物理化学学报 >> 2013, Vol. 29 >> Issue (08): 1623-1631.doi: 10.3866/PKU.WHXB201305282

热力学，动力学和结构化学 上一篇    下一篇

从DSC曲线数据计算/确定含能材料自催化分解反应动力学参数和热爆炸临界温升速率的方法

胡荣祖1, 赵凤起1, 高红旭1, 姚二岗1, 张海2, 王尧3, 常象宇3, 赵宏安4   

  1. 1 西安近代化学研究所燃烧与爆炸技术重点实验室, 西安 710065;
    2 西北大学数学系/数据分析和计算化学研究所, 西安 710069;
    3 西安交通大学信息科学与系统科学研究所, 西安 710049;
    4 西北大学信息科学与工程学院, 西安 710069
  • 收稿日期:2013-04-08 修回日期:2013-05-27 发布日期:2013-07-09
  • 通讯作者: 胡荣祖 E-mail:hurongzu88@163.com
  • 基金资助:

    国家自然科学基金(21173163)资助项目

Method to Determine the Kinetic Parameters of the Autocatalytic Decomposition Reaction and Critical Rate of Temperature Rise of Thermal Explosion of Energetic Materials from DSC Curves

HU Rong-Zu1, ZHAO Feng-Qi1, GAO Hong-Xu1, YAO Er-Gang1, ZHANG Hai2, WANG Yao3, Chang Xiang-Yu3, ZHAO Hong-An4   

  1. 1 Science and Technology on Combustion and Explosion Laboratory, Xi’an Modern Chemistry Research Institute, Xi’an 710065, P. R. China;
    2 Department of Mathematics/Institute of data analysis and computation chemistry, Northwest University, Xi’an 710069, P. R. China;
    3 Institute for Information Science and System Science, Xi’an Jiaotong University, Xi’an 710049, P. R. China;
    4 College of Communication Science and Engineering, Northwest University, Xi’an 710069, P. R. China
  • Received:2013-04-08 Revised:2013-05-27 Published:2013-07-09
  • Contact: HU Rong-Zu E-mail:hurongzu88@163.com
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21173163).

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摘要：

为应用热爆炸临界温升速率(dT/dt)Tb评价含能材料(EMs)的热安全性, 得到计算(dT/dt)Tb值的基本数据, 用合理的假设, 由Semenov的热爆炸理论和9 个自催化反应速率方程[dα/dt=Aexp(-E/RT)α(1-α) (I), dα/dt=Aexp(-E/RT)(1-α)n(1+Kcatα) (II), dα/dt=Aexp(-E/RT)[αa-(1-α)n)] (III), dα/dt=A1exp(-Ea1/RT)(1-α)+A2exp(-Ea2/RT)α(1-α) (IV), dα/dt=A1exp(-Ea1/RT)(1-α)m+A2exp(-Ea2/RT)αn(1-α)p (V), dα/dt=Aexp(-E/RT)(1-α) (VI), dα/dt=Aexp(-E/RT)(1-α)n (VII), dα/dt=A1exp(-Ea1/RT)+A2exp(-Ea2/RT)(1-α) (VII), dα/dt=A1exp(-Ea1/RT)+A2exp(-Ea2/RT)α(1-α) (IX)]导出了计算(dT/dt)Tb值的9 个表达式. 提出了从不同恒速升温速率(β)条件下的差示扫描量热(DSC)曲线数据计算/确定EMs自催化分解反应的动力学参数和自催化分解转向热爆炸时的(dT/dt)Tb的方法. 由DSC曲线数据的分析得到了用于计算(dT/dt)Tb值的β→0 时的onset 温度(Te0),热爆炸临界温度(Tb)和相应于Tb时的转化率(αb). 分别用线性最小二乘法和信赖域方法得到方程(I)和(VI)及方程(II)-(V)和方程(VII)-(IX)中的自催化分解反应动力学参数. 用上述基础数据得到了EMs的(dT/dt)Tb值. 结果表明: (1) 在非等温DSC条件下硝化棉(NC, 13.54% N)分解反应可用表观经验级数自催化反应速率方程dα/dt=1015.82exp(-170020/RT)(1-α)1.11+1015.82exp(-157140/RT)α1.51(1-α)2.51描述; (2) NC (13.54% N)自催化分解转向热爆炸时的(dT/dt)Tb值为0.103 K·s-1.

关键词: 临界温升速率, 非等温DSC, 热爆炸, 硝化棉, 信赖域方法

Abstract:

To evaluate the thermal safety of energetic materials (EMs) using the critical rate of temperature rise of thermal explosion (dT/dt)Tb and obtain basic data used to calculate (dT/dt)Tb, nine expressions to calculate (dT/dt)Tb for EMs were derived from Semenov thermal explosion theory and nine autocatalytic reaction rate equations, dα/dt=Aexp(-E/RT)α(1-α) (I), dα/dt=Aexp(-E/RT)(1-α)n(1+Kcatα) (II), dα/dt=Aexp(-E/RT)[αa-(1-α)n] (III), dα/dt=A1exp(-Ea1/RT)(1-α)+A2exp(-Ea2/RT)α(1-α) (IV), dα/dt=A1exp(-Ea1/RT)(1-α)m+A2exp(-Ea2/RT)αn(1-α)p (V), dα/dt=Aexp(-E/RT)(1-α) (VI), dα/dt=Aexp(-E/RT)(1-α)n (VII), dα/dt=A1exp(-Ea1/RT)+A2exp(-Ea2/RT)(1-α) (VII) and dα/dt=A1exp(-Ea1/RT)+A2exp(-Ea2/RT)α(1-α) (IX), using reasonable hypotheses. A method to determine the kinetic parameters in the nine autocatalytic decomposition reaction rate equations and (dT/dt)Tb of EMs when autocatalytic decomposition converts into thermal explosion from difference scanning calorimetry (DSC) curves at different heating rates (β) was presented. The onset temperature (Te0) corresponding to heating rate β→0, the critical temperature of thermal explosion (Tb) and the conversion degree (αb) corresponding to Tb used in the calculation of (dT/dt)Tb were obtained from analysis of DSC curves. The kinetic parameters of the autocatalytic decomposition reactions in Eqs.(I) and (VI), and Eqs.(II)-(V), (VII)-(IX) were estimated by the linear least-squares method and trust region approach, respectively. The values of (dT/dt)Tb for EMs were obtained from basic DSC data. Results show that (1) under non-isothermal DSC conditions, the autocatalytic decomposition reaction of nitrocotton (NC) (13.54% N) can be described by the apparent empiric-order equation dα/dt=1015.82exp(-170020/RT)(1-α)1.11+1015.82exp(-157140/RT)α1.51(1-α)2.51; (2)The value of for NC (13.54% N) when autocatalytic decomposition converts into thermal explosion is 0.103 K·s-1.

Key words: Critical rate of temperature rise, Non-isothermal DSC, Thermal explosion, Nitrocotton, Trust region approach