Films, layers and droplets: The effect of near-wall fluid structure on spreading dynamics

We present a study of the spreading of liquid droplets on a solid substrate at very small scales. We focus on the regime where effective wetting energy (binding potential) and surface tension effects significantly influence steady and spreading droplets. In particular, we focus on strong packing and layering effects in the liquid near the substrate due to underlying density oscillations in the fluid caused by attractive substrate-liquid interactions. We show that such phenomena can be described by a thin-film (or long-wave or lubrication) model including an oscillatory Derjaguin (or disjoining/conjoining) pressure, and explore the effects it has on steady droplet shapes and the spreading dynamics of droplets on both, an adsorption (or precursor) layer and completely dry substrates. At the molecular scale, commonly used two-term binding potentials with a single preferred minimum controlling the adsorption layer height are inadequate to capture the rich behaviour caused by the near-wall layered molecular packing. The adsorption layer is often sub-monolayer in thickness, i.e., the dynamics along the layer consists of single-particle hopping, leading to a diffusive dynamics, rather than the collective hydrodynamic motion implicit in standard thin-film models. We therefore modify the model in such a way that for thicker films the standard hydrodynamic theory is realised, but for very thin layers a diffusion equation is recovered

Films, layers and droplets: The effect of near-wall fluid structure on spreading dynamics

We present a study of the spreading of liquid droplets on a solid substrate at very small scales. We focus on the regime where effective wetting energy (binding potential) and surface tension effects significantly influence steady and spreading droplets. In particular, we focus on strong packing and layering effects in the liquid near the substrate due to underlying density oscillations in the fluid caused by attractive substrate-liquid interactions. We show that such phenomena can be described by a thin-film (or long-wave or lubrication) model including an oscillatory Derjaguin (or disjoining/conjoining) pressure, and explore the effects it has on steady droplet shapes and the spreading dynamics of droplets on both, an adsorption (or precursor) layer and completely dry substrates. At the molecular scale, commonly used two-term binding potentials with a single preferred minimum controlling the adsorption layer height are inadequate to capture the rich behaviour caused by the near-wall layered molecular packing. The adsorption layer is often sub-monolayer in thickness, i.e., the dynamics along the layer consists of single-particle hopping, leading to a diffusive dynamics, rather than the collective hydrodynamic motion implicit in standard thin-film models. We therefore modify the model in such a way that for thicker films the standard hydrodynamic theory is realised, but for very thin layers a diffusion equation is recovered

Binding potentials for vapour nanobubbles on surfaces using density functional theory

We calculate one-body density profiles of a simple model fluid in contact with a planar surface using density functional theory (DFT), in particular for the case where there is a vapour layer intruding between the wall and the bulk liquid. We apply the method of Hughes \emph{et al.}\ [J.\ Chem.\ Phys.\ {\bf 142}, 074702 (2015)] to calculate the density profiles for varying (specified) amounts of the vapour adsorbed at the wall. This is equivalent to varying the thickness $h$ of the vapour at the surface. From the resulting sequence of density profiles we calculate the thermodynamic grand potential as $h$ is varied and thereby determine the binding potential as a function of $h$. The binding potential obtained via this coarse-graining approach allows us to determine the disjoining pressure in the film and also to predict the shape of vapour nano-bubbles on the surface. Our microscopic DFT based approach captures information from length scales much smaller than some commonly used models in continuum mechanics