Submitted by Cláudia Bueno (claudiamoura18@gmail.com) on 2016-02-04T13:32:20Z No. of bitstreams: 2 Dissertação - Regiane Lopes dos Santos - 2010.pdf: 2296508 bytes, checksum: 8c7da40e51ba04f72f1319279074de08 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2016-02-11T11:27:11Z (GMT) No. of bitstreams: 2 Dissertação - Regiane Lopes dos Santos - 2010.pdf: 2296508 bytes, checksum: 8c7da40e51ba04f72f1319279074de08 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2016-02-11T11:27:12Z (GMT). No. of bitstreams: 2 Dissertação - Regiane Lopes dos Santos - 2010.pdf: 2296508 bytes, checksum: 8c7da40e51ba04f72f1319279074de08 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2010-10-01 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Potassium tetratitanate (K2Ti4O9) and sodium trititanate (Na2Ti3O7) were synthesized by solid state reaction at 800°C and wet impregnated using Mg2+/La3+ or nanoparticles of MgO/La2O3 varying ion/oxide content in 1, 5 or 10% of matrix weight. MgO and La2O3 synthesized by precipitation method and their mean crystallite size calculated in 11 nm and 72 nm, respectively. Synthesized materials were characterized by X ray diffractometry, termogravimetry, N2 adsorption, mid-infrared spectroscopy, transmission electron microscopy and they were applied on transesterification reactions using mixtures of methyl acetate/ethanol and ethyl acetate/methanol. Interlayer distance calculated for solids is about 8 Å. Impregnation of ion/oxide in matrices K2Ti4O9 and Na2Ti3O7 produced structural changes like loss of crystallinity for some of them including peak broadening or disappearing. All synthesized materials, after burning in an atmosphere of N2 (g), lost mass related to the exit of surface water and interlamellar water. Materials showed low surface area, with values below 5 m2/g. In general, powder utilized had conversion rates between 10 and 80%. Emphasis should be given to pure matrices which presented conversions rates equal or higher than impregnated powders, and the use of matrix K2Ti4O9 led to better results. Among the oxides chosen for impregnation, higher efficiency was observed for MgO. Some powders were reused for the same reactions and its activity decreased in each reaction cycle. Reaction mixture analysis after reuse tests to K2Ti4O9 revealed partial leaching of K+ ions, however XRD patterns profile analysis did not show structural changes occurrence. A proposal to explain layered titanate activity on transesterification reactions is made based on acid-base properties of layers and output of K+ from interlamellar area. / Tetratitanato de potássio (K2Ti4O9) e trititanato de sódio (Na2Ti3O7) foram sintetizados por meio de síntese no estado sólido a 800°C, impregnados por via úmida utilizando Mg2+/La3+ ou nanopartículas de MgO/La2O3 variando o teor do íon/óxido em 1, 5 ou 10% em relação à massa da matriz. MgO e La2O3 foram sintetizados por precipitação e tiveram seu diâmetro médio de cristalito calculados em 11 nm e 72 nm, respectivamente. Os materiais sintetizados foram caracterizados por difratometria de raios X, termogravimetria, fisissorção de N2(g), espectroscopia na região do infravermelho médio, microscopia eletrônica de transmissão e foram aplicados em reações de transesterificação utilizando misturas reacionais acetato de metila/etanol e acetato de etila/metanol. A distância interlamelar calculada para os sólidos é da ordem de 8 Å. A impregnação dos íons/óxidos nas matrizes K2Ti4O9 e Na2Ti3O7 produziu mudanças estruturais incluindo perda de cristalinidade para algumas delas incluindo alargamento ou desaparecimento de picos. Todos os materiais sintetizados, após queima sob atmosfera de N2(g), perderam massa relativa à saída de água superficial e água interlamelar. Os materiais apresentaram baixa área superficial, com valores abaixo de 5 m2/g. De um modo geral, os pós utilizados tiveram taxas de conversão entre 10 e 80%. Destaque deve ser dado às matrizes puras que apresentaram taxas de conversão iguais ou superiores aos pós impregnados, sendo que o uso da matriz K2Ti4O9 levou aos melhores resultados. Dentre os óxidos escolhidos para a impregnação, a eficiência maior foi observada para MgO. Alguns pós foram reutilizados para as mesmas reações e a atividade diminuiu a cada ciclo de reação. A análise da mistura reacional após os testes de reuso para a matriz K2Ti4O9 revelou lixiviação parcial de íons K+, entretanto a análise do perfil dos padrões de DRX dos pós após reuso não revelou a ocorrência de mudanças estruturais. Uma proposta para explicar a atividade dos titanatos lamelares nas reações de transesterificação é feita baseando-se nas propriedades ácido-base das lamelas e na saída de íons K+ da região interlamelar.

