Made available in DSpace on 2014-12-17T14:08:32Z (GMT). No. of bitstreams: 1 RicardoWO.pdf: 3213751 bytes, checksum: 8d8983eff6f68357e2e660b4041a5b84 (MD5) Previous issue date: 2009-03-19 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / In the present study we elaborated algorithms by using concepts from percolation theory which analyze the connectivity conditions in geological models of petroleum reservoirs. From the petrophysical parameters such as permeability, porosity, transmittivity and others, which may be generated by any statistical process, it is possible to determine the portion of the model with more connected cells, what the interconnected wells are, and the critical path between injector and source wells. This allows to classify the reservoir according to the modeled petrophysical parameters. This also make it possible to determine the percentage of the reservoir to which each well is connected. Generally, the connected regions and the respective minima and/or maxima in the occurrence of the petrophysical parameters studied constitute a good manner to characterize a reservoir volumetrically. Therefore, the algorithms allow to optimize the positioning of wells, offering a preview of the general conditions of the given model s connectivity. The intent is not to evaluate geological models, but to show how to interpret the deposits, how their petrophysical characteristics are spatially distributed, and how the connections between the several parts of the system are resolved, showing their critical paths and backbones. The execution of these algorithms allows us to know the properties of the model s connectivity before the work on reservoir flux simulation is started / No presente estudo foram elaborados algoritmos, utilizando conceitos da teoria da percola??o, que analisam as condi??es de conectividade em modelos geol?gicos elaborados para reservat?rios de petr?leo. A partir de seus par?metros petrof?sicos, tais como: permeabilidade, porosidade, transmissibilidade e outros, gerados por qualquer processo estat?stico, ? poss?vel conhecer qual a por??o do modelo onde ocorre o maior n?mero de c?lulas conectadas, quais s?o os po?os que est?o conectados entre si e qual o caminho m?nimo entre injetores e produtores. Permitindo, assim, classificar o reservat?rio segundo os par?metros petrof?sicos modelados. Podendo determinar, tamb?m, qual a porcentagem do reservat?rio a que cada po?o est? conectado. De uma forma geral, as regi?es conectadas e os respectivos m?nimos e/ou m?ximos da ocorr?ncia dos par?metros petrof?sicos estudados, constituem uma boa forma de caracterizar volumetricamente um reservat?rio. Os algoritmos permitem, ent?o, otimizar o posicionamento de loca??es de po?os oferecendo uma vis?o antecipada das condi??es gerais da conectividade de um determinado modelo. A inten??o n?o ? avaliar modelos geol?gicos, mas mostrar como as jazidas s?o interpretadas, como suas caracter?sticas petrof?sicas se distribuem espacialmente e como as conex?es entre as diversas partes do sistema s?o resolvidas, mostrando seus caminhos cr?ticos e backbones . A execu??o desses algoritmos permite que as caracter?sticas relativas ? conectividade do modelo sejam conhecidas mesmo antes de se iniciar o trabalho de simula??o de fluxo do reservat?rio

