Neste trabalho, os sistemas de eletrocatalisadores platina-rutênio (PtRu/C) e platina-estanho (PtSn/C) suportados em carbono de alta área superficial XC72R (Cabot) foram preparados pela redução química de precursores metálicos em solução usando o ácido cítrico como agente redutor. Os eletrocatalisadores foram preparados em diferentes valores de pH, com o objetivo de obter as condições de sínteses mais otimizadas para cada um dos sistemas preparados. O método otimizado mostrou-se eficiente na redução e ancoragem de todos os metais presente em solução, sendo possível preparar tanto catalisadores com baixos teores de segundo metal (razão atômica entre Pt:M = 90:10) quanto catalisadores com altos teores de segundo metal (Pt:M = 50:50). Os eletrocatalisadores obtidos foram caracterizados por espectroscopia de energia dispersiva de raios X, difração de raios X e microscopia eletrônica de transmissão. A atividade frente a eletro-oxidação de metanol e etanol foi avaliada através de voltametria cíclica e cronoamperometria em célula eletroquímica. Para os catalisadores com melhores desempenhos eletroquímicos foram realizados experimentos em célula a combustível unitária alimentada diretamente por metanol ou etanol. O desempenho dos eletrocatalisadores preparados foi comparado com o desempenho dos eletrocatalisadores comerciais Pt50Ru50/C e Pt75Sn25/C da linha HP (High Performance) fornecidos pela E-TEK, considerados como referência nos estudos frente a eletro-oxidação de alcoóis. Para eletro-oxidação do metanol foram obtidos eletrocatalisadores com desempenho comparável ao E-TEK e para eletro-oxidação de etanol foram obtidos eletrocalisadores com desempenho superior aos catalisadores E-TEK. / In this work, platinum ruthenium (PtRu/C) and platinum tin (PtSn/C) electrocatalysts were prepared by a chemical reduction process using citric acid as reducing agent and high surface area Vulcan Carbon XC72R (Cabot) as supports. The PtRu/C and PtSn/C catalysts were characterized by energy dispersive X-ray spectroscopy, X-ray diffraction and transmission electron microscopy. The electro-oxidation of methanol and ethanol were studied at room temperature by cyclic voltammetry and chronoamperometry. Single fuel cell experiments were carried at 90 °C and the performance of the homemade electrocatalysts prepared by citric acid method in optimized conditions were compared with commercial Pt50Ru50/C and Pt75Sn25/C E-TEK HP (High Performance) catalysts. For methanols electro-oxidation electrocatalysts with comparable E-TEKs catalysts performance were obtained and for ethanols electro-oxidation electrocatalysts with superior performance than E-TEKs electrocatalysts were obtained.

A obesidade está relacionada com uma grande variedade de disfunções, tais como as dislipidemias, resistência à insulina e diabetes tipo II. Estas patologias estão relacionadas com alterações da fisiologia mitocondrial. As mitocôndrias são o principal sítio do metabolismo oxidativo e são importantes fontes de espécies reativas de oxigênio. Alberici et al. (2006) mostraram que a atividade de canais de potássio sensíveis a ATP mitocondriais (mitoKATP), via dissipativa branda, estava aumentada em fígados de animais hipertrigliceridêmicos transgênicos. Este dado sugere um papel adaptativo importante para o mitoKATP como regulador do metabolismo e da massa corpórea. O principal objetivo deste trabalho foi investigar o papel deste canal em fígados de camundongos submetidos a uma dieta hiperlipídica, obtida por meio de suplementação de óleo de soja à única fonte de água dos animais. Foram estabelecidas correlações entre a atividade do canal e parâmetros da fisiologia mitocondrial ou parâmetros sorológicos clássicos como colesterolemia e trigliceridemia. Sendo realizados experimentos de espalhamento de luz, quantificação de peróxido de hidrogênio, potencial de membrana e consumo de oxigênio em mitocôndrias. Nossos resultados mostram aumento de massa corpórea sem dislipidemias e aumento da atividade do mitoKATP, dependente do tempo da suplementação, diretamente correlacionada com a colesterolemia. Nossos resultados apontam aumento da geração de EROs e diminuição da eficiência de conversão energética no grupo suplementado. Como conclusão: manipulações de dieta são eficazes para a indução da atividade do mitoKATP, sendo este um novo e interessante sítio de regulação do metabolismo oxidativo e da massa corpórea. / Obesity is associated with multiple dysfunctions including dyslipidemia, insulin resistance and diabetes. These malfunctions are associated with modifications in mitochondrial physiology. Furthermore, mitochondria are the most important site of energy metabolism and reactive oxygen species production. Alberici et al. (2006) demonstrated that hypertriglyceridemic transgenic mice display increased expression ad activity of mitochondrial ATP sensitive potassium channels (mitoKATP), a mild uncoupling pathway, in liver. This suggests that mitoKATP is an important adaptation to regulate body mass and metabolism. The aim of this work is to investigate the role of mitoKATP in a high fat diet induced by soy oil supplementation, correlating changes in channel activity with metabolic and mitochondrial parameters. Mitochondria were isolated from mouse livers and serological parameters were measured for each animal. Light scattering (to estimate mitoKATP activity), hydrogen peroxide generation, membrane potentials and oxygen consumption were measured in the mitochondrial suspensions. Our results indicate an increase in body mass, without dyslipidemia; and increases in mitoKATP activity, in time-dependent manner, directly correlated to cholesterol levels. In addition, we found increases in ROS generation and decreased capacity of energy conversion (ADP/O) in the high fat diet group. In conclusion, our results indicate that the activity of mitoKATP could be induced by high fat diets and that this is an novel site for metabolic and body mass control.

