Direct observation of the R ... R separation in rare-earth phosphate glasses

Cole, J. and Newport, R.J. (2007) Direct observation of the R ... R separation in rare-earth phosphate glasses. Journal of Non-crystalline Solids, 353 (18-21). pp. 1773-1778. ISSN 0022-3093. (Access to this publication is restricted)

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http://dx.doi.org/10.1016/j.jnoncrysol.2007.01.045

Abstract

Rare-earth phosphate glasses exhibit exotic optical and magnetic properties, which are dictated by their structure, principally the nature of the closest R R separation. Conventional structural characterization tools have enabled the comprehensive determination of the radial distribution from the rare-earth ion out to 4 Å. At or beyond this distance, however, lies the crucially important minimum R R separation. This study illustrates three types of non-conventional diffraction experiments that overcome the radial limitations of regular structural probes. The results from such investigations are compiled with all other known estimates of R R separations in rare-earth phosphate glasses, (R2O3)x(P2O5)1−x, in the range 0.167 < x < 0.25, both from experimental and computational means. Coupled with tabulations of all known minimum R R separations in analogous meta- and ultra-phosphate crystal structures, a collective comparison of all of these R R separations permits a hypothesis by which all results are consistent. That hypothesis indicates that where rare-earth phosphate glasses are near meta-phosphate, their minimum R R distance lies at 4.0 Å whilst a second, much broader, nearest-neighbour R R correlations is centered between 6.0–6.4 Å. However, glasses that contain rare-earth ions at least as heavy as holmium are likely to exhibit a very different structure, with a minimum R R separation of 5.4–5.6 Å. Structures that lie intermediate between the ultra-phosphate and meta-phosphate composition may display mixed characteristics of these two extremes. If present in high levels, aluminium contamination arising from the synthetic process may also affect the R R distribution significantly. Overall, there is excellent agreement between experiment and theory.

Item Type: Article
Uncontrolled keywords: neutron diffraction/scattering; synchrotron radiation; X-ray diffraction; phosphates
Subjects: Q Science > QC Physics
Divisions: Faculties > Science Technology and Medical Studies > School of Physical Sciences > Functional Materials Group
Depositing User: Louise Dorman
Date Deposited: 19 Dec 2007 19:31
Last Modified: 22 May 2012 11:28
Resource URI: http://kar.kent.ac.uk/id/eprint/2181 (The current URI for this page, for reference purposes)
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