GDY/HMX复合含能材料的热分解动力学和机理  

Thermal Decomposition Kinetics and Mechanism of GDY/HMX Composite Energetic Materials

作　　者：赵宁宁[1] 曾见有 姚二岗[3] 安亭[3] 马海霞[2] 赵凤起[3] ZHAO Ning-ning;ZENG Jian-you;YAO Er-gang;AN Ting;MA Hai-xia;ZHAO Feng-qi(School of Science,Xi'an University of Technology,Xi'an 710054,China;College of Chemical Engineering,Northwest University,Xi'an 710069,China;Science and Technology on Combustion and Explosion Laboratory,Xi'an Modern Chemistry Research Institute,Xi'an 710065,China)

机构地区：[1]西安理工大学理学院,陕西西安710054 [2]西北大学化工学院,陕西西安710069 [3]西安近代化学研究所燃烧与爆炸技术重点实验室,陕西西安710065

出　　处：《火炸药学报》2022年第5期679-687,共9页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.21673179);陕西省自然科学基础研究计划资助项目(No.2018JQ2077,No.2021JM-322);陕西省教育厅科研计划项目(No.19JK0595);西安理工大学博士科研启动基金(No.109-451117004)。

摘　　要：为探讨石墨二炔(GDY)对环四亚甲基四硝胺(HMX)热分解特性的影响,制备了GDY/HMX(质量比1∶4)含能复合物,运用差示扫描量热法(DSC)和热重-红外-质谱联用技术(TG/DTG-FTIR-MS)对比研究了HMX和GDY/HMX的热分解过程;采用Kissinger法、FWO法、KAS法、Starink法、Kissinger-迭代法及Ozawa-迭代法计算HMX和GDY/HMX的表观活化能,并引入修正后的esták-Berggren经验方程对其热分解反应动力学模型进行重建。结果表明,GDY使HMX的表观活化能降低73.6kJ/mol。GDY/HMX复合物的热分解过程遵循n级动力学方程f(α)=3.04α^(0.39)(1-α)^(1.17);在GDY催化作用下,HMX热分解以C—N键断裂为主,首先释放出C_(2)HO和N_(2)O,还检测到NO、NO_(2)、HCN、CO、N_(2)、HCNO、CO_(2)和H_(2)O气体。To explore the effect of graphdiyne(GDY)on the thermal decomposition characteristics of HMX,the GDY/HMX(mass ratio of 1∶4)composite energetic materials was prepared,and the differential scanning calorimetry(DSC)and the thermogravimetry coupled with Fourier transform infrared spectrometry and mass spectrometry(TG/DTG-FTIR-MS)technique were employed to investigate the pyrolysis processes of the HMX and GDY/HMX comparatively.The apparent activation energies of HMX and GDY/HMX were calculated by Kissinger,FWO,KAS,Starink,Kissinger-iterative,and Ozawa-iterative methods,and the modified esták-Berggren empirical equation was used to reconstruct the kinetic models of their thermal decomposition reactions.The results show that the apparent activation energy of HMX is reduced by 73.6kJ/mol in the presence of GDY.The pyrolysis process of the GDY/HMX composite follows the n-order kinetic equation f(α)=3.04α^(0.39)(1-α)^(1.17).GDY plays a crucial role in promoting the C—N bond cleavage during HMX decomposition,leading to the release firstly of the C_(2)HO and N_(2)O.And the gaseous products including NO,NO_(2),HCN,CO,N_(2),HCNO,CO_(2),and H_(2)O are also detected.

关 键 词：物理化学 石墨二炔 GDY 热分解动力学 催化活性 TG/DTG-FTIR-MS 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O64[理学—物理化学]