梯度硝基单基发射药构筑过程的Avrami模型

doi:10.12382/bgxb.2023.1190

摘要/Abstract

摘要：

梯度硝基发射药是一种绿色无烟发射药,其结构的可控构筑是复杂的物理化学过程,是决定发射药燃烧性能的核心关键。为研究梯度硝基发射药制备中反应过程的动力学模型,以圆柱粒状单基发射药为研究对象,采用液体静力称量法测试圆柱粒状单基发射药样品的密度,考察反应温度、反应液浓度对脱硝率的影响规律,借助Avrami模型研究反应过程的控制步骤,建立脱硝反应动力学方程。实验结果表明:脱硝程度越大,圆柱粒状单基发射药样品的密度越小,圆柱粒状单基发射药的脱硝反应过程符合n=0.816的Avrami模型,表观活化能为49.223kJ/mol,反应液浓度表观反应级数为1.028,脱硝反应过程由扩散和化学反应混合控制;强化化学反应效应或扩散效应,可以提高圆柱粒状单基发射药的脱硝率;所得结果为梯度硝基发射药生产工艺条件的建立提供了理论依据。

关键词: 梯度硝基发射药, 控制步骤, Avrami, 动力学方程

Abstract:

Nitro gradiently distributed propellant is a kind of environmentally friendly smokeless propellant.The controllable construction of its structure is a complex physicochemical process,which is the key to determine the combustion performance of propellant.In order to study the kinetics of reaction process of nitro gradiently distributed propellant during preparation,the cylindrical granular single-base propellant sample was used as the research object, which density was tested by the liquid static weighing method.The influence rules of denitration reaction temperature and reaction liquid concentration on the denitration rate were investigated.The control steps of the reaction process were studied by using the Avrami model,and a reaction kinetics equation was established.The experimental results showed that the bigger the degree of denitration of the cylindrical granular single-base propellant sample was,the smaller its density was.The denitration reaction process of cylindrical granular single-base propellant was consistent with the Avrami model of n=0.816,the apparent activation energy was 49.223kJ/mol,the apparent reaction order of the reaction liquid concentration was 1.028,and the denitration reaction process was controlled by the mixture of diffusion and chemical reaction.Therefore,the chemical reaction effect or diffusion effect can be strengthened to improve the denitration rate of the cylindrical granular single-base propellant.This study provides a theoretical basis for the establishment of productive process conditions for nitro gradiently distributed propellant.

Key words: nitro gradiently distributed propellant, control step, Avrami model, kinetic equation

中图分类号:

Q562⁺.21

范红蕾, 崔璠, 李杨, 李世影, 陈春林, 李纯志, 王晓倩, 肖忠良, 吴晓青. 梯度硝基单基发射药构筑过程的Avrami模型[J]. 兵工学报, 2025, 46(1): 231190-.

FAN Honglei, CUI Fan, LI Yang, LI Shiying, CHEN Chunlin, LI Chunzhi, WANG Xiaoqian, XIAO Zhongliang, WU Xiaoqing. Avrami Model for the Construction Process of Nitro Gradiently Distributed Single-base Propellant[J]. Acta Armamentarii, 2025, 46(1): 231190-.

图/表 10

图1 圆柱粒状单基发射药反应动力学研究

Fig.1 Research process of reaction kinetics of cylindrical granular single-base propellant

图2 圆柱粒状单基发射药样品截面图

Fig.2 Cross-section of cylindrical granular single-base propellant sample

表1 5种圆柱粒状单基发射药样品的密度

Table 1 Densities of five cylindrical granular single-base propellant samples

样品	反应条件			ρ/ (g·cm^-3)	α/%
样品	C/%	T'/℃	t/min	ρ/ (g·cm^-3)	α/%
原样				1.602	0
样品1	9	70	90	1.594	5.668
样品2	9	70	120	1.587	7.564
样品3	12	70	90	1.581	9.124
样品4	9	80	120	1.574	12.840

图3 不同反应温度下脱硝率随时间的变化

Fig.3 Effect of reaction temperature on denitration rate

图4 不同反应液浓度下脱硝率随时间的变化

Fig.4 Effect of reaction liquid concentration on denitration rate

图5 不同反应条件下-ln(1-α)-t的拟合曲线

Fig.5 Fitting curves of-ln(1-α)-t under different reaction conditions

表2 不同反应条件下-ln(1-α)-t的拟合结果

Table 2 Fitting effects of-ln(1-α)-t under different reaction conditions

拟合曲线编号	C/%	T'/℃	拟合关系	R²
1	6	65	-ln(1-α)=5.196×10^-4t^0.908	0.993
2	6	70	-ln(1-α)=3.597×10^-4t^1.067	0.982
3	6	75	-ln(1-α)=6.453×10^-4t^0.967	0.989
4	6	80	-ln(1-α)=1.730×10^-3t^0.824	0.979
5	9	65	-ln(1-α)=2.510×10^-3t^0.688	0.982
6	9	70	-ln(1-α)=1.290×10^-3t^0.865	0.963
7	9	75	-ln(1-α)=2.640×10^-3t^0.785	0.973
8	9	80	-ln(1-α)=5.950×10^-3t^0.657	0.990
9	12	65	-ln(1-α)=2.490×10^-3t^0.734	0.997
10	12	70	-ln(1-α)=2.240×10^-3t^0.829	0.997
11	12	75	-ln(1-α)=3.680×10^-3t^0.774	0.998
12	12	80	-ln(1-α)=9.920×10^-3t^0.595	0.985
13	15	65	-ln(1-α)=1.720×10^-3t^0.863	0.996
14	15	70	-ln(1-α)=2.350×10^-3t^0.868	0.995

图6 表观活化能的求算结果

Fig.6 Calculated results of apparent activation energy

图7 表观反应级数的求算结果

Fig.7 Calculated results of apparent reaction order

图8 脱硝过程动力学方程的建立

Fig.8 Establishment of kinetic equation of denitration process

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