<p>    </p> <p>Electrical steels are one type of soft magnetic material. They are based on Fe-Si alloys and are widely used for magnetic cores in transformers and electric motors. It is well known that Fe- 6.5Si wt% is the most efficient composition; however, at such a high silicon concentration (6.5wt.% = 12.1 at.% Si in Fe), the poor workability of the alloy makes it unacceptable for industrial production via conventional sheet steel rolling processes. This problem was approached in two different ways. First, a machining-based approach that suppresses the mechanisms that lead to cracking during conventional rolling was implemented for processing of thin metal strips. Two related machining-based sheet production technologies called free machining (FM), and hybrid cutting extrusion (HCE) were used to produce strips of high resistivity electrical steel. The maximum strip width achieved was 50 mm, and it was produced with a combination of FM and light rolling with a surface roughness comparable to cold-rolled sheet surfaces. Second, a new experimental alloy Fe-4Si-4Cr wt% was developed with improved magnetic properties compared to ~ Fe-3.2Si wt% and outstanding workability. Results report that the new experimental alloy has an electrical resistivity of 85 ± 3 𝜇Ω ∙ 𝑐𝑚 which is higher than Fe-6.5%Si. Also, the results on the Fe-4Si-4Cr workability show that this new alloy can withstand 75% cold-rolled reduction. The magnetic properties characterization was done via standard stacked toroid testing, and results show that Fe-4Si-4Cr experimental alloy exhibits excellent magnetic performance with a reduction in core losses of 33% at 400 Hz compared to commercial alloys with ~ Fe-3.2Si wt%. Recrystallization kinetics and texture evolution in the experimental alloy were evaluated for traditionally rolled and machining-based samples. Results were used to construct annealing maps. These maps represent the stages of the annealing process for a range of temperature versus time conditions, i.e., the annealing maps are a graphical summary showing the different stages of the annealing process for the Fe-4Si-4Cr experimental alloy in the two conditions. Despite the significant differences in the deformation texture of the two conditions, the recrystallization kinetics were similar. Finally, the two conditions retained the as-deformed texture in the intermediate annealing but to a lesser degree after completing a full anneal. In the case of the rolled sample, it is possible to trace the original texture fibers (γ-fiber, the partial α-fiber, and the θ -fiber) in the fully annealed data, but the texture intensity is just 2.5 mrd. On the other hand, the texture of the fully annealed HCE sample changes as compared to the as-deformed condition, located close to (110)[112] with a surprisingly strong peak of ~ 25 mrd. </p>

As the major electricity consumer, electrical machines play a key role for global energy savings. Machine manufacturers put considerable efforts into the development of more efficient electrical machines for loss reduction and higher power density achievements. A consolidated knowledge of the occurring losses in electrical machines is a basic requirement for efficiency improvements. This thesis deals with iron losses in electrical machines. The major focus is on the influences of the stator core magnetic material due to the machine manufacturing process, temperature influences, and the impact of inverter operation. The first part of the thesis gives an overview of typical losses in electrical machines, with focus put on iron losses. Typical models for predicting iron losses in magnetic materials are presented in a comprehensive literature study. A broad comparison of magnetic materials and the introduction of a new material selection tool conclude this part. Next to the typically used silicon-iron lamination alloys for electrical machines, this thesis investigates also cobalt-iron and nickel-iron lamination sheets. These materials have superior magnetic properties in terms of saturation magnetization and hysteresis losses compared to silicon-iron alloys. The second and major part of the thesis introduces the developed measurement system of this project and presents experimental iron loss investigations. Influences due to machine manufacturing changes are studied, including punching, stacking and welding effects. Furthermore, the effect of pulse-width modulation schemes on the iron losses and machine performance is examined experimentally and with finite-element method simulations. For nickel-iron lamination sheets, a special focus is put on the temperature dependency, since the magnetic characteristics and iron losses change considerably with increasing temperature. Furthermore, thermal stress-relief processes (annealing) are examined for cobalt-iron and nickel-iron alloys by magnetic measurements and microscopic analysis. A thermal method for local iron loss measurements is presented in the last part of the thesis, together with experimental validation on an outer-rotor permanent magnet synchronous machine. / <p>QC 20140516</p>

