Flame-Retardant ABS Composites for 3D Printing: Synergistic Effects of Phosphorus-Based Additives

In this study, the effects of the type and content of phosphorus-based flame retardants, namely melamine polyphosphate (MPP) and aluminum diethylphosphinate (AlDPi), as well as their hybrid systems (MPP:AlDPi ratios of 1:1, 1:3, and 3:1), on the fire performance of acrylonitrile-butadiene-styrene (ABS) composites were investigated. The obtained results indicate that the synergistic action of MPP and AlDPi, including simultaneous inhibition of combustion in the gas phase and action in the condensed phase, leads to a significant improvement in the fire-retardant properties of ABS composites. For unmodified ABS, the peak Heat Release Rate (pHRR) and Total Heat Released (THR) values were 808.7 kW/m² and 86.5 MJ/m², respectively, while for the ABS/MPP_15/AlDPi_5, these values decreased to 292.9 kW/m² and 32.3 MJ/m². Simultaneously, the Effective Heat of Combustion (EHC) decreased from 22.3 to 15.5 MJ/kg, indicating inhibition of combustion processes in the gas phase. Fourier Transform Infrared Spectroscopy (FTIR) analysis of post-combustion residues (peaks 1280 and 1168 cm⁻¹) confirmed the contribution of additives to the formation of phosphorous derivatives in the condensed phase. The hybrid system ABS/MPP_15/AlDPi_5 exhibited the most favorable fire performance in cone calorimeter tests, characterized by reduced heat release and fire growth parameters. This was confirmed by the calculated fire performance indicators, including Fire Growth Rate Index (FIGRA), Maximum Average Rate of Heat Emission (MARHE), Fire Potential Index (FPI), and Flame Retardancy Index (FRI).