Dans cette thèse nous intéressons à la conception d'un robot mobile capable d’analyser le comportement et le mouvement d’une personne en environnement intérieur et encombré, par exemple le domicile d’une personne âgée. Plus précisément, notre objectif est de doter le robot des capacités de perception visuelle de la posture humaine de façon à mieux maîtriser certaines situations qui nécessitent de comprendre l’intention des personnes avec lesquelles le robot interagit, ou encore de détecter des situations à risques comme les chutes ou encore d’analyser les capacités motrices des personnes dont il a la garde. Le suivi de la posture dans un environnement dynamique et encombré relève plusieurs défis notamment l'apprentissage en continue du fond de la scène et l'extraction la silhouette qui peut être partiellement observable lorsque la personne est dans des endroits occultés. Ces difficultés rendent le suivi de la posture une tâche difficile. La majorité des méthodes existantes, supposent que la scène est statique et la personne est toujours visible en entier. Ces approches ne sont pas adaptées pour fonctionner dans des conditions réelles. Nous proposons, dans cette thèse, un nouveau système de suivi capable de suivre la posture de la personne dans ces conditions réelles. Notre approche utilise une grille d'occupation avec un modèle de Markov caché pour apprendre en continu l'évolution de la scène et d'extraire la silhouette, ensuite un algorithme de filtrage particulaire hiérarchique est utilisé pour reconstruire la posture. Nous proposons aussi un nouvel algorithme de gestion d'occlusion capable d'identifier et d'exclure les parties du corps cachées du processus de l'estimation de la pose. Finalement, nous avons proposé une base de données contenant des images RGB-D avec la vérité-terrain dans le but d'établir une nouvelle référence pour l'évaluation des systèmes de capture de mouvement dans un environnement réel avec occlusions. La vérité-terrain est obtenue à partir d'un système de capture de mouvement à base de marqueur de haute précision avec huit caméras infrarouges. L'ensemble des données est disponible en ligne. La deuxième contribution de cette thèse, est le développement d'une méthode de localisation visuelle à partir d'une caméra du type RGB-D montée sur un robot qui se déplace dans un environnement dynamique. En effet, le système de capture de mouvement que nous avons développé doit équiper un robot se déplaçant dans une scène. Ainsi, l'estimation de mouvement du robot est importante pour garantir une extraction de silhouette correcte pour le suivi. La difficulté majeure de la localisation d'une caméra dans un environnement dynamique, est que les objets mobiles de la scène induisent un mouvement supplémentaire qui génère des pixels aberrants. Ces pixels doivent être exclus du processus de l'estimation du mouvement de la caméra. Nous proposons ainsi une extension de la méthode de localisation dense basée sur le flux optique pour isoler les pixels aberrants en utilisant l'algorithme de RANSAC. / In this thesis we are interested in designing a mobile robot able to analyze the behavior and movement of a a person in indoor and cluttered environment. Our goal is to equip the robot by visual perception capabilities of the human posture to better analyze situations that require understanding of person with which the robot interacts, or detect risk situations such as falls or analyze motor skills of the person. Motion capture in a dynamic and crowded environment raises multiple challenges such as learning the background of the environment and extracting the silhouette that can be partially observable when the person is in hidden places. These difficulties make motion capture difficult. Most of existing methods assume that the scene is static and the person is always fully visible by the camera. These approaches are not able to work in such realistic conditions. In this thesis, We propose a new motion capture system capable of tracking a person in realistic world conditions. Our approach uses a 3D occupancy grid with a hidden Markov model to continuously learn the changing background of the scene and to extract silhouette of the person, then a hierarchical particle filtering algorithm is used to reconstruct the posture. We propose a novel occlusion management algorithm able to identify and discards hidden body parts of the person from process of the pose estimation. We also proposed a new database containing RGBD images with ground truth data in order to establish a new benchmark for the assessment of motion capture systems in a real environment with occlusions. The ground truth is obtained from a motion capture system based on high-precision marker with eight infrared cameras. All data is available online. The second contribution of this thesis is the development of a new visual odometry method to localize an RGB-D camera mounted on a robot moving in a dynamic environment. The major difficulty of the localization in a dynamic environment, is that mobile objects in the scene induce additional movement that generates outliers pixels. These pixels should be excluded from the camera motion estimation process in order to produce accurate and precise localization. We thus propose an extension of the dense localization method based on the optical flow method to remove outliers pixels using the RANSAC algorithm.

