This work deals with bioceramic materials based of hydroxyapatite, bioglass and their composites. These materials are commonly used in medicine, especially as hard tissue substituents. They can be prepared by different types of syntheses, from which the most common were picked for this work – precipitation of hydroxyapatite and sol-gel method for bioglass. Thermal analysis and X-ray diffraction were used for characterization of prepared powders. This thesis studies mostly their features within the composite materials, which were foamed for better bone stimulation. Properties and possibility in bio application of materials is firstly studied through their interaction in simulated body fluids, which mimics ionic concentration of human plasma. Experimental part covers synthesis of ceramic powders, their characterization, preparation of mixtures and scaffolds foamed through in situ foaming, their sintering at ideal temperatures, characterization of porosity and phase changes due to sintering. Basic tests of apatite formation ability were provided by incubation of prepared scaffolds in simulated body fluid for 3, 7, 14 and 21 days and their assay in scanning electron microscopy. Changes in concentration of Ca2+ a PO4 3- ions as well as in weight of the specimen were tracked within the incubation period.

Kohlenstoffgebundene Filterwerkstoffe erfreuen sich stetig wachsender Beliebtheit seitens der Industrie. Deren Potenzial hinsichtlich stofflicher und verfahrenstechnischer Eigenschaften erscheint dennoch nicht in vollem Umfang genutzt. Daher wurden im Rahmen der vorliegenden Arbeit, welche innerhalb des Sonderforschungsbereiches 920 entstand, erstmals aktive (Al2O3-C) und reaktive (MgO C) Filter, sowie eine Kombination daraus entwickelt. Die aktiven Filtersysteme, deren Funktionalisierung einerseits über die Erhöhung des amorphen Kohlenstoffanteils, andererseits über die Beschichtung mit rein oxidischen Materialien stattfand, sowie die reaktiven Filter, bei denen sich der carbothermischen Reduktion des MgO bedient wurde, konnten, in Kollaboration mit der Industrie, erfolgreich getestet werden. Durch gezielte Kontamination des Stahls mit exogenen Einschlüssen auf Basis von Al2O3 und MgAl2O4, ist es gelungen dem Chemismus der jeweiligen Filter einen entscheidenden Beitrag zum Filtrationsprozess zuweisen zu können. So weist Aluminiumoxid, unabhängig vom Chemismus des Einschlusses, das vergleichsweise größte Filtrationspotenzial auf.

Made available in DSpace on 2014-12-17T14:57:55Z (GMT). No. of bitstreams: 1 EduardoGR_TESE.pdf: 4595986 bytes, checksum: 7a13884531d20feb0680378f1e5403df (MD5) Previous issue date: 2011-10-11 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Ceramics with porous cellular structure, called ceramic foams, have a potential use in several applications, such as: thermal insulation, catalyst supports, filters, and others. Among these techniques to obtain porous ceramics the replication method is an important process. This method consists of impregnation of a sponge (usually polymer) with ceramic slurry, followed by a heat treatment, which will happen the decomposition of organic material and sintering the ceramic material, resulting in a ceramic structure which is a replica of impregnated sponge. Knowledge of the mechanical properties of these ceramics is important for these materials can be used commercially. Gibson and Ashby developed a mathematical model to describe the mechanical behavior of cellular solids. This model wasn?t for describing the ceramics behavior produced by the replica method, because it doesn?t consider the defects from this type of processing. In this study were researched mechanical behavior of porous alumina ceramics obtained by the replica method and proposed modifications to the model of Gibson and Ashby to accommodate this material. The polymer sponge used in processing was characterized by thermogravimetric analysis and scanning electron microscopy. The materials obtained after sintering were characterized by mechanical strength tests on 4-point bending and compression, density and porosity and by scanning electron microscopy. From these results it was evaluated the mechanical strength behavior compared to Gibson and Ashby model for solid cellular structure and was proposed a correction of this model through a factor related to struts integrity degree, which consider fissures present in the structure of these materials besides defects geometry within the struts / Cer?micas com estrutura celular porosa, denominadas espumas cer?micas, possuem o potencial de utiliza??o em uma vasta gama de aplica??es, tais como: isolamento t?rmico, suporte catal?tico, filtros, dentre outras. Dentre as t?cnicas para obten??o destas cer?micas porosas podemos destacar o m?todo da r?plica. Este m?todo consiste na impregna??o de uma esponja (geralmente polim?rica) com uma barbotina cer?mica, seguindo-se um tratamento t?rmico, onde ocorrer? a decomposi??o do material org?nico e sinteriza??o do material cer?mico, resultando em uma cer?mica cuja estrutura ? uma r?plica da esponja impregnada. O conhecimento das propriedades mec?nicas destas cer?micas ? importante para que estas possam ser utilizadas comercialmente. Gibson e Ashby desenvolveram um modelo matem?tico para descrever o comportamento mec?nico de s?lidos celulares, por?m este modelo n?o se mostrou satisfat?rio para descrever o comportamento das cer?micas obtidas pelo m?todo da r?plica, pois o mesmo n?o leva em considera??o os defeitos provenientes deste tipo de processamento. Neste trabalho estudou-se o comportamento mec?nico de cer?micas porosas de alumina obtidas pelo m?todo da r?plica, e a partir desta an?lise se prop?s modifica??es no modelo de Gibson e Ashby para se adequar a este material. A esponja polim?rica utilizada no processamento foi caracterizada atrav?s de an?lise termogravim?trica e microscopia eletr?nica de varredura. Os materiais obtidos ap?s sinteriza??o foram caracterizados atrav?s de testes de resist?ncia mec?nica, tens?o de ruptura ? flex?o (4 pontos) e compress?o, densidade, porosidade e por fim, an?lise microsc?pica por microscopia eletr?nica de varredura. A partir destes resultados avaliou-se o comportamento da resist?ncia mec?nica em compara??o ao modelo de Gibson e Ashby para s?lidos com estrutura celular e foi proposta uma corre??o deste modelo atrav?s de um fator relacionado com o grau de integridade dos filamentos, que considera as trincas presentes na estrutura destes materiais, al?m da geometria dos defeitos no interior dos filamentos

