Influence of Surface Modification of Fly Ashes on the Fire Behavior of Polyamide 6

This study investigates the influence of surface-modified fly ash particles on the fire behavior of polyamide 6 (PA6) composites containing two types of flame retardants: melamine polyphosphate (MPP) and aluminum diethyl phosphinate (AlPi). The objective was to evaluate how interfacial modification of fly ash using amino-silane (APTES), glycidoxy-silane (GPTES), or titanate coupling agents affects dispersion, thermal stability, and combustion performance. A series of 18 formulations containing up to 25 wt% of additives was prepared by melt compounding and characterized by thermogravimetric analysis (TGA) and cone calorimetry. TGA results showed that MPP-based systems favored char formation, with residues up to 21%, whereas AlPi provided higher thermal stability (T50% ≈ 445 °C). The incorporation of untreated or surface-treated fly ash improved both thermal stability and char yield, depending on the nature of the coupling agent. Cone calorimeter results confirmed a strong synergistic effect between flame retardants and fly ash. The peak heat release rate (pHRR) decreased by 65–75% compared to neat PA6, while total heat release (THR) and mass loss were also significantly reduced. Titanate-modified fly ash showed the most homogeneous dispersion and provided the highest residue and lowest pHRR values. Energy-dispersive X-ray (EDX) analyses confirmed enhanced phosphorus retention in the residues (up to 100%), evidencing the formation of stable inorganic species and protective ceramic-like structures. These results demonstrate that surface-modified fly ash can act as an efficient synergistic additive in PA6 flame-retardant formulations, simultaneously improving fire performance and promoting the valorization of industrial by-products for sustainable polymer design.