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  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Computational simulation of urinary system

Hosseini, Ghazaleh January 2017 (has links)
The aim of the present study is to create a computational model of the ureteral system that accurately mimics its dynamic functionality. This model will be able to replicate the peristaltic movement of the ureter for a variety of physiological conditions. The objective of this research was met using our in-house fluid solid interaction model, known as coupled Cgles-Y-code in which the moving boundaries between the solid and fluid domain were replicated using a novel immersed boundary method. First, a comprehensive literature review on ureteral physiology was conducted with a focus on the anatomy of the ureter and theories behind mechanisms of ureteral peristaltic function in various physiological and pathological conditions. Next, the nonlinear tensile properties of the ureteral wall were integrated into the Y-code using the equivalent strain method and the resulting model was compared with a model with linear tensile properties. It was shown that the implementation of nonlinear tensile properties was more accurate and more closely matched the behaviour of the native ureteral wall. Next, the development of more anatomically accurate ureter model geometry was presented along with a variety of approaches to optimise the mesh resolution for this complex model. A new algorithm was then developed in order to model the Intra-Abdominal Pressure (IAP) into the Y-code. Next, two separate contraction models, constant radial and time-window-frame, were introduced. It was observed that a use of the time-window-frame contraction model coupled with the IAP algorithm exhibited a better agreement with the existing clinical data than the constant radial contraction model. Finally, a comprehensive study was conducted on the urodynamic responses when different pathological conditions are modelled. The results from using a linear tensile model, replicating an unhealthy condition, showed a high level of shear stress around the contraction lumen and a higher urine velocity in vicinity of the contraction region. In another scenario, a highly depressed amplitude of peristalsis, known to be a consequence of taking vasodilators, was simulated. It was shown that an inefficient contraction can increase the possibility of continuous reflux during the propagation of peristalsis.
2

Amélioration des propriétés physiques de matériaux de basse-dimensionnalité par couplage dans des hétérostructures Van der Waals / Enhancing physical properties of low dimensional materials by engineering its environment in composite Van der Waals heterostructures

Nayak, Goutham 18 December 2018 (has links)
Les propriétés intrinsèques extraordinaires de ces matériaux de faible dimension dépendent fortement de l'environnement auquel ils sont soumis. Par conséquent, ils doivent être préparés, traités et caractérisés sans défauts. Dans cette thèse, je discute de la manière de contrôler l'environnement des nanomatériaux de faible dimension tels que le graphène, le MoS$_{2}$ et les nanotubes de carbone afin de préserver leurs propriétés physiques intrinsèques. De nouvelles solutions pour l'amélioration des propriétés sont discutées en profondeur. Dans la première partie, nous fabriquons des dispositifs d'hétérostructure à base de graphène de Van der Waals (VdW) de dernière génération, en contact avec les bords, encapsulés dans du nitrure de bore hexagonal (hBN), afin d'obtenir un transport balistique. Nous utilisons une technique basée sur des mesures de bruit 1 / f pour sonder le transport de masse et de bord lors de régimes Quantum Hall entiers et fractionnaires. Dans la deuxième partie, le même concept de fabrication des hétérostructures VdW a été étendu pour encapsuler la couche monocouche MoS $_{2}$ dans le hBN afin d'en modifier les propriétés optiques. À cet égard, nous présentons une étude approfondie sur l'origine et la caractérisation des défauts intrinsèques et extrinsèques et leur incidence sur les propriétés optiques. En outre, nous décrivons une technique pour sonder le couplage entre couches ainsi que la génération de lumière avec une résolution spatiale inférieure à la limite de diffraction de la lumière. Enfin, nous discutons d'un processus systémique naturel visant à améliorer les propriétés mécaniques de la soie polymérique naturelle à l'aide d'une nanotubes de carbone à paroi unique fabriqués par HipCO comme aliment pour le ver à soie. / The extraordinary intrinsic properties of low dimensional materials depend highly on the environment they are subjected to. Hence they need to be prepared, processed and characterized without defects. In this thesis, I discuss about how to control the environment of low dimensional nanomaterials such as graphene, MoS2 and carbon nanotubes to preserve their intrinsic physical properties. Novel solutions for property enhancements are discussed in depth. In the first part, we fabricate state-of-the-art, edge-contacted, graphene Van der Waals(VdW) heterostructuredevices encapsulated in hexagonal-boron nitride(hBN), to obtain ballistic transport. We use a technique based on 1/f-noise measurements to probe bulk and edge transport during integer and fractional Quantum Hall regimes. In the second part, the same fabrication concept of VdW heterostructures has been extended to encapsulate monolayer MoS2 in hBN to improve optical properties. In this regard we present an extensive study about the origin and characterization of intrinsic and extrinsic defects and their affect on optical properties. Further, we describe a technique to probe the interlayer coupling along with the generation of light with spatialresolution below the diffraction limit of light. Finally, we discuss a natural systemic process to enhance the mechanical properties of natural polymer silk using HipCO-made single walled carbon nanotubes as a food for silkworm.
