Cette thèse s'inscrit dans l'étude des systèmes de particules en interaction et plus précisément dans celle des modèles de croissance aléatoire qui représentent un quantité qui grandit au cours du temps et s'étend sur un réseau. Ce type de processus apparaît naturellement quand on regarde la croissance d'un cristal ou bien la propagation d'une épidémie. Cette dernière est bien modélisée par le processus de contact introduit en 1974 par Harris. Le processus de contact est un des plus simples systèmes de particules en interaction présentant une transition de phase et l'on connaît maintenant bien son comportement sur ses phases. De nombreuses questions ouvertes sur ses extensions, notamment celles de formes asymptotiques, ont motivé ce travail. Après la présentation de ce processus et de certaines de ses extensions, nous introduisons et étudions une nouvelle variante: le processus de contact avec vieillissement où les particules ont un âge qui influence leur capacité à donner naissance à leurs voisines. Nous effectuerons pour ce modèle un couplage avec une percolation orientée inspiré de celui de Bezuidenhout-Grimmett et nous montrerons la croissance d'ordre linéaire de ce processus. Dans la dernière partie de la thèse, nous nous intéressons à la preuve d'un théorème de forme asymptotique pour des modèles généraux de croissance aléatoire grâce à des techniques sous-Additives, parfois complexes à mettre en place à cause de la non 'survie presque sûre' de nos modèles. Nous en concluons en particulier que le processus de contact avec vieillissement, le processus de contact en environnement dynamique, la percolation orientée avec immigration hostile, et le processus de contact avec sensibilisation vérifient des résultats de forme asymptotique / This thesis is a contribution to the mathematical study of interacting particles systems which include random growth models representing a spreading shape over time in the cubic lattice. These processes are used to model the crystal growth or the spread of an infection. In particular, Harris introduced in 1974 the contact process to represent such a spread. It is one of the simplest interacting particles systems which exhibits a critical phenomenon and today, its behaviour is well-Known on each phase. Many questions about its extensions remain open and motivated our work, especially the one on the asymptotic shape. After the presentation of the contact process and its extensions, we introduce a new one: the contact process with aging where each particle has an age age that influences its ability to give birth to its neighbours. We build a coupling between our process and a supercritical oriented percolation adapted from Bezuidenhout-Grimmett's construction and we establish the 'at most linear' growth of our process. In the last part of this work, we prove an asymptotic shape theorem for general random growth models thanks to subadditive techniques, which can be complicated in the case of non-Permanent models conditioned to survive. We conclude that the process with aging, the contact process in randomly evolving environment, the oriented percolation with hostile immigration and the bounded modified contact process satisfy asymptotic shape results

Les aquifères fissurés de type karst contiennent d'importantes ressources en eau. Ces aquifères sont complexes et hétérogènes sur une gamme d'échelles importantes. Leur gestion nécessite l'utilisation d'outils et de méthodologies adaptés. Dans le cadre de cette étude, différents outils et méthodologies numériques d'étude ont été développés pour la modélisation des aquifères karstiques, et plus généralement, des milieux poreux très fissurés 2D et 3D - en mettant l'accent sur la morphologie et sur le comportement hydrodynamique du milieu à travers la notion de changement d'échelle ("second changement d'échelle", reposant sur un modèle d'écoulement local de type Darcy et/ou Poiseuille avec quelques généralisations). Plusieurs axes sont explorés concernant la morphologie du milieu poreux fissuré (milieux aléatoires, milieux booléens avec réseaux statistiques de fissures, mais aussi, modèles morphogénétiques). L'étude du changement d'échelle hydrodynamique tourne autour du concept de macro perméabilité. Dans un premier temps, l'étude porte sur un modèle de perte de charge linéaire darcien. Les perméabilités effectives sont calculées numériquement en termes des fractions volumiques de fissures et du contraste de perméabilité matrice/fissures. Elles sont analysées et comparées à des modèles théoriques (analytiques). Une étude particulière des effets de quasi-percolation pour les grands contrastes aboutit à la définition de trois fractions critiques liées à des seuils de percolation. Pour tenir compte des effets inertiels dans les fissures, l'étude est étendue au cas d'une loi locale comprenant un terme quadratique en vitesse (Darcy/Ward-Forchheimer). Une perméabilité macroscopique équivalente non linéaire est définie et analysée à l'aide d'un modèle inertiel généralisé (linéaire/puissance). Enfin, l'anisotropie hydraulique à grande échelle du milieu fissuré est étudiée, en termes de perméabilités directionnelles, à l'aide d'une méthode numérique d'immersion. / Karstic aquifers contain large subsurface water resources. These aquifers are complex and heterogeneous on a large range