Development of an FIA system with amperometric detection for determination of bentazone in estuarine waters

On the basis of its electrochemical behaviour a new flow-injection analysis (FIA) method with amperometric detection has been developed for quantification of the herbicide bentazone (BTZ) in estuarine waters. Standard solutions and samples (200 µL) were injected into a water carrier stream and both pH and ionic strength were automatically adjusted inside the manifold. Optimization of critical FIA conditions indicated that the best analytical results were obtained at an oxidation potential of 1.10 V, pH 4.5, and an overall flow-rate of 2.4 mL min–1. Analysis of real samples was performed by means of calibration curves over the concentration range 2.5x10–6 to 5.0x10–5 mol L–1, and results were compared with those obtained by use of an independent method (HPLC). The accuracy of the amperometric determinations was ascertained; errors relative to the comparison method were below 4% and sampling rates were approximately 100 samples h–1. The repeatability of the proposed method was calculated by assessing the relative standard deviation (%) of ten consecutive determinations of one sample; the value obtained was 2.1%.

Improvement of a filters method in a derivative free optimization

Constraints nonlinear optimization problems can be solved using penalty or barrier functions. This strategy, based on solving the problems without constraints obtained from the original problem, have shown to be e ective, particularly when used with direct search methods. An alternative to solve the previous problems is the lters method. The lters method introduced by Fletcher and Ley er in 2002, , has been widely used to solve problems of the type mentioned above. These methods use a strategy di erent from the barrier or penalty functions. The previous functions de ne a new one that combine the objective function and the constraints, while the lters method treat optimization problems as a bi-objective problems that minimize the objective function and a function that aggregates the constraints. Motivated by the work of Audet and Dennis in 2004, using lters method with derivative-free algorithms, the authors developed works where other direct search meth- ods were used, combining their potential with the lters method. More recently. In a new variant of these methods was presented, where it some alternative aggregation restrictions for the construction of lters were proposed. This paper presents a variant of the lters method, more robust than the previous ones, that has been implemented with a safeguard procedure where values of the function and constraints are interlinked and not treated completely independently.

Filters method in direct search optimization, new measures to admissibility

Constrained nonlinear optimization problems are usually solved using penalty or barrier methods combined with unconstrained optimization methods. Another alternative used to solve constrained nonlinear optimization problems is the lters method. Filters method, introduced by Fletcher and Ley er in 2002, have been widely used in several areas of constrained nonlinear optimization. These methods treat optimization problem as bi-objective attempts to minimize the objective function and a continuous function that aggregates the constraint violation functions. Audet and Dennis have presented the rst lters method for derivative-free nonlinear programming, based on pattern search methods. Motivated by this work we have de- veloped a new direct search method, based on simplex methods, for general constrained optimization, that combines the features of the simplex method and lters method. This work presents a new variant of these methods which combines the lters method with other direct search methods and are proposed some alternatives to aggregate the constraint violation functions.

A filter algorithm: comparison with NLP solvers

The purpose of this work is to present an algorithm to solve nonlinear constrained optimization problems, using the filter method with the inexact restoration (IR) approach. In the IR approach two independent phases are performed in each iteration—the feasibility and the optimality phases. The first one directs the iterative process into the feasible region, i.e. finds one point with less constraints violation. The optimality phase starts from this point and its goal is to optimize the objective function into the satisfied constraints space. To evaluate the solution approximations in each iteration a scheme based on the filter method is used in both phases of the algorithm. This method replaces the merit functions that are based on penalty schemes, avoiding the related difficulties such as the penalty parameter estimation and the non-differentiability of some of them. The filter method is implemented in the context of the line search globalization technique. A set of more than two hundred AMPL test problems is solved. The algorithm developed is compared with LOQO and NPSOL software packages.

Controlo de qualidade microbiológica na indústria farmacêutica

O presente Relatório de Estágio teve como objectivo analisar e discutir as competências adquiridas e desenvolvidas, durante o estágio, no controlo da qualidade microbiológica na indústria farmacêutica O estágio, foi realizado no Laboratório de Microbiologia dos Laboratórios Atral, Grupo AtralCipan, localizado na Vala do Carregado, Castanheira do Ribatejo. Este teve a duração de aproximadamente dez meses e meio, com data de início a 21 de Setembro de 2011 e final de 10 de Agosto de 2012. Numa fase inicial, foram adquiridas as aptidões necessárias para a aplicação das metodologias realizadas no laboratório de microbiologia com o estudo das normas, procedimento e legislação aplicada, com foco na importância das farmacopeias na indústria farmacêutica e formação para a realização de ensaios em Áreas de Processamento Asséptico, conhecendo e compreendendo os procedimentos a ter nestas. Uma das principais metodologias realizadas, e desenvolvida neste relatório, compreendeu a análise de produtos farmacêuticos estéreis, com a aplicação de Testes de Esterilidade, pelo método de STERITEST e método Directo, com resultados que demonstraram a importância destas técnicas, da avaliação do ambiente em que são realizadas e do operador que as executa. Os Testes de Promoção de Crescimento, foram também explorados neste trabalho, realizados não só para avaliação dos meios de cultura, onde foi possível analisar os requisitos e resultados obtidos, como também para validação de metodologias, nomeadamente, na validação de meios e fluidos de marcas diferentes para utilização no método STERITEST e na validação do método de filtração de membrana para Enumeração Microbiana de um produto não estéril. Estas validações possibilitaram a redução de custos e melhoria das condições da análise e metodologias aplicadas. Com a realização do estágio foi possível adquirir aptidões práticas, que aliadas ao conhecimento teórico obtido no mestrado, proporcionaram um crescimento a nível pessoal, científico e profissional.

