Les procédés d’élaboration de Composites à Matrice Céramique (CMC) utilisés aujourd’hui à l’échelle industrielle sont longs et par conséquent coûteux. Dans ce contexte, le procédé de densification rapide ou procédé de caléfaction, jusque-là essentiellement connu pour l’élaboration de carbone, permettant de réduire considérablement les durées d’élaboration, apparaît intéressant. Cette étude est axée sur le développement du procédé de caléfaction dans le but d’élaborer des carbures, matériaux connus pour leurs bonnes propriétés à haute température, et plus particulièrement du carbure de silicium (SiC). Dans cet objectif, un équipement de laboratoire, le mini-kalamazoo, a été mis au point, adapté et instrumenté de manière à répondre aux besoins de l’étude. Les premiers essais ont été réalisés au moyen de méthyltrichlorosilane (MTS), précurseur largement connu pour la CVD/CVI du SiC. Les analyses des dépôts formés ont montré la présence de SiC mais aussi celle de carbone. Dans quelques cas spécifiques, du SiC pur peut être formé localement en début de caléfaction. Mis à part ces conditions particulières, l’utilisation de MTS pur en tant que précurseur conduit à la présence inéluctable de carbone libre dans le dépôt de SiC. Plusieurs voies d’amélioration ont alors été proposées et testées pour pallier cet excès de carbone. Certaines d’entre elles se sont avérées efficaces et prometteuses, en particulier, l’utilisation d’un mélange de MTS et d’un précurseur de silicium non carboné et l’utilisation de précurseurs de SiC non chlorés, le CVD 4000 et l’hexaméthyldisilane. Les vitesses de croissance de dépôt sont largement supérieures avec le procédé de caléfaction qu’avec les moyens d’élaboration aujourd’hui employés. L’ensemble des résultats obtenus valide l’intérêt de la caléfaction en tant que procédé d’élaboration du SiC et de nouveaux matériaux de type carbure. / The current Ceramic Matrix Composites (CMC) manufacturing processes used at the industrial scale are slow and consequently expensive. In light of this, the fast densification process, also called the film-boiling process, essentially known to produce carbon deposit up to now, reduces significantly the processing time which seems to be promising. This study was focused on the film-boiling process development in order to manufacture carbides which are materials with good properties at high temperature, and especially to synthetize silicon carbide (SiC). In this aim, a laboratory-made equipment was developed, set-up and adapted to the needs of our study. The first tests were done with the methyltrichlorosilane (MTS), precursor widely used for SiC CVD/CVI. Characterizations of the deposits showed the formation of SiC but also the occurrence of carbon. Pure SiC can be locally obtained at the beginning of the film-boiling process in some specific experimental conditions. For most of the experiments, the use of pure MTS as precursor leads inevitably to the formation of free carbon in the SiC deposit. Several improvement routes were proposed and tested to remove this carbon excess. Some of the efficient and promising routes have consisted in the use of MTS mixed with a silicon precursor free of carbon and the use of two non-chlorinated SiC precursors, CVD 4000 liquid precursor and hexamethyldisilane. The deposit growth rates were significantly superior with the film-boiling process compared to the classical processes. All the data show that the film-boiling process is promising for the manufacturing of SiC and new carbide materials.

La bonne ténacité des aciers pour gazoducs aux basses températures est nécessaire pour éviter la propagation de fissures de manière catastrophique. Cette étude vise à améliorer la compréhension physique et l'évaluation quantitative du comportement à rupture des aciers pour gazoducs laminés à chaud, en nous intéressant plus particulièrement aux températures au pied de la transition ductile-fragile .La résilience de ces aciers est généralement validée à l'aide d'essais dits drop weight tear tests (DWTT), après lesquels le faciès de rupture doit contenir moins de 15% de zone fragile. Pour les aciers mis en forme par laminage thermomécanique (TMCP), des ruptures fragiles hors plan, comme le délaminage (qui se propage dans le plan de laminage de la tôle), et la rupture fragile en biseau le long des plans dits thêta (inclinés de 40° autour de la direction de laminage par rapport au plan de laminage) apparaissent dans la transition ductile-fragile. Ces modes de rupture, observés lors des essais de résilience (DWTT, Charpy) et de ténacité (CT), affectent la résistance à la rupture de ces aciers.L'anisotropie de l'écoulement plastique, puis celle de la sensibilité à la rupture par clivage ont été caractérisées en fonction de la température, à l'aide d'essais de traction sur des éprouvettes lisses et entaillées conçues pour cette