Rapid Identification of Autocatalysis Characteristics in Energetic Materials Decomposition Reactions

doi:10.12382/bgxb.2021.0592

Abstract

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

CLC Number:

TQ560.1

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.

Figures/Tables 13

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

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

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

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) $] n - 1 n$

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) $] n - 1 n$

Fig.2 dT/dt varies with T for φ=1

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

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

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

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

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

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

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

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

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

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