CHINESE JOURNAL OF ENERGETIC MATERIALS
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复合固体推进剂高温加速试验理论与方法(1)——Arrhenius方程的适用性
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航天化学动力技术重点实验室, 湖北航天化学技术研究所, 湖北 襄阳 441003

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Theories and Methodology of High Temperature Accelerated Test for Composite Solid Propellants (Ⅰ): The Applicability of Arrhenius Equation
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Science and Technology on Aerospace Chemical Power Laboratory,Hubei Institute of Aerospace Chemotechnology, Xiangyang 441003, China

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    摘要:

    国内外普遍采用高温加速试验方法,以Arrhenius方程作为动力学模型评估聚合物材料包括复合固体推进剂的老化性能和贮存寿命。近年来,Arrhenius方程在复合固体推进剂老化和寿命评估的适用性受到一些质疑。为探讨Arrhenius方程的适用性问题,本文综述了Arrhenius方程在国内外固体推进剂贮存老化评估中的应用情况,从理论源头梳理了Arrhenius方程的形成过程和相关参数物理意义,指出了目前在Arrhenius方程理论认识和应用上的误区。理论分析表明,在Arrhenius方程形式下,频率因子和活化能两个参数之一是温度的函数;对于固体推进剂,现行标准允许的加速试验温度范围内活化能可视为定值。应用Arrhenius方程应符合下述条件:1)研究所涉及的温度范围内老化机理可视为一致;2)各加速试验温度下,老化程度相当;3)参数k应符合速率常数的物理意义。性能随时间变化的数学模型中参数k不符合速率常数定义,使用应慎重,推荐使用性能对数模型替代。

    Abstract:

    The Arrhenius equation has been widely used as kinetics model for predicating aging property and shelf life of polymer materials by extrapolating high temperature accelerated test data. However, the suitability of the equation to composite solid propellants was questioned. Therefore the application history of the Arrhenius equation on aging of composite solid propellants has been reviewed. By combing the theoretical evolution process of Arrhenius equation, physical meaning of the equation parameters was clarified, and the misunderstanding on the equation was revealed. Theoretical analysis shows that only one of the two parameters (frequency factor and activation energy) is relative to temperature in the Arrhenius equation, and the parameters can be regarded as constants to solid propellants aged between the highest acceleration temperature allowed by current industry-standard and room temperature. The following conditions should be met to apply the Arrhenius equation: 1) it can be considered as the same aging mechanism in the range of temperatures involved in, 2) it has similar aging levels at the deadline of different acceleration temperatures, and 3) it has a parameter k with physical meaning of rate constant exactly. Mathematical models with logarithmic time are unsuitable to fit performance-time relationship, while those with logarithmic performance are suitable.

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引用本文

池旭辉,彭松,赵程远,等.复合固体推进剂高温加速试验理论与方法(1)——Arrhenius方程的适用性[J].含能材料, 2022, 30(8):853-860. DOI:10.11943/CJEM2022115.
CHI Xu-hui, PENG Song, ZHAO Cheng-yuan, et al. Theories and Methodology of High Temperature Accelerated Test for Composite Solid Propellants (Ⅰ): The Applicability of Arrhenius Equation[J]. Chinese Journal of Energetic Materials, 2022, 30(8):853-860. DOI:10.11943/CJEM2022115.

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历史
  • 收稿日期: 2022-04-30
  • 最后修改日期: 2022-07-20
  • 录用日期: 2022-07-11
  • 在线发布日期: 2022-07-12
  • 出版日期: 2022-08-25