Long-term corrosion of copper alloys in the soil: new aspects of corrosion morphology in archaeological vessels from south-western Iran

Abstract

A group of copper-based objects excavated at Deh Dumen cemetery, in south-western Iran, was studied and analysed to examine the long-term corrosion morphology and mechanism in the soil burial environment. For this purpose, twenty-two samples from twenty-one copper-based vessels were studied and analysed using X-ray diffraction, scanning electron microscopy—energy dispersive X-ray spectroscopy, micro-Raman spectroscopy and metallography techniques. The results of the analyses showed that the majority of vessels are made of tin bronze, along with two arsenical copper samples. The extent of corrosion observed ranges from very thin corrosion crusts to thick crusts and entirely corroded structures. These three identified corrosion morphologies display a multi-layered corrosion stratigraphy as well as the preserved limit of the original surface. The corrosion crusts include internal tin-rich and external copper-rich layers, and the main corrosion mechanism for the formation of multi-layered corrosion crusts is decuprification or selective dissolution of copper during the long-term burial time in a moderately Cl-contaminated soil. The three identified corrosion morphologies are similar to the previously published morphologies, but some clear deviations are apparent and are discussed here.