Flame-retardant and thermal management structures have attracted great attention due to the requirement of high-temperature exposure in industrial, aerospace, and thermal power fields, but the development of protective fire-retardant structures with complex shapes to fit arbitrary surfaces is still challenging. Herein, we reported a rotation-blade casting-assisted 3D printing process to fabricate nacre-inspired structures with exceptional mechanical and flame-retardant properties, and the related fundamental mechanisms are studied. 3-(Trimethoxysilyl)propyl methacrylate (TMSPMA) modified boron nitride nanoplatelets (BNs) were aligned by rotationblade casting during the 3D printing process to build the "brick and mortar"architecture. The 3D printed structures are more lightweight, while having higher fracture toughness than the natural nacre, which is attributed to the crack deflection, aligned BN (a-BNs) bridging, and pull-outs reinforced structures by the covalent bonding between TMSPMA grafted a-BNs and polymer matrix. Thermal conductivity is enhanced by 25.5 times compared with pure polymer and 5.8 times of anisotropy due to the interconnection of a-BNs. 3D printed heat-exchange structures with vertically aligned BNs in complex shapes were demonstrated for efficient thermal control of high-power light-emitting diodes. 3D printed helmet and armor with a-BNs show exceptional mechanical and fire-retardant properties, demonstrating integrated mechanical and thermal protection.
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