Dissertationen zum Thema „PTC ceramics“

The thesis deals with the study of the influences of selected groups of chemical agents on the stability of PTC ceramics based on BaTiO3. The experimental part includes elaboration of methodology for determination of these influences, their evaluation, including the hypotheses for their description, and evaluation of groups of chemical agents having these influences.

Thesis (S.M.)--Massachusetts Institute of Technology, Dept. of Aeronautics and Astronautics, 2002.
Includes bibliographical references (leaves 99-101).
A full Particle-In-Cell code, written by James Szabo [23], was used to model a 50W TAL and 3kW SPT thruster. This code treats single and double ions, neutrals and electrons as particles, moved forward by a leapfrog algorithm at each timestep, matching the lowest of the plasma and the cyclotron times. At the end of each timestep, a successive-over-relaxation algorithm solves the Gauss' formulation of the Poisson equation. Collisions include electron-neutral single and double ionization, and elastic scattering, electron-ion double ionization, ion-neutral elastic scattering and chargeexchange. A few tricks are used to decrease the computation time: superparticles, an artificial permittivity factor and lighter-than-physical ions. We modified this code to track the different components governing the thruster efficiency, and to map average internal data in the thruster. We used these tools to track changes with higher-than- nominal voltage (600, 900 and 1200V) for the 50W, 300V mini-TAL, optimizing efficiency vs. magnetic fields at each voltage. We further modified the code to model a 3kW SPT thruster. These modifications include ceramic wall secondary electron emission, a new boundary condition model for the Poisson solver at ceramic walls, an improved sheath model, and a new anomalous diffusion algorithm. Converged results with low anomalous diffusion diffusion were obtained, along with intermediary results with higher diffusion.
by Vincent Blateau.
S.M.

The theme of this thesis is the engineering design of the automaton for the ceramic moulds production for the shell casting technology. In the first part of the thesis I occupy with the design of the mechanical part of the machine including the kinematic, dynamic and strength calculations of the chosen engineering compositions and components. In the next part of the thesis I design the control part of the machine.

Ce travail de thèse a porté sur le développement de membranes céramiques pour la filtration de colloïdes issus de la corrosion dans le circuit primaire des REP. La voie des polymères précéramiques a été mise en œuvre par la synthèse d’un polyborocarbosilane (PBC) à partir d’allylhydridopolycarbosilane conduisant à une céramique de type SiBC. Des billes de PMMA mono disperses d’une taille de 1,5 et 0,3 µm ont été préparées pour servir d’agent porogène pour créer une porosité contrôlée. Des objets micro-cellulaires 3D de forme circulaire ont été élaborés par pressage uni-axial avec ajout de billes de PMMA commercial pour servir de support macroporeux. Une étude de cristallinité à haute température (> 1000 °C) a été réalisée, montrant son influence sur la stabilité du matériau. La couche sélective a été préparée par dip-coating à partir de différentes formulations de barbotine contenant du PBC et les billes de PMMA élaborées. La stabilité physico-chimique des supports micro-cellulaires a été étudiée grâce à des essais de vieillissement en micro-autoclave en milieu primaire simulé. La résistance à la filtration a été testée grâce à un essai sur un dispositif de filtration connecté à un moyen d’essai de laboratoire permettant de simuler les conditions des REP
This work has been focused on the development of ceramic membranes for the filtration of colloids resulting from corrosion in the primary loop of PWR. SiBC ceramics were synthesized by the preceramic polymers route from a polyborocarbosilane (PBC) obtained from allylhydridopolycarbosilane. Single-dispersed PMMA beads with a size of 1.5 and 0.3 μm were prepared to be used as a porogen agent to lead to a controlled porosity of the selective layer. 3D micro-cellular objects with a circular shape were developed by uni-axial pressing with the addition of commercial PMMA beads to serve as a macroporous support. A crystallinity study at high temperature (> 1000 ° C) was carried out showing its influence on the stability of the material. The selective layer was prepared by dip-coating from various slurry formulations containing PBC and the prepared PMMA beads. The chemical and physical stability of the microcellular supports was studied by ageing tests in a simulated primary water chemistry. The filtration resistance was tested by means of tests on a filtration device connected to a laboratory loop which simulates the conditions of the PWRs

Technical challenges for developing micro sensors for Ultra High Temperature and turbine applications lie in that the sensors have to survive extremely harsh working conditions that exist when converting fuel to energy. These conditions include high temperatures (500-1500°C), elevated pressures (200-400 psi), pressure oscillations, corrosive environments (oxidizing conditions, gaseous alkali, and water vapors), surface coating or fouling, and high particulate loading. Several technologies are currently underdeveloped for measuring these parameters in turbine engines. One of them is an optical-based non-contact technology. However, these nondirective measuring technologies lack the necessary accuracy, at least at present state. An alternative way to measure these parameters without disturbing the working environments is using MEMS type sensors. Currently, the techniques under development for such harsh environment applications are silicon carbide (SiC) and silicon nitrite (Si3N4) –based ceramic MEMS sensors. But those technologies present some limitation such as narrow processing method, high cost (materials and processing cost), and limited using temperatures (typically < 800 C). In this research we propose to develop two sensors based on recently developed polymer-derived ceramics (PDCs): Constant Temperature Hot wire Anemometer, temperature/heat-flux sensor for turbine applications. PDC is a new class of high temperature ceramics. As we shall describe below, many unique features of PDCs make them particularly suitable for the proposed sensors, including: excellent thermo-mechanical properties at high temperatures, enable high temperature operation of the devices; various well-developed processing technologies, such as injection molding,photolithography, embossing, DRIE etching and precise machining, can be used for the fabrication of the devices; and tunable electric conductivity, enable the proposed sensors fabricated from similar materials, thus reliability considerations associated with thermal mismatch, which is a big concern when using MEMS-based sensors at elevated temperatures, will be minimized.
M.S.M.E.
Department of Mechanical, Materials and Aerospace Engineering;
Engineering and Computer Science
Mechanical Engineering

