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西北工业大学 固体推进全国重点实验室, 陕西 西安 710072
Received:10 June 2022,
Published Online:06 February 2024,
Published:30 January 2024
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Xuexue ZHANG, Zhihua XUE, Hongqi NIE, et al. Preparation of Energetic Burning Rate Inhibitor and Its Negative Catalytic Effect on AP Decomposition[J]. Acta Armamentarii, 2024, 45(1): 15-25.
Xuexue ZHANG, Zhihua XUE, Hongqi NIE, et al. Preparation of Energetic Burning Rate Inhibitor and Its Negative Catalytic Effect on AP Decomposition[J]. Acta Armamentarii, 2024, 45(1): 15-25. DOI: 10.12382/bgxb.2022.0518.
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(Triaminoguaniding Glyoxal two dimensional Copolymer
TAGP)含能配体
并与碱土金属离子K
+
、Ba
2+
和Ca
2+
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NH
3
并与AP分解产物HClO
4
结合
形成更难分解的
$\mathrm{M}\left(\mathrm{ClO}_{4}^{-}\right)_{n}$
;通过碱土离子与
$\mathrm{ClO}_{4}^{-}$
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。
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
+
Ba
2+
and Ca
2+
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 NH
3
during the decomposition process and combine with HClO
4
(AP decomposition product) to form
$\mathrm{M}\left(\mathrm{ClO}_{4}^{-}\right)_{n}$
which is more difficult to decompose.The HTD process of AP is inhibited by the strong electrostatic interaction between alkaline earth metal ions and
$\mathrm{ClO}_{4}^{-}$
which inhibits the decomposition of
$\mathrm{ClO}_{4}^{-}$
to generate an oxidizing atmosphere and prevent theoxidative exotherm of the adsorbed NH
3
.
王江宁 , 李伟 , 郑伟 , 等 . 铝粉含量对CL-20/Al-CMDB推进剂燃速的影响 [J ] . 火炸药学报 , 2018 , 41 ( 4 ): 404 - 407 . DOI: 10.14077/j.issn.1007-7812.2018.04.015 http://doi.org/10.14077/j.issn.1007-7812.2018.04.015 采用激光动态法测定了1,1-二氨基-2,2-二硝基乙烯(FOX-7)在4种纯溶剂(DMSO、H<sub>2</sub>O、EtOH、ACE)和3种二元混合溶剂(DMSO-H<sub>2</sub>O、DMSO-EtOH、DMSO-ACE)中的溶解度;用Apelblat、Yaws和van’t Hoff模型对溶解度数据进行拟合;以DMSO为溶剂,H<sub>2</sub>O、EtOH、ACE为非溶剂,采用溶剂-非溶剂法对FOX-7进行重结晶,并采用电子显微镜对其形貌进行观察。结果表明,FOX-7在纯溶剂中的溶解度随温度的升高而增大,在混合溶剂中的溶解度随温度的升高和DMSO含量的增加而增大;在相同温度下、同等体积比的这3种二元混合溶剂,FOX-7在DMSO-H<sub>2</sub>O中的溶解度最小,在DMSO-ACE中的溶解度最大,3个溶解度模型的相关系数(R<sup>2</sup>)均大于0.96,因此可以采用这3个模型来关联溶解度数据;用电子显微镜观察到DMSO-ACE(体积比2:1)体系中冷却结晶得到的晶体形貌规则统一且呈类球状,未出现团聚现象。
WANG J N , LI W , ZHENG W , et al . Effect of aluminum powder content on the burning rate of CL-20/Al-CMDB propellants [J ] . Chinese Journal of Explosives & Propellants , 2018 , 41 ( 4 ): 404 - 407 . (in Chinese)
侯斌 , 张祺祺 , 邵雨滴 , 等 . 二茂铁类燃速抑制剂在HTPB推进剂中的迁移性能及催化作用 [J ] . 火炸药学报 , 2021 , 44 ( 5 ): 693 - 697 . DOI: 10.14077/j.issn.1007-7812.202106010 http://doi.org/10.14077/j.issn.1007-7812.202106010 为了研究丁基-硝氧乙基硝胺(Bu-NENA)对NC基推进剂能量及燃烧性能的影响,通过俄罗斯Real软件计算了Bu-NENA对推进剂的能量性能的影响; 通过吸收-压延的方法制备了推进剂样品,测试了推进剂的密度、爆热、比容、点火延迟、燃速,计算了压强指数; 通过燃烧波、火焰照片以及熄火表面探讨了Bu-NENA对推进剂燃烧性能影响的机理。结果表明,在NC基推进剂中Bu-NENA替代NG使能量下降,但是产气量增加,使推进剂的燃速大幅度下降,2MPa下燃速降幅75%以上,20MPa下燃速降幅64%以上; 压强指数提升, NC/NG基推进剂用部分催化剂可能对NC/Bu-NENA基体系失效; 推进剂的点火延迟时间增加; 推进剂的燃速大幅度降低的原因可能是因为Bu-NENA在燃烧时挥发吸热以及燃温降低带来的热反馈降低。
HOU B , ZHANG Q Q , SHAO Y D , et al . Migration performance and catalytic effect of ferrocene-based burning rate catalysts on HTPB propellant [J ] . Chinese Journal of Explosives & Propellants , 2021 , 44 ( 5 ): 693 - 697 . (in Chinese)
张国辉 , 赵凤起 , 徐司雨 , 等 . 实现双基系推进剂低燃速的调控技术研究进展 [J ] . 兵器装备工程学报 , 2021 , 42 ( 12 ): 16 - 22 .
