Les phénomènes de non-stoehiométrie dans les ferrites du système Ba-La-Fe-O dont les structures dérivent de la perovskite, ont été étudiés au moyen de diverses techniques (diffraction X, HRTEM, spectroscopie Mössbauer...).<br />Dans le système BaFe4+O3-BaFe3+O2.50 la structure et l'ordre des lacunes des phases BaFeO3-y dépendent du taux de lacunes (y) et corrélativement du rapport Fe4+/Fe3+ (t / (1-t)) directement lié aux conditions de synthèse (PO2, T). Pour y <~ 0.35, l'empilement est un mélange des types "hexagonal compact" et "cubique compact" conduisant à des structures de type perovskite 6H ou 12H lacunaires en oxygène alors que pour des valeurs de y plus élévées (y ~> 0.35) il devient "cubique compact". Dans ce domaine de compositions, la non-stoichiométrie est accomodée grâce à la formation de structures en microdomaines soit d'une phase monoclinique (BaFeO2.50), soit d'une phase orthorombique de composition voisine de BaFe02.55.<br />En revanche pour 0.25 < y < 0.37, on observe des phénomènes d'intercroissances entre une phase de type 6H et une phase dérivée de la perovskite cubique. Pour y <= 0.25, aucun ordre des lacunes à longue distance n'apparaît.<br />Dans le système LaFeO3-BaFeO2.50, quatre phases différentes, surstructures de la perovskite cubique, apparaissent en fonction du rapport Ba/La (x/(1-x)). Leur microstructure est discutée en fonction de la composition, de l'ordre Ba-La et du taux de lacunes (y).

Electrically-small loop antennas are a complex topic, with many design concepts to consider, including: effective magnetic core permeability, antenna impedance, antenna radiation, surrounding medium effects, and optimization approaches. There is a plethora of literature available covering these subjects but many conflict, compete, or are overall lacking; this thesis seeks to compare and analyze literature then validate with measurements, allowing optimal design.

Nanopartículas magnéticas têm sido extensamente estudadas não só pelas inúmeras possibilidades de aplicações nas áreas tecnológica e biomédica, mas também do ponto de vista acadêmico, visando a uma compreensão das alterações de suas características físicas nesta escala de tamanhos. Sintetizar nanopartículas com baixa dispersão de tamanhos e homogeneidade morfológica, estrutural e estequiométrica é de grande importância para o estudo de suas características magnéticas. No presente trabalho, amostras de diferentes ferritas (MeFe2O4, M = Fe, Co e Ni) foram produzidas por um método de síntese química que envolve a decomposição do acetilacetonato de Fe em altas temperaturas na presença de um álcool de cadeia longa e dos surfactantes e estabilizantes oleilamina e ácido oléico. Como o objetivo deste trabalho é estudar a variação das propriedades magnéticas em função do metal M, foi selecionada uma amostra de cada material com diâmetros médios próximos entre si (entre 5,7 e 8,1 nm). A caracterização estrutural foi feita por microscopia eletrônica de transmissão de baixa e alta resolução, além de difração de raios-X. As propriedades magnéticas foram caracterizadas por medidas de susceptibilidade ac em função da freqüência e temperatura, magnetização em função do campo magnético e espectroscopia Mössbauer em campos magnéticos aplicados entre 0 e 12 T. As amostras apresentaram estreita distribuição de tamanhos, ausência de aglomerados, homogeneidade morfológica e altíssima cristalinidade. Das medidas magnéticas foram obtidos, por dois métodos distintos, valores da constante de anisotropia magnética de 2,56,1 para M = Ni, 23,019,3 para M = Fe e 50,042,3 para M = Co (valores em 105 erg/cm3). Estes valores estão acima do esperado para os respectivos materiais bulk, indicando uma contribuição à anisotropia além da magnetocristalina. Os valores de magnetização de saturação a 4,2 K (17,1, 74,0 e 30 emu/g para M = Fe, Co e Ni) estão em geral abaixo do valor esperado para os respectivos materiais massivos. Curvas MH obtidas acima da temperatura de bloqueio mostram o comportamento superparamagnético das partículas. Espectros Mössbauer coletados sob altos campos confirmaram a alta cristalinidade das partículas, excluindo a existência de uma camada superficial de spins desalinhados. / Magnetic nanoparticles have been extensively investigated, motivated by their potential technological and biomedical applications as well as in search of a better understanding of the physical properties modifications induced by nanoscale size. Synthesizing nanoparticles with a narrow size dispersion and good morphological, structural and stoichiometric homogeneity is an important requisite for such studies. In this work, nanocrystalline samples of different ferrites MFe2O4 (M = Fe, Co and Ni) have been prepared by a chemical synthesis method involving high-temperature decomposition of Fe acetylacetonate in the presence of a long-chain alcohol and of surfactant and stabilizing agents oleylamin and oleic acid. The main objective of this work being a comparative study of the effect of the M element on the magnetic properties, one sample was selected for each compound, with close mean diameters (5.7-8.1 nm). The structural characterization was carried out by low and high-resolution TEM and x-ray diffraction. Magnetic properties were characterized by frequency and temperature dependent ac susceptibility, magnetization vs. field measurements, and Mössbauer spectroscopy in applied magnetic fields ranging from 0 to 12 T. All samples exhibited narrow size distributions, no particle agglomeration, morphological homogeneity, and an excellent crystallinity. Magnetic anisotropy constants were obtained from magnetic data by two different methods, giving 2.5-6.1 for M = Ni, 23.0-19.3 for M = Fe, and 50.0-42.3 for M = Co (all data in 105 erg/cm3). These results are higher than those expected for the respective bulk materials, indicating an additional contribution to purely magnetocrystalline anisotropy. Saturation magnetization values at 4.2 K (17.1, 74.0 and 30 emu/g por M = Fe, Co and Ni) are generally below the corresponding bulk values. Magnetization curves above the blocking temperature exhibit superparamagnetic behavior. High-field Mössbauer spectra do not show a superficial shell of misaligned spins, thus confirming the high crystallinity of the nanoparticles.

