Passive oxidation of single crystal silicon carbide (6H-SiC) resulted in the formation of a vitreous silica layer which crystallized gradually at temperatures near 1300 degrees-1400 degrees C. During this process, statistically distributed devitrification centers appeared and disk-like aligned crystal plates (radialites) formed. The crystallization process did not necessarily start at structural defects although these often act as areas of preferred nucleation. A second structural transition from disk-like radialites to small crystalline spheres (globulites) was not connected to structural defects but a consequence of the presence of impurities. Alkaline and earth-alkaline elements are common contaminations within the atmospheres of typical furnaces fitted with alumina tubes. Globulite formation was a process of recrystallization catalyzed by an impurity-related melt formed on top of the devitrified areas. Crystallization caused exsolution of reaction gas and local impurity enrichments as the solubility for these phases is much higher in the devitrifying vitreous silica matrix. Both clean and impurity-loaded oxidation produced specific morphologies of scales and interfaces.