To meet the requirements of next-generation spacecraft thermal protection systems for lightweight materials with high strength, effective thermal insulation, and superior ablation resistance, a novel POSS-modified phenolic aerogel/quartz fiber composite (POSS-PR/QF) was developed using a thiol–ene click reaction combined with a sol–gel process. Covalent incorporation of polyhedral oligomeric silsesquioxanes (POSS) into the phenolic matrix effectively eliminates nanoparticle aggregation and improves interfacial compatibility. As a result, the modified resin is suitable for resin transfer molding (RTM) processes. The resulting composite exhibited an aerogel-like porous structure with enhanced crosslinking density, thermal stability, and oxidation resistance. At 7.5 wt% POSS loading, the composite achieved low density (~0.7 g·cm⁻³) and outstanding mechanical properties, with tensile, flexural, compressive, and interlaminar shear strengths increased by 114%, 79%, 29%, and 104%, respectively. Its thermal conductivity (0.0619 W/(m·K)) and ablation rates were also markedly reduced. Mechanistic studies revealed that POSS undergoes in situ ceramification to form SiO₂ and SiC phases, which create a dense protective barrier. In addition, this ceramification process promotes char graphitization, thereby enhancing oxidation resistance and thermal insulation. This work provides a promising approach for designing lightweight, high-performance, and multifunctional thermal protection materials for aerospace applications.

Due to the non-polar and chemically inert nature of carbon fiber surfaces, the interfacial bonding strength between carbon fibers and norbornene-polyimide (PI-NA) resin matrix is relatively weak. To address this issue, this study constructed a composite coating on the carbon fiber surface and proposed a novel method to build robust interfaces based on multiple interfacial interactions, thereby effectively enhancing the interfacial properties between carbon fibers and PI-NA resin. Inspired by mussel adhesive proteins, this study established a multi-level synergistic interfacial reinforcement system by sequentially constructing a C-PEI@OPDA coating, in situ growing zinc oxide nanorods (ZW) arrays, and grafting 3-mercaptopropyltrimethoxysilane (MPS) onto carbon fiber surfaces. The C-PEI@OPDA coating, rich in amino (–NH₂) and hydroxyl groups (–OH), enhanced adhesion to carbon fibers and adsorbed Zn²⁺ via coordination interactions to provide nucleation sites for ZW growth. Meanwhile, the active hydrogen in the coating promoted the crosslinking of PI-NA resin, thereby increasing the resin crosslinking density in the interfacial region. The vertically aligned ZW significantly increased surface roughness, enhanced mechanical interlocking effects, and provided secondary reaction sites for MPS grafting. The thiol groups (–SH) in MPS formed covalent bonds with PI-NA resin through thiol-ene click reactions, further strengthening interfacial bonding. The results showed that the ILSS, IFSS, and flexural strength of C-PEI@OPDA/ZW/MPS modified carbon fiber composites reached 75.15 MPa, 102.93 MPa, and 1735.56 MPa, representing improvements of 39.09%, 48.79%, and 31.16%, respectively. This study effectively enhanced the carbon fiber-reinforced polymer composites interfacial bonding strength through the synergistic effects of hydrogen bonding, mechanical interlocking, chemical bonding, and increased resin crosslinking density.