International cooperation for development in tourism destinations

The main goal of this thesis is to propose a conceptual theoretical model of critical success factors of International Development Cooperation programmes that are based in knowledge transfer approaches in the context of tourism development. The research was structured around three main theoretical pillars: international development cooperation (IDC), tourism as a tool for development, and knowledge transfer (KT). By exploring these pillars´ main interrelations, it was possible to gather the necessary background to develop the theoretical model and apply it to a real context. It was adopted a qualitative research approach using as a case study an IDC programme in tourism - the UNWTO.Volunteers programme. The key contribution of this thesis in the theoretical realm is the bridging of fields of study that are insufficiently covered in the scientific literature. The resulting model proposal applied to a real context of an IDC programme implementation permitted to test it partially providing useful insights for future research. It is postulated that IDC programmes in these contexts constitute a process rather than an end in itself. Therefore, they should be seen as a way of changing the state of the art of the tourism system in a sustainable manner so that it potentially generates positive development changes. This study suggested that it is not possible to achieve positive results if, instead of encouraging a KT and learning environment, it is simply disseminated knowledge in a linear, static, north-south approach. The characteristics of these interventions should be reviewed in that it was found that it is very difficult to guarantee the maintenance of the development changes induced by them if it is not safeguarded the necessary conditions and accountability to implement the recommended actions. While it was perceived a great potential for development changes to be induced by some IDC programmes in tourism destinations, it was concluded that these processes are too much dependent on the local political systems and existing power relations, as well as on the level of tourism development of the destination. However, more research is needed to examine the ability to generalise the findings to other IDC programmes and different destinations of developing countries.

Perception and software architecture for mobile robotics

When developing software for autonomous mobile robots, one has to inevitably tackle some kind of perception. Moreover, when dealing with agents that possess some level of reasoning for executing their actions, there is the need to model the environment and the robot internal state in a way that it represents the scenario in which the robot operates. Inserted in the ATRI group, part of the IEETA research unit at Aveiro University, this work uses two of the projects of the group as test bed, particularly in the scenario of robotic soccer with real robots. With the main objective of developing algorithms for sensor and information fusion that could be used e ectively on these teams, several state of the art approaches were studied, implemented and adapted to each of the robot types. Within the MSL RoboCup team CAMBADA, the main focus was the perception of ball and obstacles, with the creation of models capable of providing extended information so that the reasoning of the robot can be ever more e ective. To achieve it, several methodologies were analyzed, implemented, compared and improved. Concerning the ball, an analysis of ltering methodologies for stabilization of its position and estimation of its velocity was performed. Also, with the goal keeper in mind, work has been done to provide it with information of aerial balls. As for obstacles, a new de nition of the way they are perceived by the vision and the type of information provided was created, as well as a methodology for identifying which of the obstacles are team mates. Also, a tracking algorithm was developed, which ultimately assigned each of the obstacles a unique identi er. Associated with the improvement of the obstacles perception, a new algorithm of estimating reactive obstacle avoidance was created. In the context of the SPL RoboCup team Portuguese Team, besides the inevitable adaptation of many of the algorithms already developed for sensor and information fusion and considering that it was recently created, the objective was to create a sustainable software architecture that could be the base for future modular development. The software architecture created is based on a series of di erent processes and the means of communication among them. All processes were created or adapted for the new architecture and a base set of roles and behaviors was de ned during this work to achieve a base functional framework. In terms of perception, the main focus was to de ne a projection model and camera pose extraction that could provide information in metric coordinates. The second main objective was to adapt the CAMBADA localization algorithm to work on the NAO robots, considering all the limitations it presents when comparing to the MSL team, especially in terms of computational resources. A set of support tools were developed or improved in order to support the test and development in both teams. In general, the work developed during this thesis improved the performance of the teams during play and also the e ectiveness of the developers team when in development and test phases.

