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Title: Potential-pH diagrams considering complex oxide solution phases for understanding aqueous corrosion of multi-principal element alloys

Abstract

Abstract The potential-pH diagram, a graphical representation of the thermodynamically predominant reaction products in aqueous corrosion, is originally proposed for the corrosion of pure metals. The original approach only leads to stoichiometric oxides and hydroxides as the oxidation products. However, numerous experiments show that non-stoichiometric oxide scales are prevalent in the aqueous corrosion of alloys. In the present study, a room temperature potential-pH diagram considering oxide solid solutions, as a generalization of the traditional potential-pH diagram with stoichiometric oxides, is constructed for an FCC single-phase multi-principal element alloy (MPEA) based on the CALculation of PHAse Diagram method. The predominant reaction products, the ions in aqueous solution, and the cation distribution in oxides are predicted. The oxide solid solution is stabilized by the mixing free energy (or mixing entropy) and the stabilizing effect becomes more significant as the temperature increases. Consequently, solid solution oxides are stable in large regions of the potential-pH diagram and the mixing free energy mostly affects the equilibrium composition of the stable oxides, while the shape of stable regions for oxides is mostly determined by the structure of the stable oxides. Agreements are found for Ni 2+ , Fe 2+ , and Mn 2+ between the atomicmore » emission spectroelectrochemistry measurements and thermodynamic calculations, while deviations exist for Cr 3+ and Co 2+ possibly due to surface complexation with species such as Cl and the oxide dissolution. By incorporating the solution models of oxides, the current work presents a general and more accurate way to analyze the reaction products during aqueous corrosion of MPEAs.« less

Authors:
ORCiD logo; ORCiD logo; ; ORCiD logo; ORCiD logo
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1712542
Grant/Contract Number:  
SC0016584
Resource Type:
Published Article
Journal Name:
npj Materials Degradation
Additional Journal Information:
Journal Name: npj Materials Degradation Journal Volume: 4 Journal Issue: 1; Journal ID: ISSN 2397-2106
Publisher:
Nature Publishing Group
Country of Publication:
United Kingdom
Language:
English

Citation Formats

Wang, Kang, Han, Junsoo, Gerard, Angela Yu, Scully, John R., and Zhou, Bi-Cheng. Potential-pH diagrams considering complex oxide solution phases for understanding aqueous corrosion of multi-principal element alloys. United Kingdom: N. p., 2020. Web. https://doi.org/10.1038/s41529-020-00141-6.
Wang, Kang, Han, Junsoo, Gerard, Angela Yu, Scully, John R., & Zhou, Bi-Cheng. Potential-pH diagrams considering complex oxide solution phases for understanding aqueous corrosion of multi-principal element alloys. United Kingdom. https://doi.org/10.1038/s41529-020-00141-6
Wang, Kang, Han, Junsoo, Gerard, Angela Yu, Scully, John R., and Zhou, Bi-Cheng. Thu . "Potential-pH diagrams considering complex oxide solution phases for understanding aqueous corrosion of multi-principal element alloys". United Kingdom. https://doi.org/10.1038/s41529-020-00141-6.
@article{osti_1712542,
title = {Potential-pH diagrams considering complex oxide solution phases for understanding aqueous corrosion of multi-principal element alloys},
author = {Wang, Kang and Han, Junsoo and Gerard, Angela Yu and Scully, John R. and Zhou, Bi-Cheng},
abstractNote = {Abstract The potential-pH diagram, a graphical representation of the thermodynamically predominant reaction products in aqueous corrosion, is originally proposed for the corrosion of pure metals. The original approach only leads to stoichiometric oxides and hydroxides as the oxidation products. However, numerous experiments show that non-stoichiometric oxide scales are prevalent in the aqueous corrosion of alloys. In the present study, a room temperature potential-pH diagram considering oxide solid solutions, as a generalization of the traditional potential-pH diagram with stoichiometric oxides, is constructed for an FCC single-phase multi-principal element alloy (MPEA) based on the CALculation of PHAse Diagram method. The predominant reaction products, the ions in aqueous solution, and the cation distribution in oxides are predicted. The oxide solid solution is stabilized by the mixing free energy (or mixing entropy) and the stabilizing effect becomes more significant as the temperature increases. Consequently, solid solution oxides are stable in large regions of the potential-pH diagram and the mixing free energy mostly affects the equilibrium composition of the stable oxides, while the shape of stable regions for oxides is mostly determined by the structure of the stable oxides. Agreements are found for Ni 2+ , Fe 2+ , and Mn 2+ between the atomic emission spectroelectrochemistry measurements and thermodynamic calculations, while deviations exist for Cr 3+ and Co 2+ possibly due to surface complexation with species such as Cl − and the oxide dissolution. By incorporating the solution models of oxides, the current work presents a general and more accurate way to analyze the reaction products during aqueous corrosion of MPEAs.},
doi = {10.1038/s41529-020-00141-6},
journal = {npj Materials Degradation},
number = 1,
volume = 4,
place = {United Kingdom},
year = {2020},
month = {11}
}

Journal Article:
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https://doi.org/10.1038/s41529-020-00141-6

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