Configurational Heat Capacity of Na- and Ca-bearing Aluminosilicate Melts

The Na2O-Al2O3-SiO2 and CaO-Al2O3-SiO2 systems are used as analogs for the more complex natural magmatic systems of the Earth in studies of the physical properties, structure and flow mechanisms of silicate melts. Although the description of flow in binary alkali-silicate melts is clear; that for multi-oxide compositions quickly becomes very complex. The addition of aluminium to melts creates the need for a charge-balancing cation for the tetrahedrally co-ordinated Al3+. With the presence of both mono- and di-valent ions there are questions about which atom is preferred as the charge balancer and which will create non-bridging oxygens. This study addresses the structure of peraluminous and peralkaline/metaluminous Na2O-CaO-Al2O3-SiO2 melts and the change in structure with composition via determination of their shear viscosity and heat capacity. Viscosity has been determined using the micropenetration technique and the heat capacity and configurational heat capacity have been determined by differential scanning calorimetry. While the viscosity of these melts indicates structural changes at the condition where there are no longer enough Na+ or Ca2+ to charge balance all of the Al3+ in tetrahedral co-ordination, it is the heat capacity data which provides more information about the energy required for flow to occur in the melts as the structure changes due to changing composition. The configurational heat capacity can be determined from the difference between the liquid (cpl) and the glass (cpg) heat capacity at the glass transition temperature. To a first approximation cpg can be calculated from a linear summation of the cps of the oxide components. Similarly, if there are no anomalous changes in melt structure upon heating through Tg, the cpl will be a linear sum of the contributions of the component oxides. Configurational entropy Sconf(Tg) has been calculated from the viscosity data using the Adam-Gibbs equation for viscosity as a function of configurational entropy and temperature. In addition to the change in structure implied from changes in the trends of the viscosity and heat capacity data when there are no longer enough charge balancers for all of the Al3+ in tetrahedral co-ordination, there also appears to be a change in structure at the composition where there are no longer enough Ca2+ in the melt that each Al3+ tetrahedron has its own charge balancer that is the composition at which pairs of Al3+ tetrahedra must share a Ca2+ as charge balancer.