Th.--Électronique--Toulouse--I.N.P., 1984. N°: 78.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / FundaÃÃo de Amparo à Pesquisa do Estado do Cearà / Nos Ãltimos anos, um grande interesse na associaÃÃo de materiais magnÃticos e biolÃgicos tem sido relatado na literatura. A obtenÃÃo de novos compÃsitos constituÃdos de galactomanana (GM), nanopartÃculas magnÃticas (MNPs) de NiZn e glicerol (GL) foram produzidos em diferentes proporÃÃes com finalidade de potencializar as caracterÃsticas individuais de cada material para futuras aplicaÃÃes. Sendo assim, as propriedades estruturais, magnÃticas e dielÃtricas dos nanobiocompÃsitos foram investigadas por DifraÃÃo de Raios-X (DRX), Espectroscopia de AbsorÃÃo na RegiÃo de Infravermelho (FTIR), AnÃlise TÃrmica (TG), Calorimetria ExploratÃria Diferencial (DSC), Microscopia EletrÃnica de Varredura (MEV), Microscopia EletrÃnica de TransmissÃo (TEM), Medidas MagnÃticas e Medidas DielÃtricas. A estrutura de espinÃlio da ferrita de NiZn foi confirmada por DRX e TEM e a amostra GMGL apesar de ser um material amorfo apresentou em seus nanobiocompÃsitos picos caracteristicos da fase de NiZn. As bandas caracterÃsticas para as amostras foram confirmadas por FTIR. Estas por sua vez seguiram um perfil de degradaÃÃo de acordo com as quantidades de NiZn incorporados, confirmados nos termogramas de DSC. A caracterizaÃÃo por MEV foi importante para avaliaÃÃo da morfologia. Os resultados das medidas dielÃtricas apresentaram baixas perdas dielÃtricas e das medidas magnÃticas mostraram comportamento magnÃtico para todos os nanobiocompÃsitos. Portanto, os resultados da caracterizaÃÃo dos nanobiocompÃsitos foram satisfatÃrios para possÃveis aplicaÃÃes como biomaterias, dispositivos eletrÃnicos ou em Ãreas afins. / In recent years, a great interest in the association of magnetic and biological materials has been reported in the literature. New composite consisting of galactomannan (GM), magnetic nanoparticles (NPs) of NiZn and glycerol (GL) were produced in different proportions with the purpose of enhancing the individual characteristics of each material for future applications. Thus, the structural, magnetic and dielectric properties of nanobiocomposites were investigated by Absorption Spectroscopy in the Region of Infrared (FTIR), X-Ray Diffraction (XRD), Thermal Analysis (TG), Differential Scanning Calorimetry (DSC), Electron Microscopy (SEM), Transmission Electron Microscopy (TEM), Magnetic Measurements and Dielectric Measurements. The structure of spinel NiZn ferrite was confirmed by XRD and TEM. Sample GMGL despite being an amorphous material presented in their nanobiocomposites characteristic peaks of phase NiZn. The characteristic bands in the samples were confirmed by FTIR. These in turn followed a degradation profile in accordance with the amounts of NiZn incorporated, which was confirmed in the DSC thermograms. The characterization by SEM was important to assess the morphology. The results of dielectric measurements showed low dielectric loss and magnetic measurements showed magnetic behavior for all nanobiocomposites. Therefore, the results of the characterization of nanobiocomposites were satisfactory for potential applications as biomaterials, electronic devices or related areas.

This diploma thesis was focused on the preparation of magnetic and fluorescently labelled spinel type nanoparticles, specifically nanoparticles of zinc-doped cobalt ferrite intended for application in magnetic resonance imaging and fluorescence microscopy in experimental practice. In previous studies, various ferrite nanoparticles exhibited relatively high transverse relaxation times and strong negative T2 contrast. These properties were also supposed for the zinc-doped cobalt ferrite nanoparticles. This assumption was confirmed by studying their magnetic and contrasting properties. Fluorescence properties of the prepared nanoparticles were also successfully studied. With respect to the intended applications of these particles, the issue of suitable surface modification of magnetic cores, their colloidal stabilization in an aqueous suspension and toxicity in biological systems were studied. Key words: nanoparticles, ferrites, MRI, relaxation

MnZn ferrites are widely used in power electronics applications where the switching frequency is in the range of several tens of kilohertz to a megahertz. In this range of frequencies the combination of relatively high permeability and relatively low conductivity found in MnZn ferrite helps to minimize the size of magnetic devices while maintaining high efficiency. The continuing improvement in semiconductor switches and circuit topologies has led to use of high-frequency switching circuits at ever increasing power levels. The magnetic devices for these high-power, high-frequency circuits require magnetic CORES that are significantly larger than standard ferrite-core devices used at lower power levels. Often such large ferrite cores must be custom designed, and at present this custom design is based on available material information without regard for the physical size of the structure. This thesis examines the issues encountered in the use of larger MnZn ferrite cores for high-frequency, high-power applications. The two main issues of concern are the increased power dissipation due to induced currents in the structure and the change in inductance that results as the flux within the core is redistributed at higher frequencies. In order to model these problems using either numerical or analytical methods requires a reliable and complete set of material information. A significant portion of this work is devoted to methods for acquiring such material information since such information is not generally available from the manufacturers. Once the material constants required for the analysis are determined, they are used in both closed-form and numerical model to illustrate that large ferrite cores suffer significant increases in loss and significant decreases in inductance for frequencies as low as several hundred kilohertz. The separate impacts of the electrical and magnetic losses in the core are illustrated through the use of linear finite element analyses of several example core structures. The device impedances calculated using the FEA tools show fair agreement with measurement. An analysis of gapped structures and segmented cross-sections shows that these design options can reduce the severity of the dimensional problems for some designs. / Ph. D.