Pairwise alignment between point clouds is an important task in building 3D maps of indoor environments with partial information. The combination of 2D local features with depth information provided by RGB-D cameras are often used to improve such alignment. However, under varying lighting or low visual texture, indoor pairwise frame registration with sparse 2D local features is not a particularly robust method. In these conditions, features are hard to detect, thus leading to misalignment between consecutive pairs of frames. The use of 3D local features can be a solution as such features come from the 3D points themselves and are resistant to variations in visual texture and illumination. Because varying conditions in real indoor scenes are unavoidable, we propose a new framework to improve the pairwise frame alignment using an adaptive combination of sparse 2D and 3D features based on both the levels of geometric structure and visual texture contained in each scene. Experiments with datasets including unrestricted RGB-D camera motion and natural changes in illumination show that the proposed framework convincingly outperforms methods using 2D or 3D features separately, as reflected in better level of alignment accuracy. / O alinhamento entre pares de nuvens de pontos é uma tarefa importante na construção de mapas de ambientes em 3D. A combinação de características locais 2D com informação de profundidade fornecida por câmeras RGB-D são frequentemente utilizadas para melhorar tais alinhamentos. No entanto, em ambientes internos com baixa iluminação ou pouca textura visual o método usando somente características locais 2D não é particularmente robusto. Nessas condições, as características 2D são difíceis de serem detectadas, conduzindo a um desalinhamento entre pares de quadros consecutivos. A utilização de características 3D locais pode ser uma solução uma vez que tais características são extraídas diretamente de pontos 3D e são resistentes a variações na textura visual e na iluminação. Como situações de variações em cenas reais em ambientes internos são inevitáveis, essa tese apresenta um novo sistema desenvolvido com o objetivo de melhorar o alinhamento entre pares de quadros usando uma combinação adaptativa de características esparsas 2D e 3D. Tal combinação está baseada nos níveis de estrutura geométrica e de textura visual contidos em cada cena. Esse sistema foi testado com conjuntos de dados RGB-D, incluindo vídeos com movimentos irrestritos da câmera e mudanças naturais na iluminação. Os resultados experimentais mostram que a nossa proposta supera aqueles métodos que usam características 2D ou 3D separadamente, obtendo uma melhora da precisão no alinhamento de cenas em ambientes internos reais.

Dans ce travail, nous avons abordé le problème d’estimation automatique du regard dans des environnements utilisateur sans contraintes. Ce travail s’inscrit dans la vision par ordinateur appliquée à l’analyse automatique du comportement humain. Plusieurs solutions industrielles sont aujourd’hui commercialisées et donnent des estimations précises du regard. Certaines ont des spécifications matérielles très complexes (des caméras embarquées sur un casque ou sur des lunettes qui filment le mouvement des yeux) et présentent un niveau d’intrusivité important, ces solutions sont souvent non accessible au grand public. Cette thèse vise à produire un système d’estimation automatique du regard capable d’augmenter la liberté du mouvement de l’utilisateur par rapport à la caméra (mouvement de la tête, distance utilisateur-capteur), et de réduire la complexité du système en utilisant des capteurs relativement simples et accessibles au grand public. Dans ce travail, nous avons exploré plusieurs paradigmes utilisés par les systèmes d’estimation automatique du regard. Dans un premier temps, Nous avons mis au point deux systèmes basés sur deux approches classiques: le premier basé caractéristiques et le deuxième basé semi apparence. L’inconvénient majeur de ces paradigmes réside dans la conception des systèmes d'estimation du regard qui supposent une indépendance totale entre l'image d'apparence des yeux et la pose de la tête. Pour corriger cette limitation, Nous avons convergé vers un nouveau paradigme qui unifie les deux blocs précédents en construisant un espace regard global, nous avons exploré deux directions en utilisant des données réelles et synthétiques respectivement. / In this thesis, we tackled the automatic gaze estimation problem in unconstrained user environments. This work takes place in the computer vision research field applied to the perception of humans and their behaviors. Many existing industrial solutions are commercialized and provide an acceptable accuracy in gaze estimation. These solutions often use a complex hardware such as range of infrared cameras (embedded on a head mounted or in a remote system) making them intrusive, very constrained by the user's environment and inappropriate for a large scale public use. We focus on estimating gaze using cheap low-resolution and non-intrusive devices like the Kinect sensor. We develop new methods to address some challenging conditions such as head pose changes, illumination conditions and user-sensor large distance. In this work we investigated different gaze estimation paradigms. We first developed two automatic gaze estimation systems following two classical approaches: feature and semi appearance-based approaches. The major limitation of such paradigms lies in their way of designing gaze systems which assume a total independence between eye appearance and head pose blocks. To overcome this limitation, we converged to a novel paradigm which aims at unifying the two previous components and building a global gaze manifold, we explored two global approaches across the experiments by using synthetic and real RGB-D gaze samples.

