A series of novel triphenylstannyl-C, (triphenylstannyl)methyl- O- and (tributylstannyl)methyl-O- substituted pentofuranose compounds have been synthesised. Two methods were employed: (i) the reaction of triphenyltinlithium with derivatised and protected (or partially protected) carbohydrates, and (ii) the reactions of carbohydrate alkoxides with (iodomethyl)triphenyltin and (iodomethyl)tributylin. The solution structures of the triorganotin-carbohydrate compounds were investigated by 1H, 13C and 119Sn NMR spectroscopy. In solution all of the triorganotin-carbohydrates were shown to contain four-co-ordinate tin atoms. The solid-state structures were investigated by a combination of solid-state NMR spectroscopy and single-crystal X-ray diffraction. There were no major conformational changes between the two phases for any of the compounds. The molecular structures of methyl 5-deoxy-2,3- O-isopropylidine-5-triphenylstannyl-beta-D-ribofuranoside and 5-deoxy-1,1- O-isopropylidine-5-triphenylstannyl-alpha-D-xylofuranose were determined. Two different molecular conformations were identified for the former compound, and hydrogen-bonding between adjacent molecules was shown to be present in the latter case. The reactions of the triorganotin-carbohydrate compounds with iodine and bromine were studied. The results indicated that the rate of cleavage of butyl-tin bonds was much slower than the cleavage of phenyl-tin bonds. The reactivity of the tin-phenyl bond was found to depend greatly on the structure of the carbohydrate ligand. Evidence of increased co-ordination in solution was found for the mono-halo derivatives of methyl 5-deoxy-2,3-O-isopropylidine-5-triphenylstannyl-beta-D-ribofuranoside and 5-deoxy-1,2-O-isopropylidine-5-triphenylstannyl-alpha-D-xylofuranose. The molecular structures of 5-deoxy-5-iododiphenylstannyl-1,2-O-isopropylidine-alpha-D-xylofuranose and 5-deoxy-5-diiododiphenylstannyl-1,2-O-isopropylidene-alpha-D-xylofuranose were determined. In the solid-state the geometry about the tin atoms was found to be distorted trigonal bipyramidal.

Thermal shock resistance is a key property of refractory materials. Its determination and prediction is essential for the design of structural refractories as well as lining materials. Young’s modulus of elasticity (E) is a crucial parameter for the calculation of thermal shock resistance. For all investigated carbon-bonded alumina composition a significant increase of E was observed. This increase was attributed to a mismatch of the coefficient of thermal expansion of the composite constituents. Besides others, the graphite content as well as the maximum alumina particle size were identified as crucial factors influencing E(T). Furthermore, the influence of the porosity on E was shown and existing models were fitted to the experimental data for future predictions of E. Finally a metal melt filter structure was investigated to investigate the relationship between its strut Young’s modulus and the structures’ E at high temperatures. Further research should address the filter topic since it was uncertain how to find the normal modes of those structures.

In this manuscript, distinct problems concerning carbon-bonded materials processing and characterization were analyzed, from bulk to cellular samples. The main motivation was to address central topics that would enhance the comprehension of the material’s behavior, as well as trigger targeted improvements. Some of the topics this thesis covers are: Non-linear Young’s modulus behavior of carbon-bonded alumina at high temperatures; Influence of the processing route on the cold crushing strength of carbon-bonded alumina foam filters; Geometric characterization of ceramic foam filters as a tool to understand processing parameters; Use of advanced techniques such as computer tomography and finite element modelling to correlate processing parameters and mechanical behavior. In most of the analyses, non-standard computational strategies were adopted. In those cases, algorithms were written to facilitate the evaluations, or even enable it in the first place. All the algorithms’ concepts are described in this thesis and their codes are available in the Appendices. The current work was carried out within the framework of the Collaborative Research Center 920 (CRC 920) “Multifunctional filters for metal melt filtration - a contribution to zero defect materials” at the Technische Universität Bergakademie Freiberg funded by the German Research Foundation (DFG).

