L’objectif de cette thèse est de développer une méthode expérimentale permettant de mesurer simultanément des coefficients de co-diffusion dans les zéolithes, pour des mélanges de paraffines en C6 mono et di-branchées, dont les cinétiques de diffusion sont très différentes. Les espèces sont le 2- et le 3-methyl-pentane (2MP et 3MP) et le 2-2- et le 2-3-dimethyl-butane (22DMB et 23DMB) et l'adsorbant est une silicalite. Cette méthode est basée sur la réponse en sortie d’un lit fixe d’adsorbant à une variation cyclique de la composition à son entrée. La conception d’un modèle faisant intervenir des paramètres cinétiques et thermodynamiques a également être effectuée afin de simuler les courbes de perçages des différents constituants en mélange et sur plusieurs cycles. Les conditions expérimentales sont proches des conditions industrielles, à savoir en phase liquide et à fort taux de remplissage de l’adsorbant (185°C et 35 bars) L’écriture d’un modèle de diffusion, basé sur l’équation de Maxwell-Stefan appliquée au "Dusty Gas Model", dans ces conditions de fonctionnement, implique d’introduire des grandeurs volumiques qui permettent de redéfinir les contraintes liées à la saturation de l'adsorbant. De plus, tout en conservant la simplicité du modèle "Single File Diffusion" (pas de contre-diffusion microporeuse), nous avons montré que la prise en compte d’un flux volumique relatif associé au solide permet de conserver l’indépendance des coefficients de diffusion dans le cristal. Les simulations des courbes de perçage – sur un seul cycle pour les molécules rapides et sur plusieurs cycles pour les molécules lentes – indiquent que les coefficients de diffusion des différents isomères suivent l'ordre suivant : D3MP ˜ D2MP > D23DMB > D22DMB, avec un écart de trois ordres de grandeurs entre le 3MP et le 22DMB, ce qui laisse supposer qu'un procédé de séparation basé sur une sélectivité diffusionnelle peut être envisagé. Cependant, les tests de perçage en condition cyclique permettant de caractériser de manière plus précise le système, il a été possible de mettre en évidence une très lente accumulation du 22DMB au cours des cycles sous certaines conditions opératoires, phénomène qui peut s'avérer indétectable sur un faible nombre de cycles et/ou sur le profils de concentration des autres espèces. Ce phénomène a pour conséquence de diminuer les performances de l'adsorbant, aussi bien d'un point de vue capacitif que d'un point de vue sélectif / The aim of this work is to develop a new experimental method in order to determine simultaneously co-diffusion coefficients in zeolites for mixtures of single- and di-branched C6 paraffins, with totally different diffusion kinetics. The species are 2- and 3-methyl-pentane (2MP and 3MP) and 2-2- and 2-3-dimethyl-butane (22DMB and 23DMB) and the adsorbent is a silicalite. This method is based on the output measurement of an adsorbent column subjected to cyclic variations of its input concentration. The analysis of the mixture experimental breakthrough curves, on several cycles, is carried out using a mathematical model, based on Maxwell-Stefan theory of multi-component diffusion, allowing an estimation of thermodynamic and kinetic parameters. The experimental conditions are close to industrial constraints, i.e. at very high adsorption loading, and in the liquid phase (185°C and 35 bars). This requires to develop a modified Maxwell-Stefan diffusion model, applied to the "Dusty Gas Model", including volume constraints in the crystal which implies to redefine the adsorbent saturation. Moreover, while preserving the simplicity of the "Single File Diffusion" model (no counter-diffusion), a relative volumetric flow of the solid is taken into account, allowing to ensure the independence of the diffusion coefficient of each component in the adsorbent. The Maxwell-Stefan diffusion coefficients for the different isomers, obtained from breakthrough curves simulations – on one cycle for fast diffusing species and several cycles for slow molecules – are in the sequence : D3MP ˜ D2MP, > D23DMB > D22DMB, with a difference of three orders of magnitude between 3MP and 22DMB. This implies that a separation process based on kinetic selectivity can be considered. The cyclic breakthrough experiments, allowing a better characterization of the system, highlight a very slow accumulation of the 22DMB isomer during cycles for specific operating conditions, which may be undetectable on a small number of cycles and on the profiles of the other components.. This phenomenon involves a decrease of the adsorbent performances, in terms of capacity as well as selectivity

Le retournement temporel exploite la réversibilité temporelle de l’équation d’onde dans les milieux sans perte. Cela implique qu’une onde émise par une source peut rebrousser chemin et se focaliser sur sa source originale par le biais d’un miroir à retournement temporel. Cette focalisation permet de situer l’emplacement de cette source. Le but de cette thèse est d’exploiter le phénomène de retournement temporel d’ondes électromagnétiques en vue de la localisation et la caractérisation partielle d’objets diffractants enfouis dans un milieu sans perte. Notre étude est menée dans le domaine temporel large bande en se basant sur une modélisation numérique par la technique d’intégration finie.Le domaine temporel est un domaine assez peu exploré dans la littérature contrairement au domaine fréquentiel. La principale problématique est la détermination de l’instant de focalisation qui nous permet de choisir la distribution des champs à partir de laquelle les objets diffractants seront localisés. Nous introduisons dans ce manuscrit un critère de choix d’instant de focalisation qui est comparé tout au long des études entreprises au critère du minimum d’entropie.La démarche empruntée exploite l’analyse de cartographies d’énergie électromagnétique en deux et trois dimensions. Elle est validée dans un premier temps par l’analyse de configurations canoniques exploitant des données synthétiques obtenues par simulation. L’influence de divers paramètres relatifs aux objets diffractants est étudiée de même que l’impact du nombre d’émetteurs récepteurs du miroir à retournement temporel. Dans une seconde étape une expérimentation contrôlée en chambre anéchoïque à SUPELEC est réalisée en utilisant des antennes en régime harmonique et en régime impulsionnel. / Time reversal is, as is now well-known, exploiting the temporal reversibility of the wave equation in assumed lossless media. To summarize, it implies that a wave emitted by a given source may turn back and thereupon focus onto its original source by means of a so-called Time Reversal Mirror (TRM), which operation, properly simulated from field data acquired in a given measurement domain, could enable us to locate the source indeed. The aim of this thesis is to exploit the phenomenon of time reversal for the localization and the partial