Metallothermic Reduction of MoO3 on Combustion Synthesis of Molybdenum Silicides/MgAl2O4 Composites

Combustion synthesis involving metallothermic reduction of MoO3 by dual reductants, Mg and Al, to enhance the reaction exothermicity was applied for the in situ production of Mo3Si–, Mo5Si3− and MoSi2–MgAl2O4 composites with a broad compositional range. Reduction of MoO3 by Mg and Al is highly exothermic and produces MgO and Al2O3 as precursors of MgAl2O4. Molybdenum silicides are synthesized from the reactions of Si with both reduced and elemental Mo. Experimental evidence indicated that the reaction proceeded as self-propagating high-temperature synthesis (SHS) and the increase in silicide content weakened the exothermicity of the overall reaction, and therefore, lowered combustion front temperature and velocity. The XRD analysis indicated that Mo3Si–, Mo5Si3– and MoSi2–MgAl2O4 composites were well produced with only trivial amounts of secondary silicides. Based on SEM and EDS examinations, the morphology of synthesized composites exhibited dense and connecting MgAl2O4 crystals and micro-sized silicide particles, which were distributed over or embedded in the large MgAl2O4 crystals.

Formation of Mo5Si3/Mo3Si–MgAl2O4 Composites via Self-Propagating High-Temperature Synthesis

In situ formation of intermetallic/ceramic composites composed of molybdenum silicides (Mo5Si3 and Mo3Si) and magnesium aluminate spinel (MgAl2O4) was conducted by combustion synthesis with reducing stages in the mode of self-propagating high-temperature synthesis (SHS). The SHS process combined intermetallic combustion between Mo and Si with metallothermic reduction of MoO3 by Al in the presence of MgO. Experimental evidence showed that combustion velocity and temperature decreased with increasing molar content of Mo5Si3 and Mo3Si, and therefore, the flammability limit determined for the reaction at Mo5Si3 or Mo3Si/MgAl2O4 = 2.0. Based upon combustion wave kinetics, the activation energies, Ea = 68.8 and 63.8 kJ/mol, were deduced for the solid-state SHS reactions producing Mo5Si3– and Mo3Si–MgAl2O4 composites, respectively. Phase conversion was almost complete after combustion, with the exception of trivial unreacted Mo existing in both composites and a minor amount of Mo3Si in the Mo5Si3–MgAl2O4 composite. Both composites display a dense morphology formed by connecting MgAl2O4 crystals, within which micro-sized molybdenum silicide grains were embedded. For equimolar Mo5Si3– and Mo3Si–MgAl2O4 composites, the hardness and fracture toughness are 14.6 GPa and 6.28 MPa m1/2, and 13.9 GPa and 5.98 MPa m1/2, respectively.

Mechanically Activated Combustion Synthesis of Molybdenum Silicides and Borosilicides

ABSTRACTMolybdenum silicides and borosilicides are promising structural materials for advanced power plants. A major challenge, however, is to simultaneously achieve high oxidation resistance and acceptable mechanical properties at high temperatures. For example, molybdenum disilicide (MoSi2) has excellent oxidation resistance and poor mechanical properties, while Mo-rich silicides such as Mo5Si3 (called T1) have much better mechanical properties but poor oxidation resistance. One approach is based on the fabrication of MoSi2−T1 composites that combine high oxidation resistance of MoSi2 and good mechanical properties of T1. Another approach involves the addition of boron to Mo-rich silicides for improving their oxidation resistance through the formation of a borosilicate surface layer. In particular, Mo5SiB2 (called T2) phase and alloys based on this phase are promising materials.In the present paper, MoSi2−T1 composites and materials based on T2 phase are obtained by mechanically activated self-propagating high-temperature synthesis (MASHS). To obtain denser products, the so-called SHS compaction (quasi-isostatic pressing of hot combustion products) has been employed. Thermal analysis has shown that SHS compaction significantly improves the oxidation resistance. Self-sustained combustion of Mo/Si/B mixtures for the formation of T2 phase becomes possible if the composition is designed for adding a more exothermic reaction of MoB formation. These mixtures exhibit spin combustion. Oxidation resistance of the obtained multi-phase Mo−Si−B materials is independent on the concentration of Mo phase in the products. The “chemical oven” technique has been used to obtain a single Mo5SiB2 phase and an alloy consisting of α-Mo, Mo5SiB2, and Mo3Si phases.