Monolayers, surfactant

When a surfactant is injected into the liquid beneath an insoluble monolayer, surfactant molecules may adsorb at the surface, penetrating between the monolayer molecules. However it is difficult to determine the extent of this penetration. In principle, equilibrium penetration is described by the Gibbs equation, but the practical application of this equation is complicated by the need to evaluate the dependence of the activity of monolayer substance on surface pressure. There have been several approaches to this problem. In this paper, previously published surface pressure-area Isotherms for cholesterol monolayers on solutions of hexadecy1-trimethyl-ammonium bromide have been analysed by three different methods and the results compared. For this system there is no significant difference between the adsorption calculated by the equation of Pethica and that from the procedure of Alexander and Barnes, but analysis by the method of Motomura, et al. gives results which differ considerably. These differences indicate that an independent experimental measurement of the adsorption should be capable of discriminating between the Motomura method and the other two. 

Numerical data are available from our earlier penetration work for a number of monolayer/surfactant systems. The simplest of these systems was selected for this initial analysis the penetration of cholesterol monolayers by hexadecyl-trimethyl-ammonium bromide (CTAB) J). Cholesterol monolayers at 298 K exhibit a single, highly incompressible, condensed phase with the transition to a gaseous phase occurring at a negligibly low surface pressure. CTAB does not appear to undergo surface hydrolysis (10) and the gaseous-to-expanded phase transition occurs at a low concentration (0.043 mmol kg ) and a low surface pressure (1.0 mN m l). 

Linear-dichroic spectra of SA monolayers prepared from mixtures of OTS and a cyanine-dye surfactant established the absence of dimerization and the orientation of the chromophore parallel to the substrate [183]. In contrast, the same cyanine dye underwent sandwich-type dimer formation in LB films and had its chromophore oriented perpendicular to the water surface [192]. These results highlight an important difference between LB and SA monolayers. Parameters which determine monolayer formation on an aqueous subphase are also responsible for the orientation and organization of the surfactants therein. Furthermore, the configuration of the surfactants is retained regardless of the structure of the substrate to which the floating monolayer was subsequently transferred to by the LB technique. Conversely, in SA monolayers, surfactant organization is primarily dependent upon the nature of the substrate [183]. 

Langmuir-Blodgett film A monolayer surfactant film on a fluid surface typically formed using... 

A zero or near-zero contact angle is necessary otherwise results will be low. This was found to be the case with surfactant solutions where adsorption on the ring changed its wetting characteristics, and where liquid-liquid interfacial tensions were measured. In such cases a Teflon or polyethylene ring may be used [47]. When used to study monolayers, it may be necessary to know the increase in area at detachment, and some calculations of this are available [48]. Finally, an alternative method obtains y from the slope of the plot of W versus z, the elevation of the ring above the liquid surface [49]. 

Fig. IV 23. Penetration of cholesterol monolayers by CTAB (hexadecyl-trimethylam-monium bromide. [From D. M. Alexander, G. T. Barnes, M. A. McGregor, and K. Walker, Phenomena in Mixed Surfactant Systems, in J. F. Scamehom, ed., ACS Symposium Series 311, p. 133, 1986 (Ref. 269). Copyright 1986, American Chemical Society.]...

Barnes and co-workers have studied mixed-monolayer systems [278,281,283,284] and found some striking nonidealities. Mixed films of octadecanol and cholesterol, for example, show little evaporation resistance if only 10% cholesterol is present [278] apparently due to an uneven granular microstructure in films with cholesterol [284]. Another study of cellulose decanoate films showed no correlation between holes in the monolayer and permeation rate [285]. Polymerized surfactants make relatively poor water evaporation retarders when compared to octadecanol [286]. There are problems in obtaining reproducible values for r [287] due to impurities in the monolayer material or in the spreading solvent. 

Fig. XII-8. A schematic friction phase diagram showing the trends found in the friction forces of surfactant monolayers. (From Ref. 53.)...

The energetics and kinetics of film formation appear to be especially important when two or more solutes are present, since now the matter of monolayer penetration or complex formation enters the picture (see Section IV-7). Schul-man and co-workers [77, 78], in particular, noted that especially stable emulsions result when the adsorbed film of surfactant material forms strong penetration complexes with a species present in the oil phase. The stabilizing effect of such mixed films may lie in their slow desorption or elevated viscosity. The dynamic effects of surfactant transport have been investigated by Shah and coworkers [22] who show the correlation between micellar lifetime and droplet size. More stable micelles are unable to rapidly transport surfactant from the bulk to the surface, and hence they support emulsions containing larger droplets. 

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. 

Consider the case of an emulsion of 1 liter of oil in 1 liter of water having oil droplets of 0.6 /rm diameter. If the oil-water interface contains a close-packed monolayer of surfactant of 18 per molecule, calculate how many moles of surfactant are present. 

Yamada S and Israelachvili J N 1998 Friction and adhesion hysteresis of fluorocarbon surfactant monolayer-coated surfaces measured with the surface forces apparatus J. Rhys. Chem. B 102 234-44... 

Near-monolayer coverage (/covered 0.95) can be achieved only at surf This can pose problems for surfactants, since solution... 

The adsorbed layer at G—L or S—L surfaces ia practical surfactant systems may have a complex composition. The adsorbed molecules or ions may be close-packed forming almost a condensed film with solvent molecules virtually excluded from the surface, or widely spaced and behave somewhat like a two-dimensional gas. The adsorbed film may be multilayer rather than monolayer. Counterions are sometimes present with the surfactant ia the adsorbed layer. Mixed moaolayers are known that iavolve molecular complexes, eg, oae-to-oae complexes of fatty alcohol sulfates with fatty alcohols (10), as well as complexes betweea fatty acids and fatty acid soaps (11). Competitive or preferential adsorption between multiple solutes at G—L and L—L iaterfaces is an important effect ia foaming, foam stabiLizatioa, and defoaming (see Defoamers). 

Physical and ionic adsorption may be either monolayer or multilayer (12). Capillary stmctures in which the diameters of the capillaries are small, ie, one to two molecular diameters, exhibit a marked hysteresis effect on desorption. Sorbed surfactant solutes do not necessarily cover ah. of a sohd iaterface and their presence does not preclude adsorption of solvent molecules. The strength of surfactant sorption generally foUows the order cationic > anionic > nonionic. Surfaces to which this rule apphes include metals, glass, plastics, textiles (13), paper, and many minerals. The pH is an important modifying factor in the adsorption of all ionic surfactants but especially for amphoteric surfactants which are least soluble at their isoelectric point. The speed and degree of adsorption are increased by the presence of dissolved inorganic salts in surfactant solutions (14). 

---