Ce travail part du constat d’une part qu'il existe très peu de données expérimentales dans la littérature sur les monocristaux de zirconium et d’autre part qu’aucune loi de comportement monocristalline pour ce matériau n’est déterminée. L'objectif est donc de disposer d'une base de données expérimentale conséquente comme les cissions critiques pour le système prismatique, l'écrouissage, l'activation des systèmes de glissement et les volumes d'activation. Après avoir obtenu ces différents paramètres en utilisant la méthode de corrélation d'images, une approche multiéchelle a été mise en œuvre en s’appuyant d’une part sur la dynamique des dislocations et d’autre part sur des calculs par éléments finis. Une première loi de comportement monocristalline pour le zirconium est proposée et des simulations par éléments finis ont validé cette approche innovante. / There is only few experimental data in the literature on the zirconium single crystals and no constitutive laws for this single crystal material are provided. The goal of this work is then to create an exhaustive experimental database like the Critical Resolved Shear Stress (CRSS) for the prismatic slip, the strain-hardening, the activation of the prismatic glide system and the activation volumes. We determine theses parameters from image correlation method. Then, we develop a new multiscale approach using dislocations dynamics concept and finite element computations. Finally, a first single crystal constitutive law for the zirconium is proposed and a good agreement with the experimental data is obtained.

L'objectif de cette thèse est de créer de nouveaux mélanges thermoplastiques présentant une processabilité accrue comparée à des matrices thermoplastiques hautes performances utilisées dans l'industrie aéronautique. Ces matériaux ont vocation à être intégrés en atmosphère avionique pressurisée. Afin de combler le cahier des charges imposé par le domaine aéronautique, le choix des matériaux s'est porté sur un mélange incompatible de polyétheréthercétone PEEK et de polymères à cristaux liquides LCP présentant une morphologie fibrillaire développée grâce à des conditions particulières d'écoulement lors de la mise en oeuvre.Dans un premier temps, les propriétés rhéologiques des matériaux sont caractérisées de manière à confirmer le respect des spécifications relatives à leur processabilité. La compréhension des phénomènes régissant la baisse de viscosité du mélange permet d'assurer la répétabilité et la reproductibilité des performances rhéologiques en vue d'un transfert industriel. L'étude se concentre ensuite sur les propriétés de cristallinité des mélanges, qui permettent de déterminer que la présence de deux matériaux semi-cristallins au sein d'une même structure ne perturbe pas leurs propriétés de cristallinité garantes de leurs performances thermomécaniques.Enfin, une campagne de caractérisation complète est effectuée afin de dresser une fiche matière et de la comparer aux spécifications exigées par l'industrie aéronautique. / The aim of this thesis is to create new thermoplastic blends exhibiting improved processability incomparison with high performance aeronautical thermoplastics. These materials are dedicated tointegrating pressurized avionic structures.To reach the specific aeronautical specifications, an incompatible polymer blend made ofpolyetheretherketone PEEK and liquid crystalline polymers LCP is chosen. The particular flow conditionsset for the compounding ensure the blend a fibrillar morphology.First, the material rheological properties are characterized so as to confirm that the processabilityspecifications are met. The viscosity drop causes are explained and grant the maintaining of therheological performances in any processing configuration.The study then focuses on the blend crystallinity properties in order to determine whether two interlinkedsemi-crystalline structures do not impede the thermomechanical performances.At last, a characterization campaign is led to compare the blend performances with the demandedaeronautical specifications.

