COMPRESSIBILITY OF TITANOSILICATE MELTS

The effect of composition on the relaxed adiabatic bulk modulus (Ko) of a range of alkali- and alkaline earth-titanosilicate [X(2/n)(n+)TiSiO(5) (X = Li, Na, K, Rb, Cs, Ca, Sr, Ba)] melts has been investigated. The relaxed bulk moduli of these melts have been measured using ultrasonic interferometric methods at frequencies of 3, 5 and 7 MHz in the temperature range of 950 to 1600 degrees C (0.02 Pa s < eta(s), < 5 Pa s). The bulk moduli of these melts decrease with increasing cation size from Li to Cs and Ca to Pa, and with increasing temperature. The bulk moduli of the Li-, Na-, Ca- and Ba-bearing metasilicate melts decrease with the addition of both TiO2 and SiO2 whereas those of the K-, Rb- and Cs-bearing melts increase. Linear fits to the bulk modulus versus volume fraction of TiO, do not converge to a common compressibility of the TiO2 component, indicating that the structural role of TiO, in these melts is dependent on the identity of the cation. This proposition is supported by a number of other property data for these and related melt compositions including heat capacity and density, as well as structural inferences from X-ray absorption spectroscopy (XANES). The compositional dependence of the compressibility of the TiO2 component in these melts explains the difficulty incurred in previous attempts to incorporate TiO2 in calculation schemes for melt compressibility. The empirical relationship K proportional to V--4/3 for isostructural materials has been used to evaluate the compressibility-related structural changes occurring in these melts. The alkali metasilicate and disilicate melts are isostructural, independent of the cation. The addition of Ti to the metasilicate composition (i.e. X(2)TiSiO(5)), however, results in a series of melts which are not isostructural. The alkaline-earth metasilicate and disilicate compositions are not isostructural, but the addition of Ti to the metasilicate compositions (i.e. XTiSiO(5)) would appear, on the basis of modulus-volume systematics, to result in the melts becoming isostructural with respect to compressibility.