[pt] A reação de síntese de Fischer-Tropsch tem despertado interesse pelo seu caráter tecnológico e científico uma vez que este processo é capaz de converter o gás natural em produtos de elevado valor agregado. No presente trabalho, catalisadores de ferro suportados em sílica alumina ou em SBA-15 foram sintetizados, caracterizados, ativados e empregados na síntese de Fischer Tropsch. Os catalisadores foram preparados via impregnação incipiente do ponto úmido utilizando cloreto de ferro III, obtendo-se catalisadores de porcentagem mássica próximos a 5%, 10% e, no caso da sílica alumina, 2% também. As amostras foram caracterizadas por análise termogravimétrica (ATG), por medidas de adsorção física de N2, difração de raios-X (DRX) e redução à temperatura programada (RTP). O teor de ferro foi determinado pela espectroscopia de raios X por dispersão de energia (EDX). A ativação dos catalisadores e, em seguida, os testes catalíticos foram conduzidos em um reator tubular de bancada e os produtos gasosos foram analisados através de cromatografia gasosa com detector por ionização de chama (CG-DIC), cuja análise mostrou a formação de hidrocarbonetos C1-C5. A adsorção física de N2 revelou que, a introdução de ferro nos suportes, diminuiu a área superficial específica e o volume de poro dos materiais. A difração de raios X foi realizada para os catalisadores após a calcinação, mostrando a presença das fases α-Fe2O3 e Fe3O4; após a ativação e após a reação, onde se encontrou Fe0 e carbetos de ferro Fe5C2 e Fe2C. Os testes catalíticos mostraram maior seletividade aos hidrocarbonetos C2-3 para os catalisadores suportados em SBA-15. / [en] The Fischer-Tropsch synthesis reaction has showed interest due to its technological and scientific character since the process is able to convert natural gas into high added value products. In the present work, iron catalysts supported on SBA-15 or silica doped alumina were synthesized, characterized, activated and employed in the Fischer Tropsch synthesis. The catalysts were prepared via incipient wetness impregnation method using iron III chloride, obtaining catalysts with a weight percentage of about 5%, 10% and, in the case of silica doped alumina, 20% as well. The samples were characterized by thermogravimetric analysis (ATG), with measurements of N2 physisorption, X-ray diffraction (DRX) and temperature programmed reduction (RTP). Iron content was determined by energy dispersive X-ray spectroscopy (EDX). The catalysts activation and, subsequently, their catalytic tests were conducted in a bench tubular reactor and the products were analyzed by gas chromatography with flame ionization detector (CG-DIC), where it was detected the formation of C1-C4 hydrocarbons. The N2 physisorption showed that the introduction iron in the supports decreased the specific surface area and the pore volume of the materials. X-ray diffraction was performed for catalysts after calcination, showing the presence of α-Fe2O3 and Fe3O4 phases, after activation and after reaction, where it was found crystals of Fe0 and iron carbides Fe5C2 and Fe2C. The catalytic tests showed greater C2-3 selectivity for SBA-15 supported catalysts.

