In this work, the use of modified diamond as an electrode material with superlative physical and electrochemical properties was investigated in a number of electrochemical applications. The surface chemistry of three differing forms of diamond, namely boron-doped microcrystalline diamond, boron-doped diamond powder and detonation nanodiamond powder was modified utilising such strategies as hydrogen plasma treatment, reactive ion plasma etching along with various chemical treatments. The surface and functional properties of the modified diamond electrodes were studied using a wide spectrum of techniques. The electrochemical activity of these materials was concomitantly investigated in order to expand the knowledge of diamond electrochemistry and to establish an understanding of how the surface chemistry of these materials impacts their electrochemical performance. In the first study, the nanostructuring strategies of boron-doped diamond surface with platinum nanoparticles were developed. In particular, two types of diamond nanostructures were produced: one consisting of platinum particles located on the top of diamond nanorods, the other with platinum particles located in the bottom of diamond nanopits. For the first time, the experimental evidence proving the mechanism of the diamond nanostructuring process was reported. The electrochemical activity of these nanostructured diamond electrodes with regard to the electrochemical oxidation of glucose and methanol was investigated. In the second study, the relationship between the surface chemistry of three differing forms of diamond, including microcrystalline boron-doped diamond, boron-doped diamond powder as well as detonation nanodiamond powder, and the electrode fouling in the result of the adsorption processes in methyl viologen and anthraquinonedisulfonate solutions was investigated. The influence of two dissimilar surface terminations: hydrophobic H-terminated and hydrophilic O-terminated on the electrode performance was studied in detail. This work provides a useful insight on the likely reasons for the undesirable adsorption occurrence which may be experienced in many electroanalytical applications that utilise solid and powdered forms of diamond. The third project extends the discussion on the study of the diamond electrodes, modified with detonation nanodiamond and boron-doped diamond powders and investigates the electrochemical behaviour of these materials. In this work, charge transport within the diamond powder films, partition coefficients of different redox mediators along with heterogeneous electron transfer constants were identified. The chemical modification of these electrodes with platinum nanoparticles along with the mechanism of nucleation and growth of the latter were studied. The enhanced electrode performance with regard to methanol electrooxidation reaction was demonstrated. The fourth study investigates the preparation of nickel modified boron-doped diamond electrodes and ascertains the relationship between the surface chemistry of the modified diamond and the associated electrocatalytic performance of nickel nanoparticles in hydrogen peroxide and glucose electrooxidation. The fifth study reports on the development of a novel surface functionalization strategy, based on porphyrin and amide coupling chemistry, which allows the creation of hybrid biomimetic diamond interface that was used as the artificial β-alanine receptor.

Dans le cadre de la pulvérisation agricole, la diminution de la quantité des intrants est devenue une étape cruciale, et ce notamment en viticulture. La pulvérisation de précision en viticulture implique cependant une maitrise conjointe du matériel utilisé, des produits et de la répartition de ces produits sur le feuillage. Dans ce contexte, nombreuses sont les recherches menées sur l’optimisation d’utilisation des produits phytosanitaires, leur objectif final étant de réduire de manière significative la quantité d’intrants dans la culture. Cependant, peu de travaux ont été effectués sur l’étude du comportement des produits directement sur le feuillage, ce qui constitue donc l’objectif de cette thèse. La première partie de ce travail est consacrée particulièrement à l’analyse de l’état de la surface foliaire, en se focalisant spécifiquement sur l’étude de la rugosité de surface de la feuille qui constitue un paramètre essentiel dans le processus d’adhésion du produit pulvérisé sur la feuille. L’analyse de la surface de la feuille est réalisée en déterminant les caractéristiques texturales extraites d’images microscopiques. Un nouvel indicateur de rugosité est proposé ainsi que, des paramètres spatiaux et fréquentiels sont utilisés pour estimer et la rugosité de la feuille. Ces paramètres permettent ensuite la caractérisation