Dynamics and Statics of Three-Phase Contact Line

Wetting, which addresses either spontaneous or forced spreading of liquids on a solid surface, is a ubiquitous phenomenon in nature and can be observed by us on a daily basis, e.g., rain drops falling on a windshield and lubricants protecting our corneas. The study of wetting phenomena can be traced back to the observation of water rising in a capillary tube by Hauksbee in 1706 and still remains as a hot topic, since it lays the foundation for a wide spectrum of applications, such as fluid mechanics, surface chemistry, micro/nanofluidic devices, and phase change heat transfer enhancement. Generally, wetting is governed by the dynamic and static behaviors of the three-phase contact line. Therefore, a deep insight into the dynamics and statics of three-phase contact line at nanoscale is necessary for the technological advancement in nanotechnology and nanoscience. This dissertation aims to understand the dynamic wetting under a molecular kinetic framework and resolve the reconfiguration of liquid molecules at the molecular region of contact line.

Water spreading on polytetrafluoroethylene surfaces is selected as a classical example to study the dynamic behaviors of three-phase contact line. To accommodate the moving contact line paradox, the excess free energy is considered to be dissipated in the form of molecular dissipation. As-formed contact line friction/dissipation coefficient is calculated for water interacting with PTFE surfaces with varying structures and is found to be on the same order of magnitude with dynamic viscosity. From an ab initio perspective, contact line friction is decomposed into contributions from solid-liquid retarding and viscous damping. A mathematical model is established to generalize the overall friction between a droplet and a solid surface, which is able to clarify the static-to-kinetic transition of solid-liquid friction without introducing contact angle hysteresis. Moreover, drag reduction on lotus-leaf-like surface is accounted for as well. For the first time, the concept of contact line friction is used in the rational design of a superhydrophobic condenser surface for continuous dropwise condensation.

We focus on the transport and reconfiguration of liquid molecules confined by a solid wall to shed light on the morphology of the molecular region of a three-phase contact line. A governing equation, which originates from the free energy analysis of a nonuniform monocomponent system, is derived to describe the patterned oscillations of liquid density. By comparing to the Reynolds transport theorem, we find that the oscillatory profiles of interfacial liquids are indeed governed in a combined manner by self-diffusion, surface-induced convection and shifted glass transition. Particularly for interfacial water, the solid confining effects give rise to a bifurcating configuration of hydrogen bonds. Such unique configuration consists of repetitive layer-by-layer water sheets with intra-layer hydrogen bonds and inter-layer defects. Molecular dynamics simulations on the interfacial configuration of water on solid surfaces reveal a quadratic dependence of adhesion on solid-liquid affinity, which bridges the gap between macroscopic interfacial properties and microscopic parameters.