L’objectif de ce mémoire de thèse est de contribuer à la connaissance du comportement mécanique en grandes déformations du Polyéthylène à Haute Densité anisotrope obtenu par extrusion de plaques. Nous présentons le protocole et les résultats expérimentaux de traction séquencée, comportant des décharges, recharges et relaxations monotones et cycliques. Ces campagnes d’essais sont également centrées sur la mesure en temps réel de la variation de volume liée aux phénomènes d’endommagement. Les résultats sont présentés pour différentes orientations d’éprouvettes prélevées dans des plaques extrudées. La modélisation thermodynamique de l’ensemble des résultats, a fait l’objet d’un développement original conduisant à la prédiction unifiée de grandeurs en 3D : contrainte vraie axiale, déformations vraies transversales. Le modèle prévoit également le développement de l’endommagement et permet de mettre en évidence une variable tensorielle de dommage. L’identification des paramètres du modèle thermodynamique sur la base de données expérimentales conduit à des grandeurs physiques conformes aux caractéristiques de la microstructure. Ce travail ouvre la perspective d’un enrichissement de l’approche thermodynamique dans la direction de la prévision de l’anisotropie plastique induite des polymères semi-cristallins / The aim of this thesis is to contribute to the knowledge of the mechanical behavior in large strains of anisotropic High Density PolyEthylene (HDPE), obtained by extrusion of plates. We present the experimental procedure and the results for traction, with unloading, reloading and relaxation in monotonous and cyclic conditions. This work is also concerned with the measure in real time of the volume strain due to the phenomena of damage. The results are given for various orientations of specimen within the extruded plates. The thermodynamic modeling of the whole the results, is the subject of an original development leading to the unified prediction of measures in 3D: axial true stress, transverse true strains. The model also predicts the development of the damage and offer the possibility to introduce a tensorial damage variable. The identification of the model parameters on the basis of experimental data leads to physical quantities in conformity with the characteristics of the microstructure. This work opens the prospect for an enrichment of the thermodynamic approach in the direction of the prediction of the induced plastic anisotropy of semi-crystalline polymers

Le corail rouge de Méditerranée (Corallium rubrum) fait l'objet d'un important commerce depuis des millénaires ; il est traditionnellement utilisé pour la confection de bijoux et d'objets d'art. L'étude de son squelette permet de mieux comprendre les procédés utilisés par la nature pour fabriquer des matériaux résistants avec un coût énergétique minimal (conditions de chimie douce). D'autre part, la caractérisation des taux de croissance vertical et radial est toute aussi importante pour établir des critères à des fins de conservation de l'espèce. Dans ce travail, C. rubrum a été comparé à d'autres espèces de coraux précieux de la même famille (C. elatius et Paracorallium japonicum). Ces espèces présentent deux modes de croissance distincts: (1) un mode 'bloc par bloc' à l'apex de la branche, associé à une croissance axiale rapide (~2 mm/an) et (2) un mode 'couche par couche' se produisant en dessous de l'apex, associé à une croissance radiale lente (~0,2 mm/an). Les structures physiques et chimiques des squelettes des coraux précieux aident à mieux comprendre les mécanismes complexes de la croissance cristalline bio-assistée. / The Mediterranean red coral (Corallium rubrum) has been harvested and traded for centuries; it is highly valued in jewelry. Studies of the skeletal structures are important to better understand how nature proceeds to synthetize resistant material at low-energy cost by soft chemistry. On the other hand, the determination of vertical and axial growth rates is important to establish criterions for the sustainable management of these precious species. In this work, the skeleton of C. rubrum has been compared to skeleton of other species belonging of the same family (C. elatius and P. japonicum). All species show two distinct growth modes: (1) a block-by-block mode at the branch apex associated with a fast axial growth rate (~2 mm/year) and (2) a layer-by-layer mode associated with a slow radial growth rate (~0,2 mm/year). The physical and chemical patterns of the skeleton of precious corals provide important constraints to better understand the complex mechanisms of in bio-assisted crystalline growth.

Water is “the matrix of life” for its fascinating properties. The well-known simple water molecule consists of one oxygen atom and two hydrogen atoms, covering most of planet earth’ssurface. It is the most studied element in science; however, its properties are still not fully understood. Another essential building block of life is proteins, which manifest naturally in aqueous environments. The protein activity is controlled by the protein folding process that is dependent on the surrounding environment. It is hypothesized that the hydrogen bond network of water plays an important role in the folding process. Here, we investigate the protein lysozyme in liquid water as well as in the crystalline state ice Ih, exploring various temperatures, using FT-IR and XRD. Our main finding is that a transition occurs at approximately T=210 K, indicative of the hypothesised protein dynamic “glass” transitionobserved by previous studies in supercooled water at similar temperatures.