étude. L'analyse mécanique de ces essais à l'aide de calculs par éléments finis a permis de déterminer des contraintes critiques de clivage dans les directions perpendiculaires au plan de laminage et aux plans thêta. Les valeurs obtenues dans ces directions sont de 25% inférieures à celles correspondant aux directions de laminage et travers long.L'anisotropie de la contrainte critique de clivage a été quantitativement corrélée à l'anisotropie de microtexture du matériau. Des entités appelées « facettes de clivage potentielles » ont été définies et mesurées dans cette étude, comme des régions contenant un plan {100} défavorablement orienté et dans lesquelles les fissures de clivage se propagent sans être arrêtées. Par exemple, un plan contenant 20% de facettes de clivage potentielles aurait une contrainte critique de clivage de 20% moins élevée qu'un plan présentant seulement 10% de facettes de clivage potentielles.La taille et la forme de ces facettes de clivage potentielles évoluent avec la déformation plastique. Par conséquent, la contrainte critique de clivage est affectée par l'historique de déformation. Dans le cas du délaminage, les facettes de clivage potentielles s'allongent au cours d'un chargement dans la direction travers long, conduisant à une augmentation de leur taille effective et par conséquent à une diminution (qui peut atteindre 30%) de la contrainte critique de clivage dans le plan de la tôle. Cette diminution facilite in fine l'apparition du délaminage. De plus, la présence de micro-fissures ductiles facilite la rupture par délaminage en modifiant l'état de contrainte local. Un critère a ainsi été proposé pour prédire numériquement l'amorçage du délaminage dans des éprouvettes de traction et/ou de résilience Charpy.L'application de cette approche à des échantillons traités thermiquement et à des échantillons pré-déformés a montré que la sensibilité au délaminage pouvait être contrôlée en modifiant la texture locale initiale du matériau. / High toughness of pipeline steels at low temperature is required to avoid catastrophic propagation of brittle crack. The aim of the study is to improve physical understanding and quantitative assessment of the toughness behavior of hot-rolled pipeline steels, focusing on the lower part of the ductile to brittle transition temperature range.The impact toughness of these steels is commonly validated using drop weight tear tests (DWTT), on the basis of fracture surfaces that must exhibit less than 15% of brittle fracture appearance. In thermomechanical control processed steels, brittle out-of-plane cracks such as delamination (which propagates along the rolling plane), and brittle tilted fracture (BTF) along theta-planes (tilted around RD by 40° with respect to rolling plane), have been characterized in the ductile to brittle transition temperature range, for both industrial (DWTT) and laboratory Charpy impact tests. In both cases, as well as in fracture toughness tests, such brittle out-of-plane cracking has been shown to impair the impact toughness.The anisotropy in plastic flow and sensitivity to cleavage fracture has been characterized as a function of temperature, by using tensile tests on specifically designed smooth and notched specimens. From finite element mechanical analysis of these tests, critical cleavage stresses normal to the rolling plane and the theta-plane are considerably lower (around 25%) than for planes normal to the rolling and transverse directions.The anisotropy in critical cleavage stress has been quantitatively correlated to microtexture anisotropy. So-called “potential cleavage facets” have been defined and measured in this study, as regions with unfavorably oriented {100} planes, which are taken as unit crack paths for cleavage propagation. A sample containing 20% of potential cleavage facets had a critical cleavage stress 20% lower than a sample with only 10% of potential cleavage facets.The size and shape of these potential cleavage facets evolve during plastic deformation. Therefore, the critical cleavage stress was found to be affected by plastic strain history. In the case of delamination, potential cleavage facets along the rolling plane were elongated during loading, their area was increased and the corresponding critical cleavage stress decreased by around 30% with respect to the undeformed case. This made delamination cracking easier. Moreover, the presence of a ductile crack at the initiation site of delamination locally modified the stress state and also facilitated delamination occurrence. A criterion has been developed to numerically predict the onset of delamination in tensile and Charpy specimens.Application of this approach to heat-treated and to prestrained specimens eventually showed that it was possible to modify the sensitivity to delamination by strongly modifying the initial microtexture anisotropy.

