Le travail réalisé dans cette thèse concerne l'optimisation d’électrolytes organiques pour supercondensateur lithium-ion. Plusieurs solvants ont été sélectionnés pour la formulation de mélanges binaires ou ternaires additionnés de sel de lithium. Les propriétés physicochimiques et électrochimiques de ces électrolytes contenant LiTFSI ou LiPF6 (EC/DMC ; dinitrile/DMC ; EC/Ester/3DMC, EC/MiPC/3DMC) ont été caractérisées en vue de leur utilisation dans des dispositifs hybrides, l’objectif étant de satisfaire à la fois aux exigences des matériaux graphite et carbone activé. Les interactions solvant-solvant et solvant-sel des électrolytes ont été étudiées à partir des théories de Jones-Dole, Stocks-Einstein et Bjerrum appliquées aux mesures de viscosités et conductivités. Cela a permis de développer des modèles prédictifs de la conductivité dans des cas de solvants purs ou de mélanges simples. La deuxième partie de cette thèse a été dédiée à la réalisation de demi-cellules avec différentes formulations d'électrolytes à la fois sur carbone activé et sur graphite. Les interfaces électrodes/électrolytes et séparateurs/électrolytes ont été étudiées. La corrosion des collecteurs en Al en présence de LiTFSI a fait l'objet d'une étude qui a permis de dégager une solution consistant en la formulation d'un électrolyte additionné de 1% d'additifs source de fluorure tel que LiPF6. Enfin, des dispositifs complets graphite/carbone activé ont été réalisés en utilisant les différents électrolytes optimisés ce qui a permis de mettre en évidence le gain en énergie (x5) pour un tel système par rapport aux supercondensateurs symétriques classiques. / The objective of this thesis is to broaden the knowledge of electrochemical, thermo physical and thermodynamic properties of different efficient and safe organic electrolytes for Lithium-ion Capacitors (LICs). Several solvent structures have been first selected to design new electrolytes based on binary or ternary solvent mixtures. These solvents were then characterized through conductivity, viscosity and electrochemical studies, in order to assess their structure and properties relationships. Based on this investigation, best compromise between mobility and ionic concentration has been evaluated to formulate the best electrolytes. Generally, it was proved that the addition of solvents with very low viscosity provides efficient electrolytes. Based on conductivity and viscosity measurements, a theoretical study on solvent-solvent and solvent-salt interactions has been then performed using different well-known equations based on Stock-Einstein, Jones-Dole and Bjerrum theories to understand, rationalize, correlate and then predict their transport properties. The second part of the study concentrated on the characterization of selected electrolytes in an asymmetric LIC prior to developing such electrolytes in any high performance asymmetric capacitor devices. In other words, the main objective of this part is to verify the compatibility of designed electrolytes with each element, e.g. electrodes (graphite, activated carbon) and current collectors (aluminum), of a LIC device. To drive such analysis, different experimental investigations between electrodes/electrolytes and between collectors/electolytes were in fact investigated. Using this strategy, asymmetric systems LICs containing a formulated organic electrolyte were fully characterized to deter mine the electrochemical performances of the designed solution in LIC conditions and then compared with those observed using classical electrolyte currently used.

L’objectif de cette étude est de simuler l’érosion d’un sol cohésif sous l’effet d’un écoulement incompressible. Le modèle élaboré décrit une vitesse d’érosion interfaciale qui dépend de la contrainte de cisaillement de l’écoulement. La modélisation numérique proposée est une approche eulérienne, où une méthode de pénalisation de domaines est utilisée pour résoudre les équations de Navier-Stokes autour d’un obstacle. L’interface eau/sol est décrite par une fonction Level Set couplée à une loi d’érosion à seuil.L’approximation numérique est basée sur un schéma DDFV (Discrete Duality Finite Volume) autorisant des raffinements locaux sur maillages non-conformes et non-structurés. L’approche par pénalisation a mis en évidence une couche limite d'inconsistance à l'interface fluide/solide lors du calcul de la contrainte de cisaillement. Deux approches sont proposées pour estimer précisément la contrainte de ce problème à frontière libre. La pertinence du modèle à prédire l’érosion interfaciale du sol est confirmée par la présentation de plusieurs résultats de simulation, qui offrent une meilleure évaluation et compréhension des phénomènes d'érosion / This study focuses on the numerical modelling of the interfacial erosion occurring at a cohesive soil undergoing an incompressible flow process. The model assumes that the erosion velocity is driven by a fluid shear stress at the water/soil interface. The numerical modelling is based on the eulerian approach: a penalization procedure is used to compute Navier-Stokes equations around soil obstacle, with a fictitious domain method, in order to avoid body- fitted unstructured meshes. The water/soil interface’s evolution is described by a Level Set function coupled to a threshold erosion law.Because we use adaptive mesh refinement, we develop a Discrete Duality Finite Volume scheme (DDFV), which allows non-conforming and non-structured meshes. The penalization method, used to take into account a free velocity in the soil with non-body-fitted mesh, introduces an inaccurate shear stress at the interface. We propose two approaches to compute accurately the erosion velocity of this free boundary problem. The ability of the model to predict the interfacial erosion of soils is confirmed by presenting several simulations that provide better evaluation and comprehension of erosion phenomena.

