溶剂晶面吸附结合能对超细HMX性能的影响
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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 HM X and analyze its reaction mechanism,the submicron HM X 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 showthat the adsorption binding energy of PC solvents to HMX crystal surface is much less than that of DM SO/HMX system. When PC as solvent, HMX refined by jet spray recry stallizatio n is honeycomb-like, and HM X particles refined by DMSO as solvent is spherical of 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. Compaed with rawHMX, the appaent activation energies of HMX prepared with PC and DM SO as so lv ent s decrease by 31.26 kJ/mol and 55.73 kJ/mol, respectively,and the pre-exponential factors decrease significantly. The characteristic drop height increase from 35.65 cm to 70.50 cm and62.83 cm, respectively, and the impact sensitivity decrease significantly, indicating that the safety perfomance of HM X is effectively im pro ved.
In order to explore the effect of solvent on the recrystallization process of HM X and analyze its reaction mechanism,the submicron HM X 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 showthat the adsorption binding energy of PC solvents to HMX crystal surface is much less than that of DM SO/HMX system. When PC as solvent, HMX refined by jet spray recry stallizatio n is honeycomb-like, and HM X particles refined by DMSO as solvent is spherical of 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. Compaed with rawHMX, the appaent activation energies of HMX prepared with PC and DM SO as so lv ent s decrease by 31.26 kJ/mol and 55.73 kJ/mol, respectively,and the pre-exponential factors decrease significantly. The characteristic drop height increase from 35.65 cm to 70.50 cm and62.83 cm, respectively, and the impact sensitivity decrease significantly, indicating that the safety perfomance of HM X is effectively im pro ved.
引文
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[16]王江,刘英,李小东,等.喷雾干燥法制备球形RDX的工艺优化[J].火炸药学报,2015,38(1):16-21.WAN G Jiang,LIU Ying,LI Xiao-dong,et al.Process optimization of spherical R D X prepared by spray drying method[J].C hinese Journal of Explosives&Proprellants(Huozhayao Xuebao),2015,38(1):16-21.
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[18]胡荣祖.热分析动力学[M].北京:科学出版社,2008.
[2]侯聪花,贾新磊,王晶禹,等.非溶剂制备细化HMX及其性能表征[J].火炸药学报,2016,39(4):27-31.HO U C ong-hua,JIA Xin-lei,WAN G Jing-yu,et al.R efining HMX by non-solvent preparation and characterization of its properties[J].C hinese Journal of Explosives&Proprellants(Huoz hayao Xuebao),2016,39(4):27-31..
[3]陈芳,刘圆圆,王建龙,等.混合溶剂对β-HMX结晶形貌影响的分子动力学模拟[J].物理化学学报,2017,33(6):1140-1148.C HEN Fang,LIU Yuan-yuan,WAN G Jian-long,et al.Molecular dynamics simulation of the effect of mixed solvents on the crystal morphology of beta-HMX[J].A cta Physicochemistry,2017,33(6):1140-1148.
[4]蔡建国,周展云,邓修.超临界CO2-GAS重结晶HMX过程温度对晶体形貌的影响[J].火炸药学报,2000,23(4):42-44.C AI Jian-guo,Z HO U Z han-yun,D EN G Xiu.Effect of temperature on crystal morphology of supercritical C O2-GAS recrystallization HMX process[J].C hinese Journal of Explosives&Proprellants(Huoz hayao Xuebao),2000,23(4):42-44.
[5]马松,袁俊明,刘玉存,等.NTO结晶形貌的预测[J].火炸药学报,2014,37(1):53-57.MA Song,YU AN Jun-ming,LIU Yu-cun,et al.Prediction of crystal morphology of N TO[J].C hinese Journal of Explosives&Proprellants(Huoz hayao Xuebao),2014,37(1):53-57.
[6]汤崭,杨利,乔小晶,等.HMX晶体形貌的计算模拟[J].火炸药学报,2009,32(4):10-13.TAN G Z han,YAN G Li,Q IAO Xiao-jing,et al.C omputational simulation of HMX crystal morphology[J].C hinese Journal of Explosives&Proprellants(Huoz hayao Xuebao),2009,32(4):10-13.
