Mesoporous alumina (Al2O3) in the gamma (γ) phase is widely used as a support in catalytic applications because of its high surface area, large pore volume, acid-base characteristics, and thermal stability. To improve the thermal stability of gamma alumina, dopants such as lanthanum, magnesium, zirconia, and silica are often introduced. Current laboratory-based methods for synthesizing gamma alumina generally involve 10-15 steps and/or use toxic, expensive surfactants and solvents. Industrial methods, while simpler, lack control of pore properties and surface chemistry. In contrast, we have developed an innovative solvent deficient, one-step method that is able to synthesize a wide range of pure and silica-doped aluminas with high surface areas, pore volumes from 0.3 to 1.8 cm3/g, and pore diameters from 5 to 40 nm. More significantly, our silica-doped aluminas are stable up to temperatures as high as 1300<°>C, which is 200<°>C higher than other pure and doped gamma alumina materials.The usefulness of gamma-alumina as a catalyst support is dependent on its favorable combination of textural, thermal, structural, and chemical properties, yet the relationship between structure and these other properties is still not clearly understood due to the poorly crystallized nature of the material. In particular, the mechanism by which the gamma structure is stabilized thermally by so many dopants is still not well understood. Based on our previous PDF experiments on pure and La-doped alumina, we have developed a hypothesis regarding the mechanism by which dopants increase thermal stability. To validate or refute this hypothesis, we collected PDF data on a wider range of laboratory and industrial alumina samples. Herein, we have utilized PDF analysis to study the local to intermediate-range structure of a series of our pure and silica-doped aluminas calcined at 50<°>C intervals between 50 and 1300<°>C as well as pure and silica-doped aluminas from commercial sources and other synthetic methods. This thorough study of alumina local structure will allow us to separate general trends in the local structure from idiosyncrasies based on synthetic method/conditions, and it will help us identify the structural features responsible for improved thermal stability. Having access to these PDF experiments, we have validated our current hypothesis on the nature of stabilization afforded by dopants and, more generally, developed a better understanding of the role structure plays in the properties of aluminas.

O hexaluminato de cálcio (CaAl12O19 ou CA6) poroso é um material promissor para aplicações de isolamento térmico pois combina baixa condutividade térmica (~0,33 Wm-1K-1 a 1400 °C), resistência mecânica razoável (2 &#8211; 8 MPa), inércia química, boa refratariedade (Tf ~1830 °C) e alta resistência ao choque térmico. Existem várias rotas para se obter o CA6 por meio de reações em temperaturas acima de 1300 °C, usando diversas fontes de Al2O3 e CaO, assim como diferentes métodos de processamento. No entanto, embora suas propriedades físicas tenham sido avaliadas, dois pontos principais ainda requerem investigação: o impacto das características das matérias-primas no desenvolvimento da microestrutura de sistemas porosos formados in situ, e a evolução da microestrutura e propriedades de sistemas obtidos a partir de CA6 pré-formado. Neste trabalho, foram produzidas peças de CA6 in situ a partir de diferentes fontes de Al2O3 (alumina calcinada e hidróxido de alumínio) e carbonato de cálcio (CaCO3) de diferentes granulometrias, processados por prensagem uniaxial e moldagem direta de suspensões e submetidas a diferentes tratamentos térmicos. As amostras (verdes e secas e após tratamento térmico) foram submetidas à análise microestrutural (MEV e DRX) e dilatométrica, ensaios para determinação das propriedades físicas (porosidade total, distribuição de tamanho de poros e condutividade térmica) e propriedades mecânicas (resistência à ruptura por compressão e módulo elástico). Estruturas à base de CA6 formado in situ obtidas por prensagem e moldagem direta apresentaram elevada porosidade (até 71 %) e uma resistência à compressão acima de 10 MPa. Verificou-se que o processo de conformação determinou a porosidade à verde inicial da peça, enquanto o tamanho de partícula de alumina induziu a um crescimento de grão assimétrico (partícula grossa) ou à densificação da peça (partícula fina). Dois mecanismos antagonistas acontecem ao mesmo tempo na reação in situ: a reação expansiva da formação de aluminatos intermediários (efeito porogênico) e a densificação das partículas de Al2O3. As partículas de carbonato tiveram uma grande influência no tamanho final dos poros. O efeito porogênico do hidróxido de alumínio foi efetivo até um conteúdo máximo de 50 %vol. / Porous calcium hexaluminate (CaAl12O19 or CA6) is a promising material for thermal insulation applications because it combines low thermal conductivity (~0,33 Wm-1K-1 at 1400° C), reasonable mechanical strength (2 &#8211; 8 MPa), chemical inertia, good refractoriness (Tf ~1830 °C) and high resistance to thermal shock. There are several routes to obtain CA6 by reactions at temperatures above 1300 °C, using various sources of Al2O3 and CaO, as well as different processing methods. However, although its physical properties have been studied, two main points still require investigation: