Understanding the Magnesiothermic Reduction Mechanism of TiO2 to Produce Ti

Titanium dioxide (TiO2) powders in the mineral form of rutile were reduced to metallic and an intermediate phase via a magnesiothermic reaction in molten Mg at temperatures between 973 K and 1173 K (700 °C and 900 °C) under high-purity Ar atmosphere. The reaction behavior and pathway indicated intermediate phase formation during the magnesiothermic reduction of TiO2 using XRD (X-ray diffraction), SEM (scanning electron microscope), and TEM (transmission electron microscope). Mg/TiO2 = 2 resulted in various intermediate phases of oxygen containing titanium, including Ti6O, Ti3O, and Ti2O, with metallic Ti present. MgTi2O4 ternary intermediate phases could also be observed, but they were dependent on the excess Mg present in the sample. Nevertheless, even with excessive amounts of Mg at Mg/TiO2 = 10, complete reduction to metallic Ti could not be obtained and some Ti6O intermediate phases were present. Although thermodynamics do not predict the formation of the MgTi2O4 spinel phase, detailed phase identification through XRD, SEM, and TEM showed significant amounts of this intermediate ternary phase even at excess Mg additions. Considering the stepwise reduction of TiO2 by Mg and the pronounced amounts of MgTi2O4 phase observed, the rate-limiting reaction is likely the reduction of MgTi2O4 to the TitO phase. Thus, an additional reduction step beyond thermodynamic predictions was developed.