Το αντικείμενο της παρούσας Διδακτορικής Διατριβής είναι η ανάπτυξη και ο χαρακτηρισμός προηγμένων υλικών για εφαρμογές σε νανοδιατάξεις. Στα πλαίσια αυτής, επικεντρωθήκαμε στην ανάπτυξη και μελέτη μαγνητικών και ημιαγωγικών λεπτών υμενίων που βασίζονται σε οξείδια παραδοσιακών μετάλλων και ημιαγωγών. Ο μαγνητικός και οπτικός χαρακτηρισμός των υλικών αυτών υπό τη μορφή της νανοδομής του λεπτού υμενίου, αποκαλύπτουν νέες ιδιότητες με εξαιρετικά μεγάλο τεχνολογικό ενδιαφέρον. Πιο συγκεκριμένα, έγινε καταρχήν ανάπτυξη πολυστρωματικών μαγνητικών υμενίων Ni/NiO, μονοστρωματικών ημιαγωγικών υμενίων Cu2O, CuO και NiO, όπως επίσης και μονοστρωματικών άμορφων μονωτικών υμενίων SiOx με ή και χωρίς ενσωματωμένες κβαντικές τελείες Si. Για κάθε σειρά υμενίων από τις κατηγορίες αυτές, έγινε μελέτη των μαγνητικών ή/και των οπτικών τους ιδιοτήτων. Τα υμένια Ni/NiO αναπτύχθηκαν σε διαφορετικά υποστρώματα με τη χρήση μιας μόνο κεφαλής magnetron sputtering και της μεθόδου της φυσικής οξείδωσης. Η διαστρωμάτωση του υλικού και η επαναληψιμότητα της μεθόδου αποδείχθηκαν εξαιρετικής ποιότητας. Για υμένια Ni/NiO με διαφορετικό πάχος στρώματος Ni έγινε εκτεταμένη μελέτη της εξάρτησης της μαγνήτισης και της ανισοτροπίας από τη θερμοκρασία. Βρέθηκε ότι τα υμένια με λεπτά στρώματα Ni εμφανίζουν τάση για κάθετη μαγνητική ανισοτροπία, η οποία προέρχεται από την υπολογίσιμη θετική ανισοτροπία επιφανείας που επιδεικνύουν αυτά. Τα ημιαγωγικά υμένια οξειδίων του Cu και του Νi αναπτύχθηκαν μετά από οξείδωση υμενίων των αντίστοιχων μεταβατικών μετάλλων. Τα άμορφα μονωτικά υμένια SiOx αναπτύχθηκαν με τη τεχνική της “reactive” ιοντοβολής. Στη συνέχεια, μέρος αυτών οξειδώθηκε πλήρως μετά από θέρμανση σε θερμοκρασία 950 οC και σε περιβάλλον αέρα, ενώ κάποια άλλα υποβλήθηκαν σε θερμική αποσύνθεση μετά από θέρμανση σε συνθήκες κενού στους 1000 οC. Με τη διαδικασία της θερμικής αποσύνθεσης, όπως αποδεικνύουν και οι εικόνες ηλεκτρονικής μικροσκοπίας, σχηματίζονται νανοκρύσταλλοι Si ενσωματωμένοι σε άμορφη μήτρα οξειδίου του Si. Για τα υμένια των οξειδίων του Cu και του Ni μελετήθηκαν με τη χρήση της φασματοσκοπίας UV-VIS τα φαινόμενα κβαντικού περιορισμού που παρουσιάζουν αυτά. Βρέθηκε ότι σε κάθε περίπτωση εμφανίζεται μετατόπιση της ακμής απορρόφησης προς μεγαλύτερες ενέργειες, καθώς το πάχος του υμενίου μειώνεται και γίνεται συγκρίσιμο με την εξιτονική ακτίνα Bohr του αντίστοιχου υλικού. Τα υμένια SiOx βρέθηκε ότι μετά από τη διαδικασία της θερμικής τους αποσύνθεσης παρουσιάζουν φωτοφωταύγεια, η οποία προέρχεται από τις εξιτονικές επανασυνδέσεις στις κβαντικές τελείες Si που εμπεριέχονται σ’ αυτά. Από την εργασία στα πλαίσια αυτής της Διατριβής, διαπιστώνουμε ότι μπορούμε να μεταβάλλουμε τις ιδιότητες παραδοσιακών υλικών, όπως είναι για παράδειγμα τα μέταλλα, οι κλασσικοί ημιαγωγοί και τα οξείδια αυτών, όταν αυτά αναπτύσσονται υπό τη μορφή νανοδομών. Οι νανοδομές αυτές μπορεί να εμφανίζουν εξαιρετικό ενδιαφέρον για εφαρμογές σε νανοδιατάξεις με καινούργιες αλλά κι εντελώς ελεγχόμενες ιδιότητες. / The objective of this Thesis is the growth and the characterization of high tech materials which can be possible candidates for future applications in nanodevices. In the framework of the Thesis, we were mainly focused on the production and the study of magnetic and semiconducting thin films, which are based on oxides of metals and of conventional semiconductors. The magnetic and optical characterizations reveal that these materials, in the form of thin films exhibit new properties with exceptionally large technological interest. In more detail, magnetic Ni/NiO multilayers, semiconducting Cu2O, CuO and NiO thin films, as well as insulating amorphous SiOx thin films with or without embedded Si quantum dots, were produced. The magnetic and/or optical properties of each of the aforementioned thin film categories were studied and their impact on possible future applications was examined. The Ni/NiO multilayers were produced on various substrates with the aid of a single magnetron sputtering head and the natural oxidation process. The produced multilayers were of excellent