Biomimetic swallow nest-inspired fabrics and derived multifunctional composite ceramics via orthogonal self-assembly and conformal modification strategies

Lightweight, heat-insulating fiber composites are highly sought after for aerospace applications, yet conventional manufacturing methods often depend on specialized feedstocks and complex spinning processes, limiting designability and multifunctionality. In this work, we present a molecular orthogonal self-assembly strategy for the energy-efficient and eco-friendly synthesis of COF&HOF fibric materials. Through biomimetic design inspired by swallow's nest architectures, we fabricated advanced fabric composites via conformal coating modifications. When integrated with ablative coatings, these fabrics demonstrate exceptional dynamic thermal management capability, exhibiting minimal backside temperature rise (ΔT < 82 °C) under butane flame exposure. Pyrolysis yields ultralight ceramics with remarkably low density (0.32 g/cm 3 ) and thermal conductivity (162.0 mW·m −1 ·K −1 ), while high-temperature annealing induces the formation of 15R–SiC single-crystalline fibers. Furthermore, incorporation of refractory compounds enables in situ conversion into high-entropy ceramic composites, featuring ultralow density (0.39 g/cm 3 ), superior thermal insulation (173.39 mW·m −1 ·K −1 ), and excellent electromagnetic wave absorption. Intriguingly, the ceramicization process triggers spontaneous hierarchical self-construction, generating nanostructures such as nanofibers, ribbons, spheres, and nanowires. This work establishes a sustainable paradigm for designing advanced artificial fabrics, high-entropy ceramics, and multifunctional composites with tailored properties for next-generation aerospace applications.