Made available in DSpace on 2014-10-09T12:55:14Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:06:00Z (GMT). No. of bitstreams: 0 / Neste trabalho foi desenvolvida a t¶ecnica de Espectroscopia de Plasma Induzido por Laser aplicada µa an¶alise de patrim^onio hist¶orico atrav¶es do estudo das moedas de Um Cruzeiro de 1945 e Mil R¶eis de 1939, utilizando um laser de Nd:YAG operando em modo de chaveamento Q. Foram determinadas as melhores condi»c~oes de energia do pulso laser e tempos de atraso entre o pulso e a aquisi»c~ao dos espectros e de integra»c~ao do sinal espectrosc¶opico para aplica»c~ao da t¶ecnica em patrim^onio hist¶orico. Para garantir a reprodutibilidade da t¶ecnica, a temperatura de excita»c~ao eletr^onica, a temperatura de ioniza»c~ao e a densidade eletr^onica do plasma foram determinadas. O dano causado µas moedas foi avaliado utilizando a t¶ecnica de Tomogra¯a por Coer^encia ¶ Optica. Utilizando o m¶etodo livre de calibra»c~ao, as concentra»c~oes elementares foram determinadas, por¶em a concentra»c~ao determinada para o Alum¶³nio, presente no material de forja, estava abaixo de seu valor nominal e do valor determinado atrav¶es da t¶ecnica de An¶alise por Ativa»c~ao Neutr^onica. Uma investiga»c~ao da fra»c~ao de ioniza»c~ao revelou que a fra»c~ao de ioniza»c~ao presente no plasma estava acima do valor esperado por ioniza»c~ao t¶ermica para as temperaturas atingidas, indicando a presen»ca de processos de ioniza»c~ao n~ao t¶ermicos, que in°uenciavam nas medidas do Alum¶³nio. Foi realizada uma corre»c~ao na concentra»c~ao do elemento, utilizando a fra»c~ao de ioniza»c~ao devido aos processos de ioniza»c~ao n~ao t¶ermicos, e os novos valores de concentra»c~ao determinados obtiveram uma grande concord^ancia com os valores nominal e determinados por An¶alise por Ativa»c~ao Neutr^onica. ii / Dissertação (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

La recherche des phases hydratées à la surface de Mars est essentielle à la compréhension de son passé habitable et des changements climatiques globaux qu'elle a subis. Le rover MSL/Curiosity apporte de nouveaux moyens pour caractériser l'hydratation de la surface. En particulier, la spectroscopie de plasma induite par laser (LIBS) de l'instrument ChemCam mesure la composition élémentaire à distance. Il permet une détection de l'hydrogène par le pic d'émission H Balmer alpha à 656.6 nm. Cependant la quantification de cet élément n'a été que très peu étudiée. Le modèle de qualification de l'instrument ChemCam a été intégré à un banc LIBS afin d'analyser des séries d'échantillons hydratés au laboratoire. A l'exception de quelques échantillons révélant des phénomènes spécifiques à l'hydrogène, ces tests montrent qu'un étalonnage linéaire est obtenu avec la teneur en eau. Sur Mars, dans le cratère Gale, cette calibration révèle l'hydratation de différentes phases : la bassanite (CaSO4 × 0.5H2O) dans les veines remplissant les fractures des roches, les sulfates de magnésium, les sédiments opalifères et argileux découverts in situ. Les mesures d'abondances en eau effectuées jusqu'à présent étaient restreintes à de rares expériences de pyrolyse ; cette étude montre que ChemCam apporte maintenant un nouveau moyen opérationnel pour la mesure de l'hydrogène à la surface, à l'échelle submillimétrique et couvrant un très grand nombre de roches. / The search for hydrated phases lying at the surface of Mars is essential to understand its habitable past and the fate of water on a planet disrupted by global climate changes. The MSL/Curiosity rover provides new tools to characterize surface hydration in situ. Among these, laser induced breakdown spectroscopy (LIBS) performed by the ChemCam instrument enables remote measurement of elementary abundance. However, measuring the LIBS emission peak of hydrogen at 656.6 nm (Balmer alpha) to quantify target water content is poorly documented in the literature. Using the instrument replica, large series of hydrated samples have been analyzed in the laboratory under Martian atmospheric conditions. Except for some samples on which effects specific to the hydrogen signal have been observed, these tests show that a linear calibration can be obtained with target water content. On Mars, at Gale crater, this calibration reveals the hydration of different phases: bassanite (CaSO4 × 0.5H2O) in the veins filling the bedrock fractures, magnesium sulfates, opaline and clay rich sediments discovered in situ. Measurement of water content performed to date have been limited to sparse and bulk pyrolysis experiments; this study shows that ChemCam provides a new technique to measurement hydrogen on the surface, at a submillimeter scale and sampling a very large number of rocks.