Ce travail de thèse porte sur la formation et l’évolution des microstructures et microtextures des alliages de titane associées à la précipitation de la phase α aux JDGs β/β. L’alliage β-métastable Ti17 a été utilisé comme alliage modèle de par son aptitude à figer sa microstructure haute température, permettant de conserver la phase parente non transformée. De nombreuses analyses cristallographiques EBSD 2D et quelques analyses 3D ont été réalisées pour des microstructures formées sous diverses sollicitations thermiques (transformation en conditions isotherme (TI) ou refroidissement continu (RC)) et thermomécaniques (déformation de la phase parente puis TI ou RC). L’étude statistique automatisée des microtextures a été menée à partir de données EBSD en utilisant un algorithme spécifique conduisant aux mesures d’orientations de variants et à des grandeurs représentatives de la microtexture. Un lien étroit entre la cinétique de germination croissance de la phase α et le développement de la microtexture est mis en évidence, alors que ce paramètre est souvent négligé dans les travaux de la littérature. De plus, l’étude de différents critères de sélection de variants (SV) a conduit à montrer que la SV était fréquente pour les premiers grains formés. Ces premiers grains ont des conditions de germination plus favorables ; le variant choisi est celui qui minimise l’écart à la ROB avec les deux grains β. Autrement dit, l’énergie d’interface et surtout l’énergie élastique associée à la formation de ce variant sont minimales. Les conditions cristallographiques de formation des colonies de lamelles sont également étudiées et discutées / This work focuses on the formation and the evolution of microstructure and microtexture associated with the α phase precipitation at β/β GBs in titanium alloys. A β-metastable alloy (Ti17) has been studied, because the high temperature microstructure is frozen by a rapid quench and the untransformed parent phase remains. Numerous 2D EBSD analyses and some 3D analyses have been carried out after transformation and under various thermal and thermo-mechanical treatments (isothermal conditions and continuous cooling (CC) without and with prior deformation of the parent phase). One great originality of this study is the automated statistical approach used to characterize the microtexture from EBSD data. An algorithm has been specifically developed in order to get the variants orientation as well as different representative data characterizing the microtexture. We have identified the link between the nucleation/growth kinetics of α phase and the microtexture development, a relationship that is often neglected in the literature, where one usually associates the microtexture only to the variant selection and to the initial β texture. The occurrence of variants selection (VS) has been performed considering different VS criteria; it has been shown that VS is very active for the first grains formed. These grains have the most favorable nucleation conditions. The variant selected is the one that minimizes the deviation to the Burgers Orientation Relationship with both β grains; i.e. the one for which interfacial energy and especially the elastic energy associated to its formation are minimized. Moreover, the crystallographic conditions of α colonies formation are studied and discussed

Os aços de alta resistência e baixa liga são amplamente utilizados em dutos transportadores de óleo e gás e, atualmente, o desenvolvimento de novos projetos de liga e o uso de técnicas altamente avançadas de fabricação e processamento dos aços se tornaram essenciais para obtenção de estruturas que resistam aos danos provocados por H, principal motivo de falha de oleodutos e gasodutos em meios ricos em H2S. No presente trabalho, avaliou-se o efeito de características microestruturais na difusividade do H em dois aços grau API X65, com diferentes teores de Mn. Uma das chapas ainda está em fase experimental de desenvolvimento, tem baixo teor de Mn e foi produzida para aplicação em ambientes sour. A outra chapa tem alto teor de Mn, já é usada comercialmente há alguns anos e foi desenvolvida para trabalho em ambientes doces. Os dois materiais passaram por caracterização microestrutural nas três seções da chapa: longitudinal e transversal à direção de laminação e do topo da chapa (paralela à direção de laminação). Após a caracterização, amostras de cada seção dos aços foram submetidas a ensaios de permeabilidade ao H; o aço baixo Mn passou por análises de EBSD (Difração de Elétrons Retroespalhados), para determinação de textura. O aço baixo Mn tem microestrutura homogênea ao longo da espessura da chapa, composta por ferrita refinada e pequenas ilhas de perlita. O aço alto Mn, por sua vez, apresenta microestrutura heterogênea ao longo da espessura, formada por bandas de ferrita e perlita, com marcada presença de segregação central de elementos de liga. Os ensaios de permeabilidade ao H mostraram que os coeficientes de difusão efetiva do H, Deff, do aço baixo Mn são ligeiramente superiores aos do aço alto Mn. Outros dois importantes parâmetros que foram calculados para os dois aços são a concentração de H na sub-superfície do material, C0, e o número de traps por unidade de volume, Nt. Contrariando expectativas, o aço baixo Mn apresentou maiores valores de C0 e Nt do que o aço alto Mn. Ensaios preliminares de dessorção térmica realizados nos dois aços mostraram os mesmos resultados: o aço baixo Mn aprisiona mais H do que o aço alto Mn. Estes resultados contraditórios de C0 e Nt foram atribuídos à presença de nanoprecipitados de microadições de liga no aço baixo Mn, não detectáveis por microscopia óptica e eletrônica de varredura. Ainda, para os dois aços, os valores de Deff variaram em função da seção analisada da seguinte maneira: Deff longitudinal ? Deff transversal > Deff topo. Para entender melhor o comportamento anisotrópico da difusão do H nos dois aços calculou-se um novo coeficiente de difusão, que foi chamado de coeficiente de difusão no