characterization, whenever possible, of diffracting objects (dielectric and conducting scatterers, in which sources are induced by given antennas, usually dipole-like) that are buried in a lossless medium (it can be a free space or a half-space) within a fully 3-D transient electromagnetic context. Time-domain certainly is a less explored area in the literature than frequency-domain, and this 3-D context (even if some 2-D validation studies are led also in the present work) is particularly demanding, computatinally speaking as well as at the level of real laboratory experiments. In addition, it requires that we be able to accurately compute the vector electromagnetic field in this time domain in an appropriate wideband situation, as well as whatever field is time reversed during the experiments, which are tasks performed via a full-wave Finite Integration Technique (FIT) developed at LGEP as is validated and discussed in some length in the manuscript. The main problem however is the determination of the moment of focus which would enable us determine the location of the scatterers at least to some extent. Here, to that effect, we introduce and discuss in depth a new criterion of choice of the instant of focus, which is in particular compared throughout the studies undertaken to the usually employed minimum entropy criterion. Influences of the various parameters of the scatterers themselves and of the measurement set-ups are thoroughly discussed on the way. Let us emphasize that what matters to us is the behavior of the (time-reversed) electromagnetic energy and not only of the electric field as standard, that is, the approach taken builds and uses the analysis of energy maps obtained by the aforementioned 3-D numerical modeling. Beyond the modeling of pure synthetic field data and discussions thereof, much attention is also given to leading controlled experiments on canonical targets using both transient and frequency-diverse time-harmonic sources within an anechoic chamber which was made available to us in SUPELEC.

A presente tese de Doutorado refere-se a problemas em teoria de campos e mecânica quântica no espaço não comutativo (NC). Abordamos alguns sistemas físicos bem estudados em física teórica, como a teoria de Maxwell na presença de fontes externas, equação de Pauli, equação de Dirac em campos externos e o espectro do átomo de hidrogênio relativístico. Como um primeiro problema estudamos a teoria de calibre U(1)* e extendemos o mapa de Seiberg-Witten para incluir uma corrente externa e formulamos equações clássicas para os campos no espaço não comutativo. Soluções no vácuo e em um campo magnético externo para uma carga estática de tamanho finito a foram determinadas. Encontramos que uma carga estática além de ser um monopolo elétrico comporta-se como um dipolo magnético e um campo magnético externo modifica o campo de Coulomb a longas distâncias bem como alguns fatores de forma eletromagnéticos, comportamentos inerentes a consideração de uma geometria NC. Nesta direção analisamos a ambiguidade no mapa de Seiberg-Witten e mostramos que, no mínimo até a ordem estudada aqui, isto é equivalente a ambiguidade de se adicionar uma solução homogênea à condição de conservação da corrente. Demandando que o momento magnético NC seja menor que o erro existente na medida do momento magnético de léptons, obtemos uma estimativa superior para o parâmetro e seu comprimento fundamental associado l. Estudamos os níveis de energia do átomo de hidrogênio relativístico no formalismo da equação de Dirac no espaço NC para o campo de Coulomb. Demonstramos que no caso relativístico a não comutatividade quebra totalmente a degenerescência dos níveis 2S1/2; 2P1/2 e 2P3/2, abrindo novos canais de transição permitidos. Por fim construímos uma equação de onda não relativística para partículas de spin 1/2 através do limite não relativístico da equação de Dirac no espaço NC. Apresentamos um modelo pseudoclássico (à-la Berezin-Marinov) cuja quantização coincide com as equações de onda não relativísticas. Através da interação entre um spin não-relativístico e o campo magnético, através da equação de Pauli no espaço NC, construímos uma generalização para o modelo de Heisenberg para dois spins acoplados no espaço NC. Em tal modelo calculamos a amplitude de probabilidade de transição entre dois estados ortogonais do tipo EPR (Einstein-Podolsky-Rosen) submetidos em um campo magnético oscilatório e mostramos que, algumas de tais transições, que são proibidas no espaço comutativo são possíveis devido a não comutatividade do espaço. / The present PhD thesis refers to problems in field theory and quantum mechanics in noncommutative (NC) space. We study some well known physical systems in theoretical physics, such as the Maxwell theory in the presence of external sources, the Pauli equation, the Dirac equation with external fields and the relativistic Hydrogen atom. First we study the U(1)* gauge theory and extend the Seiberg-Witten map to include an external current and formulate classical field equations in NC space. Solutions in the vacuum and in an external magnetic field for a static charge of finite size a is determined. We find that a static charge in NC space, besides being an electric monopole, behaves as a magnetic dipole and the external magnetic field modifies the Coulomb law at large distances, as well as some electromagnetic form factors. In this direction we analyse the arbitrariness in the Seiberg-Witten map and show that, at least to the order studied here, this is equivalent to adding a homogeneous solution to the charge conservation condition. Demanding that the NC magnetic moment be less than the existing error in the measurement of leptons magnetic moment we obtain an upper bound for the NC parameter and its associated fundamental length l. In addition we consider the energy levels of a hydrogen-like atom in the framework of a -modified, due to space noncommutativity, Dirac equation with a Coulomb field. It is shown that the noncommutativity completely breaks the degeneracy of the 2S1/2; 2P1/2 and 2P3/2 levels, allowing for new transition channels. At last, but not least, we construct a nonrelativistic wave equation for spin 1/2 particles through the nonrelativistic limit of the NC Dirac equation. We present a pseudoclassical model (à-la Berezin-Marinov) whose quantization coincides with the nonrelativistic wave equations. By extracting the interaction between a nonrelativistic spin and the magnetic field, from the obtained Pauli equation in NC space, we construct a generalization of the Heisenberg model for two coupled spins in NC space. In such model, it is calculated the transition probability amplitude between two orthogonal EPR (Einstein-Podolsky-Rosen) states submitted in the presence of an oscilatory magnetic field and we shown that some of such transitions, which are forbidden in NC space are possible due to space noncommutativity.