Dans ce travail, méthodes d'estimation basées sur des images, également connu sous le nom de méthodes directes, sont étudiées qui permettent d'éviter l'extraction de caractéristiques et l'appariement complètement. L'objectif est de produire pose 3D précis et des estimations de la structure. Les fonctions de coût présenté minimiser l'erreur du capteur, car les mesures ne sont pas transformés ou modifiés. Dans la caméra photométrique estimation de la pose, rotation 3D et les paramètres de traduction sont estimées en minimisant une séquence de fonctions de coûts à base d'image, qui sont des non-linéaires en raison de la perspective projection et la distorsion de l'objectif. Dans l'image la structure basée sur le raffinement, d'autre part, de la structure 3D est affinée en utilisant un certain nombre de vues supplémentaires et un coût basé sur l'image métrique. Les principaux domaines d'application dans ce travail sont des reconstitutions d'intérieur, la robotique et la réalité augmentée. L'objectif global du projet est d'améliorer l'image des méthodes d'estimation fondées, et pour produire des méthodes de calcul efficaces qui peuvent être accueillis dans des applications réelles. Les principales questions pour ce travail sont : Qu'est-ce qu'une formulation efficace pour une image 3D basé estimation de la pose et de la structure tâche de raffinement ? Comment organiser calcul afin de permettre une mise en œuvre efficace en temps réel ? Quelles sont les considérations pratiques utilisant l'image des méthodes d'estimation basées sur des applications telles que la réalité augmentée et la reconstruction 3D ? / In this work, image based estimation methods, also known as direct methods, are studied which avoid feature extraction and matching completely. Cost functions use raw pixels as measurements and the goal is to produce precise 3D pose and structure estimates. The cost functions presented minimize the sensor error, because measurements are not transformed or modified. In photometric camera pose estimation, 3D rotation and translation parameters are estimated by minimizing a sequence of image based cost functions, which are non-linear due to perspective projection and lens distortion. In image based structure refinement, on the other hand, 3D structure is refined using a number of additional views and an image based cost metric. Image based estimation methods are usable whenever the Lambertian illumination assumption holds, where 3D points have constant color despite viewing angle. The main application domains in this work are indoor 3D reconstructions, robotics and augmented reality. The overall project goal is to improve image based estimation methods, and to produce computationally efficient methods which can be accomodated into real applications. The main questions for this work are : What is an efficient formulation for an image based 3D pose estimation and structure refinement task ? How to organize computation to enable an efficient real-time implementation ? What are the practical considerations of using image based estimation methods in applications such as augmented reality and 3D reconstruction ?

