Surface force liquid films

Thin liquid films can be formed between two coUiding emulsion droplets or between the bubbles in foam. Formation of thin films accompanies the particle-particle and particle-wall interactions in colloids. From a mathematical viewpoint, a film is thin when its thickness is much smaller than its lateral dimension. From a physical viewpoint, a liquid film formed between two macroscopic phases is thin when the energy of interaction between the two phases across the film is not negligible. The specific forces causing the interactions in a thin liquid film are called surface forces. Repulsive surface forces stabilize thin films and dispersions, whereas attractive surface forces cause film rupture and coagulation. This section is devoted to the macroscopic (hydrostatic and thermodynamic) theory of thin films, while the molecular theory of surface forces is reviewed in Section 4.4. 

Thin liquid films have proven their advantages in the study of interaction forces in foam, emulsion, and wetting films stabilized by various types of surfactants see, for example. Refs. l-3]. DLVO and non-DLVO surface forces that stabilize these films have been established in many cases the relation between surface forces and film stability has also been found. Recently, several authors have reported results of model experiments with thin liquid films (foam, emulsion and wetting films) stabilized by polymeric surfactants. In our laboratories all three types of films from aqueous solutions of A-B-A triblock copolymers [4—6] or AB hydrophobically modified inulin [8-10] have been studied. The corresponding disperse systems (foams, emulsions, suspensions) stabilized by AB polymeric surfactants have also been studied extensively see, for example. Refs. [11-14]. It was supposed that the stabilizing forces are steric surface forces but they have not been directly proven and quantitatively studied. 

Idziak S H J ef a/1994 The x-ray surface forces apparatus structure of a thin smectic liquid crystal film under confinement Science 264 1915-8... 

When the film thickens beyond two or three molecular layers, the effect of surface structure is largely smoothed out. It should therefore be possible, as Hill and Halsey have argued, to analyse the isotherm in the multilayer region by reference to surface forces (Chapter 1), the partial molar entropy of the adsorbed film being taken as equal to that of the liquid adsorptive. By application of the 6-12 relation of Chapter 1 (with omission of the r" term as being negligible except at short distances) Hill was able to arrive at the isotherm equation... 

The aim of breaking up a thin film of liquid into an aerosol by a cross flow of gas has been developed with frits, which are essentially a means of supporting a film of liquid on a porous surface. As the liquid flows onto one surface of the frit (frequently made from glass), argon gas is forced through from the undersurface (Figure 19.16). Where the gas meets the liquid film, the latter is dispersed into an aerosol and is carried as usual toward the plasma flame. There have been several designs of frit nebulizers, but all work in a similar fashion. Mean droplet diameters are approximately 100 nm, and over 90% of the liquid sample can be transported to the flame. 

Adhesion of particles Small particles experience adhesion forces, allowing them to attach to surfaces. These forces may be made up from surface tension of liquid films, or London (Van der Waals) forces. 

Another powerful tool for investigating a rheology of liquid films on nano-scale is Surface Force Apparatus (SFA)... 

Surface force apparatus has been applied successfully over the past years for measuring normal surface forces as a function of surface gap or film thickness. The results reveal, for example, that the normal forces acting on confined liquid composed of linear-chain molecules exhibit a periodic oscillation between the attractive and repulsive interactions as one surface continuously approaches to another, which is schematically shown in Fig. 19. The period of the oscillation corresponds precisely to the thickness of a molecular chain, and the oscillation amplitude increases exponentially as the film thickness decreases. This oscillatory solvation force originates from the formation of the layering structure in thin liquid films and the change of the ordered structure with the film thickness. The result provides a convincing example that the SFA can be an effective experimental tool to detect fundamental interactions between the surfaces when the gap decreases to nanometre scale. 

Berman, A., and Israelachvili, J. N., "Surface Forces and Microrheology of Molecularly Thin Liquid Films, Handbook of Micro/Nanotribology, 2nd ed., B. Bhushan, Ed., CRC Press, Boca Raton, FL, 1999. 

The shape of a droplet or of the front end of a film can be determined from the surface energies and interaction forces between the interfaces. These also determine the equilibrium thickness of a liquid film that completely wets a surface. The calculation is done by minimization of the free energy of the total system. In a two-dimensional case the free energy of a cylindrical droplet can be expressed as [5] ... 

Capillary phenomena are due to the curvature of liquid surfaces. To maintain a curved surface, a force is needed. In Eq. (8), this force is related to the second term in the integral. The so-called Laplace pressure due to the force to maintain the curved surface can be expressed as, Pl = 2-yIr, where r is the curvature radius. The combination of the capillary effects and disjoining pressure can make a liquid film climb a wall. 

