A Thermodynamic Approach To Physical Properties Of Silicate Melts

Thermophysical properties of silicate melts are strongly structure dependent. It is well known that the viscosities of slags increase with increasing the degree of polymerization of silicate anions. Even the thermodynamic properties of slags are dependent on the types of species and the population of the same in the melt. Thus, a link between the thermophysical and thermochemical properties of silicate melts is logically expected. The present paper elucidates the salient features of Darken?s excess stability approach to the Gibbs energies of solutions as applied to the viscosities of silicate melts. It is demonstrated, that the second derivatives of the viscosities of binary silicate melts with respect to composition indicate a maxima corresponding to the existence of stable compounds in these systems. The concept was successfully applied to the following systems: Al2O3-SiO2, CaO-SiO2, FeO-SiO2, MgO-SiO2and MnO-SiO2. In all the cases, the second derivative plots of viscosities with respect to composition showed peaks corresponding to the metasilicates. The second derivatives of the activation energies of viscous flow with respect to temperature has earlier been shown to reflect the formation of associates/embryos in the homogeneous silicate melts, indicating the readiness of the melt to separate a solid phase. Thermodynamic coupling of thermal diffusivities in the case of the system CaO-Al2O3-SiO2from the laser-flash measurements of these slags as a function of temperature are examined as part of the present study. Densities are estimated from integral molar enthalpies in the case of silicate systems and the results are presented. Keywords: silicate melts, viscosity; activation energy, thermal diffusivity; density