Escoamentos gás-líquido assim como escoamento líquido-líquido-gás em duto de geometria anular estão presentes em muitas aplicações industriais, por exemplo, em poços de petróleo direcionais. No entanto, até mesmo características globais de escoamento gás-líquido nessa geometria, como os padrões de escoamento ou gradiente de pressão, não são ainda totalmente compreendidas. E ainda, informações são escassas quando se refere a escoamento trifásico nessa geometria, cuja aplicação está relacionada ao fenômeno de inversão de fase, que é de extrema importância não apenas para ao setor petrolífero, como para a indústria alimentícia. O presente estudo experimental tem como objetivo avaliar o escoamento líquido-gás, apresentar dados inéditos de escoamento gás-líquido para três viscosidades de óleo, além de avaliar o fenômeno de inversão de fase em escoamento ascendente vertical em duto anular de grande diâmetro. Um aparato experimental inclinável com 10,5 m de comprimento foi projetado e construído para este trabalho. As dimensões radiais do duto anular estão em escala real, conforme se verifica em poços de petróleo e gás. A investigação em escoamento gás-líquido foi conduzida utilizando água, óleo e ar comprimido como fluidos de trabalho em escoamento ascendente vertical em duas geometrias: (i) um tubo com diâmetro de 95 mm e (ii) um duto de configuração anular e concêntrico, com diâmetro hidráulico de valor igual ao diâmetro do tubo. A avaliação do fenômeno de inversão de fase em escoamento trifásico foi conduzida em condições equivalentes em três geometrias: (i) tubo vertical menor com diâmetro de 50 mm, (ii) tubo com diâmetro de 95 mm e (iii) um duto anular concêntrico. Padrões de escoamento, queda de pressão e fração volumétrica de fase foram obtidos para ambos os escoamentos gás-líquido e líquido-líquido-gás. Os dados coletados nesse trabalho são de grande importância para o desenvolvimento de novas correlações de fechamento, que são essenciais para o projeto otimizado de poços de petróleo. Dados inéditos de escoamento bifásico óleo-gás são apresentados, bem como um estudo pioneiro em inversão de fase em escoamento trifásico com velocidade superficial de gás e viscosidade do óleo elevadas. / Two-phase flows as well as three-phase flow in annular geometry are present in many industrial applications, for example in oil directional wells. However, even global characteristics of gas-liquid flow in this geometry, such as flow patterns and pressure gradient are not fully understood. Moreover, information is scarce when it refers to three-phase flow in this geometry, which application is related to the phase inversion phenomenon, which is of extreme importance and not only for the oil industry. This experimental study aims to evaluate the liquid-gas flow, present new data from gas-liquid flow for three oil viscosities and evaluate the phase inversion phenomenon in vertical upward flow in large diameter annular duct. An experimental apparatus with 10.5 m length was designed and built for this work. The radial dimensions of the annular duct are similar to full scale, as observed in oil and gas wells. The investigation into gas-liquid flow was conducted using water, oil and compressed air as working fluids in an ascending vertical flow in two geometries: (i) a tube with 95 mm diameter and (ii) a concentric annular duct with hydraulic diameter equivalent to the tube internal diameter. The evaluation of the phase inversion phenomenon in three-phase flow was conducted under equivalent conditions for three geometries: (i) smaller vertical tube with 50 mm of internal diameter, (ii) tube with 95 mm of internal diameter and (iii) concentric annular duct with hydraulic diameter of 95 mm. Flow patterns, pressure drop and volumetric phase fraction were obtained for both gas-liquid and gas-liquid-liquid flows. The data collected in this study are of great importance for the development of new closing correlations, which are essential for the optimized design of oil wells. New two-phase flow data for three oil viscosities, not found in the literature, are presented as well as a pioneer study in three-phase-flow phase inversion with high oil viscosity and high superficial gas velocity.

