Non-equilibrium oxidation states of zirconium during early stages of metal oxidation
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Yildiz_Non-equilibrium.pdf
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Author(s)
Senanayake, Sanjaya D.
Ma, Wen
Herbert, Francis William
Yildiz, Bilge
Date Issued
March 2015
Journal
Applied Physics Letters
Publisher
American Institute of Physics (AIP)
Citation
Ma, Wen, F. William Herbert, Sanjaya D. Senanayake, and Bilge Yildiz. "Non-equilibrium oxidation states of zirconium during early stages of metal oxidation." Applied Physics Letters, vol. 106, 2015, pp.101603. © 2015 AIP Publishing LLC.
Version
Final published version
Abstract
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[superscript 1+], Zr[superscript 2+], and Zr[superscript 3+] as non-equilibrium oxidation states, in addition to Zr[superscript 4+] in the stoichiometric ZrO2. This finding resolves the long-debated question of whether it is possible to form any valence states between Zr[superscript 0] and Zr[superscript 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.
MIT Department
Massachusetts Institute of Technology. Department of Materials Science and Engineering
Massachusetts Institute of Technology. Department of Nuclear Science and Engineering
Massachusetts Institute of Technology. Laboratory for Electrochemical Interfaces
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DOI of Published Version
https://doi.org/10.1063/1.4914180
