固体氧化剂的防吸湿性能研究进展

doi:10.16085/j.issn.1000-6613.2024-0330

摘要/Abstract

摘要：

氧化剂材料在工业炸药、导弹以及固体推进剂等领域应用广泛，对工业社会的重要性不言而喻。然而，由于这些氧化剂材料具有高极性表面和特殊结构，因此这些材料极易吸湿，从而严重影响了其在固体推进剂中的性能和可靠性。为满足现代航天和导弹技术对推进剂高性能、高稳定性和高安全性的迫切需求，必须提高氧化剂的性能指标，以满足航天和导弹领域对动力源的严格标准。为此，本文首先介绍了氧化剂材料的分类、结构和化学组成，为后续的归纳概括提供了基础。其次，总结了氧化剂材料防吸湿方面的最新研究进展，进一步探讨了改进其防吸湿性能的方法。最后，通过对氧化剂材料在固体推进剂领域的优势和不足的分析，对氧化剂防吸湿性能研究给出了以下几点建议：深入研究氧化剂材料的分子结构和表面特性，引入纳米技术，开发复合氧化剂材料以及新型的表面涂层技术或封装工艺；综合考虑热稳定性、感度低以及与固体推进剂的其他组分（如黏合剂基体网络）的相容性等因素；着重关注其工业化生产和应用的可行性。这将大幅度提升氧化剂材料的性能，为我国航天和导弹等领域的发展提供保障。

关键词: 氧化剂, 高氯酸铵, 硝酸铵, 二硝酰胺铵, 防吸湿

Abstract:

The widespread applications of oxidizer materials in industries such as industrial explosives, missiles and solid propellants underscore their undeniable importance for industrial society. However, due to the highly polar surfaces and unique structures of these oxidizer materials, they exhibit high susceptibility to moisture absorption, which significantly impacts their performance and reliability in solid propellants. Therefore, this paper first introduced the classification, structure and chemical composition of oxidizer materials, laying the groundwork for subsequent summarization. Secondly, the latest research advancements in moisture prevention of oxidizer materials were summarized for further exploring methods to improve their moisture resistance. Finally, after reviewing the advantages and disadvantages of oxidizer materials in the field of solid propellants, several suggestions for research on the anti-hygroscopic properties of oxidizers were offered: conducting an in-depth study of the molecular structure and surface properties of oxidizer materials; introducing nanotechnology and developing composite materials that enhanced these properties; exploring new surface coating technologies or encapsulation processes to improve oxidizer materials; taking into account factors such as thermal stability, low sensitivity and compatibility with other components of solid propellants (like adhesive matrix networks); and focusing on the industrial production and practical application feasibility of these advancements. This would significantly enhance the oxidizer material's performance for the advancement of China's missile and aerospace industries.

Key words: oxidizer, ammonium perchlorate, ammonium nitrate, ammonium dinitramide, anti-hygroscopicity

中图分类号:

O613.61

董洁, 刘博, 杨燕飞, 南雪丽, 张俊平. 固体氧化剂的防吸湿性能研究进展[J]. 化工进展, 2025, 44(3): 1445-1453.

DONG Jie, LIU Bo, YANG Yanfei, NAN Xueli, ZHANG Junping. Design of anti-hygroscopic properties of oxidizer materials[J]. Chemical Industry and Engineering Progress, 2025, 44(3): 1445-1453.