estado estacionário, Dss. O Dss considera que todos os traps do aço estão saturados, permitindo, assim que se avalie somente o efeito de obstáculos físicos à difusão do H. No aço alto Mn, o Dss variou da mesma maneira que o Deff: Dss longitudinal ? Dss transversal > Dss topo; este comportamento foi atribuído ao bandeamento presente no material. No aço baixo Mn, o Dss variou de forma diferente do Deff: Dss transversal > Dss longitudinal >= Dss topo, indicando que a difusão do H pode ser auxiliada por contornos de grão enquanto os traps estão sendo saturados, e que a textura cristalográfica pode influenciar a difusão após o estado estacionário ser atingido. / High strength low alloy steels are widely applied as pipelines for crude oil and natural gas transportation and, currently, new approaches to alloy design, in addition to the use of advanced steelmaking and processing techniques, have become essential for obtaining structures that resist to hydrogen damage, which is the main cause of pipelines failure in H2S-rich environments. The main objective of the present work is to evaluate the influence of microstructural features on hydrogen diffusivity in two API X65 steels, with different Mn contents. One of the steel plates has been recently developed for usage in sour environments, is on its experimental stage and has a low Mn content. The other one is a commercial plate steel, with high Mn content, developed for sweet applications. Both steel plates were characterized in its three sections, in relation to the rolling direction: longitudinal, transverse and top surface of the plate (parallell to the rolling direction). After that, samples obtained from each section of the plates were submitted to hydrogen permeation tests; the low Mn steel was also analysed with EBSD, for texture determination. The low Mn steel presents a homogeneous microstructure through plate thickness, composed of refined ferrite and small pearlite islands. The high Mn steel has a heterogeneous microstructure through the plate thickness, composed of ferrite and pearlite bands, and presents centerline segregation. Hydrogen permeation tests showed that the Deff obtained for the low Mn steel sections are slightly higher than for the high Mn steel. Another two important parameters that were calculated for both steels are the subsurface hydrogen concentration, C0, and the number of traps per unit volume, Nt. Contrary to what was expected, the low Mn steel presented the higher C0 and Nt values. Thermal dessorption spectroscopy analysis confirmed that the low Mn steel traps more H atoms than the high Mn one. These results, along with the similar Deff values, were related to the presence of nanoprecipitates of microalloying elements, that cannot be detected via optical and scanning electron microscopy. Additionally, also for both steels, the Deff values varied in function of the analyzed section as it follows: Deff longitudinal ? Deff transverse > Deff top. In order to better understand this anisotropic behavior, a new diffusion coefficient, which was called diffusion coefficient at the steady state, Dss, was determined. Dss considers that all the trapping sites are saturated, enabling, thus, the evaluation of physical obstacles to H diffusion. For the high Mn steel, the Dss varied in the same matter as the Deff: Dss longitudinal ? Dss transverse > Dss top; this behavior was associated with the microstructural banding present in the material. For the low Mn steel, the Dss exhibited a different behavior: Dss transverse > Dss longitudinal >= Dss top, suggesting that H diffusion can be aided by grain boundaries while the trapping sites are being filled and that crystallographic texture may play its role after the steady state is reached.

Os aços de alta resistência e baixa liga são amplamente utilizados em dutos transportadores de óleo e gás e, atualmente, o desenvolvimento de novos projetos de liga e o uso de técnicas altamente avançadas de fabricação e processamento dos aços se tornaram essenciais para obtenção de estruturas que resistam aos danos provocados por H, principal motivo de falha de oleodutos e gasodutos em meios ricos em H2S. No presente trabalho, avaliou-se o efeito de características microestruturais na difusividade do H em dois aços grau API X65, com diferentes teores de Mn. Uma das chapas ainda está em fase experimental de desenvolvimento, tem baixo teor de Mn e foi produzida para aplicação em ambientes sour. A outra chapa tem alto teor de Mn, já é usada comercialmente há alguns anos e foi desenvolvida para trabalho em ambientes doces. Os dois materiais passaram por caracterização microestrutural nas três seções da chapa: longitudinal e transversal à direção de laminação e do topo da chapa (paralela à direção de laminação). Após a caracterização, amostras de cada seção dos aços foram submetidas a ensaios de permeabilidade ao H; o aço baixo Mn passou por análises de EBSD (Difração de Elétrons Retroespalhados), para determinação de textura. O aço baixo Mn tem microestrutura homogênea ao longo da espessura da chapa, composta por ferrita refinada e pequenas ilhas de perlita. O aço alto Mn, por sua vez, apresenta microestrutura heterogênea ao longo da espessura, formada por bandas de ferrita e perlita, com marcada presença de segregação central de elementos de liga. Os ensaios de permeabilidade ao H mostraram que os coeficientes de difusão efetiva do H, Deff, do aço baixo Mn são ligeiramente superiores aos do aço alto Mn. Outros dois importantes parâmetros que foram calculados para os dois aços são a concentração de H na sub-superfície do material, C0, e o número de traps por unidade de volume, Nt. Contrariando expectativas, o aço baixo Mn apresentou maiores valores de C0 e Nt do que o aço alto Mn. Ensaios preliminares de dessorção térmica realizados nos dois aços mostraram os mesmos resultados: o aço baixo Mn aprisiona mais H do que o aço alto Mn. Estes resultados contraditórios de C0 e Nt foram atribuídos à presença de nanoprecipitados de microadições de