Abstract
The discovery of wetting as a topic of physical science dates back two hundred years, to one of the many achievements of the eminent British scholar Thomas Young. He suggested a simple equation relating the contact angle between a liquid surface and a solid substrate to the interfacial tensions involved [1],
γlg cos θ = γsg - γsl (1)
In modern terms, γ denotes the excess free energy per unit area of the interface indicated by its indices, with l, g and s corresponding to the liquid, gas and solid, respectively [2]. After that, wetting seems to have been largely ignored by physicists for a long time. The discovery by Gabriel Lippmann that θ may be tuned over a wide range by electrochemical means [3], and some important papers about modifications of equation~(1) due to substrate inhomogeneities [4,5] are among the rare exceptions.
This changed completely during the seventies, when condensed matter physics had become enthusiastic about critical phenomena, and was vividly inspired by the development of the renormalization group by Kenneth Wilson [6]. This had solved the long standing problem of how to treat fluctuations, and to understand the universal values of bulk critical exponents. By inspection of the critical exponents of the quantities involved in equation~(1), John W Cahn discovered what he called critical point wetting: for any liquid, there should be a well-defined transition to complete wetting (i.e., θ = 0) as the critical point of the liquid is approached along the coexistence curve [7]. His paper inspired an enormous amount of further work, and may be legitimately viewed as the entrance of wetting into the realm of modern physics.
Most of the publications directly following Cahn's work were theoretical papers which elaborated on wetting in relation to critical phenomena. A vast amount of interesting, and in part quite unexpected, ramifications were discovered, such as the breakdown of universality in thin film systems [8]. Simultaneously, a number of very specific and quantitative predictions were put forward which were aimed at direct experimental tests of the developed concepts [9].
Experimentally, wetting phenomena proved to be a rather difficult field of research. While contact angles seem quite easy to measure, deeper insight can only be gained by assessing the physical properties of minute amounts of material, as provided by the molecularly thin wetting layers. At the same time, the variations in the chemical potential relevant for studying wetting transitions are very small, such that system stability sometimes poses hard to solve practical problems. As a consequence, layering transitions in cryogenic systems were among the first to be thoroughly studied [10] experimentally, since they require comparably moderate stability. First-order wetting transitions were not observed experimentally before the early nineties, either in (cryogenic) quantum systems [11,12] or in binary liquid mixtures [13,14]. The first observation of critical wetting, a continuous wetting transition, in 1996 [15] was a major breakthrough [16].
In the meantime, a detailed seminal paper by Pierre Gilles de Gennes published in 1985 [17] had spurred a large number of new research projects which were directed to wetting phenomena other than those related to phase transitions. More attention was paid to non-equilibrium physics, as it is at work when oil spreads over a surface, or a liquid coating beads off (`dewets') from its support and forms a pattern of many individual droplets. This turned out to be an extremely fruitful field of research, and was more readily complemented by experimental efforts than was the case with wetting transitions. It was encouraging to find effects analogous to layering (as mentioned above) in more common systems such as oil films spreading on a solid support [18,19]. Long standing riddles such as the divergence of dissipation at a moving contact line were now addressed both theoretically and experimentally [20,21].
However, the requirements concerning resolution of the measurements, as well as the stability and cleanliness of the systems, were immense for the reasons mentioned above. The pronounced impact of impurities was already well-known from contact angle measurements, where one invariably observes quite significant hysteresis effects and history dependence of the measured angle due to minute substrate inhomogeneity. This is why pioneering work on characteristic patterns emerging upon dewetting of thin liquid films [22] opened a long lasting, and eventually very fruitful, controversy on the question whether the underlying mechanism was unstable surface waves [24] (which was unambiguously observed for the first time in 1996 [23]) or `just' nucleation from defects.
By the mid-nineties, the physics of wetting had made its way into the canon of physical science topics in its full breadth. The number of fruitful aspects addressed by that time is far too widespread to be covered here with any ambition to completeness. The number of researchers turning to this field was continuously growing, and many problems had already been successfully resolved, and many questions answered. However, quite a number of fundamental problems remained, which obstinately resisted solution. Only a few shall be mentioned:
There was no satisfactory explanation for triple point wetting [25], in particular for its ubiquity.
The numerical values of contact line tensions in both theory and (very reproducible) experiments [26] were many orders of magnitude apart.
In the particularly interesting field of structure formation, i.e., dewetting, there was no clear interpretation of many experimental results, and no possibility to distinguish with certainty between the different possible mechanisms. Furthermore, the impact of the rather strong non-linearities of the involved van der Waals forces was entirely unclear.
In the more remote field of bionics, it was not clear how some plants manage to make liquids bead off so perfectly from their leaves.
This list, which is of course far from complete, serves to illustrate the wide scope of open questions. At that time, research groups in Germany concerned with wetting phenomena gathered and finally applied for a priority programme on wetting and structure formation at interfaces, which obtained funding from the German Science Foundation [27]. This special issue is dedicated to the research carried out within this programme. It spans the period starting from spring 1998 until summer 2004, and is presented as a combination of review over that period and original presentation of the state-of-the-art at its end.
Although only a very limited number of problems could be tackled within the programme, a few significant achievements could be attained. Some of these shall be highlighted:
It could be shown that triple point wetting is a direct consequence of topographic substrate imperfection. By taking the bending energy of a solid slab on a rough substrate into account, accordance between theory [28] and experiment [29] was finally achieved.
By applying scanning force microscopy to three phase contact lines, it could be shown that the `real' contact line tension is indeed much smaller than `observed' on macroscopic scale [39], and comes close to what is theoretically expected.
In the field of structure formation by dewetting, unprecedented agreement between experiment [31], theory [32], and particularly careful simulations [33] was achieved. The underlying mechanisms could be clearly distinguished by means of Minkowski functionals.
It could be shown both theoretically [34,35] and experimentally [36,37] that chemically patterned substrates give rise not only to a large variety of liquid morphologies, but that the latter can be manipulated and controlled in a precise manner.
It was demonstrated that spherical (colloidal) beads may not only be used like surfactants as in Pickering emulsions, but that the resulting interface configurations may be applied to generate an amazing variety of well-controlled porous membranes, with a lot of potential applications [39].
This gives a flavour of the variety of topics addressed in the papers making up this issue. They are organized in five sections, each of which is opened with a short introduction explaining their mutual relation. For further access to the pertinent literature, the reader is referred to the references given in each article separately.
References
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