Aujourd'hui, l'impact environnemental de chaque technologie fait l'objet de toutes les attentions. L'élimination des composés soufrés et surtout de H2S dans les gaz entre dans cet aspect écologique au sein de plusieurs processus industriels. L'oxyde de zinc est utilisé comme adsorbant régénérable pour la désulfuration. Le but de ce travail est la préparation de filtres monolithiques macroporeux et de nanopoudres de ZnO avec une forte capacité en soufre et facilement régénérable, ainsi que l'optimisation de leurs propriétés.Des matériaux composites ZnS/NaCl sont tout d'abord synthétisés par combustion auto-propagée à partir de mélanges de zinc, de soufre et de chlorure de sodium. NaCl est éliminé par lixiviation dans l'eau après la synthèse. Les nanopoudres de ZnS sont préparées par mécanosynthèse à partir de mélanges de zinc et de soufre. Les deux matériaux préparés ont des structures cristallines différentes, de type würtzite pour les filtres de ZnS et de type sphalerite pour les poudres. Cette différence est due aux deux voies de synthèse. Monolithes et poudres ZnS sont ensuite convertis en ZnO par traitement thermique sous air à 700 °C.Les transformations macro- et microstructurales des filtres et des poudres ont été étudiées au cours de cycles de sulfuration-oxydation par les méthodes de caractérisation telles que la diffraction des rayons X, la microscopie électronique à balayage et la porosimétrie au mercure. Les résultats montrent que les propriétés des matériaux restent très stables au cours des conversions successives. Enfin, les filtres et nanopoudres de ZnO ont été utilisés comme adsorbants au cours d'essais de désulfuration. La capacité massique en soufre des filtres est assez faible, 6,4 mg S/g ads. montrant que la porosité doit être améliorée. Quant aux nanopoudres, la capacité massique en soufre est très élevée, 272 mg S/g ads, prouvant que la surface spécifique est très importante pour ce type d'application. / Today, we have to take care of every technology's environmental effects. The removal of H2S and other sulfur compounds in hot gas enters this ecological aspect in several industrial processes. Zinc oxide is used here as a regenerable sorbent for gas desulfurization. The goal of this work is, the preparation of macroporous ZnO monolithic filters and nanopowders with high sulfur capacity and easily regenerable, and their optimization with the control of their properties. ZnS/NaCl composite materials are first obtained by Self-propagating High temperature Synthesis from mixtures of zinc, sulfur and sodium chloride powders. NaCl is then removed by lixiviation with water. ZnS nanopowders are prepared by mechanical alloying from mixtures of zinc and sulfur. The two materials have different crystalline structure, würtzite type for ZnS filters and sphalerite type for powders, because of the way of synthesis. Then, they are converted into ZnO by thermal treatment under air at 700 °C. Next, the macro- and microstructure transformations of both filter and powders during sulfidation-oxidation cycles are thus considered. Results of all characterizations like X-ray diffraction, scanning electron microscopy and Hg porosimetry show that materials properties are very stable against conversions. Afterwards, ZnO filters and nanopowders are used as adsorbent in desulfurization trials. The sulfur capacity of filters is not so high, 6,4 mg S/g ads and shows that porosity has to be improved. Regarding nanopowders, the sulfur capacity is very high, 272 mg S/g ads, proving that surface area is very important in this application.

