Order-disorder phenomena in geometrical frustrated systems are the attractive topics because of the intrinsic fluctuation. Among the geometrical frustrated systems, the material with spinel structure (AB2X4) is one of the appropriate candidates to investigate the long range ordering behavior. Corner sharing of tetrahedron and edge sharing of octahedron in the unique structural network of spinel structure are the characteristics for geometrical frustration. Hence, to study the 3d transition metal substituted in spinel system which leads to fruitful physical behavior becomes rapidly attractive. In this dissertation, long range ordering behavior in spin frustrated systems including three interesting materials LiTi2O4, NaxCoO2¡DyH2O, and CdCr2S4 were investigated. LiTi2O4 was found to show the highest superconducting transition temperature (Tc ~ 11 K) while first hydrated superconductor NaxCoO2¡DyH2O (Tc~ 4.5 K) was discovered in 2003. Superconductivity of LiTi2O4 and NaxCoO2¡DyH2O had been measured and analyzed by low temperature specific heat under magnetic field. According to the analyses of specific-heat results, isotropic (s-wave) and nodal (d-wave) gaps of superconducting pairing symmetry were proposed for LiTi2O4 and NaxCoO2¡DyH2O, respectively. Finally, LiTi2O4 was confirmed to be a typical BCS-like, fully gapped, and electron-phonon moderate-coupling type-II superconductor. Not like the case of LiTi2O4, the superconducting parameters of NaxCoO2¡DyH2O, such as Tc, HC2 and pairing symmetry, were strongly dependent on synthesized conditions. However, the evidence of nodal gap was found to be an intrinsic feature in this peculiar material NaxCoO2¡DyH2O. In the ferromagnetic insulator CdCr2S4, we first found several interesting features induced by external electric field in dielectric and magnetization measurements. Exchangestriction was proposed to be associated with the colossal change of dielectric constant value and suppression of magnetization under external electric and magnetic field in CdCr2S4. Therefore, our results supported that CdCr2S4 was a typical multiferroic material. In a conclusion, the intrinsic fluctuation of spin frustrated systems wasnecessary to pay more attention in the near future due to its fruitful physical properties and behind theoretical description.

The CoFe2O4 nanocrystals are highly attractive due to their magnetic properties - large coercivity (up to 2 T at low temperatures) with moderate saturation magnetization (80 A.m2.kg-1), remarkable chemical stability and mechanical hardness. Upon RE doping, a significant change of the properties is expected. This thesis is focused on investigation of Co1-LaxFe2O4, x = 0.05 - 0.5 and CoLaxFe2-x O4 x = 0.05 - 0.2 nanoparticles prepared by sol-gel and microemulsion method, respectively, with varying particle size according to the final heat treatment. In the former case, the particles were embedded in amorphous SiO2 matrix, while in the latter case, the samples were matrix-free. The samples were characterized using X-ray diffraction and Mössbauer spectroscopy. Measurements of the temperature dependence of the ZFC-FC magnetization revealed that the blocking temperature is above the room temperature. The values of coercivity and saturation magnetization strongly depend on particles size determined by method of preparation. The higher coercivity values of about 2 T at 10 K show the samples prepared by the sol-gel method. The obtained results are discussed in the context of preparation method, particle size and level of La doping.

