CL-20/FOX-7基PBX的制备及其性能表征
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摘要
为提高六硝基六氮杂异伍兹烷(CL?20)的安全性能,并保持其较高能量,以聚氨酯高聚物Estane为包覆剂,1,1?二氨基?2,2?二硝基乙烯(FOX?7)为含能降感成分,利用水悬浮包覆法制备了三种不同配比的CL?20/FOX?7基高聚物粘结炸药。采用扫描电子显微镜(SEM)、X射线衍射仪(XRD)、差示扫描量热仪(DSC)、撞击感度测试仪以及摩擦感度测试仪对样品的形貌结构、晶型、热分解特性以及样品的机械感度进行测试分析,用电测法对三种配比高聚物粘结炸药(PBX)爆速进行测试。结果表明,CL?20/FOX?7基炸药颗粒包覆效果较好,且CL?20和FOX?7均未发生转晶。三种CL?20/FOX?7基PBX表观活化能比细化CL?20分别提高了17.12,32.87 kJ·mol~(-1)和40.24 kJ·mol~(-1);活化焓(ΔH)较CL?20也明显提高;特性落高由细化CL?20的27.5 cm分别提高到58.3,56.5,54.2 cm。三种配比CL?20/FOX?7基PBX实测爆速分别为8474,8503,8577 mg·s~(-1),与PBXN?5相当,但特性落高较PBXN?5提升了48.5%以上,炸药安全性能明显提升。
To improve the safety performance of hexanitrohexaazaisowurtzitane(CL?20)and maintain its higher energy,three kinds of CL?20/FOX?7 polymer bonded explosives(PBXs)with different formulation proportions were prepared by water suspen?sion coating method using polyurethane polymer Estane as coating agent and 1,1?diamino?2,2?dinitroethene(FOX?7)as energet?ic sensitivity?reducing component. The morphology structure,crystal form,thermal decomposition characteristic and impact and friction sensitivity of samples were tested and analyzed by scanning electron microscopy(SEM),X?ray diffractometer(XRD),differential scanning calorimeter(DSC),impact sensitivity tester and friction sensitivity tester. The detonation velocity of three kinds of PBXs was tested by an electrical measurement method. The results show that the explosive particles based on CL?20/FOX?7 have better coating effect,and neither CL?20 nor FOX?7 has crystal transformation. The apparent activation energy of three kinds of PBXs are increased by 17.12,32.87 and 40.24 kJ·mol~(-1) compared with refined CL?20. The enthalpies of activation(ΔH) of PBX samples are also significantly improved compared with CL?20. The characteristic drop height increases from27.5 cm of refine CL?20 to 58.3,56.5 cm and 54.2 cm,respectively,compared with CL?20. The actual detonation velocities of three kinds of PBXs with different formulation proportions are 8474,8503 mg·s~(-1) and 8577 mg·s~(-1),respectively,which is equiva?lent to the detonation velocity of PBXN?5,but the characteristic drop height increases by more than 48.5% compared with PBXN?5,the safety performance of explosives is significantly improved.
To improve the safety performance of hexanitrohexaazaisowurtzitane(CL?20)and maintain its higher energy,three kinds of CL?20/FOX?7 polymer bonded explosives(PBXs)with different formulation proportions were prepared by water suspen?sion coating method using polyurethane polymer Estane as coating agent and 1,1?diamino?2,2?dinitroethene(FOX?7)as energet?ic sensitivity?reducing component. The morphology structure,crystal form,thermal decomposition characteristic and impact and friction sensitivity of samples were tested and analyzed by scanning electron microscopy(SEM),X?ray diffractometer(XRD),differential scanning calorimeter(DSC),impact sensitivity tester and friction sensitivity tester. The detonation velocity of three kinds of PBXs was tested by an electrical measurement method. The results show that the explosive particles based on CL?20/FOX?7 have better coating effect,and neither CL?20 nor FOX?7 has crystal transformation. The apparent activation energy of three kinds of PBXs are increased by 17.12,32.87 and 40.24 kJ·mol~(-1) compared with refined CL?20. The enthalpies of activation(ΔH) of PBX samples are also significantly improved compared with CL?20. The characteristic drop height increases from27.5 cm of refine CL?20 to 58.3,56.5 cm and 54.2 cm,respectively,compared with CL?20. The actual detonation velocities of three kinds of PBXs with different formulation proportions are 8474,8503 mg·s~(-1) and 8577 mg·s~(-1),respectively,which is equiva?lent to the detonation velocity of PBXN?5,but the characteristic drop height increases by more than 48.5% compared with PBXN?5,the safety performance of explosives is significantly improved.
