Synergistic Effects of Flame Retardants on the Flammability and Foamability of PS Foams Prepared by Supercritical Carbon Dioxide Foaming

[Image: see text] Halogen-free flame-retardant polystyrene (PS) foams prepared by supercritical carbon dioxide (SC-CO(2)) foaming have been achieved. The flame-retardants include expandable graphite (EG) and melamine phosphate (MP), and their influence on the foamability, decomposition behavior, fire performance, and mechanical properties of PS foams were investigated. It has been shown that flame retardants can generate inert gases and catalyze the char formation from PS, and the formed thick char layer with a notable barrier property can greatly decrease the heat release of PS foams. The addition of triphenyl phosphate (TPP) or hexaphenoxycyclotriphosphazene (HPCTP), which acts as a flame-retardant plasticizer, can obviously improve the foamability and fire performance of the foams. TPP or HPCTP can generate active phosphorous species and phenoxyl radicals to enhance the gas phase flame-retardant effect; therefore, the flame-retarded PS foams (with 25 wt % MP/EG) achieve HF1 and V-0 ratings, with limiting oxygen index (LOI) values of 30.1 or 29.6%, respectively. The numerical assessment of synergistic effects of TPP and HPCTP on further enhancing flame retardancy of PS foams has been provided by the microcalorimeter (MCC) test. Further X-ray photoelectron spectroscopy (XPS) investigation on char residues of PS foams demonstrates the formation of the P–O–C and other stable structures.