富勒烯肼硝酸盐的制备及其热分解性能

doi:10.3969/j.issn.1000-1093.2014.11.005

摘要/Abstract

摘要： 以富勒烯、水合肼为原料合成富勒烯肼，富勒烯肼再与浓硝酸反应得到一种新型含能燃烧催化剂—富勒烯肼硝酸盐，并采用红外、紫外、元素分析及X射线光电子能谱等现代分析测试技术对产物结构进行了表征。采用差热分析（DTA）法和热重分析（TGA）法对富勒烯肼硝酸盐的热稳定性进行了研究，结果表明，在动态空气气氛下，其具有一定的热稳定性。采用DTA法，对加入富勒烯肼硝酸盐前后硝胺炸药黑索今（RDX）和奥克托今（HMX）的热分解行为进行了研究，结果表明，加入富勒烯肼硝酸盐后，RDX和HMX在不同升温速率（2.5 ℃/min、5 ℃/min、10 ℃/min和20 ℃/min）条件下的放热峰值温度均降低，RDX分解活化能降低了约17 kJ/mol，HMX分解活化能降低值大于20 kJ/mol，由此表明富勒烯肼硝酸盐对RDX和HMX的热分解均有一定的催化作用。

关键词: 兵器科学与技术, 富勒烯肼硝酸盐, 结构表征, 热分解, 燃烧催化剂, 推进剂

Abstract: A new potential energetic combustion catalyst, fullerene hydrazine nitrate, is prepared via a two-step process, in which fullerene hydrazine is prepared with fullerene and hydrazine hydrate, and then fullerene hydrazine reacts with concentrated nitric acid to form fullerene hydrazine nitrate. The chemical structures of products are characterized by FT-IR, UV-visible spectra, elemental analysis and X-ray photoelectron spectroscopy. The thermal stability of fullerene hydrazine nitrate is characterized by differential thermal analysis (DTA) and thermogravimetry analysis (TGA). The results indicate that the product shows a certain thermal stability in dynamic air atmosphere. The thermal decomposition behaviours of RDX and HMX in the absence and presence of fullerene hydrazine nitrate are investigated by using DTA method. The research results show that fullerene hydrazine nitrate can accelerate obviously the decomposition of RDX and HMX. The peak temperatures of the exothermal decomposition are reduced at the different heating rates of 2.5, 5, 10 and 20 ℃/min. The corresponding activation energy of RDX is decreased by about 17 kJ/mol, and that of HMX is reduced by more than 20 kJ/mol.

Key words: ordnance science and technology, fullerene hydrazine nitrate, structural characterization, thermal decomposition, combustion catalyst, propellant

中图分类号:

TJ55

关会娟，金波，彭汝芳，赵凤起，韩文静，陈百利，楚士晋. 富勒烯肼硝酸盐的制备及其热分解性能[J]. 兵工学报, 2014, 35(11): 1756-1764.

GUAN Hui-juan, JIN Bo, PENG Ru-fang, ZHAO Feng-qi, HAN Wen-jing, CHEN Bai-li, CHU Shi-jin. The Preparation and Thermal Decomposition Performance of Fullerene Hydrazine Nitrate[J]. Acta Armamentarii, 2014, 35(11): 1756-1764.