of scales. Their management requires appropriate numerical tools and approaches. Various tools and numerical methodologies have been developed to characterize andmodel the geometry and hydraulic properties of karstic aquifers, more generally, of highly fissured 2D and 3D porous media. In this study, we emphasize morphological characterization, and we analyze hydrodynamic behavior through the concept of upscaling ("second upscaling"). Concerning the morphology of fissured porous media, several axes are explored : random media, composite random Boolean media with statistical properties, and morphogenetic models. Hydrodynamic upscaling is developed using the macro-permeability concept. This upscaling method is based on either Darcy's linear law, or on a linear/quadratic combination of Darcy's and Ward-Forchheimer's quadratic law (inertial effects). First, the study focuses on Darcy's linear head loss law, and Darcian effective permeabilities are calculated numerically in terms of volume fractions of fissures and "fissure/matrix" permeability contrasts. The results are analysed and compared with analytical results and bounds. A special study of percolation and quasi-percolation effects, for high contrasts, leads to defined three critical fractions. These critical fractions are "connected" to percolation thresholds. Secondly, in order to consider inertial effect in fissures, the study is extended to a local law with a quadratic velocity term (Darcy/Ward-Forchheimer). Then, an equivalent nonlinear macroscopic permeability is defined and analysed using a generalized inertial model (linear/power). Finally, the large scale hydraulic anisotropy of fissured medium is studied, in terms of directional permeabilities, using an "immersion" numerical method.

In the last three decades, the electronic industry has registered a tremendous progress. The continuous and aggressive downsizing of the transistor feature sizes (CMOS scaling) has been the main driver of the astonishing growth and advancement of microelectronic industry. Currently, the CMOS scaling is almost reaching its limits. The gate oxide is now only a few atomic layers thick, and this extremely thin oxide causes a huge leakage current through the oxide. Therefore, a further reduction of the gate oxide thickness is extremely difficult and new materials with higher dielectric constant are being explored. However, the phenomena of oxide breakdown and reliability are still serious issues in these thin oxides. Oxide breakdown exhibits a soft breakdown behavior at low voltages, and this is posing as one of the most crucial reliability issues for scaling of the ultra-thin oxides. In addition, the stress-induced leakage current (SILC) due to oxide has emerged as a scaling problem for the non-volatile memory technologies. In this dissertation, a percolation modeling approach is introduced to study and understand the dramatic changes in the conductivity of a disordered medium. Two different simulation methods of percolative conduction, the site and bond percolation, are studied here. These are used in simulating the post-breakdown conduction inside the oxide. Adopting a Monte-Carlo method, oxide breakdown is modeled using a 2-D percolation theory. The breakdown statistics and post-breakdown characteristics of the oxide are computed using this model. In this work, the effects of different physical parameters, such as dimension and the applied stress are studied. The simulation results show that a thinning of oxide layer and increasing the oxide area result in softening of breakdown. It is observed that the breakdown statistics appear to follow Weibull characteristics. As revealed by simulations, the Weibull slope changes linearly with oxide thickness, while not having a significant change when the area is varied and when the amount of the applied stress is varied. It is shown that the simulation results are well correlated with the experimental data reported in the literature. In this thesis, studying the conduction through the oxide using percolation model, it was discovered that a critical or a quasi-critical phenomenon occurs depending on the oxide dimensions. The criticality of the phase-transition results in a hard breakdown while the soft breakdown occurs due to a quasi-critical nature of percolation for ultra-thin oxides. In the later part of the thesis, a quantum percolation model is studied in order to explain and model the stress induced leakage current. It is explained that due to the wave nature of electrons, the SILC can be modeled as a tunneling path through the stressed oxide with the smaller tunneling threshold compared to the virgin oxide. In addition to the percolation model, a Markov chain theory is introduced to simulate the movement of electron as a random walk inside the oxide, and the breakdown is simulated using this random-walk of electron through the accumulated traps inside the oxide. It is shown that the trapping-detrapping of electrons results in an electrical noise in the post-breakdown current having 1/f noise characteristics. Using simulation of a resistor network with Markov theory, the conductance of the oxide is computed. An analytical study of a 2-D site percolation system is conducted using recursive methods and useful closed-form expressions are derived for specialized networks.