Submitted by Fabio Sobreira Campos da Costa (fabio.sobreira@ufpe.br) on 2016-08-04T12:41:31Z No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação de Mestrado - Natasha Lopes Gomes.pdf: 9410241 bytes, checksum: 569cb64525645737ca47e38f379de72c (MD5) / Made available in DSpace on 2016-08-04T12:41:31Z (GMT). No. of bitstreams: 2 license_rdf: 1232 bytes, checksum: 66e71c371cc565284e70f40736c94386 (MD5) Dissertação de Mestrado - Natasha Lopes Gomes.pdf: 9410241 bytes, checksum: 569cb64525645737ca47e38f379de72c (MD5) Previous issue date: 2016-02-26 / FACEPE / A indústria aeroespacial é um setor que contribui significativamente para o desenvolvimento econômico e social de alguns países. A confiabilidade e a disponibilidade de seus equipamentos são uma preocupação constante, uma vez que estes operam a temperaturas elevadas. Dentre os equipamentos que mais falham prematuramente devido à temperatura, destacam-se os bocais de exaustão das turbinas a gás, compostos por um conjunto de ligas à base de níquel ou à base de cobalto. No entanto, os fabricantes de turbinas tem demonstrado um maior interesse no uso de compósitos cerâmicos para revestimento nas seções quentes, devido sua maior capacidade de suportar altas temperaturas e exigência de menor refrigeração do ar. Mas a fragilidade intrínseca das cerâmicas é ainda um fator limitante para o uso destes materiais em estruturas mecânicas e aplicações industriais. Para reduzir fragilidade e aumentar resistência mecânica e tenacidade, normalmente as cerâmicas são reforçadas com incorporação de aditivos. Estudos vêm sendo realizados acerca da utilização da zircônia incorporada com outros óxidos, pois em comparação com outros cerâmicos, a zircônia tem propriedades mecânicas superiores, tais como alta resistência mecânica, estabilidade química e boa tenacidade à fratura. Neste trabalho foram produzidos compósitos cerâmicos zircônia-titânia (ZrO2-TiO2) reforçados com um óxido de terra rara, lantânio (La2O3), variando o teor de TiO2 em 5%, 10%, 15% e 20% e o teor de La2O3 em 5%, 7% e 10%. Os compósitos foram produzidos por processo termomecânico e sinterizados à 1385°C. Posteriormente, foram caracterizados quanto à estrutura, microestrutura e propriedades mecânicas através de difração de raios X, densidade relativa, microscopia óptica, microscopia eletrônica de varredura, espectroscopia de energia dispersiva e microdureza Vickers. A microestrutura do material sinterizado revelou uma boa homogeneidade em distribuição e tamanho de partículas, e a microdureza Vickers mostrou que o compósito com 15% de TiO2 e 10% de La2O3 obteve um melhor resultado, indicando que este possui boas propriedades físicas que apontam para uma possível aplicabilidade. No entanto, é necessário avaliar outras propriedades mecânicas a fim de garantir sua utilização como revestimento cerâmico de exaustores de turbinas a gás aeroespaciais. / The aerospace industry is a sector that contributes significantly to the economic and social development of some countries. The reliability and availability of your equipment is a constant concern, since they operate at high temperatures. Among the equipment more fail prematurely due to temperature, we highlight the exhaust nozzles of gas turbines, comprising a set of nickel based alloys or cobalt-based. However, turbine manufacturers have shown an increased interest in the use of ceramic composite coating on hot sections due to their greater ability to withstand high temperatures and requiring less cooling air. But the intrinsic brittleness of ceramics is still a limiting factor for the use of these materials in mechanical and industrial applications structures. To reduce brittleness and increase strength and toughness, typically ceramics are reinforced by incorporation of additives. Studies have been conducted on the use of zirconia incorporated with other oxides, as