引文
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[19]赵凤起,高红旭,徐司雨,等.含1,1-二氨基-2,2-二硝基乙烯(FOX-7)的钝感微烟推进剂能量参数和燃烧特性[J].火炸药学报,2010,33(4):1-4.ZHAO Feng-qi,GAO Hong-xu,XU Si-yu,et al.Energy parameters and combustion characteristics of the insensitive and minimum smoke propellants containing FOX-7[J].Chinese Journal of Explosives&Propellants,2010,33(4):1-4.
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[23]宋原.降感CL-20制备工艺技术研究[D].太原:中北大学,2016.SONG Yuan.The technology of the preparation process of insensitivity CL-20[D].Taiyuan:North University of China,2016.
[24]南海,王晓峰.FOX-7的表面能研究[J].含能材料,2006,14(5):388-390.NAN Hai,WANG Xiao-feng.Surface energy of FOX-7[J].Chi nese Journal of Energetic Materia ls Chinese Journal of Energertic Materials(Hanneng Cailiao),2006,14(5):388-387.
[25]石晓峰,李小东,王晶禹,等.RDX基超细球形包覆粒子的制备及热性能表征[J].固体火箭技术,2015(3):383-386.SHI Xiao-feng,LI Xiao-dong,WANG Jing-yu,et al.Preparation and thermal properties of RDX based ultrafine spherical coated particles[J].Journal of Solid Rocket Technology,2015,38(3):383-386.
[26]Jia X,Hou C,Tan Y,et al.Fabrication and Characterization of PMM A/HM X-based m icrocapsules via in situ polymerization[J].Central European Journal of Energetic Materia ls,2017,14(3):559-572.
[27]Kissinger H E.Reaction kinetics in differential thermal analysis[J].Analytical Chemistry,1957,29(1 1):1702-1 706.
[28]Ozawa T.A new method of analyzing thermogravimetric data[J].Bulletin of the chemical society of Japan,1965,38(11):1881-1886.
[29] Starink M J.Analysis of hydrogen desorption from linear heating experiments:Accuracy of activation energy determinations[J].International Journal of Hydrogen Energy,201 8,43(1 3):6632-6641.
[30] Zhang T,Hu R,Xie Y,et al.-The estimation of critical tem peratures of thermal explosion for energetic materials using non-isothermal DSC[J].Thermochimica Acta,1994,244(244):171-176.
[31]Ye B,An C,Zhang Y,et al.One-Step Ball Milling Preparation of Nanoscale CL-20/graphene oxide for significantly reduced particle size and sensitivity[J].Nanoscale research letters,2018,13(1):42.
[32]Sinditskii V P,Levshenkov A I,Egorshev V Y,et al.Study on combustion and thermal decomposition of 1,1-diamino-2,2-dinitroethylene(FOX-7)[C]//30th International Pyrotechnics Seminar(Europyro),2003.
[33]韩早,王伯良.混合炸药爆速预报的新方法[J].爆炸与冲击,2014,34(4):421-426.HAN Zao,WANG Bo-liang.A new method for predicting detonation velocity of com posite explosive[J].Explosion&Shock Waves,201 4.,34(4):421-426.
[34]王保国,张景林,陈亚芳,等.HMX/TATB基高聚物粘结传爆药传的研究[J].含能材料,2007,15(1):9-11.WANG Bao-guo,ZHANG Jing-lin,CHEN Ya-fang,et al.PBX booster explosive based on HMX/TATB[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2007,1 5(1):9-1 1.
[2]Nair U R,Sivabalan R,Gore G M,et al.Hexanitrohexaazaisowu rtzitane(CL-20)and CL-20-based form ulations(review)[J].Combustion,Explosion,and Shock Waves,2005,41(2):121-132.
[3]张朝阳.含能材料能量-安全性间矛盾及低感高能材料发展策略[J].含能材料,2018,26(1):2-10.ZHANG Chao-yang.On the energy&safety contradiction of energetic materials and the strategy for developing low-sensitive high-energetic materials[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),201 8,26(1):2-1 0.
