Estágio curricular na empresa Consulfrio

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

Aplicação de métodos estocásticos na gestão de custos de construção de condutas de saneamento

O trabalho apresentado centra-se na determinação dos custos de construção de condutas de pequenos e médios diâmetros em Polietileno de Alta Densidade (PEAD) para saneamento básico, tendo como base a metodologia descrita no livro Custos de Construção e Exploração – Volume 9 da série Gestão de Sistemas de Saneamento Básico, de Lencastre et al. (1994). Esta metodologia descrita no livro já referenciado, nos procedimentos de gestão de obra, e para tal foram estimados custos unitários de diversos conjuntos de trabalhos. Conforme Lencastre et al (1994), “esses conjuntos são referentes a movimentos de terras, tubagens, acessórios e respetivos órgãos de manobra, pavimentações e estaleiro, estando englobado na parte do estaleiro trabalhos acessórios correspondentes à obra.” Os custos foram obtidos analisando vários orçamentos de obras de saneamento, resultantes de concursos públicos de empreitadas recentemente realizados. Com vista a tornar a utilização desta metodologia numa ferramenta eficaz, foram organizadas folhas de cálculo que possibilitam obter estimativas realistas dos custos de execução de determinada obra em fases anteriores ao desenvolvimento do projeto, designadamente numa fase de preparação do plano diretor de um sistema ou numa fase de elaboração de estudos de viabilidade económico-financeiros, isto é, mesmo antes de existir qualquer pré-dimensionamento dos elementos do sistema. Outra técnica implementada para avaliar os dados de entrada foi a “Análise Robusta de Dados”, Pestana (1992). Esta metodologia permitiu analisar os dados mais detalhadamente antes de se formularem hipóteses para desenvolverem a análise de risco. A ideia principal é o exame bastante flexível dos dados, frequentemente antes mesmo de os comparar a um modelo probabilístico. Assim, e para um largo conjunto de dados, esta técnica possibilitou analisar a disparidade dos valores encontrados para os diversos trabalhos referenciados anteriormente. Com os dados recolhidos, e após o seu tratamento, passou-se à aplicação de uma metodologia de Análise de Risco, através da Simulação de Monte Carlo. Esta análise de risco é feita com recurso a uma ferramenta informática da Palisade, o @Risk, disponível no Departamento de Engenharia Civil. Esta técnica de análise quantitativa de risco permite traduzir a incerteza dos dados de entrada, representada através de distribuições probabilísticas que o software disponibiliza. Assim, para por em prática esta metodologia, recorreu-se às folhas de cálculo que foram realizadas seguindo a abordagem proposta em Lencastre et al (1994). A elaboração e a análise dessas estimativas poderão conduzir à tomada de decisões sobre a viabilidade da ou das obras a realizar, nomeadamente no que diz respeito aos aspetos económicos, permitindo uma análise de decisão fundamentada quanto à realização dos investimentos.

Detection of circulating polysaccharide antigen of Schistosoma mansoni in hamster sera by crossed immunoelectrophoresis

Crossed immunoelectrophoresis (IEC) was used for detection of free and complexed circulating polisaccharide anodic antigen (AgCA) of Schistosoma mansoni in sera of infected hamsters. An attempt was also done to detect AgCA in human sera from patients infected with S. mansoni. The conditions for isolation and detection of complexed AgCA were established. The sensitivity of IEC was increased by incorporation of 2% polyethylene glicol (PEG) to the agarose and by maintaining the system at 4°C during the electrophoretic run. Free AgCA was detected in 12 and the complexed in 30 of the 37 hamsters sera analysed. Correlation between AgCA (free and complexed) and the parasite load was observed. AgCA was not detected, under the experimental conditions used, in human sera from 7 patients in the acute and 23 in the chronic phase of infection.

Electrical ageing studies of polymeric insulation for power cables (estudo do envelhecimento eléctrico do isolante polimérico de cabos eléctricos

Dissertação apresentada para obtenção do Grau de Doutor em Engenharia Física - Física Aplicada pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Processing and characterization of 3D dense chitosan pieces, for orthopedic applications, by adding plasticizers

In this work, plasticizer agents were incorporated in a chitosan based formulation, as a strategy to improve the fragile structure of chitosan based-materials. Three different plasticizers: ethylene glycol, glycerol and sorbitol, were blended with chitosan to prepare 3D dense chitosan specimens. The properties of the obtained structures were assessed for mechanical, microstructural, physical and biocompatibility behavior. The results obtained revealed that from the different specimens prepared, the blend of chitosan with glycerol has superior mechanical properties and good biological behavior, making this chitosan based formulation a good candidate to improve robust chitosan structures for the construction of bioabsorbable orthopedic implants.

