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.

Motores termomagnéticos são dispositivos capazes de converter calor em energia mecânica através do efeito termomagnético, e são uma alternativa para a conversão de energia de rejeitos térmicos de baixa e baixíssima qualidade. Neste trabalho é proposta uma classificação dos motores termomagnéticos como sendo de dois tipos, os motores tipo Edison e os motores tipo Tesla. Feita a classificação, diferenciou-se o comportamento de operação e os ciclos termodinâmicos desenvolvidos pelos dois tipos de motores, mostrando que motores do tipo Tesla desenvolvem um ciclo termodinâmico que pode ser aproximado por um ciclo Brayton magnético, já motores do tipo Edison descrevem um ciclo mais complexo, não podendo ser aproximado por um ciclo Brayton. Compararam-se os parâmetros de interesse para ambos os motores através de análises termodinâmicas, onde se concluiu que motores do tipo Tesla apresentam melhores respostas de trabalho e eficiência que motores do tipo Edison, quando são consideradas as mesmas condições de operação. Além disso, identificou-se que a equação de força de Kelvin é a equação que corretamente descreve o comportamento da força magnética em um motor termomagnético, essa contribuição é importante, pois vários trabalhos publicados na literatura utilizam equações que não descrevem corretamente o comportamento da força magnética. Mostrou-se que o trabalho produzido em um motor termomagnético é igual ao trabalho produzido pela força magnética resultante no dispositivo. Foi desenvolvida e validada uma metodologia para o cálculo do trabalho específico produzido em um motor do tipo Tesla. Utilizando as metodologias validadas, verificou-se como a temperatura, o campo magnético aplicado, o fator de desmagnetização e o tipo de transição influenciam o comportamento dos motores termomagnéticos tipo Tesla, o que abre caminho para o desenvolvimento de dispositivos mais interessantes do ponto de vista termodinâmico. / Thermomagnetic motors are devices capable of converting heat into mechanical energy through the thermomagnetic effect. These devices are able to operate using low or very low quality thermal waste, being an alternative to avail that range of thermal energy. This work classifies the thermomagnetic motors in two types: The Tesla type and the Edison type thermomagnetic motors, differentiating the operational behavior and the thermodynamic cycles developed in each type. By using thermodynamic approaches, it is shown that the Tesla type thermomagnetic motors have best response in terms of work and efficiency than the Edison type thermomagnetic motors, when the same operating conditions are considered. In addition, an experimental approach is presented, proving that the Kelvin force equation describes the behavior of the force in thermomagnetic motors, and the work produced in a motor is the same that the work produced by the resultant magnetic force in the system. It was developed and validated a method to estimate the work produced by cycle in a Tesla type thermomagnetic motor, and using thermodynamic approaches, the relevance of the temperature, applied magnetic field, demagnetizing factor and transition type in the Tesla type thermomagnetic motor were verified.

In this thesis the integration of photovolatic (PV) generation and energy storage into the electrical grid is discussed. Although the studied system is for grid tied applications, here the integration of the PV generation and the energy storage system (ESS) on the DC-side of the system is addressed. The work contained in this thesis focuses on the integration of the DC-working parts before interfacing them with the grid through the use of an inverter and seeks an increasing in the energy that the system can deliver.First, a study of classical systems that present well-differentiated parts is presented: PV generation, a lithium-ion battery based ESS, the utility grid and a residential electricity consumer. PV installations of 3 and 10kWp are considered together with storage capacities ranging from 1 to 9kWh. This yields interesting insights on how the system works based on the timing of the generation and consumption of energy. The results are used to highlight the weaknesses of the selected converter arrangement for the interfacing of the PV source and the ESS. Results show that the system is rather stiff and lacks from conversion efficiency when it needs to work in a wide range of powers, mainly due to low consumer power demand during battery discharge. In this first part of the thesis, three solutions to workaround the efficiency problem are proposed: reducing the difference between the ESS and the DC-bus voltages, using isolated converters to interface the ESS, or adopting a new arrangement of the parts of the system. One of the first two proposed solutions should be adopted if the same system topology is to be kept. These two solutions address the efficiency problem when the ESS is involved in the energy conversion. The third solution is proposed as alternative to the classical systems that use a DC-bus to exchange power with the different parts of the system. The new proposed arrangement features a distributed maximum power point (DMPPT) type system that includes storage at module level. DMPPT systems are able to track the maximum power point (MPPT) of each panel separately by connecting a small power electronic converter (PEC) to each PV panel. They are specially useful when the PV installation receives uneven irradiance, i.e. shadows are present in some of the panels, increasing the annual yield of PV energy from 7 to 30% as reported in the literature. Unfortunately, this kind of systems cannot always handle high irradiance mismatches, and fail to track the maximum power point (MPP) throughout the whole installation in some cases. Including batteries at module level instead of connecting them to the DC-bus, allows for increasing the MPPT range of the system, virtually to any severity of irradiance mismatch (depending on the state of charge (SoC) of the battery pack), as well as adding storage capability to the system. The novel proposed system is able to workaround the problems of using non-isolated converters, achieving PV energy conversion efficiencies from 86% (for at least 10% of the peak power) to 90% and storage charge/discharge efficiencies ranging from 86% to 95%. Besides, it brings the opportunity to exploit the synergies of having storage at module level in systems that combine renewable energies and storage. Moreover, DMPPT systems achieve superior PV generation under partially shaded conditions when compared to classical PV arrays increasing the PV generation when compared to classical or centralized PV installations up to 45% in power as reported in the literature.In the second part of the thesis, the proposed novel DMPPT topology is presented. The whole system is fully designed from scratch, including PECs, sizing of the different parts of the modules, embedded control loops of the modules and supervisory control of the whole system. Finally, the results obtained from running the proposed system are shown and discussed, and suggestions given on how to operate and protect the system. Experimental results are obtained using a 1.5kWp PV power and 1.5kWh capacity test bench built for that purpose.The proposed system is able to generate PV energy, store the energy coming from PV generation and inject the generated and stored energy into the grid. The proposed system extends the MPPT capability of storage-less series-connected DMPPT systems. This is achieved by using the batteries not only to store energy when required, but also to compensate the power mismatch across DMPPT modules of the same string when the output voltage of the modules becomes a limit. It also presents a modular and upgradable approach to PV systems including storage. This modularity also brings fault tolerance, and an ability to continue working after failure of one or more of the DMPPT modules by partially or completely isolating the faulty module (depending on the nature of the fault). Moreover, the addition of the DC-DC converters allows for the use of different PV panels in the system, i.e. from different manufacturers or technologies.In conclusion, the presented system is very flexible, can be designed for a wide range of power levels and energy storage sizes, and presents improved reliability when compared to other series-connected DMPPT systems. / Doctorat en Sciences de l'ingénieur et technologie / info:eu-repo/semantics/nonPublished

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.