含氟高分子材料包覆铝核壳材料研究进展

doi:10.12382/bgxb.2022.1022

摘要/Abstract

摘要：

金属铝(Al)具有高燃烧热值、高密度、低耗氧量等优异性能,是固体复合推进剂领域最受青睐的金属添加剂。为了提高固体复合推进剂的性能,有必要采取措施对Al进行包覆改性。近年来含氟高分子包覆Al因其优异的综合性能而受到广泛关注。介绍了不同种类的含氟高分子包覆金属Al核壳材料、不同包覆方法、Al核壳材料的性能以及含氟高分子与Al的作用机理,总结发现通过Al核壳结构设计、含氟高分子引入和Al颗粒表面的自活化策略等途径,含氟高分子与氧化铝层之间的表面发生剧烈的氧化过程,增强Al核壳材料点火和燃烧性能,显著改善推进剂的燃烧团聚和燃烧效率。但目前含氟高分子包覆Al核壳材料研究过程仍存在许多不足,如缺乏新型多元含氟高分子包覆Al的能量性能的研究;缺乏Al颗粒与包覆层在高升温速率下作用机理的认识;包覆效率和批量制备能力低,阻碍了其实际应用等。未来可从进一步增强朝着研发新型含氟聚合物、研究对反应历程中产物的实时捕捉和开发工业化生产制造技术等方向发展。

关键词: 含氟高分子, 铝核壳材料, 包覆, 复合固体推进剂

Abstract:

Aluminum (Al) is the most popular metal additive in the field of composite solid propellants due to its high calorific value, high density and low oxygen consumption. In order to improve the performance of composite solid propellant, it is necessary to take measures to modify Al. In recent years, the fluorine-containing polymer coated Al has attracted wide attention due to its excellent comprehensive properties. This paper introduces the different kinds of metal aluminum core-shell materials coated with fluorine-containing polymer materials, the different coating methods, the properties of aluminum core-shell materials and the mechanism of action of fluorine-containing polymers and aluminum. The enhanced ignition and combustion performances of aluminum core-shell materials are due to the surface reaction between the fluorine-containing polymer and the alumina layer, resulting in a violent oxidation process. At the same time, the combustion agglomeration and combustion efficiency of aluminum core-shell material modified propellant are significantly improved. The problems existing in the research of fluorine-containing polymer coated aluminum materials are discussed, and the conclusion, prospect and possible research direction are put forward.

Key words: fluorinated polymer, aluminum core-shell material, coating, composite solid propellant

中图分类号:

TJ55

郭学永, 周近强, 李洪亮, 吴成成, 方华, 邓鹏, 朱艳丽, 刘睿. 含氟高分子材料包覆铝核壳材料研究进展[J]. 兵工学报, 2024, 45(5): 1534-1546.

GUO Xueyong, ZHOU Jinqiang, LI Hongliang, WU Chengcheng, FANG Hua, DENG Peng, ZHU Yanli, LIU Rui. Research Progress of Aluminum Core-shell Materials Coated with Fluorine-containing Polymer Materials[J]. Acta Armamentarii, 2024, 45(5): 1534-1546.

图/表 10

图1 高能核壳Al/PTFE的结构

Fig.1 Structure of high energy core-shell Al/PTFE

图2 Al/PTFE与水蒸汽反应机理

Fig.2 Reaction mechanism of Al/PTFE with water vapor

图3 Al/PTFE@TA和Al/PTFE@TA-Fe核壳结构示意图

Fig.3 Diagrams of Al/PTFE@/TA and Al/PTFE@TA-Fe core-shell structures

图4 粉状核壳结构PTFE/Al

Fig.4 PTFE/Al with powder core-shell structure

图5 钝化Al颗粒的氧化机理

Fig.5 Oxidation mechanism of passivated Al particles

图6 Al/PVDF和Al/AP/PVDF自支撑膜的3种制备示意图

Fig.6 Three preparation methods of Al/PVDF and Al/AP/PVDF free-standing membranes

图7 nAl/PFPE核壳材料与环氧树脂的共混制备

Fig.7 Blending preparation of nAl/PFPE core-shell material with epoxy resin

图8 PFTD(a)和PFS(b)的化学结构图

Fig.8 Chemical structures of PFTD (a) and PFS (b)

图9 开放燃烧过程中ANPs和AFNPs的燃烧图像

Fig.9 Combustion images of ANPs and AFNPs during open combustion

表1 各类含氟聚合物的理化性质及制备方法

Table 1 Physicochemical properties of various fluorine-containing polymers and preparation methods

含氟高分子	分子式	抗拉强度/ MPa	热分解温度/℃	含氟量/ %	溶解情况	与Al混合制备方法	参考文献
PTFE	(CF₂-CF₂)_n	238	508~538	76.0	几乎不溶于所有有机溶剂	化学气相沉积、机械球磨、3D打印等	文献[46,48]
PVDF	(CH₂-CF₂)_n	20~100	350	59.4	溶N-甲基吡咯烷酮,二甲基乙酰胺, N,N-二甲基甲酰胺	喷墨打印,电喷涂沉积、静电纺丝和相反转法等	文献[50- 56]
F₂₃₁₁	(CF₂-CFCl)_m-(CF₂-CH₂)_n (m∶n=1∶1)	410	200~400	72.3	溶于低分子酮类和酯类	3D打印	文献[72]
F₂₆₀₂	(CF₂-CH₂)_m-(CFCF₃-CF₂)_n (m∶n=1∶2)	210~230	≥400	73.1	溶于低分子酮类和酯类	电爆法	文献[32]
PFPE	(CF₂-O-CF₂)_n		270~300	79.3	常温为液体	机械混合、溶剂蒸发法	文献[58,60]
PFTD	C₁₄HF₂₇O₂			76.3	溶于乙醚	悬浮溶剂蒸发法、机械混合	文献[62- 63]
PFHD	C₁₆HF₃₁O₂			76.3	溶于乙醚	机械混合	文献[73]

参考文献 64

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