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The corrosion process of sterling silver exposed to a Na2S solution: monitoring and characterizing the complex surface evolution using a multi-analytical approach

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Abstract

Many historical ‘silver’ objects are composed of sterling silver, a silver alloy containing small amounts of copper. Besides the dramatic impact of copper on the corrosion process, the chemical composition of the corrosion layer evolves continuously. The evolution of the surface during the exposure to a Na2S solution was monitored by means of visual observation at macroscopic level, chemical analysis at microscopic level and analysis at the nanoscopic level. The corrosion process starts with the preferential oxidation of copper, forming mixtures of oxides and sulphides while voids are being created beneath the corrosion layer. Only at a later stage, the silver below the corrosion layer is consumed. This results in the formation of jalpaite and at a later stage of acanthite. The acanthite is found inside the corrosion layer at the boundaries of jalpaite grains and as individual grains between the jalpaite grains but also as a thin film on top of the corrosion layer. The corrosion process could be described as a sequence of 5 subsequent surface states with transitions between these states.

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Acknowledgments

The authors are grateful for the financial support by the EU-FP7 Grant PANNA No. 282998 and for the opportunity to perform SR-XPS measurements at the NanoESCA beamline of the Elettra storage ring, under the approval of the advisory Committee (Proposal No. 20135164), as well as the opportunity to perform XANES measurements at the DUBBLE beamline of the ESRF storage ring (Proposal No. 26-01-990). The authors are grateful for the financial support by the STIMPRO Project FFB150215 of the University of Antwerp. Pieter Tack is funded by a Ph.D. Grant of the Agency for Innovation by Science and Technology (IWT). We would also like to thank Peter Van den Haute for the XRD measurements that were performed at the University of Ghent.

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Authors and Affiliations

  1. Conservation Studies, University of Antwerp, Blindestraat 9, 2000, Antwerp, Belgium

    Olivier Schalm & Patrick Storme

  2. Institute of Science and Technology in Art, Academy of Fine Arts Vienna, Schillerplatz 3, 1010, Vienna, Austria

    Rita Wiesinger & Christoph Kleber

  3. Istituto per l’Energetica e le Interfasi, Corso Stati Uniti, 4, 35127, Padua, Italy

    Arianna Gambirasi & Monica Favaro

  4. EMAT, Department of Physics, University of Antwerp, Groenenborgerlaan 171, 2020, Antwerp, Belgium

    Eva Grieten & Dominique Schryvers

  5. Research Group of Electrochemical and Surface Engineering, Vrije Universiteit Brussel (VUB), Pleinlaan 2, 1050, Brussels, Belgium

    Amandine Crabbé & Herman Terryn

  6. XMI, Department of Analytical Chemistry, Ghent University, 9000, Ghent, Belgium

    Pieter Tack, Stephen Bauters & Laszlo Vincze

  7. Centre for Electrochemical Surface Technology, Viktor-Kaplan-Strasse 2, 2700, Wiener Neustadt, Austria

    Christoph Kleber

  8. Department of Physics and Astronomy, Padova University, via Marzolo 8, 35122, Padua, Italy

    Alessandro Patelli

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  1. Olivier Schalm
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  2. Amandine Crabbé
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  3. Patrick Storme
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  10. Monica Favaro
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Correspondence to Olivier Schalm.

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Schalm, O., Crabbé, A., Storme, P. et al. The corrosion process of sterling silver exposed to a Na2S solution: monitoring and characterizing the complex surface evolution using a multi-analytical approach. Appl. Phys. A 122, 903 (2016). https://doi.org/10.1007/s00339-016-0436-6

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