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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.
571

Processamento coloidal de componentes ceramicos para queimadores de gas / Colloidal processing of ceramic components for gas burners

SANTOS, SILAS C. dos 09 October 2014 (has links)
Made available in DSpace on 2014-10-09T12:27:39Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:04:18Z (GMT). No. of bitstreams: 0 / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP
572

Investigação da relação entre coeficientes termodifusivos em colóides magnéticos a base de água / Investigation of the relation between thermodiffusive coefficients in water-based magnetic colloids

André Luiz Sehnem 29 June 2018 (has links)
O presente trabalho investiga o fenômeno termodifusivo em dispersões coloidais de nanopartículas magnéticas de óxidos de ferro em água (ferrofluidos), com a formação de dupla camada elétrica em torno das partículas. A estabilidade da partícula em solução é controlada pela concentração de íons. Ao estabelecer uma diferença de temperatura através da amostra líquida, ocorre o efeito de termodifusão (efeito Soret) das partículas e de íons em solução. Este efeito é o movimento das partículas para o lado frio ou quente do gradiente de temperatura. O acúmulo para um dos lados do gradiente de temperatura depende das características da solução. O efeito Soret de ferrofluidos em soluções ácidas e básicas é descrito a partir da determinação experimental das grandezas físicas envolvidas na difusão das partículas. O coeficiente Soret ST e o coeficiente de difusão são determinados em experimentos ópticos de lente de matéria, utilizando o aparato experimental de Varredura-Z, e de espalhamento Rayleigh forçado para termodifusão. Para investigar a resposta dos íons ao gradiente de temperatura, são realizadas medidas do potencial termoelétrico em uma célula termoelétrica, gerado a partir da difusão das cargas dispersas no líquido. O potencial superficial das partículas também é investigado experimentalmente, para descrever a interação das partículas com o campo termoelétrico. Os experimentos são realizados em função da temperatura da amostra e usados para descrever os resultados ST(T) das partículas, a partir de equações dos principais modelos teóricos. Os resultados mostram as diferenças e semelhanças do efeito Soret das nanopartículas em soluções ácidas e básicas, e que em ambos os casos a termodifusão de nanopartículas reflete o comportamento termodifusivo dos íons dispersos em solução. / This work investigates the thermal diffusion phenomena in colloidal dispersions of iron oxide magnetic nanoparticles dispersed in water (ferrofluid). The particles are stable in water due to electrical double layer around the particles, controlled by the ionic concentration. A temperature gradient throughout the ferrofluid sample causes the thermodiffusion (Soret effect) of dispersed particles and ions. This effect is the movement of particles to the cold or hot side of the temperature gradient. The particles migration for a given side depends on the characteristics of the sample. The Soret effect of ferrofluids in acidic and basic solutions is described by the experimental measurements of the physical parameters associated to particles diffusion. The Soret coefficient ST and the mass diffusion coefficient are measured in the matter lens experiment in the Z-scan experimental setup, and by the use of Thermal Diffusion Forced Rayleigh Scattering experiments. Concerning the ionic response to the temperature gradient the thermoelectric field generated by charges diffusion is measured in a thermoelectric cell. The surface potential of the particles is also measured to describe its interactions with the thermoelectric field. These experiments are made as function of the temperature of the sample and the results are applied to describe the ST(T) of particles by the use of equations from the main theoretical models. The results show differences and resemblances of the Soret effect in acidic and basic nanoparticles solutions. In both kind of solutions the thermodiffusion of nanoparticles is mainly ruled by the thermodiffusion of ions dispersed in solution.
573

Investigação da influência do tamanho de partícula na termodifusão de colóides magnéticos positivamente carregados / Investigation of the particle size influence in the thermodiffusion of positively charged magnetic colloids

