Nous explorons les propriétés structurales de nanoparticules cœur-coquille, avec un cœur de ferrite MFe2O4 (M = Mn et Co) ou de ferrite mixte Mn-Zn. Ces nanoparticules sont obtenues par co-précipitation hydrothermique et sont dispersées en milieu acide par un traitement de surface empirique au nitrate ferrique, protégeant les nanograins contre une dissociation chimique par une fine couche superficielle de maghémite. La fraction volumique du cœur, de la coquille et l’épaisseur de la couche superficielle sont déterminées par dosage chimique. Nous suivons les changements structurels des nanocristaux de MnFe2O4 et CoFe2O4, pendant la durée du traitement de surface, tandis que ceux des nanoparticules de ferrite mixte Mn-Zn sont étudiés en fonction de leur teneur en zinc. Diffraction de rayons-x et de neutrons sont utilisées pour déterminer les paramètres de structure, en particulier la diffusion de cations dans les interstices de la ferrite spinelle. Pour un haut degré de fiabilité, des raffinements de Rietveld sont réalisés. Les distances inter-atomiques, l’état d’oxydation moyen et le degré d’inversion sont déterminés par spectroscopie d’absorption des rayons-x. Morphologie, cristallinité et taille des nanoparticules de ferrite mixte Mn-Zn sont étudiées par TEM/HRTEM et par diffraction des électrons. Dans les nanoparticules MnFe2O4 et de ferrite mixte Mn-Zn, on constate la présence de cations Mn3+ en environnement octaédrique, responsables de déformations anisotropes (effet Jahn-Teller). Le degré d’inversion obtenu ici diffère de celui du bulk en raison de la réduction à l’échelle nanométrique et de l'augmentation du rapport surface/volume pendant le processus de synthèse. / Structural properties of core-shell ferrite nanoparticles MFe2O4 (M = Mn and Co) and Mn-Zn ferrite nanoparticles are here investigated. The nanoparticles are synthesized by hydrothermal co-precipitation and are dispersed in acid medium thanks to an empirical surface treatment by ferric nitrate, which prevents the chemical dissociation by a thin maghemite layer incorporated at the surface of the nano-grains. Chemical titrations allow us to calculate volume fractions of core and shell, as well as the surface-layer thickness. Structural changes induced by the surface treatment are followed as a function of treatment duration in MnFe2O4 and CoFe2O4 nanocrystals. Whereas structural changes in Mn-Zn ferrite nanoparticles are investigated as a function of zinc content. X-ray and Neutron diffractions are used to determine the structural parameters, in particular cationic distribution in the spinel ferrite sites. Precise structural information with high degree of reliability is obtained by Rietveld refinements. To investigate the local structure of these materials, X-ray Absorption Spectroscopy measurements are performed, allowing determining interatomic distances, mean oxidation state and inversion degree. Morphology, crystallinity and size of mixed-ferrite nanoparticles are investigated by TEM/HRTEM and electron diffraction. In Mn-Zn ferrite nanoparticles, the presence of Mn3+ in octahedral environment is responsible for anisotropic distortions, known as Jahn-Teller effect. The inversion degree obtained in this work diverges from the bulk values due to the reduction to nanoscale and to the increase of the surface/volume ratio, associated to the synthesis process.

