<![CDATA[This study presents the development of a low-toxicity, high-performance intumescent fire-retardant coating (IFRC) through a hybrid epoxy binder doped with Mg, Si, Al, and P particles. The objective was to improve thermal stability and char cohesion and reduce the toxic aromatic emissions typically released from bisphenol-A epoxy systems during combustion. Modified epoxy resins were prepared by dispersing Mg(OH)₂ and incorporating hydroxyl-terminated PDMS, followed by formulation with APP, melamine, expandable graphite, PER, and nano-alumina. Comprehensive analyses using FTIR, ¹³C NMR, DSC, TGA, SEM–EDS, TEM, XRD, and GC–MS, along with ISO-834 furnace and ASTM E-119 flame tests, were employed to evaluate chemical structure, thermal behavior, char morphology, and fire performance. The optimized formulation produced a dense Mg–Al–silicate–phosphate char network, achieved a 6.1× expansion ratio, limited backside steel temperature to 227°C, and retained 36% char at 800°C, which significantly outperformed the unmodified epoxy system. GC–MS confirmed a substantial (≈53%) reduction in toxic volatile emissions. A machine-learning model further validated char compactness with >94% classification accuracy. Collectively, the results demonstrate that synergistic inorganic–siloxane modification offers a scalable, halogen-free pathway to next-generation epoxy-based IFRCs with enhanced fire resistance and markedly lower toxicity.]]>
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