Preparation of La2NiO4+δ powders as a cathode material for SOFC via a PVP-assisted hydrothermal route

Uniform submicron La₂NiO_4+δ (sm-LNO) powders have been synthesized by a facile polyvinylpyrrolidone (PVP)-assisted hydrothermal route. In the presence of PVP, sm-LNO of pure phase has been obtained by calcination at the relatively low temperature of 900 °C for 8 h. Compared micron-sized LNO (m-LNO) particles obtained at 1,000 °C by hydrothermal synthesis route without PVP assisted, the sm-LNO-PVP displays regularly shaped and well-distributed particles in the range of 0.3–0.5 μm. The scanning electron microscopy (SEM) results showed that the sm-LNO sample is submicronic and that the m-LNO sample shows agglomerates with a broad size distribution. The electrochemical performance of m-LNO and sm-LNO-PVP has been investigated by electrochemical impedance spectroscopy. The polarization resistance of the sm-LNO-PVP cathode reaches a value of 0.40 Ω cm² at 750 °C, which is lower than that of m-LNO (0.62 Ω cm²). This result indicates that a fine electrode microstructure with submicron particles can help to increase the active sites, accelerate oxygen diffusion, and reduce polarization resistance. An anode-supported single cell with sm-LNO cathode has been fabricated and tested over a temperature range from 650 to 800 °C. The maximum power density of the cell has achieved 834 mW cm⁻² at 750 °C. These results therefore show that this PVP-assisted hydrothermal method is an effective approach to construct submicron-structured cathode and enhance the performance of intermediate temperature solid oxide fuel cell.

Investigation into the effect of molybdenum-site substitution on the performance of Sr2Fe1.5Mo0.5O6-δ for intermediate temperature solid oxide fuel cells

In this paper, niobium doping is evaluated as a means of enhancing the electrochemical performance of a Sr₂Fe_1.5Mo_0.5O_6-δ (SFM) perovskite structure cathode material for intermediate temperature solid oxide fuel cells (IT-SOFCs) applications. As the radius of Nb approximates that of Mo and exhibits +4/+5 mixed valences, its substitution is expected to improve material performance. A series of Sr₂Fe_1.5Mo_0.5-xNb_xO_6-δ (x = 0.05, 0.10, 0.15, 0.20) cathode materials are prepared and the phase structure, chemical compatibility, microstructure, electrical conductivity, polarization resistance and power generation are systematically characterized. Among the series of samples, Sr₂Fe_1.5Mo_0.4Nb_0.10O_6-δ (SFMNb_0.10) exhibits the highest conductivity value of 30 S cm^-1 at 550°C, and the lowest area specific resistance of 0.068 Ω cm² at 800°C. Furthermore, an anode-supported single cell incorporating a SFMNb_0.10 cathode presents a maximum power density of 1102 mW cm^-2 at 800°C. Furthermore no obvious performance degradation is observed over 15 h at 750°C with wet H₂(3% H₂O) as fuel and ambient air as the oxidant. These results demonstrate that SFMNb shows great promise as a novel cathode material for IT-SOFCs.

As TIC na criação de ambientes motivadores no processo de ensino e aprendizagem da economia no ensino secundário : um estudo sobre a implementação das TIC em sala de aula na unidade didática 11 na turma C do 11º ano da Escola Secundária Anselmo de Andrade

Relatório da prática de ensino supervisionada, Ensino da Economia e da Contabilidade, Universidade de Lisboa, 2012

Contribution of direct electron transfer mechanisms to overall electron transfer in microbial fuel cells utilising Shewanella oneidensis as biocatalyst

Objectives To investigate the contribution of direct electron transfer mechanisms to electricity production in microbial fuel cells by physically retaining Shewanella oneidensis cells close to or away from the anode electrode. Results A maximum power output of 114 ± 6 mWm−2 was obtained when cells were retained close to the anode using a dialysis membrane. This was 3.5 times more than when the cells were separated away from the anode. Without the membrane the maximum power output was 129 ± 6 mWm−2. The direct mechanisms of electron transfer contributed significantly to overall electron transfer from S. oneidensis to electrodes, a result that was corroborated by another experiment where S. oneidensis cells were entrapped in alginate gels. Conclusion S. oneidensis transfers electrons primarily by direct electron transfer as opposed to mediated electron transfer.