Orientador: Celso Valentim Santilli / Banca: Rodrigo Fernando da Costa Marques / Banca: Eduardo José Nassar / Resumo: A produção de aluminas com distribuição de tamanho e volume de poros controlados pela separação de fases líquido-sólido é um assunto emergente na área de cerâmicas porosas. As aluminas foram produzidas pelo processo sol-gel acompanhado de separação de fases, usando o óxido de polietileno (PEO) como agente indutor na separação de fases e o óxido de propileno para a gelatinização, para isso foram estabelecidas condições de controle cinético e termodinâmico desses eventos, através do controle do tempo de agitação e temperatura no meio reacional. Foram otimizadas rotas de síntese através do ajuste dos parâmetros de preparação variando a concentração do agente direcionador de poros PEO durante a transição sol-gel. Esta transformação foi acompanhada in-situ por SAXS revelando que o crescimento de objetos fractais com dimensionalidade de 1,7, que é característico do mecanismo e agregação controlado pela difusão. A calcinação em 700°C possibilitou a produção de aluminas da fase gama (-Al2O3) com textura porosa formada por macro e mesoporos. O uso do agente direcionador de poros PEO em proporção molar entre 0,01-0,07 mostrou-se eficiente no ajuste da macro-mesoporosidade. Entretanto quando se emprega proporções molares de PEO acima de 0,07 obtém-se apenas famílias de mesoporos com um decaimento do volume específico de poros quando a proporção molar aumenta de 0,08 para 0,1. Estas aluminas mesoporosas apresentaram maior área superficial especifica (Área BET máximo de  305 m²/g) e uma melhor relação OH/-O-Al em comparação com as macro-mesoporosas. / Abstract: The production of alumina with volume and size distribution of pores controlled by phase separation induced by the addition of the polymer polyethylene oxide (PEO) during synthesis is an emerging issue in the area of functional ceramics. The aluminas were produced by the sol-gel process followed by phase separation, and the PEO as inducing agent phase separation and propylene oxide to gelation. Conditions for kinetic and thermodynamic control over these events were kept by controlling the stirring time and temperature in the reaction medium. Synthesis routes have been optimized by adjusting the preparation parameters varying the concentration of pores directing agent (PEO) during sol-gel process. This transformation was accompanied by in-situ SAXS and the results reveal the growth typical of fractal objects starting from a diluted solution, whose dimensionality in the Porod region was 1,7, characteristic of aggregation controlled by diffusion and the distances between the growing particles is around 2,95 nm. Gamma alumina (-Al2O3) with diversified porous texture and macro-mesopores was obtained with thermal treatment up to 700 ° C, being supported by several techniques. The macro-mesoporosity can be adjusted by PEO driver pores agent in a molar ratio from 0,01 to 0,07. Molar ratios of PEO above 0,07 produces only mesopores, decreasing the cumulative volume of this pores when the molar ratio increases from 0,08 to 0,1. These mesoporous aluminas had higher specific surface area (BET Area  305 m² / g) and better ratio OH/O-Al compared to the macro-mesoporous. / Mestre

This project addressed two main problems pertaining to Al₂O₃-FeAl2O4 nanocomposites developed via solid state precipitation: the mechanisms for precipitation in ceramic solid solution via reduction reaction, and the mechanisms for the improved mechanical properties and wear resistance of the developed Al2O3-FeAl2O4 nanocomposites. A model was proposed for precipitation in ceramic solid solutions via reduction reactions (the PRCS model). The thermodynamics of reduction reactions during aging treatments under various atmospheres were calculated and discussed relative to the second phase precipitate formation. Attempts were made to measure the corresponding diffusion kinetics using a new theory developed here based on volume fraction profiles of second phase particles in the aged samples. It was found that the measured apparent oxygen vacancy diffusivities conform well to the oxygen vacancy grain boundary diffusion coefficients reported in the literature, and the measured apparent matrix diffusivity conforms well to the Fe3+ ion matrix diffusion coefficients reported in literature. Based on the thermodynamics calculations, diffusion kinetics and some essential mechanisms that were discussed, the PRCS model was proposed. This has two aspects: macroscopic and microscopic. The macroscopic aspect of PRCS model was mainly used to explain the general aspects of microstructure and the distribution of intergranualar second phase particles. The microscopic aspect of the PRCS model was mainly used to explain the precipitation of intragranualar nanoparticles. The mechanical properties, thermal residual stress and wear resistance of selected Al2O3-FeAl2O4 nanocomposites were measured. The results revealed that the Al2O3-FeAl2O4 possessed improved fracture toughness (by around 46%), flexural strength (by around 30%) and abrasive wear resistance (by a factor of around 5) with respect to monolithic alumina. Several mechanisms were proposed to explain the improvements in both mechanical properties and wear resistance. Compressive residual stress was found in the surface layer of Al2O3-FeAl2O4 nanocomposites due to the thermal expansion coefficient mismatch between surface layer and bulk parts. Such residual stress was also interpreted as the main reason for the improvements in both mechanical properties and wear resistance.

