Do the contact angle and line tension of surface-attached droplets depend on the radius of curvature?

TL;DR

This study uses Monte Carlo simulations to analyze how the contact angle and line tension of surface-attached droplets depend on the droplet's radius of curvature, revealing a 1/R variation and discussing implications for nucleation barriers.

Contribution

It introduces a thermodynamics-based method to estimate contact angles and line tension dependence on droplet size in lattice gas and Lennard-Jones models, addressing previous ambiguities.

Findings

Contact angle varies as 1/R with droplet radius.

The method provides precise estimates of excess density and free energy.

Nucleation barriers can be estimated without shape or line tension ambiguities.

Abstract

Results from Monte Carlo simulations of wall-attached droplets in the three-dimensional Ising lattice gas model and in a symmetric binary Lennard-Jones fluid, confined by antisymmetric walls, are analyzed, with the aim to estimate the dependence of the contact angle $(\Theta)$ on the droplet radius $(R)$ of curvature. Sphere-cap shape of the wall-attached droplets is assumed throughout. An approach, based purely on "thermodynamic" observables, e.g., chemical potential, excess density due to the droplet, etc., is used, to avoid ambiguities in the decision which particles belong (or do not belong, respectively) to the droplet. It is found that the results are compatible with a variation $[\Theta(R)-\Theta_{\infty}] \propto 1/R$, $\Theta_{\infty}$ being the contact angle in the thermodynamic limit ($R=\infty$). The possibility to use such results to estimate the excess free energy related to the contact line of the droplet, namely the line tension, at the wall, is discussed. Various problems that hamper this approach and were not fully recognized in previous attempts to extract the line tension are identified. It is also found that the dependence of wall tensions on the difference of chemical potential of the droplet from that at the bulk coexistence provides effectively a change of the contact angle of similar magnitude. The simulation approach yields precise estimates for the excess density due to wall-attached droplets and the corresponding free energy excess, relative to a system without a droplet at the same chemical potential. It is shown that this information suffices to estimate nucleation barriers, not affected by ambiguities on droplet shape, contact angle and line tension.