Guided by thermodynamic calculations, this study successfully synthesized nonstoichiometric high-entropy carbide (Mo_0.2Nb_0.2Ta_0.2Ti_0.2W_0.2)C_x (x = 0.875–0.972) nanometer-sized powders using micrometer-sized metal oxides (MoO₃, Nb₂O₅, Ta₂O₅, TiO₂, and WO₃) and carbon black as raw materials through carbothermic reduction at 1400–1550 °C. The powders synthesized above 1500 °C exhibited a single-phase rock-salt structure with an average grain size as low as 270 nm. TEM analysis confirmed the lattice parameters increased from 0.4378 nm to 0.4395 nm with decreasing carbon content and synthesis temperature. After ball milling, the optimal powder was densified into a (Mo_0.2Nb_0.2Ta_0.2Ti_0.2W_0.2)C_0.9 ceramic block through spark plasma sintering (SPS, 1950 °C/10 min/20 MPa), achieving a relative density of 99.1% and an average grain size of 4.3 μm. This ceramic exhibited remarkable mechanical properties (17.3 GPa Vickers hardness, 25.9 GPa nano-hardness, 524 GPa Young’s modulus, and 4.43 MPa·m^1/2 fracture toughness) and a relatively low room-temperature thermal conductivity of 8.3 W·m⁻¹·K⁻¹. This study provides a theoretical basis and technical approach for the preparation of high-hardness and low-thermal-conductivity nonstoichiometric high-entropy carbide ceramics via low-temperature carbothermic reduction and sintering.

Silicon carbide (SiC) ceramics are regarded as high-performance structural materials due to their excellent high-temperature strength, wear resistance, and thermal stability. However, their inherent high brittleness, low fracture toughness, and difficulty in densification have limited their wider application. To overcome these challenges, introducing a second phase and/or sintering aids is necessary. In this paper, SiC–AlN–VC multiphase ceramics were fabricated via spark plasma sintering at 1800 °C to 2100 °C. The interface, mechanical, and thermal properties were examined. It was found that the VC particles effectively pin the grain boundaries and suppress the abnormal growth of SiC grains. At temperatures exceeding 1800 °C, the N atoms released from the decomposition of AlN diffuse into the VC lattice, forming a V(C,N) solid solution that enhances both the toughness and strength of the ceramics. With increasing sintering temperature, the mechanical properties of the SiC multiphase ceramics first improve and then deteriorate. Ultimately, a nearly fully dense SiC multiphase ceramic is obtained. The maximum hardness, flexural strength, and fracture toughness of SAV20 are 28.7 GPa, 508 MPa, and 5.25 MPa·m^1/2, respectively. Furthermore, the room-temperature friction coefficient and wear rate are 0.41 and 3.41 × 10⁻⁵ mm³/(N·m), respectively, and the thermal conductivity is 58 W/(m·K).