The surface of a dense Ni-YSZ anode was modified with a thin-film coating of niobium oxide (Nb2O5) in order to understand the mechanism of sulfur tolerance and the behavior of carbon deposition. Results suggest that the niobium oxide was reduced to NbO2 under operating conditions, which has high electrical conductivity. The NbOx coated dense Ni-YSZ showed sulfur tolerance when exposed to 50 ppm H2S at 700°C over 12 h. Raman spectroscopy and XRD analysis suggest that different phases of NbSx formed on the surface. Further, the DOS (density of state) analysis of NbO2, NbS, and NbS2 indicates that niobium sulfides can be considered as active surface phases in the H2S containing fuels. It was demonstrated that carbon formation was also suppressed with niobium oxide coating on dense Ni-YSZ in humidified CH4 (3% H2O) at 850ºC. In particular, under active operating conditions, there was no observable surface carbon as revealed using Raman spectroscopy due probably to electrochemical oxidation of carbon. Stable performances of functional cells consisting of Pt/YSZ/Nb2O5 coated dense Ni-YSZ in the fuel were achieved; there was no observable degradation in performance due to carbon formation. The results suggest that a niobium oxide coating has prevented carbon from formation on the surface probably by electrochemically oxidation of carbon on niobium oxide coated Ni-YSZ. On the other hand, computational results suggest that, among the metals studied, Mo seems to be a good candidate for Ni surface modification. Ni-based anodes were modified with Mo using wet-impregnation techniques, and tested in 50 ppm H2S-contaminated fuels. It was found that the Ni-Mo/CeO2 anodes have better sulfur tolerance than Ni, showing a current transient with slow recovery rather than slow degradation in 50 ppm H2S balanced with H2 at 700°C.

Mo-Si-B alloys are a leading candidate for the next generation of jet turbine engine blades and have the potential to raise operating temperatures by 300-400°C. The alloys of interest are a three-phase mixture of the molybdenum solid solution (Moss) and two intermetallic phases, Mo3Si (A15) and Mo5SiB2 (T2). A novel powder metallurgical method was developed which uses the reaction of molybdenum, silicon nitride (Si3N4) and boron nitride (BN) powders to synthesize a fine dispersion of intermetallics in a Moss matrix. The covalent nitrides are stable in oxidizing environments up to 1000ºC, allowing for fine particle processing. The process developed uses standard powder processing techniques to create Mo-Si-B alloys in a less complex and expensive manner than previously demonstrated. This powder metallurgy approach yields a fine dispersion of intermetallics in the Moss matrix with average grain sizes of 2-4μm. Densities up to 95% of theoretical were attained from pressureless sintering at 1600°C and full theoretical density was achieved by hot-isostatic pressing (HIP). Sintering and HIPing at 1300°C reduced the grain sizes of all three phases by over a factor of two. Microstructure examination by electron back-scatter diffraction imaging was used to precisely define the location of the phases and to measure the volume fractions and grain size distributions. Microstructural quantification techniques including two-point correlation functions were used to quantify microstructural features and correlate the BN reactant powder size and morphology to the distribution of the intermetallic phases. High-temperature tensile tests were conducted and yield strengths of 580MPa at 1100°C and 480MPa at 1200°C were measured for the Mo-2Si-1Bwt.% alloy. The yield strength of the Mo-3Si-1Bwt.% alloy was 680MPa at 1100°C and 420MPa at 1300°C. A review of the pertinent literature reveals that these are among the highest yield strengths measured for these compositions. The oxidation resistance in air at 1000 and 1100°C was examined. The protective borosilicate surface layer formed quickly due to the close spacing of intermetallic particles and pre-oxidation treatment was developed to further limit the transient oxidation behavior. An oxidation model was developed which factors in the different stages of oxidation to predict compositions that minimize oxidation.

