中药朱砂热稳定性等物理参数与其质量的相关性研究

Correlation between cinnabar quality and thermal stability

目的研究中药朱砂热稳定性等物理参数与其质量的相关性。方法主要采用滴定分析、X射线衍射（XRD）和热重分析法,对湖南省11批不同产地的朱砂主成分硫化汞（Hg S）从含量、热性能、主要物相结构等方面进行研究。结果中药朱砂分解温度为350~500℃,结构稳定,主要成分Hg S为α-型六方晶系,含有少量的In4As Se、Sn Zn As2（或As2Sn Zn）、Cu Se（或Cu2Se,或Cu6Se4.50）,样品中还存在Cr、Pb、Sr、Co、Mo等微量元素,均未检出含毒性的有机汞。其中样品2、5号为伪品朱砂,XRD中未检出Hg S,主要成分为Ca Mg（CO3）2和Sr2Cr O4,其中Sr2Cr O4为致癌物质。结论热重分析Hg S的失重质量与滴定法测定Hg S含量的大小顺序基本保持一致;XRD能快速鉴别中药朱砂的物相组成,初步判定有机汞的存在与否,初步鉴定朱砂的质量。两者结合,能对朱砂的真伪、优劣提供更为全面的判断,为矿物药有效性及安全性研究提供新的理论依据。

Objective To determine the correlation between cinnabar quality and thermal stability. Methods The content of Hg S, thermal properties, main components and structures of 11 batches of cinnabar from Hunan province were studied by volumetric analysis, X-ray diffraction（XRD） and thermogravimetry. Results Cinnabar was stable and its decomposition temperature was 350- 500 ℃. The main component of these samples was α-Hg S of hexagonal crystal system. There were also small amounts of In4 As Se, Sn Zn As2（or As2 Sn Zn）, Cu Se（or Cu2 Se, or Cu6Se4.50）, and trace elements, such as Cr, Pb, Sr, Co and Mo. All samples were found without toxic organic mercury. No.2 and No.5 samples were adulterants of cinnabar and both of them were tested without Hg S in XRD. The main components of them were Ca Mg（CO3）2 and Sr2 Cr O4 which was a carcinogen. Conclusion The content of Hg S obtained by thermogravimetry is basically consistent with volumetric analysis. XRD can be used to evaluate the quality of cinnabar by identifying the composition and determining whether there is organic mercury. The combination of thermogravimetry and XRD can be used to provide the evaluation of the quality of cinnabar and the judgment of its authenticity. This paper provides a new theoretical basis for the safety and effectiveness of mineral drugs.