Die vorliegende Dissertation befasst sich mit der mathematischen Modellierung semi-klassischer Licht-Materie-Interaktion. Im semiklassischen Bild wird Materie durch eine Dichtematrix "rho" beschrieben. Das Konzept der Dichtematrizen ist quantenmechanischer Natur. Auf der anderen Seite wird Licht durch ein klassisches elektromagnetisches Feld "(E,H)" beschrieben. Wir stellen einen mathematischen Rahmen vor, in dem wir systematisch dissipative Effekte in die Liouville-von-Neumann-Gleichung inkludieren. Bei unserem Ansatz sticht ins Auge, dass Lösungen der resultierenden Gleichung eine intrinsische Liapunov-Funktion besitzen. Anschließend koppeln wir die resultierende Gleichung mit den Maxwell-Gleichungen und erhalten ein neues selbstkonsistentes, dissipatives Modell vom Maxwell-Bloch-Typ. Der Fokus dieser Arbeit liegt auf der intensiven mathematischen Studie des dissipativen Modells vom Maxwell-Bloch-Typ. Da das Modell Lipschitz-Stetigkeit vermissen lassen, kreieren wir eine regularisierte Version des Modells, das Lipschitz-stetig ist. Wir beschränken unsere Analyse im Wesentlichen auf die Lipschitz-stetige Regularisierung. Für regularisierte Versionen des dissipativen Modells zeigen wir die Existenz von Lösungen des zugehörigen Anfangswertproblems. Der Kern des Existenzbeweises besteht aus einem Resultat von ``compensated compactness'''', das von P. Gérard bewiesen wurde, sowie aus einem Lemma vom Rellich-Typ. In Teilen folgt dieser Beweis dem Vorgehen einer älteren Arbeit von J.-L. Joly, G. Métivier und J. Rauch. / This thesis deals with the mathematical modeling of semi-classical matter-light interaction. In the semi-classical picture, matter is described by a density matrix "rho", a quantum mechanical concept. Light on the other hand, is described by a classical electromagnetic field "(E,H)". We give a short overview of the physical background, introduce the usual coupling mechanism and derive the classical Maxwell-Bloch equations which have intensively been studied in the literature. Moreover, We introduce a mathematical framework in which we state a systematic approach to include dissipative effects in the Liouville-von-Neumann equation. The striking advantage of our approach is the intrinsic existence of a Liapunov function for solutions to the resulting evolution equation. Next, we couple the resulting equation to the Maxwell equations and arrive at a new self-consistent dissipative Maxwell-Bloch type model for semi-classical matter-light interaction. The main focus of this work lies on the intensive mathematical study of the dissipative Maxwell-Bloch type model. Since our model lacks Lipschitz continuity, we create a regularized version of the model that is Lipschitz continuous. We mostly restrict our analysis to the Lipschitz continuous regularization. For regularized versions of the dissipative Maxwell-Bloch type model, we prove existence of solutions to the corresponding Cauchy problem. The core of the proof is based on results from compensated compactness due to P. Gérard and a Rellich type lemma. In parts, this proof closely follows the lines of an earlier work due to J.-L. Joly, G. Métivier and J. Rauch.

