Non-equilibrium oxidation states of zirconium during early stages of metal oxidation
- Laboratory for Electrochemical Interfaces, Department of Nuclear Science and Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139 (United States)
- Chemistry Department, Brookhaven National Laboratory, Upton, New York 11973 (United States)
The chemical state of Zr during the initial, self-limiting stage of oxidation on single crystal zirconium (0001), with oxide thickness on the order of 1 nm, was probed by synchrotron x-ray photoelectron spectroscopy. Quantitative analysis of the Zr 3d spectrum by the spectrum reconstruction method demonstrated the formation of Zr{sup 1+}, Zr{sup 2+}, and Zr{sup 3+} as non-equilibrium oxidation states, in addition to Zr{sup 4+} in the stoichiometric ZrO{sub 2}. This finding resolves the long-debated question of whether it is possible to form any valence states between Zr{sup 0} and Zr{sup 4+} at the metal-oxide interface. The presence of local strong electric fields and the minimization of interfacial energy are assessed and demonstrated as mechanisms that can drive the formation of these non-equilibrium valence states of Zr.
- OSTI ID:
- 22395696
- Journal Information:
- Applied Physics Letters, Vol. 106, Issue 10; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0003-6951
- Country of Publication:
- United States
- Language:
- English
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