This thesis is primarily focused on problems in extremal combinatorics, although we will also consider some questions of analytic and algorithmic nature. The d-dimensional hypercube is the graph with vertex set {0,1}^d where two vertices are adjacent if they differ in exactly one coordinate. In Chapter 2 we obtain an upper bound on the 'saturation number' of Q_m in Q_d. Specifically, we show that for m ≥ 2 fixed and d large there exists a subgraph G of Q_d of bounded average degree such that G does not contain a copy of Q_m but, for every G' such that G ⊊ G' ⊆ Q_d, the graph G' contains a copy of Q_m. This result answers a question of Johnson and Pinto and is best possible up to a factor of O(m). In Chapter 3, we show that there exists ε > 0 such that for all k and for n sufficiently large there is a collection of at most 2^{(1-ε)k} subsets of [n] which does not contain a chain of length k+1 under inclusion and is maximal subject to this property. This disproves a conjecture of Gerbner, Keszegh, Lemons, Palmer, Pálvölgyi and Patkós. We also prove that there exists a constant c ∈ (0,1) such that the smallest such collection is of cardinality 2^{(1+o(1))^ck} for all k. In Chapter 4, we obtain an exact expression for the 'weak saturation number' of Q_m in Q_d. That is, we determine the minimum number of edges in a spanning subgraph G of Q_d such that the edges of E(Q_d)\E(G) can be added to G, one edge at a time, such that each new edge completes a copy of Q_m. This answers another question of Johnson and Pinto. We also obtain a more general result for the weak saturation of 'axis aligned' copies of a multidimensional grid in a larger grid. In the r-neighbour bootstrap process, one begins with a set A₀ of 'infected' vertices in a graph G and, at each step, a 'healthy' vertex becomes infected if it has at least r infected neighbours. If every vertex of G is eventually infected, then we say that A₀ percolates. In Chapter 5, we apply ideas from weak saturation to prove that, for fixed r ≥ 2, every percolating set in Q_d has cardinality at least (1+o(1))(d choose r-1)/r. This confirms a conjecture of Balogh and Bollobás and is asymptotically best possible. In addition, we determine the minimum cardinality exactly in the case r=3 (the minimum cardinality in the case r=2 was already known). In Chapter 6, we provide a framework for proving lower bounds on the number of comparable pairs in a subset S of a partially ordered set (poset) of prescribed size. We apply this framework to obtain an explicit bound of this type for the poset 𝒱(q,n) consisting of all subspaces of 𝔽_qⁿordered by inclusion which is best possible when S is not too large. In Chapter 7, we apply the result from Chapter 6 along with the recently developed 'container method,' to obtain an upper bound on the number of antichains in 𝒱(q,n) and a bound on the size of the largest antichain in a p-random subset of 𝒱(q,n) which holds with high probability for p in a certain range. In Chapter 8, we construct a 'finitely forcible graphon' W for which there exists a sequence (ε_i)^∞_i=1 tending to zero such that, for all i ≥ 1, every weak ε_i-regular partition of W has at least exp(ε_i^-2/2^{5log∗ε_i^-2}) parts. This result shows that the structure of a finitely forcible graphon can be much more complex than was anticipated in a paper of Lovász and Szegedy. For positive integers p,q with p/q ❘≥ 2, a circular (p,q)-colouring of a graph G is a mapping V(G) → ℤ_p such that any two adjacent vertices are mapped to elements of ℤ_p at distance at least q from one another. The reconfiguration problem for circular colourings asks, given two (p,q)-colourings f and g of G, is it possible to transform f into g by recolouring one vertex at a time so that every intermediate mapping is a p,q-colouring? In Chapter 9, we show that this question can be answered in polynomial time for 2 ≤ p/q < 4 and is PSPACE-complete for p/q ≥ 4.

