Institute of Chemical Materials , China Academy of Engineering Physics , Mianyang 621900 , Sichuan , China.
School of Information Engineering , Southwest University of Science and Technology , Mianyang 621010 , China.
ACS Appl Mater Interfaces. 2019 Nov 6;11(44):41523-41530. doi: 10.1021/acsami.9b14353. Epub 2019 Oct 23.
An effective and novel design strategy for ultrafast laser-initiating materials has been established on the basis of coordination chemistry for the first time in the present work. In view of the positive effect of Ag ion and perchlorate on laser sensitivity, silver perchlorate as a representative of oxidizing inorganic metal salts was used to construct energetic cationic coordination polymers (ECCPs), which solved the inconvenient situation caused by the difficulty in applying these salts directly in energetic materials because of the unavoidable hygroscopicity and the inhomogeneity of physical mixtures of oxidants and reductants. With the nonenergetic nitrogen-rich ligand 3-amino-1-1,2,4-triazole-5-carbohydrazide (ATCA), one new laser-sensitive Ag(I)-based ECCP [Ag(ATCA)ClO] () was successfully synthesized with a compact helical structure proved by X-ray single-diffraction crystal data. The physicochemical property evaluation revealed that this Ag-ECCP was not only completely devoid of the undesirable properties of the silver perchlorate and displayed excellent tolerance to moisture and noncorrosive properties to metal shells, but was also endowed with good thermal stability and excellent safety for mechanical stimulation. Moreover, theoretical calculations based on the standard molar enthalpy of formation and the lead plate explosive test as the actual damage experiment have proved that the compound has a superior detonation performance (up to 6800 m s and 0.511 kcal g) compared to the traditional primary explosives. More importantly, the laser-initiation-experiment-based femtosecond laser-testing system and high-speed photography demonstrated that this ECCP was an energetic material with great potential for application in the safety detonator as an ultrafast photosensitive initiating material for laser direct initiation, whose initiation delay time is as low as 73 ms using only 200 mJ initiation energy.
本工作首次基于配位化学为超快激光引发材料建立了一种有效且新颖的设计策略。鉴于 Ag 离子和高氯酸盐对激光灵敏度的积极影响，以高氯酸银为代表的氧化无机金属盐被用于构建含能阳离子配位聚合物（ECCP），解决了这些盐因吸湿性和氧化剂与还原剂物理混合物的不均匀性而直接应用于含能材料时带来的不便。利用非含能富氮配体 3-氨基-1,2,4-三唑-5-甲脒（ATCA），通过 X 射线单晶衍射晶体数据证实成功合成了一种新的激光敏感 Ag(I)基 ECCP[Ag(ATCA)ClO]（），其具有紧凑的螺旋结构。理化性质评估表明，该 Ag-ECCP 不仅完全没有高氯酸银的不良性质，而且对潮气具有优异的耐受性，对金属外壳无腐蚀性，还具有良好的热稳定性和对机械刺激的优异安全性。此外，基于标准摩尔生成焓和铅板爆炸试验（实际损伤实验）的理论计算证明，该化合物的爆轰性能（高达 6800 m s 和 0.511 kcal g）优于传统的初级炸药。更重要的是，基于激光引发实验的飞秒激光测试系统和高速摄影表明，该 ECCP 是一种有前途的含能材料，作为超快光敏引发剂，可用于安全雷管中直接激光引发，其引发延迟时间低至 73 ms，仅需 200 mJ 的引发能量。
