摘要
为了评估甲基肼液体推进剂在生产、贮存、运输以及使用过程中的热安全,借助差示扫描量热法(DSC)研究了甲基肼的热分解特性和热安全性,分别计算了甲基肼的动力学、热力学和热安全性参数,并获得了半径为1 m的球形甲基肼液体推进剂在不同超临界环境温度下的热爆炸延滞期,基于等转化率法使用AKTS软件进一步计算得到了甲基肼的绝热诱导期以及自加速分解温度。结果表明:甲基肼的热分解过程只有一个较强的放热峰,采用Kissinger法和Ozawa法计算得到甲基肼的活化能值分别为159.13 kJ·mol^(-1)和158.89 kJ·mol^(-1),自加速分解温度为451.53 K,热爆炸临界温度为469.55 K,热力学参数活化熵(ΔS^(≠))、活化焓(ΔH^(≠))和吉布斯活化自由能(ΔG^(≠))分别为73.93 J·mol^(-1),155.32 kJ·mol^(-1)和121.46 kJ·mol^(-1);使用AKTS软件计算得到8、24 h和168 h绝热诱导期对应的温度分别为429.55,424.05 K和414.95 K;包装质量分别为5,25,50 kg和100 kg时,甲基肼的自加速分解温度依次为415.15,414.15,413.15 K和412.15 K。研究结果为评价甲基肼在生产、储运和使用过程中的热安全性提供了必要的理论基础。
The thermal decomposition characteristics and thermal safety of methylhydrazine(MMH)were studied by means of differential scanning calorimetry(DSC).The kinetics,thermodynamics and thermal safety parameters of MMH were calculated,respectively.The thermal explosion delay period of MMH of ball shaped with radius of 1 m at different supercritical ambient tem‑peratures were also obtained.Based on the isoconversion rate method,the adiabatic induction period and self‑accelerating decomposition temperature of MMH were further evaluated by using AKTS software.The results show that the thermal decomposition process of MMH has only one strong exothermic peak.The apparent activation energy values of MMH calculated by Kissinger and Ozawa methods are 159.13 kJ·mol^(-1) and 158.89 kJ·mol^(-1),respectively.The values of Tbp0 of MMH is 469.55 K.The values of entropy of activation(ΔS^(≠)),enthalpy of activation(ΔH^(≠)),and free energy of activation(ΔG^(≠))are 73.93 J·mol^(-1),155.32 kJ·mol^(-1) and 121.46 kJ·mol^(-1),respectively.The corresponding temperatures for adiabatic induction period at 8,24 h and 168 h are 429.55,424.05 K and 414.95 K,respectively.When the packing mass was 5,25,50 kg and 100 kg,the self‑accelerating decomposition temperatures of MMH are 415.15,414.15,413.15 K and 412.15 K in turn.The results provide the necessary theoretical basis for evaluating the thermal safety of MMH in the processes of production,storage,transportation and use.
作者
徐飞扬
吴星亮
王旭
罗一民
马腾
刘大斌
徐森
XU Fei-yang;WU Xing-liang;WANG Xu;LUO Yi-min;MA Teng;LIU Da-bin;XU Sen(School of Chemistry and Chemical Engineering,Nanjing University of Science and Technology,Nanjing 210094,China)
出处
《含能材料》
EI
CAS
CSCD
北大核心
2022年第2期171-177,共7页
Chinese Journal of Energetic Materials
基金
装备预研国防科技重点实验室基金项目(6142603200509,6142603180408)。
关键词
甲基肼
热分解特性
动力学参数
热力学参数
绝热诱导期
自加速分解温度
methylhydrazine
thermal decomposition characteristics
kinetic parameters
thermodynamic parameters
adiabatic induction period
self-accelerating decomposition temperature