[7]Andersen H C.Molecular dynamics simulations at constant pressure and/or temperature[J].The Journal of C hemical Physics,1980,72(4):2384-2393.
[8]张朝阳,舒远杰,赵小东,等.两种氟聚合物在TATB晶体表面吸附的动力学模拟[J].含能材料,2005,13(4):238-241.Z HAN G C hao-yang,SHU Yuan-jie,Z HAO Xiaodong,et al.Kinetic simulation of adsorption of two fluoropolymers on the surface of TATB crystals[J].Journal of Energetic Materials,2005,13(4):238-241.
[9]刘宁,周诚,舒远杰,等.N-脒基脲二硝酰胺盐晶体形貌的分子动力学研究[J].高等学校化学学报,2017,38(12):2231-2237.LIU N ing,Z HO U C heng,SHU Yuan-jie,et al.Molecular dynamics study on the crystal morphology of N-aminourea dinitroamide salt[J].C hemical Journal of C hinese Universities,2017,38(12):2231-2237.
[10]王晶禹,张景林,徐文峥.HMX炸药喷射结晶超细化实验研究[J].火炸药学报,2003,26(1):33-36.WAN G Jing-yu,Z HAN G Jing-lin,XU Wen-zheng.Experimental study on ultra-fine crystallization of HMXexplosives[J].C hinese Journal of Explosives&Proprellants(Huozhayao Xuebao),2003,26(1):33-36.
[11]叶宝云,王晶禹,安崇伟,等.CL-20基复合含能材料的制备及性能[J].固体火箭技术,2017,40(2):199-203..YE Bao-yun,WAN G Jing-yu,AN C hong-wei,et al.Preparation and properties of C L-20 based composite energetic materials[J].Journal of Solid Rocket Technology,2017,40(2):199-203.
[12]安崇伟.重结晶过程中HMX晶形影响因素与球形化工艺研究[D].太原:中北大学,2005.AN C hong-wei.Influencing factors and spheroidization process of HMX crystal form during recrystallization[D].Taiyuan:N orth U niversity of C hina,2005.
[13]高峰,黄辉,黄明,等.碳酸丙烯酯中HMX结晶形貌及其机理[J].含能材料,2012,20(5):575-578.GAO Feng,HU AN G Hui,HU AN G Ming,et al.C rystalline morphology and mechanism of HMX in propylene carbonate[J].Journal of Energetic Materials,2012,20(5):575-578.
[14]Kissinger H E.Reaction kinetics in differential thermal analysis[J].A nalytical C hemistry,1957,29(11):1702-1706.
[15]陈腾,李强,郭双峰,等.GAP-HDI/CL-20纳米复合含能材料的制备、表征及其热分解特性[J].火炸药学报,2018,41(3):243-249.C HEN Teng,LI Q iang,GU O Shuang-feng,et al.Preparation,characterization and thermal decomposition properties of GAP-HD I/C L-20 nanocomposite[J].C hinese Journal of Explosives&Proprellants(Huoz hayao Xuebao),2018,41(3):243-249.
[16]王江,刘英,李小东,等.喷雾干燥法制备球形RDX的工艺优化[J].火炸药学报,2015,38(1):16-21.WAN G Jiang,LIU Ying,LI Xiao-dong,et al.Process optimization of spherical R D X prepared by spray drying method[J].C hinese Journal of Explosives&Proprellants(Huozhayao Xuebao),2015,38(1):16-21.
[17]许丽娟,曹雄,冯翼鲲,等.含能材料CL-20的热安全性测试分析[J].安全与环境学报,2018(1):74-78.XU Li-juan,C AO Xiong,FEN G Yi-kun,et al.Thermal safety test analysis of energetic material C L-20[J].Journal of Safety and Environment,2018(1):74-78.
[18]胡荣祖.热分析动力学[M].北京:科学出版社,2008.