Cette thèse s'inscrit dans un cadre de vidéo-surveillance, et s'intéresse plus précisément à la détection robustesd'objets mobiles dans une séquence d'images. Une bonne détection d'objets mobiles est un prérequis indispensableà tout traitement appliqué à ces objets dans de nombreuses applications telles que le suivi de voitures ou depersonnes, le comptage des passagers de transports en commun, la détection de situations dangereuses dans desenvironnements spécifiques (passages à niveau, passages piéton, carrefours, etc.), ou encore le contrôle devéhicules autonomes. Un très grand nombre de ces applications utilise un système de vision par ordinateur. Lafiabilité de ces systèmes demande une robustesse importante face à des conditions parfois difficiles souventcausées par les conditions d'illumination (jour/nuit, ombres portées), les conditions météorologiques (pluie, vent,neige) ainsi que la topologie même de la scène observée (occultations). Les travaux présentés dans cette thèsevisent à améliorer la qualité de détection d'objets mobiles en milieu intérieur ou extérieur, et à tout moment de lajournée.Pour ce faire, nous avons proposé trois stratégies combinables :i) l'utilisation d'invariants colorimétriques et/ou d'espaces de représentation couleur présentant des propriétésinvariantes ;ii) l'utilisation d'une caméra stéréoscopique et d'une caméra active Microsoft Kinect en plus de la caméra couleurafin de reconstruire l'environnement 3D partiel de la scène, et de fournir une dimension supplémentaire, à savoirune information de profondeur, à l'algorithme de détection d'objets mobiles pour la caractérisation des pixels ;iii) la proposition d'un nouvel algorithme de fusion basé sur la logique floue permettant de combiner les informationsde couleur et de profondeur tout en accordant une certaine marge d'incertitude quant à l'appartenance du pixel aufond ou à un objet mobile. / This PhD thesis falls within the scope of video-surveillance, and more precisely focuses on the detection of movingobjects in image sequences. In many applications, good detection of moving objects is an indispensable prerequisiteto any treatment applied to these objects such as people or cars tracking, passengers counting, detection ofdangerous situations in specific environments (level crossings, pedestrian crossings, intersections, etc.), or controlof autonomous vehicles. The reliability of computer vision based systems require robustness against difficultconditions often caused by lighting conditions (day/night, shadows), weather conditions (rain, wind, snow...) and thetopology of the observed scene (occultation...).Works detailed in this PhD thesis aim at reducing the impact of illumination conditions by improving the quality of thedetection of mobile objects in indoor or outdoor environments and at any time of the day. Thus, we propose threestrategies working as a combination to improve the detection of moving objects:i) using colorimetric invariants and/or color spaces that provide invariant properties ;ii) using passive stereoscopic camera (in outdoor environments) and Microsoft Kinect active camera (in outdoorenvironments) in order to partially reconstruct the 3D environment, providing an additional dimension (a depthinformation) to the background/foreground subtraction algorithm ;iii) a new fusion algorithm based on fuzzy logic in order to combine color and depth information with a certain level ofuncertainty for the pixels classification.

The main point: Research light emiting diodes RGB (red, green, blue) matrix with controllable spectrum of light. I have made that matrix, and researching energetic, light and technicality datum. To use that light sources for lightening of emergency. To review other liht sources. Stepping stone and results: There are made review of most popular light sources, quality and limitation. There are overlook of semiconductors light sources and the range where they are using now. Experiments are made with our LED illuminator with minimal number of LED. There are noticed, that LED can take energy from light and that we use to make manage of others light sources. Illuminator are adapted to work in emergency lightening. The result can be use: The result can be use for development LED in Lithuania, to know people more about semiconductor light sources ant to use it ours home.

