Thermodynamic formulation of the barrier for heterogeneous pinned nucleation: Implication to the crossover scenarios associated with barrierless and homogeneous nucleation

摘要

The effect of contact line pinning on nucleation is reported using continuum thermodynamics. Based on the principle of the free-energy maximization, closed-form expressions in the dimensionless form for the free-energy of the three-phase metastable system and the thermodynamic barrier are formulated with respect to the system geometry and the substrate wettability. The condition of maximality limits the dynamic contact angle within the cluster-phase-phobic regime. The dimensionless nucleation barrier or the potency factor can be divided into two components related to the system geometry and the pinning effect. Depending on the relative value of the equilibrium and the critical dynamic contact angle, the contact line pinning can either have favorable or adverse effects. Associated pinning-depinning transition can also lead to the crossovers related to barrierless and homogeneous nucleation. Contact line tension is found to have a considerable effect during these transitional scenarios. Complete wetting transition associated with barrierless nucleation can take place due to the presence of tensile (negative) line tension. On the other hand, complete drying transition related to homogeneous nucleation can occur when line tension is compressive (positive) in nature. The pinning has a favorable effect only when the substrate wettability is within the cluster-phase-philic regime. There can be favorable, adverse, or no pinning effects when the substrate wettability is within the cluster-phase-phobic regime. Although the contact line is pinned, the minimum value of the potency factor is obtained when equilibrium and dynamic contact angles are equal. Published by AIP Publishing.