the impact of the characteristics of the raw materials on the development of the microstructure of in situ formed porous systems, and the evolution of the microstructure and properties of systems obtained from preformed CA6. In this study, in situ CA6 bodies were produced from different sources of Al2O3 (calcined alumina and aluminum hydroxide) and calcium carbonate (CaCO3) of different granulometries, processed by uniaxial pressing and direct molding of suspensions and thermally treated at different temperatures. The samples (green and heat treated ones) were submitted to microstructural analysis (SEM and XRD) and dilatometry, also tests to determine the physical properties (total porosity, Hg porosimetry and thermal conductivity) and mechanical properties (compression strength and elastic modulus). In situ formed CA6-based structures obtained by pressing and direct molding showed high porosity (up to 71%) and a compressive strength above 10 MPa. It was found that the conformation process determined the initial porosity of the green body, while particle size of alumina may induce asymmetric grain growth (coarse particle) or densification of the ceramic body (fine particle). Two antagonistic mechanisms occur at the same time in the in situ reaction: the expansive reaction of the formation of intermediate aluminates (porogenic effect) and the densification of Al2O3 particles. The carbonate particles had a great influence on the final pore size. The porogenic effect of aluminum hydroxide was effective up to a maximum content of 50% vol.

Excess Fluoride in drinking water is a cause for concern in several countries in the world. Various techniques have been developed to mitigate the harmful effects of fluoride. In the present work, a combined alum and activated alumina (AA) process has been investigated. Tap water with sodium fluoride dissolved in it to produce a solution having a fluoride concentration of 5 mg/L was used as the feed. It was found that pretreatment with alum extends the time required for the regeneration of the AA column. The volume of water treated increased by 89% compared to AA process alone. Though the regeneration of the AA column has been well documented, subtle issues have ot been reported. The disposal of regeneration effluent is a concern in adsorption-based processes. This study aims to examine some of the issues involved in the regeneration of the AA column such as disposal of effluent, and the quantity of acid and alkali required. The regeneration effluent from the combined process, which had a fluoride concentration of 10-16 mg/L was treated in a solar still. The distillate from the still had a fluoride concentration of 2-3 mg/L, which is much lower than the concentration of the regeneration effluent. The cost of treatment decreased with each regeneration cycle and after four regenerations the cost was Rs 0.5/L of treated water. The volume of water treated after four regenerations was 307 L/Kg of AA. Studies were also done using field water from Banavara, Hassan district, Karnataka, which had a fluoride concentration of 3,0-3.5 mg/L. The combined process successfully produced treated water having an acceptable fluoride concentration. After one regeneration cycle, the operating cost was Rs. 1/L of treated water. Studies have also been conducted on a point-of-use water filter containing a bed of AA pellets. The filter was provided by an organization called TIDE. The present results appear to suggest that a column with a smaller diameter than the TIDE filter has a better removal capacity. Ceramic candles are widely used for water filtration as they are readily available and inexpensive. Hence they are suitable for household water treatment purposes. In the present work, ceramic candles have been impregnated with nano-size alumina and nano-size magnesium oxide and tested for their defluoridation capacity. The nanoparticles were generated in situ in the pores of the candle by solution combustion synthesis. It has been found the candle impregnated with nano-size magnesium oxide has a higher defluoridation capacity than nano-size alumina. Estimation of the particle size in the samples of treated water did not give conclusive evidence for the presence or absence of nanoparticles. The volume of water treated was low and the cost of treatment was high (Rs. 12/L for the candle impregnated with MgO). Hence such candles are unsuitable for defluoridation. Batch adsorption has been employed to measure the adsorption capacity of adsorbents. A model to capture the overall picture of the batch adsorption process, obtaining the kinetic and transport parameters involved has been developed. The mathematical model takes into account external mass transfer resistance, intraparticle diffusion, adsorption, and desorption. The equilibrium adsorption data was fitted using the Langmuir isotherm. The governing equations were solved using a finite difference technique known as the Laasonen method. The parameters were estimated by fitting two sets of data using a MATLAB function. The values estimated suggest that the adsorption process may not be diffusion-limited, in contrast to the assumption commonly used in the literature. The estimated parameter values were used to predict the concentration profiles for the other data sets. It was found that predicted and measured profiles agreed reasonably well.