Dans le cadre des législations européennes relatives au traitement des déchets et aux énergies renouvelables, la méthanisation apparaît comme une alternative prometteuse pour la stabilisation et la valorisation des Ordures Ménagères Résiduelles (OMR). D'un point de vue opérationnel l'hétérogénéité et les difficultés de mise en mouvement d'une matrice aussi complexe que les OMR sont à l'origine de pertes de rendement voire de l'arrêt d'installations de méthanisation. Les performances de méthanisation sont en particulier limitées par l'étape d'hydrolyse des fractions lignocellulosiques qui représentent la majorité du potentiel méthanogène des OMR. Dans ce contexte, l'objectif principal du travail de thèse, était l'étude d'un procédé de percolation dans lequel le déchet n'est pas mis en mouvement. Au travers de ce travail nous avions également pour ambition de produire des connaissances à caractère plus générique sur l'hydrolyse afin d'en améliorer les performances. Des expériences préliminaires ont d'abord permis la définition d'un système expérimental adéquat pour l'étude à l'échelle laboratoire de l'hydrolyse des OMR. La représentativité d'un déchet reconstitué, reproductible et d'utilisation aisée, a notamment été vérifiée en termes de potentiel méthanogène, de profil hydrolytique et de flore microbienne. Suite à la définition de ce système expérimental, son comportement hydrolytique a été comparé à celui d'un test de lixiviation de référence (NF EN 12457-4) afin de valider l'intérêt opérationnel de la percolation pour l'hydrolyse des OMR. De façon inattendue, l'extraction de 38,90% de la matière carbonée initiale du déchet a ainsi été mise en évidence lors de l'hydrolyse par percolation contre 17,84% lors de l'hydrolyse par lixiviation, renforçant l'intérêt suscité par la percolation pour l'hydrolyse des OMR. L'optimisation des performances d'hydrolyse par percolation a ensuite été réalisée par le criblage de huit paramètres opérationnels afin de déterminer leur influence sur les performances d'hydrolyse des OMR, au travers de deux plans d'expérience. L'ajout d'alcalinité (12 gHCO3-.L-1) et la recirculation du percolat pendant 6 h par jour ont ainsi permis d'augmenter significativement les performances d'hydrolyse, passant de 17 à 43% d'extraction de la matière organique (DCO) initiale du déchet (autrement dit de 26 à 69% de la matière biodégradable initiale). L'étude des communautés microbiennes et de leur activité a également été réalisée. Le séquençage des pyrotags d'ADNr 16S a ainsi permis de mettre en évidence le caractère dominant des Classes Clostridia et Bacteroidia au sein des communautés hydrolytiques. Le couplage de cette démarche qualitative à une approche quantitative par qPCR sur une série de biomarqueurs taxonomiques et fonctionnels a permis de montrer qu'il existe une corrélation positive entre l'ajout de carbonates, la neutralisation du pH, la quantité de matière hydrolysée à 14 jours et soit l'abondance de la Classe Bacteroidia soit celle des gènes de la famille hydA, impliqués dans la fermentation. Finalement, l'analyse microbiologique a été approfondie au jour 4, c'est-à-dire durant la phase d'hydrolyse intense, grâce à une approche de métatranscriptomique. L'analyse des transcrits fonctionnels indique que l'alcalinité influence l'activité des microorganismes de la Classe Clostridia dès le jour 4 des essais d'hydrolyse. Plus spécifiquement, l'ajout de carbonates semble corrélé à une modification du métabolisme des sucres chez des microorganismes non cultivables apparentés à Clostridium cellulolyticum et à l'augmentation de l'expression de l'opéron nif, impliqué dans la fixation de l'azote, chez différents groupes de microorganismes. / In the framework of the European green policy, anaerobic digestion appears as a promising technology for stabilization and valorization of Municipal Solid Waste (MSW). In practice, mechanical mixing of a complex and heterogeneous matrix such as MSW induces major operational constraints. Anaerobic digestion performances are especially limited by hydrolysis of lignocellulosic fractions which represent the main part of MSW methanogenic potential. In this context, this PhD project was aiming to characterize and optimize of a percolation process in which MSW stands still. Preliminary experiments were conducted in order to define an experimental system suitable for lab-scale study of MSW hydrolysis. Therefore, the representativeness of an easy-to-use and reproducible reconstituted waste was verified in terms of methanogenic potential, hydrolytic profiles and associated microbial communities. Following system definition, hydrolysis behavior by percolation was compared to a reference lixiviation test (NF EN 12457-4). Surprisingly, hydrolysis by percolation permitted the extraction of 39% of carbonated matter initially contained in waste whereas 18% were extracted during hydrolysis by lixiviation, thus validating operational benefit of percolation for MSW hydrolysis. Optimization of hydrolysis performance was then conducted through the screening of eight operational parameters for their influence on MSW hydrolysis performances thanks to two Designs Of Experiment (DOE). Cumulative effect of alkalinity addition (12 gHCO3-.L-1) and percolate recirculation (6 hour.day-1) significantly improved hydrolysis yield, from 17 to 43% of extracted organic matter compared to the initial content of waste (corresponding to an extraction of 26 and 69% of biodegradable matter). Structure and activity of hydrolytic microbial communities were also studied. 16S rDNA-pyrotags sequencing brought out the dominance of classes Clostridia and Bacteroidia. Additionally, a quantitative approach led by qPCR revealed a correlation between carbonates addition, pH neutralization, amounts of hydrolyzed matter at day 14 and either class Bacteroidia or genes from hydA family, involved in fermentation. Finally, metatranscriptomic approach was conducted at day 4 in order to further study microbial activity during the intense hydrolysis phase. According to functional analysis, alkalinity seems have positive influence on class Clostridia activity. More specifically, carbonates addition seems correlated to a modification of carbohydrates metabolism of organisms affiliated to Clostridium cellulolyticum and to transcriptional up-regulation of nif operon, involved in nitrogen fixation, among various types of microorganisms.

