Effect of Substrate Interaction on Thermodynamics of Prefreezing
2019
T̤āriq, Muḥammad | Dolynchuk, Oleksandr | Thurn-Albrecht, Thomas
Besides heterogeneous nucleation, a solid surface can induce crystallization of a liquid via the less known process of prefreezing. Prefreezing refers to the formation of a thermodynamically stable crystalline layer at an interface to a solid surface above the bulk melting temperature of the material. Using in situ atomic force microscopy, here, we present an investigation of prefreezing of polyethylene (PE) on a molybdenum disulfide (MoS₂) substrate that allows us to make a direct comparison with earlier findings of prefreezing of PE on a graphite substrate. The experiments explicitly show that the prefrozen PE layer is stabilized over a significantly larger temperature range on MoS₂ than on graphite. By employing the recently developed phenomenological theory of prefreezing for analysis, the results quantitatively show that the larger temperature range of prefreezing is caused by a larger interfacial free energies difference γₛₘ – (γₛc + γcₘ).
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