Les travaux effectués durant cette thèse portent sur l’étude du comportement mécanique dynamique de solutions amortissantes passives utilisées pour la réduction des niveaux vibratoires et la stabilisation des systèmes optroniques embarqués au sein de l’entreprise Thales LAS France. Ces solutions intègrent des matériaux élastomères au fort pouvoir dissipatif dont le comportement doit être parfaitement maîtrisé pour un bon dimensionnement de l’isolation vibratoire, et ce malgré leur dépendance à la température et à la fréquence. L’objectif général est d’améliorer la connaissance du comportement de ces matériaux, leur caractérisation, leur prise en compte dans les simulations numériques afin d’améliorer les pratiques employées dans les bureaux d’études qui conçoivent les structures accueillant ces systèmes.Dans ce cadre, les travaux présentés portent tout d’abord sur la caractérisation, la modélisation et l’identification du comportement viscoélastique des élastomères employés dans des amortisseurs de Thales LAS France. Un modèle de type Maxwell généralisé (GMM) est utilisé pour décrire ce comportement, et est introduit dans un modèle éléments finis de l’amortisseur afin d’obtenir une représentation physique satisfaisante de son comportement mécanique dynamique. Le problème est réécrit sous la forme d’une représentation d’état originale qui est associée à une stratégie de réduction de modèle pour réduire les temps de calcul. Différentes simulations sont alors réalisées pour illustrer le potentiel de l’approche proposée, analyse modale complexe, réponse fréquentielle et réponse temporelle. La température ayant une influence primordiale sur le comportement mécanique des élastomères, un modèle matériau thermomécanique spécifique est proposé en identifiant l’évolution en température de paramètres du GMM, et une analyse de robustesse portant sur la capacité de dissipation de l’amortisseur témoin en présence de méconnaissances sur cette variable est réalisée en se basant sur la théorie Info-Gap.L’analyse d’une campagne d’essais a permis de constater l’apparition d’un assouplissement de la structure sous de fortes sollicitations, laissant augurer la présence de non-linéarités. Un autre aspect abordé durant cette thèse porte ainsi sur la caractérisation, la modélisation et l’identification des phénomènes non-linéaires pouvant impacter le comportement dynamique de l’amortisseur. Deux sources ont été mises en évidence : une non-linéarité matérielle liée à la dépendance des caractéristiques mécaniques des élastomères au taux de déformation (effet Payne), et une non-linéarité de type contact liée à la présence de butées. Ces comportements ont été implémentés dans une représentation réduite de l’amortisseur afin d’expliquer les phénomènes non-linéaires observés expérimentalement au cours des campagnes de qualification du produit.Enfin, la dernière partie de ces travaux de thèse porte sur la conception d’un réseau d’absorbeurs à masses accordées (MTMD) afin de réduire le niveau vibratoire d’une pièce structurale supportant les systèmes optiques. Après une formulation du problème éléments finis, une procédure d’optimisation des paramètres du MTMD est mise en œuvre et une analyse de robustesse de la solution optimale en présence d’incertitudes sur la fréquence propre à contrôler est effectuée. Cette étude est menée pour différents jeux de paramètres et une méthode d’optimisation robuste est proposée en combinant la procédure d’optimisation et la théorie Info-Gap. Pour finir, une maquette du système étudié est réalisée ainsi qu’une version simplifiée de son MTMD associé afin de mettre à l’épreuve les règles d’accordage issues des études numériques grâce à une série d’essais vibratoires. / The work carried out during this thesis deals with the study of the dynamic mechanical behavior of passive damping solutions used for the reduction of vibration levels and the stabilization of embedded optronic systems within Thales LAS France company. These solutions integrate elastomer materials with high dissipative power, whose behavior must be perfectly controlled for a good mechanical dimensioning of vibration isolation, despite their dependence on temperature and frequency. The general objective is to improve the knowledge of these material behavior, the characterization techniques, and the method taking into account this behavior in the numerical simulations in order to improve the practices used in the engineering department that design the structures hosting these systems.In this context, the work presented first focuses on the characterization, the modeling and the identification of the viscoelastic behavior of elastomers used in Thales LAS France damping devices. A Generalized Maxwell Model (GMM) is used to describe this behavior, and is introduced into a finite element model of the damper to obtain a satisfactory physical representation of its dynamic mechanical behavior. The problem is rewritten as an original state space representation that is associated with a model reduction strategy to reduce computation times. Various simulations are moreover performed to illustrate the potential of the proposed approach, such as complex modal analysis, frequency response and temporal response. Since temperature has a major influence on the mechanical behavior of elastomers, a specific thermomechanical material model is proposed by identifying the temperature evolution of GMM parameters, and a robustness analysis on the dissipation ability of the damper in the presence of a lack-of-knowledge on this variable is carried out based on the Info-Gap theory.Experimental test results showed the appearance of a softening of the structure under heavy load, suggesting the presence of non-linearities. Another aspect of this thesis deals with the characterization, the modeling and the identification of non-linear phenomena that can impact the dynamic behavior of the damper. Two sources have been highlighted: a material non-linearity related to the dependence of the mechanical characteristics of the elastomers to the rate of deformation (Payne effect), and a contact non-linearity related to the presence of mechanical stops. These behaviors were implemented in a reduced representation of the damper to explain the nonlinear phenomena observed experimentally during the damping device qualification campaigns.Finally, the last part of this thesis deals with the design of a network of tuned mass absorbers (MTMD) in order to reduce the vibratory level of a structural part supporting optical systems. After a formulation of the finite element problem, a procedure for optimizing the parameters of the MTMD is implemented and a robustness analysis of the optimal solution in the presence of uncertainties on the specific eigenfrequency to be controlled is performed. This study is carried out for different sets of parameters and a robust design optimization method is proposed by combining the optimization procedure and the Info-Gap theory. Finally, a model of the studied system is realized as well as a simplified version of its associated MTMD in order to test the tuning rules resulting from numerical studies thanks to a series of experimental tests.

