We use linear stability theory and numerical simulations to show that spontaneous phase separation in elastically coherent solids is fundamentally altered by the presence of free surfaces. Because of misfit stress relaxation near surfaces, phase separation is mediated by unique surface modes of spinodal decomposition that have faster kinetics than bulk modes and are unstable even when spinodal decomposition is suppressed in the bulk. Consequently, in the presence of free surfaces, the limit of metastability of supersaturated solid solutions of crystalline materials is shifted from the coherent to chemical spinodal.

• Received 15 November 2011

DOI:https://doi.org/10.1103/PhysRevLett.108.265701