基于声共振技术的CL-20基共晶材料制备及热解过程研究  

Preparation and Thermal Decomposition of CL-20-based Cocrystals Using Resonant Acoustic Mixing

作　　者：李海建 陈超[1] 张哲[2] 谢晓 马宁[2] 陈松[2] 金波 彭汝芳 仪建华[1] LI Hai-jian;CHEN Chao;ZHANG Zhe;XIE Xiao;MA Ning;CHEN Song;JIN Bo;PENG Ru-fang;YI Jian-hua(Science and Technology on Combustion and Explosion Laboratory,Xi′an Modern Chemistry Research Institute,Xi′an 710065,China;Xi′an Modern Chemistry Research Institute,Xi′an 710065,China;State Key Laboratory of Environment-friendly Energy Materials,Southwest Univeristy of Science and Technology,Mianyang Sichuan 621010,China)

机构地区：[1]西安近代化学研究所燃烧与爆炸技术重点实验室,陕西西安710065 [2]西安近代化学研究所,陕西西安710065 [3]西南科技大学环境友好能源材料国家重点实验室,四川绵阳621010

出　　处：《火炸药学报》2022年第6期848-855,共8页Chinese Journal of Explosives & Propellants

基　　金：国家自然科学基金(No.21473130,21905224,22075226);陕西省自然科学基金(No.2020JQ-984)。

摘　　要：为了满足未来火箭、战略/战术导弹及空间飞行器对高能钝感含能材料的应用需求,利用声共振技术制备了3种CL-20基共晶材料-CL-20/2-巯基-1-甲基咪唑、CL-20/4-甲基-5-硝基咪唑及CL-20/己内酰胺共晶体,并采用XRD、SEM、TG-DSC、TG-MS与激光点火试验系统研究这些共晶材料的结构、形貌、热分解与激光点火特性。结果表明,在共振加速度70g、微量溶剂的条件下混合15min可得到前两种共晶材料,混合30min后可得到CL-20/己内酰胺共晶,声共振技术与溶液挥发法制备这些共晶材料所使用的溶剂一致,不需要重新更换/筛选溶剂,而且相对于溶液挥发法,声共振技术溶剂使用量大幅减少,反应时间也更短。SEM结果表明,利用声共振技术制备的共晶材料颗粒大小不一、形状不规则;热分解研究发现3种CL-20共晶的放热峰温相对于CL-20都有所降低,热解过程、热释放量、热解产物与CL-20结合的共晶分子熔融峰温、初始热解温度等特征参数有关,CL-20/4-甲基-5-硝基咪唑共晶材料相对于CL-20热解速率更快,热释放量更大,共晶后热解产物中CO_(2)和H_(2)O明显增多;CL-20共晶后点火延迟时间与火焰传播特性有明显改变,含碳量较高的CL-20/己内酰胺共晶材料燃烧更完全、火焰更亮、强度更高。High-energy insensitive energetic materials were essential to develop future rockets,strategic/tactical missiles and space vehicles.Three CL-20-based cocrystals including CL-20/2-mercapto-1-methylimidazole,CL-20/4-methyl-5-nitroimidazole,and CL-20/caprolactam have been prepared by using Resonant Acoustic Mixing(RAM)technique,and their structures,morphology,thermal decomposition and ignition were studied by using PXRD,SEM,TG-DSC,TG-MS,and laser ignition apparatus.The results show that the first two cocrystals could be obtained after mixing for 15 min under the acceleration of 70 g and tiny solvents,and CL-20/caprolactam cocrystals were prepared successfully after mixing for 30 min under the same condition.It was found that the RAM could use the same solvents to the solvent evaporation method,and the volume of solvents was less compared to the solvent evaporation method,and the reaction time was also shorter.It can be seen from the SEM images that the cocrystal particles vary in size and shape.The decomposition peak temperature for these three CL-20 cocrystals was lower than that of the CL-20,and the thermal decomposition process,heat release,and decomposition products were strongly related to the melting temperature and initial decomposition temperature of the crystallization molecules.The CL-20/4-methyl-5-nitroimidazole cocrystal exhibited a faster decomposition rate and larger heat release than CL-20,and the decomposition gas products of these cocrystals exhibited the increase of CO_(2)and water vapor.After the CL-20 was crystallized,the ignition delay time and flame propagation have been affected,and the combustion of the CL-20/caprolactam with the high carbon content was more complete,and the flame was also lighter,and higher intensity.

关 键 词：物理化学 声共振技术 CL-20基共晶材料 共晶技术 热分解 激光点火 

分 类 号：TJ55[兵器科学与技术—军事化学与烟火技术] O64[理学—物理化学]