含能材料自催化分解特性的快速鉴别方法  

Rapid Identification of Autocatalysis Characteristics in Energetic Materials Decomposition Reactions

作　　者：平川 甘强[1] 张蕊[3] 都振华[3] 冯长根[1] PING Chuan;GAN Qiang;ZHANG Rui;DU Zhenhua;FENG Changgen(State Key Laboratory of Explosion Science and Technology,Beijing Institute of Technology,Beijing 100081,China;Xi an Aerospace Chemical Propulsion Co.,Ltd.,Xi an 710025,Shaanxi,China;Science and Technology on Applied Physical Chemistry Laboratory,Shaanxi Applied Physics and Chemistry Research Institute,Xi,an 710061,Shaanxi,China)

机构地区：[1]北京理工大学爆炸科学与技术国家重点实验室,北京100081 [2]西安航天化学动力有限公司,陕西西安710025 [3]陕西应用物理化学研究所应用物理化学重点实验室,陕西西安710061

出　　处：《兵工学报》2023年第2期368-379,共12页Acta Armamentarii

基　　金：爆炸科学与技术国家重点实验室(北京理工大学)自主课题资助项目(QNKT20-04)。

摘　　要：含能材料的自催化特性是造成含能材料极具危险性的主要原因之一,常用的自催化反应鉴别方法是利用差示扫描量热仪(DSC)、微热量热仪(C80)进行的“等温法”试验,该方法温度选择较为困难,试验周期较长且具有一定的危险性,有必要寻找一种快捷安全的自催化反应鉴别方法。基于绝热量热试验,结合反应机理函数,提出可快速鉴别含能材料自催化分解特性的方法,并利用该方法测量5种样品(过氧化二叔丁基(DTBP)与甲苯混合溶液、六硝基茋-Ⅳ(HNS-Ⅳ)、双(5-硝基四唑)合钴(Ⅲ)(BNCP)、六硝基六氮杂异伍兹烷(CL-20)、羧甲基纤维素叠氮化铅(CMC-LA)的绝热热分解特性。测量和分析结果表明:DTBP与甲苯混合溶液的热分解符合n级反应规律,HNS-Ⅳ、BNCP、CL-20、CMC-LA的热分解符合自催化反应规律,自催化反应强度随热惯性的增加而降低;新方法不需要计算准确的反应动力学参数,在自催化反应进行的初期就能完成自催化特性的鉴别,减少了测量时间的同时大大降低了测量过程的危险性,可快速鉴别物质分解是否有自催化特性,并可准确表征反应的自催化特性强度。Autocatalysis is one of the major reasons that make energetic materials extremely dangerous. The commonly used methods for identifying autocatalytic reactions is the “isothermal methods” based on differential scanning calorimetry(DSC) and microcalorimetry(C80). However, for these methods, temperature selection is one difficult problem, and the test period is long with some danger. So it is necessary to find a fast and safe method for the identification of autocatalytic reactions. This study proposes a method to quickly identify the characteristics of autocatalytic reactions and determine the reaction strength based on adiabatic thermal tests combined with reaction mechanism functions, which is used to measure the adiabatic thermal decomposition characteristics of five samples(20% DTBP and toluene mixed solution, HNS-IV, BNCP, CL-20, and CMC-LA). This method does not require the calculation of accurate reaction kinetic parameters, can identify the autocatalytic characteristics at the early stage of the autocatalytic reactions which reduces the measurement time and greatly reduces the risk in the process, and can quickly identify whether autocatalysis is involved in the decomposition of the substance and accurately characterize the autocatalytic intensity of the reactions.

关 键 词：含能材料 自催化 快速鉴别 反应机理函数 反应强度 绝热量热法 

分 类 号：TQ560.1[化学工程—炸药化工]