青铜器“粉状锈”倍半碳酸钠脱氯转化过程监测及脱氯效果评价研究
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(1.中国国家博物馆,北京 100006;2.金属文物保护国家文物局重点科研基地(中国国家博物馆),北京 100006;3.清华大学科学博物馆,北京 100084)

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成小林(1975—),女,研究馆员,研究方向为金属文物科学分析与保护,激光拉曼光谱研究,E-mail: 1246249247@qq.com

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Research on monitoring the chloride release process and evaluating the dechlorination effect of the sodium sesquicarbonate method for the stabilization of bronze disease
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(1. National Museum of China, Beijing 100006, China;2. Key Scientific Research Base of Metal Conservation (National Museum of China), National Cultural Heritage Administration, Beijing 100006, China;3. Tsinghua University Science Museum, Beijing 100084, China)

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    摘要:

    倍半碳酸钠法是一种常见的青铜“粉状锈”转化(脱氯)处理方法。本研究以一件早商时期青铜爵的倍半碳酸钠脱氯保护为例,结合拉曼光谱和离子色谱等分析手段,重新审视并评估该方法的适用范围、应用效果和脱氯规律等。研究表明,在无恒温恒湿控制的环境下,对于大面积爆发的“粉状锈”,倍半碳酸钠法依然是保持器物稳定性的有效方法,对脱氯溶液进行跟踪监测对判断溶液更换及脱氯终点判断非常重要。一般情况下,可将脱氯过程分为三个阶段,第一阶段脱氯速度较快,约脱除总氯的73%,第二和第三阶段脱氯速度较慢,分别占脱除总氯的19%和8%,浸泡至第三阶段时,溶液中的氯离子浓度下降至50 mg/L以下,日平均脱氯浓度维持在3 mg/L左右,脱除总氯变化很小则表明脱氯可以结束了。此外,研究表明脱氯溶液更换频次较高时不易有新的物相生成,且内层的“粉状锈”较表层更难以转化。本研究为金属文物倍半碳酸钠浸泡处理终点判断提供重要依据。

    Abstract:

    It is reported that the bronze artifacts stained with the “bronze disease” contain multiple corrosion layers, and the chlorine-containing corrosion product is typically located in the inner layers adjacent to the matrix. Physical methods can only often remove the chlorine-containing corrosion product on the surface of the objects; however, it is particularly difficult to involve the chlorine element deep in the corrosion layer. The sodium sesquicarbonate method is a common and safe treatment for the stabilization of “active” bronze artifacts. Since the 1970s, most of the literature has mainly focused on providing a brief introduction to the method, with limited in-depth research and discussion. In this study, taking the stabilizing process by the use of sodium sesquicarbonate for an early Shang Dynasty bronze Jue as a case study, and combining analytical measures such as Raman spectrometry and ion chromatography, we reviewed and evaluated the range of application, efficacy and rule of chloride release process of the method. After a soaking treatment for 158 days and a subsequent tracking observation for 65 months, no fresh corrosion product was found, indicating excellent results. The study shows that in the absence of constant temperature and humidity control, the sodium sesquicarbonate method is still an effective method for stabilizing serious corroded bronzes, especially for large-scale outbreaks of the “bronze disease”. It is crucial to monitor chloride concentration to determine the replacement time of the solution and endpoint of the stabilizing treatment. Generally, the stabilization process can be divided into three stages:the first wash would extract approximately 73% of the total; the second wash about 19% and the third wash the remaining 8%. At the last stage, the chloride ion concentration in the solution decreased to lower than 50 mg/L. The average daily chloride ion concentration was maintained at about 3 mg/L, and the change in chlorine removal was small, indicating that the stabilizing treatment could be complete. Additionally, samples were meticulously collected from the “active” rust on the surface layer and those in the inner layer, which contained either amorphous or nanocrystalline SnO2. Employing Raman spectrometry, we tracked both the transformation process and extent of the “active” rust. The results show that the “active” rust in the inner layer was more difficult to transform than that in the surface layer, and frequent replacement of the washing solution could reduce the possibility of new phases being formed. Dechlorination transformation is a rather complex process that requires further in-depth research in the future. The present study takes the practical conservation treatment for cultural relics as a case study, and in comparison with previous literature, it has extensions in two aspects:first, it tracked and monitored the entire dechlorination process, and evaluated the dechlorination efficacy at each distinct stage for the method; second, it traced and detected the phase transition process of the “active” rust to summarize the chlorine removal degree at different depths of corrosion layers. This study provides valuable insights into the prediction of replacement time of the solution and endpoint of the stabilizing treatment with the sodium sesquicarbonate method.

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  • 收稿日期:2024-01-23
  • 最后修改日期:2024-05-22
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  • 在线发布日期: 2024-12-30
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