A novel strategy was developed for the preparation of melamine polyphosphate (MPP) nanowires to achieve a superior flame‐retardant poly (ethylene terephthalate) (PET). Thanks to the well‐designed nanostructure, the prepared MPP nanowires exhibited great thermal stability and flame retardance. Herein with incorporation of only 1‐wt% MPP nanowires (PET/FR1.0 nanocomposite), the limiting oxygen index (LOI) value was dramatically increased to 29.4% from 20.5%, showing self‐extinguishing behavior. Moreover, PET/FR1.0 nanocomposite passed V‐0 UL‐94 rating in the vertical combustion test. However, PET containing 5‐wt% commercial MPP powder (PET/FRC5.0) only showed a LOI of 27.9% and ignited the absorbent cotton with flammable melt‐droplets. Cone results also presented that introducing 1‐wt% MPP nanowires brought about a crucial decrease in fire hazard of PET, for instance, 11.1% and 7.7% maximum reduction in heat release rate and total heat release, respectively. Thermogravimetric analysis/infrared spectrometry (TG‐FTIR) result indicated that the main pyrolysis volatiles generated from PET degradation including benzoic acid, aromatic compounds, and carbon dioxide were apparently suppressed after introducing MPP nanowires into PET matrixes, suggesting the outstanding obstructing effect of graphited char residue formed in the combustion. This enhanced flame retardancy rooting in addition of MPP nanowires can be attributed to the combined dilution effect in gaseous phase and catalytic carbonization effect in condensed phase.
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