Le besoin de sources d’énergie autonomes connaît un regain d’intérêt de plus en plus important avec la multiplication des équipements portables et le développement des réseaux de capteurs. Au-delà de l’utilisation traditionnelle des batteries, il y a un intérêt évident à générer l’énergie électrique nécessaire au cœur du système lui-même en utilisant le gisement environnemental disponible : gradients thermiques, vibrations mécaniques….Ceci est également rendu possible par la réduction importante de la consommation des composants électroniques observés ces vingt dernières années. Parmi les dispositifs susceptibles d’exploiter le gisement vibratoire, les matériaux électro-actifs occupent une place de choix. Actuellement, on recherche des matériaux légers, pouvant se déposer sur des grandes surfaces et peu coûteux à la réalisation. Ceci ouvre des perspectives séduisantes à l’utilisation de polymères électro-actifs en lieu et place des matériaux céramiques piézoélectriques. Parmi les EAP disponibles, les polyuréthanes (PU) sont des élastomères thermoplastiques d'un grand intérêt pour une vaste gamme d'applications en tant que transducteurs ou actionneurs lorsque l'on considère leur importante déformation sous champ électrique, une énergie spécifique élevée, et leur réponse rapide De plus, ces matériaux sont légers, très souples, présentent de faibles coûts de fabrication, et peuvent être facilement moulés dans n'importe quelle forme souhaitable. Des travaux récents ont montré que l'énergie récoltée peut être augmentée en incorporant des nanotubes de carbone (NTC) dans une matrice de polyuréthane. Cependant, les nanocomposites peuvent ne pas avoir été optimisées, car il est bien connu que les NTC sont difficilement dispersées dans une matrice polymère et que la force d'adhérence interfaciale est généralement médiocre. Une solution pour améliorer à la fois la dispersion et l'adhérence peut consister en greffant des chaînes de polymère sur les surfaces de la NTC. L'objectif principal de cette thèse était de développer des polymères nanocomposites à haute efficacité pour la récupération d'énergie et d'actionnement. La motivation principal était d'utiliser des NTC greffé-polymère pour améliorer la dispersion, l'adhérence interfaciale dans PU, et de comprendre comment cela peut changer les propriétés électroactifs des nanocomposites PU / NTC. En d'autres termes, ce était un projet pluridisciplinaire, y compris une optimisation du processus d'élaboration, caractérisations physiques ˗ notamment les comportements de microstructure, électriques et mécaniques dans une large gamme de fréquences et températures ˗ et la détermination des propriétés électroactifs. Il s’agissait également de développer une modélisation des lois de comportements en s’aidant de l’analyse de la microstructure par imagerie. / Harvesting systems capable of transforming dusty environmental energy into electrical energy have attracted considerable interest throughout the last decade. Several research efforts have focused on the transformation of the mechanical vibration into electrical energy. Most of these research activities deal with classical piezoelectric ceramic materials, but more recently, a promising new type of materials is represented by electroactive polymers (EAPs). Among the various EAPs, polyurethane (PU) elastomers are of great interest due to the significant electrical-field strains, and due to their attractive and useful properties such as flexibility, light weight, high chemical and abrasion resistance, high mechanical strength and easy processing to large area films as well as their ability to be molded into various shapes and biocompatibility with blood and tissues. In addition, it has recently been shown that the incorporation into a PU matrix of nanofillers, such as carbon nanotubes (CNTs), can greatly enhance the expected strain, or the harvested energy. However, it is well known that CNTs are hardly dispersed in a polymeric matrix, and that the interfacial adhesion strength is generally poor. An effective method to improves both dispersion and adhesion may consist in functionalizing CNTs by grafting polymer chains onto their surfaces. The main objective of this thesis was to develop high-efficiency polymers nanocomposites for harvesting energy and actuation. The key motivation was to use polymer-grafted CNTs to improve dispersion, interfacial adhesion in PU, and understand how this can change the electroactive properties of the PU/CNT nanocomposites. In other words, it was a pluridisciplinary project including an optimization of the elaboration process, physical characterizations ˗ including microstructural, electrical and mechanical behaviors in a wide range of frequencies and temperatures ˗ and the determination of the electroactive properties. A comprehensive study was then carried out first on pure PU to understand how their electroactive properties depend on their microstructure, and then on the nanocomposites to understand how the incorporation of functionalized CNT can improve the electromechanical properties.