3

Intégration d'oxydes fonctionnels pour applications en photonique / Integration of functional oxides for photonic applications

Marcaud, Guillaume 05 December 2018 (has links)
Le 21ème siècle est marqué par une nouvelle ère du numérique, notamment due au développement d’objets connectés toujours plus nombreux et variés. L’incroyable croissance, du flux de données produites, échangées et stockées au niveau mondial, a permis l’émergence de nouvelles technologies comme la photonique silicium. Cette dernière est cependant limitée par les propriétés intrinsèques du silicium, comme son gap indirect et sa structure cristalline centro-symétrique.En parallèle, la famille des oxydes fonctionnels présente une incroyable diversité de propriétés, comme la ferroélectricité ou la piézoélectricité. Leur intégration en photonique est principalement limitée par l’épitaxie sur silicium. En effet, la différence de paramètre de maille entre la plupart des oxydes et le silicium engendre une grande quantité de défauts et donc une forte dégradation de leurs propriétés. L’oxyde de zirconium stabilisé à l’yttrium (YSZ), qui présente un paramètre de maille intermédiaire, assure la transition entre les réseaux cristallins. Ce travail de thèse s’articule ainsi autour de la croissance d’YSZ et la caractérisation de ses propriétés en optique intégrée.Dans un premier temps, nous avons étudié la croissance d’YSZ par ablation laser pulsé (PLD), ainsi que la fabrication et caractérisation de structures photoniques sur substrat de saphir. Nous avons mis en évidence le rôle du recuit du substrat avant dépôt, sur l’orientation et la qualité du film. L’optimisation du dépôt et le développement d’un procédé de fabrication, a permis la démonstration de guides d’onde à faibles pertes, d’environs 2 dB/cm, et de composants passifs plus complexes comme des structures résonantes en anneau, micro-disques et filtres de Bragg. Nous avons également caractérisé les propriétés optiques non-linéaires du troisième ordre de l’YSZ dont les résultats expérimentaux ont été confirmés par des calculs théoriques. La valeur de l’indice de réfraction non-linéaire n2, de l’YSZ, est comparable à celle du nitrure de silicium (SiN), déjà utilisé comme matériau non-linéaire.En raison de la différence de paramètre de maille et du coefficient d’expansion thermique, l’intégration d’YSZ est susceptible d’induire de larges contraintes dans le silicium, et de briser sa centro-symétrie. De récentes études, expérimentales et théoriques, ont démontré que les contraintes permettent d’exploiter des propriétés optiques non-linéaires d’ordre deux dans le silicium, normalement inexistantes dans ce matériau. Pour caractériser la distribution des contraintes, vues par un mode optique se propageant dans un guide d’onde silicium, nous avons mis en place une nouvelle technique expérimentale basée sur l’effet Raman en optique intégrée. Des signatures d’évolutions de phonons très intéressantes ont été mesurées. Cependant, les modèles théoriques n’ont pas permis de calculer des valeurs de contraintes comparables à celles prévues par les simulations et des études complémentaires sont nécessaires.Finalement l’intégration d’YSZ en photonique silicium a été étudiée selon trois approches. La première et la deuxième consistent au dépôt d’YSZ sur des guides d’onde silicium, encapsulés ou non par une couche de silice. La troisième comprend la fabrication de guides d’onde dans une couche d’YSZ, déposée sur un substrat de silicium non structuré. Nous avons mis en évidence l’absence de