机构地区:[1]西北大学化工学院,陕西省物理无机化学重点实验室,西安710069 [2]西安近代化学研究所,燃烧与爆炸技术重点实验室,西安710065 [3]故宫博物院文保科技部,北京100009
出 处:《物理化学学报》2013年第10期2087-2094,共8页Acta Physico-Chimica Sinica
基 金:the National Natural Science Foundation of China(21101127,21073141);National Defense Pre-Research Foundation of China(9140A28020111BQ3401);National Defense Pre-Research Foundation of China(A3120110005)~~
摘 要:制备了含3,6-双(1-氢-1,2,3,4-四唑-5-氨基)-1,2,4,5-四嗪(BTATz)铅复合物(LCBTATz)的双基(DB)推进剂和黑索今(RDX)-改性双基(CMDB)推进剂.采用热重-微商热重法(TG-DTG)及差示扫描量热法(DSC)研究了其热分解行为和非等温分解动力学,并在此基础上评价了其热安全性.结果表明,LCBTATz-DB复合物中在350-540 K之间只存在一个放热分解峰,LCBTATz-CMDB复合物中存在两个连续的放热分解峰,在390-540K温度范围内,其机理方程分别为:f(α)=α^(-1)/2和f(α)=2(1-α)^(3/2).计算了热加速分解温度(T_(SADT))、热爆炸临界温度(T_b)、热点火温度(T_(TIT))和绝热至爆炸时间(t_(Tlad)),其值分别为:DB001复合物,T_(SADT)=444.50 K,T_(TITT)=453.96 K,T_b=471.84 K;t_(Tlad)=39.36 s;CMDB100复合物,T_(SADT)=442.38 K,T_(TITT)=452.89 K,T_b=464.13 K,t_(Tlad)=21.3 s,并以此来评价化合物的热安全性.考察了LCBTATz-DB以及LCBTATz-CMDB的燃烧性能,结果表明LCBTATz是一种高效的双基燃烧催化剂,在较大的压力范围内可以显著提高燃速并且大幅度降低压力指数.对于双基推进剂在2-8 MPa压力范围内出现了明显的超燃速现象,8-12 MPa出现了"麦撒"效应,对于改性双基推进剂的压力指数降到0.18.The composite double base (DB)/hexogen (RDX)-modified double base (CMDB) propellants (Nos. DB001 and CMDB100) were prepared with the lead complex of 3,6-bis(1H-1,2,3,4-tetrazol-5-yl- amino)-1,2,4,5-tetrazine (LCBTATz), with and without the ballistic modifier. Their thermal behaviors and non- isothermal decomposition reaction kinetics were investigated by therrnogravimetry, derivative thermogravimetry (TG-DTG), and differential scanning calorimetry (DSC). For the LCBTATz-DB propellant, there was onemass loss stage in the TG curve and one exothermic peak in the DSC curve over the temperature range 350-540 K. For LCBTATz-CMDB, there were two continuous exothermic stages in the TG curve, and only one corresponding exothermic peak in the DSC curve over the range 390-540 K. The exothermal decomposition reaction mechanisms of LCBTATz-DB and LCBTATz-CMDB follow the functions f(α)=α-1/2 and f(α)=2(1-α)3/2, respectively (α: conversion degree). The self-accelerating decomposition temperatures (TSADT), thermal ignition temperatures (T_TITT), critical temperatures of thermal explosion (Tb), adiabatic times- to-explosion (t_Tlad), and thermodynamic parameters of activation reaction were calculated, and the thermal safety was evaluated. For DB001, T_SADT=444.50 K, T_TITT=453.96 K, Tb=471.84 K, and t_Tlad=39.36 s. For CMDB100, TSAOT=442.38 K, T_TITT=452.89 K, Tb=464.13 K, and t_Tlad=21.3 s. As a high-efficiency combustion catalyst, LCBTATz in double-base propellants increases the propulsion rate and reduces the pressure index for larger scale pressures. This makes the DB propellant appear to have a significant super burning effect at 2-8 MPa and a "mesa effect" at 8-12 MPa. Meanwhile, the pressure exponent of the CMDB propellant decreased to 0.18.
关 键 词:3 6-双(1-氢-1 2 3 4-四唑-5-氨基)-1 2 4 5-四嗪 铅盐 双基推进剂 改性复合双基推进剂 非等温动力学 热安全性 燃烧性能
分 类 号:V512[航空宇航科学与技术—航空宇航推进理论与工程]
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