Propõe-se método novo e completo para análise de acetona em ar exalado envolvendo coleta com pré-concentração em água, derivatização química e determinação eletroquímica assistida por novo algoritmo de processamento de sinais. Na literatura recente a acetona expirada vem sendo avaliada como biomarcador para monitoramento não invasivo de quadros clínicos como diabetes e insuficiência cardíaca, daí a importância da proposta. Entre as aminas que reagem com acetona para formar iminas eletroativas, estudadas por polarografia em meados do século passado, a glicina apresentou melhor conjunto de características para a definição do método de determinação por voltametria de onda quadrada sem a necessidade de remoção de oxigênio (25 Hz, amplitude de 20 mV, incremento de 5 mV, eletrodo de gota de mercúrio). O meio reacional, composto de glicina (2 mol·L-1) em meio NaOH (1 mol·L-1), serviu também de eletrólito e o pico de redução da imina em -1,57 V vs. Ag|AgCl constituiu o sinal analítico. Para tratamento dos sinais, foi desenvolvido e avaliado um algoritmo inovador baseado em interpolação de linha base por ajuste de curvas de Bézier e ajuste de gaussiana ao pico. Essa combinação permitiu reconhecimento e quantificação de picos relativamente baixos e largos sobre linha com curvatura acentuada e ruído, situação em que métodos convencionais falham e curvas do tipo spline se mostraram menos apropriadas. A implementação do algoritmo (disponível em http://github.com/batistagl/chemapps) foi realizada utilizando programa open source de álgebra matricial integrado diretamente com software de controle do potenciostato. Para demonstrar a generalidade da extensão dos recursos nativos do equipamento mediante integração com programação externa em linguagem Octave (open source), implementou-se a técnica da cronocoulometria tridimensional, com visualização de resultados já tratados em projeções de malha de perspectiva 3D sob qualquer ângulo. A determinação eletroquímica de acetona em fase aquosa, assistida pelo algoritmo baseado em curvas de Bézier, é rápida e automática, tem limite de detecção de 3,5·10-6 mol·L-1 (0,2 mg·L-1) e faixa linear que atende aos requisitos da análise em ar exalado. O acetaldeído, comumente presente em ar exalado, em especial, após consumo de bebidas alcoólicas, dá origem a pico voltamétrico em -1,40 V, contornando interferência que prejudica vários outros métodos publicados na literatura e abrindo possibilidade de determinação simultânea. Resultados obtidos com amostras reais são concordantes com os obtidos por método espectrofotométrico, em uso rotineiro desde o seu aperfeiçoamento na dissertação de mestrado do autor desta tese. Em relação à dissertação, também se otimizou a geometria do dispositivo de coleta, de modo a concentrar a acetona num volume menor de água gelada e prover maior conforto ao paciente. O método completo apresentado, englobando o dispositivo de amostragem aperfeiçoado e o novo e efetivo algoritmo para tratamento automático de sinais voltamétricos, está pronto para ser aplicado. Evolução para um analisador portátil depende de melhorias no limite de detecção e facilidade de obtenção eletrodos sólidos (impressos) com filme de mercúrio, vez que eletrodos de bismuto ou diamante dopado com boro, entre outros, não apresentaram resposta. / A new and complete method for analyzing acetone in exhaled breath is proposed, involving sample collection by preconcentration in water, chemical derivatization and electrochemical determination assisted by a new signal processing algorithm. Breath acetone is under investigation in the medical literature as a biomarker for noninvasive monitoring of clinical conditions such as diabetes and heart failure and better analyzers are demanded. Some amines that react with acetone to form electroactive imines, already studied by polarography in the middle of the last century, were evaluated here as derivatizing agents and glycine presented the best compromise for the definition of a determination method by square wave voltammetry without purging of dissolved oxygen (20 mV pulses at 25 Hz with 5 mV scanning steps, mercury drop electrode). The derivatization medium of glycine (2 mol·L-1) and NaOH (1 mol·L-1) also serves as electrolyte and the imine reduction peak at -1.57 V vs. Ag|AgCl constitutes the analytical signal. For signal processing a novel algorithm based on baseline automatic prediction using Bézier curves was developed in combination with Gaussian peak fitting. This innovative combination enables the recognition and quantification of relatively low and broad peaks on a curved and noisy baseline while standard procedures fail and fitting of splines is less appropriate. The algorithm (available at http://github.com/batistagl/chemapps) was implemented using open source matrix algebra software directly integrated with the potentiostat control software. The generality of this approach to extend the native resources of commercial equipment was evidenced by proceeding the implementation of 3D chronocoulometry with help of the open source Octave language. The processed charge vs. potential vs. time function 3-D surfaces for