Structure and Contact Angle in Sessile Droplets of Binary Mixtures of Lennard-Jones Chains: A Molecular Dynamics Study.

Abstract

Molecular dynamics simulations were carried out to investigate cylindrical droplets consisting of binary mixtures of Lennard-Jones (LJ) fluids in contact with a solid substrate. The droplets are composed of mixtures of the monomeric LJ fluid plus linear-tangent chains of 2, 10, 20, and 30 segments per chain that interact through a harmonic potential and the spherically truncated and shifted potential Lennard-Jones. The solid surface was modeled as a semi-infinite platinum substrate with an FCC structure that interacts with the fluid by means of a LJ 9-3 potential. We place emphasis on the effect of mixing a monomeric LJ fluid with heavy components on the contact angle and on the droplet structure, especially in the liquid-solid region. The density profiles of the droplets reveal a strong discrete layering of the fluid in the vicinity of the solid-liquid interface. The layering is more pronounced at low temperatures and for mixtures of short chains (symmetric mixtures). The ordering of the fluid was much less intense for fluids of long chains (asymmetric mixtures), and some cases even show gas enrichment at the solid-liquid interface. Enrichment at the vapor-liquid interfaces and density inversion can also be observed. However, these effects are not as marked as in planar interfaces. The contact angle between the droplet and the substrate is calculated by fitting an ellipse to the vapor-liquid interface defined by the Gibbs dividing surface. In general, an increment in the concentration of the heavy component and a reduction of the temperature resulted in an increase of the contact angle, which in turn disfavored the wetting of the droplet.