Nous présentons une contribution expérimentale à l’étude des propriétés structurales et magnétiques de ferrites de gallium substituées par des terres rares. Ce travail s’inscrit dans la thématique plus générale des multiferroïques magnétoélectriques dont fait partie le composé Ga2-xFexO3 qui est ferrimagnétique et présente une polarisation spontanée à température ambiante. On s’intéresse à l’influence de la substitution d’atomes de gallium ou de fer par des éléments de terres rares (Sc, Yb, Er, Sm) sur les paramètres structuraux de Ga2-xFexO3 avec 0,9  x  1,2 et à l’effet de la substitution par Sc et Yb sur la température de transition magnétique et l’aimantation à saturation. On présente une étude expérimentale du magnétisme du composé Ga0.99Yb0.01FeO3, réalisée à partir de mesures de la susceptibilité alternative et de l’aimantation en fonction du champ magnétique, H, et de la température T. Un large domaine d’irréversibilité magnétique est observé dans le diagramme de phase H–T. Les résultats suggèrent que Ga0.99Yb0.01FeO3 constitue un verre de spin Heisenberg tridimensionnel. / We present an experimental contribution to the study of structural and magnetic properties for gallium ferrites substituted by rare earth elements. This work is part of the more general theme of magnetoelectric multiferroïc which includes the Ga2-xFexO3 compound ferrimagnetic and with a spontaneous polarization at room temperature. We study the influence of the substitution of gallium or iron atoms with rare earth elements (Sc, Yb, Er, Sm) on the structural parameters of Ga2-xFexO3 with 0.9  x  1.2 and the effect of the substitution by Sc and Yb on the magnetic transition temperature and the saturation magnetization. We present an experimental study of magnetism Ga0.99Yb0.01FeO3 compound, realized from alternative susceptibility and magnetization measurements as a function of magnetic field, H, and the temperature T. A wide irreversible magnetic area is observed in the phase diagram H–T. The results suggest that Ga0.99Yb0.01FeO3 is a three-dimensional Heisenberg spin glass.

We have modeled some magnetic systems, which consists of a number of sublattices, in the mean field approximation. This is possible in crystalline systems formed by two or more magnetic ions coupled by specific interactions such as the crystal field, exchange, among others. The main idea is to solve the microscopic Hamiltonian that models a given magnetic system in order to obtain their magnetic equation of state: M (H, T). For this, we use the appropriate arrangements to different magnetic (ferro-, ferri- and antiferro- magnetic) scheme sublattices. From the solutions of the Hamiltonian (eigenvalues and eigenvectors), physical quantities of interest were determined. In principle we consider systems with localized magnetism due to 3d and 4f electrons with the participation of non-magnetic ligands including 3d-4f systems with the presence of crystal field. In this dissertation we use the model of two-and three sublattices in order to obtain the equation of state for the following systems: RKKY exchange in RNi2B2C, superexchange in (Y3-zRz)(T1xFe1-x)(T2yFe3-y)O12, LixFe3- xO4 and (NixMn1-x)1.5[Cr(CN)6]. In these formulas, R represents a rare earth ion, T1 and T2 represent non-magnetic ions. Some representative cases are presented to illustrate the different equations of state and behavior of sublattices, metamagnetism, temperature compensation, etc. The extension to other similar systems can be direct or need to incorporate additional phenomenological parameters. / Consideramos neste estudo sistemas magnéticos modeláveis mediante sub- redes na aproximação do campo médio. Isto é possível em sistemas cristalinos formados por dois ou mais íons magnéticos acoplados por interações específicas como as do campo cristalino, troca, entre outros. A ideia central é resolver o hamiltoniano microscópico que modela um determinado sistema magnético de maneira a se obter sua equação de estado magnética: M(H,T). Para isto usamos o esquema de sub- redes adequado a diferentes arranjos magnéticos (ferro-, ferri- e antiferro- magnéticos). Com as soluções do hamiltoniano (autovalores e autovetores), grandezas físicas de interesse foram determinadas. Em princípio, consideramos sistemas com magnetismo localizado devido a elétrons 3d e 4f com participação de ligandos não magnéticos incluindo sistemas 3d-4f com presença de campo cristalino. Neste trabalho de dissertação empregamos o modelo de duas e três sub- redes para obter as equações de estado nos seguintes sistemas: troca tipo RKKY em RNi2B2C, supertroca em (Y3-zRz)(T1xFe1-x)(T2yFe3-y)O12, LixFe3-xO4 e (NixMn1- x)1.5[Cr(CN)6]. Nestas fórmulas, R representa um íon de terra rara, T1 e T2 representam íons não magnéticos. Alguns casos representativos são apresentados para exemplificar as diferentes equações de estado e comportamento das sub- redes, metamagnetismo, temperatura de compensação etc. Em princípio, a extensão para outros sistemas semelhantes, usando os modelos apresentados aqui, pode ser direta ou precisar incorporar parâmetros fenomenológicos adicionais.

