六硝基六氮杂异戊兹烷自催化分解特性与热安全性研究
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摘要
六硝基六氮杂异戊兹烷(CL-20)是一种十分重要的新型单质炸药,其热分解安全性一直备受关注。利用动态差示扫描量热(DSC)仪进行实验,初步研究了CL-20的热行为;利用中断回归法、瑞士方法研究了CL-20的自催化反应特性,并用等温DSC实验进行了验证;基于CL-20的动态DSC曲线数据,采用Friedman法求得其活化能E_α与ln[Af(α)]值随转化率α的变化曲线,并结合热平衡方程计算了其绝热诱导期TMR_(ad).结果表明:CL-20的起始分解温度为233.5~255.7℃,其分解反应为自催化反应,热履历显著降低了其起始分解温度和峰温;在反应的不同阶段,CL-20具有不同的活化能,其绝热诱导期8 h和24 h对应的温度T_(D8)和T_(D24)分别为162.3℃和152.8℃.
Hexanitrohexaazaisowurtzitane(CL-20) is a very important type of explosive,and its thermal decomposition safety has been paid attention.Differential scanning calorimetry(DSC) technique is employed to study the thermal decomposition and safety parameters of CL-20.The "interruptionrescanning" and Swiss methods are further applied to evaluate the autocatalytic effect of CL-20 during thermal decomposition,which is verified by isothermal DSC experiments.The decomposition kinetic parameters of CL-20 are determined by using the Friedman isoconversional method.The kinetic parameters with heat balance are analyzed and used to simulate the time to the maximum reaction rate under adiabatic conditions(TMRad).It is indicated that the initial thermal decomposition temperature is in the range from 233.5 to 255.7℃ at the heating rates of 2,5,10 and 20℃/min.Thermal history significantly influences the thermal stability of CL-20,where the preheating decreases its initial thermal decomposition temperature and the peak temperature.T_(D8) and T_(D24) of CL-20 were obtained to be 162.3 ℃ and 152.8℃,respectively.
Hexanitrohexaazaisowurtzitane(CL-20) is a very important type of explosive,and its thermal decomposition safety has been paid attention.Differential scanning calorimetry(DSC) technique is employed to study the thermal decomposition and safety parameters of CL-20.The "interruptionrescanning" and Swiss methods are further applied to evaluate the autocatalytic effect of CL-20 during thermal decomposition,which is verified by isothermal DSC experiments.The decomposition kinetic parameters of CL-20 are determined by using the Friedman isoconversional method.The kinetic parameters with heat balance are analyzed and used to simulate the time to the maximum reaction rate under adiabatic conditions(TMRad).It is indicated that the initial thermal decomposition temperature is in the range from 233.5 to 255.7℃ at the heating rates of 2,5,10 and 20℃/min.Thermal history significantly influences the thermal stability of CL-20,where the preheating decreases its initial thermal decomposition temperature and the peak temperature.T_(D8) and T_(D24) of CL-20 were obtained to be 162.3 ℃ and 152.8℃,respectively.
引文
[1]徐金江,孙杰,周克恩,等.CL-20重结晶过程中的晶型转变研究进展[J].含能材料,2012,20(2):248-255.XU Jin-jiang,SUN Jie,ZHOU Ke-en,et al.Review on polymorphic transformation on CL-20 recrystallization[J].Chinese Journal of Energetic Materials,2012,20(2):248-255.(in Chinese)
[2]王江宁,郑伟,舒安民,等.含CL-20改性双基推进剂的燃烧性能[J].火炸药学报,2013,36(1):61-64.WANG Jiang-ning,ZHENG Wei,SHU An-min,et al.Combustion properties of CMDB propellant containing hexaazaisowutzitane[J].Chinese Journal of Explosives and Propellants,2013,36(1):61-64.(in Chinese)
[3]王保国,陈亚芳,张景林,等.超细CL-20/Cr2O3复合物的制备、表征与性能[J].火工品,2013(3):26-29.WANG Bao-guo,CHEN Ya-fang,ZHANG Jing-lin,et al.Preparation,characterization and performances of ultrafine CL-20/Cr2O3 composite energetic materials[J].Initiators and Pyrotechnics,2013(3):26-29.(in Chinese)
[4]李玉川,祁才,孙成辉,等.2,6,8,12-四硝基-2,4,6,8,10,12-六氮杂异伍兹烷的合成及量子化学研究[J].含能材料,2010,18(2):121-127.LI Yu-chuan,QI Cai,SUN Cheng-hui,et al.Synthesis and quantum chemical study on 2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane[J].Chinese Journal of Energetic Materials,2010,18(2):121-127.(in Chinese)
[5]王东旭,陈树森,李丽洁,等.HBIW的纯度分析方法[J].火炸药学报,2011,34(2):29-32.WANG Dong-xu,CHEN Shu-sen,LI Li-jie,et al.Purity analysis method of HBIW[J].Chinese Journal of Explosives and Propellants,2011,34(2):29-32.(in Chinese)
[6]庞思平,申帆帆,吕芃浩,等.六硝基六氮杂异伍兹烷合成工艺研究进展[J].兵工学报,2014,35(5):725-732.PANG Si-ping,SHEN Fan-fan,LYU Peng-hao,et al.Research progress in synthesis of hexanitrohexaazaisowurtzitane[J].Acta Armamentarii,2014,35(5):725-732.(in Chinese)
[7]Xue X G,Ma Y,Zeng Q,et al.Initial decay mechanism of the heated CL-20/HMX cocrystal:a case of the cocrystal mediating the thermal stability of the two pure components[J].The Journal of Physical Chemistry,2017,121(9):4899-4908.