Miniemulsionen bestehen aus zwei miteinander nicht mischbaren Flüssigkeiten, von der die eine in Form kleiner Tröpfchen fein in der anderen verteilt (dispergiert) ist. Miniemulsionströpfchen sind mit Durchmessern von ungefähr 0,1 Mikrometer kleiner als herkömmliche Emulsionen und können u. a. als voneinander unabhängige Nanoreaktoren für chemische Reaktionen verwendet werden. Man unterteilt sie in direkte Miniemulsionen, in denen ein Öl in Wasser dispergiert ist, und inverse Miniemulsionen, in denen Wasser in Öl dispergiert wird. In dieser Arbeit wird das besondere chemische und physikalische Verhalten solcher Miniemulsionen unter dem Einfluß von Mikrowellenstrahlung untersucht. Dabei werden sowohl für Öl-in-Wasser als auch für Wasser-in-Öl-Miniemulsionen grundlagenwissenschaftliche Entdeckungen beschrieben und durch neue Modelle erklärt. Der praktische Nutzen dieser bislang unbeschriebenen Effekte wird durch ingenieurwissenschaftliche Anwendungsbeispiele im Bereich der Polymerchemie verdeutlicht. <br><br> 1. Polymerisation mit "überlebenden Radikalen" (Surviving Radical Polymerization)<br> Für die Herstellung von sog. Polymerlatizes (Kunststoffdispersionen, wie sie u. a. für Farben verwendet werden) aus direkten Styrol-in-Wasser Miniemulsionen werden die Styroltröpfchen als Nanoreaktoren verwendet: Sie werden mit Hilfe von Radikalen durch eine Kettenreaktion zu winzigen Polymerpartikeln umgesetzt, die im Wasser dispergiert sind. Ihre Materialeigenschaften hängen stark von der Kettenlänge der Polymermoleküle ab. In dieser Arbeit konnten durch den Einsatz von Mikrowellenstrahlung erstmals große Mengen an Radikalen erzeugt werden, die jeweils einzeln in Tröpfchen (Nanoreaktoren) auch noch lange Zeit nach dem Verlassen der Mikrowelle überleben und eine Polymerisationskettenreaktion ausführen können. Diese Methode ermöglicht nicht nur die Herstellung von Polymeren in technisch zuvor unerreichbaren Kettenlängen, mit ihr sind auch enorm hohe Umsätze nach sehr kurzen Verweilzeiten in der Mikrowelle möglich – denn die eigentliche Reaktion findet außerhalb statt. Es konnte gezeigt werden, dass durch Einsatz von Zusatzstoffen bei unvermindert hohem Umsatz die Polymerkettenlänge variiert werden kann. Die technischen Vorzüge dieses Verfahrens konnten in einer kontinuierlich betriebenen Pilotanlage nachgewiesen werden. <br><br> 2. Aufheizverhalten inverser Miniemulsionen in Mikrowellenöfen<br> Das Aufheizverhalen von Wasser-in-Öl Miniemulsionen mit kleinen Durchmessern durch Mikrowellen ist überaus träge, da sich nur das wenige Wasser in den Tröpfchen mit Mikrowellen aufheizen lässt, das Öl jedoch kaum. Solche Systeme verhalten sich gemäß der "Theorie des effektiven Mediums". Werden aber etwas größere Tröpfchen im Mikrometerbereich Mikrowellen ausgesetzt, so konnte eine wesentlich schnellere Aufheizung beobachtet werden, die auf eine Maxwell-Wagner-Grenzflächenpolarisation zurückgeführt werden kann. Die Größenabhängigkeit dieses Effekts wurde mit Hilfe der dielektrischen Spektroskopie quantifiziert und ist bislang in der Literatur nie beschrieben worden. Zur genauen Messung dieses Effekts und zu seiner technischen Nutzung wurde ein neuartiges Membranverfahren für die Herstellung von großen Miniemulsionströpfchen im Mikrometerbereich entwickelt. <br><br> 3. Herstellung von Kompositpolymeren für Mikrowellenanwendungen<br> Um die untersuchte Maxwell-Wagner-Grenzflächenpolarisation technisch nutzen zu können, wurden als dafür geeignete Materialien Kompositpolymere hergestellt. Das sind Kunststoffe, in denen winzige Wassertropfen oder Keramikpartikel eingeschlossen sind. Dazu wurden neuartige Synthesewege auf der Grundlage der Miniemulsionstechnik entwickelt. Ihr gemeinsames Ziel ist die Einschränkung der üblicherweise bei Polymerisation auftretenden Entmischung: In einem Verfahren wurde durch Gelierung die Beweglichkeit der emulgierten Wassertröpfchen eingeschränkt, in einem anderen wurde durch das Einschließen von Keramikpartikeln in Miniemulsionströpfchen die Entmischung auf deren Größe beschränkt. Anwendungen solcher Kompositpolymere könnten künstliche Muskeln, die Absorption von Radarstrahlung, z. B. für Tarnkappenflugzeuge, oder kratzfeste Lacke sein.<br><br>Bei diesen Experimenten wurde beobachtet, daß sich u. U. in der Miniemulsion große Tröpfchen bilden. Ihr Ursprung wird mit einer neuen Modellvorstellung erklärt, die die Einflüsse auf die Stabilität von Miniemulsionen beschreibt. / Miniemulsions are composed of two immiscible fluids. One of which is distributed as small droplets (dispersed) in the other one. Having diameters of down to 0.05 micrometers, droplets of miniemulsions are smaller than those of conventional emulsions. Among other applications, they can be employed as independent nano-reactors for chemical reactions. They are subdivided in direct miniemulsions, for which an oil is dispersed in an aqueous phase, and inverse miniemulsions, for which water is dispersed in an oil phase. In this work, the specific chemical and physical behaviour of miniemulsions under the influence of microwave-radiation was investigated. For water-in-oil as well as for oil-in-water miniemulsions fundamental discoveries are described and explained by new models. The practical importance