Asymmetric rolling of 5182 aluminium alloy and interstitial free steel sheets

This Ph.D. research focuses on asymmetric rolling (ASR), as an alternative method for improving mechanical responses of aluminium-magnesium alloy and interstitial free (IF) steel regarding industrial requirements. Aluminium alloys are attractive materials in various industries due to their appropriate properties such as low density and corrosion resistance; however, their low formability has limited their applications. As formability of aluminium alloys can be improved through texture development, part of this dissertation is dedicated to producing the desired crystallographic texture with the ASR process. Two types of ASR (i.e. reverse and continuous asymmetric rolling) were investigated. The impact of shear deformation imposed by ASR processes on developing the desirable texture and consequently on mechanical behaviours was observed. The developed shear texture increased the normal and also planar anisotropy. Texture evolution during plastic deformation as well as induced mechanical behaviour were simulated using the “self-consistent” and Taylor models. Interstitial free (IF) steel was the second material selected in this dissertation. Since IF steel is one of the most often used materials in automotive industries it was chosen to investigate the effect of shear deformation through ASR on its properties. Two types of reverse and continuous asymmetric rolling were carried out to deform IF steel sheets. The results of optical microscopy and atomic force microscopy observations showed no significant difference between the grains’ morphology of asymmetric and conventionally rolled samples, whereas the obtained results of transmission electron microscopy indicated that fine and equiaxed dislocation cells were formed through the asymmetric rolling process. This structure is due to imposed shear deformation during the ASR process. Furthermore, the mechanical behaviour of deformed and annealed sheets was evaluated through uniaxial tensile tests. Results showed that at low thickness reductions (18%) the asymmetric rolled sample presented higher stress than that of the conventionally rolled sheet; while for higher thickness reductions (60%) the trend was reversed. The texture analyses indicated that intense rolling texture components which developed through 60% thickness reduction of conventional rolling cause a relatively higher stress; on the contrary the fine structure resulting from ASR appears to be the source of higher stress observed after pre-deformation of 18%.

Microbe-mediated recovery of salt marshes contaminated with oil hydrocarbons

Salt marshes are highly productive intertidal habitats that serve as nursery grounds for many commercially and economically important species. Because of their location and physical and biological characteristics, salt marshes are considered to be particularly vulnerable to anthropogenic inputs of oil hydrocarbons. Sediment contamination with oil is especially dangerous for salt marsh vegetation, since low molecular weight aromatic hydrocarbons can affect plants at all stages of development. However, the use of vegetation for bioremediation (phytoremediation), by removal or sequestration of contaminants, has been intensively studied. Phytoremediation is an efficient, inexpensive and environmental friendly approach for the removal of aromatic hydrocarbons, through direct incorporation by the plant and by the intervention of degrading microbial populations in the rhizosphere (microbe-assisted phytoremediation). Rhizosphere microbial communities are enriched in important catabolic genotypes for degradation of oil hydrocarbons (OH) which may have a potential for detoxification of the sediment surrounding the roots. In addition, since rhizosphere bacterial populations may also internalize into plant tissues (endophytes), rhizocompetent AH degrading populations may be important for in planta AH degradation and detoxification. The present study involved field work and microcosms experiments aiming the characterization of relevant plant-microbe interactions in oilimpacted salt marshes and the understanding of the effect of rhizosphere and endosphere bacteria in the role of salt marsh plants as potential phytoremediation agents. In the field approach, molecular tools were used to assess how plant species- and OH pollution affect sediment bacterial composition [bulk sediment and sediment surrounding the roots (rhizosphere) of Halimione portulacoides and Sarcocornia perennis subsp. perennis] in a temperate estuary (Ria de Aveiro, Portugal) chronically exposed to OH pollution. In addition, the 16S rRNA gene sequences retrieved in this study were used to generate in silico metagenomes and to evaluate the distribution of potential bacterial traits in different microhabitats. Moreover, a combination of culture-dependent and -independent approaches was used to investigate the effect of oil hydrocarbons contamination on the structure and function of endophytic bacterial communities of salt marsh plants.Root systems of H. portulacoides and S. perennis subsp. perennis appear to be able to exert a strong influence on bacterial composition and in silico metagenome analysis showed enrichment of genes involved in the process of polycyclic aromatic hydrocarbon (PAH) degradation in the rhizosphere of halophyte plants. The culturable fraction of endophytic degraders was essentially closely related to known OH-degrading Pseudomonas species and endophytic communities revealed sitespecific effects related to the level of OH contamination in the sediment. In order to determine the effects of oil contamination on plant condition and on the responses in terms of structure and function of the bacterial community associated with plant roots (rhizosphere, endosphere), a microcosms approach was set up. The salt marsh plant Halimione portulacoides was inoculated with a previous isolated Pseudomonas sp. endophytic degrader and the 2-methylnaphthalene was used as model PAH contaminant. The results showed that H. portulacoides health and growth were not affected by the contamination with the tested concentration. Moreover, the decrease of 2-methylnaphthalene at the end of experiment, can suggest that H. portulacoides can be considered as a potential plant for future uses in phytoremedition approaches of contaminated salt marsh. The acceleration of hydrocarbon degradation by inoculation of the plants with the hydrocarbon-degrading Pseudomonas sp. could not, however, be demonstrated, although the effects of inoculation on the structure of the endophytic community observed at the end of the experiment indicate that the strain may be an efficient colonizer of H. portulacoides roots. The results obtained in this work suggest that H. portulacoides tolerates moderate concentrations of 2-methylnaphthalene and can be regarded as a promising agent for phytoremedition approaches in salt marshes contaminated with oil hydrocarbons. Plant/microbe interactions may have an important role in the degradation process, as plants support a diverse endophytic bacterial community, enriched in genetic factors (genes and plasmids) for hydrocarbon degradation.

