新型复合油相乳化炸药基质的非等温热分解特性
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摘要
为了掌握新型复合油相制备的乳化炸药的热分解特性,利用TG-DTG技术测试了其制备的乳化炸药基质在氮气气氛中的热分解过程,用Kissinger法和Ozawa法进行动力学分析,求解相关动力学参数。通过模型拟合法推测其热分解机理,并用非模型拟合法进行验证。结果表明,新型复合油相制备的乳化炸药基质分解率为15%~95%时,其热分解平均活化能(E)和指前因子lg(A/s~(-1))分别为142.12kJ/mol和13.26,热稳定性高于复合蜡制备的乳化炸药基质,热分解过程符合三维(3D)扩散控制机理(n=2)。
In order to grasp the thermal decomposition characteristics of emulsion explosives prepared by the new complex oil phase,the non-isothermal thermal decomposition process of emulsion explosive matrix was tested by TG-DTG technology in nitrogen atmosphere.The corresponding kinetic parameters such as activation energy(E)and pre-exponenitial factor(A)were obtained according to the Kissinger and Ozawa methods.The thermal decomposition mechanism of the emulsion explosive matrix was predicted by the model fitting method,and was further verified by the model-free method.The results show that the average activation energy Eand pre-exponenitial factor lg(A/s~(-1))are about 142.12kJ/mol and 13.26 respectively in the conversion rate range of 15%-95%.The thermal stability of emulsion explosive matrix prepared by new complex oil phase is better than that of the matrix prepared by complex wax.The thermal decomposition reaction mechanism follows the three dimensional(3D)diffusion control mechanism(n=2).
In order to grasp the thermal decomposition characteristics of emulsion explosives prepared by the new complex oil phase,the non-isothermal thermal decomposition process of emulsion explosive matrix was tested by TG-DTG technology in nitrogen atmosphere.The corresponding kinetic parameters such as activation energy(E)and pre-exponenitial factor(A)were obtained according to the Kissinger and Ozawa methods.The thermal decomposition mechanism of the emulsion explosive matrix was predicted by the model fitting method,and was further verified by the model-free method.The results show that the average activation energy Eand pre-exponenitial factor lg(A/s~(-1))are about 142.12kJ/mol and 13.26 respectively in the conversion rate range of 15%-95%.The thermal stability of emulsion explosive matrix prepared by new complex oil phase is better than that of the matrix prepared by complex wax.The thermal decomposition reaction mechanism follows the three dimensional(3D)diffusion control mechanism(n=2).
引文
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[17]李国红.乳化炸药专用复合蜡的研制[D].天津:天津大学,2005.LI Guo-hong.A search of complex wax for emulsion explosive[D].Tianjin:Tianjin University,2005.
[18]胡伟龙,王德军,张志银,等.MF系列乳化炸药专用复合蜡的研究[J].爆破器材,2000,29(1):11-15.HU Wei-long,WANG De-jun,ZHANG Zhi-yin,et al.The research of MF series special compound wax for emulsion explosives[J].Explosive Materials,2000,29(1):11-15.
[2]尹利,郭子如,杨庆.岩石型乳化炸药的热分解动力学[J].火炸药学报,2009,32(2):6-10.YIN Li,GUO Zi-ru,YANG Qing.Thermal decomposition kinetics of rock emulsion explosives[J].Chinese Journal of Explosives&Propellants(Huozhayao Xuebao),2009,32(2):6-10.
[3]马志钢,周易坤,王瑾.乳化炸药基质含水量对其热分解的影响及动力学参数的计算[J].火炸药学报,2009,32(1):44-47.MA Zhi-gang,ZHOU Yi-kun,WANG Jin.Influence of water content in emulsion explosives basic substance on their thermal decomposition and calculation of kinetic parameters[J].Chinese Journal of Explosives&Propellants(Huozhayao Xuebao),2009,32(1):44-47.
[4]陈晓春.添加高氯酸铵的乳化炸药配方设计和热稳定性研究[D].淮南:安徽理工大学,2014.CHEN Xiao-chun.Formulation and thermal stability research of emulsion explosive adding ammonium perchlorate[D].Huainan:Anhui University of Science and Technology,2014.