the forward and backward steps can be observed from any angle on the screen. The fast automatic electrochemical determination of acetone assisted by the Bézier based curve fitting algorithm, with an acetone detection limit of 3.5·10-6 mol·L-1 (0.2 mg·L-1) and a wide linear range is entirely satisfactory for breath analysis. Acetaldehyde, an expected component of breath, especially after ingestion of alcohol, and a common interferent for some other analytical methods, generates a peak at -1.40 V that does not interfere with the acetone determination and that is possibly suitable for simultaneous determination of this analyte. Results obtained with real samples are in agreement with spectrophotometric determinations routinely applied to breath analysis, formerly developed in the master dissertation of the author of this thesis. The geometry of the impinger sampling device was also improved (in comparison with the dissertation) in order to collect the acetone in a smaller volume of cooled water and to allow the patient to breath more freely. The complete method at its current state of development, encompassing the improved sampler and the new effective signal processing algorithm for voltammetric signals is ready for use. Evolution to a portable analyzer can be envisioned if the shortcomings of detection limits of solid (screen-printed) electrode preparation with a mercury film are overcome, once the imine signal was not observed on solid electrodes like bismuth and boron doped diamond.

Com a popularização de equipamentos tradicionais de captura de imagens, como câmeras digitais, e o avanço tecnológico dos dispositivos não invasivos, como tomografia e ressonância, cresce também a necessidade e consequente uso de métodos numéricos para simulação de fenômenos físicos em domínios definidos por imagens. Um dos pré-requisitos para a aplicação de tais métodos numéricos consiste na discretização do domínio em questão, num processo denominado geração de malhas. Embora diversos métodos de geração de malha tenham sido propostos para discretizar domínios definidos por primitivas geométricas, pouco tem sido feito no sentido de gerar uma decomposição diretamente a partir de imagens. Neste trabalho, apresentamos uma abordagem de geração de malhas de qualidade a partir de domínios definidos por imagens com textura. Mais especificamente, a pesquisa descrita nesta tese contribui com a melhoria do algoritmo Imesh, ao sanar três de suas principais limitações: tratamento de imagens com texturas; controle do nível de refinamento da malha e suporte a outros tipos de elementos. Estas contribuições flexibilizam o processo de geração da malha, e ainda ampliam o domínio de aplicações do algoritmo Imesh, à medida que são considerados domínios definidos por imagens com textura e o uso de métodos numéricos para elementos não simpliciais torna-se possível. O algoritmo de melhoria da malha gerada utiliza uma abordagem inovadora de remalhamento baseada em templates e guiada por retalhos de Bézier / With the spreading of traditional image capturing devices, such as digital cameras, and the technological advancement of more specific imaging devices such as CT and MRI, also increased the need and the following use of numerical methods for simulation of physical phenomena in domains defined by images. One of the prerequisites for the application of such numerical methods is the discretization of the corresponding domain, in a process called mesh generation. Although several methods of mesh generation have been proposed to discretize domains defined by geometric primitives, little has been done to generate a decomposition directly from images. We present an approach to generate quality meshes from domains defined by images with texture. More specifically, the research described in this thesis contributes to the improvement of the Imesh algorithm, removing three of its main limitations: treatment textured images, control of the level of the mesh refinement and support for other types of non-simplicial elements. These contributions provide flexibility to the mesh generation process, and extend the range of applications of Imesh by both handling textured images and considering the use of numerical methods for non-simplicial elements. The mesh quality improvement algorithm uses a new approach based on mesh templates and it is guided by Bezier patches