de l’homogénéité de la surface et la détection des nervures/poils au niveau de la surface de la feuille. Cette partie représente une base fondamentale pour mieux comprendre le comportement des gouttelettes pulvérisées sur la feuille de vigne. La deuxième partie de ce travail de thèse est consacrée à des études expérimentales, qui ont pour but de définir et construire des modèles statistiques permettant d’estimer la quantité de produit restant sur la feuille ou la surface occupée par les gouttes. Ces modèles prennent en considération différents paramètres de pulvérisation, tels que la taille de la goutte et sa vitesse, la tension superficielle du produit, l’angle d’inclinaison et la rugosité de la surface de la feuille. Ces modèlespourraient être vus comme des outils de décision communs pour optimiser la quantité du produit pulvérisé et l’estimation du produit restant sur la feuille, et comme un outil d’aide pour optimiser les bancs d’essais et de tests de la qualité de la pulvérisation. / In the context of agricultural spraying, reducing the amount of input became a crucial step particularly in viticulture. The development of spraying precision in this domain needs the mastery of the use of spray equipment, product and distribution of these products on the foliage. In this area, many research have been done, their main goal being to optimize the use of plant product protection and to reduce significantly the input quantity inside the culture. However, few research has been done on the behavior of the product directly on the foliage which constitutes finally the main goal of this thesis. The first part of this report deals particularly with the analysis of leaf surface state by focusing precisely on the leaf surface roughness, one of the main parameters in product adhesion process. A leaf surface analysis is performed by determining the textural features extracted from microscopic images. A new roughness indicator is proposed and, spatial and frequency parameters were used to estimate and characterize the leaf roughness. These parameters allow both the characterization of surface homogeneity and the detection of the presence of rib/hair on the leaf surface. Indeed, this part represents a fundamental basis for understanding the spray droplet behavior on the vine leaf. The second part of this thesis deals with experimental studies which aim to define and to create statistical models to estimate the amount of product remaining on the leaf surface or the surface occupied by droplets. These models consider different spray parameters, such as droplet size and velocity, surface tension of the product, slope angle and roughness of the leaf. These models could be seen as aid-decision tools to optimize the amount of spray and the estimated product remaining on the leaf.

The discovery and subsequent synthesis of metal containing fullerenes- IFS (Inorganic Fullerene-like Structures) by R. Tenne et al. has generated considerable scientific interest with great potential impact in many industrial application areas such as lubrication. The lubrication mechanism (tribofilm formation) via exfoliation and deposition of the atomic layers from this cage-like IF-particles was revealed and demonstrated first by this research group. The incorporation of the nanoparticles into lubricants (oils, greases) is however not straightforward. When two surfaces are sliding against each other and a lubricant is used, a thin layer (tribofilm) is formed on the contact area. The friction reducing effects of the nanoparticles can be altered or hindered by certain additives that are used in lubricative oils. The effects of such additives on the tribological behavior of the nanoparticles are investigated by analyzing the tribofilms formed on the worn surfaces using energy-dispersive X-ray spectroscopy in a scanning electron microscope. Another challenge of nanoparticles in lubricants is the penetration of the nanoparticles into the contact zone. A possible solution of this problem is briefly discussed. A modified burnishing technique can be used to coat sliding metallic surfaces with a friction reducing tribofilm. The morphology and composition of these tribofilms was investigated with analytical electron microscopy techniques. In the second part of the thesis electron microscopy was used to investigate the material transfer. Titanium is an elements with high adhesive ability to the counter surface, it displays poor tribological properties in sliding metallic contacts. This can lead to material transfer and consequently severe surface damage. The cold formation and machining of titanium, thus can lead rapid tool wear and poor surface finish. Electron microscopy techniques were used to study the mechanism of titanium transfer to different counter surfaces.

