화학공학소재연구정보센터
Journal of the American Ceramic Society, Vol.98, No.6, 1942-1950, 2015
Effect of Zirconium on the Structure and Congruent Crystallization of a Supercooled Calcium Aluminosilicate Melt
The influence of zirconium as a nucleating agent on the congruent crystallization and relevant physical properties of a supercooled calcium aluminosilicate melt of a composition close to CaAl2SiO6 has been investigated up to 6mol% ZrO2. Zirconium marginally affects rheological and structural properties, decreasing the viscosity of the Zr-free melt by no more than 0.25 log unit and, as observed by Raman spectroscopy, not changing significantly the polymerization state of the material. Whereas the Zr-free melt crystallizes congruently and heterogeneously from the sample surface to yield yoshiokaite, a stuffed derivative of the nepheline structure, addition of zirconia promotes instead bulk crystallization of tetragonal ZrO2 and then of yoshiokaite. The latter process takes place in two stages: dissolved Zr first promotes homogeneous precipitation of zirconia before yoshiokaite crystallizes congruently from a Zr-depleted volume of melt around zirconia precipitates. This process makes zirconium, and probably other poorly soluble oxides, valuable to control congruent crystallization in silicate glass-ceramics. From the recorded thermograms, an enthalpy of crystallization of 40 and 46kJ/mol has been determined at 1060 and 1140K, respectively, for CaAl2SiO6 yoshiokaite, a very low value that is likely due to the extensive atomic disorder of crystals precipitating at high degrees of supercooling.