Study of Thermal Stability of HMX Affected by 19-acetoxyl-2468-tetranitro-tetraaza Nonane

doi:10.3969/j.issn.1000-1093.2014.10.007

Abstract

Abstract: 1,9-acetoxyl-2,4,6,8-tetranitro-tetraaza nonane(AcAn) is one of the major impurities of HMX production. It is important to study the thermal stability of HMX affected by AcAn. The geome-trical structure of AcAn is optimized at B3LYP/6-311+G** level and two stable structures are obtained. Bond decomposition energy (BDE) of N—NO₂ of AcAn molecular is calculated at B3P86/6-31G** level, and it is found that N—NO₂ bond adjacent to acetoxy group in the end of AcAn is easy to cleave. The thermal decomposition of AcAn and the thermal stability of HMX affected by AcAn are studied. It is found that the poor compatibility of HMX-AcAn is level 4. The HMX has good stability, but the AcAn has poor stability. The stability of AcAn-HMX mixture of 50wt% AcAn is the worse. HMX product mixed with AcAn has the worse thermal stability and performance. When the content of AcAn in the AcAn-HMX mixture is more than 50wt%, the change of performance of HMX is the biggest. The most probable mechanism function is deduced by double equal double step method, and the thermal decomposition mechanism function is chemistry reaction mechanism. The integral function is g(a)=1-(1-a)^1-n1-n, and the differential function is (a)=(1-a)ⁿ ,n=2.

Key words: ordnance science and technology, AcAn, HMX, thermal decomposition, bond decomposition energy, most probable mechanism function

CLC Number:

TQ56

LI Li-jie, JIN Shao-hua, CHEN Shu-sen, ZHU Jia-ping, YANG Wei, SUN Lei. Study of Thermal Stability of HMX Affected by 19-acetoxyl-2468-tetranitro-tetraaza Nonane[J]. Acta Armamentarii, 2014, 35(10): 1562-1568.

