一种超声辅助溶剂–非溶剂法高氯酸铵/奥克托今重结晶复合物的热分析

Rapid Preparation of AP/HMX Composite by Ultrasonic-Assisted Recrystallization and Its Thermal Analysis

摘要: 以丙酮为溶剂，正丁醇和丙三醇为助剂，乙酸乙酯为非溶剂，采用超声辅助溶剂–非溶剂重结晶法快速制备了微纳米高氯酸铵(AP)/奥克托今(HMX)复合物，通过热分析及热分析动力学研究其热分解性能。通过SEM、PXRD、FTIR对晶体的形貌、结构和组成进行表征，利用TG-DSC和DSC-TG-IR对其热分解进行分析，考察了其热分析动力学参数及同步热分解产物。结果表明：所制备的AP/HMX复合物晶体粒径小于10 µm，呈较圆滑的类椭球形；HMX/AP复合物的低温分解起始温度为283.8℃，峰温294.5℃，失重率约为25%；在280℃~400℃的范围内，分解产物CO₂与N₂O的红外吸收曲线呈现出相同的变化规律，说明复合物中HMX的分解与AP的分解同步发生；AP/HMX复合物的低温分解表观活化能为106.38 kJ∙mol⁻¹，比AP提高2.94 kJ∙mol⁻¹，说明AP/HMX复合物中AP的热安定性提高；计算得到热爆炸临界温度T_b为260.6℃，比AP降低28.8℃，比HMX提高4.9℃。AP/HMX复合物的热稳定性良好。

Abstract: In order to improve the thermal stability of the complex, the micro-nano ammonium perchlorate (AP)/cyclo-tetramethylene-tetranitramine (HMX) composite energetic material was prepared by ultrasonic-assisted solvent-non-solvent recrystallization method, with acetone as solvent, n-butanol and propylene glycol as additives, and ethyl acetate as non-solvent, and its thermal decomposition properties were systematically investigated. The morphology, structure and composition of the crystals were characterized by SEM, PXRD, and FTIR, and the thermal analysis kinetic parameters and the synchronous thermal decomposition products were analyzed by TG-DSC and DSC-TG-IR. The results show that the crystal particle size of AP/HMX composite is less than 10 µm with ellipsoid-like morphology; The TG-DSC and DSC-IR analyses show that, the set on temperature of the first decomposition of AP/HMX complex is 283.8˚C with the peak temperature of 294.5˚C and the loss rate of about 25%; In the range of 280˚C to 400˚C, the infrared absorption curve of the decomposition product CO₂ shows the same change pattern as the one of N₂O, indicating that the decomposition of HMX in the complex occurs synchronously with the decomposition of AP. The thermal analysis kinetics results show that the apparent activation energy of the first decomposition of AP/HMX complex is 106.38 kJ∙mol⁻¹, which is 2.94 kJ∙mol⁻¹ higher than AP, indicating improved stability of AP in AP/HMX complex; the calculated heat explosion critical temperature T_b is 260.6˚C, which is 28.8˚C lower than AP and 4.9˚C higher than HMX. The prepared AP/HMX complex has a good thermal stability.