Submitted by Fernanda Rodrigues de Lima (fernanda.rlima@ufpe.br) on 2018-07-11T19:41:35Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) DISSERTAÇÃO Bruna de Souza Constantino.pdf: 14899698 bytes, checksum: dbb7503da8d7f9c6e978fb27870941f9 (MD5) / Approved for entry into archive by Alice Araujo (alice.caraujo@ufpe.br) on 2018-07-18T18:12:55Z (GMT) No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) DISSERTAÇÃO Bruna de Souza Constantino.pdf: 14899698 bytes, checksum: dbb7503da8d7f9c6e978fb27870941f9 (MD5) / Made available in DSpace on 2018-07-18T18:12:55Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) DISSERTAÇÃO Bruna de Souza Constantino.pdf: 14899698 bytes, checksum: dbb7503da8d7f9c6e978fb27870941f9 (MD5) Previous issue date: 2017-02-23 / FACEPE / A atual configuração energética brasileira e mundial é fortemente dependente de fontes provenientes do petróleo. No entanto, devido à composição do petróleo cru e suas condições de produção, os equipamentos responsáveis pelo seu armazenamento e transporte são vitimados por agressões corrosivas. Problemas gerados direta ou indiretamente pela corrosão representam uma grande parcela dos custos totais para as empresas produtoras de petróleo e gás. Deste modo, revestimentos cerâmicos aplicados por meio de aspersão térmica hipersônico estão sendo estudados, visando aplicações como proteção contra a corrosão em matrizes metálicas da indústria petrolífera e que devem apresentar boas características de estabilidade química, resistência à corrosão e resistência a altas temperaturas. Neste trabalho foram estudadas cerâmicas produzidas a partir dos óxidos cerâmicos Al₂O₃ – ZrO₂ La₂O₃, onde foram fixados 2% (em massa) de Lantânia e adicionados 10%, 15% e 20% de Zircônia numa matriz de Alumina. Os pós cerâmicos foram pesados, misturados em moinho de bolas, compactados em prensa uniaxial e sinterizados em um dos três ciclos térmicos diferentes – 1350ºC, 1500ºC e 1650ºC. Assim, foram obtidas 09 amostras diferentes. Foram utilizadas na caracterização dos materiais as técnicas de: Análise de Tamanho de Partículas (ATP), Microscopia Ótica (MO), Microscopia Eletrônica de Varredura (MEV), Espectrometria de Energia Dispersiva (EDS), Microdureza Vickers e Difração de Raios-X (DRX). As amostras tiveram sua estabilidade analisada após 90 dias de imersão continua em petróleo cru provenientes de poços de origem de mar e de terra do estado de Sergipe. As avaliações da estabilidade das cerâmicas indicam que todas as amostras estudadas apresentaram uma boa resposta após a imersão em petróleo cru, no entanto, quanto às propriedades mecânicas, as cerâmicas sinterizadas a 1650ºC se destacam. / The current Brazilian and world energy configuration is strongly dependent on sources from the oil. However, due to the composition of the crude oil and production conditions, equipment for its storage and transport are victimized by corrosive attacks. Problems generated directly or indirectly by corrosion represent a large portion of the total costs to the oil and gas producing companies. Thus, ceramic tiles applied through spraying hypersonic heat are being studied, aimed at applications such as protection against corrosion in metallic arrays of the oil industry and that must be chemically stable and resistant to corrosion and high temperatures. This work studied ceramics produced from ceramic oxides Al₂O₃ – ZrO₂ La₂O₃, where were fixed 2% (by mass) of Lantania and added 10%, 15% and 20% of a Zirconia in an Alumina matrix. Ceramic powders produced by mixing in ball mill, compressed in an uniaxial press and sintered in one of the three different thermal cycles – 1350ºC, 1500ºC e 1650ºC, obtaining 09 different samples. Were used in the characterization of materials techniques of: particle size analysis (PSA), optical microscopy (OM), scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), Vickers micro hardness and x-ray Diffraction (XRD). The samples had their stability analyzed after 90 days of continues immersion on crude oil from source wells of sea and land of the Sergipe. The stability evaluation of the ceramics indicates that all the studied samples presented a good response after the immersion in crude oil however, regarding the mechanical properties, the ceramics sintered at 1650ºC stand out.