Thermal shock resistance is a key property of refractory materials. Its determination and prediction is essential for the design of structural refractories as well as lining materials. Young’s modulus of elasticity (E) is a crucial parameter for the calculation of thermal shock resistance. For all investigated carbon-bonded alumina composition a significant increase of E was observed. This increase was attributed to a mismatch of the coefficient of thermal expansion of the composite constituents. Besides others, the graphite content as well as the maximum alumina particle size were identified as crucial factors influencing E(T). Furthermore, the influence of the porosity on E was shown and existing models were fitted to the experimental data for future predictions of E. Finally a metal melt filter structure was investigated to investigate the relationship between its strut Young’s modulus and the structures’ E at high temperatures. Further research should address the filter topic since it was uncertain how to find the normal modes of those structures.

In order to improve the purity of steel castings, the use of special reactive coatings on carbon-bonded ceramic foam filters was explored. Carbon nanotubes were dispersed in water by means of ultrasonic treatment, using xanthan gum to stabilize the nanotubes in suspension and control the rheological behavior. The coatings were applied by cold spraying and binding was achieved during heat treatment in reducing atmosphere, thanks to an artificial pitch added to the slurry. The coated filters were successfully immersed in molten steel for different times. The thickness of the first alumina layer generated at the interface was independent of the immersion time: concentration gradients through its thickness suggested that the formation of this structure is limited by diffusion. Investigation of the steel after solidification by means of ASPEX showed that the presence of the coating influenced the size as well as the chemical composition of the remaining inclusions. Nano-coated filters had the best filtration efficiency (up to 95% for alumina inclusions after 10 s), but longer tests resulted in worse performance. In addition, coatings based on calcium aluminates in combination with carbon showed an efficiency greater than 97% for steel samples taken directly from the melt.