André Luiz Sehnem 09 May 2014 (has links)
Esta dissertação apresenta um estudo experimental sobre o transporte de massa de nanopartículas magnéticas induzido por um gradiente de temperatura, denominado termodifusão. A técnica de Varredura-Z é utilizada para gerar o aumento de temperatura na região irradiada pelo laser Gaussiano e formar o gradiente de temperatura. A sequente migração de nanopartículas é caracterizada pelo gradiente de concentração gerado no estado estacionário do fluxo de partículas, definindo o coeficiente Soret ST. O objetivo deste trabalho é verificar a variação de ST com o tamanho médio d0 das nanopartículas de ferrofluidos eletrostaticamente carregados em solução ácida. A dependência de ST com d0 surge do coeficiente de difusão de massa, explicando a dependência linear encontrada experimentalmente. Nestes materiais, a migração de nanopartículas ocorre para a região quente da amostra. Mostramos que este comportamento ocorre pela diminuição da carga superficial da nanopartícula na parte mais quente da amostra, diminuindo a repulsão eletrostática. A influência dos íons presentes na solução é obtida através da mudança na amplitude de ST com a diminuição do pH na amostra. Uma previsão teórica, baseada na eletrostática da dupla camada elétrica, concorda com estes dados considerando alta blindagem eletrostática das nanopartículas e a diminuição da carga superficial com o aumento da temperatura. / This dissertation presents an experimental study about the mass transport of magnetic nanoparticles induced by a temperature gradient, called thermodiffusion. The Z-scan technique is used to generate the temperature increasing in the region irradiated by the Gaussian laser beam and create the temperature gradient. The following nanoparticles migration is characterized by the concentration gradient of the stationary particles flux, defining the Soret coefficient ST. The aim of this work is to obtain the variation of ST with the average size d0 of electrostatically charged ferrofluid nanoparticles in acidic solution. The ST dependence with d0 comes from the mass diffusion coefficient, in agreement with the linear dependence found experimentally. In these materials the nanoparticles migration occurs to the hot region of the sample. We show that this behavior is owing to the reduction of the nanoparticle´s surface charge in the hottest region of the sample, decreasing electrostatic repulsion. The influence of the ions from solution is obtained through the change in ST amplitude with reduction of the samples pH. A theoretical prediction, based in the electrostatic of the double layer, agrees with this data considering a high screening of the nanoparticles and decreasing of the surface charge with temperature increasing.
574

Diffusive properties of soft condensed matter systems under external confinement / Diffusive properties of soft condensed matter systems under external confinement

Diego de Lucena CamarÃo 27 August 2014 (has links)
CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / Nesta tese estudamos a influÃncia de potenciais de confinamento externos nas propriedades dinÃmicas de sistemas de matÃria condensada mole. Analisamos as propriedades difusivas de dois sistemas especÃficos utilizando simulaÃÃes computacionais (DinÃmica Molecular de Langevin e DinÃmica Browniana). No CapÃtulo 1, introduzimos o tÃpico sobre matÃria condensada mole. Mostramos vÃrios aspectos teÃricos e experimentais neste tipo de sistema. Fazemos uma breve introduÃÃo ao tÃpico de difusÃo, onde discutimos os principais aspectos do movimento Browniano. Introduzimos o problema de difusÃo em linha (SFD, do inglÃs "single-file diffusion") e o discutimos, teorica e experimentalmente, no contexto de sistemas de matÃria condensada mole. No CapÃtulo 2, introduzimos os mÃtodos computacionais utilizados nesta tese. Discutimos os mÃtodos de DinÃmica Molecular e suas variantes, o mÃtodo de DinÃmica de Langevin e DinÃmica Browniana. TambÃm introduzimos algoritmos de integraÃÃo utilizados nos capÃtulos posteriores. Nos Caps. 3, 4 e 5, analisamos dois sistemas distintos, (i) um sistema de partÃculas de Yukawa confinadas em um canal parabÃlico quasi-unidimensional (q1D) e (ii) um sistema de colÃides magnÃticos sob a influÃncia de um potencial parabÃlico e uma modulaÃÃo periÃdica externa ao longo da direÃÃo nÃo confinada. No primeiro sistema, estudamos a transiÃÃo do regime de difusÃo em linha (SFD) para o regime de difusÃo normal (2D). No segundo sistema, estudamos os efeitos de vÃrios parÃmetros que caracterizam o sistema (e.g., a magnitude do campo magnÃtico externo e a presenÃa da modulaÃÃo periÃdica externa) em suas propriedades dinÃmicas. Finalmente, apresentamos um sumÃrio dos principais resultados obtidos nesta tese e mostramos algumas questÃes em aberto como perspectivas para pesquisas futuras na Ãrea de difusÃo em sistemas de matÃria condensada mole. / In this thesis we study the influence of external confinement potentials on the dynamical properties of soft condensed matter systems. We analyze the diffusive properties of two specific systems by means of Langevin and Brownian Dynamics simulations. In Chapter 1, we introduce the subject of soft condensed matter. We show several theoretical and experimental aspects of these type of systems. We make a brief introduction to the topic of diffusion, where we discuss main aspects of Brownian motion. We introduce the single-file diffusion (SFD) problem and discuss it in the context of soft condensed matter systems, both theoretically and experimentally. In Chapter 2, we introduce the computational method used in this thesis. We discuss Molecular Dynamics (MD) and its variants, Langevin and Brownian Dynamics simulations. We also introduce numerical algorithms used in the following chapters. In Chapters 3, 4 and 5, we analyze two different systems, namely (i) a system of interacting Yukawa particles confined in a parabolic quasi-one-dimensional (q1D) channel and (ii) a system of magnetic colloidal particles under the influence of both a parabolic confinement potential and a periodic external modulation along the unconfined direction. In the former, we study the transition from the single-file diffusion (SFD) regime to the two-dimensional (2D) diffusion regime. In the latter, we study the influence of several parameters that characterizes the system, e.g., the strength of an external magnetic field and the periodic modulation along the unconfined direction, on its dynamical properties. Finally, we present the summary of the main findings reported in this thesis and we show some open questions as perspectives for future research in the field of diffusion in soft condensed matter systems.
575