The term Nanoceramics is well known in the ceramic field for at least two decades. In this project a detailed study was performed on the synthesis of α-alumina nanopowders. High solids content nanoalumina suspensions were prepared and used to form green bodies using both wet and dry forming routes. The green bodies were then sintered using both conventional single and two-step sintering approaches. Synthesis: Two different synthesis methods, viz. precipitation and hydrothermal treatment, were used to synthesize fine α-alumina powders from aluminium chloride, ammonia solution and TEAH (Tetraethyl ammonium hydroxide). XRD, TEM and FEG-SEM were used to characterise the powders produced. The presence of commercial α-alumina powder as seed particles did not affect the transformation to α-alumina phase during the hydrothermal treatment at 220˚C in either basic or acidic environments. The results obtained from the precipitation route showed that the combined effect of adding α-alumina seeds and surfactants to the precursor solution could lower the transformation temperature of α-alumina from about 1200˚C for unseeded samples to 800˚C, as well as reducing the level of agglomeration in the alumina powders. The difference in transformation temperature mainly resulted from the nucleation process by the α-alumina seeds, which enhanced the θ → α transformation kinetics. The lower level of agglomeration present in the final powders could be due to the surface modifying role of the surfactants preventing the particles from growing together during the synthesis process. By introducing a further high-temperature step for a very short duration (1 minute) to the low-temperature heat treatment route (800˚C/12 h), the unseeded sample with added surfactant transformed into pure α-alumina phase. The newly-added step was shown to be an in-situ seeding step, followed by a conventional nucleation and growth process. The best final powder was compared with a commercial α-alumina nanopowder. Processing of alumina ceramics: The effect of low-molecular weight ammonium dispersants including Dispex-A40, Darvan-C and Dolapix-CE64, on high solids content nanoalumina suspensions was investigated. The nanosuspension prepared using the most suitable dispersant, Dolapix-CE64, was slip cast into ~53% dense, very homogeneous green bodies. This nanosuspension was also spray freeze dried into crushable granules using Freon as a foaming agent. Green compacts with density of ~53.5% were then formed by dry pressing the 2 vol% Freon-added spray freeze dried granules at 40 MPa. Both slip cast and die pressed green bodies were sintered using conventional single-step and two-step routes followed by characterising the density and grain size measurement of final dense compacts. The results have been compared with that of a submicron alumina ceramic prepared using a commercial α-alumina suspension. Highly dense alumina with an average grain size of ~0.6 μm was fabricated by means of spark plasma sintering at 1200˚C. The application of 500 MPa allowed achieving almost fully dense alumina at temperature as low as 1200˚C for 30 minutes with no significant grain growth.

