超细高氮化合物TAGZT的感度和热分解动力学研究

Study on the sensitivity and thermal decomposition kinetics of superfine TAGZT

利用高能球磨法制备了偶氮四唑三氨基胍盐(TAGZT)超细微晶粉末。采用扫描电子显微镜(SEM)、红外光谱(IR)、X射线衍射(XRD)、热分析(DSC)、热重分析(TG)以及机械感度试验等方法研究了原料TAGZT和超细TAGZT的微观形貌、粒度分布、结构特征、热分解机理和感度特性。结果表明,所获得的原料TAGZT呈针状,超细TAGZT呈无规则颗粒状,相比原料TAGZT,超细TAGZT粒径更小、球形度更高,中位直径d_(50)=3.60μm;细化后TAGZT的晶型和分子结构与原料TAGZT一致;超细TAGZT的活化能为159.64 kJ/mol,较原料TAGZT(204.45 kJ/mol)降低了43.97 kJ/mol,说明其受热更易分解,通过微分法计算得出超细TAGZT和原料TAGZT的热分解机理均为三维扩散,其动力学方程为球形对称的Jander方程;超细TAGZT的撞击和摩擦感度较原料TAGZT有显著降低,且两者机械感度均明显低于HMX。设计并制备了含超细TAGZT的推进剂配方,对其进行DSC测试和使用Cpro PEP软件计算能量性能,AP/GAP/superfine TAGZT有更好的热稳定性和更高的能量,为在推进剂中的应用提供参考。

The superfine microcrystalline powder of bis-(triam inoguanidinium)-5,5′-azotetrazolate(TAGZT)was prepared by high-energy ball milling method.The microscopic morphology,particle size distribution,structural characteristics,thermal decomposition mechanism and sensitivity properties of raw TAGZT and superfine TAGZT were studied by SEM,IR,XRD,DSC,TG and mechanical sensitivity tests.The results show that the obtained raw TAGZT is needle-like,and the superfine TAGZT is irregularly granular.Compared with raw TAGZT,superfine TAGZT has smaller particle size and higher sphericity,with median diameter d_(50)=3.60μm;the crystalline shape and molecular structure of the superfine TAGZT is consistent with raw TAGZT;The activation energy of superfine TAGZT is 159.64 kJ/mol,which is 43.97 kJ/mol lower than that of raw TAGZT(204.45 kJ/mol),indicating that it is more easily decomposed by heating.It is obtained through differential calculation:the thermal decomposition mechanism of superfine TAGZT and raw TAGZT is three-dimensional diffusion,and its kinetic equation is Jander equation of spherical symmetry;the impact and friction sensitivity of superfine TAGZT are significantly lower than that of raw TAGZT,and the mechanical sensitivity of both is significantly lower than that of HMX.The propellant formulation containing superfine TAGZT is designed and prepared.The DSC test is carried out and energy performance calculated by using Cpro PEP software.AP/GAP/superfine TAGZT formulation has better thermal stability and higher energy,which provides reference for its application in propellants.