Nós calculamos o efeito da interação elétron-fonons longitudinais óticos (LO) sobre a energia de transição ls &#8594 2p+ entre os níveis de uma impureza doadora, localizada em um poço quântico de GaAs-AlxGa1-xAs. Nossos resultados para a energia de transição em função do campo magnético aplicado mostram claramente, que a saturação da energia de transição (efeito pinning) ocorre na energia dos fônons LO, em boa concordância com recentes dados experimentais. Obtemos também a massa de cíclotron de polarons confinados em fios quânticos quase-unidimensionais, com potencial de confinamento parabólico. Observamos que o comportamento da massa é diferente daquele para sistemas bi-dimensionais e que esta diferença é maior quanto maior o potencial de confinamento. Para a heterojunção de GaAs-AlGaAs e GaAs-GaSb, investigamos a importância da interação elétron-fonons interfaciais sobre a massa de cíclotron. Verificamos que a contribuição dos fonons interfaciais é fundamental nas regiões próximas às resonâncias, onde domina o espectro. Finalmente, calculamos a energia de ligação de uma impureza hidrogenóide, localizada no centro de um ponto quântico circular de GaAs-AlGaAs. Na ausência de campo magnético aplicado, obtivemos uma expressão analítica para a função de onda do elétron ligado. Notamos, que a influência do campo magnético sobre a energia de ligação é fraca nas regiões de pequenos raios, devido ao forte potencial de confinamento. / We calculate the effects of the electron-longitudinal optical (LO) phonons interaction on the intra donor ls &#8594 2p+ transition energy in GaAs-AlGaAs quantum wells structures. Our results to the transition energy as a function of the magnetic Field strength, show that the pinning effect occur in the phonon LO energy in good agreement with recent experimental data. The cyclotron mass of polarons confined in quasi.one.dimensional quantum-well wires with parabolic confinement potential, is also obtained. The behavior of electrons effective mass with magnetic field is different, of the two-dimensional systems, and the difference increase when the confinement potential increase. To heterojunctions of GaAs-AlAs and GaAs-GaSb, we investigate the electroninterfacials optical (IO) phonons interactions on the effective cyclotron mass. We find that the electron-IO-phonons interaction is fundamental near the resonances, where they dominate the spectra. Finally, the ground state binding energy of donor impurity, placed in the center of a circular quantum dot is calculated. Without magnetic field, we obtained the analytic expression to the bound electron wave function. The influence of the magnetic field on the donor binding energy is weaker, when the radius of the quantum dot became smaller.