compared to other ceramic, zirconia has superior mechanical properties such as high mechanical strength, chemical stability and good fracture toughness. In this work we were produced composite ceramic zirconia-titania (ZrO2-TiO2) reinforced with a rare earth oxide, lanthanum (La2O3), varying the TiO2 content of 5%, 10%, 15% and 20%, and the La2O3 content 5%, 7% and 10%. The composites were produced by thermomechanical process and sintered at 1385 ° C. Later, they were characterized as to structure, microstructure and mechanical properties through X-ray diffraction, relative density, optical microscopy, scanning electron microscopy, energy dispersive spectroscopy, and microhardness. The microstructure of the sintered material showed a good homogeneous distribution and particle size, and Vickers microhardness showed that the composite with 15% TiO2 and 10% La2O3 obtained best results, indicating that it has good physical properties which indicate a possible applicability. However, it is necessary to assess other mechanical properties to ensure their use as ceramic coating aerospace gas turbine exhaust.

Neste trabalho realizou-se a síntese e caracterização de materiais contendo óxidos de lantanóides incorporados em sílica mesoporosa ordenada, os quais foram utilizados como catalisadores no processo de ozonização de compostos orgânicos poluentes. Empregando-se o método de impregnação úmida, realizou-se a incorporação de óxido de cério e óxido de lantânio no suporte mesoporoso, do tipo SBA-15. Utilizaram-se diferentes precursores dos óxidos metálicos, a fim de verificar a influência que a fonte do cátion metálico exerça tanto nas características estruturais, texturais e morfológicas dos materiais quanto na atividade catalítica. A caracterização destes materiais mostrou que em todas as amostras não houve colapso da estrutura ordenada de mesoporos da SBA-15. Porém nos materiais incorporados observou-se a diminuição da área superficial específica e o volume de poro, devido à presença do CeO2 ou do La2O3 tanto na superfície do suporte quanto no interior dos mesoporos. Também foi possível identificar as fases cristalinas destes óxidos após a etapa de incorporação. Os catalisadores foram empregados na degradação de um azocorante, Preto Remazol B. Para todos os materiais verificou-se que a ozonização catalítica heterogênea proporcionou o aumento da mineralização em relação ao processo de ozonólise. Para os catalisadores que continham CeO2, os melhores resultados de mineralização do azocorante foram obtidos para os catalisadores cujos precursores eram complexos metálicos. Para estes materiais obteve-se um incremento de 65% em comparação com a ozonólise, sem que houvesse um grande aumento no consumo de ozônio. Para os materiais que continham La2O3, o catalisador cujo precursor do óxido foi um dos sais inorgânicos utilizados (nitrato de lantânio hidratado) apresentou o melhor teor de mineralização, sendo 72% superior em relação à ozonólise, ao final de 60 minutos. Os catalisadores contendo óxido de cério incorporado à SBA-15 também foram empregados no processo de ozonização catalítica de mais duas espécies orgânicas de grande relevância ambiental: fenol e ácido salicílico. Para o primeiro, houve um incremento mínimo na remoção da matéria orgânica de 70%, para todos os catalisadores testados, em relação à ozonólise, após 60 minutos. Entretanto, apenas dois deles (SBA-Ce(Gly) e SBA-Ce(Cl)) apresentaram um consumo de ozônio semelhante à ozonólise, o que indica que estes eram os mais eficientes. Na degradação do ácido salicílico a sinergia entre o suporte mesoporoso ordenado de elevada área superficial com o óxido de cério mais uma vez mostrou-se eficiente na mineralização da espécie orgânica, sendo obtidos teores de mineralização superiores a 90% para a ozonização catalítica contra 60% para a ozonólise, ao final de 60 