图/表 5

图1 本文概况示意图

图2 氧化剂吸湿机理

图3 ADN防吸湿性能

图4 ADN防吸湿性能

图5 AP防吸湿性能

参考文献 45

1	李瑞东, 黄辉, 同国虎, 等. 原油精馏塔中铵盐吸湿特性及其腐蚀行为[J]. 化工进展, 2023, 42(6): 2809-2818.
	LI Ruidong, HUANG Hui, TONG Guohu, et al. Hygroscopic properties and corrosion behavior of ammonium salt in a crude oil distillation column[J]. Chemical Industry and Engineering Progress, 2023, 42(6): 2809-2818.
2	韩郑良, 肖鑫. 复合固体干燥剂的研究进展[J]. 化工进展, 2023, 42(2): 839-853.
	HAN Zhengliang, XIAO Xin. Research progress of composite solid desiccant[J]. Chemical Industry and Engineering Progress, 2023, 42(2): 839-853.
3	GEZERMAN Ahmet Ozan. A novel industrial-scale strategy to prevent degradation and caking of ammonium nitrate[J]. Heliyon, 2020, 6(3): e03628.
4	严昱, 夏芯, 骆俊鹏, 等. 氧化剂类型对rGO/CNTs催化膜去除水中消炎药成分的影响[J]. 化工进展, 2024, 43(3): 1436-1445.
	YAN Yu, XIA Xin, LUO Junpeng, et al. Effects of peroxide types on the removal of anti-inflammatory medicines in water with rGO/CNTs catalytic membranes[J]. Chemical Industry and Engineering Progress, 2024, 43(3): 1436-1445.
5	Alessandro SCHÖNBORN, LEE Kangki. Hydroxylamine NH₂OH and ammonium dinitramide NH₄N(NO₂)₂ aqueous solutions in combination with ammonia and aqueous ammonia as marine fuels[J]. Sustainable Energy Technologies and Assessments, 2024, 64: 103692.
6	ABDELAZIZ Amir, TRACHE Djalal, TARCHOUN Ahmed Fouzi, et al. Application of co-crystallization method for the production of ammonium perchlorate/ammonium nitrate oxidizer for solid rocket propellants[J]. Chemical Engineering Journal, 2024, 487: 150654.
7	ELZAKI Baha I, ZHANG Yuejun. Surface modification of ammonium nitrate by coating with surfactant materials to reduce hygroscopicity[J]. Defence Technology, 2019, 15(4): 615-620.
8	CHEN Dingning, YU Haojie, WANG Li, et al. Establishing a coating of ferrocene-based hyperbranched polymer on ammonium perchlorate: Enhancing the anti-migration and catalytic performance[J]. Materials Research Bulletin, 2024, 174: 112708.
9	RAHMAN Asad, CHIN Jitkai, CHEAH Kean. Prilling and coating of ammonium dinitramide (ADN) solid green propellant in toluene mixture using ultrasound sonication[J]. Aerospace, 2018, 5(1): 29.
10	KAVITAKE Digambar, TIWARI Swati, DEVI Palanisamy Bruntha, et al. Production, purification, and functional characterization of glucan exopolysaccharide produced by Enterococcus hirae strain OL616073 of fermented food origin[J]. International Journal of Biological Macromolecules, 2024, 259: 129105.
11	ZHANG Kai, YAO Sijing, GU Siyi, et al. Modified biochar activated by traditional Chinese medicine extract and its removal of tetracycline[J]. Surfaces and Interfaces, 2024, 48: 104293.
12	李玥其. 基于硬脂酸盐提升超细高氯酸铵热分解、安全及防吸湿性能的研究[D]. 绵阳: 西南科技大学, 2022.
	LI Yueqi. Study on stearate improvement of thermal decomposition, safety and anti-hygroscopic properties of ultrafine ammonium perchlorate[D]. Mianyang: Southwest University of Science and Technology, 2022.
13	Jisna JOS, MATHEW Suresh. Ammonium nitrate as an eco-friendly oxidizer for composite solid propellants: Promises and challenges[J]. Critical Reviews in Solid State and Materials Sciences, 2017, 42(6): 470-498.
14	YANG Hongyu, CHEN Fuyao, HU Yiwen, et al. A review on surface coating strategies for anti-hygroscopic of high energy oxidizer ammonium dinitramide[J]. Defence Technology, 2024, 33: 237-269.
15	王道林, 钱勖, 孙晓飞, 等. 复合固体推进剂力学性能调控方法研究进展[J]. 固体火箭技术, 2022, 45(5): 729-740.
	WANG Daolin, QIAN Xu, SUN Xiaofei, et al. Research progress on regulation method in mechanical properties of composite solid propellant[J]. Journal of Solid Rocket Technology, 2022, 45(5): 729-740.
16	吴军. 高氯酸铵的微纳结构化及其防吸湿性能的研究[D]. 绵阳: 西南科技大学, 2017.
	WU Jun. Study on the micro-nano structure of ammonium perchlorate and it’s anti-hygroscopicity property[D]. Mianyang: Southwest University of Science and Technology, 2017.
17	侯文斌. 脂肪酸类表面活性剂包覆改性硝酸铵防吸湿性能研究[D]. 南京: 南京理工大学, 2016.
	HOU Wenbin. Study on anti-hygroscopicity of modified ammonium nitrate particles by the fatty acid surfactant[D]. Nanjing: Nanjing University of Science and Technology, 2016.
18	LI Lei, LI Guoxiu, LI Hongmeng, et al. Effects of ignition voltage and electrode structure on electric ignition and combustion characteristics of ammonium dinitramide (ADN)-based liquid propellants in electric ignition mode in inert gas environment[J]. Chinese Journal of Aeronautics, 2024, 37(4): 229-242.
19	任晓雪, 赵凤起, 郑斌. ADN推进剂的研究发展[J]. 飞航导弹, 2007(12): 53-55.
	REN Xiaoxue, ZHAO Fengqi, ZHENG Bin. Research and development of ADN propellant[J]. Winged Missiles Journal, 2007(12): 53-55.
20	吕俊. 新型改性硝酸铵拒爆机理及拒爆改性剂复配研究[D]. 青岛: 中国石油大学(华东), 2007.
	Jun LYU. Research on anti-explosivity mechanisms and additives combination technology of new modified ammonium nitrate[D]. Qingdao: China University of Petroleum (East China), 2007.
21	张箭, 王庭鹏, 郭腾龙, 等. 添加剂对二硝酰胺铵热分解行为的影响[J]. 火炸药学报, 2019, 42(1): 37-40, 47.
	ZHANG Jian, WANG Tingpeng, GUO Tenglong, et al. Influences of additives on thermal decomposition behavior of ammonium dinitramide[J]. Chinese Journal of Explosives & Propellants, 2019, 42(1): 37-40, 47.
