铁基功能配位聚合物对高氯酸铵热分解的调控研究

doi:10.15541/jim20260118

摘要/Abstract

摘要： 以高氯酸铵（AP）为氧化剂、羟基封端聚丁二烯（HTPB）为黏合剂的固体推进剂在固体火箭发动机中应用广泛。然而,AP固有的热分解起始温度较高、高温分解速率较低等热化学性能缺陷,制约了推进剂整体燃烧效率与能量释放速率。传统燃烧催化剂普遍存在催化活性不足、压强指数偏高以及难以兼顾超细AP颗粒分散稳定性与吸湿性抑制等多重局限,因而其在面向高可靠性要求与规模化工业生产的推进剂配方体系中的工程适用性仍显不足。本研究采用铁基功能配位聚合物含能复合材料Fe-CPs@AP作为调控AP热分解过程的催化剂。结果表明,添加4%(质量分数)Fe-CPs@AP的推进剂,其燃烧速率较空白样品提升56%~76%,压强指数为0.571,显著低于传统催化体系（>0.7）。该性能提升源于Fe-CPs@AP与HTPB基体间强化的界面相容性,不仅促进了AP热解过程中纳米金属氧化物的原位均匀析出,亦显著提升了催化活性中心的稳定性。催化机理分析与密度泛函理论共同证实,铁基活性组分作为多功能催化介质,可增强AP在低温分解过程中的电子传输效率,优化ClO₄^-与NH₄⁺之间的电荷转移路径,促进活性氧物种吸附,并提高高温阶段放热量与整体分解反应速率。此外,本研究为解决AP固有的吸湿性、颗粒团聚倾向性及高压敏感性等工程应用瓶颈提供了一种解决方案,为高性能、低压强敏感的固体推进剂设计与开发提供了兼具理论深度与工程可行性的新范式。

关键词: 铁基功能配位聚合物, AP-HTPB复合推进剂, 燃速催化剂, AP热分解

Abstract: Hydroxyl-terminated polybutadiene (HTPB)-based solid propellants using ammonium perchlorate (AP) as the oxidizer are widely used in solid rocket motors. However, the inferior defects of AP, such as high thermal decomposition initiation temperature and low high-temperature decomposition rate, limits propellant combustion performance. Conventional combustion catalysts exhibit insufficient catalytic activity, elevated pressure exponent, and inability to concurrently inhibit ultrafine AP agglomeration and mitigate its hygroscopicity. Thus, their adoption in high-reliability, production-ready propellant formulations remains limited. This work investigates the thermal decomposition of AP using Fe-based functional coordination polymer energetic composites (Fe-CPs@AP). Propellants containing 4% (in mass) Fe-CPs@AP show enhanced combustion performance, with burning rates increasing by 56%-76% over the baseline propellant. The pressure exponent is 0.571, significantly lower than that of conventional catalyzed systems (typically>0.7). This improvement results from optimized interfacial interactions between Fe-CPs@AP and the propellant matrix, promoting the in situ formation of uniformly dispersed metal oxide nanoparticles during AP decomposition and maximizing catalytic activity. Mechanistic and density functional theory studies indicate that Fe-containing species serve as catalytic mediators. They enhance electron transport in the low-temperature decomposition phase, optimize electron transfer between ClO₄^- and NH₄⁺, promote oxygen species adsorption, increase thermal energy release at high temperatures, and improve AP decomposition efficiency. This work tackles issues such as AP’s hygroscopicity, particle aggregation, and pressure sensitivity, offering theoretical and practical support for developing high-performance combustion propellants.

Key words: Fe-based functional coordination polymer, AP-HTPB propellant, combustion catalyst, decomposition of AP

中图分类号:

TB34

赵燕, 李辩, 刘贵玺, 张焘, 吕晓宇, 国朝晖, 翁洁鑫, 周星, 刘硕, 马忠云. 铁基功能配位聚合物对高氯酸铵热分解的调控研究[J]. 无机材料学报, DOI: 10.15541/jim20260118.

ZHAO Yan, LI Bian, LIU Guixi, ZHANG Tao, LÜ Xiaoyu, GUO Chaohui, WENG Jiexin, ZHOU Xing, LIU Shuo, MA Zhongyun. Regulating Thermal Decomposition of Ammonium Perchlorate by Fe-based Functional Coordination Polymers[J]. Journal of Inorganic Materials, DOI: 10.15541/jim20260118.

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