Optimal methodology for distribution systems reconfiguration based on OPF and solved by decomposition technique

This paper presents a new and efficient methodology for distribution network reconfiguration integrated with optimal power flow (OPF) based on a Benders decomposition approach. The objective minimizes power losses, balancing load among feeders and subject to constraints: capacity limit of branches, minimum and maximum power limits of substations or distributed generators, minimum deviation of bus voltages and radial optimal operation of networks. The Generalized Benders decomposition algorithm is applied to solve the problem. The formulation can be embedded under two stages; the first one is the Master problem and is formulated as a mixed integer non-linear programming problem. This stage determines the radial topology of the distribution network. The second stage is the Slave problem and is formulated as a non-linear programming problem. This stage is used to determine the feasibility of the Master problem solution by means of an OPF and provides information to formulate the linear Benders cuts that connect both problems. The model is programmed in GAMS. The effectiveness of the proposal is demonstrated through two examples extracted from the literature.

Fractional order control on a wind turbine benchmark

This paper is about a hierarchical structure with an event-based supervisor in a higher level and a fractional-order proportional integral (FOPI) in a lower level applied to a wind turbine. The event-based supervisor analyzes the operation conditions to determine the state of the wind turbine. This controller operate in the full load region and the main objective is to capture maximum power generation while ensuring the performance and reliability required for a wind turbine to be integrated into an electric grid. The main contribution focus on the use of fractional-order proportional integral controller which benefits from the introduction of one more tuning parameter, the integral fractional-order, taking advantage over integer order proportional integral (PI) controller. Comparisons between fractional-order pitch control and a default proportional integral pitch controller applied to a wind turbine benchmark are given and simulation results by Matlab/Simulink are shown in order to prove the effectiveness of the proposed approach.

Fuzzy, integer and fractional-order control: application on a wind turbine benchmark model

This paper presents a comparison between proportional integral control approaches for variable speed wind turbines. Integer and fractional-order controllers are designed using linearized wind turbine model whilst fuzzy controller also takes into account system nonlinearities. These controllers operate in the full load region and the main objective is to extract maximum power from the wind turbine while ensuring the performance and reliability required to be integrated into an electric grid. The main contribution focuses on the use of fractional-order proportional integral (FOPI) controller which benefits from the introduction of one more tuning parameter, the integral fractional-order, taking advantage over integer order proportional integral (PI) controller. A comparison between proposed control approaches for the variable speed wind turbines is presented using a wind turbine benchmark model in the Matlab/Simulink environment. Results show that FOPI has improved system performance when compared with classical PI and fuzzy PI controller outperforms the integer and fractional-order control due to its capability to deal with system nonlinearities and uncertainties. © 2014 IEEE.

Mode III interlaminar fracture of carbon/epoxy laminates using the edge crack torsion (ECT) test

The mode III interlaminar fracture of carbon/epoxy laminates was evaluated with the edge crack torsion (ECT) test. Three-dimensional finite element analyses were performed in order to select two specimen geometries and an experimental data reduction scheme. Test results showed considerable non-linearity before the maximum load point and a significant R-curve effect. These features prevented an accurate definition of the initiation point. Nevertheless, analyses of non-linearity zones showed two likely initiation points corresponding to GIIIc values between 850 and 1100 J/m2 for both specimen geometries. Although any of these values is realistic, the range is too broad, thus showing the limitations of the ECT test and the need for further research.

