The relationships between fabrication variables, microstructure and selected properties of carbon bonded magnesia-graphite refractory composite materials have been investigated. A novel optical microscope method of characterizing the morphology of flake graphites was developed and used to determine distributions of length and thickness and average aspect ratios for the four graphite samples used in the study. The compaction behaviour of magnesia alone and in combination with the flake graphites has been studied in some detail and the microstructures of the products elucidated. It is shown that the amount of magnesia of small particle size plays a significant role in determining the graphite-graphite contact area in the structure. An irreversible volume expansion is observed on firing composites, the magnitude of which can be related to the microstructure and the graphite content. A phenolic resin binder restricts this expansion. It is shown that the carbon binder does not bond to the graphite phase and only weakly, if at all, to the magnesia. Consequently the strengths and moduli are low and show only a small variation with graphite type. The effect of adding graphite to carbon-bonded magnesia is to lower the strength slightly, but increasing the graphite content from 20-30% causes a small increase in strength. Increasing the amount of carbon bond from pitch has little effect on strength at levels of 5-15% whereas over the range 5-13% the resin binder has a more pronounced effect. The most significant factor affecting the strength and modulus of fired composites is the amount of silicon or aluminium, added as oxidation inhibitors, which react to form carbide and nitride phases. Finally, a brief study of slag penetration shows that this can be reduced by decreasing the amount of oxide fines in the composite because of the changes in microstructure that, result.

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Inaug.-diss. - Munich. / Vitae curriculum. Filmed with: Tragoediae Aeschyleae, quae inscribitur Prometheus vinctus, v. 561-940 -- Martini, Edgar / Analecta Laertiana -- Mekler, Siegfried / Euripidea : textkritische Studien -- Mangold, Bernhard / De diectasi Homerica imprimis verborum in -ao -- Miller, Thomas / Euripides rhetoricus -- Marx, Friedrich / Studia Luciliana -- Dahler, Johann Georg / Exercitationes in Appiani Alexandrini romanas historias -- Michael, Hugo / Die Heimat des Odysseus : ein Beitrag zur Kritik der Dörpfeld'schen Leukas-Ithaka-Hypothese -- Lange, Wilhelm Marius / Quaestiones in Aristophanis Thesmophoriazusas -- Merz, Konrad / Forschungen über die Anfänge der Ethnographie bei den Griechen -- Kern, Johann Michael / Accentuum veterum Graecorum genuina pronuntiatio -- Kurz, Emil / Ueber den Octavius des Minucius Felix : mit dem Text von Cap. 20-26 incl. -- Klein, Otto / Beiträge zur Kenntnis der syrischen Übersetzungen des Neuen Testaments, nebst Probe eines syrisch-griechischen Evangelien-Vokabulars -- Klein, Josef / Die kleineren inschriftlichen Denkmäler des Bonner Provinzial-Museums : 3 -- Klein, Josef / Die kleineren inschriftlichen Denkmäler des Bonner Provinzial-Museums : 4 -- Klein, Josef / Römische Inschriften aus Bonn -- Klein, Josef / Kleinere Mittheilungen aus dem Provinzial-Museum zu Bonn : 4 -- Kosegarten, Ludwig Gotthard / Plato de Legibus Lib. VII -- Lagus, Jacob Johan Wilhelm / Plutarchus Varronis studiosus -- Klossman, Johann Friedrich / Prolegomena in dialogum de oratoribus claris qui Tacito vulgo adscribitur. Includes bibliographical references.