O objetivo deste trabalho foi investigar a influência da variação da concentração micelar crítica do surfactante cetiltrimetil brometo de amônio (CTAB) na síntese, pelo método de coprecipitação, do composto Zn0,25Mn0,75Fe2O4 (Frankilinita) e ainda a influência do processamento das amostras por reação hidrotermal. Foram utilizadas concentrações de 1, 2, 3, 4, 5 e 10 vezes a concentração micelar crítica de CTAB, resultando em 12 amostras: seis com e seis sem tratamento hidrotermal. As amostras foram caracterizadas por difração de raios X, espectrometria de infravermelho (FTIR) e medidas magnéticas. A análise magnética foi realizada por um susceptometria AC, sendo possível obter a susceptibilidade magnética e a densidade de energia magnética. Foram realizadas análises dos espectros de absorção por FTIR, identificando duas fases, Frankilinita e Akaganéita. A estrutura e morfologia das nanoferritas foram analisadas por difração de raios X, mostrando que na síntese por coprecipitação existiu uma tendência no aumento do tamanho médio de cristalitos da fase Akaganéita e diminuição do tamanho médio de cristalitos da fase Frankilinite. As amostras submetidas a tratamento hidrotermal apresentaram tendência à diminuição do tamanho médio de cristalitos de ambas as fases, bem como o aumento da porcentagem da fase Frankilinite, comparativamente às amostras sintetizadas apenas por coprecipitação, sugerindo que o tratamento hidrotermal foi efetivo na obtenção de materiais nanoestruturados de partículas menores. / The objective of this work was to investigate the influence of the critical micelle concentration of the CTAB surfactant on the synthesis of the compound Zn0.25Mn0.75Fe2O4 (Frankilinite) by the coprecipitation method and then processing fractions of the synthesized material by hydrothermal treatment. The magnetic characterization was performed by AC susceptometry, being possible to determine the magnetic susceptibility and the dissipated energy. The FTIR analysis identified two phases, Frankilinite and Akaganéite. The structure and morphology of the nanoferrites were analyzed by X-ray diffraction and it was shown that the samples synthesized by coprecipitation only presented the tendency to increasing of crystallite sizes of the akaganéita phase and decreasing of crystallite sizes of the Frankilinite phase as a function of CTAB concentration. The samples submitted to subsequent hydrothermal treatment presented a tendency to decreasing the crystallite sizes of both phases and increasing in Frankilinite phase fraction, compared to the samples synthesized only by coprecipitation, suggesting that the hydrothermal treatment was effective in obtaining nanostructured materials of smaller particles.