Dimensionamento de uma central de miniprodução fotovoltaica para uma exploração agrícola direcionada à indústria de laticínios

Este documento apresenta o trabalho desenvolvido no âmbito da disciplina de “Dissertação/Projeto/Estágio”, do 2º ano do Mestrado em Energias Sustentáveis. O crescente consumo energético das sociedades desenvolvidas e emergentes, associado ao consequente aumento dos custos de energia e dos danos ambientais resultantes, promove o desenvolvimento de novas formas de produção de energia, as quais têm como prioridade a sua obtenção ao menor custo possível e com reduzidos impactos ambientais. De modo a poupar os recursos naturais e reduzir a emissão com gases de efeito de estufa, é necessária a diminuição do consumo de energia produzida a partir de combustíveis fósseis. Assim, devem ser criadas alternativas para um futuro sustentável, onde as fontes renováveis de energia assumam um papel fundamental. Neste sentido, a produção de energia elétrica, através de sistemas solares fotovoltaicos, surge como uma das soluções. A presente dissertação tem como principal objetivo a realização do dimensionamento de uma central de miniprodução fotovoltaica, com ligação à rede elétrica, em uma exploração agrícola direcionada à indústria de laticínios, e o seu respetivo estudo de viabilidade económica. A exploração agrícola, que serve de objeto de estudo, está localizada na Ilha Graciosa, Açores, sendo a potência máxima a injetar na Rede Elétrica de Serviço Público, pela central de miniprodução, de 10 kW. Para o dimensionamento foi utilizado um software apropriado e reconhecido na área da produção de energia elétrica através de sistemas fotovoltaicos – o PVsyst –, compreendendo as seguintes etapas: a) definição das caraterísticas do local e do projeto; b) seleção dos módulos fotovoltaicos; c) seleção do inversor; d) definição da potência de ligação à rede elétrica da unidade de miniprodução. Posteriormente, foram estudadas diferentes hipóteses de sistemas fotovoltaicos, que se distinguem na opção de estrutura de fixação utilizada: dois sistemas fixos e dois com eixo incorporado. No estudo de viabilidade económica foram realizadas duas análises distintas a cada um dos sistemas fotovoltaicos considerados no dimensionamento, nomeadamente: uma análise em regime remuneratório bonificado e uma análise em regime remuneratório geral. Os resultados obtidos nos indicadores económicos do estudo de viabilidade económica realizado, serviram de apoio à decisão pelo sistema fotovoltaico mais favorável ao investimento. Conclui-se que o sistema fotovoltaico com inclinação adicional é a opção mais vantajosa em ambos os regimes remuneratórios analisados. Comprova-se, assim, que o sistema fotovoltaico com maior valor de produção de energia elétrica anual, que corresponde ao sistema fotovoltaico de dois eixos, não é a opção com maior rentabilidade em termos económicos, isto porque a remuneração proveniente da sua produção excedente não é suficiente para colmatar o valor do investimento mais acentuado de modo a obter indicadores económicos mais favoráveis, que os do sistema fotovoltaico com inclinação adicional. De acordo com o estudo de viabilidade económica efetuado independentemente do sistema fotovoltaico que seja adotado, é recuperado o investimento realizado, sendo a remuneração efetiva superior à que foi exigida. Assim, mesmo tendo em consideração o risco associado, comprova-se que todos os sistemas fotovoltaicos, em qualquer dos regimes remuneratórios, correspondem a investimentos rentáveis.

Autoconsumo fotovoltaico, um elemento de eficiência energética. Caso de estudo: ISEP

Mestrado em Energias Sustentáveis

L’évaluation de la compétence professionnelle des futurs maitres du Québec à intégrer les technologies de l'information et des communications (TIC) : maitrise et usages