References

［1］ Lee J S, Hsu C K, Chang C L. A study on the thermal decomposition behaviors of PETN, RDX, HNS and HMX[J]. Thermochimica Acta, 2002:392-393,173-176.
[2] 黄亨建，董海山，舒远杰，等.HMX中晶体缺陷的获得及其对热感度和热安定性的影响[J].含能材料，2003，11（3）：123-126.
HUANG Heng-jian, DONG Hai-shan, SHU Yuan-jie, et al. The preparation of HMX crystals with defects and the influences of crystal defects on thermal sensitivity and stability［J］. Energetic Materials, 2003,11(3):123-126. (in Chinese)
[3] Keshavarz M H. Simple method for prediction of activation energies of the thermal decomposition of nitramines[J]. Journal of Hazardous Materials, 2009,162(2):1557-1562.
[4] 姜富灵,翟高红,丁黎,等.NO₂,OH和OH^-对环四甲撑四硝胺初始热解的影响［J］.物理化学学报,2010,26(2):409-414.
JIANG Fu-ling, ZHAI Gao-hong, DING Li, et al. Effects of NO₂, OH and OH^- on the initial pyrolysis of β-octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine［J］. Acta Phys Chim Sin,2010,26(2): 409-414. (in Chinese)
[5] 宋秀铎,赵凤起,王江宁,等.3,3-二叠氮甲基氧丁环与3-叠氮甲基-3-甲基氧丁环均聚物的嵌段共聚物热分解机理及非等温裂解动力学分析［J］.兵工学报，2011，32（11）：1320-1326.
SONG Xiu-duo, ZHAO Feng-qi,WANG Jiang-ning,et al. Thermal decomposition mechanism and non-isothermal pyrolysis kinetic analysis of BAMO-AMMO copolymer［J］. Acta Armamentarii, 2011，32（11）：1320-1326. (in Chinese)
[6] 贾会平,白木兰.HMX的热分解及其自催化作用［J］.兵工学报，1993，14(4)：53-57.
JIA Hui-ping, BAI Mu-lan. Thermal decomposition of HMX and its autocalysis［J］. Acta Armamentarii, 1993，14(4)：53-57. (in Chinese)
[7] 金韶华,松全才.黑索今、奥克托今和有机阻燃剂混合物的热分解研究［J］.火炸药学报,1999,22(1):27-30.
JIN Shao-hua, SONG Quan-cai. Thermal decomposition of the mixture of RDX, HMX and organic flame retardants［J］. Chinese Journal of Explosives and Propellants,1999,22(1):27-30. (in Chinese)
[8] 刘进全,欧育湘,王艳飞,等.六硝基六氮杂异伍兹烷中杂质的结构表征及热分解研究［J］.兵工学报，2007，28（1）：122-124.
LIU Jin-quan, OU Yu-xiang, WANG Yan-fei, et al. A study of structure characterization and thermal decomposition of the impurities of HNIW［J］. Acta Armamentarii, 2007,28(1):122-124. (in Chinese)
[9] 金韶华,陈树森,雷向东.HNIW与二甲基甲酰胺、二甲基亚砜分子加合物的研究［J］.兵工学报,2008，29（1）：90-93.
JIN Shao-hua, CHEN Shu-sen, LEI Xiang-dong. Investigation of adducts of HNIW with DMF and DMSO［J］. Acta Armamentarii, 2008,29(1):90-93. (in Chiense)
[10] 汤崭,任雁,杨利,等.一种判定RDX热分解机理函数与热安全性的方法［J］.火炸药学报,2011，34（1）：19-24.
TANG Zhan, REN Yan, YANG Li, et al. A new way to estimate the thermal decomposition mechanism function and thermal safety of RDX［J］. Chinese Journal of Explosives and Propellants, 2011，34（1）：19-24. (in Chinese)
[11] 李伟明.醋酐法生产HMX工艺研究［D］.太原：中北大学,2009.
LI Wei-ming.Study on process of HMX by acetic anhydride method［D］. Taiyuan: North University of China,2009. (in Chinese)
[12] 张芳沛，张红，刘子江，等.含能材料中键离解能的密度泛函理论计算[J].原子与分子物理学报，2005，22（1）:168-170.
ZHANG Fang-pei, ZHANG Hong, LIU Zi-jiang, et al. Calculations of bond dissociation energies and dipole moments in energetic materials density functional methods[J]. Journal of Atomic and Molecular Physics, 2005, 22(1):168-170. (in Chinese)
[13] 王罗新，刘勇，庹新林，等.H⁺、NH⁺₄对HMX的N-NO₂键解离能的影响[J].物理化学学报，2007，23（10）：1560-1564.
WANG Luo-xin, LIU Yong, TUO Xin-lin, et al. Effect of H⁺ and NH⁺₄ on the N-NO₂ bond dissociation energy of HMX [J]. Acta Physico-Chimica Sinica,2007,23(10): 1560-1564. (in Chinese)
[14] Chakraborty D, Muller R P, Dasgupta S, et al. Mechanism for unimolecular decomposition of HMX(1,3,5,7-tetranitro-1,3,5,7-tetrazocine), an ab initio study[J]. The Journal of Physical Chemistry A,2001,105(8):1302-1314.
[15] Zhou T T, Huang F L. Effects of defects on thermal decomposition of HMX via ReaxFF molecular dynamics simulation[J]. The Journal of Physical Chemistry B, 2011,115(2):278-287.
[16] Isayev O, Gorb L, Qasim M, et al. Ab initio molecular dynamics study on the initial chemical events in nitramines: thermal decomposition of CL-20[J]. The Journal of Physical Chenristry B,2008,112(35):11005-11013.
[17] 金韶华,松全才.炸药理论［M］.西安：西北工业大学出版社，2010.
JIN Shao-hua, SONG Quan-cai. Theory of explosive［M］. Xi'an: Northwestern Polytechnical University Press,2010. (in Chinese)

