The confinement of magnetic nanoparticles (Prussian blue analogues (PBAs) has been achieved using mesostructured silica as a matrix. The PBAs have the general formula AxMy[M'(CN)n]z, where A is an alkali metal cation; M: CoII, NiII, SmIII; and M': CoII. The two reactions were run in parallel and led to a mesostructured silica matrix that contains nanoparticles of PBA homogeneously distributed within the silica framework. As initially reported for the synthesis of Co3[Fe(CN)6]2 magnetic nanoparticles, in the research conducted for this thesis, this synthesis has been extended to other compounds and to lanthanides such as Sm and has also included the study of the influence of different parameters (pH, concentration). As these nanocomposites are potentially good candidates for the preparation of bimetallic nanoparticles and oxides through controlled thermal treatment, the second goal of the research was to employ an adapted thermal treatment in order to prepare metal and metal oxide nanoparticles from PBA, directly embedded in the silica matrix. To this end, the influence of the thermal treatment (temperature, time, atmosphere) on the nature and structure of the resulting materials was investigated, with a focus on the potential use of the combustion of the organic templates as in-situ reducing agents. For some compounds, the preparation of bimetallic nanoparticles was successful. This method was tentatively applied to the preparation of specific Sm:Co bimetallic compounds, are well known as one of the best permanent magnets currently available.

The confinement of magnetic nanoparticles (Prussian blue analogues (PBAs) has been achieved using mesostructured silica as a matrix. The PBAs have the general formula AxMy[M'(CN)n]z, where A is an alkali metal cation; M: CoII, NiII, SmIII; and M': CoII. The two reactions were run in parallel and led to a mesostructured silica matrix that contains nanoparticles of PBA homogeneously distributed within the silica framework. As initially reported for the synthesis of Co3[Fe(CN)6]2 magnetic nanoparticles, in the research conducted for this thesis, this synthesis has been extended to other compounds and to lanthanides such as Sm and has also included the study of the influence of different parameters (pH, concentration). As these nanocomposites are potentially good candidates for the preparation of bimetallic nanoparticles and oxides through controlled thermal treatment, the second goal of the research was to employ an adapted thermal treatment in order to prepare metal and metal oxide nanoparticles from PBA, directly embedded in the silica matrix. To this end, the influence of the thermal treatment (temperature, time, atmosphere) on the nature and structure of the resulting materials was investigated, with a focus on the potential use of the combustion of the organic templates as in-situ reducing agents. For some compounds, the preparation of bimetallic nanoparticles was successful. This method was tentatively applied to the preparation of specific Sm:Co bimetallic compounds, are well known as one of the best permanent magnets currently available.

Cette thèse porte sur l’élaboration de nanocomposites anisotropes à base de nanofils de cobalt/polymères pour la fabrication d’aimants permanents qui ne contiennent pas de terres rares et l’optimisation des propriétés magnétiques de ces matériaux composites. La préparation de nanofils de cobalt mono-domaines (R~6-10 nm et L~250-350 nm) a été réalisée par voie thermique conventionnelle et par voie micro-onde. Des films de composites Co/polymère alignés ont été élaborés avec de très bonnes propriétés magnétiques (μ0Hc=0.75T, Mr/Ms=0.92). Le (BH)max est de 160 kJ/m3 qui est dans la gamme des aimants SmCo (BHmax~ 120-200 kJ/m3). Les techniques de diffusion de neutrons et de rayons-X aux petits angles (DNPA et DXPA) ont été utilisées pour la caractérisation des dispersions et des systèmes anisotropes. Les fils dans le chloroforme sont mieux dispersés par rapport aux autres solvants et forment des agrégats moins gros. Pour les films de composites, l’agrégation des nanofils est relativement plus dense dans le polystyrène que dans le poly(vinyl pyrrolidone). La qualité de l’alignement est proportionnelle à l’amplitude du champ appliqué même pour des champs très élevés. Cependant, un meilleur alignement ne conduit pas automatiquement à une meilleure coercivité. Les interactions entre des nanofils ont été caractérisées par Henkel plots. Les valeurs de ΔM sont faibles (ΔM<-0.2). En outre, la DNPA polarisée a permis de suivre le renversement magnétique à l’échelle nanométrique. Le champ coercitif Hc est défini par le renversement global de gros paquets de fils. Au-delà de Hc, il n’y a plus que des processus de retournements de fils individuels. Afin d’optimiser le Hc, l’optimisation de la microstructure (organisation des fils) est plus importante que l’optimisation des propriétés des fils individuels. / This thesis focuses on the development of nanocomposites made from anisotropic cobalt nanowires / polymer for the manufacture of permanent magnets which do not contain any rare earth and the optimization of the magnetic properties of these composite materials.The preparation of single-domain cobalt nanowires (R ~ 6-10 nm and L ~ 250-350 nm) was performed by conventional thermal route and by microwave route. The films of composite aligned Co nanowires/polymer have been elaborated with very good magnetic properties (μ0Hc = 0.75T, Mr / Ms = 0.92). The (BH)max is 160 kJ/m3 which is in the range of SmCo magnets (~ 120-200 BHmax kJ/m3). The techniques of small angles neutron and X-ray small angle scattering (SANS and SAXS) were used for the characterization of anisotropic systems and dispersions. The wires in chloroform are better dispersed compared to other solvents and form aggregates smaller. For the films of composite, the aggregation of the nanowires is relatively denser in polystyrene than in poly (vinyl pyrrolidone). The quality of alignment is proportional to the amplitude of the applied field, even for very high fields. However, a better alignment does not automatically lead to a better coercivity. The interactions between nanowires were characterized by Henkel plots. The ΔM values are pretty low (ΔM <-0.2). In addition, polarized SANS was used to track the magnetic reversal at the nanoscale. The coercive field Hc is defined by global reversal of large packets of wires. Beyond Hc, there are more processes than reversals of individual wires. To optimize Hc, optimizing the microstructure (organization of wires) is more important than optimizing the properties of the individual wires.