Processamento coloidal de componentes ceramicos para queimadores de gas / Colloidal processing of ceramic components for gas burners

SANTOS, SILAS C. dos 09 October 2014 (has links)
Made available in DSpace on 2014-10-09T12:27:39Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:04:18Z (GMT). No. of bitstreams: 0 / A ítria vem sendo muito utilizada como material luminescente e estrutural resistente a altas temperaturas, devido às suas excelentes características ópticas e refratárias. No processamento coloidal da ítria, o controle da estabilidade da suspensão consiste em uma importante etapa quando se objetiva produzir componentes reprodutivos, com densidade controlada, microestrutura homogênea e estabilidade estrutural. Desta maneira, os estudos envolvendo o comportamento de superfície, as condições de estabilidade das suspensões e o comportamento frente às condições de conformação (fluxo), fornecem importantes subsídios para controle dos processos na fabricação de componentes cerâmicos para queimadores de gás. Neste sentido, realizaram-se estudos sobre o comportamento de superfície, de estabilidade e reológico de suspensões aquosas de ítria e do concentrado de terras raras contendo ítria a fim de adequá-las para o processo de conformação por impregnação, onde foram testados diferentes materiais orgânicos como matrizes de réplica, para a confecção de membranas porosas para queimadores de gás. Neste estudo foram avaliados os parâmetros como: pH do meio, concentrações de dispersante, sólidos e ligante na estabilidade e no comportamento ao fluxo das suspensões cerâmicas, e também os aspectos dos distintos materiais orgânicos selecionados como matrizes de réplica para impregnação com as suspensões cerâmicas otimizadas. Os resultados obtidos indicam que se pode confeccionar membranas cerâmicas porosas pelo método de réplica a partir das suspensões aquosas de ítria e do concentrado de terras raras contendo ítria, utilizando-se pH alcalino, polieletrólito aniônico e uma tela mista de nylon-algodão como matriz de réplica. / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP
576

Synthèse d'oxydes par voie sol-gel colloïdale : application aux précurseurs de combustibles nucléaires / Synthesis of oxides by colloidal sol-gel route : application to precursors of nuclear fuel