In the last three decades, the electronic industry has registered a tremendous progress. The continuous and aggressive downsizing of the transistor feature sizes (CMOS scaling) has been the main driver of the astonishing growth and advancement of microelectronic industry. Currently, the CMOS scaling is almost reaching its limits. The gate oxide is now only a few atomic layers thick, and this extremely thin oxide causes a huge leakage current through the oxide. Therefore, a further reduction of the gate oxide thickness is extremely difficult and new materials with higher dielectric constant are being explored. However, the phenomena of oxide breakdown and reliability are still serious issues in these thin oxides. Oxide breakdown exhibits a soft breakdown behavior at low voltages, and this is posing as one of the most crucial reliability issues for scaling of the ultra-thin oxides. In addition, the stress-induced leakage current (SILC) due to oxide has emerged as a scaling problem for the non-volatile memory technologies. In this dissertation, a percolation modeling approach is introduced to study and understand the dramatic changes in the conductivity of a disordered medium. Two different simulation methods of percolative conduction, the site and bond percolation, are studied here. These are used in simulating the post-breakdown conduction inside the oxide. Adopting a Monte-Carlo method, oxide breakdown is modeled using a 2-D percolation theory. The breakdown statistics and post-breakdown characteristics of the oxide are computed using this model. In this work, the effects of different physical parameters, such as dimension and the applied stress are studied. The simulation results show that a thinning of oxide layer and increasing the oxide area result in softening of breakdown. It is observed that the breakdown statistics appear to follow Weibull characteristics. As revealed by simulations, the Weibull slope changes linearly with oxide thickness, while not having a significant change when the area is varied and when the amount of the applied stress is varied. It is shown that the simulation results are well correlated with the experimental data reported in the literature. In this thesis, studying the conduction through the oxide using percolation model, it was discovered that a critical or a quasi-critical phenomenon occurs depending on the oxide dimensions. The criticality of the phase-transition results in a hard breakdown while the soft breakdown occurs due to a quasi-critical nature of percolation for ultra-thin oxides. In the later part of the thesis, a quantum percolation model is studied in order to explain and model the stress induced leakage current. It is explained that due to the wave nature of electrons, the SILC can be modeled as a tunneling path through the stressed oxide with the smaller tunneling threshold compared to the virgin oxide. In addition to the percolation model, a Markov chain theory is introduced to simulate the movement of electron as a random walk inside the oxide, and the breakdown is simulated using this random-walk of electron through the accumulated traps inside the oxide. It is shown that the trapping-detrapping of electrons results in an electrical noise in the post-breakdown current having 1/f noise characteristics. Using simulation of a resistor network with Markov theory, the conductance of the oxide is computed. An analytical study of a 2-D site percolation system is conducted using recursive methods and useful closed-form expressions are derived for specialized networks.

