A novel pathway for the magnesiothermic reduction of boron oxide and magnesium dodecaboride (MgB12) in the presence of carbon by a self-propagating high-temperature synthesis method was proposed that was aimed at the direct preparation of boron carbide nanopowder. The combined utilization of two boron sources, boron oxide and MgB12, allowed tailoring the overall caloric effect of the process, increasing the yield of the target product and lessening the laborious leaching process. In addition, it is an alternative way to utilize magnesium borides, which are inevitable side products at boron production. Multivariate thermodynamic calculations performed in the B2O3-MgB12-Mg-C system allowed estimating equilibrium compositions of the products and deducing the optimum composition of the initial mixture for obtaining B4C. For the latter, the adiabatic temperature (Tad) is 2100 °C, which is theoretically enough for the implementation of the self-propagating reaction. The combustion reaction was shown to be extremely sensitive to the initial mixture composition, external pressure, as well as sample diameter (heat losses). It proceeds in self-oscillatory mode and leads to the product of a layered macrostructure. The combustion product was then consolidated by the spark plasma sintering technique at different conditions. Vickers microhardness was measured, and the wear erosion behavior was examined. The variation in lattice parameters of boron carbide reflected the influence of synthesis, sintering and erosion conditions on the ordering/disordering of the boron carbide structure.