Treatment of aqueous effluents contaminated with ionic liquids

Ionic liquids are a class of solvents that, due to their unique properties, have been proposed in the past few years as alternatives to some hazardous volatile organic compounds. They are already used by industry, where it was possible to improve different processes by the incorporation of this kind of non-volatile and often liquid solvents. However, even if ionic liquids cannot contribute to air pollution, due to their negligible vapour pressures, they can be dispersed thorough aquatic streams thus contaminating the environment. Therefore, the main goals of this work are to study the mutual solubilities between water and different ionic liquids in order to infer on their environmental impact, and to propose effective methods to remove and, whenever possible, recover ionic liquids from aqueous media. The liquid-liquid phase behaviour of different ionic liquids and water was evaluated in the temperature range between (288.15 and 318.15) K. For higher melting temperature ionic liquids a narrower temperature range was studied. The gathered data allowed a deep understanding on the structural effects of the ionic liquid, namely the cation core, isomerism, symmetry, cation alkyl chain length and the anion nature through their mutual solubilities (saturation values) with water. The experimental data were also supported by the COnductor-like Screening MOdel for Real Solvents (COSMO-RS), and for some more specific systems, molecular dynamics simulations were also employed for a better comprehension of these systems at a molecular level. On the other hand, in order to remove and recover ionic liquids from aqueous solutions, two different methods were studied: one based on aqueous biphasic systems, that allowed an almost complete recovery of hydrophilic ionic liquids (those completely miscible with water at temperatures close to room temperature) by the addition of strong salting-out agents (Al2(SO4)3 or AlK(SO4)2); and the other based on the adsorption of several ionic liquids onto commercial activated carbon. The first approach, in addition to allowing the removal of ionic liquids from aqueous solutions, also makes possible to recover the ionic liquid and to recycle the remaining solution. In the adsorption process, only the removal of the ionic liquid from aqueous solutions was attempted. Nevertheless, a broad understanding of the structural effects of the ionic liquid on the adsorption process was attained, and a final improvement on the adsorption of hydrophilic ionic liquids by the addition of an inorganic salt (Na2SO4) was also achieved. Yet, the development of a recovery process that allows the reuse of the ionic liquid is still required for the development of sustainable processes.

Electromechanical properties of engineered lead free potassium sodium niobate based materials

