Yang Fang, Chen Ya, Zhao Chuande, Zhang Long
Institute of Chemical Materials, China Academy of Engineering Physics Mianyang Sichuan 621900 China
RSC Adv. 2019 Jul 17;9(39):22198-22204. doi: 10.1039/c9ra03385h.
Thermal decomposition of a highly thermostable explosive dihydroxylammonium 2,4,8,10-tetranitro-benzopyrido-1,3,6,6-tetraazapentalene (BPTAP) was studied using conventional thermal analysis techniques (Thermal Gravimetric Analysis and Differential Scanning Calorimetry). To obtain more comprehensive insight into the kinetics mechanism of BPTAP decomposition, thermoanalytical experiments were performed under non-hermetic and hermetic conditions. Several widely used thermoanalytical data processing techniques based on model-free kinetics (Flynn-Wall-Ozawa, Kissinger, Freidman, numerical optimization) were studied and compared. Furthermore, to fully understand the thermal safety property of BPTAP, the kinetic model and the kinetic parameters were evaluated based on the non-isothermal DSC data by using a non-linear optimization method. The kinetic models of thermal decomposition of BPTAP under non-hermetic and hermetic conditions were different, which were identified as the generalized autocatalysis reaction and two parallel generalized autocatalysis reactions, respectively. On the basis of the aforementioned study, two important safety parameters including the time to maximum rate under adiabatic conditions and self-accelerating decomposition temperature for BPTAP in DEWAR were calculated and discussed.
采用传统热分析技术（热重分析和差示扫描量热法）研究了高热稳定性炸药二羟基铵2,4,8,10-四硝基苯并吡啶并-1,3,6,6-四氮杂戊搭烯（BPTAP）的热分解。为了更全面地了解BPTAP分解的动力学机制，在非密封和密封条件下进行了热分析实验。研究并比较了几种基于无模型动力学的广泛使用的热分析数据处理技术（弗林-沃尔-小泽法、基辛格法、弗里德曼法、数值优化法）。此外，为了充分了解BPTAP的热安全性能，采用非线性优化方法基于非等温DSC数据评估了动力学模型和动力学参数。BPTAP在非密封和密封条件下的热分解动力学模型不同，分别被确定为广义自催化反应和两个平行的广义自催化反应。基于上述研究，计算并讨论了两个重要的安全参数，包括绝热条件下达到最大反应速率的时间和杜瓦瓶中BPTAP的自加速分解温度。