Au Québec, la compétence professionnelle à intégrer les technologies de l’information et de la communication (TIC) est une compétence professionnelle à acquérir par les étudiants en enseignement. Cependant, son acquisition est problématique à plusieurs niveaux. Afin d’évaluer et mieux comprendre la compétence, cette thèse présente trois objectifs : 1) décrire le degré de maitrise des TIC et leurs usages dans les salles de classe 2) identifier les facteurs qui influencent l’intégration des TIC en fonction de la compétence professionnelle, et finalement 3) décrire le niveau d’atteinte des composantes de la compétence. Pour atteindre les objectifs de l’étude, une méthodologie mixte fut employée. Ce sont 2065 futurs enseignants du Québec provenant de neuf universités québécoises qui ont complété le questionnaire en plus de 34 participants à des groupes de discussion (n = 5). Cette thèse rédigée sous forme d’articles, répondra à chacun des objectifs visés. Dans le but de mieux comprendre l’utilisation actuelle des TIC par les futurs maitres, le premier article fournira un aperçu de la maitrise d’outils technologiques susceptibles d’être utilisés lors des stages. Le deuxième article visera à identifier les variables externes ainsi que les différentes composantes de la compétence qui ont une influence sur l’intégration des TIC lors des stages. Dans le troisième article, afin de comprendre où se situent les forces et les faiblesses des futurs maitres quant à la compétence professionnelle à intégrer les TIC, une description du niveau d’atteinte de chacune des composantes sera réalisée afin d’en dégager une appréciation globale. Les principaux résultats montrent que pour la moitié des répondants, seuls cinq outils sur 12 sont intégrés en stage et ce sont principalement les outils peu complexes qui sont bien maitrisés. Le logiciel de présentation Power Point, est le plus fréquemment utilisé. Les données considérées dans le premier article suggèrent aussi l’importance d’augmenter, de façon générale, la maitrise technique des futurs enseignants. Les résultats du second article ont permis de constater que la « prévision d’activités faisant appel aux TIC » est une variable prédictive majeure pour l’intégration des TIC. L’analyse des résultats suggèrent le besoin d’enseigner aux futurs maitres comment développer le réflexe d’inclure les TIC dans leurs plans de leçons. De plus, l’appropriation de la sixième composante de la compétence joue un rôle important sur la probabilité d’intégrer les TIC. Les résultats du troisième article indiquent que les composantes 2, 4, 5 et 6 de la compétence sont partiellement maitrisées. La mieux maitrisée est la première composante. Finalement, la troisième composante de la compétence s’est avérée être encore non atteinte et reste à être développer par les futurs enseignants. Cette thèse nous apprend que des efforts considérables restent encore à accomplir quant à la maitrise de la compétence professionnelle à intégrer les TIC. Ces efforts doivent être accomplis à la fois par les futurs enseignants ainsi que par les universités au niveau de la structure des cours de TIC en formation initiale des maitres.