O objetivo deste trabalho foi investigar a influência da variação da concentração micelar crítica do surfactante cetiltrimetil brometo de amônio (CTAB) na síntese, pelo método de coprecipitação, do composto Zn0,25Mn0,75Fe2O4 (Frankilinita) e ainda a influência do processamento das amostras por reação hidrotermal. Foram utilizadas concentrações de 1, 2, 3, 4, 5 e 10 vezes a concentração micelar crítica de CTAB, resultando em 12 amostras: seis com e seis sem tratamento hidrotermal. As amostras foram caracterizadas por difração de raios X, espectrometria de infravermelho (FTIR) e medidas magnéticas. A análise magnética foi realizada por um susceptometria AC, sendo possível obter a susceptibilidade magnética e a densidade de energia magnética. Foram realizadas análises dos espectros de absorção por FTIR, identificando duas fases, Frankilinita e Akaganéita. A estrutura e morfologia das nanoferritas foram analisadas por difração de raios X, mostrando que na síntese por coprecipitação existiu uma tendência no aumento do tamanho médio de cristalitos da fase Akaganéita e diminuição do tamanho médio de cristalitos da fase Frankilinite. As amostras submetidas a tratamento hidrotermal apresentaram tendência à diminuição do tamanho médio de cristalitos de ambas as fases, bem como o aumento da porcentagem da fase Frankilinite, comparativamente às amostras sintetizadas apenas por coprecipitação, sugerindo que o tratamento hidrotermal foi efetivo na obtenção de materiais nanoestruturados de partículas menores. / The objective of this work was to investigate the influence of the critical micelle concentration of the CTAB surfactant on the synthesis of the compound Zn0.25Mn0.75Fe2O4 (Frankilinite) by the coprecipitation method and then processing fractions of the synthesized material by hydrothermal treatment. The magnetic characterization was performed by AC susceptometry, being possible to determine the magnetic susceptibility and the dissipated energy. The FTIR analysis identified two phases, Frankilinite and Akaganéite. The structure and morphology of the nanoferrites were analyzed by X-ray diffraction and it was shown that the samples synthesized by coprecipitation only presented the tendency to increasing of crystallite sizes of the akaganéita phase and decreasing of crystallite sizes of the Frankilinite phase as a function of CTAB concentration. The samples submitted to subsequent hydrothermal treatment presented a tendency to decreasing the crystallite sizes of both phases and increasing in Frankilinite phase fraction, compared to the samples synthesized only by coprecipitation, suggesting that the hydrothermal treatment was effective in obtaining nanostructured materials of smaller particles.

