1,3,3-三硝基氮杂环丁烷的热安全性

借助不同加热速率(β)的非等温DSC曲线离开基线的初始温度(T₀)、onset温度(T_e)和峰顶温度(T_p), Kissinger法和Ozawa法求得的热分解反应的表观活化能(E_k和E_O)和指前因子(A_k), Hu-Zhao-Gao方程ln β_i＝lnA₀/(b_{e0 or p0}G(α))]＋   b_{e0 or p0}T_{ei or pi}求得的b_{e0 or p0}, Zhao-Hu-Gao方程ln β_i＝lnA₀/((a_{e0 or p0}＋1)G(α))]＋(a_{e0 or p0}＋1) ln T_{ei or pi}求得的a_{e0 or p0}, 微热量法确定的比热容(C_p), 以及密度(ρ)、热导率(λ)和分解热(Q_d, 取爆热之半)数据, Zhang-Hu-Xie-Li公式、Hu-Yang-Liang-Xie公式、Hu-Zhao-Gao公式、Zhao-Hu-Gao公式、Smith方程、Friedman公式和Bruckman-Guillet公式, 计算了TNAZ在β→0时的T₀, T_e和T_p值(T₀₀, T_eo和T_p0)、热爆炸临界温度(T_be和T_bp)、绝热至爆时间(t_Tlad)、撞击感度50%落高(H₅₀)和热点起爆临界温度(T_cr), 得到了评价TNAZ热安全性的结果: T_SADT＝T_e0＝485.81 K, T_p0＝497.38 K, T_beo＝499.50 K, T_bp0＝513.45 K, t_Tlad＝8.90 s (n＝0), t_Tlad＝8.96 s (n＝1), t_Tlad＝9.01 s (n＝2), H₅₀＝28.88 cm, T_cr＝641.46 K (T_room＝293.15 K), T_cr＝658.89 K (T_room＝300 K), 表明: (1) TNAZ对热是稳定的; (2)撞击感度好于环三亚甲基三硝胺(RDX); (3)热点起爆临界温度高于RDX, 而界于1,3,5-三氨基-2,4,6-三硝基苯(TATB)和六硝基茋(HNS)之间.

Thermal Safety of 1,3,3-trinitroazetidine(TNAZ)

With the help of the initial temperature (T_0), at which DSC curves deviate from the baseline, the onset temperature (T_e) and maximum peak temperature (J_p) from the non-isothermal DSC curves of TNAZ at different heating rates (β), the thermal decomposition activation energy (E_k and E_o) and pre-exponential constant (A_k) obtained by Kissinger's method and Ozawa's method, the value of b_(e0 or p0) from Hu-Zhao-Gao's equation In β_i=lnA_0/(b_(e0 or p0)G(a))]+ b_(e0 or p0)T_(ei or pi) and the value of a_(e0 or p0) from Zhao-Hu-Gao's equation Inβ_i=lnA_0/((a_(e0 or p0)+1)G(a))]+(a_(e0 or p0)+1) ln T_(ei or pi), the values of specific heat capacity (C_p) obtained by microcalorimetry, density (p) and thermal conductivity (A), the decomposition heat (Q_d, taking half-explosion heat), Zhang-Hu-Xie-Li's formula, Hu-Yang-Liang-Xie's formula, Hu-Zhao-Gao's formula, Zhao-Hu-Gao's formula, Smith's equation, Friedman's formula and Bruckman-Guillet's formula, the values (T_(00), T_(eo) and T_(p0)) of T_0, T_e and T_p corresponding to β→0, thermal explosion temperature (T_(be) and T_(bp)), adiabatic time-to-explosion (t_(Tlad)), 50% drop height (H_(50)) of impact sensitivity, critical temperature of hot-spot initiation (T_(cr)), of TNAZ were calculated. The following results of evaluating the thermal safety of TNAZ were obtained: T_(SADT)= T_(e0)=485.81 K, T_(p0)=497.38 K, T_(beo)=499.50 K, T_(bp0)=513.45 K, t_(Tlad)=8.90 s (n=0), t_(Tlad)=8.96 s (n=1), t_(Tlad)=9.01 s (n=2), H_(50)=28.88 cm, T_(cr)=641.46 K (T_(room)= 293.15 K), T_(cr)=658.89 K (r_(room)=300 K), showing that (1) TNAZ is thermally stable; (2) its impact sensitivity is better than that of cyclotrimethylene trinitramine (RDX); (3) the critical temperature of hot-spot initiation is higher than that of RDX and between those of triaminotrinitrobenzene (TATB) and hexanitrostilbene (HNS).