Les matériaux céramiques à base de bore dans le système quaternaire Si-B-C-N présentent des propriétés de grand intérêt grâce aux liaisons covalentes et à la faible mobilité des éléments bore et silicium dans leurs phases nitrure et carbure, ce qui amène une grande fiabilité mécanique et une bonne stabilité thermique. Ces dernières années, la voie « polymères précéramiques » est devenue la plus intéressante pour la préparation des ce type de céramiques avancées. En utilisant la thermolyse de polymères, une large variété de céramiques dérivées de polymères précéramiques peut être produite à partir de précurseurs moléculaires, en contrôlant la structure de l'unité monomérique, la polymérisation et la procédure de thermolyse. Notamment la thermolyse directe des polymères est une voie compatible avec plusieurs types de techniques de mise en forme, entre autres l'infiltration ou le filage, qui offrent la possibilité de réaliser structures et objets avec des formes complexes avec une approche simple et à faible coût. La première génération de fibres SiBCN a été obtenue à partir du polymère de type [B(C2H4SiCH3NCH3)3]n. Celle-ci présentait de bonnes propriétés mécaniques et une bonne stabilité thermique. Ce manuscrit présente une étude sur le développement de ce type de polymères, en particulier l'optimisation du filage et de la qualité de fibres à travers la modification des voies de synthèse et des traitements de thermolyse. De plus, une élaboration de nouveaux précurseurs moléculaires est développée afin de produire une nouvelle génération de fibres SiBCN
Boron-based ceramic materials in the quaternary Si-B-C-N system are of great interest because of their covalent bonding and the poor mobility of boron and silicon elements in their respective nitride and carbide which both provide mechanical reliability and high temperature stability. In recent years, the PDCs route became of increasing interest for the preparation of such advanced ceramics. Using the general polymer thermolysis route, a large variety of net-shaped polymerderived ceramics can be built up from molecular units and shaped by controlling the structure of the molecular units as well as the polymerization and thermolysis procedures. Interestingly, the direct polymer thermolysis route makes polymers compatible with many shaping techniques such as infiltration or melt-spinning offering the opportunity to realize complex shapes/structures in a simple and cost-efficient way.The first generation of such fibers obtained from a polymer type [B(C2H4SiCH3NCH3)3]n showed good mechanical properties and thermal stability. This document is about the development of such a polymer in order to optimize spinnability and fibers quality throught synthesis modification and thermolysis treatments. Moreover, design of new preceramic polymers is investigate to produce a new generation of SiBCN fibers

Ceramics have a number of applications as coating material due to their high hardness, wear and corrosion resistance, and the ability to withstand high temperatures. Critical to the success of these materials is the effective heat transfer through a material to allow for heat diffusion or effective cooling, which is often limited by the low thermal conductivity of many ceramic materials. To meet the challenge of improving the thermal conductivity of ceramics without lowering their performance envelope, carbon nanotubes were selected to improve the mechanical properties and thermal dispersion ability due to its excellent mechanical properties and high thermal conductivity in axial direction. However, the enhancements are far lower than expectation resulting from limited carbon nanotube content in ceramic matrix composites and the lack of alignment. These problems can be overcome if ceramic coatings are reinforced by carbon nanotubes with good dispersion and alignment. In this study, the well-dispersed and aligned carbon nanotubes preforms were achieved in the form of vertically aligned carbon nanotubes (VACNTs) and Buckypaper. Polymer derived ceramic (PDC) was selected as the matrix to fabricate carbon nanotube reinforced ceramic nanocomposites through resin curing and pyrolysis. The SEM images indicates the alignment of carbon nanotubes in the PDC nanocomposites. The mechanical and thermal properties of the PDC nanocomposites were characterized through Vickers hardness measurement and Thermogravimetric Analysis. The ideal anisotropic properties of nanocomposites were confirmed by estimating the electrical conductivity in two orthogonal directions.
M.S.M.E.
Masters
Mechanical and Aerospace Engineering
Engineering and Computer Science
Mechanical Engineering; Mechanical Systems Track

L'obésité et le diabète de type 2 sont associés à la sédentarité et à une alimentation riche en graisses. En effet, les acides gras saturés s'accumulent dans les tissus non adipeux, comme les muscles squelettiques pour générer des lipides appelés céramides (CER). Mon projet de thèse s'est articulé en deux parties dont l'objectif est d'empêcher les CER d'agir. Nous avons montré que, selon la structure de la membrane plasmique, les CER altèrent la voie de signalisation insulinique en ciblant la PKB, protéine clef de la voie insulinique, via la voie PKC? dans les myotubes L6 et la voie PP2A dans les myotubes C2C12. Nous avons aussi mis en évidence que les CER altèrent la sensibilité à l'insuline via la voie PKC? dans les cellules musculaires humaines. Une fois les CER produits au niveau du réticulum endoplasmique (RE), ils sont transportés au Golgi par un transporteur CERT pour y être métabolisés en sphingomyéline (SM) et des études ont montré que la transformation des CER en SM pouvait être une étape cruciale pour empêcher les CER d'agir. Dans plusieurs modèles d'insulino-résistance musculaire, l'expression de CERT est diminuée et nous avons démontré l'importance du transport des céramides du RE vers le Golgi en inhibant artificiellement l'activité ou l'expression de CERT. A l'opposé, la surexpression de CERT améliore la sensibilité à l'insuline dans les cellules musculaires dans des conditions lipotoxiques. Nos résultats montrent que CERT joue un rôle crucial dans les mécanismes conduisant au développement de l'insulinorésistance musculaire puisque sa présence est essentielle pour le maintien d'un trafic normal des CER entre le RE et le golgi
Obesity and type 2 diabetes are associated with a sedentary lifestyle and a diet rich in fat. Indeed, saturated fatty acids accumulate in non-adipose tissue such as skeletal muscle to generate lipids called ceramides (CER). My thesis project was divided into two parts with the objective to prevent CER to act. We have shown that, depending on the structure of the plasma membrane, CER alter the insulin signaling pathway by targeting PKB, a key insulin signalling protein, via a PKCζ pathway in L6 myotubes and a PP2A pathway in C2C12 myotubes. We also demonstrated that CER affect insulin sensitivity via the PKCζ pathway in human muscle cells. Once CER generated in the endoplasmic reticulum (ER), they are transported to the Golgi by a carrier called CERT to be metabolized into sphingomyelin (SM). Studies have shown that the transformation of CER into SM could be a crucial step to prevent CER to act. In several muscle insulin resistance models, expression of CERT is decreased and we demonstrated the importance of the transport of ceramide from the ER to the Golgi by inhibiting artificially the activity or the expression of CERT. In contrast, overexpression of CERT enhances insulin sensitivity in muscle cells in lipotoxiques conditions. Our results show that CERT plays a crucial role in mechanisms leading to the development of muscle insulin resistance since its presence is essential for maintaining normal traffic of CER between the ER and the Golgi

