Investigation of the Mixed Alkali Effect in a Range of Phosphate Glasses

Abstract

This study investigated the mixed alkali effect in a series of phosphate based glasses. These glasses were of the composition 0.5P2O5-0.2CaO-0.3-xNa2O-xK2O where x=0 to 0.3 in steps of 0.05. This study considered density measurements using Archimedes’s principle, thermal characterisation using differential scanning calorimetry, phase analysis following crystallisation using X-ray powder diffraction (XRD), and degradation studies combined with ion release. The results showed that these mixed alkali glasses showed a linear decrease in density, with the ternary single alkali glass with 0.3mol K2O showing a 3% reduction in density as compared to that with 0.3mol Na2O which correlated well with the difference in ionic diameter and atomic weight of both cations. These glasses also showed intermediate glass transition temperature (Tg) values, compared to those of the ternary single alkali glasses having the same alkali oxide content, and the minimum Tg value was recorded for equimolar amounts of both alkali oxides. However, they did not show any significant change in the degradation rate compared to the glass with 0.3mol Na2O with the exception of the 0.25mol K2O glass. The single alkali glass with 0.3mol K2O showed a significant increase in the degradation rate by an approximate one order of magnitude. For the mixed alkali glasses with low molar concentration of K2O, only sodium phosphate-rich phases [NaCa(PO3)3 and Na4Ca(PO3)6] were detected from XRD; at high molar concentrations however, potassium phosphate-rich phases [KCa(PO3)3 and KPO3] were detected. At equimolar concentration of both alkali cations, KCa(PO3)3 and Na4Ca(PO3)6 were identified. K+, Ca2+, and P3O9 3- release followed the degradation behaviour where the highly degrading glasses with 0.25 and 0.3mol K2O released the highest amount of these ions; however, there was no definite trend in the remaining glass compositions.