Gossard, Alban 17 November 2014 (has links)
Le recyclage des actinides mineurs produits en réacteur nucléaire est un point clé pour les cycles du combustible du futur. Différentes options sont ainsi envisagées : leur réintégration au sein d'un nouveau combustible « refabriqué » ou leur transmutation dans le but de réduire significativement la radiotoxicité des déchets ultimes. Dans ces deux cas de figure, la synthèse de matériaux innovants intégrant les actinides mineurs de manière homogène est nécessaire.En ce sens, les voies sol-gel présentent des avantages certains par rapport aux autres voies de synthèse (co-précipitation, métallurgie des poudres) tels que l'organisation du matériau à l'échelle colloïdale ou la création de porosité de manière contrôlée grâce à l'utilisation d'un « template ». De plus, la possibilité de travailler en milieu humide, de la solution précurseur au matériau final, permet d'éviter la formation de poudres pulvérulentes et contaminantes, point essentiel dans le cas de matériaux incorporant des éléments radioactifs. Cette thèse vise à démontrer l'adaptabilité de ce type de procédé au domaine du nucléaire. Dans un premier temps, une méthodologie de synthèse par voie sol-gel colloïdale et de caractérisation sur un système non-actif à base de zirconium a été mise en place et a permis la compréhension des mécanismes mis en jeu au cours de cette synthèse. Suite à cela, des études de mise en forme, et notamment d'insertion de porosité, ont été réalisées. Des monolithes de zircone ont de cette manière pu être obtenus grâce au couplage entre le procédé sol-gel colloïdal et la formation d'une émulsion stabilisée par des clusters de particules solides.Finalement, une transposition de ces travaux sur un système à base d'uranium a été initiée, soulevant différentes perspectives prometteuses concernant les possibilités de mise en forme du matériau final. / One of the main objectives for the future nuclear fuel cycle is the recycling of the minor actinides. Different options are considered: their integration into a new fuel for a prospect of a closed fuel cycle or their transmutation in order to significantly decrease the long-term radiotoxicity of ultimate wastes. In both cases, the synthesis of new advanced materials integrating the actinides jointly is required.Sol-gel processes allow the organization of the material at the colloidal scale or the insertion of controlled porosity using « templates ». Furthermore, the possibility to work in a « wet environment » prevents the formation of pulverulent powders which are contaminant in the case of materials incorporating radioactive elements. The main purpose of this work is to demonstrate the adaptability of this route to the nuclear field.Firstly, a methodology of synthesis from a colloidal sol-gel route was set up on a non-radioactive zirconium-based system in order to characterize and understand of the different mechanisms of this synthesis. Then, studies on shaping, including insertion of porosity, were performed. Zirconia monoliths have been obtained thanks to a coupling between a colloidal sol-gel process and the formation of an emulsion stabilized by clusters of solid particles. Finally, a transposition of this work to an uranium-based system was introduced, pointing out different promising perspectives specially concerning the possibilities of shaping of the final material.
577

Structuration par voie colloïdale de nanopoudres de boehmite à partir de systèmes mixtes organique/inorganique / Structuration by colloidal way of nanopowders boehmite from organic/inorganic hybrid systems