of these new effects is exemplified by applications in the field of polymer-chemistry. <br><br> 1. Polymerization with "surviving radicals"<br> For the production of so-called polymer-latices (dispersions of plastics, as they are used in paints and coatings) from direct styrene-in-water miniemulsions, the styrene-droplets can be considered as separate nano-reactors. Upon radical polymerization, they may be transformed to polymer particles dispersed in water in a 1:1 conversion. Their material properties strongly depend on the chain-length of the polymer molecules. In this work, using microwave radiation, for the first time great quantities of radicals could be generated that survive within the individual droplets (nano-reactors) even for a long time after leaving the microwave oven, carrying out polymerization. This method is suited for the production of polymers with great chain-lengths that cannot be obtained with other technically relevant methods. Moreover, it yields great conversion after very short residence-times in the microwave-oven: the actual reaction takes place outside of the oven. Employing additives allows the variation of chain-length at the same great net rates of conversion. The technical promises of this method could be demonstrated in a continuously operated pilot plant. <br><br> 2. Heating behaviour of inverse miniemulsions with microwave-radiation<br> The heating of water-in-oil miniemulsions with small droplets using microwaves is very slow, as only the water absorbs microwave-radiation and not the oil. The system behaves according to the "effective medium theory". If slightly larger droplets with diameters of about a micron are subjected to microwaves, they are being heated much more readily, which can be attributed to a Maxwell-Wagner-effect. The size-dependence of this effect has never been described in the literature. It could be quantified with dielectric spectroscopy. For the controlled production of big miniemulsion droples on the micron-scale and for the technical application of the size-dependence, a continuously operated membrane-emulsification device was developed. <br><br> 3. Production of composite polymers for microwave-applications<br> Suitable composite polymers were produced in order to technically exploit the size-dependence of the Maxwell-Wagner-effect. They may contain sub-micron sized water droplets or ceramic nanoparticles. For their synthesis, new strategies on the basis of miniemulsion-systems were developped, which avoid the usual phase-separation upon polymerization. In one approach, the mobility of the dispersed water droplets was limited through the gelation of the oil phase, in another approach phase separation of ceramic nanoparticles entrapped within miniemulsion droplets was restricted to the dimensions of the droplets. Applications of such composite polymers could be the development of artificial muscles, the absorption of radar radiation (e.g. for stealth applications) or scratch-resistant coatings.<br><br> In these experiments the existence of stable big droplets in miniemulsions was discovered. Their origin can be explained by a new model that describes the influences on miniemulsion stability.

Ziel der Arbeit ist es, auf der Basis von Messungen ein rheologisches Materialmodell für technische Gummiwerkstoffe zu erstellen, welches deren Eigenschaften nachbildet, insbesondere vorhandene komplexe Zusammenhänge zwischen Relaxation, Erholung, Versuchsgeschwindigkeit und Belastungsamplitude. Dabei wird sich auf die Simulation von großen einfachen, aber beliebigen Scherverformungen beschränkt, woraus ein skalarwertiges Modell resultiert. Anwendung finden generalisierte Maxwell-Elemente und generalisierte kontinuierliche Prandtl-Elemente. Verschiedene Modellvarianten werden diskutiert. Es wird ein Berechnungsprogramm unter MATLAB erstellt.

Οι ζεόλιθοι είναι κρυσταλλικά αργιλοπυριτικά υλικά με πόρους μοριακών διαστάσεων και για το λόγο αυτό συχνά καλούνται και ως μοριακά κόσκινα. Χαρακτηρίζονται από την ικανότητα ρόφησης αερίων και ατμών, ανταλλαγής των κατιόντων της δομής τους, καθώς και κατάλυσης σημαντικού αριθμού χημικών αντιδράσεων. Λόγω των ιδιαίτερων φυσικοχημικών ιδιοτήτων τους, οι ζεόλιθοι αποτελούν ιδανικά υλικά για το διαχωρισμό μορίων με διαφορετικό σχήμα, μέγεθος ή πολικότητα γι’αυτό την τελευταία δεκαετία μέρος του ερευνητικού ενδιαφέροντος έχει επικεντρωθεί στην ανάπτυξη πολυκρυσταλλικών μεμβρανών από ζεόλιθους με σκοπό το διαχωρισμό αερίων και υγρών μιγμάτων. Στην παρούσα Διατριβή μελετήθηκε η κρυστάλλωση μεμβρανών φωγιασίτη πάνω σε πορώδη υποστρώματα από α-Al2O3 με επίπεδη και κυλινδρική γεωμετρία συναρτήσει διαφόρων παραμέτρων σύνθεσης όπως ήταν η σύσταση, η θερμοκρασία, ο χρόνος και η γήρανση των αιωρημάτων σύνθεσης των μεμβρανών Συνολικά εξετάστηκαν πέντε διαφορετικές συστάσεις. Η σύσταση 4.17Na2O : 1.0Al2O3 : 10TEA (τριαιθανολαμίνη) : 1.87SiO2 : 460H2O οδήγησε στην ανάπτυξη μεμβρανών φωγιασίτη με λιγότερες ατέλειες και για αυτό μελετήθηκε περισσότερο. Η ικανότητα των μεμβρανών να διαχωρίζουν μίγματα CO2 / H2, CO2 / N2, CO2 / CH4, CO2 / H2 / N2 / CH4, C3H6 / C3H8, C3H6 / N2, C3H8 / N2 και C3H6 / C3H8 / N2 εξετάστηκε συναρτήσει της θερμοκρασίας, της σύστασης και της πίεσης της τροφοδοσίας καθώς και