Macroscopic thin liquid films are entities that are important in biophysics, physics, and engineering, as well as in natural settings. They can be composed of common liquids such as water or oil, rheologically complex materials such as polymers solutions or melts, or complex mixtures of phases or components. When the films are subjected to the action of various mechanical, thermal, or structural factors, they display interesting dynamic phenomena such as wave propagation, wave steepening, and development of chaotic responses. Such films can display rupture phenomena creating holes, spreading of fronts, and the development of fingers. In this review a unified mathematical theory is presented that takes advantage of the disparity of the length scales and is based on the asymptotic procedure of reduction of the full set of governing equations and boundary conditions to a simplified, highly nonlinear, evolution equation or to a set of equations. As a result of this long-wave theory, a mathematical system is obtained that does not have the mathematical complexity of the original free-boundary problem but does preserve many of the important features of its physics. The basics of the long-wave theory are explained. If, in addition, the Reynolds number of the flow is not too large, the analogy with Reynolds's theory of lubrication can be drawn. A general nonlinear evolution equation or equations are then derived and various particular cases are considered. Each case contains a discussion of the linear stability properties of the base-state solutions and of the nonlinear spatiotemporal evolution of the interface (and other scalar variables, such as temperature or solute concentration). The cases reducing to a single highly nonlinear evolution equation are first examined. These include: (a) films with constant interfacial shear stress and constant surface tension, (b) films with constant surface tension and gravity only, (c) films with van der Waals (long-range molecular) forces and constant surface tension only, (d) films with thermocapillarity, surface tension, and body force only, (e) films with temperature-dependent physical properties, (f) evaporating/condensing films, (g) films on a thick substrate, (h) films on a horizontal cylinder, and (i) films on a rotating disc. The dynamics of the films with a spatial dependence of the base-state solution are then studied. These include the examples of nonuniform temperature or heat flux at liquid-solid boundaries. Problems which reduce to a set of nonlinear evolution equations are considered next. Those include (a) the dynamics of free liquid films, (b) bounded films with interfacial viscosity, and (c) dynamics of soluble and insoluble surfactants in bounded and free films. The spreading of drops on a solid surface and moving contact lines, including effects of heat and mass transport and van der Waals attractions, are then addressed. Several related topics such as falling films and sheets and Hele-Shaw flows are also briefly discussed. The results discussed give motivation for the development of careful experiments which can be used to test the theories and exhibit new phenomena.

Long-scale evolution of thin liquid films

Wetting phenomena are ubiquitous in nature and technology. A solid substrate exposed to the environment is almost invariably covered by a layer of fluid material. In this review, the surface forces that lead to wetting are considered, and the equilibrium surface coverage of a substrate in contact with a drop of liquid. Depending on the nature of the surface forces involved, different scenarios for wetting phase transitions are possible; recent progress allows us to relate the critical exponents directly to the nature of the surface forces which lead to the different wetting scenarios. Thermal fluctuation effects, which can be greatly enhanced for wetting of geometrically or chemically structured substrates, and are much stronger in colloidal suspensions, modify the adsorption singularities. Macroscopic descriptions and microscopic theories have been developed to understand and predict wetting behavior relevant to microfluidics and nanofluidics applications. Then the dynamics of wetting is examined. A drop, placed on a substrate which it wets, spreads out to form a film. Conversely, a nonwetted substrate previously covered by a film dewets upon an appropriate change of system parameters. The hydrodynamics of both wetting and dewetting is influenced by the presence of the three-phase contact line separating "wet" regions from those that are either dry or covered by a microscopic film only. Recent theoretical, experimental, and numerical progress in the description of moving contact line dynamics are reviewed, and its relation to the thermodynamics of wetting is explored. In addition, recent progress on rough surfaces is surveyed. The anchoring of contact lines and contact angle hysteresis are explored resulting from surface inhomogeneities. Further, new ways to mold wetting characteristics according to technological constraints are discussed, for example, the use of patterned surfaces, surfactants, or complex fluids.