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Barium titanate (BaTiO3 - BT) is a ferroelectric material with important technological applications. When partially doped with trivalent cations at the barium sublattice or pentavalent at the titanium sublattice, BaTiO3-based ceramics exhibit a semiconductive character, accompanied by a Positive Temperature Coefficient of Resistivity (PTCR). Several ways of BT modifications have been proposed in literature, as example, the use of different synthesis methods and the doping with different ions. Therefore, in the present work we have as objective the synthesis, sintering and electrical characterization of the rare earth ions (RE = La3+, Y3+, Er3+, Nd3+ e Eu3+) doped barium calcium titanate ceramics (Ba0,77Ca0,227RE0,003TiO3 BCT_RE) in order to study mainly the PTCR behavior. The powder synthesis was done by the polymeric precursor method followed by the sinterization at reducing atmosphere during the heating up ramp and different atmosphere during cooling down ramp in order to investigate the atmosphere and dopant effect on PTCR behavior. The characterization was done using the Differential Thermal Analysis, Thermogravimetry, Scanning Differential Calorimetry, X-ray Powder Diffraction, Scanning Electron Microscopy and Impedance Spectroscopy techniques. The calcined powder at 600ºC/4h presented majority BCT phase and after sintering at 1350ºC/6h, a small amount of Ba6Ti17O40 phase was observed. The sintered ceramics presented a homogeneous grain size distribution but with the presence of a secondary phase at the grain boundary for all compositions, and Curie temperature at about 120ºC. The PTCR characteristics of the ceramics were studied as a function of the sintering atmosphere and dopant type. In summary, all the samples, exception of the Eu doped samples, presented PTCR behavior in all the studied conditions. .
O titanato de bário (BaTiO3 - BT) é um material ferroelétrico com importantes aplicações tecnológicas. Quando dopado com íons trivalentes no sítio do bário ou pentavalentes no sítio do titânio, cerâmicas de BaTiO3 exibem um caráter semicondutor, acompanhado por um coeficiente positivo da resistência com o aumento da temperatura (PTCR). Diversas formas de modificação do BT têm sido sugeridas na literatura, por exemplo, a utilização de diferentes métodos de síntese e a dopagem com diferentes íons. Dessa forma, no presente trabalho tivemos como objetivo a síntese, a sinterização e a caracterização elétrica de cerâmicas de titanato de bário e cálcio (Ba0,77Ca0,227RE0,003TiO3 BCT_RE) dopados com íons terras raras (RE = La3+, Y3+, Er3+, Nd3+ e Eu3+), visando principalmente o estudo do comportamento PTCR. A síntese dos pós foi realizada pelo método dos precursores poliméricos, seguido pela sinterização em atmosfera redutora durante o aquecimento e diferentes atmosferas no resfriamento com o intuito de investigar a influência da atmosfera e do dopante no comportamento PTCR. A caracterização foi feita utilizando as técnicas de Análise Térmica Diferencial, Termogravimetria, Calorimetria Exploratória Diferencial, Difração de Raios X, Microscopia Eletrônica de Varredura e Espectroscopia de Impedância. Os pós calcinados a 600ºC/4h apresentaram fase majoritária BCT e após sinterizados a 1350ºC/6h foi observada a presença da fase Ba6Ti17O40. As cerâmicas sinterizadas apresentaram uma distribuição homogênea de tamanho de grão, porém com a presença de uma segunda fase na região de contorno de grão para todas as composições, com temperatura de Curie em torno de 120ºC. As características PTCR das cerâmicas foram estudadas em função da atmosfera de sinterização e do tipo do dopante. Em resumo, todas as amostras, com exceção das dopadas com Eu, apresentaram comportamento PTCR para todas as condições estudadas.

La photo-catalyse est une voie très prisée pour la dépollution de l’eau ou de l’air. Le photo-catalyseur le plus employé est le dioxyde de titane (TiO2) mais l’activité photo-catalytique peut fortement varier d’une poudre à l’autre. De plus, il est très avantageux, voire nécessaire, de le déposer sur un support, pour une manipulation aisée, notamment s’il s’agit d’un monolithe poreux. Le but de cette thèse, menée en collaboration entre le LMCPA et l’IEM, est de produire un photo-catalyseur supporté : une mousse céramique, issue de précurseurs céramiques polymériques (voie PDC), revêtue de TiO2, tout en visant une cristallisation et une intégration du TiO2 dans la mousse, en une seule étape, par voie hydrothermale. Nous avons étudié la synthèse de TiO2 par voie hydrothermale formant ainsi des poudres de diverses natures (anatase, brookite, oxyde hydraté de titane et mélanges de ces phases) ; certaines présentent une activité photo-catalytique supérieure, dans certaines conditions, à celle de la référence commerciale le P25 de Degussa. Cette étude a également permis de produire de la brookite pure à une température relativement basse, bien plus performante que le P25 et l’anatase dans certaines conditions. Parallèlement, divers polymères précéramiques ont été investigués pour la confection de supports macro-poreux via la méthode des charges sacrificielles. Nous avons ainsi réalisé des mousses en céramique amorphe en SiBCN et SiBC, hautement poreuses, ouvertes et robustes. Enfin, les poudres de TiO2 les plus efficaces ont été déposées sur les mousses, par la voie hydrothermale, pour former le photocatalyseur supporté dont l’activité photo-catalytique a été évaluée
Photocatalysis is a method of choice for water and air depollution. Titanium dioxide (TiO2) is the most used photocatalyst but photocatalytic activity can widely differ from one powder to another. Moreover, it is useful, or even necessary, to immobilize it on a support; in particular, a porous monolithic support for an easier handling. The purpose of this PhD thesis, consisting in a collaboration between the LMCPA and the IEM, is to produce a supported photocatalyst: an amorphous ceramic foam produced from polymeric ceramic precursors (PDC route) coated with TiO2. The objective is also to target a one pot process the crystallization and the incorporation of the photocatalyst, in a single stage, through a hydrothermal treatment. We studied the hydrothermal synthesis of TiO2 powders composed of various crystalline phases (anatase, brookite, titanium oxide hydrate and mixtures of thereof); some of them showed higher photocatalytic activity than the commercial reference, Degussa’s P25. This study also lead to the synthesis of pure brookite, at a relatively low temperature, much more efficient than P25 and anatase under certain conditions. At the same time, various preceramic polymers were studied for the production of macroporous supports through the sacrificial filler technique. We were able to produce highly porous, opened and robust amorphous ceramic foams in the Si-B-C-N and Si-B-C systems. Lastly, the foams were coated with the most efficient TiO2 powders in order to produce supported photocatalysts by the hydrothermal route; their photocatalytic activity was then evaluated