Secondary hardening ultra-high strength (SHUHS) steels possess a unique combination of strength, fracture toughness and stress corrosion cracking resistance, which makes them candidate materials for aircraft landing gear and armour applications. There is a sustained drive to develop stronger and tougher materials for such applications. The objectives of this thesis are two-fold: first, to develop a new SHUHS alloy that is stronger than the existing SHUHS steel developed at Defence Metallurgical Research Laboratory (DMRL), Hyderabad and second, to establish processing-structure-property correlations for the new alloy. Empirical design and development of these complex steels involves enormous effort, cost, time and materials resources. To avoid this, a semi-empirical approach was espoused in this thesis wherein thermodynamic calculations using ThermoCalc were conducted to computationally design a series of alloys with varying levels of Cr and Mo. The design space was constrained by two objectives related to M2C carbides which are the primary cause of secondary hardening in these alloys. The first objective was to increase the amount of M2C to increase the peak strength, while the second objective was to lower the Cr/Mo ratio of the M2C to control its over-ageing behavior. Two new alloys C23 (with 2Cr-3Mo, wt. %) and C55 (with 5Cr-5Mo, wt. %) and a base alloy akin to the DMRL SHUHS steel, C21 were selected for experimental validation. These alloys were melted, rolled and subjected to a battery of heat treatments. Austenitization studies revealed that the new alloys required higher austenitization temperatures to dissolve primary carbides. However such a treatment also resulted in an austenite composition that was not conducive for obtaining a fully martensitic microstructure on quenching. Based on these studies, the design space was modified to include additional criteria related to the Ms and precipitate dissolution temperatures. C55 failed to clear either criteria, while C23 cleared both, and so tempering studies were limited to C23. Isochronal tempering studies revealed that C23 in the peak aged condition was >10% stronger than C21 indicating that the alloy design objective of strength enhancement was achieved successfully. Microstructural characterization revealed that the strength enhancement was due to the higher number density and volume fraction of the M2C-like solute clusters in C23, which resist shearing in the under-aged condition and strengthen by Orowan mechanism in the over-aged condition. This thesis has successfully demonstrated that the design paradigm of enhancing strength by increasing the amount of M2C is justified and that ThermoCalc can be used to as an objective-oriented alloy design tool in this class of the steels.

In order to increase the waste loading efficiency of nuclear waste glasses, alternative composite structures are sought that trap molybdenum in a water-durable CaMoO4 phase. In this thesis, the formation and stability of CaMoO4 in a borosilicate glass against the attack of internal radiation was investigated. It is a fundamental study that simplified the composition to known contributors of molybdate speciation, and further splits the com- ponents of α and β-decay into integral parts that replicated both nuclear and electronic interactions. Irradiation experiments using 2.5 MeV β, 7 MeV Au, and 92 MeV Xe ions were enlisted to test the hypotheses of whether 100−1000 years of radiation damage given current waste loading standards would: (i) induce phase separation in homogeneous re- gions, (ii) increase the extent of existing phase separation, (iii) induce local annealing that could cause amorphisation of crystalline phases or increase mixing between amorphous phases, or (iv) cause some combination of the above. Results from XRD, SEM, EPR, and Raman spectroscopy suggest that powellite is stable against replicated radiation damage with only minor modifications observed. The main mechanisms of alteration involved: (i) thermal and defect-assisted diffusion, (ii) relaxation from the added ion’s energy, (iii) localised damage recovery from ion tracks, and (iv) the accumulation of point defects or the formation of voids that created significant strain, and led to longer-range modifications. It can be further concluded that no precip- itation or increased phase separation was observed in single-phased glasses. In isolated cases, radiation-induced precipitation of CaMoO4 occurred, but these crystallites were reamorphised at higher doses. At high SHI fluences, minor amorphisation of powellite was also observed, but this occurred alongside bulk-to-surface reprecipitation of CaMo- species. Overall, the components of internal radiation were often found to have opposing effects on the alteration of Si−O−B mixing in the glass, ion migration, and crystallite size. This led to the prediction that a steady-state damage structure could form from cumulative decay processes. These results suggest that CaMoO4 containing borosilicate GCs are resistant to radiation, and that excess molybdenum from increased waste loading can be successfully incorporated into these structures without altering the overall dura- bility of the wasteform. Furthermore, the identified saturation in modifications occurring around 8 x 10¹⁴ Xe ions/cm² can be used as a benchmark in future investigations on more complex systems where the maximum damage state is required.