摘要
为了探究溶剂对HMX重结晶过程的影响并分析其反应机理,以水为非溶剂、碳酸丙烯酯(PC)及二甲基亚砜(DMSO)为溶剂,采用喷射重结晶细化装置制备不同形貌的亚微米HMX;采用分子动力学(MD)模拟对不同形貌HMX的形成机理进行分析;采用扫描电子显微镜(SEM)、X射线粉末衍射仪(P-XRD)、差式扫描量热法(DSC)对制备的亚微米HMX进行表征和热分析,并测试了其撞击感度。结果表明,PC溶剂与HMX晶面的吸附结合能远小于DMSO/HMX体系;以PC为溶剂,采用喷射重结晶细化后的HMX呈类蜂巢状,以DMSO为溶剂细化后的HMX颗粒呈球形或短棒状,溶剂晶面结合能与晶面生长速率成负相关,不同溶剂与晶面结合能的差异引起晶体生长形态的变化;与原料HMX相比,以PC和DMSO为溶剂制备的超细HMX表观活化能分别降低31.26kJ/mol和55.73kJ/mol,指前因子均大幅度减小;特性落高由原来的35.65cm分别提高至70. 50cm和62.83cm,撞击感度均明显降低,表明安全性能明显提高。
In order to explore the effect of solvent on the recrystallization process of HMX and analyze its reaction mechanism, the submicron HMX with different morphologies was prepared by spray recrystallization refining device with water as anti-solvent, propylene carbonate (PC) and dimethyl sulfoxide (DMSO) as solvents. The forming mechanism of HMX with different morphologies was analyzed by molecular dynamics (MD)simulation. The prepared submicron HMX was characterized by scanning electron microscopy (SEM), X-ray powder diffraction (P-XRD) and differential scanning calorimetry (DSC), and its impact sensitivity was tested. The results show that the adsorption binding energy of PC solvents to HMX crystal surface is much less than that of DMSO/HMX system. When PC as solvent, HMX refined by jet spray recrystallization is honeycomb-like, and HMX particles refined by DMSO as solvent is spherical or short rod-like. The binding energy of solvents is negatively correlated with the growth rate of crystal surface. The difference of binding energy between solvents and crystal surface causes the change of crystal growth morphology. Compared with raw HMX, the apparent activation energies of HMX prepared with PC and DMSO as solvents decrease by 31.26kJ/mol and 55.73kJ/mol, respectively, and the pre-exponential factors decrease significantly. The characteristic drop height increase from 35.65cm to 70.50cm and 62.83cm, respectively, and the impact sensitivity decrease significantly, indicating that the safety performance of HMX is effectively improved.
作者
侯聪花
李聪聪
张诗敏
贾新磊
郭晨
张园萍
HOU Cong-hua;LI Cong-cong;ZHANG Shi-min;JIA Xin-lei;GUO Chen;ZHANG Yuan-ping(School of Environment and Safety Engineering, North University of China, Taiyuan 030051, China)
出处
《火炸药学报》
EI
CAS
CSCD
北大核心
2019年第3期262-267,I0003,共7页
Chinese Journal of Explosives & Propellants
基金
国家安全重大基础研究项目
山西省研究生教育创新项目(No.2018BY089)
关键词
物理化学
HMX
喷射重结晶细化
热分析
分子动力学模拟
撞击感度
physical chemistry
HMX
jet-recrystallization refinement
thermal analysis
molecular dynamics simulation
impact sensitivity