22	REN Zhongqi, CHEN Xinjian, YU Guojia, et al. Molecular simulation studies on the design of energetic ammonium dinitramide co-crystals for tuning hygroscopicity[J]. CrystEngComm, 2020, 22(31): 5237-5244.
23	QIAO Shen, LI Hongzhen, YANG Zongwei. Decreasing the hygroscopicity of ammonium dinitramide (ADN) through cocrystallization[J]. Energetic Materials Frontiers, 2022, 3(2): 84-89.
24	GIBSON Neil, KUCHENBECKER Petra, RASMUSSEN Kirsten, et al. Volume-specific surface area by gas adsorption analysis with the BET method[M]//Characterization of Nanoparticles. Amsterdam: Elsevier, 2020: 265-294.
25	陈加娜, 叶红齐, 谢辉玲. 超细粉体表面包覆技术综述[J]. 安徽化工, 2006, 32(2): 12-15.
	CHEN Jiana, YE Hongqi, XIE Huiling. Surface coating of superfine powders[J]. Anhui Chemical Industry, 2006, 32(2): 12-15.
26	谭君蕊, 李晖. 溶液结晶方法与技术的现状与发展[J]. 大学化学, 2021, 36(4): 110-121.
	TAN Junrui, LI Hui. Current situations and developments of the solution crystallization methods and techniques[J]. University Chemistry, 2021, 36(4): 110-121.
27	祁栋梁, 罗庆平, 崔鹏腾, 等. 溶剂-非溶剂法制备纳米FOX-7及其性能[J]. 含能材料, 2019, 27(1): 53-59.
	QI Dongliang, LUO Qingping, CUI Pengteng, et al. Preparation of nano-FOX-7 by solvent-non-solvent method and its properties[J]. Chinese Journal of Energetic Materials, 2019, 27(1): 53-59.
28	JOSHI Bhavana, SAMUEL Edmund, KIM Yong-il, et al. Electrostatically sprayed nanostructured electrodes for energy conversion and storage devices[J]. Advanced Functional Materials, 2021, 31(14): 2008181.
29	GEORGE S M, OTT A W, KLAUS J W. Surface chemistry for atomic layer growth[J]. The Journal of Physical Chemistry, 1996, 100(31): 13121-13131.
30	LI Jingjing, YANG Rongjie, CUI Yuanlu, et al. Construction of ammonium dinitramide@monoaminopropyl heptaphenylsilsesquioxane core-shell energetic microspheres with enhanced hygroscopicity inhibition and thermal decomposition properties[J]. Materials Chemistry and Physics, 2023, 303: 127822.
31	YAN Ning, BIAN Cheng, LI Hongyan, et al. Pickering emulsion-templated encapsulation of ammonium dinitramide by graphene sheets for hygroscopic inhibition[J]. Applied Surface Science, 2021, 537: 147994.
32	LIANG Xiao, ZHANG Jiyizhe, LI Min, et al. Dynamic interfacial tension and adsorption kinetics of nonionic surfactants during microfluidic droplet formation process[J]. Chemical Engineering Journal, 2022, 445: 136658.
33	郭长平, 田璐, 王敦举, 等．基于界面张力制备超疏水球形二硝酰胺铵的方法:CN109134170B[P]. 2021-02-09.
	GUO Changping, TIAN Lu, WANG Dunju, et al. Preparation of superhydrophobic spherical ammonium dinitramides based on interfacial tension: CN109134170B[P]. 2021-02-09.
34	龚婷, 秦利军, 严蕊, 等. 原子层沉积技术合成氧化铝薄膜包覆二硝酰胺铵[J]. 无机材料学报, 2014, 29(8): 869-874.
	GONG Ting, QIN Lijun, YAN Rui, et al. Alumina thin film coated ammonium dinitramide fabricated by atomic layer deposition[J]. Journal of Inorganic Materials, 2014, 29(8): 869-874.
35	CHENG Minmin, LIU Xun, LUO Qingping, et al. Cocrystals of ammonium perchlorate with a series of crown ethers: Preparation, structures, and properties[J]. CrystEngComm, 2016, 18(43): 8487-8496.
36	GOU Xiaodong, MA Zhongliang, LIU Wei, et al. Preparation of AP@ZIF-7 composite materials by chemical precipitation method: A good strategy for simultaneously improving its thermal performance, energy property and moisture absorption[J]. Powder Technology, 2024, 433: 119230.
37	LI Yueqi, WEN Tao, HUANG Xinyang, et al. Bio-inspired hydrophobic copper stearate coating to reduce the moisture absorption of fine-grained ammonium perchlorate and improve safety and thermal decomposition performance[J]. Journal of Physics and Chemistry of Solids, 2023, 179: 111416.
38	GOU Xiaodong, LIU Wei, MA Zhongliang, et al. In-situ synthesis of AP@Co/BIM composites with improved thermal performance and anti-hygroscopicity[J]. Materials Chemistry and Physics, 2023, 309: 128347.
39	张杰, 杨荣杰, 刘云飞. 硝酸铵的吸湿性研究[J]. 火炸药学报, 2001, 24(3): 22-25.
	ZHANG Jie, YANG Rongjie, LIU Yunfei. Study on hygroscopicity of ammonium nitrate[J]. Chinese Journal of Explosives & Propellants, 2001, 24(3): 22-25.
40	NAGAYAMA Seiichiro, KATOH Katsumi, HIGASHI Eiko, et al. Moisture proofing of spray dried particles comprising ammonium nitrate/potassium nitrate/polymer[J]. Propellants, Explosives, Pyrotechnics, 2015, 40(4): 544-550.
41	ELZAKI Baha I, ZHANG Yuejun. Relationships between structures of surfactants and their anti-hygroscopicity performance of ammonium nitrate particles[J]. Arabian Journal of Chemistry, 2020, 13(11): 7626-7636.
42	DAMSE R S. Waterproofing materials for ammonium nitrate[J]. Defence Science Journal, 2004, 54(4): 483-492.
43	熊言涛, 刘祖亮. 用改性直链烷烃改善硝酸铵的吸湿性[J]. 火炸药学报, 2013, 36(4): 50-52, 68.
	XIONG Yantao, LIU Zuliang. Improvement of the hygroscopicity of AN by modified paraffin[J]. Chinese Journal of Explosives & Propellants, 2013, 36(4): 50-52, 68.
44	ELZAKI Baha I, ZHANG Yuejun. Anti-hygroscopic surface modification of ammonium nitrate (NH₄NO₃) coated by surfactants[J]. Arabian Journal of Chemistry, 2020, 13(1): 3460-3473.
45	中华人民共和国国务院新闻办公室. 白皮书: 2021中国的航天[R/OL]. (2022-01-28) [2024-04-22]. .
	State Council Information Office of the People’s Republic of China. White Paper: China’s Aerospace in 2021[R/OL]. (2022-01-28)[2024-04-22]. .

