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含能材料  2014 

HNF的热分解动力学和热安全性

DOI: 10.11943/j.issn.1006-9941.2014.06.012

Keywords: 物理化学,硝仿肼(HNF),差示扫描量热法(DSC),热重法(TG),热分解动力学,热安全性

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Abstract:

为了解硝仿肼(HNF)的热分解动力学和热安全性,用真空安定性试验(VST)、差示扫描量热法(DSC)和热重法(TG)研究了HNF的热分解特性。根据HNF在升温速率为5,10,15,20℃·min-1时的DSC曲线的峰温和TG曲线的分解深度(α),分别用Kissinger法和Ozawa法计算了HNF热分解反应的表观活化能(Ek和Ea)和指前因子(Ak)、提出了描述HNF放热分解过程的动力学方程。计算了HNF热分解反应的热力学参数(活化自由能ΔGSymbolyB@,活化焓ΔHSymbolyB@和活化熵ΔSSymbolyB@)和HNF的热安全性参数(自发火温度Tbpo和自加速分解温度TSADT)。结果表明,HNF的放气量为0.41mL·g-1,不超过2mL·g-1的标准,显示HNF有良好的热安定性。HNF吸热熔融后的放热分解反应过程可分两个阶段。Ek=257.10kJ·mol-1,Ak=1.74×1033s-1,ΔGSymbolyB@=103.37kJ·mol-1、ΔHSymbolyB@=253.82kJ·mol-1,ΔSSymbolyB@=380.78J·K-1·mol-1,Tbpo=400.28K和TSADT=395.10K。放热分解反应的动力学方程可描述为:对α=0.20~0.65的第一阶段dα/dt=kf(α)=Ae-ERTf(α)=5.14×1021×(1-α)-ln(1-α)12exp(-1.81×104/T)对α=0.65~0.80的第二阶段dα/dt=kf(α)=Ae-ERTf(α)=3.30×1014×(1-α)-ln(1-α)-1exp(-1.33×104/T)

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