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.

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Wetting and Spreading

We discuss in this review how the roughness of a solid impacts its wettability. We see in particular that both the apparent contact angle and the contact angle hysteresis can be dramatically affected by the presence of roughness. Owing to the development of refined methods for setting very well-controlled micro- or nanotextures on a solid, these effects are being exploited to induce novel wetting properties, such as spontaneous filmification, superhydrophobicity, superoleophobicity, and interfacial slip, that could not be achieved without roughness.

Wetting and Roughness

This is a review of Collected Works of John Tate. Parts I, II, edited by Barry Mazur and Jean-Pierre Serre. American Mathematical Society, Providence, Rhode Island, 2016. For several decades it has been clear to the friends and colleagues of John Tate that a “Collected Works” was merited. The award of the Abel Prize to Tate in 2010 added impetus, and finally, in Tate’s ninety-second year we have these two magnificent volumes, edited by Barry Mazur and Jean-Pierre Serre. Beyond Tate’s published articles, they include five unpublished articles and a selection of his letters, most accompanied by Tate’s comments, and a collection of photographs of Tate. For an overview of Tate’s work, the editors refer the reader to [4]. Before discussing the volumes, I describe some of Tate’s work. 1. Hecke L-series and Tate’s thesis Like many budding number theorists, Tate’s favorite theorem when young was Gauss’s law of quadratic reciprocity. When he arrived at Princeton as a graduate student in 1946, he was fortunate to find there the person, Emil Artin, who had discovered the most general reciprocity law, so solving Hilbert’s ninth problem. By 1920, the German school of algebraic number theorists (Hilbert, Weber, . . .) together with its brilliant student Takagi had succeeded in classifying the abelian extensions of a number field K: to each group I of ideal classes in K, there is attached an extension L of K (the class field of I); the group I determines the arithmetic of the extension L/K, and the Galois group of L/K is isomorphic to I. Artin’s contribution was to prove (in 1927) that there is a natural isomorphism from I to the Galois group of L/K. When the base field contains an appropriate root of 1, Artin’s isomorphism gives a reciprocity law, and all possible reciprocity laws arise this way. In the 1930s, Chevalley reworked abelian class field theory. In particular, he replaced “ideals” with his “idèles” which greatly clarified the relation between the local and global aspects of the theory. For his thesis, Artin suggested that Tate do the same for Hecke L-series. When Hecke proved that the abelian L-functions of number fields (generalizations of Dirichlet’s L-functions) have an analytic continuation throughout the plane with a functional equation of the expected type, he saw that his methods applied even to a new kind of L-function, now named after him. Once Tate had developed his harmonic analysis of local fields and of the idèle group, he was able prove analytic continuation and functional equations for all the relevant L-series without Hecke’s complicated theta-formulas. Received by the editors September 5, 2016. 2010 Mathematics Subject Classification. Primary 01A75, 11-06, 14-06. c ©2017 American Mathematical Society

The collected works

1: Magnetic Particles: Preparation, Properties and Applications: M. Ozaki. 2: Maghemite (gamma-Fe2O3): A Versatile Magnetic Colloidal Material C.J. Serna, M.P. Morales. 3: Dynamics of Adsorption and Oxidation of Organic Molecules on Illuminated Titanium Dioxide Particles Immersed in Water M.A. Blesa, R.J. Candal, S.A. Bilmes. 4: Colloidal Aggregation in Two-Dimensions A. Moncho-Jorda, F. Martinez-Lopez, M.A. Cabrerizo-Vilchez, R. Hidalgo Alvarez, M. Quesada-PMerez. 5: Kinetics of Particle and Protein Adsorption Z. Adamczyk.

Surface and Colloid Science

This review is aimed at presenting the evaporation of macroscopic sessile droplets on inert substrates in normal atmosphere in simple cases, as a basis for more complex analyses.

Evaporation of macroscopic sessile droplets

Comparaison des vitesses d'etalement des liquides non volatils sur des surfaces lisses et des surfaces rugueuses

Dynamics of wetting: Effects of surface roughness.

The spontaneous spreading of non-volatile liquid droplets on solid substrates poses a classic problem in the context of wetting phenomena. It is well known that the spreading of a macroscopic droplet is in many cases accompanied by a thin film of macroscopic lateral extent, the so-called precursor film, which emanates from the three-phase contact line region and spreads ahead of the latter with a much higher speed. Such films have been usually associated with liquid-on-solid systems, but in the last decade similar films have been reported to occur in solid-on-solid systems. While the situations in which the thickness of such films is of mesoscopic size are fairly well understood, an intriguing and yet to be fully understood aspect is the spreading of microscopic, i.e. molecularly thin, films. Here we review the available experimental observations of such films in various liquid-on-solid and solid-on-solid systems, as well as the corresponding theoretical models and studies aimed at understanding their formation and spreading dynamics. Recent developments and perspectives for future research are discussed.

https://iopscience.iop.org/article/10.1088/0953-8984/24/24/243102/pdf

Precursor films in wetting phenomena

Via ellipsometry, we study the profile evolution of very small drops (about ${10}^{\mathrm{\ensuremath{-}}4}$ \ensuremath{\mu}l) of nonvolatile liquids, spreading completely on silicon wafers. The evolution of the profiles are studied at molecular thicknesses, and for the first time it is shown that (i) the final stage of spreading in the cases studied is not a pancake, as predicted by the theory of de Gennes and Joanny (for S/\ensuremath{\gamma}\ensuremath{\ll}1), but rather is a two-dimensional gas and (ii) short-range forces and molecular dymanics may drastically affect the profile of the droplet.

Dynamics of wetting of tiny drops: Ellipsometric study of the late stages of spreading.

Via ellipsometry, the time-dependent profiles of liquid droplets spreading completely on plane solid substrates are measured in the range 0--200 \AA{} Two different surfaces are used, a ``high-energy'' surface (wettable by water) and a ``low-energy'' surface (Langmuir-Blodgett layer of a double-bond-terminated fatty acid), respectively We have observed that the shape of spreading droplets of the same fluid (polydimethylsiloxane) are quite different on these two surfaces: On the low-energy surface, the spreading occurs by the macroscopic lateral spreading of essentially one monolayer, away from the central part of the drop On the contrary, for the high-energy surface, spreading occurs by the macroscopic lateral spreading of several monolayers in a kind of hierarchical process Nevertheless, in both cases there is a signature of molecular structuring in the fluid flow at the center of the drop

Anne-Marie Cazabat

Papers

Evaporation of macroscopic sessile droplets

Dynamics of wetting: Effects of surface roughness.

Precursor films in wetting phenomena

Dynamics of wetting of tiny drops: Ellipsometric study of the late stages of spreading.

Experiments on wetting on the scale of nanometers: Influence of the surface energy.