De nombreuses structures industrielles soumises à des chargements à long terme statique (fluage) ou cyclique (fatigue) sont constituées de matériaux polymères semi-cristallins. C’est le cas notamment des canalisations et réservoirs sous pression. Il est donc essentiel de traiter les problématiques de durabilité pour être capable d'anticiper et de contrôler leur fin de vie. Par ailleurs, elles présentent généralement des formes complexes et sont soumises à des états de contrainte multiaxiaux.Le matériau de l'étude est un polymère semi-cristallin : le Polyamide 6. Il est caractérisé par la coexistence d'une phase cristalline et d'une phase amorphe qui s'arrangent selon une microstructure sphérolitique.Dans un premier temps, les liens entre comportement mécanique à l'échelle globale de l'éprouvette et les micro-mécanismes de déformation sous-jacents conduisant à la rupture sont établis expérimentalement pour des sollicitations en traction monotone et en fluage qui présentent des résultats similaires puis en fatigue. L'influence de la multiaxialité de l'état de contrainte est étudiée à partir d’éprouvettes axisymétriques entaillées de différents rayons de fond d'entaille et d'éprouvettes « Compact Tensile ». Les phénomènes de cavitation sont caractérisés grâce aux techniques de tomographie et laminographie à rayonnement X synchrotron qui permettent d'observer et de quantifier les distributions spatiales de taux de porosité volumique et le caractère anisotrope des cavités. Et l'analyse des faciès de rupture a permis de mettre en évidence que les mécanismes de croissance et de coalescence de cavités étaient à l'origine de l’amorçage ductile de la rupture.Ensuite, un modèle poro-visco-plastique à deux mécanismes (permettant de différencier le comportement des phases amorphe et cristalline) a été utilisé. Ce modèle permet de reproduire à la fois le comportement global (courbes de chargement) en traction monotone et en fluage mais aussi les distributions spatiales de taux de porosité obtenues expérimentalement. De plus, les calculs par éléments finis permettent d'étudier les distributions spatiales du champ de contrainte et d'établir l'influence de l'état de contrainte sur l'état de cavitation. Les évolutions temporelles en cours de déformation de la pression hydrostatique (ou contrainte moyenne) ont été reliées aux distributions spatiales de taux de porosité volumique. Et l'anisotropie de cavitation (et donc la morphologie et les facteurs de forme des cavités) a été reliée aux évolutions des composantes du tenseur des contraintes de Cauchy. Enfin, la définition d'un critère de rupture en taux de porosité critique a permis de simuler l'amorçage et la propagation de fissures en traction monotone et fluage. / Many industrial structures subjected to quasi-static (creep) or cyclic (fatigue) long-term loadings are made of semi-crystalline polymers. Such is the case, for instance, of pressure vessels and pipes. It is therefore considered critical to study the issues related to their durability in order to be able to anticipate and control their end of life. Furthermore, they generally have complex designs and are subjected to multiaxial stress states.The material which has been studied was a semi-crystalline Polyamide 6. Its structure consisted of amorphous and the crystalline phases and a spherolitic microstructure.As a first step, the links between the mechanical behaviour at the global scale of the specimens and the underlying micro-mechanisms of deformation that lead to failure have been established experimentally for monotonic and creep loadings that show similar results and then for fatigue loadings. The influence of the multiaxiality of the stress state has been studied using circumferentially notched round bars with different notch root radii and Compact Tensile specimens. The cavitation phenomena were characterized using synchrotron radiation tomography and laminography techniques that enabled the observation and quantification of the spatial distributions of the voids and the anisotropy of the cavities. An analysis of the fracture surfaces has shown that the initiation of ductile failure resulted from void growth and coalescence mechanismsA poro-visco-plastic model with two mechanisms (that allow the behaviours of the amorphous and crystalline phases to be distinguished) has been used. Thanks to this model, the global behaviour (loading curves) under steady strain rates and steady loads but also the spatial distributions of the void volume fraction could be reproduced numerically. In addition finite element calculations have permitted the spatial distributions of the stress field to be studied and the influence of the stress state on the cavitation state to be investigated. The temporal evolutions during the deformation of the hydrostatic pressure have been linked to the spatial distributions of void volume fraction. The void anisotropy (and thus the void morphology and shape factors) has been related to the evolutions of the components of the Cauchy stress tensor. Finally, the definition of a rupture criterion based on a critical value of the void volume fraction has enabled crack propagation under steady strain rate and steady load to be simulated.