[4]冀威,李小东,王晶禹,等.纳米ε-CL-20/Estane制备与表征[J].含能材料,2015,23(11):1084-1088.JI Wei,LI Xiao-dong,WANG Jing-yu,et al.Preparation and characterization of nano-ε-C L-20/Estane explosive[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2015,23(11):1084-1088.
[5]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,WANG Jing-yu,AN Chong-wei,et al.Preparation and properties of CL-20 based composite energetic material[J].Journal of Solid Rocket Technology,2017,40(2):199-203.
[6]魏华,焦清介,郭学永.石蜡/Estane5703复合钝感包覆CL-20的研究[J].含能材料,2017,25(4):321-325.WEI Hua,JIAO Qing-jie,GUO Xue-yong.Desensitizing technology of CL-20 by coating wax and Estane5703[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2017,25(4):321-325.
[7]王晶禹,高康,徐文峥,等.硬脂酸钙对CL-20/Estane复合粒子性能的影响[J].火炸药学报,2015,38(4):22-26.WANG Jing-yu,GAO Kang,XU Wen-zheng,et al.Effect of calcium stearate on the characteristics of CL-20/Estane composite particles[J].Chinese Journal of Explosives&Propellants,2015,38(4):22-26.
[8]陈鲁英,赵省向,杨培进,等.CL-20炸药的包覆钝感研究[J].含能材料,2006,14(3):171-173.CHEN Lu-ying,ZHAO Sheng-xiang,YANG Pei-jin,et al.The coating and desensitization of CL-20[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2006,14(3):171-1 70.
[9]杨志剑,刘晓波,何冠松,等.混合炸药设计研究进展[J].含能材料,2017,25(1):2-1 1.YANG Zhi-jian,LIU Xiao-bo,HE Guan-song,et al.Advances in design and research of composite explosives[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),201 7.
[10] Yang Z,Li J,Huang B,et al.Preparation and properties study of core-shell CL-20/TATB composites[J].Propellants,Explosives,Pyrotechnics,201 4,39(1):51-58.
[11]Tappan B C,Brill T B.Thermal decomposition of energetic materials 86.cryogel synthesis of nanocrystalline CL-20 coated with cured nitrocellulose[J].Propellants,Explosives,Pyrotechnics,2003,28(5):223-230.
[12]边红莉.CL-20基核-壳结构颗粒的制备及其性能表征[D].太原:中北大学,2017.BIAN Hong-li.Preparation and characterization of CL-20based core-shell structu re particle[D].Taiyuan:North University of China,201 7.
[13]徐容,田野,刘春.TA-TB对CL-20降感研究[J].含能材料,2003,11(4):219-221.XU Rong,TIAN Ye,LIU Chun.Study on the desensitization of CL-20 with TATB[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2003,1 1(4):21 9-221.
[14] Trzcinski W A,Belaada A.1,1-Diamino-2,2-dinitroethene(DADNE,FOX-7)-properties and form ulations(a review)[J].Central European Journal of Energetic Materials,2016,13(2):527-544.
[15]Helte A,Carlsson T E,Eldsater C,et al.Performance of FOX-7(1,1-diamino-2,2-dinitroethylene)in shaped charge applications[C]//23rd International Symposium on Ballistics,Tarragona.2007.
[1 6] Daniel M A,Davies P J,Lochert I J.FOX-7 for insensitive boosters[R].Defence Science and Technology Organisation Edinburgh(Australia)Weapons Systems DIV,2010.
[17] Trzcinski W A,Cudzilo S,Chylek Z,et al.Detonation properties and thermal behavior of FOX-7-based explosives[J].Journal of Energetic Materials,2013,31(1):72-85.
[18] Chytek Z,Jurkiewicz R.Investigation of the properties of polymer bonded explosives based on 1,1-diam ino-2,2-dinitroethene(FOX-7)and 1,3,5,7-tetranitro-1,3,5,7-tetraazacyclooctane(HMX)[J].Central European Journal of Energetic Materials,201 6,13(4):859-870.
