含不同质量分数三价铁离子乳胶基质的绝热分解研究

Study on the adiabatic decomposition of emulsion matrix containing different mass fractions of ferric ions

为研究绝热条件下Fe^(3+)对乳胶基质的热稳定性和热危险性的影响,采用加速量热仪研究了含不同质量分数Fe^(3+)的乳胶基质的绝热分解行为,计算了绝热分解动力学参数和TSAD。结果表明,绝热条件下,Fe^(3+)会促进乳胶基质的热分解,使其起始分解温度降低,绝热温升和放热量提高,释放更多的气体产物,这种促进效果随着Fe^(3+)质量分数提高会有所减弱,Fe^(3+)质量分数为0.04%时,乳胶基质的起始分解温度降低了34.65℃,放热量提高了44.74%。加入Fe^(3+)后,乳胶基质达到最高放热温度所需时间更短,Fe3+质量分数为0.08%时反应最快,但Fe3+质量分数达到0.10%时,乳胶基质内部结构被严重破坏,到达最高放热温度所需时间增加。通过比较选取不同反应级数时所作回归直线的拟合优度,得到4种样品绝热分解反应的反应级数为2,含Fe^(3+)乳胶基质的活化能和TSAD都有一定程度降低,热危险性更高,在Fe^(3+)处于低含量时更明显,Fe^(3+)质量分数为0.04%时,乳胶基质的活化能降低了44.61%,TSAD降低了60.61℃。

To study the effect of Fe3+on the thermal stability and thermal hazard of emulsion matrix under adiabatic conditions,four kinds of emulsion matrix containing different mass fractions of Fe3+were prepared based on previous studies and preliminary experiments.Different samples were studied by accelerating calorimeter,and the adiabatic decomposition behavior,the adiabatic decomposition kinetic parameters,and TSAD of each sample were analyzed and calculated.The results show that Fe3+can promote the thermal decomposition of the emulsion matrix under the adiabatic condition,which leads to the reduction of the initial decomposition temperature,the increase of adiabatic temperature,and the release of more gas products during the thermal decomposition process.This promoting effect is weakened with the increase of Fe^(3+)content.Compared with the emulsion matrix without Fe^(3+),the initial decomposition temperature of the emulsion matrix with 0.04%Fe^(3+)decreases by 34.65℃,and the heat release increases by 44.74%.Besides,the time needed to reach the maximum exothermic temperature of the emulsion matrix containing 0.08%Fe3+is shorter and the reaction rate is the fastest.The internal structure of the emulsion matrix with 0.10%Fe3+is seriously damaged and the reaction takes longer to reach its peak temperature.Comparing the goodness of fit of linear regression under different reaction orders,the reaction order of adiabatic decomposition of four samples is 2.The activation energy and TSAD of the emulsion matrix containing Fe3+are decreased,which means that the thermal decomposition reaction needs less energy.The self-accelerating decomposition reaction can occur at a lower temperature,which is more obvious at lower Fe^(3+)content.Compared with the emulsion matrix without Fe^(3+),the activation energy of the emulsion matrix decreases by 44.61%and TSAD decreases by 60.61℃when the Fe3+content is 0.04%.This study can provide a theoretical reference for the safe production of emulsion matrices and the prevention of thermal explosion accidents.