Effect of alumina on enthalpy of mixing of mixed alkali silicate glasses

The enthalpy of mixing of mixed alkali (Na2O and K2O) silicate glasses containing various concentrations of alumina was determined using an ion-exchange equilibrium method. For glasses with a constant alkali concentration, the enthalpy of mixing was found to become less negative with alumina addition. Consistent with our previous results on the enthalpy of mixing of alumina-free mixed alkali silicate glasses, the magnitude of enthalpy of mixing exhibited a good correlation with the molar volume mismatch of the corresponding two single alkali glasses as well as with the extent of conductivity mixed alkali effect, e.g. excess activation energy of conductivity, ΔE. The reduction of the magnitude of the enthalpy of mixing with alumina addition can be attributed to the reduction of non-bridging oxygen and ionic field strength. Combining the present results with results obtained earlier, the magnitude of the enthalpy of mixing for all mixed alkali (Na2O and K2O) silicate glasses with and without alumina was expressed by a simple function of a modified Tobolsky parameter, which takes into account the alkali concentration and the difference in cation-to-effective anion distances. The enthalpy of mixing data of the mixed alkali glasses was then compared with reported experimental data on the conductivity of mixed alkali aluminosilicate glasses. What appears to be conflicting experimental data can be understood in terms of the magnitude of the enthalpy of mixing and we can conclude that the mixed alkali effect is closely correlated with the negative enthalpy of mixing.