Surfactant orientation, interface

To resolve the problem of negative /3 values obtained with the Frumkin theory, the improved Szyszkowski-Langmuir models which consider surfactant orientational states and aggregation at the interface have been considered [17]. For one-surfactant system with two orientational states at the interface, we have two balances, i.e., Ft = Fi + F2 and Ftco = Ficoi + F2C02, which can be used in conjunction with Eq. 24 to derive two important equations for determining the total surface excess and averaged molecular area required in the calculation of surface tension, i.e.,... 

The adsorption of nonionic surfactants on polar and nonpolar surfaces also exhibits various features, depending on the nature of the surfactant and the substrate. Three types of isotherms may be distinguished, as illustrated in Fig. 7. These isotherms can be accounted for by the different surfactant orientations and their association at the solid/liquid interface as illustrated in Fig. 8. Again, bilayers, hemimicelles, and micelles can be identified on various substrates. 

As discussed in Section 2.2, surfactant has a tendency to adsorb at interfaces since the polar head group has a strong preference for remaining in water while the hydrocarbon tail prefers to avoid water. The surfactant concentration affects the adsorption of surfactants at interfaces. Surfactant molecules lie flat on the surface at very low concentration. Surfactant molecules on the surface increase with increasing surfactant concentration in the bulk and surfactant tails start to orient towards gas or non-polar liquid since there is not enough space for the surfactant molecules to lie flat on the surface. Surfactant molecules adsorb at the interface and form monolayer until the surface is occupied at which point surfactant molecules start forming self-assembled structures in the liquid (Section 2.3). 

Crystallization from the emulsified state may lead to different nucleation processes than observed for the same fat in bulk liquid form. It has been suggested that nucleation often occurs at the interface of the droplet where surface-active agents are located. The general similarity of the lipophilic components of surfactants oriented at the surface may provide some ordering and structure for the lipid molecules within the droplet and enhance nucleation, as found for example by Kaneko et al. (40) for a hydrocarbon emulsion. Walstra (11) also suggests that formation of compound crystals from emulsions of natural fats may be different than the same fat crystallized from bulk liquid. The initial polymorph formed may also be different, with more stable polymorphs more likely to form in the emulsion (38). 

Air consists of molecules that are mainly non-polar. Surface tension reduction by surfactants at the air-aqueous interface occurs due to adsorption of surfactants at the interface, with the hydrophilic end of the surfactant oriented toward the liquid. The presence of the surfactant molecules reduces the net inward pull toward the bulk liquid, and therefore reduces the surface tension. 

As an example, a fluorocarbon surface layer can be obtained by dissolving a small amount (less than 1%) of a polymerizable fluorosurfactant in a lacquer and cross-linking the surfactant monolayer formed at the surface. Figure 17.31 shows two fluorocarbon surfactants, one polymerizable (a) and the other non-reactive (b), used in such an experiment. The surfactants were added to a poly(methyl methacrylate) (PMMA) lacquer. PMMA is more polar than the hydrocarbon part of the surfactant so the surfactant orients at the film-air interface with... 

Surfactants are surface-active compounds that consist of a hydrophihc head group attached to a hydrophobic tail (usually a long alkyl chain). They have a high affinity for water or oil depending on the dominant moiety (Walz, 1998 McClements, 2004). When present in sufficiently high concentrations, surfactants form a monolayer at the interface between the oil and water, with the hydrophobic tails of the surfactant orientated towards the oil phase and the hydrophilic head groups towards the aqueous phase. There are four categories of surfactants available in the food industry ionic, non-ionic, zwitterionic and cationic. 

The results obtained by Mukerjee and Handa substantiate the fundamental difference between liquid-air and liquid-liquid interfaces. The surface tension of a surfactant solution depends mainly on interactions with the solvent and adsorption at the liquid-air interface. Interactions with air or vapor are weak. In contrast, a surfactant at a liquid-liquid interface interacts with two liquid phases. The lyophobic part of a surfactant oriented away from one of the liquid phases interacts with the second liquid phase in contact. The interaction between the lyophobic film and the second liquid phase is much more significant than the interaction with air or a vapor. 

