Sulfuric acid and nitric acid are two typical additives in manufacturing, storage, processing, and transportation of nitrocellulose. This paper performed a comparative study of the decomposition behavior of nitrocellulose supplemented with nitric acid or sulfuric acid using a micro calorimeter under slow heating condition. Different from the single heat flow peak of nitrocellulose, two exothermic peaks were observed after adding 30 wt% acids into nitrocellulose. The kinetics parameter of pure nitrocellulose and its mixture with acids were obtained by isoconversional kinetics method and compared to that by other methods. The self-heating property was analyzed by isothermal experiments. The involvement of nitric acid and sulfuric acid influenced thermal behavior with different mechanisms. The involvement of nitric acid highly reduced the onset temperature by 44% ~ 50%, and decreased the activation energy from over 110 kJ/mol to less than 80 kJ/mol. Both onset temperature and activation energy for the mixture involving sulfuric acid were not slightly improved. Comparing to sulfuric acid, nitrocellulose mixed with the same amount of nitric acid is more likely to undergo self-accelerating decomposition and cause thermal hazards.

Graphical abstract

中文翻译：

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硝酸和硫酸对硝化纤维素热行为的影响的慢加热实验

硫酸和硝酸是硝化纤维素制造、储存、加工和运输过程中的两种典型添加剂。采用微量热仪对慢热条件下添加硝酸或硫酸的硝化纤维素的分解行为进行了对比研究。与硝酸纤维素的单一热流峰不同，在硝酸纤维素中加入 30 wt% 的酸后观察到两个放热峰。采用等转化动力学方法得到纯硝酸纤维素及其与酸的混合物的动力学参数，并与其他方法进行了比较。通过等温实验分析了自热性能。硝酸和硫酸的参与以不同的机制影响热行为。硝酸的参与使起始温度大大降低了44%~50%，活化能从110 kJ/mol以上降低到80 kJ/mol以下。涉及硫酸的混合物的起始温度和活化能都没有略微提高。与硫酸相比，硝酸纤维素与等量的硝酸混合后更容易发生自加速分解并产生热危害。

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