Composition driven structural phase transitions in the (Y1-xLax)2Ti2O7 system

Harvey, E. J. and Ashbrook, S. E. and Lumpkin, G. R. and Redfern, S. A. T. (2006) Composition driven structural phase transitions in the (Y1-xLax)2Ti2O7 system. Materials Research Society Symposium Proceedings, 932. pp. 631-638.

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Abstract

The structural characteristics of samples in the (Y1-xLax)2Ti2O system have been studied as a function of bulk composition using time-of-flight (TOF) powder neutron diffraction, powder X-ray diffraction (XRD), Electron Microscopy and 89Y (I = ½) Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR). Analysis of the neutron diffraction data suggests the following: For compositions where 0 ≤ x ≤ 0.132, a single cubic phase is present (Fd3,¯ m, Z = 8). Between 0.832 ≤ x ≤ 1, a solid solution with the La2Ti2O7 structure (P21, Z = 4) forms. The two phases coexist between x values of 0.132 and 0.832. XRD suggests that the limits of the two regions of solid solution fall within the ranges of x = 0.1-0.125 and x = 0.875-0.9. The variation in the limits found by the two diffraction methods may be due to stoichiometric errors in the samples. Line-shape analysis of NMR spectra for Y rich compositions suggests that increasing proportions of La are incorporated onto the pyrochlore A site in a statistically random manner, up to the limit of solid solution. The NMR spectra of the monoclinic phase suggest that occupation of the four crystallographically distinct ‘A’ type sites within the structure is not random. At low Y concentrations, two of these sites are preferentially occupied by Y. These sites are suggested to be those found at the edge of the perovskite slabs, which exhibit smaller coordination numbers (based on the number of oxygens within bonding distance of the ‘A’ type cation) than the true perovskite A sites found at the slab centres.

Item Type: Article
Uncontrolled Keywords: 2006 AREP IA49 IA52 2006 P
Subjects: 03 - Mineral Sciences
Divisions: 03 - Mineral Sciences
Journal or Publication Title: Materials Research Society Symposium Proceedings
Volume: 932
Page Range: pp. 631-638
Depositing User: Sarah Humbert
Date Deposited: 16 Feb 2009 13:02
Last Modified: 23 Jul 2013 10:07
URI: http://eprints.esc.cam.ac.uk/id/eprint/360

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