铅丹-硅系延期药贮存中的化学反应机理
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摘要
基于铅丹和硅的物理化学特性,对铅丹-硅系延期药在常温封闭贮存下发生自发氧化还原反应的可能性及其反应机理进行了研究。给出了药剂贮存中可能发生的化学反应方程式,计算了各反应的主要热力学参数ΔrGθm、ΔrHθm、ΔrSθm,通过对热力学参数的分析,讨论了各反应的自发性。结合固体化学和薄膜生长理论,建立了药剂氧化还原反应的扩散模型和硅粉表面的氧化模型。结果表明,单一Pb3O4在贮存中不会自发分解,但是,当Pb3O4与Si混合后贮存时,两者发生氧化还原反应,部分反应产物PbO会驻留在SiO2的网络结构中。
Based on the physical and chemical properties of red lead and silicon,the possibilities and reaction mechanism of the spontaneous redox reaction occurred in the red lead/silicon delay composition were researched,which were stored at normal temperature and closed environment.The possible chemical reaction equations in the storage course of delay composition were enumerated.The thermodynamic parameters of these reactions,such asΔrGθ m、Δr Hθ m、ΔrSθ mwere calculated.The spontaneity of each reaction was discussed by analyzing the thermodynamic parameters.Combined the theory of solid chemistry with thin film growth,the redox diffusion model of the delay composition and the oxidation model on the surface of silicon powder were established.Results indicate that the single Pb3O4 has no spontaneous decomposition reaction in the storage,but when Pb3O4is mixed with silicon and then stored,the redox reaction happens in the two components,and part of the reaction product PbO will reside in network structure of SiO2.
Based on the physical and chemical properties of red lead and silicon,the possibilities and reaction mechanism of the spontaneous redox reaction occurred in the red lead/silicon delay composition were researched,which were stored at normal temperature and closed environment.The possible chemical reaction equations in the storage course of delay composition were enumerated.The thermodynamic parameters of these reactions,such asΔrGθ m、Δr Hθ m、ΔrSθ mwere calculated.The spontaneity of each reaction was discussed by analyzing the thermodynamic parameters.Combined the theory of solid chemistry with thin film growth,the redox diffusion model of the delay composition and the oxidation model on the surface of silicon powder were established.Results indicate that the single Pb3O4 has no spontaneous decomposition reaction in the storage,but when Pb3O4is mixed with silicon and then stored,the redox reaction happens in the two components,and part of the reaction product PbO will reside in network structure of SiO2.
引文
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[4]钟国清,朱云云.无机及分析化学[M].北京:科学教育出版社,2006.
[5]曹锡章,宋天佑,王杏乔.无机化学[M].北京:高等教育出版社,1994.
[6]叶迎华.火工品技术[M].北京:北京理工大学出版社,2007.
[7]宋肯彭,宋小兰,张树海,等.纳米Si/Pb3O4延期药热反应动力学研究[J].火工品,2011(2):24-28.SONG Ken-peng,SONG Xiao-lan,ZHANG Shu-hai,et al.Kinetic evaluation for thermal reaction of nanometer delay composition Si/Pb3O4[J].Initiating Explosive Devices,2011(2):24-28.
[8]Yoganarasimhan S R,Josyulu O S.Reactivity of the ternary pyrotechnic system red lead-silicon-ferric oxide[J].IDL Chemicals Limited,1987,37(1):73-83.
[9]张克立.固体无机化学[M].武汉:武汉大学出版社,2005.
[10]郑忠,胡纪华.固相反应动力学[M].广州:广东科技出版社,1993.
[11]洪广言.无机固体化学[M].北京:科学教育出版社,2002.
[12]吴自勤,王兵.薄膜生长[M].北京:科学教育出版社,2001.
[13]张长瑞,杨以文,张光.扩散控制的固相反应动力学模型[J].物理化学学报,1988,4(5):539-543.ZHANG Chang-rui,YANG Yi-wen,ZHANG Guang.Models for kinetic analyses of diffusion control solid reaction[J].Chinese Journal of Chemical Physics,1988,4(5):539-543.
[14]冯志祥.提高硅系延期药时间精度的探讨[J].火工品,1990(1):5-8.FENG Zhi-xiang.Investigate on improve the time accuracy of silicon delay composition[J].Initiating Explosive Devices,1990(1):5-8.
[15]张立生,孙仁江.硅系延期药生产工艺的优选[J].爆破器材,2001(1):18-21.ZHANG Li-sheng,SUN Ren-jiang.The optimum production craft in silicon delay chemicals[J].Explosive Materials,2001(1):18-21.
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[17]Stesmans A.Low-temperature ESR study of PbO defects residing in the(111)Si/native oxide interface[J].Applied Surface Science,1987(30):134-141.
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