La déformation visco-plastique de la glace est fortement anisotrope, le plan de glissement préferé étant la plan de base. Le fait que dans un polycristal chaque grain possède sa propre direction de déformation produit des incompatibilités et un champ de contrainte complexe. La déformation à été étudiée expérimentellement en mésurant la dis- tortion des plans cristallins de mono- et polycristaux de glace artificielle. Les expériences ont été réalisées à l'aide d'un faisceau synchrotron. Une nouvelle procédure éxperimental, basée sur les méthodes de l'imagerie en diffraction de Bragg, comme lumière blanche, im- agerie sur la courbe de diffraction et topographie laminaire et ponctuelle, a été dévéloppée. Les désorientations angulaires, les largeurs à mi-hauteur et les intensités intégrées ont été mésurées dans les trois dimensions spatiales de l'échantillon et avec une résolution de 50× 50 × 50µm3. Les algorithmes d'analyse de données ont été écrits pour extraire des données des résultats quantitatifs, et pour calculer les neuf composantes du tenseur de courbure ainsi que la distortion entière des plans cristallins. Les résultats ont permis d'observer les premières étappes de la déformation de la glace. Par example la polygonisation d'un grain à été observée. / The viscoplastic deformation of ice is strongly anisotropic. The preferred glide system is on the basal plane. In a polycrystal each grain exhibits its own deformation direction. As a result the deformation of polycrystalline ice is associated with strain in- compatibilities, especially at the grain boundaries and the triple junction. The deforma- tion process was experimentally investigated by measuring crystal lattice distortions of single- and polycrystalline, artificially grown ice crystals. The experiments were benefic- ing from a synchrotron X-ray beam. A new experimental method, based on Bragg diffrac- tion imaging (X-ray topography) methods, as white beam X-ray diffraction topography, rocking curve imaging, section- and pinhole X-ray topography was used. Angular mis- orientations, full-width-half-maxima and integrated Bragg diffracted intensities have been measured along the three spatial dimensions of the sample and with a spatial resolution of around 50µm × 50µm × 50µm. Data analysis algorithms were written in order to extract quantitative results from the data and to calculate all nine components of the curvature ten- sor, as well as the entire lattice distortion in the sample. The results give an insight into the early stages of plastic deformation of ice, i.e. the polygonisation of a grain was observed.

Le travail présenté dans ce manuscrit concerne la modélisation du comportementthermomécanique de films thermoplastiques déformés à l’état caoutchoutique. Lamodélisation du comportement des films amorphes isotropes est réalisée sur la base desmodèles de Lodge ou MSF. L’amélioration des prédictions des modèles pour destempératures de déformations proches de la température de transition vitreuse est possible enconsidérant dans le spectre des temps de relaxation des temps courts provenant de la zone detransition vitreuse. La modélisation du comportement de films amorphes anisotropes a étéeffectuée en considérant que l’anisotropie est due à une pré-déformation équivalente lors duprocédé de fabrication.Au cours de cette étude, les relations entre l’orientation de la phase cristalline et les propriétésmécaniques à température ambiante des films semi-cristallins ont été démontrées Au cours dela déformation à l’état caoutchoutique de ces films, la phase cristalline tend à s’orienterparallèlement à la direction de sollicitation par fragmentation des cristaux initiaux. En sebasant sur ces observations expérimentales, la modélisation du comportement mécanique desfilms semi-cristallins est possible en découplant les contributions en contrainte de la phasecristalline et de la phase. La réorientation des cristaux génère un phénomène de durcissementstructural sous contrainte qui peut être prédit par le modèle. / The work presented in this manuscript is devoted to the modeling of the thermomechanicalbehavior of polymer films deformed at the rubbery state. The modeling of the isotropicamorphous films is realized using the Lodge and the MSF models. For deformations appliednear the glass transition temperature, the predictions of these models are improved byincluding relaxation times coming from the glass transition domain in the spectra. Forpre-oriented amorphous films, the anisotropy is modeled by considering that it is due to aprevious equivalent deformation during the fabrication process.The relationship between the crystalline phase and the mechanical behavior at roomtemperature for the semi-crystalline films is established. During the deformation at therubbery sate of the semi-crystalline films, a reorientation of the crystalline phase occurs alongthe stretching direction. Based on the experimental observations, a semi-empirical model isdeveloped in order to describe the mechanical behavior of the semi-crystalline films. In thismodel, the contributions of both phases, amorphous and crystalline are separated. Thereorientation of the crystalline phase leads to a strain hardening stage which could bepredicted by the model

