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Kinetics of Dewetting by N K Agnihotri

Kinetics of Dewetting by N K Agnihotri

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What is Corasening and What is the kinetics of rupture of Ultra thin liquid films?
What is Corasening and What is the kinetics of rupture of Ultra thin liquid films?

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Categories:Types, Research, Science
Published by: Dr. Narendra Agnihotri on Jul 04, 2010
Copyright:Attribution Non-commercial


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Chapter 6Kinetics of Dewetting
Rajesh Khanna and Narendra Kumar AgnihotriDepartment of Chemical EngineeringIndian Institute of Technology DelhiNew Delhi – 110016, IndiaandAshutosh SharmaDepartment of Chemical EngineeringIndian Institute of Technology KanpurKanpur – 208016, India.
6.1 Introduction
In this chapter, we will study the
kinetics of dewetting 
, i.e., the appearanceand growth of dry (uncovered) portions on surfaces covered with liquids. Thisprocess is analogous to the process of phase separation, which has been dis-cussed in previous chapters. The liquid cover breaks as a result of sustainedlocal thinning due to the flow of liquid from thinner to thicker parts. Thisflow, which is the main operative mechanism for dewetting, can be achievedby a variety of mechanical means, e.g., impact by a gas jet or dust particles.In some cases, this uphill liquid flow can also be spontaneous under the in-262
fluence of chemical-potential gradients. In this case, dewetting occurs evenif the system is free of any destabilizing mechanical input. This spontaneousdewetting is dependent on the thickness of the liquid cover. The thickness of the intervening film (see Fig. 6.1) has to be small enough for the film surfaceto feel the attraction of molecules in the solid surface and get pulled (thin)towards the solid surface. Naturally, this thickness has to be less than theeffective range of intermolecular interactions (
100 nm).
 ¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡¡ 
h < 100 nmBounding FluidThin Lquid FilmSolid Substrate
Figure 6.1: A solid surface covered by a liquid layer. The break-up of theliquid layer by local thinning leads to the dewetting of the solid.The occurrence of dewetting under favorable chemical-potential gradientsgives rise to several scientific and technological challenges, as well as solutions.Dewetting is present in many situations in the industrial and scientific worlds.For example, the cleaning of household items such as dinner tables, mirrors,dishes, floors, etc. requires the greasy oil films on the surface to break intodrops (or the surface to dewet) so that their detachment can occur. Inindustry, dewetting is important in many processes such as flotation, coatingand cleaning of surfaces, trickle-bed reactors, contact equipments for heat andmass transfer, etc. [1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17]. Inflotation, the thinning and rupture of the liquid film between the particle andthe bubble can be the rate-determining step of the process. The dewettingof coated surfaces where the coating layer breaks down is important in, e.g.,photographic films, paints, adhesives, dielectrics, bio-compatible and opticalcoatings [7, 8, 9, 10, 11, 12]. Any break-up of these coatings will generallydilute, and in extreme cases nullify, their utility.Dewetting is encountered in many situations of scientific interest also.Thin mucous and aqueous coatings of the cornea can become unstable in263
dry eyes [18, 19, 20]. The hydrophilic ingredients of dry-eye solutions restorethe stability of the protective tear film [19] and prevent dewetting of thecornea. Furthermore, dewetting results in adhesion failure of fluid particlesto surfaces [6, 21]. It is also important in the formation of precursor filmsin wetting [22, 23, 24, 25, 26, 27], heterogeneous nucleation, film boilingand condensation [28, 29, 30], morphology of nanostructures [10, 31, 32, 33,34, 35], multilayer adsorption [36, 37, 38], near-interface diffusion and phaseseparation [39, 40]. In another highly topical application, the instability of thin films (and associated dewetting) is now being used to make nano- andmicro-patterns.Now, why do some surfaces dewet whereas others do not? The answerlies in the amplification of any small perturbation on the thin film’s surfaceunder the attractive force due to the solid surface. The attractive pull, orthe pressure experienced by the thin film’s free surface, is characterized bythe
disjoining pressure
. This is the extra pressure which has to be deductedfrom the interfacial pressure of the film-bounding fluid interface due to thepresence of the nearby film-solid interface – its magnitude depends on thethickness of the film. If the film is thicker than the effective range of inter-molecular forces (about 100 nm), then the disjoining pressure is zero as thefilm-solid interface is not seen by the film-bounding interface. If the variationof disjoining pressure [1, 2, 3, 4, 5] with thickness is such that thinner parts of the film are at higher pressure, then any fluctuation in the film’s surface canamplify by the flow of liquid from thinner to thicker parts. The fluctuationof the molecules due to thermal energy, aided by any additional mechanicalvibrations which may also be present, ensure that the film’s surface is nevercompletely flat. The initial fluctuations will amplify whenever the decreasein free energy of the system due to thinning of the film can compensate forthe increase due to extra interface created during amplification. In thesecases, the initial inhomogeneity triggers a series of morphological changes.These result in the transformation of a flat film into a high-curvature phase,consisting of an array of droplets surrounded by low-curvature (almost flat)and thinner film. This process is commonly known as
morphological phaseseparation 
(MPS) [34, 35, 8, 41, 42].In some cases, the changes lead to an assembly of circular dry spots whichgrow laterally. The neighboring dry spots coalesce, entrapping the remainingliquid as cylindrical ridges, which break into droplets due to the Rayleighinstability. The underlying solid becomes devoid of any liquid away from thedroplets. This scenario is known as
true dewetting 
(TD). In contrast, MPS is264

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