FOX-7 在<i>α</i>→<i>β</i>相变过程中的特性

顾晓飞; 樊思琪; 李如江; 李洪珍

doi:10.11858/gywlxb.20200653

FOX-7 在α→β相变过程中的特性

doi: 10.11858/gywlxb.20200653

顾晓飞^{1, 2,},
樊思琪¹,
李如江²,
李洪珍^1,*, ,

1.
中国工程物理研究院化工材料研究所，四川绵阳　621999
2.
中北大学环境与安全工程学院，山西太原　030051

基金项目: 国家自然科学基金（21875231）

详细信息

作者简介:
顾晓飞（1995－），男，硕士研究生，主要从事含能材料性能与评价研究. E-mail：1617356877@qq.com

通讯作者:
李洪珍（1971－），女，硕士，研究员，主要从事含能材料晶体学研究. E-mail：hongzhenli@caep.com

中图分类号: TJ55；O521.2
计量
- 文章访问数: 3315
- HTML全文浏览量: 1435
- PDF下载量: 33
出版历程
- 收稿日期: 2020-12-10
- 修回日期: 2020-12-30

α→β Phase Transition Characteristics of High-Energy and Low-Sensitivity Explosive FOX-7

GU Xiaofei^{1, 2
,},
FAN Siqi¹,
LI Rujiang²,
LI Hongzhen^{1,*
, ,}

1.
Institute of Chemical Materials, CAEP, Mianyang 621999, Sichuan, China
2.
School of Environmental and Safety Engineering, North University of China, Taiyuan 030051, Shanxi, China

摘要

摘要: 为了解新型高能低感炸药FOX-7的α→β相变具体过程，采用扫描电子显微镜、在线热台仪和显微共聚焦拉曼测试等方法，从晶体的宏观结构和微结构角度详细研究了α→β相变过程中晶体的变化情况，探究了升温速率、晶体形貌和晶体缺陷等不同因素对相变的影响。结果表明：在α→β相变过程中，相变是从晶体的某一缺陷处开始逐步扩散至整个晶体；晶体尺寸、升温速率和晶体形貌对相变有不同程度的影响，晶体尺寸越大、升温速率越慢、晶体外形呈块状时相对更易于发生相变，但差异并不明显；晶体发生相变后经常会出现裂纹、破碎、透明度降低等现象。采用多巴胺原位聚合包覆FOX-7晶体可以在一定程度上延缓α→β相变的发生。
- FOX-7 /
- 晶体 /
- α→β相变 /
- 拉曼光谱 /
- 多巴胺包覆
Abstract: In order to understand the specific process of α→β phase transition in FOX-7, some experimental methods are used to analyze the α→β phase transition, such as scanning electron microscope, THMSG600 heating stage instrument, and micro-confocal Raman spectrum. The changes of the crystal morphology during the α→β phase transition in FOX-7 are studied at the overall and individual levels of the crystal in detail. At the same time, the effects of different factors such as heating rate, crystal morphology, and crystal defects of α→β phase transition are explored. The results show that during the α→β phase transition, cracks and breakages appear in the crystals, and the crystals become opaque. Meanwhile, it was found that the crystal size, heating rate, and crystal morphologies have effects on the phase transition in different degrees. It is relatively more prone to phase change in the case of larger massive crystals under a slower heating rate. Besides, the phase transition of α→β is a continuous process, and it gradually diffuses from a certain defect to the entire crystal. For this reason, in-situ polymerization of dopamine can be used to coat FOX-7 crystals to achieve the purpose of inhibiting the α→β phase transition.
- FOX-7 /
- crystal /
- α→β phase transition /
- Raman spectra /
- dopamine-coated

HTML全文

图 1 在相变前、后FOX-7晶体的形貌变化(a)和拉曼光谱(b)

Figure 1. Morphology changes (a) and Raman spectra (b) of the FOX-7 crystal before and after phase transition

下载: 全尺寸图片幻灯片

图 2 116 ℃下FOX-7晶体的不同测试点(a)及拉曼光谱(b)

Figure 2. Test points (a) and Raman spectra (b) of the FOX-7 crystal at 116 ℃

下载: 全尺寸图片幻灯片

图 3 FOX-7晶体缺陷在相变过程中的演化

Figure 3. Evolution process of the defects during the phase transition of the FOX-7 crystal

下载: 全尺寸图片幻灯片

图 4 3种不同升温速率下FOX-7晶体的形貌变化

Figure 4. Changes of the FOX-7 crystal morphology under three different heating rates