contrainte dans chacune des configurations, justifiée par la présence de silice à l’interface entre l’YSZ et le silicium. Les pertes de propagation dans de tels guides hybrides YSZ/Si, initialement supérieures à 250 dB/cm ont été réduites à 7,5 dB/cm par l’optimisation de la croissance et de la géométrie des guides. / 21st century stands out as a new numeric area, particularly due to the development of Internet of Things. The exceptional growth of produced, transmitted and stored data all around the world led to new emerging technologies such as silicon photonics. However, silicon has intrinsic limitations for photonic applications including indirect bandgap and centrosymmetry of its lattice.In parallel, functional oxides family exhibits an impressive panel of properties such as ferroelectricity or piezoelectricity. The epitaxial growth is the main limitation for their integration in silicon photonics. Indeed, the lattice mismatch between most of the oxides and silicon induces high defects density which strongly degrades their properties. Nevertheless, one of these oxides, Yttria-Stabilized Zirconia (YSZ), can be used for the lattice transition. The objectives of the PhD work was then to study the YSZ growth mechanisms and to determine its properties in integrated optics.First, the epitaxial growth of YSZ, using Pulsed-Laser Deposition (PLD), as well as the fabrication and characterization of photonics structures have been developed on sapphire substrate. We reported the role of substrate annealing before deposition, on the orientation and quality of YSZ thin film. The optimization of the epitaxial growth, and the development of a fabrication process, allowed the demonstration of YSZ-based waveguides with propagation losses as low as 2 dB/cm. We also characterized more complex passives structures, in particular ring resonators, micro-disks and Bragg filters. Furthermore, third-order optical nonlinear properties in YSZ waveguides were experimentally determined for the first time. The n2 value, obtained experimentally, is in agreement with theoretical calculation and is in the same order of magnitude than the value reported for silicon nitride SiN, a well-known nonlinear material.Due to lattice mismatch and thermal expansion coefficient difference, the growth of YSZ is expected to induce large strain in silicon, breaking its crystal centrosymmetry. Recent experimental and theoretical studies have demonstrated the possibility to exploit second-order optical nonlinear effects in strained silicon, usually vanishing in this material. To probe the strain distribution, seen by an optical mode propagating in a silicon waveguide, we developed an innovative Raman-based experimental technique for integrated optics. Even if typical phonons behaviors have been revealed, theoretical modeling of experimental data did not lead to strain values comparable to the simulation predictions and complementary studies are required.Finally, three approaches have been tested for the integration of YSZ in silicon photonics. The first and second one include the growth of YSZ on silicon waveguides, buried or not in a silica layer. The third one involves the fabrication of waveguides in a YSZ thin film, deposited on a flat silicon substrate. No strains in the silicon have been observed, justified by the silica interfacial layer between YSZ and silicon. Propagation losses of hybrid YSZ/Si waveguides, initially more than 250 dB/cm, have been reduced to 7.5 dB/cm thanks to YSZ growth optimization and an adapted waveguides geometry.
