40 K Liquid Neon Energy Storage Unit

A thermal Energy Storage Unit (ESU) could be used to attenuate inherent temperature fluctuations of a cold finger, either from a cryocooler working or due to sudden income heat bursts. An ESU directly coupled to the cold source acts as a thermal buffer temporarily increasing its cooling capacity and providing a better thermal stability of the cold finger (“Power Booster mode”). The energy storage units presented here use an enthalpy reservoir based on the high latent heat of the liquid-vapour transition of neon in the temperature range 38 - 44 K to store up to 900 J, and that uses a 6 liters expansion volume at RT in order to work as a closed system. Experimental results in the power booster mode will be described: in this case, the liquid neon cell was directly coupled to the cold finger of the working cryocooler, its volume (12 cm3) allowing it to store 450 J at around 40 K. 10 W heat bursts were applied, leading to liquid evaporation, with quite reduced temperature changes. The liquid neon reservoir can also work as a temporary cold source to be used after stopping the cryocooler, allowing for a vibration-free environment. In this case the enthalpy reservoir implemented (24 cm3) was linked to the cryocooler cold finger through a gas gap heat switch for thermal coupling/decoupling of the cold finger. We will show that, by controlling the enthalpy reservoir’s pressure, 900 J can be stored at a constant temperature of 40 K as in a triple-point ESU.

Simulação de uma linha de produção com elevada variabilidade: uma abordagem Teoria das Restrições/DBR

A exigente corrida pela satisfação do cliente conduziu as organizações a uma generalizada aplicação de metodologias de melhoria contínua. Não obstante, frequentemente as expectativas não são correspondidas, levando ao insucesso destas aplicações. Para solucionar o problema vários autores defendem uma integração entre a Teoria das Restrições, Lean e Seis Sigma, denominada TLS. Ao invés de atacar, simultaneamente, todos os problemas do sistema, as equipas de melhoria devem focar-se nos elementos que impedem a organização de atingir o seu propósito. Nesta integração a Teoria das Restrições fornece o foco na restrição, ao passo que o Lean e Seis Sigma facultam as ferramentas necessárias à implementação da melhoria, através da redução de desperdícios e variação nos pontos de alavancagem do sistema. Na sua aplicação aos sistemas produtivos, o Drum-Buffer-Rope (DBR) é um mecanismo fundamental para lidar com a variabilidade e potenciar o Throughput do sistema. A presente dissertação é baseada na linha de produção da Fábrica de Transformadores Siemens do Sabugo. Recorreu-se à simulação para construir um modelo da linha de produção, identificar as restrições do sistema, verificar o impacto que a variabilidade tem no mesmo, dimensionar os seus recursos e simular as potenciais melhorias da aplicação do DBR. Para obter uma representação fiel do sistema real foi imprescindível observar o sistema, recolher dados correspondentes ao input no modelo e desenvolver uma análise criteriosa dos mesmos. Em linhas com elevada variabilidade decorrente de uma produção por encomenda, a análise do input ganha maior importância. Para tal foi proposta uma metodologia recorrendo a métodos de inferência estatística. Os resultados do estudo indicam as melhorias obtidas com a introdução do DBR na linha de produção e validam a simulação como poderosa ferramenta no apoio à tomada de decisão.

Banco BPI and the reimbursement of contingent convertible subordinated bonds (CoCos)

This case study focuses on the BPI’s recapitalization plan, its causes and the reasons for the early reimbursement of CoCos in June 2014. The need for a capital intervention and the subsequent subscription agreement with the Portuguese Government of €1 500 million Core Tier 1 instruments were the result of a temporary capital buffer for sovereign debt exposures imposed by the European Banking Authority. The capital increase, the positive earnings in 2012 and 2013, the improvements in the sovereign debt crisis, the implementation of Basel III, in addition to the public exchange offer and the conversion of deferred tax assets into tax credits are the main factors for concluding the entire recapitalization operation three years before the deadline.

