De-alloying of type 316 stainless steel in hot, concentrated sodium hydroxide solution

Abstract

The formation of “nickel” layers on austenitic stainless steel in strong caustic solutions was reported in 1979. We now report a detailed study that clarifies the nature of this de-alloying process and establishes firm links with other metal-environment systems that show de-alloying and associated stress corrosion cracking. De-alloying of iron from 316SS in 50% NaOH at 140 °C proceeds only as far as a solid solution with a Ni/Fe atomic ratio of ca. 1.3 (56 at.% Ni if we neglect the other elements present). Chromium is mostly dissolved and/or reprecipitated during this process. X-ray diffraction shows that the residue is a solid solution of intermediate composition, not a mixture of pure Ni and stainless steel. The removal of only half the iron conveniently explains why the de-alloyed layer is a connected porous network. Electrode capacitance measurements and FEG-SEM examination show that the de-alloyed layer has extremely fine nanoporosity.