Carbon fiber fabric-reinforced phenolic resin composites are widely used as thermal protection materials for thermal protection systems in hypersonic vehicles and capsules. In this work, carbon fiber fabric-reinforced boron phenolic resin composites modified with MoSi2 and B4C were prepared via a compression molding technique. The high-temperature performance of the composites as well as the oxidation behavior of the carbon fibers was studied. The results indicate that the incorporation of B4C improves the performance of composites at high temperatures. The residual weight rate of composites with 15 phr B4C (BP-15) sufficiently increased from 23.03% to 32.91% compared with the composites without B4C (BP-0). After being treated at 1400 °C for 15 min, the flexural strength of BP-15 increased by 17.79% compared with BP-0. Compared with BP-0, the line ablation rate and mass ablation rate of BP-15 were reduced by 53.96% and 1.56%, respectively. In addition, MoSi2 and B4C particles had a positive effect on the oxidation of carbon fibers in the composites. After treatment at 1400 °C, the diameter of the as-received carbon fiber was reduced by 31.68%, while the diameter of the carbon fiber in BP-0 and BP-15 decreased by 15.12% and 6.14%, respectively. At high temperatures, the liquid B2O3 from B4C and MoSi2-derived complex-phase ceramics (MoB, MoB2, Mo2C, Mo4.8Si3C0.6) acted as an oxygen barrier, effectively mitigating the oxidation degree of the carbon fibers.
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