ZHANG G H , ZHAO F Q , XU S Y , et al . Research progress on control technology of low burning rate for double base propellants [J ] . Journal of Ordnance Equipment Engineering . 2021 , 42 ( 12 ): 16 - 22 . (in Chinese)
XU S , PANG A M , WANG Y , et al . A review on the use of burning rate suppressants in AP‐based composite propellants [J ] . Propellants, Explosives, Pyrotechnics , 2022 , 47 ( 1 ): e202000327 . DOI: 10.1002/prep.v47.1 http://doi.org/10.1002/prep.v47.1 https://onlinelibrary.wiley.com/toc/15214087/47/1 https://onlinelibrary.wiley.com/toc/15214087/47/1
陈永 , 赵凤起 , 李辉 , 等 . 固体推进剂降速剂研究现状及发展趋势 [J ] . 火炸药学报 , 2021 , 44 ( 5 ): 567 - 577 . DOI: 10.14077/j.issn.1007-7812.202107014 http://doi.org/10.14077/j.issn.1007-7812.202107014 The burning rate reduction effects of different burning rate inhibitors in HTPB propellant, double base propellant, modified double base propellant and NEPE solid propellants are compared, and the burning rate reduction mechanism in different propellants is also summarized. Modified ammonium oxalate and metal salts are the most studied burning rate inhibitors for HTPB propellant; both ordinary and functional burning rate inhibitors can reduce the burning rate of double base propellant; most of the modified double base propellants are sucrose octaacetate(SOA), the burning rate of the propellant is reduced by 2.3—8.12mm/s over the pressure range of 2—15MPa; under the same conditions, the composite or bifunctional burning rate inhibitor in NEPE propellant has better burning rate reduction effect. It is suggested that the key research directions of the burning rate inhibitor in the future should be focused on the following aspects: the development of high-efficient burning rate inhibitors, the in-depth study of composite burning rate inhibitors, the exploration of energetic burning rate inhibitors and the development of micro- or nano-burning rate inhibitors.With 53 references.
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YADAV N , SRIVASTAVA P K , VARMA M . Recent advances in catalytic combustion of AP-based composite solid propellants [J ] . Defence Technology , 2021 , 17 ( 3 ): 1013 - 1031 . DOI: 10.1016/j.dt.2020.06.007 http://doi.org/10.1016/j.dt.2020.06.007 Composite solid propellants (CSPs) have widely been used as main energy source for propelling the rockets in both space and military applications. Internal ballistic parameters of rockets like characteristic exhaust velocity, specific impulse, thrust, burning rate etc., are measured to assess and control the performance of rocket motors. The burn rate of solid propellants has been considered as most vital parameter for design of solid rocket motors to meet specific mission requirements. The burning rate of solid propellants can be tailored by using different constituents, extent of oxidizer loading and its particle size and more commonly by incorporating suitable combustion catalysts. Various metal oxides (MOs), complexes, metal powders and metal alloys have shown positive catalytic behaviour during the combustion of CSPs. These are usually solid-state catalysts that play multiple roles in combustion of CSPs such as reduction in activation energy, enhancement of rate of reaction, modification of sequences in reaction-phase, influence on condensed-phase combustion and participation in combustion process in gas-phase reactions. The application of nanoscale catalysts in CSPs has increased considerably in recent past due to their superior catalytic properties as compared to their bulk-sized counterparts. A large surface-to-volume ratio and quantum size effect of nanocatalysts are considered to be plausible reasons for improving the combustion characteristics of propellants. Several efforts have been made to produce nanoscale combustion catalysts for advanced propellant formulations to improve their energetics. The work done so far is largely scattered. In this review, an effort has been made to introduce various combustion catalysts having at least a metallic entity. Recent developments of nanoscale combustion catalysts with their specific merits are discussed. The combustion chemistry of a typical CSP is briefly discussed for providing a better understanding on role of combustion catalysts in burning rate enhancement. Available information on different types of combustion nanocatalysts is also presented with critical comments. © 2020 The Authors
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