Submitted by Pedro Silva Filho (pfsilva@ipen.br) on 2017-11-16T17:36:39Z No. of bitstreams: 0 / Made available in DSpace on 2017-11-16T17:36:39Z (GMT). No. of bitstreams: 0 / Os eletrocatalisadores PtRh/C foram preparados nas seguintes proporções atômicas: (100,0), (0,100), (90,10), (70,30) e (50,50). Os métodos empregados nas sínteses foram redução via borohidreto de sódio e redução por álcool. Os sais metálicos empregados foram H2PtCl6.6H2O e (RhNO3)3 e o suporte de carbono utilizado foi carbon Vulcan XC72, a composição metálica em massa foi de 20%; e o suporte, 80%. Os eletrocatalisadores foram caracterizados por técnicas físico-químicas, espectroeletroquímica e por experimento em célula a combustível, cujo emprego se deu por uma célula unitária direta a álcool com membrana alcalina. Os eletrodos de trabalho foram preparados pela técnica de camada fina porosa. A técnica de difração de raios X permitiu verificar ligas metálicas, fases segregadas e calcular a porcentagem de ligas metálicas, bem como constatar os tipos de fases cristalinas. A técnica de espectroscopia no infravermelho permitiu verificar que a oxidação eletroquímica do etanol se dá pelo mecanismo indireto de oxidação, ou seja, para todos materiais estudados houve a produção de espécies intermediárias, em que PtRh(70:30)/C sintetizado pelo médodo de redução via borohidreto de sódio produziu grandes quantidades de CO2 e C2H4O. Rh/C mostrou-se ativo eletroquimicamente para ambos os métodos de síntese empregados. A técnica de microscopia eletrônica de transmissão permitiu calcular o tamanho médio e a área superficial média dos eletrocatalisadores. As técnicas eletroquímicas permitiram verificar a estabilidade, potencial onset e pares redox dos sistemas considerados. / Dissertação (Mestrado em Tecnologia Nuclear) / IPEN/D / Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

A incorporação do gadolínio diretamente no combustível de reatores nucleares para geração de eletricidade é importante para compensação da reatividade e para o ajuste da distribuição da densidade de potência, permitindo ciclos de queima mais longos, com intervalo de recarga de 18 meses, otimizando-se a utilização do combustível. A incorporação do Gd2O3 sob a forma de pó homogeneizado a seco diretamente com o pó de UO2 é o método comercialmente mais atraente devido à sua simplicidade . Contudo, este método de incorporação conduz a dificuldades na obtenção de corpos sinterizados com a densidade niínima especificada, devido a um bloqueio no processo de sinterização. Pouca informação existe na literatura específica sobre o possível mecanismo deste bloqueio, restrita principalmente à hipótese da formação de uma fase (U,Gd)O2 rica em gadolínio com baixa difusividade. Este trabalho tem como objetivo a investigação do mecanismo de bloqueio da sinterização neste sistema, contribuindo para o esclarecimento da causa deste bloqueio e na elaboração de possíveis soluções tecnológicas. Foi comprovado experimentalmente que o mecanismo responsável pelo bloqueio é baseado na formação de poros estáveis devido ao efeito Kirkendall, originados por ocasião da formação da solução sólida durante a etapa intermediária da sinterização, sendo difícil a sua eliminação posterior, nas etapas finais do processo de sinterização. Com base no conhecimento deste mecanismo, possíveis propostas são apresentadas na direção da solução tecnológica do problema de densificação característico do sistema UO2-Gd203. / The incorporation of gadolinium directly into nuclear power reactor fuel is important from the point of reactivity compensation and adjustment of power distribution enabling thus longer fliel cycles and optimized fuel utilization. The incorporation of Gd2O3 powder directly into the UO2 powder by dry mechanical blending is the most attractive process because of its simplicity. Nevertheless, processing by this method leads to difficulties while obtaining sintered pellets with the minimum required density. This is due to blockages during the sintering process. There is little information in published literature about the possible mechanism for this blockage and this is restricted to the hypothesis based on formation of a low difiiisivity Gd rich phase (U,Gd)O2. The objective of this investigation has been to study the blockage mechanism in this system during the sintering process, contributing thus, to clarify the cause for the blockage and to propose feasible technological solutions. Experimentally it has been shown that the blocking mechanism is based on pore formation because of the Kirkendall effect. Formation of a solid solution during the intermediate stage of sintering leads to formation of large pores, which are difficult to remove in the final stage of sintering. Based on this mechanism, technical solutions have been proposed to resolve densification problems in the UO2-Gd2O3 system.