Orientador: Rubens Maciel Filho / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-08T18:46:56Z (GMT). No. of bitstreams: 1 Oliveira_PatriciaCandiotoMigliari_D.pdf: 1584587 bytes, checksum: 8622cb86aacfe987908422e98c40d2c8 (MD5) Previous issue date: 2007 / Resumo: O trabalho envolveu modelo estruturado adaptado de um modelo estruturado de crescimento para processo de fermentação contínua realizado em um bioreator do tipo torre com células imobilizadas para produção de etanol. O modelo estruturado utilizado inclui equações de balanço para as rotas metabólicas fermentativa e respiratória, assim como termos cinéticos para o efeito de inibição pelo etanol, substrato e saturação celular no pellet. Os parâmetros cinético do modelo estruturado foram otimizados através da metodologia desenvolvida por Rivera (2005) onde envolve a aplicação de Algoritmo Genético, Planejamento Fatorial Fracionário proposto por Plackett Burman (1946) e Algoritmo Quasy Newton. Os resultados obtidos na simulação do modelo utilizando os parâmetros otimizados por esta metodologia representou de forma efetiva o modelo. A otimização do processo teve inicio com a Análise de Superfície de Resposta, que consistiu em um planejamento fatorial em estrela de dois níveis (-1 e +1) com um ponto central. A metodologia por Superfície de Resposta mostrou-se uma ferramenta poderosa para otimização preliminar das variáveis operacionais no sentido de que seus resultados foram usados como estimativas iniciais para o procedimento formal de otimização, SQP (Programação Quadrática Sucessiva). Esta metodologia de Superfície de resposta possibilita visualização do comportamento das variáveis que se quer otimizar, identificando a região do ponto ótimo, o que não é possível pelo método SQP. A metodologia SQP foi implementada com sucesso no modelo determinístico, obtendo as melhores condições de operação para as variáveis manipuláveis / Abstract: The work involved adapted of a structured model of growth structured model for process of continuous fermentation accomplished in a bioreator of the type tower with immobilized cells for etanol production. The used structured model includes reaction rate equations for the respiratory and glicolitic metabolic pathways, as well as kinetic terms for the inhibition effect for the etanol, substrate and cellular saturation in the pellet. The kinetic of the structured model parameters went optimized through to methodology developed by Rivera (2005) where it involves the application of Genetic Algorithm, methodology of Plackett¿Burman (1946) and Algorithm Quasi Newton. The results obtained in the simulation of the model using the parameters optimized for this methodology represented in an effective way the model. The optimization of the process had I begin with the Analysis of Surface of Answer, that consisted of a planning fatorial in star of two levels (-1 and +1) with a central point. The methodology for Surface of Answer a powerful tool was shown for preliminary optimization of the operational variables in the sense that its results were used as initial estimates for the formal procedure of optimization, SQP. This methodology of answer Surface facilitates visualization of the behavior of the variables that if that otimizar, identifying the area of the great point, what is not possible for the method SQP. The methodology SQP was implemented with success in the model deterministic, obtaining the best operation conditions for the variables manipulated. / Doutorado / Desenvolvimento de Processos Químicos / Doutor em Engenharia Química

This dissertation is concerned with three-dimensional (3D) sensing and 3D scan representation. Three-dimensional records are important tools in several disciplines; such as medical imaging, archaeology, and mobile robotics. This dissertation proposes the normal-distributions transform, NDT, as a general 3D surface representation with applications in scan registration, localisation, loop detection, and surface-structure analysis. After applying NDT, the surface is represented by a smooth function with analytic derivatives. This representation has several attractive properties. The smooth function representation makes it possible to use standard numerical optimisation methods, such as Newton’s method, for 3D registration. This dissertation extends the original two-dimensional NDT registration algorithm of Biber and Straßer to 3D and introduces a number of improvements. The 3D-NDT scan-registration algorithm is compared to current de facto standard registration algorithms. 