liga no aço baixo Mn, não detectáveis por microscopia óptica e eletrônica de varredura. Ainda, para os dois aços, os valores de Deff variaram em função da seção analisada da seguinte maneira: Deff longitudinal ? Deff transversal > Deff topo. Para entender melhor o comportamento anisotrópico da difusão do H nos dois aços calculou-se um novo coeficiente de difusão, que foi chamado de coeficiente de difusão no estado estacionário, Dss. O Dss considera que todos os traps do aço estão saturados, permitindo, assim que se avalie somente o efeito de obstáculos físicos à difusão do H. No aço alto Mn, o Dss variou da mesma maneira que o Deff: Dss longitudinal ? Dss transversal > Dss topo; este comportamento foi atribuído ao bandeamento presente no material. No aço baixo Mn, o Dss variou de forma diferente do Deff: Dss transversal > Dss longitudinal >= Dss topo, indicando que a difusão do H pode ser auxiliada por contornos de grão enquanto os traps estão sendo saturados, e que a textura cristalográfica pode influenciar a difusão após o estado estacionário ser atingido. / High strength low alloy steels are widely applied as pipelines for crude oil and natural gas transportation and, currently, new approaches to alloy design, in addition to the use of advanced steelmaking and processing techniques, have become essential for obtaining structures that resist to hydrogen damage, which is the main cause of pipelines failure in H2S-rich environments. The main objective of the present work is to evaluate the influence of microstructural features on hydrogen diffusivity in two API X65 steels, with different Mn contents. One of the steel plates has been recently developed for usage in sour environments, is on its experimental stage and has a low Mn content. The other one is a commercial plate steel, with high Mn content, developed for sweet applications. Both steel plates were characterized in its three sections, in relation to the rolling direction: longitudinal, transverse and top surface of the plate (parallell to the rolling direction). After that, samples obtained from each section of the plates were submitted to hydrogen permeation tests; the low Mn steel was also analysed with EBSD, for texture determination. The low Mn steel presents a homogeneous microstructure through plate thickness, composed of refined ferrite and small pearlite islands. The high Mn steel has a heterogeneous microstructure through the plate thickness, composed of ferrite and pearlite bands, and presents centerline segregation. Hydrogen permeation tests showed that the Deff obtained for the low Mn steel sections are slightly higher than for the high Mn steel. Another two important parameters that were calculated for both steels are the subsurface hydrogen concentration, C0, and the number of traps per unit volume, Nt. Contrary to what was expected, the low Mn steel presented the higher C0 and Nt values. Thermal dessorption spectroscopy analysis confirmed that the low Mn steel traps more H atoms than the high Mn one. These results, along with the similar Deff values, were related to the presence of nanoprecipitates of microalloying elements, that cannot be detected via optical and scanning electron microscopy. Additionally, also for both steels, the Deff values varied in function of the analyzed section as it follows: Deff longitudinal ? Deff transverse > Deff top. In order to better understand this anisotropic behavior, a new diffusion coefficient, which was called diffusion coefficient at the steady state, Dss, was determined. Dss considers that all the trapping sites are saturated, enabling, thus, the evaluation of physical obstacles to H diffusion. For the high Mn steel, the Dss varied in the same matter as the Deff: Dss longitudinal ? Dss transverse > Dss top; this behavior was associated with the microstructural banding present in the material. For the low Mn steel, the Dss exhibited a different behavior: Dss transverse > Dss longitudinal >= Dss top, suggesting that H diffusion can be aided by grain boundaries while the trapping sites are being filled and that crystallographic texture may play its role after the steady state is reached.

The properties of titanium alloys are based on alloy compositions and microstructures that consist of mixtures of the two allotropic modifications of titanium, the low temperature α (hcp) and the high temperature β (bcc) phases. This thesis deals with the hot working behaviour of three commercial titanium alloy compositions designated IMI834, Ti17 and Ti5553 with a focus and detailed analysis of the Ti5553 alloy. These alloys represent the differing uses of titanium alloys in the aerospace industry. IMI834 is a near α alloy used in high temperature creep resistant applications as compressor discs and blades in aeroengines. Ti17 is a high strength alloy α+β used at intermediate temperatures in fan and compressor discs of aeroengines, while Ti5553 is a high strength-high toughness metastable β alloy used in the undercarriages of aircraft. The three alloys have widely differing β transus temperatures (related to α phase stability) and compositions. Titanium alloys are vacuum arc melted and thermomechanically processed. This process involves ingot breakdown in β (bcc) phase, and subsequent thermomechanical processing in two-phase α+β (hcp+bcc) region at temperatures that typically involve volume fractions of α in lath or plate form ranging from 15% to about 30%. The thermomechanical processing breaks down lath α to spheroidal particles, a process known as globularisation. Chapter I of this thesis reviews the current understanding of the hot working of titanium alloys and microstructure evolution during the hot working process. Chapter II summarises the main experimental techniques used: the hot compression test, and subsequent microstructure and microtexture analysis by scanning electron microscopy and related electron back scattered diffraction techniques (EBSD), transmission electron microscopy and related precession electron diffraction