Miniaturization has become a driving force in different areas of technology including microelectronics, sensoric- and bio-technologies and in fundamental science. Because of the well-known limitations of conventional lithographic methods, newly emerging bottom-up approach, utilizing self-assembly of various nanoobjects including single polymer molecules and carbon nanotubes constitutes a very promising alternative for fabrication of ultimately small devices. Carbon nanotubes are attractive materials for nanotechnology and hold much promise to revolutionize fundamental science in a investigation of phenomena, associated with the nanometer–sized objects.It was found in this work that grafted chains of poly(2-vinylpyridine) form a shell covering the carbon nanotubes that makes them dispersible in organic solvents and in acidic water (CNTs-g-P2VP).The positively charged poly(2-vinylpyridine) shell is responsible for the selective deposition of carbon nanotubes onto oppositely charged surfaces. It was established that the deposition CNTs-g-P2VP from aqueous dispersions at low pH is an effective method to prepare ultra-thin films with a tunable density of carbon nanotubes.It was shown that poly(2-vinylpyridine) grafted to carbon nanotubes is a universal support for the immobilization of various nanoclusters at the carbon nanotube's surface. Prussian Blue nanoparticles were selectively attached to the surface of CNTs-g-P2VP.Conducting polymer nanowires are another very promising kind of nanomaterials that could be also suitable for applications in nanodevices and nanosensors. In this work was developed a simple method to control the conformation and orientation of single adsorbed polyelectrolyte molecules by co-deposition with octylamine. A simple chemical route to conductive polypyrrole nanowires by the grafting of polypyrrole from molecules of polystyrensulfonic acid was developed. The dc conductivity of individual polypyrrole nanowires approaches the conductivity of polypyrole in bulk.The conductivity can be described using variable-range hopping model.

