Les cellules photovoltaïques électrochimiques (CPE) ont besoin d'un milieu électrolytique transparent à la lumière, qui ne montre pas de fuite de solvant sous forme vapeur et doté de bonnes propriétés électrochimiques dans la plage de températures d'utilisation. La performance des CPE dépend de la minimisation des pertes d'énergie en surtensions anodique et cathodique (∆Eр), ainsi que d'une densité de courant (J) et d'un photovoltage élevés. Les mélanges de cinq couples rédox (CR) étudiés, composés principalement de thiourées et de leur disulfure doublement chargé en présence du liquide ionique EMI-TFSI, laissent passer les photons jusqu'à 3,2 eV et pourraient être utilisés avec une anode semi-conductrice de bande interdite optimale de ≈1,5 eV. Pour le développement de thiourées ou de disulfures liquides, deux corrélations au volume équivalent ont été établies pour les températures de transition vitreuse (Tg) et de fusion (Tf). Deux thiourées liquides ont été développées (1-diéthyl-3-diméthylthiourée, C (Tf : -7°C) et 1,3-bis(éthylméthyl)thiourée, E (Tf : 11°C)) et permettent d'autosolvater le CR sans solvant ou d'augmenter la proportion du CR en solution et le photocourant (Jph). L'anion TFSI (trifluorométhanesulfonylimide), plastifiant pour les cations monochargés, ne diminue pas la Tf des disulfures étudiés : les deux gros anions TFSI semblent s'insérer entre les disulfures sans en perturber la structure. Pour les systèmes électrolytiques (SE), les thiourées liquides, présentant une bonne pression de vapeur, doivent être utilisées avec un liquide ionique (non-volatil, par exemple EMI-TFSI : Éthylméthylimidazolium-TFSI) dont le pourcentage molaire choisi est un compromis entre une plus grande densité de courant (faible pourcentage) et un plus faible ∆Ep (fort pourcentage). Le solvant le plus visqueux du SE (thiourée ou liquide ionique) contrôle la viscosité et la conductance équivalente. Dues probablement à la formation de complexes de transfert de charge entre les espèces réduite et oxydée, de grandes attractions intermoléculaires sont présentes (écart à l'idéalité du volume molaire (Vm) des SE). Au-delà d'un seuil minimal de force ionique, les différences de viscosité, de Vm et de conductivité ionique des SE ne semblent induire aucune variation de ∆Ep. Les plus faibles valeurs de ∆Ep sont obtenues à 4,5% molaire en disulfure, entre 84% et 97% molaire en liquide ionique, pour tous les CR, et de ces derniers, le couple 1,3diéthylimidazolidine-2-thione (I) / dithio bis(1,3-diéthylimidazolidinium) bisTFSI (J2+) présente le plus faible ∆Ep grâce à une plus faible surtension cathodique |nc|. L'accès de l'espèce oxydée à l'électrode de travail pourrait être à l'origine de la diffusion plus difficile pour les disulfures de thiourées non-cycliques. Ces disulfures présentant un coeur structurel identique jusqu'aux azotes diffèrent par leurs substituants, en rotation, sur les groupes aminos. Le ∆Ep similaire de I/J²⁺ à celui des CR CsT(5-mercapto-1-méthyltétrazolate de césium) / son disulfure (T2), et tétraméthylthiourée (A) / dithiobis(tétraméthylformamidinium) bis TFSI (B²⁺) en solvant organique (travaux antérieurs du laboratoire), pourrait probablement s'expliquer par l'absence de rotation des groupes aminos (T2) et la petite taille des substituants méthyles sur les groupes aminos pour B²⁺. Pour le SE à base de I/J²⁺ très dilué dans EMI-TFSI, le photovoltage maximal théorique de la CPE est prometteur et estimé à 1,32 V pour un semi-conducteur de CdSe. ______________________________________________________________________________ MOTS-CLÉS DE L’AUTEUR : Pile solaire, Thiourées, Conductivité, Viscosité, Produit de Walden, Voltampérométrie cyclique, Transition de phases.