4

Selection mechanisms for microstructures and reversible martensitic transformations

Della Porta, Francesco M. G. January 2018 (has links)
The work in this thesis is inspired by the fabrication of Zn<sub>45</sub>Au<sub>30</sub>Cu<sub>25</sub>. This is the first alloy undergoing ultra-reversible martensitic transformations and closely satisfying the cofactor conditions, particular conditions of geometric compatibility between phases, which were conjectured to influence reversibility. With the aim of better understanding reversibility, in this thesis we study the martensitic microstructures arising during thermal cycling in Zn<sub>45</sub>Au<sub>30</sub>Cu<sub>25</sub>, which are complex and different in every phase transformation cycle. Our study is developed in the context of continuum mechanics and nonlinear elasticity, and we use tools from nonlinear analysis. The first aim of this thesis is to advance our understanding of conditions of geometric compatibility between phases. To this end, first, we further investigate cofactor conditions and introduce a physically-based metric to measure how closely these are satisfied in real materials. Secondly, we introduce further conditions of compatibility and show that these are nearly satisfied by some twins in Zn<sub>45</sub>Au<sub>30</sub>Cu<sub>25</sub>. These might influence reversibility as they improve compatibility between high and low temperature phases. Martensitic phase transitions in Zn<sub>45</sub>Au<sub>30</sub>Cu<sub>25</sub> are a complex phenomenon, especially because the crystalline structure of the material changes from a cubic to a monoclinic symmetry, and hence the energy of the system has twelve wells. There exist infinitely many energy-minimising microstructures, limiting our understanding of the phenomenon as well as our ability to predict it. Therefore, the second aim of this thesis is to find criteria to select physically-relevant energy minimisers. We introduce two criteria or selection mechanisms. The first involves a moving mask approximation, which allows one to describe some experimental observations on the dynamics, while the second is based on using vanishing interface energy. The moving mask approximation reflects the idea of a moving curtain covering and uncovering microstructures during the phase transition, as appears to be the case for Zn<sub>45</sub>Au<sub>30</sub>Cu<sub>25</sub>, and many other materials during thermally induced transformations. We show that the moving mask approximation can be framed in the context of a model for the dynamics of nonlinear elastic bodies. We prove that every macroscopic deformation gradient satisfying the moving mask approximation must be of the form 1 + a(x) ⊗ n(x), for a.e. x. With regards to vanishing interface energy, we consider a one-dimensional energy functional with three wells, which simplifies the physically relevant model for martensitic transformations, but at the same time highlights some key issues. Our energy functional admits infinitely many minimising gradient Young measures, representing energy-minimising microstructures. In order to select the physically relevant ones, we show that minimisers of a regularised energy, where the second derivatives are penalised, generate a unique minimising gradient Young measure as the perturbation vanishes. The results developed in this thesis are motivated by the study of Zn<sub>45</sub>Au<sub>30</sub>Cu<sub>25</sub>, but their relevance is not limited to this material. The results on the cofactor conditions developed here can help for the understanding of new alloys undergoing ultra-reversible transformations, and as a guideline for the fabrication of future materials. Furthermore, the selection mechanisms studied in this work can be useful in selecting physically relevant microstructures not only in Zn<sub>45</sub>Au<sub>30</sub>Cu<sub>25</sub>, but also in other materials undergoing martensitic transformations, and other phenomena where pattern formation is observed.