La corrosion des parties métalliques du circuit primaire des centrales REP engendre la formation de produits de corrosion. Ceux-ci peuvent circuler dans le circuit primaire sous forme de particules colloïdales ou d'espèces dissoutes qui peuvent être activées lors de leur passage sous flux puis adhérer sur les parties métalliques des circuits et sur les gaines des assemblages combustible. Le dépôt des particules ou d'ions activés sur les zones hors flux est alors responsable de la contamination surfacique. Afin d'avoir une meilleure maîtrise de la contamination, la caractérisation (surface spécifique, granulométrie, PCN...) des différentes particules présentes dans le circuit primaire ainsi que l'étude des interactions des produits de corrosion entre eux ou avec les parois (adhésion, sorption...) est nécessaire. Les espèces prises en compte dans cette étude sont, pour les particules : les ferrites de cobalt et de nickel ainsi que la magnétite, pour les matériaux du circuit primaire : l'Inconel 690, le Zircaloy 4 et l'acier inoxydable 304L. La sorption du cobalt et du nickel, principaux responsables de la contamination surfacique, sur les différents produits de corrosion a été réalisée expérimentalement et modélisée grâce au code de calcul ECOSAT. L'évolution de leur charge de surface a également été étudiée. Les données obtenues alimenteront, in fine, différents codes permettant la modélisation de la contamination dans les circuits en tenant compte de l'hydraulique. Le phénomène de sorption est en compétition avec celui de précipitation pour des teneurs en ions supérieures à 10-5 M et un pH élevé. Le dépôt des produits de corrosion, ayant subi ou non la sorption, est favorisé sur une large gamme de pH et quelque soit l'épaisseur de la couche d'oxyde à la surface des matériaux métalliques du circuit. La modélisation confirme que l'hydraulique est à prendre en compte lors de l'étude des phénomènes de dépôt.

This thesis compiles results of research in two mutuallydependent parts: 1) development of ferromagnetic resonance(FMR) spectrometer to study microwave properties offerromagnetic materials, and 2) characterization of new irongarnets: pulsed laser deposited Y3Fe5O12and Bi3Fe5O12films and Ce:Y3Fe5O12single crystal. First part describes a novelBroadbandFMRSpectrometerdesigned to characterize thin ferromagneticfilms. The spectrometer uses two probeheads: one is the X-bandmicrowave reflection cavity for room temperature measurementsand the in-cryostat microstrip line probe to perform FMRexperiments in the frequency range from 50 MHz to 40 GHz. Veryuniform and stable magnetic field up to 2.4 T, temperatures 4 Kto 420 K, and continuous frequency scan performed byHP8722Dvector network analyzer provide various modes ofoperation. Both probeheads are equipped with two-circlegoniometers to ensure accurate study of magneticanisotropy. The spectrometer was used to make express-analysis ofquality thus to optimize processing parameters of epitaxialiron garnet films grown by pulsed laser deposition (PLD).Comprehensive study of uniaxial and cubic magnetocrystallineanisotropy has been performed for Ce:Y3Fe5O12bulk crystal as well as for Y3Fe5O12and Bi3Fe5O12films grown on different substrates by PLD andreactive ion beam sputtering techniques. BroadbandFMR-spectroscopy revealed difference in spectra of domain wallresonances: instead of“soft”spin modes in filmsgrown by liquid phase epitaxy, PLD-made films show“diffuse”transformation of domains near thesaturation field. This effect indicates non-uniformity ofsaturation magnetization and field of uniaxial anisotropy inPLD-iron garnets. Spin wave resonances in comparison withuniform FMR have been studied to evaluate“localquality”of ferromagnetic films. The resonance field andFMR linewidth behavior were studied at various crystallographicdirections determined by X-ray diffraction. FMR was used to choose PLD-made YIG films with low losses atmicrowave frequencies and to build magnetostatic surface wavesmicrowave bandpass filter. The filter was designed as a planarfilm structure with a microstrip line for transducers. It is afirst demonstration of feasibility to introduce PLD processingtechnique to magnetostatic wave technology. Magneto-optical study of Ce:Y3Fe5O12single crystal complements results ofFMR-spectroscopy of new garnets. <b>Keywords:</b>ferrites, thin films, ferromagnetic resonance,microwaves, FMR spectrometer, magnetic anisotropy,magnetostatic waves.