Proposta de implementação de cartas de controlo na gestão de projetos pela cadeia crítica

O risco de ocorrência de desvios significativos dos custos orçamentados e de incumprimento dos prazos de execução constituem duas das principais preocupações da gestão de projetos. A derrapa-gem de prazos de projetos é um dos motivos apontados para a falta de competitividade da indústria portuguesa (Tenera, 2012). Estes atrasos, para além de falta de competitividade, podem resultar ainda, por exemplo, em sanções financeiras e perda de confiança dos clientes. Goldratt, em 1997, alertou que as limitações das técnicas clássicas de planeamento e controlo pode-riam estar na origem do não cumprimento dos prazos dos projetos, propondo a aplicação da Teoria das Restrições à gestão de projetos, a Gestão de Projetos pela Cadeia Critica (Critical Chain Project Management - CCPM). A CCPM tem os seus princípios vocacionados para a gestão do tempo e introduz mudanças signifi-cativas na forma como os projetos são geridos, preconizando uma redução nas durações programadas das atividades, para contrariar tendências comportamentais humanas de atrasar a execução das tare-fas, introduzindo ainda estrategicamente reservas temporais agregadas, que procuram proteger o pro-jeto de derrapagens temporais. Um dos principais fatores de diferenciação da CCPM é precisamente a forma de monitorizar os projetos, sendo a Gestão das Reservas (Buffer Management - BM) o prin-cipal mecanismo de gestão do tempo de execução dos mesmos. No presente trabalho foi realizada uma revisão bibliográfica dos conceitos associados à gestão de riscos em geral e em particular à gestão de tempo em projetos, através da CCPM. Estudou-se ainda, a metodologia geral de implementação das cartas de controlo, com o objetivo de se desenvolver um modelo adaptado ao controlo de reservas temporais em projetos. Assim, e de acordo com o estudo realizado, foi proposto, desenvolvido e implementado um modelo, que complementa a gestão clássica de reservas temporais da CCPM com a utilização de cartas de controlo. O modelo proposto foi testado numa empreitada de reabilitação de edifícios, na Marinha Portuguesa, com o objetivo de se avaliar a sua aplicabilidade, as suas vantagens e limitações. No presente trabalho procurou-se propor e implementar um modelo robusto de gestão de reservas na CCPM, com aplicabilidade efetiva à gestão de riscos de derrapagem de prazos de projetos, não só na indústria da construção civil como em projetos de outras áreas. Com a aplicação do modelo proposto num caso de estudo, foi possível concluir o projeto dentro do prazo contratualizado, tendo-se verificado que a implementação de cartas de controlo na BM permi-tiu antecipar a deteção de consumos excessivos das reservas temporais do projeto.

Caracterização dos padrões de mortalidade e identificação dos pontos negros de mortalidade da fauna na A21

A monitorização da mortalidade da fauna nas estradas tem vindo a receber mais atenção no decorrer dos anos sendo uma temática em que ainda existe potencial para investigação assim como de propostas para medidas de mitigação. Em Portugal, os estudos mais desenvolvidos são geralmente realizados por concessionárias como a Infraestruturas de Portugal, a Brisa entre outras. Reconhece-se a importância desta temática devido aos impactes negativos a nível ecológico e ambiental resultantes da expansão da rede viária. Um fator agravante é a fraca sensibilidade dos condutores para a presença de animais na estrada e problemas devido às caraterísticas da estrada. Existem espécies que são atraídas para a estrada para se alimentarem da vegetação envolvente ou de cadáveres de outros animais, para realizarem a termorregulação ou por simplesmente precisarem de atravessar a estrada regularmente sendo por isso mais propícias a serem atingidas por veículos. A presença de animais na estrada pode acarretar riscos de acidentes assim como perdas humanas e financeiras. Deste modo, as concessionárias implementam estudos de monitorização da mortalidade da fauna nas estradas para perceberem os locais com maior número de atropelamentos, quais as espécies mais afetadas e assim conseguirem introduzir medidas de minimização que podem ser desde vedações a passagens próprias para a fauna. O objetivo deste trabalho consistiu na caracterização dos padrões de mortalidade e identificação dos pontos negros de mortalidade da fauna na autoestrada nº 21 (A21), bem como a sua relação com o habitat envolvente. Conclui-se que os animais mais afetados são os coelhos seguindo-se as cobras e as corujas e mochos. Através do buffer do habitat envolvente e do teste estatístico de Spearman não se conseguiu provar a influência do habitat envolvente sobre a mortalidade. Finalmente, foram propostas algumas medidas de minimização para os pontos negros identificados.

