Bulk Diffusion of Cl through O Vacancies in α-Cr 2 O 3 : A Density Functional Theory Study

Oware Sarfo, Kofi; Isgor, O. Burkan; Santala, Melissa K.; Tucker, Julie D.; Árnadóttir, Líney

doi:10.1149/1945-7111/ac0ec9

Bulk Diffusion of Cl through O Vacancies in α-Cr ₂ O ₃ : A Density Functional Theory Study

Journal Article · Tue Jul 06 00:00:00 UTC 2021 · Journal of the Electrochemical Society

DOI:https://doi.org/10.1149/1945-7111/ac0ec9· OSTI ID:1835416

Oware Sarfo, Kofi; Isgor, O. Burkan; Santala, Melissa K.; Tucker, Julie D.;

Many metals form passive oxides which are broken or weakened by anionic-induced degradation leading to material failure and anionic diffusion is an important step of this degradation process. The diffusion of anionic species through oxides involves a combination of diffusion along grain boundaries, cracks, and channels, as well as bulk diffusion via point defects which is the focus of this study. Using density functional theory, we study bulk diffusion of Cl through O vacancies in α -Cr ₂ O ₃ as a model system for passive metal oxides. Little is known about Cl diffusion and bonding characteristics, so we benchmark our work through comparison to numerous studies on O diffusion in α -Cr ₂ O ₃ to analyze similarities and differences between the O and Cl diffusion in the passivation and degradation process of α -Cr ₂ O ₃ respectively. Unlike O diffusion, the lowest diffusion barrier for Cl is cross-plane diffusion between two (0001) planes through a vacant cation site but the much shorter in-plane diffusion path within the same coordination polyhedron has 35% higher barrier. This work provides the basis for considering the contributions of Cl bulk-diffusion in the overall diffusion kinetics of Cl through α -Cr ₂ O ₃ .

View Journal Article

Sponsoring Organization:: USDOE

Grant/Contract Number:: NE0008668

OSTI ID:: 1835416

Alternate ID(s):: OSTI ID: 1850526

Journal Information:: Journal of the Electrochemical Society, Journal Name: Journal of the Electrochemical Society Journal Issue: 7 Vol. 168; ISSN 0013-4651

Publisher:: The Electrochemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (69)

