Contribuição para a caracterização da emissão de nanopartículas em processos de soldadura e avaliação de riscos decorrentes do processo

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Química e Biológica Ramo de processos químicos

Implementação e validação de um método para determinação de contaminantes em vinho por microextração em fase sólida e gc-ms/ms e sua correlação com a análise sensorial

Cada vez mais começa a notar-se, na indústria vitivinícola, uma grande preocupação com a qualidade dos seus produtos, motivada pela maior sensibilização e exigência dos consumidores. Deste modo, a presença de defeitos organoléticos no vinho representa uma fonte de perda financeira nesta indústria, pelo que o seu controlo se torna indispensável para que se obtenha um produto de elevada qualidade. Neste sentido, torna-se interessante desenvolver um método de análise que seja rápido de forma a permitir a quantificação simultânea das moléculas identificadas como principais responsáveis pelos distúrbios olfativos dos vinhos. Assim, este trabalho surge com o objetivo de implementar e validar um método para a determinação de contaminantes em vinho por microextração em fase sólida (SPME) e cromatografia gasosa acoplada à espetrometria de massa tandem (GC-MS/MS) e a sua correlação com a análise sensorial. A técnica de microextração em fase sólida é simples e rápida na medida em que não requer um pré-tratamento da amostra. Por sua vez, a análise por GC-MS permite identificar de forma clara os compostos em estudo, nomeadamente, 4-Etilfenol (4-EP), 4-Etilguaiacol (4-EG), 2,4,6-Tricloroanisol (TCA), 2,3,4,6-Tetracloroanisol (TeCA) e 2,4,6-Tribromoanisol (TBA). Foram realizados estudos de otimização das condições de extração, comparando as fibras 100 μm PDMS e 50/30 μm DVB/CAR/PDMS. Obtiveram-se resultados mais satisfatórios, em termos de resposta e da relação sinal/ruído, com a fibra 50/30 μm DVB/CAR/PDMS e estabeleceram-se como condições de extração 55ºC para a temperatura de incubação/extração, uma velocidade de agitação de 250 rpm e 60 minutos de tempo de extração. Ao longo deste trabalho, analisaram-se 50 amostras de vinho, das quais 48 eram amostras de Vinho Tinto do Douro e 2 de Vinho do Porto. Para validar a metodologia foram realizados estudos de linearidade, limiares analíticos, repetibilidade, precisão intermédia e recuperação. De um modo geral, obtiveram-se bons resultados ao nível da linearidade para as gamas de concentração escolhidas. Quanto aos limites de deteção e de quantificação, o 4-EP é o contaminante que apresenta uma gama de concentrações mais alta, notando-se limiares analíticos mais elevados, com valores próximos dos últimos níveis de concentração, oscilando entre 65 e 583 μg/L. No caso dos Anisóis, o TBA apresenta limites de deteção mais baixos, entre 0,4 e 17,0 ng/L. Os limiares analíticos foram validados com recurso a estudos de precisão intermédia e repetibilidade, cujos resultados se encontram dentro das especificações descritas no documento SANCO/10684/2009 (%RSD ≤ 30% para os Anisóis e %RSD ≤ 20% para os Fenóis Voláteis). Foram, ainda, realizados estudos de exatidão recorrendo a ensaios de recuperação e a ensaios interlaboratoriais. Muitas vezes conseguem-se boas recuperações, no entanto notam-se maiores dificuldades para o TBA e para o TeCA. Relativamente aos ensaios interlaboratoriais, verificam-se maiores discrepâncias para o 4-EP. Já os restantes contaminantes apresentam resultados, geralmente, satisfatórios (|z-score| ≤ 2).

