Thermostimulated surface segregation processes in ionic crystals: Potassium chloride

Abstract

The chemical and phase composition, and cleavage surface morphology and the vapor composition of potassium chloride (KCl) crystals formed as a result of the thermostimulated surface autosegregation (TSAS) are studied by methods of microprobe analysis, high-resolution scanning electron microscopy, optical digital microscopy, and quadrupole mass spectrometry. It is experimentally found that the stoichiometry (K/Cl <1) in the surface layers changes due to a decrease in the potassium surface concentration from 5% in the initial samples to 12% after annealing at a temperature of 1023 K. After annealing at a temperature of 573 K for 5 h at P = 10⁻³ Pa, the potassium deficiency increases to 17%. The competing processes resulting in TSAS in potassium chloride are the self-diffusion of potassium to the surface and its subsequent sublimation. During the annealing processes the sublimation of potassium dominates, but at a temperature near fusion, the self-diffusion of potassium to the surface increases. It is concluded that potassium chloride analogous to sodium chloride is a rather stable compound to TSAS. This is an additional argument of the important role of ionic bonds in a decrease in the tendency of chemical compounds to surface autosegregation.