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Title: DFT-Based Calculation of Dissolution Activation Energy and Kinetics of Ni–Cr Alloys

Abstract

A density functional theory investigation of the process of dissolution of Ni and Cr adatoms from model Ni–Cr(111) alloy surfaces is presented, both in vacuum and with explicit water molecules. The goal is to understand how the electronic structures solved using DFT can provide insights as to changes in valence, energy and coordination of the adatoms in the process of dissolving from the alloy surface. It is found that nearby Cr solute atoms increase the dissolution activation energy of Ni. Cr adatoms have a similar dissolution activation energy as Ni adatoms, except for one particular surface configuration that has a much smaller dissolution activation energy, which might promote selective dissolution of Cr in Ni–Cr alloys. To interpret the first-principles modeling results for the potential energy trajectory along the dissolution reaction coordinate, we provide a thermodynamic breakdown of the various terms that contribute to the dissolution activation and total reaction energy. The role of addition of Cr is explored on the dissolution kinetics of a Ni–Cr alloys of varying composition by constructing a model for the corrosion current density with DFT-based activation energies. Lastly, dissolution resistance index is proposed as a quantifiable descriptor of the dissolution resistance of corrosion resistant alloys.

Authors:
ORCiD logo [1]; ORCiD logo [2]
  1. Ohio State University, Columbus, OH (United States)
  2. Ohio State University, Columbus, OH (United States); DNV GL USA, Dublin, OH (United States)
Publication Date:
Research Org.:
The Ohio State Univ., Columbus, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1670418
Grant/Contract Number:  
SC0016584
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society (Online)
Additional Journal Information:
Journal Volume: 167; Journal Issue: 13; Journal ID: ISSN 1945-7111
Publisher:
IOP Publishing
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Ke, Huibin, and Taylor, Christopher D. DFT-Based Calculation of Dissolution Activation Energy and Kinetics of Ni–Cr Alloys. United States: N. p., 2020. Web. doi:10.1149/1945-7111/abbbbd.
Ke, Huibin, & Taylor, Christopher D. DFT-Based Calculation of Dissolution Activation Energy and Kinetics of Ni–Cr Alloys. United States. doi:10.1149/1945-7111/abbbbd.
Ke, Huibin, and Taylor, Christopher D. Mon . "DFT-Based Calculation of Dissolution Activation Energy and Kinetics of Ni–Cr Alloys". United States. doi:10.1149/1945-7111/abbbbd.
@article{osti_1670418,
title = {DFT-Based Calculation of Dissolution Activation Energy and Kinetics of Ni–Cr Alloys},
author = {Ke, Huibin and Taylor, Christopher D.},
abstractNote = {A density functional theory investigation of the process of dissolution of Ni and Cr adatoms from model Ni–Cr(111) alloy surfaces is presented, both in vacuum and with explicit water molecules. The goal is to understand how the electronic structures solved using DFT can provide insights as to changes in valence, energy and coordination of the adatoms in the process of dissolving from the alloy surface. It is found that nearby Cr solute atoms increase the dissolution activation energy of Ni. Cr adatoms have a similar dissolution activation energy as Ni adatoms, except for one particular surface configuration that has a much smaller dissolution activation energy, which might promote selective dissolution of Cr in Ni–Cr alloys. To interpret the first-principles modeling results for the potential energy trajectory along the dissolution reaction coordinate, we provide a thermodynamic breakdown of the various terms that contribute to the dissolution activation and total reaction energy. The role of addition of Cr is explored on the dissolution kinetics of a Ni–Cr alloys of varying composition by constructing a model for the corrosion current density with DFT-based activation energies. Lastly, dissolution resistance index is proposed as a quantifiable descriptor of the dissolution resistance of corrosion resistant alloys.},
doi = {10.1149/1945-7111/abbbbd},
journal = {Journal of the Electrochemical Society (Online)},
issn = {1945-7111},
number = 13,
volume = 167,
place = {United States},
year = {2020},
month = {10}
}

Journal Article:
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Works referenced in this record:

Localized Corrosion: Passive Film Breakdown vs. Pit Growth Stability: Part III. A Unifying Set of Principal Parameters and Criteria for Pit Stabilization and Salt Film Formation
journal, January 2018

  • Li, Tianshu; Scully, J. R.; Frankel, G. S.
  • Journal of The Electrochemical Society, Vol. 165, Issue 11
  • DOI: 10.1149/2.0251811jes

Localized Corrosion: Passive Film Breakdown vs. Pit Growth Stability: Part IV. The Role of Salt Film in Pit Growth: A Mathematical Framework
journal, January 2019

