Role of Ti4+ and Sn4+ ions in spinel formation and reactive sintering of magnesia-rich ceramics

The solid solubility of magnesia in magnesium aluminate spinel and magnesium aluminate spinel in magnesia does not change with temperature thus not creating bonds or precipitation over periclase grains in a single stage sintering process. In comparison, the precipitated spinels in magnesia-chromia refractories form complex spinel due to inversion in the position of bivalent and trivalent cations within the structure, making them more stable at high temperature than either normal or inverse spinel. Additives form low-temperature compounds that diffuse into the spinel structure and create defects that change the properties of spinel solid solution. In the present study, magnesia and alumina powders along with tetravalent oxide additives were analyzed for their role in reactive densification of spinel in a single stage firing process in order to achieve a better binding system for magnesia-based refractories. These tetravalent oxides on reaction with magnesia form spinel solid solution with MgAl2O4 as they have similar crystal structure. The spinel solid solution formed using oxide additives is expected to have higher solubility in magnesia than magnesium aluminate spinel, resulting in improvement of the bonding during sintering through increased in solid solubility at elevated temperatures followed by precipitation of secondary spinel phases, similar to the complex spinel in magnesia-chrome refractories. The formation of spinel during firing remains as a second phase that retards the grain growth of periclase. The changes in unit cell dimensions with temperature and amount of additive were analyzed using Reitveld method and correlated with the densification behaviour at different temperatures.