Οι μονοδιάστατες μεταλλικές νανοδομές, όπως νανοσύρματα και νανοσωλήνες, έχουν ελκύσει το ενδιαφέρον της επιστημονικής κοινότητας τα τελευταία χρόνια λόγο του σημαντικού ρόλου που παίζουν στην κατασκευή νανοσυσκευών, όπως ανιχνευτές, ηλεκτρονικά και οπτικά συστήματα και συστήματα αποθήκευσης πληροφορίας. Μια απλή και αποτελεσματική τεχνική για την κατασκευή μεγάλου αριθμού νανοσυρμάτων και νανοσωλήνων με μεγάλη αναλογία μήκους προς διάμετρο είναι η ονομαζόμενη «σύνθεση μήτρας», η οποία βασίζεται στην ηλεκτροχημική εναπόθεση μετάλλου μέσα στους πόρους κατάλληλου υλικού το οποίο λειτουργεί σαν μήτρα. Η πορώδης αλουμίνα είναι ένα υλικό που χρησιμοποιείται ευρέως για τον σκοπό αυτό λόγο της χημικής και μηχανικής της σταθερότητας και της αντοχής της σε υψηλές θερμοκρασίες. Επίσης, τα γεωμετρικά της χαρακτηριστικά μπορούν να ελέγχουν εύκολα κατά την διάρκεια της διαδικασίας παρασκευής της. Στην εργασία περιγράφεται η διαδικασία κατασκευής μεμβρανών πορώδους αλουμίνας με εξαγωνική κατανομή πόρων, ανοιχτών και στις δύο επιφάνειες και με συγκεκριμένα γεωμετρικά χαρακτηριστικά. Για να κατασκευασθούν οι μήτρες οι οποίες θα χρησιμοποιηθούν στην ηλεκτροεναπόθεση και για άλλες εφαρμογές εξήχθη η σχέση μεταξύ του ρυθμού ανάπτυξης της μεμβράνης πορώδους αλουμίνας και των παραμέτρων της ανοδίωσης (πυκνότητα ρεύματος, θερμοκρασία) για ανοδίωση σε υδατικό διάλυμα με περιεκτικότητα 0.3Μ οξαλικό οξύ. Επιπλέον, μελετήθηκε ο απαραίτητος χρόνος για την διάλυση του συμπαγούς διαχωριστικού στρώματος (barrier layer) της πορώδους αλουμίνας με την χρήση υδατικού διαλύματος 5%wt. φωσφορικού οξέος. Τέλος, στην εργασία αυτή μελετήθηκε η ανάπτυξη νανοσυρμάτων νικελίου σε πορώδης αλουμίνα με μέση διάμετρο πόρων 240nm. Για την καλύτερη κατανόηση των μηχανισμών ανάπτυξης των νανοσυρμάτων μελετήθηκε η σχέση της κρυσταλλογραφικής δομής των νανοσυρμάτων με την εφαρμοζόμενη τάση κατά την ανάπτυξη τους με την χρήση της τεχνικής dc ηλεκτροεναπόθεσης. Κατά την μελέτη αυτή αναπτύχθηκαν μονοκρυσταλλικά νανοσύρματα νικελίου προσανατολισμένα κατά την διεύθυνση [110] και πολυκρυσταλλικά νανοσύρματα με ισχυρό προσανατολισμό κατά την διεύθυνση [111]. / One-dimensional metallic nanostructured materials, like nanowires and nanotubes, have attracted extensive attention in recent years because of their importance in the fabrication of nanometer-scale devices such as sensors, electronics, and optics and information storage systems. A simple and effective technique to fabricate large number of metallic nanowires and nanotubes with high aspect ratio is the so called “template synthesis”, which involves electrochemically depositing metal into nanopores of a suitable material used as a template. Porous alumina membrane is a commonly used material for this purpose because of its chemical and mechanical stability and durability at high temperatures. Moreover, its geometrical characteristics are easily controlled during the fabrication process. In this work the fabrication process of free- standing porous alumina membranes with highly organized hexagonal structure and with specific geometrical characteristics is described. In order to fabricate templates for use in electrodeposition and other applications the dependence relation between the thickness growth rate and the anodization parameters (current density and temperature) for anodization in aqueous solution of 0.3M oxalic acid was derived. Furthermore, the time needed for barrier layer dissolution of porous alumina membrane with the use of hydrate solution of 5%wt. phosphoric acid. Finally, nickel nanowires were fabricated inside porous alumina membranes with mean pore diameter of 240nm. For better understanding of the nanowires growth mechanism the dependence of the crystal structure of nickel nanowire fabricated with dc electrodeposition from the applied voltage was studied. As a result, single crystal nickel nanowires oriented along [110] and polycrystalline nickel nanowires with a strong orientation along [111] have been fabricated.