Modern pig farming production may over burden the environment with organic substances, exposure of bacterial pathogens and introduction of resistance gene. This may be caused by the pig’s droppings, lack of seepage management or accidental spillage of seepage which may impact on the environment and its physicochemical parameters. The objective of this study is to determine and assess the level of bacteriological pollution emanating from the pig farm and their impact on the physicochemical parameters of soil and water as well as to identify the presence of antibiotic resistance gene of these prevailing bacteria. Soil and water samples were collected monthly for a period of six months (March- August 2013). Samples were collected at pig enclosures, soil 20 m and 100 m away from pig enclosures, constructed wetland used for treating pig farm wastewater, soil 20m and 100 m away from constructed wetland. Procedure followed for analysing soil and water samples includes physicochemical analyses, viable cell counts of 10-1 to 10-8 dilutions, identification of bacteria using API 20E test kit, antibiotic susceptibility analyses, and identification of resistance gene using molecular procedures. The media that were used for viable cell counts were, Nutrient agar, MacConkey Agar, Xylose Lysine Deoxycholate agar (XLD agar), and Eosin Methylene Blue (EMB). Physicochemical parameters of water showed unacceptable high levels of analysed parameters for BOD (163 mg/L to 3350 mg/L), TDS (0.77 g/L to 6.48 mg/L), COD (210 mg/L to 9400 mg/L), NO3 (55 mg/L to 1680 mg/L), NO2 (37.5 mg/L to 2730 mg/L), and PO43− (50 mg/L to 1427 mg/L) were higher than the maximum permissible limits set by Department of Water Affairs and Forestry (DWAF). For soil samples TDS (0.01g/L to 0.88 g/L), COD (40 mg/L to 304 mg/L), NO3 (32.5 mg/L to 475 mg/L), and NO2 (7.35 mg/L to 255 mg/L) and PO43- (32.5 mg/L to 475 mg/L ) were observed to be higher than recommended limits set by Federal Ministry for the Environmental (FME). The viable cells in soil samples 30cm depth ranged from 0 cfu/mL to 2.44 x 1010cfu/mL, in soil 5cm depth ranged from 1.00 x 101 cfu/mL to 1.91 x 1010 cfu/mL, and in water samples viable cells ranged from 5.00 x 101 to 5.05 x 109. Pseudomonas luteola (Ps. luteola), Escherichia vulneris (E. vulneris), Salmonella choleraesuis spp arizonae, Escherichia coli 1(E. coli 1), Enterobacter cloacae, Pseudomonas flourescens/putida (Ps. flourescens/putida), Enterobacter aerogenes, Serratia ordoriferal, Pasteurella pneumotropica, Ochrobactrum antropi, Proteus vulgaris group, Proteus vulgaris, Salmonella spp, Aeromonas Hydrophila/caviae/sobria1, Proteus Mirabillis, Vibrio fluvials, Rahnella aquatillis, Pseudomonas aeruginosa (Ps. aeruginosa), Burkholderia Cepacia, Stenotrophomonas maltophilia (St. maltophilia), Shwenella putrefaciens, Klebsiela pneumonia, Cedecea davisa, Serratia liquefaciens, Serratia plymuthica, Enterobacter sakaziki, Citrobacter braakii, Enterobacter amnigenus 2, Yersinia pestis, Serratia ficaria, Enterobacter gergoriae, Enterobacter amnigenus 1, Serratia marcescens, Raoutella terrigena, Hafnia alvei 1, Providencia rettgeri, and Pantoa were isolated from soil and water samples from the pig farm. Isolates were highly resistant to Penicillin G, Sulphamethaxazole, Vancomycin, Tilmocozin, Oxytetracycline, Spectinomycin, Lincomycin, and Trimethoprim. The most resistance genes detected in most isolates were aa (6’)-le-aph (2”)-la, aph (2”)-lb, aph (3”)-llla, Van A, Van B, Otr A and Otr B. Pig farm seepage is causing bacterial pollution which is impacting negatively on the natural environment in the vicinity of pig farm by introducing bacterial pathogens that have an antibiotic resistance gene and is increasing the physicochemical parameters for soil and water in the natural environment at the pig farm. It is therefore recommended that pig farms should consider the need to implement appropriate regulatory agencies that may include the regular monitoring of the qualities of final effluents from waste water treatment facilities. In addition there is a need to limit soil pollution in order to safe guard the natural environment in the vicinity of pig farm from bacteriological pollution and introduction of antibiotic resistance gene. It is also recommended that more advanced technologies should be introduced that will assist pig farms to manages the seepage properly. / Environmental Sciences / M. Sc. (Environmental Sciences)