Cette thèse a pour objectif de développer des méthodes ultrasonores pour l’END de l’adhésion de joints collés. Pour aborder ce problème, les assemblages sont réalisés avec des substrats en aluminium (isotrope, élastique) et un adhésif de type époxy(isotrope, viscoélastique). Selon la géométrie des assemblages, deux méthodes sont proposées pour obtenir une information quantitative sur le niveau d’adhésion. La première est adaptée à des échantillons de type tri-couches avec recouvrement total.Elle consiste à analyser la transmission d’ondes ultrasonores planes de volume à travers l’assemblage immergé dans l'eau.Les conséquences d'un mauvais traitement de surface des substrats sur la mesure des modules de viscoélasticité du joint adhésif sont étudiées. Il a été montré que des interphases dégradées provoquent une anisotropie apparente des modules mesurés pour le joint de colle. Cette anisotropie a été quantifiée à l'aide de deux paramètres β1 et β2 dont les valeurs permettent de révéler la qualité des interphases. Ensuite, les modules élastiques (ou raideurs kL et kT) des interphases ont été estimés, en supposant les propriétés de l'adhésif connues. On montre que leurs valeurs sont maximales lorsque l'adhésion est nominale, et qu’elles diminuent franchement lorsque l'adhésion est dégradée, mais dans des proportions différentes. Des mesures de la contrainte à rupture, réalisées sur des échantillons préparés dans les mêmes conditions, corroborent la chute des modules des interphases. La seconde méthode est adaptée à des échantillons collés avec un recouvrement partiel. Elle es tbasée sur la mesure du coefficient de transmission d'ondes de Lamb se propageant d'un substrat à l'autre, à travers la zone de recouvrement. Une étude de sensibilité numérique (par éléments finis) des coefficients de transmission des modes de Lamb a montré que les propriétés mécaniques des interphases (modélisées par des raideurs surfaciques) peuvent être évaluées si les autres caractéristiques de l’assemblage sont connues. Des mesures expérimentales de ces coefficients de transmission ont ensuite été réalisées avec deux échantillons. L’un d’eux possède des interphases à adhésion nominale et l’autre des interphases dégradées. Une confrontation entre les résultats des mesures obtenus pour les différents modes et les simulations numériques permet de déterminer les valeurs des raideurs d’interfaces pour chaque échantillon. Là encore, il est observé qu’une mauvaise adhésion se traduit par des valeurs faibles des raideurs d’interfaces, qui peuvent être quantifiées, cette fois,grâce aux ondes ultrasonores guidées. / The aim of this thesis is to develop NDT ultrasonic methods for the evaluation of the adhesion at interfaces in bonded joints.To address this problem, the assemblies are made of aluminum substrates (isotropic, elastic) and epoxy adhesive (isotropic,viscoelastic). Depending on the geometry of the studied assemblies, two methods are proposed to obtain quantitativeinformation on the adhesion level. The first method is suitable for three-layered plate-like samples. It consists in analyzingthe transmission of bulk ultrasonic plane waves through the assembly immersed in water. The consequences of a inapropriatesurface treatment of the substrates on the measurement of viscoelastic moduli of the joint are studied. It has been shown thatdegraded interphases cause an apparent anisotropy of the measured elastic moduli of the joint. This anisotropy was quantifiedusing two parameters β1 and β2 whose values can reveal the quality of the interphases. Then, the elastic moduli (or stiffnesseskL and kT) of the interphases were estimated, assuming that the adhesive layer properties are known. It was shown that theirvalues are higher when the adhesion is nominal, and are strongly decreased when the adhesion is degraded. Measurements ofthe mechanical strength, on samples prepared under the same conditions, confirmed the drops in these elastic moduli. Thesecond method is more suitable for lap joint samples. It is based on the Lamb wave transmission coefficient measured fromone substrate to the other, across the overlap zone. A numerical sensitivity analysis (finite element model) of the transmissioncoefficients of Lamb waves showed that the mechanical properties of the interphases (modeled by interfacial stiffnesses) canbe evaluated if the other characteristics of the assembly are well known. Experimental measurements of the transmissioncoefficients were then performed on two samples. One of them has interphases with nominal adhesion and the other hasdegraded interphases. A comparison between the measured results obtained for the different modes and numericalsimulations was used to determine the values of the interfacial stiffnesses for each sample. Again, it was observed that pooradhesion leads to low values of the interfacial stiffnesses of the interphases, that can be quantified using guided ultrasonicwaves.