Vielschichtige Eigenschaftsprofile benötigen zunehmend moderne Verbundwerkstoffe und Werkstoffverbunde einschließlich der raschen Entfaltung neuer Fertigungstechnologien, da der monolithische Werkstoff bzw. ein einziger Werkstoff den heutigen komplexen Anforderungen nicht mehr genügen kann. Zukünftige Werkstoffsysteme haben wirtschaftlich eine Schlüsselposition und sind auf den Wachstumsmärkten von grundlegender Bedeutung. Gefragt sind maßgeschneiderte Leichtbauwerkstoffe (tailor-made composites) mit einem adaptierten Design. Dazu müssen Konzepte entwickelt werden, um die Kombination der Komponenten optimal zu gestalten. Das erfordert werkstoffspezifisches Wissen und Korrelationsvermögen sowie die Gestaltung komplexer Technologien, auch unter dem Aspekt der kontinuierlichen Massen- und Großserienfertigung (in-line, in-situ) und damit der Kostenreduzierung bislang teurer Verbundwerkstoffe und Werkstoffverbunde. In der vorliegenden Arbeit wird in vergleichbarer und vergleichender Art und Weise sowie abstrahierter Form ein Bogen über das Gesamtgebiet der Verbundwerkstoffe und Werkstoffverbunde gespannt. Eine zusammenfassende Publikation über dieses noch sehr junge, aber bereits breit aufgestellte Wissenschaftsgebiet fehlt bislang. Das ist der Separierung der einzelnen, fest aufgeteilten Gruppierungen der Verbundwerkstoffe geschuldet. Querverbindungen werden selten hergestellt. Dieses Defizit in einem gewissen Maße auszugleichen, ist Ziel der Arbeit. Besondere Berücksichtigung finden Begriffsbestimmungen und Klassifikationen, Herstellungsverfahren und Eigenschaften der Werkstoffe. Es werden klare Strukturierungen und Übersichten herausgearbeitet. Zuordnungen von etablierten und neuen Technologien sollen zur Begriffsstabilität der Terminologien „Mischbauweise“ und „Hybrider Verbund“ beitragen. Zudem wird die Problematik „Recycling und Recyclingtechnologien“ diskutiert. Zusammenfassend werden Handlungsfelder zukünftiger Forschungs- und Entwicklungsprojekte spezifiziert. Aus dem Blickwinkel der verschiedenen Herstellungsrouten insbesondere für Halbzeuge und Bauteile und der dabei gewonnenen Erkenntnisse werden verallgemeinerte Konzepte für tailor-made Verbundwerkstoffe und Werkstoffverbunde vorgeschlagen („Stellschraubenschema“). Diese allgemeinen Werkstoffkonzepte werden auf eigene aktuelle Forschungsprojekte der Schwerpunktthemen Metallmatrix- und Polymermatrix-Verbundwerkstoffe sowie der hybriden Werkstoffverbunde appliziert. Forschungsfelder für zukünftige Projekte werden abgeleitet. Besonderes Augenmerk gilt den hybriden Verbunden als tragende Säule zukünftiger Entwicklungen im Leichtbau. Hier spielen in-line- und in-situ-Prozesse eine entscheidende Rolle für eine großseriennahe, kosteneffiziente und ressourcenschonende Produktion
Complex property profiles require increasingly advanced composite materials and material compounds, including the rapid deployment of new production technologies, because the monolithic material or a single material can no longer satisfy today's complex requirements. Future material systems are fundamentally important to growth markets, in which they have an economically key position. Tailor-made lightweight materials (tailor-made composites) with an adapted design are needed. These concepts have to be developed to design the optimum combination of components. This requires material-specific knowledge and the ability to make correlations, as well as the design of complex technologies. Continuous large-scale and mass production (in-line, in-situ), thus reducing the costs of previously expensive composite materials and material compounds, is also necessary. The present work spans the entire field of composite materials and material compounds in a comparable and comparative manner and abstract form. A summarizing publication on this still very new, but already broad-based scientific field is not yet available. The separation of the individual, firmly divided groups of the composite materials is the reason for this. Cross-connections are rarely made. The objective of this work is to compensate to some extent for this deficiency. Special consideration is given to definitions and classifications, manufacturing processes and the properties of the materials. Clear structures and overviews are presented. Mapping established and new technologies will contribute to the stability of the terms "mixed material compounds" and "hybrid material compounds". In addition, the problem of recycling and recycling technologies is discussed. In summary, areas for future research and development projects will be specified. Generalized concepts for tailor-made composite materials and material compounds are proposed ("adjusting screw scheme") with an eye toward various production routes, especially for semi-finished products and components, and the associated findings. These general material concepts are applied to own current research projects pertaining to metal-matrix and polymer-matrix composites and hybrid material compounds. Research fields for future projects are extrapolated. Particular attention is paid to hybrid material compounds as the mainstay of future developments in lightweight construction. In-line and in-situ processes play a key role for large-scale, cost- and resource-efficient production