L ’intérêt des nano-particules pour le domaine de l ’optique visible a été suscité lors du premier rapport rédigé par Faraday en 1857 et qui a initié les bases de la production de nanoparticules métalliques en vue de leur propriété optiques inattendues (coloration des solutions). Plus récemment, le contrôle et le guidage de la lumière basés sur l’excitation de résonance plasmon dans les nanostructures a permis beaucoup d’applications liées à la vie quotidienne et impliquant la lumière. La résonance plasmonique de structures métalliques estun phénomène essentiel qui conduit à des propriétés optiques uniques à travers l’interaction de la lumière avecles électrons libres du métal. L’excitation de la résonance plasmon localisé (LSPR) permet d’exalter localement l’énergie électromagnétique comme dans le cas des nano-antennes mais aussi d’acheminer la lumière à travers des canaux de dimensions sub-l sur de grandes distances distances grâce à l’excitation du Plasmonde Surface Propagatif (PSP). Au cours de cette thèse, nous avons étendu un algorithme existant afin de calculer la réponse optique (sections efficaces de diffusion et d’absorption) de NPs ayant une forme géométrie quelconque. Ce type de NP anisotrope (vis-à-vis de la polarisation incidente) peut présenter à la résonance plasmonique une section efficace de diffusion 25 fois supérieure à celle géométrique. De plus, une étude systématique importante a été effectuée afin d’optimiser la géométrie de tels Nps.En ce qui concerne la PSP qui est impliqué dans la transmission exaltée à travers les matrices d’ouvertures annulaires AAA, nous avons entrepris une étude systématique des propriétés de l’excitation du mode particul particulier sans coupure de ces nano - guides. Il s’agit du mode Transverse Electrique et Magnétique (TEM). Une étude numérique complète est alors effectuée pour correctement concevoir la structure avant qu’elle ne soit expérimentalement fabriquée et caractérisée. Pour palier certaines contraintes expérimentale, une structure inclinée est proposée et étudiée dans le cas d’un métal parfaitement conducteur. Nous avons démontrée numériquement et analytiquement certaines propriétés intrinsèques de la structure montrant un coefficient de d’au moins 50% d’un faisceau incident non polarisé indépendamment des conditions d’éclairage (polarisation,angle et plan d’incidence). Lorsque le mode TEM est excité, le flux laminaire de l’énergie à travers la structure présente une déviation géante sur de très petites distances inférieures à la longueur d’onde. Les résultats présentés dans cette thèse pourraient être considérés comme une contribution importante à la compréhension du phénomène de transmission exaltée basé sur l’excitation de ce type de mode guidé. / The release of the rst report by Faraday in 1857 set the foundation of the production of metal nanoparticlesand their unexpected optical properties (coloring). More recently, controlling and guiding light via plasmonicresonance in nanostructures enable a lot of applications affecting everyday life that involves light. Plasmonresonance of metallic structures is a key phenomenon that allows unique optical properties through the interactionof light with the free electrons of the metal. The excitation of Localized Surface Plasmon Resonance(LSPR) leads to turn-on large local enhancements of electromagnetic energy as within antennas or to routelight as waveguide to desired region with high transmission through the excitation of Propagating SurfacePlasmon (PSP). During this thesis, we have developed an existing algorithm in order to calculate the opticalresponse of NPs of any shape. We have especially determined the localized energy enhancement factor interm of optical response of nano-antenna. This anisotropic (polarization dependent) NPs type can feature, atplasmon resonance, scattering efciency factor higher than 25. Moreover, an important systematic study hasbeen performed in order to optimize design of such NPs.Concerning the PSP that are involved in the enhanced transmission through Annular Aperture Arrays (AAAs),we systematically study the properties of the excitation of the peculiar Transverse ElectroMagnetic (TEM) guidedmode inside such nano-apertures. A complete numerical study is performed to correctly design the structurebefore it is experimentally characterized. For reasons associated to fabrication constraints and efciency,a slanted AAA made in perfectly conducting metal is proposed and studied. We numerically and analyticallydemonstrate some intrinsic properties of the structure showing a transmission coefcient of at least 50%ofan un-polarized incident beam independently of the illumination configuration (polarization, angle, and planeof incidence). At the TEM peak transmission, the laminar flow of the energy through the structure can exhibitgiant deviation over very small distances ( ). The results presented in this thesis could be considered as animportant contribution to the understanding of the enhanced transmission phenomenon based on the excitationof guided modes

