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題名 | 中國古代青銅器的銹蝕產物與其造成的機理=The Corrosion Products and Corrosion Mechanisms of Ancient Chinese "Qington" (Copper Alloys) |
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作者 | 錢憲和; 方建能; 余炳盛; 譚立平; Tsien, Hsien-ho; Fang, Jiann-neng; Yu, Bing-sheng; Tan, Li-ping; |
期刊 | 國立臺灣博物館學刊 |
出版日期 | 20050600 |
卷期 | 58:1 民94.06 |
頁次 | 頁25-46 |
分類號 | 793.5 |
語文 | chi |
關鍵詞 | 青銅; 銹蝕產物; 銹蝕機理; 分類; 孔雀石; 鋅孔雀石; 藍銅礦; 白鉛礦; 菱鋅礦; 氯銅礦; 水膽礬; 赤銅礦; 黑銅礦; 鑑定; Qingtong; Bronze; Corrosion products; Corrosion mechanisms; Classification; Malachite; Rosasite; Azurite; Cerussite; Smithsonite; Atacamite; Brochantite; Cuprite; Tenorite; Heqigu; Identification; |
中文摘要 | 一般認為中國古代的青銅是銅錫二元合金或是銅錫鉛三元合金,實際上中國古代的銅合金配方是複雜的,每一地區可能因銅礦床的不同、冶金術士的不同而有不同的青銅器。古代的青銅可以是銅錫二元合金、銅錫鉛三元合金或者是銅鋅鉛錫多元合金,這些不同的青銅在不同埋藏環境中就會產生不同的複雜的銹蝕產物。我們討論了不同埋藏環境下所產生的銹蝕產物,最常見的是Cu、Pb、Zn的碳酸鹽礦物,其次為硫酸鹽與氯化物,及Cu、Zn的氧化物。在鹼性環境中可生成孔雀石、藍銅礦;在中性環境則產生白鉛礦;在有鋅的情況下,Zn會取代部分的Cu離子產生鋅孔雀石(鹼性環境)或菱鋅礦(中性環境);外界如有硫鹽及氯,就容易生成水膽礬及氯銅礦;在氧化條件下會產生赤銅礦及錫石;在多氧的情況下則生成黑銅礦。銅合金的銹蝕產物可反應合金的組成及埋藏環境。我們建議用化學成分內的陰離子或陰離子團作為銹蝕礦物的分類依據,這樣可以幫助我們便於了解及鑑定銹蝕產物。銹蝕產物的了解可用來鑑定青銅器的真偽。 |
英文摘要 | Chinese "qingtong" is a general term for the family of cooper alloys in which major alloying elements are tin, lead and zinc. Cooper, lead and zinc produce different corrosion products in different burial environments. Consequently, the corrosion of ancient chinese "qingtong" is complex. A classification of corrosion products based on their chemical composition is proposed. In this way, corrosion products are classified into groups depending on the dominant anion or anionic group (e.g. carbonates, chlorides, sulfides, oxides, etc.). Using this classification, it is easier to understand the corrosion mechanisms of corrosion products. Corrosion products related by the same anion show similar characteristics and tend to occur together in similar burial environments. For example, basic carbonate corrosion products resemble each other and are produced in similar carbonate rich burial condition. The morphology and mineralogy of different corrosion products are described. Corrosion processes of copper alloys are reviewed. We suggest chemical composition and environmental control to explain the formation of corrosion products. The corrosion products show, generally, layered structure on the surface of corroded alloys. Microscopic examination revealed different mineralized zones which are formed mainly by basic copper carbonates, lead and zinc carbonate and/or basic copper chlorides, and copper and tin oxides. Basic carbonate layers of malachite (characterized by green color, show incrusting with botryoidal, reniform or stalactitic surface) and azurite (characterized by azure-blue color) were founded under basic condition in CO₃¯¯ rich soil water. The incorporation of zinc in corrosion products can produce rosasite (in mamillary spherules). While, cerussite and smithsonite layers were founded in CO₃¯¯ rich soil water under normal condition. In the presence of Cl¯, atacamite can be produced. The presence of sulfides can lead to the formation of brochantite. Under acid condition, copper react directly with dissolved O₂ to produce cuprite. If both Cl¯ adn CO₃¯¯ are lacking, tenorite can be produced. Therefore, these minerized layers or zonations suggest environmental changes. Corrosion products can also provide information about original composition of the alloys and the burial environment in which they were preserved. They can reflect, as a consequence, the authenticity of the copper alloy artifacts. |
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