Submitted by VITOR HUGO MARQUES LUIZ null (vitorhmluiz@hotmail.com) on 2016-03-14T14:35:25Z No. of bitstreams: 1 tese Vitor Hugo repositório.pdf: 12742690 bytes, checksum: 808cc9757cd523a743880c2238379bc1 (MD5) / Approved for entry into archive by Sandra Manzano de Almeida (smanzano@marilia.unesp.br) on 2016-03-14T17:09:34Z (GMT) No. of bitstreams: 1 luiz_vhm_dr_araiq_par.pdf: 1804257 bytes, checksum: 83b423fb984c5b0c70d305405ab840c2 (MD5) / Made available in DSpace on 2016-03-14T17:09:34Z (GMT). No. of bitstreams: 1 luiz_vhm_dr_araiq_par.pdf: 1804257 bytes, checksum: 83b423fb984c5b0c70d305405ab840c2 (MD5) Previous issue date: 2016-02-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Este trabalho descreve o desenvolvimento de métodos analíticos para a determinação quantitativa de furosemida e bumetanida em amostras de urina utilizando espectroscopia por reflectância difusa (para a furosemida) e por imagem por scanner com quantificação através do histograma de cores utilizando o padrão RGB (para ambas). Envolve também o desenvolvimento de um método quantitativo para a detecção de chumbo em resíduos de armas de fogo (GSR) nas mãos de atiradores utilizando membranas de celulose bacteriana como substrato de coleta, visando o descobrimento do tempo de disparo. Também foi realizada a quantificação de chumbo em amostras de tintura para cabelos utilizando método previamente desenvolvido, visando detecção da adulteração destes produtos e controle de qualidade. Estuda também a potencialidade do uso das membranas de celulose bacteriana para a coleta de impressões digitais. Os métodos desenvolvidos consistem na reação da furosemida (FUR) com o regente cromogênico paradimetilaminocinamaldeído (p-DAC) 0,70% e ácido clorídrico (HCl) 1,72 mol L-1 em papel de filtro qualitativo com barreiras hidrofóbicas, com detecção espectrofotométrica e por histograma de cores; na reação do íon chumbo(II) (Pb2+) com rodizonato de sódio (ROD) 0,16% em meio micelar de dodecil sulfato de sódio (SDS) 5 mmol L-1 em membranas de celulose bacterianas, com detecção espectrofotométrica e por microscopia eletrônica de varredura (MEV); na reação de bumetanida (BMT) com o reagente p-DAC 0,6% e HCl 0,26 mol L-1 em papel de filtro qualitativo com barreiras hidrofóbicas, com detecção por histograma de cores e na coleta de impressões digitais utilizando membrana de celulose bacteriana impregnadas com ninidrina, nitrato de prata ou óxido de zinco, dos quais o nitrato de prata e a ninidrina atuaram como agentes de coleta razoáveis. Todas as concentrações foram otimizadas por planejamentos quimiométricos. As reações foram realizadas na forma de spot test, envolvendo a formação de um produto colorido em 545 nm para o chumbo, em 585 nm para a furosemida e 520 nm para a bumetanida. As curvas analíticas foram contruídas a partir de soluções padrões dos respectivos analitos. Os métodos desenvolvidos para a bumetanida e para a furosemida foram aplicados em amostras de urina sintética e natural fortificadas e os resultados obtidos foram comparados estatisticamente com métodos comparativos. A validação dos métodos foi realizada por adição de padrão e recuperação e por comparação de métodos, no caso da FUR e da BMT, obtendo-se recuperações entre 98,0 e 115,3% para os métodos de quantificação da furosemida e entre 93,0 e 102,0% para o método de quantificação da bumetanida. O método de coleta de GSR é baseado na utilização de membranas finas de celulose bacteriana desenvolvidas pelo Grupo de Materiais Fotônicos do IQ-UNESP.Para os GSR foram realizadas 40 coletas totais em tempos de coleta após o disparo (diferentes e conhecidos), sendo sua comparação realizada através das curvas analíticas, mostrando ser possível a detecção do tempo de disparo com uma margem de erro de aproximadamente 5 minutos. Os resultados foram comparados estatisticamente e os valores obtidos a partir de testes estatísticos mostraram que os métodos podem ser usados para análises de rotina em laboratórios forenses. / This work describes the development of analytical methods for the quantitative determination of furosemide and bumetanide in urine samples using diffuse reflectance spectroscopy (for furosemide) and scanning imaging with quantification by color histogram using RGB color pattern (for both). It involves also the development of a quantitative method for the detection of lead in gunshot residues (GSR) in the hands of the shooters using bacterial cellulose membranes as substrate collection, aiming the discovery of shooting time. It is also done the quantification of lead in progressive hair lotions samples using a previously developed method, aiming the detection of products adulterations and quality control. It also studies the potentiality of the usage of bacterial cellulose membranes for the collection of fingerprints. The developed methods are consisted in the reaction of furosemide (FUR) with the cromogenic reagent p-dimethylamino cinnamaldehyde (p-DAC) 0.70% and hydrochloric acid (HCl) 1.72 mol