Deposition of alumina thin films in the presence of fluorine as a method for reducing thehydrogen incorporation in the films was investigated in this thesis. Hydrogen incorporated in alumina thin films have been shown to cause a lower density and refractive index in amorphous films, assist electrical conduction through thin amorphous films as well as inhibiting the formation of the thermally stable α-phase. The depositions were made in a ultra high vacuum system where high vacuum conditions were simulated by leaking water vapor into the system. No substrate heating or substratebias was applied. Films were deposited at a range of fluorine partial pressures, from 2,5×10-6- 5×10-5 Torr, and were analyzed by elastic recoil detection analysis, nuclear reaction analysis, scanning electron microscopy and x-ray diffraction. Mass spectrometry measurements were done during the depositions to analyze the deposition process. The mass spectrometry investigations show that there is a trend of increasing O2 partial pressures with increasing fluorine partial pressures during the depositions. This is attributed to the well known reaction: 2H2O+F2→O2+4HF. However, no trend in the measured water partial pressures can be observed. The increase in the O2 partial pressure is therefore attributed to a reaction between water and fluorine on the chamber walls. The chemical analysis show that the hydrogen incorporation in the films were lowered from ~10 at.% when deposited in the presence of water vapor to ~3 at.% when deposited in the presence of water vapor and 2×10-5 Torr fluorine. The hydrogen incorporation stabilize at ~3 at.% at higher fluorine partial pressures. However, there is also a large amount of fluorine incorporated in the films, ~20 at.% with a fluorine partial pressure during the deposition of 2×10-5 Torr and ~46 at.% with a fluorine partial pressure of 5×10-5 Torr. There is a slight increase in the aluminum concentration in the films deposited with fluorine. This is attributed to bonding the hydrogen in aluminum hydroxide while the reminder forms Al2O3 or Al leading to an increase in the aluminum concentration in the film. A linear decrease in the deposition rate with increasing fluorinepartial pressures during the deposition was observed, this can be explained by sputter etching of AlFx and AlOxFy by energetic O- ions. The XRD investigation show that the films deposited with the highest fluorine partial pressures were x-ray amorphous, the films with deposited with lower fluorine partial pressures are therefore also assumed to be amorphous.

Με αφορμή τις πολλές εφαρμογές που έχουν οι διεπιφάνειες μετάλλου με κεραμικό υπόστρωμα όπως τη μικροηλεκτρονική και την ετερογενή κατάλυση, τα συστήματα αυτά έχουν μελετηθεί με πρότυπα πειράματα σε συνθήκες υπερυψηλού κενού (UHV). Στην εργασία αυτή μελετήθηκε η αλληλεπίδραση κατά τη θέρμανση σε UHV υπέρλεπτων υμενίων NIκαι NiO με επιφάνειες οξειδίων. Συγκεκριμένα, η μελέτη έγινε σε μοκνοκρυσταλλικές επιφάνειες ζιρκονίας σταθεροποιημένης με ύττρια (YSZ), α-αλούμινας και σε πολυκρυσταλλική επιφάνεια γ-αλούμινας ανεπτυγμένης σε φύλλο αλουμινίου. Έμφαση δόθηκε στην επίδραση που έχει η κατεργασία της επιφάνειας του οξεοιδίου στη συμπεριφορά του Ni και του NiO κατά τη θέρμανση. Τα πειράματα έγιναν σε σύστημα UHV με επιφανειακά ευαίσθητες τεχνικές φασματοσκοπίας φωτοηλεκτρονίων και ηλεκτρονίων Auger από ακτίνες-Χ(XPS/XAES). Βρέθηκε ότι το Ni σε YSZ οξειδώνεται κατά τη θέρμανση από ευκίνητα ιόντα οξυγόνου της YSZ και ο ρυθμός οξείδωσης εξαρτάται σημαντικά από την κατάσταση της επιφάνειας. Η κατάσταση της επιφάνειας επηρεάζει την θερμική σταθερότητα του NiO αφού η ελάττωση του οξυγόνου στο εσωτερικό της YSZ οδηγεί σε σημαντική μείωση της θερμοκρασίας διάσπασης του NiO. Σε επιφάνεια α-Al2O3 η κατεργασία έχει σαν αποτέλεσμα το Ni είτε να συσσωματώνεται είτε να οξειδώνεται ενώ η θερμική σταθερότητα του NiO επίσης εξαρτάται από την παρουσία επιφανειακών ατελειών που δημιουργούνται με την κατεργασία. Επίσης, βρέθηκε ότι το πάχος του υμενίου γ-Al2O3 είναι καθοριστικό για την οξείδωση του αποτιθέμενου Ni από τα επιφανειακά υδροξύλια της γ-Al2O3 και το σχηματισμό επιφανειακής ένωσης NiAlx μέσω διάχυσης του Ni προς το φύλλο Al από μικροοπές του υμενίου. / Metal-ceramic systems have many technological applications in composite materials, microelectronics and heterogeneous catalysis. The interaction of Ni and NiO ultrathin films with different oxide surfaces yttria stabilized zirconia (9% mol Y2O3, YSZ)and α-alumina monocrystalline and polycrystalline γ-alumina films developed on Al foil upon heating in ultrahigh vacuum (UHV) was examined. Upon heating the Ni/YSZ system at 480-850K, nickel was oxidized via the substrate oxygen ions excess and the rate of oxidation depended strongly on the state of the surface. Reduction of oxygen excess leads to a decrease of the NiO decomposition temperature, which is higher than 900 K in UHV. The oxidation capability of the YSZ is