layering and interface quality. An extended study of both the magnetization and the anisotropy as a function of the temperature and the varying Ni layer thickness was performed. It is found from the magnetic investigations, that the multilayers with thin Ni layers exhibit a trend for perpendicular magnetic anisotropy, which is attributed to the considerable positive surface anisotropy of the Ni/NiO interfaces. The semiconducting copper and nickel oxide thin films were produced via the oxidation of the corresponding metallic films. The amorphous SiOx films were fabricated via the reactive sputtering method. Part of the as deposited films was fully oxidized at 950 oC under the ambient air environment, whereas another part was thermally decomposed under vacuum conditions at 1000 oC. Electron microscopy investigations reveal that upon the thermal decomposition process of the films, embedded Si nanocrystals are formed in the amorphous matrix of the Si oxide. The Cu and Ni oxide films exhibited quantum confinement effects, which were studied via the UV-VIS spectroscopy. The recorded spectra reveal that the absorption edge shifts towards higher energies, as the layer thickness is reduced and becomes comparable with the excitonic Bohr radius of the material. The Si oxide thin films, after the thermal decomposition treatment are found to exhibit photoluminescence at the region between 1.3 and 1.5 eV which is originated to the excitonic recombination in the embedded Si quantum dots. Finally, it is deduced that conventional materials like metals, semiconductors and the oxides of them, can exhibit new properties when they are prepared in the form of nanostructure. These nanostructures can attract a lot of interest for possible applications in nanodevices with new but completely controllable properties.

Iron platinum (FePt) has attracted growing interest because of its high Curie temperature, magneto-crystalline anisotropy and chemical stability. Nanoparticles (NPs) made of this alloy are promising candidates for a wide range of biomedical applications including magnetic separation, magnetic targeted drug delivery, hyperthermia for cancer therapy and also as magnetic resonance imaging (MRI) contrast agents. This thesis presents the synthesis, functionalization and characterization of FePt NPs along with a toxicity study and an investigation into their application as MRI contrast agents. Regarding their synthesis, different approaches have been explored including the co-reduction of Fe and Pt precursors in an aqueous media, the thermal decomposition in a conventional high-boiling solvent such as benzyl ether, and in low-melting organic salts (ionic liquids). The data revealed an inhomogeneous composition distribution of Fe and Pt between particles obtained in aqueous media, due to the iron salts hydrolysis, and a mismatch in the co-reduction kinetic of the two metal precursors. While the iron content in the NPs could be increased by using more hydrolytically stable iron precursors or stronger reducing agents, there are remaining limiting parameters which prevent further Fe content increase in NPs. In contrast, by excluding the water from the reaction system and using a Fe²⁻ iron precursor, homogenous 1:1 Fe to Pt ratio NPs can be obtained through a modified thermal decomposition pathway in benzyl ether. Based on the study of synthesis in this conventional chemical, the potential of ionic liquids (ILs) to be used as novel solvents for FePt NPs synthesis was further explored. It was then demonstrated that ionic liquids (ILs) can not only be used as a solvent for synthesis of FePt NPs, but also can provide an exciting alternative pathway to direct synthesis fct-FePt NPs. In the context of the bioapplication of FePt NPs, a family of FePt NPs was specifically designed to enhance their MRI contrast agents properties. In contrast with previous reports, this thesis demonstrates that FePt NPs can be made non-toxic and provides the first data on their cellular uptake mechanisms. A six times increase in the FePt based T₂ contrast properties compared to clinical iron oxide NPs is reported. The relationship between the MRI contrast properties and the NPs architecture is explored and rationalised as the basis for the design of NPs as enhanced MRI contrast agents. Finally, the first observations of cellular and in vivo MR imaging with FePt NPs is also reported. This study opens the way for several applications of FePt NPs such as regenerative medicine and stem cell therapy, thus providing a bio-platform to develop novel diagnostic and therapeutic agents.

