The discovery of blue copper salts prompted scientific studies of a collection of 'silver' white metal jewellery from Bulgaria and the former Yugoslavia dated from the end of the nineteenth to the beginning of the twentieth century. Surface examination along with compositional and microstructural analysis was carried out to explore the alloys and manufacturing techniques of the artefacts. A total of 120 pieces including 90 from Bulgaria and 30 from former Yugoslavia were analysed by X-ray fluorescence spectroscopy. A few samples were also taken from broken pieces for metallographic study and compositional analysis using scanning electron microscopy with energy dispersive X-ray spectrometry. This study reveals that materials used in the production of Balkan 'silver' jewellery covers a wide range of variety, including alloys of copper-silver-arsenic, copper-silver, copper-nickel-zinc, copper-nickel, copper-zinc, copper, silver, and recycled metals. The copper-silver-arsenic alloys were dominant and were used for most of the main components of the jewellery to produce a silvery colour. Silver plating and gilding were applied to some pieces. These results add to the understanding of the material culture of the Balkan regions and help to guide future storage and display of the objects.
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