Afin de déterminer la conduction thermique de sols en climat continental humide, l'étude des paramètres minéralogiques, physiques, physico-chimiques et géophysiques est essentielle. Le diffractomètre à rayons X, le microscope électronique à balayage et le terramètre sont utilisés pour la caractérisation et le calcul de la conduction thermique, soit la capacité volumétrique, la conductivité et la diffusivité thermique. La teneur en eau gravimétrique est la caractéristique qui interfère le plus fortement sur le bilan thermique. La minéralogie, quant à elle, joue deux rôles importants: (1) le quartz, minéral dominant dans la plupart des échantillons, possède une forte conductivité thermique et (2) la minéralogie des particules fines inférieures à 63 microns influencent la perméabilité des sols. L'interaction qui existe entre la température du sol, le contenu en eau et la minéralogie est clairement définie. Un lien direct unit les quantités de vermiculite et d'interstratifiés chlorite-smectite, potentiellement absorbantes, et les quantités d'eau retrouvées dans certains échantillons. Ainsi, la définition du bilan thermohydrodynamique représentatif des sols doit inclure une étude minéralogique. ______________________________________________________________________________ MOTS-CLÉS DE L’AUTEUR : Conduction thermique, Sols agricoles, Vermiculite, Diffraction aux rayons X, Microscopie électronique à balayage, Résistivité électrique.

The performance of some polymeric materials is profoundly affected by long-term exposure to moisture during service. This poses problems for high precision and/or load bearing components in engineering applications where moisture-induced changes in mechanical properties and dimensional stability could compromise the reliability of the device or structure. In addition to external factors such as moisture, the material properties are also evolving due to inherent structural relaxation within the polymeric material through a process known as physical aging. Based on the current knowledge of both mechanisms, they have opposite effects on material properties. The common approach to studying the effects of moisture is to expose the polymeric material to combined moisture and heat, also referred to as hygrothermal conditions. The application of heat not only increases the rate of moisture diffusion but also accelerates physical aging processes which would otherwise be very slow. In spite of this coupled response, nearly all hygrothermal studies ignore physical aging in their investigations due to the complexity of the coupled problem. The goal of this work is to develop a numerical model for simulating the interactive effects of moisture diffusion and physical aging in a glassy polymer. The intent is to develop a capability that would also allow one to model these effects under various mechanical loading and heat transfer conditions. The study has chosen to model the response of polycarbonate/acrylonitrile-butadiene-styrene (PC/ABS), which is a glassy polymer blend that has very similar behaviour to polycarbonate. In this study, a comprehensive approach which considers four physical mechanisms – structural mechanics, moisture diffusion, heat conduction, and physical aging – has been applied. The most current analytical models in the literature usually attempt to model two or three coupled physical phenomena. To develop the four coupled phenomena model, the current work has undertaken an extensive scope of work involving experimental characterization and finite element modeling. In the experimental part of this work, seven sets of different tests were conducted to characterize the behaviour of PC/ABS exposed to moisture diffusion and accelerated physical aging. These experiments provided a comparative study between the effects of physical aging and moisture diffusion on the material’s behaviour; and at the same time, provided data for the numerical modeling. The dual glass transition temperatures (Tg) of the material were determined using two techniques: dynamic mechanical analysis (DMA) and thermo-mechanical analysis (TMA). The DMA tests provided data for studying the effects of hygrothermal aging on the Tg’s of the material and were also useful for mechanical tests such as creep and stress relaxation performed using the DMA. The Tg’s obtained using the TMA were also required for physical aging experiments using the dilatometry mode of TMA. Structural relaxation of the blend was studied by aging the material at 80 °C for 7 aging times in the TMA. These experiments gave an insight into the volume relaxation behaviour of the blend at a constant temperature. Specific heat capacity of the PC/ABS blend was also measured using another thermal analysis technique; i.e., differential scanning calorimeter (DSC), before and after test specimens were exposed to hygrothermal aging for 168 hours. The interactive effects of physical aging and moisture diffusion on the moisture uptake of the material were studied using gravimetric experiments performed at 5 different hygrothermal conditions. The experimental results were used to determine the coefficient of diffusion as well as the equilibrium moisture uptake of the samples. Furthermore, the effects of both moisture diffusion and physical aging on the mechanical behaviour of the polymer blend were investigated using stress relaxation tests. The comparison of the results of the tests performed on un-aged specimens with those of thermally and hygrothermally aged samples showed how physical aging effects competed with moisture diffusion. Also, the coefficient of hygroscopic expansion of the PC/ABS blend was determined using a so-called TMA/TGA technique. The numerical modeling of the four-coupled physics was achieved using the governing equations in the form of partial differential equations. Modeling was performed using the commercial finite element software package, COMSOL Multiphysics®. First, the uncoupled physical mechanisms of structural mechanics, moisture diffusion, and heat conduction were modeled separately to investigate the validity of the PDEs for each individual phenomenon. The modeling of the coupled physics was undertaken in two parts. The three coupled physics of structural mechanics, moisture diffusion, and heat conduction was first simulated for a gas pipe having a linear elastic behaviour. The comparison of the results with similar analysis available in the literature showed the capability of the developed model for the analysis of the triple coupled mechanisms. The second part modeled the four coupled phenomena by incorporating the experimentally determined coupling coefficients. In the developed numerical model, the material behaviour was considered to be linear viscoelastic, which complicated the model further but provided more realistic results for the behaviour of the polymer blend. Moreover, an approximation method was proposed for estimating the coupling coefficients that exist between different coupled physics in this study. It was also suggested that the anomalous moisture diffusion in the material can be modeled using a time varying boundary condition. Finally, the model was successfully verified and demonstrated using test case studies with thin thermoplastic plates. The proposed four-coupled physics model was able to predict with good accuracy the deflection of thin thermoplastic plates under bending for a set of hygorthermal test condition.

