3,4-二硝基吡唑的性能表征及应用
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摘要
为了探究3,4-二硝基吡唑(DNP)替代TNT作为新型熔铸炸药载体的可行性,采用光学显微镜、傅里叶红外变换光谱仪、紫外可见分光光度计及DTA/TG热分析仪器对其结构进行了表征,利用氧弹量热仪、电测法分别测试了DNP爆热、爆速,并应用VLW程序计算了TNT/CL-20,DNP/CL-20混合炸药的爆轰参数。结果表明,DNP热分解过程主要分为吡唑环断裂和硝基脱环、自催化加速反应两个阶段,热分解表观活化能为131 k J·mol-1;DNP爆热、爆速分别为4326 k J·Kg~(-1)、7633 m·s~(-1),计算得出DNP/CL-20混合炸药爆轰性能明显优于TNT/CL-20混合炸药,当DNP/CL-20=2∶3(质量比)时,计算爆压为39.4 GPa,爆速为8961 m·s~(-1)。
To explore the possibility of 3,4-dinitropyrazole( DNP) instead of TNT as a new carrier for melt-cast explosives.,its structure w as characterized by optical microscope,FT IR spectrometer,U V VIS spectrophotometer,TG/DTA thermal analysis instrument. The heat of detonation and detonation velocity of DNP were respectively tested by an oxygen bomb calorimeter and the electrical measuring method.T he detonation property parameters of DNP/CL-20 and TNT/CL-20 composite explosives were calculated by the VLW program. R esults show that thermal decomposition of DNP,can be divided into tw o stages: ring's breaking、nitro 's falling off from the ring of D N P and autocatalytic reaction. T he apparent activation energy of thermal decomposition of DNP is 131 k J·mol- 1. T he experimental values of heat of detonation and detonation velocity of DN P are 4326 kJ·kg~(-1) and 7633 m ·s~(-1),respectively. The detonation performances of DNP/CL-20 composite explosive are better than those of TNT/CL-20 composite explosive. T he calculated values of detonation pressure and detonation velocity of DNP/CL-20 mixed explosive are 39. 4 GPa and 8961 m·s~(-1),respectively when DNP/CL-20 = 2:3( mass ratio).
To explore the possibility of 3,4-dinitropyrazole( DNP) instead of TNT as a new carrier for melt-cast explosives.,its structure w as characterized by optical microscope,FT IR spectrometer,U V VIS spectrophotometer,TG/DTA thermal analysis instrument. The heat of detonation and detonation velocity of DNP were respectively tested by an oxygen bomb calorimeter and the electrical measuring method.T he detonation property parameters of DNP/CL-20 and TNT/CL-20 composite explosives were calculated by the VLW program. R esults show that thermal decomposition of DNP,can be divided into tw o stages: ring's breaking、nitro 's falling off from the ring of D N P and autocatalytic reaction. T he apparent activation energy of thermal decomposition of DNP is 131 k J·mol- 1. T he experimental values of heat of detonation and detonation velocity of DN P are 4326 kJ·kg~(-1) and 7633 m ·s~(-1),respectively. The detonation performances of DNP/CL-20 composite explosive are better than those of TNT/CL-20 composite explosive. T he calculated values of detonation pressure and detonation velocity of DNP/CL-20 mixed explosive are 39. 4 GPa and 8961 m·s~(-1),respectively when DNP/CL-20 = 2:3( mass ratio).
引文
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[22]吴雄,龙新平,何碧,等.VLW爆轰产物状态方程[J].中国科学(B辑),2008,38(12):1129-1132.W U X iong,LO N G X in-ping,HE Bi,et al.T he VLW equation of state for detonation products[J].Science in C hina(B),2008,38(12):1129-1132.
[23]祝明水,何碧,蒋小华,等.Fortran VLW代码的可视化软件[J].含能材料,2007,15(2):307-310.Z HU M ing-shui,HE bi,JIAN G X iao-hua,et al.D etonation performance caculation of explosive w ith visualized fortran VLW code[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2007,15(2):307-310.
[2]王永川,唐兴民.梯黑药柱的改性研究[J].含能材料,1994,2(1):7-11.W AN G Yong-chuan,T AN G X ing-min.Study on modification of cast T N T-R D X charges[J].C hinese Journal of Energetic Materials(Hanneng Cailiao),1994,2(1):7-11.
[3]Stoltz C A,Manson B P,Hooper J.Neutron scattering study of internal void structure in R D X[J].Journal of A pplied physics,2010,107(5):1-6.
[4]王亲会.熔铸混合炸药用载体炸药评述[J].火炸药学报,2011,34(5):25-28.W AN G Q in-hui.O ver view of carrier explosive for melt-cast composite explosive[J].C hinese Journal of Explosives&Propellants,2011,34(5):25-28.
[5]Doll Daniel W,Hanks Jami M,Allred Alan G,et al.Reduced sensitivity melt-pourable T N T replacements[P]:U S2003/0005988.2003.