K0.5Na0.5NbO3 (KNN), is the most promising lead free material for substituting lead zirconate titanate (PZT) which is still the market leader used for sensors and actuators. To make KNN a real competitor, it is necessary to understand and to improve its properties. This goal is pursued in the present work via different approaches aiming to study KNN intrinsic properties and then to identify appropriate strategies like doping and texturing for designing better KNN materials for an intended application. Hence, polycrystalline KNN ceramics (undoped, non-stoichiometric; NST and doped), high-quality KNN single crystals and textured KNN based ceramics were successfully synthesized and characterized in this work. Polycrystalline undoped, non-stoichiometric (NST) and Mn doped KNN ceramics were prepared by conventional ceramic processing. Structure, microstructure and electrical properties were measured. It was observed that the window for mono-phasic compositions was very narrow for both NST ceramics and Mn doped ceramics. For NST ceramics the variation of A/B ratio influenced the polarization (P-E) hysteresis loop and better piezoelectric and dielectric responses could be found for small stoichiometry deviations (A/B = 0.97). Regarding Mn doping, as compared to undoped KNN which showed leaky polarization (P-E) hysteresis loops, B-site Mn doped ceramics showed a well saturated, less-leaky hysteresis loop and a significant properties improvement. Impedance spectroscopy was used to assess the role of Mn and a relation between charge transport – defects and ferroelectric response in K0.5Na0.5NbO3 (KNN) and Mn doped KNN ceramics could be established. At room temperature the conduction in KNN which is associated with holes transport is suppressed by Mn doping. Hence Mn addition increases the resistivity of the ceramic, which proved to be very helpful for improving the saturation of the P-E loop. At high temperatures the conduction is dominated by the motion of ionized oxygen vacancies whose concentration increases with Mn doping. Single crystals of potassium sodium niobate (KNN) were grown by a modified high temperature flux method. A boron-modified flux was used to obtain the crystals at a relatively low temperature. XRD, EDS and ICP analysis proved the chemical and crystallographic quality of the crystals. The grown KNN crystals exhibit higher dielectric permittivity (29,100) at the tetragonal-to-cubic phase transition temperature, higher remnant polarization (19.4 μC/cm2) and piezoelectric coefficient (160 pC/N) when compared with the standard KNN ceramics. KNN single crystals domain structure was characterized for the first time by piezoforce response microscopy. It could be observed that <001> - oriented potassium sodium niobate (KNN) single crystals reveal a long range ordered domain pattern of parallel 180° domains with zig-zag 90° domains. From the comparison of KNN Single crystals to ceramics, It is argued that the presence in KNN single crystal (and absence in KNN ceramics) of such a long range order specific domain pattern that is its fingerprint accounts for the improved properties of single crystals. These results have broad implications for the expanded use of KNN materials, by establishing a relation between the domain patterns and the dielectric and ferroelectric response of single crystals and ceramics and by indicating ways of achieving maximised properties in KNN materials. Polarized Raman analysis of ferroelectric potassium sodium niobate (K0.5Na0.5)NbO3 (KNN) single crystals was performed. For the first time, an evidence is provided that supports the assignment of KNN single crystals structure to the monoclinic symmetry at room temperature. Intensities of A′, A″ and mixed A′+A″ phonons have been theoretically calculated and compared with the experimental data in dependence of crystal rotation, which allowed the precise determination of the Raman tensor coefficients for (non-leaking) modes in monoclinic KNN. In relation to the previous literature, this study clarifies that assigning monoclinic phase is more suitable than the orthorhombic one. In addition, this study is the basis for non-destructive assessments of domain distribution by Raman spectroscopy in KNN-based lead-free ferroelectrics with complex structures. Searching a deeper understanding of the electrical behaviour of both KNN single crystal and polycrystalline materials for the sake of designing optimized KNN materials, a comparative study at the level of charge transport and point defects was carried out by impedance spectroscopy. KNN single crystals showed lower conductivity than polycrystals from room temperature up to 200 ºC, but above this temperature polycrystalline KNN displays lower conductivity. The low temperature (T < 200 ºC) behaviour reflects the different processing conditions of both ceramics and single crystals, which account for less defects prone to charge transport in the case of single crystals. As temperature increases (T > 200 ºC) single crystals become more conductive than polycrystalline samples, in which grain boundaries act as barriers to charge transport. For even higher temperatures the conductivity difference between both is increased due to the contribution of ionic conduction in single crystals. Indeed the values of activation energy calculated to the high temperature range (T > 300 ºC) were 1.60 and 0.97 eV, confirming the charge transport due to ionic conduction and ionized oxygen vacancies in single crystals and polycrystalline KNN, respectively. It is suggested that single crystals with low defects content and improved electromechanical properties could be a better choice for room temperature applications, though at high temperatures less conductive ceramics may be the choice, depending on the targeted use. Aiming at engineering the properties of KNN polycrystals towards the performance of single crystals, the preparation and properties study of (001) – oriented (K0.5Na0.5)0.98Li0.02NbO3 (KNNL) ceramics obtained by templated grain growth (TGG) using KNN single crystals as templates was undertaken. The choice of KNN single crystals templates is related with their better properties and to their unique domain structure which were envisaged as a tool for templating better properties in KNN ceramics too. X-ray diffraction analysis revealed for the templated ceramics a monoclinic structure at room temperature and a Lotgering factor (f) of 40% which confirmed texture development. These textured ceramics exhibit a long range ordered domain pattern consisting of 90º and 180º domains, similar to the one observed in the single crystals. Enhanced dielectric (13017 at TC), ferroelectric (2Pr = 42.8 μC/cm2) and piezoelectric (d33 = 280 pC/N) properties are observed for textured KNNL ceramics as compared to the randomly oriented ones. This behaviour is suggested to be due to the long range ordered domain patterns observed in the textured ceramics. The obtained results as compared with the data previously reported on texture KNN based ceramics confirm that superior properties were found due to ordered repeated domain pattern. This study provides an useful approach towards properties improvement of KNN-based piezoelectric ceramics. Overall, the present results bring a significant contribution to the pool of knowledge on the properties of sodium potassium niobate materials: a relation between the domain patterns and di-, ferro-, and piezo-electric response of single crystals and ceramics was demonstrated and ways of engineering maximised properties in KNN materials, for example by texturing were established. This contribution is envisaged to have broad implications for the expanded use of KNN over the alternative lead-based materials.

