Dewetting

In fluid mechanics, dewetting is one of the processes that can occur at a solid–liquid or liquid–liquid interface. Generally, dewetting describes the rupture of a thin liquid film on the substrate (either a liquid itself, or a solid) and the formation of droplets. The opposite process—spreading of a liquid on a substrate—is called wetting. The factor determining the spontaneous spreading and dewetting for a drop of oil placed on a liquid substrate (water here) with ambient gas, is the so-called spreading coefficient $S$:^[1]

$S\ =\gamma _{{\text{gw}}}-\gamma _{{\text{go}}}-\gamma _{{\text{ow}}}$

where $\gamma _{{\text{gw}}}$ is the gas-water surface tension, $\gamma _{{\text{go}}}$ is the gas-oil surface tension and $\gamma _{{\text{ow}}}$ is the oil water surface tension (measured on the fluids before they are brought in contact with each other)

When $S>0$, the spontaneous spreading occurs, and if $S<0$, dewetting occurs.

Spreading and dewetting are important processes for many applications, including adhesion, lubrication, painting, printing, and protective coating. For most applications, dewetting is an unwanted process, because it destroys the applied thin film.

In most dewetting studies a thin polymer film is spun onto a substrate. Even in the case of $S<0$ the film does not dewet immediately if it is in a metastable state, e.g. if the temperature is below the glass transition temperature of the polymer. Annealing such a metastable film above its glass transition temperature increases the mobility of the polymer-chain molecules and dewetting takes place.^[2][3]

When starting from a continuous film, an irregular pattern of droplets is formed. The droplet size and droplet spacing may vary over several orders of magnitude, since the dewetting starts from randomly formed holes in the film. There is no spatial correlation between the dry patches that develop. These dry patches grow and the material is accumulated in the rim surrounding the growing hole. In the case where the initially homogeneous film is thin (in the range of 100 nm (4×10⁻⁶ in)), a polygon network of connected strings of material is formed, like a Voronoi pattern of polygons. These strings then can break up into droplets, a process which is known as the Plateau-Rayleigh instability. At other film thicknesses, other complicated patterns of droplets on the substrate can be observed, which stem from a fingering instability of the growing rim around the dry patch.

Dewetting can be inhibited or prevented by photocrosslinking the thin film prior to annealing, or by incorporating nanoparticle additives into the film. ^[4]

Surfactants can have a significant effect on the spreading coefficient. When a surfactant is added, it's amphiphilic properties cause it to be more energetically favorable to migrate to the surface, decreasing the interfacial tension and thus increasing the spreading coefficient (i.e. making S more positive). As more surfactant molecules are absorbed into the interface, the free energy of the system decreases in tandem to the surface tension decreasing, eventually causing the system to become completely wetting.

In biology, by analogy with the physics of liquid dewetting, the process of tunnel formation through endothelial cells has been referred to as cellular dewetting.

References

1. Rosen, Milton J. (2004). Surfactants and Interfacial Phenomena (3rd ed.). Hoboken, New Jersey: Wiley-Interscience. p. 244. ISBN 978-0-471-47818-8. OCLC 475305499.
2. Leroux, Frédéric; Campagne, Christine; Perwuelz, Anne; Gengembre, Léon (2008). "Polypropylene film chemical and physical modifications by dielectric barrier discharge plasma treatment at atmospheric pressure". Journal of Colloid and Interface Science. 328 (2): 412–20. doi:10.1016/j.jcis.2008.09.062. PMID 18930244.
3. Karapanagiotis, Ioannis; Gerberich, William W. (2005). "Polymer film rupturing in comparison with leveling and dewetting". Surface Science. 594 (1–3): 192–202. Bibcode:2005SurSc.594..192K. doi:10.1016/j.susc.2005.07.023.
4. Carroll, Gregory T.; Turro, Nicholas J.; Koberstein, Jeffrey T. (2010) Patterning Dewetting in Thin Polymer Films by Spatially Directed Photocrosslinking Journal of Colloid and Interface Science, Vol. 351, pp 556-560 doi:10.1016/j.jcis.2010.07.070