纳米六硝基六氮杂异伍兹烷与三氨基三硝基苯含能复合物的制备及性能研究

doi:10.3969/j.issn.1000-1093.2020.01.006

摘要/Abstract

摘要： 为提高六硝基六氮杂异伍兹烷（CL-20）的安全性能，通过一步球磨法制得CL-20与三氨基三硝基苯（CL-20/TATB）含能复合物。采用扫描电镜（SEM）、粉末X射线衍射（XRD）、红外光谱（FT-IR）、差示扫描量热法（DSC）对原料和含能复合物的性能进行表征，并进行撞击感度测试与分析。结果表明：制备的产物不是CL-20和TATB的简单物理混合，而是生成新的晶型；在SEM图中，与原料相比，CL-20/TATB含能复合物表面更加光滑，球形化效果明显，形貌呈规则的小颗粒状，粒度分布约在50~200 nm之间；在XRD图谱中，最终产物的主要衍射峰分布明显不同于原料和简单混合物的衍射峰，有新的衍射峰出现，说明最终产物中有新的晶型出现，同时由于粒径变小导致衍射峰谱带弥散且宽化；在CL-20/TATB含能复合物的FT-IR图中，由于CL-20（—NO₂或—CH）和TATB（—NO₂或—NH₂）之间的氢键作用，导致红外谱峰发生偏移；在DSC图中，CL-20/TATB含能复合物的放热峰比原料CL-20和原料TATB的都提前，说明CL-20/TATB含能复合物的热分解活性比原料CL-20和原料TATB有所增强；撞击感度测试中，CL-20/TATB含能复合物的特性落高比CL-20高62 cm，具有更好的撞击安全性能。

关键词: 六硝基六氮杂异伍兹烷, 三氨基三硝基苯, 含能复合物, 一步球磨法, 热分解

Abstract: In order to reduce the sensitivity of 2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20), CL-20/1,3,5-triamino-2,4,6-trinitrobenzene (TATB) energetic composites were prepared by using one-step ball milling method. The properties of raw materials and energetic composites were characterized by using scanning electron microscope, X-ray diffractometer, infrared spectrometer and diffrential scanning calorimetery.The impact sensitivity test was carried out. The results show that the as-prepared product is not a simple physical mixture of CL-20 and TATB, but a new crystalline phase is formed. In the SEM pattern, compared with the raw materials, the morphology of CL-20/TATB composite is regular spherical or ellipsoidal, and the particle size is in the range of 50-200 nm. In the XRD pattern, the main diffraction peak in the final product is obviously different from the main diffraction peaks in the raw CL-20 and the raw TATB. New XRD diffraction peaks arise, which indicates that a new crystal form appears in the final product. The diffraction peak become wider due to the decrease in particle size. In FT-IR pattern, the position of characteristic vibration peak of the functional group in the CL-20/TATB composite is shifted due to the hydrogen bond between CL-20 (—NO₂ or —CH) and TATB (—NO₂ or —NH₂). In the DSC curve, compared with raw CL-20 and raw TATB, the exothermic peak of the CL-20/TATB composite is advanced, which indicates that the thermal decomposition activity of CL-20/TATB composite is stronger than those of raw CL-20 and raw TATB. In the impact sensitivity test, the characteristic height of CL-20/TATB composite is 62 cm higher than that of CL-20 , indicating that the impact safety of CL-20/TATB is better than that of CL-20. Key

Key words: CL-20, 1,3,5-triamino-2,4,6-trinitrobenzene, energeticcomposite, one-stepballmillingmethod, thermaldecomposition

中图分类号:

刘燕，安崇伟，罗进，王晶禹. 纳米六硝基六氮杂异伍兹烷与三氨基三硝基苯含能复合物的制备及性能研究[J]. 兵工学报, 2020, 41(1): 49-55.

LIU Yan， AN Chongwei， LUO Jin， WANG Jingyu. Preparation and Characterization of Nano 24681012-hexanitro-24681012-hexaazaisowurtzitane/135-triamino-246-trinitrobenzene Energetic Composites[J]. Acta Armamentarii, 2020, 41(1): 49-55.

参考文献

［1］欧育湘. 炸药分析 [M]. 北京：兵器工业出版杜, 1994:1-3.
OU Y X. Explosive analysis[M]. Beijing：Publishing House of Ordnance Industry, 1994:1-3. (in Chinese)
[2] SONG N M, YANG L, HAN J M, et al. Catalytic study on thermal decomposition of Cu-en/(AP, CL-20, RDX and HMX) composite microspheres prepared by spray drying [J]. New Journal of Chemistry, 2018, 42(23): 19062-19069.
［3］王凯, 肖松, 申孝立, 等. 六硝基六氮杂异戊兹烷自催化分解特性与热安全性研究［J］. 兵工学报, 2018，39(1): 57-62.
WANG K, XIAO S, SHEN X L, et al. Research on autocatalytic thermal decomposition properties and thermal safety of CL-20［J］. Acta Armamentarii, 2018, 39(1): 57-62.(in Chinese)
［4］欧阳刚, 郭效德, 席海军, 等. 亚微米六硝基六氮杂异伍兹烷的制备及其性能研究［J］. 兵工学报, 2015, 36(1): 64-69.
OUYANG G, GUO X D, XI H J, et al. Preparation and characterization of submicron hexanitrohexaazaisowurtzitane［J］. Acta Armamentarii, 2015, 36(1): 64-69. (in Chinese)