Políticas, conceções e práticas dominantes do ensino superior em Moçambique

O presente trabalho começa por analisar a evolução dos sistemas ao longo de vários períodos históricos, bem como os conceitos e tipologias que os sustentam, no quadro da problemática e da conceptualização teórica do ensino superior. A origem da universidade na idade média, na Europa e em outras partes do mundo, fundamenta-se, principalmente, na procura do saber e nas condicionantes socioeconómicas da época. A evolução da universidade sustentada pela narrativa da modernidade, resultou em modelos diferenciados de ensino superior, que mantinham, no entanto, a razão e a epistemologia do conhecimento académico, como fatores unificadores. O modelo utilizado para traduzir a referida evolução, é proposto por Scott (1995) e configura a relação que se estabelece entre a universidade e outras formas de ensino superior. Na sequência do desenvolvimento dos sistemas, suscitados pelas relações entre os diversos atores envolvidos no ensino superior, procurou-se evidenciar a relação entre o Estado o mercado e os académicos, bem como outros atores sociopolíticos, institucionais e da sociedade civil. O quadro de análise dos mecanismos de coordenação destas envolventes, baseou-se no “Triângulo de Clark”, complementado com o modelo da “Metáfora da Flutuação”. Desde o início da década de 80 do século XX, que a missão, o modo de organização e o funcionamento das IES têm vindo a ser questionadas, como resultado das mudanças económicas de cariz neoliberal. Este cenário, propiciador de crises e de transformações, não tem impedido, porém, de manter o papel fundamental da universidade como produtora e difusora do conhecimento. No contexto da globalização e da cada vez maior influência do mercado no ensino superior, procura-se impor um modelo hegemonizado de racionalidade económica, competitividade e eficiência - o managerialismo. Não obstante alguns êxitos, esta ideologia não tem sido completamente bem-sucedida. Aliás, à tentativa da globalização de gerar uma ordem uniformista, têm sido contrapostos modelos de recontextualização que procuram refletir as realidades locais. Embora num reduzido número de países, África, registou formas de ensino superior endógenas, no período pré-colonial. Depois do espectro colonial que mantém, ainda hoje, a sua influência, os sistemas debatem-se na atualidade com diferentes dilemas, originados pelas correntes da globalização. Porém, o ensino superior em África assume um papel central no contexto do desenvolvimento dos diferentes países contribuindo, igualmente, para a construção da Nação e da sua identidade. Esta dimensão, não é impeditiva do seu envolvimento, nos desafios da sociedade e da economia do conhecimento, buscando, ao mesmo tempo, modelos e práticas equilibradoras, que proporcionem uma resposta satisfatória às necessidades sociais e económicas, nacionais e regionais. Ao enquadrar o sistema de ensino superior em Moçambique merecem destaque as etapas do processo histórico, nomeadamente o surgimento dos estudos gerais universitários como primeira forma de ensino superior mais tarde transformada em universidade, a mudança de paradigma após a independência nacional, a abertura ao setor privado e, ainda, a expansão do sistema. A discussão sobre políticas e estratégias é sustentada pela análise dos respetivos planos estratégicos bem como, pela compreensão das leis fundamentais e respetivos documentos reguladores. Este conjunto de instrumentos concorre para a reforma do sistema, que se procura implementar em Moçambique. Nesta sequência, é de salientar o debate público realizado em torno das qualificações e graus oficialmente estabelecidos, que parece constituir uma problemática ainda não completamente resolvida. Numa outra parte do trabalho, procede-se à apresentação e análise dos resultados de uma investigação sobre o ensino superior em Moçambique. Seguindo uma metodologia de análise qualitativa, foi possível estruturar a informação obtida, em diferentes dimensões e categorias. A informação foi recolhida e tratada, a partir de entrevistas efetuadas a diferentes grupos de atores, direta ou indiretamente relacionados com o ensino superior em Moçambique. Os resultados da análise conduziram à sistematização de um conjunto de linhas de força e ao traçar de conclusões, contributivas para a melhoria do quadro de referência sobre políticas, conceções e práticas do ensino superior em Moçambique.

Contratos de autonomia nas escolas públicas : um estudo de caso múltiplo em duas organizações educativas portuguesas