Vielschichtige Eigenschaftsprofile benötigen zunehmend moderne Verbundwerkstoffe und Werkstoffverbunde einschließlich der raschen Entfaltung neuer Fertigungstechnologien, da der monolithische Werkstoff bzw. ein einziger Werkstoff den heutigen komplexen Anforderungen nicht mehr genügen kann. Zukünftige Werkstoffsysteme haben wirtschaftlich eine Schlüsselposition und sind auf den Wachstumsmärkten von grundlegender Bedeutung. Gefragt sind maßgeschneiderte Leichtbauwerkstoffe (tailor-made composites) mit einem adaptierten Design. Dazu müssen Konzepte entwickelt werden, um die Kombination der Komponenten optimal zu gestalten. Das erfordert werkstoffspezifisches Wissen und Korrelationsvermögen sowie die Gestaltung komplexer Technologien, auch unter dem Aspekt der kontinuierlichen Massen- und Großserienfertigung (in-line, in-situ) und damit der Kostenreduzierung bislang teurer Verbundwerkstoffe und Werkstoffverbunde. In der vorliegenden Arbeit wird in vergleichbarer und vergleichender Art und Weise sowie abstrahierter Form ein Bogen über das Gesamtgebiet der Verbundwerkstoffe und Werkstoffverbunde gespannt. Eine zusammenfassende Publikation über dieses noch sehr junge, aber bereits breit aufgestellte Wissenschaftsgebiet fehlt bislang. Das ist der Separierung der einzelnen, fest aufgeteilten Gruppierungen der Verbundwerkstoffe geschuldet. Querverbindungen werden selten hergestellt. Dieses Defizit in einem gewissen Maße auszugleichen, ist Ziel der Arbeit. Besondere Berücksichtigung finden Begriffsbestimmungen und Klassifikationen, Herstellungsverfahren und Eigenschaften der Werkstoffe. Es werden klare Strukturierungen und Übersichten herausgearbeitet. Zuordnungen von etablierten und neuen Technologien sollen zur Begriffsstabilität der Terminologien „Mischbauweise“ und „Hybrider Verbund“ beitragen. Zudem wird die Problematik „Recycling und Recyclingtechnologien“ diskutiert. Zusammenfassend werden Handlungsfelder zukünftiger Forschungs- und Entwicklungsprojekte spezifiziert. Aus dem Blickwinkel der verschiedenen Herstellungsrouten insbesondere für Halbzeuge und Bauteile und der dabei gewonnenen Erkenntnisse werden verallgemeinerte Konzepte für tailor-made Verbundwerkstoffe und Werkstoffverbunde vorgeschlagen („Stellschraubenschema“). Diese allgemeinen Werkstoffkonzepte werden auf eigene aktuelle Forschungsprojekte der Schwerpunktthemen Metallmatrix- und Polymermatrix-Verbundwerkstoffe sowie der hybriden Werkstoffverbunde appliziert. Forschungsfelder für zukünftige Projekte werden abgeleitet. Besonderes Augenmerk gilt den hybriden Verbunden als tragende Säule zukünftiger Entwicklungen im Leichtbau. Hier spielen in-line- und in-situ-Prozesse eine entscheidende Rolle für eine großseriennahe, kosteneffiziente und ressourcenschonende Produktion.
Complex property profiles require increasingly advanced composite materials and material compounds, including the rapid deployment of new production technologies, because the monolithic material or a single material can no longer satisfy today's complex requirements. Future material systems are fundamentally important to growth markets, in which they have an economically key position. Tailor-made lightweight materials (tailor-made composites) with an adapted design are needed. These concepts have to be developed to design the optimum combination of components. This requires material-specific knowledge and the ability to make correlations, as well as the design of complex technologies. Continuous large-scale and mass production (in-line, in-situ), thus reducing the costs of previously expensive composite materials and material compounds, is also necessary. The present work spans the entire field of composite materials and material compounds in a comparable and comparative manner and abstract form. A summarizing publication on this still very new, but already broad-based scientific field is not yet available. The separation of the individual, firmly divided groups of the composite materials is the reason for this. Cross-connections are rarely made. The objective of this work is to compensate to some extent for this deficiency. Special consideration is given to definitions and classifications, manufacturing processes and the properties of the materials. Clear structures and overviews are presented. Mapping established and new technologies will contribute to the stability of the terms "mixed material compounds" and "hybrid material compounds". In addition, the problem of recycling and recycling technologies is discussed. In summary, areas for future research and development projects will be specified. Generalized concepts for tailor-made composite materials and material compounds are proposed ("adjusting screw scheme") with an eye toward various production routes, especially for semi-finished products and components, and the associated findings. These general material concepts are applied to own current research projects pertaining to metal-matrix and polymer-matrix composites and hybrid material compounds. Research fields for future projects are extrapolated. Particular attention is paid to hybrid material compounds as the mainstay of future developments in lightweight construction. In-line and in-situ processes play a key role for large-scale, cost- and resource-efficient production.

Ce travail traite de l'analyse de la texture cristallographique de ceramiques et de couches minces du compose yba#2cu#3o#7-#, et de l'effet de cette texture sur les proprietes supraconductrices, principalement la densite de courant critique (jc). La diffraction des rayons x a ete surtout utilisee, completee pour certains echantillons par la diffraction des neutrons et la retrodiffusion des electrons. Dans le cas de l'utilisation des rayons x et de la geometrie de schulz par reflexion, les corrections de defocalisation indispensables a l'analyse quantitative des orientations preferentielles dans des couches minces et des multicouches ont ete developpees. Par ailleurs les conditions experimentales adaptees a l'etude d'echantillons tres textures, massifs ou minces ont ete precisees. Les echantillons massifs les plus textures ont ete elabores par des methodes derivees de la technique melt texture growth. En general, les echantillons textures en volume presentent deux orientations proches l'une de l'autre permettant d'expliquer les valeurs relativement faibles des densites de courant critique mesurees. La phase verte y#2bacuo#5 ne semble pas texturee dans les echantillons etudies. L'importance de la texture sur jc est clairement mise en evidence dans ce type d'echantillons, meme si l'etablissement d'une relation quantitative reste delicate. Pour les couches minces hetero-epitaxiees, l'utilisation d'un substrat monocristallin mgo oriente (001) entraine une interface tres perturbee pouvant expliquer les mauvaises proprietes supraconductrices des couches deposees (par rapport aux depots realises sur des substrats offrant un meilleur accord de maille avec ybco). La densite de courant critique est reliee quantitativement au degre de texture des films. De faibles pourcentages d'orientations secondaires diminuent jc de facon importante, inversement la presence de precipites de cuo peut avoir un effet benefique. Enfin l'analyse de la texture de dispositifs experimentaux a permis la caracterisation quantitative des orientations imposees artificiellement et necessaires a la creation de jonctions josephson

