Cette thèse porte sur l'étude de la diffusion des asphaltènes dans les catalyseurs d'hydrotraitement. La revue bibliographique met en évidence d'importantes lacunes dans les connaissances, d'une part sur l'impact sur les processus de diffusion des fortes températures rencontrées dans les procédés de raffinage et d'autre part, sur la dynamique des asphaltènes dans les réseaux poreux des catalyseurs. Ainsi, une double approche expérimentale a été développée, s'articulant dans un premier temps autour d'une étude de diffusion et d'adsorption dans des conditions proches de celles des procédés, puis dans un second temps une étude de la diffusion en milieu confiné par Résonance Magnétique Nucléaire (RMN) à travers des techniques de mesure de temps de relaxation ainsi que la RMN à gradient de champ pulsé (DOSY). Les résultats obtenus montrent que même à haute température, la diffusion des asphaltènes dans les catalyseurs est un processus très lent, plusieurs jours étant nécessaires pour que le coeur soit atteint. Les techniques de RMN utilisées montrent le caractère fortement confiné des asphaltènes dans le milieu poreux ainsi que de fortes interactions entre les asphaltènes et la surface alumine des catalyseurs, à l'origine d'une très faible dynamique bien que le processus d'adsorption soit dans une certaine mesure quand même réversible / This PhD thesis deals with the diffusion of asphaltenes in hydrotreatment catalysts. The literature review shows weaknesses in knowledge about both, how does the high temperature impact the diffusion phenomena and, what is the dynamic of asphaltenes in the porous media. Therefore, a double experimental approach has been developed, first the diffusion and the adsorption of asphaltenes near process conditions have been studied, and then the dynamic in porous media has been studied by Nuclear Magnetic Resonance (NMR) technics which involves relaxation times measurements and Diffusion Ordered SpectroscopY (DOSY). Results show that even at high temperature, the diffusion of asphaltenes in catalysts is relatively slow; several days are needed to reach the center. The NMR results highlight a slow dynamic of asphaltenes in the porous media, since they are in confined environment and they are in strong interactions with alumina, even if the adsorption is to a certain extent reversible

Au cours de cette thèse, réalisée dans le cadre du projet Iseult/INUMAC, nous avons réalisé un travail de développements méthodologiques et technologiques, dans l'optique de permettre à l'IRM de devenir un outil quantitatif pour l'imagerie moléculaire de pathologies cérébrales sur des modèles rongeurs. Pour cela, nous avons développé une stratégie de quantification, utilisant des séquences de cartographie T1 et T2, pour acquérir des cartes de concentration en agents de contraste paramagnétiques et superparamagnétiques avec une excellente sensibilité, une résolution spatiale élevée, ainsi qu'une résolution temporelle compatible avec l'imagerie in vivo. La méthodologie générale que nous avons mise en place lors de ces travaux de thèse nous a permis d'aborder un certain nombre de problématiques propres à l'imagerie moléculaire de pathologies cérébrales par IRM. Dans un premier temps, nous nous sommes intéressés à l'imagerie d'un biomarqueur endovasculaire de l'angiogenèse tumorale sur un modèle de glioblastome cérébral induit chez des souris immuno-déprimées. Nous avons étudié la fixation d'une émulsion paramagnétique, fonctionnalisée par l'ajout de peptides RGD, sur l'intégrine alpha-nu-beta-3 surexprimée à la surface des cellules endothéliales de capillaires tumoraux. Nous nous sommes ensuite intéressés à la délivrance des agents de contraste aux tissus cérébraux. À l'aide d'un protocole optimisé d'ouverture de la barrière hématoencéphalique (BHE) par ultrasons focalisés sous IRM, nous avons étudié les caractéristiques de cette ouverture, ainsi que la dynamique de refermeture sur des modèles de rats et souris sains. Dans une autre étude, la mesure du coefficient de diffusion apparent d'agents de contraste dans les tissus cérébraux de rats sains nous a permis d'évaluer le temps nécessaire à ces agents de tailles différentes pour atteindre leurs cibles, une fois la BHE franchie. Ces caractéristiques représentent des informations capitales dans le cadre de la délivrance d'agents de contraste aux tissus cérébraux. Ils sont en effet susceptibles d'intéresser les industriels pharmaceutiques pour optimiser la conception d'agents diagnostiques et thérapeutiques dédiés aux pathologies cérébrales. / In this thesis, which was part of the Iseult/INUMAC project, we propose several methodological and technological developments aiming to allow MRI to become a quantitative tool for molecular imaging of brain pathologies. To do so, we developed a quantification strategy based on T1 and T2 mapping sequences in order to acquire quantitative concentration maps of paramagnetic and superparamagnetic contrast agents with excellent sensitivity, high spatial resolution and temporal resolution compatible with in vivo imaging. This general methodology allowed us to address several issues specific to molecular imaging of cerebral pathologies using MRI. First, we focused on the imaging of a vascular biomarker of tumor angiogenesis on a glioblastoma mouse model. We studied the binding of a paramagnetic emulsion, functionalized using RGD peptides, on alpha-nu-beta-3 integrin over-expressed at the surface of freshly formed endothelial cells. Then, we focused on the delivery of contrast agents to brain parenchyma. A system was developed and optimized to open transiently and non-invasively rodents blood brain barrier (BBB) using focalized ultrasound monitored by MRI. The BBB opening features and closure dynamics induced by this protocol were extensively characterized. In another study, we measured the apparent diffusion coefficient of contrast agents with different sizes in cerebral tissues of healthy rats. From these measures we could estimate the time necessary for these particles to reach their targets once the BBB is crossed. These parameters are highly valuable in the context of drug delivery to the brain. They might indeed be used by pharmaceutical industries to optimize the design of diagnostic and therapeutic agents dedicated to cerebral diseases.

