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

The boundary layer equations for plane, incompressible, and steady flow are 

$$\matrix{ {u{{\partial u} \over {\partial x}} + v{{\partial u} \over {\partial y}} = - {1 \over \varrho }{{\partial p} \over {\partial x}} + v{{{\partial ^2}u} \over {\partial {y^2}}},} \cr {0 = {{\partial p} \over {\partial y}},} \cr {{{\partial u} \over {\partial x}} + {{\partial v} \over {\partial y}} = 0.} \cr }$$

Boundary Layer Theory

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.

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Wetting and Spreading

Jets, ie collimated streams of matter, occur from the microscale up to the large-scale structure of the universe Our focus will be mostly on surface tension effects, which result from the cohesive properties of liquids Paradoxically, cohesive forces promote the breakup of jets, widely encountered in nature, technology and basic science, for example in nuclear fission, DNA sampling, medical diagnostics, sprays, agricultural irrigation and jet engine technology Liquid jets thus serve as a paradigm for free-surface motion, hydrodynamic instability and singularity formation leading to drop breakup In addition to their practical usefulness, jets are an ideal probe for liquid properties, such as surface tension, viscosity or non-Newtonian rheology They also arise from the last but one topology change of liquid masses bursting into sprays Jet dynamics are sensitive to the turbulent or thermal excitation of the fluid, as well as to the surrounding gas or fluid medium The aim of this review is to provide a unified description of the fundamental and the technological aspects of these subjects

Physics of liquid jets

The dynamics and stability of thin liquid films have fascinated scientists over many decades: the observations of regular wave patterns in film flows down a windowpane or along guttering, the patterning of dewetting droplets, and the fingering of viscous flows down a slope are all examples that are familiar in daily life. Thin film flows occur over a wide range of length scales and are central to numerous areas of engineering, geophysics, and biophysics; these include nanofluidics and microfluidics, coating flows, intensive processing, lava flows, dynamics of continental ice sheets, tear-film rupture, and surfactant replacement therapy. These flows have attracted considerable attention in the literature, which have resulted in many significant developments in experimental, analytical, and numerical research in this area. These include advances in understanding dewetting, thermocapillary- and surfactant-driven films, falling films and films flowing over structured, compliant, and rapidly rotating substrates, and evaporating films as well as those manipulated via use of electric fields to produce nanoscale patterns. These developments are reviewed in this paper and open problems and exciting research avenues in this thriving area of fluid mechanics are also highlighted.

Dynamics and stability of thin liquid films

Small drops sliding down a partially wetting substrate bifurcate between different shapes depending on their capillary number Ca. At low Ca, they are delimited by a rounded, smooth contact line. At intermediate values they develop a corner at the trailing edge, the angle of which evolves from flat to 60 degrees with increasing velocity. Further up, they exhibit a cusped tail that emits smaller drops ("pearls"). These bifurcations may be qualitatively and quantitatively recovered by considering the dynamic contact angle along the contact line.

Corners, Cusps, and Pearls in Running Drops

Regular patterns of cracks formed by directional drying of a collodial suspension.

We report experiments on the shape and motion of millimetre-sized drops sliding down a plane in a situation of partial wetting. When the Bond number based on the component of gravity parallel to the plane . When this velocity is increased by tilting the plate, the drops change their aspect ratio: they become longer and thinner, but maintain a constant, millimetre-scale height. As their aspect ratio changes, a threshold is reached at which the drops are no longer rounded but develop a ‘corner’ at their rear: the contact line breaks into two straight segments meeting at a singular point or at least in a region of high contact line curvature. This structure then evolves such that the velocity normal to the contact line remains equal to the critical value at which the corner appears, i.e. to a maximal speed of dewetting. At even higher velocities new shape changes occur in which the corner changes into a ‘cusp’, and later a tail breaks into smaller drops (pearling transition). Accurate visualizations show four main results. (i) The corner appears when a critical non-zero value of the receding contact angle is reached. (ii) The interface then has a conical structure in the corner regime, the in-plane and out-of-plane angles obeying a simple relationship dictated by a lubrication analysis. (iii) The corner tip has a finite non-zero radius of curvature at the transition to a corner, and its curvature diverges at a finite capillary number, just before the cusp appears. (iv) The cusp transition occurs when the corner opening in-plane half-angle reaches a critical value of about 45°.

Shape and motion of drops sliding down an inclined plane

We study experimentally and theoretically the evolution of two-dimensional patterns in the Rayleigh—Taylor instability of a thin layer of viscous fluid spread on a solid surface. Various kinds of patterns of different symmetries are observed, with possible transition between patterns, the preferred symmetries being the axial and hexagonal ones. Starting from the lubrication hypothesis, we derive the nonlinear evolution equation of the interface, and the amplitude equation of its Fourier components. The evolution laws of the different patterns are calculated at order two or three, the preferred symmetries being related to the non-invariance of the system by amplitude reflection. We also discuss qualitatively the dripping at final stage of the instability.

Two-dimensional patterns in Rayleigh-Taylor instability of a thin layer

We propose a simple model of the dynamics of a contact line under evaporation and partial wetting conditions, taking into account the divergent nature of evaporation near the contact line, as evidenced by Deegan et al. (Nature, 389 (1997) 827). We show that evaporation can induce a non-negligible change of the contact angle together with modification of the flow near the contact line. We apply our results to dip-coating of a substrate with non volatile solutes. We show that at small velocities the coating thickness increases and scales like the inverse of the square of the velocity which implies a minimum of the coating thickness at the cross-over with the more familiar Landau-Levich regime.

https://iopscience.iop.org/article/10.1209/0295-5075/83/14003/pdf

Laurent Limat

Papers

Corners, Cusps, and Pearls in Running Drops

Regular patterns of cracks formed by directional drying of a collodial suspension.

Shape and motion of drops sliding down an inclined plane

Two-dimensional patterns in Rayleigh-Taylor instability of a thin layer

Evaporation-induced flow near a contact line: Consequences on coating and contact angle