Belounis, Fahouzi 02 July 2015 (has links)
La recherche s’appuie pour une grande part sur le développement de nanomatériaux. Ceux-ci constituent, en effet, les matières premières des nanosciences et ouvrent à l’industrie des perspectives extrêmement larges. Le développement des céramiques nécessite une grande maîtrise des procédés d'élaboration qui permettent d'obtenir des microstructures appropriées à l’élaboration de matériaux denses pour différentes applications par exemple biomédicales. Les évolutions récentes concernent les matériaux hybrides et bio-inspirés ; les problèmes de mise en forme et de structuration multi-échelles de ces derniers incitent au développement de nouveaux procédés telle que l’approche nouvelle dite ascendante (bottom-up) consistant à fabriquer un matériau à échelle microscopique voir macroscopique à partir de ses particules nanométriques.Dans ce contexte, les travaux de cette thèse ont pour objectif de faciliter, par l’intermédiaire d’une modification de surface, la mise au point d’une technique de mise en forme originale pour l’élaboration de céramiques issues d’un matériau nanométrique de type oxyde: la granulation par coagulation. Nous nous sommes intéressés au cas d’une nanopoudre de boehmite (AlO(OH)). Cependant, cette poudre nanométrique de boehmite présente de multiples instabilités en suspension. En effet, cette poudre est soumise à de fortes gélifications en fonction du pH et à basse concentration. Il est nécessaire dans ce cas pour obtenir une suspension stable de modifier les propriétés de surface. En conséquence, une partie de ces travaux est consacrée à la fonctionnalisation de surface par des organosilanes. Cette modification de surface n’est cependant qu’une étape à l’obtention d’une particule hybride constituée d’un cœur de boehmite et d’une couche polymérique. En réalité, le greffage d’organosilane à la surface permet de créer un pont entre la partie centrale inorganique et la partie externe organique constituée de latex pouvant se lier à l’organosilane utilisé (le MPS).Le matériau hybride boehmite-MPS-latex ainsi obtenu peut être utilisé dans une nouvelle technique de mise en forme colloïdale inspirée de la granulation par hétérocoagulation. En milieu aqueux, la polarité opposée des charges de surfaces de deux entités différentes conduit à l’hétérocoagulation en suspension. La coagulation observée dans cette thèse, met en relation deux particules identiques possédant chacune, les deux charges opposées à leur surface. Le principe de la granulation consiste à induire, sous l’effet d’un mouvement de rotation des échantillons, la coalescence des agglomérats en forçant leurs surfaces à interagir par contacts réciproques. En sélectionnant la formulation, la coalescence conduit à l'élaboration d'objets sphériques homogènes en taille et en forme. / Research in this field is multidisciplinary and relies largely on the development of nanomaterials. These are, in fact, the raw materials of nanoscience and open to industry extremely broad prospects. In the field of material sciences, nanostructured materials, among them nanostructured ceramics have grown considerably in recent years. Development of ceramic requires a mastery of production processes that achieve appropriate microstructures in the development of dense materials for various applications such biomédicals. Recent developments include hybrid and bio-inspired materials; the problems of shaping and multi-scale structure of these encourage the development of new processes such as the new so-called bottom-up approach of manufacturing and make macroscopic material from its nanoparticles. In this context, the work of this PhD aim to facilitate, through surface modification, the development of an original layout technique for the development of ceramics from a material nano-oxide type: granulation coagulation. We were interested in the case of a boehmite nanopowder (AlO(OH)). However, this nanoscale boehmite powder has many instabilities in suspension. Indeed, the powder is subjected to strong gelation as function of pH and at low concentrations. It is necessary in this case to obtain a stable suspension by modifying the surface properties. Accordingly, a part of this work is devoted to surface functionalization by organosilanes. This surface modification, however, is only one stage to obtain a hybrid particle comprised of a heart of boehmite and a polymeric layer. In reality, the grafting organosilane (MPS) at the surface permit to create a bridge between the inorganic core and organic outer part consists of latex. The boehmite-MPS-latex hybrid material thus obtained can be used in a new colloidal shaping technique inspired by heterocoagulation granulation. In aqueous medium, the opposite polarity of the charges of the surfaces of two different entities leads to heterocoagulation in suspension. Clotting observed in this thesis, connects two identical particles with each, the two charges opposite to the surface. The principle of the granulation is to induce, under the effect the rotational movement, the coalescence of the agglomerates by forcing their surfaces to interact by mutual contact. By selecting the formulation, coalescence leads to the development of homogeneous spherical objects in size and shape.
578

Theory of colloidal stabilization by unattached polymers / Théorie de la stabilisation colloïdale par des polymères non-attachés