Ceramic joining III bonding of alumina via Cu/Nb/Cu interlayers Shalz, M. L.; Dalgleish, B. J.; Tomsia, A. P. Journal of Materials Science, Vol. 29, Issue 14 https://doi.org/10.1007/BF00357335	journal	July 1994
Diffusion of18O in massive Cr2O3 and in Cr2O3 scales at 900�C and its relation to the oxidation kinetics of chromia forming alloys Tsai, S. C.; Huntz, A. M.; Dolin, C. Oxidation of Metals, Vol. 43, Issue 5-6 https://doi.org/10.1007/BF01046900	journal	June 1995
Relation between the oxidation growth rate of chromia scales and self-diffusion in Cr2O3 Sabioni, A. C. S.; Huntz, A. M.; Philibert, J. Journal of Materials Science, Vol. 27, Issue 17 https://doi.org/10.1007/BF01166020	journal	January 1992
Transport processes in passivity breakdown—II. Full hydrolysis of the metal ions Galvele, JoséR. Corrosion Science, Vol. 21, Issue 8 https://doi.org/10.1016/0010-938X(81)90009-3	journal	January 1981
The pit initiation mechanism on passive iron under both open-circuit and controlled potential conditions Ogura, Kotaro; Kaneko, Minoru Corrosion Science, Vol. 23, Issue 11 https://doi.org/10.1016/0010-938X(83)90050-1	journal	January 1983
The passivity of iron-chromium alloys Kirchheim, R.; Heine, B.; Fischmeister, H. Corrosion Science, Vol. 29, Issue 7 https://doi.org/10.1016/0010-938X(89)90060-7	journal	January 1989
Compositional changes of passive films due to different transport rates and preferential dissolution Kirchheim, R.; Heine, B.; Hofmann, S. Corrosion Science, Vol. 31 https://doi.org/10.1016/0010-938X(90)90164-Z	journal	January 1990
The entry of chloride ions into passive films on nickel studied by spectroscopic (ESCA) and nuclear (36Cl radiotracer) methods Marcus, P.; Herbelin, J. -M. Corrosion Science, Vol. 34, Issue 7 https://doi.org/10.1016/0010-938X(93)90293-P	journal	July 1993
A combined surface analytical and electrochemical study of the formation of passive layers on alloys in 0.5 M H2SO4 Haupt, S.; Strehblow, H. -H. Corrosion Science, Vol. 37, Issue 1 https://doi.org/10.1016/0010-938X(94)00104-E	journal	January 1995
Pressure dependence of the Néel temperature of Cr2o3 Worlton, T. G.; Brugger, R. M.; Bennion, R. B. Journal of Physics and Chemistry of Solids, Vol. 29, Issue 3 https://doi.org/10.1016/0022-3697(68)90120-0	journal	March 1968
Growth mechanism of Cr2O3 scales: oxygen and chromium diffusion, oxidation kinetics and effect of yttrium Tsai, S. C.; Huntz, A. M.; Dolin, C. Materials Science and Engineering: A, Vol. 212, Issue 1 https://doi.org/10.1016/0921-5093(96)10173-8	journal	July 1996
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
Cost of corrosion Koch, Gerhardus Trends in Oil and Gas Corrosion Research and Technologies: Production and Transmission https://doi.org/10.1016/B978-0-08-101105-8.00001-2	book	January 2017
Oxygen vacancy diffusion in bulk SrTiO3 from density functional theory calculations Zhang, Lipeng; Liu, Bin; Zhuang, Houlong Computational Materials Science, Vol. 118 https://doi.org/10.1016/j.commatsci.2016.02.041	journal	June 2016
XPS investigations of electrochemically formed passive layers on Fe/Cr-alloys in 0.5 M H2SO4 Keller, Petra; Strehblow, Hans-Henning Corrosion Science, Vol. 46, Issue 8 https://doi.org/10.1016/j.corsci.2004.01.007	journal	August 2004
Semiconducting and passive film properties of nitrogen-containing type 316LN stainless steels Ningshen, S.; Kamachi Mudali, U.; Mittal, V. K. Corrosion Science, Vol. 49, Issue 2 https://doi.org/10.1016/j.corsci.2006.05.041	journal	February 2007
Ab initio study of the interaction of chlorides with defect-free hydroxylated NiO surfaces Bouzoubaa, Asmae; Diawara, Boubakar; Maurice, Vincent Corrosion Science, Vol. 51, Issue 4 https://doi.org/10.1016/j.corsci.2009.01.028	journal	April 2009
