Monte Carlo studies of phase transitions and adsorption : application to n-6 Lennard-Jones, C60 and zeolite systems

The solid-fluid transition properties of the n - 6 Lennard-Jones system are studied by means of extensive free energy calculations. Different values of the parameter n which regulates the steepness of the short-range repulsive interaction are investigated. Furthermore, the free energies of the n < 12 systems are calculated using the n = 12 system as a reference. The method relies on a generalization of the multiple histogram method that combines independent canonical ensemble simulations performed with different Hamiltonians and computes the free energy difference between them. The phase behavior of the fullerene C60 solid is studied by performing NPT simulations using atomistic models which treat each carbon in the molecule as a separate interaction site with additional bond charges. In particular, the transition from an orientationally frozen phase at low temperatures to one where the molecules are freely rotating at higher temperatures is studied as a function of applied pressure. The adsorption of molecular hydrogen in the zeolite NaA is investigated by means of grand-canonical Monte Carlo, in a wide range of temperatures and imposed gas pressures, and results are compared with available experimental data. A potential model is used that comprises three main interactions: van der Waals, Coulomb and induced polarization by the permanent electric field in the zeolite.

Wind energy resource modelling in Portugal and its future large-scale alteration due to anthropogenic induced climate changes

The high dependence of Portugal from foreign energy sources (mainly fossil fuels), together with the international commitments assumed by Portugal and the national strategy in terms of energy policy, as well as resources sustainability and climate change issues, inevitably force Portugal to invest in its energetic self-sufficiency. The 20/20/20 Strategy defined by the European Union defines that in 2020 60% of the total electricity consumption must come from renewable energy sources. Wind energy is currently a major source of electricity generation in Portugal, producing about 23% of the national total electricity consumption in 2013. The National Energy Strategy 2020 (ENE2020), which aims to ensure the national compliance of the European Strategy 20/20/20, states that about half of this 60% target will be provided by wind energy. This work aims to implement and optimise a numerical weather prediction model in the simulation and modelling of the wind energy resource in Portugal, both in offshore and onshore areas. The numerical model optimisation consisted in the determination of which initial and boundary conditions and planetary boundary layer physical parameterizations options provide wind power flux (or energy density), wind speed and direction simulations closest to in situ measured wind data. Specifically for offshore areas, it is also intended to evaluate if the numerical model, once optimised, is able to produce power flux, wind speed and direction simulations more consistent with in situ measured data than wind measurements collected by satellites. This work also aims to study and analyse possible impacts that anthropogenic climate changes may have on the future wind energetic resource in Europe. The results show that the ECMWF reanalysis ERA-Interim are those that, among all the forcing databases currently available to drive numerical weather prediction models, allow wind power flux, wind speed and direction simulations more consistent with in situ wind measurements. It was also found that the Pleim-Xiu and ACM2 planetary boundary layer parameterizations are the ones that showed the best performance in terms of wind power flux, wind speed and direction simulations. This model optimisation allowed a significant reduction of the wind power flux, wind speed and direction simulations errors and, specifically for offshore areas, wind power flux, wind speed and direction simulations more consistent with in situ wind measurements than data obtained from satellites, which is a very valuable and interesting achievement. This work also revealed that future anthropogenic climate changes can negatively impact future European wind energy resource, due to tendencies towards a reduction in future wind speeds especially by the end of the current century and under stronger radiative forcing conditions.

Barrier properties of poly(lactic acid) based films

In recent years, the search for a environmentally friendly products has increased. One of the major challenges has been the demand for biodegradable materials that can replace plastic. If a few decades ago, plastic replaced, for example, the ivory in billiard balls, and in other products, saving the lives of thousands elephants, nowadays a replacement for that plastic is being searched, to prevent the change of the environmental conditions, essential to life in harmonly with the fauna and flora that the human specie has, in recent years, destroyed. Plastic is a petroleum derivate, whose price has been growing exponentially, mainly due to the fact of beind a cheap material and also to enable the production of products that are essential to modern life. Therefore, the petrochemical era is going to come to an end and a new environmentally sustainable era, based on biodegradable materials from renewable sources, will follow. The change to green routes only will be possible with the support of the major companies, and the implementation of drastic governmental law. Poly(lactic acid), PLA, is produced from the lactose present in the corn or sugarcane and has been intensively studied in recent years because if some limitants properties required its extrusion are overcome, it has the potential to replace the traditional polymers. PLA have high brittleness, low toughness and low tensile elongation. In this work, natural antioxidant (alpha-tocopherol) and synthetics antioxidants (BHT ant TBHQ) were added to the PLA with the aim not only to improve their flexibility, but also to create an active packaging to extend the shelf life of the foods and improve the organoleptic properties by preventing food losses. The impact of the addition of antioxidants into the PLA films, in its mechanical, thermal and barrier properties were studied by FTIR, DSC, SEM, AFM, DMA, TGA, QCM and time-lag techniques.