minutos de tratamento / The aim of this work was the synthesis and characterization of materials with lanthanide oxides incorporated in ordered mesoporous silica, which were used as catalysts on the ozonation of organic pollutants. The incorporation of cerium and lanthanum oxides on the mesoporous support, SBA-15 type, was made by wet impregnation method. Different metal oxides precursors were used in order to investigate the influence in structural, textural and morphological characteristics of the materials and in catalytic activity. No collapse in the ordered mesopores structure of SBA-15 was observed after lanthanide oxides incorporation. However the hybrid compounds presented lower specific surface area and pore volume. It was observed the presence of CeO2 and La2O3 in the external support surface and in the interior of the mesopores. It was also possible to identify crystalline phases of these oxides after the incorporation step. The catalysts were employed on the degradation of an azo dye, Remazol Black B. For all samples it was found that the heterogeneous catalytic ozonization provided an increase in the mineralization levels of this organic species compared with the results of the ozonolysis. For the CeO2-based materials, the best results were achieved for the catalysts whose precursors were the metal complexes. For these materials the mineralization of the Remazol Black B was, at least, 65% superior to ozonolysis alone, without a great increase in the consumption of ozone. For the La2O3-based materials, the best result was obtained for the catalyst which oxide precursor was one of the inorganic salt (lanthanum nitrate hydrate). The mineralization was 72% higher than the ozonolysis alone after 60 minutes of treatment. The catalysts containing cerium oxide incorporated into the SBA-15 were also employed in the catalytic ozonization of two other organic species of great environmental importance: phenol and salicylic acid. For the first, there was a minimal increase in the removal of the organic matter when compared with ozonolysis alone. However, only two of them (SBA-Ce(Gly) e SBA-Ce(Cl)) showed a consumption of ozone similar to ozonolysis, indicating that these were the most efficient. In salicylic acid degradation, the mineralization achieved was greater than 90% for the catalytic ozonation versus 60% for the ozonolysis alone, after 60 minutes of treatment

Neste trabalho realizou-se a síntese e caracterização de materiais contendo óxidos de lantanóides incorporados em sílica mesoporosa ordenada, os quais foram utilizados como catalisadores no processo de ozonização de compostos orgânicos poluentes. Empregando-se o método de impregnação úmida, realizou-se a incorporação de óxido de cério e óxido de lantânio no suporte mesoporoso, do tipo SBA-15. Utilizaram-se diferentes precursores dos óxidos metálicos, a fim de verificar a influência que a fonte do cátion metálico exerça tanto nas características estruturais, texturais e morfológicas dos materiais quanto na atividade catalítica. A caracterização destes materiais mostrou que em todas as amostras não houve colapso da estrutura ordenada de mesoporos da SBA-15. Porém nos materiais incorporados observou-se a diminuição da área superficial específica e o volume de poro, devido à presença do CeO2 ou do La2O3 tanto na superfície do suporte quanto no interior dos mesoporos. Também foi possível identificar as fases cristalinas destes óxidos após a etapa de incorporação. Os catalisadores foram empregados na degradação de um azocorante, Preto Remazol B. Para todos os materiais verificou-se que a ozonização catalítica heterogênea proporcionou o aumento da mineralização em relação ao processo de ozonólise. Para os catalisadores que continham CeO2, os melhores resultados de mineralização do azocorante foram obtidos para os catalisadores cujos precursores eram complexos