参考文献

［1］ Pichierri F. Proposal for using C₆₀ anions as propellants for ion engines[J]. Physics Letters A, 2003, 318(4): 425-428.
[2］ Greiner B E, Frederick R A, Moster M D. Combustion effects of C₆₀ soot in ammonium nitrate propellants[J]. Journal of Propulsion and Power, 2003, 19(4): 713-715.
[3］彭汝芳, 金波, 马冬梅, 等. 2-(2-硝基苯基)吡咯烷[3′, 4′: 1,2][60]富勒烯的合成[J]. 火炸药学报, 2007, 30(2): 29- 32.
PENG Ru-fang, JIN Bo, MA Dong-mei, et al. Synthesis of 2- (2-nitrophenyl) fulllerenopyrrolidine[J]. Chinese Journal of Explosives & Propellants, 2007, 30(2): 29-32.(in Chinese)
[4］ JIN B, PENG R F, TAN B S, et al. Synthesis and characterization of nitro fulleropyrrolidine derivatives[J]. Chinese Journal of Energetic Materials, 2009, 17(3): 287-292.
[5］ WANG N X, LI J S, JI G J. Synthesis of trinitrophenyl C₆₀ derivative[J]. Propellants, Explosives, Pyrotechnics, 1996, 21(6): 317-318.
[6］宋秀铎, 赵凤起, 张蕊娥, 等. 柠檬酸铋的制备、结构表征及其在固体推进剂中的催化作用[J]. 兵工学报,2006, 27(4) : 643-647.
SONG Xiu-duo, ZHAO Feng-qi, ZHANG Rui-e, et al. Synthesis of bismuth citrate and its effect on combustion of double-base propellant and RDX-CMDB propellant [J]. Acta Armamentarii, 2006, 27(4): 643-647.(in Chinese)
[7］张衡, 安亭, 赵凤起, 等. 没食子酸锆铜的制备及其在双基系推进剂中的燃烧催化作用[J]. 兵工学报, 2013, 34(6): 690- 697.
ZHANG Heng, AN Ting, ZHAO Feng-qi,et al. Preparation of zirconium/copper gallate and its effect on combustion of double-base and RDX-CMDB propellants[J]. Acta Armamentarii, 2013, 34(6): 690-697.(in Chinese)
[8］李疏芬, 何德球, 苏航, 等. 球烯在RDX-CMDB推进剂中作用初探[J]. 固体火箭技术, 1997, 20(4): 40-43.
LI Shu-fen, HE De-qiu, SU Hang, et al.A preliminary exploration of the function of fullerene in solid propellant[J]. Journal of Solid Rocket Technology, 1997, 20(4): 40-43.(in Chinese)
[9］赵凤起, 李上文, 单文刚, 等. 不同形态碳物质对RDX-CMDB推进剂燃烧性能的影响[J]. 推进技术, 2000, 21(2): 72-76.
ZHAO Feng-qi, LI Shang-wen,SHAN Wen-gang, et al. Influence of fullerene-soot and carbon black on combustion properties of catalyzed RDX-CMDB propellants[J]. Journal of Propulsion Techno-logy, 2000, 21(2): 72-76.(in Chinese)
[10］潘清, 汪渊, 陈智群, 等. NEPE推进剂的热分解研究(IV)[J]. 固体火箭技术, 2003, 26(4): 45-47.
PAN Qing, WANG Yuan, CHEN Zhi-qun, et al.Study on the thermal decomposition of NEPE propellant(IV)[J]. Journal of Solid Rocket Technology, 2003, 26(4): 45-47. (in Chinese)
[11］李疏芬, 何德球, 单文刚, 等. C₆₀对NC、RDX热分解作用的探讨[J]. 火炸药学报, 1997, 21(2): 13-16.
LI Shu-fen, HE De-qiu, SHAN Wen-gang, et al. The effect of C₆₀ on the pyrolysis of NC and RDX[J]. Chinese Journal of Explosives & Propellants, 1997, 21(2): 13-16.(in Chinese)
[12］王晗, 赵凤起, 李上文, 等. 碳物质在固体推进剂中的功能及其作用机理[J]. 火炸药学报, 2006, 29(4): 32-35.
WANG Han, ZHAO Feng-qi, LI Shang-wen, et al.Function of carbon materials used in solid propellants and their action mechanism[J]. Chinese Journal of Explosives & Propellants, 2006, 29(4): 32-35.(in Chinese)
[13］ Greiner B E, Frederick R A, Moser M D. Combustion effects of C60 soot in ammonium nitrate propellants [J]. Journal of Propulsion and Power, 2003, 19(4):713-715.
