压力作用下DNTF的热分解动力学及机理研究  

Thermal decomposition kinetics and mechanism of DNTF under pressure

作　　者：周静静 祝艳龙 黄蒙 安静[1] 周静[1] 禄旭 丁黎[1] 常海[1] ZHOU Jingjing;ZHU Yanlong;HUANG Meng;AN Jing;ZHOU Jing;LU Xu;DING Li;CHANG Hai(Xi’an Modern Chemistry Research Institute,Xi’an710065,China;Institute for Hygiene of Ordance Industry,Xi’an710065,China)

机构地区：[1]西安近代化学研究所,西安710065 [2]兵器工业卫生研究所,西安710065

出　　处：《固体火箭技术》2023年第4期581-587,共7页Journal of Solid Rocket Technology

摘　　要：为了研究压力对3,4-二硝基呋咱基氧化呋咱(DNTF)热分解的影响机制,从实验测试分析和动力学模拟两方面探究了不同压力下DNTF的热分解特性和分解机理。采用高压差示扫描量热(PDSC)技术在0.1、1.0、2.0、4.0、6.0 MPa下考察了DNTF的热分解特性,并通过Kissinger方程得到了其热分解动力学参数;采用同步热分析-红外-质谱(TG/DSC-FTIR-MS)联用技术研究了DNTF的热分解产物组成及种类,推测了DNTF的热分解机理;采用耐驰热动力学软件获得了不同压力下DNTF的热分解动力学参数。结果表明:压力增大时,DNTF的分解峰温会略向高温方向移动,热分解气相产物对凝聚相产物分解的促进作用更加显著;DNTF在热分解过程中环内N—O键先断裂,产生具有催化作用的气态氮氧化物(NO、N_(2)O),经自催化反应使C—NO_(2)键断裂、呋咱环碎片和氧化呋咱环碎片进一步分解,生成CO_(2)、NO、NO_(2)及N_(2)O等气态小分子,并借助动力学模拟验证了对DNTF热分解机理的推测。In order to study the effect of pressure on the thermal decomposition of 3,4⁃dinitrofurazan oxyfurazan(DNTF),the decomposition properties and mechanism of DNTF under different pressures were explored from both experimental analysis and ki⁃netic simulation.The thermal decomposition properties of DNTF at 0.1,1.0,2.0,4.0,and 6.0 MPa were investigated by means of high pressure differential scanning calorimetry(PDSC),and its thermal decomposition kinetic parameters were obtained through Kissinger equation.Simultaneous thermal analysis⁃FTIR⁃Mass spectrometry(TG/DSC⁃FTIR⁃MS)was used to study the composition and types of decomposition products of DNTF,and to speculate the thermal decomposition mechanism.Thermal decomposition kinetics parameters of DNTF under different pressures were obtained via NETZSCH Thermokinetics Software.The results show that with the pressure in⁃creasing,the decomposition peak temperature of DNTF would move slightly to the high temperature,and gaseous products would pro⁃mote the decomposition of condensed phase products more significantly.In the thermal decomposition process of DNTF,N—O bond in rings is broken first to generate catalytic gaseous nitrogen oxides(NO,N_(2)O).Through autocatalytic reaction,C—NO_(2)bond is bro⁃ken,and segments of furoxan rings as well as oxidized furoxan rings are further decomposed to generate small gaseous molecules such as CO_(2),NO,NO_(2)and N_(2)O.The thermal decomposition mechanism of DNTF is verified by kinetic simulation.

关 键 词：DNTF 高能量密度含能材料 氧化剂 压力 分子动力学模拟 热分解 分解机理 

分 类 号：V512[航空宇航科学与技术—航空宇航推进理论与工程]