Dual phase magnesia-zirconia ceramics were developed, characterized, and evaluated as a potential matrix material for use in light water reactor inert matrix fuel intended for the disposition of plutonium and minor actinides. Ceramics were fabricated from the oxide mixture using conventional pressing and sintering techniques. Characterization of the final product was performed using optical microscopy, scanning electron microscopy, x-ray diffraction analysis, and energy-dispersive x-ray analysis. The final product was found to consist of two phases: cubic zirconia-based solid solution and cubic magnesia. Evaluation of key feasibility issues was limited to investigation of long-term stability in hydrothermal conditions and assessment of the thermal conductivity. With respect to hydrothermal stability, it was determined that limited degradation of these ceramics at 300^oC occurred due to the hydration of the magnesia phase. Normalized mass loss rate, used as a quantitative indicator of degradation, was found to decrease exponentially with the zirconia content in the ceramics. The normalized mass loss rates measured in static 300^oC de-ionized water for the magnesia-zirconia ceramics containing 40, 50, 60, and 70 weight percent of zirconia are 0.00688, 0.00256, 0.000595, 0.000131 g/cm2/hr respectively. Presence of boron in the water had a dramatic positive effect on the hydration resistance. At 300^oC the normalized mass loss rates for the composition containing 50 weight percent of zirconia was 0.00005667 g/cm2/hr in the 13000 ppm aqueous solution of the boric acid. With respect to thermal conductivity, the final product exhibits values of 5.5-9.5 W/(m deg) at 500^oC, and 4-6 W/(m deg) at 1200^oC depending on the composition. This claim is based on the assessment of thermal conductivity derived from thermal diffusivity measured by laser flash method in the temperature range from 200 to 1200^oC, measured density, and heat capacity calculated using rule of mixtures. Analytical estimates of the anticipated maximum temperature during normal reactor operation in a hypothetical inert matrix fuel rod based on the magnesia-zirconia ceramics yielded the values well below the melting temperature and well below current maximum temperatures authorized in light water reactors.

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.

A dissertation submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in fulfilment of the requirements for the degree of Master of Science in Engineering Johannesburg, 11 October 2016 / Refractory lining failure of damaged magnesia bricks and used alumina bricks was investigated by XRF, XRD, SEM-EDS analysis and computational thermochemistry (phase diagrams). In addition, the effect of oxygen partial pressure towards the refractory lining and alkali sulphate ratio were also determined. The presence of low melting phases of KCl, (Na, K) Cl, K2SO4 and CaSO4 compromised the refractoriness of the magnesia bricks because they are liquid at temperatures below clinkerisation temperature (1450 °C). Sodium oxide and potassium oxide in the kiln feed and chlorine and sulphur in the kiln gas atmosphere migrated into the magnesia brick and react to form KCl, (Na, K) Cl and K2SO4. Components of the magnesia brick, CaO reacted with the excess sulphur in the kiln gas atmosphere forming CaSO4. The presence of these impurity phases indicated that the magnesia bricks suffered chemical attack. Potassium and part of components of high-alumina brick reacted to form K2 (MgSi5O12) impurity phase. Phase diagram predictions indicated that the presence of sodium at any given concentration automatically results in liquid formation in the high alumina brick. This confirms that the chemical attack is also the cause of the failure of the high alumina brick. The analysis of the microstructures of both unused and damaged magnesia bricks revealed that the fracture was predominantly intergranular whereas, in high alumina brick, the fracture was transgranular. The absence of evidence of micro-cracks in both magnesia and alumina bricks rules out thermal shock as a failure mechanism. The absence of clinker species and phases in the examined magnesia and alumina bricks indicated that corrosion by clinker diffusion was absent. The partial pressure of oxygen is low (1.333×10−4 atm), it indicates the stability of Fe3O4 and Mn3O4 and therefore does not favour the oxidation of Fe3O4 to formation of Fe2O3 and Mn3O4 to formation of Mn2O3. The values of alkali sulphate ratio indicated that the kiln operating conditions were favourable for chemical attack to occur. / MT2017

The cement industry contributes around 5-7% of man-made CO2 emissions globally because of the Portland Cement (PC) production. Therefore, innovative reactive magnesia cement, with significant sustainable and technical advantages, has been proposed by blending reactive MgO and hydraulic binders in various proportions. MgO is currently produced from the calcination of magnesite (MgCO3), emitting more CO2 than the production of PC, or from seawater/brine which is also extremely energy intensive. Hence this research aims to investigate an innovative method to produce MgO from reject brine, a waste Mg source, through carbon sequestration, by its reaction with CO2, to provide a comparable low carbon manufacturing process due to the recycling of CO2. The produced deposits are then calcined to oxides with potential usage in construction industry. The entire system is a closed loop to achieve both environmental optimisation and good productivity. This research focuses on the chemical manufacturing process, integrated with material science knowledge and advancements, instead of concentrating purely on chemistry evaluations. Six series of studies were conducted, utilising MgCl2, CaCl2, MgCl2-CaCl2, MgCl2-CaCl2-NaCl, and MgCl2-CaCl2-NaCl-KCl to react with CO2 under alkaline conditions. The precipitates include hydrated magnesium carbonates, calcium carbonates and magnesian calcite. Generated carbonates were then calcined in a furnace to obtain MgO, CaO or dolime (CaO•MgO). All six series of carbonation processes were carried out under a controlled pH level, to study the constant pH’s effect on the process and resulting precipitates. Other controllable factors include pH, temperature, initial concentration, stirring speed, and CO2 flux rate. In conclusion, the optimum parameters for the production of the carbonated precipitates are: 0.25MgCl2 + 0.05CaCl2 + 2.35NaCl + 0.05KCl, 700rpm stirring speed, 25oC room temperature, pH=10.5, and 500cm3/min CO2 infusion rate. Reaction time is within a day. These parameters are chosen based on the sequestration level, particle performance morphology and the operational convenience. The optimum calcination parameters are at 800oC heating temperature with a 4h retention time.

