物理化学学报 >> 2013, Vol. 29 >> Issue (10): 2087-2094.doi: 10.3866/PKU.WHXB201308301

热分析动力学和热动力学 上一篇    下一篇

BTATz-Pb复合物对双基和RDX-改性双基推进剂的热行为、非等温动力学及燃烧性能的影响

李文1, 任莹辉1,2, 赵凤起2, 张鲜波1, 马海霞1, 徐抗震1, 王伯周2, 仪建华2, 宋纪蓉1,3, 胡荣祖2   

  1. 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, 火炸药国防燃烧重点实验室, 西安 710065;
    3 故宫博物院文保科技部, 北京 100009
  • 收稿日期:2013-06-14 修回日期:2013-08-30 发布日期:2013-09-26
  • 通讯作者: 任莹辉 E-mail:nwuryh@163.com
  • 基金资助:

    国家自然科学基金(21101127, 21073141);中国总装预研基金(9140A28020111BQ3401)及中国总装预研基金(A3120110005)资助项目

Effects of Lead Complex-Based BTATz on Thermal Behaviors, Non-Isothermal Reaction Kinetics and Combustion Properties of DB/RDX-CMDB Propellants

LI Wen1, REN Ying-Hui1,2, ZHAO Feng-Qi2, ZHANG Xian-Bo1, MA Hai-Xia1, XU Kang-Zhen1, WANG Bo-Zhou2, YI Jian-Hua2, SONG Ji-Rong1,3, HU Rong-Zu2   

  1. 1 Shaanxi Key Laboratory of Physico-inorganic Chemistry, School of Chemical Engineering, Northwest University, Xi'an 710069, P. R. China;
    2 Science and Technology on Combustion and Explosion Laboratory, Xi'an Modern Chemistry Research Institute, Xi'an 710065, P. R. China;
    3 Conservation Technology Department, The Palace Museum, Beijing 100009, P. R. China
  • Received:2013-06-14 Revised:2013-08-30 Published:2013-09-26
  • Contact: REN Ying-Hui E-mail:nwuryh@163.com
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21101127, 21073141), National Defense Pre-Research Foundation of China (9140A28020111BQ3401), and 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)的双基推进剂和改性双基推进剂. 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390-540 K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(TSADT)、热爆炸临界温度(Tb)、热点火温度(TTIT)和绝热至爆时间(tTlad),其值分别为: DB001复合物TSADT=444.50 K, TTITT=453.96 K, Tb=471.84 K; tTlad=39.36 s; CMDB100复合物, TSADT=442.38 K, TTITT=452.89 K,Tb=464.13 K,tTlad=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的提高燃速并且大幅度的降低压力指数. 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.

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, 复合双基推进剂, 非等温动力学, 热安全性, 燃烧性能

Abstract:

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-ylamino)-1,2,4,5-tetrazine (LCBTATz), with and without the ballistic modifier. Their thermal behaviors and nonisothermal decomposition reaction kinetics were investigated by thermogravimetry, derivative thermogravimetry (TG-DTG), and differential scanning calorimetry (DSC). For the LCBTATz-DB propellant, there was one mass 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 (TTITT), critical temperatures of thermal explosion (Tb), adiabatic timesto-explosion (tTlad), and thermodynamic parameters of activation reaction were calculated, and the thermal safety was evaluated. For DB001, TSADT=444.50 K, TTITT=453.96 K, Tb=471.84 K; tTlad=39.36 s. For CMDB100, TSADT=442.38 K, TTITT=452.89 K,Tb=464.13 K,tTlad=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.

Key words: 3,6-Bis(1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine, Lead salt, Double-bas propellant, Composite modified double base propellant, Nonisothermal kinetics, Thermal safety, Combustion property

MSC2000: 

  • O643