A multi-objective approach for the motion planning of redundant manipulators

Kinematic redundancy occurs when a manipulator possesses more degrees of freedom than those required to execute a given task. Several kinematic techniques for redundant manipulators control the gripper through the pseudo-inverse of the Jacobian, but lead to a kind of chaotic inner motion with unpredictable arm configurations. Such algorithms are not easy to adapt to optimization schemes and, moreover, often there are multiple optimization objectives that can conflict between them. Unlike single optimization, where one attempts to find the best solution, in multi-objective optimization there is no single solution that is optimum with respect to all indices. Therefore, trajectory planning of redundant robots remains an important area of research and more efficient optimization algorithms are needed. This paper presents a new technique to solve the inverse kinematics of redundant manipulators, using a multi-objective genetic algorithm. This scheme combines the closed-loop pseudo-inverse method with a multi-objective genetic algorithm to control the joint positions. Simulations for manipulators with three or four rotational joints, considering the optimization of two objectives in a workspace without and with obstacles are developed. The results reveal that it is possible to choose several solutions from the Pareto optimal front according to the importance of each individual objective.

Evolutionary trajectory optimization for redundant robots

The trajectory planning of redundant robots is an important area of research and efficient optimization algorithms have been investigated in the last years. This paper presents a new technique that combines the closed-loop pseudoinverse method with genetic algorithms. In this case the trajectory planning is formulated as an optimization problem with constraints.

An evolutionary approach for the motion planning of redundant and hyper-redundant manipulators

The trajectory planning of redundant robots is an important area of research and efficient optimization algorithms are needed. The pseudoinverse control is not repeatable, causing drift in joint space which is undesirable for physical control. This paper presents a new technique that combines the closed-loop pseudoinverse method with genetic algorithms, leading to an optimization criterion for repeatable control of redundant manipulators, and avoiding the joint angle drift problem. Computer simulations performed based on redundant and hyper-redundant planar manipulators show that, when the end-effector traces a closed path in the workspace, the robot returns to its initial configuration. The solution is repeatable for a workspace with and without obstacles in the sense that, after executing several cycles, the initial and final states of the manipulator are very close.

Approximating fractional derivatives in the perspective of system control

The theory of fractional calculus goes back to the beginning of the theory of differential calculus, but its application received attention only recently. In the area of automatic control some work was developed, but the proposed algorithms are still in a research stage. This paper discusses a novel method, with two degrees of freedom, for the design of fractional discrete-time derivatives. The performance of several approximations of fractional derivatives is investigated in the perspective of nonlinear system control.

Trajectory planning of redundant manipulators using genetic algorithms

The trajectory planning of redundant robots is an important area of research and efficient optimization algorithms are needed. This paper presents a new technique that combines the closed-loop pseudoinverse method with genetic algorithms. The results are compared with a genetic algorithm that adopts the direct kinematics. In both cases the trajectory planning is formulated as an optimization problem with constraints.

Experimental and numerical study on the evaluation of ventilation efficiency

Buildings account for 40% of total energy consumption in the European Union. The reduction of energy consumption in the buildings sector constitute an important measure needed to reduce the Union's energy dependency and greenhouse gas emissions. The Portuguese legislation incorporate this principles in order to regulate the energy performance of buildings. This energy performance should be accompanied by good conditions for the occupants of the buildings. According to EN 15251 (2007) the four factors that affect the occupant comfort in the buildings are: Indoor Air Quality (IAQ), thermal comfort, acoustics and lighting. Ventilation directly affects all except the lighting, so it is crucial to understand the performance of it. The ventilation efficiency concept therefore earn significance, because it is an attempt to quantify a parameter that can easily distinguish the different options for air diffusion in the spaces. The two indicators most internationally accepted are the Air Change Efficiency (ACE) and the Contaminant Removal Effectiveness (CRE). Nowadays with the developed of the Computational Fluid Dynamics (CFD) the behaviour of ventilation can be more easily predicted. Thirteen strategies of air diffusion were measured in a test chamber through the application of the tracer gas method, with the objective to validate the calculation by the MicroFlo module of the IES-VE software for this two indicators. The main conclusions from this work were: that the values of the numerical simulations are in agreement with experimental measurements; the value of the CRE is more dependent of the position of the contamination source, that the strategy used for the air diffusion; the ACE indicator is more appropriate for quantifying the quality of the air diffusion; the solutions to be adopted, to maximize the ventilation efficiency should be, the schemes that operate with low speeds of supply air and small differences between supply air temperature and the room temperature.