Cette thèse porte sur la caractérisation non destructive de structures 2D magnéto-diélectriques inhomogènes complexes. L’ensemble des étapes allant de l’expérience au traitement du problème inverse est traité. Dans un premier temps, un modèle direct reliant le champ diffusé aux propriétés électromagnétiques du matériau a été mis en place. Ce modèle requiert des calculs par éléments finis de la propagation de l’onde électromagnétique, en présence de l’objet observé lorsque celui-ci est positionné sur un support métallique. Une validation expérimentale a été réalisée via la mise en place d'un banc de mesure multi statique. Différentes étapes d'ajustements et d'étalonnages ont permis la réduction du bruit de mesure ainsi que des biais. L’inversion est traitée principalement par une approche linéaire, avec un choix attentif de la valeur des hyper paramètres qui y sont associés. Une fois les outils mis en place, six études ont été réalisées pour la validation de notre système d’imagerie 2D des propriétés électromagnétiques de matériaux magnéto-diélectriques inhomogènes. Cela comprend l’évaluation des incertitudes de mesure, de la résolution spatiale, la mesure de différents matériaux magnétiques et l’utilisation de différents supports à géométries variées. L’ensemble des résultats expérimentaux réalisés se place dans une hypothèse de géométrie 2D. C’est pourquoi, nous avons ensuite orienté nos travaux vers la recherche d’un design innovant permettant de faire évoluer le banc de mesure en un dispositif d’imagerie 3D. Dans cette perspective, une source secondaire vient se déplacer proche de la cible pour acquérir de l’information selon la troisième dimension. / The subject of this thesis is the non-destructive characterization of complex inhomogeneous magneto-dielectric structures. Successively, the experimental developments, the modelling and the data treatments stages are addressed. A forward model that links the scattered field to the electromagnetic properties is established. This model requires some finite element computations in order to estimate the propagation of the electromagnetic wave in presence of the magneto-dielectric object which is glued on a metallic support. A multistatic bench has been designed and constructed in order to collect measured scattered fields. Several adjustments and calibration procedures have been carried out to reduce the measurement noise and biases. Next, the inverse problem has been dealt with, in order to retrieve the electromagnetic properties of the samples, from the measured scattered field. The inverse problem is mainly solved with a linear approach, with a careful selection of the hyperparameters. Once the system has been fine tuned, six studies have been realized to validate our 2D imaging system. The assessment of the measurement uncertainty, the evaluation of the spatial resolution, the characterization of various magnetics materials and the use of different supports with variable geometries have been performed. So far, all the developments were done under a 2D hypothesis. That is why, we have then focused our research on the design of a 3D innovative imaging setup. To this end, a secondary source moving close to the target has been added in order to gain information in the third direction. A numerical study has been performed to assess the expected performances of this new setup.