[14］ Wang N X. Review on the nitration of [60］ fullerene[J]. Propellants, Explosives, Pyrotechnics, 2001, 26(3): 109-111.
[15］ Christian A, Yalaha F L. Explosive/energetic fullerenes:US,7025840B1 [P]. 2006-4-11.
[16］ Jin B, Peng R F, Yang W N, et al. Solvent-free synthesis of N-arylfulleropyrro lidine derivatives without using phase-transfer catalyst under microwave irradiation[J]. Synthetic Communications, 2010, 40(4): 580-586.
[17］ Kratschmer W, Lamb L D, Fostiropoulos K, et al. Solid C₆₀: a new form of carbon[J]. Nature, 1990, 17(4): 354-358.
[18］邱介山, 周颖, 王琳娜, 等. 煤基富勒烯的制备研究[J]. 大连理工大学学报, 2000, 40(S1): 41-45.
QIU Jie-shan, ZHOU Ying, WANG Lin-na,et al. Preparation of fullerenes from coals[J]. Journal of Dalian University of Technology, 2000, 40(S1): 41-45.(in Chinese)
[19］李丽, 彭汝芳, 金波, 等. 富勒烯乙二胺铅盐的制备及研究[J]. 功能材料, 2013, 44(6): 814-817.
LI Li, PENG Ru-fang, JIN Bo, et al. Preparation and characterization of fullerene ethylene diamine lead salt[J]. Journal of Functional Materials, 2013, 44(6): 814-817.(in Chinese)
[20］钟劲茅, 张正华, 毕明亮, 等. N, N′-二吡啶基-1, 2-乙二胺-稀土硝酸盐配合物的合成与表征[J].中国稀土学报, 2005, 23(2): 250-252.
ZHONG Jin-mao, ZHANG Zheng-hua, BI Ming-liang, et al. Synthesis and characterization of complexes of rare earth nitrate with N, N′-bis(3-pyridylmethyl)-1, 2-ethylenediamine [J]. Journal of The Chinese Rare Earth Society, 2005, 23(2): 250-252.(in Chinese)
[21］孔祥飞, 郭强, 李春, 等. 金刚石薄膜对硝酸钾红外吸收特性的影响[J]. 光谱学与光谱分析, 2012, 32(9): 2362-2365.
KONG Xiang-fei, GUO Qiang, LI Chun, et al. Effect of diamond film on infrared absorption properties of potassium nitrate[J]. Spectroscopy and Spectral Analysis, 2012, 20(5): 579-582. (in Chinese)
[22］陈远荫, 方鹏飞, 朱綾, 等. C₆₀乙二胺衍生物铂配合物的合成及其催化硅氢化性能[J]. 高等学校化学学报, 1998, 19(7): 1011-1015.
CHEN Yuan-yin, FANG Peng-fei, ZHU Ling, et al. Synthesis of fullerene ethylenediamine derivative platinum complex and its catalytic behavior in the hydrosilylation of olefins[J]. Chemical Journal of Chinese University, 1998, 19(7): 1011-1015.(in Chinese)
[23］王国建, 金吉琼. 聚乙烯马来酸酐接枝聚合物修饰多壁碳纳米管[J]. 新型炭材料, 2012，27(1): 19-25.
WANG Guo-jian, JIN Ji-qiong.Chemical modification of multiwalled carbon nanotubes by polyethylene-grafted maleic anhydride[J]. New Carbon Materials, 2012，27(1): 19-25.(in Chinese)
[24］ Bruce C B. Cellulose nitrate as a binding energy reference in N(ls) XPS studies[J]. Applied Surface Science, 1990, 45(3): 221-227.
[25］ Kissinger H E. Reaction kinetics on differential thermal analysis[J]. Analytical Chemistry, 1957, 29(11): 1702-1706.
[26］刘强强, 金波, 彭汝芳, 等. 丙烯酸-2, 4, 6- 三硝基苯乙酯的合成及热分解[J]. 含能材料, 2012, 20(5): 579-582.
LIU Qiang-qiang, JIN Bo, PENG Ru-fang, et al. Synthesis and thermal decomposition performance of acrylic 2, 4, 6-trinitrophenethyl ester[J]. China Journal of Energetic Materials, 2012, 20(5): 579-582.(in Chinese)

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