Nickel alloys and stainless have been the material of choice for a wide range of industrial applications like power and petrochemical plants that involve exposure to corrosive environments. For instance, Alloy 800 (Fe-30Ni-20Cr) has been used as the tubing material in CANDU and Siemens steam generators (SGs) for decades with excellent in-service performance. However, despite their good resistance to general to localize corrosion, Ni- and Fe-based alloys are susceptible to environmentally assisted cracking (EAC) in certain environments, such as hot caustic aqueous solutions. Laboratory experiments have shown that these materials are susceptible to dealloying in hot caustic environments due to the selective removal of Fe, Cr and Mo (less noble elements). As a result of dealloying, a brittle nanoporous film forms on the surface that is enriched in Ni (the more noble element). This film has been proposed to act as a precursor to stress corrosion cracking (SCC) by a film-induced cleavage (FIC) mechanism, where the brittle film injects a high speed/energy crack to the substrate material.

The fast kinetics of dealloying requires a connected percolating pathway of less noble element atoms to exist within the alloy that extends from the surface into the material. The presence of this pathway depends on the composition of the alloy. The parting limit defines the minimum amount of the more reactive element(s) in a particular alloy system that makes it susceptible to dealloying. Below the parting limit composition, dealloying will be suppressed by surface diffusion of the more noble element, even at very oxidizing potentials, and the surface of the material will show a passive-like behavior (general dissolution would eventually occur at high anodic overpotentials). Besides the alloy composition, dealloying highly depends on the electrode potential. Below a threshold potential (dealloying critical potential), surface diffusion of the more noble element will overcome the dissolution of the less noble element(s) and suppress dealloying.

In this study, we examine different factors that affect dealloying and the geometry of a dealloyed layer through electrochemical measurements and nano-scale characterization techniques. Several engineering Ni- and Fe-based alloys were tested in deaerated boiling caustic solutions to understand the effect of alloy composition on the susceptibility to dealloying. Results indicate that an increase in Ni content will shift the dealloying critical potential to more positive potentials and subsequently the resistance to dealloying. Although Ni is the alloying element that provides nobility and resistance in hot caustic environments, our results show that the thermodynamic and kinetic behaviour, and the content of the less noble elements play an important role in these environments. A comparison between different alloys with similar Ni-content but different Cr and Mo contents shows the beneficial and detrimental role of Cr and Mo in dealloying, respectively. The air-formed chromia-based oxide on the surface of alloys with high Cr-content slowly dissolves in the caustic environment, delays the dissolution of less noble elements, and increases the resistance to dealloying.

Changes in electrode potential and time of exposure to the caustic environments, alter the geometry of the dealloyed layer. Results show an increase in the diameter and coarsening of ligaments with increasing time of exposure to the caustic environment. Coarsening of ligaments is believed to impair the ability of a dealloyed layer to inject a micro-crack to the underlying material and initiate SCC. Also, results show that an increase in anodic overpotential of only a few millivolts in the vicinity of dealloying critical potential would change the geometry of the dealloyed layer significantly. The surface diffusion of the more noble element (i.e. Ni) cannot keep up with the fast removal of atoms of the less noble elements (i.e. Cr, Mo, and Fe) at more positive electrode potentials compared to the dealloying critical potential which results in a weak bonding at the film/metal interface. The weak bonding may not be able to support the transmission of a high-speed crack to the substrate material, reducing the likelihood of SCC initiation.