Eletrônica utilizando polímero em substituição ao silício é uma área de pesquisa recente com perspectivas econômicas promissoras. Compósitos de polímeros com partículas metálicas apresentam interessantes propriedades elétricas, magnéticas e ópticas e têm sido produzidos por uma grande variedade de técnicas. Implantação iônica de metais utilizando plasma é um dos métodos utilizados para obtenção desses compósitos condutores. Neste trabalho é realizada implantação de íons de ouro de baixa energia em PMMA utilizando plasma. O PMMA tem grande importância tecnológica sendo largamente utilizado como resiste em litografias por feixe de elétrons, raios-X, íons e deep-UV. Como resultado da implantação iônica de baixa energia em PMMA há formação de uma camada nanométrica de material condutor. Esse novo material, denominado compósito isolante-condutor, permite criar micro e nanodispositivos através de técnicas largamente utilizadas em microeletrônica. Medidas elétricas são realizadas in situ em função da dose de íons metálicos implantada, o que permite um estudo das propriedades de transporte desses novos materiais, que podem ser modeladas pela teoria da percolação. Simulações utilizando o programa TRIDYN permitem obter a profundidade e o perfil da implantação dos íons. São mostradas caracterizações importantes tais como Microscopia Eletrônica de Transmissão, Microscopia de Varredura por Tunelamento, Espalhamento de Raios-X a Baixos Ângulos, Difração de Raios-X e Espectroscopia UV-vis. Essas técnicas permitem visualizar e investigar o caráter nanoestruturado do compósito metal-polímero. Ainda como parte deste projeto, as camadas condutoras formadas no polímero são caracterizadas quanto à manutenção das suas características de elétron resiste. / Electronics using polymers instead of silicon is a recent research area with promising economic perspectives. Polymer with metallic particles composites presents interesting electrical, magnetic and optical properties and they have been produced by a broad variety of techniques. Metal ion implantation using plasma is one of the used methods to obtain conductor composites. In this work it is performed low energy gold ion implantation in PMMA by using plasma. PMMA has great technological importance once it is broadly used as resist in electron-beam, X-ray, ion and deep UV lithography. As a result of low energy ion implantation in PMMA, a nanometric conducting layer is formed. This new material, named insulator-conductor composite, can allow the creation of micro and nanodevices through well known microelectronics techniques. Electrical measurements are performed in situ as a function of metal ions implanted dose, which allows the investigation of electrical transport of these new materials, which can be modeled by the percolation theory. Simulations using TRIDYN computer code provide the prediction of depth profile of implanted ions. Important characterizations are showed such as Transmission Electron Microscopy, Scanning Tunneling Microscopy, Small Angle X-Ray Scattering, X-Ray Diffraction and UV-vis Spectroscopy. These techniques allow to visualize and to investigate the nanostructured character of the metal-polymer composite. Still as a part of this project, the conducting layers formed are characterized in relation to the maintenance of their characteristics as electron-beam resist.

O principal objetivo deste trabalho foi avaliar um procedimento de campo para testar o comprimento mínimo que fraturas devem ter para construir uma rede de fluxo em escala de dezenas de metros ao longo de maciços cristalinos. O comprimento mínimo é determinado a partir do limite de percolação, definido por modelos baseados na Teoria da Percolação e a densidade de fraturas no poço, determinada pela perfilagem ótica. Para testar o valor de 3,9 metros que foi encontrado, foram realizados bombeamentos em dois poços próximos enquanto o nível estático era registrado no poço de observação. O método apresenta facilidades em termos de operação e para obter-se o número de fraturas que interceptam o poço, no entanto o registro do nível estático é afetado por fatores externos, como presença de efeitos de maré e variação da pressão atmosférica, e correções são necessárias para permitir identificar a interferência proveniente somente do bombeamento. / The objective of this work is to develop a field procedure to determine a minimum characteristic length forming a connected fracture network in crystalline rocks. This minimum length is determined as a percolation threshold defined by models based on Percolation Theory and fracture density data determined from borehole imaging with well-logging probes. The characteristic length (3.9 meters) once estimated for a testing well was evaluated by monitoring its water head meanwhile nearby wells at different distances were pumped. The water head variation recorded in the testing well was disturbed by interfering effects associated to earth tides and atmospheric pressure, requiring further corrections to isolate effects induced by pumping. The results of these tests validate the percolation limit determined from logging data suggesting a rock mass with very low connectivity. The proposed test can be regarded as simple and easy to apply in many practical situations, for example when evaluating groundwater resources or geotechnical properties in fractured crystalline rocks.