techniques (PED) for orientation imaging. The starting structure in the α+β domain of hot work is generally not a random distribution of the 12 variant Burgers Orientation Relationship (BOR) between the α and β phases, (11̅0)β || (0001)α and <111>β || <112̅0>α . A variety of morphologies and distributions ranging from the typical colony structures of near α and α+β alloys to the fine distributions of variants arranged in a triangular fashion are observed with specific growth directions and habit planes. Chapter III describes a quantitative evaluation of α distribution that are typical of some of the starting structures for the hot working conditions used in this thesis, specifically in the Ti5553 alloy. For this purpose, a Matlab based script has been developed to measure the spatially correlated misorientation distribution. It was found that experimental spatially correlated misorientation distribution varies significantly from a random frequency for both pair and triplet wise distribution of α laths. The analysis of these structures by established techniques of analysis of self-accommodated structures based on strain energy minimisation shows that the observed variant distribution arise from the residual strain energy accommodation of the semi-coherent α plates. The hot working process has been examined through hot compression tests of the 3 alloys at strain rates ranging from 10-3 s-1 to 10 s-1 over a temperature range designed to maintain constant volume fractions of the α and β phases during deformation ranging from about 30% α to a fully β structure. Since extensive prior work has been carried on the processing of titanium alloys, Chapter IV focuses on a comparative study of hot deformation behaviour of the three alloys with an emphasis on isolating microstructural and other effects. The macroscopic flow behaviour has been analysed in terms of conventional rate equations relating stress, strain, strain rate and temperature. The three alloys show very similar features in their stress-strain behaviour. β phase deformation exhibits yield points whose magnitude varies with strain rate and temperature. The flow stress curves are typical of materials undergoing dynamic recovery and recrystallization processes. The stress-strain behaviour in the α+β domain of hot work exhibits significant flow softening in the early stages of deformation with a subsequent approach to steady-state behaviour at true strain of about 0.5. Activation energy analysis of the steady state condition suggests that the rate controlling mechanism is related to recovery in the β phase in both α+β and β processing. Zener-Hollomon plots of the flow stress in the three alloys indicate that their flow stress can be normalized to a temperature-compensated strain rate and they differ only in the slopes of the plots that are related to the stress exponent. Empirical constitutive models were developed for a predictive understanding of the flow stress as a function of strain, strain rate and temperature using conventional rate equations for the flow stress Chapter V and VI examine the evolution of microstructure and microtexture in detail during hot deformation and subsequent heat treatment in Ti5553. A combination of EBSD (micron and submicron scale) and PED (nano meter scale) is used in orientation imaging to examine the globularisation process of the α phase and the recovery and recrystallization in the β phase in both supertransus and subtransus hot compression. The understanding of these processes is enhanced by tracking the same starting β grain through the deformation process. The effect of strain, strain rate and temperature on the evolution of subgrains in α and its fragmentation into spheroidal α is quantified. In the absence of shear bands, the globularisation process is seen to evolve from a strain driven Raleigh instability of the plate α, by subgrain formation in α and β phases. The related microtexture evolution is analysed. The analysis of recovery and microtexture evolution in the β phase described here has not been attempted earlier in the literature. The overall evolution of structure and texture is seen to result from the complex interplay between recovery and recrystallisation in the α and β phases in substranus deformation. While the Burgers orientation relationship between α and β is lost in the early stages of deformation, it appears to be restored at large strains as a consequence of ‘epitaxial’ recrystallisation processes that seem to result from the discontinuous nucleation of recrystallization of either phase at interphase interfaces in the Burgers orientation. The effect of substranus deformation on β texture following supertransus post deformation heat treatment is also examined and compared with β textures resulting from alternative strain paths such as friction stir processing. Finally Chapter VII summarises these results and the new insights into the evolution of structure and microtexture during hot deformation of titanium alloys and suggests directions for future work.

La transition entre le comportement effusif et explosif des volcans de magma riche en silice est en partie contrôlée par la capacité des surpressions gazeuses à se dissiper hors du magma. La libération efficace des gaz est associée aux éruptions effusives tandis que la rétention de ces gaz contribue aux processus explosifs. L’une des approches pour évaluer la facilité d’échappement des gaz est de considérer l’évolution et le développement de la perméabilité dans la colonne magmatique et dans l'édifice. J'évalue dans ce travail de thèse le rôle des changements post-mise en place sur la microstructure dans des andésites basaltiques du Merapi (Indonésie). La perméabilité de ces roches est principalement contrôlée par des fissures liées à leur mise en place. Malgré l’influence importante de ces fissures post-mise en place pour dégazer à travers l'édifice, elles ne contribuent pas au dégazage intrinsique du magma en cours d’ascension. Pour s’affranchir de l'influence des