Un nanonet possède des propriétés remarquables qui proviennent non seulement des propriétés intrinsèques de chaque nanostructure mais aussi de leur assemblage en réseau ce qui les rend particulièrement attractifs pour de multiples applications, notamment dans les domaines de l’optique, l’électronique ou encore le biomédical. Dans ce travail de thèse, des nanonets constitués de nanofils de silicium ont été intégrés pour la première fois sous forme de transistors à effet de champ avec une grille en face arrière. La filière technologique développée est parfaitement compatible avec une production des dispositifs en masse, à bas coût et à grande échelle pour un budget thermique n’excédant pas 400°C. Des avancées technologiques majeures ont été réalisées grâce à la maîtrise du frittage des jonctions entre nanofils, de la siliciuration des contacts et de la passivation des nanofils avec de l’alumine. Les transistors à nanonets fabriqués présentent des caractéristiques électriques excellentes, stables sous air et reproductibles qui sont capables de concurrencer celles des transistors à nanofil unique. Une étude approfondie de la percolation par des mesures expérimentales et des simulations Monte-Carlo a mis en évidence que la limitation de la conduction par les jonctions entre nanofils permet d’améliorer considérablement les performances électriques. Après une intégration des dispositifs sous forme de biocapteurs, il a été montré que les transistors sont sensibles électriquement à l’hybridation de l’ADN. Bénéficiant d’un procédé de fabrication compatible avec l’industrie de la microélectronique, une intégration 3D de ces transistors à nanonet sur un circuit de lecture peut alors être envisagée ce qui ouvre la voie à des biocapteurs portables, capables de détecter l’ADN en temps réel et sans marquage. De plus, la flexibilité mécanique et la transparence optique du nanonet offrent d’autres opportunités dans le domaine de l’électronique flexible. / A nanonet exhibits remarkable properties which arises from, not only, the intrinsic properties of each nanostructure but also from their assembly into network which makes them particularly attractive for various applications, notably in the field of optics, electronics or even biomedical. During this Ph.D. work, silicon nanowire-based nanonets were integrated for the first time into field effect transistors with a back gate configuration. The developed technological process is perfectly suitable with a large-scale and massive production of these devices at low cost without exceeding a thermal budget of 400°C. Major technological breakthroughs were achieved through the control of the sintering of nanowire junctions, the contact silicidation and the nanowire passivation with alumina. The as-fabricated nanonet transistors display outstanding, air stable and reproducible electrical characteristics which can compete with single nanowire-based devices. An in-depth study of percolation using experimental measurements and Monte-Carlo simulations highlighted that the conduction limitation by nanowire junctions allow to enhance drastically the electrical performances. After device integration into biosensors, it has been shown that transistors are electrically sensitive to DNA hybridization.Beneficiating from a fabrication process compatible with the microelectronic industry, a 3D integration of these nanonet-based transistors onto a readout circuit can therefore be envisioned which opens new avenues for portable biosensors, allowing direct and label-free detection of DNA. Furthermore, mechanical flexibility and optical transparency offer other opportunities in flexible electronic field.

