Made available in DSpace on 2017-07-21T19:26:07Z (GMT). No. of bitstreams: 1 Simoneapa.pdf: 1470043 bytes, checksum: b380a790ad5236069470caa27e038eed (MD5) Previous issue date: 2007-03-02 / In this work, it was accomplished an experimental study about the substitution of the yttrium atom (Y) in the YBa2Cu3O7-x superconductor system for a rare earth oxide (RE2O3), gotten from the xenotime ore. Chemically, this substitution is possible due to the equality of the oxidation state between the Y3+ ions and the earth rare ions, which form the oxide. This way, this substitution should not modify the properties of the superconductor system significantly. The xenotime in its natural form is composed of a rare earth phosphate, zirconita and other heavy elements. The zirconita and the heavy elements can be separated by magnet or gravimetric process. The rare earth phosphate is chemically treated by the acid or the alkaline leaching process, resulting in a rare earth oxide (RE2O3). The xenotime ore used in this work was extracted from the Pitinga mine (AM, Brazil). Four polycrystalline samples were processed through the solid-state reaction, from the precursors: rare earth oxide (RE2O3), barium carbonate (BaCO3) and copper oxide (CuO), forming the REBa2Cu3O7-x superconducting oxide. The chracterization of the samples crystalline structures was studied by x-ray diffraction. The analysis of the samples superficial morphology was studied by optical microscopy and scanning electron microscopy (SEM). The properties of electronic transportation were analyzed by measurements of electric resistivity. Among the analyzed samples, one did not present null state of electric resistance. The measurements of electric resistivity for the other samples revealed superconductor behavior and showed that the critical temperature of the REBa2Cu3O7-x system is around 90 K, as in the YBa2Cu3O7-x system. Such values were confirmed by the measurement of magnetic susceptibility. The analyses of the Xray diffractograms of the samples revealed that the cell parameters of both systems are equal. These results indicate that the substitution of the Y for the rare earth oxide is possible, which may have important implications both from the point of view of basic research and the applied research. / Neste trabalho foi realizado um estudo experimental da substituição do átomo de ítrio (Y) no sistema supercondutor YBa2Cu3O7-x, por um óxido de terras-raras (RE2O3), obtido a partir do minério xenotima. Quimicamente essa substituição é possível devido à igualdade do estado de oxidação entre os íons Y3+ e os íons de terras-raras que formam o óxido. Dessa forma, essa substituição não deve alterar de forma significativa as propriedades supercondutoras do sistema. A xenotima em sua forma natural é constituída por um fosfato de terras-raras, zirconita e outros elementos pesados. A zirconita e os elementos pesados podem ser separados por processos magnéticos ou gravimétricos. O fosfato de terras-raras é tratado quimicamente pelo processo de lixiviação ácida ou alcalina, resultando em um óxido de terras-raras (RE2O3). O minério xenotima utilizado neste trabalho foi extraído da mina do Pitinga (AM, Brasil). Foram processadas quatro amostras policristalinas através da reação de estado sólido, a partir dos precursores: óxido de terras raras (RE2O3), carbonato de bário (BaCO3) e óxido de cobre (CuO), formando o óxido supercondutor REBa2Cu3O7-x. A caracterização das estruturas cristalinas das amostras foi estudada por difração de raios X. A análise da morfologia superficial das amostras foram estudadas por microscopia óptica e microscopia eletrônica de varredura (MEV). As propriedades de transporte eletrônico foram analisadas através de medidas de resistividade elétrica. Das amostras processadas, uma não apresentou estado de resistência elétrica nula. As medidas de resistividade elétrica para as demais amostras revelaram comportamento supercondutor e mostraram que a temperatura crítica do sistema REBa2Cu3O7-x, está em torno de 90 K, como no sistema YBa2Cu3O7-x. Esses valores foram confirmados pelas medidas de susceptibilidade magnética. As análises dos difratogramas de raios X das amostras revelaram que os parâmetros de cela dos dois sistemas são iguais. Esses resultados indicam que substituição do Y pelo óxido de terras-raras é possível, podendo ter importantes implicações tanto do ponto de vista de pesquisa básica como da pesquisa aplicada.

Ce travail se compose de deux parties : la première partie traite de la formation de dépôts épais du composé YBa2Cu3O7-x par la technique électrophorétique (EPD) tandis que la seconde décrit la réalisation de dépôts par la technique de projection plasma. Dans le cadre de la méthode EPD, des suspensions aqueuses et non-aqueuses ont été étudiées. Plus particulièrement, des suspensions à base dacétone en présence ou non diode ont été caractérisées de manière approfondie. A laide de ces résultats, un mécanisme de charge des particules a été proposé. La cinétique de dépôt de lYBa2Cu3O7-x par EPD a également été étudiée. Les dépôts formés ont montré des propriétés supraconductrices sur substrat dAg. Une densité de courant critique Jc (77 K, H=0) de lordre de 103 A/cm² a été obtenue. Finalement, une méthode de texturation sous champ magnétique appliquée à lEPD a été explorée. Pour la technique de projection plasma, différents paramètres opératoires ont été étudiés. Par un traitement thermique adéquat du dépôt sur substrat de Ni, la phase supraconductrice a été obtenue.

