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Phenomenological Theory of First-Order Prefreezing
Oleksandr Dolynchuk1, Muhammad Tariq1, Thomas Thurn-Albrecht1
1Experimental Polymer Physics, Institute of Physics , Martin Luther University Halle-Wittenberg , Halle 06120 , Germany.
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.
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