High-Entropy Diborides-Silicon Carbide Composites by Reactive and Non-Reactive Spark Plasma Sintering: A Comparative Study

The reactive spark plasma sintering (R-SPS) method was compared in this work with the two-step SHS-SPS route, based on the combination of the self-propagating high-temperature synthesis (SHS) with the SPS process, for the fabrication of dense (Hf_0.2Mo_0.2Ti_0.2Ta_0.2Nb_0.2)B₂-SiC and (Hf_0.2Mo_0.2Ti_0.2Ta_0.2Zr_0.2)B₂-SiC ceramics. A multiphase and inhomogeneous product, containing various borides, was obtained at 2000 °C/20 min by R-SPS from transition metals, B₄C, and Si. In contrast, if the same precursors were first reacted by SHS and then processed by SPS under the optimized condition of 1800 °C/20 min, the desired ceramics were successfully attained. The resulting sintered samples possessed relative densities above 97% and displayed uniform microstructures with residual oxide content <2.4 wt.%. The presence of SiC made the sintering temperature milder, i.e., 150 °C below that needed by the corresponding additive-free system. The fracture toughness was also markedly improved, particularly when considering the Nb-containing system processed at 1800 °C/20 min, whereas the fracture toughness progressively decreased (from 7.35 to 5.36 MPa m^1/2) as the SPS conditions became more severe. SiC addition was found to inhibit the volatilization of metal oxides like MoO₃ formed during oxidation experiments, thus avoiding mass loss in the ceramics. The benefits above also likely took advantage of the fact that the two composite constituents were synthesized in parallel, according to the SHS-SPS approach, rather than being produced separately and combined subsequently, so that strong interfaces between them were formed.