Shvets, Alexey 19 May 2014 (has links)
Les dispersions colloïdales ont beaucoup d’applications technologiques importantes. A cause du mouvement brownien, les particules ont des collisions fréquentes entre elles. Les forces d’attraction de van der Waals,dérivant de potentiels à longue portés, conduisent à l’agrégation et à la précipitation des particules. Plusieurs méthodes ont été proposées pour diminuer ou contrebalancer l’effet d’attraction de van der Waals et augmenter la stabilité colloïdale. Par exemple, le choix du solvant possédant l’indice de réfraction le plus proche possible de celui des particules peut diminuer les forces de van der Waals. D'autres facteurs influencent la stabilité comme les interactions électrostatiques et les interactions spécifiques liées aux chaînes de polymères. Dans le cas des polymères, les chaînes peuvent être greffées à la surface des particules ou être dissoutes dans le solvant (chaînes libres). Dans ce travail de thèse, nous avons étudié l’effet de la stabilisation par déplétion dans le cas des chaînes de polymères libres (FPI, "free polymer induced interaction"). Des modèles théoriques précédents portent un caractère trop simplifié et utilisent des approximations sans vérification. De plus, l’influence des paramètres de la solution, c’est-à-dire, de la structure de polymères et de son interaction avec la surface de particule, n’a pas été étudiée.Les chaînes polymères libres ont été modélisées comme des marches aléatoires dans un champ moléculaire auto-cohérent qui satisfait à l'équation intégro-différentielle de diffusion. Pour le domaine moléculaire, nous avons utilisé un potentiel chimique qui, pour la solution de polymère semi-dilué, peut être représenté comme une expansion du viriel où nous n’avons pris en considération que les deuxième et troisième coefficients du viriel de la solution de polymère. En variant des paramètres tels que la rigidité du polymère, la longueur du polymère, la concentration en polymère et le régime du solvant (comme le solvant thêta), que ce soit pour une surface colloïdale purement répulsive, pour une surface adsorbée ou pour la surface d'une couche de polymère greffé, nous avons été en mesure d'améliorer la barrière répulsive due aux polymères libres entre les particules et donc nous avons trouvé des conditions de la stabilisation cinétique du système. / Stable colloidal dispersions with evenly distributed particles are important for many technological applications. Due to Brownian motion colloidal particles have constant collisions with each other which often lead to their aggregation driven by the long range van der Waals attraction. As a result the colloidal systems often tend to precipitate. A number of methods have been devised to minimize the effect of long-range van der Waals attraction between colloidal particles or to override the influence of the attraction in order to provide the colloidal stability.In the PhD thesis we investigated the colloidal stabilization in solutions of free polymers which is commonly referred to as depletion stabilization. Previous theoretical studies of free-polymer induced (FPI) stabilization were based on oversimplified models involving uncontrolled approximations. Even the most basic features of the depletion stabilization phenomenon were unknown. It was unclear how the PI repulsion depends on the solution parameters, polymer structure and monomer/surface interactions.The free polymer chains were modeled as random walks in a self-consistent molecular field that satisfied to diffusion-like integro-differential equation. As the molecular field we used the chemical potential that for semi-dilute polymer solution can be represented as a virial expansion where we took into account only second and third virial coefficients of the polymer solution. Varying the parameters like polymer stiffness, polymer length, polymer concentration and solvent regime (like theta solvent) whether it is for purely repulsive colloidal surface, adsorbed surface or surface with grafted polymer layer we were able to enhance the repulsive barrier due to the free polymers between the particles and therefore found conditions for kinetic stabilization of the system.
579

Viscosité et dynamique microscopique dans les suspensions colloïdales concentrées / Viscosity and microscopic dynamic in dense colloidal suspensions

