C/C-SiC-(Zr_xHf_1−x)C composites were prepared by the reactive melt infiltration method. The microstructure of the porous C/C skeleton and the C/C-SiC-(Zr_xHf_1−x)C composites, as well as the structural evolution and ablation behavior of the C/C-SiC-(Zr_xHf_1−x)C composites, were systematically investigated. The results show that the C/C-SiC-(Zr_xHf_1−x)C composites were mainly composed of carbon fiber, carbon matrix, SiC ceramic, (Zr_xHf_1−x)C and (Zr_xHf_1−x)Si₂ solid solutions. The refinement of the pore structure is beneficial to promote the formation of (Zr_xHf_1−x)C ceramic. The C/C-SiC-(Zr_xHf_1−x)C composites exhibited outstanding ablation resistance under an air–plasma environment at around 2000 °C. After ablation for 60 s, CMC-1 appeared to possess the minimum mass and linear ablation rates of only 2.696 mg/s and −0.814 µm/s, respectively, which are lower than those of CMC-2 and CMC-3. During the ablation process, a Bi-liquid phase and a liquid–solid two-phase structure were formed on the ablation surface which could act as an oxygen diffusion barrier to retard further ablation, which is responsible for the excellent ablation resistance of the C/C-SiC-(Zr_xHf_1−x)C composites.

Carbon-fiber-reinforced carbon and silicon carbide (C/C-SiC) composites were prepared using chemical vapor infiltration (CVI) combined with reactive melt infiltration (RMI). The microstructure and flexural properties of C/C-SiC composites after oxidation in different temperature water vapor environments were studied. The results indicate that the difficulty of oxidation in water vapor can be ranked from easy to difficult in the following order: carbon fiber (CF), pyrolytic carbon (PyC), and ceramic phase. The surface CFs become cone-shaped under corrosion. PyC has a slower oxidation rate and lower degree of oxidation compared to CF. The SiO₂ layer formed by the oxidation of SiC and residual Si was insufficient to fully cover the surface of CFs and PyC. As the temperature increased, the oxide film thickened, but the corrosion degree of CF and PyC intensified, and the flexural performance continuously deteriorated. The flexural strength of C/C-SiC composites was 271.86 MPa at room temperature. Their strength retention rates were all higher than 92.19% after water vapor corrosion at 1000 °C, still maintaining the “pseudoplastic” fracture characteristics. After water vapor corrosion at 1200 °C, the CFs inside the composites sustained more severe damage, with a strength retention rate as low as 48.75%. The fracture mode was also more inclined towards brittle fracture.