Kandidatuppsatsen består av en kvalitativ forskningsstudie med innehållsanalys som metod. Syftet är att genomföra en jämförande studie över hur vuxna som tidigare varit familjehemsplacerade som barn ser tillbaka på sin tid som placerad. Variabeln som eftersöks  att undersöka är om det finns skillnad i uttryck om sin placering hos de som hade kontinuitet i sin placering i jämförelse med de som haft ett sammanbrott i sin placering vid minst ett tillfälle. Intervjuerna genomfördes med hjälp av en semistrukturerad metod, vilket innebär att att intervjuerna utgår flexibelt från en färdigställd mall, detta innebär att respondenten har friheten att utrycka sig fritt samtidigt som att intervjun får en viss inriktning för att underlätta analysen av materialet. Det insamlade materialet från intervjuerna bearbetades sedan genom transkribering, kodning och kategorisering. För att kunna behandla det bearbetade materialet konstruerades en forskningsöversikt för att kunna begripliga det insamlade materialet. Det framtagna resultatet antyder att personer som har haft sammanbrott i placering upplever större svårigheter att skapa kontaktnät, svårare skolgång samt belyser ett mer utåtagerande beteende. Vidare visar  även studien på att ålder vid placering är en viktig faktor för den placerades upplevelse av inkludering i familjehemmet.