Les procédés de traitement de surface sont utilisés à l'échelle industrielle pour améliorer les performances de pièces mécaniques en introduisant des contraintes résiduelles de compression. Cette mise en compression de surface permet de limiter l'amorçage et la propagation de fissures dans le matériau. Ceci permet d'augmenter de façon significative la durée de vie en fatigue des pièces mécaniques ainsi traitées. L'utilisation de ces procédés dans l'industrie a démontré leur efficacité, mais aussi leurs limitations et inconvénients. Les défauts récurrents consistent en une profondeur traitée faible, une dégradation de l'état de surface (rugosité), des difficultés de contrôle, une contamination du matériau traité, etc. Ces défauts ont conduit à l'élaboration de nouveaux procédés innovants qui permettent de meilleures performances en évitant certains des inconvénients succinctement évoqués. Parmi ces procédés innovants, le traitement de surface par impulsion électromagnétique semble particulièrement intéressant. Ce procédé met en œuvre un puissant champ magnétique transitoire pour engendrer des forces de Laplace dans une pièce métallique et induire des contraintes résiduelles. Il n'existe que peu d'informations dans la littérature et il n'existe aucun dispositif expérimental de ce procédé. Cette thèse est dédiée à la conception et la réalisation d'un prototype de mise en compression électromagnétique. Le premier chapitre de cette thèse est un état de l'art des technologies de mise en compression et du procédé de mise en compression par impulsion électromagnétique. Ainsi, les besoins de ce procédé sont identifiés et les technologies pouvant répondre à ces besoins sont explorées. Le deuxième chapitre, après une sélection de la structure globale du dispositif, va consister aux dimensionnements des éléments du prototype EMP. Cette étude commencera avec une étude sur l'inducteur qui va être utilisé avant de continuer sur le dimensionnement du stockage d'énergie et de l'interrupteur de décharge. Afin de valider le dimensionnement des composants précédents, une simulation électromagnétique 3D du système est réalisée. L'assemblage du prototype est présenté dans le troisième chapitre ainsi qu'une première campagne d'essai sur un alliage d'aluminium. Deux types d'éprouvettes sont testées : une éprouvette fine pour vérifier visuellement la mise en compression (essai Almen) et une éprouvette massive afin d'évaluer la profondeur traitée. Une modélisation multiphysique 3D du procédé est réalisée afin de corréler ces résultats avec l'expérience. Dans un dernier chapitre, une étude exploratoire est menée sur un matériau ferromagnétique, le mumétal, pour visualiser l'influence des contraintes résiduelles sur les propriétés magnétiques de ce dernier. / Penning processes are widely used in industries to apply compressive residual stresses into the most solicited part of mechanical pieces. In that way, the compressive residual stresses limit the priming and the propagation of micro-cracks in the material. This increases significantly the lifespan of the treated mechanical piece under fatigue stresses. These existing peening processes have proved their efficiency and also their limitations and weaknesses. The main recurrent defaults are a shallow depth of treatment, a degradation of the surface condition, a random control of the treatment, a material contamination, etc. These problems have led towards the development of news innovative peening processes which allow better performance avoiding some previous defaults briefly evoked. Among these news processes, the electromagnetic peening process seems especially interesting. This process uses high energy electromagnetic fields to induce Lorentz forces into a metallic piece and thus residual stresses. Actually, there is not much information about this process in the literature and no prototype was ever built. The work of this thesis is dedicated to development and realization of an electromagnetic peening prototype. The first chapter of this thesis adresses the state of the art of major peening processes actually in industrial use. Next, the electromagnetic peening process, or EMP process, is described and the electrical needs are exposed. A second state of the art is made about the technological solutions to respond to the EMP needs. The second chapter is about the conception of the EMP prototype with the electrical structure adopted in the previous chapter. The first step is about the inductor sizing to generate an electromagnetic field sufficient enough for a peening application. Next, the storage system is designed depending on the inductor parameters and finally the closing switch is created considering the electrical parameters used for the EMP process. To validate the previous results, a 3D electromagnetic simulation is done. The prototype assembly is presented in the third chapter and also the first experimental test on the EMP prototype. To begin with, an aluminium alloy with low yield strength is selected to be treated. Two different samples forms are used, a thin one, to realize a similar test to the Almen test and thick one to check the EMP depth of treatment. A 3D multiphysics simulation of these experiments is made and these numeric results are next correlated to the experimental ones. In the fourth chapter, an exploratory study is realized on the effects of the residual stresses on magnetic properties of ferromagnetic material, the mumetal