Geotechnical engineers often face important discrepancies between the observed and the predicted behavior of geosystems. Two conceptual frameworks are hypothesized as possible causes: the ubiquitous spatial variability in soil properties and process-dependent terminal densities inherent to granular materials. The effects of spatial variability are explored within conduction and diffusion processes. Mixtures, layered systems, inclusions and random fields are considered, using numerical, experimental and analytical methods. Results include effective medium parameters and convenient design and analysis tools for various common engineering cases. In addition, the implications of spatial variability on inverse problems in diffusion are numerically explored for the common case of layered media. The second hypothesis states that there exists a unique terminal density for every granular material and every process. Common geotechnical properties are readily cast in this framework, and new experimental data are presented to further explore its implications. Finally, an unprecedented field study of blast densification is documented. It involves comprehensive laboratory and site characterization programs and an extensive field monitoring component. This full scale test lasts one year and includes four blasting events.

With the progress of technology, large capacity and scalable are required for the future. Recent years, the physical limit is approached and a next-generation memory is needed in the future. In addition, non- volatile memory occupies more than 96% in the memory market, and RRAM has great advantages such as simple structure, high scalable, low operation voltage, high operation speed, high endurance and retention. That is the reason RRAM is the candidate in the next generation. In this experiment, multi-sputtering was used to deposit Zr:SiO 2 and Pt on TiN bottom electrode. The sandwich structure was metal/insulator/metal (MIM). With the different dielectric constant material, a different electrical field will be produced. And then I-V measurement and materials analysis were used to investigate the characteristic of the RRAM. At first, a forming process is required to the RRAM. The device was swept from negative to positive voltage and obtained the conduction mechanism from curve fitting. The different dielectric constant materials were used to fabricate the RRAM. High and low dielectric materials were HfO 2 and BN, respectively. The electric field distribution is centralized in low dielectric material so the electrons will drift to the direction of electric field. Hence, the Vset will be centralized and more stable. We also fabricated a Zr:SiO 2 /C:SiO 2 RRAM as an high K and low K material. The current fitting results that a hopping conduction occurs in low resistive state (LRS) and high resistive state (HRS). Both from Raman spectrum and FT-IR spectrum, a graphene oxide was existed in the C:SiO 2 thin film. While the filament was form, the tip of the filament will approach the graphene oxide because of the point effect. Hence, the resistance switching will happen in the grapheme oxide and set voltage will be more stable and lower the operated current. Next, an ICP treatment was used in order to "burn" the carbon in SiO 2 . The purpose is to make an extremely low K material and ignore the effect of the existence of carbon. From the FT-IR spectrum, the carbon signals were disappeared after the ICP oxygen plasma treatment. In the I-V fitting diagram, space char limit results in the high voltage region. The electrical field simulation was an auxiliary tool which shows a strong electrical field occurs in the extremely low K area. While the electrons flow through the conduction path, they will be confined in the porous area. The operation current will decrease because of the limited conduction area.