Dietary biodiesel-derived crude glycerol in gilthead seabream juveniles (Sparus aurata): effects on growth performance and metabolism

In the European Union the turn towards renewable energy sources has increased the production of biodiesel from rapeseed oil, leaving glycerol (also known as glycerin) as a valuable by-product. For every litre of biodiesel produced, approximately 79 g of crude glycerol are generated. As the biodiesel production grows, the quantity of crude glycerol generated will be considerable and its utilization will become an urgent topic. One possibility is the use of crude glycerol on animal feeds. Glycerol has been evaluated as a dietary energy source for several farm animals, including fish. A study was undertaken to assess the effect of dietary biodiesel-derived glycerol (from rapeseed oil) on the overall growth performance, digestive capacity and metabolic nutrient utilization in juvenile gilthead seabream fed a low fishmeal level diet. Two practical diets were formulated to be isonitrogenous (crude protein, 45.4% DM), isolipidic (18.5% DM) and isoenergetic (gross energy, 21.3 kJ/g DM). The control diet (CTRL) was formulated with intermediate levels of marine-derived proteins (19%). In the same basal formulation, 5% glycerol (GLY) was incorporated at the expenses of wheat. Each dietary treatment was tested in triplicate tanks over 63 days, with 20 gilthead seabream (Sparus aurata), with a mean initial body weight (IBW) of 27.9  0.12 g. At the end of the trial, fish fed the CTRL diet reached a final body weight of 84.3  2.2 g (more than 3-fold increase of initial body weight). Fish fed the GLY diet showed a significantly higher (P<0.05) growth, expressed in terms of final body weight and specific growth rate. Voluntary feed intake was similar between the two treatments, but both feed efficiency and protein efficiency ratio were significantly improved (P<0.05) in fish fed the GLY diet. Dietary glycerol had no effect (P>0.05) on the apparent digestibility of protein. In comparison to the control treatment, dietary glycerol significantly improved (P<0.05) protein and fat retention. Activities of digestive enzymes were significantly affected by the various dietary treatments. Fish fed the GLY diet showed an enhanced activity of alkaline phosphatase (ALP) and pepsin, while activities of lipase and leucine-alanine peptidase (LAP) were little affected by dietary glycerol. Fish show the ability to use crude glycerol as a dietary energy substrate.

Estudo de soluções energéticas para a cabine de pintura automóvel

O processo de pintura de automóveis passa por várias fases que requerem grandes quantidades de energia térmica, uma vez que é necessário garantir uma temperatura mínima de aproximadamente 20ºC, na fase de aplicação, e de 60ºC, na fase de secagem. Pretende-se realizar uma auditoria energética a uma cabine de pintura automóvel, tendo em vista a optimização de todo o processo, desde a fase de aplicação até à fase de secagem. O objectivo principal deste trabalho consiste em encontrar alternativas energéticas ao usual gás propano que sejam economicamente viáveis. Assim, foram estudadas como alternativas as seguintes soluções: Opção 1 – Sistema solar térmico; Opção 2 - Sistema recuperação de calor (Extracção e Insuflação); Opção 3 – Sistema solar térmica mais recuperação de calor; Opção 4 – Sistema de recuperação de calor do compressor; Apresentadas a respectivas opções, realizaram-se então os estudos de viabilidade económica para cada solução.