Ce travail porte sur les mouvements moléculaires dans les caoutchoucs composants les pneumatiques : les polybutadiènes (PB) et les copolymères de polystyrène et polybutadiène (SBR). L’intérêt de cette étude est double : Nous souhaitons à partir de résultat de spectroscopies mécanique et diélectrique, comprendre l’origine moléculaire des relaxations dans ces élastomères, mais aussi voir le rôle de la microstructure chimique dans la mobilité moléculaire. Nous travaillons donc sur des matériaux différents par leur microstructure chimique à travers leurs taux respectifs de butadiène 1,2 vinyle, de butadiène 1,4 cis/trans ou encore de styrène pour les SBR. L’étude de la modification de la microstructure passe aussi par l’ajout de diluants qui servent de perturbateurs à la mobilité. La gamme de température balayée est comprise entre 90K et 350K et permet ainsi l’étude systématique de toutes les relaxations présentent dans les polymères de l’étude : La relaxation β, à plus basse température, la relaxation α pour des températures proches de Tg mais aussi, à plus haute température, les relaxations de bouts de chaine et enfin les phénomènes de reptation de chaines libres pour des températures 90K supérieures à Tg. Les techniques de spectroscopie mécanique (1.10-4/1 Hz) et diélectrique (0,1/1.106Hz) permettent d’obtenir des résultats sur un large domaine fréquence /température. Par ailleurs, les couplages mécanique d'une part et électrique d'autre part étant de nature différente, les informations obtenues par les deux techniques sont complémentaires. Le développement d’un modèle nous permet de démontrer que les mouvements des groupements butadiène 1,2 (vinyle) sont responsables de la contribution haute température de la relaxation β alors que ceux des groupements butadiène 1,4 cis et trans sont responsables de la partie basse température. L’étude approfondie de la relaxation α à l’aide du modèle de Perez amène à penser que ces mêmes groupements butadiène 1,2 vinyles jouent aussi un rôle non négligeable dans cette relaxation α. La dilution par une huile polaire provoque la suppression de la partie haute température de la relaxation β et amène ainsi à une modification de sa mobilité basse température. Diminuer la réticulation dans un polymère entraine revient à augmenter la longueur des bouts de chaine. Ces bouts de chaines peuvent alors relaxer selon les lois de rétraction de bouts de chaine développées par Curro à partir des modèles de Pearson et Helfand. Enfin, les chaines libres introduites dans un polymère réticulé suivent la théorie de la reptation de De Gennes-Doi-Edwards. / This work deals with the study of the molecular mobility in rubbers used for pneumatic applications, namely, polybutadiene (PB) and styrene butadiene rubber (SBR). They exhibit relaxation processes, which are in fact responsible for their main behaviors (adhesion, energy consumption, etc.). From mechanical and dielectric spectroscopy data, we tried to understand the molecular origins of these elastomers relaxation, but, also the role of their chemical microstructure on molecular mobility. We studied materials with different chemicals microstructures, i.e., with different butadiene 1,2 vinyl, butadiene 1,4 cis and 1,4 trans and styrene (for SBR only) ratio. The impact of microstructure modification was also studied with addition of diluents, which modifies the molecular mobility. Experimental temperature range was between 90 and 350K, so all relaxations present in polymer can be studied: the β relaxation at low temperature, the α relaxation for temperature near Tg, the chain-end relaxation at higher temperature and free chain reptation phenomenon at Tg+90K. Mechanical (10-4 Hz to 1 Hz) and dielectric spectroscopy (0,1 Hz to 106 Hz) allow obtaining large frequency range. Besides that, mechanical and dielectric induced stresses are different so both methods are complementary. The β relaxation exhibits two main contributions, so-called here high and low temperature contributions. The use of modeling permits to show that movements responsible for the high temperature contribution are those of butadiene 1,2 vinyl, whereas butadiene 1,4 cis and trans are responsible from low temperature contribution. Perez model used for studying the α relaxation shows that 1,2 vinyl also impact it. High temperature contribution of the β relaxation disappears after dilution by polar oil. Decreasing the crosslinking density in polymers results in the increase of average chain-end length. These chain-ends relax, and it has been found that their relaxation processes follow the chain-end retraction model developed by Curro from Pearson and Helfand works. On the contrary, free chains motions, when introduced in the already cross-linked polymer network follow De Gennes-Doi-Edwards reptation theory.