The continuously increasing demand for clean renewable energy has rekindled interest in multi-terminal high voltage direct current (HVDC) grids. Although such grids have several advantages and a great potential, their materialization has been thwarted due to the absence of HVDC breakers. In comparison with traditional alternating current (AC) breakers, they should operate and interrupt fault currents in a time frame of a few milliseconds. The aim of this thesis is focused on the design of ultra-fast electro-mechanical actuator systems suitable for such HVDC breakers.Initially, holistic multi-physics and hybrid models with different levels of complexity and computation time were developed to simulate the entire switch. These models were validated by laboratory experiments. Following a generalized analysis, in depth investigations involving simulations complemented with experiments were carried out on two of the sub-components of the switch: the ultra-fast actuator and the damper. The actuator efficiency, final speed, peak current, and maximum force were explored for different design data.The results show that models with different levels of complexity should be used to model the entire switch based on the magnitude of the impulsive forces. Deformations in the form of bending or elongation may deteriorate the efficiency of the actuator losing as much as 35%. If that cannot be avoided, then the developed first order hybrid model should be used since it can simulate the behavior of the mechanical switch with a very good accuracy. Otherwise, a model comprising of an electric circuit coupled to an electromagnetic FEM model with a simple mechanics model, is sufficient.It has been shown that using a housing made of magnetic material such as Permedyn, can boost the efficiency of an actuator by as much as 80%. In light of further optimizing the ultra-fast actuator, a robust optimization algorithm was developed and parallelized. In total, 20520 FEM models were computed successfully for a total simulation time of 7 weeks. One output from this optimization was that a capacitance of 2 mF, a charging voltage of 1100 V and 40 turns yields the highest efficiency (15%) if the desired velocity is between 10 m/s and 12 m/s.The performed studies on the passive magnetic damper showed that the Halbach arrangement gives a damping force that is two and a half times larger than oppositely oriented axially magnetized magnets. Furthermore, the 2D optimization model showed that a copper thickness of 1.5 mm and an iron tube that is 2 mm thick is the optimum damper configuration. / <p>QC 20150422</p>

High dielectric constant materials have tremendous impact on miniaturization of devices that are used in various applications like wireless communication systems, microelectronics, global positioning systems, etc. To store electric charge in a very small space necessarily needs a capacitor with very high dielectric constant. Thus, these materials are very important in fabricating capacitors, or metal oxide semiconductor filed effect transistor (MOSFET). Among the existing commercially available devices, silicon-based microelectronic devices are commonly used based on the moderately stable dielectric constants of silicon with low losses and minimal temperature and frequency dependence. However, now-a-days, the perovskite based transition metal oxides have drawn attention that have the ability to fulfill all the requirements for being a good dielectric material in all the industrial applications. In this thesis we have studied a few selected perovskite based transition metal oxide systems in terms of their dielectric and magnetic behaviour. In Chapter 1, we have have given brief introductions about the some application of dielectric materials and the origin of dielectric and magnetic properties in the materials. We have also discussed about the polarisation in the dielectric materials to understand it’s frequency dependence and also to formalise different relaxation behaviour with the help of physical and mathematical explanation. In Chapter 2, we describe the various methodologies adopted in this thesis. In Chapter 3, we have studied the dielectric behaviour of Nd2NiMnO6, a rare earth based double perovskite ferromagnetic insulator. We successfully synthesised and characterised the compounds, settled the valency issues with the help of temperature dependent XAS of the transition metal atom in contrast to the existing controversy available in literature. We have found that this material shows relaxor kind behaviour with a colossal dielectric constant value. We have studied in details the origin of the colossal dielectric constant and the relaxation behaviour along with the