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In situ study of the initiation of hydrogen bubbles at the aluminium metal/oxide interface

Nature Materials volume 14, pages 899–903 (2015)Cite this article

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Abstract

The presence of excess hydrogen at the interface between a metal substrate and a protective oxide can cause blistering1,2,3 and spallation of the scale4,5,6,7,8. However, it remains unclear how nanoscale bubbles manage to reach the critical size in the first place. Here, we perform in situ environmental transmission electron microscopy experiments of the aluminium metal/oxide interface under hydrogen exposure. It is found that once the interface is weakened by hydrogen segregation, surface diffusion of Al atoms initiates the formation of faceted cavities on the metal side, driven by Wulff reconstruction. The morphology and growth rate of these cavities are highly sensitive to the crystallographic orientation of the aluminium substrate. Once the cavities grow to a critical size, the internal gas pressure can become great enough to blister the oxide layer. Our findings have implications for understanding hydrogen damage of interfaces.

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Figure 1: Schematic illustration of the development of a blister on a metal surface.
Figure 2: Sample morphology before and after hydrogen exposure.
Figure 3: Cavity nucleation and growth below the metal/oxide interface.
Figure 4: Blister formation accompanying the receding faceted surface.
Figure 5: Orientation-dependent blister distribution.

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Acknowledgements

The authors acknowledge support from the Natural Science Foundation of China (51231005, 11132006, 51401159 and 51321003), and 973 Programs of China (2012CB619402). We also appreciate the support from the 111 project (B06025). J.L. acknowledges support by NSF DMR-1120901 and DMR-1410636. E.M. acknowledges support from US DoE-BES-DMSE, under Contract No. DE-FG02-09ER46056. We also thank P. H. Lu and M. Li for assistance in EELS characterization and data processing.

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Authors and Affiliations

  1. Center for Advancing Materials Performance from the Nanoscale (CAMP-Nano) & Hysitron Applied Research Center in China (HARCC), State Key Laboratory for Mechanical Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, China

    De-Gang Xie, Zhang-Jie Wang, Jun Sun, Ju Li, Evan Ma & Zhi-Wei Shan

  2. Department of Nuclear Science and Engineering, Cambridge, Massachusetts 02139, USA

    Ju Li

  3. Department of Materials Science and Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA

    Ju Li

  4. Department of Materials Science and Engineering, Johns Hopkins University, Baltimore, Maryland 21218, USA

    Evan Ma

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  1. De-Gang Xie
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Contributions

Z.-W.S., J.L. and E.M. conceived and designed the project. D.-G.X. conducted the experimental work. D.-G.X., Z.-W.S., J.L. and E.M. wrote the paper. All authors contributed to discussions of the results.

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Correspondence to Ju Li, Evan Ma or Zhi-Wei Shan.

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Xie, DG., Wang, ZJ., Sun, J. et al. In situ study of the initiation of hydrogen bubbles at the aluminium metal/oxide interface. Nature Mater 14, 899–903 (2015). https://doi.org/10.1038/nmat4336

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