Webb, Sharon L.; Knoche, Ruth; Dingwell, Donald B.
Determination of silicate liquid thermal expansivity using dilatometry and calorimetry.
In: European Journal of Mineralogy, Vol. 4, Nr. 1: S. 95-104
A method for the determination of relaxed silicate liquid molar volume and expansivity at temperatures just above the glass transition is discussed. The method involves the comparison of heat capacity and molar expansivity in the glass transition region. Glassy and liquid heat-capacity data are obtained using differential scanning calorimetry, and glassy thermal expansion data are obtained using scanning dilatometry. The molar expansivity of the liquid is calculated by a fictive temperature normalization of the relaxation behavior of both the heat capacity and the molar expansivity in the glass transition region, with the normalized heat capacity curve being used to extend the dilatometric data into the liquid temperature range. This comparison is based upon the assumed equivalence of the parameters describing the relaxation of volume and enthalpy. The molar expansivity of relaxed sodium trisilicate (Na2Si3O7) has been determined in this manner at temperatures above the glass transition temperature. This low-temperature determination of liquid molar expansivity has been tested against high-temperature liquid expansivity data obtained from high temperature Pt double bob Archimedean buoyancy measurements. The low-temperature molar expansivity (26.43±0.83xl0~4 cm3 mole"lßC_1 at 540°C) determined in this manner agrees within error with the high-temperature molar expansivity (23.29±1.39xl0~4 cm3 mole^ºC1 at 1400°C). This dilatometric/calorimetric method of liquid molar expansivity determination greatly increases the temperature range accessible for thermal expansion measurements. A weighted linear fit to the combined low and high temperature volume data gives a molar expansivity of 23.0010.25x10^ cm3 mole^ºC"1. The volume-temperature relationship thus derived reproduces the measured volumes from both dilatometry and densitometry with a RMSD value of 0.033 cm3 mole"1 or 0.14%. This represents a substantial increase in precision, which is especially important for liquids whose high liquidus temperatures restrict the temperature range accessible to liquid volume determinations.