The introduction of a nanoscopic reinforcing phase to a polymer matrix offers great possibilities of obtaining improved properties, enabling applications outside the boundaries of traditional composites. The majority of the work in this thesis has been devoted to polymer/clay nanocomposites in coating applications, using the hydroxyl-functional hyperbranched polyester Boltorn® as matrix and montmorillonite clay as nanofiller. Nanocomposites with a high degree of exfoliation were readily prepared using the straightforward solution-intercalation method with water as solvent. Hard and scratch-resistant coatings with preserved flexibility and transparency were obtained, and acrylate functionalization of Boltorn® rendered a UV-curable system with similar property improvements. In order to elucidate the effect of the dendritic architecture on the exfoliation process, a comparative study on the hyperbranched polyester Boltorn® and a linear analogue of this polymer was performed. X-ray diffraction and transmission electron microscopy confirmed the superior efficiency of the hyperbranched polymer in the preparation of this type of nanocomposites. Additionally, an objective of this thesis was to investigate how cellulose nanofibers can be utilized in high performance polymer nanocomposites. A reactive cellulose “nanopaper” template was combined with a hydrophilic hyperbranched thermoset matrix, resulting in a unique nanocomposite with significantly enhanced properties. Moreover, in order to fully utilize the great potential of cellulose nanofibers as reinforcement in hydrophobic polymer matrices, the hydrophilic surface of cellulose needs to be modified in order to improve the compatibility. For this, a grafting-from approach was explored, using ring-opening polymerization of ε-caprolactone (CL) from microfibrillated cellulose (MFC), resulting in PCL-modified MFC. It was found that the hydrophobicity of the cellulose surfaces increased with longer graft lengths, and that polymer grafting rendered a smoother surface morphology. Subsequently, PCL-grafted MFC film/PCL film bilayer laminates were prepared in order to investigate the interfacial adhesion. Peel tests demonstrated a gradual increase in the interfacial adhesion with increasing graft lengths. / QC20100621

In this thesis, the focus has been on micro-mechanical mechanisms in polymer-based materials and structures. The first part of the thesis treats length-scale effects on polymer materials. Experiments have showed that the smaller the specimen, the stronger is the material. The length-scale effect was examined experimentally in two different polymers materials, polystyrene and epoxy. First micro-indentations to various depths were made on polystyrene. The experiments showed that length-scale effects in inelastic deformations exist in polystyrene. It was also possible to show a connection between the experimental findings and the molecular length. The second experimental study was performed on glass-sphere filled epoxy, where the damage development for tensile loading was investigated. It could be showed that the debond stresses increased with decreasing sphere diameter. The debonding grew along the interface and eventually these cracks kinked out into the matrix. It was found that the length to diameter ratio of the matrix cracks increased with increasing diameter. The experimental findings may be explained by a length-scale effect in the yield process which depends on the strain gradients. The second part of the thesis treats mechano-sorptive creep in paper, i.e. the acceleration of creep by moisture content changes. Paper can be seen as a polymer based composite that consists of a network of wood fibres, which in its turn are natural polymer composites. A simplified network model for mechano-sorptive creep has been developed. It is assumed that the anisotropic hygroexpansion of the fibres leads to large stresses at the fibre-fibre bonds when the moisture content changes. The resulting stress state will accelerate creep if the fibre material obeys a constitutive law that is non-linear in stress. Fibre kinks are included in order to capture experimental observations of larger mechano-sorptive creep effects in compression than in tension. Furthermore, moisture dependent material parameters and anisotropy are taken into account. Theoretical predictions based on the developed model are compared to experimental results for anisotropic paper both under tensile and compressive loading at varying moisture content. The important features in the experiments are captured by the model. Different kinds of drying conditions have also been examined. / QC 20100910

The present work was initiated to investigate the surface- and interfacial phenomena for iron and slag/iron systems. The aim was to understand the mechanism of the effect of surface active elements on surface and interfacial properties. In the present work, the adsorption of oxygen and sulfur on iron surface as well as adatom surface movements were studied based on the ab initio method. BCC iron melting phenomena and sulfur diffusion in molten iron were investigated by Monte Carlo simulations. The impact of oxygen potential on interfacial mass transfer was carried out by X-ray sessile drop method. Firstly, the structural, electronic and magnetic properties as well as thermodynamic stability were studied by Density functional theory (DFT). The hollow site was found to be the most stable adsorption site both for oxygen and sulfur adsorbed