Cette étude est consacrée à l'élaboration d'une méthodologie de détermination des vitessesfondamentales des flammes laminaires, en utilisant un diagnostic de Vélocimétrie par Imagerie deParticules (PIV). Ce dernier est appliqué aux écoulements réactifs avec point de stagnation, permettant lastabilisation de flammes planes, stationnaires et en conditions quasi adiabatiques. Les effets d’étirementssubits par la flamme sont également quantifiables et parfaitement maîtrisés. L’approche ici développée atout d’abord été appliquée aux mélanges méthane/air pour validation. Une comparaison exhaustive desrésultats obtenus avec les données de la littérature est effectuée. Les codes de combustion 1D (PREMIX,OPPDIF) et 2D (Fluent©) ont été utilisés afin de confirmer la fiabilité et la précision de l’approche proposée.Une attention particulière a été accordée à la caractérisation du mouvement des particules ensemencéesdans les écoulements réactifs divergents, avec notamment la prise en considération de la force dethermophorèse. La méthode développée a ensuite été appliquée à la détermination des vitesses deflammes laminaires de divers mélanges de syngas (H2+CO). Une étude comparative sur ces mélanges aété conduite en utilisant des approches expérimentales multiples comprenant : les flammes à contrecourant,les flammes à propagation sphérique ainsi que les flammes stabilisées coniques. Les résultatsobtenus pour chaque approche ont été confrontés et la sensibilité à l’étirement des flammes de syngas aété caractérisée pour une large gamme de richesses (E.R.=0.4 to 5.0) et de compositions de mélanges(5/95 to 50/50 % H2/CO). / In the context of CO2 emission reduction, the present study is devoted to the development of alaminar flame speed measurement methodology, using the Digital Particle Image Velocimetry (DPIV)diagnostic. The latter is applied to stagnation flow flames, seen to have considerable assets for suchstudies. Indeed, flames stabilized in these diverging flows are planar, steady and in near-adiabaticconditions, while subtraction of strain effects on flame is intrinsically allowed. The methodology developedherein has been applied to the well-characterized methane/air mixtures for validation. An extensivecomparison with the literature datasets has been provided. Both 1D (PREMIX, OPPDIF) as well as 2D(Fluent©) numerical tools have been used to confirm the reliability and accuracy of the developed approach.A particular attention has been given to the characterization of the seeding particle motion within thediverging flow, with consideration of the often-neglected thermophoretic force. Fundamental flame velocitiesof various syngas (H2+CO) mixtures have been investigated using multiple experimental approachesincluding the aforementioned counterflow methodology as well as spherical and conical flameconfigurations. Performed measurements from the different approaches have been confronted and flamesensitivities to stretch have been characterized for a wide range of equivalence ratios (E.R.=0.4 to 5.0) andmixture compositions (5/95 to 50/50 % H2/CO).

This thesis presents a research into the solder interconnects made through the reactive bonding process based on the self-propagating reaction. A numerical study of soldering conditions in the heat affected zone (HAZ) during bonding was initially carried out in order to understand the self-propagating reactive bonding and the related influencing factors. This was subsequently followed by an extensive experimental work to evaluate the feasibility and reliability of the reactive bonding process to enable the optimisation of processing parameters, which had provided a detailed understanding in terms of interfacial characteristics and bonding strengths. In addition, by focusing on the microstructure of the bonds resulted from the self-propagating reactions, the interfacial reactions and microstructural evolution of the bonded structures and effects of high-temperature aging were studied in details and discussed accordingly. To study the soldering conditions, a 3D time-dependent model is established to describe the temperature and stress field induced during self-propagating reactions. The transient temperature and stress distribution at the critical locations are identified. This thus allows the prediction of the melting status of solder alloys and the stress concentration points (weak points) in the bond under certain soldering conditions, e.g. ambient temperature, pressure, dimension and type of solder materials. Experimentally, the characterisation of interconnects bonded using various materials under different technical conditions is carried out. This ultimately assists the understanding of the feasibility, reliability and failure modes of reactive bonding technique, as well as the criteria and optimisation to form robust joints. The formation of phases such as intermetallic compounds (IMCs) and mechanism of interfacial reactions during reactive bonding and subsequent aging are elaborated. The composition, dimension, distribution of phases have been examined through cross-sectional observations. The underlying temperature and stress profile determining the diffusion, crystallization and growth of phases are defined by numerical predictions. XXI Through the comparative analysis of the experimental and numerical results, the unique phases developed in the self-propagating joints are attributed to the solid-liquid-convective diffusion, directional solidification and non-equilibrium crystallization. The recrystallization and growth of phases during aging are revealed to be resulted from the solid-state diffusion and equilibration induced by the high-temperature heating. In conclusion, the interfacial reactions and microstructural evolution of interconnect developed through self-propagating reactive bonding are studied and correlated with the related influencing factors that has been obtained from these predictions and experiments. The results and findings enable the extensive uses of self-propagating reactive bonding technology for new design and assembly capable of various applications in electronic packaging. It also greatly contributes to the fundamentals of the crystallization and soldering mechanism of materials under the non-equilibrium conditions.

