静电喷雾法制备纳米复合含能材料RDX@NGEC及性能

doi:10.12382/bgxb.2022.0228

摘要/Abstract

摘要：

通过静电喷雾干燥技术,以黑索金(RDX)、纤维素甘油醚硝酸酯(NGEC)为原料,以丙酮为溶剂,制备一种新型的RDX@NGEC核-壳结构纳米复合含能材料。通过扫描电子显微镜、傅里叶变换红外光谱、X射线衍射和拉曼光谱,对复合粒子的结构和组成进行表征;采用差示扫描量热法,通过Kissinger和Ozawa两种方法分别对复合材料的热分解反应动力学和热力学进行分析;另外进行撞击和摩擦感度实验研究其机械性能。研究结果表明:采用静电喷雾法制备的RDX@NGEC复合粒子形貌均匀且呈球形,具有典型的核壳结构;与原料RDX相比,复合粒子的热分解表观活化能从122.050kJ/mol提高到131.701kJ/mol,且随着NGEC含量的增加活化能逐渐增大;其中10%质量分数NGEC的添加,复合粒子的热爆炸临界温度由513.696K提高到524.989K。机械感度研究表明:NGEC可以作为有效的缓冲层赋予RDX良好的钝感效果,当比例为2∶8时撞击和摩擦感度的降低幅度最大分别可达44.1%,24.8%,安全性能大大提高。

关键词: 纳米复合含能材料, 静电喷雾, 热分解, 感度, RDX@NGEC

Abstract:

In this study, RDX and nitrate glycerol ether cellulose (NGEC) were selected as the raw materials, and acetone as the solvent to prepare precursor solution. A novel RDX@NGEC core-shell structured nanocomposite energetic material was prepared using the electrostatic spray drying technology. The structure and composition of the composite were characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), and Raman spectroscopy (Raman). Differential scanning calorimetry (DSC) was carried out to analyzed the thermal decomposition reaction kinetics and thermodynamics of the composites using the Kissinger and the Ozawa methods. In addition, impact and friction sensitivity experiments were carried out to study the mechanical properties of the composite. The results showed that the particle size of the composite RDX@NGEC prepared by electrostatic spray drying technology exhibited uniform distribution and an even spherical morphology, forming a typical core-shell structure. Besides, compared with the raw material RDX, the activation energy (E_a) of the composite increased from 122.05kJ/mol to 131.70kJ /mol, with E_a gradually increasing as the NGEC content increased. The addition of an appropriate amount of NGEC significantly increased the critical temperature of thermal explosion for the composite from 513.696K to 524.989K, thereby enhancing the safety performance.

Key words: nano-energetic composite materials, electrostatic spray, thermal decomposition, sensitivity, RDX@NGEC

李强, 陈令, 甘怀银, 朱永晨, 何卫东. 静电喷雾法制备纳米复合含能材料RDX@NGEC及性能[J]. 兵工学报, 2023, 44(7): 1985-1992.

LI Qiang, CHEN Ling, GAN Huaiyin, ZHU Yongchen, HE Weidong. Electrostatic Spraying Preparation and Performance of Nanocomposite Energetic Material RDX@NGEC[J]. Acta Armamentarii, 2023, 44(7): 1985-1992.

图/表 8

图1 RDX@NGEC复合材料的制备流程

Fig.1 Preparation of the RDX@NGEC composite

图2 原料RDX和复合颗粒的SEM图

Fig.2 SEM images of raw materials and the composite particles

图3 原料RDX和复合粒子的红外光谱曲线图

Fig.3 FTIR spectra curves of raw materials and the composite particles

图4 原料RDX和复合粒子的XRD曲线图

Fig.4 XRD curves of raw materials and the composite particles

图5 原料RDX、NGEC和复合粒子RDX@NGEC-1、RDX@NGEC-2的拉曼图谱

Fig.5 Raman spectra of raw materials RDX, NGEC, and composite particles RDX@NGEC-1 and RDX@NGEC-2

图6 NGEC、RDX、RDX@NGEC-1、RDX@NGEC-2和n-RDX在不同加热速率下的DSC轨迹图(上)和Kissinger、Ozawa(下)法热力学计算的线性拟合图

Fig.6 DSC trajectories (top) of NGEC, RDX, RDX@NGEC-1, RDX@NGEC-2 at different heating rates and the linearity of the thermodynamic calculations by Kissinger and Ozawa (bottom) methods, respectively Fitting graph

表1 热力学、动力学和热稳定性参数

Table 1 Thermodynamics, kinetics and thermal stability parameters

样品	T_p/K	热力学参数			动力学参数				热稳定性
样品	T_p/K	ΔH^≠/ (kJ·mol^-1)	ΔG^≠/ (kJ·mol^-1)	ΔS^≠/ (J·mol^-1·K^-1)	E_a/(kJ·mol^-1) Kissinger	E_a/(kJ·mol^-1) Ozawa	lnA_k	k	T_b/K
NGEC	465.3	133.063	122.840	21.970	136.931	137.898	33.545	0.157	479.245
RDX	495.72	117.929	131.285	-26.942	122.050	124.261	27.725	0.151	513.696
n-RDX	502.96	133.224	149.005	-31.376	137.406	138.900	27.207	0.00351	519.276
1	507.59	127.481	149.556	-43.490	131.701	133.493	25.759	0.00430	524.989
2	496.07	133.081	149.900	-33.904	137.206	138.749	26.889	0.00170	511.952

图7 样品的机械感度

Fig.7 Mechanical sensitivity of the samples

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