L’analyse en ligne et in situ constitue aujourd’hui un axe de développement stratégique pour la chimie analytique. C’est particulièrement vrai dans le domaine nucléaire pour lequel les contraintes de sécurité liées à la radioactivité des échantillons, et la nécessité de limiter au maximum les déchets issus des analyses, plaident en faveur de techniques de mesure à distance, sans prélèvement ni préparation d’échantillon. La spectroscopie d’émission de plasma créé par laser (ou LIBS pour laser-induced breakdown spectroscopy), technique d’analyse élémentaire des matériaux basée sur l’ablation laser et la spectroscopie d’émission optique, possède ces qualités. C’est donc une technique de choix pour l’analyse en ligne. Cependant, la maîtrise de la mesure est délicate pour plusieurs raisons. D’abord, la LIBS est multiparamétrique et l’effet des paramètres expérimentaux sur les performances analytiques n’est pas toujours clairement établi. Ensuite, les phénomènes physiques donnant lieu au signal LIBS sont non linéaires, couplés, et transitoires. Enfin, un système d’analyse en ligne doit être le plus robuste possible face aux variations non contrôlées des conditions de mesure. L’objectif de cette thèse est donc d’améliorer la maîtrise et les performances de l’analyse quantitative par LIBS en utilisant des méthodes multivariées capables de gérer la multidimensionalité, la non linéarité et le couplage des paramètres et des données. Pour cela, le travail se décompose en deux parties. Dans un premier temps, nous avons réalisé un plan d’expériences composite centré visant à relier les paramètres expérimentaux de l’ablation laser (énergie de l’impulsion et paramètres de focalisation du faisceau) et de la détection du signal (délai après le tir laser) aux caractéristiques physiques du plasma (masse ablatée, température) et aux performances analytiques (intensité et répétabilité du signal). L’optimisation des paramètres qui en résulte est alors interprétée comme le meilleur compromis, pour l’analyse quantitative, entre efficacité d’ablation laser et chauffage du plasma. Dans un deuxième temps, nous avons développé une méthodologie multivariée basée sur les techniques MCR-ALS, ICA et PLS, pour quantifier certains éléments dans différentes matrices métalliques en exploitant, en plus de la dimension spectrale habituelle, la dimension temporelle du signal LIBS. Cette dernière, pourtant essentielle, est généralement négligée dans la littérature. Dans cette partie, nous discutons donc de l’intérêt de cette approche par rapport aux méthodes usuelles de quantification (univariée et multivariée), et de l’apport de cette méthodologie pour diagnostiquer, comprendre et éventuellement compenser les effets de matrice observés en LIBS. / Online and in situ analysis is now a strategic development for analytical chemistry. This is especially true in the nuclear field for which the security constraints related to the radioactivity of samples, and the need to minimize waste from analyzes argue for remote measurement techniques without sampling or sample preparation. Laser-Induced Breakdown Spectroscopy (LIBS) technique for elemental analysis of materials based on laser ablation and the optical emission spectroscopy, has these qualities. It is a technique of choice for online analysis. However, the processes involved in LIBS, namely laser ablation, atomization, plasma formation and emission, are quite complex and difficult to control because the underlying physical phenomena are coupled and nonlinear. In addition, the analytical performance of the LIBS technique depends strongly on the choice of experimental conditions. Finally, an online analysis system should be as robust as possible face to uncontrolled variations in measurement conditions. The processes involved in LIBS, namely laser ablation, atomization, plasma formation and emission, are quite complex and difficult to control because the underlying physical phenomena are coupled and nonlinear. In addition, the analytical performance of the LIBS technique depends strongly on the choice of experimental conditions. The objective of this thesis is to improve control and performance of quantitative analysis by LIBS using multivariate methods capable of handling multi-dimensionality, nonlinearity and the coupling between parameters and data. For this, the work is divided into two parts. First the optimization is carried out using a central composite design to model the relationship between the experimental parameters of laser ablation (pulse energy and beam focusing parameters) and signal detection (delay time) to the physical characteristics of plasma (ablated mass, temperature) and the analytical performance (intensity and repeatability of the signal). The optimization parameters that results is then interpreted as the best compromise for the quantitative analysis between efficiency of laser ablation and plasma heating. Secondly, we developed a multivariate methodology based on MCR-ALS, ICA and PLS techniques to quantify certain elements in different metallic matrices operator, in addition to the usual spectral dimension, the time dimension of LIBS signal. In this part, we discuss the value of this approach over conventional methods of quantification (univariate and multivariate) and the contribution of this methodology to diagnose, understand and possibly compensate matrix effects observed in LIBS.

Mica/Epoxy machine insulation is a composite material of the mineral mica, fibre-glass mesh and epoxy resin. The material is used in motors and generators rated for high voltage, where the material must withstand multiple stresses such as elevated temperatures, mechanical and electrical stresses. This is a novel investigation that focuses on the breakdown mechanisms related to electrical stress of the insulation. These include partial discharges and electrical treeing. The micro Computed Tomography (μCT) uses a series of X-ray images to visualise the interior. This provides a method for non-invasively examination of the insulation for any signs of material degradation caused by high electrical fields. The following thesis presents an initial study on how this material system interacts with the μCT, the production of 16 samples capable of being electrically aged and scanned in the μCT, with minimal interference, sample preparation and an analysis of the images produced from the μCT. The samples produced are electrically aged at different voltages after which they are scanned with the μCT. The images produced are then analysed for signs of material degradation using different software. Some of the samples did have a complete electrical breakdown and an attempt of correlating these breakdowns to the amount of folds in the insulation is done. It is found that samples with an aluminium core are suitable for μCT imaging. The visualisation of defects such as voids, resin rich parts or folds in insulation is also possible. The detection of material degradation due to electrical aging is not clear enough to draw any conclusions although some possible signs are found. For samples that had an electrical breakdown the result is much clearer. It shows the breakdown channels path inside the insulation, moving in between the mica tape layers. The samples with a complete breakdown also had tendencies that the breakdown channels followed the resin rich part in the sample. Even if no signs of electrical treeing can be seen in the samples during aging, the breakdown channels visualised still show what path the final treeing did take and how it did so by moving around the mica tape.