Earthen plasters based on illitic soils from Barrocal region of Algarve: contributions for building performance and sustainability

Clayish earth-based mortars can be considered eco-efficient products for indoor plastering since they can contribute to improve important aspects of building performance and sustainability. Apart from being products with low embodied energy when compared to other types of mortars used for interior plastering, mainly due to the use raw clay as natural binder, earth-based plasters may give a significant contribution for health and comfort of inhabitants. Due to high hygroscopicity of clay minerals, earth-based mortars present a high adsorption and desorption capacity, particularly when compared to other type of mortars for interior plastering. This capacity allows earth-based plasters to act as a moisture buffer, balancing the relative humidity of the indoor environment and, simultaneously, acting as a passive removal material, improving air quality. Therefore, earth-based plasters may also passively promote the energy efficiency of buildings, since they may contribute to decreasing the needs of mechanical ventilation and air conditioning. This study is part of an ongoing research regarding earth-based plasters and focuses on mortars specifically formulated with soils extracted from Portuguese ‘Barrocal’ region, in Algarve sedimentary basin. This region presents high potential for interior plastering due to regional geomorphology, that promote the occurrence of illitic soils characterized by a high adsorption capacity and low expansibility. More specifically, this study aims to assess how clayish earth and sand ratio of mortars formulation can influence the physical and mechanical properties of plasters. For this assessment four mortars were formulated with different volumetric proportions of clayish earth and siliceous sand. The results from the physical and mechanical characterization confirmed the significantly low linear shrinkage of all the four mortars, as well as their extraordinary adsorption-desorption capacity. These results presented a positive correlation with mortars´ clayish earth content and are consistent with the mineralogical analysis, that confirmed illite as the prevalent clay mineral in the clayish earth used for this study. Regarding mechanical resistance, although the promising results of the adhesion test, the flexural and compressive strength results suggest that the mechanical resistance of these mortars should be slightly improved. Considering the present results the mortars mechanical resistance improvement may be achieved through the formulation of mortars with higher clayish earth content, or alternatively, through the addition of natural fibers to mortars formulation, very common in this type of mortars. Both those options will be investigated in future research.

Analysis and treatment of a nineteenth century portrait, study of Artsorb® and a proposal for a microclimate frame

The present work is divided in two parts: Part 1 is focused on the analysis and treatment of a 19th century portrait of Domingos Affonso, which belongs to the Ecomuseu Municipal do Seixal; and Part 2, which is entitled “The Microclimate Frame Project” is focused on the study of Artsorb® and on the planning of a microclimate frame for the painting. In Part 1, a study of the painting’s materials was performed using complementary analytical techniques and the painting’s condition was carefully evaluated. The painting exhibited signs of mould growth, and a more detailed investigation was made of this topic to understand if the fungal community was active and if it represented a real danger to the painting. A treatment was proposed, appropriate to the painting’s condition. A description of the treatment carried out, comprising the treatment options, is also present in this section. Within the study of the microclimate frame, in Part 2, the study of the potential corrosiveness of Artsorb® was a central subject. Artsorb® sheets are one of the most widely used materials for buffering relative humidity fluctuations in microclimate frames and its reported excellent performance is enhanced by its availability in lightweight sheets that can be easily placed inside microclimate frames. However, concerns have arisen regarding the presence of the corrosive salt lithium chloride in the composition of this buffer. Consequently, the present work also aimed to understand the potential risks of using Artsorb® and the possibility of avoiding exposure of lithium chloride to the artworks through the use of Tyvek®. Results from the preliminary tests seem to indicate that Artsorb® releases lithium chloride into air. This study also showed that a Tyvek® cover over Artsorb® reduces but does not eliminate evidence of chlorine contamination, and it significantly reduces the effectiveness of the buffering material. Considering that Artsorb® appears to be unsuitable due to the release of the corrosive salt, that Tyvek® was not efficient as a barrier for lithium chloride or as a permeable material to enable the proper functioning of Artsorb®, the buffering material proposed for the use in the microclimate frames is silica gel without indicator. Based on the choice of buffering material, as a result of this study, a microclimate frame is proposed.

(Un)suitability of the use of pH buffers in biological, biochemical and environmental studies and their interaction with metal ions - a review

The use of buffers to maintain the pH within a desired range is a very common practice in chemical, biochemical and biological studies. Among them, zwitterionic N-substituted aminosulfonic acids, usually known as Good's buffers, although widely used, can complex metals and interact with biological systems. The present work reviews, discusses and updates the metal complexation characteristics of thirty one commercially available buffers. In addition, their impact on biological systems is also presented. The influences of these buffers on the results obtained in biological, biochemical and environmental studies, with special focus on their interaction with metal ions, are highlighted and critically reviewed. Using chemical speciation simulations, based on the current knowledge of the metal-buffer stability constants, a proposal of the most adequate buffer to employ for a given metal ion is presented.