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Single sensitive sequential AdSV methods were developed and optimized for the determination of trace zirconium, vanadium, titanium and molybdenum in river, estuary and seawater, independent of the salinity and content of organic matter in the sample. The methods are based on the accumulation of Zr(IV)-and V(V)-cupferron-oxalic acid-1,3-diphenylguanidine complexes and the accumulation of Ti(IV)-and Mo(VI)-mandelic acid at the hanging mercury drop electrode (HMDE). Differential pulse, adsorption potential of -0.6, -0.2, -0.1 and -0.1 V (vs. Ag/AgCl), adsorption time of 400, 20, 120 and 1 s and scan rates of 0.01, 0.06, 0.02 and 0.02 V s-1 for Zr(IV), V(V), Ti(IV) and Mo(VI), respectively, were used as instrumental parameters. The reduction peak for the complexes of Zr(IV), V(V), Ti(IV) and Mo(VI) appeared nearly -0.95, -0.65, -0.85 and -0.4 V, respectively. The variations of the peak current as well as the peak potential of each metal complexes were plotted against the apparent ionic strengths. The proposed voltammetric methods were applied in German and Brazilian rivers and estuaries as well as in seawater from the North Sea collected at the north of Germany and the Atlantic Ocean, collected during scientific cruise between Chile and Germany, as interesting and very simple alternatives to very laborious and time-consuming pre-existent methods, based on outline pre-concentration and separation from the matrix and subject to external contamination. The limits of detection and determination were in the range of ppt-levels and the methods accuracy were evaluated by recoveries tests and by measuring V(V) and Mo(VI) in two NRCC reference materials. Estuarine mixtures experiments were also carried out with the aim to get more insight on the distribution of Ti(IV), Zr(IV), Mo(VI) and V(V) along the estuaries of the rivers Rhine, Weser and Elbe with the North Sea. In this context, natural fresh waters were mixed with seawater at different ratios. / Métodos sensíveis e sequenciais de voltametria adsortiva de redissolução foram desenvolvidos e otimizados para a determinação de traços e ultra-traços de zircônio, vanádio, titânio e molibdênio em águas de rio, estuário e mar, independentemente da salinidade e conteúdo de matéria orgânica na amostra. Os métodos são baseados na acumulação de complexos de Zr(IV) e V(V) com cupferron-ácido oxálico-1,3-difenilguanidina e de complexos de Ti(IV) e Mo(VI) com ácido mandélico no eletrodo de mercúrio de gota pendente (HMDE). Pulso diferencial, potenciais de adsorção de -0,6; -0,2; -0,1 e -0,1 V (vs Ag/AgCl), tempos de adsorção de 400, 20, 120 e 1 s e velocidades de varredura de 0,01; 0,06; 0,02 e 0,02 V s-1, para Zr(IV), V(V), Ti(IV) e Mo(VI), respectivamente, foram usados como parâmetros instrumentais. Os picos de redução para os complexos de Zr(IV), V(V), Ti(IV) e Mo(VI) surgiram próximos de -0,95; -0,65; -0,85 e -0,4 V, respectivamente. As variações de corrente de pico assim como de potencial de pico de cada complexo dos metais foram plotados contra as forças-iônicas aparentes das amostras. Os métodos voltamétricos propostos foram aplicados em águas de rio e estuário coletadas na Alemanha e no Brasil e em amostras de água do mar do Mar do Norte coletadas no norte da Alemanha e Oceano Atlântico, coletadas durante expedição científica entre o Chile e Alemanha. Estes métodos se mostraram ser alternativas simples a métodos bastante complexos e demorados, baseados em pré-concentração outline e separação da matriz, sujeitos a contaminação externa. Os limites de detecção e quantificação estavam na ordem de partes por trilhão e a exatidão dos métodos foi avaliada através de teste de recuperação de amostras adicionadas com os analitos em estudo e em 2 materiais de referência certificados. Também foram realizados experimentos de mistura estuarina com o objetivo de obter informações da distribuição de Ti(IV), Zr(IV), Mo(VI) e V(V) ao longo de estuários dos rios Reno, Weser e Elba com o Mar do Norte. Neste intuito, as águas dos rios e do mar foram misturadas em diferentes razões.

