Oliwa Rafał, Bulanda Katarzyna, Oleksy Mariusz
Faculty of Chemistry, Department of Polymer Composites, Rzeszow University of Technology, Al. Powstańców Warszawy 6, 35-959 Rzeszów, Poland.
Materials (Basel). 2025 Jul 7;18(13):3202. doi: 10.3390/ma18133202.
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 (-40.3%), MARHE = 234 kW/m (-40.7%), FIGRA = 3.1 kW/m·s (-56.3%), FPI = 0.061 m·s/kW (+64.9%), FRI = 2.068 (+106.8%).
作为这项工作的一部分,开发了用于快速成型的聚合物复合材料,特别是用于采用材料挤出技术的3D打印。为此,选择了一种聚合物基体,即丙烯腈-丁二烯-苯乙烯(ABS)三元共聚物,以及一种阻燃剂,即四(2,6-二甲基苯基)-间苯二酚双磷酸酯,商品名为PX200。研究了所引入添加剂的存在及用量(5、10、15和20 wt.%)对ABS基复合材料的流变性能、结构性能、燃烧性(极限氧指数,LOI;UL94)和阻燃性能(微型锥形量热仪,MLC)的影响。此外,使用热重分析(TGA)和MLC测试后残留物的傅里叶变换红外光谱(FT-IR)研究了热降解和阻燃机理。在工作的第一部分,使用作者的工艺生产线,从未填充的ABS及其复合材料中获得了长丝。测试样品通过熔融沉积建模(FDM)技术进行3D打印获得。为了确定火灾的定量和定性蔓延以及所生产复合材料中磷阻燃剂PX200的有效性,测定了最大平均热释放速率(MARHE)、火灾增长速率指数(FIGRA)、火灾潜力指数(FPI)和阻燃指数(FRI)。根据所得结果发现,本工作中使用的芳基双磷酸酯在气相中表现出活性,这通过使用微型锥形量热仪的数据以及700℃燃烧和热解后的无残留物进行定量评估得到证实。结果,燃烧等级没有变化(HB40),对于阻燃剂含量为20%的复合材料,LOI略有增加至20%。此外,该复合材料的燃烧指数如下:pHRR = 482.9 kW/m(-40.3%),MARHE = 234 kW/m(-40.7%),FIGRA = 3.1 kW/m·s(-56.3%),FPI = 0.061 m·s/kW(+64.9%),FRI = 2.068(+106.8%)。