No description available.

Zur numerischen Simulation piezoelektrischer Probleme mit linearem Materialgesetz wird die adaptive Finite-Element-Methode genutzt. Bei der Lösung der entstehenden Gleichungssysteme vom Sattelpunktstyp wird auf eine Variante des Bramble-Pasciak-CG zurückgegriffen. Die Einbettung von Projektionstechniken in den Löser erlaubt eine Behandlung von verschiedenen Problembesonderheiten, speziell wird hier auf die Fälle konstanten Potentials auf Teilrändern sowie Kontaktprobleme an wachsenden Rissen eingegangen. Erste numerische Ergebnisse werden an einigen Beispielen demonstriert.:1 Einführung 1.1 Problembeschreibung Piezoelektrizität 1.2 Abgeleitete Größen, Materialgesetz, Gleichungen 1.3 Bilinearformen, schwache Formulierung 2 Implementierung 2.1 Sattelpunktsproblem 2.2 FE-Formulierung 2.3 Löser und Vorkonditionierung 2.4 Adaptivität 3 Besonderheiten von Randbedingungen 3.1 Konstantes Potential auf Teilrändern 3.2 Rissproblem 4 Rissschließen und Kontaktproblem 4.1 Motivation für Risskontaktbetrachtung 4.2 Bezeichnungen 4.3 Kontaktproblem für Verschiebung und Behandlung des Potentials 4.4 FEM-Implementierung des Risskontaktes 4.5 Numerische Beispiele

Malgré leurs contribution dans plusieurs domaines, les biopuces à lecture plasmonique conventionnelles basées sur l'utilisation d’un film métallique plan d'or, sont limitées en terme de sensibilité surtout quand il s'agit de détecter des molécules de faible masse molaire à l’état de trace.Dans ce cadre, nous étudions numériquement et expérimentalement le potentiel de détection d’interactions biomoléculaires d’une nouvelle génération de biopuces à lecture plasmonique intégrant un film métallique micro-nano-structurée en réseau rectangulaire 1D. L’étude numérique développée met en œuvre une méthode hybride, basée sur la combinaison de deux méthodes classiques : la méthode des éléments finis et la méthode modale de Fourier. Grâce à ce nouvel outil numérique, nous présentons une cartographie exhaustive du potentiel de détection d’une couche biologique, en variant les paramètres de la structuration liés aux dimensions du réseau. La réponse de la biopuce à l’accrochage de biomolécules est ensuite interprétée théoriquement par les différents phénomènes plasmoniques notamment les «points chauds» et les bandes plasmoniques interdites. Nos calculs soulignent l'importance de l’exploitation du confinement de la lumière à travers la structuration sub-longueur d’onde des surfaces plasmoniques. Ceci permet non seulement d’optimiser les paramètres géométriques afin d’améliorer la sensibilité vis-à-vis de la réponse d’une biopuce conventionnelle, mais aussi de mettre en évidence la transition entre le régime où les plasmons propagatifs dominent et le régime où les plasmons localisés dominent. De nouvelles figures de mérite sont introduites pour évaluer les performances des biopuces structurées.Cette étude montre également que de nouvelles opportunités pour améliorer davantage la bio-sensibilité sont offertes, si la localisation de biomolécules peut être effectuée dans les régions où le champ électrique est amplifié et confiné. / Surface plasmons resonance imaging with continuous thin metallic films have become a central tool for the study of biomolecular interactions. However, in order to extend the field of applications of surface plasmons resonance systems to the trace detection of biomolecules having low molecular weight, a change in the plasmonic sensing methodology is needed. In this study, we investigate theoretically and experimentally the sensing potential of 2D nano- and micro- ribbon grating structuration on the surface of Kretschmann-based surface plasmon resonance biosensors when they are used for detection of biomolecular binding events. Numerical simulations were carried out by employing a fast and novel model based on the hybridization of two classical methods, the Fourier Modal Method and the Finite Element Method. Our calculations confirm the importance of light manipulation by means of structuration of the plasmonic thin film surfaces on the nano- and micro- scales. Not only does it highlight the geometric parameters that allow the sensitivity enhancement, and associated figures of merit, compared with the response of the conventional surface plasmon resonance biosensor based on a flat surface, but