Phenomenological theory of First-order prefreezing

Abstract

Prefreezing is the prewetting of the crystalline phase at the interface of a melt to a solid substrate via a first-order phase transition. We present a phenomenological theory of prefreezing and analyze thermodynamic properties of the prefrozen crystalline layer. The theory enables a clear thermodynamic explanation of the abrupt formation of a mesoscopically thick crystalline layer during cooling and defines the corresponding transition temperature as a function of the interfacial free energies. It is shown that the interfacial energy difference γsm – (γsc + γcm) acts as a driving force for prefreezing. The analytical results are congruent with recent experimental outcomes for poly(ε-caprolactone) crystallized on graphite via prefreezing. The calculated interfacial free energies take reasonable values being close to the experimental estimates.