The densities of mixed glass former 0.35 Na2O+0.65 [xB2O3 + (1-x)P2O5] glasses related to the atomic fractions and volumes of short range structures

The mixed glass former effect (MGFE) is defined as a non-linear and non-additive change in the ionic conductivity with changing glass former fraction at constant modifier composition between two binary glass forming compositions. In this study, mixed glass former (MGF) sodium borophosphate glasses, 0.35 Na2O + 0.65 [xB(2)O(3) + (1 - x)P2O5], 0 <= x <= 1, which have been shown to have a strong positive MGFE, have been prepared and their physical properties, density and molar volume, have been examined as predictors of structural change. The density exhibits a strong positive non-linear and non-additive change in the density with x and a corresponding negative non-linear and non-additive change in the molar volume. In order to understand the structural origins of these changes, a model of the molar volume was created and best-fit to the experimentally determined molar volumes in order to determine the volumes of the short range order (SRO) structural units in these glasses, how these volume change from the molar volumes of the binary glasses, and how these volumes change across the range of x in the ternary glasses. The best-fit model was defined as the model that required the smallest changes in the volumes of the ternary phosphate and borate SRO structural groups from their values determined by the densities of the binary sodium phosphate and sodium borate glasses. In this best-fit molar volume model, it was found that the volumes of the various phosphate and borate SRO structural groups decreased by values ranging from a minimum value of similar to 1% for x=0.1 and 0.9 to a maximum value of similar to 6% for the phosphate and similar to 9% for the borate SRO groups at the minimum in molar volume at x=0.4. The free volume was found to have a negative deviation from linear which is unexpected given the positive deviation in ionic conductivity. (C) 2011 Elsevier B.V. All rights reserved.