it also describes the transition from the regime where the propagating surface plasmon mode dominates to the regime where the localized surface plasmon mode dominates. An exhaustive mapping of the biosensing potential of the nano- and micro- structured biosensors surface is presented, varying the structural parameters related to the ribbon grating dimensions. New figures of merit are introduced to evaluate the performance of the structured biosensors. The structuration also leads to the creation of regions on biosensor chips that are characterized by strongly enhanced electromagnetic fields. New opportunities for further improving the bio-sensitivity are offered if localization of biomolecules can be carried out in these regions of high electromagnetic fields enhancement and confined.

Habilitation - Universität, Bayreuth, 2006. / Includes bibliographical references (p. [289]-321) and index.

[pt] O projeto mecânico de componentes estruturais para vidas longas à fadiga requer limites de fadiga confiáveis. Porém, a previsão do limite de fadiga ainda apresenta alguns desafios, especialmente por causa dos inevitáveis entalhes e pela presença de pequenos defeitos intrínsecos do material que podem ser considerados como microtrincas. Os entalhes atuam como concentradores de tensão e microtrincas podem ser geradas na ponta destes. Tais microtrincas (geradas ou intrínsecas) podem propagar até provocar a falha do componente ou parar de propagar depois de crescer uma pequena distância e se tornarem não-propagantes, dependendo do nível de carga e do gradiente de tensão à frente do entalhe. Modelos empíricos e teóricos têm sido propostos para fazer previsão do limite de fadiga de componentes entalhados. Entre os teóricos, o chamado modelo do Gradiente de Tensão (GT), que utiliza conceitos da mecânica da fratura linear elástica, apresenta-se como um modelo promissor. No entanto, a validação experimental das previsões deste modelo ainda não tem sido completamente realizada. Neste contexto, corpos de prova tipo C(T) do aço 1020 e com vários valores do raio da ponta do entalhe foram testados sob controle de amplitude de carga constante, frequência de 40 Hz e razão de tensão R igual a 0.1 para avaliar o limite de fadiga através de testes acelerados com cargas tipo step up durante blocos de 3.10 elevado a sexta potência ciclos. O limite de fadiga determinado experimentalmente foi comparado com as previsões do modelo GT e do Método do Ponto, um dos métodos da chamada Teoria da Distância Crítica (TDC). No modelo GT foram considerados três métodos: GTc-p, GTs-e e GTquebra, segundo o método usado para achar o fator geométrico para determinar o fator de intensidade de tensão. As previsões dos modelos GTc-p, GTquebra e TDC são similares no caso de entalhes com raios de ponta grandes, e bem próximas do limite de fadiga medido experimentalmente, enquanto que eles são não-conservativos no caso de entalhes afiados (raios de ponta pequenos). As previsões do modelo GTs-e foram conservativas para entalhes afiados e não afiados. Devido a que os dois modelos são baseados em conceitos lineares elásticos, foi demonstrado que uma análise elástica apresenta limitações para modelar o comportamento à fadiga em entalhes afiados, pois nesses casos a tensão local no ponto crítico pode exceder o limite de escoamento do material. Alem disso, o modelo GT também permite estimar o tamanho da maior trinca curta não-propagante (TCNP) associada ao limite de fadiga. Tais TCNP foram monitoradas nas faces do C(T) através de técnicas não-destrutivas tais como microscopia óptica, correlação digital de imagens e tomografia; enquanto que as TCNP internas foram detectadas usando a técnica destrutiva da metalografia. Os tamanhos das TCNP detectadas foram muito menores do que as estimadas pelo modelo GT, dificultando ainda mais o problema de detecção daquelas trincas. / [en] The mechanical design of structural components for high cycle fatigue applications needs reliable fatigue limits. However, mainly because of notches and the unavoidable presence of small defects, such a task still presents some challenges. Notches cause a stress concentration effect that can initiate short cracks at their tips, but such short cracks may propagate or become non-propagating, depending not only on the load level, but on the stress