Foams Thin Liquid films

Ordinary foams from detergent solutions are initially thick (measured in micrometers), and, as the fluid hows away, due to gravity or capillary forces or surface evaporation, the him becomes thinner (by a few hundred angstroms). 

Outer monolayer of detergent molecule Some amount of water Inner monolayer of detergent molecule Air on outer layer 

The orientation of the detergent molecule in TLF is such as that the polar group (OO) is pointing toward the water phase, and the apolar alkyl part (CCCCCCCCCC) is pointing toward the air, as 

The thickness of the water phase can vary from over 100 pm to less than 100 nm. Foams are thermodynamically unstable since there is a decrease in total free energy when they collapse. As the thickness increases around the wavelength of light (nm), one starts to observe rainbow colors (arising from the interference). The TLF forms at an even smaller thickness (50 A or 5 nm). 

However, certain kinds of foams are known to persist for very long periods of time, and many attempts have been made to explain their metastability. 

---

The application area of surface and colloid science has increased dramatically during the past decades. For example, the major industrial areas have been soaps and detergents, emulsion technology, colloidal dispersions (suspensions, nanoparticles), wetting and contact angle, paper, cement, oil recovery (enhanced oil recovery [FOR] and shale oil/gas reservoir technology), pollution control, fogs, foams (thin liquid films), food industry, biomembranes, membranes, and pharmaceutical industry. 

Foam formation in a boiler is primarily a surface active phenomena, whereby a discontinuous gaseous phase of steam, carbon dioxide, and other gas bubbles is dispersed in a continuous liquid phase of BW. Because the largest component of the foam is usually gas, the bubbles generally are separated only by a thin, liquid film composed of several layers of molecules that can slide over each other to provide considerable elasticity. Foaming occurs when these bubbles arrive at a steam-water interface at a rate faster than that at which they can collapse or decay into steam vapor. 

Monolayers are thus very useful in understanding various aspects of molecular packing (such as liquid crystals, etc.). With the information from area/molecule, the packing and other interaction parameters can be estimated. These monolayer studies have been found to be important in understanding the thin-liquid film (TLF) structures (bubbles, foams). 

Diverse foam structure applications In foam rubber, foamed polymers, shaving foams, milk shakes, and whipped creams, slowly draining thin liquid films (TLF) are needed. Accordingly, the rate of drainage is the most important factor in such industrial foam applications. 

Thin-liquid-film stability. The effect of surfactants on film and foam stability. Surface elasticity. Froth flotation. The Langmuir trough and monolayer deposition. Laboratory project on the flotation of powdered silica. 

The main factor determining the stability of such foams is the rate and extent of drainage from the thin liquid film. In general, this type of foam is relatively unstable. The stability may be enhanced by increasing the viscosity of the liquid by increasing the dry matter content or adding certain hydrocolloids. The foam stability may also be enhanced with hydrocolloids, in particular microcrystalline cellulose. 

A foam is a coarse dispersion of gas in liquid, and two extreme structural situations can be recognised. The first type (dilute foams) consist of nearly spherical bubbles separated by rather thick films of somewhat viscous liquid. The other type (concentrated foams) are mostly gas phase, and consist of polyhedral gas cells separated by thin liquid films (which may develop from more dilute foams as a result of... 

A foam is a colloidal dispersion in which a gas is dispersed in a continuous liquid phase. The dispersed phase is sometimes referred to as the internal (disperse) phase, and the continuous phase as the external phase. Despite the fact that the bubbles in persistent foams are polyhedral and not spherical, it is nevertheless conventional to refer to the diameters of gas bubbles in foams as if they were spherical. In practical occurrences of foams, the bubble sizes usually exceed the classical size limit given above, as may the thin liquid film thicknesses. In fact, foam bubbles usually have diameters greater than 10 pm and may be larger than 1000 pm. Foam stability is not necessarily a function of drop size, although there may be an optimum size for an individual foam type. It is common but almost always inappropriate to characterize a foam in terms of a given bubble size since there is inevitably a size distribution. This is usually represented by a histogram of sizes, or, if there are sufficient data, a distribution function. 

In concentrated emulsions and foams the thin liquid films that separate the droplets or bubbles from each other are very important in determining the overall stability of the dispersion. In order to be able to withstand deformations without rupturing, a thin liquid film must be somewhat elastic. The surface chemical explanation for thin film elasticity comes from Marangoni and Gibbs (see Ref. [199]). When a surfactant-stabilized film undergoes sudden expansion, then immediately the expanded... 

