High-energy explosives prompt stringent control over their experimental environment, which limits the feasibility of conducting experiments. This study explores the use of melamine (Me), a safe material with a structure and physical properties similar to 1,3,5-triamino-2,4,6-trinitrobenzene (TATB), as a substitute for TATB in composite formulations aimed at improving the thermal conductivity of polymer-bonded explosives (PBXs). In waterborne polyurethane emulsion (WPU), graphene oxide (GO) was reduced and self-assembled into graphene aerogels (GA) on the surface of Me, resulting in the formation of Me@GA/PU (MGP) particles with a core-shell structure. The GA surface coating enhanced the interfacial bonding between the thermally conductive fillers (GA) and Me, improving the dispersion of the fillers within the composite. After freeze-drying and hot pressing, cylinders of MGP with a segregated thermally conductive network were obtained. The segregated network, formed by GA at low filler loading, provided an effective pathway for heat transfer and improved the thermal stability of the composites. The thermal conductivity of the MGP composite, prepared with 0.5 wt.% GO content, increased by 80% compared to the pure sample. The temperature gradient and thermal stress distribution in the composite cylinders during complex thermal cycling were evaluated using finite element analysis.
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