5

Estudo por espectroscopia MÃssbauer e difraÃÃo de raios-x da cinÃtica de reaÃÃo da soluÃÃo sÃlida FeMo obtida por moagem mecÃnica / Study by MÃssbauer spectroscopy and X-ray diffraction of the reaction kinetics of the FeMo solid solution obtained by mechanical milling

Francisco Iran Sousa da Silva 30 November 2012 (has links)
A cinÃtica de reaÃÃo da soluÃÃo sÃlida Fe 50 at.% Mo produzida por moagem mecÃnica de altas energias foi estudada por espectroscopia MÃssbauer e difraÃÃo de raios-X. O material foi processado com velocidade de 400 rpm e 500 rpm por vÃrios tempos de moagem de forma a se obter amostras de vÃrios estÃgios da reaÃÃo. Os difratogramas de raios-X mostraram a presenÃa de duas fases com estrutura CCC, correspondentes ao Fe e Mo metÃlicos, em todas as amostras. A anÃlise dos difratogramas indicou que, com a moagem, houve difusÃo de Mo na matriz do Fe e de Fe na matriz do Mo e a esperada reduÃÃo do tamanho de grÃo para ambas as fases. Foi tambÃm observado que o mÃtodo de Williamson-Hall nÃo à apropriado para analisar essas amostras em razÃo do alto grau de desordem do material moÃdo. Enquanto a difraÃÃo de raios-X nÃo permitiu a identificaÃÃo de uma fase cristalogrÃfica claramente sendo transformada, o que dificulta o estudo da cinÃtica de reaÃÃo, a espectroscopia MÃssbauer possibilitou identificar duas fases magnÃticas que sofrem transformaÃÃo durante o curso da moagem: um sexteto ferromagnÃtico correspondente ao Fe metÃlico e um dubleto paramagnÃtico correspondente a Ãtomos de Fe com uma maioria de vizinhos de Mo (o molibdÃnio metÃlico nÃo possui momento magnÃtico), seja na matriz CCC do Fe ou na matriz CCC do Mo. A cinÃtica de transformaÃÃo do sexteto foi estudada utilizando um modelo baseado nas transformaÃÃes dos volumes das fases representando pela quantidade afinidade triboquÃmica. Os resultados foram comparados com outros de trabalhos anteriores obtidos da aplicaÃÃo do mesmo modelo a sistemas Fe-Cu e Fe-N. Foi observado um comportamento similar Ãquele do Fe-N, que como o sistema Fe-Mo e ao contrÃrio do Fe-Cu, que tem entalpia de mistura positiva. / A cinÃtica de reaÃÃo da soluÃÃo sÃlida Fe 50 at.% Mo produzida por moagem mecÃnica de altas energias foi estudada por espectroscopia MÃssbauer e difraÃÃo de raios-X. O material foi processado com velocidade de 400 rpm e 500 rpm por vÃrios tempos de moagem de forma a se obter amostras de vÃrios estÃgios da reaÃÃo. Os difratogramas de raios-X mostraram a presenÃa de duas fases com estrutura CCC, correspondentes ao Fe e Mo metÃlicos, em todas as amostras. A anÃlise dos difratogramas indicou que, com a moagem, houve difusÃo de Mo na matriz do Fe e de Fe na matriz do Mo e a esperada reduÃÃo do tamanho de grÃo para ambas as fases. Foi tambÃm observado que o mÃtodo de Williamson-Hall nÃo à apropriado para analisar essas amostras em razÃo do alto grau de desordem do material moÃdo. Enquanto a difraÃÃo de raios-X nÃo permitiu a identificaÃÃo de uma fase cristalogrÃfica claramente sendo transformada, o que dificulta o estudo da cinÃtica de reaÃÃo, a espectroscopia MÃssbauer possibilitou identificar duas fases magnÃticas que sofrem transformaÃÃo durante o curso da moagem: um sexteto ferromagnÃtico correspondente ao Fe metÃlico e um dubleto paramagnÃtico correspondente a Ãtomos de Fe com uma maioria de vizinhos de Mo (o molibdÃnio metÃlico nÃo possui momento magnÃtico), seja na matriz CCC do Fe ou na matriz CCC do Mo. A cinÃtica de transformaÃÃo do sexteto foi estudada utilizando um modelo baseado nas transformaÃÃes dos volumes das fases representando pela quantidade afinidade triboquÃmica. Os resultados foram comparados com outros de trabalhos anteriores obtidos da aplicaÃÃo do mesmo modelo a sistemas Fe-Cu e Fe-N. Foi observado um comportamento similar Ãquele do Fe-N, que como o sistema Fe-Mo e ao contrÃrio do Fe-Cu, que tem entalpia de mistura positiva. / The reaction kinetics of Fe 50 at.