Conceção e construção de um simulador de controlo de vibrações

Trabalho Final de Mestrado para obtenção do grau de Mestre em Engenharia Mecânica

A STR mutation in a heteropaternal twin case

A heteropaternal male twin case with two men being alleged fathers was investigated as requested by the Court. Up to 37 PCR-based polymorphic DNA systems were studied in this case which was complicated by a paternal ACTBP2 mutation detected in one twin. This is the first report on a STR mutation in a double paternity case where both biological fathers were indisputably identified. The STR systems enable the resolution of these complex genetic relationships even in a case where a mutation in one STR locus was encountered.

Regularização de barras e soldaduras aluminotérmicas

Relatório de Estágio para obtenção do grau de Mestre em Engenharia Civil

Impacto da influência do ar novo na climatização de edifícios

Este trabalho surgiu do âmbito da Tese de Dissertação do Mestrado em Energias Sustentáveis do Instituto Superior de Engenharia do Porto, tendo o acompanhamento dos orientadores da empresa Laboratório Ecotermolab do Instituto de Soldadura e Qualidade e do Instituto Superior de Engenharia do Porto, de forma a garantir a linha traçada indo de acordo aos objectivos propostos. A presente tese abordou o estudo do impacto da influência do ar novo na climatização de edifícios, tendo como base de apoio à análise a simulação dinâmica do edifício em condições reais num programa adequado, acreditado pela norma ASHRAE 140-2004. Este trabalho pretendeu evidenciar qual o impacto da influência do ar novo na climatização de um edifício com a conjugação de vários factores, tais como, ocupação, actividades e padrões de utilização (horários), iluminação e equipamentos, estudando ainda a possibilidade do sistema funcionar em regime de “Free-Cooling”. O princípio partiu fundamentalmente por determinar até que ponto se pode climatizar recorrendo único e exclusivamente à introdução de ar novo em regime de “Free-Cooling”, através de um sistema tudo-ar de Volume de Ar Variável - VAV, sem o apoio de qualquer outro sistema de climatização auxiliar localizado no espaço, respeitando os caudais mínimos impostos pelo RSECE (Decreto-Lei 79/2006). Numa primeira fase foram identificados todos os dados relativos à determinação das cargas térmicas do edifício, tendo em conta todos os factores e contributos alusivos ao valor da carga térmica, tais como a transmissão de calor e seus constituintes, a iluminação, a ventilação, o uso de equipamentos e os níveis de ocupação. Consequentemente foram elaboradas diversas simulações dinâmicas com o recurso ao programa EnergyPlus integrado no DesignBuilder, conjugando variáveis desde as envolventes à própria arquitectura, perfis de utilização ocupacional, equipamentos e taxas de renovação de ar nos diferentes espaços do edifício em estudo. Obtiveram-se vários modelos de forma a promover um estudo comparativo e aprofundado que permitisse determinar o impacto do ar novo na climatização do edifício, perspectivando a capacidade funcional do sistema funcionar em regime de “Free-Cooling”. Deste modo, a análise e comparação dos dados obtidos permitiram chegar às seguintes conclusões: Tendo em consideração que para necessidades de arrefecimento bastante elevadas, o “Free-Cooling” diurno revelou-se pouco eficaz ou quase nulo, para o tipo de clima verificado em Portugal, pois o diferencial de temperatura existente entre o exterior e o interior não é suficiente de modo a tornar possível a remoção das cargas de forma a baixar a temperatura interior para o intervalo de conforto. Em relação ao “Free-Cooling” em horário nocturno ou pós-laboral, este revelou-se bem mais eficiente. Obtiveram-se prestações muito interessantes sobretudo durante as estações de aquecimento e meia-estação, tendo em consideração o facto de existir necessidades de arrefecimento mesmo durante a estação de aquecimento. Referente à ventilação nocturna, isto é, em períodos de madrugada e fecho do edifício, concluiu-se que tal contribui para um abaixamento do calor acumulado durante o dia nos materiais construtivos do edifício e que é libertado ou restituído posteriormente para os espaços em períodos mais tardios. De entre as seguintes variáveis, aumento de caudal de ar novo insuflado e o diferencial de temperatura existente entre o ar exterior e interior, ficou demonstrado que este último teria maior peso contributivo na remoção do calor. Por fim, é ponto assente que de um modo geral, um sistema de climatização será sempre indispensável devido a cargas internas elevadas, requisitos interiores de temperatura e humidade, sendo no entanto aconselhado o “Free- Cooling” como um opção viável a incorporar na solução de climatização, de forma a promover o arrefecimento natural, a redução do consumo energético e a introdução activa de ar novo.

