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ABSTRACT The presence of water vapour, intentional or unavoidable, is crucial to many materials applications, such as in steam generators, turbine engines, fuel cells, catalysts and

corrosion1,2,3,4. Phenomenologically, water vapour has been noted to accelerate oxidation of metals and alloys5,6. However, the atomistic mechanisms behind such oxidation remain elusive.

Through direct in situ atomic-scale transmission electron microscopy observations and density functional theory calculations, we reveal that water-vapour-enhanced oxidation of a

nickel–chromium alloy is associated with proton-dissolution-promoted formation, migration, and clustering of both cation and anion vacancies. Protons derived from water dissociation can

occupy interstitial positions in the oxide lattice, consequently lowering vacancy formation energy and decreasing the diffusion barrier of both cations and anions, which leads to enhanced

oxidation in moist environments at elevated temperatures. This work provides insights into water-vapour-enhanced alloy oxidation and has significant implications in other material and

chemical processes involving water vapour, such as corrosion, heterogeneous catalysis and ionic conduction. Access through your institution Buy or subscribe This is a preview of subscription

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* Learn about institutional subscriptions * Read our FAQs * Contact customer support SIMILAR CONTENT BEING VIEWED BY OTHERS MECHANISTIC STUDY OF MOISTURE CORROSION OF FECR ALLOYS IN MOLTEN

SALTS BY AB-INITIO MOLECULAR DYNAMICS SIMULATIONS Article Open access 01 June 2024 MECHANISTIC UNDERSTANDING OF SPECIATED OXIDE GROWTH IN HIGH ENTROPY ALLOYS Article Open access 12 June 2024

ATOMIC-SCALE UNDERSTANDING OF OXIDE GROWTH AND DISSOLUTION KINETICS OF NI-CR ALLOYS Article Open access 02 January 2025 REFERENCES * Steele, B. C. H. & Heinzel, A. Materials for

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ACKNOWLEDGEMENTS This work was supported by the US Department of Energy (DOE), Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division. The work was conducted

in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), a DOE User Facility operated by Battelle for the DOE Office of Biological and Environmental Research. Pacific

Northwest National Laboratory is operated for the DOE under contract DE-AC05-76RL01830. Binghamton University’s work was supported by DOE-BES Division of Materials Sciences and Engineering

under award no. DE-SC0001135. AUTHOR INFORMATION Author notes * These authors contributed equally: Langli Luo, Mao Su, Pengfei Yan. AUTHORS AND AFFILIATIONS * Environmental Molecular

Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA, USA Langli Luo, Pengfei Yan, Donald R. Baer, Zihua Zhu & Chongmin Wang * Computational Mathematics Group,

Pacific Northwest National Laboratory, Richland, Washington, USA Mao Su & Zhijie Xu * CAS Key Laboratory of Theoretical Physics, Institute of Theoretical Physics, Chinese Academy of

Sciences, Beijing, China Mao Su & Yanting Wang * School of Physical Sciences, University of Chinese Academy of Sciences, Beijing, China Mao Su & Yanting Wang * Department of

Mechanical Engineering & Multidisciplinary Program in Materials Science and Engineering, State University of New York, Binghamton, NY, USA Lianfeng Zou & Guangwen Zhou * Energy and

Environment Directorate, Pacific Northwest National Laboratory, Richland, WA, USA Daniel K. Schreiber & Stephen M. Bruemmer Authors * Langli Luo View author publications You can also

search for this author inPubMed Google Scholar * Mao Su View author publications You can also search for this author inPubMed Google Scholar * Pengfei Yan View author publications You can

also search for this author inPubMed Google Scholar * Lianfeng Zou View author publications You can also search for this author inPubMed Google Scholar * Daniel K. Schreiber View author

publications You can also search for this author inPubMed Google Scholar * Donald R. Baer View author publications You can also search for this author inPubMed Google Scholar * Zihua Zhu

View author publications You can also search for this author inPubMed Google Scholar * Guangwen Zhou View author publications You can also search for this author inPubMed Google Scholar *

Yanting Wang View author publications You can also search for this author inPubMed Google Scholar * Stephen M. Bruemmer View author publications You can also search for this author inPubMed 

Google Scholar * Zhijie Xu View author publications You can also search for this author inPubMed Google Scholar * Chongmin Wang View author publications You can also search for this author

inPubMed Google Scholar CONTRIBUTIONS C.W., L.L., D.K.S. and S.M.B. conceived the idea and designed the in situ ETEM experiments. L.L. and P.Y. conducted the in situ ETEM and ex-situ S/TEM

analysis. Z.X. and M.S. performed the DFT calculations. L.Z. and G.Z. grew the alloy thin-film samples. D.K.S., D.R.B., Z.Z., Y.W. and S.M.B. discussed the results. L.L., C.W., M.S. and Z.X.

wrote the manuscript and all authors have approved the final version. CORRESPONDING AUTHORS Correspondence to Zhijie Xu or Chongmin Wang. ETHICS DECLARATIONS COMPETING INTERESTS The authors

declare no competing interests. ADDITIONAL INFORMATION PUBLISHER’S NOTE: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional

affiliations. SUPPLEMENTARY INFORMATION SUPPLEMENTARY INFORMATION Supplementary Tables: S1–S2, Supplementary Figures: Figures S1–S22, Supplementary References 1–11 SUPPLEMENTARY VIDEOS:

Movie S1: In situ atomic-scale observation of NiO growth in O2 through the adatom mechanism. The video is three times faster than actual time SUPPLEMENTARY VIDEOS: Movie S2: In situ

atomic-scale observation of NiO growth in H2O, revealing vacancy formation andclustering in NiO. The video is 16 times faster than actual time SUPPLEMENTARY VIDEOS: Movie S3: In situ

observation of the growth of a large NiO planar island on the initial oxide layer in O2. The video is 16 times faster than actual time SUPPLEMENTARY VIDEOS: Movie S4: In situ observation of

the growth of a large NiO planar island on the initial oxide layer in H2O. The video is 16 times faster than actual time RIGHTS AND PERMISSIONS Reprints and permissions ABOUT THIS ARTICLE

CITE THIS ARTICLE Luo, L., Su, M., Yan, P. _et al._ Atomic origins of water-vapour-promoted alloy oxidation. _Nature Mater_ 17, 514–518 (2018). https://doi.org/10.1038/s41563-018-0078-5

Download citation * Received: 16 November 2016 * Accepted: 12 April 2018 * Published: 07 May 2018 * Issue Date: June 2018 * DOI: https://doi.org/10.1038/s41563-018-0078-5 SHARE THIS ARTICLE

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