Thermosonic ball bonding is a key technology in electrical interconnections between an integrated circuit and an external circuitry in microelectronics. Although this bonding process has been extensively utilised in electronics packaging industry, certain fundamental aspects behind all the practice are still not fully understood. This thesis is intended to address the existing knowledge gap in terms of bonding mechanisms and interfacial characteristics that are involved in thermosonic gold and copper ball bonding on aluminium pads. The research specifically targets the fine pitch interconnect applications where a thin metal wire of approximately 20 µm in diameter is commonly used. In thermosonic ball bonding process, a thin gold or copper ball formed at the end of a wire is attached to an aluminum pad through a combination of ultrasonic energy, pressure and heat, in order to initiate a complex solid-state reaction. In this research, the mechanisms of thermosonic ball bonding were elaborated by carefully examining interfacial characteristics as the results of the bonding process by utilising dual-beam focused ion beam and high resolution transmission electron microscopy, including the breakdown of the native alumina layer on Al pads, and formation of initial intermetallic compounds (IMCs). The effect of bonding parameters on these interfacial behaviours and bonding strength is also investigated in order to establish an inter-relationship between them. Interfacial evolution in both Au-Al and Cu-Al bonds during isothermal annealing in the temperature rage from 175ºC to 250ºC was investigated and compared. The results obtained demonstrated that the remnant alumina remains inside IMCs and moves towards the ball during annealing. The IMCs are formed preferentially in the peripheral and the central areas of the bonds during bonding and, moreover, they grow from the initially formed IMC particles. Growth kinetics of Cu-Al IMCs obey a parabolic growth law before the Al pad is completely consumed. The activation energies calculated for the growth of CuAl2, Cu9Al4 and the combination (CuAl2 + Cu9Al4) are 60.66 kJ/mol, 75.61 kJ/mol, and 65.83 kJ/mol, respectively. In Au-Al bonds, Au-Al IMC growth is controlled by diffusion only at the start of the annealing process. A t^0.2-0.3 growth law can be applied to the Au-Al IMC growth after the Al pad is depleted. The sequence of IMC phase transformation in both Au-Al and Cu-Al bonds were investigated. Voids in Au-Al bonds grow dramatically during annealing, however, only a few voids nucleate and grow very slowly in Cu-Al bonds. The mechanisms of void formation, including volumetric shrinkage, oxidation and metal diffusion were proposed and discussed.

Orientador: Luis Vicente de Andrade Scalvi / Banca: Valmor Roberto Mastelaro / Banca: Margarida Juri Saeki / O Programa de Pós Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi / Resumo: O escopo deste trabalho é a obtenção de filmes finos de óxido de alumínio (alumina) através da evaporação resitiva de alumínio, seguido da oxidação térmica em atmosfera adequada (ar ou rica em O2), com varaiação do tempo e da temperatura do tratamento térmico. A investigação deste material tem por finalidade sua utilização como camada isolante em transistores de efeito de campo, mais especificamente do tipo metal-óxido-semicondutor (MOSTFET), visando a diminuição da corrente de fuga no gate e aumento do controle de corrente no canal de condução. Além de se tratar de dipositivo transparente, que permite a interação com luz. A análise das propriedades ópticas e estruturais dos filmes investigados mostra que na temperatura de 550ºC ocorre uma completa oxidação do material, a qual é acelerada em atmosfera de oxigênio. Valores de resistividade elétrica concordam com a tendência de oxidação revelada pelos dados de Difração de Raios X (DRX). Além disso, resultados de espectroscopia no infravermelho (FTIR) e Raman, em bom acordo com resultados de DRX, apresentam-se estrutura y-Al2O3. Amostras de alumina depositadas sobre substrato de vidro sodalime apresentam silício cristalino na interface com o Al2O3 advindo do substrato, enquanto amostras de Al2O3 sobre SnO2 não apresentaram esse material. A heterojunção entre SnO2:4at%Sb e Al2O3 foi caracterizada por DRX, Microscopia eletrônica de varredura (MEV) e Microscopia Confocal, que mostraram alta rugosidade do filme isolante sobre o semicondutor, e um provável processo de difusão entre as camadas isolante e semicondutora, em concordância com resultados de corrente x voltage (IxV), obtidos a partir da construção de um dispositivo simples, com contatos de Sn, ao qual foram submetidos dispositivos com diferentes números de camadas isolantes... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The goal of this work is is to obtain aluminum oxide (alumina) thin films deposited by resistive evaporation of Al, followed by thermal oxidation in proper atmosphere (air or O2-rich), with varying time and temperature of thermal annealing. The investigation of this material of this material aims using this material for application as insulating layer in field effect transistors, specifically metal-oxide-semiconductor (MOSFET), seeking for low leakage current and efficient current control in the conduction channel. Besides, it is a transparent device, which allows interaction with light. Analysis of optical and structural properties of investigated films reveals that temperature of 550ºC is responsable for fair oxidation, which is accelerated in oxygen-rich atmosphere. Results of electrical resistivity agree with the oxidation, which is accelerated in oxygen-rich atmosphere. Results of electrical resistivity agree with the oxidation tendency found in the X-ray diffraction data (XRD). Moreover, results of infrared spectroscopy (FTIR) and Raman show the presence of y-Al2O3, also found in XRD data. Alumina samples deposited on soda-line glass substrates leads to the presence of crystalline Si, coming from the substrate leads to the presence of crystalline Si, coming from the substrate, whereas... (Complete abstract click electronic access below) / Mestre

O objetivo desse trabalho é confeccionar e caracterizar dosímetros luminescentes de óxido de alumínio, dopados com o elemento químico magnésio, para aplicação em dosimetria das radiações ionizantes. O óxido de alumínio é obtido pelo método do precursor polimérico; através da obtenção de resina polimérica que resulta em material cerâmico em pó após tratamentos térmicos em temperaturas específicas. As análises dosimétricas são realizadas durante ciclos de aquecimento de amostras que já tenham absorvido certa quantidade de radiação ionizante, ou dose radioativa, é a chamada Termoluminescência. Neste trabalho as fontes radioativas são emissoras de radiação- ou raios-X, que são mais presentes nos campos da radioterapia, radiodiagnóstico, geração de energia elétrica e estudos científicos. Devido às propriedades físicas do cristal, ocorre emissão de luz quando elétrons e buracos recebem energia térmica, permitindo a sua liberação de estados quânticos meta-estáveis e a recombinação com cargas opostas, liberando fótons no espectro UV/visível. A análise química por ICP AES indica as concentrações de 0,47; 0,88; 1,33; 2,61 e 3,36 mol% de Mg2+ para as cinco amostras preparadas com diferentes massas do reagente MgCO3; estes valores indicam que o procedimento para obtenção das amostras foi realizado com uniformidade adequada e, portanto, os resultados alcançados são proporcionais às concentrações de Mg2+. Inicialmente, analisando os resultados da difração de Raios-X, percebe-se que a menor temperatura utilizada para a calcinação do material cerâmico não foi suficiente para que se obtivesse a fase estrutural desejada (fase alfa), uma vez que a estrutura gama não exibiu propriedades dosimétricas para doses baixas. Este fato implicou em tratamentos térmicos adicionais em temperatura superior (1100°C). Os difratogramas obtidos comprovam a viabilidade do processo e metodologia, com amostras altamente cristalinas e ausência de fases desconhecidas que poderiam ocorrer caso houvesse contaminação. As medidas de TL acusaram uma forte emissão luminescente na região do espectro visível e UV, com picos de emissão em 125, 200, 280, 350 e 430°C, aproximadamente. Os últimos não puderam ser estudados para doses baixas, pois suas intensidades são sobrepostas pela incandescência do porta amostras. Entretanto, o pico de emissão em 200°C mostrou comportamento satisfatório e, portanto, empregado para estudos mais aprofundados. Os picos de alta temperatura (280, 360 e 430ºC) exibiram ótima resposta luminescente para altas doses absorvidas (acima de 100 Gy), sem que seu ponto de saturação fosse alcançado para doses de até 1 kGy. Variando sensivelmente a energia do feixe de irradiação foi possível determinar que a luminescência do material apresenta baixa dependência energética para energias abaixo de 40 keV, o que está de acordo com a teoria de interação energia/matéria. Acima desta energia, há diminuição do fenômeno fotoelétrico em detrimento do espalhamento Compton. As imagens obtidas por Microscopia Eletrônica de Transmissão detectaram, nas amostras dopadas, a presença de estruturas superficiais compostas por espinélio (MgAl2O4) sobre aglomerados de Al2O3. Este resultado faz crer que a ocorrência desta camada superficial aumenta significativamente a concentração de centros de recombinação e, conseqüentemente, a intensidade de emissão também é aumentada. / The aim of the present work is to obtain and characterize luminescent dosimeters made of magnesium doped aluminium oxide, for ionizing radiation dosimetry purposes. The material is produced by Pechini Method (US Patent 