% Mo solid solutions produced by high-energy mechanical milling was studied by X-ray diffraction and MÃssbauer spectroscopy. The material was milled with velocity of rotation of 400 rpm and 500 rpm for several milling times in order to obtain samples of various reaction stages. X-ray diffraction patterns shown the presence of two BCC phases, corresponding to metallic Fe and Mo, in all the samples. Analysis of these diffractograms pointed to diffusion of Mo within the Fe matrix and diffusion of Fe within the Mo matrix as well as the expected grain size reduction of both phases, as a result of the milling process. It was also observed that the Williamson-Hall method is not appropriate to analyze these samples due to the high degree of disorder of the milled material. While the X-ray diffraction technique did not allow for the identification of a crystallographic phase being clearly transformed, which makes it difficult to study reaction kinetics, MÃssbauer spectroscopy allowed for the identification of two magnetic phases that suffer transformation during the course of milling: a ferromagnetic sextet corresponding to metallic Fe and a paramagnetic doublet corresponding to Fe atoms with a majority of Mo neighbors (metallic Mo does not posses magnetic moment). Both magnetic phases may be present in the BCC Fe matrix or the BCC Mo matrix. Transformation kinetics of the sextet was studied using a method based on phase volume transformation, depicted by the tribochemical affinity parameter. Results were compared to previous work on the application of these method to Fe-Cu and Fe-N systems. It was observed a behavior similar to that o Fe-N, which as the Fe-Mo system and as opposed to the Fe-Cu system, posses positive enthalpy of mixing. / The reaction kinetics of Fe 50 at.% Mo solid solutions produced by high-energy mechanical milling was studied by X-ray diffraction and MÃssbauer spectroscopy. The material was milled with velocity of rotation of 400 rpm and 500 rpm for several milling times in order to obtain samples of various reaction stages. X-ray diffraction patterns shown the presence of two BCC phases, corresponding to metallic Fe and Mo, in all the samples. Analysis of these diffractograms pointed to diffusion of Mo within the Fe matrix and diffusion of Fe within the Mo matrix as well as the expected grain size reduction of both phases, as a result of the milling process. It was also observed that the Williamson-Hall method is not appropriate to analyze these samples due to the high degree of disorder of the milled material. While the X-ray diffraction technique did not allow for the identification of a crystallographic phase being clearly transformed, which makes it difficult to study reaction kinetics, MÃssbauer spectroscopy allowed for the identification of two magnetic phases that suffer transformation during the course of milling: a ferromagnetic sextet corresponding to metallic Fe and a paramagnetic doublet corresponding to Fe atoms with a majority of Mo neighbors (metallic Mo does not posses magnetic moment). Both magnetic phases may be present in the BCC Fe matrix or the BCC Mo matrix. Transformation kinetics of the sextet was studied using a method based on phase volume transformation, depicted by the tribochemical affinity parameter. Results were compared to previous work on the application of these method to Fe-Cu and Fe-N systems. It was observed a behavior similar to that o Fe-N, which as the Fe-Mo system and as opposed to the Fe-Cu system, posses positive enthalpy of mixing.
6

Méthode pour l’analyse de l’activité de la réduction de l’oxygène de catalyseurs sans métaux nobles par microscopie électrochimique. / Method to Analyze the Oxygen Reduction Reaction Activity of Noble Metal-free Catalysts by Electrochemical Microscopy.