Made available in DSpace on 2014-06-12T18:05:21Z (GMT). No. of bitstreams: 2 arquivo2577_1.pdf: 1425861 bytes, checksum: 6b478a5b001cb3d32788925e389ba3b6 (MD5) license.txt: 1748 bytes, checksum: 8a4605be74aa9ea9d79846c1fba20a33 (MD5) Previous issue date: 2009 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / O desenvolvimento do processo de reforma do metano com dióxido de carbono abordado na presente pesquisa recorre à ação do catalisador de níquel suportado em alumina, disposto em reator de leito fixo com membrana seletiva para hidrogênio associada. Atividade e estabilidade do sistema de níquel (50mg), foram avaliadas através de contato catalisador com uma mistura gasosa de composição em razões molares de alimentação CH4/CO2/Ar (10%/40%/50%), a uma vazão total fixa de 100 cm3/min, operando-se na faixa de temperatura de 1.023 K e 1.073 K, sob pressão de 1,0 bar. A reação de Boudouard (C+CO2→2CO) foi utilizada como base para a regeneração do catalisador de níquel, sob coqueamento, tendo-se observado retomadas de níveis de conversão do metano e de produção de hidrogênio. Operações em reator de membrana, na linha de desenvolvimento do processo, com 2 g de catalisador de níquel (3,31% em massa suportado em alumina), utilizaram uma mistura de reagentes em razões molares CH4/CO2/Ar (40,50%/14,00%/45,50%), com uma vazão total de 110 cm3/min , aplicando-se as temperaturas de 773 K, 823 K e 873 K, sob pressão de 1,0 bar. O processo de reforma seca do metano com dióxido de carbono foi operado em reator de leito fixo de membrana com permeação de hidrogênio, evidenciando uma importante conversão do metano com um rendimento em hidrogênio elevado. A 873 K, sob 1,0 bar de pressão, converteu-se neste sistema 35% de metano rendendo 47% de hidrogênio, significando aumentos de conversão em cerca de 83 % e de rendimento em hidrogênio de mais de 100%, em relação às operações em leito fixo sem permeação. Modelagem e simulações foram elaboradas a partir da cinética já ajustada, permitindo simulações retratando perfis de concentração dos reagentes (CH4 + CO2) e produtos (H2 + CO) com e sem permeação do hidrogênio através da membrana Pd-Ag, destacando-se os efeitos da temperatura

Made available in DSpace on 2014-07-29T15:07:08Z (GMT). No. of bitstreams: 1 Dissertacao Alexandre Miranda de Oliveira.pdf: 4426704 bytes, checksum: 904266306eab31523948c4d6634abfe0 (MD5) Previous issue date: 2010-12-15 / This work is to study the crystallization of compounds in the form of post system alumina-yttria-silica prepared by sol-gel mixed methodology and Pechini. Powders (x / 2) Y ² ³ - (X / 2) Al ² O ³ - (1-x) SiO ² (x = 0.1 0.2, 0.3, 0.4 and 0.5 mol) were doped with erbium prepared and characterized. The physical properties of composite SiO ² ¹ YO-, 5 - AlO ¹, 5 were studied by x-ray diffraction, FTIR spectroscopy, thermogravimetry, differential thermal analysis and photoluminescence measurements. It was possible to maintain the amorphous compositions at high temperatures, no crystallization below 900 ° C and the formation of phase Y ² ² O7 Si at 1100 ° C. We obtained a reasonable life time of some compositions treated at 1000 ° C. We observed the emission of green upconversion to excite the samples with high power laser. All synthesized samples exhibit photoluminescence emission and have maximum emission at 1530 nm with a width of ~ 47nm. This broad issue is a desirable property for amplifiers used in systems division multiplexing wavelengths (WDM) and suggests that Er ³ + ions are hosted in the amorphous phase. / Neste trabalho estudo-se a cristalização de compostos na forma de pós do sistema alumina-ítria-sílica preparados pela metodologia mista sol-gel e Pechini. Pós de (x/2) Y²O³-(X/2) Al²O³-(1-x) SiO² (x=0,1 0,2, 0,3, 0,4 e 0,5 em mol) dopados com érbio foram preparados e caracterizados. As propriedades físicas dos composto de SiO²-YO¹,5- AlO¹,5 foram estudadas por difração