Construção e caracterização de fugas de referência de gases frigorigéneos

Dissertação para obtenção do Grau de Mestre em Engenharia Física

Electrochemical and quantum chemical investigations of the insecticide fipronil.

This work describes an electrochemical and quantum chemical investigation of the fipronil insecticide. Cyclic voltammetry (CV) and square wave voltammetry (SWV) experiments were performed over a graphite-polyurethane (GPU) composite electrode. The fipronil molecule presents an one?electron irreversible oxidation reaction. Profiting the SWV signal a square wave stripping voltammetry (SWSV) procedure to determine the fipronil molecule in a 0.10 mol L-1 Britton-Robinson buffer solution, pH 8.0 was developed with accumulation potential and time of 0.50 V and 120 s, respectively. The limits of detection and quantification were 0.80 and 2.67 ?g L-1, respectively. Recovery tests were performed in three natural waters samples with values ranging from 99.67 to 101.37%. Quantum chemical studies showed that the nitrogen atom of the pyrazole group is the most probable oxidation site of the fipronil molecule.

Método para deteção de 2,4,6-TCA por contaminação de gases halogenados de uma superfície emissora de iões positivos

Dissertação para obtenção do Grau de Mestre em Engenharia Física

Avaliação económica de um projecto de investimento num sistema de retorno de gases num Terminal Portuário

Dissertação para obtenção do grau de Mestre em Engenharia e Gestão Industrial

Reactive electron scattering from biomolecules and technologically relevant molecules

The role of a set of gases relevant within the context of biomolecules and technologically relevant molecules under the interaction of low-energy electrons was studied in an effort to contribute to the understanding of the underlying processes yielding negative ion formation. The results are relevant within the context of damage to living material exposed to energetic radiation, to the role of dopants in the ion-molecule chemistry processes, to Electron Beam Induced Deposition (EBID) and Ion Beam Induced Deposition (IBID) techniques. The research described in this thesis addresses dissociative electron attachment (DEA) and electron transfer studies involving experimental setups from the University of Innsbruck, Austria and Universidade Nova de Lisboa, Portugal, respectively. This thesis presents DEA studies, obtained by a double focusing mass spectrometer, of dimethyl disulphide (C2H6S2), two isomers, enflurane and isoflurane (C3F5Cl5) and two chlorinated ethanes, pentachloroethane (C2HCl5) and hexachloroethane (C2Cl6), along with quantum chemical calculations providing information on the molecular orbitals as well as thermochemical thresholds of anion formation for enflurane, isoflurane, pentachloroethane and hexachloroethane. The experiments represent the most accurate DEA studies to these molecules, with significant differences from previous work reported in the literature. As far as electron transfer studies are concerned, negative ion formation in collisions of neutral potassium atoms with N1 and N3 methylated pyrimidine molecules were obtained by time-of-flight mass spectrometry (TOF). The results obtained allowed to propose concerted mechanisms for site and bond selective excision of bonds.

Solution processed quantum dot photodetectors

To find sustainable solutions for the production of energy, it is necessary to create photovoltaic technologies that make every photon count. To pursue this necessity, in the present work photodetectors of zinc oxide embedded with nano-structured materials, that significantly raise the conversion of solar energy to electric energy, were developed. The novelty of this work is on the development of processing methodologies in which all steps are in solution: quantum dots synthesis, passivation of their surface and sol-gel deposition. The quantum dot solutions with different capping agents were characterized by UVvisible absorption spectroscopy, spectrofluorimetry, dynamic light scattering and transmission electron microscopy. The obtained quantum dots have dimensions between 2 and 3nm. These particles were suspended in zinc acetate solutions and used to produce doped zinc oxide films with embedded quantum dots, whose electric response was tested. The produced nano-structured zinc oxide materials have a superior performance than the bulk, in terms of the produced photo-current. This indicates that an intermediate band material should have been produced that acts as a photovoltaic medium for solar cells. The results are currently being compiled in a scientific article, that is being prepared for possible submission to Energy and Environmental Science or Nanoscale journals.

