A phenomenological theory of the size dependence of the melting temperature of small crystalline particles is offered. Fluctuations and deviation of the crystals form from the equilibrium one are shown to produce a considerable effect on the melting of small particles. An experimental study of the melting of small particles of Sn, Pb, Bi, and In in island films is carried out. The fraction of the melted particles is determined by the curves of temperature dependence for integral intensity of one of the reflexes of the electron diffraction pattern. The results obtained by the authors are easy to describe with the thermodynamic theory taking into account the effect of fluctuations and nonequilibrium habit.

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The thermodynamics of the liquid–solid phase transition in small particles in the size range where the phase transition hysteresis vanishes, is considered. The crystallization of small droplets in discontinuous films of tin, lead, bismuth, and gallium is studied experimentally. The fraction of the crystallized particles is determined from the temperature dependence of the integral intensity of one of the reflections of the electron diffraction pattern. The experimental results are compared with the theory of homogeneous nucleation at the crystallization of supercooled liquids.