La thèse présente l'élaboration et l'étude des films minces (35 nm) cristallins et stœchiométriques de la magnétite Fe304(001)/MgO. La qualité de ces films est étudiée par différentes techniques (DEL, XPS, XMCD, Effet Kerr, Auger). Nous supposons que les films se recouvrent partiellement, même sous ultra vide, par de Fe2O3. Pour la première fois, l'étude de la structure électronique de la bande t2g de ces films est réalisée par photoémission résolue en angle (ARPES)à température ambiante et à 75 K, en utilisant des photons à basses énergies (6eV - 21 eV). Nous avons constaté que le signal de la photoémission est composé des états électroniques de deux périodicités liées à la zone de Brillouin primitive de la surface (a=4.2 Å) et à la zone de Brillouin de la reconstruction de la surface (a=8.4 Å). Nous pensons que la présence des états liés à la reconstruction sont probablement responsables de la chute de la densité d'état à EF. Une signature de Verwey est observée par ARPES à basse température. Nous estimons que la réalisation des films ultra minces de magnétite est difficilement aboutie. / With its half-metallic behavior predicted theoretically, the magnetic oxideFe3O4 (TC = 863 K) is promising for applications in spintronics as thin films.High quality films and the electronic band structure are still a challenge to faceexperimentally. We managed to develop single crystalline Fe3O4(0 0 1) films(35 nm) on MgO. Analysis by XPS, XAS and XMCD allowed to characterizethe quality of the films prepared. The magnetic study shows a perfect XMCDsignal and a form magnetic anisotropy which lays down the axis of easy magnetizationin the film plane. Our samples are stable during the photoemissionmeasurements. The photoemission measurements of the t2g band show thatthe electronic bands cannot be described by a DFT calculation. Indeed, spinpolarons due to strong electron-phonon coupling mechanism are involved inthe electronic transport. Angle-resolved photoemission shows a dispersion ofthe t2g band in the ����M direction corresponding to two periodicities [the unitcell of the surface reconstruction a = 8,4 Å (30% of the signal) and the simpleunit cell of the surface a = 4;2 Å]. At a temperature T < TV (TV = 120 K,Verwey temperature), the angle-resolved photoemission shows the opening ofa 100 meV band gap, with a rigid shift of the spectral weight of the t2g bandto the high binding energy side.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第24107号 / 工博第5029号 / 新制||工||1785(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 安部 武志, 教授 作花 哲夫, 教授 阿部 竜 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

Made available in DSpace on 2016-12-08T15:56:17Z (GMT). No. of bitstreams: 1 Resumo Sonia Richartz Prim.pdf: 159893 bytes, checksum: ea0b9f6ba4434f44e947a911ca700ada (MD5) Previous issue date: 2014-08-20 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / The search for ceramic pigments with good properties are the basis of research conducted in this industry, in view of the importance of color for the final finished product. Aiming at seeking new pigments to replace or optimize existing ones, new synthesis methods and the incorporation of alternative raw materials are under study. In this work, we studied the possibility of using industrial waste from the treatment of effluents from the galvanoplasty process to synthetize pigments with spinel structure. The characterization of this type of waste and analysis of its potential to be used as chromophoric source were assessed in terms of chemical and mineralogical composition, thermal behavior, among others. The proportion of the transition elements, nickel and chromium present in the waste, allowed for the formation of important spinel structures. The synthesis method adopted consisted of the following steps: formulation; homogenization; calcination; and washing, when necessary. Firstly, we studied the addition of chromophoric ions Cr, Ni and Co in the structures MAl2O4, M=Zn, Mg, as well as the adoption of different temperatures (1000 to 1400 ºC/3h). The effect caused by solid dissolution of each ion in the structures and its relationship with the synthesis temperature was evaluated. It was possible to develop pigments with interesting color performance and different hues. Afterwards, the selection of a structure to obtain pigments from this selected chromophoric source was evaluated. We chose to work with structures NiCr2O4 and (Ni,Fe)(FeCr)2O4. The calcination temperature adopted was 1200 ºC/3h. The structures allowed for black pigments, however, with low pigmenting performance. In order to improve the performance of pigments with the addition of residue, we chose to further investigate the pigments formed with the 17 three elements nickel, iron and chromium at an equal molar ratio, resulting in the supposed structure (Ni0,5Fe0,5)(Fe0,5Ni0,5Cr1,0)O4, taking into consideration their degree of inversion. For this new step of the study, the synthetizing temperature adopted was 1000 ºC/3h. The aim was to assess the possibility of recovering the CaSO4 derived from