Adsorption water-fluid interfaces

Miller, R., Fainerman, V.B., Makievski, A.V., Kragel, J., Grigoriev, D.O., Kazakov, V.N., Sinyachenko, O.V. (2000a). Dynamics of protein and mixed protein + surfactant adsorption layers at the water-fluid interface. Advances in Colloid and Interface Science, 86, 39-82. 

V. B. Fainerman, E. H. Lucassen-Reynders and R. Miller, Description of the adsorption behaviour of proteins at water/fluid interfaces in the framework of a two-dimensional solution model, Adv. Colloid Interface Sci. 106, 237-259 (2003). 

Solutes are one of the major components of foods, and they have significant effects on their adsorption at fluid interfaces. In addition, the study of the effects of ethanol and/or sucrose on protein adsorption at fluid interfaces is of practical importance in the manufacture of food dispersions. The presence of ethanol in the bulk phase apparently introduces an energy barrier for the protein diffusion towards the interface. This could be attributable to competition with previously adsorbed ethanol molecules for the penetration of the protein into the interface. However, if ethanol causes denaturation and/or aggregation of the protein in the bulk phase, the diffusion of the protein towards the interface could be diminished. The causes of the higher rate of protein diffusion from aqueous solutions of sucrose, in comparison with that observed for water, must be different in aqueous ethanol solutions. Since protein molecules are preferentially hydrated in the presence of sucrose, it is possible that sucrose limits protein unfolding in the bulk phase and reduces protein-protein interactions in the bulk phase and at the interface. Both of these phenomena may increase the rate of protein diffusion towards the interface. Clearly, the kinetics of adsorption of proteins at interfaces are highly complex, especially in the presence of typical food solutes such as ethanol and sucrose in the aqueous phase. 

To summarise the results obtained for the theoretical background, it was shown that essentially the same model can be used to describe the adsorption of ionic surfactants at the water/air, water/alkane vapor and water/liquid alkane interfaces. For the water/air interface we use the set of Eqs. (l)-(4), for the water/vapor interface Eqs. (7)-(9), and for the water/bulk oil interface Eqs. (7), (9) and (10). In the following sections the theoretical models are used to fit experimental surface and interfacial tension data obtained in studies of CnTABs at the three mentioned different water/fluid interfaces. 

Using surface and interfacial tension data for some members of the homologous series of cationic surfactants we want to demonstrate to suitability of the thermodynamic approach of competitive adsorption for the formation of adsorption layers at different water/fluid interfaces, including those to alkane vapor and liquid alkane. We will restrict ourselves here to hexane as the oil or vapor phase. The particular effects of the alkane chain length have been discussed for example in [9]. For oils different from alkanes less systematic data exist, however, a specific impact of the molecular structure can be expected and the molecular characteristics might be rather different from those we obtained for alkanes. 

The rheological properties of a fluid interface may be characterized by four parameters surface shear viscosity and elasticity, and surface dilational viscosity and elasticity. When polymer monolayers are present at such interfaces, viscoelastic behavior has been observed (1,2), but theoretical progress has been slow. The adsorption of amphiphilic polymers at the interface in liquid emulsions stabilizes the particles mainly through osmotic pressure developed upon close approach. This has become known as steric stabilization (3,4.5). In this paper, the dynamic behavior of amphiphilic, hydrophobically modified hydroxyethyl celluloses (HM-HEC), was studied. In previous studies HM-HEC s were found to greatly reduce liquid/liquid interfacial tensions even at very low polymer concentrations, and were extremely effective emulsifiers for organic liquids in water (6). 

Information on the chemical potentials of components in a solution of biopolymers can serve as a guide to trends in surface activity of the biopolymers at fluid interfaces (air-water, oil-water). In the thermodynamic context we need look no further than the Gibbs adsorption equation,... 

When a dielectric phase (solid or fluid) is placed in contact with polar hquid, such as water, the interface becomes charged due to either specific adsorption of ions initially dissolved in the polar liquid, or dissociation of surface ionizable groups. - The final result of these two processes is the formation of an electric double layer (EDL) (Figure 5.67), which may contain three types of ions ... 

