Modification of Ni-20Cr corrosion dealloying behavior in molten fluorides via cold work induced plastic deformation

The corrosion dealloying behavior of cold-worked (CW) Ni20Cr alloy (wt%) was studied in molten LiF-NaF-KF (or FLiNaK) salts at 600 °C, equal to a homologous temperature (TH) of 0.52. Alloys were cold-rolled to achieve reductions of thickness of 10%, 30%, and 50% introducing plastic deformation and a high density of dislocations. Potentiostatic holds (Eapplied) were applied in two different electrode potential regimes. At 1.75 $${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$ , Cr dealloying to Cr(II) and Cr(III) is predominant, while at 1.90 $${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$ , both Ni and Cr are oxidized in molten FLiNaK at 600 °C. In these potential regimes, dealloyed Ni20Cr displayed bicontinuous porosity within the grain interior and at grain boundaries, driven by the high driving force for Cr dissolution and sustained by defect mediated outward solid state diffusion of Cr in parallel with surface diffusion of Ni. The bicontinuous porous structure developed was observed to undergo further coarsening and densification of the Ni-rich ligaments at a higher electrode potential. The main effect of CW observed is the introduction of plastic deformation and dislocation substructures that serve as short-circuit paths for Cr solid state diffusion to surfaces exposed to FLiNaK. This modified the evolution of the bicontinuous porous structure which increased with CW substantially. Kinetic analysis reveals that the Cr dealloying at +1.75 $${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$ and 1.90 $${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$ is initially charge transfer controlled, except for the 50% CW condition at 1.90 $${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$ , where the process becomes limited by slow Cr defect mediated bulk diffusion. The rate determining factors are explored and compared to experimental results.

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Journal
npj Materials Degradation
Published
2025-11-11
DOI
https://doi.org/10.1038/s41529-025-00678-4
Primary Topic
Nanoporous metals and alloys
Type
article
Field-Weighted Citation Impact
0.00

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article

Modification of Ni-20Cr corrosion dealloying behavior in molten fluorides via cold work induced plastic deformation

Andrew M. Minor, Peter Hosemann, Harjot Singh, John R. Scully et al.
npj Materials Degradation
Nanoporous metals and alloys
article

Modification of Ni-20Cr corrosion dealloying behavior in molten fluorides via cold work induced plastic deformation

Andrew M. Minor, Peter Hosemann, Harjot Singh, John R. Scully, Sean H. Mills, Ho Lun Chan, Elena Romanovskaia, Xikai Wang, Iliana Marrujo
article en

Abstract

The corrosion dealloying behavior of cold-worked (CW) Ni20Cr alloy (wt%) was studied in molten LiF-NaF-KF (or FLiNaK) salts at 600 °C, equal to a homologous temperature (TH) of 0.52. Alloys were cold-rolled to achieve reductions of thickness of 10%, 30%, and 50% introducing plastic deformation and a high density of dislocations. Potentiostatic holds (Eapplied) were applied in two different electrode potential regimes. At 1.75 $${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$ , Cr dealloying to Cr(II) and Cr(III) is predominant, while at 1.90 $${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$ , both Ni and Cr are oxidized in molten FLiNaK at 600 °C. In these potential regimes, dealloyed Ni20Cr displayed bicontinuous porosity within the grain interior and at grain boundaries, driven by the high driving force for Cr dissolution and sustained by defect mediated outward solid state diffusion of Cr in parallel with surface diffusion of Ni. The bicontinuous porous structure developed was observed to undergo further coarsening and densification of the Ni-rich ligaments at a higher electrode potential. The main effect of CW observed is the introduction of plastic deformation and dislocation substructures that serve as short-circuit paths for Cr solid state diffusion to surfaces exposed to FLiNaK. This modified the evolution of the bicontinuous porous structure which increased with CW substantially. Kinetic analysis reveals that the Cr dealloying at +1.75 $${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$ and 1.90 $${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$ is initially charge transfer controlled, except for the 50% CW condition at 1.90 $${\text{V}}_{{\text{K}}^{+}/{\text{K}}}$$ , where the process becomes limited by slow Cr defect mediated bulk diffusion. The rate determining factors are explored and compared to experimental results.

npj Materials DegradationVol. 9(1)
Lawrence Berkeley National Laboratory (US), University of Virginia (US), University of California, Berkeley (US)
National Science Foundation, U.S. Department of Energy, Office of Science, Basic Energy Sciences
Openalex Percentile: Top 73%
Nanoporous metals and alloys
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