a.c and d.c. transport properties. We have shown the origin of the ferromagnetism (TC ∼ 200 K) with a low temperature antiferromagnetic ordering (TN ∼ 55 K) with the help of detailed studies of temperature dependent d.c., a.c. magnetism and their XMCD. We have also investigated the isothermal variation of magnetodielectric and magnetoresistance behaviour as a function of magnetic field and their origin. In Chapter 4,we study the effect of cation anti-site disorder on the magnetic, dielectric and transport properties of another rare earth based ferromagnetic double perovskite insulator La2NiMnO6 by controlling different extent of anti-site disordered. We have confirmed the valency of the transition metal cations using XAS technique and followed by shown, different types of magnetic interaction between the transition metal cations using d.c magnetic, quantitative XMCD analysis and the origin of large dielectric response, a.c. transport & dielectric relaxation using temperature variation dielectric measurement as an experimental evidence in contrast of our previous speculation published in literature. We further have studied, the coupling between the magnetic and electric spin through isothermal magnetodielectric measurement. In Chapter 5, we have successfully synthesised and characterised a solid solution of YMnxIn1−xO3 series via different mol % of In doping in the multiferroic YMnO3 system. YMnO3 is a well known multiferroic material studied rigorously during past few decades. We have seen, YMnO3 which has a antiferromagnetic ordering temperature of ∼ 75 K suppressed with increasing the dopant concentration In. We have figured out the effect of In doping in the suppression of multiferroic phase and extended it to the dielectric properties. We have found that, the temperature dependence of dielectric constant shows an anomaly at the magnetic ordering temperature and studied magnetodielectric coupling. We have also investigated the temperature variation of dielectric relaxation and a.c. transport behaviour as a function of composition. In Chapter 6, we have identified the phase seperation and proposed a phase diagram as function of Gd doping in the Ho2−xGdxCuTiO6 double perovskite, where two end member, namely Ho2CuTiO6 and Gd2CuTiO6 are found to be in two different crystallographic phase as, hexagonal (P63cm) and orthorhombic (Pnmm), respectively. We have characterised the valency of the transition metal cations using XAS.We have seen very less temperature and frequency dependence of dielectric constant in hexagonal phase in compare to the orthorhombic phase and tried to figuring out from experimental analysis by performing temperature dependence dielectric const measurement. We also have shown the effect of doping in the origin of dielectric relaxation, a.c transport and magnetic behaviour of this system. In Chapter 7, we have synthesised and characterised successfully two different rare earth based layered perovskite La3Cu2VO9 and La4Cu3MoO12 compounds are of centrosymmetric space group. We have figured it of the valency of the different atoms present in the compound using XAS. We also do have observed the good temperature stability of dielectric constant of these materials and explored origin of mechanism in the dielectric relaxation, a.c. transport property by performing the temperature dependance dielectric measurement. The magnetic structure also have shown with the help of d.d. magnetic measurements. In Appendix A, we have seen the very stable dielectric constant constant from very low to above room temperature of the 2D nano PbS. The frequency stability of dielectric constant is also remarkable in compare to bulk PbS values available in literature. We have explored the origin of the conductivity and relaxation mechanism performing dielectric constant measurement. In conclusion, we investigate, in this thesis, dielectric properties of different transition metal oxides system and the mechanism of dielectric relaxation, a.c, d.c transport and their origin of magnetic response.

Notre étude à caractère pluridisciplinaire comprend l'élaboration de composés intermétalliques ainsi que la caractérisation de leurs propriétés tant structurales que magnétiques. Nos travaux ont porté sur des borures RT12B6 où R est un élément de terre rare ou l'yttrium et T un métal de transition 3d ainsi que des phases de Laves (Hf,Ta)Fe2. Pour appréhender les propriétés physiques de ces composés, nous avons mis en œuvre diverses variables externes (température, champ magnétique, pression) mais aussi internes telle que la pression chimique liée à la substitution d'un élément par un autre. Nous apportons une contribution à l'étude des propriétés magnétiques des composés RCo12B6. Les propriétés magnétiques de ces composés sont caractérisées à la fois par une température d'ordre qui varie peu avec l'élément de terre rare R et un moment magnétique de Co remarquablement faible. Nous montrons que les interactions d'échange R-Co sont de plus d'un ordre de grandeur plus faibles que les interactions Co-Co existant dans ces composés. La