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Kinetic Characteristics of Thermal Decomposition and Thermal Safety for Methylhydrazine
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School of Chemistry and Chemical Engineering, Nanjing University of Science and Technology, Nanjing 210094, China

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    Abstract:

    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 temperatures 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.

    表 2 基于DSC曲线不同升温速率下试样放热分解反应的动力学参数Table 2 Kinetic parameters from the exothermic decomposition reaction for MMH at various heating rates based on DSC curves
    表 1 不同升温速率下甲基肼放热分解阶段的热特征参数Table 1 Thermal characteristic parameters of the exothermic decomposition stage-determined from DSC curves at various heating rates
    图1 甲基肼的DSC曲线Fig.1 DSC curves of MMH at four different heating rates
    图2 Friednman计算获得的Ea、ln(A(α)·f(α))随转化率的关系Fig.2 Relationship between Ea and ln(A(α)·f(α)) calculated by Friednman with conversion rate
    图3 甲基肼在不同起始温度下的绝热温度历程Fig.3 Adiabatic temperature courses of MMH at different starting temperatures
    图4 甲基肼在不同起始温度下的绝热诱导期Fig.4 Adiabatic induction periods of MMH at different starting temperatures
    图5 甲基肼自加速分解温度计算结果(25 kg包装)Fig.5 Calculation results of SADT of MMH(25 kg package)
    图6 甲基肼自加速分解温度与包装质量关系Fig.6 Relation between SADT temperature and packaging quality of MMH
    表 4 甲基肼在不同超临界环境温度下的延滞期Table 4 Different times to ignition under different super critical ambient temperatures for MMH
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徐飞扬,吴星亮,王旭,等.甲基肼热分解的动力学特性及热安全性[J].含能材料,2022,30(2):171-177.
XU Fei-yang, WU Xing-liang, WANG Xu, et al. Kinetic Characteristics of Thermal Decomposition and Thermal Safety for Methylhydrazine[J]. Chinese Journal of Energetic Materials,2022,30(2):171-177.

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History
  • Received:April 21,2021
  • Revised:May 16,2021
  • Adopted:July 28,2021
  • Online: March 17,2022
  • Published: February 25,2022