the residue composition. For such, a washing stage was added to the pigment synthesis process. This new formulation favored the formation of the desired spinel phase, reducing the presence and intensity of secondary phases. The absence of the characteristic peaks indicating the presence of CaSO4 no DRX indicates the effectiveness of the washing process, which contributes to a reduction of a liquid phase formation and a better granulometric control. The results obtained after application showed that the synthesized pigments presented some instability during the application process. Therefore, studies were conducted to assess the influence of adding different concentrations of cobalt. The pigments synthetized with the addition of 0.3 mol of cobalt presented better pigmenting properties compared to pigments synthetized with the same structure. Adding waste into this composition led to the formation of pigments with improved performance, especially after application testing. The results allowed to associate this effect with the presence of secondary phases such as pyroxene, derived from the presence of SiO2 and CaO in the waste, resulting from the treatment process. The reproducibility of pigments synthesized with different batches of waste for the best composition studied was also evaluated. It was observed that they presented a good performance in face of the industrial conditions. / A busca por pigmentos cerâmicos com boas propriedades são a base das pesquisas realizadas neste setor, tendo em vista, a importância da cor para o produto final acabado. Com o intuito de buscar novos pigmentos que substituam ou otimizem os já conhecidos, novos métodos de síntese estão sendo pesquisados, bem como, a incorporação de matérias primas alternativas. No presente trabalho, estudou-se a possibilidade de aproveitamento de um resíduo industrial, proveniente do tratamento de efluentes do processo de galvanoplastia, na síntese de pigmentos com estrutura espinélio. A caracterização do resíduo e análise de suas potencialidades para uso como fonte cromófora, foram avaliadas em termos de composição química e mineralógica, comportamento térmico, entre outros. Os percentuais dos elementos de transição Níquel e Cromo presentes no resíduo possibilitaram a formação de estruturas de espinélios importantes. O método de síntese adotado englobou as seguintes etapas: formulação; homogeneização; calcinação e lavagem quando necessário. Primeiramente, foi estudada a adição dos íons cromóforos Cr, Ni e Co nas estruturas, MAl2O4, M=Zn, Mg, bem como, de diferentes temperaturas (1000 a 1400 ºC/3h). Avaliou-se o efeito causado pela dissolução sólida de cada íon nas estruturas, e sua relação com a temperatura de síntese. Foi possível desenvolver pigmentos com desempenho cromático interessante e tonalidades distintas. Posteriormente, foi avaliada a seleção de uma estrutura para a obtenção de pigmentos a partir desta fonte cromófora selecionada. Optou-se por trabalhar com as estruturas NiCr2O4 e (Ni,Fe)(FeCr)2O4. A temperatura de calcinação adotada foi de 1200 ºC/3h. As estruturas permitiram obter pigmentos negros, entretanto, com baixo desempenho pigmentante. A fim de aprimorar o desempenho dos pigmentos com adição de resíduo, 15 optou-se por investigar melhor os pigmentos formados com os três elementos Níquel, Ferro e Cromo, em uma igual proporção molar, resultando na suposta estrutura (Ni0,5 Fe0,5)(Fe0,5Ni0,5Cr1,0)O4, tendo em consideração o seu grau de inversão. Para esta nova etapa do trabalho a temperatura de sinterização adotada foi de 1000 ºC/3h. O objetivo foi avaliar a possibilidade de recuperação do CaSO4 proveniente da composição do resíduo. Para tanto, uma etapa de lavagem foi inserida no processo de síntese dos pigmentos. Esta nova formulação favoreceu a formação da fase espinélio desejada, diminuindo a presença e intensidade das fases secundárias. A não observância dos picos característicos da presença de CaSO4 no DRX, indica a eficácia do processo de lavagem, contribuindo para redução da formação de fase líquida e melhor controle granulométrico. Os resultados obtidos após aplicação permitiram concluir que os pigmentos sintetizados apresentaram certa instabilidade durante o processo de aplicação. Portanto, foram realizados estudos para avaliar a influência da adição de diferentes concentrações de Cobalto. Os pigmentos sintetizados com adição de 0,3 mol de Cobalto apresentaram melhores propriedades pigmentante ao serem comparados aos pigmentos sintetizados com a mesma estrutura. A incorporação de resíduo nesta composição propiciou a formação de pigmentos com melhor desempenho, principalmente após os testes de aplicação. A análise dos resultados permitiu associar este efeito a presença de fases secundárias, como o piroxênio, provenientes da presença de SiO2 e CaO no resíduo, resultante do processo de tratamento. A reprodutibilidade dos pigmentos, sintetizados com distintos lotes de resíduo para a melhor composição estudada, também foi avaliada. Pode-se observar que os mesmos apresentaram bom desempenho frente às condições industriais.