[5] 刘杰. 具有降感特性纳米硝胺炸药的可控制备及应用基础研究 [D]. 南京:南京理工大学，2015.
LIU J. Controlled preparation of lower sensitivity characterized nanometer nitramine explosives and their applying basic research [D]. Nanjing:Nanjing University of Science and Technology, 2015. (in Chinese)
[6] ZHU Y F, LUO J, LU Y W, et al. Emulsion synthesis of CL-20/DNA composite with excellent superfine spherical improved sensitivity performance via a combined ultrasonic-microwave irradiation approach [J]. Journal of Materials Science, 2018, 53(20):14231-14240.
[7] BOND A D. What is a co-crystal? [J]. CrystEngComm, 2007, 9: 833-834.
[8] LARAOCHOA F, ESPINOSAPREZ G. Cocrystals definitions [J]. Supramolecular Chemistry, 2007, 19(8): 553-557.
[9] 郭长艳, 张浩斌, 王晓川, 等. 共晶炸药研究进展 [J]. 材料导报, 2012, 26 (19): 49-53.
GUO C Y, ZHANG H B, WANG X C, et al. Research progress of cocrystal explosive [J]. Materials Review, 2012, 26 (19): 49-53. (in Chinese)

[10] 杨光成, 聂福德, 曾贵玉. 超细TATB-BTF核-壳型复合粒子的制备[J]. 火炸药学报, 2005, 28 (2): 72-74.
YANG G C, NIE F D, ZENG G Y. Preparation of fine TATB-BTF core-shell composite particles [J]. Chinese Journal of Explosive & Propellants, 2005, 28 (2): 72-74. (in Chinese)
[11] LUO Q P, LONG X P, NIE F D, et al. The safety properties of a potential kind of novel green primary explosive: Al/Fe₂O₃/RDX nanocomposite [J]. Materials, 2018, 11(10): 1930-1940.
[12] YANG Z J, GONG F Y, HE G S, et al. Perfect energetic crystals with improved performances obtained by thermally metastable interfacial self-assembly of corresponding nanocrystals [J]. Crystal Growth & Design, 2018, 18(3): 1657-1665.
[13] YANG Z J, DING L, WU P, et al. Fabrication of RDX, HMX, and CL-20 based microcapsules via in situ polymerization of melamine-formaldehyde resins with reduced sensitivity [J]. Chemical Engineering Journal, 2015, 268: 60-66.
[14] 王晶禹, 李鹤群, 安崇伟, 等. 超细CL-20/TNT共晶炸药的喷雾干燥制备与表征 [J]. 含能材料, 2015, 23 (11): 1103-1106.
WANG J Y, LI H Q, AN C W, et al. Preparation and characterization of ultrafine CL-20/TNT cocrystal explosive by spray drying method [J]. Chinese Journal of Energetic Materials, 2015, 23 (11): 1103-1106. (in Chinese)
[15] WANG Y, SONG X L, SONG D, et al. Synthesis, thermolysis, and sensitivities of HMX/NC energetic nanocomposites [J]. Journal of Hazardous Materials, 2016, 312: 73-83.
[16] QIU H W, PATEL R B, DAMAVARAPU R S, et al. Nanoscale 2CL-20·HMX high explosive cocrystal synthesized by bead milling [J]. CrystEngComm, 2015, 17(22): 4080-4083.
[17] ZHANG Z B, LI T, YIN L, et al. A novel insensitive cocrystal explosive BTO/ATZ: preparation and performance [J]. RSC Advances, 2016, 6(79): 76075-76083.
[18] XU M, BI X R, YU C Y, et al. Ball-milling synthesized hydrotalcite supported Cu-Mn mixed oxide under solvent-free conditions: an active catalyst for aerobic oxidative synthesis of 2-acylbenzothiazoles and quinoxalines [J]. Green Chemistry, 2018, 20:4638-4644.
[19] XIAO L, ZHANG Y, WANG X H, et al. Preparation of a superfine RDX/Al composite as an energetic material by mechanical ball-milling method and the study of its thermal properties [J]. RSC Advances, 2018, 8(66): 38047-38055.
[20] AN C W, LI H Q, YE B Y, et al. Nano-CL-20/HMX cocrystal explosive for significantly reduced mechanical sensitivity [J]. Journal of Nanomaterials, 2017, 2017(5):3791320.
[21] WANG Z X, GUO X D, WU F, et al. Preparation of HMX/TATB composite particles using a mechanochemical approach [J]. Propellants, Explosives, Pyrotechnics, 2016, 41(2):327-333.
[22] 沈金朋. HMX/TATB共晶炸药的制备和表征[D]. 绵阳:西南科技大学, 2011.
SHEN J P. Preparation and characterization of HMX/TATB cocrystal explosive [D]. Mianyang:Southweat University of Science and Technology, 2011. (in Chinese)