L-1 in qualitative filter papers with hydrophobic barrier, with spectrophotometric detection and by color histogram; in the reaction of lead(II) ion (Pb2+) with sodium rhodizonate (ROD) 0.16% in micellar medium of sodium dodecyl sulfate (SDS) 5 mmol L-1 in bacterial cellulose membranes with spectrophotometric detection and by scanning electron microscopy; in the reaction of bumetanide (BMT) with the reagent p-dimethylamino cinnamaldehyde (p-DAC) 0.6% and hydrochloric acid (HCl) 0.27 mol L-1 in qualitative filter papers with hydrophobic barrier with color histogram detection an in the collect of fingerprints using bacterial cellulose membranes impregnated with ninhydrine, silver nitrate or zinc oxide, of which the silver nitrate and ninhydrin acted as reasonable collection agents. All concentrations were optimized through chemometrics designs. The reactions were carried out as spot test, involving the formation of a colored product at 545 nm for lead, in 585 nm for furosemide and in 520 nm for bumetanide. Analytical curves were built from standard solutions of the respective analytes. The methods developed for furosemide and bumetanide were applied in fortified synthetic and natural urine samples and the results obtained were compared statistically with comparative methods. The validation of the methods were performed by standard addition and recovery and by comparison of methods, for FUR and BMT, yielding recoveries between 98.0 and 115.3% for furosemide quantification methods and between 93.0 and 102.0% for the quantification method for bumetanide. GSR collection method is based on the use of thin membranes of bacterial cellulose developed by Photonic Materials Group IQ-UNESP. For GSR, 40 total collections were carried out in known and different times of collection after shooting times and their comparison through analytical curves were done, showing the possibility of the detection of the shooting time with an error of 5 minutes, approximately. The results were statistically compared and the values obtained from statistical tests showed that the methods can be used for routine analysis in forensic laboratories.

Submitted by Maike Costa (maiksebas@gmail.com) on 2017-06-21T14:26:33Z No. of bitstreams: 1 arquivototal.pdf: 3690977 bytes, checksum: 752560aa5c7d78968c32cb55f0778788 (MD5) / Made available in DSpace on 2017-06-21T14:26:33Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 3690977 bytes, checksum: 752560aa5c7d78968c32cb55f0778788 (MD5) Previous issue date: 2016-02-29 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Total hardness and Total alkalinity are important physico-chemical parameters for the evaluation of water quality and are determined by volumetric analytical methods. These methods have difficult to detect the endpoint of the titration due to the difficult of viewing the color transition inherent to each of them. To circumvent this problem, here is proposed a new automatic method for the detection of the titration end point for the determination of total hardness and total alkalinity in mineral water samples. The proposed flow-batch titrator consists of a peristaltic pump, five three-way solenoid valves, a magnetic stirrer, an electronic actuator, an Arduino MEGA 2560TM board, a mixing chamber and a webcam. The webcam records the digital movie (DM) during the addition of the titrant towards mixing chamber, also recording the color variations resulting from chemical reactions between titrant and sample within chamber. While the DM is recorded, it is decompiled into frames ordered sequentially at a constant rate of 30 frames per second (FPS). The first frame is used as a reference to define the region of interest (RI) of 48 × 50 pixels and the R channel values, which are used to calculate the Pearson's correlation coefficient (r) values. r is calculated between the R values of the initial frame and each subsequent frame. The titration curves are plotted in real time using the values of r (ordinate axis) and the total opening time of the valve titrant (abscissa axis). The end point is estimated by the second derivative method. A software written in ActionScript 3.0 language manages all analytical steps and data treatment in real time. The feasibility of the method was attested by its application for the analysis of natural water samples. Results were compared with classical titration and did not present statistically significant differences when the paired ttest at the 95% confidence level was applied. The proposed method is able to process about 71 samples per hour, and its precision was confirmed by overall relative standard deviation (RSD) values, always lower than the 2,4% for total hardness and 1,4% for total alkalinity. / A dureza total e a alcalinidade total são importantes parâmetros físico-químicos para avaliação da qualidade de águas e são determinados por métodos volumétricos de análise. Estes métodos apresentam difícil detecção do ponto final da titulação devido à dificuldade de visualização