Atomic origins of water-vapour-promoted alloy oxidation

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.

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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.

References

  1. 1.

    Steele, B. C. H. & Heinzel, A. Materials for fuel-cell technologies. Nature 414, 345–352 (2001).

    Article  Google Scholar 

  2. 2.

    Eliaz, N., Shemesh, G. & Latanision, R. M. Hot corrosion in gas turbine components. Eng. Fail. Anal. 9, 31–43 (2002).

    Article  Google Scholar 

  3. 3.

    Dutta, R. S. Corrosion aspects of Ni–Cr–Fe based and Ni–Cu based steam generator tube materials. J. Nucl. Mater. 393, 343–349 (2009).

    Article  Google Scholar 

  4. 4.

    Zope, B. N., Hibbitts, D. D., Neurock, M. & Davis, R. J. Reactivity of the gold/water interface during selective oxidation catalysis. Science 330, 74–78 (2010).

    Article  Google Scholar 

  5. 5.

    Douglass, D. L., Kofstad, P., Rahmel, P. & Wood, G. C. International workshop on high-temperature corrosion. Oxid. Met. 45, 529–620 (1996).

    Article  Google Scholar 

  6. 6.

    Saunders, S. R. J., Monteiro, M. & Rizzo, F. The oxidation behaviour of metals and alloys at high temperatures in atmospheres containing water vapour: a review. Prog. Mater. Sci. 53, 775–837 (2008).

    Article  Google Scholar 

  7. 7.

    Hultquist, G., Tveten, B. & Hörnlund, E. Hydrogen in chromium: influence on the high-temperature oxidation kinetics in H2O, oxide-growth mechanisms, and scale adherence. Oxid. Met. 54, 1–10 (2000).

    Article  Google Scholar 

  8. 8.

    Henry, S., Mougin, J., Wouters, Y., Petit, J. P. & Galerie, A. Characterization of chromia scales grown on pure chromium in different oxidizing atmospheres. Mater. High. Temper. 17, 231–234 (2000).

    Article  Google Scholar 

  9. 9.

    Michalik, M., Hänsel, M., Zurek, J., Singheiser, L. & Quadakkers, W. J. Effect of water vapour on growth and adherence of chromia scales formed on Cr in high and low pO2-environments at 1000 and 1050 °C. Mater. High. Temper. 22, 213–221 (2005).

    Article  Google Scholar 

  10. 10.

    Essuman, E. et al. Enhanced internal oxidation as trigger for breakaway oxidation of Fe–Cr alloys in gases containing water vapour. Scri. Mater. 57, 845–848 (2007).

    Article  Google Scholar 

  11. 11.

    Zurek, J. et al. Growth and adherence of chromia based surface scales on Ni-base alloys in high- and low-pO2 gases. Mater. Sci. Eng. A 477, 259–270 (2008).

    Article  Google Scholar 

  12. 12.

    Zhou, G. et al. Step-edge-induced oxide growth during the oxidation of Cu surfaces. Phys. Rev. Lett. 109, 235502 (2012).

    Article  Google Scholar 

  13. 13.

    Li, L. et al. Surface-step-induced oscillatory oxide growth. Phys. Rev. Lett. 113, 136104 (2014).

    Article  Google Scholar 

  14. 14.

    LaGrow, A. P., Ward, M. R., Lloyd, D. C., Gai, P. L. & Boyes, E. Visualizing the Cu/Cu2O interface transition in nanoparticles with environmental scanning transmission electron microscopy. J. Am. Chem. Soc. 139, 179–185 (2017).

    Article  Google Scholar 

  15. 15.

    Fujita, T. et al. Atomic origins of the high catalytic activity of nanoporous gold. Nat. Mater. 11, 775–780 (2012).

    Article  Google Scholar 

  16. 16.

    Yoshida, H. et al. Visualizing gas molecules interacting with supported nanoparticulate catalysts at reaction conditions. Science 335, 317–319 (2012).

    Article  Google Scholar 

  17. 17.

    Gai, P. L. et al. Visualisation of single atom dynamics in water gas shift reaction for hydrogen generation. Catal. Sci. Tech. 6, 2214–2227 (2016).

    Article  Google Scholar 

  18. 18.

    Zhang, X. et al. Direction-specific van der Waals attraction between rutile TiO2 nanocrystals. Science 356, 434–437 (2017).

    Article  Google Scholar 

  19. 19.

    Luo, L. et al. In situ atomic scale visualization of surface kinetics driven dynamics of oxide growth on a Ni-Cr surface. Chem. Commun. 52, 3300–3303 (2016).

    Article  Google Scholar 

  20. 20.

    Henderson, M. A. The interaction of water with solid surfaces: fundamental aspects revisited. Surf. Sci. Rep. 46, 1–308 (2002).

    Article  Google Scholar 

  21. 21.

    Norby, T. Protonic defects in oxides and their possible role in high temperature oxidation. J. Phys. IV Fr. 03, C9-99–C99-106 (1993).

    Article  Google Scholar 

  22. 22.

    AtkinsonA. The Role of Active Elements in the Oxidation Behaviour of High Temperature Metals and Alloys: Effect of Active Elements on Diffusion Properties of Synthetic Oxides, 55. (Elsevier Science Publishing, New York, NY, 1989).

    Google Scholar 

  23. 23.

    Gai, P. L. et al. Atomic-resolution environmental transmission electron microscopy for probing gas–solid reactions in heterogeneous catalysis. MRS Bull. 32, 1044–1050 (2007).

    Article  Google Scholar 

  24. 24.

    Gai, P. L., Lari, L., Ward, M. R. & Boyes, E. D. Visualisation of single atom dynamics and their role in nanocatalysts under controlled reaction environments. Chem. Phys. Lett. 592, 355–359 (2014).

    Article  Google Scholar 

  25. 25.

    Gómez-Rodríguez, A., Beltrán-del-Río, L. M. & Herrera-Becerra, R. SimulaTEM: multislice simulations for general objects. Ultramicroscopy 110, 95–104 (2010).

    Article  Google Scholar 

  26. 26.

    Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

    Article  Google Scholar 

  27. 27.

    Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. Rev. B 47, 558–561 (1993).

    Article  Google Scholar 

  28. 28.

    Dudarev, S. L., Botton, G. A., Savrasov, S. Y., Humphreys, C. J. & Sutton, A. P. Electron-energy-loss spectra and the structural stability of nickel oxide: an LSDA+ U study. Phys. Rev. B 57, 1505–1509 (1998).

    Article  Google Scholar 

  29. 29.

    Yu, J., Rosso, K. M. & Bruemmer, S. M. Charge and ion transport in NiO and aspects of Ni oxidation from first principles. J. Phys. Chem. C 116, 1948–1954 (2012).

    Article  Google Scholar 

  30. 30.

    Henkelman, G., Uberuaga, B. P. & Jónsson, H. A climbing image nudged elastic band method for finding saddle points and minimum energy paths. J. Chem. Phys. 113, 9901–9904 (2000).

    Article  Google Scholar 

Download references

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.

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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.

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Correspondence to Zhijie Xu or Chongmin Wang.

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The authors declare no competing interests.

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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). https://doi.org/10.1038/s41563-018-0078-5

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