A autonomia para as escolas públicas do Ensino Básico e Secundário em Portugal, prevista desde 1989, tem sido sistematicamente adiada enquanto a retórica do discurso político a vai alimentando, sem contudo, proceder à sua implementação. Em 2007, a coberto do DL n.º 115-A/98, de 4 de maio, avançou-se para a assinatura de 22 contratos de autonomia (CA) com escolas e agrupamentos pelo que, este trabalho de investigação se propõe avaliar alguns dos efeitos e resultados desta medida de política educativa. Este estudo no âmbito do doutoramento em Didática e Formação – Ramo Avaliação, comporta uma primeira avaliação exploratória ao desenvolvimento dos 22 CA a que se segue uma avaliação ao desenvolvimento do CA numa escola secundária e num agrupamento de escolas, numa abordagem de caso duplo. Neste projeto de investigação, construímos um dispositivo de avaliação com o qual procuramos identificar evidências dos efeitos da autonomia contratualizada. Na fase exploratória, analisando CA e as respostas a questionário enviado aos diretores com CA, efetuamos uma aproximação global à problemática. Na segunda fase, efetuamos entrevistas a dirigentes intermédios e de topo de uma Escola Secundária e de um Agrupamento de Escolas com CA e analisamos documentos. Com o referencial construído estabelecemos categorias de análise obtendo resultados que nos permitem compreender alguns efeitos da assinatura do CA ao nível das Organizações participantes. Os resultados obtidos indicam, o cumprimento dos objetivos da contratualização gerando-se novas dinâmicas. São notórias as diferenças no cumprimento de critérios, daí que a sustentabilidade da autonomia se perspetive diferente para cada Organização face a diferentes pontos de partida. Pode afirmar-se, face aos resultados, que os efeitos da contratualização são positivos e que esta contribuiu para a melhoria da qualidade na prestação do serviço público de educação. Contudo, existem debilidades no que diz respeito à intervenção dos parceiros educativos e a mecanismos de avaliação para que deixamos sugestões de melhoria no âmbito da continuação da autonomia contratualizada. Para futura investigação deixamos também sugestão de estudo de eventuais aprofundamentos da autonomia bem como da sua sustentabilidade.

Extension of electrochemically active sites in SOFCs and SOECs

Solid oxide fuel (SOFCs) and electrolyzer (SOECs) cells have been promoted as promising technologies for the stabilization of fuel supply and usage in future green energy systems. SOFCs are devices that produce electricity by the oxidation of hydrogen or hydrocarbon fuels with high efficiency. Conversely, SOECs can offer the reverse reaction, where synthetic fuels can be generated by the input of renewable electricity. Due to this similar but inverse nature of SOFCs and SOECs, these devices have traditionally been constructed from comparable materials. Nonetheless, several limitations have hindered the entry of SOFCs and SOECs into the marketplace. One of the most debilitating is associated with chemical interreactions between cell components that can lead to poor longevities at high working temperatures and/or depleted electrochemcial performance. Normally such interreactions are countered by the introduction of thin, purely ionic conducting, buffer layers between the electrode and electrolyte interface. The objective of this thesis is to assess if possible improvements in electrode kinetics can also be obtained by modifying the transport properties of these buffer layers by the introduction of multivalent cations. The introduction of minor electronic conductivity in the surface of the electrolyte material has previously been shown to radically enhance the electrochemically active area for oxygen exchange, reducing polarization resistance losses. Hence, the current thesis aims to extend this knowledge to tailor a bi-functional buffer layer that can prevent chemical interreaction while also enhancing electrode kinetics.The thesis selects a typical scenario of an yttria stabilized zirconia electrolyte combined with a lanthanide containing oxygen electrode. Gadolinium, terbium and praseodymium doped cerium oxide materials have been investigated as potential buffer layers. The mixed ionic electronic conducting (MIEC) properties of the doped-cerium materials have been analyzed and collated. A detailed analysis is further presented of the impact of the buffer layers on the kinetics of the oxygen electrode in SOFC and SOEC devices. Special focus is made to assess for potential links between the transport properties of the buffer layer and subsequent electrode performance. The work also evaluates the electrochemical performance of different K2NiF4 structure cathodes deposited onto a peak performing Pr doped-cerium buffer layer, the influence of buffer layer thickness and the Pr content of the ceria buffer layer. It is shown that dramatic increases in electrode performance can be obtained by the introduction of MIEC buffer layers, where the best performances are shown to be offered by buffer layers of highest ambipolar conductivity. These buffer layers are also shown to continue to offer the bifunctional role to protect from unwanted chemical interactions at the electrode/electrolyte interface.