下载: 全尺寸图片幻灯片

图 5 相同升温速率下不同形貌、尺寸FOX-7晶体的变化

Figure 5. Morphology changes of the FOX-7 crystals with different sizes and shapes under the same heating rate

下载: 全尺寸图片幻灯片

图 6 多巴胺包覆前、后的FOX-7晶体对比

Figure 6. Comparisons of FOX-7 crystals before and after dopamine coating

下载: 全尺寸图片幻灯片

图 7 多巴胺包覆FOX-7晶体α→β相变的DSC曲线

Figure 7. DSC curves of dopamine-coated FOX-7 crystal transition from α phase to β phase

下载: 全尺寸图片幻灯片

参考文献(26)

[1]	LATYPOV N V, BERGMAN J, LANGLET A, et al. Synthesis and reactions of 1, 1-diamino-2, 2-dinitroethylene [J]. Tetrahedron, 1998, 54(38): 11525–11536. doi: 10.1016/S0040-4020(98)00673-5
[2]	BELLAMY A J. FOX-7 (1, 1-Diamino-2, 2-dinitroethene) [M]//KLAPÖTKE T M. High Energy Density Materials. Berlin, Heidelberg: Springer, 2007: 1–33.
[3]	TRZCIŃSKI W, BELAADA A. 1, 1-diamino-2, 2-dinitroethene (DADNE, FOX-7)-properties and formulations (a review) [J]. Central European Journal of Energetic Materials, 2016, 13(2): 527–544. doi: 10.22211/cejem/65000
[4]	BEMM U, ÖSTMARK H. 1, 1-Diamino-2, 2-dinitroethylene: a novel energetic material with infinite layers in two dimensions [J]. Acta Crystallographica Section C, 1998, 54(12): 1997–1999. doi: 10.1107/S0108270198007987
[5]	SUN Q, ZHANG Y, XU K Z, et al. Studies on thermodynamic properties of FOX-7 and its five closed-loop derivatives [J]. Journal of Chemical and Engineering Data, 2015, 60(7): 2057–2061. doi: 10.1021/acs.jced.5b00021
[6]	YAN C, QI X J, WANG K C, et al. Revisiting the reactive chemistry of FOX-7: cyclization of FOX-7 affords the fused-ring polynitro compounds [J]. Chemical Communications, 2019, 55(24): 3497–3500. doi: 10.1039/c8cc10178g
[7]	YAN C, YANG H W, QI X J, et al. A simple and versatile strategy for taming FOX-7 [J]. Chemical Communications, 2018, 54(67): 9333–9336. doi: 10.1039/C8CC05562A
[8]	ZHOU T H, LI Y F, XU K Z, et al. The new role of 1, 1-diamino-2, 2-dinitroethylene (FOX-7): two unexpected reactions [J]. New Journal of Chemistry, 2017, 41(1): 168–176. doi: 10.1039/C6NJ03370A
[9]	FANG X, MCLUCKIE W G. Laser ignitibility of insensitive secondary explosive 1, 1-diamino-2, 2-dinitroethene (FOX-7) [J]. Journal of Hazardous Materials, 2015, 285: 375–382. doi: 10.1016/j.jhazmat.2014.12.006
[10]	LAN G C, JIN S H, CHEN M L, et al. Preparation and thermal properties study of HNIW/FOX-7 based high energy polymer bonded explosive (PBX) with low vulnerability to thermal stimulations [J]. Journal of Energetic Materials, 2020, 38(1): 83–97. doi: 10.1080/07370652.2019.1665146
[11]	JENSEN T L, UNNEBERG E, KRISTENSEN T E. Smokeless GAP-RDX composite rocket propellants containing diaminodinitroethylene (FOX-7) [J]. Propellants Explosives Pyrotechnics, 2017, 42(4): 381–385. doi: 10.1002/prep.201600278
[12]	郜婵, 孙晓宇, 梁文韬, 等. RDX、HMX及CL-20晶体的高温高压相变研究进展 [J]. 含能材料, 2020, 28(9): 902–914. doi: 10.11943/CJEM2020088 GAO C, SUN X Y, LIANG W T, et al. Review on phase transition of RDX, HMX and CL-20 crystals under high temperature and high pressure [J]. Chinese Journal of Energetic Materials, 2020, 28(9): 902–914. doi: 10.11943/CJEM2020088
[13]	EVERS J, KLAPÖTKE T M, MAYER P, et al. α- and β-FOX-7, Polymorphs of a high energy density material, studied by x-ray single crystal and powder investigations in the temperature range from 200 to 423 K [J]. Inorganic Chemistry, 2006, 45(13): 4996–5007. doi: 10.1021/ic052150m