substitution du fer au cobalt dans les composés RCo12B6 est possible et donne lieu à une localisation préférentielle. Grâce à la spectroscopie Mössbauer et à la diffraction neutronique, nous avons démontré l'extrême sensibilité de l'orientation des moments magnétiques à la substitution Fe/Co. Le composé LaFe12B6 présente des propriétés magnétiques remarquables avec un état fondamental antiferromagnétique (AFM) et une transition vers un état ferromagnétique (FM) qui peut être induite par le champ appliqué ou par la température. A basse température la transition métamagnétique AFM-FM est accompagnée d'une hystérésis très large et est caractérisée par des sauts spectaculaires comme l'illustre nos mesures magnétiques, de magnétostriction ou de transport. La transition métamagnétique s'avère également fort sensible à la pression appliquée. Le composé intermétallique LaFe12B6 est caractérisé par une forte expansion thermique linéaire, un large effet magnétovolumique et présente à la fois des effets magnétocaloriques inverse et normal. L'effet de la substitution du cobalt ou du manganèse au fer ou du cérium au lanthane sur les propriétés structurales et magnétiques a été étudié de façon détaillée. La substitution Co/Fe ou Mn/Fe entraine dans les deux cas une forte augmentation du champ critique de la transition métamagnétique. Inversement la substitution Ce/La, quant à elle, réduit fortement le champ de transition. L'étude de l'alliage amorphe LaFe12B6, préparé par hypertrempe, montre des propriétés magnétiques radicalement différentes puisque la phase amorphe devient alors ferromagnétique avec une haute température de Curie. Enfin nous avons étudié les propriétés magnétiques intrinsèques du système intermétallique Hf1-xTaxFe2 pour lequel la solution solide est complète. L'analyse de l'ensemble des mesures a mis en lumière des comportements originaux du magnétisme du fer et ceci tant dans l'état ordonné que dans l'état paramagnétique. Le caractère inhabituel du magnétisme de ces composés est attribué au comportement d'électrons itinérants, lequel est à l'origine de la transition métamagnétique entre l'état AFM et l'état FM. / Our multidisciplinary study includes the synthesis of intermetallic compounds and the characterization of their structural and magnetic properties. Our work has focused on RT12B6 borides where R is a rare earth element or yttrium and T a 3d transition metal as well as (Hf, Ta)Fe2 Laves phases. In order to understand the physical properties of these compounds, we have implemented various external variables (temperature, magnetic field, pressure) as well as internal variables such as the chemical pressure due to the substitution of one element with another. Through this experimental work, we investigated the magnetic properties of RCo12B6 compounds. The magnetic properties of these compounds present both an ordering temperature which is quasi independent of the rare earth element R and a remarkably small magnetic moment of Co. We show that the R-Co exchange interactions are more than an order of magnitude smaller that the Co-Co occurring in these compounds. We demonstrated that the iron for cobalt substitution in RCo12B6 compounds gives rise to a preferential substitution scheme. Combining Mössbauer spectroscopy and neutron diffraction, we have found that the magnetic ordering direction is extremely sensitive to Fe/Co substitution. LaFe12B6 compound presents remarkable magnetic properties with an antiferromagnetic (AFM) ground state but it can be transformed into a ferromagnetic (FM) state by the applied magnetic field or by the temperature. At low temperature, the field-induced AFM-FM metamagnetic transition has a large hysteresis and exhibits ultra sharp jumps as shown in our magnetic, magnetostriction and transport measurements. The metamagnetic transition is also very sensitive to the applied pressure. LaFe12B6 intermetallic compound shows a large linear thermal expansion, a huge volume magnetostriction and both normal and inverse magnetocaloric effects. The effect of cobalt or manganese for iron substitution or cerium for lanthanum substitution on the structural and magnetic properties was deeply investigated. Co/Fe or Mn/Fe substitution in both cases leads to a strong increase of the critical field of the metamagnetic transition. However Ce/La substitution reduces strongly the transition field. The investigation of LaFe12B6 amorphous alloy, prepared by melt spinning, shows radically different magnetic properties since the amorphous phase becomes ferromagnetic with a high Curie temperature. Finally we studied the intrinsic magnetic properties of the Hf1-xTaxFe2 system for which the solid solution is complete. The analysis of all the measurements highlighted original behaviours of the iron magnetism and this both in the ordered state and in the paramagnetic state. These remarkable properties are attributed to the itinerant character of the Fe 3d band magnetism, which gives rise to the metamagnetic transition between the AFM and FM states.

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