La cuve des réacteurs à eau sous pression forme la seconde barrière de confinement de l'assemblage combustible nucléaire. Dans les centrales françaises, elle est constituée d'acier 16MND5 faiblement allié (équivalent de la nuance ASTM A508 Cl.3). Diverses techniques expérimentales (microscopie électronique, diffraction des rayons X etc.) sont mises en oeuvre lors d'essais de tractions in-situ afin de mettre en évidence les hétérogénéités mécaniques apparaissant au sein du matériau. Ces mesures se font en cours de sollicitation pour diverses basses températures [-150°C;-60°C]. Les hétérogénéités mécaniques sont principalement dues aux deux aspects "polycristallins" et "composite"(effet des amas de cémentite) de la microstructure. Des écarts de contraintes résiduelles interphases (jusqu''a 150 MPa en moyenne entre bainite et ferrite), et intraphases (jusqu''a 100 MPa en moyenne par orientation pour la ferrite) sont mis en évidence. Une modélisation complexe est mise en oeuvre afin de représenter le comportement. Elle inclut une loi micromécanique, un modèle de transition d'échelle, et une représentation par éléments finis d'agrégats 3D, le tout associé dans une démarche multi-échelles. L'identification se fait sur le comportement à différentes températures, et permet de reproduire les hétérogénéités de contraintes mises en évidence expérimentalement. Cette modélisation sert de base à l'application déterministe d'un critère local de rupture fragile micromécanique et cristallographique. L'utilisation de divers tirages de répartitions de carbures réalistes permet d'obtenir une probabilité de rupture du volume élémentaire en accord avec les hypothèses formulées par l'approche locale de la rupture. A ceci près que contrairement aux approches habituelles, on ne suppose pas de dépendance de cette probabilité par rapport au chargement ou à la microstructure, celle-ci est naturellement introduite.

Establishing process-structure-property relationships is an important objective in the paradigm of materials design in order to reduce the time and cost needed to develop new materials. A method to link phase field (process-structure relations) and microstructure-sensitive finite element (structure-property relations) modeling is demonstrated for subsolvus polycrystalline IN100. A three-dimensional (3D) experimental dataset obtained by orientation imaging microscopy performed on serial sections is utilized to calibrate a phase field model and to calculate inputs for a finite element analysis. Simulated annealing of the dataset realized through phase field modeling results in a range of coarsened microstructures with varying grain size distributions that are each input into the finite element model. A rate dependent crystal plasticity constitutive model that captures the first order effects of grain size, precipitate size, and precipitate volume fraction on the mechanical response of IN100 at 650°C is used to simulate stress-strain behavior of the coarsened polycrystals. Model limitations and ideas for future work are discussed.