[14]	ZAKHAROV V V,CHUKANUV N V,CHERVONNYI A D. phase transitions α→β and β→α in 1, 1-Diamino-2, 2-dinitroethylene [J]. Russian Journal of Physical Chemistry B, 2014, 8(6): 822–828. doi: 10.1134/S1990793114110104
[15]	BISHOP M M, VELISAVLJEVIC M N, CHELLAPPA R, et al. High pressure-temperature phase diagram of 1, 1-Diamino-2, 2-dinitroethylene (FOX-7) [J]. The Journal of physical Chemistry A, 2015, 119: 9739. doi: 10.1021/acs.jpca.5b07811
[16]	BISHOP M M, CHELLAPPA R S, LIU Z, et al. High pressure-temperature polymorphism of 1,1-Diamino-2,2-dinitroethylene [J]. Journal of Physics: Conference Series, 2014: 500.
[17]	DREGER Z A, TAO Y, GUPTA Y M. Polymorphs of 1,1-diamino-2,2- dinitroethene (FOX-7): isothermal compression versus isobaric heating [J]. Chemical Physics Letters, 2013, 584: 83–87. doi: 10.1016/j.cplett.2013.08.070
[18]	DREGER Z A, STASH A I, YU Z G, et al. High-pressure crystal structures of an insensitive energetic crystal: 1, 1-diamino-2, 2-dinitroethene [J]. The Journal of Physical Chemistry C, 2016, 120(2): 1218–1224. doi: 10.1021/acs.jpcc.5b10644
[19]	ZAKHAROV V V, CHUKANOV N V, DREMOVA N N, et al. High-temperature structural transformations of 1, 1-diamino-2, 2-dinitroethene (FOX-7) [J]. Propellants Explosives Pyrotechnics, 2016, 41(6): 1006–1012. doi: 10.1002/prep.201600071
[20]	DREGER Z A, TAO Y H, GUPTA Y M. Phase diagram and decomposition of 1, 1-diamino-2, 2-dinitroethene single crystals at high pressures and temperatures [J]. The Journal of Physical Chemistry C, 2016, 120(20): 11092–11098. doi: 10.1021/acs.jpcc.6b02360
[21]	CRAWFORD M J, EVERS J, GÖBEL M, et al. γ-FOX-7: structure of a high energy density material immediately prior to decomposition [J]. Propellants Explosives Pyrotechnics, 2007, 32(6): 478–495. doi: 10.1002/prep.200700240
[22]	GONG F Y, ZHANG J H, DING L, et al. Mussel-inspired coating of energetic crystals: a compact core–shell structure with highly enhanced thermal stability [J]. Chemical Engineering Journal, 2017, 309: 140–150. doi: 10.1016/j.cej.2016.10.020
[23]	叶方青, 曾贵玉, 吕春绪, 等. 聚合物对硝酸铵相转变的影响 [J]. 含能材料, 2008, 16(1): 77–79. doi: 10.3969/j.issn.1006-9941.2008.01.022 YE F Q, ZENG G Y, LÜ C X, et al. Effects of polymers on phase transition of ammonium nitrate [J]. Chinese Journal of Energetic Materials, 2008, 16(1): 77–79. doi: 10.3969/j.issn.1006-9941.2008.01.022
[24]	曾贵玉, 周建华, 吕春绪, 等. 无机物对硝酸铵相转变的影响 [J]. 含能材料, 2007, 15(4): 400–403. doi: 10.3969/j.issn.1006-9941.2007.04.027 ZENG G Y, ZHOU J H, LÜ C X, et al. Effect of inorganic additives on phase transition of ammonium nitrate [J]. Chinese Journal of Energetic Materials, 2007, 15(4): 400–403. doi: 10.3969/j.issn.1006-9941.2007.04.027
[25]	叶毓鹏, 曹欣茂, 叶玲, 等. 炸药结晶工艺学及其应用[M]. 北京: 兵器工业出版社, 1995: 47–48. YE Y P, CAO X M, YE L, et al. Explosive crystallization technology and its application [M]. Beijing: Weapon Industry Press, 1995: 47–48.
[26]	关羽翔. 热刺激下奥克托金β→δ相变的缺陷演化规律研究[D]. 太原: 中北大学, 2018: 17–22. GUAN Y X. Study on the defect evolution law from the transition of β→δ in HMX [D]. Taiyuan: North University of China, 2018: 17−22.