restored after heating in oxygen atmosphere. The Ni/α-Al2O3 interaction depended on the chemical state of the surface, on the presence of C, -OH and non-lattice oxygen (surface defects).Interaction between deposited nickel and surface defects leads to Ni coalescence, partial oxidation and NiAlxOy chemical compound formation. The surface defects affects the thermal stability of NiO, which decomposes to Ni at lower temperature than 900K. On clean α-Al2O3 surfaces the NiO is stable up to 900K. Upon heating to 600K Ni deposits on γ-Al2O3/Al surfaces, the reduction of the alumina film thickness leads on the one hand to a decrease of the tendency of surface -OH groups to oxidize nickel and on the other hand to an increased formation of a NiAlx due to Ni diffusion on the Al substrate through the microholes in the alumina film. Upon heating up to 790K, the initially formed NiO decomposes to metallic Ni, whereas the Ni of the NiAlx compound diffuses inside the metallic Al.

Submitted by Gustavo Nascimento (gustavo.diniz@ufcg.edu.br) on 2018-01-29T11:51:13Z No. of bitstreams: 1 DANIELLA CIBELE BEZERRA - TESE PPGCMAT 2014.pdf: 4550868 bytes, checksum: d91b2b560040e4f5f101c7f129c13aab (MD5) / Made available in DSpace on 2018-01-29T11:51:13Z (GMT). No. of bitstreams: 1 DANIELLA CIBELE BEZERRA - TESE PPGCMAT 2014.pdf: 4550868 bytes, checksum: d91b2b560040e4f5f101c7f129c13aab (MD5) Previous issue date: 2014-11-03 / CNPq / Um dos principais problemas do isolamento elétrico externo é o acúmulo de contaminantes em sua superfície. A ocorrência deste evento faz com que a resistência da superfície diminua, aumentando a presença de correntes de fuga pela superfície. Entre as técnicas desenvolvidas para diminuir esse tipo de efeito, está o revestimento do isolador existente convencional (porcelana ou vidro, conforme o caso) com uma borracha de silicone que é vulcanizada à temperatura ambiente (BS). O objetivo deste trabalho foi desenvolver uma mistura de borracha de silicone/alumina trihidratada/nanosílica (BS/ATH:NS) para ser usada em revestimento de isoladores elétricos de vidro. Cargas de ATH e NS foram adicionadas à BS, produzindo uma mistura feita em diferentes proporções mássicas (79/21; 77/23 e 75/25) de BS/ATH:NS, utilizada nos revestimento dos isoladores elétricos de vidro. As cargas e os revestimentos foram caracterizados por difração de raios X (DRX), microscopia eletrônica de varredura (MEV), teste de inflamabilidade, ensaio na câmara de névoa salina, molhabilidade e avaliação da hidrofobicidade. As cargas apresentaram características morfológicas bem distintas, o que interferiu diretamente na morfologia dos revestimentos. A silanização das cargas favoreceu uma interação entre elas, assim como houve uma pequena melhora na interação das cargas com a BS. Observou-se também que no teste de inflamabilidade, os revestimentos que continham ATH, apresentaram resultados mais significativos, não havendo queima. Para os ensaios na câmara de névoa salina, o revestimento com BS/20:1 e os revestimentos com cargas silanizadas apresentaram os menores valores de corrente de fuga, o que foi comprovado com a avaliação da hidrofobicidade, na qual estes conseguiram recuperar a hidrofobicidade até HC=1 (nível de hidrofobicidade), de acordo com o guia STIR (Swedish Transmission Research Institute). / One of the main problems of external electrical isolation is due to accumulation of contaminants on its surface. The occurrence of this event causes the insulation resistance of the surface decreases, increasing the flow of leakage currents on the surface. Among the techniques developed to reduce this type of event is the coating of the conventional existing insulator (porcelain or glass, as appropriate) with a silicone rubber vulcanized at room temperature (BS). The aim of this study was to develop a mixture of silicone rubber/ alumina trihydrate/nanosílica (BS/ATH:NS) for use in coating glass electrical insulators. Loads of ATH and NS were added to BS, producing a mixture made in different mass ratios (79/21, 77/23 and 75/25) BS/ATH:NS used in the coating of glass electrical insulators. Loads and coatings were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), flammability test, measurement salt spray chamber, test of wettability and hydrophobicity. Loads showed distinct morphological features, which directly affects the morphology of the coatings. The silanization loads favored interaction among them, as there was a small improvement in the interaction of the loads with the BS. It was also observed that the flammability test, the coatings containing ATH showed more significant results, without burning. For tests of the salt spray chamber, coat with BS/20:1 and with silanized fillers had the lowest leakage current, which was confirmed by measuring the hydrophobicity, where they managed to recover the hydrophobicity HC = 1 (level of hydrophobicity) according to STIR (Swedish Transmission Research Institute) guide.