gradient ahead of the notch tip as well. Notch-like defects, such as scratches, pores, and inclusions, behave in the same way. There are empirical and theoretical models to predict the fatigue limit of notched components. The latter includes the so-called Stress Gradient (SG) model, based on linear elastic fracture mechanics concepts and using the El Haddad-Topper-Smith (ETS) characteristic size aR, as a promissory approach. However, there is a lack of experimental data verifying their fatigue limit predictions. In this context, C(T)-like notched specimens of SAE 1020 steel with several notch root radii were tested under constant load amplitude control at 40 Hz and a stress ratio R equal 0.1, to evaluate their fatigue limit through accelerated tests involving step loading procedures with blocks of 3.10 to sixth power cycles. The experimental fatigue limit was compared with values predicted by SG model, following three approaches: SGc-p, SGs-e, and SGquebra, according to the determination of the geometric factor of the stress concentration factor; and with an alternative prediction by the Point Method based on the theory of critical-distance (TCD). SGc-p, SGquebra and TCD model predictions are almost coincident for blunt notches and they present a good agreement with experimental results, but they are non-conservatives in the case of sharp notches; while SGc-p predictions are conservative for both blunt and sharp notches. Since both models are based on linear elastic concepts, it was demonstrated that an elastic analysis presents limitations to model the behavior of short cracks emanating from sharp notches, due to the local stress at the critical point can exceed the yield strength of the material. Furthermore, according to SG model, the fatigue limit is related to the presence of non-propagating short cracks (NPSC). Such surface NPSCs on the face of the specimens were monitored by non-destructive techniques including optical microscopy, digital image correlation (DIC) and micro-computed tomography; whereas subsurface NPSCs were detected through destructive metallographic technique. The sizes of the detected NPSCs were much smaller than those values predicted by SG model, which in turn makes the detection of these cracks a more complex problem.

L'attraction d'ondes dans des systèmes contra-propagatifs est un phénomène général, établi initialement en Physique dans le contexte de l'attraction de polarisation entre deux ondes contra-propagatives se propageant dans des fibres optiques. Ce phénomène a été observé expérimentalement, et ses propriétés étudiées via des simulations numériques. Les modèles qui s'y rattachent sont des systèmes hyperboliques d'équations aux dérivées partielles, avec des conditions aux bords dépendant du temps sur un intervalle fini. Le mécanisme sous-jacent peut être expliqué par l'existence de tores singuliers dans les équations stationnaires correspondantes. Le but de cette thèse est d'analyser en détail l'exemple le plus simple dans cette famille de modèles. Nous montrons que la plupart des phénomènes de processus d'attraction d'ondes sont en fait existants dans un modèle linéaire avec intéraction résonnante. Nous établissons l'existence et la régularité des solutions et analysons la relaxation vers la solution stationnaire qui caractérise les propriétés de l'attraction d'ondes. / Wave attraction in counter-propagating waves systems is a general phenomenon that was first established in Physics in the context of the attraction of the polarization between two counter-propagating waves in optical fibers. This phenomenon has been observed experimentally, and its properties were studied through numerical simulations. The models are Hamiltonian hyperbolic systems of partial differential equations, with time-dependent boundary conditions on a finite interval. The underlying mechanism can be traced back to the existence of singular tori in the corresponding stationary equations. In this work we analyze in detail the simplest example in this family of models. We show that most of the phenomena of the wave attraction process are already present in a linear model with resonant interaction. We establish the existence and regularity of the solutions and analyze the relaxation towards a stationary solution that features the wave attraction properties.