<div>The aviation industry is continuously growing amid tight restrictions on global emission</div><div>reductions. Alternative aviation fuels have gained attention and developed to replace the</div><div>conventional petroleum-derived aviation fuels. The replacement of conventional fuels with</div><div>alternative fuels, which are composed solely of hydrocarbons (non-petroleum), can mitigate</div><div>impacts on the environment and diversify the energy supply, potentially reducing fuel costs.</div><div>To ensure the performance of alternative fuels, extensive laboratory and full-scale engine</div><div>testings are required, thereby a lengthy and expensive process. The National Jet Fuel Combustion</div><div>Program (NJFCP) proposed a plan to reduce this certification process time and</div><div>the cost dramatically by implementing a computational model in the process, which can be</div><div>replaced with some of the testings. This requires an understanding of the influence of chemical/</div><div>physical properties of alternative fuels on combustion performance. The main objective</div><div>of this work is to investigate the spray characteristics of alternative aviation fuels compared</div><div>to that of conventional aviation fuels, which have been characterized by different physical</div><div>liquid properties at different gas turbine-relevant conditions.</div><div>The experimental work focuses on the spray characteristics of standard and alternative</div><div>aviation fuels at three operating conditions such as near lean blowout (LBO), cold engine</div><div>start, and high ambient pressure conditions. The spray generated by a hybrid pressureswirl</div><div>airblast atomizer was investigated by measuring the drop size and drop velocity at</div><div>a different axial distance downstream of the injector using a phase Doppler anemometry</div><div>(PDA) measurement system. This provided an approximate trajectory of the largest droplet</div><div>as it traveled down from the injector. At LBO conditions, the trend of decreasing drop size</div><div>and increasing drop velocity with an increase in gas pressure drop was observed for both</div><div>conventional (A-2) and alternative aviation fuels (C-1, C-5, C-7, and C-8), while the effect of</div><div>fuel injection pressure on the mean drop size and drop velocity was observed to be limited.</div><div>Moreover, the high-speed shadowgraph images were also taken to investigate the effect of</div><div>the pressure drop and fuel injection pressures on the cone angles. Their effects were found</div><div>to be limited on the cone angle.</div><div><div>The spray characteristics of standard (A-2 and A-3) and alternative (C-3) fuels were</div><div>investigated at engine cold-start conditions. At such a crucial condition, sufficient atomization</div><div>needs to be maintained to operate the engine properly. The effect of fuel properties,</div><div>especially the viscosity, was investigated on spray drop size and drop velocity using both</div><div>conventional and alternative aviation fuels. The effect of fuel viscosity was found to be minimal</div><div>and dominated by the effect of the surface tension, even though it showed a weak trend</div><div>of increasing drop size with increasing surface tension. The higher swirler pressure drop</div><div>reduced the drop size and increased drop velocity due to greater inertial force of the gas for</div><div>both conventional and alternative aviation fuels at the cold start condition. However, the</div><div>effect of pressure drop was observed to be reduced at cold start condition compared to the</div><div>results from the LBO condition.</div><div>The final aspect of experimental work focuses on the effect of ambient pressures on the</div><div>spray characteristics for both conventional (A-2) and alternative (C-5) aviation fuels. Advanced</div><div>aviation technology, especially in turbomachinery, has resulted in a greater pressure</div><div>ratio in the compressor; therefore, greater pressure in combustors for better thermal efficiency.</div><div>The effect of ambient pressure on drop size, drop velocity, and spray cone angle was</div><div>investigated using the PDA system and simultaneous Planar Laser-Induced Fluorescence</div><div>(PLIF) and Mie scattering measurement. A significant reduction in mean drop size was</div><div>observed with increasing ambient pressure, up to 5 bar. However, the reduction in the mean</div><div>drop size was found to be limited with a further increase in the ambient pressure. The effect</div><div>of the pressure drop across the swirler was observed to be significant at ambient pressure of</div><div>5 bar. The spray cone angle estimation at near the swirler exit and at 25.4 mm downstream</div><div>from the swirler exit plane using instantaneous Mie images was found to be independent of</div><div>ambient pressure. However, the cone angle at measurement plane of 18 mm in the spray</div><div>was observed to increase with increasing ambient pressure due to entrainment of smaller</div><div>droplets at higher ambient pressure. Furthermore, the fuel droplet and vapor distribution in</div><div>the spray were imaged and identified by comparing instantaneous PLIF and Mie images.