Made available in DSpace on 2014-12-17T14:07:09Z (GMT). No. of bitstreams: 1 JoseFTJ_TESE.pdf: 4834280 bytes, checksum: 1a618560296186081bd6c34117d226be (MD5) Previous issue date: 2012-07-04 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Thin commercial aluminum electrolytic and passed through reactions was obtained with anodic alumina membranes nanopores. These materials have applications in areas recognized electronic, biomedical, chemical and biological weapons, especially in obtaining nanostructures using these membranes as a substrate or template for processing nanowires, nanodots and nanofibers for applications noble. Previous studies showed that the membranes that have undergone heat treatment temperature to 1300? C underwent changes in morphology, crystal structure and optical properties. This aim, this thesis, a study of the heat treatment of porous anodic alumina membranes, in order to obtain and to characterize the behavior changes structures during the crystallization process of the membranes, at temperatures ranging between 300 and 1700? C. It was therefore necessary to mount a system formed by a tubular furnace resistive alumina tube and controlled environment, applying flux with special blend of Ag-87% and 13% N2, in which argon had the role of carrying out the oxygen nitrogen system and induce the closing of the pores during the densification of the membrane. The duration of heat treatment ranged from 60 to 15 minutes, at temperatures from 300 to 1700? C respectively. With the heat treatment occurred: a drastic reduction of porosity, grain growth and increased translucency of the membrane. For the characterization of the membranes were analyzed properties: Physical - thermogravimetric, X-ray diffraction, BET surface area; morphological - SEM, EDS through compositional and, optical absorbance, and transmittance in the UV-VIS, and FTIR. The results using the SEM showed that crystallization has occurred, densification and significant changes in membrane structure, as well as obtaining microtube, the BET analysis showed a decrease in specific surface area of the membranes has to 44.381 m2.g-1 to less than 1.8 m2.g-1 and in the analysis of transmittance and absorbance was found a value of 16.5% in the range of 800 nm, characteristic of the near infrared and FTIR have confirmed the molecular groups of the material. Thus, one can say that the membranes were mixed characteristics and properties which qualify for use in gas filtration system, as well as applications in the range of optical wavelength of the infra-red, and as a substrate of nanomaterials. This requires the continuation and deepening of additional study / L?minas delgadas de alum?nio comercial passaram por rea??es eletrol?ticas e obtiveram-se membranas de alumina an?dica com nanoporos. Estes materiais t?m reconhecidas aplica??es nas ?reas eletr?nicas, biom?dicas, qu?micas e biol?gicas, principalmente, na obten??o de nanoestruturas utilizando estas membranas como substrato ou molde para processamento de nanofios, nanopontos e nanofibras para aplica??es nobres. Estudos anteriores apontaram que as membranas que passaram por tratamentos t?rmicos at? a temperatura de 1300? C, sofreram altera??es na morfologia, na estrutura cristalina e nas propriedades ?pticas. O objetivo deste trabalho foi o estudo do tratamento t?rmico de membranas de alumina an?dica porosas, com o intuito de obter e caracterizar as altera??es de comportamento das estruturas, durante o processo de cristaliza??o das membranas, em temperaturas que variaram entre 300 e 1700? C. Assim, foi necess?rio montar um sistema formado por um forno resistivo tubular e tubo de alumina com ambiente controlado, aplicando fluxo com mistura especial de Ar-87% e N2-13%, no qual o arg?nio teve o papel de carrear o oxig?nio para fora do sistema e o nitrog?nio de induzir o fechamento dos poros, durante a densifica??o das membranas. A dura??o dos tratamentos t?rmicos variou de 60 a 15 minutos, para as temperaturas de 300 at? 1700? C respectivamente. Com o tratamento t?rmico ocorreu redu??o dr?stica da porosidade, crescimento do gr?o e aumento da translucidez da membrana. Para a caracteriza??o das membranas, foram feitas an?lises das propriedades: f?sica - termogravim?trica; difra??o de raios-X, ?rea superficial BET; morfol?gica - MEV, composicional atrav?s do EDS; e, ?ptica - transmit?ncia e absorb?ncia no UV-VIS e FTIR. Os resultados por meio do MEV mostraram que ocorreu cristaliza??o, densifica??o e mudan?as significativas na estrutura das membranas, bem como, a obten??o de microtubo; a an?lise de BET constatou uma diminui??o na ?rea superficial espec?fica das membranas que passou de 44,381m2.g-1, para menos de 1,8m2.g-1; na an?lise de transmit?ncia e absorb?ncia foi encontrado um valor de 16,5 % na faixa de 800nm, caracter?stico do infravermelho pr?ximo e no FTIR foram confirmadas os grupos moleculares do material. Assim, pode-se afirmar que as membranas apresentaram caracter?sticas mistas e propriedades que as qualificam para o uso em sistema de filtra??o de gases, bem como, de aplica??es ?ticas na faixa do comprimento de onda do Infravermelho, e como substrato de nanomateriais. Isto requer a continuidade e aprofundamento em estudos complementares