Comparison of contaminant removal effectiveness and air change efficiency as indicator of air diffusion quality.

The ventilation efficiency concept is an attempt to quantify a parameter that can easily distinguish the different options for air diffusion in the building spaces. Thirteen strategies of air diffusion were measured in a test chamber through the application of the tracer gas method, with the objective to validate the calculation by Computational fluid dynamics (CFD). Were compared the Air Change Efficiency (ACE) and the Contaminant Removal Effectiveness (CRE), the two indicators most internationally accepted. The main results from this work shows that the values of the numerical simulations are in good agreement with experimental measurements and also, that the solutions to be adopted for maximizing the ventilation efficiency should be the schemes that operate with low speeds of supply air and small differences between supply air temperature and the room temperature.

O sistema de controlo interno numa empresa do sector hoteleiro: estudo de caso: âmbito da área de vendas

Trabalho de Projecto apresentado ao Instituto de Contabilidade e Administração do Porto para a obtenção do grau de Mestre em Auditoria, sob a orientação da Doutora Alcina Augusta de Sena Portugal Dias. “Esta versão contém as críticas e sugestões dos elementos do júri”

Contribuição da produção em regime especial na garantia do abastecimento de energia elétrica e o impacto no planeamento da rede

Esta dissertação apresenta um estudo sobre a garantia de fornecimento de energia elétrica por parte dos produtores em regime especial com tecnologia cogeração e o impacto que estes traduzem na fase de planeamento da rede. Este trabalho foi realizado na Energias de Portugal - Distribuição (EDP-D) na direção de planeamento da rede (DPL). Para este estudo foi utilizado o caso de uma subestação com dezoito produtores em regime especial agregados à sua rede, em que dezasseis desses produtores são cogeração. A proposta de estudo para o caso concreto, passa pela análise das condições de funcionamento da subestação e apurar se a mesma necessita de alguma reformulação, tendo em vista as cargas a satisfazer atuais e possível incremento de carga futura. Considerando que a subestação está inserida num ambiente industrial e atendendo que existem diversos produtores de energia elétrica nas imediações da subestação. Para a resolução da garantia do fornecimento de energia por parte da cogeração, estudou-se a possibilidade de prever a energia produzida por estes produtores, através dos seguintes modelos de previsão: árvore de regressão, árvore de regressão com aplicação bagging e uma rede neuronal (unidirecional). Com a implementação destes modelos pretende-se estimar qual a potência que se pode esperar na garantia de abastecimento da carga, prevenindo maior solicitação de potência por parte da subestação. A metodologia utilizada baseia-se em simulações computacionais.

Análise e identificação do sinal de aceleração num pé

Com a massificação do uso da tecnologia no dia-a-dia, os sistemas de localização têm vindo a aumentar a sua popularidade, devido à grande diversidade de funcionalidades que proporcionam e aplicações a que se destinam. No entanto, a maior parte dos sistemas de posicionamento não funcionam adequadamente em ambientes indoor, impedindo o desenvolvimento de aplicações de localização nestes ambientes. Os acelerómetros são muito utilizados nos sistemas de localização inercial, pelas informações que fornecem acerca das acelerações sofridas por um corpo. Para tal, neste trabalho, recorrendo à análise do sinal de aceleração provindo de um acelerómetro, propõe-se uma técnica baseada na deteção de passos para que, em aplicações futuras, possa constituir-se como um recurso a utilizar para calcular a posição do utilizador dentro de um edifício. Neste sentido, este trabalho tem como objetivo contribuir para o desenvolvimento da análise e identificação do sinal de aceleração obtido num pé, por forma a determinar a duração de um passo e o número de passos dados. Para alcançar o objetivo de estudo foram analisados, com recurso ao Matlab, um conjunto de 12 dados de aceleração (para marcha normal, rápida e corrida) recolhidos por um sistema móvel (e provenientes de um acelerómetro). A partir deste estudo exploratório tornou-se possível apresentar um algoritmo baseado no método de deteção de pico e na utilização de filtros de mediana e Butterworth passa-baixo para a contagem de passos, que apresentou bons resultados. Por forma a validar as informações obtidas nesta fase, procedeu-se, seguidamente, à realização de um conjunto de testes experimentais a partir da recolha de 33 novos dados para a marcha e corrida. Identificaram-se o número de passos efetuados, o tempo médio de passo e da passada e a percentagem de erro como as variáveis em estudo. Obteve-se uma percentagem de erro igual a 1% para o total dos dados recolhidos de 20, 100, 500 e 1000 passos com a aplicação do método proposto para a contagem do passo. Não obstante as dificuldades observadas na análise dos sinais de aceleração relativos à corrida, o algoritmo proposto mostrou bom desempenho, conseguindo valores próximos aos esperados. Os resultados obtidos permitem afirmar que foi possível atingir-se o objetivo de estudo com sucesso. Sugere-se, no entanto, o desenvolvimento de futuras investigações de forma a alargar estes resultados em outras direções.