Micelles surfactant adsorption

After reviewing various earlier explanations for an adsorption maximum, Trogus, Schechter, and Wade [244] proposed perhaps the most satisfactory one so far (see also Ref. 243). Qualitatively, an adsorption maximum can occur if the surfactant consists of at least two species (which can be closely related) what is necessary is that species 2 (say) preferentially forms micelles (has a lower CMC) relative to species 1 and also adsorbs more strongly. The adsorbed state may also consist of aggregates or hemi-micelles, and even for a pure component the situation can be complex (see Section XI-6 for recent AFM evidence of surface micelle formation and [246] for polymeric surface micelles). Similar adsorption maxima found in adsorption of nonionic surfactants can be attributed to polydispersity in the surfactant chain lengths [247], Surface-active impuri-... 

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. 

When p approaches infinity, Equation 7 reveals that equals zero, which corresponds to infinitely fast sorption kinetics and to an equilibrium surfactant distribution. In this case Equation 6 becomes that of Bretherton for a constant-tension bubble. Equation 6 also reduces to Bretherton s case when a approaches zero. However, a - 0 means that the surface tension does not change its value with changes in surfactant adsorption, which is not highly likely. Typical values for a with aqueous surfactants near the critical micelle concentration are around unity (2JL) ... 

In the present work, we have synthesized two betaines and three sulfobetaines in very pure form and have determined their surface and thermodynamic properties of micellization and adsorption. From these data on the two classes of zwitterionics, energetics of micellization and adsorption of the hydrophilic head groups have been estimated and compared to those of nonionic surfactants. 

Fig. 36 Schematic diagram of surfactant-adsorption on silica surface as monomer, hemimicelle, and at surfactant concentration above CMC where pyrene is bound to micelle...

This overview will outline surfactant mixture properties and behavior in selected phenomena. Because of space limitations, not all of the many physical processes involving surfactant mixtures can be considered here, but some which are important and illustrative will be discussed these are micelle formation, monolayer formation, solubilization, surfactant precipitation, surfactant adsorption on solids, and cloud point Mechanisms of surfactant interaction will be as well as mathematical models which have been be useful in describing these systems,... 

Surface aggregates formed by ionic surfactant adsorption on oppositely charge surfaces have been shown to be bi layered structures (1.) and are called admicelles<2) in this paper, though they are sometimes referred to as hemimicelles. The concentration at which admicelles first form on the most energetic surface patch is called the Critical Admicellar Concentration (CAC) in analogy to the Critical Micelle Concentration (CMC), where micelles are first formed. Again, in much of the literature, the CAC is referred to as the Hemimicellar Concentration (HMC). 

A few papers have been published recently on the problem of surfactant adsorption maxima on solids in the region of the CMC (1-5). Scamehorn et al. (1,2) and Trogus et al. (3) expTTined the origin of these maxima by various radios of the surfactant solution to the solid, in connection with isomeric impurity of the surfactant. Ananthapadmanabhan and Soniasundaran (4) examined critically the presence of such maxima from the viewpoint of various proposed adsorption mechanisms. They have shown that a mechanism including micellar exclusion, mixed micelle formation and properties of solids, such as the pore size, cannot explain satisfac-... 

The appeareance of maxima on the adsorption isotherms and decrease in flotability can be explained by the hypothesis that in the presence of micelles no adsorption layer of the surfactant can be formed, the character of which corresponds to the equilibrium state only with monomers (sufficiently hydrophobic adsorption layer). Due to a heterogeneity of forces acting at the surfactant ion mineral interface it can be assumed that at concentrations S CMC some of the molecules will be bound much more firmly in a three-dimensional micelle than in... 

According to Groot (2000), the mechanism of interaction between a polymer and surfactant may be deduced by considering parameters such as polymer size, mode of surfactant adsorption (continuous or discrete micelles), and possible sites of interaction (head group or tail). For the case of the mechanism of the interaction between chitosan and sorbitan esters, the polymer concentration (dilute, semi-dilute, concentrated) of... 

In the various sections of this chapter, I will briefly describe the major characteristics of FT-IR, and then relate the importance of these characteristics to physiochemical studies of colloids and interfaces. This book is divided into two major areas studies of "bulk" colloidal aggregates such as micelles, surfactant gels and bilayers and studies of interfacial phenomena such as surfactant and polymer adsorption at the solid-liquid interface. This review will follow the same organization. A separate overview chapter addresses the details of the study of interfaces via the attenuated total reflection (ATR) and grazing angle reflection techniques. 