Gallium nitride (GaN) has been targeted for use in high power (>30 W/mm) and high frequency (>160 GHz) application due to its wide band gap and its large break down field. One of the most significant advances in GaN devices has evolved from the AlGaN/GaN high electron mobility transistor (HEMT). As a result of the large power densities being applied to these devices there can develop intense hot spots near areas of highest electric field. The hot spot phenomenon has been linked to a decrease in device reliability through a range of degradation mechanisms. In order to minimize the effect that hot spot temperatures have on device reliability a detailed understanding of relevant transport mechanisms must be developed. This study focuses on two main aspects of phonon transport within GaN devices. The first area of focus was to establish an understanding of phonon relaxation times within bulk GaN. These relaxation times were calculated from an application of Fermi's Golden Rule and explicitly conserve energy and crystal momentum. This analysis gives insight into the details behind the macroscopic thermal conductivity parameter. Once relaxation times for GaN were established a multiscale phonon transport modeling methodology was developed that allowed the Boltzmann Transport Equation to be coupled to the energy equation. This coupling overcomes some computational limits and allows for nanoscale phenomena to be resolved within a macroscopic domain. Results of the transport modeling were focused on benchmarking the coupling method as well as calculating the temperature distribution within an operating 6 finger HEMT.

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The calculation of the electron–phonon coupling from first principles is computationally very challenging and remains mostly out of reach for systems with a large number of atoms. Semi-empirical methods, like density functional tight binding (DFTB), provide a framework for obtaining quantitative results at moderate computational costs. Herein, we present a new method based on the DFTB approach for computing electron–phonon couplings and relaxation times. It interfaces with PHONOPY for vibrational modes and DFTB+ to calculate transport properties. We derive the electron–phonon coupling within a non-orthogonal tight-binding framework and apply them to graphene as a test case.