  • Li, Tianshu; Scully, J. R.; Frankel, G. S.
  • Journal of The Electrochemical Society, Vol. 166, Issue 6
  • DOI: 10.1149/2.0211906jes

Localized Corrosion: Passive Film Breakdown vs Pit Growth Stability: Part II. A Model for Critical Pitting Temperature
journal, January 2018

  • Li, Tianshu; Scully, J. R.; Frankel, G. S.
  • Journal of The Electrochemical Society, Vol. 165, Issue 9
  • DOI: 10.1149/2.0591809jes

Localized Corrosion: Passive Film Breakdown vs Pit Growth Stability: Part V. Validation of a New Framework for Pit Growth Stability Using One-Dimensional Artificial Pit Electrodes
journal, January 2019

  • Li, Tianshu; Scully, J. R.; Frankel, G. S.
  • Journal of The Electrochemical Society, Vol. 166, Issue 11
  • DOI: 10.1149/2.0431911jes

Density Functional Theory: An Essential Partner in the Integrated Computational Materials Engineering Approach to Corrosion
journal, May 2019

  • Ke, Huibin; Taylor, Christopher D.
  • CORROSION, Vol. 75, Issue 7
  • DOI: 10.5006/3050

An Atomistic Description of Dealloying
journal, January 2004

  • Erlebacher, Jonah
  • Journal of The Electrochemical Society, Vol. 151, Issue 10
  • DOI: 10.1149/1.1784820

Relationship between the parting limit for de-alloying and a particular geometric high-density site percolation threshold
journal, July 2009


Surface Diffusion and Dissolution Kinetics in the Electrolyte–Metal Interface
journal, January 2010

  • Policastro, S. A.; Carnahan, J. C.; Zangari, G.
  • Journal of The Electrochemical Society, Vol. 157, Issue 10
  • DOI: 10.1149/1.3478572

Ab Initio Monte Carlo Simulations of the Acidic Dissolution of Stainless Steels: Influence of the Alloying Elements
journal, January 2016

  • Malki, B.; Saedlou, S.; Guillotte, I.
  • Journal of The Electrochemical Society, Vol. 163, Issue 14
  • DOI: 10.1149/2.0151614jes

First-Principles and Kinetic Monte Carlo Simulation Studies of the Reactivity of Tc(0001), MoTc(111) and MoTc(110) Surfaces
journal, December 2013

  • Kim, Eunja; Weck, Philippe F.; Taylor, Christopher D.
  • Journal of The Electrochemical Society, Vol. 161, Issue 3
  • DOI: 10.1149/2.097401jes

Crystallographic orientation and electrochemical activity of AZ31 Mg alloy
journal, August 2010


First-principles modeling of anisotropic anodic dissolution of metals and alloys in corrosive environments
journal, May 2017


Metal desorption from Fe(110) and its alloyed surfaces
journal, October 2013


Mn ion dissolution from MnS: a density functional theory study
journal, January 2013

  • Wang, Y. J.; Hu, P.; Ma, X. L.
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 40
  • DOI: 10.1039/c3cp52472h

Projector augmented-wave method
journal, December 1994


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Python Materials Genomics (pymatgen): A robust, open-source python library for materials analysis
journal, February 2013


Saturated Vapour Pressure and Enthalpy of Sublimation of Nickel
journal, January 1992


The Vapor Pressure and Heat of Sublimation of Chromium
journal, November 1965

  • Dickson, D. S.; Myers, J. R.; Saxer, R. K.
  • The Journal of Physical Chemistry, Vol. 69, Issue 11
  • DOI: 10.1021/j100895a508

Bond-order bond energy model for alloys
journal, October 2019


On some fundamental factors in the effect of alloying elements on passivation of alloys
journal, December 1994


Can an electrode reaction occur without electron transfer across the metal/solution interface?
journal, August 2004


Energy levels of nickel, Ni I through Ni XXVIII
journal, January 1981

  • Corliss, Charles; Sugar, Jack
  • Journal of Physical and Chemical Reference Data, Vol. 10, Issue 1
  • DOI: 10.1063/1.555638

On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I
journal, May 1956

  • Marcus, R. A.
  • The Journal of Chemical Physics, Vol. 24, Issue 5
  • DOI: 10.1063/1.1742723

Simultaneous two-electron transfer in electrode kinetics
journal, September 2002


The absolute electrode potential: an explanatory note (Recommendations 1986)
journal, January 1986


Ionic hydration enthalpies
journal, September 1977

  • Smith, Derek W.
  • Journal of Chemical Education, Vol. 54, Issue 9
  • DOI: 10.1021/ed054p540

Structure of the metal/electrolyte solution interface: new data for theory
journal, January 1991


Integrated computational materials engineering of corrosion resistant alloys
journal, February 2018