[pt] A redução na emissão de CO2 na atmosfera é um dos desafios atuais mais importantes enfrentados por diferentes indústrias no mundo. A geração de energia através da queima de combustíveis fósseis utilizando oxigênio puro [1], também chamada de tecnologia de oxicombustão, é uma opção utilizada pelas indústrias de geração de energia para minimizar os índices de concentração de CO2 até emissão ZERO [1,2]. Inevitavelmente, as tubulações dos trocadores de calor que conformam aquelas plantas de energia, sofrem corrosão em contato com os gases de combustão (H2O-CO2) em altas temperaturas. Estas tubulações, fabricadas com aço ou com ligas ferro-cromo vem sendo utilizadas no intuito de reduzir a corrosão. Tubulações com revestimentos/recobrimentos protetores tem sido também considerados para aumentar a resistência a processos corrosivos sem requerer o emprego de ligas de alto custo. Um revestimento adequado deve ser inerte e estável em altas temperaturas como é o caso dos materiais cerâmicos. A alumina, sendo um material estável em ambientes característicos do processo de oxicombustão apresenta características favoráveis para esta proteção [3]. Amostras de Fe-Cr foram oxidadas sob condições que simularam processos de Oxicombustão nos laboratórios do Bundesanstalt Für Materialforschung Und-Prüfung (BAM) Berlim-Alemanha. O processo ocorreu a 650 graus Celsius durante 2000 h, em atmosfera contendo 60 por cento CO2,30 por cento H2O, 7 por cento N2, 2 por cento O2 e 1 por cento SO2. A caracterização microestrutural das amostras oxidadas foi realizada nos laboratórios do instituto Nacional de Tecnologia (INT), utilizando técnicas de Microscopia Eletrônica de Varredura (MEV) e Espectroscopia por Dispersão de Energia de Raios-X (EDS). Foram produzidos riscos na superfície do revestimento de Al2O3, previamente aos testes de oxidação, para simular falhas no revestimento; além da eficácia do revestimento de alumina, foi também avaliado o papel do cromo como meio protetor contra a corrosão e de outros elementos de liga no processo de oxidação do aço P92, buscando identificar o mecanismo de oxidação. Como resultado do fluxo dos gases de oxicombustão há formação de camadas de Fe3O4, Fe2O3 e cromo-espinélio nas ligas sem revestimento. As amostras que possuíam o revestimento de alumina apresentaram ótima proteção, com resultados de uma alta eficácia, enquanto as amostras que tinham riscos apresentaram uma oxidação interna de oxidação cromo-espinélio protetor na matriz logo abaixo da região afetada. / [en] The reduction in the emission of CO2 in the atmosphere is one of the most important problems faced by different industries in the world. The generation of energy from oxyfuel oxygen, [1], also called Oxyfuel technology, is a matter of CO2 emission for ZERO [1,2]. Inevitably, as pipes of the heat exchangers that make up these power plants, they suffer corrosion in contact with the flue gases (H2O-CO2) at high temperatures. These pipes, made of steel or iron-chromium alloys, are not used instead of reducing corrosion. Pipes with protective coatings have already been submitted to increase resistance to corrosive processes without requiring the use of high cost alloys. One which must be inert and static at high temperatures is the case of ceramic materials. An alumina, being a suitable material to the environments characteristic of the Oxyfuel process, presents characteristics favorable to the protection [3]. Fe-9Cr samples were oxidized under conditions that simulated Oxyfuel processes in the laboratories of the Bundesanstalt Für Materialforschung Und-Prüfung (BAM) Berlin-Germany. The process occurred at 650 degree Celsius for 2000 h, in an atmosphere containing 60 percent CO2, 30 percent H2O, 7 percent N2, 2 percent O2 and 1 percent SO2. The microstructural characterization of the oxidized samples was performed in the laboratories of the National Institute of Technology (INT), using Scanning Electron Microscopy (SEM) and X-ray Energy Dispersion Spectroscopy (EDS) techniques. Risks were produced on the Al2O3 coating surface, prior to the oxidation tests, to simulate coating failures; besides the effectiveness of the alumina coating, the role of chromium as a protective medium against corrosion and other alloying elements in the oxidation process of P92 steel was also evaluated, in order to identify the oxidation mechanism. As a result of the flow of oxyfuel gases, Fe3O4, Fe2O3 and chromium-spinel layers are formed in the alloys without coating. The samples that had the alumina coating presented optimum protection, with results of a high efficiency, while the samples that had scratches presented an internal oxidation of protective chromium-spinel oxidation in the matrix just below the affected region.

