A new framework has been developed in recent works to describe pit growth stability ^1-4. In this framework, the concept of maximum pit dissolution current density, i_diss,max, was proposed to consider the competition between the dissolution and diffusion processes within a pit ^{2, 3}, an issue that has not been satisfactorily addressed previously. The quantity i_diss,max is the rate of dissolution in a pit in the absence of a salt film. According to this new framework, the pit stability and salt film formation can be defined by the critical conditions of i_diss,max = i_diff,crit and i_diss,max = i_lim, respectively, where i_diff,crit and i_lim are diffusion current densities related to maintain critical and saturated pit concentration ³. Unifying sets of principal parameters for pit stability and salt film formation were developed based on these critical conditions: (T_crit, E_crit, r_crit) and (T_sat, E_sat, r_sat), respectively ³.

This talk described experiments using 1D artificial pit electrodes that validate this new framework for pit stability. According to the model prediction, the critical potential for salt film formation (E_sat) should decrease with the log of pit depth. The results from experiments on 1D pits followed this relationship exactly, which provides strong support of the validity of the new model. Additionally, a critical pit concentration equal to 43% of the saturation concentration, C_sat, was determined, which is much lower than the critical concentration determined by others. Furthermore, i_diss,max values at fixed pit surface solution concentrations (100%C_sat and 70%C_sat) were determined using pits of varying depth. The Tafel slope was found to be about 116 mV in both environments. This is the first ever determination of pit dissolution kinetics in pit solutions of fixed concentration.

This new framework provides an opportunity to revisit several key topics of this field and generates new insights to interpret previous observations in a self-consistent way, such as to understand the effects of alloy composition, bulk chloride concentration, ohmic potential drop of the solution, etc.

Acknowledgments: This work was supported as part of the Center for Performance and Design of Nuclear Waste Forms and Containers, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0016584.

Reference

1. G. S. Frankel, T. Li and J. R. Scully, Journal of the Electrochemical Society 164, C180-C181 (2017).
2. T. Li, J. R. Scully and G. S. Frankel, Journal of The Electrochemical Society 165, C484-C491 (2018).
3. T. Li, J. R. Scully and G. S. Frankel, Journal of The Electrochemical Society 165, C762-C770 (2018).
4. T. Li, J. R. Scully and G. S. Frankel, Journal of The Electrochemical Society 166, C115-C124 (2019).