Nous présentons dans ce travail une étude approfondie de la rhéologie à l'état fondu de composites très chargés en particules inorganiques. Les systèmes modèles étudiés sont composés de particules de ferrites ou de fibres de verre dispersées dans une matrice polypropylène. Le comportement rhéologique linéaire et non-linéaire ainsi que la morphologie des composants du mélange ont été étudiés. Sous différentes conditions d'écoulement, nous avons pu mettre en évidence la relation étroite qu'il existe entre la microstructure du matériau, sa formulation et ses propriétés rhéologiques. Nous avons ainsi évalué les principaux paramètres liés à la charge (e.g., distribution de taille, facteur de forme, chimie de surface) sur la viscosité du mélange. Ces travaux ont montré que l'ajout de charges dans une matrice thermoplastique change fondamentalement la rhéologie linéaire et non-linéaire du mélange. Sous écoulement dynamique, nous avons pu quantifier les interactions entre les charges (force de contact) et charges-polymère. D'une part, les systèmes ferrites/polypropylène ont montré une forte structuration dans le temps, ce qui se traduit par un comportement type réseaux à très faibles déformation. D'autre part, les systèmes fibres/polypropylène ont montré qu'un facteur de forme plus élevé et de meilleures interactions fibre-fibre favorisaient la création du réseau de particules. Sous écoulement permanent, les phénomènes non-linéaires ont été également étudiés. Nous n'avons pas mis en évidence de phénomènes de glissement pour l'ensemble de ces systèmes. Plus particulièrement, le système ferrites/polypropylène a montré une atténuation du comportement pseudo-plastique à haute vitesse de cisaillement. Ainsi, ce travail expérimental a contribué à la compréhension des propriétés d'écoulement de ces systèmes complexes / We present in this work a complete study of the melt rheological behavior of highly filled polymers. We study the rheological behavior of two model systems, ferrite particles and short-glass fibers dispersed in polypropylene. We investigate the structural features of such complex materials by linear and non-linear rheological behavior. Under different flow conditions, we show the close relationship between the variation in the microstructure, the formulation and the flow properties. We evaluate the effect of the main parameters related to the filler (e.g., particle size distribution, aspect ratio, surface chemistry) on the viscosity of the mixture. This work shows that the addition of fillers fundamentally changes the linear and non-linear viscoelasticity of the molten composite. Under dynamic flow, we are able to quantify the particle-particle and matrix-particle interactions. Therefore, we study the creation of the filler network with increasing the particulate phase. On the one hand, ferrite/polypropylene systems presented a network structure that evolves over time which manifest by a solid-like behavior accentuation at very low deformations. On the other hand, fibers/polypropylene composites showed that the higher the aspect ratio and the interparticle interactions, the higher is the probability to create a network structure. Under steady state flow, the non-linear behavior is studied. Wall slip effects were found to be negligible under the flow conditions studied in this work. In particular, ferrite/polypropylene showed an attenuation of the shear-thinning behavior at low shear rates. Thus, this experimental work has contributed to the understanding of the flow properties of these complex materials