Geossintéticos em vias de comunicação: influência das condições climáticas

Trabalho de Dissertação de Natureza Científica para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização de Vias de Comunicação e Transportes

Desenvolvimento do Filme Plástico Paper Like

A indústria de transformação de material plástico contribui de forma relevante para o desenvolvimento da economia mundial. Com o objetivo de desenvolvimento dessa indústria, a empresa Pentaplast S. A., situada em Água Longa, Santo Tirso, desenvolve a conceção de novos produtos para novas aplicações. Esta empresa para continuar na posição de destaque que possui, tem que conduzir a sua existência na melhoria contínua e atualização fase ao mercado. Na indústria termoformadora existe uma procura constante de novos materiais, visto ser um mercado muito competitivo. Neste contexto, o presente trabalho tem como objetivo desenvolver um filme plástico com o aspeto de papel para a indústria termoformadora, criando desta forma um impacto no consumidor para a preocupação ambiental. De forma a encontrar soluções para o problema mencionado, conduziu-se ao estudo e desenvolvimento de um novo produto – Paper Like, sendo este, um produto reciclável e adotado às necessidades da termoformação. Para isso, desenvolveu-se o projeto utilizando o processo de termolaminação, com a adição de um aditivo na camada externa, permitindo incorporar ao filme plástico, o aspeto e textura de papel. Foram testados, separadamente, dois aditivos, X e Y, base PET e PE, respetivamente, com diferentes percentagens de incorporação. O aditivo X foi desenvolvido especialmente para este projeto, tendo como base politereftalato de etileno, no entanto com a sua incorporação não se obteve os resultados esperados, somente dava um aspeto mate ao filme extrudidos. O aditivo Y, já existe no mercado mas nunca utilizado em extrusão plana, tem como base polietileno e a sua incorporação permitiu obter um filme com aspeto de papel, comprovando-se a sua compatibilidade com pigmentos, os quais dão diversas cores aos filmes, permitindo assim competir com os filmes tradicionais. Infelizmente a termolaminação do filme com o aditivo Y não foi possível, o que inviabiliza a selagem da embalagem.

Graphene-based biomimetic materials targeting urine metabolite as potential cancer biomarker: Application over different conductive materials for potentiometric transduction

This work presents a novel surface Smart Polymer Antibody Material (SPAM) for Carnitine (CRT, a potential biomarker of ovarian cancer), tested for the first time as ionophore in potentiometric electrodes of unconventional configuration. The SPAM material consisted of a 3D polymeric network created by surface imprinting on graphene layers. The polymer was obtained by radical polymerization of (vinylbenzyl) trimethylammonium chloride and 4-styrenesulfonic acid (signaling the binding sites), and vinyl pivalate and ethylene glycol dimethacrylate (surroundings). Non-imprinted material (NIM) was prepared as control, by excluding the template from the procedure. These materials were then used to produce several plasticized PVC membranes, testing the relevance of including the SPAM as ionophore, and the need for a charged lipophilic additive. The membranes were casted over solid conductive supports of graphite or ITO/FTO. The effect of pH upon the potentiometric response was evaluated for different pHs (2-9) with different buffer compositions. Overall, the best performance was achieved for membranes with SPAM ionophore, having a cationic lipophilic additive and tested in HEPES (4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid) buffer, pH 5.1. Better slopes were achieved when the membrane was casted on conductive glass (-57.4 mV/decade), while the best detection limits were obtained for graphite-based conductive supports (3.6 × 10−5mol/L). Good selectivity was observed against BSA, ascorbic acid, glucose, creatinine and urea, tested for concentrations up to their normal physiologic levels in urine. The application of the devices to the analysis of spiked samples showed recoveries ranging from 91% (± 6.8%) to 118% (± 11.2%). Overall, the combination of the SPAM sensory material with a suitable selective membrane composition and electrode design has lead to a promising tool for point-of-care applications.

