火炸药学报2013，Vol.36Issue(1)：9-16,8.
二(2,2,2-三硝基乙基)硝胺的热安全性和密度泛函理论研究
The Thermal Safety and A Density Functional Theoretical Study on Bis(2,2,2-Trinitroethyl)-Nitramine (BTNNA)
摘要
Abstract
With the help of the constant-volume standard combustion heat (Qc) of bis(2,2,2-trinitroethyl)-nitramine (BTNNA),the initial temperature (T0),at which DSC curves deviates from the baseline,the onset temperature (Te) and maximum peak temperature (Tp) from the non-isothermal DSC curves at different heating rates(β),the thermal decomposition activation energy(EK and Eo) and pre-exponential constant(AK) obtained by Kissinger's method and Ozawa's method,the value of be0(or p0) from equation lnβi=ln[A0/be0(or p0)G(α)] +be0(or p0) Te(or p)i and the value of ae0(or p0) from equation Inβt =ln[A0/(αe0(or p0) + 1)G(α)] + (αe0(orp0)) lnTe(ir p)i,the value of b from equation ln(βi/Tei-T0i)=ln[A0/G(α)]+bTei,the value of a from equation ln(β1/Tei-Toi=ln[A0/G(α))]+alnTei,the estimated values of specific heat capacity(cp),density (ρ) and thermal conductivity(λ),the decomposition beat (Qd,taking half-explosion heat),Zhang-Hu-Xie-Li formula,Hu Yang-Liang-Xie formula,formulae of calculating the critical temperature of thermal explosion based on Berthelot's equation and Harcourt-Esson's equation,Smith's equation,Friedman's formula,Bruckman-Guillet formula,thermodynamic formulae and Wang-Du formulas,the constant-volume standard combustion energy △cU (BTNNA,s,298.15K) and standard enthalpy of formation △fH0m(BTNNA,s,298.15K) obtained by ideal combustion reaction and Hess's law,the values(T00,Te0 and Tp0) of T0,Tc and Tp corresponding to β→0,critical temperature of thermal explosion (Tbe0 and Tbp0),adiabatic time-to-explosion(tTIad),50 ％ drop height (H50) of impact sensitivity,critical temperature of hotspot initiation (Tcr),thermal sensitivity probability density function S(T) for infinite platelike,infinite cylindrical and spheroidic BTNNA with half thickness and radius of 1m surrounded with surrounding of 310K,peak temperature corresponding to the maximum value of S(T) vs T relation curve(Ts(T) max),safety degree (SD),critical thermal explosion ambient temperature (Tacr) and thermal explosion probability (PTE) of BTNNA were calculated.The following results of evaluating the thermal safety of BTNNA were obtained:(1) △cU(BTNNA,s,298.15K) =-2 184.57kJ · mol 1 and △1H0m(BTNNA,s,298.15K)=(14.08±0.53)kJ ·mol 1; (2)T00 =356.89K,TSADT=Te0=374.75K,Tp0=430.04K;Tbe0=387.11K,Tbp0=439.20K;(3) when Ek=128040J ·mol-1,Ak,1012.865s 1,cp=1.21J· g-1 · K-1,Qd=2725.88J·g-1·T0=Te0=430.04K,,T=Tb=442.68K,f(a)=(1-a)n,a=10-3cm,ρ=1.97g·cm-3,t-t0=10-4s,Troom=293.15Kandλ=31.4×10-1J·cm-1 ·s-1 · K-1,H50=12.50cm,tTIad=1.73(n=0)s,1.74(n=1)s,1.75(n=2)s,Tcr,hot spot =446.41℃,for infinite plate,TS(T)max=303 5K,Tacr=298.77K,SD=14.57 ％,PT E=85.43％,for infinite cylinder,TS(T)max=308.5K,Tacr=303.82K,SD=25.57％,PTE=74.43％,for sphere,TS(T)max=312.0K,Tacr =307.02K,SD=33.67 ％,PTE =66 33 ％.The optimiaed geometry of BTNNA was obtained using H F/6-31 + G* method.The NMR chemical shift were obtained.The frontier orbital energy,atomic net charges and stabilization energy were discussed.关键词
物理化学/BTNNA/热分解/热安全性/自加速分解温度/热爆炸临界温度/撞击感度Key words
physical chemistry/ BTNNA/thermal decomposition/ thermal safety/ self-accelerating decomposition temperature/critical temperature of thermal explosion/ impact sensitivity分类
军事科技引用本文复制引用
胡荣祖,赵凤起,高红旭,马海霞,张海,徐抗震,赵宏安,姚二岗..二(2,2,2-三硝基乙基)硝胺的热安全性和密度泛函理论研究[J].火炸药学报,2013,36(1):9-16,8.基金项目
Project supported:Science and Technology Foundation of Key Laboratory on Combustion and Explosion of China (No.9140C3501010601) （No.9140C3501010601）