Les ceramiques supraconductrices des composes bi-(pb)-sr-ca-cu-o ont une capacite de transport de courant electrique a 77 k faible qui est due a la presence des porosites et a la desorientation des feuillets. Pour obtenir des densites de courant critique de transport elevees dans ces materiaux, il est necessaire de les densifier et d'induire une orientation cristallographique preferentielle. Un procede permettant de texturer par effet combine du champ magnetique et de la contrainte uniaxiale a haute temperature a ete mis au point. Le dispositif experimental permet d'appliquer une pression uniaxiale de 60 mpa sous un champ magnetique de 8 t jusqu'a une temperature de 1100c. Les echantillons elabores sont obtenus a partir des precurseurs industriels (hoechst) de la phase bi:2223. La technique de texturation par solidification sous champ magnetique s'est averee tres efficace pour obtenir des echantillons massifs polycristallins bi-(pb)-sr-ca-cu-o orientes avec l'axe-c des cristallites parallele au champ magnetique applique. Les densites de courant critiques (jc) obtenues par ce procede sont de 1450 a/cm#2 pour une densite de 5. 1 g/cm#3 (82% de la densite theorique). La texturation par fluage sous contrainte uniaxiale, a permis d'obtenir des ceramiques denses ( 6 g/cm#3), homogenes ayant des densites de courant critiques de 2500 a/cm#2. Les rubans ag/bi:2223 fournis par alcatel alsthom ont aussi ete textures avec succes par le procede de pressage a chaud. La combinaison du champ magnetique et de la contrainte uniaxiale permet d'ameliorer la texture et la densite des echantillons qui par ailleurs sont tres homogenes et possedent une bonne tenue mecanique. Les densites de courant critique de transport a 77 k atteignent 3800 a/cm#2 suivant les plans (a,b) et 1100 a/cm#2 suivant l'axe-c. Par ailleurs, nous avons mis en evidence la possibilite d'utiliser ces ceramiques texturees dans le domaine de l'electrotechnique pour limiter le courant

Nuclear techniques such as perturbed angular correlation (PAC) sample the hyperfine interactions of a large number of probe atoms in specific crystallographic sites. Real crystals contain static defects producing a distribution of electric field gradients (EFGs) that add to the ideal EFG of the crystal at any given probe site. Also, dynamic defects like moving vacancies and interstitial atoms can be present in the crystal and contribute to the distribution of EFGs. The distribution of EFGs leads to line broadening and a change in the observed asymmetry parameter η since the total EFG no longer has the symmetry of the perfect crystal. When both defects are present in a material, obtaining quantitative information from the analysis of PAC spectra is usually very difficult since great care has to be taken to ensure that the source of line broadening is identified correctly. In order to relate the relationship between the static line broadening and changes in the asymmetry parameter η, a uniform random distribution of point charges was used to simulate the static defect EFG. PAC spectra collected on cubic niobium metal, cubic stabilized zirconia and Nb-doped tetragonal zirconia were fitted with this model. Although the quality of the fits is good, more work is needed to clarify the relationship between the new model parameters and the line broadening and asymmetry parameter derived from conventional model fits. The PAC spectra of Nb-doped tetragonal zirconia were fitted with a conventional static model to establish a reliable relationship between line broadening and the asymmetry parameter when only static defects are present in a sample. To account for effects of dynamic defects, a four state stochastic model for vacancy motion was adapted in order to include the line broadening and changes in the asymmetry produced by static defects. As a result, the activation energies corresponding to the rates at which a oxygen vacancy is trapped by, detraps from, and hops among equivalent sites about a PAC probe atom were calculated. The values that were found are physically reasonable, indicating that the dynamics of an oxygen vacancy around a PAC probe atom are satisfactorily described.
Graduation date: 2003

Ceramic membranes (CM) are robust membranes attributed with high production, long life span and stability against critical conditions. While capital costs are high, these are partially offset by lower operation and maintenance costs compared to polymeric membranes. Like any other low-pressure membrane (LPM), CM faces problems of fouling, low removal of organic matter and poor removal of trace organic compounds (TOrCs). Current pretreatment approaches that are mainly based on coagulation and adsorption can remove some organic matter but with a low removal of the biopolymers component which is responsible for fouling. Powdered activated carbon (PAC) accompanied with a LPM maintains good removal of TOrCs. However, enhanced removal of TOrCs to higher level is required. Submicron powdered activated carbon (SPAC), obtained after crushing commercial activated carbon into very fine particle, and novel activated carbon (KCU 6) which is characterized with larger pores and high surface area were employed. A pre-coating approach, which provides intimated contact between PAC and contaminants, was adopted for wastewater and (high DOC) surface water treatment. For seawater, in-line coagulation with iron III chloride was adopted. Both SPAC and KCU 6 showed good removal of biopolymers at a dose of 30 mg/L with > 85 % and 90 %, respectively. A dose of 40 mg/L of SPAC and 30 mg/L KCU 6 pre-coats were successful used in controlling membrane fouling. SPAC is suggested to remove biopolymers by physical means and adsorption while KCU 6 removed biopolymers through adsorption. Both KCU 6 and SPAC attained high removal of TOrCs whereas KCU 6 showed outstanding performance. Out of 29 TOrCs investigated, KCU 6 showed > 87 % TOrCs rejection for 28 compounds. In seawater pretreatment, transparent exopolymer particles (TEP) were found to be an important foulant. TEP promoted both reversible and irreversible fouling. TEP are highly electronegative while alumina CM is positively charged which support strong TEP–alumina binding. The influence of TEP fouling was minimized with a low dose of 0.5 – 1 mg/l Fe coagulant. Bacteria were almost completely removed; Silt Density Index (SDI) value was maintained to 2 % per minute and a constant permeate turbidity of 0.05 NTU was achieved.

The main aim of my master thesis is to describe the development of painted folk decor on ceramics since the arrival of Anabaptism in the Czech Republic. Selected Moravia workshops are used to track the decor development. Another goal of this thesis is to find out whether workshops that produce ceramics and subsequently paint it in the traditional way exit even today. Next part of my thesis is devoted to selected Czech workshops that produce painted ceramics. A presentation consisting of photos is included as well as a literature research.