Desde a descoberta das ligas amorfas em 1960, os motivos pelos quais algumas ligas podem ser facilmente amorfizadas enquanto outras não podem, não é claramente conhecido, assim não há teoria universal para predizer a habilidade de formação vítrea em sistemas metálicos. No presente trabalho, um critério de seleção foi aplicado ao sistema Ni-Nb-Zr com o objetivo de predizer as melhores estequiometrias com as mais altas tendências de formação vítrea. As habilidades de formação vítrea das ligas foram avaliadas pelo parâmetro térmico γm e os resultados mostraram uma pobre correlação com as predições. Este critério preditivo correlaciona as taxas de resfriamento para a formação vítrea com a instabilidade topológica de estruturas cristalinas, as diferenças médias de função trabalho e densidade eletrônica entre os elementos constituintes da liga. O parâmetro térmico depende de temperaturas características de transformações de fases que podem ser facilmente determinadas a partir de curvas de calorimetria exploratória diferencial dos vidros metálicos. As hipóteses iniciais para explicar a pobre correlação entre os resultados e as predições foram atribuídas às influências de fatores não considerados nos cálculos como os compostos intermetálicos desconhecidos e contaminação por oxigênio. Assim, algumas ligas solidificadas rapidamente foram investigadas com mais rigor com o objetivo de entender a formação das fases cristalinas que competem contra a formação vítrea. As fases cristalinas foram caracterizadas e comparadas com estruturas cristalinas encontradas na literatura como também alguns diagramas de fases. Os diagramas de fases foram utilizados como guias para o melhor entendimento do comportamento de cristalização. Em adição, o critério de seleção também foi utilizado para predizer o melhoramento da tendência de formação vítrea de uma liga do sistema Ni-Nb-Zr com pequenas adições dos elementos terras-raras Y ou Er. É bem conhecido que uma pequena adição de um elemento terra-rara apropriado pode aumentar significativamente a habilidade de formação vítrea de algumas ligas. As tendências de formação vítrea da liga base e das ligas dopadas com terras-raras também foram avaliadas pelo parâmetro térmico &#947m e os resultados concordaram muito bem com a tendência predita pelo cálculo. As amostras amorfas volumosas foram produzidas por injeção em molde de cobre. A natureza amorfa foi analisada por difração de raios-X e calorimetria exploratória diferencial. As fases cristalinas foram analisadas por microscopia eletrônica de transmissão, microscopia eletrônica de varredura, espectroscopia de raios-X por dispersão em energia e difração de raios-X. A contaminação por oxigênio foi quantificada pelo método de fusão em gás inerte. / Since the discovering of amorphous alloys in 1960, the actual causes of why some alloys can be easily formed into glasses while others cannot, are not clearly known, thus there is no universal theory to predict the glass forming ability in metallic systems. In the present work, a selection criterion was applied in the Ni-Nb-Zr system in order to predict the best stoichiometries with high glass forming ability. The actual glass forming ability of alloys were evaluated by the thermal parameter γm and the results have shown a poor correlation with the predictions. This criterion correlates critical cooling rate for glass formation with topological instability of stable crystalline structures; average work function difference and average electron density difference among the constituent elements of the alloy. The thermal parameter depends on the characteristic temperatures of phase transformations which can be easily measured from differential scanning calorimetry curves of metallic glasses. The initial hypotheses to explain the poor correlation between the experimental results and the predictions concerned with the influence of factors not considered in the calculation, such as unknown intermetallic compounds and oxygen contamination. Thus some rapidly quenched alloys were investigated with more accuracy in order to understand the formation of crystalline phases which compete against the glass formation. We characterized the crystalline phases and compared them to crystalline structures found in literature as well as some phase diagrams. The phase diagrams were used as guides in order to understand the crystallization behavior. In addition, the selection criterion also was used to predict the glass forming ability improvement of a Ni-Nb-Zr alloy with minor additions of rare-earth elements Y or Er. It is well known that the minor amount addition of proper rare-earth elements can greatly enhance the glass forming ability of some glass-forming alloys. The actual glass forming ability of the base alloy and rare-earth doped alloys also were evaluated by the thermal parameter &#947m and the results agree very well with the tendency predicted by the calculation. Bulk amorphous specimens were produced by injection casting. The amorphous nature was analyzed by X-ray diffraction and differential scanning calorimetry. The crystalline phases were analyzed by transmission electron microscopy, scanning electron microscopy, energy dispersive X-ray spectroscopy and x-ray diffraction. Oxygen contamination was quantified by the inert gas fusion method.