Com a popularização de equipamentos tradicionais de captura de imagens, como câmeras digitais, e o avanço tecnológico dos dispositivos não invasivos, como tomografia e ressonância, cresce também a necessidade e consequente uso de métodos numéricos para simulação de fenômenos físicos em domínios definidos por imagens. Um dos pré-requisitos para a aplicação de tais métodos numéricos consiste na discretização do domínio em questão, num processo denominado geração de malhas. Embora diversos métodos de geração de malha tenham sido propostos para discretizar domínios definidos por primitivas geométricas, pouco tem sido feito no sentido de gerar uma decomposição diretamente a partir de imagens. Neste trabalho, apresentamos uma abordagem de geração de malhas de qualidade a partir de domínios definidos por imagens com textura. Mais especificamente, a pesquisa descrita nesta tese contribui com a melhoria do algoritmo Imesh, ao sanar três de suas principais limitações: tratamento de imagens com texturas; controle do nível de refinamento da malha e suporte a outros tipos de elementos. Estas contribuições flexibilizam o processo de geração da malha, e ainda ampliam o domínio de aplicações do algoritmo Imesh, à medida que são considerados domínios definidos por imagens com textura e o uso de métodos numéricos para elementos não simpliciais torna-se possível. O algoritmo de melhoria da malha gerada utiliza uma abordagem inovadora de remalhamento baseada em templates e guiada por retalhos de Bézier / With the spreading of traditional image capturing devices, such as digital cameras, and the technological advancement of more specific imaging devices such as CT and MRI, also increased the need and the following use of numerical methods for simulation of physical phenomena in domains defined by images. One of the prerequisites for the application of such numerical methods is the discretization of the corresponding domain, in a process called mesh generation. Although several methods of mesh generation have been proposed to discretize domains defined by geometric primitives, little has been done to generate a decomposition directly from images. We present an approach to generate quality meshes from domains defined by images with texture. More specifically, the research described in this thesis contributes to the improvement of the Imesh algorithm, removing three of its main limitations: treatment textured images, control of the level of the mesh refinement and support for other types of non-simplicial elements. These contributions provide flexibility to the mesh generation process, and extend the range of applications of Imesh by both handling textured images and considering the use of numerical methods for non-simplicial elements. The mesh quality improvement algorithm uses a new approach based on mesh templates and it is guided by Bezier patches

Les artistes apprécient les images vectorielles car elles sont compactes et facilement manipulables. Cependant, beaucoup d’artistes expriment leur créativité en dessinant, en peignant ou encore en prenant des photographies. Digitaliser ces contenus produit des images rasterisées. L’objectif de cette thèse est de convertir des images rasterisées en images vectorielles qui sont facilement manipulables. Nous avons formulé le problème de vectorisation comme un problème de minimisation d’énergie que nous avons défini par deux termes. Le premier terme, plutôt classique, mesure la fidélité de l’image vectorielle générée avec l’image rasterisée d’origine. La nouveauté principale est le second terme qui mesure la simplicité de l’image vectorielle générée. Le terme de simplicité est global et contient des variables discrètes, ce qui rend sa minimisation difficile. Nous avons proposé deux algorithmes de vectorisation : un pour la vectorisation de croquis et un autre pour la vectorisation multicouches d’images couleurs. Ces deux algorithmes commencent par extraire des primitives géométriques (un squelette pour les croquis et une segmentation pour les images couleurs) qu’ils assemblent ensuite pour former l’image vectorielle. Dans la dernière partie de la thèse, nous proposons un nouvel algorithme qui est capable de vectoriser des croquis sans étapes préliminaires : on extrait et assemble les primitives simultanément. Nous montrons le potentiel de ce nouvel algorithme pour une variété de problèmes de vision par ordinateur comme l’extraction de réseaux linéiques, l’extraction d’objets et la compression d’images. / Artists appreciate vector graphics for their compactness and editability. However many artists express their creativity by sketching, painting or taking photographs. Digitizing these images produces raster graphics. The goal of this thesis is to convert raster graphics into vector graphics that are easy to edit. We cast image vectorization as an energy minimization problem. Our energy is a combination of two terms. The first term measures the fidelity of the vector graphics to the input raster graphics. This term is a standard term for image reconstruction problems. The main novelty is the second term which measures the simplicity of the vector graphics. The simplicity term is global and involves discrete unknowns which makes its minimization challenging. We propose two stochastic optimizations for this formulation: one for the line drawing vectorization problem and another one for the color image vectorization problem. These optimizations start by extracting geometric primitives (skeleton for sketches and segmentation for color images) and then assembling these primitives together to form the vector graphics. In the last chapter we propose a generic optimization method for the problem of geometric shape extraction. This new algorithm does not require any preprocessing step. We show its efficiency in a variety of vision problems including line network extraction, object contouring and image compression.