Notre travail a pour objectif l'étude de l'influence de l'ajout de nanocristaux de cellulose dans des matrices biodégradables sur leurs propriétés. Des films composites et des pièces injectées ont été préparés et caractérisés. Dans ce but, ont été choisis comme matrices le poly(acide lactique), PLA, et le poly (butylène adipate-co-téréphtalate)), PBAT. Deux matières première d'où des nanocristaux de celulose ont été extraites ont été sélectionnées : le bois balse et la cellulose microcrystalline (CMC). En raison du caractère fortement polaire des nanocristaux de cellulose différentes voies de modifications chimiques de la surface de ces particules ont été testées afin d'assurer une bonne dispersion de ceux-ci lorsqu'ils sont ajoutés à des matrices polymères de polarité inférieure. En effet, les approches testées étaient: (a) le greffage de deux types d'isocyanates, dont l'un aliphatique et l'autre aromatique: l'octadécyl isocyanate (NCC_oct) et le phényl-butyle isocyanate (NCC_fb), respectivement; (b) le greffage de poly(butylène glutarate) à travers la technique de polymérisation in situ (NCC_PBG); (c) le greffage de l'acide polyacrylique à travers la technique appelée click chemistry (NCC_PA); et (d) la silanisation avec le - methacryloxy-propyle-trimethoxy-silane(NCC_MPS). Les NCCs initiaux et modifiés ont été ajoutés aux matrices de PBAT ou du PLA par procédés de mélanges à partir de solution (casting) ou à partir de l'état fondu (par extrusion ou en utilisent un homogénisateur de type Drais). En général, la modification chimique de la surface de NCC a augmenté la résistance thermique de celui-ci, a diminué son caractère hydrophile et a amélioré la dispersion des NCCs dans les matrices de PLA et PBAT. Cela a provoqué des augmentations encore plus grandes dans les propriétés de ces polymères, en fonction du type de modification et du procédé de fabrication utilisé. La caractérisation des nanocomposites a démontré que, en général, l'addition des NCCs a augmenté le module d'élasticité de la matrice et a conservé sa rigidité même à températures relativement élevées. Des niveaux plus élevés de NCC conduisent à de plus grandes augmentations de la rigidité. La perméabilité à la vapeur d'eau de PBAT a été réduite par l'introduction de NCC et n'a pas changé dans le cas du PLA. Les résullts de ces travaux ont indiqué de bonnes perspectives concernant l'utilisation des nanocristaux de cellulose comme élément de renfort de matrices polymères. De manière générale, le présent travail a démontré que les NCCs étaient capables d'améliorer les propriétés mécaniques, thermiques et de barrières du PBAT et du PLA, qui sont deux polymères biodégradables largement utilisés dans les applications de films ou de pièces plastiques. De plus, les résultats montrent qu'il est possible de modifier la polarité des NCC en les soumettant à des modifications chimiques de surface afin d'éviter leur agglomération par la formation de ponts de liaisons hydrogènes et de les rendre compatibles avec différentes matrices polymères. Ces modifications chimiques tendent aussi à élever la résistance thermique des NCCs. De cette manière, les procédés à l'échelle industrielle comme l'extrusion et l'injection peuvent être utilisés et fournissent de bons résultats. / This study aimed at evaluating the potential of application of cellulose nanocrystals as reinforcing elements of biodegradable polymeric matrices, in the films and injection molded pieces applications. Two polymeric matrices with different properties were used, namely: poly(butylene adipate-co-terephthalate), PBAT, and poly(lactic acid), PLA. For the extraction of cellulose nanocrystals (NCC), two sources were selected: microcrystalline cellulose (CMC) and balsa wood . Due to the high polarity of cellulose nanocrystals, different approaches of surface chemical modifications of these particles were tested, in order to ensure their good dispersion when added to polymeric matrices of lower polarity. They were: a) chemical modification with two types of isocyanates, an aliphatic one (octadecyl isocyanate) and an aromatic one (phenylbutyl isocyanate); b) grafting of poly (butylene glutarate) using the in situ polymerization technique; c) silanization treatment; and d) grafting of poly(acrylic acid) through click chemistry technique. Modified and unmodified NCCs were processed with PBAT and PLA by casting or melt extrusion processing techniques. In general, the chemical modification of NCC surface increased their thermal resistance, decreased their polarity and improved their dispersion into PLA