This was shown e.g. by investigating adsorption isotherms of Na dodecylbenzene-4-sulfonate and Na 4-hexadecyloxytolyl-2-sulfonate on various mineral surfaces differing from each other by the kind of PDFs86 . The potential value in relation to the surfactant concentration reached its maximum in the region of micelle formation and confirmed thus the shape of the adsorption isotherm. The presence of adsorption maxima is explained by a decrease in surfactant adsorption resulting from a desorption effect of micelles on the adsorption film, and by setting a three-component equilibrium (adsorption film - micelle - monomer) at concentrations CMC. This happens because of different ratios of the counter ions to the surfactant ions at the micelle and on the adsorption film. 

The more recent neutron reflectivity studies have established that flattened surface micelle or fragmented bilayer structure in more detail and with more certainty, using contrast variation in the surfactant and the solvent [24, 31]. However, the extent of the lateral dimension (in the plane of the surface) and the detailed structure in that direction is less certain. From those neutron reflectivity measurements [24, 31] and related SANS data on the adsorption of surfactants onto colloidal particles [5], it is known that the lateral dimension is small compared with the neutron coherence length, such that averaging in the plane is adequate to describe the data. The advent of the AFM technique and its application to surfactant adsorption [15] has provided data that suggest that there is more structure and ordering in the lateral direction than implied from other measurements. This will be discussed in more detail in a later section of the chapter. At the hydrophobic interface, although the thickness of the adsorbed layer is now consistent with a monolayer, the same uncertainties about lateral structure exist. 

Correlation equations relating surfactant chemical structure to performance characteristics and physical properties have been established. One atmosphere foaming properties of alcohol ethoxyl-ates and alcohol ethoxylate derivatives have been related to surfactant hydrophobe carbon chain length, ethylene oxide content, aqueous phase salinity, and temperature. Similar correlations have been established for critical micelle concentration, surfactant cloud point, and surfactant adsorption. 

Surfactant critical micelle concentration (cmc) may be related to chemical structure using multiple correlation analysis. The cmc value plays an important role in surfactant adsorption, foaming, and interfacial tension properties. The 25 C cmc values of a series of high purity single component highly linear primary alcohol ethoxylates (Table 6) were analyzed using equation 4 ... 

As a case study we discuss some aspects of the adsorption of non-ionic surfactants, non-ionics for short, from aqueous solution. Such surfactants have Invariably long molecules and strongly associate In solution to form micelles. The latter aspect is beyond the confines of the present chapter. Here we shall briefly Introduce some main features of the adsorption of non-ionics. Ionic surfactant adsorption belongs to the domain of electrosorption see sec. 3.12d. 

Extensive neutron reflectivity studies on surfactant adsorption at the air-water interface show that a surfactant monolayer is formed at the interface. Even for concentration cmc, where complex sub-surface ordering of micelles may exist,the interfacial layer remains a monolayer. This is in marked contrast to the situation for amphiphilic block copolymers, where recent measurements by Richards et al. on polystyrene polyethylene oxide block copolymers (PS-b-PEO) and by Thomas et al. on poly(2-(dimethyl-amino)ethylmethacrylamide-b-methyl methacrylate) (DMAEMA-b-MMA) show the formation of surface micelles at a concentration block copolymer, where an abrupt change in thickness is observed at a finite concentration, and signals the onset of surface micellisation. 

The nonpolar portion of surfactant ions has an important role in promoting the adsorption process because it increases the affinity of these organic ions to the interfacial region. The effect derives from mutual attraction between the hydrophobic tails as well as their tendency to escape from an aqueous environment. That mechanism is precisely the same one which causes the spontaneous formation of micelles in aqueous solution and is known as the hydrophobic effect [78]. In the case of surfactant adsorption, it is responsible for the formation of surface aggregates. However, it is not easy to accurately predict the shape and the size of such molecular associations in the same way that the structure of bulk aggregates can be determined from the geometry of the molecule. This is because the surface imposes different restrictions on the organization of the adsorbed layer. 

In sufficiently dilute aqueous solutions surfactants are present as monomeric particles or ions. Above critical micellization concentration CMC, monomers are in equilibrium with micelles. In this chapter the term micelle is used to denote spherical aggregates, each containing a few dozens of monomeric units, whose structure is illustrated in Fig. 4.64. The CMC of common surfactants are on the order of 10 " -10 mol dm . The CMC is not sharply defined and different methods (e.g. breakpoints in the curves expressing the conductivity, surface tension, viscosity and turbidity of surfactant solutions as the function of concentration) lead to somewhat different values. Moreover, CMC depends on the experimental conditions (temperature, presence of other solutes), thus the CMC relevant for the expierimental system of interest is not necessarily readily available from the literature. For example, the CMC is depressed in the presence of inert electrolytes and in the presence of apolar solutes, and it increases when the temperature increases. These shifts in the CMC reflect the effect of cosolutes on the activity of monomer species in surfactant solution, and consequently the factors affecting the CMC (e.g. salinity) affect also the surfactant adsorption. 

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