The magnetic separation approach has several advantages compared with conventional separation methods / it can be performed directly in crude samples containing suspended solid materials without pretreatment, and can easily isolate some biomolecules from aqueous systems in the presence of magnetic gradient fields. This thesis focused on the development of new class of magnetic separation material particularly useful for the separation of histidine-tagged proteins from the complex matrixes through the use of imidazole side chains of histidine molecules. For that reason surface modified cobalt ferrite nanoparticles which contain Ni-NTA affinity group were synthesized. Firstly, cobalt ferrite nanoparticles with a narrow size distribution were prepared in aqueous solution using the controlled coprecipitation method. In order to obtain small size of agglomerates two different dispersants, oleic acid and sodium chloride, were tried. After obtaining the best dispersant and optimum experimental conditions, ultrasonic bath was used in order to decrease the size of agglomerates. Then, they were coated with silica and this was followed by surface modification of these nanoparticles by amine in order to add functional groups on silica shell. Next, &ndash / COOH functional groups were added to silica coated cobalt ferrite magnetic nanoparticles through the NH2 groups. After that N&alpha / ,N&alpha / -Bis(carboxymethyl)-L-lysine hydrate, NTA, was attached to carboxyl side of the structure. Finally, nanoparticles were labeled with Ni (II) ions. The size of the magnetic nanoparticles and their agglomerates were determined by FE-SEM images, particle size analyzer, and zeta potential analyzer (zeta-sizer). Vibrational sample magnetometer (VSM) was used to measure the magnetic behavior of cobalt ferrite and silica coated cobalt ferrite magnetic nanoparticles. Surface modifications of magnetic nanoparticles were followed by FT-IR measurements. ICP-OES was used to find the amount of Ni (II) ion concentration that was attached to the magnetic nanoparticle.

<p>This thesis compiles results of research in two mutuallydependent parts: 1) development of ferromagnetic resonance(FMR) spectrometer to study microwave properties offerromagnetic materials, and 2) characterization of new irongarnets: pulsed laser deposited Y₃Fe₅O₁₂and Bi₃Fe₅O₁₂films and Ce:Y₃Fe₅O₁₂single crystal.</p><p>First part describes a novel<i>Broadband</i>FMR<i>Spectrometer</i>designed to characterize thin ferromagneticfilms. The spectrometer uses two probeheads: one is the X-bandmicrowave reflection cavity for room temperature measurementsand the in-cryostat microstrip line probe to perform FMRexperiments in the frequency range from 50 MHz to 40 GHz. Veryuniform and stable magnetic field up to 2.4 T, temperatures 4 Kto 420 K, and continuous frequency scan performed by<i>HP8722D</i>vector network analyzer provide various modes ofoperation. Both probeheads are equipped with two-circlegoniometers to ensure accurate study of magneticanisotropy.</p><p>The spectrometer was used to make express-analysis ofquality thus to optimize processing parameters of epitaxialiron garnet films grown by pulsed laser deposition (PLD).Comprehensive study of uniaxial and cubic magnetocrystallineanisotropy has been performed for Ce:Y₃Fe₅O₁₂bulk crystal as well as for Y₃Fe₅O₁₂and Bi₃Fe₅O₁₂films grown on different substrates by PLD andreactive ion beam sputtering techniques. BroadbandFMR-spectroscopy revealed difference in spectra of domain wallresonances: instead of“soft”spin modes in filmsgrown by liquid phase epitaxy, PLD-made films show“diffuse”transformation of domains near thesaturation field. This effect indicates non-uniformity ofsaturation magnetization and field of uniaxial anisotropy inPLD-iron garnets. Spin wave resonances in comparison withuniform FMR have been studied to evaluate“localquality”of ferromagnetic films. The resonance field andFMR linewidth behavior were studied at various crystallographicdirections determined by X-ray diffraction.</p><p>FMR was used to choose PLD-made YIG films with low losses atmicrowave frequencies and to build magnetostatic surface wavesmicrowave bandpass filter. The filter was designed as a planarfilm structure with a microstrip line for transducers. It is afirst demonstration of feasibility to introduce PLD processingtechnique to magnetostatic wave technology.</p><p>Magneto-optical study of Ce:Y₃Fe₅O₁₂single crystal complements results ofFMR-spectroscopy of new garnets.</p><p><b>Keywords:</b>ferrites, thin films, ferromagnetic resonance,microwaves, FMR spectrometer, magnetic anisotropy,magnetostatic waves.</p>

Thèse doctorat : Dispositifs de l'Electronique Intégrée : INSA LYON : 2002. / Titre provenant de l'écran-titre. Bibliogr. p. 170-178.