Die Arbeit führt Methoden zur Durchführung von Zugversuchen und bruchmechanischen Versu-chen ein und liefert mechanische Kennwerte für zwei kohlenstoffgebundene FFW im Bereich von RT bis 1500°C. Dafür standen ein grobkörniges MgO-C und ein feinkörniges Al2O3-C zur Ver-fügung. Die Werkstoffe zeigten bis 1200°C keine Duktilität und sprachen spröde. Die Schädigung erfolgte ausschließlich durch Risswachstum. Dieses fand beim MgO-C temperaturunabhängig auf Grund der rissbehafteten Mikrostruktur durch stabiles Risswachstum bereits vorhandener Risse statt. Es kam dabei zur Bildung von Rissnetzwerken sowie zu zahlreichen energiedissipierenden Prozessen. Beim Al2O3-C trat be RT instabiles Risswachstum auf. Bei hohen Temperaturen kam es durch thermisch aktivierte Prozesse zu duktilem Verhalten und stabilem Risswachstum. Beim grobkörnigen MgO-C wurden große Verformungen durch das starre Oxidgerüst verhindert. Zu-sätzlich zeigten die Werkstoffe auf Grund ihrer Mikrostruktur eine Zunahme der Festigkeit mit steigender Temperatur. Aus den Versuchen wurde ein Heißpressverfahren zur Herstellung von gradierten Werkstoffen abgeleitet.:1 Einleitung 2 Grundlagen 2.1 Feuerfestwerkstoffe 2.1.1 Einsatz und Beanspruchung von FFW 2.1.2 Einteilung von FFW 2.2 Kohlenstoffgebundene FFW 2.2.1 Kohlenstoff und seine Terminologie 2.2.2 Grundlegende Eigenschaften kohlenstoffgebundener FFW 2.2.3 Anwendungen kohlenstoffgebundener FFW 2.2.4 Aufbau und Mikrostruktur kohlenstoffgebundener FFW 2.2.5 Herstellungsparameter kohlenstoffgebundener FFW 2.2.6 Chemische Eigenschaften kohlenstoffgebundener FFW 2.3 Mechanische Eigenschaften kohlenstoffgebundener FFW 2.3.1 Mechanische Eigenschaften kohlenstoffgebundener FFW bei RT 2.3.2 Mechanische Eigenschaften kohlenstoffgebundener FFW bei HT 2.4 Grundlagen zur Werkstoffprüfung bei RT und hohen Temperaturen 2.4.1 Streuung und Einfluss der Probengröße 2.4.2 Belastungsrate 2.4.3 Zugversuche 2.4.4 Druckversuche 2.4.5 Biegeversuche 2.4.6 Bruchmechanische Untersuchungen 2.4.7 Temperaturwechselbeständigkeit 2.4.8 Kriechen 2.4.9 Spannungsrelaxation 2.4.10 Härtemessung 2.4.11 Hochtemperaturprüfung in Kaltkammerofen mit induktiver Heizung 2.4.12 Temperaturmessung mit Thermoelement, Pyrometrie, Thermographie 2.4.13 Bestimmung elastischer Konstanten mittels akustischer Methoden 2.4.14 Optische in situ Schadensbeschreibung mittels Mikroskopie und DIC 2.5 Heißpressverfahren 3 Experimentelles 3.1 Werkstoffe 3.1.1 Kohlenstoffgebundenes Magnesiumoxid (MgO-C) 3.1.2 Kohlenstoffgebundenes Aluminiumoxid (Al2O3-C) 3.1.3 Graphit (ISEM 8) 3.2 Mechanische Tests 3.2.1 Prüfmaschine für Druck- und Biegeversuche 3.2.2 Prüfmaschine für Zug-Druck-Versuche 3.2.3 Probengeometrien 3.2.4 Druckversuche 3.2.5 Biegeversuche 3.2.6 Bruchmechanische Versuche 3.2.7 Versuche mit Zugbeanspruchung 3.2.8 Versuchsabläufe der Hochtemperaturversuche 3.2.9 Temperaturmessung mittels Thermographie 3.3 Weitere Versuchsmethoden 3.3.1 Mikrostrukturuntersuchung mittels Mikroskopie und Röntgenbeugung 3.3.2 Porositäts- und Dichtemessung 3.3.3 Härtemessung 3.3.4 Dynamischer E-Modul 4 Methodische Erkenntnisse und Voruntersuchungen 4.1 Temperaturmessung und -verteilung 4.1.1 Temperaturmessung mittels Thermoelement und Pyrometer 4.1.2 Emissionskoeffizient und Probenbeschichtung 4.1.3 Temperaturverteilung 4.2 Dehnungsmessung 4.3 Zugversuche an Keramiken 4.3.1 Übertragung von Zugkräften 4.3.2 Axialität in Zugversuchen 4.4 Bruchmechanische Versuche 4.4.1 Kerbeinbringung 4.4.2 Überprüfung des optischen Messsystems 4.4.3 Bestimmung der Risslänge während des Versuchs 4.5 Überprüfung der Messmethodik mit dem Referenzwerkstoff Graphit ISEM-8 5 Ergebnisse 5.1 Mikrostrukturbeschreibung der untersuchten FFW 5.1.1 Mikrostruktur des MgO-C’s 5.1.2 Mikrostruktur des Al2O3-C’s 5.2 Mechanisches Verhalten bei RT 5.2.1 Mechanisches Verhalten von MgO-C bei RT 5.2.2 Mechanisches Verhalten von Al2O3-C bei RT 5.3 Mechanische Eigenschaften bei HT 5.3.1 Mechanisches Verhalten von MgO-C bei HT 5.3.2 Mechanisches Verhalten von Al2O3-C bei HT 5.4 Heißpressverfahren für kohlenstoffgebundene FFW 5.4.1 Beschreibung des Heißpressverfahrens 5.4.2 Physikalische Eigenschaften und Mikrostruktur des Presslings 5.4.3 Mechanische Eigenschaften des Presslings 6 Diskussion 7 Zusammenfassung und Ausblick Literatur Anhang

In order to improve the purity of steel castings, the use of special reactive coatings on carbon-bonded ceramic foam filters was explored. Carbon nanotubes were dispersed in water by means of ultrasonic treatment, using xanthan gum to stabilize the nanotubes in suspension and control the rheological behavior. The coatings were applied by cold spraying and binding was achieved during heat treatment in reducing atmosphere, thanks to an artificial pitch added to the slurry. The coated filters were successfully immersed in molten steel for different times. The thickness of the first alumina layer generated at the interface was independent of the immersion time: concentration gradients through its thickness suggested that the formation of this structure is limited by diffusion. Investigation of the steel after solidification by means of ASPEX showed that the presence of the coating influenced the size as well as the chemical composition of the remaining inclusions. Nano-coated filters had the best filtration efficiency (up to 95% for alumina inclusions after 10 s), but longer tests resulted in worse performance. In addition, coatings based on calcium aluminates in combination with carbon showed an efficiency greater than 97% for steel samples taken directly from the melt.