Henrotte, Olivier 15 November 2018 (has links)
La synthèse de catalyseurs sans métaux nobles est une voie prometteuse pour rendre accessible à l’échelle mondiale les piles à combustible. L’analyse électrochimique de ces matériaux n’est pas aisée que ce soit pour comparer les propriétés électro catalytiques ou pour comprendre le fonctionnement de ces catalyseurs. Ceci provient du fait que la communauté scientifique évalue les performances catalytiques à l’échelle du matériau, donc sur un très grand nombre d’objets dont la réponse est moyennée. Les travaux présentés dans ce mémoire ont mis en place une méthode d’analyse de l’activité électrocatalytique de matériaux sans métaux nobles pour la réduction de l’oxygène en milieu acide par microscopie électrochimique à balayage. Cette approche permet d’étudier aussi bien macroscopiquement que microscopiquement les catalyseurs et d’étudier simultanément plusieurs catalyseurs, ce qui rend plus fiable la comparaison des résultats. Le dispositif présenté dans ce travail a permis de comparer différents catalyseurs avec des compositions proches ainsi que d’étudier l’influence de différentes paramètres sur un catalyseur : le chargement, la surface, la masse déposée et la quantité de Nafion ajoutée. Il a aussi été montré qu’il était possible d’étudier la stabilité des catalyseurs via ce dispositif. Ces différents résultats suggèrent que la méthode mise en place est polyvalente et permettra de nombreuses autres études. / The decrease of fuel cells cost is necessary to provide a worldwide access to the technology. Synthesis of noble metal-free catalysts is a promising way to achieve this goal. The electrochemical analysis of these materials is however not easy either to compare the electrocatalytic properties or to understand the performances of these catalysts. The scientific community generally studies catalysts at a macroscale, where the recorded response is averaged on a very large number of catalytic objects. The works presented here shows the setup of a method to analyze the electrocatalytic activity of noble metal-free catalyst for the oxygen reduction reaction in acidic media by scanning electrochemical microscopy. This method brings several advantages such as the possibility to study and compare multiple catalysts on the same sample at a macro- or a microscale. The comparison of several catalysts with this setup is then. A catalyst has been studied under various conditions of: loading, surface area, weight of catalyst and quantity of additives such as Nafion. The investigation of the material stability is also illustrated. These results suggest large range of application of the technique and many possibilities in the future are now open to investigated noble metal-free electrocatalytic materials.
7

De la phytoextraction en Nouvelle-Calédonie aux Eco-Mn : étude structurale de catalyseurs biosourcés et innovants / From phytoextraction in New Caledonia to Eco-Mn : structural study of biosourced and innovative catalysts

Garel, Claire 01 December 2017 (has links)
Les ressources minérales s’épuisent inexorablement, les minerais riches sont de plus en plus difficilement accessibles, et le traitement des minerais implique d’importants impacts environnementaux. En Nouvelle-Calédonie, l’extraction du nickel nécessite la destruction de l’horizon fertile supérieur des sols, et les mines se présentent comme des carrières à ciel ouvert, soumises à l’érosion et menaçant la biodiversité du territoire. Bien que l’exploitation du nickel soit au cœur de l’économie locale, la réhabilitation écologique des sites miniers, et la réintroduction durable d’un couvert végétal sont une nécessité.Le laboratoire ChimEco a démontré qu’il était possible de revégétaliser les sites miniers en réintroduisant des espèces végétales pionnières, résistantes et accumulatrices de manganèse. Ces plantes accumulatrices sont capables d’extraire le manganèse naturellement présent dans le sol et de l’accumuler dans leurs parties aériennes : on parle de phytoextraction. Le laboratoire ChimEco propose en outre une valorisation scientifique et à terme économique des efforts de réhabilitation engagés sur le terrain. En effet, à partir de la biomasse riche en manganèse des plantes accumulatrices, le laboratoire ChimEco a développé un procédé innovant de recyclage des éléments métalliques d’origine végétale en catalyseurs polymétalliques pour la chimie. Il s’agit de l’Ecocatalyse. Ces écocatalyseurs riches