2,2,2-三硝基乙基-N-硝基甲胺的热安全性（英文）

Thermal Safety of 2,2,2-Trinitroethyl-N-nitromethyl Amine

为评价2,2,2-三硝基乙基-N-硝基甲胺(TNMA)的热安全性,得到计算TNMA热安全性参数用的基本数据,用经验式估算了TNMA的比热容(C_p)和热导率(λ).用键能贡献于生成热Q_f的加和法,估算了TNMA的标准生成焓△_fH_m^(θ)(TNMA,s,298.15 K).用热力学公式计算了TNMA的标准燃烧焓△_CH_m^(θ)(TNMA,s,298.15 K)和标准燃烧能△U_m^(θ)(TNMA,s,298.15 K).用Kamlet-Jacobs公式估算了爆速、爆压和爆热.用经验式估算了分解热(Q_d).通过差示扫描量热(DSC)曲线和高灵敏度布鲁顿玻璃薄膜压力计测得的逸出气体标准体积(V_H)-时间(t)曲线,得到了TNMA放热分解反应的动力学参数.用上述基本数据得到了评价TNMA的热安全性参数:自加速分解温度(T_(SADT)),热爆炸临界温度(T_(be0)和T_(bp0)),绝热至爆时间(t_(Tlad)),撞击感度50%落高(H_(50)),热点起爆临界温度(T_(cr)),被300 K环境包围的半厚和半径为1 m的无限大平板、无限长圆柱和球形TNMA的热感度概率密度函数S(T),相应于S(T)-T关系曲线最大值的峰温(T_(S(T)max)),安全度(SD),临界热爆炸环境温度(T_(acr))和热爆炸概率(P_(TE)).结果表明:(1)TNMA有较好的热安全性和对热抵抗能力,与环三亚甲基三硝胺(RDX)相比,TNMA易从热分解过渡到热爆炸;(2)不同形状大药量TNMA热安全性降低的次序为:球>无限长圆柱>无限大平板;(3)TNMA有高的燃烧能、高的爆轰化学能(爆热)和接近环四亚甲基四硝胺(HMX)的爆炸性能,其对冲击敏感,冲击感度与季戊四醇四硝酸酯(PETN)和特屈尔接近,可用作混合炸药主组分.

To evaluate the thermal safety of 2,2,2-trinitroethyI-N-nitromethyl amine （TNMA）, basic data, including specific heat capacity （Cp） and thermal conductivity （λ）, were estimated using empirical formulae. The standard enthalpy of formation of TNMA,△ fHm （TNMA, s, 298.15 K）, was calcutated by an additive method of contributing bond energy to heat of formation Qf, and the standard combustion enthalpy △cHm （TNMA, s, 298.15 K） and standard combustion energy △Um （TNMA, s, 298.15 K） were calculated by thermodynamic formulae. The detonation velocity, detonation pressure, and heat of detonation were estimated using the Kamlet-Jacobs equation. The heat of decomposition reaction （Qd） of TNMA was estimated by an empirical formula, and the thermal behavior of TNMA was studied by differential scanningcalorimetry （DSC）. The kinetic parameters of the exothermic decomposition reaction of TNMA were obtained from analysis of DSC curves and standard volume of gas evolved （V.） vs time （t） curves determined using a highly sensitive Bourdon glass membrane manometer. The parameters used to evaluate the thermal safety of TNMA, such as the self-accelerating decomposition temperature （TSADT）, critical temperature of thermal explosion （Tbe0 and Tbp0）, adiabatic time-to-explosion （tTlad）, 50% drop height （H50） of impact sensitivity, critical temperature of hot-spot initiation （Tcr）, thermal sensitivity probability density function S（T） for infinite plate-like, infinite cylindrical and spheroidal TNMAwith half-thickness and radius of 1 m at 300 K, peak temperature corresponding to the maximum value of the S（T） vs T curve （TS（T）max）, safety degree （SD）, critical thermal explosion ambient temperature （Tacr）, and thermal explosion probability （PTE）, were obtained from the abovementioned basic data. Results show that （1） TNMA has better thermal safety and heat-resistant ability than cyclotrimethylenetrinitramine （RDX）, and that in TNMA, the transition from thermal decomposition to thermal explosion occurs readily; （2） the thermal safety of large amounts of TNMA of different shapes decreases in the order： sphere〉infinite cylinder 〉 infinite plate; （3） TNMA has high standard combustion energy and high chemical energy （heat） of detonation, with an explosion performance level approaching that of cyclotetramethylenetetranitramine （HMX）. It is sensitive to shock, and has an impact sensitivity level approaching those of pentaerythritol tetranitrate （PETN） and tetryl, so TNMA can be used as a main ingredient in composite explosives.