Renewable energy sources including photovoltaic cells, fuel cells, and wind turbines require converters with high voltage gain in order to interface with power transmission and distribution networks. These conversions are conventionally made using bulky, complex, and costly transformers. Multiple modules of single-switch, single-inductor DC-DC converters can serve these high-gain applications while eliminating the transformer. This work generally classifies multiple modules of single-switch, single-inductor converters as high gain DC-DC converters transformers. The gain and efficiency of both series and cascade configurations are investigated analytically, and a method is introduced to determine the maximum achievable gain at a given efficiency. Simulations are used to verify the modeling approach and predict the performance at different power levels. Experimental prototypes for both low power and high power applications demonstrate the value of multiple module converters in high gain DC-DC converters for renewable energy applications.

Heat transfer of two-dimensional, hydrodynamically developed, thermally developing, single phase, laminar flow inside a microtube is studied analytically with constant wall temperature thermal boundary condition. The flow is assumed to be incompressible and thermo-physical properties of the fluid are assumed to be constant. Viscous dissipation and the axial conduction are included in the analysis. Rarefaction effect is imposed to the problem via velocity slip and temperature jump boundary conditions for the slip flow regime. The temperature distribution is determined by solving the energy equation together with the fully developed velocity profile. Analytical solutions are obtained for the temperature distribution and local and fully developed Nusselt number in terms of dimensionless parameters / Peclet number, Knudsen number, Brinkman number, and the parameter &amp / #954 / . The results are verified with the well-known ones from literature.

Conduction based compact thermal modeling of DC/DC converters, which are electronic components commonly used in military applications, are investigated. Three carefully designed numerical case studies are carried out at component, board and system levels using ICEPAK software. Experiments are conducted to gather temperature data that can be used to study compact thermal models (CTMs) with different levels of simplification. In the first (component level) problem a series of conduction based CTMs are generated and used to study the thermal behavior of a Thin-Shrink Small Outline Package (TSSOP) type DC/DC converter under free convection conditions. In the second (board level) case study, CTM alternatives are produced and investigated for module type DC/DC converter components using a printed circuit board (PCB) of an electro-optic system. In the last case study, performance of the CTM alternatives generated for the first case are assessed at the system level using them on a PCB placed inside a realistic avionic box. v Detailed comparison of accuracy of simulations obtained using CTMs with various levels of simplification is made based on experimentally obtained temperature data. Effects of grid size and quality, choice of turbulence modeling and space discretization schemes on numerical solutions are discussed in detail. It is seen that simulations provide results that are in agreement with measurements when appropriate CTMs are used. It is also showed that remarkable reductions in modeling and simulation times can be achieved by the use of CTMs, especially in system level analysis.