metálicos. Para estes materiais obteve-se um incremento de 65% em comparação com a ozonólise, sem que houvesse um grande aumento no consumo de ozônio. Para os materiais que continham La2O3, o catalisador cujo precursor do óxido foi um dos sais inorgânicos utilizados (nitrato de lantânio hidratado) apresentou o melhor teor de mineralização, sendo 72% superior em relação à ozonólise, ao final de 60 minutos. Os catalisadores contendo óxido de cério incorporado à SBA-15 também foram empregados no processo de ozonização catalítica de mais duas espécies orgânicas de grande relevância ambiental: fenol e ácido salicílico. Para o primeiro, houve um incremento mínimo na remoção da matéria orgânica de 70%, para todos os catalisadores testados, em relação à ozonólise, após 60 minutos. Entretanto, apenas dois deles (SBA-Ce(Gly) e SBA-Ce(Cl)) apresentaram um consumo de ozônio semelhante à ozonólise, o que indica que estes eram os mais eficientes. Na degradação do ácido salicílico a sinergia entre o suporte mesoporoso ordenado de elevada área superficial com o óxido de cério mais uma vez mostrou-se eficiente na mineralização da espécie orgânica, sendo obtidos teores de mineralização superiores a 90% para a ozonização catalítica contra 60% para a ozonólise, ao final de 60 minutos de tratamento / The aim of this work was the synthesis and characterization of materials with lanthanide oxides incorporated in ordered mesoporous silica, which were used as catalysts on the ozonation of organic pollutants. The incorporation of cerium and lanthanum oxides on the mesoporous support, SBA-15 type, was made by wet impregnation method. Different metal oxides precursors were used in order to investigate the influence in structural, textural and morphological characteristics of the materials and in catalytic activity. No collapse in the ordered mesopores structure of SBA-15 was observed after lanthanide oxides incorporation. However the hybrid compounds presented lower specific surface area and pore volume. It was observed the presence of CeO2 and La2O3 in the external support surface and in the interior of the mesopores. It was also possible to identify crystalline phases of these oxides after the incorporation step. The catalysts were employed on the degradation of an azo dye, Remazol Black B. For all samples it was found that the heterogeneous catalytic ozonization provided an increase in the mineralization levels of this organic species compared with the results of the ozonolysis. For the CeO2-based materials, the best results were achieved for the catalysts whose precursors were the metal complexes. For these materials the mineralization of the Remazol Black B was, at least, 65% superior to ozonolysis alone, without a great increase in the consumption of ozone. For the La2O3-based materials, the best result was obtained for the catalyst which oxide precursor was one of the inorganic salt (lanthanum nitrate hydrate). The mineralization was 72% higher than the ozonolysis alone after 60 minutes of treatment. The catalysts containing cerium oxide incorporated into the SBA-15 were also employed in the catalytic ozonization of two other organic species of great environmental importance: phenol and salicylic acid. For the first, there was a minimal increase in the removal of the organic matter when compared with ozonolysis alone. However, only two of them (SBA-Ce(Gly) e SBA-Ce(Cl)) showed a consumption of ozone similar to ozonolysis, indicating that these were the most efficient. In salicylic acid degradation, the mineralization achieved was greater than 90% for the catalytic ozonation versus 60% for the ozonolysis alone, after 60 minutes of treatment