In spite of its significance in industrial applications, the prediction of the influence of microstructure on the early stages of crack formation and growth in engineering alloys remains underdeveloped. The formation and early growth of fatigue cracks in the high cycle fatigue regime lasts for much of the fatigue life, and it is strongly influenced by microstructural features such as grain size, twins and morphological and crystallographic texture. However, most fatigue models do not predict the influence of the microstructure on early stages of crack formation, or they employ parameters that should be calibrated with experimental data from specimens with microstructures of interest. These post facto strategies are adequate to characterize materials, but they are not fully appropriate to aid in the design of fatigue-resistant engineering alloys. This thesis considers finite element computational models that explicitly render the microstructure of selected FCC metallic systems and introduces a fatigue methodology that estimates transgranular and intergranular fatigue growth for microstructurally small cracks. The driving forces for both failure modes are assessed by means of fatigue indicators, which are used along with life correlations to estimate the fatigue life. Furthermore, cracks with meandering paths are modeled by considering crack growth on a grain-by-grain basis with a damage model embedded analytically to account for stress and strain redistribution as the cracks extend. The methodology is implemented using a crystal plasticity constitutive model calibrated for studying the effect of microstructure on early fatigue life of a powder processed Ni-base RR1000 superalloy at elevated temperature under high cycle fatigue conditions. This alloy is employed for aircraft turbine engine disks, which undergo a thermomechanical production process to produce a controlled bimodal grain size distribution. The prediction of the fatigue life for this complex microstructure presents particular challenges that are discussed and addressed. The conclusions of this work describe the mechanistic of microstructural small crack. In particular, the fatigue crack growth driving force has been characterized as it evolves within grains and crosses to other grains. Furthermore, the computational models serve as a tool to assess the effects of microstructural features on early stages of fatigue crack formation and growth, such as distributions of grain size and twins.

In this research, the homogenization relations for elastic properties in isotropic and anisotropic materials are studied by applying two-point statistical functions to composite and polycrystalline materials. The validity of the results is investigated by direct comparison with experimental results. In todays technology, where advanced processing methods can provide materials with a variety of morphologies and features in different scales, a methodology to link property to microstructure is necessary to develop a framework for material design. Statistical distribution functions are commonly used for the representation of microstructures and also for homogenization of materials properties. The use of two-point statistics allows the materials designer to consider morphology and distribution in addition to properties of individual phases and components in the design space. This work is focused on studying the effect of anisotropy on the homogenization technique based on two-point statistics. The contribution of one-point and two-point statistics in the calculation of elastic properties of isotropic and anisotropic composites and textured polycrystalline materials will be investigated. For this purpose, an isotropic and anisotropic composite is simulated and an empirical form of the two-point probability functions are used which allows the construction of a composite Hull. The homogenization technique is also applied to two samples of Al-SiC composite that were fabricated through extrusion with two different particle size ratios (PSR). To validate the applied methodology, the elastic properties of the composites are measured by Ultrasonic methods. This methodology is then extended to completely random and textured polycrystalline materials with hexagonal crystal symmetry and the effect of cold rolling on the annealing texture of near- Titanium alloy are presented.

Lead-free solders such as SnAg and SnAgCu are used extensively as replacements of SnPb solders in microelectronics packaging. But these alloys have several drawbacks, such as poor wetting ability and formation of intermetallic compounds (IMC). Doping of rare earth element (RE) on SnAg alloys has been found to improve the wetting property, reduce IMCs and their growth, and refine the microstructure which results in improved mechanical properties of the solder. This study focuses on establishing the quantitative effects of RE doping on the microstructure and mechanical behavior of 96.5Sn3.5Ag alloy. SnAg alloys with different amounts of Lanthanum were made. Specimens were cast under typical reflow conditions, and then aged at different temperatures for three different aging times. Quantitative microscopy was conducted on samples with different amounts of La doping. It was found that doping greatly reduces the grain size, as well as the size of the intermetallic particles Ag3Sn. However, the inter-particle spacing remains relatively unaffected by the La doping amount. Creep tests at various temperatures and strain rates were conducted. The results show that La doping increases creep resistance of the SnAg alloy by ~15%. The creep test result can be fit into a modified microstructure dependent Anand model. A new constitutive law was also proposed to account for the hierarchal microstructure over multiple length scales. Specifically, at the sub micrometer scale, the SnAg eutectic region is treated as a particulate-reinforced composite with the Ag3Sn being the particle and Sn being the matrix. At the micrometer length scale, the solder alloys is treated as a two-phase composite with the Sn dendrite as the particle and the SnAg eutectic region as the matrix. Good agreement was found between the model predictions and the creep test results. Fatigue test was performed on bulk samples. It was found that RE doping increases the fatigue life of SnAg alloy by a factor of 5.

