Effects of alloy composition in traditional Japanese shakudo patination.

Japanese craftspeople have dominated the art of patinating copper-alloys since the 15th century, using precise alloy compositions and complicated patination processes in different hot solutions to create a variety of colours on swords fittings such as tsuba. While this complex tradition is increasingly popular in the East, the reasons behind the choices made by craftspeople in the selection of the components of the alloys and are still not fully understood. This paper investigates the effect of different alloying elements (tin, gold, and silver) on the resulting patina. Experimental results are compared with optical and compositional analyses on historical Japanese artefacts, confirming the effects of the different alloying elements on the patina characteristics and colour. The absence of tin and the presence of gold limit the growth of an oxide layer and promote the formation of a thin patina characterised by a smooth appearance without visible grains. Therefore, a limited thickness of the patinas is a key aspect for the production of the desired colour and appearance of the patinas. The first colorimetric analysis on historical Japanese artefacts demonstrates the influence of gold, silver and tin in the final patina colour, validating the observations in the experimental replicas.

Surface chromium on Terracotta Army bronze weapons is neither an ancient anti-rust treatment nor the reason for their good preservation.

For forty years, there has been a widely held belief that over 2,000 years ago the Chinese Qin developed an advanced chromate conversion coating technology (CCC) to prevent metal corrosion. This belief was based on the detection of chromium traces on the surface of bronze weapons buried with the Chinese Terracotta Army, and the same weapons' very good preservation. We analysed weapons, lacquer and soils from the site, and conducted experimental replications of CCC and accelerated ageing. Our results show that surface chromium presence is correlated with artefact typology and uncorrelated with bronze preservation. Furthermore we show that the lacquer used to cover warriors and certain parts of weapons is rich in chromium, and we demonstrate that chromium on the metals is contamination from nearby lacquer after burial. The chromium anti-rust treatment theory should therefore be abandoned. The good metal preservation probably results from the moderately alkaline pH and very small particle size of the burial soil, in addition to bronze composition.