de raios-x, espectroscopia FTIR, termogravimetria, análise térmica diferencial e medidas de fotoluminescência. Foi possível manter as composições amorfas a altas temperaturas, não houve cristalização abaixo de 900° C e a formação da fase Y²Si²O7 a 1100 °C. Obtivemos um tempo de vida razóavel de algumas composições tratadas a 1000°C. Observamos a emissão verde de upconversion ao excitar as amostras com laser de alta potência. Todas as amostras sintetizadas apresentam emissão fotoluminescente e possuem máximo de emissão em 1530 nm com largura a meia altura de ~47nm. Essa emissão larga é uma propriedade desejável para amplificadores usados em sistemas de multiplexação por divisão de comprimentos de onda (WDM) e sugere que os íons Er³+ estão hospedados na fase amorfa.

The availability of high quality thermodynamic data on solid solutions and compounds present in multicomponent systems assists in optimizing processing parameters for synthesis, and in evaluating stability domains and materials compatibility under different conditions. Several oxide systems of technological interest, for which thermodynamic data was either not available or is inconsistent were selected for study. Thermodynamic properties of phases present in the binary systems Nb-O and Ta-O were measured in the temperature range from 1000 to 1300 K using solid state electrochemical cells based on (Y2O3) ThO2 as the electrolyte. Based on these measurements and more recent data on heat capacity and phase transitions reported in the literature, Gibbs energy of formation for NbO, NbO2, NbO2.422, Nb2O5-x and Ta2O5 were reassessed. Significant improvements in the data for NbO2, Nb2O5 and Ta2O5 are suggested. The pseudo binary system MoO2-TiO2 was investigated because of the inconsistency between the phase diagram and thermodynamic properties of the solid solution reported in the literature. Based on new electrochemical measurements, a new improved phase diagram for the system MoO2-TiO2, incorporating recently discovered monoclinic to tetragonal phase transition in MoO2 at 1533 K, is presented. Isothermal section of the phase diagram for the ternary systems Cr-Rh-O and Ta-Rh-O and thermodynamic properties of ternary oxides CrRhO3 and TaRhO4 were measured for the first time in the temperature range from 900 to 1300 K. Phase relations for these systems have been computed as a function of oxygen potential at fixed temperature and as a function of temperature at selected oxygen partial pressures. Metal-spinel-corundum three-phase equilibrium in the Ni-Al-Cr-O system at 1373 K has been explored because of its relevance to high temperature corrosion of super alloys. The Gibbs energy of mixing of spinel solid solution was derived from the tie-line data and is compared with the values calculated from cation distribution models. An oxygen potential diagram is developed for the decomposition of spinel solid solution to nickel and corundum solid solution at 1373 K under reducing conditions. The high temperature thermodynamic properties of the phases present in quaternary systems Ca-Co-Al-O and Ca-Cu-Ti-O have been measured by solid state electrochemical cells based on stabilized zirconia. Gibbs energies of formation of the quaternary oxides Ca3CoAl4O10 in the temperature range from 1150 to1500 K and CaCu3Ti4O12 in the range from 900 to 1350 K are presented. Chemical potential diagrams have been computed for the system Al2O3-CaO-CoO at 1500 K. The oxygen potential corresponding to the decomposition of the complex perovskite CaCu3Ti4O12 (CCTO) has been calculated as a function of temperature from the emf of the cell. The effect of the oxygen partial pressure on the phase relations in the pseudo-ternary system CaO-(CuO/Cu2O)-TiO2 at 1273 K has been evaluated. The phase diagrams are useful for the control of the secondary phases that form during synthesis of CCTO, a material exhibiting colossal dielectric response.

