| Summary: | In order to solve the problem of difficult sintering and high brittleness of B<sub>4</sub>C-based ceramics, B<sub>4</sub>C@ZrB<sub>2</sub>-TiB<sub>2</sub> composite powder was synthesized by molten salt method, and B<sub>4</sub>C–(Zr, Ti)B<sub>2</sub> composite ceramics were successfully prepared by spark plasma sintering. The effects of different raw material ratios on the composition, microstructure, and mechanical properties of the prepared composite ceramics were characterized by XRD, XPS, SEM, and TEM. The results show that ZrB<sub>2</sub> and TiB<sub>2</sub> were grown on the surface of B<sub>4</sub>C by template mechanism to form a dense nanocrystalline coating, and the original surface of B<sub>4</sub>C was exposed gradually with the decrease of the ratio of metal powder. When the composite powders were sintered at 1700 °C, ZrB<sub>2</sub> and TiB<sub>2</sub> formed a solid solution, which can refine grains and improve strength. When the raw material ratio is n(B<sub>4</sub>C): n(Zr): n(Ti) = 12:1:1, the composite ceramics have excellent comprehensive properties, the Vickers hardness reaches 41.2 GPa.
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