The surface forces apparatus (SEA) can measure the interaction forces between two surfaces through a liquid [10,11]. The SEA consists of two curved, molecularly smooth mica surfaces made from sheets with a thickness of a few micrometers. These sheets are glued to quartz cylindrical lenses ( 10-mm radius of curvature) and mounted with then-axes perpendicular to each other. The distance is measured by a Fabry-Perot optical technique using multiple beam interference fringes. The distance resolution is 1-2 A and the force sensitivity is about 10 nN. With the SEA many fundamental interactions between surfaces in aqueous solutions and nonaqueous liquids have been identified and quantified. These include the van der Waals and electrostatic double-layer forces, oscillatory forces, repulsive hydration forces, attractive hydrophobic forces, steric interactions involving polymeric systems, and capillary and adhesion forces. Although cleaved mica is the most commonly used substrate material in the SEA, it can also be coated with thin films of materials with different chemical and physical properties [12]. 

Figure 8 shows H2SO4 droplets on mica at very low humidity (<5%). The contact line aronnd the drops is smooth and circnlar, revealing that no pinning has occurred [49]. Although the area between drops is flat, it does not correspond to clean mica but to a liquid film covering it of a few monolayers thickness. This is deduced from the hysteresis in the force versns distance experiments, where the tip is brought into contact with the surface and then pulled off. 

However, on rigid substrates, the growth of dry zones is accompanied by a rim of excess liquid with width X (Fig. 10). As the dewetting proceeds, X increases. For short times and < K, the growth of dry patches is controlled only by surface tension forces and the dewetting speed is constant. A constant dewetting speed of 8 mm-s has been measured when a liquid film of tricresyl phosphate (TCP) dewets on Teflon PFA, a hard fluoropoly-mer of low surface free energy (p. = 250 MPa, 7 = 20 mJ-m ). 

Liquid Metal Sources. The source feed is a metal of low melting point - Ga and In are commonly employed. It is introduced as a liquid film flowing over a needle towards the tip whose radius is relatively blunt (10 pm). The electrostatic and surface tension forces form the liquid into a sharp point known as the Taylor cone. Here the high electric field is sufficient to allow an electron to tunnel from the atom to the surface, leaving the atom ionized. 

To our knowledge, none of the developed SLP and SAP catalysts made their way into a technical process. Obviously, the possibility of using a supported liquid catalyst in a continuous liquid phase reaction is generally very restricted. The reason is that a very low solubility of the liquid in the feedstock/product mixture is enough to remove the catalyst from the surface over time (due to the very small amounts of liquid on the support). Even worse, the immobilised liquid film can be removed from the support physically by the mechanical forces of the continuous flow even in the case of complete immiscibility. 

When particles approach the gas-liquid interface, the surface-tension force acts on the particles through the liquid film. The bubble-surface-tension induced force can be described by... 

Comparing the 3-D images simulated and the experimental photographs in Fig. 10, it can be seen that the droplet shapes are well reproduced by the present model. During the first 3.5 ms of the impact (frames 1-3), a liquid film with flattened disc shape is formed immediately after the impact. The inertial force drives the liquid to continue spreading on the solid surface, while the surface tension and the viscous forces resist the spreading of the liquid film. As a result, the droplet spreading speed decreases and the fluid mass starts to accumulate at... 

Fig. 14 shows the comparison of the photographs from Chandra and Avedisian (1991) with simulated images of this study for a subcooled 1.5 mm n-heptane droplet impact onto a stainless-steel surface of 200 °C. The impact velocity is 93 cm/s, which gives a Weber number of 43 and a Reynolds number of 2300. The initial temperature of the droplet is room temperature (20 °C). In Fig. 14, it can be seen that the evolution of droplet shapes are well simulated by the computation. In the first 2.5 ms of the impact (frames 1-2), the droplet spreads out right after the impact, and a disk-like shape liquid film is formed on the surface. After the droplet reaches the maximum diameter at about 2.1ms, the liquid film starts to retreat back to its center (frame 2 and 3) due to the surface-tension force induced from the periphery of the droplet. Beyond 6.0 ms, the droplet continues to recoil and forms an upward flow in the center of the... 

Another notable example of the dripping mechanism is the slow formation of a drop by breakaway from a liquid film on the bottom surface of a flat, horizontal plate under the action of gravity. The size of the drop formed can be estimated using the following expression derived on the basis of a force balance between gravity and surface tension)1 ... 

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