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