富氮高能物质BTATz的热分解动力学和分解机理  

Study on thermal decomposition kinetics and mechanism of nitrogen-rich compound BTATz

作　　者：张兴高[1] 朱慧[1] 阳世清[1] 张炜[1] 赵凤起[2] 刘子如[2] 潘清[2] 

机构地区：[1]国防科技大学航天与材料工程学院,湖南长沙410073 [2]西安近代化学研究所,陕西西安710065

出　　处：《推进技术》2007年第3期322-326,共5页Journal of Propulsion Technology

基　　金：国家自然科学基金委员会-中国工程物理研究院"NSAF"联合基金资助(10376042);火炸药燃烧国防科技重点实验室基金项目资助(51455010104KG0101)

摘　　要：为获得富氮高能物质3,6-双(1氢-1,2,3,4-四唑-5-氨基)-1,2,4,5-四嗪(BTATz)的热分解动力学参数、热分解机理函数、气相和凝聚相变化,为建立燃烧过程数学模型提供关键性热化学、热力学和化学动力学参数,通过热重(TG)、差示扫描量热(DSC)和气体(固体)原位反应池/快速扫描傅里叶变换红外光谱(RSFTIR)联用技术,研究了BTATz的热分解。实验结果显示BTATz的热分解过程对压强不敏感。基于Ozawa,Kissinger和Coats-Redfern方法,计算获得了BTATz的热分解动力学参数和方程。Kissinger法求得的活化能Ea和指前因子lgA分别为317.41 kJ.mol-1和28.07s-1。热分解反应机理服从n=1.5的Avrami-Erofeev方程,其热分解反应的动力学方程为dαdt=1.5×1028.07exp(-3.8178×104/T)(1-α)[-1n(1-α)]1/3。分析提出了BTATz的热分解机理,BTATz的热分解是从四嗪和四唑环的开环断裂开始的,分解产物又发生二次反应,465℃热分解凝聚相产物为NH4N3,聚胺和嘧嘞胺。　To obtain the thermal decomposition kinetics parameter,mechanism function and gas（solid） phase product of nitrogen-rich high energetic material 3,6-bis（1H-1,2,3,4-tetrazol-5-yl-amino）-1,2,4,5-tetrazine（BTATz） which can provide pivotal thermochemistry,thermodynamics and kinetic parameters for modeling the combustion process.The thermal decomposition of BTATz was investigated by using themogravimetry（TG）,differential scanning calorimetry（DSC） and gas（solid） in-situ thermolysis rapid scanning Fourier transform infrared spectroscopy（RSFTIR） coupling technique.The results show that the thermal decomposition characteristics of BTATz is insensitive to pressure.The thermal decomposition kinetic parameters and equation of BTATz are obtained based on Ozawa,Kissinger and Coats-Redfern method.Based on Kissinger method,the Ea and lgA values are 317.41kJ·mol^-1,28.07s^-1,respectively.The kinetic equation of BTATz can be expressed as dα/dt=1.5×10^28.07exp（-3.8178×10^4/T）（1-α）[-1n（1-α）]^1/3.The possible thermal decomposition mechanism of BTATz is presented.The primary step in the thermal decomposition of BTATz is the opening of the tetrazine and tetrazole ring.Then the products have the secondary reation.The solid residue consists of NH4N3,polyamine and melem at 465 ℃.

关 键 词：高能推进剂 富氮化合物^+ 热分解 动力学 分解机理^+ 红外光谱 

分 类 号：V512[航空宇航科学与技术—航空宇航推进理论与工程]