This dissertation focuses on projects where optical techniques were employed to characterize novel materials, developing concepts toward next generation of devices. The materials that I studied included InAsP, InMnSb and InMnAs, and BT-BCN. I have employed several advanced time resolved and magneto-optical techniques to explore unexplored properties of these structures. The first class of the materials were the ternary alloys InAsP. The electron g-factor of InAsP can be tuned, even allowing for g=0, making InAsP an ideal candidate for quantum communication devices. Furthermore, InAsP shows promises for opto-electronics and spintronics, where the development of devices requires extensive knowledge of carrier and spin dynamics. Thus, I have performed time and polarization resolved pump-probe spectroscopy on InAsP with various compositions. The carrier and spin relaxation time in these structures were observed and demonstrated tunability to the excitation wavelengths, composition and temperature. The sensitivity to these parameters provide several avenues to control carrier and spin dynamics in InAsP alloys. The second project focused on the ferromagnetic narrow gap semiconductors InMnAs and InMnSb. The incorporation of Mn can lead to ferromagnetic behavior of InMnAs and InMnSb, and enhance the g-factors, making them ideal candidates for spintronics devices. When grown using Molecular Beam Epitaxy (MBE), the Curie temperature (textit{$T_c$}) of these structures is textless 100 K, however structures grown using Metalorganic Vapor phase Epitaxy (MOVPE) have textit{$T_c$} textgreater 300 K. Magnetic circular dichroism was performed on MOVPE grown InMnAs and InMnSb. Comparison of the experimental results with the theoretical calculations provides a direct method to map the band structure, including the temperature dependence of the spin-orbit split-off band to conduction band transition and g-factors, as well as the estimated sp-d electron/hole coupling parameters. My final project was on the lead-free ferroelectric BT-BCN. Ferroelectric materials are being investigated for high speed, density, nonvolatile and energy efficient memory devices; however, commercial ferroelectric memories typically contain lead, and use a destructive reading method. Reflectometry measurements were used in order to determine the refractive index of BT-BCN with varying thicknesses, which can provide a means to nondestructively read ferroelectric memory through optical methods. / Ph. D. / This dissertation focuses on the characterization of materials that are important for the next generation computer architecture through optical techniques. These materials include the ternary alloy InAsP, the ferromagnetic semiconductors InMnAs and InMnSb, and the lead-free ferroelectric BT-BCN. InAsP is a ternary alloy composed of the technologically important InAs and InP, and by changing the alloy composition, the band gap and g-factor can be tuned. This allows for InAsP to have band gaps within the communication band, which is important for fiber optic communications as well as infrared photodetectors. As the functionality of these devices depends on the carrier dynamics, I have performed pump-probe spectroscopy in order to probe the carrier and spin relaxation times of this material system. These relaxation times were found to vary with excitation wavelengths, allowing flexibility in the application of this material system for devices. InAs and InSb are attractive materials for device applications because they offer large electron g-factor, small effective masses, and high mobilities. With the incorporation of Mn, these materials can become ferromagnetic, allowing for their use in ferromagnetic memories as well as other possible devices. The theory of ferromagnetism in semiconductors relies on the interaction between the itinerant holes and the Mn ions, however, in narrow gap semiconductors there is a large band mixing between the conduction and valence band states, and thus the interaction between the conduction band electrons and the Mn is important. In this study, my measurements revealed several interband transitions, which allowed for the calculation of the coupling constants between the electrons, holes and the Mn. My final study involved the lead-free ferroelectric BT-BCN. Ferroelectric materials are ideal for fast, low power and nonvolatile memories; however, typical implementation utilizes materials that contain lead, and a destructive reading mechanism, requiring a rewrite step. Optical, nondestructive reading methods are being explored based off of the rotation of the polarization of light as it passes through the sample. As this requires knowledge of the refractive index, I performed reflectometry measurements in order to determine the refractive indices of several BT-BCN films.

Stimuli-responsive (stimuli-sensitive, intelligent, or smart) polymers are polymer materials which, after small external stimuli, evidently change their physical or chemical properties. Smart polymers can be classified according stimuli they respond to such as: temperature changes, mechanical stress, light irradiation, ultrasonic treatment, application of external magnetic as well as electric field, changes of pH, ionic strength, addition of the chemical agents and presence of biomolecules and bioactive molecules. Stimuli-responsive synthetic polymer systems has attracted considerable attention due to wide range of applications, i.e. controlled drug delivery and release systems, diagnostics, tissue engineering and 'smart' optical systems, as well as biosensors, microelectromechanical systems, coatings, and textiles. Among the types of stimuli for this dissertation temperature, pH and reactive oxygen species (ROS) responsive polymer systems were studied. In case of thermoresponsive polymers, when polymer chains are molecularly dissolved in a good solvent, changes (increasing or decreasing) of temperature result in insolubility (globular nanoparticles formation) of polymer chains, called temperature induced phase-separation. pH responsive polymers change properties such as: solubility, volume (gels),...