Roger, Valentin 14 December 2015 (has links)
Dans ce travail, nous avons étudié la relation entre la viscosité et la dynamique microscopique (caractérisée par le temps de relaxation structurale) d'une suspension colloïdale en fonction de la fraction volumique. Nous avons mis au point une expérience originale nous permettant de mesurer la viscosité et le temps de relaxation simultanément sur le même échantillon. La dynamique microscopique est mesurée à l'aide de techniques conventionnelles de diffusion dynamique de la lumière "multi-speckles" ; la viscosité est quant à elle obtenue en mesurant la vitesse de sédimentation de particules-sondes micrométriques. Ces mesures nous ont permis d'étendre d'au moins deux décades la gamme de viscosités à taux de cisaillement nul préalablement explorée. Nous montrons que la viscosité et le temps de relaxation structurale mesuré au pic du facteur de structure statique, sont couplés jusqu'à des fractions volumiques situées bien au-delà de la transition vers un régime surfondu. Par ailleurs, nous avons constaté que le fort accroissement du temps de relaxation à l'approche de la transition vitreuse était bien décrit par une divergence exponentielle, plutôt que par une loi de puissance critique prévue par la Théorie de Couplage des Modes (MCT). / In this work, we have investigated the relation between the viscosity and the microscopic dynamics (structural relaxation time) of colloidal suspensions, as a function of volume fraction. We have designed and implemented an original setup which allows us to measure the viscosity and the relaxation time simultaneously on the very same sample. The dynamics are measured by conventional multispeckle dynamic light scattering, while the viscosity is obtained by measuring the sedimentation velocity of micron-sized tracer particles. Our measurements extend the range of previous measurements of the zero-shear viscosity by two decades. We find that the viscosity and the relaxation time measured at the peak of the static structure factor are coupled up to deep in the supercooled regime, thereby extending previous observations that were limited to the onset of supercooling. Furthermore, we show that the steep growth of the relaxation time on approaching the glass transition is well described by an exponential divergence, rather than by a critical power law as predicted by Mode Coupling Theory (MCT).
580

Single particle dynamics in liquid crystalline phases formed by filamentous viruses / Dynamique des particules individuelles dans les phases de cristaux liquides formées par les bactériophages filamenteux

Álvarez Francés, Laura 21 December 2016 (has links)
Cette thèse porte sur la dynamique des différentes mésophases liquides cristallines et des transitions de phase d'un modèle colloïdal de particules en forme de bâtonnent: les virus fd. L'étude de l'auto-organisation des cristaux liquides colloïdaux traite des phénomènes les plus simples de formation de systèmes structurés. Dans un système où les particules anisotropes ont des interactions de noyau rigide, l'auto-organisation est purement entropique en raison de la maximisation du volume libre du système. Ainsi, il y a une modification de la dynamique qui peut être mesurée, et fournisse des informations sur le volume libre disponible et la structure de la mésophase.La dynamique des bâtonnets fd peut être mesurée avec précision à l'aide de techniques de microscopie à fluorescence. Nous quantifions la dynamique autour des transitions de phase et l'effet de la flexibilité et de la longueur en tant que mécanisme pour relâcher la contrainte de leurs voisins. En outre, dans une structure lamellaire guest-host, nous avons prouvé la pérmeation favorisée des bâtonnets longs guest à travers les couches de la matrice Smectique hast formée de plus petites particules. Dans ces conditions, la super-diffusion de la particule invitée est également observée lorsqu'elle se diffuse dans une limite de grain. Il s'agit d'un pas en avant pour comprendre la dynamique des systèmes structurés colloïdaux et aussi dans le développement des nouveaux matériaux basés sur des diffuseurs rapides avec des applications potentielles dans la biologie médicale. Les résultats expérimentaux sont très prometteurs et stimulantes. / This thesis treats the dynamics of the different liquid crystalline mesophases and phase transitions of a model colloïdal of rod-like particles: the fd viruses. The study of the self-organization of colloïdal liquid crystals treats the simplest phenomena of forming structured systems. In a system where anisotropie particles have hard core interactions, the self-organization is purely entropy driven due to the maximization of the free volume of the system. Thus, there is a change on the dynamics at single particle level that can be measured, providing information on the available free volume and the structure of the mesophase.The fd rods are a versatile colloïdal system and their self-dynamics can be accurately measured using fluorescence microscopy techniques. We quantify the relaxation of the dynamics around the phase transitions and the effect of flexibility and length as a mechanism to release the constraint of their neighbors. Moreover, in a guest-host lamellar structure we demonstrate that a big guest particle is faster than the small host, if the guest particle is not commensurate in the host energy landscape. In these conditions, also the super-diffusion of the guest particle is observed when it diffuses into a grain boundary. This is a step forward to understand the dynamics of colloïdal structured systems and also in the development the new materials based on fast diffusers with potential applications in drug delivery. The extensive experimental results are completed by a whole analysis and interpretation, being very promising and challenging.

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