and PBAT matrices. Some of these treatments, as well as the processing conditions enabled an increase in the overall mechanical properties of the polymers. Thus, the characterization of the nanocomposites showed that NCC addition increased the elastic modulus of the matrix and retained its higher stiffness even under relatively high temperatures. Higher NCC contents led to larger increases in the stiffness of the ensuing composites. The water vapor permeability of PBAT was also reduced with the introduction of NCC. This work points out several potential good perspectives for the use of celulose nanocrystals as reinforcing elements of polymeric matrices. It showed also that it is possible to obtain significant improvements in the polymer properties using the same processing techniques as those used at industrial scale, such as melt extrusion and injection molding. / O presente estudo de doutorado teve como objetivo avaliar o potencial deaplicação de nanocristais de celulose como reforço em matrizes poliméricasbiodegradáveis, em aplicações de filmes ou em peças moldadas por injeção.Duas matrizes poliméricas de diferentes propriedades foram utilizadas paraestudo nessas aplicações, sendo elas: poli(butileno adipato-co-tereftalato),PBAT, e poli(ácido láctico), PLA. Foram também selecionadas duas fontes paraextração dos nanocristais de celulose (NCC): a celulose microcristalina (CMC)e a madeira balsa.Devido ao caráter altamente polar dos nanocristais de celulose diferentesrotas de modificações químicas superficiais dessas partículas foram testadas,visando garantir a boa dispersão dos mesmos quando adicionados às matrizespoliméricas de menor polaridade. Foram elas: a) modificação química com doistipos de isocianatos, sendo um de cadeia alifática (octadecil isocianato) e outrode cadeia aromática (fenilbutil isocianato); b) enxertia do poli(butileno glutarato)através da técnica de polimerização in situ; c) tratamento de silanização com -metacriloxi-propil-trimetoxi-silano; d) enxertia de poli(ácido acrílico) através datécnica de click chemistry.NCC modificados e não modificados foram processados com PBAT ouPLA através de mistura com o polímero em solução (casting) ou no estadofundido (extrusão ou homogeneizador de alta rotação do tipo Drais).De modo geral, modificações químicas superficiais dos NCC aumentarama estabilidade térmica dos mesmos, diminuíram sua polaridade e melhoraram adispersão dos NCC nas matrizes de PBAT ou PLA. Isso fez com queincrementos ainda maiores nas propriedades desses polímeros pudessem serxxivalcançados, dependendo do tipo de modificação e do processo de misturautilizados.A caracterização dos nanocompósitos obtidos mostrou que a adição deNCC elevou o módulo elástico das matrizes e conservou sua maior rigidezmesmo em temperaturas relativamente elevadas, sendo que maiores teores deNCC levaram a maiores aumentos na rigidez. A permeabilidade a vapor deágua do PBAT também foi reduzida com a introdução dos NCC e não foialterada no caso do PLA.Os resultados desse trabalho apontaram boas perspectivas no uso dosnanocristais de celulose como reforços de matrizes poliméricas. Tambémmostraram que é possível obter melhorias nas propriedades de polímerosmesmo através da utilização de processos de maior reprodutibilidade emescala industrial, como extrusão e injeção.

Made available in DSpace on 2014-12-17T15:14:47Z (GMT). No. of bitstreams: 1 DarlanAM.pdf: 1159480 bytes, checksum: d201bf0e3558be6b14b14c9a86a46f20 (MD5) Previous issue date: 2005-03-10 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico / In this work we have studied the problem of percolation in a multifractal geometric support, in its different versions, and we have analysed the conection between this problem and the standard percolation and also the connection with the critical phenomena formalism. The projection of the multifractal structure into the subjacent regular lattice allows to map the problem of random percolation in the multifractal lattice into the problem of correlated percolation in the regular lattice. Also we have investigated the critical behavior of the invasion percolation model in this type of environment. We have discussed get the finite size effects / Nesta disserta??o estudamos o problema da percola??o num suporte geom?trico multifractal, em suas diferentes vers?es, e analisamos a conex?o deste problema com a percola??o convencional e com o formalismo dos fen?menos cr?ticos. A proje??o da estrutura multifractal numa rede regular subjacente permite mapear o problema da percola??o aleat?ria no multifractal num problema de percola??o correlacionada numa rede regular. Tamb?m investigamos o comportamento cr?tico do modelo da percola??o por invas?o neste tipo de ambiente e discutimos a quest?o do efeito de tamanho finito