Ces travaux de thèse portent sur la caractérisation thermique à l’échelle micrométrique d’un alliage à base de tellure lorsque ce matériau se trouve à l’état fondu, à haute température. À cette fin, une cellule innovante d’emprisonnement du matériau fondu a été conçue, et mise en place. Des structures de tellure au volume du microlitre ont été déposées sur un substrat de silicium et recouverts par la suite d’une couche de protection capable de les emprisonner dans une matrice : silice amorphe et alumine amorphe. La technique de la Radiométrie Photothermique Modulée a été utilisée pour étudier les propriétés thermiques de ce type de cellules et de ces constituants. La résistance thermique de dépôt a été ainsi estimée en utilisant un modèle d’étude des transferts de la chaleur utilisant le formalisme des impédances thermiques. Ceci nous a permit dans le cas de l’alumine amorphe de déterminer sa conductivité thermique et la résistance thermique de contact avec le substrat jusqu’à 600°C. Un long processus de conception, de mesure et d’analyse a été nécessaire afin d’obtenir une cellule capable de résister aux contraintes des hautes températures. À l’heure actuelle seule la caractérisation thermique jusqu’à 300°C a été possible à cause de l’instabilité mécanique de ce dépôt hétérogène. Ceci a été confirmé par des caractérisations physico-chimiques par techniques XRR, XRD et SEM. / This thesis is devoted to the thermal characterization of molten materials, namely chalcogenide glass-type tellurium alloys, at the micrometer scale. An experimental setup of Photothermal Radiometry (PTR), formerly developed for solid state measurements, has been adapted for this purpose. Using MOCVD technique, a random lattice of sub-micrometric tellurium alloy structures is grown on a thermally oxidized silicon substrate. These structures are then embedded in a protective layer (silica or alumina) to prevent evaporation during melting. Measurements are then performed from room temperature up to 650°C. SEM and XRD measurements performed after annealing show that these samples withstand thermal stress only up to 300°C. The coating’s thermal boundary resistance is estimated by a heat transfer model based on the thermal impedance formalism. Moreover, the thermal conductivity and thermal boundary resistance of thin amorphous alumina by low temperature ALD are measured from the room temperature to 600°C.

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No description available.

X-ray computed tomography is a nondestructive method for 3D imaging of inner structure of objects; it is, however, restricted by absorption properties of materials. With phase contrast imaging, observation of samples with low absorption or with parts with similar absorption becomes possible. For a long time, phase contrast imaging has been restricted to synchrotron radiation sources or special techniques due to requirement of spatial coherence of radiation. Along with recent development of X-ray micro and nanofocus tubes and X-ray detectors a phase contrast imaging becomes available also with laboratory sources. In this work an overview of phase contrast imaging methods is given, with an emphassis on propagation based method. Examples of this method and application of phase retrieval algorithm on samples from RIGAKU Nano3DX and GE phoenix v|tome|x L240 stations within Laboratory of X-ray micro and nanotomography CEITEC BUT are shown.

Cette thèse vise à démontrer la pertinence de la chromatographie en phase supercritique (SFC) et de son couplage à la spectrométrie de masse tandem haute résolution (HRMS/MS) quant à l’étude de produits naturels en mélange complexe. Pour y parvenir trois projets ont été menés en parallèle.Une méthode d’analyse structurale ciblée sur les acétogénines d’Annonaceae a été développée. Le recours à une cationisation post-colonne par des sels de lithium a permis d’obtenir les informations structurales recherchées. Des études ont également été menées quant à l’influence de la nature du cation sur la conformation de l’adduit formé et les voies de fragmentation observées.Une séparation de composés polaires et ionisables a également été mise au point à travers l’étude des nucléosides modifiés de l’ARN. La SFC-HRMS permet la séparation et l’étude d’un grand nombre de modifications et constitue donc un nouvel outil d’analyse pour le biologiste.Pour finir, une étude en lipidomique globale a également été entreprise. Bien que préliminaires, les premiers résultats semblent très prometteurs avec pour but de développer des méthodes d’analyses non ciblées associés à des outils d’annotation automatique.Pour chaque projet, la pertinence de nos approches a été vérifiée par l’étude d’échantillons réels et complexes permettant de tirer des conclusions réalistes quant aux possibilités de la SFC-HRMS/MS pour l’étude de composés naturels. / This PhD work aims to demonstrate the relevance of supercritical fluid chromatography (SFC) and its hyphenation to high resolution tandem mass spectrometry (HRMS/MS) in the field of natural product analysis. Three different research projects were carried out.A new strategy for structural analysis of Annonaceous acetogenins was developed by SFC and targeted HRMS/MS including post-column lithium cationisation to give access to the relevant structural information. Investigations were conducted to observe the influence of cations onto the gas-phase conformation and fragmentation pathways.A separation of polar and ionisable compounds was also developed using modified nucleosides from RNA as models. The SFC-HRMS method led to the separation and analysis of several tens of modifications and demonstrated to be a new performant analytical tool for biologists.Finally, a global lipidomic approach was optimized. Preliminary results look compatible with the development of untargeted approaches using automatic annotation tools.For each project, the relevance of our work was evaluated analyzing complex samples to obtain a realistic point of view of the capabilities for SFC-HRMS/MS systems for natural product studies.