Figure S.6 The total interaction energy, VT, between the surfaces of a thin liquid film or foam lamella, as a function ofthe film thickness, t.

The thin liquid films bounded by gas on one side and by oil on the other, denoted air/water/oil are referred to as pseudoemulsion films [301], They are important because the pseudoemulsion film can be metastable in a dynamic system even when the thermodynamic entering coefficient is greater than zero. Several groups [301,331,342] have interpreted foam destabilization by oils in terms of pseudoemulsion film stabilities [114]. This is done based on disjoining pressures in the films, which may be measured experimentally [330] or calculated from electrostatic and dispersion forces [331], The pseudoemulsion model has been applied to both bulk foams and to foams flowing in porous media. 

Although many factors, such as film thickness and adsorption behaviour, have to be taken into account, the ability of a surfactant to reduce surface tension and contribute to surface elasticity are among the most important features of foam stabilization (see Section 5.4.2). The relation between Marangoni surface elasticity and foam stability [201,204,305,443] partially explains why some surfactants will act to promote foaming while others reduce foam stability (foam breakers or defoamers), and still others prevent foam formation in the first place (foam preventatives, foam inhibitors). Continued research into the dynamic physical properties of thin-liquid films and bubble surfaces is necessary to more fully understand foaming behaviour. Schramm et al. [306] discuss some of the factors that must be considered in the selection of practical foam-forming surfactants for industrial processes. 

A dispersion of gas bubbles in a liquid, in which at least one dimension falls within the colloidal size range. Thus a foam typically contains either very small bubble sizes or, more commonly, quite large gas bubbles separated by thin liquid films. The thin liquid films are called lamellae (or laminae ). Sometimes distinctions are drawn as follows. Concentrated foams, in which liquid films are thinner than the bubble sizes and the gas bubbles are polyhedral, are termed polyederschaum . Low-concentration foams, in which the liquid films have thicknesses on the same scale or larger than the bubble sizes and the bubbles are approximately spherical, are termed gas emulsions , gas dispersions , or kugelschaum . See also Evanescent Foam, Froth, Aerated Emulsion. 

In general, any dividing wall between two cavities. Example the thin liquid films (lamellae) between bubbles in a foam. 

Malhotra, A.K. Wasan, D.T. Interfacial Rheological Properties of Adsorbed Surfactant Films with Applications to Emulsion and Foam Stability in Thin Liquid Films, Ivanov, I.B. (Ed.), Dekker New York, 1988, pp. 829-890. 

A foam consists of a high volume fraction of gas dispersed in a liquid where the liquid forms a continuous phase. Wet foams with a high water content, e.g. immediately after the formation, can have more or less spherical bubbles. As a consequence of a drainage process of the foam lamellae, the wet foam loses water with time. Due to the resulting high volume fraction of gas, the bubbles are no longer spherical but they are deformed into a polyhedral shape. The polyhedra are separated from each other by thin liquid films. The intersection lines of the lamella are termed plateau borders (see Figure 3.28). 

In order to generate foam, surfaces of thin liquid films always have to be stabilised by layers of surfactants, polymers or particles. This is why pure liquids never foam. Foaming is always accompanied by an increase in the interfacial area and, hence, its free energy. Thus, in a thermodynamic sense foams are basically unstable and are, therefore, sooner or later destroyed. The lifetime of a foam can span a remarkable range from milliseconds to very long duration. 

Thin liquid films bordering a gas phase on both sides, or the so-called free films, are one of the oldest objects of research in the physical chemistry of disperse systems. The reason is probably the ease of their formation, simplicity, uniformity of surfaces, etc. Thin films, including foam films, are an efficient and useful model for the study of many surface phenomena. 

The special properties of thin liquid films, in particular of foam films, involve studying various colloid-chemical aspects, such as kinetics of thinning and rupture of films, transition from CBF to NBF, isotherms of disjoining pressure, thermodynamic (equilibrium) properties, determination of the electrical parameters of surfactant adsorption layer at the liquid/gas... 

Details about the theory of stability of thin liquid films, including foam films, can be found in some monographs [3-6]. However, the literature reflecting the theory of black foam films is rather poor. For this reason it will be granted special attention here. The new theoretical and experimental results accumulated during the recent years have brought nearer... 

