Preparation of Energetic Burning Rate Inhibitor and Its Negative Catalytic Effect on AP Decomposition
张雪雪 1薛智华 1聂洪奇 1严启龙1
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作者信息
1. 西北工业大学 固体推进全国重点实验室,陕西 西安 710072
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摘要
燃速抑制剂作为固体推进剂的核心功能组分,在降低固体推进剂高压燃速方面起关键作用.精准设计具有降速效应的季铵与醛基结构,获得高氮三氨基胍乙二醛二维共聚物(Triamin-oguaniding Glyoxal two dimensional Copolymer,TAGP)含能配体,并与碱土金属离子K+、Ba2+和Ca2+发生络合反应,制备系列新型含能燃速抑制剂(TAGP-M).采用粉末衍射、X射线光电子能谱、扫描电镜/能谱和差示扫描量热/热重联用等技术分析其形貌、结构和热稳定性,并研究这些含能燃速抑制剂对高氯酸铵(Ammonium Perchlorate,AP)热分解的负催化作用.研究结果表明:TAGP-K对AP转晶抑制最为显著,使AP 的转晶吸热峰温提高 5.9℃、低温分解峰峰温升高 28.7℃;添加10 wt%的TAGP-K,可使AP的最大热分解速率降低 58%;TAGP-Ca燃速抑制剂可使AP的释能效应集中在高温分解过程,AP/TAGP-Ca 混合体系的放热量比纯 AP 提高 50%以上;TAGP-Ca 和TAGP-Ba燃速抑制剂在抑制含AP分解的同时提高了其释能效率;TAGP-M燃速抑制剂在分解过程中释放NH3并与AP分解产物HClO4结合,形成更难分解的M(ClO4-)n;通过碱土离子与ClO4-离子强静电作用,抑制后者分解产生氧化性气氛,进而抑制AP高温放热反应过程.
Abstract
As the key functional component of solid propellant,the burning rate inhibitor plays an important role in regulating the burning rate of solid propellant.In this paper,the quaternary ammonium and aldehyde-based structures with combustion suppression effect are precisely designed and evaluated.The high nitrogen triaminoguanidine glyoxal two-dimensional copolymer(TAGP)is used as an energetic ligand.It is complexed with alkaline earth metal ions,such as K+,Ba2+ and Ca2+,to prepare a series of novel energetic burning rate inhibitors(so called TAGP-M).The morphologies,structure and thermal stability of the as-prepared compoundsare characterized by X-ray diffraction,X-ray photoelectron spectroscopy,scanning electron microscope/energy dispersive spectrometer,and differential scanning calorimetry and thermogravimetric analysis techniques.The negative catalytic effect of energetic burning rate inhibitor on ammonium perchlorate(AP)decomposition is analyzed.It shows that TAGP-K has obvious inhibitory effect on the crystal transition of AP.In presence of TAGP-K,the endothermic peak temperature of AP crystal transition is increased by 5.9℃,whereas the first peak decomposition temperature is increased by 28.7℃.More importantly,the use of 10 wt%TAGP-K could reduce the maximum thermal decomposition rate of AP by 58%.The corresponding energy release of AP is focused to high-temperature decomposition(HTD)process.The heat release of AP/TAGP-Ca is more than 50%higher than that of pure AP during HTD process.It shows that TAGP-Ca and TAGP-Ba increase the energy release efficiency of AP while inhibitingits decomposition.The TAGP-M burning rate inhibitors release NH3 during the decomposition process and combine with HClO4(AP decomposition product)to form M(ClO4-)nwhich is more difficult to decompose.The HTD process of AP is inhibited by the strong electrostatic interaction between alkaline earth metal ions and ClO4-,which inhibits the decomposition of ClO4-to generate an oxidizing atmosphere and prevent theoxidative exotherm of the adsorbed NH3.
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