Ceramic metal matrix composites (CMMCs) are materials generally created by mixing of hard ceramic particles in a metal matrix. They were expected to combine the ductility and toughness of the metal with the high strength and elastic modulus of the ceramic. MMCs have potential applications in automotive, aeronautical and aerospace industries. Hence, a simple and economical method for fabricating MMCs is an area of intense research. In MMCs, damage evolution starts preferentially at particle matrix interface or at particle clusters in the matrix. This is due to the different physical and mechanical properties of the particle and matrix. Higher local particle volume content leads to higher stress triaxiality making it a preferential site for damage nucleation. Problems with lowering of ductility, fatigue, fracture and impact resistance, agglomeration of ceramic phase and issues related to the predictability of properties of MMCs have been the major issues that have limited their use. In order to overcome some of these shortcomings, the use of nano particles has been attracting increasing attention. The reason is their capability in improving the mechanical and physical properties of traditional MMCs. The dispersion of a nanoscale ceramic phase is needed in order to overcome the problems related to fatigue, fracture toughness, and creep behaviour at high temperatures. However, manufacturing costs, preparation of nano composites and environmental concerns have to be addressed. Agglomeration of nano particles, when produced by the melt stir casting route, the primary route to produce MMCs, is a serious issue that limits the use of nano-particles to produce MMCs with good properties. To avoid agglomeration of the ceramic phase MMCs/nano MMCs have been produced through the powder metallurgy route. Agglomeration is avoided as this is a solid state process. Secondary processing, such as extrusion and rolling are often needed to fully consolidate materials produced in this manner. A high extrusion ratio is often required to get MMCs without porosity. A new method of making nano-ceramic MMC using a polymer derived ceramics (PDC) has been reported. A polymer derived ceramic is a material that converts itself into a ceramic when heated above a particular temperature. In the PDC method a polymer precursor is dispersed in the metal and then converted in-situ to a ceramic phase. A feature of this process is that all the constituents of the ceramic phase are built into the organic molecules of the precursor (e.g., polysilazanes contain silicon, carbon, and nitrogen); therefore, a reaction between the polymer and the host metal or air is not required to produce the ceramic phase. The polymer can be introduced through casting or powder metallurgy route. In the casting route, the polymer powder is directly added to molten metal and pyrolyzed in-situ to create castings of metal-matrix composites. These composites have shown better properties at elevated temperatures but the problem of agglomeration of particles due to Van der Waal's forces and porosity still remains. In the powder method, the organic precursor was milled with copper powder and then plasma sprayed to produce a metal matrix composite. It is reported that these composites retains its mechanical strength close to the melting point of the copper. However, getting a nano sized distribution is difficult through this route as the plasma spray route is a melting and solidification method. Solid state processing by powder metallurgy is possibly a better method to produce well dispersed nano-MMCs. However, powder metallurgy routes are much more expensive and only parts of limited sizes can be produced by this method. Another solid state process Friction Stir Processing (FSP) has successfully evolved as an alternative technique to fabricating metal matrix composites. FSP is based on the principles of Friction Stir Welding (FSW). In FSW, a rotating tool with a pin and a shoulder is inserted into the material to be joined, and traversed along the line of the joint. The friction between the tool and the work piece result in localized heating that softens and plasticizes the material. During production of MMCs using FSP method, the material undergoes intense plastic deformation resulting in mixing of ceramic particles and the metal. FSP also results in significant grain refinement of the metal and has also been used to homogenize the microstructure. FSP technology has also been used to fabricate surface/bulk composites of Al-SiC, friction stir surfacing of cast aluminum silicon alloy with boron carbide and molybdenum disulphide powders and to produce ultra-fine grained Cu-SiC composites. A major problem in the FSP of MMCs is severe tool wear that results from abrasion with hard ceramic particles. The progressive wear of the tool has been reported to increase the likelihood of void or defect development. This change in geometry has been reported in the friction stir welding of several MMCs. The problems concerning the tool life has become a serious issue in the application of FSP for producing MMCs. In the present work the advantages of the PDC method and FSP have been combined to produce polymer derived nano ceramic MMCs. This method mainly consists of three steps. In the first step, a polymer, which pyrolysis to form a PDC at temperatures lower than the melting point of the metal, is dispersed in the metal by FSP. This step is different from the melt route where the PDC forms at temperatures above the melting point of the metal. In the second step, external pyrolysis of the polymer dispersed material is carried out. Since this is a solid state process at stresses much higher than the shear or fracture of the polymer is expected to get evenly and finely distribution in the metal. This is done by heating the polymer dispersed material to a temperature above the pyrolysation temperature of the ceramic but lower than the melting point of the metal matrix. It should be mentioned that some pyrolysis of the polymer is possible during the FSP process itself. In the third step FSP is carried out on the pyrolised material for removing porosity that would form due to gas evolution during pyrolysis and to get a more uniform dispersion of polymer derived ceramic particles in the matrix. This method will produce nano-scale metal matrix composites with a relatively high volume fraction of the ceramic phase. This method can be extended to big sheets or a particular region in a sheet with no or low wear of tools. The material selected for the present study were pure Copper (99.9%) and Nickel Aluminum Bronze (NAB) copper alloy. The polymer precursor was poly (urea methyl vinyl) silazane, which is available commercially as CERASET. The polymer consists of silicon, carbon, nitrogen, oxygen and hydrogen atoms. The liquid precursor was thermally cross-linked into a rigid polymer, which was milled into a powder. This powder, having angular shaped particles of an average size of 10 µm, was used as the reinforcement. The polysilazanes convert into a highly refractory and amorphous ceramic upon pyrolysis and is known as polymer-derived silicon carbonitride which consists principally of silicon, carbon and nitrogen. The in-situ process is feasible because copper melts above the temperature at which the organic phase begins to pyrolise. The polysilazanes pyrolise in the temperature range of 973 to 1273 K, which lie below the melting temperature of copper, 1356K.The precursor has a density of approximately 1 gcm-3 in the organic phase and approximately 2 gcm-3 in the ceramic state. In the present work, we seek to introduce approximately 20 vol% of the ceramic phase into copper. The microstructure and mechanical properties of the developed copper-based in-situ polymer derived nano MMCs have been characterized in detail to understand the distribution of particles. The microstructure of the as received, processed as well as the FSP composite material was characterized using Optical Microscope (OM), Scanning Electron Microscope (SEM), Electron Probe Micro Analyzer (EPMA) and Transmission Electron Microscope (TEM). OM and SEM microstructural observations show that PDC particles are distributed uniformly with a bimodal (submicron+micron) distribution. In addition, TEM micrographs reveal the formation of very fine PDC particles of diameter 10-30 nm. X-ray diffraction and Thermo-gravimetric analysis confirms the presence of ceramic phase (Si3N4/SiC) in the matrix. Significant improvement in mechanical properties of the FSP PD-MMCs has been observed. This in-situ formed Cu/PDC composites show five times increase in micro-hardness (260Hv - 2.5GPa) compared to processed copper base metal and in-situ NAB/PDC composite shows two times increase in micro-hardness (325Hv- 3.2GPa) compared to NAB matrix. The Cu-PDC composites exhibited better tensile strength at room temperature. In-situ formed Cu-PDC composite’s yield strength increased from 110MPa to 235MPa as compared to processed base metal, where as ultimate tensile strength increases from 246MPa to 312MPa compared to processed base metal at room temperature. This strengthening could be attributed to the presence of in-situ formed hard phases and the concomitant changes in the microstructure of the matrix material such as reduction in grain size and contribution from Orowan strengthening. In the present work, we have observed tool wear by observing tool after each FSP pass and apart from producing a significantly harder material with higher elastic modulus, possibly for the first time, the issue of tool wear has been overcome. This is due to the fact that the composite is made by the polymer route and that the ceramic fractures easily till it reaches the nano-size. Wear studies of this composite was carried out in a pin-on-disc machine by sliding a pin made from the composite against an alumina disc. The wear rate of the FSP PD-MMC composites increased from 1.63×10-5 to 5.72×10-6 mm3/Nm. Improved wear resistance could be attributed to the presence of the in-situ formed hard nano-phase.

