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 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

Aggregates of charged amphiphilic molecules have been found to access a structure at elevated temperature that templates alignment of supramolecular fibrils over macroscopic scales. The thermal pathway leads to a lamellar plaque structure with fibrous texture that breaks on cooling into large arrays of aligned nanoscale fibres and forms a strongly birefringent liquid. By manually dragging this liquid crystal from a pipette onto salty media, it is possible to extend this alignment over centimetres in noodle-shaped viscoelastic strings. Using this approach, the solution of supramolecular filaments can be mixed with cells at physiological temperatures to form monodomain gels of aligned cells and filaments. The nature of the self-assembly process and its biocompatibility would allow formation of cellular wires in situ that have any length and customized peptide compositions for use in biological applications.

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A self-assembly pathway to aligned monodomain gels

Preface 1. Nonlinear behavior in the physical sciences and biology: some typical examples 2. Quantitative formulation 3. Dynamical systems with a finite number of degrees of freedom 4. Linear stability analysis of fixed points 5. Nonlinear behavior around fixed points: bifurcation analysis 6. Spatially distributed systems, broken symmetries, pattern formation 7. Chaotic dynamics Appendices References Index.

Introduction to Nonlinear Science

Hydrodynamic and hydromagnetic stability

The dynamics of a free‐liquid film with insoluble surfactants is followed until film rupture with a simple model based on three nonlinear evolution equations for the film thickness, the surfactants concentration and the tangential velocity of the fluid in the film. This model is derived asymptotically from the full Navier–Stokes equations for free films and incorporates the effect of van der Waals attraction, capillary forces and Marangoni forces due to gradients of surface tension. Different stability regimes are observed numerically for periodic and fixed boundary conditions and several initial conditions. Furthermore, the role of the relevant parameters (Hamaker constant, tension, Marangoni number) on the rupture time is assessed and comparison is made with the flow dynamics for a liquid film with insoluble surfactants on a solid substrate.

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Nonlinear evolution equations for thin liquid films with insoluble surfactants

Interfacial instability at cell membranes

The problem of pattern formation in thin liquid films with insoluble surfactants under attractive and repulsive forces is addressed. A thin fluid film bounded by a wall is modeled by a set of two nonlinear evolution equations for the film thickness and surfactant concentration on the free interface. We perform a bifurcation analysis valid for the general case of apolar and polar forces and predict a supercritical bifurcation to new stationary and periodic structures. Numerical simulations for the particular case of a negative apolar spreading coefficient (attractive van der Waals forces) and a positive polar spreading coefficient (repulsive hydration pressure) are discussed in terms of the analytical predictions. Nonlinearities in the competition between attractive and repulsive forces can lead to formation of periodic patterns for the film thickness with homogeneously distributed surfactants. Due to diffusion and Marangoni effects, insoluble surfactants alter the time required for pattern formation but do not alter the final pattern profile itself. Bifurcation analysis allows us then to predict the ranges of film parameters in which pattern formation, rupture, or total film spreading is possible.

Dominique Gallez

Papers

Nonlinear evolution equations for thin liquid films with insoluble surfactants

Interfacial instability at cell membranes

Pattern formation in thin liquid films with insoluble surfactants

On the dynamic stability of fluid dielectric films

Dynamics of a Thin Liquid Film with a Surface Chemical Reaction