solid state cracking and a specific solid state cracking phenomenon known as ductility dip cracking is specifically common in Ni-based superalloys. Ductility dip cracking is identified by intergranular cracks and the occurrence of specific precipitates, among other things. This work investigates the possibility that the decreased ductility is due to ductility dip cracking. Furthermore, other possible explanations are investigated. Visual examination was conducted through LOM, SEM and chemical analysis using EDS technique. Combined with thermodynamic calculations, the existence of Cr-rich M23C6 carbides, Ti(N,C) and Mo-rich particles, most likely M3B2, were confirmed. Further, it is established that the ductility dip is related to the lack of dynamic recrystallization at 1000˚C. It is not confirmed that the ductility dip in alloy 617 is due to ductility dip cracking. / Nickelbaslegeringen 617 uppvisar en minskning i duktilitet under Gleeble-dragprovning vid exakt 1000˚C vilket leder till sprött brott. En plötslig sänkning av duktiliteten vid varmdragning av Ni-baserade superlegeringar är ett välkänt fenomen, dock är orsaken inte fastställd. Många mekanismer har bekräftats som bidrag till problemet och under de senaste åren har den simultana närvaron av fler av dessa mekanismer bekräftats som orsaken. Sänkningen i duktilitet leder till sprickbildning i fast fas och en specifik typ av sprickbildning känd som ”ductility dip cracking” är speciellt förekommande i Ni-bas legeringar. Denna identifieras bland annat genom intergranulära sprickor och närvaron av specifika utskiljningar. Detta arbete undersöker möjligheten att duktilitetssänkningen beror på  ”ductility dip cracking”. Dessutom undersöks fler tänkbara förklaringar. Visuell granskning genomfördes via LOM och SEM och analys av sammansättningar via EDS-analys. I kombination med termodynamiska simuleringar blev förekomsten av Cr-rika M23C6 karbider, Ti(N,C) och Mo-rika partiklar, troligtvis M3B2, bekräftad. Fortsatt är det bekräftat att duktilitetssänkningen är relaterat till avsaknaden av rekristallisation vid 1000˚C. Det är inte bekräftat i detta arbete att duktilitetssänkningen i legering 617 beror av ”ductility dip cracking”.

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[pt] O desenvolvimento de novas tecnologias com Hidrogênio como fonte de energia ressalta um antigo desafio nos meios de transporte e armazenamento desse, visto que todos materiais estruturais têm susceptibilidade a fragilização pelo hidrogênio. A forma usual de resolver esse problema é o uso de materiais nobres e mais resistentes a fragilização pelo hidrogênio. Uma alternativa para o dimensionamento mecânico em condições de fragilização pelo hidrogênio vem da modelagem de trincas curtas através da mecânica da fratura linear elástica ou Elasto-Plástica. Esses modelos consideram dois parâmetros do material, o Limite de Resistência ao Trincamento Assistido pelo Ambiente e o Limiar de Propagação de Trincas no meio. Nesse trabalho o modelo proposto é validado experimentalmente em condições de Corrosão sob Tensão Induzida por Sulfetos (aço de alta resistência e baixa liga e o aço inoxidável super martensítico UNS S41426 expostos ao sulfeto de hidrogênio), bem como o aço 17-4PH em 200bar(g) de H2. O método de teste T-WOL recomendado no código ASME BPVC para a obtenção da tenacidade à fratura sob alta pressão de H2 é avaliada para materiais com alta tenacidade, a qual não apresentou bons resultados. Como alternativa, uma metodologia modificada a partir da norma ASTM E1820 para obter a curva J-R em H2 a alta pressão é testada, obtendo o limiar de propagação de trincas em condições Elasto-Plásticas. Durante as atividades, uma célula de carga utilizada no interior da autoclave de teste falhou quando exposta a 200bar(g) de H2. Foi realizada análise de falha e redimensionamento, conforme o modelo de trincas curtas proposto, para que células semelhantes pudessem ser utilizadas nos testes subsequentes / [en] The development of new technologies with hydrogen as an energy source underscores a longstanding challenge in its transportation and storage, since all structural materials are susceptible to hydrogen embrittlement. The usual approach to solve this problem is to use nobler materials more resistant to hydrogen embrittlement. An alternative approach to mechanical design under hydrogen embrittlement conditions involves the modeling of the behavior of short cracks through linear elastic or elastoplastic fracture mechanics. These models consider two key material parameters: the Environmental Assisted Cracking Resistance Limit and the Crack Propagation Threshold in the environment. In this study, the proposed model is validated by suitable tests under sulfide stress corrosion cracking - High Strength and Low Alloy steel and a supermartensitic stainless steel UNS S41426 exposed to hydrogen sulfide, and in a 17-4PH steel exposed to high-pressure gaseous hydrogen, at 200 bar(g) of H2. A T-WOL test methodology recommended in ASME BPVC code for measuring the fracture toughness at high pressure of H2 for materials with high toughness is evaluated, and it yields unsatisfactory results. As an alternative, a modified ASTM E1820 test method is proposed to obtain the J-R curve under high-pressure H2, obtaining the crack propagation threshold at elastoplastic conditions. During these activities, a load cell used within the test autoclave failed when exposed to 200 bar(g) of H2. Failure analysis and a new design were conducted according the short crack tolerance model, to allow the use of similar load cells in the following tests.