das transições de cores inerentes a cada um deles. Para contornar este problema, foi proposta neste trabalho uma nova metodologia automática para a detecção do ponto final nas determinações de dureza total e alcalinidade total em águas. O titulador em fluxo-batelada proposto é composto de uma bomba peristáltica, cinco válvulas solenoides de três vias, um agitador magnético, um acionador de válvulas, uma placa Arduíno MEGA 2560TM, uma câmara de mistura e uma webcam. O programa de gerenciamento e controle do titulador foi escrito em linguagem ActionScript 3.0. A webcam grava o filme digital durante a adição do titulante na câmara de mistura, registrando as variações de cor decorrentes das reações químicas entre titulante e amostra no interior de câmara. Enquanto o filme é gravado, este é decomposto em quadros ordenados sequencialmente a uma taxa constante de 30 quadros por segundo (FPS). O primeiro quadro é utilizado como referência para definir uma região de interesse (RI) com 48 x 50 pixels, na qual seus valores R, G e B são utilizados para calcular os valores de coeficiente de correlação de Pearson (r). O valor de r é calculado entre os valores de R do quadro inicial e de cada quadro subsequente. As curvas de titulação são obtidas em tempo real usando os valores de r (ordenadas) e o tempo total de abertura da válvula de titulante (abscissas). O ponto final é estimado pelo método de segunda derivada. O método foi aplicado na análise de águas minerais e os resultados foram comparados com a titulação clássica, não apresentando diferenças estatisticamente significativas com aplicação do teste t pareado a 95% de confiança. O método proposto foi capaz de processar até 71 amostras por hora e a sua precisão foi confirmada pelos valores de desvio padrão relativos (DPR) globais, sempre inferiores as 2,4% para dureza total e 1,4% para alcalinidade total.

Made available in DSpace on 2015-05-14T13:21:11Z (GMT). No. of bitstreams: 1 arquivototal.pdf: 3039736 bytes, checksum: b5085a1b7abd18466b736a0a3c3e8de7 (MD5) Previous issue date: 2012-03-09 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This study proposes a digital image-based flow-batch analyzer (DIB-FBA) for the determination of Al(III) and Cr(VI) in waters. The proposed DIB-FBA uses a webcam with CCD sensor for acquisition of the images generated according to the RGB (Red-Green-Blue) colour system. The method for determination of Al(III) is based on reaction of this ion with quercetin and cetyltrimethylammonium bromide, yielding a yellow complex with maximum absorption at 428 nm. Chromium(VI) determination is accomplished by reaction of this ion with 1,5-diphenylcarbazide, whose product is a violet complex with maximum absorption at 548 nm. All calibration solutions were prepared in-line, and all analytical processes completed by simply changing the operational parameters in the DIB-FBA control software. The linear response ranges from 10 to 600 μg L−1 for Al (III) and from 10 to 300 μg L−1 for Cr (VI). Linear models for analytical curves were validated using ANOVA, F-test for lack of fit and residual plots. The limits of detection and sampling rates were estimated as 3,97 μg L−1 and 137 h−1, for Al(III) and 3,40 μg L−1 and 134 h−1, for Cr(VI), respectively. DIB-FBA performance was compared with the reference methods for determination of both analytes, and no statistically significant difference was observed between results by applying the paired t-test at a 95% confidence level. / Esse estudo propõe um analisador fluxo-batelada baseado em imagem digital (DIB-FBA) para determinação de Al(III) e Cr(VI) em águas. O DIB-FBA utiliza uma webcam com sensor CCD para a aquisição das imagens geradas de acordo com o sistema de cor RGB (Red-Green-Blue). O método para a determinação de Al(III) baseia-se na reação com quercetina e o brometo de cetiltrimetilamônio, produzindo um complexo amarelo com máximo de absorção em 428 nm. A determinação de cromo é baseada na reação do íon Cr(VI) com 1,5-difenilcarbazida, cujo o produto é um complexo de coloração violeta com máximo de absorção em 548 nm. Todas as soluções de calibração foram preparadas in-line e todos os processos analíticos foram realizados simplesmente mudando os parâmetros operacionais do aplicativo de controle do DIB-FBA. A resposta linear para o Al(III) se estende de 10 a 600 μg L−1 e para o Cr(VI) de 10 a 300 μg L−1. Os modelos lineares das curvas analíticas foram validados por intermédio de ANOVA, teste F para falta de ajuste e da análise gráfica dos resíduos deixados pelos modelos. Os limites de detecção e as frequências analíticas foram estimadas como sendo, respectivamente, 3,97 μg L−1 e 137 h−1, para o Al(III) e 3,40 μg L−1 e 134 h−1, para o Cr(VI). Os resultados da aplicação do DIB-FBA foram comparados com os obtidos empregando os respectivos métodos de referência. Constatou-se que não existe nenhuma diferença estatisticamente significativa entre os resultados, aplicando o teste t-pareado ao nível de confiança de 95%.