Sustentabilidade em infraestruturas desportivas : caso dos estádios de futebol

É evidente a crescente preocupação da opinião pública com os conceitos de Sustentabilidade. Nesta época de mudança, de crise económica global, é de todo premente a sua utilização efetiva, em especial na área da construção que tem sido o reflexo desta nova realidade. A Sustentabilidade na construção deve focar para além das fases de projeto e execução, a fase de exploração, gestão operacional, ou seja, em todo o ciclo de vida da construção. Verifica-se que as cidades sendo grandes aglomerados tanto de edifícios como de instalações são os focos de mudança para a Sustentabilidade. As grandes instalações, em especial os Estádios de Futebol, apresentam assim um impacte muito significativo na Sustentabilidade global. Em Portugal, para o campeonato Europeu de 2004, foram efetuados oito novos Estádios e remodelados dois, que tem vindo a verificar alguns problemas na sua gestão, em especial devido à ausência ou reduzida utilização. Estes Estádios podem ter um mecanismo para acompanhar e promover a sua Sustentabilidade. O desenvolvimento desse mecanismo deve ter como base o estudo dos diversos conceitos referidos anteriormente, como têm sido abordados, bem como os mecanismos existentes de avaliação da Sustentabilidade. A recolha de informação relativa à Sustentabilidade tanto nos Estádios Nacionais, verificando em especial a perspetiva dos respetivos gestores, como de outros Estádios Europeus que apresentam na sua Gestão conceitos de Sustentabilidade e os Estádios que estão a ser finalizados para o Campeonato do Mundo de 2014, que é definido que será um evento Sustentável. A partir desses dados desenvolvem-se um Sistema de Gestão Dinâmico para a Sustentabilidade dos Estádios. Este Sistema apresenta diversos mecanismos que devem ser utilizados para a promoção da Sustentabilidade na Gestão dos Estádios, sendo iniciado através de uma Avaliação do Desempenho Inicial da Sustentabilidade. Através de uma Simulação de Avaliação do Desempenho Inicial ao Estádio do Dragão verifica-se a aplicabilidade. Da parte da equipa de Gestão do Estádio do Dragão considera-se o conceito desenvolvido com elevada relevância e aplicabilidade para apoiar a melhoria da sua Gestão com vista à Sustentabilidade. A Sustentabilidade na Gestão de Infraestruturas Desportivas é possível em qualquer fase do seu ciclo de vida, podendo ser desde uma pequena mudança até à aplicação de um Sistema de Gestão para o efeito. As cidades devem potenciar mecanismos para a promoção da Sustentabilidade no seu território, em especial nas grandes instalações, para o impacte na redução de emissões de CO2 ser significativo.

Micro/nanoreservoirs for controlled release of active species in smart functional coatings

This work reports one possible way to develop new functional coatings used to increase the life time of metallic structures. The functionalities selected and attributed to model coatings in the frame of this work were corrosion protection, self-sensing and prevention of fouling (antifouling). The way used to confer those functionalities to coatings was based on the encapsulation of active compounds (corrosion inhibitors, pH indicators and biocides) in micro and nanocontainers followed by their incorporation into the coating matrices. To confer active corrosion protection, one corrosion inhibitor (2-mercaptobenzothiazole, MBT) was encapsulated in two different containers, firstly in silica nanocapsules (SiNC) and in polyurea microcapsules (PU-MC). The incorporation of both containers in different models coatings shows a significant improvement in the corrosion protection of aluminum alloy 2024 (AA2024). Following the same approach, SiNC and PU-MC were also used for the encapsulation of phenolphthalein (one well known pH indicator) to introduce sensing properties in polymeric coatings. SiNC and PU-MC containing phenolphthalein acted as corrosion sensor, showing a pink coloration due to the beginning of cathodic reaction, resulting in a pH increase identified by those capsules. Their sensing performance was proved in suspension and when integrated in coatings for aluminium alloy 2024 and magnesium alloy AZ31. In a similar way, the biocide activity (antifouling) was assigned to two polymeric matrices using SiNC for encapsulation of one biocide (Dichloro-2-octyl-2H-isothiazol-3-one, DCOIT) and also SiNC-MBT was tested as biocide. The antifouling activity of those two encapsulated compounds was assessed through inhibition and consequent decrease in the bioluminescence of modified E. coli. That effect was verified in suspension and when incorporated in coatings for AISI 1008 carbon steel. The developed micro and nanocontainers presented the desired performance, allowing the introduction of new functionalities to model coatings, showing potential to be used as functional additives in the next generation of multifunctional coatings.

Assessing the effectiveness of chemical treatment with nanomaterials in improving the quality of different industrial effluents

