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To address the relatively mediocre mechanical properties of single-phase multi-component carbide ceramics, a phase transition from a single phase to multiple phases was proposed to achieve superior mechanical properties. A series of (TiZrVxNb)C0.8 ceramics with different V contents were fabricated by spark plasma sintering (SPS). The influence of the V content on the phase composition, microstructural evolution, and mechanical properties was investigated in detail. The transition behavior from a single phase to multiple phases is discovered and discussed. The formation of the Zr-rich phase and Zr-poor phase can be attributed to the increase in lattice distortion and mixed enthalpy caused by the addition of V. A nanometer lamellar structure with a semi-coherent interface obtained via in situ decomposition is reported for the first time in multi-component carbide ceramics. The semi-coherent interfaces with high dislocation density and strain concentration effectively improve the mechanical properties, grain refinement, and multi-phase formation. The optimal comprehensive mechanical properties of the Vickers hardness (26.3 GPa), flexural strength (369 MPa), and fracture toughness (3.1 MPa·m1/2) were achieved for the sample with 20 mol% V.
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