La construction des courbes parallèles est fondamentale pour différentes applications en modélisation géométrique, telles que l'étude des trajectoires d'outils pour les machines à commande numérique ou pour la définition des zones de tolérance. En général, la courbe parallèle d'une courbe rationnelle n'est pas rationnelle, ce qui conduit à déterminer une approximation de cette courbe parallèle par une courbe spline. Récemment, J. C. Fiorot et T. Gensane et indépendamment H. Pottmann ont donné la forme générale de toutes les courbes rationnelles à parallèles rationnelles (courbes à hodographe pythagorien). Dans cette dernière famille figurent les quartiques de Tschirnhausen. Ces courbes ont même flexibilité que les coniques, leurs courbes parallèles sont rationnelles de degré quatre et sont exactement les développantes des cubiques de Tschirnhausen. En se basant sur cette caractérisation, nous présentons un algorithme d'approximation, avec un contact d'ordre deux, d'une courbe et de ses parallèles par des quartiques de Tschirnhausen préservant la variation de la courbure. Par ailleurs, le caractère judicieux de la représentation Bézier duale des courbes à hodographe pythagorien et de leurs parallèles, nous a permis de construire des ovales et des rosettes rationnelles à largeur constante qui jouent un rôle important en mécanique des cames. Enfin, suite aux travaux de H. Busemann et H. Guggenheimer sur la géométrie plane de Minkowski, nous généralisons la notion de courbes parallèles ainsi que les résultats de H. Pottmann (concernant la caractérisation Bézier duale et la caractérisation géométrique des courbes à hodographe pythagorien) au plan de Minkowski

L'objet de ce mémoire est de montrer que désormais l'informatique permet de réaliser un vieux rève : se débarasser du carcan du plomb et créer de nouveaux caractères adaptés à de nouvelles technologies.<br /><br />Ce mémoire comprend deux parties. La première est une courte synthèse sur la typographie. Nous rappelons ce qu'est un caractère et comment on les fabriquait autrefois puis comment on les manipule aujourd'hui, c'est-à-dire ce qu'est une fonte numérique et comment, depuis peu, on arrive à atteindre les exigences du passé.<br /><br />La seconde partie montre les recherches auxquelles nous avons participé : nous montrons d'abord une possibilité fondamentale en matière de créativité : on peut désormais calculer la forme d'un caractère lorsque l'on l'utilise et non plus avant, une fois pour toutes. Nous donnons comme première application celui du dessin des symboles mathématiques. Nous montrons ensuite comment ce concept de fonte dynamique permet de créer de nouveaux caractères en fonction du contexte.<br /><br />En guise de conclusion, nous indiquons plusieurs voies de recherche.