[1]	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.
[2]	XU Ruixuan, XU Jiaxing, XUE Zhihua, LÜ Jieyao, YAN Qilong. Preparation and Thermal Decomposition Properties of Multi-scale Interface-Tunable Al/RDX Energetic Composites [J]. Acta Armamentarii, 2023, 44(3): 691-701.
[3]	HUANG Longjie, LIU Rui, GAO Feiyan, CHEN Pengwan. Dynamic Tensile Deformation and Failure Mechanism of β-HMX Single Crystal With Defect Distribution [J]. Acta Armamentarii, 2023, 44(12): 3872-3883.
[4]	FENG Xiaojun， XUE Lexing， FENG Bo， PAN Wen. Preparation of HMX/Al Composite Particles with “Surface Embedded and Inner Coated” Microstructure bySpray Coating and Its Applied Performance [J]. Acta Armamentarii, 2021, 42(8): 1631-1637.
[5]	QI Xiao-fei, XIE Wu-xi, YAN Qi-long, LIU Qing, LIU Chun. Interfacial Interaction Between NPBA and HMX [J]. Acta Armamentarii, 2017, 38(10): 1942-1949.
[6]	MAO Ming, WANG Jian-bing. Research on Influence of Breakwater on Hydrodynamic Characterisitics of Displacement Amphibious Vehicles [J]. Acta Armamentarii, 2016, 37(9): 1553-1560.
[7]	GAO Jun-qiang, TANG Xia-qing, HUANG Xiang-yuan, CHENG Xu-wei. FEA Method for Analysis of SINS Error Caused by Vibration Isolation System [J]. Acta Armamentarii, 2016, 37(9): 1570-1577.
[8]	NI Yan-jie， CHENG Nian-kai, JIN Yong， YANG Chun-xia， LI Hai-yuan， LI Bao-ming. Numerical Simulation on Pressure Wave in a 30mm Electrothermal-chemical Gun [J]. Acta Armamentarii, 2016, 37(9): 1578-1584.
[9]	LU Ye, ZHOU Ke-dong, HE Lei, LI Jun-song, HUANG Xue-ying. Research on Influence of Muzzle Brake Efficiency on a New Large Caliber Machine Gun Based on Floating Principle [J]. Acta Armamentarii, 2016, 37(9): 1585-1591.
[10]	LIU Guo-qing， XU Cheng. The Study of Bullet-Barrel Matching Design Method of High Precision Sniper Rifle [J]. Acta Armamentarii, 2016, 37(9): 1592-1598.
[11]	LI Zhen-xiao， ZHANG Ya-zhou， NI Yan-Jie， LI Bao-ming. Analysis on the Influence of Turn-off Characteristics of Thyristor on Augmented Railgun [J]. Acta Armamentarii, 2016, 37(9): 1599-1605.
[12]	HU Ming, WANG Jiong, WU Xiao-lang. Estimation Method for Storage Life of Magnetorheological Fluid Fuze Arming Device [J]. Acta Armamentarii, 2016, 37(9): 1606-1611.
[13]	ZHOU Peng， CAO Cong-yong， DONG Hao. Analysis of Interior Ballistic Characteristics and Muzzle Flow Field of High-pressure Gas Launcher [J]. Acta Armamentarii, 2016, 37(9): 1612-1616.
[14]	ZHAO Xue-wei， YU Yong-gang， MANG Shan-shan. Influence of Injection Pressure Change on Expansion Characteristics of Pulsed Plasma Jet [J]. Acta Armamentarii, 2016, 37(9): 1617-1623.
[15]	LIN Xiang-yang, LI Han, ZHENG Wen-fang, PAN Ren-ming. Formation Mechanism of Pore Structure of Ball Propellant with Micro-pores Made by Double Emulsion Method [J]. Acta Armamentarii, 2016, 37(9): 1633-1638.