As tecnologias usualmente aplicadas no mercado fotovoltaico mundial são, em sua maioria, voltadas aos painéis rígidos de células de silício cristalino, em função da redução de seus preços proporcionada pela economia de escala. No entanto, a crescente demanda no País de novos domicílios, principalmente de apartamentos, tem exigido soluções mais apropriadas: com menor ocupação de área horizontal e instaladas na fachada dos edifícios. Nesse sentido vão surgindo tecnologias fotovoltaicas como as de filmes finos como soluções mais apropriadas do que as emergentes de terceira geração, pelo fato dessas últimas ainda se encontrarem em fase de maturação técnica com poucas opções de fornecimento no mercado em nível comercial. Portanto, a abordagem desta dissertação se limitou às tecnologias de filmes finos e de vidros fotovoltaicos semi transparentes, além daquela mais usual que é a de silício cristalino. Contudo, o dinamismo do mercado mundial vem estimulando uma evolução no fator de desempenho dessas tecnologias, o que justificou a necessidade de uma revisão bibliográfica. Além disso, a maioria dos projetos fotovoltaicos vem adotando como base os painéis rígidos com células de silício cristalino, sem, no entanto, avaliarem alternativas com a aplicação de outras tecnologias. O que se nota é a falta de conhecimento mais profundo dos projetistas sobre as tecnologias de filmes finos e das melhores opções para sua aplicação em um edifício, no que tange ao seu desempenho e seu comportamento dentro do espectro de frequência. Assim, esta dissertação teve por objetivo contribuir com uma análise de desempenho energético com base em simulações para tomada de decisão técnica sobre as tecnologias mais adequadas de célula fotovoltaica para sistemas a serem instalados em fachadas de edifícios, auxiliadas por uma ferramenta computacional existente no mercado, o PVSYST. A tomada de decisão foi vista pela perspectiva de desempenho na geração de energia elétrica, pela análise comparativa dos resultados de simulações aplicadas na fachada de um edifício hipotético em São Paulo. Os resultados mostraram que as tecnologias baseadas no silício cristalino são as mais adequadas nos casos em que o pico de demanda de energia no ano seja no verão, como nos edifícios comerciais. Já os sistemas compostos pelos filmes finos do grupo do seleneto de índio e cobre são os mais indicados para os edifícios residenciais, em que o período de maior demanda é no inverno. / Technologies commonly applied in the global photovoltaic market are mostly with the rigid panels of crystalline silicon cells, due to the reduction of their prices provided by economies of scale. However, growing demand in the country of new housing units, mainly apartments, has required more appropriated solutions: with lower occupancy of horizontal area and installed on the building\'s facade. In this direction photovoltaic technologies are emerging such as thin films as better solutions than the emerging technologies of third generation, because still they are in technical maturation phase with few options of suppliers in the commercial market. Therefore, the approach of this dissertation was limited to technologies of thin films and semitransparent photovoltaic glazing, in addition to the more usual one that is crystalline silicon. However, the dynamism of the global market has stimulated an evolution in the performance factor of these technologies, which justified the necessity of literature review. Furthermore, most PV projects have been based on the rigid panels with crystalline silicon cells, not considering the alternatives using other technologies. What is noticed is the lack of deeper understanding of the designers about the thin film technologies and the best options for their application in a building, in terms of their performance and their behavior within the frequency spectrum. Thus, this work aimed to contribute to an energy performance analysis based on simulations for technical decision on the most appropriate photovoltaic cell technologies for systems to be installed on the facades of buildings, aided by an existing software tool on the market, PVSYST. Decision making was seen from the perspective of performance in electricity generation, by comparative analysis of simulations results applied on the facade of a hypothetical building in São Paulo. The results showed that the technologies based on crystalline silicon are the most appropriate in cases where energy demand peak in the year is in the summer, as in commercial buildings. On the other hand, the systems composed of the thin films based on indium and copper selenium group are the most suitable for residential buildings, where the period of greatest demand is in the winter.