Liu Xue-yong, Wang Lin, Zheng Min-xia, Jiang Yan, Luo Yi-wei
Institute of Chemical Materials, China Academy of Engineering Physics, Mianyang 621900, China.
Guang Pu Xue Yu Guang Pu Fen Xi. 2007 Oct;27(10):1951-4.
In-situ FTIR spectroscopy is a rising and dynamic technique. This technique combines the advantages of investigation in-situ and accurate structure analysis by FTIR spectroscopy, and can detect real time chemical change in materials at different temperatures and obtain the relationship between micromechanism of materials and temperature. In the present paper, thermal decomposition of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) heated with a rate of 5, 10, 20 and 40 degrees C x min(-1), respectively, was investigated by in-situ diffuse reflection FTIR spectroscopy. The results demonstrate that intramolecular cyclization occurs in breakage of HMX with a heating rate of 5 degrees C x min(-1), while intermolecular cyclization appears with a heating rate of 10, 20 and 40 degrees C x min(-1). With increasing temperature, the rupture rate of C-N bond is faster than that of N-N bond, which verifies that the cleavage of C-N bond is the dominant rupture form. With increasing heating rate, the decomposition beginning temperature of C-N bond increases. Eight kinds of gaseous products such as CO2, N2O, CO, NO, HCHO, HONO, NO2 and HCN were determined. The decomposition mechanism of HMX was not affected with changing heating rate.
原位傅里叶变换红外光谱是一种新兴的动态技术。该技术结合了原位研究和傅里叶变换红外光谱精确结构分析的优点,能够检测材料在不同温度下的实时化学变化,并获得材料微观机制与温度之间的关系。本文采用原位漫反射傅里叶变换红外光谱分别研究了八氢-1,3,5,7-四硝基-1,3,5,7-四氮杂环辛烷(HMX)以5、10、20和40℃·min⁻¹的速率加热时的热分解情况。结果表明,加热速率为5℃·min⁻¹时,HMX断裂过程中发生分子内环化,而加热速率为10、20和40℃·min⁻¹时出现分子间环化。随着温度升高,C-N键的断裂速率比N-N键快,这证实了C-N键的断裂是主要的断裂形式。随着加热速率的增加,C-N键的分解起始温度升高。确定了CO₂、N₂O、CO、NO、HCHO、HONO、NO₂和HCN等八种气态产物。HMX的分解机理不受加热速率变化的影响。