Structural Change in Li and Na Aluminophosphate Glasses : Evidence of a "Structural Mixed Alkali Effet"
Laboratoire des Colloïdes, Verres et Nanomatériaux, UMR/CNRS 5587, Université de Montpellier II -- Place E. Bataillon, 34095 Montpellier Cedex 5, France. The Journal of Physical Chemistry B
(Impact Factor: 3.3).
05/2006; 110(14):7281-8. DOI: 10.1021/jp055835g
The short- and long-range structure of a series of single and mixed aluminophosphate glasses with the general composition [xNa(2)O (46 - x)Li(2)O], [yAl(2)O(3) (54 - y)P(2)O(5)] is analyzed using (31)P and (27)Al magic-angle spinning (MAS) NMR as well as small-angle X-ray scattering. These series of glasses allow analyzing both the effect of alumina incorporation in these glasses, for small alumina content (y = 0, 4, 8), and the structural changes associated with the so-called mixed alkali effect (x = 0, 11.5, 23, 34.5, 46). Our results indicate that aluminum is mainly octahedrally coordinated in these glasses and that there is most likely some segregation of the Al(OP)(6) species. In the pure phosphate glasses, we observe a "classical" continuous variation of the structural properties with the relative alkali content, but in the aluminophosphate, both local and long-range structural results reveal for the first time some nonlinear change as a function of the relative alkali content.
Available from: Nathalie Boudet
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ABSTRACT: Electron paramagnetic resonance (EPR) spectra of Mn(II) ions in cadmium phosphate glasses are presented with mixed alkali variation as xLi2O + (20 - x) Na2O + 20 CdO + 59.5 P2O5 + 0.5 MnO glass system with 5 ≤ x ≤ 15 mol%. The EPR spectra of Mn(II) ions doped samples exhibit a sextet centered at g = 2·0. The optical absorption spectrum at room temperature shows three bands for Mn(II) ions in octahedral symmetry. The crystal field (Dq) and Racah parameters (B and C) are evaluated. From EPR and optical spectral studies reveals the nature of the bonding is dominantly ionic and its site symmetry is octahedral. At equal composition of alkali content, i.e. for x = 10 the glass system shows the mixed alkali effect.
IOP Conference Series Materials Science and Engineering 07/2009; 2(1). DOI:10.1088/1757-899X/2/1/012058
Available from: Jose Fabian Schneider
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ABSTRACT: The local order and distribution of Na in the mixed alkali metaphosphate glasses K(x)Na(1-x)PO(3) were analyzed, with the aim to identify segregation or a random mixture of both cation species. X-Ray photoelectron spectroscopy and several nuclear magnetic resonance (NMR) techniques were applied, including (31)P and (23)Na high-resolution spectroscopy, (23)Na triple quantum-MAS NMR, rotational echo double resonance between (31)P and (23)Na, and (23)Na NMR spin echo decay. The structural picture emerging from these results reveals the similarity in the local Na environments in the glasses but also subtle structural adjustments with increasing degree of K replacement. While both cations are intimately mixed at the atomic scale, the (23)Na spin echo decay data suggest a detectable like-cation preference in the spatial distribution of the ions. These structural properties are consistent with those determined in Li-Rb metaphosphates, indicating that the origin of the mixed alkali effect observed in the conductivity of Na-K metaphosphate glasses may also be explained by structurally blocked ion diffusion.
Physical Chemistry Chemical Physics 03/2010; 12(12):2879-87. DOI:10.1039/b920716c · 4.49 Impact Factor
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