Design and development of smart sensors for rapid flame detection in postcombustion and early fire warning in precombustion situations are critically needed to improve the fire safety of combustible materials in many applications. Herein, we describe the fabrication of hierarchical coatings created by assembling a multilayered graphene oxide (GO)/silicone structure onto different combustible substrate materials. The resulting coatings exhibit distinct temperature-responsive electrical resistance change as efficient early warning sensors for detecting abnormal high environmental temperature, thus enabling fire prevention below the ignition temperature of combustible materials. After encountering a flame attack, we demonstrate extremely rapid flame detection response in 2-3 s and excellent flame self-extinguishing retardancy for the multilayered GO/silicone structure that can be synergistically transformed to a multiscale graphene/nanosilica protection layer. The hierarchical coatings developed are promising for fire prevention and protection applications in various critical fire risk and related perilous circumstances.

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Smart fire alarm sensor (FAS) materials with mechanically robust, excellent flame retardancy as well as ultra-sensitive temperature-responsive capability are highly attractive platforms for fire safety application. However, most reported FAS materials can hardly provide sensitive, continuous and reliable alarm signal output due to their undesirable temperature-responsive, flame-resistant and mechanical performances. To overcome these hurdles, herein, we utilize the multi-amino molecule, named HCPA, that can serve as triple-roles including cross-linker, fire retardant and reducing agent for decorating graphene oxide (GO) sheets and obtaining the GO/HCPA hybrid networks. Benefiting from the formation of multi-interactions in hybrid network, the optimized GO/HCPA network exhibits significant increment in mechanical strength, e.g., tensile strength and toughness increase of ~ 2.3 and ~ 5.7 times, respectively, compared to the control one. More importantly, based on P and N doping and promoting thermal reduction effect on GO network, the excellent flame retardancy (withstanding ~ 1200 °C flame attack), ultra-fast fire alarm response time (~ 0.6 s) and ultra-long alarming period (> 600 s) are obtained, representing the best comprehensive performance of GO-based FAS counterparts. Furthermore, based on GO/HCPA network, the fireproof coating is constructed and applied in polymer foam and exhibited exceptional fire shielding performance. This work provides a new idea for designing and fabricating desirable FAS materials and fireproof coatings.

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