On March 13th, 2006, the Division of Electricity at Uppsala University deployed its first wave energy converter, L1, in the ocean southwest of Lysekil. L1 consisted of a buoy at the surface, connected through a line to a linear generator on the seabed. Since the deployment, continuous investigations of how L1 works in the waves have been conducted, and several additional wave energy converters have been deployed. This thesis is based on ten publications, which focus on different aspects of the interaction between wave, buoy, and generator. In order to evaluate different measurement systems, the motion of the buoy was measured optically and using accelerometers, and compared to measurements of the motion of the movable part of the generator - the translator. These measurements were found to correlate well. Simulations of buoy and translator motion were found to match the measured values. The variation of performance of L1 with changing water levels, wave heights, and spectral shapes was also investigated. Performance is here defined as the ratio of absorbed power to incoming power. It was found that the performance decreases for large wave heights. This is in accordance with the theoretical predictions, since the area for which the stator and the translator overlap decreases for large translator motions. Shifting water levels were predicted to have the same effect, but this could not be seen as clearly. The width of the wave energy spectrum has been proposed by some as a factor that also affects the performance of a wave energy converter, for a set wave height and period. Therefore the relation between performance and several different parameters for spectral width was investigated. It was found that some of the parameters were in fact correlated to performance, but that the correlation was not very strong. As a background on ocean measurements in wave energy, a thorough literature review was conducted. It turns out that the Lysekil project is one of quite few projects that have published descriptions of on-site wave energy measurements.

Magnetized planets, such as Earth, are strongly influenced by the solar wind. The Sun is very dynamic, releasing varying amounts of energy, resulting in a fluctuating energy and momentum exchange between the solar wind and planetary magnetospheres. The efficiency of this coupling is thought to be controlled by magnetic reconnection occurring at the boundary between solar wind and planetary magnetic fields. One of the main tasks in space physics research is to increase the understanding of this coupling between the Sun and other solar system bodies. Perhaps the most important aspect regards the transfer of energy from the solar wind to the terrestrial magnetosphere as this is the main source for driving plasma processes in the magnetosphere-ionosphere system. This may also have a direct practical influence on our life here on Earth as it is responsible for Space Weather effects. In this thesis I investigate both the global scale of the varying solar-terrestrial coupling and local phenomena in more detail. I use mainly the European Space Agency Cluster mission which provide unprecedented three-dimensional observations via its formation of four identical spacecraft. The Cluster data are complimented with observations from a broad range of instruments both onboard spacecraft and from groundbased magnetometers and radars. A period of very strong solar driving in late October 2003 is investigated. We show that some of the strongest substorms in the history of magnetic recordings were triggered by pressure pulses impacting a quasi-stable magnetosphere. We make for the first time direct estimates of the local energy flow into the magnetotail using Cluster measurements. Observational estimates suggest a good energy balance between the magnetosphere-ionosphere system while empirical proxies seem to suffer from over/under estimations during such extreme conditions. Another period of extreme interplanetary conditions give rise to accelerated flows along the magnetopause which could account for an enhanced energy coupling between the solar wind and the magnetosphere. We discuss whether such conditions could explain the simultaneous observation of a large auroral spiral across the polar cap. Contrary to extreme conditions the energy conversion across the dayside magnetopause has been estimated during an extended period of steady interplanetary conditions. A new method to determine the rate at which reconnection occurs is described that utilizes the magnitude of the local energy conversion from Cluster. The observations show a varying reconnection rate which support the previous interpretation that reconnection is continuous but its rate is modulated. Finally, we compare local energy estimates from Cluster with a global magnetohydrodynamic simulation. The results show that the observations are reliably reproduced by the model and may be used to validate and scale global magnetohydrodynamic models.

