接触引起的奇特腐蚀化合物:博物馆展品玻璃诱导金属腐蚀研究综述(GIMME)

G. Eggert, Andrea Fischer
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引用次数: 3

摘要

许多文物是由玻璃和金属接触而成的。通过离子与吸收的水交换,在玻璃表面形成碱性水膜。它们含有钠和/或钾、氢氧化物和碳酸盐(吸收二氧化碳)离子。这些电解质与金属接触时引起腐蚀。令人惊讶的是,这一现象直到最近二十年才被斯图加特的研究发现。与此同时,在一些文物收藏中发现了大约350件受影响的物品。由于特殊的电解液,经常会形成不寻常的腐蚀产物。其中三种化合物的未知结构和分子式可通过现代x射线粉末衍射数据评定确定。一个例子是碱式碳酸铅钾,KOH·2PbCO3,在一个玻璃壶的锡盖上检测到。已知结构的钠类似物是在中空玻璃球中发现的,玻璃球内部与熔融铅镜像。Chalconatronite, Na2[Cu(CO3)2]·3H2O,是铜合金与苏打溶液(此处为玻璃降解)接触时的腐蚀产物。暴露于醋酸排放物(例如来自木材的排放物)中,它会转化为迄今尚未确定结构的醋酸铜钠碳酸。普遍存在的污染物甲醛在玻璃降解提供的碱性介质中直接与甲酸盐反应。因此,在与玻璃接触的铜合金上,甲酸酯是常见的:在所有情况下,Na4Cu4O(HCOO)8(OH)2·4H2O占50%,Cu2(HCOO)(OH)3占33%。锌(来自黄铜)形成Zn(HCOO)2·2H2O和Zn4Cu3(Zn1−xCux)6(HCOO)8 (OH)18·6H2O。还有许多其他的腐蚀产物,例如,含有锌和羧酸盐,等待进一步的表征。预防性保护需要通过干燥储存(不低于35% rH)来减缓腐蚀。需要通过仔细选择储存、展示和保存的材料来避免污染物。
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Curious Corrosion Compounds Caused by Contact: A Review of Glass-Induced Metal Corrosion on Museum Exhibits (GIMME)
Many heritage objects consist of glass in contact with metals. By ion exchange with absorbed water, alkaline aqueous films are formed on the glass surface. They contain sodium and/or potassium, hydroxide, and carbonate (uptake of carbon dioxide) ions. These electrolytes induce corrosion while in contact with metal. Surprisingly, this phenomenon has only been realised by research in Stuttgart in the last two decades. About 350 affected objects were detected in the meantime in a number of heritage collections. Because of the special electrolytes, unusual corrosion products are often formed. The unknown structure and formula of three of them could be determined by modern X-ray powder diffraction data evaluation. One example is the basic potassium lead carbonate, KOH‧2PbCO3, detected on a pewter lid of a glass jug. The sodium analogon of already known structure was found in hollow glass balls mirrored on the inside with molten lead. Chalconatronite, Na2[Cu(CO3)2]‧3H2O, is known as a corrosion product of copper alloys in contact with soda solutions (here: from glass degradation). Exposed to acetic acid emissions (e.g., from wood), it transforms to a sodium copper acetate carbonate of hitherto undetermined structure. The ubiquitous pollutant formaldehyde reacts directly to formate in the alkaline medium provided by glass degradation. On copper alloys in contact with glass, formates are, therefore, frequent: Na4Cu4O(HCOO)8(OH)2‧4H2O in 50% of all cases and in 33% Cu2(HCOO)(OH)3. Zinc (from brass) forms Zn(HCOO)2‧2H2O and Zn4Cu3(Zn1−xCux)6(HCOO)8 (OH)18·6H2O. There are a number of other corrosion products, e.g., containing zinc and carboxylates awaiting further characterisation. Preventive conservation needs to slow down corrosion by dry storage (not lower than 35% rH). Pollutants need to be avoided by careful selection of materials for storage, display, and conservation.
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