Face à la nécessité de trouver de nouvelles sources d'énergie, on assiste au développement des centrales solaires thermiques à concentration et plus particulièrement à tour. L'air est utilisé comme fluide caloporteur circulant dans un récepteur sur lequel sont concentrés les rayons solaires. L'absorbeur, situé dans le récepteur, est l'élément clé de ces dispositifs ; il doit absorber le rayonnement solaire tout en ayant une faible émissivité infrarouge pour limiter les pertes par rayonnement thermique observées. Le projet OPTISOL, dans lequel s'inscrivent ces travaux de thèse, a pour objectif d'optimiser les propriétés thermo-optiques d'un absorbeur volumique. Pour cela, une mousse en carbure de silicium a été choisie en tant que support mécanique de l'absorbeur, pour sa bonne tenue aux hautes températures, et pour sa capacité à absorber fortement le rayonnement solaire. Plusieurs laboratoires ont travaillé sur ce projet et le rôle du CIRIMAT fut, dans un premier temps, de caractériser ces mousses de carbure de silicium, par des techniques conventionnelles mais aussi par des techniques moins usuelles telles que la microtomographie X. Dans un second temps, les mousses de carbure de silicium ont été fonctionnalisées par un oxyde sélectif, YBaCuO, dans le but d'optimiser la sélectivité spectrale du système global. Pour cela, les techniques en voie liquide (sol-gel, suspensions, ...) ont été choisies et un procédé de fonctionnalisation a été développé, permettant de revêtir des substrats plans (pastille) et volumiques (mousse poreuse). La sélectivité spectrale du carbure de silicium ainsi fonctionnalisé a été étudiée par spectrométrie infrarouge-visible et les résultats obtenus sont prometteurs puisque une diminution de l'émissivité infrarouge a été observée tout en conservant une forte absorptivité du rayonnement solaire. / The necessity of finding new energy sources leads to the development of concentrated solar thermal power plants and more particularly the one using towers. Air is used as a heat transfer fluid flowing in a receiver heated by concentrated sunlight. The absorber, located in the receiver, is the key element of these devices; it must both absorb solar radiation and have a low infrared emissivity to limit thermal radiation losses. This work is part of the OPTISOL project, which aim is to optimize the thermo-optical properties of a volumetric absorber. For this purpose, a silicon carbide foam was selected as the mechanical support of the absorber for its good resistance to high temperatures and for its ability to be efficient to absorb sunlight. Several laboratories have worked on this project and the role of CIRIMAT was, at first, to characterize these silicon carbide foams using conventional and less conventional techniques such as X microtomography. Secondly, silicon carbide foams have been functionalized by a selective oxide, YBaCuO, in order to optimize the spectral selectivity of the system. For this, liquid routes such as sol-gel or suspension techniques have been selected and a functionalization process was implemented for coating planar (pellet) and volumetric (porous foam) substrates. The spectral selectivity of the functionalized silicon carbide was studied by infrared-visible spectrometry and the results are promising since a decrease in the infrared emissivity was observed while maintaining a high absorptivity of solar radiation.