on iron (100) surface, which is in agreement with the experiment. The relaxation geometries and difference charge density of the different adsorption systems were calculated to analyze the interaction and bonding properties between Fe and O/S. It can be found that the charge redistribution was related to the geometry relaxation. In addition, the sulfur coverage is considered from a quarter of one monolayer (1ML) to a full monolayer. It was found that the work function and its change Δφ increased with S coverage, in very good agreement with experiment. Due to a recent discussion regarding the influence of charge transfer on Δφ, it is shown in the present work that the increase in Δφ can be explained by the increasing surface dipole moment as a function of S coverage. S strongly interacts with the surface Fe layer and decreases the surface magnetic moment as the S coverage increases. Secondly, a two dimensional (2D) gas model based on density functional calculations combined with thermodynamics and statistical physics, was proposed to simulate the movement of the surface active elements, viz. oxygen and sulfur atoms on the Fe(100) surface. The average velocity of oxygen and sulfur atoms was found to be related to the vibration frequencies and energy barrier in the final expression developed. The calculated results were based on the density function and thermodynamics & statistical physics theories. In addition, this 2D gas model can be used to simulate and give an atomic view of the complex interfacial phenomena in the steelmaking refining process. A distance dependent atomistic Monte Carlo model was developed for studying the iron melting phenomenon as well as effect of sulfur on molten iron surface. The effect of boundary conditions on the melting process of an ensemble of bcc iron atoms has been investigated using a Lennard-Jones distance dependent pair potential. The stability of melting process was energetically and spatially analyzed under fixed wall and free surface conditions and the effects of short and long-range interactions were discussed. The role of boundary conditions was significantly reduced when long-range interactions were used in the simulation. This model was further developed for investigating the effect of sulfur on molten iron surface. A combination of fixed wall and free surface boundary condition was found to well-represent the molten bath configuration while considering the second nearest neighbor interactions. Calculations concerning the diffusion of sulfur on molten surface were carried out as a function of temperature and sulfur concentration. Our results show that sulfur atoms tended to diffuse away from the surface into the liquid bulk and the diffusion rate increased by increasing temperature. Finally, impact of oxygen potential on sulfur mass transfer at slag/metal interface, was carried out by X-ray sessile drop method. The movement of sulfur at the slag/metal interface was monitored in dynamic mode at temperature 1873 K under non-equilibrium conditions. The experiments were carried out with pure iron and CaO-SiO2-Al2O3-FeO slag (alumina saturated at the experimental temperature) contained in alumina crucibles with well-controlled partial pressures of oxygen and sulfur. As the partial pressure of oxygen increased, it was found that interfacial velocity as well as the oscillation amplitude increased. The thermo-physical and thermo-chemical properties of slag were also found to influence interfacial velocity. / QC 20101123

This study was conducted to determine how the structure and surface chemistry of bulk CaCO3 differs from that of nanometer-sized CaCO3 and then to determine rate, extent and mechanisms of As adsorption on various synthetic CaCO3 materials. Additionally, we sought to devise a chemical CaCO3 precipitate that approximates biogenic CaCO3. The bulk CaCO3 precipitation was performed by using a solution that was highly oversaturated so that large CaCO3 precipitates rapidly form. Two different methods were employed for the synthesis of nanometer size CaCO3 i) an in situ deposition technique and ii) an interfacial reaction (water in oil emulsion). Mineral characterization of all CaCO3 precipitates was done with Nitrogen Porosimetry (Brunauer Emmett Teller method), particle size analysis, X-ray diffraction and Fourier Transform Infrared/ Fourier Transform Raman spectroscopy. The principal objective of the research was to assess the overall reactivity of As(III) and As(V) with different synthetic CaCO3 minerals. This was accomplished by i) running adsorption isotherms (varying As concentration), ii) measuring pH envelopes (varying pH at a fixed concentration) and iii) kinetic experiments (varying reaction time). Also, electrophoretic mobility experiments were performed in the presence of As(III) and As(V), and these studies revealed that As(III) forms stronger inner-sphere complexes with CaCO3 than As(V). Also, it was found that nanometer-sized CaCO3 prepared via deposition formed stronger inner-sphere complexes with As oxyanions (q = 5.26 µmol/m2) compared to either nano-sized CaCO3 from interfacial reactions (q = 4.51 µmol/m2) or bulk CaCO3 (q = 4.39 µmol/m2).<p> The PEG-based nano CaCO3 prepared by an in-situ deposition technique presents a novel and readily available synthesis route that can be used as proxy for the biogenic CaCO3 known to be present in many different environmental conditions. The results of this study suggest that CaCO3 can be used as a sorbent for As in groundwater.