[5]罗宁,李晓杰,王小红,等.复合乳化剂制备乳化炸药的热分解行为[J].火炸药学报,2009,32(3):5-15.LUO Ning,LI Xiao-jie,WANG Xiao-hong,et al.Thermal decomposition behavior of emulsion explosives prepared by multiple emulsion[J].Chinese Journal of Explosives&Propellants(Huozhayao Xuebao),2009,32(3):5-15.
[6]朱晶,谢兴华,罗伟,等.含有二价铁离子乳化炸药基质的热分解动力学研究[J].爆破器材,2011,40(3):8-10.ZHU Jing,XIE Xing-hua,LUO Wei,et al.Thermal decomposition kinetics of emulsion explosive containing ferrous ion[J].Explosive Materials,2011,40(3):8-10.
[7]魏焕曹.一种乳化炸药用复合油相:CN,201310432413.2[P].2016-07-13.
[8]胡荣祖,高胜利,赵凤起,等.热分析动力学[M].第二版.北京:科学出版社,2008.
[9]王瑾,马志钢,熊强青.乳化炸药热分解特性研究[J].爆破器材,2009,38(4):6-11.WANG Jin,MA Zhi-gang,XIONG Qiang-qing.Study on thermal decomposition characters of emulsion explosives[J].Explosive Materials,2009,38(4):6-11.
[10]Skarlis S A,Nicolle A,Berthout D,et al.Combined experimental and kinetic modeling approaches of ammonium nitrate thermal decomposition[J].Thermochimica Acta,2014,584:58-66.
[11]王小红.硝酸铵与乳化炸药典型组分混合物的热分解特性研究[D].淮南:安徽理工大学,2005.WANG Xiao-hong.Study on the thermal decomposition characteristics of typical components mixture of ammonium nitrate and emulsion explosives[D].Huainan:Anhui University of Science and Technology,2005.
[12]谭德新,王艳丽,甘颖,等.双酚芴乙二胺苯并噁嗪树脂的非等温热分解[J].固体火箭技术,2015,38(3):419-425.TAN De-xin,WANG Yan-li,GAN Ying,et al.Non-isothermal thermal decomposition of bisphenol fluorene diamine benzoxazine resin[J].Journal of Solid Rocket Technology,2015,38(3):419-425.
[13]彭浩梁,陈利平,路贵斌,等.乌洛托品的热分解动力学[J].含能材料,2016,24(5):497-502.PENG Hao-liang,CHEN Li-ping,LU Gui-bin,et al.Thermal decomposition kinetics of urotropin[J].Chinese Journal of Energetic Materials,2016,24(5):497-502.
[14]Vyazovkin S,Wight C A.Model-free and model-fitting approaches to kinetic analysis of isothermal and nonisothermal data[J].Thermochim Acta,1999,340/341:53-68.
[15]谭德新,王艳丽,唐玲,等.聚乙烯基三苯乙炔基硅烷的热分解动力学[J].材料科学与工艺,2015,23(4):81-86.TAN De-xin,WANG Yan-li,TANG Ling,et al.The thermal decomposition kinetics of poly(vinyltri-(phenylethynyl)silane)s[J].Materials Science and Technology,2015,23(4):81-86.
[16]张咪咪.新型复合油相及其专用乳化剂的研究[D].南京:南京理工大学,2015.ZHANG Mi-mi.Study on a new type of composite oil phase and special emulsifiers[D].Nanjing:Nanjing University of Science and Technology,2015.
[17]李国红.乳化炸药专用复合蜡的研制[D].天津:天津大学,2005.LI Guo-hong.A search of complex wax for emulsion explosive[D].Tianjin:Tianjin University,2005.
[18]胡伟龙,王德军,张志银,等.MF系列乳化炸药专用复合蜡的研究[J].爆破器材,2000,29(1):11-15.HU Wei-long,WANG De-jun,ZHANG Zhi-yin,et al.The research of MF series special compound wax for emulsion explosives[J].Explosive Materials,2000,29(1):11-15.
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