This dissertation presents the first reported identification and analyses of the phase relations in the YBa2Cu3O7-x (YBCO)-SiO2 system at elevated temperatures. In this regard, a rigorous characterization study of the reaction phases within YBCO glass fibers, heat-treated YBCO+SiO2 pellets, rapid thermally annealed YBCO+SiO2 rods and rapid thermally annealed YBCO powder inside a fused silica tube is provided. These analyses are based on a vast set of generated novel results obtained using energy dispersive spectroscopy analyses on an environmental scanning electron microscope, X-Ray diffraction analyses, Raman spectroscopy, X-ray photoelectron spectroscopy analyses and a cross-polarized light study. First, original drawings of YBCO into glass fibers using the molten-core approach on a fiber draw tower in air and oxygen atmospheres are presented and analyzed. The performed analyses reveal the occurrence of reactions between the YBCO core and the silica cladding in as-drawn fibers as well as after additional heat-treatments. A detailed analysis and characterization of the occurring dissolution and diffusion based reaction processes is, then, provided along with the identification of the arising phase separation. Moreover, in order to analyze drawing YBCO glass fibers at lower temperatures, the use of borosilicate as the preform material is also investigated. This varied set of experiments and associated analyses reveal that the as-drawn YBCO fibers contain an amorphous core and that cuprite (Cu2O) is the first phase to crystallize out of the amorphous silicate matrix upon heat-treatment. Furthermore, the obtained results demonstrate the dissolution of the fused silica cladding into Si4+ and O2- ions and their subsequent diffusion into the molten YBCO core, leading to phase separation due to an occurring miscibility gap in the YBCO-SiO2 system as well as to silicate formation and amorphization of the YBCO core. This, as a result, prohibits the formation of the superconductive YBCO (Y-123) phase upon annealing. In addition, heat-treatment analyses show that higher temperatures or prolonged dwelling times at lower temperatures lead to the formation of barium copper and yttrium barium silicates. The analysis focusing on the use of borosilicate as the preform material reveals that drawing at lower temperatures reduces the dissolution and diffusion based reactions, but does not prevent them. Furthermore, the analysis on YBCO glass fibers with a fused silica cladding drawn in oxygen atmosphere shows that a higher oxygen content increases the dissolution of the fused silica cladding into its ions and their subsequent diffusion into the molten YBCO core. In addition, the performed heat-treatments on YBCO+SiO2 pellets in air and oxygen atmospheres demonstrate the gradual decomposition of the Y-123 phase with an increase in SiO2 content. Moreover, the rapid thermal annealing experiments with a subsequent quenching step on YBCO+SiO2 rods and on YBCO powder inserted inside a fused silica tube show the decomposition of the Y-123 phase and the formation of phases similar to the phases obtained in the YBCO glass fiber study, thus corroborating the results thereof. In summary, this dissertation enables the determination of the phase relations and reaction processes within the YBCO-SiO2 system, the identification of the direct effects of the silicon content on the Y-123 phase decomposition, as well as a rigorous characterization of the dissolution and diffusion based reactions within the YBCO-SiO2 glass-clad fiber system. The generated results and drawn conclusions build a fundamental understanding of phase relations in the YBCO-SiO2 system, which enables a definite assessment of the feasibility of manufacturing long-scale purely superconductive YBCO glass fibers using the molten-core approach and introduces advanced contributions to general glass-clad fiber systems manufactured using this method. / Doctor of Philosophy / This dissertation provides the first reported identification and analysis of the phase relations in the YBa2Cu3O7-x (YBCO)-SiO2 system at high temperatures. In this regard, a thorough characterization study of the reaction phases within YBCO glass fibers drawn using the molten-core approach on a fiber draw tower is provided. In addition, heat-treatment analyses considering YBCO+SiO2 pellets, rapid thermally annealed YBCO+SiO2 rods and rapid thermally annealed YBCO powder inside a fused silica tube are performed to gain further fundamental insights. The performed analyses are based on a wide set of characterization methods including energy dispersive spectroscopy on an environmental scanning electron microscope, X-Ray diffraction analyses, Raman spectroscopy, X-ray photoelectron spectroscopy and a cross-polarized light study. Our experimental results and performed analyses identify the phase relations and reaction processes within the YBCO-SiO2 system at elevated temperatures, demonstrate the direct effects of the silicon content on the superconductive YBCO phase decomposition, enable drawing definite conclusions regarding the feasibility of manufacturing long-scale purely superconductive YBCO glass fibers using the molten-core approach, and, characterize the dissolution and diffusion based reactions occurring within the YBCO-SiO2 glass-clad fiber system. In a nutshell, this dissertation provides a fundamental understanding of phase relations in the YBCO-SiO2 glass-clad system as well as key insights covering general glass-clad fibers drawn using the molten-core approach, paving the way for improved glass-clad fiber manufacturing using this method.