</div><div>Lastly, a semi-empirical model was also developed using a phenomenological three-step</div><div>approach for the atomization process of the hybrid pressure-swirl airblast atomizer. This</div><div>model includes three sub-models: pressure-swirl spray droplet formation, droplet impingement, and film formation, and aerodynamic breakup. The model predicted drop sizes as a</div><div>function of ALR, atomizing gas velocity, surface tension, density, and ligament length and</div><div>diameter and successfully demonstrated the drop size trend observed with fuel viscosity,</div><div>surface tension, pressure drop, and ambient pressure. The model provided insights into the</div><div>effect of fuel properties and engine operating parameters on the drop size. More experimental</div><div>work is required to validate the model over a wider range of operating conditions and</div><div>physical fuel properties.</div><div>Overall, this work provides valuable information to increase understanding of the spray</div><div>characteristics of conventional and alternative aviation fuels at various engine operating</div><div>conditions. This work can provide valuable data for developing an advanced computational</div><div>combustor model, ultimately expediting the certification of new alternative aviation fuels.</div></div>

Presently, heavy-duty trucks are responsible for approximately 25% of global CO2 emissions. Although the world seems to incline towards the transport sector's electrification, the electrification of long-range freight trucks is profoundly challenging. The dominant disincentives are the required infrastructure, cost/size of batteries, limited mileage, and long charging sessions. However, despite the efforts to reduce emissions, current trends indicate that these continue to rise, mostly because of the continually increasing freight transit. Regional economies are heavily dependent on the latter. Thus, the imminent depletion of fossil fuels and the emerging environmental issues are disquieting aspects for the sustainability of this crucial sector. This thesis focuses on the possible alternative powertrain/drivetrain solutions for heavy-duty, long-range freight trucks in conjunction with sustainable energy carriers for the transportation sector overall. In terms of viable fuelling alternatives, the following are being reviewed: Electric Power, Bio-Fuels, and Synthetic Fuels, along with their current status, advantages, disadvantages and future prospects. In terms of powertrain/drivetrain alternatives, the following are being theoretically and critically evaluated and compared against a direct drive conventional Diesel engine truck (25.2% wheel efficiency): Battery Electric, Electric powered with overhead cables or underground conductive coils, combined Gas Turbine/Stirling Engine Hybrid Electric in series, combined Diesel engine/Stirling engine Hybrid Electric in series, and Diesel engine Hybrid Electric in series.  It is concluded that the best scenario for future freight trucks, is the use of an electric drivetrain/powertrain in conjunction with overhead powering cables along the highways. However, due to uncertainties in the universal realization of such infrastructure, to ensure uninterrupted transportation of goods, a plausible transitional solution could be the use of a Diesel engine/Stirling engine Hybrid Electric in series technology. This could reduce emissions/consumption by a factor of 2.4 (60% wheel efficiency). For the case of Gas turbine/Stirling engine and Diesel engine (both) Hybrid Electric in-series arrangements, this factor drops to 1.7 and 1.4 (42.9% and 34.3% wheel efficiency), respectively. Furthermore, this can be a clean and sustainable solution if biofuels are employed as the prime energy carriers. Such an approach is future-proof for use with overhead cables, since the suggested powertrain is electric, rendering a freight truck as a very versatile heavy-duty, long-range vehicle. Electro-fuels are not considered as a viable option due to their inefficient formulation, elevated costs, and problematic handling (Hydrogen).

