Surface energy and solute strain energy effects in surface segregation

Previous models of surface segregation have generally been based on the assumption that a decrease in surface free energy constitutes the predominant driving force for the phenomenon. In contrast, grain boundary segregation models have been founded on the postulate that the major driving force for that phenomenon is the reduction in lattice strain energy which accompanies the transfer of misfitting solute atoms from the lattice to the boundary. These two concepts have been combined here into a single unified formalism of surface segregation. In addition, the temperature dependence of surface composition of both nickel-rich and gold-rich nickelgold alloys has been measured by Auger electron spectroscopy. Comparisons of the predictions of the combined formalism with the experimental results show excellent agreement between measured and calculated heats of adsorption (segregation). Furthermore, the present formalism provides estimates of the entropies of adsorption which can be used to explain apparent incompatibilities between the behavior of gold-rich and nickel-rich alloys.