火炸药学报

为了解决硝酸羟铵/聚乙烯醇(HAN/PVA)的点火和燃烧困难问题,采用热重-差示扫描量热-红外光谱-质谱联用技术研究了HAN/PVA的热分解机理,并通过多重扫描速率的非等温法探索了卡托辛、乙基二茂铁、辛基二茂铁和叔丁基二茂铁等对HAN/PVA热分解性能的影响。结果表明,HAN/PVA的热分解主要发生在457.0～485.2K,失重73.7%,放热量为1312.1J/g,活化能Ea为88.8kJ/mol,在加热过程中固体样品基本转变成气态产物; 本研究所用二茂铁类衍生物对HAN/PVA的热分解均具有明显的催化效果,催化作用由强到弱依次为叔丁基二茂铁、辛基二茂铁、卡托辛及乙基二茂铁,分别使HAN/PVA的热分解温度降低了42.9、27.5、17.5和12.3K; 含辛基二茂铁、卡托辛和乙基二茂铁样品热分解反应的Ea分别为81.2、90.5和77.7kJ/mol; HAN/PVA/卡托辛样品热分解的Ea虽然最高,但指前因子A提高了2个数量级,反应速率常数大幅增加,催化效果最佳。

In order to increase the ignition and combustion performance of hydroxyl ammonium nitrate/polyvinyl alcohol(HAN/PVA), the thermal decomposition process of HAN/PVA was investigated by using simultaneous thermogravimetric analysis(TGA)-differential scanning calorimetry(DSC)-fourier transform infrared spectroscopy(FTIR)-mass spectrometry(MS), and the effect of catocene, ethylferrocene, octylferrocene and t-butylferrocene on the thermal decomposition of HAN/PVA was studied by multiple scanning methods. The results show that the decomposition process of HAN/PVA mainly occurs at 457.0-485.2K, with the mass loss, heat release and activation energy Ea of 73.7%, 1312.1J/g and 88.8kJ/mol respectively, and the solid samples mostly decomposed into gaseous products. The four ferrocene derivatives have obvious catalytic effects on the thermal decomposition of HAN/PVA, and the descending order of the catalysts effects is as follows: t-butylferrocene, octylferrocene, catocene and ethylferrocene, which make the decomposition temperature decrease by 42.9, 27.5, 17.5 and 12.3K, respectively. The Ea of HAN/PVA thermal decomposition with octylferrocene, catocene and ethylferrocene are 81.2, 90.5 and 77.7kJ/mol, respectively. The Ea of HAN/PVA/Catocene is the highest, however, the pre-exponential factor(A)increases 2 magnitudes,and the reaction rate constant greatly increased, leading to the best catalytic effect induced by catocene.

引言
1 实验
2 结果与讨论
3 结论

表1 实验样品组成及二茂铁类衍生物的理化性能<br/>Table 1 Components of experiment samples and physicochemical properties of ferrocene derivatives

表1 实验样品组成及二茂铁类衍生物的理化性能
Table 1 Components of experiment samples and physicochemical properties of ferrocene derivatives

图1 HAN/PVA样品的TGA-DTG曲线<br/>Fig.1 TGA-DTG curves of HAN/PVA sample

图1 HAN/PVA样品的TGA-DTG曲线
Fig.1 TGA-DTG curves of HAN/PVA sample

图2 不同升温速率下HAN/PVA样品的DSC曲线<br/>Fig.2 DSC curves of HAN/PVA sample at different heating rates

图2 不同升温速率下HAN/PVA样品的DSC曲线
Fig.2 DSC curves of HAN/PVA sample at different heating rates

图3 逸出气体的红外吸收光谱和质谱图<br/>Fig.3 FTIR spectrum and MS spectrum of evolved gas

图3 逸出气体的红外吸收光谱和质谱图
Fig.3 FTIR spectrum and MS spectrum of evolved gas

图4 样品1～样品5的TGA-DSC曲线<br/>Fig.4 TGA-DSC curves of samples 1-5

图4 样品1～样品5的TGA-DSC曲线
Fig.4 TGA-DSC curves of samples 1-5

表2 二茂铁类衍生物催化HAN/PVA热分解特征值<br/>Table 2 Characteristic values of catalyzing the thermal decomposition of HAN/PVA by ferrocene derivative

表2 二茂铁类衍生物催化HAN/PVA热分解特征值
Table 2 Characteristic values of catalyzing the thermal decomposition of HAN/PVA by ferrocene derivative

图5 Starink法下不同转化率对应的活化能<br/>Fig.5 Ei at various values of αi calculated by Starink method

图5 Starink法下不同转化率对应的活化能
Fig.5 Ei at various values of αi calculated by Starink method

表3 不同计算方法下样品的活化能Ea<br/>Table 3 Ea of samples calculated by different methods

表3 不同计算方法下样品的活化能Ea
Table 3 Ea of samples calculated by different methods

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备注

引言

1 实验

2 结果与讨论

3 结论

期刊信息

备注

引言

1 实 验

2 结果与讨论

3 结 论

期刊信息

1 实验

3 结论