Two-phase equilibrium states in individual Cu-Ni nanoparticles: size, depletion and hysteresis effects.

In isolated bimetallic nanoscale systems the limit amount of matter and surface-induced size effects can change the thermodynamics of first-order phase transformation. In this paper we present theoretical modification of Gibbs free energy concept describing first-order phase transformation of binary alloyed nanoparticles taking into account size effects as well as depletion and hysteresis effects. In such a way the hysteresis in a form of nonsymmetry for forth and back transforming paths takes place; compositional splitting and the loops-like splitted path on the size dependent temperature-composition phase diagram occur. Our calculations for individual Cu-Ni nanoparticle show that one must differentiate the solubility curves and the equilibrium loops (discussed here in term of solidification and melting loops). For the first time we have calculated and present here on the temperature-composition phase diagram the nanomelting loop at the size of 80 nm and the nanosolidification loop at the size of 25 nm for an individual Cu-Ni nanoparticle. So we observe the difference between the size-dependent phase diagram and solubility diagram, between two-phase equilibrium curves and solubility curves; also intersection of nanoliquidus and nanosolidus is available. These findings lead to the necessity to reconsider such basic concepts in materials science as phase diagram and solubility diagram.