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Made available in DSpace on 2015-03-26T13:39:49Z (GMT). No. of bitstreams: 1 texto completo.pdf: 661910 bytes, checksum: 2bedd7f74c199a1b511a83b5349efd07 (MD5) Previous issue date: 2012-07-27 / Conselho Nacional de Desenvolvimento Científico e Tecnológico / In areas cultivated frequently with common bean at Zona da Mata of Minas Gerais state, Mo application on foliage have been used instead of N topdressing to sustain yields around 2000 kg ha-1. However, there is a doubt about the effectiveness of this technology in higher yield conditions. The objectives of this work were: 1) determinate the maximal rate of N topdressing in which common bean respond to molybdenum fertilizer; 2) verify if the Mo fertilization replace the N topdressing in high yielding conditions. The experiments were conducted at three municipalities of Zona da Mata: Coimbra, Oratórios, and Viçosa. They were installed on April or May of 2011. The treatments were arranged as a 5 x 2 factorial: 0, 30, 60, 90 and 120 kg ha-1 of N and 0 and 80 g ha-1 of Mo. N as urea was applied the following way: 30 = at sowing, 60 = 30 (sowing) + 30 (15 days after emergence - DAE), 90 = 30 (sowing) + 30 (15 DAE) + 30 (25 DAE), 120 = 30 (sowing) + 45 (15 DAE) + 45 (25 DAE). Mo was applied as sodium molybdate solution onto the foliage at V4 stage. In order to reach the first objective, the effect of Mo was evaluated at each N rate. In order to reach the second objective, the ten treatments formed by the combination of N and Mo factors were considered. In this case, Dunnett test was utilized in order to compare the association of 30 kg ha-1 of N at the sowing + Mo with each other treatments. The cultivar Ouro Vermelho was used. A randomized complete block design with four replications was used. The highest yields were 3437, 2185 and 3270 kg ha-1 at Viçosa, Oratórios, and Coimbra, respectively. In Viçosa, differently from the others municipalities, N and/or Mo did not affect yield. In Coimbra, Mo increased yield when zero (level of 30 kg ha-1 de N) or 30 kg ha-1 de N topdressing (level of 60 kg ha-1 de N) was used. In Oratórios and Coimbra, plants sprayed with Mo and fertilized with N at sowing yielded as much as plants fertilized with N topdressing at a rate of 90 kg ha-1. Results suggest that common bean can respond in yield to Mo even when N topdressing of 30 kg ha is used and that Mo can replace topdressing N for yield levels of up to 3000 kg ha-1. / Em áreas cultivadas regularmente com feijão na Zona da Mata de Minas Gerais, a aplicação de molibdênio (Mo) na folhagem dos feijoeiros tem sido usada no lugar do adubo nitrogenado de cobertura para sustentar produtividades em torno de 2000 kg ha-1. Há duvida, no entanto, quanto à efetividade dessa tecnologia em níveis de produtividades mais altos. Os objetivos com este estudo foram: (1) determinar até que dose de nitrogênio (N) em cobertura o feijoeiro responde à adubação molíbdica; (2) verificar se a adubação com molibdênio (Mo) substitui a adubação em cobertura com N em condições de alta produtividade. Foram conduzidos experimentos em três municípios da Zona da Mata: Coimbra, Oratórios e Viçosa. Os experimentos foram instalados entre abril e maio de 2011. Os tratamentos foram arranjados no esquema fatorial 5 x 2: 0, 30, 60, 90 ou 120 kg ha-1 de N e 0 ou 80 g ha-1 de Mo. O nitrogênio, na forma de ureia, foi aplicado da seguinte forma: 30 = no plantio; 60 = 30 (plantio) + 30 (15 dias após a emergência - DAE); 90 = 30 (plantio) + 30 (15 DAE) + 30 (25 DAE); 120 = 30 (plantio) + 45 (15 DAE) + 45 (25 DAE). O Mo foi aplicado na forma de solução de molibdato de sódio sobre a folhagem no estádio V4. Para atingir o primeiro objetivo, o efeito do Mo foi avaliado dentro de cada dose de N. Para atingir o segundo objetivo, consideraram-se os 10 tratamentos formados pelas combinações dos fatores N e Mo. Neste caso, foi usado o teste de Dunnett para comparar a combinação 30 kg ha-1 de N no plantio + Mo com os demais. Foi usada a cultivar Ouro Vermelho. O delineamento foi em blocos casualizados, com quatro repetições. As maiores produtividades foram 3437, 2185 e 3270 kg ha-1 em Viçosa, Oratórios e Coimbra, respectivamente. Em Viçosa, diferentemente dos outros dois municípios, não houve efeito de N e/ou Mo na produtividade. Em Coimbra, o uso de Mo aumentou a produtividade com zero (nível de 30 kg ha-1 de N) ou 30 kg ha-1 de N em cobertura (nível de 60 kg ha-1 de N). Em Oratórios e Coimbra, o feijão que recebeu Mo associado ao N de plantio produziu tanto quanto o feijão que recebeu 90 kg ha-1 de N em cobertura (nível de 120 kg ha-1 de N). Os resultados sugerem que o feijão pode responder ao Mo mesmo quando se usa adubação de cobertura com 30 kg ha-1 de N e que o Mo pode substituir a adubação de N em cobertura em níveis de produtividade de até 3000 kg ha-1.