Thesis (PhD (Electrical and Electronic Engineering))--University of Stellenbosch, 2010. / Dissertation presented for the degree of Doctor of Philosophy in Engineering at the University of Stellenbosch / ENGLISH ABSTRACT: Planar weak link structures, such as micro-bridges, variable thickness bridges and nanobridges, have always attracted a lot of attention. Their potential to behave as real Josephson elements make them useful devices, with numerous applications. Powerful techniques, such as focused ion-beam and electron-beam lithography, were successfully used and are well understood in planar weak link structure fabrication. In this dissertation the results of an experimental study on planar weak link structures are presented. For the first time these structures have been successfully fabricated using AFM nanolithography on hard high-temperature superconducting YBCO tracks, where diamond coated silicon tips were used as a ploughing tool. Superconducting YBCO thin films were deposited on different substrates, using inverted cylindrical magnetron sputtering. The films were used to fabricate micro-bridges, variable thickness bridges and nano-bridges, by using conventional photolithography, argon ion-beam milling and AFM nanolithography. The measured I-V characteristics of the fabricated micro-bridges (width down to 1.9 µm), variable thickness bridges (thickness down to 15 nm) and nano-bridge (width down to 490 nm) showed well defined DC and AC Josephson effect characteristics. For better understanding of the behaviour of these types of weak links, critical current versus temperature measurements, and magnetic field modulation of the critical current measurements, were also performed, with the results and discussions given inside the chapters. The major challenges that were experienced in the laboratory during the fabrication processes and the operation of the fabricated devices are also discussed, with the solutions given where appropriate. / AFRIKAANSE OPSOMMING: Swak-skakel vlakstrukture, soos mikrobr.ue, br.ue met veranderlike dikte en nanobr.ue, het nog altyd baie aandag getrek. Hul het die potensiaal om soos werklike Josephson-elemente te kan funksioneer en is, as gevolg hiervan, nuttige toestelle met veelvuldige toepassings. Kragtige tegnieke, soos gefokuste ioonstraal- en elektronstraal litografie, is suksesvol gebruik en word goed verstaan in die vervaardiging van swak-skakel vlakstrukture. In hierdie proefskrif word die resultate van ¡¦n eksperimentele studie van swak-skakel vlakstrukture voorgel.e. Vir die eerste keer is hierdie strukture suksesvol vervaardig, deur gebruik te maak AFMnanolitografie op harde, ho¡Le-temperatuur supergeleier YBCO (Yttrium Barium Koperoksied) spore, waar diamantbedekte silikonpunte gebruik is as ploeginstrument. ¡¦n Dun lagie van supergeleidende YBCO is op verskillende substrate gedeponeer, deur gebruik te maak van omgekeerde silindriese magnetron verstuiwing. Die dun lagies is gebruik in die vervaardiging van mikrobr.ue, br.ue met veranderlike dikte en nanobr.ue, deur die gebruik van gewone fotolitografie, argon-ioonstraal frees en AFM nanolitografie. Die gemete I-V eienskappe van die vervaardigde mikrobr.ue (met breedte so laag as 1.9 µm), veranderlike-dikte br.ue (dikte tot 15 nm) en nanobr.ue (breedte so min as 490 nm) toon goed gedefinieerde GS en WS eienskappe van die Josephson-effek. Ten einde die gedrag van hierdie tipes swak-skakels beter te kan verstaan, is metings gedoen van kritieke stroom teenoor temperatuur, asook magnetiese veld modulasie van die kritieke stroom. Hierdie resultate en besprekings daarvan word binne die toepaslike hoofstukke aangebied. Die grootste uitdagings wat in die laboratorium, sowel as met die toetsing van die vervaardigde toestelle ondervind is, word ook bespreek. Waar moontlik, word toepaslike oplossings voorgestel.

L' étude d'une technique originale de croissance cristalline, basée sur l'utilisation d'un échangeur thermique et nommée HEM (Heat Exchanger Method), a été entreprise. Un dispositif expérimental a été développé et optimisé. La modélisation des échanges thermiques a conduit a l'élaboration d'un code de calcul numérique. Ce dernier est valide par confrontation des résultats de la simulation aux données expérimentales obtenues lors de la croissance d'un matériau école, le germanium. Le champ d'application de la technique HEM a alors été étendu à l'obtention de céramiques texturées du supraconducteur à haute température critique YBa2Cu3O7-x. Après une étude de la microstructure des textures, un mécanisme de texturation est proposé. Enfin, des cristaux du compose NaMgF3 (perovskite) sont obtenus par HEM. Leur étude en température, par observation des domaines ferroélastiques et par spectroscopie Raman, révèle l'existence d' une seule transition de phase.