M.Ing. (Engineering Management) / “A robust set of estimates puts a project on a firm footing from day 1, allowing the project manager to apply the right level of resources at the appropriate time. If the plan has been based on poor estimates, problems will occur during the execution of the project …” This statement places great importance on the ability to estimate costs as accurately as practicable early during a project life cycle. Many techniques have been proposed with the aim of aiding with the production of early cost estimates,which have acceptable accuracies necessary for Feasibility Study purposes. One such technique is Parametric Cost Estimating for developing Parametric Cost Models used in producing these conceptual estimates.At the heart of Parametric Cost Estimating Technique, is a fundamental statistical technique commonly known as Linear Regression Analysis.The problem that the research addresses is that of the general misconception found to prevail within project houses that some engineering systems are too complex to model using the Parametric Cost Estimating Technique. The objectives of this research are to investigate and demonstrate the effectiveness of this technique in predicting the costs of a system for Feasibility Study purposes. The objectives were achieved by conducting a secondary literature review of case studies of similar Parametric Cost Models that were developed by others for engineering systems of varying complexities. A second method used in achieving the objectives included formulating a case study in which a Parametric Cost Model was developed to illustrate the concept and to prove that the accuracies produced by the model meet the requirements for Feasibility Studies.The research was limited to initial project costs required for Feasibility Studies,ignoring the effects of qualitative factors,focusing only on the acquisition costs and not the total life cycle costs of the system.The case study was developed for a passenger motor vehicle as the system of interest because sufficient cost data in the form of vehicle retail price and performance specifications is publicly available in car magazines making it possible to build a meaningful Parametric Cost Model. The Parametric Cost Model was developed using Microsoft Excel 2007 and had a Mean Absolute Error Rate of 10.9% and the range of accuracy obtained, -20% to 10% with 67% confidence level and -30% to 30% with 95% confidence level, conforming to a Class 4 estimate which meets the accuracy requirements for a Feasibility Study.

This master thesis is focused on methods of outlier detection. The aim of this work is to assess the suitability of using robust methods on real data of EKO-KOM, a.s. The first part of the thesis provides an overview and a theoretical treatise on classic and robust methods of outlier detection. These methods are subsequently applied to the obtained data file of EKO-KOM, a.s. in the practical part of the thesis. At the conclusion of the thesis, there are recommendations about suitability of methods, which are based on comparison of classical and robust methods.

Large-scale unsteady flow structures play an influential role in the dynamics of many practical flows, such as those found in gas turbine combustion chambers. This thesis is concerned primarily with large-scale unsteady structures that arise due to self-sustained hydrodynamic oscillations, also known as global hydrodynamic instability. Direct numerical simulation (DNS) of the Navier--Stokes equations in the low Mach number limit is used to obtain a steady base flow, and the most unstable direct and adjoint global modes. These are combined, using a structural sensitivity framework, to identify the region of the flow and the feedback mechanisms that are responsible for causing the global instability. Using a Lagrangian framework, the direct and adjoint global modes are also used to identify the regions of the flow where steady and unsteady control, such as a drag force or heat input, can suppress or promote the global instability. These tools are used to study a variety of reacting and non-reacting flows to build an understanding of the physical mechanisms that are responsible for global hydrodynamic instability in swirling diffusion flames. In a non-swirling lifted jet diffusion flame, two modes of global instability are found. The first mode is a high-frequency mode caused by the instability of the low-density jet shear layer in the premixing zone. The second mode is a low-frequency mode caused by an instability of the outer shear layer of the flame. Two types of swirling diffusion flames with vortex breakdown bubbles are considered. They show qualitatively similar behaviour to the lifted jet diffusion flames. The first type of flame is unstable to a low-frequency mode, with wavemaker located at the flame base. The second type of flame is unstable to a high-frequency mode, with wavemaker located at the upstream edge of the vortex breakdown bubble. Feedback from density perturbations is found to have a strong influence on the unstable modes in the reacting flows. The wavemaker of the high-frequency mode in the reacting flows is very similar to its non-reacting counterpart. The low-frequency mode, however, is only observed in the reacting flows. The presence of reaction increases the influence of changes in the base flow mixture fraction profiles on the eigenmode. This increased influence acts through the heat release term. These results emphasize the possibility that non-reacting simulations and experiments may not always capture the important instability mechanisms of reacting flows, and highlight the importance of including heat release terms in stability analyses of reacting flows.