Das Transport- und Relaxationsverhalten verschiedener Quantenmodelle wird untersucht. Den ersten Teil der vorliegenden Arbeit bildet die Untersuchung der Transporteigenschaften von speziellen finiten modularen Quantensystemen bzgl. einer Boltzmann-Gleichung (BG). Diese Systeme, in denen unter bestimmten Bedingungen diffusiver Transport beobachtet werden kann, wurden mit verschiedenen Methoden zur Beschreibung von Quantentransport untersucht. Dabei zeigt sich, dass sich das diffusive Transportverhalten in diesen Systemen aus der zugrunde liegenden Schrödinger Dynamik heraus beschreiben lässt. Ob die diffusive Dynamik in diesen Systemen ebenfalls auf der Basis einer BG beschrieben werden kann, wird analytisch und numerisch untersucht. Im zweiten Teil wird die Relaxationsdynamik in quantenmechanischen Vielteilchensystemen untersucht. Speziell wird versucht, die Lebensdauern von angeregten Elektronen (Löchern) in Metallen, welche mit dem Fermi-See der Elektronen wechselwirken, mittels der zeitfaltungsfreien Projektionsoperator-Methode (TCL) zu bestimmen. Letztere liefert einen analytischen Ausdruck für die Dämpfungsrate (inverse Lebensdauer), welche temperaturabhängig ist und im Rahmen von Standard-Streuprozessen interpretiert werden kann. Um dieses analytische Ergebnis zu testen, wird es angewendet, um die Lebensdauern angeregter Elektronen (Löcher) in Aluminium zu bestimmen, für das ein Jellium Modell verwendet wird. Die Ergebnisse, die man über Monte-Carlo-Integration erhält, werden mit experimentellen und theoretischen Daten aus Selbstenergie-Rechnungen verglichen. Des Weiteren werden die Lebensdauern angeregter Elektronen in Kupfer ermittelt, für das ein Tight-Binding-Modell verwendet wird.

<p>In this study, we concentrate on spin-1/2 systems. A series of tools using the Liouville space method have been developed for simulating of NMR of arbitrary pulse sequences.</p> <p>We have calculated one- and two-spin symbolically, and larger systems numerically of steady states. The one-spin calculations show how SSFP converges to continuous wave NMR. A general formula for two-spin systems has been derived for the creation of double-quantum signals as a function of irradiation strength, coupling constant, and chemical shift difference. The formalism is general and can be extended to more complex spin systems.</p> <p>Estimates of transverse relaxation, R₂, are affected by frequency offset and field inhomogeneity. We find that in the presence of expected B₀ inhomogeneity, off-resonance effects can be removed from R₂ measurements, when ||omega||<= 0.5 gamma\,B₁ in Hahn echo experiments, when ||omega||<=gamma\,B₁ in CPMG experiments with specific phase variations, by fitting exact solutions of the Bloch equations given in the Lagrange form.</p> <p>Approximate solutions of CPMG experiments show the specific phase variations can significantly smooth the dependence of measured intensities on frequency offset in the range of +/- 1/2 gamma\,B₁. The effective R₂ of CPMG experiments when using a phase variation scheme can be expressed as a second-order formula with respect to the ratio of offset to pi-pulse amplitude.</p> <p>Optimization problems using the exact or approximate solution of the Bloch equations are established for designing optimal broadband universal rotation (OBUR) pulses. OBUR pulses are independent of initial magnetization and can be applied to replace any pulse of the same flip angles in a pulse sequence. We demonstrate the process to exactly and efficiently calculate the first- and second-order derivatives with respect to pulses. Using these exact derivatives, a second-order optimization method is employed to design pulses. Experiments and simulations show that OBUR pulses can provide more uniform spectra in the designed offset range and come up with advantages in CPMG experiments.</p> / Doctor of Philosophy (PhD)