广州地区汉墓出土青铜器腐蚀机理研究
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(1.广州市文物考古研究院,广东广州 510006;2..南汉二陵博物馆,广东广州 510006;3.海上丝绸之路(广州)文化遗产保护管理研究中心,广东广州 510006)

作者简介:

吕良波(1983—),男,2006年毕业于西北大学文物保护技术专业,研究馆员,研究方向为金属文物保护与冶金考古,E-mail: 80999487@qq.com

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国家重点研发计划资助(2020YFC1522002)


Research on the corrosion mechanism of bronzes unearthed from Han tombs in Guangzhou
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(1. Guangzhou Municipal Institute of Cultural Heritage and Archaeology, Guangzhou 510006, China;2. Southern Han Mausoleums Museum, Guangzhou 510006, China;3. Guangzhou Conservation and Research Center for Cultural Heritage of Maritime Silk Road, Guangzhou 510006, China)

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    摘要:

    广州地区汉墓出土不少青铜器,但腐蚀矿化非常严重。为了研究其腐蚀机理,采用金相分析、扫描电镜-能谱分析、锈蚀产物X衍射分析、土壤pH值以及可溶盐测定等多种检测分析手段,对青铜器提取典型样品进行基体、锈蚀产物和埋藏土壤等三个方面的分析。结果表明8件样品可以分出2种材质,即铅锡青铜7件、锡青铜1件。合金铅锡配比有一定的波动,机械性能并不是最佳。基体金相组织显示,大部分样品为铸造组织。暗场可见由内向外层状分布腐蚀矿化过程。X射线衍射分析结果均为无含氯铜盐。广州埋藏环境氯离子的含量与国内其他地区比较并不低,而酸性却是最强。三元合金配比中的铅和锡相对于铜来说是阳极。金相组织树枝晶存在大量的晶间和晶界,各种不同的相之间电位存在差异。含有不少夹杂物及缩孔,化学成分的不均匀性,合金杂质电位高于基体部位,形成大量的微阴极和微阳极等等,均有利于青铜器发生电化学反应。而广州地区汉墓出土青铜器腐蚀过程,主要还是H+主导青铜器腐蚀。广州地区丰富地下水的酸性土壤环境下,充足的氧气、二氧化碳和水,促使铜离子和铅离子不断往外迁移,造成青铜器腐蚀矿化非常严重。

    Abstract:

    Many bronzes have been unearthed from Han tombs in Guangzhou, but their corrosion and mineralization are very serious. In order to study the mechanisms of corrosion, metallographic analysis, SEM-EDS, XRD of corrosion products, soil pH measurement and soluble salt determination were used. Typical samples extracted from bronze ware were analyzed with regard to three aspects:matrix, corrosion products and soil. The results show that there are two kinds of materials in eight of samples, namely seven pieces of lead-tin bronze and one piece of tin bronze. The mechanical properties of the alloy were not the best because of the fluctuation of the ratio of lead to tin. According to the microstructure of the matrix, most of the samples were cast microstructure. The dark field demonstrated that the mineralization corrosion process was from inside to outside. The XRD results show that all lacked copper chloride. The content of chloride ion in the burial environment of Guangzhou is not low compared with other areas in China, but the acidity is the strongest. The lead and tin in the ternary alloy were anodes relative to copper. There were a lot of intercrystalline and grain boundaries in dendrites and the potentials of different phases were different. There were a lot of inclusions and much shrinkage, the chemical composition was not uniform, the impurity potential of the alloy was higher than that of the matrix, and a lot of microcathodes and microanodes were formed. However, the main corrosion process of bronze vessels unearthed from Han tombs in Guangzhou area was H+ corrosion. The acidic soil environment, due to the abundant groundwater in Guangzhou, as well as abundant oxygen and carbon dioxide make copper and lead ions move outwards continuously, which results in serious corrosion and mineralization of bronzes.

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  • 收稿日期:2022-10-14
  • 最后修改日期:2023-04-07
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  • 在线发布日期: 2024-12-30
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