O interesse em materiais com gradiente funcional (MGF) tem crescido nos últimos anos devido à possibilidade de se obter peças com variação de propriedades ao longo de uma ou mais dimensões, gerando desempenho ótimo dependendo da solicitação imposta ao material. Por outro lado, a sinterização em dois estágios, consiste em aquecer a peça conformada até que esta apresente densidade relativa entre 75% e 92% da densidade teórica, e, em seguida, submetê-la a um resfriamento rápido até uma temperatura inferior, onde deve permanecer por um período até o fim da densificação. Desta maneira, é possível obter peças densas, com tamanho médio de grãos inferior ao obtido via sinterização convencional, melhorando suas propriedades mecânicas. Neste trabalho, foram caracterizados, por dilatometria, compósitos alumina-zircônia parcialmente estabilizada com ítria (3Y-ZrO2), com teor de ZrO2 variando de 0 a 30% massa/massa. Após compatibilização do comportamento destes compósitos durante a sinterização e determinação da temperatura de pico do processo de sinterização em dois estágios (TSS), foram montadas peças com gradiente de composição. Estas peças foram sinterizadas em dois estágios, com temperatura de pico de 1450°C e temperatura de patamar de 1350°C por 8 horas. A microestrutura foi avaliada com o uso de microscópio eletrônico de varredura e realizou-se a caracterização mecânica por ensaios de dureza, tenacidade à indentação, a fim de se fazer um estudo comparativo dos resultados obtidos para as peças sinterizadas em dois estágios com os das peças com gradiente funcional densificadas via sinterização convencional a 1500°C. A co-prensagem, seguida da técnica de sinterização em dois estágios utilizada para obtenção de peças com gradiente funcional, foi eficiente em produzir peças com densidade aparente relativa de 98,1% DT, valores de tenacidade a indentação variando entre 4,3 MPa.m1/2 a 9,8 MPa.m1/2 e valores de dureza entre 17,5 GPa a 18,4 GPa. / The interest for functionally graded materials (FGM) has grown up during last 2 decades owing to the possibility of developing pieces and devices with a gradual properties variation along one or more dimensions, which allows an optimum performance as a function of imposed solicitation. On the other hand, two stage sintering is a relative new sintering technique, where the shaped pieces are heated up to a relative density of 75-92% t.d., followed by a fast cooling step, up to an inferior temperature, where the piece in maintained up to the end of dense structures, whit finer microstructures, responsible for better mechanical properties. In this work, we characterized alumina-ytria-stabilized zirconia composites, with different amounts of 3Y-ZrO2, by dilatometry. After fitting thermal behavior of the distinct composites during sintering and determining temperature of maximum densification rate, co-pressed FGMs were constructed. Then pieces were sintered by pressureless traditional technique and two stage sintering, with a peak temperature of 1450°C and soaking temperature of 1350°C x 8 hours. Microstructure was studied by SEM and mechanical properties: microhardness and indentation toughness, in order to compare pressureless sintered FGMs at 1500°C and two stage sintered FGMs.