No description available.

The 21st century marks the defining point of human history in terms of technological advancement. In 2014, we were at the edge of acquiring a complete understanding of the fundamental construct to all life forms. The capability to manipulate and recreate lives as desired will soon be at our hands and will eventually lead to the redefinition of life and humanity. This brave new world, for better or worse, will be stitched together by scientific breakthroughs in many disciplines. Nanopore fluidic system – and microfluidic in general – might be one of the key puzzles towards the future. It is seen as a likely candidate for the next generation of rapid and low-cost genetic sequencing technology, which will allow us to gain thorough insight into the genetic code of every living organism on earth. It can also have the capability to individually detect and manipulate virtually any biological molecules, possibly allowing it to be a universal diagnostic tool or a bio-molecule synthesiser. The future of nanopore fluidic system is prosperous, but the difficulties are equally challenging. Currently, both biological and solid-state nanopores are non-trivial to create. For instance, a small solid-state nanopore can only be fabricated with expansive machinery in a low-yield, low-throughput manner. To overcome this challenge, a new set of methods involving high electric field to fabricate and enlarge a solid-state nanopore has been developed. It was found that a nanopore, when subjected to a high electric field, can be enlarged in angstrom increments and cleared of unidentified obstructions that cause low-frequency ionic current fluctuations. It was also found that an intact solid-state membrane, when subjected to a high electric field for a period of time, can leave a single nanopore imprinted onto it. The process of creation is best describe as a dielectric breakdown event and can be modeled by the percolation theory for dielectric breakdown. The resulting nanopores are cylindrical in shape and are shown to be equally capable of single molecule sensing compare to pores created by other methods. To accommodate future nanopore designs and applications and to examine the scope of applicability of the new fabrication approach, more advanced nanopore devices were created on some dual-layer solid-state membranes comprising of a metallic and a dielectric layer. Experiments indicated that the method could indeed create nanopore on such advanced membranes. It was further shown that the metallic layer receded further than the dielectric layer, forming a hollow conical shape at the opening of the dielectric nanopore. Such metalized bi-layer nanopore system was found to interact strongly with short single stranded DNA molecules, resulting in prolonged DNA translocation time. A simple picture of the mechanism was proposed to explain the observation. Lastly, to extend the limit of the new fabrication approach, I attempted to fabricate nanopore on complex multi-layer membranes involving a graphene film sandwiched in several dielectric materials. It was found that the quality of the graphene film and the transfer method were vital to the success of this project. Nevertheless, preliminary results indicated that the new method could create a nanopore through this complex multi-layer membrane. The new method to fabricate and tune both simple and complex nanopores is amongst the simplest, the least costly and the most efficient one that one can imagine. The research work has already sparked a dramatic increase in scientific throughput in our laboratory and other laboratories we had collaboration with. It fueled more than a dozen projects and involved close to a thousand nanopores in total. Such projects are far from possible if they were to rely on conventional fabrication methods. However, these are insignificant if we consider the new method is simple enough that, for the very first time, general public can easily access nanofabrication and single-molecule manipulation technology. The liberation of nanotechnology to the general public symbolically marks the beginning of a brave new world.