Synthesis, Characterization and Applications of Modified TiO2 Systems

This thesis is divided in to 9 chapters and deals with the modification of TiO2 for various applications include photocatalysis, thermal reaction, photovoltaics and non-linear optics. Chapter 1 involves a brief introduction of the topic of study. An introduction to the applications of modified titania systems in various fields are discussed concisely. Scope and objectives of the present work are also discussed in this chapter. Chapter 2 explains the strategy adopted for the synthesis of metal, nonmetal co-doped TiO2 systems. Hydrothermal technique was employed for the preparation of the co-doped TiO2 system, where Ti[OCH(CH3)2]4, urea and metal nitrates were used as the sources for TiO2, N and metals respectively. In all the co-doped systems, urea to Ti[OCH(CH3)2]4 was taken in a 1:1 molar ratio and varied the concentration of metals. Five different co-doped catalytic systems and for each catalysts, three versions were prepared by varying the concentration of metals. A brief explanation of physico-chemical techniques used for the characterization of the material was also presented in this chapter. This includes X-ray Diffraction (XRD), Raman Spectroscopy, FTIR analysis, Thermo Gravimetric Analysis, Energy Dispersive X-ray Analysis (EDX), Scanning Electron Microscopy(SEM), UV-Visible Diffuse Reflectance Spectroscopy (UV-Vis DRS), Transmission Electron Microscopy (TEM), BET Surface Area Measurements and X-ray Photoelectron Spectroscopy (XPS). Chapter 3 contains the results and discussion of characterization techniques used for analyzing the prepared systems. Characterization is an inevitable part of materials research. Determination of physico-chemical properties of the prepared materials using suitable characterization techniques is very crucial to find its exact field of application. It is clear from the XRD pattern that photocatalytically active anatase phase dominates in the calcined samples with peaks at 2θ values around 25.4°, 38°, 48.1°, 55.2° and 62.7° corresponding to (101), (004), (200), (211) and (204) crystal planes (JCPDS 21-1272) respectively. But in the case of Pr-N-Ti sample, a new peak was observed at 2θ = 30.8° corresponding to the (121) plane of the polymorph brookite. There are no visible peaks corresponding to dopants, which may be due to their low concentration or it is an indication of the better dispersion of impurities in the TiO2. Crystallite size of the sample was calculated from Scherrer equation byusing full width at half maximum (FWHM) of the (101) peak of the anatase phase. Crystallite size of all the co-doped TiO2 was found to be lower than that of bare TiO2 which indicates that the doping of metal ions having higher ionic radius into the lattice of TiO2 causes some lattice distortion which suppress the growth of TiO2 nanoparticles. The structural identity of the prepared system obtained from XRD pattern is further confirmed by Raman spectra measurements. Anatase has six Raman active modes. Band gap of the co-doped system was calculated using Kubelka-Munk equation and that was found to be lower than pure TiO2. Stability of the prepared systems was understood from thermo gravimetric analysis. FT-IR was performed to understand the functional groups as well as to study the surface changes occurred during modification. EDX was used to determine the impurities present in the system. The EDX spectra of all the co-doped samples show signals directly related to the dopants. Spectra of all the co-doped systems contain O and Ti as the main components with low concentrations of doped elements. Morphologies of the prepared systems were obtained from SEM and TEM analysis. Average particle size of the systems was drawn from histogram data. Electronic structures of the samples were identified perfectly from XPS measurements. Chapter 4 describes the photocatalytic degradation of herbicides Atrazine and Metolachlor using metal, non-metal co-doped titania systems. The percentage of degradation was analyzed by HPLC technique. Parameters such as effect of different catalysts, effect of time, effect of catalysts amount and reusability studies were discussed. Chapter 5 deals with the photo-oxidation of some anthracene derivatives by co-doped catalytic systems. These anthracene derivatives come underthe category of polycyclic aromatic hydrocarbons (PAH). Due to the presence of stable benzene rings, most of the PAH show strong inhibition towards biological degradation and the common methods employed for their removal. According to environmental protection agency, most of the PAH are highly toxic in nature. TiO2 photochemistry has been extensively investigated as a method for the catalytic conversion of such organic compounds, highlighting the potential of thereof in the green chemistry. There are actually two methods for the removal of pollutants from the ecosystem. Complete mineralization is the one way to remove pollutants. Conversion of toxic compounds to another compound having toxicity less than the initial starting compound is the second way. Here in this chapter, we are concentrating on the second aspect. The catalysts used were Gd(1wt%)-N-Ti, Pd(1wt%)-N-Ti and Ag(1wt%)-N-Ti. Here we were very successfully converted all the PAH to anthraquinone, a compound having diverse applications in industrial as well as medical fields. Substitution of 10th position of desired PAH by phenyl ring reduces the feasibility of photo reaction and produced 9-hydroxy 9-phenyl anthrone (9H9PA) as an intermediate species. The products were separated and purified by column chromatography using 70:30 hexane/DCM mixtures as the mobile phase and the resultant products were characterized thoroughly by 1H NMR, IR spectroscopy and GCMS analysis. Chapter 6 elucidates the heterogeneous Suzuki coupling reaction by Cu/Pd bimetallic supported on TiO2. Sol-Gel followed by impregnation method was adopted for the synthesis of Cu/Pd-TiO2. The prepared system was characterized by XRD, TG-DTG, SEM, EDX, BET Surface area and XPS. The product was separated and purified by column chromatography using hexane as the mobile phase. Maximum isolated yield of biphenyl of around72% was obtained in DMF using Cu(2wt%)-Pd(4wt%)-Ti as the catalyst. In this reaction, effective solvent, base and catalyst were found to be DMF, K2CO3 and Cu(2wt%)-Pd(4wt%)-Ti respectively. Chapter 7 gives an idea about the photovoltaic (PV) applications of TiO2 based thin films. Due to energy crisis, the whole world is looking for a new sustainable energy source. Harnessing solar energy is one of the most promising ways to tackle this issue. The present dominant photovoltaic (PV) technologies are based on inorganic materials. But the high material, low power conversion efficiency and manufacturing cost limits its popularization. A lot of research has been conducted towards the development of low-cost PV technologies, of which organic photovoltaic (OPV) devices are one of the promising. Here two TiO2 thin films having different thickness were prepared by spin coating technique. The prepared films were characterized by XRD, AFM and conductivity measurements. The thickness of the films was measured by Stylus Profiler. This chapter mainly concentrated on the fabrication of an inverted hetero junction solar cell using conducting polymer MEH-PPV as photo active layer. Here TiO2 was used as the electron transport layer. Thin films of MEH-PPV were also prepared using spin coating technique. Two fullerene derivatives such as PCBM and ICBA were introduced into the device in order to improve the power conversion efficiency. Effective charge transfer between the conducting polymer and ICBA were understood from fluorescence quenching studies. The fabricated Inverted hetero junction exhibited maximum power conversion efficiency of 0.22% with ICBA as the acceptor molecule. Chapter 8 narrates the third order order nonlinear optical properties of bare and noble metal modified TiO2 thin films. Thin films were fabricatedby spray pyrolysis technique. Sol-Gel derived Ti[OCH(CH3)2]4 in CH3CH2OH/CH3COOH was used as the precursor for TiO2. The precursors used for Au, Ag and Pd were the aqueous solutions of HAuCl4, AgNO3 and Pd(NO3)2 respectively. The prepared films were characterized by XRD, SEM and EDX. The nonlinear optical properties of the prepared materials were investigated by Z-Scan technique comprising of Nd-YAG laser (532 nm,7 ns and10 Hz). The non-linear coefficients were obtained by fitting the experimental Z-Scan plot with the theoretical plots. Nonlinear absorption is a phenomenon defined as a nonlinear change (increase or decrease) in absorption with increasing of intensity. This can be mainly divided into two types: saturable absorption (SA) and reverse saturable absorption (RSA). Depending on the pump intensity and on the absorption cross- section at the excitation wavelength, most molecules show non- linear absorption. With increasing intensity, if the excited states show saturation owing to their long lifetimes, the transmission will show SA characteristics. Here absorption decreases with increase of intensity. If, however, the excited state has strong absorption compared with that of the ground state, the transmission will show RSA characteristics. Here in our work most of the materials show SA behavior and some materials exhibited RSA behavior. Both these properties purely depend on the nature of the materials and alignment of energy states within them. Both these SA and RSA have got immense applications in electronic devices. The important results obtained from various studies are presented in chapter 9.