A novel microstructure-sensitive extreme value probabilistic framework is introduced to evaluate material performance/variability for damage evolution processes (e.g., fatigue, fracture, creep). This framework employs newly developed extreme value marked correlation functions (EVMCF) to identify the coupled microstructure attributes (e.g., phase/grain size, grain orientation, grain misorientation) that have the greatest statistical relevance to the extreme value response variables (e.g., stress, elastic/plastic strain) that describe the damage evolution processes of interest. This is an improvement on previous approaches that account for distributed extreme value response variables that describe the damage evolution process of interest based only on the extreme value distributions of a single microstructure attribute; previous approaches have given no consideration of how coupled microstructure attributes affect the distributions of extreme value response. This framework also utilizes computational modeling techniques to identify correlations between microstructure attributes that significantly raise or lower the magnitudes of the damage response variables of interest through the simulation of multiple statistical volume elements (SVE). Each SVE for a given response is constructed to be a statistical sample of the entire microstructure ensemble (i.e., bulk material); therefore, the response of interest in each SVE is not expected to be the same. This is in contrast to computational simulation of a single representative volume element (RVE), which often is untenably large for response variables dependent on the extreme value microstructure attributes. This framework has been demonstrated in the context of characterizing microstructure-sensitive high cycle fatigue (HCF) variability due to the processes of fatigue crack formation (nucleation and microstructurally small crack growth) in polycrystalline metallic alloys. Specifically, the framework is exercised to estimate the local driving forces for fatigue crack formation, to validate these with limited existing experiments, and to explore how the extreme value probabilities of certain fatigue indicator parameters (FIPs) affect overall variability in fatigue life in the HCF regime. Various FIPs have been introduced and used previously as a means to quantify the potential for fatigue crack formation based on experimentally observed mechanisms. Distributions of the extreme value FIPs are calculated for multiple SVEs simulated via the FEM with crystal plasticity constitutive relations. By using crystal plasticity relations, the FIPs can be computed based on the cyclic plastic strain on the scale of the individual grains. These simulated SVEs are instantiated such that they are statistically similar to real microstructures in terms of the crystallographic microstructure attributes that are hypothesized to have the most influence on the extreme value HCF response. The polycrystalline alloys considered here include the Ni-base superalloy IN100 and the Ti alloy Ti-6Al-4V. In applying this framework to study the microstructure dependent variability of HCF in these alloys, the extreme value distributions of the FIPs and associated extreme value marked correlations of crystallographic microstructure attributes are characterized. This information can then be used to rank order multiple variants of the microstructure for a specific material system for relative HCF performance or to design new microstructures hypothesized to exhibit improved performance. This framework enables limiting the (presently) large number of experiments required to characterize scatter in HCF and lends quantitative support to designing improved, fatigue-resistant materials and accelerating insertion of modified and new materials into service.

