Surface segregation in a dilute copper-silver alloy

The equilibrium surface composition of a Cu-0.83 at. % Ag alloy has been studied over the range from 600 degrees-400 degrees C. Above 450 degrees C the alloy consists of a single phase, whereas below that temperature the material separates into copper-rich and silver-rich phases. The kinetics of equilibration appear to be controlled by grain boundary diffusion, leading to more rapid equilibration than expected on the basis of lattice diffusion-controlled kinetics. In the single-phase regime, silver segregates to the surface with an average enthalpy of segregation of -24 kJ/mol and an entropy of segregation of 0.94 J/mol K, and displays a trend of increasing equilibrium silver surface concentration with decreasing temperature. Theoretical estimates of the enthalpy of segregation yield the somewhat more negative values of -60 and -47 kJ/mol, respectively. In the two-phase regime, the surface continues to be enriched in silver, but the silver surface concentration decreases with decreasing temperature as a result of the rapidly decreasing equilibrium solubility of silver in copper.