Study of processes leading to rupture of foam films can serve to establish the reasons for their stability. The nature of the unstable state of thin liquid films is a theoretical problem of major importance (it has been under discussion for the past half a century), since film instability causes the instability of some disperse systems. On the other hand, the rupture of unstable films can be used as a model in the study of various flotation processes. The unstable state of thin liquid films is a topic of contemporary interest and is often considered along with the processes of spreading of thin liquid films on a solid substrate (wetting films). Thermodynamic and kinetic mechanisms of instability should be clearly distinguished so that the reasons for instability of thin liquid films could be found. Instability of bilayer films requires a special treatment, presented in Section 3.4.4. 

Microscopic foam films are most successfully employed in the study of surface forces. Since such films are small it is possible to follow their formation at very low concentrations of the amphiphile molecules in the bulk solution. On the other hand, the small size permits studying the fluctuation phenomena in thin liquid films which play an important role in the binding energy of amphiphile molecules in the bilayer. In a bilayer film connected with the bulk phase, there appear fluctuation holes formed from vacancies (missing molecules) which depend on the difference in the chemical potential of the molecules in the film and the bulk phase. The bilayer black foam film subjected to different temperatures can be either in liquid-crystalline or gel state, each one being characterised by a respective binding energy. 

Thin liquid films (especially foam films) stabilised with phospholipids, proteins, etc., prove to be very suitable in the study of surface forces, since they could model the interacting biological membranes in aqueous medium. 

The DLVO-theory considers only the molecular van der Waals and electrostatic interactions. A complete analysis of the theory can be found in several monographs [e.g. 3-6] where original and summarised data about the different components of disjoining pressure in thin liquid films, including in foam films are compiled. 

The method of equilibrium foam film employs the experimental measurement of the equilibrium thickness and from the DVLO theory it is possible to determine (po and, respectively, the surface charge at the solution/air interface. This is a very valuable possibility since an equilibrium potential can be evaluated and all complications occurring at kinetic measurements, are avoided. The equilibrium values of (fo are important in the interpretation of electrostatic forces in thin liquid films, along with the other surface forces, acting in them. 

Microscopic foam films from amphiphilic ABA triblock copolymers have been used to assess steric interactions. Most of the work on copolymers [128,129] has been carried out with the Thin Liquid Film-Pressure Balance Technique (see Chapter 2, Section 2.1.8). Nevertheless, some intriguing results have been obtained with the dynamic method for surface force measurement [127]. 

The most detailed information about the interaction of two interfaces can be obtained from the disjoining pressure vs. thickness isotherm. Disjoining pressure isotherms were obtained for foam films from 0.7-1.410 5 mol dm 3 F108 aqueous solutions. A disjoining pressure range encompassing 4 orders of magnitude (1 -104 Pa) has been monitored by two complementary techniques the dynamic method and the Thin Liquid Film-Pressure Balance Technique [128,129] (see Section 2.1.8). 

In order to understand the nature of surface forces which characterise the thermodynamic state of black foam films as well as to establish the CBF/NBF transition, their direct experimental determination is of major importance. This has been first accomplished by Exerowa et al. [e.g. 171,172] with the especially developed Thin Liquid Film-Pressure Balance Technique, employing a porous plate measuring cell (see Section 2.1.8). This technique has been applied successfully by other authors for plotting 11(A) isotherms of foam films from various surfactants solutions [e.g. 235,260,261]. As mentioned in Chapter 2, Section 2.1.2, the Pressure Balance Technique employing the porous ring measuring cell has been first developed by Mysels and Jones [262] for foam films and a FI(A) isotherm was... 

Similarity of Foam Films with Emulsion and Asymmetric Thin Liquid Films... 

The comparison of the results for foam films with those for emulsion films has proved to be very useful, especially with respect to emulsion films of the O/W type. Reason for such a comparison provides the fact that in both cases the thin liquid film is in contact with two hydrophobic phases. It is anticipated that the effects related to adsorption and orientation of surfactant molecules at the film/hydrophobic phase interface are very similar, and there are examples illustrating it. Hence, some regularities established for foam films can be applied to emulsion films and vice versa. 

Fig. 5.12 depicts the lg Wit dependence for NaDoS foams with thin liquid films, h 16 nm, with CBF, h 8 nm and with NBF, h 4.2 nm. The differences between curve 1, 2 and 3, corresponding to the different foam film types, is clearly expressed and is valid not only for the curve slopes but also for t at which a plateau is reached, that itself corresponds to hydrostatic equilibrium. Fig. 5.12,a and 5.12,b plots the initial linear parts of the experimental Wit dependences where the black circles are for NBF, and the black squares are for CBF. It can be seen that the drainage rate is different for the different types of foam films. 

---