Multianalytical study of corrosion layers in some archaeological copper alloy artefacts

摘要

Corrosion layers in some copper and bronze archaeological objects from Haft Tappeh archaeological site, southwest Iran, were studied. For this purpose, optical microscopy, scanning electron microscopy with energy dispersive X-ray microanalysis, micro-Raman spectroscopy and X-ray diffraction methods were applied to observe corrosion stratigraphy and their characteristics as well as identification of chemical composition and phase determination of different corrosion layers. Based on optical and electron microscopy, three different corrosion strata were identified in cross section of different metallic objects including various red, green, white-grey powdery and dark internal compact layers. Scanning electron microscopy with energy dispersive X-ray microanalysis on different corrosion layers revealed that Cu, Sn and Cl are the main elements in the chemical composition of different layers. Tin-rich phases were detected in white-grey and dark layers that may be formed because of the internal oxidation of tin as well as the decuprification (selective dissolution of copper) phenomena occurring during long-term burial period in the soil. Also, the XRD and micro-Raman spectroscopy results proved that the main corrosion products are nantokite (CuCl), copper trihydroxychlorides and copper oxides. The combination of these analytical methods allows us to explore the surface and internal corrosion layers of the archaeological copper and bronze samples, and major interest is on studying their chemistry, microstructural properties and corrosion stratigraphy. Copyright (C) 2015 John Wiley & Sons, Ltd.