Im Rahmen der vorliegenden Arbeit wurden neuartige keramik- und stahlreiche Verbundwerkstoffe, auf Basis von MgO-teilstabilisiertem Zirkoniumdioxid und hochlegiertem austenitischem TRIP Stahl entwickelt. Die keramikreiche Verbundwerkstoffe mit bis zu 30 Vol.% metallischer Partikelverstärkung wurden über die Schlickergusstechnologie bzw. die Druckschlickergusstechnologie hergestellt und können als thermo-mechanisch beanspruchte Bauteile zum Einsatz kommen. Es wurden weiterhin metallreiche Verbundwerkstoffe mit bis zu 10 Vol.% keramischer Partikelverstärkung erstmalig über die Papiertechnologie hergestellt. Dadurch ergeben sich vielfältige Möglichkeiten metallreiche Leichtbaustrukturen mit verbesserten Energieabsorptionsvermögen zu erzeugen. Im Mittelpunkt der vorliegenden Arbeit stand die Entwicklung der keramikreichen Schlicker, die Formgebungstechnologien, die Entwicklung geeigneter Entbinderungs- und Sinterregime sowie die Charakterisierung der Verbundwerkstoffe hinsichtlich ihrer Mikrostruktur sowie der mechanischen bzw. der thermo-mechanischen Eigenschaften.

In order to considerably improve the quality of steel products, efforts are being made to increase the cleanness of steel. It is known that the size, type and distribution of non-metallic inclusions (NMIs) in metals significantly influence their mechanical properties. Within the frame of the Collaborativ Research Centre 920 'Multifunc-tional filters for metal melt filtration – a contribution to zero defect materials.”, carbon-bonded alumina filters for steel melt filtration has been investigated. In the present thesis, the interactions between coated carbon-bonded alumina filters and a steel melt were investigated in more detail, with the porous coatings being based on alumina. The time-depended behaviour was evaluated by immersing coated filters for different dwell times. After the immersion tests, the microstructure of the filter surface and the NMIs remaining in the solidified steel were examined to comprehend the interactions. The here presented results imply that carbon of the carbon-bonded alumina sub-strate took part in the filter–steel interactions. The presence of dissolved carbon at the filter–steel melt interface is essential to promote alumina dissolution and pre-cipitation processes. Thereby, the melt was locally supersaturated with aluminium, which reacted with dissolved oxygen to form secondary corundum. During these interactions, a liquid oxide film was formed directly at the ceramic surface and provided nuclei for heterogeneous nucleation of secondary corundum. After immersion during cooling, a characteristic layer built-up formed at the filters surface. All alumina-based coated filters contributed to the filtration of especially alumina-based NMIs, and outperformed the uncoated carbon-bonded alumina filter. During the first experimental trials, it became obvious that the thermal shock resistance of the alumina coating has to be enhanced. For this purpose, a material combination was investigated which so far has not been used as a coating material to the author’s knowledge: alumina-zirconia-titania in the ration 95 : 2.5 : 2.5. This material is known for its excellent thermal shock resistance. Thereby, the influence of zirconia or titania doping of the coating were considered. The addition of titania enhanced wetting of this filter by the steel melt. As a result, alumina inclusions of the steel melt were modified: they were more in number, but distinctly smaller compared to trials without filter or the immersion of the other filter types. Especially, the decreased average area of the alumina inclusions is interesting because the particle size of NMIs strongly influences the fatigue life of a steel product. The deformability of a steel product, however, is determined by the amount of NMIs. Thus, the modification of alumina inclusions by adding titania to the filter coating might present a way to tailor these inclusions depending on the product’s application.

Carbon-bonded alumina filters and their binders, lactose, tannin and CarboresP, were investigated by Raman spectroscopy. Special emphasis was placed on the pyrolysis study of the binders. In situ measurements were performed on the tannins gallic acid, ellagic acid and tannic acid to determine the pyrolysis temperatures and products. Furthermore, the binder samples fired in a reducing atmosphere in a coke bed were analyzed by Raman spectroscopy and their transition from an amorphous carbon system to nanocrystalline graphite was observed. The influence of different binders on the carbon-bound alumina filters was studied, as well as the influence of different additives. However, no significant difference was observed between samples with different binder compositions or with additives. In addition, Raman measurements on the spinel MgAlON indicate an increased disorder of the structure due to the incorporated nitrogen.