Correlação entre macro e nanopartículas emitidas em fumos de soldadura MAG de aços inoxidáveis com diferentes gases de protecção

A soldadura é o processo mais utilizado na ligação de materiais. Os efeitos na saúde dos trabalhadores expostos a fumos de soldadura estão normalmente associados a danos pulmonares agudos e crónicos, mas também a outras condições médicas e doenças. O principal objectivo deste estudo foi correlacionar as emissões de macro e nanopartículas libertadas durante o processo de soldadura MIG/MAG de aços inoxidáveis com diferentes gases de protecção. Usando diferentes misturas gasosas utilizadas industrialmente com diferentes entregas térmicas, determinaram-se taxas de formação de fumos e áreas superficiais de nanopartículas com capaciade de deposição alveolar por volume pulmonar. Verificou-se como os diferentes modos de transferências e tipos de protecção gasosa, em particular, a percentagem de elementos activos na composição química do gás, afectam a quantidade de fumos gerados bem como a existência de nanopartículas com uma elevada capacidade de deposição alveolar. O modo de transferência por spray apresenta sempre valores superiores de área de superfície das partículas por volume pulmonar, ao contrário da taxa de formação de fumos. A mistura 82% Ar + 18% gera maiores emissões de nanopartículas bem como de fumos formados. A extracção na fonte e a regeneração do ar ambiente são a solução mais segura e eficiente de controlo das emissões de macro e nanopartículas em soldadura.

Incêndios na Amazônia Brasileira: estimativa da emissão de gases do efeito estufa pela queima de diferentes ecossistemas de Roraima na passagem do evento “El Nino” (1997/98)

Foi estimada a área queimada, a biomassa vegetal total acima e abaixo do solo, a formação de carvão, a eficiência de queimada e a concentração de carbono de diferentes paisagens naturais e agroecossistemas que foram atingidos pelos incêndios ocorridos durante a passagem do “El Niño” em 1997/98 no Estado de Roraima, extremo norte da Amazônia Brasileira. O objetivo foi o de calcular a emissão bruta de gases do efeito estufa liberados por combustão das diversas classes de biomassa que compõem cada tipo fitofisionômico atingido. A área total efetivamente queimada foi estimada entre 38.144-40.678 km2, sendo 11.394-13.928 km2 de florestas primárias (intactas, em pé) e, o restante, de savanas (22.583 km2), campinas / campinaranas (1.388 km2) e ambientes florestais já transformados como pastagens, área agrícolas e florestas secundárias (2.780 km2). O total de carbono afetado pelos incêndios foi de 42,558 milhões de toneladas, sendo que 19,73 milhões foram liberados por combustão, 22,33 milhões seguiram para a classe de decomposição e 0,52 milhões foram depositados nos sistemas na forma de carvão (estoque de longo prazo). A emissão bruta de gases do efeito estufa, em milhões de toneladas do gás, considerando apenas o emitido por combustão foi de 17,3 de CO2, 0,21-0,35 de CH4, 1,99-3,68 de CO, 0,001-0,003 de N,O, 0,06-0,09 de NOx e 0,25 de hidrocarbonetos não-metânicos (HCNM). O total de carbono equivalente a CO2 emitido por combustão, quando considerado o potencial de aquecimento global de cada gás em um horizonte de tempo de 100 anos utilizado pelo IPCC, foi de 6,1-7,0 milhões de toneladas.

Effect of polymeric matrix on morphology and photoelectric properties of polymer-quantum dots nanocomposites

Recently, CdTe semiconductor quantum dots (QDs) have attracted great interest due to their unique properties [1]. Their dispersion into polymeric matrices would be very for several optoelectronics applications. Despite its importance, there has been relatively little work done on charge transport in the QD polymeric films [2], which is mainly affected by their structural and morphological properties. In the present work, polymer-quantum dot nanocomposites films based on optically transparent polymers in the visible spectral range and CdTe QDs with controlled particle size and emission wavelength, were prepared via solvent casting. Photoluminescent (PL) measurements indicate different emission intensity of the nanocomposites. A blue shift of the emission peak compared to that of QDs in solution occurred, which is attributed to the QDs environment changes. The morphological and structural properties of the CdTe nanocomposites were evaluated. Since better QDs dispersion was achieved, PMMA seemed to be the most promising matrix. Electrical properties measurements indicate an ohmic behavior.

