Adsorption surfactants

As noted above, surfactant adsorption may be described in terms of simple interaction parameters. However, in some cases these interaction parameters may involve ill-defined forces, such as hydrophobic bonding, solvation forces and chemisorption. In addition, the adsorption of ionic surfactants involves electrostatic forces, particularly with polar surfaces containing ionogenic groups. Thus, the adsorption of ionic and nonionic surfactants will be treated separately. Surfaces (substrates) can be also hydrophobic or hydrophilic and these may be treated separately. 

In regime II Koopal and co-workers characterize adsorption in terms of 

The surface forces apparatus (Section VI-3C) has revealed many features of surfactant adsorption and its effect on the forces between adsorbent surfaces [180,181]. A recent review of this work has been assembled by Parker [182]. 

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Fig. XI-13. Adsorption isotherms for SNBS (sodium p-3-nonylbenzene sulfonate) (pH 4.1) and DPC (dodecyl pyridinium chloride) (pH 8.0) on mtile at approximately the same surface potential and NaCl concentration of O.OlAf showing the four regimes of surfactant adsorption behavior, from Ref. 175. [Reprinted with permission from Luuk K. Koopal, Ellen M. Lee, and Marcel R. Bohmer, J. Colloid Interface Science, 170, 85-97 (1995). Copyright Academic Press.]...

Surface heterogeneity may be inferred from emission studies such as those studies by de Schrijver and co-workers on P and on R adsorbed on clay minerals [197,198]. In the case of adsorbed pyrene and its derivatives, there is considerable evidence for surface mobility (on clays, metal oxides, sulfides), as from the work of Thomas [199], de Mayo and co-workers [200], Singer [201] and Stahlberg et al. [202]. There has also been evidence for ground-state bimolecular association of adsorbed pyrene [66,203]. The sensitivity of pyrene to the polarity of its environment allows its use as a probe of surface polarity [204,205]. Pyrene or ofter emitters may be used as probes to study the structure of an adsorbate film, as in the case of Triton X-100 on silica [206], sodium dodecyl sulfate at the alumina surface [207] and hexadecyltrimethylammonium chloride adsorbed onto silver electrodes from water and dimethylformamide [208]. In all cases progressive structural changes were concluded to occur with increasing surfactant adsorption. 

If an ionic surfactant is present, the potentials should vary as shown in Fig. XIV-5c, or similarly to the case with nonsurfactant electrolytes. In addition, however, surfactant adsorption decreases the interfacial tension and thus contributes to the stability of the emulsion. As discussed in connection with charged monolayers (see Section XV-6), the mutual repulsion of the charged polar groups tends to make such films expanded and hence of relatively low rr value. Added electrolyte reduces such repulsion by increasing the counterion concentration the film becomes more condensed and its film pressure increases. It thus is possible to explain qualitatively the role of added electrolyte in reducing the interfacial tension and thereby stabilizing emulsions. 

Sharma R (ed) 1995 Surfactant Adsorption and Surface Solubilization (Washington, DC American Chemical Society)... 

Lignosulfonate has been reported to increase foam stabihty and function as a sacrificial adsorption agent (175). Addition of sodium carbonate or sodium bicarbonate to the surfactant solution reduces surfactant adsorption by increasing the aqueous-phase pH (176). 

In a foam where the films ate iaterconnected the related time-dependent Marangoni effect is mote relevant. A similar restoring force to expansion results because of transient decreases ia surface concentration (iacteases ia surface tension) caused by the finite rate of surfactant adsorption at the surface. 

Colloidal Stabilization. Surfactant adsorption reduces soil—substrate interactions and faciUtates soil removal. For a better understanding of these interactions, a consideration of coUoidal forces is required. 

For the solid-liquid system changes of the state of interface on formation of surfactant adsorption layers are of special importance with respect to application aspects. When a liquid is in contact with a solid and surfactant is added, the solid-liquid interface tension will be reduced by the formation of a new solid-liquid interface created by adsorption of surfactant. This influences the wetting as demonstrated by the change of the contact angle between the liquid and the solid surface. The equilibrium at the three-phase contact solid-liquid-air or oil is described by the Young equation ... 

FIG. 28 Surfactant adsorption as a function of blend composition. Initial [surfactant] = 900 ppm. Adsorption on montmorillonite from 5% NaCl. (From Ref. 87.)... 