Made available in DSpace on 2014-12-17T15:26:35Z (GMT). No. of bitstreams: 1 IsaacDBS.pdf: 539336 bytes, checksum: ac9f1f2543159f0c009f0242077b1d5c (MD5) Previous issue date: 2008-07-25 / In this work, we study and compare two percolation algorithms, one of then elaborated by Elias, and the other one by Newman and Ziff, using theorical tools of algorithms complexity and another algorithm that makes an experimental comparation. This work is divided in three chapters. The first one approaches some necessary definitions and theorems to a more formal mathematical study of percolation. The second presents technics that were used for the estimative calculation of the algorithms complexity, are they: worse case, better case e average case. We use the technique of the worse case to estimate the complexity of both algorithms and thus we can compare them. The last chapter shows several characteristics of each one of the algorithms and through the theoretical estimate of the complexity and the comparison between the execution time of the most important part of each one, we can compare these important algorithms that simulate the percolation. / Nesta disserta??o estudamos e comparamos dois algoritmos de percola??o, um elaborado por Elias e o outro por Newman e Ziff, utilizando ferramentas te?ricas da complexidade de algoritmos e um algoritmo que efetuou uma compara??o experimental. Dividimos este trabalho em tr?s cap?tulos. O primeiro aborda algumas defini??es e teoremas necess?rios a um estudo matem?tico mais formal da percola??o. O segundo apresenta t?cnicas utilizadas para o c?lculo estimativo de complexidade de algoritmos, sejam elas: pior caso, melhor caso e caso m?dio. Utilizamos a t?cnica do pior caso para estimar a complexidade de ambos algoritmos e assim podermos compar?-los. O ?ltimo cap?tulo mostra diversas caracter?sticas de cada um dos algoritmos e atrav?s da estima- tiva te?rica da complexidade e da compara??o entre os tempos de execu??o da parte mais importante de cada um, conseguimos comparar esses importantes algoritmos que simulam a percola??o

Ce travail propose une optimisation de la conductivité électrique transverse des composites structuraux matrice/fibres de carbone. L'influence de la fonctionnalisation électrique de l'ensimage sur la conductivité des composites est particulièrement étudiée. Des feuillets submicroniques d'argent (AgNpts) ont été élaborés en présence de citrate de sodium (TSC). Leur morphologie plane est particulièrement adaptée à une dispersion dans un ensimage. Les feuillets ont été dispersés dans une matrice modèle. Le seuil de percolation électrique des feuillets est déterminé à 5,9 %. Cette valeur est cohérente avec un facteur de forme modéré, compris entre 12 et 28. L'ensimage fonctionnalisé a ensuite été déposé sur une mèche de fibres de carbone, elle-même imprégnée par une matrice PAEK hautes performances. Avant imprégnation des fibres de carbone, des fils submicroniques d'argent ont été introduits dans la matrice PAEK. Des composites matrice-fils submicroniques d'argent/fibres de carbone avec ensimage conducteur ont été mis en œuvre. Leur conductivité électrique est élevée (7 S.m-1), alors que la fraction volumique en particules d'argent (fils et feuillets) est inférieure à 1 % en volume. / This PhD thesis deals with the optimization of transverse electrical conductivity of Thermoplastic Carbon Fiber Reinforced Polymer. The influence of an electrically conductive sizing has been investigated. Silver nanoplates (AgNpts) have been successfully synthesized by a soft chemical reduction, with trisodiumcitrate (TSC) as surfactant. Silver nanoplates have been dispersed into a model matrix, percolation threshold has been determined near 5.9 % in volume fraction. This value is consistent with their moderate aspect ratio (between 12 and 28). Size and morphology of silver nanoplates are suitable for their dispersion in the sizing. Carbon fiber has been coated with conductive sizing. Carbon fiber will be further impregnated by a PAEK thermoplastic matrix. A higher conductivity level has been achieved by introducing silver nanowires in the PAEK matrix. Structural composites consisting of matrix-silver nanowires / continuous carbon fiber sized with conductive sizing have been elaborated. Their electrical conductivity reached 7 S.m-1 for a total silver volume fraction of 1 %.vol.

