新干商墓青铜器非晶与纳米晶锈蚀产物结构的分析研究

Research on the Mineral Phase and Component of Non-Crystalline and Nano-Crystalline Corrosion Products on Bronzes Unearthed from Shang Tomb in Xingan

应用微区X射线衍射仪(μXRD)及高分辨透射电镜(HTEM)分析江西新干商墓出土的青铜器粉状锈蚀产物,结果表明锈蚀产物主要为具有锡石结构的SnO2,晶态形式为非晶与晶粒尺寸为4～5.7nm的纳米晶共混;能谱分析表明样品中除含有大量锡外,还有少量的铜、硅、铅与铁等元素。通过对锈蚀产物的高分辨透射电镜晶格条纹像计算,说明纳米晶SnO2的晶格中并没有其他原子的掺杂;对该锈蚀产物拉曼光谱的分析研究表明,样品不含有表征SnO2的体相拉曼峰,更具有非晶SnO2的特征,而973cm-1的弱而宽的峰表明样品含有非晶的硅酸盐类的锈蚀物,推测锈蚀产物中的少量铜、硅、铅与铁等元素应以非晶的形式存在。

The patinas on bronzes in Shang Tomb of Xingan were powdery,pale green,which were more like ＂bronze disease＂,but the mineral composition of patinas was not paratacamite or atacamite.Micro X-ray diffraction（XRD） and high performance transmission electroscope（HTEM） showed that the patinas were mainly composed of non-crystalline and nano-crystalline SnO2,and the size of nano-crystalline particle was in the range of 4~5.7 nm;Moreover,the energy-dispersive X-ray spectrometry showed that element tin is the primary ingredient of the sample,as well as little copper,silicon,lead and iron were detected.By studying the crystal lattice stripe image of the nanometer SnO2,it was deduced that the chemical formula of nano-crystalline SnO2 did not include other elements;The Raman spectrum of the sample showed that there were not any characteristic peaks of SnO2,the spectrum was more like non-crystalline SnO2,and the weak and broad peak of 973 cm-1 indicated that the sample may contain silicate grains,It was inferred that little of copper,silicon,lead and iron should exist in the form of non-crystalline silicate particles.