含能材料自催化分解特性的快速鉴别方法

doi:10.12382/bgxb.2021.0592

摘要/Abstract

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n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。

关键词: 含能材料, 自催化, 快速鉴别, 反应机理函数, 反应强度, 绝热量热法

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.

Key words: energetic materials, autocatalysis, rapid identification, reaction mechanism function, reaction strength, adiabatic calorimetry

中图分类号:

TQ560.1

平川, 甘强, 张蕊, 都振华, 冯长根. 含能材料自催化分解特性的快速鉴别方法[J]. 兵工学报, 2023, 44(2): 368-379.

PING Chuan, GAN Qiang, ZHANG Rui, DU Zhenhua, FENG Changgen. Rapid Identification of Autocatalysis Characteristics in Energetic Materials Decomposition Reactions[J]. Acta Armamentarii, 2023, 44(2): 368-379.

图/表 13

表1 常见的固体自催化反应机理函数

Table 1 Common autocatalytic reaction mechanism functions for solid

简称	反应类型	机理函数
$B 1$ ^[13]	简单的P-T反应	α(1-α)
$B n a$ ^[14]	扩展的P-T反应	α³(1-α)ⁿ
$C n - x$ ^[15]	复合式自催化反应	(1-α)ⁿ(1-K_catX)
$A n$ ^{[16⇓⇓-19]}	成核式A-E反应	n(1-α)[-ln(1-α)]⁽ⁿ^-1)^/n

表1 常见的固体自催化反应机理函数

Table 1 Common autocatalytic reaction mechanism functions for solid

简称	反应类型	机理函数
$B 1$ ^[13]	简单的P-T反应	α(1-α)
$B n a$ ^[14]	扩展的P-T反应	α³(1-α)ⁿ
$C n - x$ ^[15]	复合式自催化反应	(1-α)ⁿ(1-K_catX)
$A n$ ^{[16⇓⇓-19]}	成核式A-E反应	n(1-α)[-ln(1-α)]⁽ⁿ^-1)^/n

图1 不同机理函数f(αn)/f(α1)随转化率α变化的计算结果

Fig.1 Calculation of different mechanism functions f(αn)/f(α1) with the conversion rate α

表2 4种常见反应类型的dT/dt的表达式

Table 2 Expressions for dT/dt for several common reaction types

反应类型	dT/dt表达式
n级反应	$d T d t$ = $Q ∞ c p φ$ A $e - E a / (R T)$ (1-α)ⁿ
P-T反应	$d T d t$ = $Q ∞ c p φ$ A $e - E a / (R T) α n 1$ (1-α $) n 2$
C_nm反应	$d T d t$ = $Q ∞ c p φ$ A $e - E a / (R T)$ [(1-α $) n 1$ +K_cat(1- α $) n 1 α n 2$ ]
A-E反应	$d T d t$ = $Q ∞ c p φ$ A $e - E a / (R T)$ n(1-α)[-ln(1- α) $] n - 1 n$

表2 4种常见反应类型的dT/dt的表达式

Table 2 Expressions for dT/dt for several common reaction types

反应类型	dT/dt表达式
n级反应	$d T d t$ = $Q ∞ c p φ$ A $e - E a / (R T)$ (1-α)ⁿ
P-T反应	$d T d t$ = $Q ∞ c p φ$ A $e - E a / (R T) α n 1$ (1-α $) n 2$
C_nm反应	$d T d t$ = $Q ∞ c p φ$ A $e - E a / (R T)$ [(1-α $) n 1$ +K_cat(1- α $) n 1 α n 2$ ]
A-E反应	$d T d t$ = $Q ∞ c p φ$ A $e - E a / (R T)$ n(1-α)[-ln(1- α) $] n - 1 n$

图2 φ=1时dT/dt随T变化

Fig.2 dT/dt varies with T for φ=1

表3 仿真计算参数

Table 3 Parameters used in the simulations

参数	数值
A	10³²
E_a/(kJ·mol^-1)	133.2
T_on/℃	100
C_p/(J·g^-1·k^-1)	2.5
R/(J·mol^-1·k^-1)	8.314
Q_∞/(kJ·kg^-1)	1000
K_cat	30
n	1

图3 不同热惯性下5种反应机理的dT/dt随α变化

Fig.3 Variation of dT/dt with α for five reaction mechanisms with different thermal inertia

图4 热惯性对4种反应机理函数初始转化率的影响

Fig.4 Effect of thermal inertia on the initial conversion rate of the four reaction mechanism functions

图5 不同热惯性下5种反应机理函数随α变化

Fig.5 Variation of the five reaction mechanism functions with α for different thermal inertia

表4 模拟计算自催化机理函数的f(αn)/f(α1)最大值

Table 4 Calculated maximum value of f(αn)/f(α1) by the autocatalytic mechanism function

热惯性	P-T反应	C_nm反应	A-E反应
φ=1	3.21	5.60	2.10
φ=2	1.74	3.69	1.45
φ=3	1.27	2.77	1.19
φ=4	1.07	2.21	1.07
φ=5	1.04	1.87	1.01
φ=6	1	1.62	1

图6 5种样品的热分解初始阶段放热曲线

Fig.6 Exothermic curves for the initial stages of thermal decomposition of the five samples

图7 5种样品的f(αn)/f(α1)计算值

Fig.7 Calculated values of f(αn)/f(α1) for the five samples

表5 f(αn)/f(α1)值的计算条件

Table 5 Conditions for calculating the value of f(αn)/f(α1)

样品	E_a/ (kJ·mol^-1)	选用放热曲线φ值
HNS-Ⅳ	100/150/200/250	27.046
BNCP	100/150/200/250	23.917
CL-20	100/150/200/250	29.851
CMC-LA	100/150/200/250	23.75

图8 不同活化能下5种样品f(αn)/f(α1)计算值

Fig.8 Calculated values of f(αn)/f(α1) for the five samples at different activation energies

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