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Kinetics of electrochemical dissolution of metals in porous media

Nature Materials volume 18, pages 942–947 (2019)Cite this article

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Abstract

Metals embedded in porous media interact electrochemically with the liquid phase contained in the pores. A widespread form of this, adversely affecting the integrity of engineered structures, is corrosion of steel in porous media or in natural environments. While it is well documented that the rate of this electrochemical dissolution process can vary over several orders of magnitude, understanding the underlying mechanisms remains a critical challenge hampering the development of reliable predictive models. Here we study the electrochemical dissolution kinetics of steel in meso-to-macro-porous media, using cement-based materials, wood and artificial soil as model systems. Our results reveal the dual role of the pore structure (that is, the influence on the electrochemical behaviour through transport limitations and an area effect, which is ultimately due to microscopic inhomogeneity of the metal/porous material interface). We rationalize the observations with the theory of capillary condensation and propose a material-independent model to predict the corrosion rate.

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Fig. 1: Influence of porosity and moisture conditions on electrochemical dissolution kinetics.
Fig. 2: Master curve of corrosion of steel in porous media.
Fig. 3: Schematic representation of the proposed model.
Fig. 4: Measured corrosion rates (icorr,app) as a function of the calculated volume fraction of electrolyte in the porous material (Psat).
Fig. 5: Influence of matrix porosity on the distance to which corrosion products diffuse from the electrode.
Fig. 6: Relationship between total porosity and the effective corrosion current density.

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Data availability

The experimental data supporting the findings of this study are available in the main text or in the Supplementary Information. Additional data are available from the corresponding author upon reasonable request.

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Acknowledgements

Research supported by the Swiss National Foundation for Research (SNF) project no. 154062 entitled ‘Formulation, use and durability of concrete with low clinker cements’ is gratefully acknowledged. The authors would also like to thank K. Scrivener and the LMC laboratory of EPFL Lausanne for the MIP measurements. ScopeM from ETH Zurich and A. M. Aguilar from the Physical Chemistry of Building Materials group also from ETH Zurich are acknowledged for the SEM/EDX analysis. P. Lura from EMPA is acknowledged for the use of the carbonation chamber. I. Burgert’s Wood Materials Science group of ETH Zurich is acknowledged for providing the wood specimens for this study.

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Authors and Affiliations

  1. Institute for Building Materials, ETH Zurich, Zurich, Switzerland

    Matteo Stefanoni, Ueli M. Angst & Bernhard Elsener

  2. Department of Chemical and Geological Science, University of Cagliari, Monserrato, Italy

    Bernhard Elsener

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  1. Matteo Stefanoni
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M.S. was the main investigator. He developed the experimental protocols and carried out the experiments. All authors designed the research, and contributed to the analysis and interpretation of the results and to the preparation of the manuscript.

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Correspondence to Ueli M. Angst.

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Supplementary Information

Supplementary Notes 1–6, Figs. 1–12, Tables 1–4 and refs. 1–20.

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Stefanoni, M., Angst, U.M. & Elsener, B. Kinetics of electrochemical dissolution of metals in porous media. Nat. Mater. 18, 942–947 (2019). https://doi.org/10.1038/s41563-019-0439-8

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