Document Type

Article

Publication Date

2-21-2013

Journal or Book Title

The Journal of Physical Chemistry B

Volume

117

Issue

7

First Page

2169

Last Page

2179

DOI

10.1021/jp308494a

Abstract

The mixed glass former (MGF) effect (MGFE) is defined as a nonlinear and nonadditive change in the ionic conductivity with changing glass former composition at constant modifier composition. In this study, sodium borophosphate 0.35Na2O + 0.65[xB2O3 + (1 – x)P2O5], 0 ≤ x≤ 1, glasses which have been shown to exhibit a positive MGFE have been prepared and examined using Raman and 11B and 31P magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopies. Through examination of the short-range order (SRO) structures found in the ternary glasses, it was determined that the minority glass former, B for 0.1 ≤ x ≤ 0.7 and P for 0.7 ≤ x ≤ 0.9, is “overmodified” and contains more Na+ ions than would be expected from simple linear mixing of the binary sodium borate, x = 1, and sodium phosphate, x = 0, glasses, respectively. Changes in the intermediate range order (IRO) structures were suggested by changes in the NMR spectral chemical shifts and Raman spectra wavenumber shifts over the full composition range x in the Raman and MAS NMR spectra. The changes observed in the chemical shifts of 31P MAS NMR spectra with x are found to be too large to be caused solely by changing sodium modification of the phosphate SRO structural groups, and this indicates that internetwork bonding between phosphorus and boron through bridging oxygens (BOs), P–O–B, must be a major contributor to the IRO structure of these glasses. While not fully developed, a first-order thermodynamic analysis based upon the Gibbs free energies of formation of the various SRO structural units in this system has been developed and can be used to account for the preferential formation of tetrahedral boron groups, B4, by the reaction of B3 with P2 groups to form B4 and P3 groups, respectively, where the superscript denotes the number of BOs on these units, in these glasses. This preference for B4 units appears to be a predominate cause of the changing modifier to glass former ratio with composition x in these ternary MGF glasses and appears to be associated with the large negative value of the Gibbs free energy of formation of this group.

Comments

Reprinted with permission from The Journal of Physical Chemistry B 117 (2013): 2169–2179, doi:10.1021/jp308494a. Posted with permission.

Copyright Owner

American Chemical Society

Language

en

File Format

application/pdf

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