Owing to tunable dielectric properties, light weight and high porosity, polymer-derived SiBCN ceramic aerogels possess significant application prospects in electromagnetic wave (EMW) absorption and thermal insulation. However, due to inadequate oxidation resistance, the structural collapse and performance deterioration of SiBCN aerogels will easily occur in high-temperature aerobic environments, limiting their application. Herein, to address this issue, a novel and straightforward strategy based on typical polymer-derived-ceramic (PDC) aerogel method and impregnation with boehmite sol was proposed for synthesizing SiBCN/Al2O3 composite ceramic aerogels. The microstructure, phase composition, thermal insulation, oxidation resistance and EMW absorption properties of SiBCN/Al2O3 ceramic aerogels were investigated. The resulting SiBCN/Al2O3 composite aerogel demonstrates superior high-temperature structural stability, exhibiting an ultra-low linear shrinkage of only 6.5 % following heat treatment at 1200 °C for 2 h in air. Additionally, the composite aerogel shows a low thermal conductivity of 0.039 W/mK and a low density of 0.112 g/cm3. The SiBCN/Al2O3 composite aerogel, composed of dielectric SiBCN, conductive free carbon, and insulating alumina, demonstrates outstanding EMW absorption properties with a minimum reflection loss of −48.6 dB and an effective bandwidth of 5.8 GHz. The enhanced microwave absorption performance is mainly attributed to the improved impedance matching, multiple reflection, and enhanced interfacial polarization resulting from the introduction of Al2O3. Given prominent oxidation resistance, thermal insulation and EMW absorption properties, the SiBCN/Al2O3 composite aerogel paves the way for developing microwave absorption and thermal insulation integrated material in high-speed vehicles.
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