Passivity breakdown, pit initiation and propagation of pits in metallic materials – Review Soltis, J. Corrosion Science, Vol. 90 https://doi.org/10.1016/j.corsci.2014.10.006	journal	January 2015
Passivity breakdown of 316L stainless steel during potentiodynamic polarization in NaCl solution Saadi, Sara Al; Yi, Yongsun; Cho, Pyungyeon Corrosion Science, Vol. 111 https://doi.org/10.1016/j.corsci.2016.06.011	journal	October 2016
The effect of surface vacancies on the interactions of Cl with a α-Fe2O3 (0001) surface and the role of Cl in depassivation Pang, Qin; DorMohammadi, Hossein; Isgor, O. Burkan Corrosion Science, Vol. 154 https://doi.org/10.1016/j.corsci.2019.03.052	journal	July 2019
The history of the Point Defect Model for the passive state: A brief review of film growth aspects Macdonald, Digby D. Electrochimica Acta, Vol. 56, Issue 4 https://doi.org/10.1016/j.electacta.2010.11.005	journal	January 2011
Study of Al alloy corrosion in neutral NaCl by the pitting scan technique Trueba, Monica; Trasatti, Stefano P. Materials Chemistry and Physics, Vol. 121, Issue 3 https://doi.org/10.1016/j.matchemphys.2010.02.022	journal	June 2010
Low Valence Cation Doping of Bulk Cr ₂ O ₃ : Charge Compensation and Oxygen Vacancy Formation Carey, John J.; Legesse, Merid; Nolan, Michael The Journal of Physical Chemistry C, Vol. 120, Issue 34 https://doi.org/10.1021/acs.jpcc.6b05575	journal	August 2016
Vacancies and Vacancy-Mediated Self Diffusion in Cr ₂ O ₃ : A First-Principles Study Medasani, Bharat; Sushko, Maria L.; Rosso, Kevin M. The Journal of Physical Chemistry C, Vol. 121, Issue 3 https://doi.org/10.1021/acs.jpcc.7b00071	journal	January 2017
First-Principles Investigation of Native Interstitial Diffusion in Cr ₂ O ₃ Medasani, Bharat; Sushko, Maria L.; Rosso, Kevin M. The Journal of Physical Chemistry C, Vol. 122, Issue 24 https://doi.org/10.1021/acs.jpcc.8b04383	journal	May 2018
Temperature Dependence of Self-Diffusion in Cr ₂ O ₃ from First Principles Medasani, Bharat K.; Sushko, Maria L.; Rosso, Kevin M. The Journal of Physical Chemistry C, Vol. 123, Issue 36 https://doi.org/10.1021/acs.jpcc.9b03218	journal	August 2019
Anodic Dissolution of Pure Aluminum during Electrocoagulation Process: Influence of Supporting Electrolyte, Initial pH, and Current Density Mansouri, Khaled; Ibrik, Karim; Bensalah, Nasr Industrial & Engineering Chemistry Research, Vol. 50, Issue 23 https://doi.org/10.1021/ie201206d	journal	November 2011
The Crystal Structures of Hematite and Corundum Pauling, Linus; Hendricks, Sterling B. Journal of the American Chemical Society, Vol. 47, Issue 3 https://doi.org/10.1021/ja01680a027	journal	March 1925
Structural, Magnetic, Electronic, Defect, and Diffusion Properties of Cr ₂ O ₃ : A DFT+ U Study Lebreau, François; Islam, Mazharul M.; Diawara, Boubakar The Journal of Physical Chemistry C, Vol. 118, Issue 31 https://doi.org/10.1021/jp5039943	journal	July 2014
Unmasking chloride attack on the passive film of metals Zhang, B.; Wang, J.; Wu, B. Nature Communications, Vol. 9, Issue 1 https://doi.org/10.1038/s41467-018-04942-x	journal	July 2018
Anisotropic ion diffusion in α-Cr ₂ O ₃ : an atomistic simulation study Cao, Penghui; Wells, Daniel; Short, Michael Philip Physical Chemistry Chemical Physics, Vol. 19, Issue 21 https://doi.org/10.1039/C7CP00838D	journal	January 2017
Enhancing the oxygen vacancy formation and migration in bulk chromium( iii ) oxide by alkali metal doping: a change from isotropic to anisotropic oxygen diffusion Carey, John J.; Nolan, M. Journal of Materials Chemistry A, Vol. 5, Issue 30 https://doi.org/10.1039/C7TA00315C	journal	January 2017