O principal objetivo deste trabalho foi avaliar um procedimento de campo para testar o comprimento mínimo que fraturas devem ter para construir uma rede de fluxo em escala de dezenas de metros ao longo de maciços cristalinos. O comprimento mínimo é determinado a partir do limite de percolação, definido por modelos baseados na Teoria da Percolação e a densidade de fraturas no poço, determinada pela perfilagem ótica. Para testar o valor de 3,9 metros que foi encontrado, foram realizados bombeamentos em dois poços próximos enquanto o nível estático era registrado no poço de observação. O método apresenta facilidades em termos de operação e para obter-se o número de fraturas que interceptam o poço, no entanto o registro do nível estático é afetado por fatores externos, como presença de efeitos de maré e variação da pressão atmosférica, e correções são necessárias para permitir identificar a interferência proveniente somente do bombeamento. / The objective of this work is to develop a field procedure to determine a minimum characteristic length forming a connected fracture network in crystalline rocks. This minimum length is determined as a percolation threshold defined by models based on Percolation Theory and fracture density data determined from borehole imaging with well-logging probes. The characteristic length (3.9 meters) once estimated for a testing well was evaluated by monitoring its water head meanwhile nearby wells at different distances were pumped. The water head variation recorded in the testing well was disturbed by interfering effects associated to earth tides and atmospheric pressure, requiring further corrections to isolate effects induced by pumping. The results of these tests validate the percolation limit determined from logging data suggesting a rock mass with very low connectivity. The proposed test can be regarded as simple and easy to apply in many practical situations, for example when evaluating groundwater resources or geotechnical properties in fractured crystalline rocks.

Eletrônica utilizando polímero em substituição ao silício é uma área de pesquisa recente com perspectivas econômicas promissoras. Compósitos de polímeros com partículas metálicas apresentam interessantes propriedades elétricas, magnéticas e ópticas e têm sido produzidos por uma grande variedade de técnicas. Implantação iônica de metais utilizando plasma é um dos métodos utilizados para obtenção desses compósitos condutores. Neste trabalho é realizada implantação de íons de ouro de baixa energia em PMMA utilizando plasma. O PMMA tem grande importância tecnológica sendo largamente utilizado como resiste em litografias por feixe de elétrons, raios-X, íons e deep-UV. Como resultado da implantação iônica de baixa energia em PMMA há formação de uma camada nanométrica de material condutor. Esse novo material, denominado compósito isolante-condutor, permite criar micro e nanodispositivos através de técnicas largamente utilizadas em microeletrônica. Medidas elétricas são realizadas in situ em função da dose de íons metálicos implantada, o que permite um estudo das propriedades de transporte desses novos materiais, que podem ser modeladas pela teoria da percolação. Simulações utilizando o programa TRIDYN permitem obter a profundidade e o perfil da implantação dos íons. São mostradas caracterizações importantes tais como Microscopia Eletrônica de Transmissão, Microscopia de Varredura por Tunelamento, Espalhamento de Raios-X a Baixos Ângulos, Difração de Raios-X e Espectroscopia UV-vis. Essas técnicas permitem visualizar e investigar o caráter nanoestruturado do compósito metal-polímero. Ainda como parte deste projeto, as camadas condutoras formadas no polímero são caracterizadas quanto à manutenção das suas características de elétron resiste. / Electronics using polymers instead of silicon is a recent research area with promising economic perspectives. Polymer with metallic particles composites presents interesting electrical, magnetic and optical properties and they have been produced by a broad variety of techniques. Metal ion implantation using plasma is one of the used methods to obtain conductor composites. In this work it is performed low energy gold ion implantation in PMMA by using plasma. PMMA has great technological importance once it is broadly used as resist in electron-beam, X-ray, ion and deep UV lithography. As a result of low energy ion implantation in PMMA, a nanometric conducting layer is formed. This new material, named insulator-conductor composite, can allow the creation of micro and nanodevices through well known microelectronics techniques. Electrical measurements are performed in situ as a function of metal ions implanted dose, which allows the investigation of electrical transport of these new materials, which can be modeled by the percolation theory. Simulations using TRIDYN computer code provide the prediction of depth profile of implanted ions. Important characterizations are showed such as Transmission Electron Microscopy, Scanning Tunneling Microscopy, Small Angle X-Ray Scattering, X-Ray Diffraction and UV-vis Spectroscopy. These techniques allow to visualize and to investigate the nanostructured character of the metal-polymer composite. Still as a part of this project, the conducting layers formed are characterized in relation to the maintenance of their characteristics as electron-beam resist.