en Mn, notés Eco-Mn, ont montré une activité catalytique intéressante dans plusieurs synthèses organiques.Les résultats obtenus en écologie et en chimie par le laboratoire ChimEco prouvent la nécessité d’étudier finement la structure des écocatalyseurs en les considérant comme des matériaux innovants, afin de comprendre et d’améliorer leur activité en synthèse organique, et d’exploiter au mieux les possibilités du procédé. C’est précisément dans ce contexte que s’inscrivent ces travaux de thèse.Plusieurs techniques d’analyse ont été utilisées. Les analyses ICP-MS ont permis de déterminer la composition élémentaire des Eco-Mn. La DRX a permis de mettre en évidence la présence de sels mixtes originaux tels que K3NaMnCl6 sous forme cristalline dans les Eco-Mn. Enfin l’absorption des rayons X a permis de déterminer la nature des espèces présentes dans les catalyseurs, ainsi que le degré d’oxydation du manganèse et du fer. En outre, l’étude du réarrangement d’un acétal cyclique, ainsi que le suivi de la désorption de la pyridine à la surface des Eco-Mn, ont été utilisés pour étudier les propriétés acides des écocatalyseurs. Ces analyses ont permis de répondre à deux objectifs précis : d’une part déterminer la nature des complexes qui composent les Eco-Mn, et d’autre part, mieux comprendre les propriétés physico-chimiques de ces catalyseurs, leur degré d’oxydation et leurs propriétés acides. Ces analyses ont également permis de mieux appréhender les deux étapes du procédé de synthèse des Eco-Mn. Enfin, des catalyseurs synthétiques et témoins ont également été produits et étudiés dans les mêmes conditions d’analyse que les Eco-Mn, dans le but de déterminer si les Eco-Mn ont une spécificité et une empreinte végétale. / Mineral resources are running out, ores are hardly accessible, and ores processing damage the environment. In New-Caledonia, nickel ores mining requires to remove all the upper layers of the ground, leading to open-cast mines subjected to erosion, which threaten the environment and the biodiversity of the archipelago. Although mining ores exploitation is important for the economy of New-Caledonia, the ecological remediation of mining areas through the restoration of a vegetation cover, are necessary.ChimEco laboratory has demonstrated that it is possible to reintroduce pioneering endemic plant species, which are resistant to climate conditions and accumulate manganese, to restore New-Caledonian mining sites. These accumulating plants extract Mn from the ground to their aerial parts: it is called phytoextraction. Besides, ChimEco laboratory puts forward a new scientific and economic valorisation of phytoremediation efforts in New-Caledonia. Indeed, an innovative process has been developed to recycle metallic elements from manganese enriched biomass into innovative and polymetallic catalysts for organic synthesis. This new process is called Ecocatalysis. Ecocatalysts enriched in manganese, Eco-Mn, have demonstrated interesting and promising catalytic activities in several reactions.Regarding the good results achieved by ChimEco in ecology and in chemistry with accumulating plants and resulting Eco-Mn, it is necessary to better and precisely characterise Eco-Mn catalysts, by considering them as innovative materials, in order to understand and foresee their catalytic activity. This PhD work belongs within this context.Several analyses have been performed to characterise Eco-Mn catalysts. First, ICP-MS enables to identify metallic composition of Eco-Mn. Besides, XRD analyses highlight the presence of complex crystallized manganese salts, like K3NaMnCl6. Finally, X-ray absorption spectroscopy enables us to study the nature of manganese species which compose Eco-Mn catalysts, and to understand the oxidation states of Mn and Fe. Moreover, acid properties of Eco-Mn were demonstrated thanks to the study of a cyclic acetal rearrangement and infra-red spectroscopy of adsorbed pyridine. All these analyses were performed in order to determine first the composition of Eco-Mn catalysts, and secondly to highlight their physico-chemical properties, their oxidation state and their acid properties. Furthermore, this study also enable us to better understand the different steps of the ecocatalysts production process. Finally, synthetic catalysts were also produced and analysed in the same conditions as Eco-Mn, in order to bring out the specificities of Eco-Mn.

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