Le verre SON68 est dans un premier temps altéré en mode dynamique dans l’eau de COx riche en silicium (42mg/L) à pH 8, à fort S/V (14000 m⁻¹) et à 35, 50 et 90°C. Les résultats montrent que l’altération du verre semble être gouvernée par un mélange de processus de diffusion et de réaction de surface. La vitesse résiduelle à 90°C est de l’ordre de 10⁻⁴ g.m⁻².j⁻¹, l’énergie d’activation est de l’ordre de 70 kJ.mol⁻¹. Un mécanisme de dissolution/précipitation et d’hydrolyse/condensation sont responsables du développement de la couche d’altération. Les silicates de Mg et la calcite précipitent à 35 et 50°C, mais en plus la powellite et l’apatite ont été identifiées à90°C. Les résultats de la modélisation géochimique reproduisent les données expérimentales. Le verre est ensuite hydraté à des températures allant de 35 à 125°C et des valeurs d’humidité relative (HR) entre 92 et 99,9%. L’hydratation du verre augmente avec la température et l’HR. L’énergie d’hydratation est de l’ordre de 34,2 kJ.mol⁻¹. Les épaisseurs des couches d’altération varient entre 0,3μm à 35°C et 5μm à 125°C. La couche d’altération est appauvrie en (B, Li, Na) et enrichie en (Si, Al, Fe, Ca, Zn et Ni). Les principales phases secondaires formées sont la calcite, la powellite, l’apatite, la tobermorite et un gel hydraté.L’influence des matériaux en champ proche sur l’altération du verre SON68 dopé en ²⁹Si a été étudiée. La présence d’acier augmente le pH et diminue la concentration en Si et en Mo sans modifier la vitesse globale de corrosion du verre. Le Si est retenu sur les produits de corrosion d’acier, sa concentration en solution semble être contrôlée par la dissolution de l’argilite. La corrosion du verre en présence d’acier et d’argile à 90°C conduit à la formation de magnétite, sidérite, ferrosilicates, silice pure, sulfures de fer (pyrite, troïlite, pyrrhotite etmackinawite), calcite, apatite, powellite et silicates de Mg. Les résultats de modélisation sont en bon accord avec les données expérimentales. / The SON68 glass is initially altered in dynamic mode under silica rich COx water (42 mg/L) at pH8, high S/V ratio (14000 m⁻¹) and at 35, 50 and 90°C. The results showed that the glass alteration seems to be governed by both diffusion and surface reaction process. The residual rate at 90°C is around 10-4 g.m⁻².d⁻¹. The activation energy is about 70 kJ.mol⁻¹. The dissolution /precipitation and hydrolysis/condensation mechanisms are responsible for the development of the alteration layer. Mg silicates and calcites precipitate at 35 and 50°C, the same phases in addition to powellite and apatite precipitate at 90°C. The results predicted by the model reproduce well experimental data. The glass is then hydrated at temperatures ranging from 35 to 125°C and relative humidity values (RH) between 92 an 99.9%. The glass hydration increases with the temperature and RH, the hydration energy is about 34.2 kJ.mol⁻¹. The alteration layers thicknesses vary between 0.3μm at 35°C and 5μm at 125°C. The alteration layer is depleted in (B, Li, Na) and enriched in (Si, Al, Fe, Zn and Ni). The secondary phases are calcite, powellite, apatite and tobermorite in adition to a hydration gel. The effect of near field materials on the ²⁹Si doped SON68 glass alteration was studied. The presence of steel increases the pH and decreases the Si and Mo concentrations without changing the overall rate of glass corrosion. The Si is retained on the steel corrosion products, its concentration in solution seems to be controlled by the clay dissolution. The glass corrosion in the presence of steel and clay at 90°C leads to the formation of magnetite, siderite, ironsilicates, pure silica, iron sulphur (pyrite, troilite,pyrrhotite and mackinawite), calcite, apatite, powellite and Mg silicates. The modelling results agree well with the experimental data.