Three-phase porous composites containing electrolyte (ionic conductor), electronic conductor, and porosity phases are frequently used for solid oxide fuel cell (SOFC) electrodes. Performance of such electrodes is microstructure sensitive. Topological connectivity of the microstructural phases and total length of triple phase boundaries are the key microstructural parameters that affect the electrode performance. These microstructural attributes in turn depend on numerous process parameters including relative proportion, mean sizes, size distributions, and morphologies of the electrolyte and electronic conductor particles in the powder mix used for fabrication of the composites. Therefore, improvement of the performance of SOFC composite electrodes via microstructural engineering is a complex multivariate problem that requires considerable input from microstructure modeling and simulations. This dissertation presents a new approach for geometric modeling and simulation of three-dimensional (3D) microstructure of three-phase porous composites for SOFC electrodes and provides electrode performance optimization guidelines based on the parametric studies on the effects of processing parameters on the total length and topological connectivity of the triple phase boundaries. The model yields an equation for total triple phase boundary length per unit volume (LTPB) that explicitly captures the dependence of LTPB on relative proportion of electrolyte and electronic conductor phases; volume fraction of porosity; and mean size, coefficient of variation, and skewness of electrolyte and electronic conductor particle populations in the initial powder mix. The equation is applicable to electrolyte and electronic conductor particles of any convex shapes and size distributions. The model is validated using experimental measurements performed in this research as well as the measurements performed by other researchers. Computer simulations of 3D composite electrode microstructures have been performed to further validate the microstructure model and to study topological connectivity of the triple phase boundaries in 3D microstructural space. A detailed parametric analysis reveals that (1) non-equiaxed plate-like, flake-like, and needle-like electrolyte and electronic conductor particle shapes can yield substantially higher LTPB; (2) mono-sized electrolyte and electronic conductor powders lead to higher LTPB as compared to the powders having size distributions with large coefficients of variation; (3) LTPB is inversely proportional to the mean sizes of electrolyte and electronic conductor particles; (4) a high value of LTPB is obtained at the lowest porosity volume fraction that permits sufficient connectivity of the pores for gas permeability; and (5) LTPB is not sensitive to the relative proportion of electrolyte and electronic conductor phases in the composition regime of interest in composite electrode applications.

Le prix efficient est latent, il est contaminé par les frictions microstructurelles ou bruit. On explore la mesure et la prévision de la volatilité fondamentale en utilisant les données à haute fréquence. Dans le premier papier, en maintenant le cadre standard du modèle additif du bruit et le prix efficient, on montre qu’en utilisant le volume de transaction, les volumes d’achat et de vente, l’indicateur de la direction de transaction et la différence entre prix d’achat et prix de vente pour absorber le bruit, on améliore la précision des estimateurs de volatilité. Si le bruit n’est que partiellement absorbé, le bruit résiduel est plus proche d’un bruit blanc que le bruit original, ce qui diminue la misspécification des caractéristiques du bruit. Dans le deuxième papier, on part d’un fait empirique qu’on modélise par une forme linéaire de la variance du bruit microstructure en la volatilité fondamentale. Grâce à la représentation de la classe générale des modèles de volatilité stochastique, on explore la performance de prévision de différentes mesures de volatilité sous les hypothèses de notre modèle. Dans le troisième papier, on dérive de nouvelles mesures réalizées en utilisant les prix et les volumes d’achat et de vente. Comme alternative au modèle additif standard pour les prix contaminés avec le bruit microstructure, on fait des hypothèses sur la distribution du prix sans frictions qui est supposé borné par les prix de vente et d’achat. / The high frequency observed price series is contaminated with market microstructure frictions or noise. We explore the measurement and forecasting of the fundamental volatility through novel approaches to the frictions’ problem. In the first paper, while maintaining the standard framework of a noise-frictionless price additive model, we use the trading volume, quoted depths, trade direction indicator and bid-ask spread to get rid of the noise. The econometric model is a price impact linear regression. We show that incorporating the cited liquidity costs variables delivers more precise volatility estimators. If the noise is only partially absorbed, the remaining noise is closer to a white noise than the original one, which lessens misspecification of the noise characteristics. Our approach is also robust to a specific form of endogeneity under which the common robust to noise measures are inconsistent. In the second paper, we model the variance of the market microstructure noise that contaminates the frictionless price as an affine function of the fundamental volatility. Under our model, the noise is time-varying intradaily. Using the eigenfunction representation of the general stochastic volatility class of models, we quantify the forecasting performance of several volatility measures under our model assumptions. In the third paper, instead of assuming the standard additive model for the observed price series, we specify the conditional distribution of the frictionless price given the available information which includes quotes and volumes. We come up with new volatility measures by characterizing the conditional mean of the integrated variance.