It was pointed out in Section XIII-4A that if the contact angle between a solid particle and two liquid phases is finite, a stable position for the particle is at the liquid-liquid interface. Coalescence is inhibited because it takes work to displace the particle from the interface. In addition, one can account for the type of emulsion that is formed, 0/W or W/O, simply in terms of the contact angle value. As illustrated in Fig. XIV-7, the bulk of the particle will lie in that liquid that most nearly wets it, and by what seems to be a correct application of the early oriented wedge" principle (see Ref. 48), this liquid should then constitute the outer phase. Furthermore, the action of surfactants should be predictable in terms of their effect on the contact angle. This was, indeed, found to be the case in a study by Schulman and Leja [49] on the stabilization of emulsions by barium sulfate. 

Rasing Th, Shen Y R, Kim M W, Valint P Jr and Bock J 1985 Orientation of surfactant molecules at a liquid-air interface measured by optical second-harmonic generation Phys. Rev. A 31 537-9... 

Two kinds of barriers are important for two-phase emulsions the electric double layer and steric repulsion from adsorbed polymers. An ionic surfactant adsorbed at the interface of an oil droplet in water orients the polar group toward the water. The counterions of the surfactant form a diffuse cloud reaching out into the continuous phase, the electric double layer. When the counterions start overlapping at the approach of two droplets, a repulsion force is experienced. The repulsion from the electric double layer is famous because it played a decisive role in the theory for colloidal stabiUty that is called DLVO, after its originators Derjaguin, Landau, Vervey, and Overbeek (14,15). The theory provided substantial progress in the understanding of colloidal stabihty, and its treatment dominated the colloid science Hterature for several decades. 

Ionic surfactants adsorb at the foam interface and orient with the... 

Recently an alternative approach for the description of the structure in systems with self-assembling molecules has been proposed in Ref. 68. In this approach no particular assumption about the nature of the internal interfaces or their bicontinuity is necessary. Therefore, within the same formahsm, localized, well-defined thin films and diffuse interfaces can be described both in the ordered phases and in the microemulsion. This method is based on the vector field describing the orientational ordering of surfactant, u, or rather on its curlless part s defined in Eq. (55). 

NOTE The orientation of surfactant molecules at an interface (water-solvent, water-gas, water-metal) confers performance characteristics on the molecule that permit it to be employed as an emulsifier, demulsifier, wetting agent, antifoam, lubricant, or other agent. 

The interfacial activity is determined by the sterical properties of the molecule. At the interface the spatial demand A0 of the hydrophobic part of the molecule is higher because of the second chain of the internal sulfonate compared with the terminal sulfonate. Thus, the surface concentration of the surfactant molecules is lower. That means that the hydrocarbon chains are laterally oriented and therefore cover the interface between the solution surface and air more completely. Because the ratio of the spatial demand of the head group to the volume of the alkyl chain governs the radius of the micellar surface, it... 

The Gibbs equation allows the amount of surfactant adsorbed at the interface to be calculated from the interfacial tension values measured with different concentrations of surfactant, but at constant counterion concentration. The amount adsorbed can be converted to the area of a surfactant molecule. The co-areas at the air-water interface are in the range of 4.4-5.9 nm2/molecule [56,57]. A comparison of these values with those from molecular models indicates that all four surfactants are oriented normally to the interface with the carbon chain outstretched and closely packed. The co-areas at the oil-water interface are greater (heptane-water, 4.9-6.6 nm2/molecule benzene-water, 5.9-7.5 nm2/molecule). This relatively small increase of about 10% for the heptane-water and about 30% for the benzene-water interface means that the orientation at the oil-water interface is the same as at the air-water interface, but the a-sulfo fatty acid ester films are more expanded [56]. 

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