Climate change is raising huge challenges for all industries worldwide. It is mainly due to anthropogenic activity and energy consumption which is the cause for emissions of greenhouse gas (GHG) among other environmental impacts and is expected to have huge impact on our societies globally. Of those global GHG emissions, around a quarter is emitted by transportations of all kinds as transportation relies heavily on fossil fuels. If the past years have seen a rising share of electrification within the passenger car industry, the commercial transportation isn’t that prone to electrification and other pathway to decarbonization are studied. Shipping is responsible for around 90% of the world commercial transportation work and therefore is a keyplayer in the transition toward low carbon transportation. It relies exclusively on fossil fuels with different kinds of oil-based fuels being the historical fuel suppliers and has seen a quick increase of the share of liquefied natural gas (LNG) in the past decade. Yet the international maritime organization (IMO) has set ambitious emission reduction targets for shipping and alternative fuel technologies are considered to be a relevant pathway if not the most promising pathway to low carbon or even zero carbon shipping. This study aims at evaluating and comparing different alternative fuels pathways available to perform the shift toward low carbon fuel technologies within Swedish short sea shipping (SSS) and inland waterway transportation (IWT) based on a set of criteria designed to reflect all aspects of the implementation of an alternative fuel pathway implementation. Those criteria are divided into 5 different categories which are technological, technical, economic, environmental, and finally social. There are 2 main categories to consider for low carbon fuels, biofuels and electrofuels. Fossil fuels are also included within the study so that the alternative pathways get compared not only with one another but also with the current marine fuels. The first comparison between different alternative fuel pathways is relevant to choose the most promising and feasible one while the comparison between a chosen alternative fuelpathway and the main marine fossil fuels is what stakeholders will look at when considering an alternativefuel pathway implementation challenge. The electrofuels included within the comparison are ammonia and hydrogen within 2 similar pathways which include production using water electrolysis and renewableelectricity (the carbon intensity of the Swedish grid is considered) before consumption within fuel cells (FC)instead of internal combustion engines (ICE). Those electrofuels end up with the last ranks within the comparison due to low technological maturity, technical and economic challenges remaining and social issued to address despite being the most environmentally promising pathways. Biofuel’s pathways on the other hand include both fischer tropsch diesel (FTD) and bio-methanol production using as feedstock various mixes of black liquor (BL) andpyrolysis oil (PO). FTD ends up as the most promising alternative fuel pathway within the whole studywhile bio-methanol appears more challenging but also more promising toward environmental criteria. / Klimatförändringarna innebär stora utmaningar för alla branscher världen över. Den beror främst på antropogen aktivitet och energikonsumtion som orsakar utsläpp av växthusgaser bland andra miljöeffekter och förväntas få stora konsekvenser för våra samhällen globalt. Av de globala utsläppen av växthusgaser kommer omkring en fjärdedel från alla typer av transporter, eftersom transporterna är starkt beroende avfossila bränslen. Under de senaste åren har man sett en ökande andel elektrifiering inom personbilsindustrin,men kommersiella transporter är inte lika benägna att elektrifieras och andra vägar till avkolning studeras. Sjöfarten står för cirka 90 % av världens kommersiella transportarbete och är därför en nyckelspelare i övergången till koldioxidsnåla transporter. Den är uteslutande beroende av fossila bränslen med olika typer av oljebaserade bränslen som historiska bränsleleverantörer och har sett en snabb ökning av andelen flytande naturgas (LNG) under det senaste decenniet. Internationella sjöfartsorganisationen (IMO) har dock fastställt ambitiösa mål för minskning av utsläppen för sjöfarten, och tekniker för alternativa bränslen anses vara enr elevant väg, om inte den mest lovande, för att uppnå en sjöfart med låga koldioxidutsläpp eller till och med utan koldioxidutsläpp. Syftet med denna studie är att utvärdera och jämföra olika alternativa bränslen som finns tillgängliga för att genomföra övergången till bränsleteknik med låga koldioxidutsläpp