Outdoor and indoor benzene evaluation by GC-FID and GC-MS/MS

The evaluation of benzene in different environments such as indoor (with and without tobacco smoke), a city area, countryside, gas stations and near exhaust pipes from cars running on different types of fuels was performed. The samples were analyzed using gas chromatography (GC) with flame ionization detection (FID) and tandem mass spectrometric detection (MS/MS) (to confirm the identification of benzene in the air samples). Operating conditions for the GC-MS analysis were optimized as well as the sampling and sample preparation. The results obtained in this work indicate that i) the type of fuel directly influences the benzene concentration in the air. Gasoline with additives provided the highest amount of benzene followed by unleaded gasoline and diesel; ii) the benzene concentration in the gas station was always higher than the advisable limit established by law (5 μg m−3) and during the unloading of gasoline the achieved concentration was 8371 μg m−3; iii) the data from the countryside (Taliscas) and the urban city (Matosinhos) were below 5 μg m−3 except 5 days after a fire on a petroleum refinery plant located near the city; iv) it was proven that in coffee shops where smoking is allowed the benzene concentration is higher (6 μg m−3) than in coffee shops where this is forbidden (4 μg m−3). This method may also be helpful for environmental analytical chemists who use GC-MS/MS for the confirmation or/and quantification of benzene.

Organochlorine pesticide residues in strawberries from integrated pest management and organic farming

A rapid, specific, and sensitive method based on theQuick Easy Cheap Effective Rugged and Safe (QuEChERS) method and a cleanup using dispersive solid-phase extraction with MgSO4, PSA, and C18 sorbents has been developed for the routine analysis of 14 pesticides in strawberries. The analyses were performed by three different analytical methodologies: gas chromatography (GC) with electron capture detection (ECD), mass spectrometry (MS), and tandem mass spectrometry (MS/MS). The recoveries for all the pesticides studied were from 46 to 128%, with relative standard deviation of <15% in the concentration range of 0.005-0.250 mg/kg. The limit of detection (LOD) for all compoundsmetmaximumresidue limits (MRL) accepted in Portugal for organochlorine pesticides (OCP). A survey study of strawberries produced in Portugal in the years 2009-2010 obtained from organic farming (OF) and integrated pest management (IPM) was developed. Lindane and β-endosulfan were detected above the MRL in OF and IPM. Other OCP (aldrin, o,p0-DDT and their metabolites, and methoxychlor) were found below the MRL. The OCP residues detected decreased from 2009 to 2010. The QuEChERS method was successfully applied to the analysis of strawberry samples.

Development of a simple analytical method for the simultaneousdetermination of paracetamol, paracetamol-glucuronide andp-aminophenol in river water

Paracetamol is among the most worldwide consumed pharmaceuticals. Although its occurrence in the environment is well documented, data about the presence of its metabolites and transformation products is very scarce. The present work describes the development of an analytical method for the simultaneous determination of paracetamol, its principal metabolite (paracetamol-glucuronide) and its main transformation product (p-aminophenol) based on solid phase extraction (SPE) and high performance liquid chromatography coupled to diode array detection (HPLC-DAD). The method was applied to analysis of river waters, showing to be suitable to be used in routine analysis. Different SPE sorbents were compared and the use of two Oasis WAX cartridges in tandem proved to be the most adequate approach for sample clean up and pre-concentration. Under optimized conditions, limits of detection in the range 40–67 ng/L were obtained, as well as mean recoveries between 60 and 110% with relative standard deviations (RSD) below 6%. Finally, the developed SPE-HPLC/DAD method was successfully applied to the analysis of the selected compounds in samples from seven rivers located in the north of Portugal. Nevertheless all the compounds were detected, it was the first time that paracetamol-glucuronide was found in river water at concentrations up to 3.57 μg/L.