Cette thèse est une étude de base qui traite de la transformation de la dualité géométrique entre un point et un hyperplan d'un espace affine. Une étape indispensable est alors d'établir une définition rigoureuse de la dualité géométrique ainsi que ses propriétés et caractéristiques. Cette notion de dualité peut se généraliser pour toute forme géométrique décrite à l'aide d'une famille de points ou d'hyperplans. Ainsi une courbe duale d'une courbe paramétrique plane est définie comme enveloppe d'une famille de droites. Ces courbes duales sont ensuite analysées pour trouver des relations de correspondances entre une courbe paramétrique et son image duale. En effet, des correspondances d'interpolation et de convexité sont établies et des exemples de courbes de Bézier duales sont illustrés. On fait ensuite une étude complète des correspondances de singularités entre courbes primales et duales. Enfin, une généralisation de la dualité géométrique à l'aide d'une matrice symétrique inversible a permis d'associer à une courbe paramétrique quelconque une famille de courbes duales dépendant de la matrice symétrique considérée.

La tesis ha centrado su estudio en los mecanismos de leva con palpador circular de traslación por ser éstos ampliamente utilizados en la industria actual. Para el diseño de la ley de desplazamiento se utiliza curvas de Bézier de continuidad 2 C , 3 C y 4 C con tramos rectos y se busca como objetivos de la tesis: aportar conocimiento y fundamento teórico al cálculo del ángulo de presión, radio de curvatura y distribución de la presión entre palpadores de rodillo y levas de modo que se facilite el estudio y la aplicación de dichos mecanismos.En la investigación se han abordado las tres etapas de diseño de un mecanismo leva palpador: definición de la ley de desplazamiento del palpador, obtención del perfil de leva y comprobación del perfil de la leva. Dentro de la etapa de la definición de la ley de desplazamiento se presentan las características que tienen las leyes de desplazamiento de Bézier. En lo referente a la obtención del perfil de la leva en la tesis se propone el diseño de la ley de desplazamiento por tramos de unión en lugar del diseño por trayectos completos de movimiento de la leva (giro total de la leva) y en lo referente a la comprobación del perfil se estudia el ángulo de presión, el radio de curvatura y la distribución de presiones relacionadas con el contacto entre la leva y el palpador.La tesis se divide en siete capítulos. En el primero de ellos se presenta una introducción, en el segundo se expone el estado del arte actual en el diseño de los mecanismo leva palpador, en el tercer capítulo se exponen las características de las leyes de desplazamiento del palpador diseñadas por tramos de unión, en el cuarto capítulo se estudia el ángulo de presión y el radio de curvatura y se muestran las tablas y gráficas para el cálculo de los mismo, en el quinto capítulo se expone la distribución de las presiones y los esfuerzos generados por el contacto entre la leva y el palpador. Es en éstos dos últimos capítulo donde se recogen las aportaciones principales de la investigación. El sexto capítulo presenta las conclusiones y recomendaciones del trabajo y el séptimo la bibliografía y referencias consultadas. / Circular follower-cam mechanisms have a vast range of machinery applications. Bézier curves, in comparison with conventional methods, seems to be a potential route to optimize the design of displacement law in cam mechanisms The aim of this thesis is to provide further knowledge about calculation of pressure angle, curvature radius and pressure distribution for cam mechanisms designed by Bézier curves in order to facilitate the study, thus new applications, of these systems. The investigation has included the three main stages in cam mechanism design: (1) definition of follower's displacement law, (2) development of cam profile, and (3) assessment of the cam profile. Bézier curves are used in the first stage of the process. In addition, a novel method to obtain the cam profile is proposed and supported. With respect to cam profile design, cam displacement law is obtained by segments instead of through cycle motion; with respect to cam profile verification, pressure angle, curvature ratio and pressure distribution due to contact between cam and follower are the design issue.This monography has been organized as follows. First chapter regards with an introduction to the research topic. A detailed literature review about cam-follower mechanism design is summarized in the second chapter. Next chapter enclose explanations of the displacement law's features, followed by a study of pressure angle and curvature radius which include tables and graphics that allow calculated, in the fifth chapter methodology to calculate pressure distribution and stress due to contact forces between cam and follower are present. In these last two chapters, the main contributions of the Ph.D. thesis are described. Conclusions and suggestions for further investigations are summarized in chapter sixth. Finally, literature reviewed is referenced in the seventh section.