This thesis presents the results of investigations of the synthesis, structure and physical properties of multiferroic materials. Multiferroics are materials in which two or all three of ferroelectricity, ferromagnetism and ferroelasticity occur in the same phase. Such materials have the potential applications of their parent materials, as well as new ones because of the interaction between the order parameters. The thesis is organized into four sections. Section 1 gives an overview of multiferroics, explaining the origin of mul-tiferroicity , occurrence of magnetoelectric coupling, their possible technological ap-plications and the challenges involved. Section 2 gives the scope of the investigations. The specific objectives of the present research on yttrium chromite, heavy rare earth chromites, solid solutions of yttrium chromite, rare earth manganites doped with alkaline earth metals, charge-ordered rare earth ferrites and indium manganite are outlined. Experimental aspects of the work carried out are discussed in section 3. It gives details of the experimental set up and the basic operation principles of various structural and physical characterizations of the materials prepared. In section 4, results of the investigations are discussed. Magnetic and di-electric properties of yttrium chromite (YCrO3), heavy rare earth chromites and YCr1-xMnxO3 are reported in section 4.1. These materials show canted antiferro-magnetic behavior below the Nel transition temperatures and dielectric transitions at high temperatures. Role of local non-centrosymmetry is discussed based on high-resolution neutron powder diffraction data. In 4.2 we discuss the results of charge-ordered rare earth ferrites which show good magnetoelectric effect. Magnetic, dielectric and magneto-dielectric properties of YCr1-xMnxO3 (Ln = rare earth) are discussed in 4.3. These materials show magneto-dielectric effect. In 4.4 we discuss the near normal incidence far infrared reflectivity spectra of a single crystal of TbMnO3, in the spectral range of 50cm−1 to 700 cm−1 from 10 K to 300 K. Finally in 4.5, magnetic and dielectric properties of bulk and thin films of indium manganite are discussed.

V práci je zkoumán vliv podmínek na průběh hydrolýzy alkoxidů titanu a vlastností připravovaných nanočástic oxidu titaničitého s důrazem na teplotu a množství vody přítomné v systému. Připravované hydrolyzáty alkoxidů titanu a nanočástice oxidu titaničitého připravené z hydrolyzátů jsou studovány metodami XRD, DTA – TGA, SEM – EDS, BET a PCCS. Nanočástice magnetitu byly syntetizovány pomocí precipitační reakce z roztoku Mohrovy soli a jejich krystalová struktura, velikost a povrchové vlastnosti byly sledovány s vyhodnocením vlivu teploty a při modifikaci povrchu polykarboxyletherovým superplastifikátorem. Pro upevnění TiO2 na povrch magnetitu byla použita kombinovaná metoda aplikace vybraných nanočástic TiO2 s hydrolýzou TiO2 pomocí alkoxidů titanu za účelem přípravy fotokatalyticky aktivního core-shell práškového katalyzátoru s vylepšenými vlastnostmi adsorpce na povrchu. Studovány byly možnosti aplikace TiO2 na povrch Mn-Zn feritu, kdy byl studován vliv depozice tenkých vrstev C a Au na morfologii povrchu. Fotokatalytická aktivita vybraných připravených materiálů byla studována pomocí dekompozice methylenové modři v roztoku a par isopropanolu a ethanolu rozkládaných pomocí Mn-Zn feritu v experimentálním chemickém reaktoru s magnetickým polem stabilizovaným ložem nosiče katalyzátoru.

