Structure-Viscosity Relationship of Low-silica Calcium Aluminosilicate Melts

Abstract

The structure-viscosity relationship of the low-silica (SiO2 <= 10 wt%) calcium aluminosilicate melts, which represent the secondary refining ladle slag systems, was investigated by employing the rotatingcylinder viscosity measurement in conjunction with the Raman spectroscopy measurement for linking the macroscopic thermophysical property and molecular (ionic) structural information. Furthermore, the influence of CaF2 on the structure-property relationship was explored. The viscosity of low-silica calcium aluminosilicate melts decreased with increasing both CaO/Al2O3 and CaO/SiO2 ratios. However, the effect of the former on the viscosity of low-silica calcium aluminosilicate melts was larger than that of the latter. By employing the Neuville's structure model, in which the silicate structural units with various NBO, i.e. Q(n)si are located at the boundary of the AlO4 aluminate, and the Raman scattering data of the glass samples, it was demonstrated that the aluminate and silicate units are more effectively modified by increasing the CaO/Al2O3 ratio at fixed silica content. The addition of small amounts of CaF2 (similar to 5 wt%) to the low-silica calcium aluminosilicate melts decreased the viscosity of the melts. From the analysis of Raman scattering data, the liberation of SiO44- (Q(Si)(0)) units from the AlO4 aluminate structure by addition of CaF2 was understood. However, the effect of CaF2 addition on the viscosity became less discernible at higher CaF2 content (>= 10 wt%) region, where the F ions simply substitute for the non-bridging oxygen ions in AlO4 tetrahedra.