[6]Doll Daniel W,Hanks Jami M,Allred Alan G,et al.Reduced sensitivity melt-pourable T ritonal replacements[P]:U S2003/0140993.2003.
[7]Doll Daniel W,Hanks Jami M,Highsmith T homas K,et al.R educed sensitivity m elt-cast explo sives[P]:W o rld:01/46092.2001.
[8]Doll D,Hanks J,Allred A,et al.R educed Sensitivity,M eltPo urable T N T R eplacem ents[P]:W ipo Patent 2003002486.2003-1-10.
[9]田新.3,4-二硝基吡唑合成及性能研究[D].北京:中国工程物理研究院.2012.T IAN X in.Improved synthesis of 3,4-dinitropyrazole[D].Beijing:C hina Academy of Engineering Physic.2012.
[10]Janssen J,Koeners H J,Kruse C G,et al.Pyrazoles.XII.Preparation of 3(5)-nitropyrazoles by thermal rearrangeent of N nitr-opyrazoles[J].T he Journal of O rganic C hemistry,1973,38(10):1777-1782.
[11]Gabitov F A,Fridman A L,Kremleva O B.Peculiarities of the reaction of aliphatic diazo compounds w ith vicinal dinitroalke-nes[J].C hemistry of H eterocyclic C om pounds,1975,11(11):1342-1342.
[12]Latypov N V,Silevich V A,Ivanov P A,et al.Diazotization of aminonitropyrazoles[J].C hemistry of H ete rocyclic C ompoun-ds,1976,12(12):1355-1359.
[13]蒋秋黎,王浩,罗一鸣,等.3,4-二硝基吡唑的热行为及其与某些炸药组分的相容性[J].含能材料,2013,21(3):297-300.JIAN G Q iu-li,W AN G Hao,LU O Yi-ming,et al.T hermal behaviors of 3,4-dinitropyrazole and its compatibility w ith some explosive component materials[J].C hinese Journal of Energetic Materials(H anneng cailiao),2013,21(3):297-300.
[14]汪营磊,姬月萍,陈斌,等.3,4-二硝基吡唑合成与性能研究[J].含能材料,2011,19(4):377-379.W AN G Ying-lei,JI Yue-ping,C HEN Bin,et al.Improved synthesis of 3,4-dinitropyrazole[J].C hinese Journal of Energetic Materials(H anneng C ailiao),2011,19(4):337-379.
[15]杜闪,李永祥,王建龙,等.3,4-二硝基吡唑合成方法及性能研究综述[J].化学研究,2011,22(5):106-110.D U Shan,LI Yong-xiang,W AN G Jian-long,et al.R eview for synthetic method and properties of 3,4-dinitropyrazole[J].C hemical Research,2011,22(5):106-110.
[16]杜闪.3,4-二硝基吡唑合成及性能研究[D].太原:中北大学.2012.D U Shan.Synthesis and properties of3,4-dinitropyrazole[D].T aiyuan:N orth U niversity of C hina.2012.
[17]舒小艳.废弃炸药中HMX的回收及炸药晶体特性[D].绵阳:西南科技大学.2011.D U Shan.Synthesis and properties of 3,4-dinitropyrazole[D].M ianyang:Southw est U niversity of Science and T echnology.2011.
[18]Makashir P S,Kurian E M.Spectroscopic and Thermal Studies on 2,4,6-T rinitro T oluene(T N T)[J].Journal of T hermal A nalysis and C alorimetry,1999,55:173-185.
[19]刘子如.含能材料热分析[M].北京:国防工业出版社,2008.141-143.LIU Z i-ru.T hermal Analyses for Energetic M aterials[M].Beijing:N ational D efense Industry Press,2008.141-143.
[20]Ozawa T.A new method of analyzing thermogravimetric data[J].Bulletin of C hemical Society of Japan,1965,38(11):1881-1886.
[21]高大元,董海山,李波涛.炸药热分解动力学研究及其应用[J].含能材料(增刊),2004:307-310.GAO D a-yuan,D O N G Hai-shan,LI Bo-tao.R esearch and application of thermal decomposition kinetics for explosives[J].C hinese Journal of Energetic Materials(Supplement),2004:307-310.
[22]吴雄,龙新平,何碧,等.VLW爆轰产物状态方程[J].中国科学(B辑),2008,38(12):1129-1132.W U X iong,LO N G X in-ping,HE Bi,et al.T he VLW equation of state for detonation products[J].Science in C hina(B),2008,38(12):1129-1132.
[23]祝明水,何碧,蒋小华,等.Fortran VLW代码的可视化软件[J].含能材料,2007,15(2):307-310.Z HU M ing-shui,HE bi,JIAN G X iao-hua,et al.D etonation performance caculation of explosive w ith visualized fortran VLW code[J].Chinese Journal of Energetic Materials(Hanneng Cailiao),2007,15(2):307-310.