3.330.697, 1967), starting from a polymer that generates powder ceramic, after firing at predetermined temperatures. Dosimetric measurements were taken during heating cycles (Thermoluminescence) with gamma and X-rays irradiated samples. Due to physical properties of the crystal, light is emitted during heating, because of free carriers being released from trap centers and recombining with opposite sigh charges. Chemical analysis indicated the Mg2+ concentrations 0.47, 0.88, 1.32, 2.61 and 3.36 mol%; reactants masses and process parameters were adequate to obtain uniformity. From X-Ray Diffraction, samples calcinated at lower temperatures did not reach the properly structural phase. The gamma phase did not show dosimetric properties for the preferred spectra (UV/visible region). Calcinations at higher temperatures were necessary to obtain alpha phase, which exhibited TL emission. For doped sample, diffractograms indicated the occurrence of highly crystalline sample. TL glow curves showed high visible and UV emission, with peaks at 125, 200, 280, 365 and above 450°C. The lowest peak was faded within 24 hours after irradiation and those above 280°C could not be exactly determined due to peak overlapping. Nevertheless, the emission peak at 200°C showed itself a great achievement for the present work, because of its energy depth and dose response. For higher absorbed doses (above 100 Gy), the emission generated by deeper traps could be studied with more details: acceptable TL response and exponential growth were exhibited. The peak at 280 was not reported. Low energy dependence luminescence in observed for doses as high as 40 keV. This limitation is due to decreasing of photoelectric phenomena, which is responsible for charges trapping. Images obtained using Transmission Electron Microscopy detected surface layer in doped samples; such layer is composed by spinel (MgAl2O4). The presence of spinel layer increases recombination centers concentration, once luminescence enhancement was perceived for doped samples.

Pesquisas realizadas em todo o mundo exploram a possibilidade de utilizar o hidrogênio como combustível para a geração de energia, já que ele produz a chamada \"energia limpa\". O hidrogênio pode ser obtido a partir das reações de reforma de etanol, fonte renovável, em contraste com o clássico processo de obtenção a partir de derivados de petróleo. Desta forma, há um crescente interesse em pesquisa e desenvolvimento de catalisadores eficientes para gerar hidrogênio. Assim, no presente trabalho foram estudados catalisadores de ródio contendo 0,5; 1 e 3% (m/m) suportados em CeO2, Al2O3 e 20%CeO2- Al2O3 nas reações de reforma a vapor de etanol (RVE) e reforma oxidativa de etanol (ROE) visando a geração de hidrogênio. As amostras foram preparadas pelo método de impregnação úmida e caracterizadas por difração de Raios-X (XRD), área superficial específica - método B.E.T., espectroscopia dispersiva em emissão de Raios-X (EDX), espectroscopia de fotoelétrons excitada por Raios-X (XPS), espectroscopia na região do ultra-violeta e do visível (UV-vis- NIR) e redução à temperatura programada (RTP-H2). Os ensaios catalíticos, realizados entre 400 e 600ºC, mostraram altas conversões de etanol para todos os catalisadores. As maiores produções de H2, a partir das reações de RVE e ROE, foram obtidas à 600ºC com os catalisadores Rh/CeO2 e Rh/20%CeO2-Al2O3. Foi observado que a adição de oxigênio proporcionou um aumento na produção de H2, bem como na razão CO2/CO e nas deposições de carbono. / The researches made in the world explore the possibility in the use of hydrogen like a fuel for energy generation, since it produces the called \"clean energy\". The hydrogen can be obtained through of the ethanol reforming reaction, i.e. renewable source, in contrast with the classical process for obtaining from petroleum derivates. In this way, there is a crescent interest in research and development of efficient catalysts in order to obtain hydrogen. Thus, in this work were studied the rodium catalysts with 0,5; 1 e 3% (w/w) supported on CeO2, Al2O3 e 20%CeO2-Al2O3 for the ethanol steam reforming (ESR) and oxidative reforming (EOR) reactions aiming to the hydrogen generation. The samples were prepared by wet impregnation method and characterized by X-ray diffraction (XRD), specific superficial area - BET method, energy dipersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), UV-vis spectroscopy (UVvis), and temperature-programmed reduction (TPR-H2). In according to the catalytic tests, performed between 400 and 600ºC, it was obtained higher ethanol conversion values for all catalysts. The highest H2 yield it was obtained at 600ºC, with the Rh/CeO2 e Rh/20%CeO2-Al2O3 catalysts. It was observed that the addition of oxygen caused an increase in H2 production, as well as, in the CO2/CO ratio and in the carbon deposition.