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Crystal structure and isothermal compression of Fe2O3, Cr2O3, and V2O3 to 50 kbars Finger, Larry W.; Hazen, Robert M. Journal of Applied Physics, Vol. 51, Issue 10 https://doi.org/10.1063/1.327451	journal	January 1980
Charged vacancy diffusion in chromium oxide crystal: DFT and DFT+U predictions Gray, Corinne; Lei, Yinkai; Wang, Guofeng Journal of Applied Physics, Vol. 120, Issue 21 https://doi.org/10.1063/1.4970882	journal	December 2016
Self-diffusion in cr ₂ o ₃ I. Chromium diffusion in single crystals Sabioni, A. C. S.; Lesage, B.; Huntz, A. M. Philosophical Magazine A, Vol. 66, Issue 3 https://doi.org/10.1080/01418619208201560	journal	September 1992
Self-diffusion in cr ₂ o ₃ II. Oxygen diffusion in single crystals Sabioni, A. C. S.; Huntz, A. M.; Millot, F. Philosophical Magazine A, Vol. 66, Issue 3 https://doi.org/10.1080/01418619208201561	journal	September 1992
Self-diffusion in cr ₂ o ₃ III. Chromium and oxygen grain-boundary diffusion in polycrystals Sabioni, A. C. S.; Huntz, A. M.; Millot, F. Philosophical Magazine A, Vol. 66, Issue 3 https://doi.org/10.1080/01418619208201562	journal	September 1992
Diffusion of ¹⁸ O in Cr ₂ O ₃ : Bulk and scales and relation with oxidation kinetics Tsai, S. C.; Huntz, A. M.; Dolin, C. Radiation Effects and Defects in Solids, Vol. 137, Issue 1-4 https://doi.org/10.1080/10420159508222736	journal	December 1995
Electronic and magnetic structure of (CrCl ₃ ) ₃ Grodzicki, M.; Mallick, B.; Mudring, A-V Journal of Physics: Conference Series, Vol. 200, Issue 3 https://doi.org/10.1088/1742-6596/200/3/032020	journal	January 2010
Specific heat of Cr 2 O 3 near the Néel temperature Bruce, Richard H.; Cannell, David S. Physical Review B, Vol. 15, Issue 9 https://doi.org/10.1103/PhysRevB.15.4451	journal	May 1977
High-precision sampling for Brillouin-zone integration in metals Methfessel, M.; Paxton, A. T. Physical Review B, Vol. 40, Issue 6 https://doi.org/10.1103/PhysRevB.40.3616	journal	August 1989
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y. Physical Review B, Vol. 57, Issue 3, p. 1505-1509 https://doi.org/10.1103/PhysRevB.57.1505	journal	January 1998
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
*Ab initio* study of the (0001) surfaces of hematite and chromia: Influence of strong electronic correlations Rohrbach, A.; Hafner, J.; Kresse, G. Physical Review B, Vol. 70, Issue 12 https://doi.org/10.1103/PhysRevB.70.125426	journal	September 2004
Magnetism of chromia from first-principles calculations Shi, Siqi; Wysocki, A. L.; Belashchenko, K. D. Physical Review B, Vol. 79, Issue 10 https://doi.org/10.1103/PhysRevB.79.104404	journal	March 2009
Density functional calculation of activation energies for lattice and grain boundary diffusion in alumina Lei, Yinkai; Gong, Yu; Duan, Zhiyao Physical Review B, Vol. 87, Issue 21 https://doi.org/10.1103/PhysRevB.87.214105	journal	June 2013
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011
Anion Diffusion in alpha-Cr2O3 Hagel, William C. Journal of the American Ceramic Society, Vol. 48, Issue 2 https://doi.org/10.1111/j.1151-2916.1965.tb11802.x	journal	February 1965
Chloride Uptake by Oxide Covered Aluminum as Determined by X-Ray Photoelectron and X-Ray Absorption Spectroscopy Natishan, P. M. Journal of The Electrochemical Society, Vol. 146, Issue 5 https://doi.org/10.1149/1.1391835	journal	January 1999
XPS and STM Study of Passive Films Formed on Fe-22Cr(110) Single-Crystal Surfaces Maurice, V. Journal of The Electrochemical Society, Vol. 143, Issue 4 https://doi.org/10.1149/1.1836616	journal	January 1996
In Situ Determination of the Composition of Surface Films Formed on Fe-Cr Alloys Oblonsky, L. J. Journal of The Electrochemical Society, Vol. 145, Issue 6 https://doi.org/10.1149/1.1838577	journal	January 1998
