不同粒径黑火药点火过程中与纤维素壳体材料的热相互作用

doi:10.12382/bgxb.2022.1060

摘要/Abstract

摘要：

为了研究点火装置中纤维素外壳对不同粒径黑火药固相反应放热特性、反应气相产物、点火燃烧特性等方面的影响,制备系列黑火药/纤维素复合物样品,并采用扫描电子显微镜表征其微观结构和形貌。通过同步热分析仪和傅里叶变换红外光谱仪联用,研究纤维素对黑火药热反应性能的影响。用氧弹量热仪测量各样品的爆热,利用综合燃烧诊断系统(高速相机和高速红外热像仪)获得黑火药及其纤维素复合物燃速与火焰温度分布。研究结果表明:纤维素会降低黑火药放热量,当纤维素含量为33.33%时,两种黑火药的总放热量分别降低了66.4%和58.5%;纤维素并未改变黑火药热解路径;黑火药的主要气相产物分别为H₂O、CO₂和NO₂,与纤维素复合后除浓度变化外,气相产物种类保持不变;纤维素仅影响黑火药能量释放过程,但对不同粒径黑火药的能量释放影响的差别较小,与纤维素复合后能量释放变化仅相差3.1%。实验研究发现,小粒径黑火药及其纤维素复合物燃烧更剧烈,火焰面积更大、燃温更高;纤维素对黑火药的燃烧起消极作用,主要是降低黑火药的燃速和火焰辐射强度,火焰温度分别降低273.7℃和299.4℃;黑火药及其纤维素复合物的凝聚相产物形貌表明纤维素一定程度上促进了黑火药凝相产物团聚,即纤维素会降低其燃烧效率。

关键词: 黑火药, 热相互作用, 分解产物, 燃速, 火焰结构

Abstract:

In order to study the effect of cellulose shell on the thermal behaviors, including pyrolysis gaseous products, ignition and combustion characteristics of black powder with different particle sizes, a series of black powder/cellulose composite samples are prepared. Various characterization techniques, including scanning electron microscopy(SEM), simultaneous thermal analysis (DSC-TG-FTIR), X-ray diffraction (XRD), bomb calorimetry, and home-made combustion diagnostic system, are used to investigate the prepared composites and their combustion condensed products (CCPs). The results show that the overall heat releases of two black powders are decreased by 66.4% and 58.5% with the cellulose content of 33.3%, respectively. Moreover, the gas phase product analysis shows that the cellulose does not change the pyrolysis pathways of black powder, of which gas-phase products mainly include H₂O, CO₂ and NO₂. The cellulose only affects the energy release process of black powder, but has little effect on the energy release of black powder with different particle sizes, the difference between the energy release changes of these two composites is only 3.1%. It is found that the black powder with smaller particle size and its cellulose composite burns more violently, with larger flame area and higher combustion temperature. However, the cellulose has a negative effect on the combustion performance of black powder, mainly reducing the burning rate and flame radiation intensity of black powder, and decreasing the flame temperature by 273.7℃ and 299.4℃. In addition, the cellulose promotes the agglomeration of condensed phase products of black powder and reduces its combustion efficiency.

Key words: black powder, thermal interaction, decomposition product, burning rate, flame structure

中图分类号:

TJ55
V512

李玉雪, 田小涛, 马伊凡, 刘佩进, 严启龙. 不同粒径黑火药点火过程中与纤维素壳体材料的热相互作用[J]. 兵工学报, 2024, 45(5): 1582-1592.

LI Yuxue, TIAN Xiaotao, MA Yifan, LIU Peijin, YAN Qilong. Thermal Interaction Mechanisms of Black Powders with Different Particle Sizes and Cellulose as Packing Material during Ignition[J]. Acta Armamentarii, 2024, 45(5): 1582-1592.

图/表 13

表1 所测样品基本配方

Table 1 Formulations of the test samples

样本	质量比例				黑火药粉体体积平均粒径/μm
样本	C	S	KNO₃	XWS	黑火药粉体体积平均粒径/μm
HY-2	15	10	75		17.3
HY-5	15	10	75		12.4
HY-2/XWS	15	10	75	50	17.3
HY-5/XWS	15	10	75	50	12.4
HY-2/XWS	15	10	75	33.3	17.3
HY-5/XWS	15	10	75	33.3	12.4

图1 黑火药及其纤维素复合物的SEM图像

Fig.1 SEM morphologies of rawmaterials and prepared composites

图2 黑火药及其纤维素复合物分解的TG/DTG和DSC曲线(升温速率5℃/min)

Fig.2 The DSC and TG/DTG curves of black powder and its cellulose composites(heating rate: 5℃/min)

表2 黑火药及其纤维素复合物在5℃/min氩气气氛加热速率下的TG/DTG 参数

Table 2 TG/DTG parameters of black powder and the corresponding composites at a heating rate of 5℃/min in Ar atmosphere

样本	TG参数				DTG参数
样本	T_i/℃	T_o/℃	T_e/℃	ML/%	T_p/℃	L_max/(%·℃^-1)
HY-2-1st	190.0	195.3	215.0	3.4	192.5	-0.18
HY-2-2nd	345.0	345.2	442.5	29.3	407.5	-0.50
HY-5-1st	167.5	170.4	195.0	3.3	180.0	-0.17
HY-5-2nd	340.0	373.9	450.0	24.6	390.0	-0.40
HY-2/XWS-1st	177.8	188.2	220.3	19.3	200.3	-0.70
HY-2/XWS-2nd	337.8	359.7	420.3	20.2	395.3	-0.30
HY-5/XWS-1st	177.5	189.4	216.3	19.6	190.0	-0.70
HY-5/XWS-2nd	335.0	344.9	417.5	18.5	382.5	-0.30

表3 黑火药及其纤维素复合物热分解DSC参数

Table 3 DSC parameters of black powder and corresponding composites under Ar atmosphere

样本	放热峰		T_p1-T_i/℃	ΔH/ (J·g^-1)
样本	T_i/℃	T_p1/T_p2/℃	T_p1-T_i/℃	ΔH/ (J·g^-1)
HY-2	344.4	409.4/none	65.0	3108.0
HY-5	341.8	387.3/none	45.5	2569.0
HY-2/XWS	180.3	200.3/397.8	20.0	215.2/830.2
HY-5/XWS	181.3	198.8/391.3	17.5	274.7/719.8

图3 分解气相产物红外吸收光谱图

Fig.3 Decomposition of infrared absorption spectra of gas phase products

表4 黑火药及其纤维素复合物的爆热

Table 4 The heat of detonation of black powder and corresponding composites J/g

参数	样品
参数	HY-2	HY-5	HHY-2/XWS	HHY-5/XWS
爆热	2621.0	2615.1	2395.0	2335.4
归一化热	2621.0	2615.1	3592.4	3503.0

图4 黑火药及其纤维素复合物稳定燃烧火焰结构

Fig.4 Igniting pyrotechnics and its cellulose composites stabilizing the combustion flame structure

图5 黑火药及其纤维素复合物燃烧过程与燃速

Fig.5 The combustion process and combustion rate of black powder and its cellulose-based composites

图6 黑火药及其纤维素复合物连续火焰图像

Fig.6 Continuous flame images of black powder and its cellulose composites

图7 火焰特征点温度随时间的变化曲线

Fig.7 Temperature change curves of flame landmarks over time

图8 凝聚相燃烧产物的SEM图像

Fig.8 SEM images of combustion product of the condensed phase

图9 黑火药及其纤维素复合物凝相燃烧产物的XRD光谱

Fig.9 XRD spectra of combustion products of black powder and its cellulose composites

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