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Cette thèse a été réalisée dans le cadre d’une cotutelle de thèse (3 ans) Franco-Libanaise entre l’Université Pierre et Marie Curie de Paris et l’Université Libanaise de Beyrouth. Nabil Tabaja a été entièrement financé par le Groupe de Recherche MAPE (Nanosized Porous Materials, Preparation, Advanced Characterization and Environmental Applications) de Beyrouth que nous tenons à remercier. Le but de ce travail était de tester et de valoriser des catalyseurs à base d’oxydes de fer et de ferrites pour la dépollution des eaux par photocatalyse sous lumière visible puis solaire. Les catalyseurs étudiés ont été préparés en employant des silices poreuses en tant que gabarits pour obtenir majoritairement : soit des nanoparticules, NP, d’oxydes de fer ayant cristallisé à l’intérieur des pores des silices (INTERNES, répliquées), soit des nanoparticules ayant cristallisé à l’extérieur des grains de silice et formées lors des traitements d’activation thermiques (EXTERNES). Nous avons employées des techniques faciles à transférer pour obtenir les silices (Chapitre 1). Notre objectif à ce niveau était d’obtenir plus de 50g d’au moins six silices ayant des diamètres de mésopores différents. La variation de ces diamètres s’accompagne de modifications des connections entre les mésopores principaux et des propriétés des surfaces des silices. Différents sels précurseurs de fer (chlorure, nitrate) ou des mélanges de métaux ont été déposées sur les différentes silices obtenues par des techniques de dépôt de type deux solvants (2S). Les échantillons ont été traités thermiquement à 700°C sous air pour obtenir des nanoparticules d’oxydes (Chapitre 2). Nous montrons que, si le diamètre des NP nanorépliquées est en général proche du diamètre des pores des silices initiales, les formes et la dispersion des nanoparticules internes dans les grains de silice dépendent de différents facteurs expérimentaux, des sels précurseurs, des solvants et du type de silice sélectionnée. Nous montrons également que la formation des particules externes est associée au traitement thermique imposé et peut être favorisée en choisissant le bon solvant et le bon sel précurseur pour une silice déterminée. Des premiers tests ayant démontrés un taux de lixiviation important dans le cas de catalyseur au fer, nous avons testé des ferrites de différentes compositions (cations (II) de différentes électronégativités, Ni(II), Co(II), Cd(II), Zn(II) ; cation (III), Cr(III)). Afin de comparer la réactivité catalytique des catalyseurs, deux types de réactions sont introduites successivement. Le premier type de réaction, l’oxydation photocatalytique du méthanol et du formaldéhyde, a été employé à titre fondamental. Dans ce cas, notre objectif était d’étudier la sélectivité de la réaction et d’identifier de façon inambigue quelles nanoparticules présentes dans la formulation des catalyseurs permettent, partant d’une espèce à un seul carbone, d’obtenir des produits à 2 ou plus atomes de carbone (Chapitre III). La seconde réaction, l’oxydation photocatalytique d’un pesticide, a été employée pour démontrer que les catalyseurs peuvent être utiles à titre appliqué. Le pesticide sélectionné a été le carbendazime (Chapitre IV) dont nous avons suivi la décomposition. Ces études n’ont été possibles que grâce à l’emploi de techniques de caractérisation avancées, de type TOC et GC-MS. Les meilleures activités catalytiques ont été analysées en fonction de la présence d’une majorité de NP internes et/ou externes et d’autres espèces plus dispersées et non visibles par DRX. / This thesis was carried out as part of a Franco-Lebanese collaboration thesis (3 years) between the University of Pierre et Marie Curie in Paris and the Lebanese University in Beirut. Nabil Tabaja was fully funded by the Research Group MAPE (nanosized Porous Materials, Preparation, Advanced Characterization and Environmental Applications) Beirut that we thank.The purpose of this study was to test and develop catalysts based on iron oxides and ferrites for decontamination of water by photocatalysis under visible and sunlight. The catalysts studied were prepared by using porous silica as templates to obtain predominantly either nanoparticles, NP, iron oxides having crystallized within the pores of the silica (INTERNAL, replicated), or nanoparticles having crystallized outside the silica grains formed and during the thermal activation treatments (external). We employed techniques easily transferable to obtain silicas (Chapter 1). Our goal at this level was more than 50 grams of at least six silicas having different diameters of mesopores. The change in these diameters is accompanied by changes in connections between major mesoporous silicas and the properties of surfaces. Various iron precursor salts (chloride or nitrate) or metal mixtures were deposited on the various silicas obtained by the two solvents techniques (2S). The samples were calcined at 700 ° C in air to obtain oxide nanoparticles (Chapter 2). We show that, if the diameter of NP nanoreplicated is generally close to the pore diameter of the initial silicas, and forms the dispersion of nanoparticles in the inner silica grain depends on various experimental factors of the precursor salts, solvents and the type of the selected silica. We also show that the formation of particles is associated with the external heat treatment can be promoted and imposed by choosing the right solvent and the right precursor salt for a specific silica. Initial tests have demonstrated an important release rate in the case of iron catalyst, we tested different compositions ferrites ((II) cations of different electronegativities, Ni (II), Co (II), Cd (II), Zn (II) cation (III), Cr (III)). In order to compare the catalytic activity of the catalysts, two types of reactions are successively introduced. The first type of reaction, the photocatalytic oxidation of methanol and formaldehyde was employed as fundamental. In this case, our objective was to study the selectivity of the reaction and identify what way inambigue nanoparticles in the formulation of catalysts allow, starting from a species to a single carbon, to obtain products with 2 or more carbon atoms (Chapter III). The second reaction, the photocatalytic oxidation of a pesticide, was used to demonstrate that the catalysts may be useful as applied. The pesticide was selected carbendazim (Chapter IV) which we have followed the breakdown. These studies have been possible thanks to the use of advanced characterization techniques, type TOC and GC-MS. The best catalytic activities were analyzed according to the presence of a majority of internal and / or external NP and other species more dispersed and invisible by XRD.

Thèse doctorat : Génie des Matériaux : Villeurbanne, INSA : 2004. / Titre provenant de l'écran-titre. Bibliogr. p. 187-195.

Thèse doctorat : Génie des Matériaux : Villeurbanne, INSA : 2007. / Titre provenant de l'écran-titre. Bibliogr. p. 220-234.

Thèse de doctorat : Physique de la matière condensée : Strasbourg 1 : 2006. / Thèse soutenue sur un ensemble de travaux. Titre provenant de l'écran-titre. Bibliogr. 10 p.