During the Central European Iron Age, more specifically between 600 and 100 BC, red precious corals (Corallium rubrum) became very popular in many regions, often associated with the so-called (early) Celts. Red corals are ideally suited to investigate several key questions of Iron Age research, like trade patterns or social and economic structures. While it is fairly easy to distinguish modern C. rubrum from bone, ivory or shells, archaeologists are confronted with ancient, hence altered, artifacts. Due to ageing processes, archaeological corals lose their intensive red color and shiny surface and can easily be confused with these other light colored materials. We propose a non-destructive multi-stage approach to identify archaeological corals amongst other biominerals used as ornament during the central European Iron Age with emphasis on optical examination and mobile Raman spectroscopy. Our investigations suggest that the noticeably high amount of misidentifications or at least uncertain material declarations existing in museums or even in the literature (around 15%) could be overcome by the proposed approach. Furthermore, the range of different materials is higher than previously expected in archaeological research. This finding has implications for contemporary concepts of social structures and distribution networks during the Iron Age.
The corrosion of bronzes was examined in the context of single-acid versus mixed-acid (as in urban acid rain) solutions. Two bi-component bronzes (copper with either 3% Sn or 7% Sn) that closely represent those of historic artifacts were immersed for five weeks in conditions designed to replicate those experienced by statues and ornaments in cities where rainfall and humidity constantly produce an electrolyte layer on the surfaces of bronzes. Ions, acids, and particles of pollutants can dissolve in this layer, resulting in a variety of harsh corrosion processes. The kinetics of corrosion and the properties of the resulting patinas were monitored weekly by electrochemical impedance spectroscopy and open-circuit potential measurements. The sizes and appearances of the corrosion products were monitored and used to estimate the progress of the corrosion, whose crystalline structures were visualized using scanning electron microscopy with energy dispersive spectroscopy, identified by X-ray diffraction, and characterized by spectrocolorimetry. The electrochemical measurements demonstrated that greater damage (in terms of color change and corrosion product formation) did not correspond to deficiencies in protection. The mixed-acid solution did not corrode the bronzes, as would be expected from the additive effects of the single acids. The postulated mechanisms of metal dissolution appear to be specific to a particular bronze alloy, with the tin component playing an important role.
In this paper, the influence of the tin content on the corrosion behaviour of copper alloys was investigated. Three different bicomponent bronze alloys were exposed to a natural urban environment. The kinetic corrosion processes and the patina properties were monitored using the open circuit potential, electrochemical impedance spectroscopy and spectrocolorimetry. Results show that the bronze corrosion behaviour improves upon increasing the tin content. In addition, the mechanism of the patina formation is different for the three alloys
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