The saturation of the near surface layers of metals with different elements is a powerful tool to change their surface properties. In this work, structure and transport changes induced by incorporation of large amounts of nitrogen at moderate temperatures (∼370−430°C) in austenitic stainless steel are investigated. The structural study of the plasma nitrided ASS has been carried out using a combination of global (X-ray diffraction, nuclear reaction analysis) and local probe techniques (Mossbauer, X-ray absorption near edge structure, extended X-ray absorption fine structure spectroscopies). It reveals that nitriding at moderate temperatures (∼400°C) results in the nitrided layer with Fe, Cr and Ni being in different local chemical environments: Cr in the CrN-like state, Fe in the Fe4N-like state, Ni in the metallic state. The results demonstrate that the incorporation of interstitial nitrogen destabilizes homogeneous distribution of the ASS constituents, which leads to the segregation of the elements into small zones rich in Cr and Ni and provide strong evidence that the decomposition is of a spinodal nature. These experimental findings contradict the widely accepted view that the phase formed during nitriding at moderate temperatures is a homogeneous supersaturated nitrogen solid solution. The nitrogen atomic transport study has been carried out by using ion beam nitriding of single-crystalline stainless steel, and the issues of the influence of the crystalline orientation, nitriding temperature, ion flux and ion energy are addressed. The diffusion coefficients have been extracted from the fitting of the nitrogen depth profiles by using the trapping-detrapping model. It is shown that the crystalline orientation plays a significant role in nitrogen diffusion: the penetration depth is largest, intermediate and lowest for the (001), (110) and (111) orientation, respectively. The pre-exponential factor D0 varies by two orders of magnitude depending on the orientation, while the activation energy E is similar (∼1.1 eV) for the (111) and (110) orientations and higher for the (001) orientation (∼1.4 eV). It is found that the nitrogen ion energy and the flux have the effect on the nitrogen transport in the bulk with higher energies (or fluxes) showing larger diffusion coefficients. The ion energy effect is more pronounced for the (001) than for the (111) orientation, while the flux effect is similar in both orientations. In addition, the diffusivity during post-nitriding thermal annealing without ion irradiation is found to be independent of the crystalline orientation. The observed radiation enhanced diffusion and anisotropy are discussed on the basis of nitrogen incorporation induced changes in the matrix structure (ASS decomposition and formation heterogeneous structure), ion bombardment induced effects (defects, localized vibrations) and correlated diffusion.

