Viscosity Relaxation in Molten HgZnTe

Abstract

Rotating cup measurements of the viscosity of the pseudo-binary melt, HgZnTe have shown that the isothermal liquid with ZnTe mole fraction 0.16 requires tens of hours of equilibration time before a steady viscous state can be achieved. Over this relaxation period, the viscosity at 790C increases by a factor of two, while the viscosity at 810C increases by 40%. Noting that the Group VI elements tend to polymerize when molten, we suggest that the viscosity of the melt is enhanced by the slow formation of Te atom chains. To explain the build-up of linear Te n -mers, we propose a scheme, which contains formation reactions with second-order kinetics that increase the molecular weight, and decomposition reactions with first-order kinetics that inactivate the chains. The resulting rate equations can be solved for the time dependence of each molecular weight fraction. Using these molecular weight fractions, we calculate the time dependence of the average molecular weight. Using the standard semi-empirical relation between polymer average molecular weight and viscosity, we then calculate the viscosity relaxation curve. By curve fitting, we find that the data imply that the rate constant for n -mer formation is much smaller than the rate constant for n -mer deactivation, suggesting that Te atoms only weakly polymerize in molten HgZnTe. The steady-state toward which the melt relaxes occurs as the rate of formation of an n -mer becomes exactly balanced by the sum of the rate for its deactivation and the rate for its polymerization to form an ( n + 1)-mer.