O impacte da política comum de pescas na gestão de um recurso natural a nível regional: a actividade pesqueira no Algarve

Dissertação de mestrado, Ciências Económicas e Empresariais, Unidade de Ciências Económicas e Empresariais, Universidade do Algarve. Instituto Superior de Economia e Gestão, Universidade Técnica de Lisboa, 1995

Gestão otimizada de cargas em microgrids

Dissertação de Mestrado, Engenharia Elétrica e Eletrónica, Instituto Superior de Engenharia, Universidade do Algarve, 2015

Radiological protection and nuclear engineering studies in multi-MW target systems

Tese de doutoramento, Física, Universidade de Lisboa, Faculdade de Ciências, 2014

New synthetic methodologies from biorenewable resources

Tese de doutoramento, Farmácia (Química Farmacêutica e Terapêutica), Universidade de Lisboa, Faculdade de Farmácia, 2014

High temperature vapour-liquid equilibria of water-polyalcohol mixtures

Tese de doutoramento, Química (Química Tecnológica), Universidade de Lisboa, Faculdade de Ciências, 2014

O Mercado do carbono: novas oportunidades com base no desenvolvimento

Dissertação para a obtenção do Grau de Mestre em Contabilidade e Finanças

Computational analysis of quinoxalines N,N-Dioxide and ITS Derivates

A quinoxalina e seus derivativos são uma importante classe de compostos heterocíclicos, onde os elementos N, S e O substituem átomos de carbono no anel. A fórmula molecular da quinoxalina é C8H6N2, formada por dois anéis aromáticos, benzeno e pirazina. É rara em estado natural, mas a sua síntese é de fácil execução. Modificações na estrutura da quinoxalina proporcionam uma grande variedade de compostos e actividades, tais como actividades antimicrobiana, antiparasitária, antidiabética, antiproliferativa, anti-inflamatória, anticancerígena, antiglaucoma, antidepressiva apresentando antagonismo do receptor AMPA. Estes compostos também são importantes no campo industrial devido, por exemplo, ao seu poder na inibição da corrosão do metal. A química computacional, ramo natural da química teórica é um método bem desenvolvido, utilizado para representar estruturas moleculares, simulando o seu comportamento com as equações da física quântica e clássica. Existe no mercado uma grande variedade de ferramentas informaticas utilizadas na química computacional, que permitem o cálculo de energias, geometrias, frequências vibracionais, estados de transição, vias de reação, estados excitados e uma variedade de propriedades baseadas em várias funções de onda não correlacionadas e correlacionadas. Nesta medida, a sua aplicação ao estudo das quinoxalinas é importante para a determinação das suas características químicas, permitindo uma análise mais completa, em menos tempo, e com menos custos.

A engenharia Civil e a produção industrial de energia eólica

Dissertação para obtenção do grau de Engenharia Civil na Área de Especialização de Edificações

Determinantes do comportamento de compra verde em Portugal

Apesar do avanço tecnológico, uma grande maioria dos consumidores contínua a utilizar excessivamente os recursos naturais não renováveis do planeta, resultado de um consumo exagerado e inconsciente. Atualmente, os consumidores possuem mais informação sobre as questões ambientais e, alguns, refletem esse conhecimento nas suas decisões de compra. Com a crescente preocupação e atenção, quer por parte da população, quer por parte das organizações governamentais e empresas, para com o meio ambiente e a sua preservação, as questões ecológicas têm cada vez mais importância nas estratégias das empresas. Na presente investigação é analisado o comportamento de compra verde com a utilização das variáveis sociodemográficas (género, idade, número de filhos, rendimento e habilitações literárias) e psicográficas (conhecimento ecológico, coletivismo e individualismo), indo ao encontro do objetivo geral de investigação que visa compreender qual a relevância destas variáveis face ao comportamento de compra verde. O estudo desenvolvido é operacionalizado por via de um método quantitativo, através da utilização de um inquérito por questionário com base nas escalas do conhecimento ecológico (Laroche et al., 2001), coletivismo e individualismo (Singelis et al., 1995 e Triandis & Gelfand (1998)) e do comportamento de compra verde (Jain & Kaur, 2004). O questionário foi aplicado a uma amostra de conveniência (N=350), dando origem a uma análise quantitativa face aos dados obtidos. Os resultados indicam que as variáveis psicográficas exercem maior influência no comportamento de compra verde do que as variáveis sociodemográficas. As variáveis psicográficas, conhecimento ecológico e coletivismo, têm uma grande influência no comportamento de compra verde, ao contrário do individualismo. Por seu lado, do conjunto das variáveis sociodemográficas, apenas a idade e o número de filhos influenciam significativamente o comportamento de compra verde.

Climatização passiva em edifício de serviços

Dissertação Final de Mestrado para obtenção do grau de Mestre em Engenharia Civil no Ramo de Edificações