The origin of the reversibility of the environmental embrittlement of an Ag-20 at. % gold alloy in 1 M HClO4 has been investigated. The structure of the porous gold layer formed on this alloy under potentiostatic polarization has been studied by electrochemical impedance spectroscopy (EIS). In the as-dealloyed state, a 50-μm layer has impedance behavior electrically equivalent to a layer containing 1011 cylindrical pores/cm2 (geometric area) each with a radius of 9 nm. Upon aging, the pores closest to the substrate coarsen first, destroying the ability of the layer to inject a brittle crack into the uncorroded substrate. This change in structure is observable as a change in the low-frequency portion of the impedance spectrum. The observed potential dependence of this coarsening indicates that it occurs due to surface diffusion of gold atoms.
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