Rapid Identification of Autocatalysis Characteristics in Energetic Materials Decomposition Reactions

Chuan PING; Qiang GAN; Rui ZHANG; Zhenhua DU; Changgen FENG

doi:10.12382/bgxb.2021.0592

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Rapid Identification of Autocatalysis Characteristics in Energetic Materials Decomposition Reactions

更新时间：2025-08-18

- Rapid Identification of Autocatalysis Characteristics in Energetic Materials Decomposition Reactions
- Acta Armamentarii Vol. 44, Issue 2, Pages: 368-379(2023)
- 作者机构：
  
  1. 北京理工大学爆炸科学与技术国家重点实验室, 北京 100081
  2. 西安航天化学动力有限公司, 陕西西安 710025
  3. 陕西应用物理化学研究所应用物理化学重点实验室, 陕西西安 710061
- 作者简介：
- 基金信息：
- DOI：10.12382/bgxb.2021.0592
  CLC：
- Received：01 September 2021，
  
  Published Online：10 March 2023，
  
  Published：28 February 2023
- 稿件说明：
移动端阅览
Chuan PING, Qiang GAN, Rui ZHANG, et al. Rapid Identification of Autocatalysis Characteristics in Energetic Materials Decomposition Reactions[J]. Acta Armamentarii, 2023, 44(2): 368-379.
DOI：

Chuan PING, Qiang GAN, Rui ZHANG, et al. Rapid Identification of Autocatalysis Characteristics in Energetic Materials Decomposition Reactions[J]. Acta Armamentarii, 2023, 44(2): 368-379. DOI： 10.12382/bgxb.2021.0592.

摘要

含能材料的自催化特性是造成含能材料极具危险性的主要原因之一

常用的自催化反应鉴别方法是利用差示扫描量热仪(DSC)、微热量热仪(C80)进行的“等温法”试验

该方法温度选择较为困难

试验周期较长且具有一定的危险性

有必要寻找一种快捷安全的自催化反应鉴别方法。基于绝热量热试验

结合反应机理函数

提出可快速鉴别含能材料自催化分解特性的方法

并利用该方法测量5种样品(过氧化二叔丁基(DTBP)与甲苯混合溶液、六硝基茋-Ⅳ(HNS-Ⅳ)、双(5-硝基四唑)合钴(Ⅲ)(BNCP)、六硝基六氮杂异伍兹烷(CL-20)、羧甲基纤维素叠氮化铅(CMC-LA)的绝热热分解特性。测量和分析结果表明:DTBP与甲苯混合溶液的热分解符合

级反应规律

HNS-Ⅳ、BNCP、CL-20、CMC-LA的热分解符合自催化反应规律

自催化反应强度随热惯性的增加而降低;新方法不需要计算准确的反应动力学参数

在自催化反应进行的初期就能完成自催化特性的鉴别

减少了测量时间的同时大大降低了测量过程的危险性

可快速鉴别物质分解是否有自催化特性

并可准确表征反应的自催化特性强度。

Abstract

Autocatalysis is one of the major reasons that make energetic materials extremely dangerous. The commonly used methods for identifying autocatalytic reactions is the “isothermal methods” based on differential scanning calorimetry (DSC) and microcalorimetry (C80). However

for these methods

temperature selection is one difficult problem

and the test period is long with some danger. So it is necessary to find a fast and safe method for the identification of autocatalytic reactions. This study proposes a method to quickly identify the characteristics of autocatalytic reactions and determine the reaction strength based on adiabatic thermal tests combined with reaction mechanism functions

which is used to measure the adiabatic thermal decomposition characteristics of five samples (20% DTBP and toluene mixed solution

HNS-IV

BNCP

CL-20

and CMC-LA). This method does not require the calculation of accurate reaction kinetic parameters

can identify the autocatalytic characteristics at the early stage of the autocatalytic reactions which reduces the measurement time and greatly reduces the risk in the process

and can quickly identify whether autocatalysis is involved in the decomposition of the substance and accurately characterize the autocatalytic intensity of the reactions.

关键词

Keywords

references

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王凯 , 肖松 , 申孝立 , 等 . 六硝基六氮杂异戊兹烷自催化分解特性与热安全性研究 [J ] . 兵工学报 , 2018 , 39 ( 1 ): 57 - 62 . (in Chinese) DOI: 10.3969/j.issn.1000-1093.2018.01.006 http://doi.org/10.3969/j.issn.1000-1093.2018.01.006 六硝基六氮杂异戊兹烷（CL-20）是一种十分重要的新型单质炸药，其热分解安全性一直备受关注。利用动态差示扫描量热（DSC）仪进行实验，初步研究了CL-20的热行为；利用中断回归法、瑞士方法研究了CL-20的自催化反应特性，并用等温DSC实验进行了验证；基于CL-20的动态DSC曲线数据，采用Friedman法求得其活化能Eα与ln\[Af(α)\]值随转化率α的变化曲线，并结合热平衡方程计算了其绝热诱导期TMRad. 结果表明：CL-20的起始分解温度为233.5~255.7 ℃，其分解反应为自催化反应，热履历显著降低了其起始分解温度和峰温；在反应的不同阶段，CL-20具有不同的活化能，其绝热诱导期8 h和24 h对应的温度TD8和TD24分别为162.3 ℃和152.8 ℃.

WANG K , XIAO S , SHEN X L , et al. Research on autocatalytic thermal decomposition properties and thermal safety of CL-20 [J ] . Acta Armamentarii , 2018 , 39 ( 1 ): 57 - 62 . (in Chinese) DOI: 10.3969/j.issn.1000-1093.2018.01.006 http://doi.org/10.3969/j.issn.1000-1093.2018.01.006 Hexanitrohexaazaisowurtzitane (CL-20) is a very important type of explosive, and its thermal decomposition safety has been paid attention. Differential scanning calorimetry (DSC) technique is employed to study the thermal decomposition and safety parameters of CL-20. The “interruption-rescanning ” and Swiss methods are further applied to evaluate the autocatalytic effect of CL-20 during thermal decomposition, which is verified by isothermal DSC experiments. The decomposition kinetic parameters of CL-20 are determined by using the Friedman isoconversional method. The kinetic parameters with heat balance are analyzed and used to simulate the time to the maximum reaction rate under adiabatic conditions (TMRad). It is indicated that the initial thermal decomposition temperature is in the range from 233.5 to 255.7 ℃ at the heating rates of 2, 5, 10 and 20 ℃/min. Thermal history significantly influences the thermal stability of CL-20, where the preheating decreases its initial thermal decomposition temperature and the peak temperature. TD8 and TD24 of CL-20 were obtained to be 162.3 ℃ and 152.8 ℃, respectively. Key

刘剑超 , 姜雨彤 , 张同来 , 等 . 动态真空安定性方法评估 LA和CMC-LA热安定性 [J ] . 含能材料 , 2015 , 23 ( 10 ): 1020 - 1023 .

LIU J C , JIANG Y T , ZHANG T L , et al. Evaluation of the thermal stability of LA and CMC-LA by dynamic vacuum stability test method [J ] . Chinses Journal of Energetic Materials , 2015 , 23 ( 10 ): 1020 - 1023 . (in Chinese)

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