Conselho Nacional de Desenvolvimento CientÃfico e TecnolÃgico / A viabilidade econÃmica da produÃÃo do biodiesel depende do uso do glicerol, subproduto com estrutura multifuncional, considerado matÃriaâprima bio-renovÃvel, de grande potencial para ser transformado a combustÃveis ou produtos quÃmicos de maior valor agregado. Com o intuito de contribuir para o desenvolvimento dessa linha de pesquisa, foi realizado estudo do potencial catalÃtico da γ-Al2O3 modificada com Ãxido de molibdÃnio e promotores (Cu, Ni ou Co), na reaÃÃo de desidrataÃÃo do glicerol a intermediÃrios quÃmicos com aplicaÃÃo industrial. A estratÃgia foi sintetizar esferas de Al2O3 por mÃtodo hÃbrido, as quais apresentam interessantes propriedades estruturais, texturais e quÃmicas para em seguida impregnar com precursores dos metais via mÃtodo nÃo-convencional (Pechini). A composiÃÃo dos materiais foi escolhida com o objetivo de avaliar o efeito bifuncional causado pela combinaÃÃo das propriedades Ãcido/bÃsicas e redox de catalisadores de molibdÃnio suportado em alumina. Para fins comparativos foi testado catalisador comercial Ni-Mo/Al2O3 com elevada acidez e porosidade. Os catalisadores foram caracterizados por: ICP-OES, FRX, TGA/DTA, DRX, MEV, IV, TPR-H2, TPD-CO2, isotermas de adsorÃÃo/dessorÃÃo de N2, e acidez atravÃs de adsorÃÃo de piridina. O desempenho dos catalisadores foi avaliado na desidrataÃÃo do glicerol, sob fluxo de N2 ou H2, a 1atm e 250ÂC. As mudanÃas na atividade e seletividade devido à troca do gÃs de arraste estÃo associadas a alteraÃÃes nas propriedades Ãcido/redox dos catalisadores, como sugerido pelas medidas de acidez e TPR-H2. AcroleÃna foi o principal produto observado para todos os catalisadores, porÃm a amostra contendo cobre (CuMoAl), mostrou maior atividade catalÃtica e superior seletividade a Ãlcool alÃlico, bem como produÃÃo do 1-propanol; o que està associado a transferÃncia de hidrogÃnio. Essa seletividade concorda com resultados de TPR-H2, que mostram maior influÃncia do cobre sobre a reduÃÃo do Ãxido de molibdÃnio, quando comparado aos promotores (Co ou Ni). Ao final sÃo propostos passos reacionais envolvidos na conversÃo do glicerol a Ãlcool alÃlico. / The economic viability of biodiesel production depends of the use of glycerol, by-product with multifunctional structure, considered a bio-renewable feedstock of great potential to be transformed to fuel or higher value-added chemicals products. In order to contribute to the development of this research area, study was carried out in order to explore the catalytic potential γ-Al2O3 modified with molybdenum oxide and promoter (Cu, Ni or Co) in the glycerol dehydration reaction to chemical intermediates with industrial application was performed. The strategy was to synthesize Al2O3 spheres by hybrid method with interesting structural, textural and chemical properties for then impregnating with precursors of metals via unconventional method (Pechini). The material composition was chosen with the aim of evaluating the bifunctional effect caused by the combination of acid-base and redox properties of molybdenum catalysts supported on alumina. For comparison was evaluated commercial Ni-Mo/Al2O3 catalyst with high acidity and porosidade. The catalysts were characterized for: ICP-OES, XRF, TGA/DTA, XRD, SEM, IR, H2-TPR, TPD-CO2, N2 adsorption/desorption isotherms, and acidity measurements through pyridine adsorption. The catalytic performance was evaluated in the glycerol dehydration under N2 or H2 flow at atmospheric pressure and 250ÂC. The modification in the activity and selectivity due to the change of carrier gas are attributed to the changes of acid/redox properties of the catalyst, as suggested by acidity measurements and TPR-H2. Acrolein was the main product observed for all catalysts, but the cupper containing catalyst (CuMoAl) showed higher catalytic activity and, and superior selectivity to allyl alcohol, as well as the production of 1-propanol, which is due to the hydrogen transfer. This selectivity agrees with H2-TPR results, which show stronger effect of the copper over the molybdenum oxide reduction, if compared to the others promoter (Co or Ni). At the end it is proposed the reaction steps mechanism for the glycerol conversion to allyl alcohol.