microstructures post-mise en place du magma, j'étudie le développement et l'évolution in situ des réseaux perméables en déformant des magmas à deux phases (bulles de gaz et liquide silicaté) en cisaillement simple dans une presse Paterson selon des viscosités et des vitesses de déformation réalistes pour la partie haute des conduits des strato-volcans. Le développement de la perméabilité est confirmé in situ et se développe à des vitesses de déformation supérieures à 4,5 x 10⁻⁴ s⁻¹. À des vitesses de déformation élevées (> 5 x 10⁻⁴ s⁻¹) le magma est fragile et l’échappement du gaz est lente, facilitée par l'interconnexion de courtes fractures de Mode I. À des vitesses de déformation < 5 × 10⁻⁴ s⁻¹, le magma se comporte à la fois de manière fragile et visqueuse et la perméabilité se développe lorsque la déformation est importante; le gaz s’échappe rapidement par de longues fractures de Mode I bien développées. Les fractures de Mode I sont idéalement orientées pour le dégazage du conduit central et sont, surtout, soumises à peu de déformation jusqu'à ce qu'elles soient réorientées dans la direction de cisaillement. Ces caractéristiques de dégazage peuvent, à long terme, favoriser un dynamisme éruptif effussif. / The transition from effusive to explosive behaviour at silicic volcanoes is, in part, governed by how efficiently gas overpressures are dissipated from the volcanic plumbing. Efficient gas release is associated with effusive eruptions while inadequate outgassing contributes to explosive processes. One approach to assessing the facility of gas escape is by considering how permeability develops and evolves in the magma column and surrounding edifice. Here, I appraise the role of post-emplacement changes to microstructure in edifice-forming basaltic andesites from Merapi (Indonesia). The permeability of these rocks is dominantly crack-controlled and while these features exert important controls on gas escape through the edifice, they do not represent the escape pathways available to gas within ascending magma. To avoid the influence of postemplacement microstructure, I investigate the development and evolution of permeable networks in magmas by deforming initially impermeable two-phase magmas in simple shear. This is done in a Paterson apparatus at viscosities and shear strain rates appropriate to upper conduits in stratovolcanoes. Permeability development is confirmed in situ and develops at moderate to high shear strain rates (> 4.5 × 10⁻⁴ s⁻¹). At very high strain rates (> 5 × 10⁻⁴ s⁻¹) the magma behaves in a brittle manner and gas egress is slow, facilitated by the interconnection of short, Mode I fractures. At moderate shear strain rates (< 5 × 10⁻⁴ s⁻¹), the magma displays both brittle and viscous behaviour and permeability develops at high strain; gas escape is rapid owing to long, well-developed, sample-length Mode I fractures. Mode I fractures are ideally oriented for outgassing of the central conduit and, critically, accommodate little deformation until they are rotated into the direction of shear, making them long-lived outgassing features that may favour volcanic effusion.

Les alliages de titane β-métastables comme le Ti-10V-2Fe-3Al se substituent progressivement aux alliages α/β dans les applications aéronautiques du fait de leur résistance spécifique améliorée. Leurs microstructures d'emploi sont cependant complexes et multi-échelles, constituées d'une matrice β (de grains millimétriques) partiellement transformée en nodules primaires αp (micrométriques) et en lamelles secondaires αs (sub-micrométriques). Les propriétés finales peuvent être très sensibles aux variations locales de microstructures et sont souvent non maîtrisées lors du forgeage de pièces massives. De plus la matrice β qui représente ~40% du volume et qui a un comportement élastique et plastique fortement anisotrope, comme la phase α, complique la compréhension des mécanismes de déformation en jeu. Le premier objectif de cette thèse est de mettre en œuvre des techniques de caractérisation multi-échelles (la diffraction des neutrons, l'imagerie électronique couplée à l'analyse d'image et l'EBSD, la reconstruction des microtextures de haute température β/αp) pour analyser efficacement la microstructure/texture des constituants β/αp/αs et caractériser leurs hétérogénéités au sein de demi-produits et de pièces obtenues par matriçage. Les résultats permettent d'analyser la fragmentation des grains β en sous-grains, les macrozones αp, le maintien de relation d'orientation entre β/αp et l'organisation des lamelles αs en colonies ou paniers tressés, en pointant les différences de taille de domaines révélés par la cristallographie et l'imagerie standard. Le second objectif est d'appliquer cette méthodologie à l'analyse de facies de rupture d'éprouvettes présentant un comportement singulier (en traction ou en fatigue) pour caractériser les configurations microstructurales à l'origine de l'amorçage de fissures. Cette analyse a principalement été réalisée par polissage manuel du faciès couplé à des acquisitions EBSD mais également en exploitant le potentiel de l'imagerie 3D par MEB-FIB (Focus Ion Beam) et la technique TKD (Transmission Kikuchi Diffraction) sur lame mince prélevée au niveau d'un site d'amorçage par FIB. Enfin, cette étude expérimentale a été complétée par une première approche en simulation micromécanique sur une microstructure modèle 100% β. L'objectif était d'évaluer l'influence de l’anisotropie élastique de la phase β sur la genèse de contraintes d'incompatibilités dans les régimes élastique et élasto-plastique. L'ensemble des résultats contribue à une meilleure compréhension des variations de propriétés mécaniques en lien avec la microstructure locale / The β-metastable titanium alloys such as Ti-10V-2Fe-3Al are gradually replacing α/β alloys in aeronautical applications thanks to their improved specific strength. However, their microstructures are complex and multi-scale, consisting of a β matrix (of millimetric grains) partially transformed