拉曼光谱分析青铜器本体中锈蚀产物

发布时间：2018-01-29 14:06

本文关键词： 青铜器金属文物拉曼光谱腐蚀机理　出处：《光谱学与光谱分析》2015年01期 　论文类型：期刊论文

【摘要】：青铜器锈蚀研究能够揭示出青铜器腐蚀机理,为制定科学的保护措施提供重要的参考资料。目前,青铜器锈蚀研究主要从其外部锈蚀产物入手,通过锈蚀组成结构分析,探讨其腐蚀机理。本文选择了保存较好青铜器本体样品进行了内部锈蚀情况研究。首先采用金相制备技术,通过打磨、抛光和超声清洗处理后,制备了断面相组织形态清晰的24件秦早期青铜器青铜本体样品。然后利用共聚焦显微拉曼光谱仪对样品夹杂物进行了光谱学研究,发现其物相为PbCO3和PbO及Cu2O,都属于常见的青铜合金腐蚀产物。样品金相组织中圆形或者大面积无规则亮灰色区域为Cu2O,反映出青铜器表面不仅易于形成一定厚度Cu2O锈蚀层,在相界之间也容易发生氧化反应生成Cu2O,存在合金内部和外部同时发生腐蚀生成赤铜矿锈蚀的情况。此外,拉曼光谱分析显示黑灰色物质主要为铅腐蚀产物——PbCO3和PbO,反映出铅元素的腐蚀过程:Pb→PbO→PbCO3。在铸造态青铜合金组织中,铅一般呈近圆形颗粒状态分布在相界之间。青铜器内部分布的铅颗粒在土壤埋藏环境中会发生氧化反应生成PbO,再与地下水中溶解的CO2-3发生化学反应生成比较稳定的PbCO3。结果表明:外界腐蚀因素(水、溶解氧和碳酸根等)能够通过合金中相界间通道进入青铜器内部,在相界表面逐步发生反应形成以金属氧化物为主的腐蚀产物。
[Abstract]:The study of copper rust can reveal the corrosion mechanism of bronze ware and provide important reference for scientific protection measures. At present, the study of bronze rust mainly starts with its external corrosion products. Through the analysis of corrosion composition and structure, the corrosion mechanism was discussed. In this paper, the internal corrosion was studied by using better preserved bronze body samples. Firstly, metallographic preparation technology was used and polished. After polishing and ultrasonic cleaning, 24 samples of early Qin bronze bronze with clear morphology were prepared. Then the inclusion was studied by confocal Raman spectrometer. It was found that the phases of the samples were PbCO3, PbO and Cu _ 2O, which belonged to the common corrosion products of bronze alloy. In the metallographic structure of the sample, the circular or large area of irregular bright gray area was Cu2O. It is shown that the copper surface is easy to form a certain thickness of Cu2O corrosion layer, and the oxidation reaction between the phase boundaries is also easy to produce Cu2O. In addition, Raman spectroscopy analysis shows that the black gray substances are mainly lead corrosion products, PbCO3 and PbO. It reflects the corrosion process of lead element: Pb. 鈫扨bO. 鈫扨bCO _ 3. In the cast bronze alloy, lead is generally distributed in the near circular particle state between the phase boundaries, and the lead particles distributed in the bronze ware will oxidize to form PbO in the soil buried environment. And then chemical reaction with dissolved CO2-3 in groundwater to form a relatively stable PbCO _ 3. The results show that: external corrosion factors (water). Dissolved oxygen and carbonate) can enter into the bronze ware through the interphase channel in the alloy, and the corrosion products are formed mainly by metal oxides on the surface of the phase boundary.
【作者单位】：西北大学科学技术史博士后科研流动站;陕西师范大学材料科学与工程学院;
【基金】：中国博士后科学基金面上项目(2013M542380) 陕西省博士后科研特别项目陕博管办[2013]10号陕西师范大学中央高校基本科研业务费项目(GK201302038)资助
【分类号】：TG115
【正文快照】： 引言拉曼光谱技术以其检测区域小,干扰小信号强等独特的优点,广泛应用于众多行业。特别地,它作为一种原位无损检测技术,在考古学研究领域发挥着重要作用[1,2],被成功地用于字画档案、壁画、玻璃、皮革、有机残留物、陶器、玉器、漆器和青铜器等研究领域。拉曼光谱在青铜器锈蚀

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