Die vorliegende Arbeit befasst sich mit magnetischen Tunnelkontakten (magnetic tunnel junctions, MTJs) auf Basis des Oxids Zinkferrit (ZnxFe3-xO4). Dabei soll das Potential dieses Materials durch die Demonstration des Tunnelmagnetowiderstandes (tunnel magnetoresistance, TMR) in zinkferritbasierten Tunnelkontakten gezeigt werden. Dazu wurde ein Probendesign für MTJs auf Basis der „pseudo spin valve“-Geometrie entwickelt. Die Basis für dieseStrukturen ist ein Dünnfilmstapel aus MgO (Substrat) / TiN / ZnxFe3-xO4 / MgO / Co. Dieser ist mittels gepulster Laserabscheidung (pulsed laser deposition, PLD) hergestellt. Im Rahmen dieser Arbeit wurden die strukturellen, elektrischen und magnetischen Eigenschaften der Dünnfilme untersucht. Des weiteren wurden die fertig prozessierten MTJ-Bauelemente an einem im Rahmen dieser Arbeit entwickeltem und aufgebautem TMR-Messplatz vermessen. Dabei ist es gelungen einen TMR-Effekt von 0.5% in ZnxFe3-xO4-basierten MTJs nachzuweisen. Das erste Kapitel der Arbeit gibt eine Einführung in die spintronischen Effekte Riesenmagnetowiderstand (giant magnetoresistance, GMR) und Tunnelmagnetowiderstand (TMR). Deren technologische Anwendungen sowie die grundlegenden physikalischen Effekte und Modelle werden diskutiert. Das zweite Kapitel gibt eine Übersicht über die Materialklasse der spinellartigen Ferrite. Der Fokus liegt auf den Materialien Magnetit (Fe3O4) sowie Zinkferrit (ZnxFe3-xO4). Die physikalischen Modelle zur Beschreibung der strukturellen, magnetischen und elektrischen Eigenschaften dieser Materialien werden dargelegt sowie ein Literaturüberblick über experimentelle und theoretische Arbeiten gegeben. Im dritten Kapitel werden die im Rahmen dieser Arbeit verwendeten Probenpräparations- und Charakterisierungsmethoden vorgestellt und technische Details sowie physikalische Grundlagen erläutert. Die Entwicklung eines neuen Probendesigns zum Nachweis des TMR-Effekts in ZnxFe3-xO4-basierten MTJs ist Gegenstand des vierten Kapitels. Die Entwicklung des Probenaufbaus sowie die daraus resultierende Probenprozessierung werden beschrieben. Die beiden letzten Kapitel befassen sich mit der strukturellen, elektrischen und magnetischen Charakterisierung der mittels PLD abgeschiedenen Dünnfilme sowie der Tunnelkontaktstrukturen.

Les rejets des Usines à Zinc de Kolwezi contiennent majoritairement du zinc sous forme réfractaire (ferrite) au traitement hydrométallurgique conventionnel. Ils contiennent d’autres métaux « lourds » qui les rendent dangereux vis-à-vis de l’environnement dans lequel ils sont actuellement entreposés. Ces métaux, dont la plupart peuvent être valorisés, font de ces rejets un véritable gisement secondaire. Il est donc impératif de mettre au point un procédé adéquat de valorisation ;d’où le thème de la présente thèse :« Etude de valorisation des rejets des Usines à Zinc de Kolwezi, RDC ». <p>A l’aide des techniques modernes de caractérisation (physico–chimique, minéralogique et morphologique), nous sommes arrivés à cibler, à adapter et à justifier l’utilisation d’une technique de valorisation des matières minérales existantes. Les minéraux utiles contenus dans les rejets UZK ont été sulfatés par digestion et sélectivement mis en solution après un grillage. La sulfatation s’est avérée l’étape déterminante du procédé et un intérêt particulier a été focalisé sur cette étape en réalisant une étude cinétique approfondie.<p>Les données et informations récoltées tout le long de cette recherche nous ont permis de réaliser une simulation du procédé par le logiciel ASPEN PLUS. Ce qui a permis de faire une ébauche d’un schéma de traitement industriel. Ce dernier s’est avéré souple vis-à-vis de l’utilisation d’autres matières comme les calcines des concentrés sulfurés cuivre-zinc.<p><p>Residues from the Kolwezi Zinc Plant (Usines à Zinc de Kolwezi UZK) essentially contain zinc in a refractory (ferrite) form, which is difficult to recover by conventional hydrometallurgical methods. « Heavy» metals are also present that make them hazardous towards the environment in which they are currently stored. Most of these metals are valuable; thus, the UZK residues are a real secondary deposit. It is therefore imperative to develop an appropriate method of treatment, hence the theme of the present thesis: « Recovery study of values metals from Kolwezi Zinc Plant residues, DRC ».