[8]Gao H X,Zhao F Q,Hu R Z,et al.Estimation of kinetic parameters of thermal decomposition reaction and thermal safety on hexanitrohexaazaisowurtzitane[J].Chinese Journal of Explosives and Propellants,2013,36(5):41-50.
[9]蔡如琳,胡伟,王敏,等.AP/HNIW混合体系的热分解研究[J].化学推进剂与高分子材料,2015,13(5):52-57.CAI Ru-lin,HU Wei,WANG Min,et al.Study on thermal decomposition of AP/HNIW mixed systems[J].Chemical Propellants and Polymeric Materials,2015,13(5):52-57.(in Chinese)
[10]欧阳刚,郭效德,席海军,等.亚微米六硝基六氮杂异伍兹烷的制备及其性能研究[J].兵工学报,2015,36(1):64-69.OUYANG Gang,GUO Xiao-de,XI Hai-jun,et al.Preparation and characterization of submicron hexanitrohexaazaisowurtzitane[J].Acta Armamentarii,2015,36(1):64-69.(in Chinese)
[11]宋乃孟,张同来,高红旭,等.亚微米级球形间苯三酚铁的制备及对六硝基六氮杂异伍兹烷热分解的影响[J].兵工学报,2016,37(3):547-552.SONG Nai-meng,ZHANG Tong-lai,GAO Hong-xu,et al.The preparation of sub-micron spherical phloroglucinol-Fe and its effects on thermal decomposition of hexanitrohexaazaisowurtzitane[J].Acta Armamentarii,2016,37(3):547-552.(in Chinese)
[12]Stoessel F.化工工艺热安全:风险评估与工艺设计[M].陈网桦,彭金华,陈利平,译.北京:科学出版社,2009.Stoessel F.Thermal safety of chemical processes:risk assessment and process design[M].CHEN Wang-hua,PENG Jinhua,CHEN Li-ping,translated.Beijing:Science Press,2009.(in Chinese)
[13]Roduit B,Hartmanna M,Follyb P,et al.Parameters influencing the correct thermal safety evaluations of autocatalytic reactions[J].Chemical Engineering Transactions,2013,31:907-912.
[14]杨庭,陈利平,陈网桦,等.分解反应自催化性质快速鉴别的实验方法[J].物理化学学报,2014,30(7):1215-1222.YANG Ting,CHEN Li-ping,CHEN Wang-hua,et al.Experimental method on rapid identification of autocatalysis in decomposition reactions[J].Acta Physico-Chimica Sinica,2014,30(7):1215-1222.(in Chinese)
[15]Bou-Diab L,Fierz H.Autocatalytic decomposition reactions,hazards and detection[J].Journal of Hazardous Materials,2002,93(1):137-146.
[16]Vyazovkin S,Burnham A K,Criado J M,et al.ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data[J].Thermochimica Acta,2011,520(1/2):1-19.
[17]Long G T,Brems B A,Wight C A.Autocatalytic thermal decomposition kinetics of TNT[J].Thermochimica Acta,2002,388(1/2):175-181.
[18]Singh A,Soni P K,Singh M,et al.Thermal degradation,kinetic and correlation models of poly(vinylidene fluoridechlorotrifluoroetheylene)copolymers[J].Thermochimica Acta,2012,548:88-92.
[19]Roduit B,Brogli F,Mascarello F,et al.Eestimation of TMRad using kinetics parameters derived from DSC-investigation of thermal behavior of 3-methy-4-nitrophenol[J].Journal of Thermal Analysis and Calorimetry,2009,94:1-9.