Μελετήθηκε η αντίδραση αναμόρφωσης της αιθανόλης με ατμό προς παραγωγή υδρογόνου για την τροφοδοσία στοιχείων καυσίμου. Η παραγωγή υδρογόνου από αιθανόλη, αποτελεί ελκυστική διεργασία τόσο από οικονομική, όσο και από περιβαλλοντική άποψη. Το παραγόμενο υδρογόνο μπορεί να χρησιμοποιηθεί σε στοιχεία καυσίμου ως ρεύμα τροφοδοσίας, όπου οξειδώνεται ηλεκτροχημικά παρουσία αέρα αποδίδοντας ηλεκτρική ενέργεια και θερμότητα με μοναδικό προϊόν καύσης το νερό. Η αντίδραση αναμόρφωσης της αιθανόλης με ατμό είναι θερμοδυναμικά εφικτή και η αύξηση της θερμοκρασίας οδηγεί σε αυξημένη απόδοση σε υδρογόνο. Η συνολική διεργασία παραγωγής υδρογόνου από ατμοαναμόρφωση της αιθανόλης έχει υψηλότερη θεωρητική απόδοση από την ατμοαναμόρφωση του μεθανίου, η οποία είναι η κύρια διεργασία παραγωγής υδρογόνου σήμερα. Οι μελέτες της αντίδρασης αναμόρφωσης της αιθανόλης με ατμό σε καταλύτες κοβαλτίου, ευγενών μετάλλων και νικελίου, έδειξαν ότι οι βέλτιστοι καταλύτες της διεργασίας είναι οι 2% Rh/Al2O3, 5% Ru/Al2O3 και 17% Ni/(La2O3/Al2O3). Οι καταλύτες νικελίου εναποτεθειμένοι σε γ-Al2O3, La2O3 και La2O3/Al2O3 μελετήθηκαν προκειμένου να διερευνηθεί το δίκτυο των αντιδράσεων της αιθανόλης με τον ατμό με χρήση δυναμικών τεχνικών και τεχνικών μόνιμης κατάστασης. Προσεγγίστηκε το δίκτυο αντιδράσεων και τιτλοδοτήθηκε ο εναποτεθειμένος άνθρακας. Αναπτύχθηκαν κεραμικοί και μεταλλικοί θερμικά ολοκληρωμένοι αντιδραστήρες αναμόρφωσης της αιθανόλης με ατμό. Η πραγματοποίηση των αντιδράσεων αναμόρφωσης και καύσης στον κεραμικό αντιδραστήρα οδήγησε σε ικανοποιητική απόδοση. Παράλληλα, διεξήχθησαν πειράματα αναμόρφωσης και καύσης της αιθανόλης στο μεταλλικό αντιδραστήρα με χρήση καταλυτικών κλινών. Τα πειράματα αναμόρφωσης - καύσης απέδειξαν τη λειτουργικότητα του συστήματος, ενώ η σχετική θέση των καταλυτικών κλινών διαπιστώθηκε ότι αποτελεί σημαντικό παράγοντα στην απόδοση του αντιδραστήρα. Τέλος, αναπτύχθηκαν καινοτόμοι μέθοδοι εναπόθεσης καταλυτικών στρωμάτων στις επιφάνειες μεταλλικών σωλήνων. Στην εξωτερική επιφάνεια εναποτέθηκε αλούμινα ως υπόστρωμα για τον καταλύτη αναμόρφωσης με ψεκασμό πλάσματος, ενώ στο εσωτερικό του σωλήνα χρησιμοποιήθηκε μέθοδος εναπόθεσης αλουμινίου για τη δημιουργία του απαιτούμενου συγκολλητικού υποστρώματος. Οι καταλύτες που παρήχθησαν είχαν υψηλή αντοχή σε θερμικούς κύκλους και μεγάλη απόδοση στην αντίδραση αναμόρφωσης. / Production of hydrogen from steam reforming of ethanol is examined for application in fuel cells. The production of hydrogen from ethanol is an attractive operation from economical as well as from environmental point of view. The produced hydrogen can be fed to fuel cells, undergoing oxidation and producing electric energy and heat with the only combustion product being water. Steam reforming of ethanol is thermodynamically feasible and high temperatures result in high efficiency towards hydrogen production. The overall thermal efficiency of the operation is calculated and proven to be higher than the respective value of steam reforming of methane, which is the main commercial hydrogen producing operation. Steam reforming of ethanol was studied with catalysts based on Co, noble metals and Ni. The most promising materials were found to be the 2% Rh/Al2O3, 5% Ru/Al2O3 and 17% Ni/(La2O3/Al2O3) catalysts. The reaction network of steam reforming of ethanol, as well as carbon deposition, over nickel catalysts supported on γ-Αl2O3, La2O3 and La2O3/γ-Al2O3 is investigated employing transient and steady state techniques. Ceramic and metallic heat integrated reactors were developed for the reaction of steam reforming of ethanol. Experiments of coupled combustion – reformation in the ceramic reactor resulted in increased efficiency. In addition, experiments of coupled combustion – reformation were carried out in a metallic reactor by use of catalytic beds. The combustion-reformation experiments proved the effectiveness of the reactor, while the relative position of the two catalytic beds plays important role in the efficiency of the reactor. Finally, novel methods of catalyst deposition over metallic tubes were developed. On the outer surface an intermediate film of aluminum oxide was deposited by means of thermal plasma spraying in order to support the catalyst. Over the inner surface of the tube, aluminum powder was deposited and thermally processed to produce the necessary intermediate substrate. The materials produced by the above mentioned methods, were rigid and stable under extreme thermal-cycles, additionally the reforming material exhibited high efficiency.