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.
Preparation of Energetic Burning Rate Inhibitor and Its Negative Catalytic Effect on AP Decomposition
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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维普
