Thermal Degradation and Flame Resistance Mechanism of Phosphorous-Based Flame Retardant of ABS Composites Used in 3D Printing Technology

用于3D打印技术的ABS复合材料中磷基阻燃剂的热降解和阻燃机理

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Abstract

As part of the work, polymer composites dedicated to rapid prototyping were developed, especially for 3D printing using the material extrusion technique. For this purpose, a polymer matrix was selected, which was an acrylonitrile-butadiene-styrene (ABS) terpolymer and a flame retardant, which was tetrakis (2,6-dimethylphenyl)-m-phenylenebisphosphate, commercially known as PX200. The effect of the presence and amount (5, 10, 15 and 20 wt.%) of the introduced additive on the rheological properties, structural properties, flammability (limiting oxygen index, LOI; UL94) and flame retardant properties (microcone calorimeter, MLC) of ABS-based composites was investigated. In addition, the mechanism of thermal degradation and flame resistance was investigated using thermogravimetric analysis, TGA and Fourier transform infrared spectroscopy, FT-IR of the residue after the MLC test. In the first part of the work, using the author's technological line, filaments were obtained from unfilled ABS and its composites. Samples for testing were obtained by 3D printing in Fused Deposition Modeling (FDM) technology. In order to determine the quantitative and qualitative spread of fire and the effectiveness of the phosphorus flame retardant PX200 in the produced composites, the Maximum Average Rate of Heat Emission (MARHE); Fire Growth Rate Index (FIGRA); Fire Potential Index (FPI) and Flame Retardancy Index (FRI) were determined. Based on the obtained results, it was found that the aryl biphosphate used in this work exhibits activity in the gas phase, which was confirmed by quantitative assessment using data from a microcone calorimeter and non-residues after combustion and thermolysis at 700 °C. As a result, the flammability class did not change (HB40), and the LOI slightly increased to 20% for the composite with 20% flame retardant content. Moreover, this composite was characterized by the following flammability indices: pHRR = 482.9 kW/m(2) (-40.3%), MARHE = 234 kW/m(2) (-40.7%), FIGRA = 3.1 kW/m(2)·s (-56.3%), FPI = 0.061 m(2)·s/kW (+64.9%), FRI = 2.068 (+106.8%).

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