3D-NDT scan registration with the proposed extensions is shown to be more robust, more accurate, and faster than the popular ICP algorithm. An additional benefit is that 3D-NDT registration provides a confidence measure of the result with little additional effort. Furthermore, a kernel-based extension to 3D-NDT for registering coloured data is proposed. Approaches based on local visual features typically use only a small fraction of the available 3D points for registration. In contrast, Colour-NDT uses all of the available 3D data. The dissertation proposes to use a combination of local visual features and Colour-NDT for robust registration of coloured 3D scans. Also building on NDT, a novel approach using 3D laser scans to perform appearance-based loop detection for mobile robots is proposed. Loop detection is an importantproblem in the SLAM (simultaneous localisation and mapping) domain. The proposed approach uses only the appearance of 3D point clouds to detect loops and requires nopose information. It exploits the NDT surface representation to create histograms based on local surface orientation and smoothness. The surface-shape histograms compress the input data by two to three orders of magnitude. Because of the high compression rate, the histograms can be matched efficiently to compare the appearance of two scans. Rotation invariance is achieved by aligning scans with respect to dominant surface orientations. In order to automatically determine the threshold that separates scans at loop closures from nonoverlapping ones, the proposed approach uses expectation maximisation to fit a Gamma mixture model to the output similarity measures. In order to enable more high-level tasks, it is desirable to extract semantic information from 3D models. One important task where such 3D surface analysis is useful is boulder detection for mining vehicles. This dissertation presents a method, also inspired by NDT, that provides clues as to where the pile is, where the bucket should be placed for loading, and where there are obstacles. The points of 3D point clouds are classified based on the surrounding surface roughness and orientation. Other potential applications include extraction of drivable paths over uneven surfaces.

La synthèse de catalyseurs sans métaux nobles est une voie prometteuse pour rendre accessible à l’échelle mondiale les piles à combustible. L’analyse électrochimique de ces matériaux n’est pas aisée que ce soit pour comparer les propriétés électro catalytiques ou pour comprendre le fonctionnement de ces catalyseurs. Ceci provient du fait que la communauté scientifique évalue les performances catalytiques à l’échelle du matériau, donc sur un très grand nombre d’objets dont la réponse est moyennée. Les travaux présentés dans ce mémoire ont mis en place une méthode d’analyse de l’activité électrocatalytique de matériaux sans métaux nobles pour la réduction de l’oxygène en milieu acide par microscopie électrochimique à balayage. Cette approche permet d’étudier aussi bien macroscopiquement que microscopiquement les catalyseurs et d’étudier simultanément plusieurs catalyseurs, ce qui rend plus fiable la comparaison des résultats. Le dispositif présenté dans ce travail a permis de comparer différents catalyseurs avec des compositions proches ainsi que d’étudier l’influence de différentes paramètres sur un catalyseur : le chargement, la surface, la masse déposée et la quantité de Nafion ajoutée. Il a aussi été montré qu’il était possible d’étudier la stabilité des catalyseurs via ce dispositif. Ces différents résultats suggèrent que la méthode mise en place est polyvalente et permettra de nombreuses autres études. / The decrease of fuel cells cost is necessary to provide a worldwide access to the technology. Synthesis of noble metal-free catalysts is a promising way to achieve this goal. The electrochemical analysis of these materials is however not easy either to compare the electrocatalytic properties or to understand the performances of these catalysts. The scientific community generally studies catalysts at a macroscale, where the recorded response is averaged on a very large number of catalytic objects. The works presented here shows the setup of a method to analyze the electrocatalytic activity of noble metal-free catalyst for the oxygen reduction reaction in acidic media by scanning electrochemical microscopy. This method brings several advantages such as the possibility to study and compare multiple catalysts on the same sample at a macro- or a microscale. The comparison of several catalysts with this setup is then. A catalyst has been studied under various conditions of: loading, surface area, weight of catalyst and quantity of additives such as Nafion. The investigation of the material stability is also illustrated. These results suggest large range of application of the technique and many possibilities in the future are now open to investigated noble metal-free electrocatalytic materials.