Thesis (Doctoral)--Ruhr-Universität Bochum, 1982.

Among the most impressive developments observed in the last 20 years, the improvement of the installation methods of monolithic refractories is certainly to be taken into account. However, this evolution, from vibratable castables to shotcrete and drycrete was not applied to materials based on magnesia, which are still mostly commercialized as ramming mixes, or as pouring castables with poor properties due to excessive water use. The major issues associated to this lack of technology is the scarcity of submicrometric powders compatible to magnesian systems, and the expansion followed by hydration of the magnesia, which is a disruptive reaction. By a thorough research on the literature, some potential additives were identified to be tested as anti-hydration additives. Hydration tests of powders in autoclave, complemented by pH and rheological measurements on magnesia pastes have identified five possible additives which can be used to inhibit the hydration: tartaric acid, citric acid, boric acid, magnesium fluoride and microsilica. Salts from the organic acids can also be successfully used. Of these, microsilica also presented the advantage of providing the submicrometric particles necessary to improve the flow of the castable, and to improve the bond of the castable. The three acids are very effective in inhibiting the formation of magnesium hydroxide, but affect negatively flow properties and mechanical resistance after cure. Microsilica prevented hydration cracks due to the reaction between the silicic acid generated under basic environment with the newly formed brucite, leading to the precipitation of a magnesium-silica-hydrated phase of poor crystallinity between the magnesia grains. This phase does not promote volumetric change, and also enable water release at a wider temperature range. Due to its nature close to serpentine minerals, it forms forsterite and enstatite at low temperatures, thus generating suitable strength between room temperature and at least 1400 °C. Magnesium fluoride changed the nature of this magnesium-silica-hydrated phase, by being incorporated to it and forming a phase more similar to the humite minerals. These minerals present higher MgO:SiO2 molar ratio than serpentine, and their formation requires a lower content of microsilica for a same effect against hydration, which is beneficial for the overall properties of the castable. The properties of the castable, as well as the influence of a number of other variables (for instance, refractoriness under load, creep, cold crushing strength, cold modulus of rupture, bulk density and apparent porosity) were also studied and hereby reported. It is believed that this technology can be further developed for industrial use, provided that some issues regarding the properties at high temperatures are solved. Not only had the study and comprehension of the nature of the bond between microsilica and magnesia, and the role of magnesium fluoride been pioneered by this work, but also the methodology used to evaluate the hydration after the drying process of castings, which was close to real refractory components.

Um einen dauerhaften Einsatz Al2O3-basierter Feuerfestwerkstoffe in Hochtemperaturanlagen zur Synthesegaserzeugung zu ermöglichen, erfolgte die Entwicklung neuer Materialien mit verbesserter Thermoschock- und Korrosionsbeständigkeit gegenüber flüssiger Kohleschlacke. In einem industrienahen Spinell-Alumina-Verbundwerkstoff lässt sich die Mikro- und Porenstruktur durch Zugabe von 6 Gew.-% eines Spinell-reichen Zements optimieren, wodurch die Infiltration und zugleich die Korrosion durch saure Braunkohleasche erheblich reduziert werden konnte. Die Zugabe von 2,5 Gew.-% TiO2 zu einer Al2O3-Gießmasse führt ebenfalls zur Verbesserung der Thermoschockbeständigkeit und verhindert während des Tiegeltests die weitere Auflösung der Al2O3-Matrix, indem sich auf dem Werkstoff durch Reaktion mit MgO der Schlacke eine dichte in situ Spinell-Schutzschicht ausbildet. So erfolgte die Entwicklung von Materialien mit hervorragenden thermomechanischen Eigenschaften und ausreichender Korrosionsbeständigkeit, welche als umweltfreundliche und kostengünstige Alternative zu den derzeit eingesetzten Cr2O3-reichen Werkstoffen angesehen werden können.

In Rahmen der vorliegenden Arbeit wurde die Charakterisierung einer hochtonerdehaltigen Feuerfestmasse mit Spinellzusatz vorgenommen. Es wurde eine weitgehende Übereinstimmung bei der Untersuchung der Feuerfestmasse unter Labor- und Betriebsbedingungen gefunden und die ermittelten Ergebnisse konnten auf reale Betriebsbedingungen übertragen werden. Das im Rahmen der Arbeit erarbeitete Programm zur Vorhersage der Zustellungshaltbarkeit nach bestimmten Chargenzahlen führt zur Optimierung der Einsatzplanung und Reparaturdurchführung und kann für die Kontrolle der Pfannenverfügbarkeit im Stahlwerk herangezogen werden.

