Kinetics of Isothermal Melt Crystallization in CaO-SiO2-CaF2-Based Mold Fluxes

Abstract

A kinetic study for isothermal melt crystallization of CaO-SiO2-CaF2-based mold fluxes with different basicity of 0.94 and 1.34 has been carried out systematically by DSC measurements. The kinetic parameters were determined by Johnson-Mehl-Avrami equation. The average Avrami exponent of cuspidine (3CaO center dot 2SiO(2)center dot CaF2) crystallization for mold flux of lower basicity (0.94) is calculated to be 3.1, implying that the crystallization mode is instantaneous nucleation followed by 3-dimensional growth. For the mold flux of higher basicity (1.34), the average Avrami exponent of cuspidine equals to 3.4, strongly suggesting that the growth is still 3 dimensional but the nucleation should be continuous. It was found that the effective crystallization rate constant for both mold fluxes increases as the crystallization temperature decreases, showing that the crystallization rate could be governed by nucleation rate. The negative effective activation energy indicates an anti-Arrhenius behavior for crystallization of the mold fluxes studied. Therefore, it is concluded that the melt crystallization for the commercial mold fluxes will be determined by thermodynamics of nucleation which is relevant to degree of undercooling. The morphology of cuspidine crystals observed by SEM agreeds well with the isothermal crystallization kinetics results.