The interest in conjugated polymers has been two-fold. A rich variety of intriguing physical phenomena, combined with its immense technological implications in the area of molecular electronics, sensors etc. has inspired the researchers all over the globe. The work presented in this thesis is focussed on one of the most widely studied conjugated polymers, namely polyaniline (PANI), which is well known for its high conductivity and remarkable stability in the proton-doped form. The thesis is divided into two chapters and each chapter is further divided into several parts. In the first chapter, we take a look at some novel systems based on PANI that exhibit interesting electrical and optical properties. To begin with, we report the synthesis and characterization (Part I, Chapter 3) a new class of highly conducting polyaniline doped with electron deficient Lewis acids, namely the boron trihalides (BX3, X = F, Cl, and Br). We discuss the various attributes of this interesting class of materials that set it apart from the conventional proton-doped PANI systems. It is known that the conductivity in doped PANI is greatly influenced by the presence of structural disorder. Previous studies have associated the conductivity in doped PANI with the partial crystallinity that is achieved upon proton doping. At the same time, the amorphous regions that have a high degree of disorder were believed to suppress the metallic nature in these doped systems. In view of this "higher-crystallinity-higher-conductivity" picture, it is interesting to note that the BX3 doped PANI remain absolutely amorphous despite being more conducting than previously known samples. Through our investigation, we have been able to address some of the most important and long-standing questions pertaining to the nature of the charge carriers and the role of disorder in doped PANI. A detailed study of the transport properties in Part II, Chapter 3 helps us to understand the mechanism of charge transfer in these novel systems. With the help of our results, we establish that the present systems do not belong to the family of quasi one-dimensional conductors, in stark contrast to the conventional proton-doped samples. Instead, our systems are best described as granular metals, where the conduction mechanism is controlled by the size of the conducting grains and the nature of the grain boundaries. Through a comprehensive study of the magnetic properties based on d. c. magnetic susceptibility and EPR spectroscopy, we further establish that the intrinsic conductivity of these samples are much higher than the previously known systems. By studying the interaction of the mobile charge carriers and the localized spins in the systems, we have established that our samples are far less disordered, and therefore qualify as superior systems when compared to the more conventional proton-doped PANI. One of the serious disadvantages of the conventional protonated PANI lies in its thermal instability. On heating above 75 ±C in air, the polymer backbone undergoes an irreversible aerial oxidation that disrupts the extended conjugated structure. This is marked by a rapid drop in conductivity by a few orders of magnitude. BF3-doped PANI, which has the highest conductivity sample among the present series of samples, exhibits a remarkable thermal stability in air (Part III, Chapter 3). Upon heating, the conductivity initially increases and then reaches a saturation value. The polymer can be heated at temperatures as high as 225 ±C, without any signs of degradation. With the help of temperature dependent conductivity, XPS and FTIR spectroscopy we have tried to understand this unexpected phenomenon. In Part IV, Chapter 3, we report the synthesis and characterization of a novel class of functionalized PANI that exhibit an intense deep-blue photoluminescence. A de- tailed characterization based on absorption, photoluminescence, XPS, NMR and FTIR spectroscopy has been carried out to study the chemical state of this new class of light- emitting polymers. Further, we note that the synthetic procedure followed in this work can provide a very general route to the synthesis of diversely useful derivatives of PANI. In Chapter 4, we have investigated the microscopic origin of conductivity in doped PANI. Among the several factors that can influence the conductivity of doped polymers, one is the microstructural order. To understand this better, we carried out a detailed investigation, based on scanning tunneling microscopy (STM) and spectroscopy (STS) of undoped and doped PANI films (Part I, Chapter 4). We have shown for the ¯rst time that solution processed thin films of undoped PANI has an abundance of PANI anorods self organized over very large areas. Further, we observe that this ordered orphology is Preface vii very sensitive to the choice of dopants and the doping procedure. We have shown that the morphological order can greatly influence the electronic structure and therefore the properties of these systems. To understand the role of dopant-polymer interaction in controlling the conductivity of doped PANI, we carried out x-ray photoelectron spectroscopy (XPS) studies on a large number of partially and fully doped samples (Part II, Chapter 4). We find an interesting trend in the higher binding energy feature and the asymmetry of the N and C 1s spectra, which correlates directly with the respective conductivities of different samples. The analysis of these spectra brings out interesting facts about the chemical state and the electronic structure of these samples. In summary, we have reported new PANI based systems with improved electrical and interesting optical properties, and have studied various factors that influence the properties of these as well as some of conventional doped PANI systems.

Thèse de doctoral : Sciences pour l'ingénieur : Besançon : 2008. Thèse de doctoral : Sciences pour l'ingénieur : Belfort-Montbéliard : 2008. / Réf. bibliogr. à la fin de chaque chapitre.