In this work, homojunction interfacial workfunction internal photoemission (HIWIP) detectors based on GaAs, and heterojunction interfacial workfunction internal photoemission (HEIWIP) detectors based mainly on the Gallium Arsenide/Aluminum Gallium Arsenide material system are presented. Design principles of HIWIP and HEIWIP detectors, such as free carrier absorption, photocarrier generation, photoemission, and responsivity, are discussed in detail. Results of p-type HIWIPs based on GaAs material are presented. Homojunction detectors based on p-type GaAs were found to limit their operating wavelength range. This is mainly due to band depletion arising through carrier transitions from the heavy/light hole bands to the split off band. Designing n-type GaAs HIWIP detectors is difficult as it is strenuous to control their workfunction. Heterojunction detectors based on Gallium Arsenide/Aluminum Gallium Arsenide material system will allow tuning their threshold wavelength by adjusting the alloy composition of the Aluminum Gallium Arsenide/Gallium Arsenide barrier, while keeping a fixed doping density in the emitter. The detectors covered in this work operate from 1 to 128 micron (300 to 2.3 THz). Enhancement of detector response using resonance cavity architecture is demonstrated. Threshold wavelength extension of HEIWIPs by varying the Al composition of the barrier was investigated. The threshold limit of approximately 3.3 THz (92 micron), due to a practical Al fraction limit of approximately 0.005, can be overcome by replacing GaAs emitters in Gallium Arsenide/Aluminum Gallium Arsenide HEIWIPs with Aluminum Gallium Arsenide/Gallium Arsenide emitters. As the initial step, terahertz absorption for 1 micron-thick Be-doped Aluminum Gallium Arsenide epilayers (with different Al fraction and doping density) grown on GaAs substrates was measured. The absorption probability of the epilayers was derived from these absorption measurements. Based on the terahertz absorption results, an Aluminum Gallium Arsenide/Gallium Arsenide HEIWIP detector was designed and the extension of threshold frequency (f0) to 2.3 THz was successfully demonstrated. In a different study, switching in Gallium Arsenide/Aluminum Gallium Arsenide heterostructures from a tunneling dominated low conductance branch to a thermal emission dominated high conductance branch was investigated. This bistability leads to neuron-like voltage pulses observed in some heterostructure devices. The bias field that initiates the switching was determined from an iterative method that uses feedback information, such as carrier drift velocity and electron temperature, from hot carrier transport. The bias voltage needed to switch the device was found to decrease with the increasing device temperature.

This study was conducted to determine how the structure and surface chemistry of bulk CaCO3 differs from that of nanometer-sized CaCO3 and then to determine rate, extent and mechanisms of As adsorption on various synthetic CaCO3 materials. Additionally, we sought to devise a chemical CaCO3 precipitate that approximates biogenic CaCO3. The bulk CaCO3 precipitation was performed by using a solution that was highly oversaturated so that large CaCO3 precipitates rapidly form. Two different methods were employed for the synthesis of nanometer size CaCO3 i) an in situ deposition technique and ii) an interfacial reaction (water in oil emulsion). Mineral characterization of all CaCO3 precipitates was done with Nitrogen Porosimetry (Brunauer Emmett Teller method), particle size analysis, X-ray diffraction and Fourier Transform Infrared/ Fourier Transform Raman spectroscopy. The principal objective of the research was to assess the overall reactivity of As(III) and As(V) with different synthetic CaCO3 minerals. This was accomplished by i) running adsorption isotherms (varying As concentration), ii) measuring pH envelopes (varying pH at a fixed concentration) and iii) kinetic experiments (varying reaction time). Also, electrophoretic mobility experiments were performed in the presence of As(III) and As(V), and these studies revealed that As(III) forms stronger inner-sphere complexes with CaCO3 than As(V). Also, it was found that nanometer-sized CaCO3 prepared via deposition formed stronger inner-sphere complexes with As oxyanions (q = 5.26 µmol/m2) compared to either nano-sized CaCO3 from interfacial reactions (q = 4.51 µmol/m2) or bulk CaCO3 (q = 4.39 µmol/m2).<p> The PEG-based nano CaCO3 prepared by an in-situ deposition technique presents a novel and readily available synthesis route that can be used as proxy for the biogenic CaCO3 known to be present in many different environmental conditions. The results of this study suggest that CaCO3 can be used as a sorbent for As in groundwater.