University of Macau / Faculty of Science and Technology / Department of Electrical and Electronics Engineering

The solar cell technology based on Cu(In,Ga)Se2 (CIGS) thin-films provides a promising route to cost competitive solar electricity. The standard device structure is ZnO:Al/ZnO/CdS/CIGS/Mo films on a glass substrate, where the first three layers are n-type semiconductors with wide bandgaps, forming a pn-junction with the p-type CIGS absorber layer; the Mo layer serves as a back contact. This thesis deals with analysis of the generation and recombination of electron-hole pairs throughout the device. These processes determine the maximum output power: generation limits the current; recombination limits the voltage. The generation is calculated with an optical model based on complex refractive indices determined for the individual layers. The main features of the optical response of the solar cell can be reproduced with a specular model neglecting scattering. A model including ideally Lambertian scattering at the front and back surface of the CIGS absorber layer is introduced to investigate the possibility to maintain a high current generation with thin absorber layers. The result highlights the relatively poor optical performance of the Mo back contact. TiN and ZrN are explored as alternatives, and improved optical performance is experimentally demonstrated for both materials. The recombination analysis emphasizes that, in general, more than one recombination path of comparable magnitude are operative in parallel. For cells with absorber bandgap increasing from 1.0 eV (CuInSe2) to 1.7 eV (CuGaSe2), a relative increase of interface recombination is found. When these cells are subject to accelerated ageing, degradation is smallest for intermediate bandgaps; an explanation involving different sensitivity to decreased absorber band bending and activation of grain boundaries is suggested. The optical gain with ZrN back contacts is counteracted by increased back contact recombination and contact resistance, but an intermediate layer of MoSe2 is shown to alleviate these problems, allowing for an overall improved efficiency.

Current environmental and energy sustainability trends have instigated considerable interest in alternative energy technologies that exhibit reduced dependence on fossil fuels. The advantages of such a direction are two-fold: reduced greenhouse gas emissions (notably CO2) and improved energy sustainability. Fuel cells are recognized as a potential technology that achieves both of these goals. However, improvements to fuel cell power density and stability must be realized to make them economically competitive with traditional, fossil-based technologies. The work in this dissertation is largely focused on the use of analytical tools for the study of transport processes in three fuel cell systems toward improvement of fuel cell performance. Polymer electrolyte membrane fuel cells (PEMFCs) are fueled by hydrogen and oxygen to generate electrical current. Microbial fuel cells (MFCs) use bacteria to degrade carbon compounds, such as those found in wastewaters, and simultaneously generate an electric current. Enzyme fuel cells (EFCs) operate similarly to PEMFCs but replace precious metal catalysts, such as platinum, with biologically-derived enzymes. The use of enzymes also allows EFCs to utilize simple carbon compounds as fuel. The operation of all three fuel cell systems involves different modes of ion and electron transport and can be affected negatively by transport limitations. Electrochemical impedance spectroscopy (EIS) was used in this work to study the distribution of transport resistances in all three fuel cell systems. The results of EIS were used to better understand the transport resistances that limited fuel cell power output. By using this technique, experimental conditions (including operating conditions, construction, and materials) were identified to develop fuel cells with greater power output and longevity. In addition to EIS, neutron imaging was employed to quantify the distribution of water in PEMFCs and EFCs. Water content is an integral aspect of providing optimal power output from both fuel cell systems. Neutron imaging contributed to developing an explanation for the loss of water observed in an operating EFC despite conditions designed to mitigate water loss. The findings of this dissertation contribute to the improvement of fuel cell technology in an effort to make these energy devices more economically viable.

Thesis (Ph.D.)--Mississippi State University. Department of Mechanical Engineering. / Title from title screen. Includes bibliographical references.

