Diffusion-controlled solidification of a ternary melt from a cooled boundary

Abstract

We present details of an experimental study of crystallization adjacent to a cooled boundary from an aqueous solution of potassium nitrate and sodium nitrate. This transparent system is typical of many ternary melts that do not form solid solutions, including examples in igneous petrology and metallurgy. We have measured the rates of advance of the front of crystallization and the eutectic front, behind which the system is completely solid. From careful measurements of the concentration and temperature fields, we have been able to infer the location of an internal phase boundary: the cotectic front separating a region in which only one component of the ternary system forms crystals from a region in which two components form crystals. Our experiments were conducted under conditions in which fluid flow is minimal, so that rates of crystallization are determined principally by the diffusive transport of heat. We have confirmed that the thicknesses of the various regions all grow in proportion to the square root of time, as is expected of diffusion-limited growth, and have determined the constants of proportionality for a range of different initial concentrations and boundary temperatures. We have found evidence to suggest that there may be a significant nucleation delay in the secondary and tertiary crystallization. Our measurements of concentration provide much more information about the ternary phase diagram than has hitherto been available.