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Initial corrosion observed on the atomic scale

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Abstract

Corrosion destroys more than three per cent of the world's GDP1. Recently, the electrochemical decomposition of metal alloys has been more productively harnessed to produce porous materials with diverse technological potential2,3. High-resolution insight into structure formation during electrocorrosion is a prerequisite for an atomistic understanding and control of such electrochemical surface processes. Here we report atomic-scale observations of the initial stages of corrosion of a Cu3Au(111) single crystal alloy within a sulphuric acid solution. We monitor, by in situ X-ray diffraction with picometre-scale resolution, the structure and chemical composition of the electrolyte/alloy interface as the material decomposes. We reveal the microscopic structural changes associated with a general passivation phenomenon of which the origin has been hitherto unclear. We observe the formation of a gold-enriched single-crystal layer that is two to three monolayers thick, and has an unexpected inverted (CBA-) stacking sequence. At higher potentials, we find that this protective passivation layer dewets and pure gold islands are formed; such structures form the templates for the growth of nanoporous metals2. Our experiments are carried out on a model single-crystal system. However, the insights should equally apply within a crystalline grain of an associated polycrystalline electrode fabricated from many other alloys exhibiting a large difference in the standard potential of their constituents4, such as stainless steel (see ref. 5 for example) or alloys used for marine applications, such as CuZn or CuAl.

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Figure 1: Voltammogram and passivation layer formation.
Figure 2: In-situ structural characterization of the passivation layer.
Figure 3: Transformation of the passivation layer into Au islands.
Figure 4: Integrated anomalous in-plane diffraction intensities of the ultrathin passivation layer, and Au islands.

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Acknowledgements

We thank B. Krause, A. Reicho, S. Warren, B. C. C. Cowie, S. Thiess, O. Bunk and W. Drube for their help with the synchrotron measurements, and F. D'Anca and R. Felici for collaboration in developing the in-situ cell and installing the electrochemistry laboratory at INFM-OGG/ESRF. The Bundesministerium für Forschung und Bildung (BMBF) is acknowledged for financial support.

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Authors and Affiliations

  1. Max-Planck-Institut für Metallforschung, Heisenbergstrasse 3, D-70569, Stuttgart, Germany

    F. U. Renner, A. Stierle & H. Dosch

  2. European Synchrotron Radiation Facility, Boîte Postale 220, F-38043, Grenoble, France

    F. U. Renner, T.-L. Lee & J. Zegenhagen

  3. Abteilung Elektrochemie, Universität Ulm, Albert-Einstein-Allee 47, D-89081, Ulm, Germany

    D. M. Kolb

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  1. F. U. Renner
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  2. A. Stierle
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  4. D. M. Kolb
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  5. T.-L. Lee
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  6. J. Zegenhagen
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Correspondence to F. U. Renner.

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Renner, F., Stierle, A., Dosch, H. et al. Initial corrosion observed on the atomic scale. Nature 439, 707–710 (2006). https://doi.org/10.1038/nature04465

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