[19]赵凤起,高红旭,徐司雨,等.含1,1-二氨基-2,2-二硝基乙烯(FOX-7)的钝感微烟推进剂能量参数和燃烧特性[J].火炸药学报,2010,33(4):1-4.ZHAO Feng-qi,GAO Hong-xu,XU Si-yu,et al.Energy parameters and combustion characteristics of the insensitive and minimum smoke propellants containing FOX-7[J].Chinese Journal of Explosives&Propellants,2010,33(4):1-4.
[20]刘国涛,刘少武,于慧芳,等.含FOX-7发射药的燃烧性能[J].火炸药学报,2012,35(2):82-85.LIU Guo-tao,LIU Shao-wu,YU Hui-fang,et al.Combustion performance of propellant containing FOX-7[J].Chinese Journal of Explosives&Propellants,2012,35(2):82-85.
[21]张阔,罗亚军,陈晓明,等.一种含FOX-7的发射药燃烧性能研究[J].兵工自动化,2013(11):60-62.ZHANG Kuo,LUO Ya-jun,CHEN Xiao-ming,et al.Study on combustion performance of gun propellant containing FOX-7[J].Ordnance Industry Automation,201 3(11):60-62.
[22]Lem pert D B,Dorofeenko E M,Shu Y.Energy potential of solid composite propellants based on 1,1-diamino-2,2-dinitroeth-ylene[J].Russian Journal of Physical Chemistry B,2016,10(3):483-489.
[23]宋原.降感CL-20制备工艺技术研究[D].太原:中北大学,2016.SONG Yuan.The technology of the preparation process of insensitivity CL-20[D].Taiyuan:North University of China,2016.
[24]南海,王晓峰.FOX-7的表面能研究[J].含能材料,2006,14(5):388-390.NAN Hai,WANG Xiao-feng.Surface energy of FOX-7[J].Chi nese Journal of Energetic Materia ls Chinese Journal of Energertic Materials(Hanneng Cailiao),2006,14(5):388-387.
[25]石晓峰,李小东,王晶禹,等.RDX基超细球形包覆粒子的制备及热性能表征[J].固体火箭技术,2015(3):383-386.SHI Xiao-feng,LI Xiao-dong,WANG Jing-yu,et al.Preparation and thermal properties of RDX based ultrafine spherical coated particles[J].Journal of Solid Rocket Technology,2015,38(3):383-386.
[26]Jia X,Hou C,Tan Y,et al.Fabrication and Characterization of PMM A/HM X-based m icrocapsules via in situ polymerization[J].Central European Journal of Energetic Materia ls,2017,14(3):559-572.
[27]Kissinger H E.Reaction kinetics in differential thermal analysis[J].Analytical Chemistry,1957,29(1 1):1702-1 706.
[28]Ozawa T.A new method of analyzing thermogravimetric data[J].Bulletin of the chemical society of Japan,1965,38(11):1881-1886.
[29] Starink M J.Analysis of hydrogen desorption from linear heating experiments:Accuracy of activation energy determinations[J].International Journal of Hydrogen Energy,201 8,43(1 3):6632-6641.
[30] Zhang T,Hu R,Xie Y,et al.-The estimation of critical tem peratures of thermal explosion for energetic materials using non-isothermal DSC[J].Thermochimica Acta,1994,244(244):171-176.
[31]Ye B,An C,Zhang Y,et al.One-Step Ball Milling Preparation of Nanoscale CL-20/graphene oxide for significantly reduced particle size and sensitivity[J].Nanoscale research letters,2018,13(1):42.
[32]Sinditskii V P,Levshenkov A I,Egorshev V Y,et al.Study on combustion and thermal decomposition of 1,1-diamino-2,2-dinitroethylene(FOX-7)[C]//30th International Pyrotechnics Seminar(Europyro),2003.
[33]韩早,王伯良.混合炸药爆速预报的新方法[J].爆炸与冲击,2014,34(4):421-426.HAN Zao,WANG Bo-liang.A new method for predicting detonation velocity of com posite explosive[J].Explosion&Shock Waves,201 4.,34(4):421-426.
[34]王保国,张景林,陈亚芳,等.HMX/TATB基高聚物粘结传爆药传的研究[J].含能材料,2007,15(1):9-11.WANG Bao-guo,ZHANG Jing-lin,CHEN Ya-fang,et al.PBX booster explosive based on HMX/TATB[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2007,1 5(1):9-1 1.