The mechanisms that affect heat transfer in single-phase and two-phase aqueous surfactant solutions is a conjugate problem involving the heater and liquid properties (viscosity, thermal conductivity, heat capacity, surface tension). Besides the effects of heater geometry, its surface characteristics, and wall heat flux level, the bulk concentration of surfactant and its chemistry (ionic nature and molecular weight), surface wetting, surfactant adsorption and desorption, and foaming should be considered. 

Dobias B (1984) Surfactant Adsorption on Minerals Related to Flotation. 56 91-147 Doi K, Antanaitis BC, Aisen P (1988) The Binuclear Iron Centres of Uteroferrin and the Purple Acid Phosphatases. 70 1-26 Domcke W, see Bradshaw AM (1975) 24 133-170 Dophin D, see Morgan B (1987) 64 115-204... 

The colloid probe technique was first applied to the investigation of surfactant adsorption by Rutland and Senden [83]. They investigated the effect of a nonionic surfactant petakis(oxyethylene) dodecyl ether at various concentrations for a silica-silica system. In the absence of surfactant they observed a repulsive interaction at small separation, which inhibited adhesive contact. For a concentration of 2 X 10 M they found a normalized adhesive force of 19 mN/m, which is small compared to similar measurements with SEA and is probably caused by sufactant adsorption s disrupting the hydration force. The adhesive force decreased with time, suggesting that the hydrophobic attraction was being screened by further surfactant adsorption. Thus the authors concluded that adsorption occurs through... 

Nanoparticles of the semicondnctor titanium dioxide have also been spread as mono-layers [164]. Nanoparticles of TiOi were formed by the arrested hydrolysis of titanium iso-propoxide. A very small amount of water was mixed with a chloroform/isopropanol solution of titanium isopropoxide with the surfactant hexadecyltrimethylammonium bromide (CTAB) and a catalyst. The particles produced were 1.8-2.2 nm in diameter. The stabilized particles were spread as monolayers. Successive cycles of II-A isotherms exhibited smaller areas for the initial pressnre rise, attributed to dissolution of excess surfactant into the subphase. And BAM observation showed the solid state of the films at 50 mN m was featureless and bright collapse then appeared as a series of stripes across the image. The area per particle determined from the isotherms decreased when sols were subjected to a heat treatment prior to spreading. This effect was believed to arise from a modification to the particle surface that made surfactant adsorption less favorable. 

Another method is based on the evaporation of a w/o microemulsion carrying a water-soluble solubilizate inside the micellar core [221,222], The contemporaneous evaporation of the volatile components (water and organic solvent) leads to an increase in the concentration of micelles and of the solubilizate in the micellar core. Above a threshold value of the solubilizate concentration, it starts to crystallize in confined space. Nanoparticle coalescence could be hindered by surfactant adsorption and nanoparticle dispersion within the surfactant matrix. 

Marches JR, NJ Russel, GF White, WA House (1991) Effects of surfactant adsorption and biodegradability on the distribution of bacteria between sediments and water in a freshwater microcosm. Appl Environ Microbiol 57 2507-2513. 

Dobids, B. Surfactant Adsorption on Minerals Related to Flotation. Vol. 56, pp. 91-147. 

One important advantage of the polarized interface is that one can determine the relative surface excess of an ionic species whose counterions are reversible to a reference electrode. The adsorption properties of an ionic component, e.g., ionic surfactant, can thus be studied independently, i.e., without being disturbed by the presence of counterionic species, unlike the case of ionic surfactant adsorption at nonpolar oil-water and air-water interfaces [25]. The merits of the polarized interface are not available at nonpolarized liquid-liquid interfaces, because of the dependency of the phase-boundary potential on the solution composition. 

For instance, the time course of SPE demonstrates that the solvent phase surfactant concentration steadily decreases (Fig. 3) [58]. The w/o-ME solution s water content decreases at the same rate as the surfactant [58]. The protein concentration at first increases, presumably due to the occurrence of Steps 2 and 3 above, but then decreases due to the adsorption of filled w/o-MEs by the solid phase (Fig. 3) [58]. Additional evidence supporting the mechanism given above is the occurrence of a single Langmuir-type isotherm describing surfactant adsorption in the solid phase for several SPE experiments employing a given protein type (Fig. 4) [58]. Here, solid-phase protein molecules can be considered as surfactant adsorption sites. Similar adsorption isotherms occurred also for water adsorption [58]. 

Mutual solvents have been used to reduce surfactant adsorption on formation minerals, particularly oil-wetting surfactants (131). Ethylene glycol monobutyl ether is the most commonly used mutual solvent. 

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