I have worked on many projects, but there are several things that they all had in common. First, nearly all projects involved searching for the structural parameters that governed the macroscopic properties of the polymers and composite materials. A second common denominator is that even though my work was performed in an “academic context”, the goals were targeted toward industrial needs. Lastly, the methods and procedures were similar; they were all based on experimental results obtained for various scales of measurement (see Fig. 1). Hence, multi-scale modeling was very useful and beneficial for these projects. The models developed (mainly numerical and sometimes analytical) were initially derived from experimental evidence and then validated and improved with further experimentation. The refined models provided an efficient means of: (i) optimizing the composites according to specific needs, (ii) better understanding the hierarchical relations between the different scales, (iii) controlling the micro or meso structure and thereby the macroscopic properties. This study of the relations between structure and properties was performed on a wide variety of physical properties and materials. However, the electric and dielectric properties of composites constituted the major- ity of it and will be presented in this report. The remaining property investigations provided supplemental but valuable information. This work often requires altering various conventional experimental techniques or using well-known techniques for new purposes. I also developed, when needed, several unconventional but necessary measurement techniques. This report contains two major parts which are separated according to the nature of the fillers: Part I : Conducting fillers. In the first part, the main interest both for application and fundamental point of view, is related to the changes in properties in the vicinity of the sharp percolation transition. After a brief introduction to the percolation theory, this part will be subdivided in three chapters: Chapter 1. presents a numerical method that correlates the mesostructure to the macroscopic electrical properties both in two and three dimensions. Chapter 2. will show that an external variable (the mechanical stress) may largely alter the microstruc- ture of the percolating network within composites as revealed the macroscopic conductivity. The understanding of the mesoscale changes will be based on the chemical structure of the polymer matrix. Chapter 3. is devoted to the description of a unique case in term of percolation behavior, which made possible the control of the phase arrangement within the composite and thereby the control of the macroscopic resistivity. p. 2 Multiscale relationships in polymer–based heterogeneous systems. . . Part II : Insulating fillers. In the second part, the main interest is to obtain good electrical insulators, i.e. that can withstand large electric fields. This part thus starts with a brief introduction to the common failure mechanisms, associated with the dielectric breakdown and is also divided in three chapters: Chapter 4. is devoted to the description of a numerical simulation of the relationships between mesostructure and dielectric breakdown. Chapter 5. reveals the influence of the processing conditions of a composite utilized in the industry on the microstructure and the quantitative consequences on breakdown properties. Chapter 6. presents the aging of these composites under “real word” conditions which will further be compared to accelerated aging performed in controlled conditions, in the laboratory. A comparison of the two aging situations will furnish a quantitative understanding of the relative influence of the chemical and physical contributions to the aging process. This report will then be concluded with a description of the current and future projects.