Synthesis and formation mechanisms of molybdenum silicides by mechanical alloying

The synthesis and formation of MoSi₂, Mo₅Si₃, and Mo₃Si compounds by the mechanical alloying of Mo-Si powder mixtures has been investigated. Ball-milling experiments were conducted for the composition range of 10-80 at.% Si. The formation of molybdenum silicides, especially MoSi₂, during mechanical alloying and the relevant reaction rates markedly depended on the powder composition. The spontaneous formation of αMoSi₂ during mechanical alloying at 67 at.% Si (MoSi₂ stoichiometry) proceeded by a mechanically-induced self-propagating reaction (MSR), the mechanism of which is analogous to that of the self-propagating high-temperature synthesis (SHS). At the compositions of 54 and 80 at.% Si, however, the formation of MoSi₂ proceeded by the gradual formation of both the α and β phases instead of the MSR mode. The formation of Mo₅Si₃ during mechanical alloying was characterized by a slow reaction rate as the reactants and product coexisted over a long period. The milling of Mo-rich powder mixtures up to 150 h did not lead to the direct formation of Mo₃Si. The Mo₃Si phase appeared only after brief annealing at temperatures of 800°C and above.