New modified electrochemical conductive paper support for BSA detection

Chemical sensors and biosensors are widely used to detect various kinds of protein target biomolecules. Molecularly Imprinted Polymers (MIPs) have raised great interest in this area, because these act as antibody-like recognition materials, with high affinity to the template molecule. Compared to natural antibodies, these are also of lower cost and higher stability. There are different types of supports used to carry MIP materials, mostly of these made of gold, favourably assembled on a Screen Printed Electrode (SPE) strategy. For this work a new kind of support for the sensing layer was developed: conductive paper. This support was made by modifying first cellulose paper with paraffin wax (to make it waterproof), and casting a carbon-ink on it afterwards, to turn it conductive. The SPAM approach previously reported in1 was employed herein to assemble to MIP sensing material on the conductive paper. The selected charged monomers were (vinylbenzyl) trimethlammonium chloride (positive charge) or vinylbenzoic acid (negative charge), used to generate binding positions with single-type charge (positive or negative). The non-specific binding area of the MIP layer was assembled by chronoamperometry-assisted polymerization (at 1 V, for 60, 120 or 180 seconds) of vinylbenzoate, cross-linked with ethylene glycol vinyl ether. The BSA biomolecules lying within the polymeric matrix were removed by Proteinase K action. All preparation stages of the MIP assembly were followed by FTIR, Raman spectroscopy and, electrochemical analysis. In general, the best results were obtained for longer polymerization times and positively charged binding sites (which was consistent with a negatively-charged protein under physiological pH, as BSA). Linear responses against BSA concentration ranged from 0.005 to 100 mg/mL, in PBS buffer standard solutions. The sensor was further calibrated in standard solutions that were prepared in synthetic or real urine, and the analytical response became more sensitive and stable. Compared to the literature, the detection capability of the developed device is better than most of the reported electrodes. Overall, the simplicity, low cost and good analytical performance of the BSA SPE device, prepared with positively charged binding positions, seems a suitable approach for practical application in clinical context. Further studies with real samples are required, as well as gathering with electronic-supporting devices to allow on-site readings.

Detection of cardiac biomarker proteins using a disposable based on a molecularly imprinted polymer grafted onto graphite

A low-cost disposable was developed for rapid detection of the protein biomarker myoglobin (Myo) as a model analyte. A screen printed electrode was modified with a molecularly imprinted material grafted on a graphite support and incorporated in a matrix composed of poly(vinyl chloride) and the plasticizer o-nitrophenyloctyl ether. The protein-imprinted material (PIM) was produced by growing a reticulated polymer around a protein template. This is followed by radical polymerization of 4-styrenesulfonic acid, 2-aminoethyl methacrylate hydrochloride, and ethylene glycol dimethacrylate. The polymeric layer was then covalently bound to the graphitic support, and Myo was added during the imprinting stage to act as a template. Non-imprinted control materials (CM) were also prepared by omitting the Myo template. Morphological and structural analysis of PIM and CM by FTIR, Raman, and SEM/EDC microscopies confirmed the modification of the graphite support. The analytical performance of the SPE was assessed by square wave voltammetry. The average limit of detection is 0.79 μg of Myo per mL, and the slope is −0.193 ± 0.006 μA per decade. The SPE-CM cannot detect such low levels of Myo but gives a linear response at above 7.2 μg · mL−1, with a slope of −0.719 ± 0.02 μA per decade. Interference studies with hemoglobin, bovine serum albumin, creatinine, and sodium chloride demonstrated good selectivity for Myo. The method was successfully applied to the determination of Myo urine and is conceived to be a promising tool for screening Myo in point-of-care patients with ischemia.

Biomimetic Sensor Potentiometric System for Doxycycline Antibiotic Using a Molecularly Imprinted Polymer as an Artificial Recognition Element

Molecular imprinting is a useful technique for the preparation of functional materials with molecular recognition properties. A Biomimetic Sensor Potentiometric System was developed for assessment of doxycycline (DOX) antibiotic. The molecularly imprinted polymer (MIP) was synthesized by using doxycycline as a template molecule, methacrylic acid (MAA) and/or acrylamide (AA) as a functional monomer and ethylene glycol dimethacrylat (EGDMA) as a cross-linking agent. The sensing elements were fabricated by the inclusion of DOX imprinted polymers in polyvinyl chloride (PVC) matrix. The sensors showed a high selectivity and a sensitive response to the template in aqueous system. Electrochemical evaluation of these sensors under static (batch) mode of operation reveals near-Nernstian response. MIP/MAA membrane sensor was incorporated in flow-through cells and used as detectors for flow injection analysis (FIA) of DOX. The method has the requisite accuracy, sensitivity and precision to assay DOX in tablets and biological fluids.