Design of assemblies based on polymer-coated quantum dots and organic dye

During last years, photophysical properties of complexes of semiconductor quantum dots (QDs) with organic dyes have attracted increasing interest. The development of different assemblies based on QDs and organic dyes allows to increase the range of QDs applications, which include imaging, biological sensing and electronic devices.1 Some studies demonstrate energy transfer between QDs and organic dye in assemblies.2 However, for electronic devices purposes, a polymeric matrix is required to enhance QDs photostability. Thus, in order to attach the QDs to the polymer surface it is necessary to chemically modify the polymer to induce electronic charges and stabilize the QDs in the polymer. The present work aims to investigate the design of assemblies based on polymer-coated QDs and an integrated acceptor organic dye. Polymethylmethacrylate (PMMA) and polycarbonate (PC) were used as polymeric matrices, and nile red as acceptor. Additionally, a PMMA matrix modified with 2-mercaptoethylamine is used to improve the attachment between both the donor (QDs) and the acceptor (nile red), as well as to induce a covalent bond between the modified PMMA and the QDs. An enhancement of the energy transfer efficiency by using the modified PMMA is expected and the resulting assembly can be applied for energy harvesting.

Strain induced edge magnetism at zigzag edge of a graphene quantum dot

We study the temperature dependent magnetic susceptibility of a strained graphene quantum dot by using the determinant quantum Monte Carlo method. Within the Hubbard model on a honeycomb lattice, our unbiased numerical results show that a relative small interaction $U$ may lead to a edge ferromagnetic like behavior in the strained graphene quantum dot, and a possible room temperature transition is suggested. Around half filling, the ferromagnetic fluctuations at the zigzag edge is strengthened both markedly by the on-site Coulomb interaction and the strain, especially in low temperature region. The resultant strongly enhanced ferromagnetic like behavior may be important for the development of many applications.

Quantum field theory approach to the optical conductivity of strained and deformed graphene

The computation of the optical conductivity of strained and deformed graphene is discussed within the framework of quantum field theory in curved spaces. The analytical solutions of the Dirac equation in an arbitrary static background geometry for one dimensional periodic deformations are computed, together with the corresponding Dirac propagator. Analytical expressions are given for the optical conductivity of strained and deformed graphene associated with both intra and interbrand transitions. The special case of small deformations is discussed and the result compared to the prediction of the tight-binding model.

Otimização de custos, consumos energéticos e emissões de gases com efeito de estufa na reabilitação de edifícios residenciais de baixa densidade

Dissertação de mestrado integrado em Engenharia Civil

Influence of ischemic preconditioning in myocardial protection in patients undergoing myocardial revascularization with intermittent crossclamping of the aorta. Analysis of ions and blood gases

OBJECTIVE: To test the hypothesis that short periods of ischemia may increase the myocardial protection obtained with intermittent crossclamping of the aorta. METHODS: In the control group (18 patients), surgery was performed with systemic hypothermia at 32ºC and intermittent crossclamping of the aorta. Extracorporeal circulation was used. In the preconditioning group (17 patients), 2 crossclampings of the aorta lasting 3min each were added prior to the intermittent crossclamping of the conventional technique with an interval of 2min of reperfusion between them. Blood samples for analyses of pH, pCO2, pO2, sodium, potassium, calcium, and magnesium were obtained from the coronary sinus at the beginning of extracorporeal circulation (time 1), at the end of the first anastomosis (time 2), and at the end of extracorporeal circulation (time 3). RESULTS: No difference was observed in the results of the 2 groups, except for a variation in the ionic values in the different times of blood withdrawal; sodium values, however, remained stable. All patients had a good clinical outcome. CONCLUSION: The results of intermittent crossclamping of the aorta with moderate hypothermia were not altered by the use of ischemic preconditioning.