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Complex diffusion behavior of oxygen in nanocrystalline BaTiO sub(3) ceramics
Ist Teil von
Physical chemistry chemical physics : PCCP, 2014-01, Vol.16 (6), p.2568-2575
Erscheinungsjahr
2014
Quelle
Alma/SFX Local Collection
Beschreibungen/Notizen
super(18)O/ super(16)O exchange annealing and subsequent Time-of-Flight Secondary Ion Mass Spectrometry (ToF-SIMS) analysis is used to investigate oxygen transport in dense, nanocrystalline (average grain size d approximately 300 nm) ceramics of nominally un-doped BaTiO sub(3). Isotope penetration profiles are obtained as a function of temperature, 973 < T/K < 1173, at an oxygen activity aO sub(2) = 0.20 and as a function of oxygen activity, 0.002 < aO sub(2) < 0.20, at T= 1073 K. All isotope profiles show the same unusual shape: a flattened profile over the first similar to 10 super(2) nm, followed by a short, conventional diffusion profile. We demonstrate that the entire isotope profile can be described quantitatively by a numerical solution to the diffusion equation based on an increase in the local oxygen diffusion coefficient close to the surface. This position-dependent increase is attributed to additional oxygen vacancies that are generated by diffusion of chlorine impurities out of the ceramics. The presence of chlorine derives from the chemical route necessary to produce nanometric powders: it thus indicates a new manner in which nanocrystalline ceramics may differ from their microcrystalline counterparts.