原子层沉积氧化物包覆层对奥克托金感度的影响

doi:10.7503/cjcu20141009

摘要/Abstract

摘要：

通过原子层沉积(ALD)技术在微米级奥克托今(HMX)炸药颗粒表面包覆了氧化铝和氧化锌薄膜. 采用X射线光电子能谱和扫描电子显微镜对包覆后HMX颗粒的表面化学组成和形貌进行了表征, 利用差示扫描量热法和热重法分析了包覆后HMX的热分解行为. 测试了ALD氧化物包覆的HMX的机械感度和静电火花感度, 研究了HMX颗粒表面包覆层的组成和厚度对其感度的影响. 结果表明, ALD氧化铝或氧化锌薄膜均能够完整、均匀地覆盖HMX颗粒的全部外表面, 薄膜厚度在纳米尺度范围内精确可调. ALD氧化铝或氧化锌薄膜对HMX的热分解性能影响很小. 由于金属氧化物具有很高的硬度, ALD氧化铝或氧化锌包覆膜不能降低HMX的机械感度. 但氧化物薄膜具有一定的导电性, 可降低HMX的静电火花感度.

关键词: 原子层沉积(ALD), 奥克托今(HMX), 感度, 氧化铝, 氧化锌

Abstract:

Micron-scale Octogen(HMX) particles were coated by alumina and zinc oxide thin films via atomic layer deposition(ALD). The surface chemical compositions and morphologies of ALD metal oxides coated HMX particles were characterized by X-ray photoelectron spectroscopy(XPS) and scanning electron microscopy(SEM). The thermal decomposition behaviors of the fabricated HMX particles were analyzed by differential scanning calorimetry(DSC) and thermogravimetry(TG) techniques. The mechanical sensitivity and electrostatic spark sensitivity of the metal oxides coated HMX were tested. The influences of film composition and thickness on the sensitivities of HMX were analyzed. The results indicate that the HMX particles are completely and uniformly encapsulated by ALD alumina or zinc oxide thin films. The thickness of the encapsulation layer can be precisely controlled in nanometer-scale. The thin films of metal oxides have little influence on the thermal decomposition properties of HMX. Due to the hardness of the metal oxides, ALD encapsulation layers do not decrease the mechanical sensitivity of HMX. However, the inorganic ALD coatings increase the surface electrical conductivity of HMX particles and therefore reduce the electrostatic spark sensitivity.

Key words: Atomic layer deposition(ALD), Octogen(HMX), Sensitivity, Alumina, Zinc oxide

中图分类号:

TrendMD:

秦利军, 龚婷, 郝海霞, 王克勇, 冯昊. 原子层沉积氧化物包覆层对奥克托金感度的影响. 高等学校化学学报, 2015, 36(3): 420.

QIN Lijun, GONG Ting, HAO Haixia, WANG Keyong, FENG Hao. Influences of Metal Oxide Encapsulation by Atomic Layer Deposition on the Sensitivities of Octogen^†. Chem. J. Chinese Universities, 2015, 36(3): 420.

图/表 6

Table 1 Thicknesses of ALD oxide coatings on AAO*

ALD cycles	m₁/mg	m₂/mg	△m/mg	△m/m₁(%)	h/nm
150-cycle Al₂O₃	11.0	14.2	3.20	29.1	18.0
150-cycle ZnO	5.50	8.40	2.90	52.7	17.5
300-cycle ZnO	7.50	14.7	7.20	96.0	34.5
50-cycle Al₂O₃ + 150-cycle ZnO	11.6	20.3	8.70	75.0	23.5

Table 2 Thicknesses of ALD oxide coatings on HMX

ALD cycles	Mass increase(%)	h/nm	ALD cycles	Mass increase(%)	h/nm
150-cycle Al₂O₃	2.65	22.7	300-cycle ZnO	4.61	20.8
300-cycle Al₂O₃	4.80	41.2	50-cycle Al₂O₃ + 150-cycle ZnO	4.00	20.6
150-cycle ZnO	1.44	6.5	50-cycle Al₂O₃ + 300-cycle ZnO	7.50	36.4

Fig.1 XPS spectra of unmodified HMX and the HMX coated with Al2O3(A, B) and ZnO(C, D) (A), (C) Survey scans; (B), (D) N1s precision scans.

Fig.2 SEM images of unmodified HMX particles(A, B) and the HMX coated by 300-cycle Al2O3(C, D),50-cycle Al2O3+300-cycle ZnO(E, F) and 300-cycle ZnO(G, H) (A), (C), (E), (G): SEM images after the first scan; (B), (D), (F), (H) SEM images after the second scan.

Fig.3 DSC(A) and TG(B) curves of unmodified HMX(a) and the HMX coated with 150-cycle Al2O3(b), 300-cycle Al2O3(c), 50-cycle Al2O3+150-cycle ZnO(d) and 50-cycle Al2O3+300-cycle ZnO(e) (B) t0/℃: a. 252; b. 243; c. 228; d. 211; e. 216.

Table 3 Sensitivities of the HMX coated with ALD metal oxides

Sample	Impact sensitivity, H₅₀/cm	Friction sensitivity, P(%)	Electrostatic spark sensitivity, E₅₀/mJ
HMX	26.3	96	29.9
HMX+150-cycle Al₂O₃	30.9	100	69.0
HMX+300-cycle Al₂O₃	19.5	100	73.5
HMX+50-cycle Al₂O₃ +150-cycle ZnO	20.4	92	45.9
HMX+50-cycle Al₂O₃ +300-cycle ZnO	9.1	100	37.4

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