[23] 石晓峰, 李小东, 王晶禹, 等. RDX基超细球形包覆粒子的制备及热性能表征 [J]. 固体火箭技术, 2015, 38(3): 383-386.
SHI X F, LI X D, WANG J Y, et al. Preparation and thermal properties of RDX based ultrafine spherical coated particles [J]. Journal of Solid Rocket Technology, 2015, 38(3): 383-386. (in Chinese)
[24] 刘燕, 安崇伟, 罗进, 等. 纳米CL-20/AP含能复合粒子的制备及性能表征 [J]. 含能材料, 2018, 26(12): 1009-1013.
LIU Y, AN C W, LUO J, et al. Preparation and properities of nano CL-20/AP energetic composite particles [J]. Chinese Journal of Energetic Materials, 2018, 26 (12): 1009-1013. (in Chinese)

第41卷第1期
2020 年1月兵工学报ACTA
ARMAMENTARIIVol.41No.1Jan.2020

[1]	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.
[2]	许睿轩, 徐家兴, 薛智华, 吕杰尧, 严启龙. 多尺度界面可调型Al-RDX含能复合物的制备及其热分解特性[J]. 兵工学报, 2023, 44(3): 691-701.
[3]	刘正, 聂建新, 徐星, 朱英中, 刘攀, 郭学永, 闫石, 张韬. 密闭空间内六硝基六氮杂异伍兹烷基复合炸药能量释放特性[J]. 兵工学报, 2022, 43(3): 503-512.
[4]	霍俊达, 闫振展, 鲁月文, 韩纪旻, 杨利. 多孔聚丙烯酸盐制备及对高氯酸铵热分解的催化[J]. 兵工学报, 2021, 42(6): 1215-1222.
[5]	李宽宽，郭效德，梁力，张正金，夏亮，常志鹏. 纳米碳酸锶/高氯酸铵复合粒子的制备及其撞击感度和热分解性能研究[J]. 兵工学报, 2020, 41(7): 1317-1322.
[6]	管发扬，于兰，任慧，焦清介，刘洁. 硝化石墨烯制备及对高氯酸铵热分解的催化作用[J]. 兵工学报, 2020, 41(7): 1323-1329.
[7]	吴亚琛，沈忱，孙晓乐，焦清介，刘海伦，闫石. 浇注六硝基六氮杂异伍兹烷基混合炸药驱动性能[J]. 兵工学报, 2020, 41(12): 2458-2465.
[8]	张正金，郭效德，刘杰，梁力，李宽宽，夏亮，常志鹏，田淑宝，黄东彦，杨雪芹. 超细亚铁氰化铅/高氯酸铵复合粒子的制备及热分解、防团聚性能研究[J]. 兵工学报, 2019, 40(11): 2220-2228.
[9]	张伟，闫石，郭学永，任慧，焦清介. 端羟基聚叠氮缩水甘油醚与六硝基六氮杂异伍兹烷基四元混合炸药能量释放研究[J]. 兵工学报, 2018, 39(7): 1299-1307.
[10]	谭凯元，韩勇，曹落霞，文尚刚，王翔，叶辉. 装药密度小幅变化对三氨基三硝基苯基聚合物粘结炸药短脉冲冲击起爆特性的影响[J]. 兵工学报, 2018, 39(3): 468-473.
[11]	曹雄，张云，曹卫国，张玉龙，戴鹏，薛晨露，谭迎新. 质量效应及热历史对硝酸铵热分解特性的影响研究[J]. 兵工学报, 2018, 39(11): 2153-2158.
[12]	袁俊明，张林炎，唐鑫，刘玉存，张喜亮，陈银刚，李硕. 小型传爆装置慢燃实验及数值计算[J]. 兵工学报, 2017, 38(8): 1541-1546.
[13]	李广超，梁振宗，梁力，郭效德. 基于气流粉碎法的超细类球形高氯酸铵批量制备及其表征[J]. 兵工学报, 2017, 38(11): 2098-2104.
[14]	宋乃孟，张同来，高红旭，杨利. 亚微米级球形间苯三酚铁的制备及对六硝基六氮杂异伍兹烷热分解的影响[J]. 兵工学报, 2016, 37(3): 547-552.
[15]	刘海，何远航. 梯恩梯/萘共晶初始热分解的反应分子动力学模拟[J]. 兵工学报, 2016, 37(3): 414-423.