Multiresidue pesticides analysis in soils using modified QuEChERS with disposable pipette extraction and dispersive solid-phase extraction

QuEChERS original method was modified into a new version for pesticides determination in soils. The QuEChERS method is based on liquid–liquid portioning with ACN and was followed by cleanup step using dispersive SPE and disposable pipette tips. Gas chromatographic separation with MS detection was carried out for pesticides quantification. The method was validated using recovery experiments for 36 multiclass pesticides. Mean recoveries of pesticides at each of the four spiking levels between 10–300 µg/kg of soil ranged from 70–120% for 26 pesticides with RSD values less than 15%. The method achieved low limit of detection less than 7.6 µ g/kg. Matrix effects were observed for 13 pesticides. Matrix effects were compensated by using matrix-matched calibration. The method was applied successfully using d-SPE or DPX in the analysis of the pesticides in soils from organic farming and integrated pest management.

Optimization of QuEChERS procedure coupled to GC-ECD for organochlorine pesticide determination in carrot samples

An optimised version of the Quick, Easy, Cheap, Effective, Rugged and Safe (QuEChERS) method for simultaneous determination of 14 organochlorine pesticides in carrots was developed using gas chromatography coupled with electron-capture detector (GC-ECD) and confirmation by gas chromatography tandem mass spectrometry (GC-MS/MS). A citrate-buffered version of QuEChERS was applied for the extraction of the organochlorine pesticides, and for the extract clean-up, primary secondary amine, octadecyl-bonded silica (C18), magnesium sulphate (MgSO4) and graphitized carbon black were used as sorbents. The GC-ECD determination of the target compounds was achieved in less than 20 min. The limits of detection were below the EUmaximum residue limits (MRLs) for carrots, 10–50 μg kg−1, while the limit of quantification did exceed 10 μg kg−1 for hexachlorobenzene (HCB). The introduction of a sonication step was shown to improve the recoveries. The overall average recoveries in carrots, at the four tested levels (60, 80, 100 and 140 μg kg−1), ranged from 66 to 111% with relative standard deviations in the range of 2– 15 % (n03) for all analytes, with the exception of HCB. The method has been applied to the analysis of 21 carrot samples from different Portuguese regions, and β-HCH was the pesticide most frequently found, with concentrations oscillating between less than the limit of quantification to 14.6 μg kg−1. Only one sample had a pesticide residue (β-HCH) above the MRL, 14.6 μg kg−1. This methodology combines the advantages of both QuEChERS and GC-ECD, producing a very rapid, sensitive and reliable procedure which can be applied in routine analytical laboratories.

Tensile behaviour of a structural adhesive at high temperatures by the extended finite element method

Component joining is typically performed by welding, fastening, or adhesive-bonding. For bonded aerospace applications, adhesives must withstand high-temperatures (200°C or above, depending on the application), which implies their mechanical characterization under identical conditions. The extended finite element method (XFEM) is an enhancement of the finite element method (FEM) that can be used for the strength prediction of bonded structures. This work proposes and validates damage laws for a thin layer of an epoxy adhesive at room temperature (RT), 100, 150, and 200°C using the XFEM. The fracture toughness (G Ic ) and maximum load ( ); in pure tensile loading were defined by testing double-cantilever beam (DCB) and bulk tensile specimens, respectively, which permitted building the damage laws for each temperature. The bulk test results revealed that decreased gradually with the temperature. On the other hand, the value of G Ic of the adhesive, extracted from the DCB data, was shown to be relatively insensitive to temperature up to the glass transition temperature (T g ), while above T g (at 200°C) a great reduction took place. The output of the DCB numerical simulations for the various temperatures showed a good agreement with the experimental results, which validated the obtained data for strength prediction of bonded joints in tension. By the obtained results, the XFEM proved to be an alternative for the accurate strength prediction of bonded structures.