[1]	王建, 赵亚风, 乔晓林, 李兴刚, 赵慧. 复合固体推进剂中固体填料的安息角测试与仿真[J]. 化工进展, 2020, 39(S2): 312-318.
[2]	滕雯, 陈勇, 隋猛, 李法社. TEPA与[MI][C₆H₂(OH)₃COO]复配对小桐子生物柴油抗氧化性的影响[J]. 化工进展, 2020, 39(11): 4427-4434.
[3]	王清良, 陈鹏, 胡鄂明, 李乾, 王红强, 阳奕汉, 李德, 徐屹群. 耐冷嗜酸硫杆菌快速氧化地浸采铀吸附尾液中Fe²⁺[J]. 化工进展, 2018, 37(10): 3995-4005.
[4]	董如林，方敏，陈智栋，金长春，罗敦泉. 基于硝酸铵气孔诱导剂的多孔TiO2薄膜的制备[J]. 化工进展, 2012, 31(06): 1285-1289.
[5]	井淑波，朱万春，管景奇，王国甲. 环境友好氧化剂催化氧化合成己二酸研究进展 [J]. 化工进展, 2009, 28(1): 62-.
[6]	孙果宋，黄科林，杨波，周纯海，陈文纳，宁红，李若华. 二氧化碳作为温和氧化剂的研究进展 [J]. 化工进展, 2007, 26(2): 216-.
[7]	张乐观 . 组合光催化技术在水处理中的应用 [J]. 化工进展, 2006, 25(9): 1036-.