To simulate increasingly complex physical phenomena and systems, tightly integrated design-through-analysis (DTA) tools are essential. In this dissertation, the complementary strengths of isogeometric analysis and T-splines are coupled and enhanced to create a seamless DTA framework. In all cases, the technology de- veloped meets the demands of both design and analysis. In isogeometric analysis, the smooth geometric basis is used as the basis for analysis. It has been demonstrated that smoothness offers important computational advantages over standard finite elements. T-splines are a superior alternative to NURBS, the current geometry standard in computer-aided design systems. T-splines can be locally refined and can represent complicated designs as a single watertight geometry. These properties make T-splines an ideal discretization technology for isogeometric analysis and, on a higher level, a foundation upon which unified DTA technologies can be built. We characterize analysis-suitable T-splines and develop corresponding finite element technology, including the appropriate treatment of extraordinary points (i.e., unstructured meshing). Analysis-suitable T-splines form a practically useful subset of T-splines. They maintain the design flexibility of T-splines, including an efficient and highly localized refinement capability, while preserving the important analysis-suitable mathematical properties of the NURBS basis. We identify Bézier extraction as a unifying paradigm underlying all isogeometric element technology. Bézier extraction provides a finite element representation of NURBS or T-splines, and facilitates the incorporation of T-splines into existing finite element programs. Only the shape function subroutine needs to be modified. Additionally, Bézier extraction is automatic and can be applied to any T-spline regardless of topological complexity or polynomial degree. In particular, it represents an elegant treatment of T-junctions, referred to as "hanging nodes" in finite element analysis We then detail a highly localized analysis-suitable h-refinement algorithm. This algorithm introduces a minimal number of superfluous control points and preserves the properties of an analysis-suitable space. Importantly, our local refinement algorithm does not introduce a complex hierarchy of meshes. In other words, all local refinement is done on one control mesh on a single hierarchical “level” and all control points have similar influence on the shape of the surface. This feature is critical for its adoption and usefulness as a design tool. Finally, we explore the behavior of T-splines in finite element analysis. It is demonstrated that T-splines possess similar convergence properties to NURBS with far fewer degrees of freedom. We develop an adaptive isogeometric analysis framework which couples analysis-suitable T-splines, local refinement, and Bézier extraction and apply it to the modeling of damage and fracture processes. These examples demonstrate the feasibility of applying T-spline element technology to very large problems in two and three dimensions and parallel implementations. / text

Various industries have embraced 3D printing for manufacturing on-demand, custom printed parts. However, 3D printing requires intelligent data processing and algorithms to go from CAD model to machine instructions. One of the most crucial steps in the process is the slicing of the object. Most 3D printers build parts by accumulating material layers by layer. 3D printing software needs to calculate these layers for manufacturing by slicing a model and calculating the intersections. Finding exact solutions of intersections on the original model is mathematically complicated and computationally demanding. A preprocessing stage of tessellation has become the standard practice for slicing models. Calculating intersections with tessellations of the original model is computationally simple but can introduce inaccuracies and errors that can ruin the final print. This dissertation shows that a point cloud approach to preprocessing and slicing models is robust and accurate. The point cloud approach to object slicing avoids the complexities of directly slicing models while evading the error-prone tessellation stage. An algorithm developed for this dissertation generates point clouds and slices models within a tolerance. The algorithm uses the original NURBS model and converts the model into a point cloud, based on layer thickness and accuracy requirements. The algorithm then uses a gridding structure to calculate where intersections happen and fit B-spline curves to those intersections. This algorithm finds accurate intersections and can ignore certain anomalies and error from the modeling process. The primary point evaluation is stable and computationally inexpensive. This algorithm provides an alternative to challenges of both the direct and tessellated slicing methods that have been the focus of the 3D printing industry.