Thermal Stability Evaluation and Thermal Decomposition Mechanism of Hydroxylamine Nitrate
LIU Jianguo1, AN Zhentao1,2, ZHANG Qian1,2, DU Shiguo1,2, YAO Kai1, WANG Jin3
1 Department of Ammunition Engineering, Ordnance Engineering College, Shijiazhuang 050003; 2 Military Key Laboratory for Ammunition Support and Safety Evaluation, Ordnance Engineering College, Shijiazhuang 050003; 3 Centre of Material Thermal Analysis, Tsinghua University, Beijing 100084
Abstract: To evaluate the thermal stability of oxidizer hydroxylamine nitrate (HAN), the standard aluminum crucibles for liquid was used, and DSC measurements of hydroxylamine nitrate were performed using simultaneous thermal analysis at heating rates of 3 K/min, 4 K/min, 5 K/min. With the help of parameter values from the non-isothermal DSC curves of HAN, the thermal decomposition activation energy and pre-exponential constant were obtained by Kissinger method and Ozawa method. The self-acce-lerating decomposition temperature and thermal explosion temperature were calculated by Zhang-Hu-Xie-Li formula, Hu-Yang-Liang-Xie formula, Hu-Zhao-Gao method and Zhao-Hu-Gao method. And the most probable mechanism was studied. To study thermal decomposition mechanism, seven different paths of the thermal decomposition mechanism of hydroxylamine nitrate were designed, and density functional theory (DFT) with B3LYP/6-311++G (d, p) methods was used to carry out the kinetic analysis and thermodynamic analysis. The calculation results showed that TSADT=370.05 K, Tbe0=388.68 K,and Tbp0=397.54 K. Differential form of the most probable mechanism is 公式. Path 6, Path 5, Path 4 and Path 1 which produce NO and NO2 were supported in priority, and Path 2, Path 7 and Path 3 which produce N2 and N2O were supported in secondary place. When the temperature was below 373 K, the reaction of Path 1′ could not occur spontaneously, and thermal decomposition of hydroxylamine nitrate could not be spontaneous. From the perspective of thermodynamics, it is safe for hydroxylamine nitrate storage at 370.05 K.
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2017, Vol. 31 