Optimization study of hybrid spot-welded/bonded single-lap joints

Joining of components with structural adhesives is currently one of the most widespread techniques for advanced structures (e.g., aerospace or aeronautical). Adhesive bonding does not involve drilling operations and it distributes the load over a larger area than mechanical joints. However, peak stresses tend to develop near the overlap edges because of differential straining of the adherends and load asymmetry. As a result, premature failures can be expected, especially for brittle adhesives. Moreover, bonded joints are very sensitive to the surface treatment of the material, service temperature, humidity and ageing. To surpass these limitations, the combination of adhesive bonding with spot-welding is a choice to be considered, adding a few advantages like superior static strength and stiffness, higher peeling and fatigue strength and easier fabrication, as fixtures during the adhesive curing are not needed. The experimental and numerical study presented here evaluates hybrid spot-welded/bonded single-lap joints in comparison with the purely spot-welded and bonded equivalents. A parametric study on the overlap length (LO) allowed achieving different strength advantages, up to 58% compared to spot-welded joints and 24% over bonded joints. The Finite Element Method (FEM) and Cohesive Zone Models (CZM) for damage growth were also tested in Abaqus® to evaluate this technique for strength prediction, showing accurate estimations for all kinds of joints.

Feasibility of the extended finite element method for the simulation of composite bonded joints

Adhesive-bonding for the unions in multi-component structures is gaining momentum over welding, riveting and fastening. It is vital for the design of bonded structures the availability of accurate damage models, to minimize design costs and time to market. Cohesive Zone Models (CZM’s) have been used for fracture prediction in structures. The eXtended Finite Element Method (XFEM) is a recent improvement of the Finite Element Method (FEM) that relies on traction-separation laws similar to those of CZM’s but it allows the growth of discontinuities within bulk solids along an arbitrary path, by enriching degrees of freedom. This work proposes and validates a damage law to model crack propagation in a thin layer of a structural epoxy adhesive using the XFEM. The fracture toughness in pure mode I (GIc) and tensile cohesive strength (sn0) were defined by Double-Cantilever Beam (DCB) and bulk tensile tests, respectively, which permitted to build the damage law. The XFEM simulations of the DCB tests accurately matched the experimental load-displacement (P-d) curves, which validated the analysis procedure.

SiC pinpin photonic for linking the visible spectrum to the telecom gap

Expanding far beyond traditional applications at telecommunications wavelengths, the SiC photonic devices has recently proven its merits for working with visible range optical signals. Reconfigurable wavelength selectors are essential sub-systems for implementing reconfigurable WDM networks and optical signal processing. Visible range to telecom band spectral translation in SiC/Si can be accomplished using wavelength selector under appropriated optical bias, acting as reconfigurable active filters. In this paper we present a monolithically integrated wavelength selector based on a multilayer SiC/Si integrated optical filters that requires optical switches to select wavelengths. The selector filter is realized by using double pin/pin a-SiC:H photodetector with front and back biased optical gating elements. Red, green, blue and violet communication channels are transmitted together, each one with a specific bit sequence. The combined optical signal is analyzed by reading out the generated photocurrent, under different background wavelengths applied either from the front or the back side. The backgrounds acts as channel selectors that selects one or more channels by splitting portions of the input multi-channel optical signals across the front and back photodiodes. The transfer characteristics effects due to changes in steady state light, irradiation side and frequency are presented. The relationship between the optical inputs and the digital output levels is established. (C) 2014 Elsevier B.V. All rights reserved.