During this PhD thesis, cobalt (Co) catalysts have been prepared, characterized and studied in the carbon monoxide hydrogenation (CO+H2) reaction (also known as “Fischer-Tropsch” (FT) reaction). In industry, the FT synthesis aims at producing long chain hydrocarbons such as gasoline or diesel fuels. The interest is that the reactants (CO and H2) are obtained from other carbonaceous sources than crude oil: natural gas, coal, biomass or even petroleum residues. As it is well known that the worldwide crude oil reserves will be depleted in a few decades, the FT reaction represents an attractive alternative for the production of various fuels. Moreover, this reaction can also be used to produce high value specialty chemicals (long chain alcohols, light olefins…). Two different types of catalysts have been investigated during this thesis: cobalt with magnesia used as support or dispersant (Co/MgO) and cobalt with silica used as support (Co/SiO2). Each catalyst from the first class is prepared by precipitation of a mixed Co/Mg oxalate in acetone. This coprecipitation is followed by a thermal decomposition under reductive atmosphere leading to a mixed Co/MgO catalyst. On the other hand, Co/SiO2 catalysts are prepared by impregnation of a commercial silica support with a chloroform solution containing Co nanoparticles. This impregnation is then followed by a thermal activation under reductive atmosphere. The mixed Co/Mg oxalates and the resulting Co/MgO catalysts have been extensively characterized in order to gain a better understanding of the composition, the structure and the morphology of these materials: thermal treatments under reductive and inert atmospheres (followed by MS, DRIFTS, TGA and DTA), BET surface area measurements, XRD and electron microscopy studies have been performed. Moreover, an original in situ technique for measuring the H2 chemisorption surface area of catalysts has been developed and used over our catalysts. The performances of the Co/MgO and Co/SiO2 catalysts have then been evaluated in the CO+H2 reaction at atmospheric pressure. Chemical Transient Kinetics (CTK) experiments have been carried out in order to obtain information about the reaction kinetics and mechanism and the nature of the catalyst active surface under reaction conditions. The influence of several experimental parameters (temperature, H2 and CO partial pressures, total volumetric flow rate) and the effect of passivation are also discussed with regard to the catalyst behavior. Our results indicate that the FT active surface of Co/MgO 10/1 (molar ratio) is entirely covered by carbon, oxygen and hydrogen atoms, most probably associated as surface complexes (possibly formate species). Thus, this active surface does not present the properties of a metallic Co surface (this has been proved by performing original experiments consisting in switching from the CO+H2 reaction to the propane hydrogenolysis reaction (C3H8+H2) which is sensitive to the metallic nature of the catalyst). CTK experiments have also shown that gaseous CO is the monomer responsible for chain lengthening in the FT reaction (and not any CHx surface intermediates as commonly believed). Moreover, CO chemisorption has been found to be irreversible under reaction conditions. The CTK results obtained over Co/SiO2 are quite different and do not permit to draw sharp conclusions concerning the FT reaction mechanism. More detailed studies would have to be carried out over these samples. Finally, Co/MgO catalysts have also been studied on a combined DRIFTS/MS experimental set-up in Belfast. CTK and Steady-State Isotopic Transient Kinetic Analysis (SSITKA) experiments have been carried out. While formate and methylene (CH2) groups have been detected by DRIFTS during the FT reaction, the results indicate that these species play no role as active intermediates. These formates are most probably located on MgO or at the Co/MgO interface, while methylene groups stand for skeleton CH2 in either hydrocarbon or carboxylate. Unfortunately, formate/methylene species have not been detected by DRIFTS over pure Co catalyst without MgO, because of the full signal absorption.