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. / Doctor of Philosophy / 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. The conventional hydrodynamic analysis with no slip boundary condition predicts a diverging shear stress at the contact line as well as an unbounded shear force exerted on the solid surface. To accommodate this paradox, different mechanism and models have been proposed to clarify the slip between a moving contact line and a solid surface. Although almost all models yield reasonable agreement with experimental observations or numerical simulations, it is still difficult to pick up a specific model using only macroscopic properties and experiment-accessible quantities, because the energy dissipation mechanism during dynamic wetting is not identified and the contact line deforms over different length scales.
In this dissertation, we ascribe the energy dissipation in dynamic wetting to contact line friction/dissipation under the framework of molecular kinetic theory, as it is assumed that the contact line is constantly oscillating around its equilibrium position. By decomposing contact line friction into two contributions: solid-liquid retarding and viscous damping, we are able to derive a universal model for the contact line friction. This model predicts a decaying solid-liquid friction on superhydrophobic surfaces, corresponding to the lotus effect. In the meantime, this model is able to clarify the recently-discovered static-to-kinetic transition of frictional force between a sessile drop and a solid surface. Later, we used the concept of contact line friction in the droplet growth process in dropwise condensation so as to promote the rational design of superhydrophobic condenser surfaces for sustainable dropwise condensation.
As the morphology of a contact line is dependent on the length scale of interest, we focus on the molecular region of contact line. We study the transport and structural change of liquid molecules that are several molecular layers away from the solid surface. It is found that liquid molecules in this region experience patterned density oscillations, which cannot be simply attributed to the random deviations from continuum limit. By combining free energy analysis and Reynolds transport theorem, it is demonstrated that the omnipresent density oscillations arise from the collective effects of self-diffusion, surface-induced convection and shifted glass transition. For liquid water, we propose a bifurcating hydrogen bonding network in contrast to its tetrahedron configuration in bulk water.
| Identifer | oai:union.ndltd.org:VTETD/oai:vtechworks.lib.vt.edu:10919/102649 |
| Date | 17 September 2019 |
| Creators | Zhao, Lei |
| Contributors | Mechanical Engineering, Cheng, Jiangtao, Cheng, Shengfeng, Qiao, Rui, Paul, Mark R. |
| Publisher | Virginia Tech |
| Source Sets | Virginia Tech Theses and Dissertation |
| Detected Language | English |
| Type | Dissertation |
| Format | ETD, application/pdf, application/pdf |
| Rights | In Copyright, http://rightsstatements.org/vocab/InC/1.0/ |
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