inom svensk närsjöfart (SSS) och transport på inre vattenvägar (IWT) utifrån en uppsättning kriterier som är utformade för att återspegla alla aspekter av genomförandet av en alternativ bränslesatsning. Dessa kriterier är indelade i fem olika kategorier som är tekniska, tekniska, ekonomiska, miljömässiga och slutligen sociala. Det finns två huvudkategorier att ta hänsyn till när det gäller bränslen med låga koldioxidutsläpp, nämligen biobränslen och elektrobränslen. Fossila bränslen ingår också i studien så att de alternativa vägarna inte bara jämförs med varandra utan också med de nuvarande marina bränslena. Den första jämförelsen mellan olika alternativa bränslevägar är relevant för att välja den mest lovande och genomförbara, medan jämförelsen mellan en vald alternativ bränsleväg och de viktigaste marina fossila bränslena är vad intressenterna kommer att titta på när de överväger att genomföra en alternativ bränsleväg. De elektrobränslen som ingår i jämförelsen är ammoniak och vätgas inom två liknande vägar som omfattar produktion med hjälp av vattenelektrolys och förnybar el (det svenska elnätets koldioxidintensitet beaktas) innan de förbrukas i bränsleceller i stället för i förbränningsmotorer. Dessa elektrobränslen hamnar på de sista platserna i jämförelsen på grund av låg teknisk mognad, återstående tekniska och ekonomiska utmaningar och sociala problem som måste lösas, trots att de är de miljömässigt mest lovande vägarna. Biobränslevägar omfattar å andra sidan både fischer tropsch diesel(FTD) och produktion av biometanol med olika blandningar av svartlut (BL) och pyrolysolja (PO) som råmaterial. FTD är den mest lovande alternativa bränslevägen i hela studien, medan bio-metanol verkar vara en större utmaning men också mer lovande när det gäller miljökriterier.

Master of Agribusiness / Department of Agricultural Economics / Allen M. Featherstone / During the past 10 years, ethanol production in the United States has grown exponentially. From 2000 to 2009 U.S. ethanol production increased from 1.6 billion gallons annually to 10.8 billion gallons annually. In 2010, U.S ethanol production increased by 23 percent from 2009 to 13.23 billion gallons. The increase in ethanol production was due to lawmakers reacting to skyrocketing oil prices by implementing a Renewable Fuels Standard (RFS) in 2005 and expanding the RFS in 2007. The RFS requires the use of specified amounts of biofuels, such as ethanol, through the year 2022. The creation of the RFS represented a step beyond lawmakers’ usual policy of using the tax code to promote ethanol production. There is a long history of encouraging ethanol production by using the tax code, but the implementation of a biofuels mandate is new and therefore there is not a great deal of research on the effects of such a policy. This study analyzes U.S. oil, unleaded gasoline, corn and ethanol prices dating back to 1985 to determine the impact that the RFS has had on corn prices. The key question answered is whether the creation and expansion of the RFS has brought the instability of the oil market into the corn market. The prices that an ethanol plant in western Kansas paid for the grain it used to produce ethanol and the price that the plant received for the ethanol that it produced are also analyzed. The plant began operation in January 2004, so it is possible to analyze the grain and ethanol prices both before and after the implementation and expansion of the RFS. To study the impact of the RFS creation and expansion, the prices were analyzed to see if there was an increase in the correlation after the creation and expansion of the RFS. Regression analysis of the national corn prices and the prices that Western Plains Energy paid for the grain that it used to produce ethanol; and regression analysis of the national price of ethanol and the price that Western Plains Energy sold its ethanol for were also used to study the impact of the RFS. Finally, the vector autoregression (VAR) model is used to analyze the dynamic relationships between the variables in the system: corn price, oil price, ethanol price and unleaded gasoline price. The analysis of the correlation reveals that both at the national and plant level grain and oil prices track much more closely together after the creation and then expansion of the RFS. The VAR reveals that there is some relationship between corn and oil prices contemporaneously. The correlation matrix of residuals reveals that there is not a strong correlation between national corn and oil prices. The results suggest the need for greater research in this area. The creation and expansion of the RFS represented a step into uncharted territory and the consequences are still not known.