της παρουσίας ή μη υγρασίας στο ρεύμα της τροφοδοσίας. Τα πειράματα διαπερατότητας απέδειξαν, ότι ευνοείται η εκλεκτική μεταφορά κυρίως του CO2 και του C3H6 μέσα από τις μεμβράνες. Η εκλεκτικότητα μπορεί να αποδοθεί στην ισχυρή αλληλεπίδραση των μορίων αυτών με τα κατιόντα Na+ που περιέχονται στη δομή του φωγιασίτη. Τέλος, μελετήθηκαν οι μηχανισμοί μεταφοράς μάζας των μιγμάτων CO2 / H2 και CO2 / H2 / N2 / CH4 με τη χρήση της θεωρίας Stefan-Maxwell. Επιπρόσθετα εξετάστηκαν διάφορες περιπτώσεις αργού σταδίου (διάχυση και εκρόφηση) καθώς και συνδυασμοί διαφορετικών μηχανισμών διάχυσης (επιφανειακή διάχυση και ενεργοποιημένη διάχυση αερίων). Οι συντελεστές διάχυσης υπολογίστηκαν από το συνδυασμό των πειραματικών δεδομένων ρόφησης και διαπερατότητας των καθαρών συστατικών. Η ανάλυση που πραγματοποιήθηκε οδήγησε στο συμπέρασμα ότι η μεταφορά των μιγμάτων μέσα από τις μεμβράνες μπορεί να προβλεφθεί κυρίως από το μηχανισμό της επιφανειακής διάχυσης. / Zeolites are crystalline aluminosilicate materials. They are frequently called molecular sieves because they have pores of molecular dimensions. They are able to adsorb gases or vapors, to exchange framework cations and to catalyze a large number of chemical reactions. Due to their physicochemical properties they are ideal materials for the discrimination of molecules based on their shape, size or polarity. The last decade part of the research attention has been focused on the synthesis of polycrystalline zeolite membranes for the separation of gas and vapor mixtures. In the present thesis the crystallization of faujasite membranes on porous flat or tubular α-Al2O3 substrates was studied as a function of several synthesis parameters such as composition, temperature, time and aging of sol mixtures. Five different compositions were examined. Membranes synthesized using sols with composition 4.17Na2O : 1.0Al2O3 : 10TEA (triethanolamine) : 1.87SiO2 : 460H2O, had the best separation performance. The ability of the membranes to separate CO2 / H2, CO2 / N2, CO2 / CH4, CO2 / H2 / N2 / CH4, C3H6 / C3H8, C3H6 / N2, C3H8 / N2 and C3H6 / C3H8 / N2 mixtures was examined as a function of temperature, feed mixture composition, total feed pressure and the presence or not of humidity in the feed side. In all cases the membranes were either CO2 or C3H6 selective. The separation ability can be attributed to the strong interaction between those molecules with the Na+ cations of the faujasite framework. The transport of CO2, H2, N2 and CH4 through the membranes was modeled using the Maxwell-Stefan theory. Two different cases of rate limiting step (diffusion and desorption) as well as several combinations of different diffusion mechanisms (surface diffusion and activated gaseous diffusion) were considered. The diffusion coefficients were calculated using the single-component permeation and adsorption data. It has been possible to predict the multicomponent permeation fluxes when surface diffusion was assumed the transport mechanism of all species.

Σκοπός της διπλωματικής αυτής εργασίας ήταν η μελέτη των ηλεκτρομαγνητικών δυνάμεων που δημιουργούνται μέσα σε μια ασύγχρονη ηλεκτρική μηχανή, ειδικότερα των ακτινικών δυνάμεων, καθώς και η μηχανική συμπεριφορά της μηχανής λόγω των δυνάμεων αυτών. Χρησιμοποιήθηκε ένας τριφασικός ασύγχρονος κινητήρας βραχυκυκλωμένου δρομέα, ισχύος 4 kW, συνδεσμολογίας τριγώνου. Η προσομοίωση και η μελέτη έγινε με τη χρήση του προγράμματος Opera 2-D της εταιρείας Vector Fields, το οποίο χρησιμοποιεί τη μέθοδο των πεπερασμένων στοιχείων για την επίλυση των μερικών διαφορικών εξισώσεων που περιγράφουν τη ηλεκτρομαγνητική λειτουργία της μηχανής. Πρώτα γίνεται η ηλεκτρομαγνητική ανάλυση των μοντέλων της μηχανής στη μόνιμη κατάσταση. Μετά χρησιμοποιώντας τα μοντέλα αυτά, υπολογίστηκαν οι ηλεκτρομαγνητικές πιέσεις που ασκούνται σε δόντια του δρομέα και του στάτη και η συνολική ακτινική και εφαπτομενική δύναμη που ασκείται πάνω στον δρομέα. Όταν οι ιδιοσυχνότητες ταλάντωσης της μηχανής είναι κοντά στις συχνότητες που υπάρχουν στο φάσμα συχνοτήτων της ακτινικής δύναμης, δημιουργείται συντονισμός και προκαλεί θορύβους και ταλαντώσεις στη μηχανή. Για να αποφευχθούν τέτοιου είδους θόρυβοι και ταλαντώσεις υπολογίζονται τα πλάτη και οι συχνότητες της ακτινικής δύναμης καθώς και οι ιδιοσυχνότητες της μηχανής. Οι ίδιες μετρήσεις έγιναν και σε μοντέλο μηχανής με μια σπασμένη μπάρα του κλωβού. Απεικονίσθηκαν οι ακτινικές δυνάμεις και συγκρίθηκαν με αυτές του υγιούς μοντέλου στο πεδίο του χώρου, του χρόνου και της συχνότητας. Επίσης παρουσιάζεται μια μέθοδος για την ανίχνευση «υπογραφών» ηλεκτρικών σφαλμάτων, μέσω ανάλυσης Fourier της ακτινικής ηλεκτρομαγνητικής δύναμης και πίεσης. Τα αποτελέσματα δείχνουν πως η ηλεκτρομαγνητική δύναμη είναι μια καλή παράμετρος με τη χρήση της οποίας μπορεί να ανιχνευτεί το σφάλμα της σπασμένης μπάρας. / The aim of this thesis was to study the electromagnetic forces generated in an asynchronous electric machine, especially the radial forces and the mechanical behavior of the machine due to these forces. A three-phase squirrel cage asynchronous motor, 4 kW power, was used. The simulation and the study was performed using the program Opera 2-D of Vector Fields, which uses the finite element method to solve