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / CerÃmica Aurivillius sÃo conhecidas por sua excelente resistÃncia à fadiga e a sua alta temperatura de Curie, a qual apresenta cÃlula unitÃria ortorrÃmbica. A cerÃmica a ser estudada, SrBi2Nb2O9 (SBN), à matÃria-prima potencial na fabricaÃÃo de memÃrias ferroelÃtricas, com polarizaÃÃo espontÃnea e bons coeficientes piezelÃtricos. Dentro deste grupo cerÃmico, o SrBi2Nb2O9 (SBN) à o material com menor estrutura octaÃdrica distorcida. Apesar disto, o SBN sofre de perda dielÃtrica elevada, devido à evaporaÃÃo de Ãxido de bismuto durante a preparaÃÃo, vindo a limitar sua utilizaÃÃo. A ativaÃÃo mecÃnica usada foi a de moinho planetÃrio, que nos permite calcinar o composto por temperaturas mais baixas que as geralmente apresentadas na literatura. ApÃs a calcinaÃÃo, moemos por mais duas horas, e obtemos um pà de boa densidade e reduzida temperatura de sinterizaÃÃo. Este fato previne a perda de elementos volÃteis (Pb ou Bi) e controla o crescimento do grÃo que à produzido quando a alta temperatura à necessÃria para a obtenÃÃo dessa cerÃmica. No presente trabalho, esta cerÃmica Aurivillius serà estudada em suas propriedades estruturais e dielÃtricas com dopagem de Ãxido de lantÃnio, de bismuto e de chumbo, em diversas porcentagens. Adicionalmente, houve a necessidade de um estudo comparativo com respeito a diferentes tipos de ligantes, e os testes obedeceram Ãs dopagens mencionadas acima. Os resultados foram obtidos pelo mÃtodo Hakki & Coleman, pela Espectroscopia de ImpedÃncia e medidas de RadiofreqÃÃncia, para a caracterizaÃÃo elÃtrica. DifraÃÃo de Raios-X, juntamente com o Refinamento Rietveld, Espectroscopia Raman e de Infravermelho, para anÃlise estrutural, dentre outras medidas e mÃtodos. / Aurivillius ceramic are know by is excellent resistence to high use and itÂs high Curie temperature, in wich it presents unicell ortorrÃmbic. The ceramic to be study SrBi2Nb2O9 (SBN), is a potential prime-mater in the production of ironelectric memories with sponteneous polarization and good piezelectric coeficient. Within this ceramic group, SrBi2Nb2O9 (SBN) is the material with less twisted octaÃdric structure. Even so, SBN, have high loss of dielectric, due to the evaporation of bismut oxide during preparation, inposing a limit to is use. The mechanical activation used was of a planetarium will, that allows us to calcinate the compost by very low temperatures that are presented in literature. After the calcination, we will it for two more hours and have dust that have good density and low sinterization temperature. That fact privine us the lost of volatile elements ( Pb or Bi ) and controls the grow of the seed wich is produced when high Temperature is needed to obtain this ceramic . In the present work, this Aurivillius ceramic wil be studyed in is dielectric and structure properties with dopage of lantÃnium oxide, lead oxide and bismut oxide, on different percentages. In addiction there was necessety of a comparative study, regarding the different types of leagues and tests obay the dopage already menttionated. The results were obtained by the Hakki & Coleman method by the Impendence Espectroscopic and radiofrequense mesures, to the electric caracterization . X-rays Defraction with Rictveld refiament , Raman and infrared espectroscopic, to structural analises , within other mesures and methods .