Ces travaux de thèse abordent la problématique du développement d'internes destinés à la distillation réactive. La méthodologie à suivre est appliquée dans le cas des mousses céramiques en Carbure de Silicium. Le comportement hydrodynamique a été étudié ainsi que la capacité en transfert de matière validant la possible application des mousses en tant que garnissage destiné à la distillation. L'activation catalytique du support a ensuite été développée afin de dégager la méthode la plus intéressante permettant d'approcher le garnissage de référence, le KATAPAK, en termes d'activité catalytique. Le greffage d'Amberlyst 15 est alors apparu comme la voie la plus intéressante pour la possible application des mousses greffées comme interne catalytique destiné à la distillation réactive. / This work of thesis approaches the problems of the development of packings intended for reactive distillation. Methodology to be followed is so applied in the case of ceramic foam in Silicon Carbide. The hydrodynamic behaviour was studied as well as the mass transfer efficiency demonstrating the possible application of ceramic foam as a packing for distillation. The aspect of the catalytic activation of the support was then developed in order to determine the most efficiency method in terms of catalytic activity making it possible to approach reference packing, the KATAPAK. The coating of Amberlyst 15 then appeared as the most interesting way for the possible application of coating foam as catalytic packing for reactive distillation.

Deponierte Abfälle emittieren auch Dekaden nach dem Ende der Einlagerung am Standort eine Vielzahl von Schadstoffen. Durch verantwortungsvollen Aufbau und Betrieb oder eine nachträgliche Sanierung kann das Gewicht von unkontrollierten Emissionen hin zu kontrollierten verschoben werden, die wiederum einer entsprechenden Entsorgung zugeführt werden können. Neben dem Deponiesickerwasser spielt das Deponiegas mit den Hauptbestandteilen Methan und Kohlendioxid auf Grund des lokalen und globalen (anthropogener Treibhauseffekt) Gefährdungspotentials eine wichtige Rolle. Sowohl die Gasmenge als auch der Gehalt an brennbaren Methan verringern sich mit zunehmender Standzeit der Deponie. Für Stark- und Mittelgase (ca. 25-60 Vol.-% Methan) ist eine entsprechende Nutzungs- und Entsorgungstechnik etabliert. Für den Schwachgasbereich ist die Entsorgung durch Verbrennung auf Grund der schlechten Verbrennungseigenschaften problematisch. Es existieren einige Lösungsansätze, von denen sich jedoch angesichts verschiedener technologiebedingter Nachteile noch keiner für die Schwachgasentsorgung über den gesamten relevanten Bereich an Methangehalten etablieren konnte. Ziel der vorliegenden Arbeit war es, einen neuen Ansatz für eine einfache, kostengünstige und robuste Technologie zu erarbeiten, die eine vollständige Eliminierung des Methans und weiterer schädlicher Bestandteile gewährleistet. Im Weiteren sollen Methangehalte im Deponiegas von 5-11 Vol.-% bzw. Modellgemische mit einem Äquivalenzverhältnis von 0,3-0,5 betrachtet werden. Dieser Bereich erweist sich als besonders problematisch hinsichtlich einer stabilen Entsorgung. Bei Grubengasen und methanbeladener Abluft sind unter Umständen ähnliche Fragestellungen anzutreffen. Neben experimentellen Arbeiten in Labor und Technikum liefern vor allem numerische Simulationen einen wesentlichen Beitrag zur wissenschaftlichen Durchdringung der ablaufenden Prozesse und der Vorausberechnung technischen Reaktoren und Brennern. Für hier behandelte Problemstellung bietet sich die Software Ansys Fluent® an. Für die Entsorgung von Schwachgasen bieten sich mehrere grundsätzliche Herangehensweisen an. Für diese Arbeit wurde sich auf die Oxidation des Methans in porösen Medien, z.B. Füllkörperschüttungen oder offenzellige SiC-Schaumkeramiken, konzentriert. In einem ersten Ansatz wurde eine katalytische Funktionalisierung von SiC-Schaumkeramik mit Manganoxid dotierter Calciumaluminat-Beschichtung durchgeführt, um so die hervorragenden thermischen Eigenschaften des Siliciumcarbids mit der Oxidationsaktivität eines Katalysators zu kombinieren. Nach der Evaluierung einer optimalen hochtemperaturfesten Katalysatorkombination und experimentellen Erarbeitung kinetischer Parameter bilden Modellrechnungen im einfach durchströmten Monolith (1D) die Basis für eine Beurteilung dieser Variante. Der zweite Ansatz verfolgt eine nicht-katalytische, rein thermische Umsetzung des Methans. Eine Verbesserung der Verbrennungseigenschaften durch Vorwärmung des Brenngases erfolgt über interne Rekuperation ohne externen Abgaswärmeübertrager. Auf Basis von theoretischen Überlegungen und Simulationsrechnungen wurde eine entsprechende Technikumsanlage mit einer aus Alumina-Raschig-Ringen bestehenden porösen Matrix entworfen und aufgebaut. Ausgewählte Versuchsreihen dienten zur Demonstration der Funktionalität und zur Validierung des CFD-Modells. Mit Hilfe des Modells sind eine Variation der Eigenschaften der porösen Matrix und ein Upscaling auf einen technischen Maßstab möglich. Die Berechnung des Einsatzbereiches erfolgt beispielhaft mit einem Vorschlag für eine technisch relevante Größe an einem typischen Deponie-Schwachgas. Für die Modellierung von Oxidationsprozessen in porösen Strukturen ist die Implementierung des Wärmetransports ein wesentlicher Baustein. Ein entscheidender Parameter hierin ist die effektive Wärmeleitfähigkeit der porösen Matrix. Insbesondere für keramische Schäume ist die Anzahl der publizierten Arbeiten gering. Durch Vermessung der SiC-Keramikschäume mit Hilfe der Hot-Disk-Methode (Raumtemperatur) und mit dem Plattenmessverfahren (300-1000 °C) konnte auch an dieser Stelle ein Beitrag erbracht werden.