Actuellement, les codes de calcul de composants thermohydrauliques de réacteurs nucléaires du CEA et d'EDF utilisent des modèles physiques diphasiques de mélange à 3 ou 4 équations. Or, il existe un fort besoin industriel pour des modèles physiques plus sophistiqués tels que le modèle diphasique à 6 équations voire des modèles multichamps. Par ailleurs, le code système CATHARE du CEA, un des codes systèmes les plus utilisés aujourd'hui sur le plan international, utilise un modèle physique diphasique à 6 équations et un schéma numérique semi-implicite de type ICE à maillages décalés. Le schéma de CATHARE est connu pour sa robustesse dans une large gamme de configurations d'écoulement. En s'inspirant de l'expérience de CATHARE, on propose de mettre en œuvre un schéma volumes finis colocalisés de type « pressure based ». Le but est d'obtenir un décentrement des flux qui assure la robustesse du schéma tout en gardant une bonne précision. De plus, le fait de pouvoir utiliser des maillages colocalisés (structurés ou non-structurés) permet de traiter de différentes configurations complexes de cœur de réacteurs et de réaliser des calculs fin d'inter assemblage. Le schéma doit conserver exactement la masse et l'énergie et la solution numérique doit converger lorsque l'on raffine le maillage. Le schéma doit être capable de traiter des cas d'apparition et de disparition des phases, par exemple le cas de la colonne bouillante où il y a changement de phase dû au transfert de chaleur, des cas de tuyères avec changement de phase dû à un élargissement ou un rétrécissement brusque, ou de séparation de phase par gravité. En outre le schéma doit être capable de traiter des configurations de calcul à faible nombre de Mach, par exemple le cas du renoyage d'un cœur de réacteur. L'objet de la thèse consistera à développer une méthode Volumes Finis co-localisés (dans l'esprit de Ghidaglia et al.) et la direction d'investigation s'inspirera des travaux de Jeong et al. qui a conduit au code CUPID. Références. Ghidaglia, J. M., Kumbaro, A., & Le Coq, G. (2001). On the numerical solution to two fluid models via a cell centered finite volume method. European Journal of Mechanics-B/Fluids, 20(6), 841-867. Jeong, J. J., Yoon, H. Y., Cho, H. K., Kim, J., & Park, I. K. (2008). A semi-implicit numerical scheme for a transient two-fluid three-field model on an unstructured grid. International Communications in Heat and Mass Transfer, 35(5), 597-605. / Currently, there is a strong industrial need for sophisticated physical models such as the two-phase model with 6 equations or multi-field models for the thermo-hydraulic calculation of nuclear reactor components. In addition, the system code CATHARE of CEA, one of the most utilized system codes at the international level, employs a two-phase 6 equations and a semi-implicit numerical scheme of ICE type on staggered grids. The code CATHARE is known for its robustness in a wide range of flow configurations. Drawing on the experience of CATHARE, we propose to implement a collocated finite volume pressure based scheme. The aim is to obtain a decentering of flux which ensures the robustness of the scheme while keeping good accuracy. In addition, being able to use collocated grids (structured or unstructured) can handle different complex configurations. The scheme should conserve exactly the mass and energy and the numerical solution needs to converge when the mesh is refined. The scheme should be able to handle cases of phase appearance and disappearance, for example in the case of boiling column where phase change is due to heat transfer, the case of nozzles with phase change due to a widening or abrupt narrowing, or phase separation by gravity. In addition the scheme should be capable of calculation configurations at low Mach number. The purpose is to develop a co-located Finite Volume method (in the spirit of Ghidaglia et al.) And direction of investigation is build on work of Jeong et al. which led to CUPID code. References: Ghidaglia, J. M., Kumbaro, A., & Le Coq, G. (2001). On the numerical solution to two fluid models via a cell centered finite volume method. European Journal of Mechanics-B/Fluids, 20(6), 841-867. Jeong, J. J., Yoon, H. Y., Cho, H. K., Kim, J., & Park, I. K. (2008). A semi-implicit numerical scheme for a transient two-fluid three-field model on an unstructured grid. International Communications in Heat and Mass Transfer, 35(5), 597-605.

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Patman is a fluorescent membrane probe related to Laurdan. The structural distinctions between the two probes are the lengths of the aliphatic tails (eleven carbons in Laurdan and fifteen in Patman) and the presence of a trimethylammonium group on Patman that produces a positively-charged head. Preliminary studies exploring Patman as a probe to detect membrane properties during apoptosis revealed that the fluorescence intensity of two edges of the emission spectrum (435 and 500 nm) stabilizes at different rates as the probe binds to the cell membrane. To test whether these differences represent dissimilarities in probe binding to ordered and disordered domains, experiments were conducted to monitor Patman equilibration with bilayers composed of various mixtures of saturated and unsaturated phosphatidylcholines at temperatures above, at, and below the main thermotropic phase transition. In general, Patman equilibrated more rapidly with bilayers in the liquid-disordered phase than in the solid-ordered phase. With solid phase membranes, the fluorescence stabilized faster at 500 nm than at 435 nm. Similar, yet more subtle, results occurred in the lipid disordered phase. In contrast, the situation was reversed at the phase transition temperature; equilibration was faster at 435 nm than at 500 nm. To determine whether these results reflected specific properties of Patman, the experiments were repeated with Laurdan, and several distinctions were observed. First, equilibration with solid phase lipids was faster than for Patman and not different from equilibration with the fluid phase. Second, differences in rates between the two wavelengths were less than with Patman for solid phase membranes but greater than with Patman for melted bilayers. Third, at the phase transition temperature, the difference in equilibration rates was the opposite of the result obtained with Patman. Computer simulations were used to assist with interpretation of these results. The data suggest that both probes bind superficially to the membrane before incorporating among the lipid molecules. Once within the membrane, Patman localizes to at least two distinct depths within the bilayer. Probe molecules in the shallow, more hydrated position favor 500 nm emission and those occupying a deeper, dehydrated position emit primarily at 435 nm. Laurdan's equilibration additionally represents movement of the probe between leaflets and multiple bilayers.