Tungsten (W) based materials can be used in fusion reactors due to several advantages. Different fabrication routes can be applied to develop tungsten materials with intended microstructure and properties for specific application including nanostructured grades. Therein, innovative chemical routes are unique in their approach owing numerous benefits. This thesis summarizes the development of W-based composites dispersed-strengthened by rare earth (RE) oxides and their evaluation for potential application as plasma facing armour material to be used in fusion reactor. Final material development was carried out in two steps; a) fabrication of nanostructured metallic tungsten powder dispersed with RE-oxides and b) powder sintering into bulk oxide-dispersed strengthened (ODS) composite by spark plasma process. With the help of advanced characterization tools applied at intermediate and final stages of the material development, powder fabrication and sintering conditions were optimized. The aim was to achieve a final material with a homogenous fine microstructure and improved properties, which can withstand under extreme conditions of high temperature plasma. Two groups of starting materials, synthesized via novel chemical methods, having different compositions were investigated. In the first group, APT-based powders doped with La or Y elements in similar ways, had identical particles’ morphology (up to 70 μm). The powders were processed into nanostructured composite powders under different reducing conditions and were characterized to investigate the effects on powder morphology and composition. The properties of sintered tungsten materials were improved with dispersion of La2O3 and Y2O3 in the respective order. The oxide dispersion was less homogeneous due to the fact that La or Y was not doped into APT particles. The second group, Ydoped tungstic acid-based powders synthesized through entirely different chemistry, contained nanocrystalline particles and highly uniform morphology. Hydrogen reduction of doped-tungstic acid compounds is complex, affecting the morphology and composition of the final powder. Hence, processing conditions are presented here which enable the separation of Y2O3 phase from Y-doped tungstic acid. Nevertheless, the oxide dispersion reduces the sinterability of tungsten powders, the fabricated nanostructured W-Y2O3 powders were sinterable into ultrafine ODS composites at temperatures as low as 1100 °C with highly homogeneous nano-oxide dispersion at W grain boundaries as well as inside the grain. The SPS parameters were investigated to achieve higher density with optimum finer microstructure and higher hardness. The elastic and fracture properties of the developed ODS-W have been investigated by micro-mechanical testing to estimate the materials’ mechanical response with respect to varying density and grain size. In contrast from some literature results, coarse grained ODS-W material demonstrated better properties. The developed ODS material with 1.2 Y2O3 dispersion were finally subjected to high heat flux tests in the electron beam facility “JUDITH-1”. The samples were loaded under ELM-like thermal-shocks at varying base temperatures up to an absorbed power density of 1.13 GW/m2, for armour material evaluation. Post mortem characterizations and comparison with other reference W grades, suggest lowering the oxide contents below 0.3 wt. % Y2O3. As an overview of the study conducted, it can be concluded that innovative chemical routes can be potential replacement to produce tungsten based materials of various composition and microstructure, for fusion reactor applications. The methods being cheap and reproducible, are also easy to handle for large production at industrial scale. / <p>QC 20120827</p>

Widespread use of solid oxide fuel cells is hindered by a lack of long-term durability of seals between metallic and ceramic components caused by thermal expansion mismatch induced cracking. A novel gas seal design incorporating an engineered thermal expansion gradient in a SrO-La₂O₃-A₂O₃-B₂O₃-SiO₂ glass matrix with a TiNiHf shape memory alloy mesh for active stress relief and crack healing is being developed. Coefficient of thermal expansion (CTE) measurements of the seal and fuel cell components shows the possibility for a thermal expansion gradient. Differential scanning calorimetry and microscopy have shown that the TiNiHf alloy has a shape memory transition in the desired range of 200-250ºC. The oxide glass partially crystallizes during thermal cycling which has been observed through X-ray diffraction and dilatometry. The CTE decreases from 9.3Ã 10-6/°C to 6.6Ã 10-6/°C after thermal cycling. Neutron diffraction data from TiNiHf /glass composite samples reveals that the TiNiHf alloy has the ability of absorbing residual stresses from a glass matrix during martensitic phase transition. There is evidence from microscopy that the glass composition is important in determining if reaction will occur with the TiNiHf alloy. The TiNiHf alloy mesh structures can be created using the 3D printing process. This process has been adapted to allow for printing of very thin wire mesh structures of Ni and NiTi powders with a more suitable binder solution. A bi-layer test fixture has been developed which will be useful for assessing leak rate through seal materials. / Master of Science