<p>Using modern techniques of characterization (physical and chemical, mineralogical and morphological), we focused, adapted and justified the use of a technique for efficient recovery of the existing valuable minerals. The minerals contained in UZK residues have been sulphated by digestion and thereafter selectively dissolved after roasting. Sulphatation proved to be the decisive step of the process and a particular attention has been given to this step by performing a detailed kinetic study. <p>The data and information collected throughout this research allowed a simulation of the developed method by using the « Aspen Plus » software. This allowed us to propose a draft scheme of industrial processing. The latter proved flexible towards the use of other materials such as calcines of copper-zinc sulphide concentrates.<p> / Doctorat en Sciences de l'ingénieur / info:eu-repo/semantics/nonPublished

In the modern practice, a sustainable development strategy in a domain of wasteutilization is shifting its focus from a general completeness of recycling to a morespecific attention to efficiently utilize elements in the wastes. This is well-illustrated bythe steelmaking slag industries. The major waste product from the steelmaking practiceis slag and its main constituents are: CaO, SiO2, Al2O3, MnO, FeO and so on. The mainfield of application for the steelmaking slags is civil engineering, especially for road andwaterway construction. However, a significant amount of the slag remains in the dumps,damaging the environment as well as requiring a land for secure storage. Efficientrecycling of these materials is of increasing interest worldwide as a result of increasingsustainability in processes with respect to increasing raw material costs and wastereduction.In order to find a practical solution, joint efforts are currently made at the RoyalInstitute of Technology, Sweden and National Metallurgical Academy of Ukraine. Theconcept is based on transformation of non-magnetic wüstite (FeO) to magneticmagnetite (Fe3O4) using an oxidizing atmosphere was proposed.In order to verify the feasibility of the proposed way of slag utilization, experiments onthe ternary CaO-FeO-SiO2 and quaternary CaO-FeO-SiO2-MnO slags systems,accompanied by thermodynamic and kinetic modelling, were performed. The crystalprecipitation during synthetic slag oxidation was observed by Confocal Scanning LaserMicroscopy (CSLM). Precipitated phases were found to be magnetite and manganeseferrite in the spinel form.Obtained magnetite and manganese ferrite can be separated from the slag by magneticseparation.The formation of nanosize manganese ferrite from the CaO-FeO-SiO2-MnO slag systemduring oxidation was investigated. Experiments were conducted in a horizontalresistance furnace in an oxidizing atmosphere (air). The final product was analysed by Xraydiffraction (XRD). The particles size of the manganese ferrite was estimated by theScherrer formula and was found to be of the order of 23-25 nm. In order to get anunderstanding of the magnetic properties of the manganese ferrite recovered from slagtreatment, it was necessary to synthesize a reference compound from pure precursors.The MnFe2O4 nanopowder was synthesized by the oxalate route. The size effects on themagnetic properties of manganese ferrite particles were investigated.IIThe potential way of the magnetite particles separation from liquid slags was investigatedby cold model studies. The experimental technique of mobilising non-conducting,nonmagnetic particles in conducting liquid in crossed electric and magnetic fields wasinvestigated in order to find the way of the particle separation from the liquidsteelmaking slags. The effects of the current density, magnetic field, size and shape ofthe particle on the particle velocity under action of the electromagnetic buoyancy force(EBF) in the electrolyte were analyzed. / QC 20100916