Typescript. / Digitized by Kansas Correctional Industries

Digitized by Kansas Correctional Industries

Call number: LD2668 .T4 1984 M37 / Master of Science

Nuclear energy can be used to reliably generate large quantities of electricity while providing minimal lifetime CO2 emissions. Given the extreme importance of safety in the nuclear industry, it is necessary to have a fundamental understanding of the materials used throughout the nuclear fuel cycle. It is of particular to importance to develop an understanding of these materials at an atomic level. In this thesis, X-ray absorption spectroscopy (XAS), along with several other X-ray based techniques, has been used to study materials that are produced or proposed for use in the nuclear fuel cycle. Uranium mining and milling operations generate large quantities of waste, known as mine and mill tailings. At their McClean Facility in Northern Saskatchewan, AREVA Resources Canada disposes of the tailings waste using the JEB Tailings Management Facility (TMF). AREVA monitors the mineralization of elements of concern (i.e., Ni, As, Fe, Mo, Ra, and U) within the TMF as part of its on-going commitment towards managing the facility’s environmental impact. Molybdenum (Mo) is predicted to mineralize as insoluble powellite (CaMoO4) within the TMF. However, no experimental evidence confirmed the presence of powellite in the TMF. In Chapter 2, the presence of powellite, and other Mo-bearing minerals, was determined using powder X-ray diffraction (XRD), X-ray fluorescence imaging, and Mo K-edge XAS. The results of this study confirmed that powellite was present in the TMF and showed that Mo K-edge XAS was the only effective way to detect the Mo minerals within the TMF. New materials for use as nuclear fuels were also investigated in this thesis. Spent nuclear fuel must be securely stored for long periods of time due to the presence transuranic elements (TRU; i.e., Pu, Am, Np, Cm), and the use of inert matrix fuels (IMF), which consist of actinides embedded in a neutron transparent (inert) material, have been proposed for to “burn-up” or transmute these TRU species. Stabilized ZrO2 materials have been proposed for use in IMF applications, and in Chapter 3 the thermal stability of a series of NdxYyZr1-x-yO2-\delta materials made by a ceramic synthetic route have been studied using powder XRD, scanning electron microscopy (SEM), and X-ray absorption spectroscopy. (Nd was used as a surrogate for Am.) The results of this study showed that the fluorite structure of the NdxYyZr1-x-yO2- \delta materials was stabilized when y >= 0.05, and that the local environment around Zr was independent of composition or annealing temperature. The effect of synthetic method on the thermal stability of the NdxYyZr1-x-yO2-\delta materials was also determined, and this is the subject of Chapter 4. In this study a series of NdxY0.25-xZr0.75O1.88 materials were synthesized using a low-temperature co precipitation synthesis, and these then annealed at 1400 °C and 1500 °C. The as-synthesized and annealed materials were characterized by powder XRD, SEM, and XAS. This study confirmed that the thermal stability of the materials was dependent on synthetic method, and that materials made using a solid-state method were superior to those produced by a solution-based approach. Y-stabilized zirconia has a low thermal conductivity, which is not ideal for a nuclear fuel. The thermal conductivity could be increased if a lighter cation, such as Sc, was used to stabilize the fluorite structure. In Chapter 5, the thermal stability of a series of NdxScyZr1-x-yO2-\delta materials was investigated. The as-synthesized and annealed materials were studied by powder XRD, SEM, and XAS. These results showed that the fluorite structure was only stable in the annealed materials when x+y >= 0.15 and y >= 0.10. The results of this study provided insight into the possible use of scandia-stabilized zirconia for use as an inert matrix fuel. This studies presented in this thesis have used X-ray absorption spectroscopy and a number of other techniques to characterize materials important to the nuclear fuel cycle. The studies presented here were only possible because of the unique information that can be obtained using XAS. This thesis serves to highlight the importance of XAS as a technique and how it can be applied to solve problems related to the material science of the nuclear fuel cycle.