Atomic origins of water-vapour-promoted alloy oxidation


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.

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Fig. 1: In situ observation of dynamic growth of oxides on the Ni–Cr alloy in O2 and H2O.
Fig. 2: Defect-dependent vacancy formation and clustering.
Fig. 3: Effect of defects on diffusion and microstructure of the oxide layer formed in O2 and H2O.
Fig. 4: Microscale quantification of enhanced oxidation of Ni–Cr alloy in H2O compared to O2.


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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




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.

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Correspondence to Zhijie Xu or Chongmin Wang.

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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

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Luo, L., Su, M., Yan, P. et al. Atomic origins of water-vapour-promoted alloy oxidation. Nature Mater 17, 514–518 (2018).

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