A novel antibody-like material for breast cancer antigen CA15-3, used to track breast cancer by potentiometric transduction

This work presents the development of a low cost sensor device for the diagnosis of breast cancer in point-of-care, made with new synthetic biomimetic materials inside plasticized poly(vinyl chloride), PVC, membranes, for subsequent potentiometric detection. This concept was applied to target a conventional biomarker in breast cancer: Breast Cancer Antigen (CA15-3). The new biomimetic material was obtained by molecularly-imprinted technology. In this, a plastic antibody was obtained by polymerizing around the biomarker that acted as an obstacle to the growth of the polymeric matrix. The imprinted polymer was specifically synthetized by electropolymerization on an FTO conductive glass, by using cyclic voltammetry, including 40 cycles within -0.2 and 1.0 V. The reaction used for the polymerization included monomer (pyrrol, 5.0×10-3 mol/L) and protein (CA15-3, 100U/mL), all prepared in phosphate buffer saline (PBS), with a pH of 7.2 and 1% of ethylene glycol. The biomarker was removed from the imprinted sites by proteolytic action of proteinase K. The biomimetic material was employed in the construction of potentiometric sensors and tested with regard to its affinity and selectivity for binding CA15-3, by checking the analytical performance of the obtained electrodes. For this purpose, the biomimetic material was dispersed in plasticized PVC membranes, including or not a lipophilic ionic additive, and applied on a solid conductive support of graphite. The analytical behaviour was evaluated in buffer and in synthetic serum, with regard to linear range, limit of detection, repeatability, and reproducibility. This antibody-like material was tested in synthetic serum, and good results were obtained. The best devices were able to detect 5 times less CA15-3 than that required in clinical use. Selectivity assays were also performed, showing that the various serum components did not interfere with this biomarker. Overall, the potentiometric-based methods showed several advantages compared to other methods reported in the literature. The analytical process was simple, providing fast responses for a reduced amount of analyte, with low cost and feasible miniaturization. It also allowed the detection of a wide range of concentrations, diminishing the required efforts in previous sample pre-treating stages.

Carnitine tailored Sensors on Surface Molecular Imprinting based on Graphene layers

III Jornadas de Electroquímica e Inovação (Electroquímica e Nanomateriais), na Universidade de Trás-os-Montes e Alto Douro, Vila Real, 16 a 17 de Setembro de 2013

Host-Tailored Sensors for Carnitine Potentiometric Measurements based on Surface Molecular Imprinting

Graduate Student Symposium on Molecular Imprinting 2013, na Queen’s University, Belfast, United Kingdom, 15 a 17 de Agosto de 2013

Embalagens Flexíveis: estudo do processo de reticulação de adesivos e do coeficiente de atrito

A dissertação foi realizada em ambiente industrial, mais precisamente na empresa Monteiro, Ribas – Embalagens Flexíveis, S.A.. Esta empresa dedica-se à impressão e laminagem de filmes, assim como à confeção de sacos. Os seus produtos são direcionados na sua maioria para a indústria alimentar, exportando mais de 50% da sua produção, e dizem respeito a complexos (dois ou mais filmes unidos pela presença de um adesivo) que podem possuir impressão ou não. Estes complexos podem ser enviados para o cliente em bobina ou já em saco. Os objetivos propostos pela empresa diziam respeito a estudos relacionados com a força de laminagem dos complexos, com o coeficiente de atrito dos mesmos e com a identificação dos espetros dos componentes dos adesivos, assim como o estudo do processo de reticulação dos mesmos por espetrofotometria de Infravermelho. Relativamente aos resultados obtidos verificou-se que tanto a tinta como os metalizados influenciam negativamente a força de laminagem. Por sua vez o coeficiente de atrito é afetado por vários fatores. Através dos ensaios experimentais verificou-se que o adesivo, a tinta e o verniz mate favorecem o aumento do valor do COF. Além disso, nos complexos em que se utilizaram filmes de polietileno de maior espessura obtiveram-se valores de COF mais baixos, e no que diz respeito à temperatura e à tensão de enrolamento, verificou-se que valores mais elevados e muito baixos da primeira traduzem-se num aumento do valor do COF e uma tensão de enrolamento maior também tem o mesmo efeito. Relativamente ao tipo de filme impresso, substratos com maior energia superficial atraem mais o agente de deslizamento (slip). Por último, não se conseguiu perceber qual o tipo de adesivo (com ou sem solvente) que tem maior impacto no COF uma vez que em 55% dos casos o valor do COF é superior nas amostras que foram complexadas com adesivo sem solvente e em 45% o COF era superior nas amostras complexadas com adesivo base solvente. No que diz respeito aos espetros obtidos verificou-se que a reticulação dos adesivos é identificada pela diminuição da extensão do pico correspondente à ligação N=C=O.