partial differential equations describing the operation of the electromagnetic machine. First of all, the electromagnetic analysis of models of the machine in steady state was performed. Using these models, the electromagnetic pressure on teeth of the rotor and stator was calculated and the total radial and tangential force exerted on the rotor was estimated. When the natural frequencies of oscillation of the machine are close to the frequencies of the radial force, coordination is generated and causes noise and vibrations in the machine. To avoid such noises and vibrations, the amplitudes and frequencies of the radial force and the natural frequencies of the machine must be calculated. The same measurements were made on a model engine with a broken bar. The radial forces were plotted and compared with those of the healthy model, in the field of space, time and frequency. Also, a method for the detection of "signatures" electrical fault, through Fourier analysis of the radial electromagnetic force and pressure is disclosed. The results showed that the electromagnetic force is a good parameter to use for the detection of the broken bar fault.

Made available in DSpace on 2014-06-11T19:22:35Z (GMT). No. of bitstreams: 0 Previous issue date: 2008-03-28Bitstream added on 2014-06-13T20:49:17Z : No. of bitstreams: 1 silvafilho_eb_me_ilha.pdf: 1002165 bytes, checksum: 7b47e608bd37c2b8a03cccc84f847230 (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Este trabalho analisa a aplicação em linhas de transmissão do método dos elementos de contorno para cálculo de potencial e campo elétrico, com um enfoque em eletrostática. O método dos elementos de contorno baseia-se numa formulação integral que elimina a discretização do domínio, restando apenas o contorno, permitindo o cálculo do potencial e do campo elétrico no contorno e na região estudada. O trabalho configura-se como uma revisão sobre eletrostática, ressaltando as equações de Laplace e Poisson, que serão utilizadas para encontrar as equações integrais do contorno. Há também vários tópicos relacionados ao campo elétrico de linhas de transmissão, bem como, ás normas brasileiras e recomendações internacionais que devem ser utilizadas no projeto de linhas de transmissão. O método dos elementos de contorno utiliza tais equações integrais para encontrar o potencial e o campo no contorno, e após conhecidos o potencial e o campo no contorno, pode-se aplicar o método em todo o domínio, obtendo o potencial e o campo. Para isso, apenas o contorno do domínio de interesse deve ser discretizado, o que trás uma enorme vantagem sobre os métodos que utilizam formulação diferencial. Neste trabalho, serão descritas as principais características do código computacional desenvolvido e suas sub-rotinas mais importantes. Para validar o programa, os resultados serão comparados com aqueles calculados por um procedimento analítico, sendo mostrada a eficiência da discretização do solo. São apresentados os resultados obtidos da análise do campo elétrico gerado por algumas silhuetas de linhas de transmissão. Os valores do campo elétrico gerado por estruturas compactas são comparados com estruturas convencionais e estruturas reduzidas (semi-compactas), também serão comparados os valores do gradiente de potencial na superfície dos condutores e suas capacitâncias equivalentes. / This paper analyses the application in transmission lines of the Boundary Element Method (BEM) of the calculation of potential and electric field, with a focus on electrostatic. The Boundary Element Method is based on an integral formulation that eliminates the discretisation of the domain, remaining only the contour, allowing the calculation of the potential and the electric field in the contour and in the region studied. The work is configured as revision on electrostatic, underscoring the equations of Laplace and Poisson, which will be used to find the integral equations of the contour. There are also several topics related to the electric field of transmission lines, as well as to the standards Brazilian and international recommendations to be used in the design of transmission lines. The Boundary Element Method uses such integral equations for finding the potential and electric field in the contour, and after having known the potential and electric field in the contour, the BEM can be applied in the whole domain, and getting the potential and electric field. Therefore, only the contours of the domain of interest should just be discretized, which backward an enormous advantage on the methods that use formulation differential. This paper will describe the main characteristics of computer code developed and their sub-routines more important. To validate the program, the results will be compared with those calculated by an analytic procedure, being shown the efficiency of discretisation of the soil. The results obtained from analysis of the electric field generated by some silhouettes of transmission lines are presented. The values of the electric field generated by compact structures are compared with conventional structures and reduced structures, also will be compared the values of the gradient of potential on the surface of the conductors and their equivalents capacitances.