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High‐performance thermal protective composites with lightweight, micro‐ ablation and high‐efficient thermal insulation are urgently required for thermal protection systems in advanced hypersonic speed vehicles. However, the practical applications of thermal protective composites have long been hampered by the main issues such as low mass residual rate and poor long‐term antioxidation of the matrix in high‐temperature aerobic environments. Here, we report a novel silica‐polybenz oxazine (SiO2‐PBO) aerogels with interpenetrated networks, possessing the ability to antioxidation, thermal insulation, and flame‐retardant properties. The resulting SiO2‐PBO aerogels exhibit low density (0.25 g/cm3), low thermal conductivity (0.035 W/(m·K)), and superior peak heat release rate value (15.3 W/g). Moreover, the mass residual rate is up to 70.46 wt% in the N2 atmosphere and remains 57.83 wt% despite existing in the air atmosphere and experiencing the highest temperature of 800°C. Briefly, SiO2‐PBO aerogels as‐prepared could be a potential matrix for a new gene ration of high‐performance thermal protective composites in the future. [ABSTRACT FROM AUTHOR]

The lightweight ablation materials that have been successfully applied in thermal protection systems (TPS) are the focus of attention owing to the urgent demand for aerospace vehicles to have efficient thermal insulation materials with lightweight, long-term antioxidant, and micro-ablation. However, improving the antioxidant ablation properties in a long-term aerobic atmosphere is still a significant challenge. Herein, a novel strategy to fabricate needle quartz fiber (NQF) reinforced SiO 2 aerogel interpenetrating polybenzoxazine (PBO) aerogel thermal protection composites (NQF/SiO 2 –PBOs) with a binary network structure is proposed. The as-prepared NQF/SiO 2 –PBOs perfectly inherited their porous nanostructure and captivating properties, including lightweight (0.53 g/cm3), high mechanical strengths, and low thermal conductivity of 0.048 W/(m·K) at 25 °C and 0.079 W/(m·K) at 1100 °C. Moreover, the NQF/SiO 2 –PBOs exhibited outstanding high-temperature thermal insulation and long-time antioxidant ablation with low linear and mass ablation rates. The cold surface temperature peaked at approximately 307.2 °C within 1800 s when the hot surface temperature exceeded 1100 °C. The ablation/thermal insulation mechanism was also discussed through the analysis of the microstructure, chemical structure, and crystal structure. This research provides a meaningful reference for the development and exploitation of new advanced lightweight, long-term antioxidant, and micro-ablative thermal protective materials. [ABSTRACT FROM AUTHOR]