L’apoptose est une forme de mort cellulaire essentielle au développement et au maintien de l’homéostase chez les animaux multicellulaires. La machinerie apoptotiq ue requiert la participation des caspases, des protéases conservées dans l’évolution et celle des organelles cytoplasmiques. Les lysosomes subissent des ruptures partielles, labilisation de la membrane lysosomale (LML), qui entraînent l’activation des cathepsines dans le cytoplasme de cellules cancéreuses humaines en apoptose induite par la camptothecin (CPT), incluant les histiocytes humains U-937. Ces modifications lysosomales se manifestent tôt durant l’activation de l’apoptose, concomitamment avec la perméabilisation de la mitochondrie et l’activation des caspases. Une étude protéomique quantitative et comparative a permis d’identifier des changements précoces dans l’expression/localisation de protéines lysosomales de cellules U-937 en apoptose. Lors de deux expériences indépendantes, sur plus de 538 protéines lysosomales identifiées et quantifiées grâce au marquage isobarique iTRAQ et LC-ESIMS/ MS, 18 protéines augmentent et 9 diminuent dans les lysosomes purifiés de cellules en cours d’apoptose comparativement aux cellules contrôles. Les candidats validés par immuno-buvardage et microscopie confocale incluent le stérol-4-alpha-carboxylate 3- déhydrogénase, le prosaposin et la protéine kinase C delta (PKC-d). Des expériences fonctionnelles ont démontrées que la translocation de PKC-d aux lysosomes est requise pour la LML puisque la réduction de son expression par ARN interférents ou l’inhibition de son activité à l’aide du rottlerin empêche la LML lors de l’apoptose induite par la CPT. La translocation de PKC-d aux lysosomes conduit à la phosphorylation et l’activation de la sphingomyelinase acide lysosomale (ASM), et à l’accroissement subséquent du contenu en céramide (CER) à la membrane lysosomale. Cette accumulation de CER endogène aux lysosomes est un évènement critique pour la LML induite par la CPT car l’inhibition de l’activité de PKC-d ou de ASM diminue la formation de CER et la LML.Ces résultats révèlent un nouveau mécanisme par lequel la PKC-d active l’ASM qui conduit à son tour à l’accumulation de CER à la membrane lysosomale et déclenche la LML et l’activation de la voie lysosomale de l’apoptose induite par la CPT. En somme, ce mécanisme confirme l’importance du métabolisme des sphingolipides dans l’activation de la voie lysosomale de l’apoptose.
Apoptosis is a distinct form of regulated cell death which is essential for the development and homeostasis maintenance of multicellular animals. Apoptosis is an evolutionary conserved process involving a specific molecular pathway, known as the caspase cascade, and the different cytoplasmic organelles. A lysosomal pathway, characterized by partial rupture, labilization of lysosomal membranes (LML), and cathepsin activation in the cytoplasm, is evoked during camptothecin-induced apoptosis in human cancer cells, including human histiocytic lymphoma U-937 cells. These lysosomal events begin rapidly and simultaneously with mitochondrial permeabilization and caspase activation within 3 h after drug treatment. Comparative and quantitative proteome analyses were performed to identify early changes in lysosomal protein expression/localization from U-937 cells undergoing apoptosis. In two independent experiments, among a total of more than 538 proteins putatively identified and quantitated by iTRAQ isobaric labelling and LC-ESI-MS/MS, 18 proteins were found to be upregulated and 9 downregulated in lysosomes purified from early apoptotic compared to control cells. Protein expression was validated by Western blotting on enriched lysosome fractions, and protein localization confirmed by fluorescence confocal microscopy of representative protein candidates, whose functions are associated with lysosomal membrane fluidity and dynamics. These include sterol-4-alpha-carboxylate 3-dehydrogenase (NSDHL), prosaposin (PSAP) and protein kinase C delta (PKC-d). Functional experiments demonstrate that PKC-d translocation to lysosomes is required for LML, as silencing its expression with RNA interference or suppressing its activity with the inhibitor rottlerin prevents CPT-induced LLM. PKC-d translocation to lysosomes is associated with lysosomal acidic sphingomyelinase (ASM) phosphorylation and activation, which in turn leads to an increase of ceramide (CER) content at lysosomes. The accumulation of endogenous CER at lysosomes is a critical event for CPT-induced LLM as suppressing PKC-d or ASM activity reduces both CPT-mediated CER generation at lysosomes and CPT-induced LLM.These findings reveal a novel mechanism by which PKC-d mediates ASM phosphorylation/activation and CER accumulation at lysosomes in CPT-induced LLM, rapidly activating the lysosomal pathway of apoptosis after CPT treatment. Taken together, these results confirm the importance of sphingolipid metabolism in the activation of the lysosomal pathway of apoptosis.