Investigación, intercambio y comparación de los entornos de Bolonia y Sanlúcar de Barrameda.

Se presenta memoria final de proyecto educativo que pretende mediante la participación activa del alumnado, conocer el entorno paisajístico de Bolinia y Sanlúcar de Barrameda. Se realiza en el CPR Campiña de Tarifa, Cádiz. Los objetivos son: el principal se ha basado en en la percepción que la enseñanza debe ser una actividad innovadora e interdisciplinar y en la convicción de que el conocimiento nunca queda cerrado; integración del alumnado con necesidades educativas especiales en la normalización escolar, en todos sus sentidos y actividades; como objetivos secundarios se establecen: la necesidad de conocer nuestro medio por procedimientos investigativos directos; el poder aplicar esta metodología con nuestro alumnado, posibilitar el aprendizaje y la diversión, potenciar el placer por el aprendizaje y tener como herramienta poderosa en el aprendizaje la motivación. El proceso: realización de una reunión de programación y distribución del trabajo, salidas al entorno de manera conjunta, recogida constante de materiales bibliográficos y aportaciones teóricas, elaboración conjunta de un dvd. El material resultante ha sido, la realización de un dvd en el que se incluyen las conclusiones e imágenes mediante montajes en Power Point, con el fin de visualizar las fotos y las conclusiones, así como el catálogo de imágenes de plantas costeras sobre las que hemos trabajado.

Convivencia y mejora de las relaciones en el aula.

Materiales didácticos en Power-Point secuenciando actividades para trabajar con el alumnado respecto a comportamientos asertivos- comportamientos no asertivos,educando en la convivencia y mejora de las relaciones personales, previniendo la violencia y reduciendo el absentismo escolar utilizando el material informático.

II=segundo curso sobre el uso racional del medicamento.

El cuaderno se compone de 220 diapositivas impresas que corresponden a la presentación de los contenidos del curso en Power Point