A presente dissertação de mestrado tem o propósito de relatar o desenvolvimento de um sensor planar eletroquímico com três eletrodos para o monitoramento de nitrito e seus interferentes (ácido úrico, ácido ascórbico e paracetamol). Para tal, no procedimento experimental é descrito o desenvolvimento do aparato extracorpóreo (mini-bomba compressora, válvulas solenóides e cela de análise). Esse é acoplado a um sistema de Análise por Injeção em Fluxo Automatizada (do inglês, Flow-injection Analysis) FIA-automatizada. Este trabalho também descreve a fabricação dos sensores em substrato de alumina, o processo de limpeza padrão dos eletrodos, o processo de obtenção dos eletrodos de referência em HCl (0,1 mol L-1) e ativação eletroquímica da superfície do eletrodo de trabalho com H2SO4 (0,1 mol L-1). Em seguida, é mostrada a estabilização dos eletrodos de referência Ag/AgCl em solução salina contendo cloretos, o estudo da secagem dos eletrodos em temperatura ambiente com exposição à luz e a caracterização dos mesmos por três métodos distintos, a saber: i) teste de reversibilidade (corrente redox vs. potencial); ii) variação do potencial com o tempo (coeficiente de degradação termodinâmica) e iii) variação do potencial com a concentração de cloretos. Também, apresenta-se a caracterização da área efetiva exposta do eletrodo de medição (trabalho) e os resultados da deposição de 1-2 Diaminobenzeno (DAB) como polímero seletivo. Além disso, são apresentados os resultados e discussões dos pseudo-eletrodos (recoberto ou não com Náfion® 117). Um ponto relacionado, a histerese associada à irreversibilidade dos eletrodos de referência resultou da ordem de 40 mVAg/AgCl Náfion® 117. Os potencias termodinâmicos observados foram da ordem de 100 ± 6 mVAg/AgCl Náfion® 117 para pseudo-eletrodo de referência sem e com Náfion® 117. Depois, foi realizado um estudo criterioso dos potenciais de resposta ao nitrito e aos interferentes por meio da técnica de DPV (do inglês, Differencial Pulse Voltammetry). Para evitar degradação acelerada (corrosão) do polímero sobre o eletrodo de trabalho, optou-se por realizar as medições com potencial igual a 0,50 VAg/AgCl Náfion® 117. Nessa condição, apresenta-se a monitoração de nitrito por FIA-automatizada na faixa de concentração de 50 a 250 mol L-1. Os resultados para a medição de nitrito mostraram que o sensor planar eletroquímico amperométrico desenvolvido é promissor, pois esse apresentou ótimo desempenho de reprodutividade (99,66%), sensibilidade (90 microA mol-1 L mm-2), seletividade (0,32%), repetitividade (91,28%) e estabilidade (15 ± 0,3 pA). / In this Master of Science, it has been developed an electrochemical planar sensor defined with three electrodes for nitrite measuring and its interferents (uric acid, ascorbic acid and paracetamol). In the experimental procedure, it is shown the development of an extracorporis set up (mini-pump, solenoid valves and analysis cell) which is coupled to a system of Flow-injection Analysis (FIA). This work also describes the sensor fabrication using alumina substrates, the standard cleaning of the electrodes, the process to obtain Ag/AgCl reference electrodes in HCl (0.1 mol L-1) and electrochemical activation of the working-electrode surface with H2SO4 (0.1 mol L-1). Following, it is shown the study of drying for electrodes at room temperature with exposition to room light and their characterization using three different methods: i) reversibility test (redox current vs. potential); ii) variation of the potential with the time (thermodynamics degradation coefficient) and iii) variation of the potential with the chloride concentration. Also, it is presented the characterization of the effective exposed area of the working electrode and the results of the deposited 1-2 Diaminobenzene (DAB) is presented as a selective polymer. In addition, the results and discussions of the pseudo-reference (recovered or not with Nafion® 117) are presented. Related to irreversibility is the hysteresis associated to the reference electrodes which resulted in the order of 40 mVAg/AgCl Nafion® 117. The observed thermodynamic potentials were of (100 ± 6) mVAg/AgCl Nafion® 117 for pseudo-electrodes recovered with Nafion® 117. Later on, a careful study of the response to nitrite and to its interferents was performed by means of the DPV technique (Differential Pulse Voltammetry). In order to avoid accelerated degradation (corrosion) of the polymer, measurements were performed at a potential of 0,5 VAg/AgCl Nafion® 117. In this condition, nitrite was monitored using the automatized-FIA (Flow Injection Analysis) for concentration in the range of 50 to 250 mol L-1. The results have shown that the planar amperometric sensor for nitrite measuring is usefull since it was observed excellent performance related to reproducibility (99.66%), sensitivity (90 microA mol-1 L mm-2), selectivity (0.32%), repetibility (91.28%) and stability (15.0 ± 0.3 pA).