/pdf/wetting-and-spreading-56ditqbfmj.pdf

Wetting and Spreading

A study of the spreading of silicone oil drops is presented, with particular attention to the dominant effect of the conditions near the edge and the surface tension forces acting there. It is shown that the drop profiles can be predicted and that this leads to a relation between the edge velocity and the maximum slope, which occurs at an inflection point close to the edge. This relation leads to others governing the variation of drop size and slope with time. The predictions are compared with experiment, using silicone oils, and good agreement obtained. The lubrication approximation theory gives no solution for thicknesses below a value varying from 2 to 9*10-8 m at the drop edge. At thicknesses of this order, or possibly even larger, other effects become important, and some observations on edge behaviour are included.

https://iopscience.iop.org/article/10.1088/0022-3727/12/9/009/pdf

The spreading of silicone oil drops on horizontal surfaces

An investigation is made into the moving contact line dynamics of a Cahn–Hilliard–van der Waals (CHW) diffuse mean-field interface. The interface separates two incompressible viscous fluids and can evolve either through convection or through diffusion driven by chemical potential gradients. The purpose of this paper is to show how the CHW moving contact line compares to the classical sharp interface contact line. It therefore discusses the asymptotics of the CHW contact line velocity and chemical potential fields as the interface thickness e and the mobility κ both go to zero. The CHW and classical velocity fields have the same outer behaviour but can have very different inner behaviours and physics. In the CHW model, wall–liquid bonds are broken by chemical potential gradients instead of by shear and change of material at the wall is accomplished by diffusion rather than convection. The result is, mathematically at least, that the CHW moving contact line can exist even with no-slip conditions for the velocity. The relevance and realism or lack thereof of this is considered through the course of the paper.The two contacting fluids are assumed to be Newtonian and, to a first approximation, to obey the no-slip condition. The analysis is linear. For simplicity most of the analysis and results are for a 90° contact angle and for the fluids having equal dynamic viscosity μ and mobility κ. There are two regions of flow. To leading order the outer-region velocity field is the same as for sharp interfaces (flow field independent of r) while the chemical potential behaves like r−ξ, ξ = π/2/max{θeq, π − θeq}, θeq being the equilibrium contact angle. An exception to this occurs for θeq = 90°, when the chemical potential behaves like ln r/r. The diffusive and viscous contact line singularities implied by these outer solutions are resolved in the inner region through chemical diffusion. The length scale of the inner region is about 10√μκ – typically about 0.5–5 nm. Diffusive fluxes in this region are O(1). These counterbalance the effects of the velocity, which, because of the assumed no-slip boundary condition, fluxes material through the interface in a narrow boundary layer next to the wall.The asymptotic analysis is supplemented by both linearized and nonlinear finite difference calculations. These are made at two scales, experimental and nanoscale. The first set is done to show CHW interface behaviour and to test the qualitative applicability of the CHW model and its asymptotic theory to practical computations of experimental scale, nonlinear, low capillary number flows. The nanoscale calculations are carried out with realistic interface thicknesses and diffusivities and with various assumed levels of shear-induced slip. These are discussed in an attempt to evaluate the physical relevance of the CHW diffusive model. The various asymptotic and numerical results together indicate a potential usefullness for the CHW model for calculating and modelling wetting and dewetting flows.

Contact-line dynamics of a diffuse fluid interface

A model for the movement of a small viscous droplet on a surface is constructed that is based on the lubrication equations and uses the dynamic contact angle to describe the forces acting on the fluid at the contact line. The problems analysed are: the spreading or retraction of a circular droplet; the advance of a thin two-dimensional layer; the creeping of a droplet or cell on a coated surface to a region of greater adhesion; the distortion of droplet shape owing to surface contamination. Relevant biological problems concerning cell movement and adhesion are described.

/pdf/on-the-motion-of-a-small-viscous-droplet-that-wets-a-surface-cqvf9v0xir.pdf

Jaime Lopez

Papers

Spreading kinetics of liquid drops on solids