This thesis deals with wireless power transfer from an external source to embedded small devices (such as for conditioning monitoring, control etc.) located at different distances from the source. The proposed designs can be used in a variety of applications, including mobile phones, electric cars, unmanned aerial vehicles, robots, etc. where it could be very convenient to transmit power without wires/cables. The wireless charging method which avoids using conventional cables and wires for energizing or charging electrical devices has been one of the fastest developed recent technologies. The inductive coupling technique is one way to transfer power wirelessly and works fairly well over very short distances. For distances greater than the radius of the emitter, however, inductive coupling rapidly declines. An improved approach is to create inductive-capacitive resonance which improves efficiency and transfer distance, which was proposed by Tesla. Other methods using more than two coils have lately been proposed, which improve transfer characteristics even further. Several designs were proposed consisting of two, three and four coil combinations, with different shapes and sizes. A ferrite cored solenoid was also chosen as emitter in some setups over air cored solenoid, for better field enhancement in longitudinal energy transfer applications. To have low resistive high energy transfer, coil-capacitor designs were proposed. Several simulations were performed using COMSOL Multiphysics software to understand the magnetic field distribution and transfer to the adjacent coils in air medium. Based on this power transfer efficiency graphs were plotted for every proposed design. For validation, few simulations were contrasted with lab experiments. The focus was to develop and contribute to the improvement of existing techniques. For this, it is sometimes enough to transfer a small amount of power (e.g., 0.5 W) at different distances and frequencies with different set ups. The results obtained from the simulation and measurements were used to evaluate the impact of frequency and transfer distance on energy transfer in wireless power transfer techinque for proposed design. The analysis was used to suggest the improvements or part of future work in the designs such as use of Litz wire and ferrite concentrators with thin conductive laminates. / Detta examensarbete behandlar trådlös kraftöverföring från en extern källa till inbyggda små enheter (såsom för tillståndsövervakning, kontroll etc.) placerade på olika avstånd från källan. De föreslagna designerna kan användas i en mängd olika applikationer, inklusive mobiltelefoner, elbilar, obemannade flygfordon, robotar, etc. där det kan vara mycket bekvämt att överföra ström utan ledningar/kablar. Den trådlösa laddningsmetoden som undviker att använda konventionella kablar och ledningar för att strömsätta eller ladda elektriska apparater har varit en av de snabbast utvecklade nya teknologierna. Den induktiva kopplingstekniken är ett sätt att överföra ström trådlöst och fungerar ganska bra över mycket korta avstånd. För avstånd större än sändarens radie avtar emellertid den induktiva kopplingen snabbt. Ett förbättrat tillvägagångssätt är att skapa induktiv-kapacitiv resonans som förbättrar effektiviteten och överföringsavståndet, vilket föreslogs av Tesla. Andra metoder som använder mer än två spolar har nyligen föreslagits, vilka förbättrar överföringsegenskaperna ytterligare. Flera konstruktioner föreslogs bestående av två, tre och fyra spolar kombinationer, med olika former och storlekar. En solenoid med ferritkärna valdes också som sändare i vissa inställningar framför solenoid med luftkärna, för bättre fältförstärkning i longitudinella energiöverföringstillämpningar. För att ha låg resistiv hög energiöverföring föreslogs spolkondensatorkonstruktioner. Flera simuleringar utfördes med COMSOL Multiphysics programvara för att förstå magnetfältets distribution och överföring till intilliggande spolar i luftmedium. Baserat på detta ritades grafer för effektöverföringseffektivitet för varje föreslagen design. För validering kontrasterades få simuleringar med labbexperiment. Fokus var att utveckla och bidra till förbättringen av befintliga tekniker. För detta räcker det ibland att överföra en liten mängd effekt (t.ex. 0,5 W) på olika avstånd och frekvenser med olika uppsättningar. Resultaten från simuleringarna och mätningarna användes för att utvärdera effekten av frekvens och överföringsavstånd på energiöverföring i trådlös kraftöverföringsteknik för föreslagen design. Analysen användes för att föreslå förbättringar eller delar av framtida arbete i designen, såsom användning av Litz-tråd och ferritkoncentratorer med tunna ledande laminat.