The thesis is concerned with creating of a computational model of open-cell ceramic foam and determining mechanical properties of open-cell ceramic foam using computational modeling. The geometry of Kelvin cell was used for creating the model of geometry of the foam. The model of geometry of ceramic foam structure was meshed with solid elements, with beam elements and with combination of rigid beam and beam elements. Elastic properties of the foam were determined by two types of mechanical loading. Young´s modulus and Poisson´s ratio were determined by tensile/compressive mechanical loading and shear modulus was determined by shear mechanical loading. The relationship between mechanical properties of the foam and the ratio of diameter of strut D and length of strut L was analysed in the thesis. A good agreement was found out between Young´s modulus determined by solid element based and Young´s modulus determined by modified beam based model of geometry of the foam structure – for ratio D/L up to 0,6. In the case of Poisson´s ratio a good agreement was determined up to D/L = 0,4. In conclusion the value of Young´s modulus 1,97 GPa which was determined by computational modeling was compared with the value 1,56 GPa which was determined experimentally on ceramic foam. This difference was caused by idealization of geometry of the real ceramic foam material. In addition, mechanical properties of the ceramic foam material are influenced by structural imperfections of the material.

Final thesis, elaborated within the master study field of Foundry technology, deals with determination of some parameters of ceramic foam filters that are necessary for using numerical simulation during foundry practice. Thesis foccuses on defining methodology, manufacturing messuring device and measuring pressure drop on several type sof ceramic foam filters in dependence on flow rate of measuring medium. Measuring medium selected is water, mening this thesis deals also with water simulation in foundry technology.

The thesis deals with computational modelling of ceramic foams and analysis of influence of structural manufacturing defects (like broken struts, closed pores and material clumps) have on foam strength. Model of foam geometry was discretized using beam elements in order to decrease computational cost. In place where several struct join, rigid beam element was used so that the increased stiffness is better modelled. Closed walls of pores were modelled and discretised by shell elements. Influence of loading direction was analysed on foams containing no defects and then influence of amount of defects in foam on strength was further analysed. Highest strength show foams created by cells whose structs are oriented in direction of loading. These were losing strength most rapidly. Foam with structure of rhombic dodecahedral cell was least influenced by presence of closed pore defects but it also showed lowest strength even without defects. Cells with struts oriented in direction of loading experienced biggest drop in strength. Kelvin cell is a compromise. It was shown that difference in strength of strut with constant and varying cross-section is tenths of percent.

The master’s thesis deals with a numerical simulation of failure of ceramic foams with open-cell structure and with understanding of conditions required for the failure of the structure under various mechanical loading conditions. To this purpose, the so-called stress-energy coupled criterion was utilized. The motivation for this thesis was to create a model able of the most accurate prediction of the ceramic foam strength in comparison with experimental observations. First part of the thesis is focused on the theoretical background required for solving the problem. More specifically there are mentioned methods of the foam material modelling, Linear Elastic Fracture Mechanic (LEFM) and coupled stress-energy criterion used for definition of the crack initiation. In the second part of the thesis, numerical Finite Element Analyses (FEA) whose main purpose was to determine critical conditions necessary for the initiation of strut failure within the foam structure, were performed. These pieces of knowledge were then used for creation of the numerical simulation algorithm of the mechanical test of foam material with regular cell pattern. Outputs of numerical simulations were at the end of this work compared with experimental results (of the compression test) made on the real Al_2 O_3 foams prepared by 3D printing technology and provided by the Institute of Physics of Materials Czech Academy of Science. It can be concluded that a good agreement between results of both approaches was reached and the prediction of the ceramic foam mechanical strength using the developed model is in the meanwhile the most accurate estimation from recently published approaches.