Aminobenzocoumarinylmehtyl esters as photoactive precursors for the release of butyric acid

The evaluation of the photorelease of a carboxylic acid drug, using butyric acid as a representative model, was carried out by using 7-amino-4-chloromethyl-2-oxo-2Hnaphtho[1,2-b] pyran, an aminobenzocoumarin, and its mono- and di-methylated or ethylated derivatives. This study was intended to improve the release of butyric acid from benzocoumarins by the addition of an amino group to the heterocycle by applying the knowledge of second-generation coumarinylmethyl-based photoremovable protecting groups. Photolysis studies were performed on the resultant ester cages by irradiation in a photochemical reactor at 254, 300, 350 and 419 nm, using methanol/HEPES buffer 80:20 solutions as solvent. The data obtained showed that these new fluorescent aminobenzocoumarins are superior to all the previously tested benzocoumarins with the same or different ring fusions. As well as the photolysis, the photophysics of the compounds were characterised by both steady state and time-resolved methods.

Effect of NaCl additive on solute-solvent interactions in aqueous polyethylene glycol-sodium sulfate two-phase systems

Abstract Partition behavior of eight small organic compounds and six proteins was examined in poly(ethylene glycol)-8000-sodium sulfate aqueous two-phase systems containing 0.215 M NaCl and 0.5 M osmolyte (sorbitol, sucrose, TMAO) and poly(ethylene glycol)-10000-sodium sulfate-0.215 M NaCl system, all in 0.01 M sodium phosphate buffer, pH 6.8. The differences between the solvent properties of the coexisting phases (solvent dipolarity/polarizability, hydrogen bond donor acidity, and hydrogen bond acceptor basicity) were characterized with solvatochromic dyes using the solvatochromic comparison method. Differences between the electrostatic properties of the phases were determined by analysis of partitioning of sodium salts of dinitrophenylated (DNP-) amino acids with aliphatic alkyl side-chain. The partition coefficients of all compounds examined (including proteins) were described in terms of solute-solvent interactions. The results obtained in the study show that solute-solvent interactions of nonionic organic compounds and proteins in polyethylene glycol-sodium sulfate aqueous two-phase system change in the presence of NaCl additive.

Microencapsulation of ellagic acid from pomegranate husk and karaya gum by spray drying

Objective: The aim of this study was to obtain and characterize microcapsules with Ellagic Acid (EA) from pomegranate as core material and Karaya Gum (KG) as wall material. Methods: EA was obtained from dry pomegranate peel powder via methanolysis and quantified by HPLC. Microcapsules were obtained preparing a dispersion containing KG and EA in phosphate buffer pH 8. The dispersion was processed in a spray dryer under specific conditions (inlet temperature at 150 °C, feed flow at 30% and aspirator at 100 %) for obtaining of microcapsules. Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC) and scanning electron microscopy (SEM) were used for characterization. Results: Obtained material contains 98.03±2.82 mg EA/g of pomegranate peel. FTIR showed that there were changes in the molecular structure of microcapsules referred to raw materials. SEM confirmed that particles obtained had micron-size (1-5 µm). DSC analysis showed that raw materials had glass transition temperatures of 79.58 and 83.41 °C and for microcapsules the value was67.25 °C. Conclusion: Methanolysis is a viable technique for the obtaining of EA from the peel of pomegranate. KG shows good potential for be used as wall material for EA microencapsulation.

Photoactivation of butyric acid from 6-aminobenzocoumarin cages

A new benzocoumarin bearing an amino group is proposed as a photocleavable protecting group for carboxylic acids. The novel heterocycle, 6-amino-4-chloromethyl-2-oxo-2H-naphtho[1,2-b]pyran was used in the preparation of ester conjugates of butyric acid, and of the corresponding mono- and di-methylated or ethylated derivatives. The photolability of the ester conjugates was studied by irradiation at selected wavelengths in methanol/HEPES buffer (80:20) solutions, and the release of butyric acid was followed with HPLC/UV and 1H NMR monitoring. Release of the carboxylic acid was faster for the monoalkylated derivatives (approximately within 20 min), at the longer wavelengths of irradiation (350 and 419 nm). The photophysics of the heterocyclic conjugates was also evaluated by both steady state and time-resolved methods.

Development of a thermoelectric generator for the exhaust of a vehicle

Dissertação de mestrado integrado em Engenharia Mecânica

Influence of river ecological condition on changes in physico-chemical water parameters along rivers

Dissertação de mestrado em Ecology

Análise de alterações de uso do solo no Parque Nacional da Peneda-Gerês

Dissertação de mestrado integrado em Engenharia Civil