into primary αp nodules (micrometric) and secondary αs lamellae (sub-micrometric). The final mechanical properties are very sensitive to local variations of the microstructure, which are not always fully controlled during forging of massive parts. Moreover, the β matrix, which represent 40% of the volume and whose elastic and plastic behavior is strongly anisotropic (like the α phase) complicates the understanding of the mechanisms of deformation. The first objective of this thesis was to efficiently characterize the microstructure/texture of the different constituents (β/αp/αs) and their heterogeneities within half-finished products and forged parts by using techniques of multi-scale characterization (neutron diffraction, electronic imaging coupled with image analysis and EBSD, reconstruction of high temperature microtextures β/αp). As a result the fragmentation of the β grains into subgrains, the αp macrozones, the destruction of the orientation relation between β/αp and the organization of the αs lamellae in colonies or basket weave was quantified and the differences in size of domains revealed by crystallography and by standard imaging were pointed out. The second objective is to apply this methodology to the analysis of fracture surfaces of samples exhibiting singular behavior (in tension or in fatigue) in order to characterize the microstructural configurations leading to early cracking. This analysis was mainly performed by manual polishing coupled with EBSD acquisitions but also by using 3D imaging by SEM-FIB (Focus Ion Beam) and TKD (Transmission Kikuchi Diffraction) technique on a thin foil FIB-extracted from the crack initiation site. Finally, this experimental study was completed by a micromechanical simulation on a 100% β model microstructure. The objective was to evaluate the influence of the elastic anisotropy of the β phase on the genesis of incompatibility stresses in the elastic and elasto-plastic regimes. The overall results contribute to a better understanding of the variations of mechanical properties related to the local microstructure

La présente thèse concerne l'adhérence des pneumatiques avec les chaussées routières, et la possibilité de prévoir son évolution à l'aide d'essais de laboratoire et de modélisations. Tout d'abord, une méthodologie originale de polissage et de mesure de l'adhérence en laboratoire est présentée ; elle s'appuie sur la machine de Wehner et Schulze, développée en Allemagne. Grâce à elle, on peut mesurer l'évolution du coefficient de frottement avec la durée du polissage. Des chantiers routiers sont suivis dans le temps, afin de comparer la simulation en laboratoire et l'évolution réelle de l'adhérence. Parallèlement à la simulation expérimentale, des lois d'évolution sont établies. Un modèle à cinq paramètres est tout d'abord proposé, que l'on tente de relier aux caractéristiques des granulats (PSV, diamètre maximal, microtexture, etc.). Ensuite, un modèle plus physique est ébauché, explicitant les mécanismes de vieillissement et de décapage du bitume, et de polissage des granulats. Un coefficient d'équivalence entre le trafic poids lourd et le nombre de cycles d'usure en laboratoire est proposé, devant permettre à terme de choisir entre différents matériaux de couche de surface, et de prévoir l'évolution de l'adhérence d'une chaussée neuve. Enfin, les profils de surface sont examinés à différents états de polissage, dans le but de relier l'évolution de l'adhérence aux paramètres de rugosité, et aux caractéristiques des granulats (PSV, MDE, LA).

Ce travail s'inscrit dans le cadre des études de l'interaction argile/polluant, concernant l'utilisation des argiles comme barrière d'un site de stockage de surface. Le travail présenté se propose de relier les variations de la perméabilité avec les modifications structurales et microtexturales pouvant être induites par la fixation d'un cation métallique sur une argile. Parmi 3 matériaux argileux albanais présélectionnés, celui de Prrenjas, formé par pédogenèse puis sédimentation continentale aux dépens d'une roche mère (ultrabasique), a été choisi en raison de ses caractéristiques proches d'une bentonite. Cette bentonite se caractérise par la présence majoritaire de smectite, par une CEC élevée, (90 meq/100 g), de Mg2+ majoritaire en position interfoliaire et la présence d'illite (11%) interstratifiée. Au MET la bentonite de Prrenjas a une morphologie particulière, avec une texture en microagrégats constitués de petites particules, qui la différencie des bentonites «modèles», du type Wyoming. Les études de l'interaction de l'argile en suspension avec des solutions de concentrations variées en Pb(NO3)2 couplées à l'étude de l'évolution structurale et microtexturale du matériau ont permis d'observer l'effet de Pb2+ sur l'argile de Prrenjas et sur l'argile de référence, Wyoming (SPV) échangée-Mg. Une diminution de l'hydratation de l'espace interfoliaire en fonction de la fraction molaire de Pb2+ a été observée par DRX. Les clichés de MET ont montré, pour l'argile de Prrenjas, une fragmentation des microagrégats qui la constituent en petites particules. Par contre, l'argile de référence paraît peu modifiée. La spectrométrie XPS indique une fixation de Pb2+, en surface des particules, plus importante pour l'argile de Prrenjas que pour l'argile de référence. Les essais de longue durée de fixation de Pb2+, par percolation d'une solution de Pb(NO3)2 à forte concentration (10-2 M) à travers l'argile compactée, ont montré une augmentation de la perméabilité d'un facteur 40, comportement, sans commune mesure, avec celui de la montmorillonite de référence (facteur 2). Les observations au cryo-MEB de l'argile compactée après la percolation de Pb(NO3)2 10-2M montrent des chemins d'écoulement connectés qui expliquent l'augmentation observée du débit. Finalement, ce travail montre que l'augmentation de la perméabilité, observée pour l'argile de Prrenjas, est une conséquence des modifications structurales aux différentes échelles d'organisation du matériau.