Anlagen zur Herstellung von Synthesegas (CO·H2) aus kohlenstoffhaltigen Rohstoffen werden durch hohe Temperaturen bis zu 1600 °C und Drücken bis zu 50 bar beansprucht und benötigen daher Schutz durch eine feuerfeste Ausmauerung. Zur Steigerung der Effizienz und Lebensdauer solcher Vergasungsanlagen ist die Entwicklung neuer keramischer Hochtemperaturwerkstoffe erforderlich. Solch ein Material stellt eine Al2O3-reiche Gießmasse dar, welche durch den gezielten Einsatz verschiedener ZrO2- und TiO2-Gehalte optimiert wurde. Es hat sich gezeigt, dass bereits durch die Zugabe geringer Mengen an ZrO2 bzw. TiO2 sowohl die Temperaturwechselbeständigkeit als auch die Korrosionsbeständigkeit von Al2O3 gegenüber Kohleschlacken erheblich verbessert werden kann, was auf die Ausbildung einer Spinell-Schutzschicht während des Korrosionsvorgangs zurückzuführen ist.

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).

In Rahmen der vorliegenden Arbeit wurde die Charakterisierung einer hochtonerdehaltigen Feuerfestmasse mit Spinellzusatz vorgenommen. Es wurde eine weitgehende Übereinstimmung bei der Untersuchung der Feuerfestmasse unter Labor- und Betriebsbedingungen gefunden und die ermittelten Ergebnisse konnten auf reale Betriebsbedingungen übertragen werden. Das im Rahmen der Arbeit erarbeitete Programm zur Vorhersage der Zustellungshaltbarkeit nach bestimmten Chargenzahlen führt zur Optimierung der Einsatzplanung und Reparaturdurchführung und kann für die Kontrolle der Pfannenverfügbarkeit im Stahlwerk herangezogen werden.

Among the most impressive developments observed in the last 20 years, the improvement of the installation methods of monolithic refractories is certainly to be taken into account. However, this evolution, from vibratable castables to shotcrete and drycrete was not applied to materials based on magnesia, which are still mostly commercialized as ramming mixes, or as pouring castables with poor properties due to excessive water use. The major issues associated to this lack of technology is the scarcity of submicrometric powders compatible to magnesian systems, and the expansion followed by hydration of the magnesia, which is a disruptive reaction. By a thorough research on the literature, some potential additives were identified to be tested as anti-hydration additives. Hydration tests of powders in autoclave, complemented by pH and rheological measurements on magnesia pastes have identified five possible additives which can be used to inhibit the hydration: tartaric acid, citric acid, boric acid, magnesium fluoride and microsilica. Salts from the organic acids can also be successfully used. Of these, microsilica also presented the advantage of providing the submicrometric particles necessary to improve the flow of the castable, and to improve the bond of the castable. The three acids are very effective in inhibiting the formation of magnesium hydroxide, but affect negatively flow properties and mechanical resistance after cure. Microsilica prevented hydration cracks due to the reaction between the silicic acid generated under basic environment with the newly formed brucite, leading to the precipitation of a magnesium-silica-hydrated phase of poor crystallinity between the magnesia grains. This phase does not promote volumetric change, and also enable water release at a wider temperature range. Due to its nature close to serpentine minerals, it forms forsterite and enstatite at low temperatures, thus generating suitable strength between room temperature and at least 1400 °C. Magnesium fluoride changed the nature of this magnesium-silica-hydrated phase, by being incorporated to it and forming a phase more similar to the humite minerals. These minerals present higher MgO:SiO2 molar ratio than serpentine, and their formation requires a lower content of microsilica for a same effect against hydration, which is beneficial for the overall properties of the castable. The properties of the castable, as well as the influence of a number of other variables (for instance, refractoriness under load, creep, cold crushing strength, cold modulus of rupture, bulk density and apparent porosity) were also studied and hereby reported. It is believed that this technology can be further developed for industrial use, provided that some issues regarding the properties at high temperatures are solved. Not only had the study and comprehension of the nature of the bond between microsilica and magnesia, and the role of magnesium fluoride been pioneered by this work, but also the methodology used to evaluate the hydration after the drying process of castings, which was close to real refractory components.

Um einen dauerhaften Einsatz Al2O3-basierter Feuerfestwerkstoffe in Hochtemperaturanlagen zur Synthesegaserzeugung zu ermöglichen, erfolgte die Entwicklung neuer Materialien mit verbesserter Thermoschock- und Korrosionsbeständigkeit gegenüber flüssiger Kohleschlacke. In einem industrienahen Spinell-Alumina-Verbundwerkstoff lässt sich die Mikro- und Porenstruktur durch Zugabe von 6 Gew.-% eines Spinell-reichen Zements optimieren, wodurch die Infiltration und zugleich die Korrosion durch saure Braunkohleasche erheblich reduziert werden konnte. Die Zugabe von 2,5 Gew.-% TiO2 zu einer Al2O3-Gießmasse führt ebenfalls zur Verbesserung der Thermoschockbeständigkeit und verhindert während des Tiegeltests die weitere Auflösung der Al2O3-Matrix, indem sich auf dem Werkstoff durch Reaktion mit MgO der Schlacke eine dichte in situ Spinell-Schutzschicht ausbildet. So erfolgte die Entwicklung von Materialien mit hervorragenden thermomechanischen Eigenschaften und ausreichender Korrosionsbeständigkeit, welche als umweltfreundliche und kostengünstige Alternative zu den derzeit eingesetzten Cr2O3-reichen Werkstoffen angesehen werden können.