Industrial activities are the major sources of pollution in all environments. Depending on the type of industry, various levels of organic and inorganic pollutants are being continuously discharged into the environment. Although, several kinds of physical, chemical, biological or the combination of methods have been proposed and applied to minimize the impact of industrial effluents, few have proved to be totally effective in terms of removal rates of several contaminants, toxicity reduction or amelioration of physical and chemical properties. Hence, it is imperative to develop new and innovative methodologies for industrial wastewater treatment. In this context nanotechnology arises announcing the offer of new possibilities for the treatment of wastewaters mainly based on the enhanced physical and chemical proprieties of nanomaterials (NMs), which can remarkably increase their adsorption and oxidation potential. Although applications of NMs may bring benefits, their widespread use will also contribute for their introduction into the environment and concerns have been raised about the intentional use of these materials. Further, the same properties that make NMs so appealing can also be responsible for producing ecotoxicological effects. In a first stage, with the objective of selecting NMs for the treatment of organic and inorganic effluents we first assessed the potential toxicity of nanoparticles of nickel oxide (NiO) with two different sizes (100 and 10-20 nm), titanium dioxide (TiO2, < 25 nm) and iron oxide (Fe2O3, ≈ 85x425 nm). The ecotoxicological assessment was performed with a battery of assays using aquatic organisms from different trophic levels. Since TiO2 and Fe2O3 were the NMs that presented lower risks to the aquatic systems, they were selected for the second stage of this work. Thus, the two NMs pre-selected were tested for the treatment of olive mill wastewater (OMW). They were used as catalyst in photodegradation systems (TiO2/UV, Fe2O3/UV, TiO2/H2O2/UV and Fe2O3/H2O2/UV). The treatments with TiO2 or Fe2O3 combined with H2O2 were the most efficient in ameliorating some chemical properties of the effluent. Regarding the toxicity to V. fischeri the highest reduction was recorded for the H2O2/UV system, without NMs. Afterwards a sequential treatment using photocatalytic oxidation with NMs and degradation with white-rot fungi was applied to OMW. This new approach increased the reduction of chemical oxygen demand, phenolic content and ecotoxicity to V. fischeri. However, no reduction in color and aromatic compounds was achieved after 21 days of biological treatment. The photodegradation systems were also applied to treat the kraft pulp mill and mining effluents. For the organic effluent the combination NMs and H2O2 had the best performances in reduction the chemical parameters as well in terms of toxicity reduction. However, for the mine effluent the best (TiO2/UV and Fe2O3/UV) were only able to significantly remove three metals (Zn, Al and Cd). Nonetheless the treatments were able of reducing the toxicity of the effluent. As a final stage, the toxicity of solid wastes formed during wastewater treatment with NMs was assessed with Chironomus riparius larvae, a representative species of the sediment compartment. Certain solid wastes showed the potential to negatively affect C. riparius survival and growth, depending on the type of effluent treated. This work also brings new insights to the use of NMs for the treatment of industrial wastewaters. Although some potential applications have been announced, many evaluations have to be performed before the upscaling of the chemical treatments with NMs.

Participação parental : papel da web social numa comunidade educativa com surdos

A inclusão de crianças com surdez pode ser potenciada pelo recurso às ferramentas da web social, destacando-se, neste processo, a importância da construção de relações de colaboração entre toda a comunidade educativa, sendo fundamental valorizar o papel das famílias como potenciadoras de aprendizagem nos diferentes contextos para além da escola. Com o estudo apresentado na presente tese pretende-se compreender de que forma a web social é facilitadora do desenvolvimento de comunidades de partilha que potenciem a aprendizagem de novas competências nos pais, nos alunos e nos profissionais envolvidos. Através de uma metodologia de investigação-ação, ao longo de dois ciclos de investigação, foram analisadas as dinâmicas evolutivas de uma comunidade online desenvolvida numa Escola de Referência para a Educação Bilingue de Alunos Surdos e identificados fatores de mudança e melhoria. Houve evidências de melhoria das competências de literacia digital dos vários grupos de participantes e da mais valia da utilização da comunidade online para a comunicação entre pais e profissionais e entre pais e filhos, gerando um maior suporte à aprendizagem das crianças com surdez. Os resultados indicaram haver ainda a necessidade de promover uma maior formação para profissionais e famílias sobre a implementação de dinâmicas de participação parental e sobre a utilização das ferramentas da web social para a personalização de atividades para as crianças com surdez e para a maior comunicação entre casa e escola. A realização deste estudo contribuiu para identificar dinâmicas promotoras da participação parental, alertando para a necessidade de incluir as famílias como parceiros ativos, adequando e individualizando as práticas pedagógicas, onde as próprias crianças têm um papel essencial na aproximação família-escola.

Segmentação de imagens acústicas

O processamento de imagem tem entre outras aplicações a melhoria a codificação e o reconhecimento de padrões, pode se citar como exemplos de áreas onde se efectua essa aplicação: o diagnostico medico (raios X, ressonância magnética, ultra som) a detecção remota (aviões e satélites) e a geologia (análise dados sonares e sísmocos).

A formação profissional e a qualidade dos serviços prestados a idosos institucionalizados

Dissertação de Mestrado, Ciências da Educação - Educação e Formação de Adultos, Faculdade de Ciências Humanas e Sociais, Universidade do Algarve; Escola Superior de Educação, Instituto Politécnico de Beja, 2008