[2]王江宁,郑伟,舒安民,等.含CL-20改性双基推进剂的燃烧性能[J].火炸药学报,2013,36(1):61-64.WANG Jiang-ning,ZHENG Wei,SHU An-min,et al.Combustion properties of CMDB propellant containing hexaazaisowutzitane[J].Chinese Journal of Explosives and Propellants,2013,36(1):61-64.(in Chinese)
[3]王保国,陈亚芳,张景林,等.超细CL-20/Cr2O3复合物的制备、表征与性能[J].火工品,2013(3):26-29.WANG Bao-guo,CHEN Ya-fang,ZHANG Jing-lin,et al.Preparation,characterization and performances of ultrafine CL-20/Cr2O3 composite energetic materials[J].Initiators and Pyrotechnics,2013(3):26-29.(in Chinese)
[4]李玉川,祁才,孙成辉,等.2,6,8,12-四硝基-2,4,6,8,10,12-六氮杂异伍兹烷的合成及量子化学研究[J].含能材料,2010,18(2):121-127.LI Yu-chuan,QI Cai,SUN Cheng-hui,et al.Synthesis and quantum chemical study on 2,6,8,12-tetranitro-2,4,6,8,10,12-hexaazaisowurtzitane[J].Chinese Journal of Energetic Materials,2010,18(2):121-127.(in Chinese)
[5]王东旭,陈树森,李丽洁,等.HBIW的纯度分析方法[J].火炸药学报,2011,34(2):29-32.WANG Dong-xu,CHEN Shu-sen,LI Li-jie,et al.Purity analysis method of HBIW[J].Chinese Journal of Explosives and Propellants,2011,34(2):29-32.(in Chinese)
[6]庞思平,申帆帆,吕芃浩,等.六硝基六氮杂异伍兹烷合成工艺研究进展[J].兵工学报,2014,35(5):725-732.PANG Si-ping,SHEN Fan-fan,LYU Peng-hao,et al.Research progress in synthesis of hexanitrohexaazaisowurtzitane[J].Acta Armamentarii,2014,35(5):725-732.(in Chinese)
[7]Xue X G,Ma Y,Zeng Q,et al.Initial decay mechanism of the heated CL-20/HMX cocrystal:a case of the cocrystal mediating the thermal stability of the two pure components[J].The Journal of Physical Chemistry,2017,121(9):4899-4908.
[8]Gao H X,Zhao F Q,Hu R Z,et al.Estimation of kinetic parameters of thermal decomposition reaction and thermal safety on hexanitrohexaazaisowurtzitane[J].Chinese Journal of Explosives and Propellants,2013,36(5):41-50.
[9]蔡如琳,胡伟,王敏,等.AP/HNIW混合体系的热分解研究[J].化学推进剂与高分子材料,2015,13(5):52-57.CAI Ru-lin,HU Wei,WANG Min,et al.Study on thermal decomposition of AP/HNIW mixed systems[J].Chemical Propellants and Polymeric Materials,2015,13(5):52-57.(in Chinese)
[10]欧阳刚,郭效德,席海军,等.亚微米六硝基六氮杂异伍兹烷的制备及其性能研究[J].兵工学报,2015,36(1):64-69.OUYANG Gang,GUO Xiao-de,XI Hai-jun,et al.Preparation and characterization of submicron hexanitrohexaazaisowurtzitane[J].Acta Armamentarii,2015,36(1):64-69.(in Chinese)
[11]宋乃孟,张同来,高红旭,等.亚微米级球形间苯三酚铁的制备及对六硝基六氮杂异伍兹烷热分解的影响[J].兵工学报,2016,37(3):547-552.SONG Nai-meng,ZHANG Tong-lai,GAO Hong-xu,et al.The preparation of sub-micron spherical phloroglucinol-Fe and its effects on thermal decomposition of hexanitrohexaazaisowurtzitane[J].Acta Armamentarii,2016,37(3):547-552.(in Chinese)
[12]Stoessel F.化工工艺热安全:风险评估与工艺设计[M].陈网桦,彭金华,陈利平,译.北京:科学出版社,2009.Stoessel F.Thermal safety of chemical processes:risk assessment and process design[M].CHEN Wang-hua,PENG Jinhua,CHEN Li-ping,translated.Beijing:Science Press,2009.(in Chinese)
[13]Roduit B,Hartmanna M,Follyb P,et al.Parameters influencing the correct thermal safety evaluations of autocatalytic reactions[J].Chemical Engineering Transactions,2013,31:907-912.
[14]杨庭,陈利平,陈网桦,等.分解反应自催化性质快速鉴别的实验方法[J].物理化学学报,2014,30(7):1215-1222.YANG Ting,CHEN Li-ping,CHEN Wang-hua,et al.Experimental method on rapid identification of autocatalysis in decomposition reactions[J].Acta Physico-Chimica Sinica,2014,30(7):1215-1222.(in Chinese)
[15]Bou-Diab L,Fierz H.Autocatalytic decomposition reactions,hazards and detection[J].Journal of Hazardous Materials,2002,93(1):137-146.
[16]Vyazovkin S,Burnham A K,Criado J M,et al.ICTAC Kinetics Committee recommendations for performing kinetic computations on thermal analysis data[J].Thermochimica Acta,2011,520(1/2):1-19.
[17]Long G T,Brems B A,Wight C A.Autocatalytic thermal decomposition kinetics of TNT[J].Thermochimica Acta,2002,388(1/2):175-181.
[18]Singh A,Soni P K,Singh M,et al.Thermal degradation,kinetic and correlation models of poly(vinylidene fluoridechlorotrifluoroetheylene)copolymers[J].Thermochimica Acta,2012,548:88-92.
[19]Roduit B,Brogli F,Mascarello F,et al.Eestimation of TMRad using kinetics parameters derived from DSC-investigation of thermal behavior of 3-methy-4-nitrophenol[J].Journal of Thermal Analysis and Calorimetry,2009,94:1-9.