Made available in DSpace on 2015-05-14T13:21:45Z (GMT). No. of bitstreams: 1 parte1.pdf: 2505729 bytes, checksum: e872a92484e063cf1f264ba7b16d9e2e (MD5) Previous issue date: 2010-03-19 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / This work proposes the use of digital images captured by a Webcam for determination of total acidity in red wines by means of an acid-base titration without using an external indicator. Digital images present the colour of the emergent radiation, which is complementary to the radiation absorbed by molecules of anthocyanines presents in wines. Each image, generated according to RGB system, yields a matrix of the values of the R, G and B components whose averages define a the colour value obtained as: 2R ⋅2G ⋅2B. This value was adopted as analytical response to build titrations curves based on digital images (DIB). For a more precise localization of the end point, titrations curves were generated on the basis of the second derivative values of the analytical response. Anthocyanines present different colours according to medium pH and, from the variation of the colour values of the images obtained during the titration of the red wines, the end point could be detected with precision. The official method recommends the use of potenciometric titration for determination of total acidity in red wines. This method requires a dilution of the sample before the titration that must be carried out until a fixed value of pH (8.2 8.4). In order to illustrate the feasibility of the proposed method titrations involving the determination of total acidity in ten red wines samples were carried out. Results were compared to the ones obtained by potenciometric titration used as reference method. No statistic difference has been observed between the results by applying the paired t-test at 95% confidence level. The proposed method yielded results with a better precision than the official method. These advantageous characteristics are attributed to the trivariate nature of the measures associated to digital images. / Neste trabalho, propõe-se o uso de imagens digitais, capturadas com uma Webcam, para determinação da acidez total de vinhos tintos por meio de titulação ácido-base sem a utilização de indicador externo. As imagens digitais apresentam a cor da radiação emergente que é complementar à da radiação absorvida por moléculas de antocianinas presentes nos vinhos. Cada imagem, gerada de acordo com o sistema vermelho-verde-azul (RGB), fornece uma matriz de valores dos componentes R, G e B cujas médias definem o valor de cor obtido como: 2R ⋅2G ⋅2B. Esse valor foi adotado como resposta analítica para a construção das curvas de titulação baseadas em imagens digitais (DIB). Para a localização mais precisa do ponto final, foram geradas as curvas de titulação com base nos valores da segunda derivada da resposta analítica. As antocianinas apresentam diferentes cores de acordo com o pH do meio e, a partir das variações do valor de cor das imagens obtidas durante a titulação dos vinhos tintos, o ponto final pôde ser detectado com precisão. O método oficial recomenda o uso da titulação potenciométrica para a determinação da acidez total de vinhos tintos. Este método requer diluição da amostra antes da titulação que deve ser efetuada até um valor fixo de pH (8,2-8,4). A fim de ilustrar a viabilidade do método proposto, foram realizadas titulações envolvendo a determinação da acidez total em dez amostras de vinhos tintos. Os resultados foram comparados com os obtidos pela titulação potenciométrica usada como método de referência. Constatou-se que não há diferença sistemática estatisticamente significativa entre os resultados, aplicando-se o teste t emparelhado ao nível de 95% de confiança. O método proposto produziu resultados com uma precisão melhor que a do método oficial. Essas características vantajosas da titulação DIB são atribuídas à natureza trivariada das medidas associadas às imagens digitais.