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Assessing the oxidation states and structural stability of the Ce analogue of brannerite
Author(s) -
Aluri Esther Rani,
Bachiu Lisa M.,
Grosvenor Andrew P.,
Forbes Scott H.,
Greedan John E.
Publication year - 2017
Publication title -
surface and interface analysis
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.52
H-Index - 90
eISSN - 1096-9918
pISSN - 0142-2421
DOI - 10.1002/sia.6265
Subject(s) - x ray photoelectron spectroscopy , oxidation state , stoichiometry , materials science , chemical state , xanes , oxygen , absorption spectroscopy , spectroscopy , ion , analytical chemistry (journal) , chemistry , nuclear magnetic resonance , metallurgy , metal , physics , organic chemistry , quantum mechanics , chromatography
The Ce‐containing analogue of brannerite (ie, UTi 2 O 6 ) was previously considered to be stoichiometric (ie, CeTi 2 O 6 ); however, it has recently been determined that the material is O deficient. This oxygen‐deficient material has been suggested to be charged balanced by the presence of a minor concentration of Ce 3+ or by the A‐site being cation deficient with the Ce oxidation state being 4+. A variety of Ti‐containing oxides (including brannerite) have been investigated as potential nuclear wasteforms, and it is necessary to understand the electronic structure of a proposed nuclear wasteform material as well as how the structure responds to radiation from incorporated waste elements. The radiation resistance of a material can be simulated by ion implantation. The objective of this study was to confirm the Ce oxidation state in the cation‐ and oxygen‐deficient material (ie, Ce 0.94 Ti 2 O 6 − δ ) and to determine how radiation damage affects this material. X‐ray photoelectron spectroscopy (XPS) and X‐ray absorption near‐edge spectroscopy were used to study Ce 0.94 Ti 2 O 6 − δ before and after being implanted with 2 MeV Au − ions. Analysis of the Ce 3d XPS spectra from the as‐synthesized samples by using a previously developed fitting method has unequivocally shown that Ce adopts both 4+ (major) and 3+ (minor) oxidation states, which was confirmed by examination of magnetic susceptibility data. Analysis of XPS and X‐ray absorption near‐edge spectroscopy spectra from ion‐implanted materials showed that both Ce and Ti were reduced because of radiation damage and that the local coordination environments of the cations are greatly affected by radiation damage.