High concentrations and fluxes of dissolved organic carbon (DOC) in fluvial systems are associated with the dark brown water colour familiar in many upland, peat-dominated areas and may indicate a depletion of the terrestrial carbon store. The removal of this colour can also be problematic and expensive for water companies as well as affecting the ecological functioning of the water body through factors such as reduced light penetration through the water column. Disturbance resulting from activities such as land use change can also enhance the loss of carbon and this may manifest itself in elevated concentrations and fluxes of DOC from aquatic systems. This thesis describes and explains patterns of change in DOC quantity and quality from the Crosswater, Crosswater of Luce and Tig catchments draining Arecleoch Forest, a peatland in south Ayrshire, Scotland, from 2008 to 2010. This time period incorporates the installation of a 60-turbine wind farm built and operated by Scottish Power Renewables (SPR). Water samples were collected from Arecleoch at different spatial scales ranging from catchments to soil pore water and temporal scales ranging from daily to seasonally. Concentrations of DOC were measured and fluxes estimated at the catchment scale. DOC concentrations from all three catchments exhibited the well-established seasonal pattern with maxima in late August/early September and minima seen in February/March. The Tig catchment experienced the greatest burden of disturbance from the wind farm development and returned the highest DOC concentrations and fluxes. The Crosswater catchment, used as a control site due to its isolation from wind farm activities, had higher DOC concentrations than the Crosswater of Luce throughout the monitoring period possibly due to a greater proportion of forest cover. ii DOC flux ranged from 35.0 g C m-2 yr-1 from the Crosswater of Luce catchment in 2008 to 55.0 g C m-2 yr-1 from the Crosswater in 2009. The Tig catchment was not monitored for the whole period but returned the highest DOC fluxes of the three catchments between January and June 2010 (15.7 g C m-2). These values are considered high for UK peatlands. It is possible to make a tentative estimate of an extra 12 g C m-2 being exported from the Crosswater of Luce in 2009 that may have been a result of wind farm and/or forestry activities in the catchment. At the sub-catchment scale, “hot spots” of high DOC concentrations (up to 113.4 mg L-1) were found during the final survey of headwater streams inside the development area of the wind farm site during construction in August 2010. Further surveys are recommended to assess whether DOC concentrations have decreased since completion of the wind farm. Daily water samples were collected upstream and downstream of turbine 33 during the excavation of the turbine base. DOC concentrations were higher downstream before work began on the turbine base and although the gap between upstream and downstream DOC concentrations increased over the monitoring period, statistical comparisons of these differences before and after the start of excavation work were not significant at the 95 % confidence level. Challenges arose from the practicability of conducting robust research on a construction site and novel approaches to monitoring DOC were developed. Activity scores were used to quantify the effect of peatland disturbance on DOC concentrations at the catchment scale. The results suggest that this approach may have merit but requires comprehensive site records from the developer. The non-linear nature of the individual wind farm development and forestry activities made it impractical to disentangle the impact of each, particularly for forest harvesting. iii Activity scores could, together with other information gathered from site records, be useful to developers as an indicator of the most likely periods for peat disturbance. Knowledge of the differing disturbance potential of the various activities could also provide useful information to feed into the carbon payback calculator. DOC quality was explored using ultraviolet (UV) absorbance, specific UV absorbance (SUVA) and E4/E6 ratios. The latter metric identified changes in the composition of DOC related to disturbance with water samples from areas draining land subject to disturbance having lower E4/E6 ratios indicating a greater degree of humification of the DOC. This research provides one of only three studies to investigate concentrations and fluxes of DOC in water courses draining land subject to disturbance relating to wind farm construction. It is the only study that incorporates a period of time prior to work beginning and takes in the whole of the development phase. In this respect it provides a valuable addition to our understanding of the way in which peatlands respond to land use change and may provide useful tools to assist developers in minimising the impact of their activities on these valuable carbon stores.

Studies of the radiative properties of thin films and near-field radiation transfer in layered structures are important for applications in energy, near-field imaging, coherent thermal emission, and aerospace thermal management. A comprehensive study is performed on the optical constants of dielectric tantalum pentoxide (Ta₂O₅) and hafnium oxide (HfO₂) thin films from visible to the far infrared using spectroscopic methods. These materials have broad applications in metallo-dielectric multilayers, anti-reflection coatings, and coherent emitters based on photonic crystal structures, especially at high temperatures since both materials have melting points above 2000 K. The dielectric functions of HfO₂ and Ta₂O₅ obtained from this work may facilitate future design of devices with these materials. A parametric study of near-field TPV performance using a backside reflecting mirror is also performed. Currently proposed near-field TPV devices have been shown to have increased power throughput compared to their far-field counterparts, but whose conversion efficiencies are lower than desired. This is due to their low quantum efficiency caused by recombination of minority carriers and the waste of sub-bandgap radiation. The efficiency may be improved by adding a gold mirror as well as by reducing the surface recombination velocity, as demonstrated in this thesis. The analysis of the near-field TPV and proposed methods may facilitate the development or high-efficiency energy harvesting devices. Many near-field devices may eventually utilize metallo-dielectric structures which exhibit unique properties such as negative refraction due to their hyperbolic isofrequency contour. These metamaterials are also called indefinite materials because of their ability to support propagating waves with large lateral wavevectors, which can result in enhanced near-field radiative heat transfer. The energy streamlines in such structures are studied for the first time. Energy streamlines illustrate the flow of energy through a structure when the fields are evanescent and energy propagation is not ray like. The energy streamlines through two semi-infinite uniaxially anisotropic effective medium structures, separated by a small vacuum gap, are modeled using the Green’s function. The lateral shift and penetration depth are calculated from the streamlines and shown to be relatively large compared to the vacuum gap dimension. The study of energy streamlines in hyperbolic metamaterials helps understand the near-field energy propagation on a fundamental level.