The objective of the research was to develop high quality GaN epitaxial growth on alternative substrates that could result in higher external quantum efficiency devices. Typical GaN growth on sapphire results in high defect materials, typically 10⁸⁻¹⁰cm⁻², due to a large difference in lattice mismatch and thermal expansion coefficient. Therefore, it is useful to study epitaxial growth on alternative substrates to sapphire such as ZnO which offers the possibility of lattice matched growth. High-quality metalorganic chemical vapor deposition (MOCVD) of GaN on ZnO substrate is hard to grow due to the thermal stability of ZnO, out-diffusion of Zn, and H₂back etching into the sample. Preliminary growths of GaN on bare ZnO substrates showed multiple cracks and peeling of the surface. A multi-buffer layer of LT-AlN/GaN was found to solve the cracking and peeling-off issues and demonstrated the first successful GaN growth on ZnO substrates. Good quality InGaN films were also grown showing indium compositions of 17-27% with no indium droplets or phase separation. ZnO was found to to sustain a higher strain state than sapphire, and thereby incorporating higher indium concentrations, as high as 43%, without phase separation, compared to the same growth on sapphire with only 32%. Si doping of InGaN layers, a known inducer for phase separation, did induce phase separation on sapphire growths, but not for growths on ZnO. This higher strain state for ZnO substrates was correlated to its perfect lattice match with InGaN at 18% indium concentration. Transmission electron microscopy results revealed reduction of threading dislocation and perfectly matched crystals at the GaN buffer/ZnO interface showing coherent growth of GaN on ZnO. However, Zn diffusion into the epilayer was an issue. Therefore, an atomic layer deposition of Al₂O₃was grown as a transition layer prior to GaN and InGaN growth by MOCVD. X-ray and PL showed distinct GaN peaks on Al₂O₃/ZnO layers demonstrating the first GaN films grown on Al₂O₃/ZnO. X-ray photoelectron spectroscopy showed a decrese in Zn diffusion into the epilayer, demonstrating that an ALD Al₂O₃layer was a promising transition layer for GaN growth on ZnO substrates by MOCVD.

Graphene has been considered for a variety of applications including novel nanoelectronic device concepts. However, the deposition of ultra-thin high-k dielectrics on top of graphene has still been challenging due to graphene's lack of dangling bonds. The formation of large islands and leaky films has been observed resulting from a much delayed growth initiation. In order to address this issue, we tested a pre-treatment with NF³ instead of XeF² on CVD graphene as well as epitaxial graphene monolayers prior to the Atomic Layer Deposition (ALD) of Al²O³. All experiments were conducted in vacuo; i. e. the pristine graphene samples were exposed to NF³ in the same reactor immediately before applying 30 (TMA - H²O) ALD cycles and the samples were transferred between the ALD reactor and a surface analysis unit under high vacuum conditions. The ALD growth initiation was observed by in-situ real-time Spectroscopic Ellipsometry (irtSE) with a sampling rate above 1 Hz. The total amount of Al²O³ material deposited by the applied 30 ALD cycles was cross-checked by in-vacuo X-ray Photoelectron Spectroscopy (XPS). The Al²O³ morphology was determined by Atomic Force Microscopy (AFM). The presence of graphene and its defect status was examined by in-vacuo XPS and Raman Spectroscopy before and after the coating procedure, respectively.