Bockris Reddy (1970) describes the Butler-Volmer-equation as the "central equation of electrode kinetics . In equilibrium the adsorption and desorption fluxes of charges at the interface are equal. There are common principles for the kinetics of charge exchange at the polarisable mercury/water interface and the adsorption kinetics of charged surfactants at the liquid/fluid interface. Theoretical considerations about the electrostatic retardation for the adsorption kinetics of ions were first introduced by Dukhin et al. (1973). 

Adsorption layers of the same kind as at fluid interfaces are also formed at low-energy solid -water surfaces, as it was established on PE, polystyrene, paraffin, carbon black, and other related materials. The classical Langmuir or Frumkin adsorption isotherm is often applicable to describe this behaviour. Studies on surfactant adsorption at various solid surfaces have been summarised in a great number of reviews [2, 7, 8, 54, 98, 101, 111, 121, 126, 141, 144, 145, 177, 186, 190, 194-198]. The adsorption at the solid/liquid interfaces is governed by a number of factors ... 

Kinetics. Kinetics also play a role in wettability alteration of porous media by surfactants. In reservoirs, surfactants must be transported through the pore networks by an injected fluid phase, usually water or oil. The ability to alter wettability is related to surfactant diffusion rates and adsorption rates. Surfactants must diffuse through the bulk fluid phase to the meniscus interface and the fluid-pore interface. Surfactants must also interact and adsorb on the pore surfaces. If the diffusion rate or the adsorption rate for surfactant is slow relative to the creation of new water-rock interfaces, because of the water displacement rate, the wettability of the pore surfaces may vary with time. These types of non-... 

An interesting question that arises is what happens when a thick adsorbed film (such as reported at for various liquids on glass [144] and for water on pyrolytic carbon [135]) is layered over with bulk liquid. That is, if the solid is immersed in the liquid adsorbate, is the same distinct and relatively thick interfacial film still present, forming some kind of discontinuity or interface with bulk liquid, or is there now a smooth gradation in properties from the surface to the bulk region This type of question seems not to have been studied, although the answer should be of importance in fluid flow problems and in formulating better models for adsorption phenomena from solution (see Section XI-1). 

Work in the area of simultaneous heat and mass transfer has centered on the solution of equations such as 1—18 for cases where the stmcture and properties of a soHd phase must also be considered, as in drying (qv) or adsorption (qv), or where a chemical reaction takes place. Drying simulation (45—47) and drying of foods (48,49) have been particularly active subjects. In the adsorption area the separation of multicomponent fluid mixtures is influenced by comparative rates of diffusion and by interface temperatures (50,51). In the area of reactor studies there has been much interest in monolithic and honeycomb catalytic reactions (52,53) (see Exhaust control, industrial). Eor these kinds of appHcations psychrometric charts for systems other than air—water would be useful. The constmction of such has been considered (54). 

In a detersive system containing a dilute surfactant solution and a substrate bearing a soHd polar sod, the first effect is adsorption of surfactant at the sod—bath interface. This adsorption is equivalent to the formation of a thin layer of relatively concentrated surfactant solution at the interface, which is continuously renewable and can penetrate the sod phase. Osmotic flow of water and the extmsion of myelin forms foHows the penetration, with ultimate formation of an equdibrium phase. This equdibrium phase may be microemulsion rather than Hquid crystalline, but in any event it is fluid and flushable... 

This natural process by which dissolved and/or particulate surface-active materials end up in the atmosphere has been modeled and studied in the laboratory. As summarized by Detwiler and Blanchard (ref. 46), tests in suspensions of bacteria (ref. 76,96,97), latex spheres (ref. 98), dyes (ref. 99), and in sea water and river water (ref. 96,100,101) have demonstrated successful transfer of all manner of surface-active material from the bulk fluid, or the bulk interface, to the droplets ejected when bubbles burst. (This situation can be pictured as an extension of the common industrial adsorptive-bubble-separation process (ref. 102) into a third dimension or phase — the atmosphere.) Further laboratory tests with various tap waters, distilled waters, and salt solutions have shown that no water sample was ever encountered that did not contain at least traces of surface-active material (ref. 46). 

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