For several decades, the field of magneto-optics (MO) has demonstrated applications that have impact on every day applications such as in optical data storage, magnetic field sensing, crucial for magnetoencephalography and magnetocardiography; and compact and efficient optical isolators, among others. In the past, many of these applications and the devices designed for them have heavily relied on inorganic materials. Organic materials with a high MO response represent an interesting alternative to the inorganic equivalent by not only being a more cost efficient solution, but also by allowing the user to modify a number of variables to control and optimize the MO performance depending on the application and level of performance desired. In this dissertation I discuss the MO properties of novel organic materials, starting with polythiophene, which has been of interest due to the strong relationship between its high MO performance and its lamellar structure and regioregularity. I will also be discussing another material system that provides several degrees of MO tunability: magnetite based nanocomposites. A unique and novel synthetic approach described in this dissertation yields both highly transparent and MO responsive polymer films. I will be describing a systematic approach that indicates a strong influence of the size of the nanoparticle as well as the nanoparticle concentration in the MO performance of the bulk polymer, while maintaining high optical quality with minimal scattering and absorption in the visible and near infrared. Finally, I will be discussing the implementation of both a magnetite nanocomposite and a cobalt ferrite based nanocomposite in a free space magnetic field system and demonstrate the proof-of-principle operation of a sensing system.

Les composants passifs hyperfréquences deviennent de plus en plus commercialisés et employés dans les systèmes de télécommunications. La croissance technologique et l’augmentation de la demande des nouvelles applications requièrent de meilleures performances et de moindres coûts. Dans les applications sans fil et notamment dans les modules « émission/réception », les circulateurs sont utilisés pour l’émission et la réception des signaux simultanément à l’aide d’une seule antenne. Les couches magnétiques traditionnellement déposées et intégrées exigent une cristallisation à haute température ainsi que l’application d’un champ magnétique externe pour garder l’orientation des moments magnétiques. Cette orientation est cependant obtenue par des aimants lourds et volumineux. Devant ces limitations technologiques ainsi que la demande de miniaturisation, l’emploi de l’hexaferrite de baryum sous sa forme particulaire devrait permettre le développement de circulateurs auto-polarisés et miniaturisés à matériaux magnétiques composites. Les travaux présentés dans ce manuscrit ont pour objectif d’étudier et de réaliser un circulateur hyperfréquence à nano particules magnétiques orientées dans la bande 40-60 GHz. L’état de l’art expose les différentes topologies de circulateurs dont la topologie coplanaire est choisie pour notre application. L’étude analytique est basée sur les travaux de Bosma permettant de modéliser le circulateur triplaque. Les principales dimensions géométriques obtenues sont ensuite transposées vers la structure coplanaire en 3D à l’aide de l’outil de simulation HFSS. Devant les limitations de cet outil, différentes structures ont été étudiées et simulées numériquement pour présenter au mieux le matériau composite. Plusieurs séries de prototypes sont ensuite fabriquées à partir des structures optimisées en simulation numérique. Le matériau magnétique composite déposé a des épaisseurs de 40 et 100 μm. Les caractérisations hyperfréquences montrent la performance des dispositifs réalisés. Des pistes de recherche sont proposées pour l’amélioration des performances de nos prototypes / Microwave passive components become increasingly commercialized and used in telecommunications systems. Technological growth and the increased demand for new applications require higher performance and lower costs. In wireless applications, especially in "transceivers", circulators are used for transmitting and receiving signals simultaneously using a single antenna. Magnetic layers traditionally deposited and integrated require a high crystallization temperature and the application of an external magnetic field to keep the orientation of magnetic moments. This orientation is however obtained by heavy and bulky magnets. Given these technological limitations and the need to miniaturize, the use of barium hexaferrite particles envisages the development of self-biased and miniaturized circulators having magnetic composite materials. The ambition of this work is to study and to fabricate a microwave circulator with magnetic nanoparticles oriented in the 40 - 60 GHz range. The state of the art describes various topologies coplanar circulators from which the coplanar topology is chosen for our application. The analytical study is based on Bosma’s work to model the stripline circulator. The main geometric dimensions obtained are then transposed to the coplanar structure using the 3D simulation tool HFSS. Faced with this tool’s limitations, different structures were studied and simulated numerically to shape the best the composite material. Several series of prototypes are then manufactured. The magnetic composite material was deposited in layers having thicknesses of 40 and 100 μm. The microwave characterizations show the performance of the fabricated device. Research tracks are proposed to improve the performance of our prototypes