Pitting Corrosion of Metals Frankel, G. S. Journal of The Electrochemical Society, Vol. 145, Issue 6 https://doi.org/10.1149/1.1838615	journal	January 1998
The Point Defect Model for the Passive State Macdonald, Digby D. Journal of The Electrochemical Society, Vol. 139, Issue 12 https://doi.org/10.1149/1.2069096	journal	January 1992
Use of SIMS to Investigate the Induction Stage in the Pitting of Iron Bardwell, Jennifer A. Journal of The Electrochemical Society, Vol. 136, Issue 5 https://doi.org/10.1149/1.2096916	journal	January 1989
Passive Film Formation on Iron and Film Breakdown in a Sodium Hydroxide Solution Containing Chloride Ions Zakroczymski, T. Journal of The Electrochemical Society, Vol. 132, Issue 12 https://doi.org/10.1149/1.2113685	journal	January 1985
The Specific Effects of Chloride and Sulfate Ions on Oxide Covered Aluminum Heine, M. A.; Keir, D. S.; Pryor, M. J. Journal of The Electrochemical Society, Vol. 112, Issue 1 https://doi.org/10.1149/1.2423459	journal	January 1965
Chloride Interactions with the Passive Films on Stainless Steel Natishan, P. M.; O’Grady, W. E.; Martin, F. J. Journal of The Electrochemical Society, Vol. 158, Issue 2 https://doi.org/10.1149/1.3520000	journal	January 2011
Density Functional Theory Study of the Initial Stages of Cl-Induced Degradation of α-Cr ₂ O ₃ Passive Film Oware Sarfo, Kofi; Murkute, Pratik; Isgor, O. Burkan Journal of The Electrochemical Society, Vol. 167, Issue 12 https://doi.org/10.1149/1945-7111/abb381	journal	January 2020
A DFT-Study of Cl Ingress into α-Al ₂ O ₃ (0001) and Al(111) and Its Possible Influence on Localized Corrosion of Al Liu, Min; Jin, Ying; Leygraf, Christofer Journal of The Electrochemical Society, Vol. 166, Issue 11 https://doi.org/10.1149/2.0161911jes	journal	January 2019
Influence of Chloride on Passive Film Chemistry of 304 Stainless Steel in Sulphuric Acid Solution by Glow Discharge Optical Emission Spectrometry Analysis Deng, Saifu International Journal of Electrochemical Science https://doi.org/10.20964/2017.02.43	journal	February 2017
Diffusion of ⁵⁴Cr and ¹⁸O in Cr₂O₃ Scales and Growth Mechanism Tsaï, S. C.; Huntz, Anne Marie; Philibert, Jean Defect and Diffusion Forum, Vol. 143-147 https://doi.org/10.4028/www.scientific.net/DDF.143-147.1195	journal	January 1997
Diffusivity of Point Defects in the Passive Film on Stainless Steel Fattah-alhosseini, A.; Alemi, M. H.; Banaei, S. International Journal of Electrochemistry, Vol. 2011 https://doi.org/10.4061/2011/968512	journal	January 2011
Kinetics of Passivation and Chloride-Induced Depassivation of Iron in Simulated Concrete Pore Solutions Using Electrochemical Quartz Crystal Nanobalance Gunay, H. Burak; Isgor, O. Burkan; Ghods, Pouria CORROSION, Vol. 71, Issue 5 https://doi.org/10.5006/1346	journal	May 2015
Kinetics of Pitting Dissolution of Austenitic Stainless Steel 304 in Sodium Chloride Solution Saadawy, M. ISRN Corrosion, Vol. 2012 https://doi.org/10.5402/2012/916367	journal	October 2012

Similar Records

Bulk Diffusion of Cl through O Vacancies in α-Cr ₂ O ₃ : A Density Functional Theory Study

Journal Article · Thu Jul 01 04:00:00 UTC 2021 · Journal of the Electrochemical Society · OSTI ID:1850526

Density Functional Theory Study of the Initial Stages of Cl-Induced Degradation of α-Cr₂O₃ Passive Film

Journal Article · Wed Sep 09 00:00:00 UTC 2020 · Journal of the Electrochemical Society · OSTI ID:2371688

Thermokinetics of point defects in α-Fe ₂ O ₃

Journal Article · Fri May 19 00:00:00 UTC 2023 · Electronic Structure · OSTI ID:1974503

Bulk Diffusion of Cl through O Vacancies in α-Cr 2 O 3 : A Density Functional Theory Study

Citation Formats

References (69)

Similar Records

Related Subjects

Bulk Diffusion of Cl through O Vacancies in α-Cr ₂ O ₃ : A Density Functional Theory Study