Die heterogene Katalyse spielt in der industriellen chemischen Synthese sowie in umwelttechnischen Prozessen eine herausragende Rolle. Viele Katalysatoren zeichnen sich durch eine hohe strukturelle Komplexität aus, welche ein detailliertes Verständnis von entscheidenden Parametern sowie zugrunde liegenden Reaktionsmechanismen meist verhindert. Daher ist die Untersuchung von geeigneten Modellsystemen unerlässlich. Im Rahmen dieser Arbeit wurde ein dünner, kristalliner Aluminiumoxid-Film auf NiAl(110) mittels Rastertunnelmikroskopie (STM) und -spektroskopie (STS) bei 5K untersucht. Dieser Film konnte bereits in zahlreichen Studien als Modell für Alumi-niumoxid-Trägermaterialien etabliert werden, obwohl seine atomare Struktur nicht bekannt war. Hier wurden nun atomar aufgelöste STM-Bilder des Films aufgenommen, die sich später verschiedenen Lagen des Films zugeordnen ließen. Ferner konnten Antiphasendomänengrenzen (APDB), d.h. regelmäßig auftretende Liniendefekte des Oxidfilms, mit STM und STS charakterisiert werden. Es gelang somit, deren elektronische und geometrische Struktur zu korrelieren. Im zweiten Teil der Arbeit wurde das Adsorptionsverhalten des Aluminiumoxid-Films gegenüber einzelnen Au-Atomen untersucht. Nach der Präparartion waren Au-Monomere, Dimere und kleine Cluster auf der Oberfläche vorhanden, die mit STM und STS untersucht wurden. Die Ergebnisse zeigen, dass das NiAl(110)-Substrat an der Bindung von Au-Atomen auf dem Oxid-Film beteiligt ist, und dass dünne Filme offenbar ein anderes Adsorptionsverhalten aufweisen können als die entsprechenden Bulk-Oxide. Im dritten Teil dieser Arbeit wurden die Eigenschaften von Metall-Clustern (Ag, Pd) auf dem Aluminiumoxid-Film in Abhängigkeit von ihrer Größe untersucht. Leitfähigkeits-Spektren zeigen eine charakteristische Signatur, die am besten mit einer Coulomb-Blockade erklärt werden kann. Somit reflektieren die Spektren eher Eigenschaften des Tunnelkontakts als intrinsische Cluster-Eigenschaften. / Heterogeneous catalysis plays an important role in industrial synthesis and in environmental chemistry. Due the difficulties related with the investigation of working catalysts, the study of well-defined model systems is very important to gain a fundamental understanding of the principles and reaction mechanisms. Within the scope of this work, a well-ordered, thin alumina film on NiAl(110) has been investigated by scanning tunneling microscopy (STM) and spectroscopy (STS) at 5K. This film was established as model for bulk alumina supports in previous studies, though its exact structure remained unknown. Here, atomically resolved STM images of the film have been obtained, which could later be assigned to distinct atomic layers. Furthermore, anitiphase domain boundaries (APDB), regularly appearing line defects in the oxide film, were characterized by STM and STS. These studies provide a detailed understanding of how their geometric and electronic structure are related. The second part of this thesis addressed the adsorption behavior of the alumina film toward single Au atoms. The sample preparation yielded Au monomers, dimers and small clusters on the surface, which were investigated with STM and STS. Accordingly, the NiAl(110) substrate participates in the binding of Au atoms, demonstrating that adsorption properties of thin oxide films can deviate significantly from bulk oxides, whereby the metal adatom seems to play an important role. The third part of this work presents size-dependent STM/STS studies on metal clusters (Ag, Pd) deposited onto alumina/NiAl(110). Conductance spectra reveal a distinct signature, which can be explained by a Coulomb blockade effect. Another interpretation based on quantized electronic levels, is also discussed, but cannot account for all experimental findings. Thus, the spectroscopic data reflect most likely no intrinsic properties of the metal clusters but are due to the specific behavior of a double-barrier tunneling junction.