Micellar thermodynamic stability

Since they act as surfactants, copolymers are added in only small amounts, typically from a thousandth parts to a few hundredth parts. Theoretically, Leibler [30] showed that only 2% of a diblock copolymer may thermodynamically stabilize an 80%/20% incompatible blend with an optimum morphology (submicronic droplets). However, in practice kinetic control and micelle formation interfere in this best-case scenario. To a some extent, compatibilization increases with copolymer concentration [8,31,32], Beyond a critical concentration (critical micellar concentration cmc) little or no improvement is observed (moreover, for high amounts, the copolymer can act as a plasticizer). Copolymer molecular weight influence is similar to that of the concentration effect. For example, in a PS/PDMS system [8,31,32], when the copolymer molecular weight increases, domain size decreases to a certain extent. Hu et al. [31] correlated their experimental results with theoretical prediction of the Leibler s brush theory [30]. Leibler distinguishes two regimes to characterize the behaviour of the copolymer at the interface... 

Micellar aggregates are considered in chapter 3 and a critical concentration is defined on the basis of a change in the shape of the size distribution of aggregates. This is followed by the examination, via a second order perturbation theory, of the phase behavior of a sterically stabilized non-aqueous colloidal dispersion containing free polymer molecules. This chapter is also concerned with the thermodynamic stability of microemulsions, which is treated via a new thermodynamic formalism. In addition, a molecular thermodynamics approach is suggested, which can predict the structural and compositional characteristics of microemulsions. Thermodynamic approaches similar to that used for microemulsions are applied to the phase transition in monolayers of insoluble surfactants and to lamellar liquid crystals. 

The term microemulsion, which implies a close relationship to ordinary emulsions, is misleading because the microemulsion state embraces a number of different microstructures, most of which have little in common with ordinary emulsions. Although microemulsions may be composed of dispersed droplets of either oil or water, it is now accepted that they are essentially stable, single-phase swollen micellar solutions rather than unstable two-phase dispersions. Microemulsions are readily distinguished from normal emulsions by their transparency, their low viscosity, and more fundamentally their thermodynamic stability and ability to form spontaneously. The dividing line, however, between the size of a swollen micelle ( 10-140 nm) and a fine emulsion droplet ( 100-600 nm) is not well defined, although microemulsions are very labile systems and a microemulsion droplet may disappear within a fraction of a second whilst another droplet forms spontaneously elsewhere in the system. In contrast, ordinary emulsion droplets, however small, exist as individual entities until coalescence or Ostwald ripening occurs. 

Micellar dispersions, which contain micelles along with individual surfactant molecules, are the typical examples of lyophilic colloidal systems. Micelles are the associates of surfactant molecules with the degree of association, represented by aggregation number, i.e. the number of molecules in associate, of 20 to 100 and even more [1,13,14]. When such micelles are formed in a polar solvent (e.g. water), the hydrocarbon chains of surfactant molecules combine into a compact hydrocarbon core, while the hydrated polar groups facing aqueous phase make the hydrophilic shell. Due to the hydrophilic nature of the outer shell that screens hydrocarbon core from contact with water, the surface tension at the micelle - dispersion medium interface is lowered to the values othermodynamic stability of micellar systems with respect to macroscopic surfactant phases. 

The field of microemulsion microstructure started to develop forcefully in the 1970s. Realizing the thermodynamic stability and the relation to other surfactant self-assemblies, it became natural to assume that they were akin to micellar solutions, the most studied aspect of surfactant-water systems, and they were discussed in terms such as swollen micelles. ... 

We found that the studied micelles containing long PEO chains, which should assure their solubility and thermodynamic stability, are surprisingly apt to a secondary aggregation and formation of micellar clusters. We suspected that the secondary aggregation of the PEO sheU is caused by a hindered and incomplete solvation. Therefore, we supplemented the LS study of micellar solutions by SRM, with the aim of obtaining detailed information on the solvation of micellar shells. 

The studied triblock copolymer PS-PVP-PEO was purchased from Polymer Source (Dorval, Canada). The number-average molar masses of PS, PVP, and PEO blocks were 2.1 x 10 , 1.2 x 10 , and 3.5 x 10 g mol , respectively, and the poly-dispersity index of the sample was 1.10. The copolymer is insoluble in aqueous media, but the micelles can be prepared indirectly both in acidic and alkaline aqueous solutions by dialysis from 1,4-dioxane-methanol mixtures [88]. The micelles can be transferred from acidic to alkaline alkaline solutions and vice versa, but the addition of a base together with intense stirring promotes aggregation. Two factors contribute to the destabilization of micelles after the pH increase (a) In alkaline media, the PVP blocks become insoluble, collapse and form an upper layer of the core. Since the cores of micelles are kinetically frozen, the association number does not change. The mass of insoluble cores increases, while the length of soluble shellforming chains decreases, which results in a deteriorated thermodynamic stability of micellar solutions, (b) The PVP middle layer shrinks and PEO chains come close to each other, which worsens the solubility due to insufficient solvation of PEO blocks. 

Microemulsions and surfactant-stabilized (macro) emulsions are distinctively different with respect to thermodynamic stability and, therefore, while most significant for both types of systems, the role of studies of phase behavior is different in the two cases. For emulsions we are con-eemed with two- or multi-phase regions in the phase diagrams, and for microemulsions with one-phase regions. Beeause of that micro emulsion studies are closely related to studies of other thermo-dynamically stable phases, notably liquid crystalline phases and micellar solutions. Structural models of microemulsions have to a considerable extent been advanced on the basis of our understanding of other stable phases the formation and stability of a micro-emulsion phase for a certain surfactant results from the comope-tition with alternative phases. The principal differences between micro emulsions and emulsions, together with the related nomenclature, is bound to lead to considerable confusion for example, the persistence in literature of emulsion-based structural pictures of microemulsions can be traced to the related names. However, the term microemulsions is kept for historical reasons. 

Further experimental and theoretical investigations are expected to give us a better understanding of the existence of low interfacial tensions and of the thermodynamic stability of the phases. Indeed, interfacial tensions can be related theoretically to micellar interactions in bulk phases (3). The role of surface viscosity is less clear. But it probably influences the phase stability as it happens for ordinary emulsions. 

Microemulsion/Micellar Flooding. Microemulsions are stable emulsions of hydrocarbons and water in the presence of surfactants and co-surfactants. They are characterized by spontaneous formation, ultra-low interfacial tension, and thermodynamic stability. The wide-spread... 

Another, more recent example by Rodriguez-Hornedo and co-workers elegantly displayed how micellar additives, such as surfactants, can bring thermodynamic stability to unstable co-crystal phases. An incongruently dissolving carbamazepine salicyclic acid co-crystal was tested and it was found that by introducing various concentrations of aqueous solutions of sodium lauryl sulfate (surfactant), a congruently saturated system resulted. 

Dijferential solubilization, where micelles interact preferentially with one of the co-crystal components, is the underlying mechanism by which otherwise unstable co-crystals achieve thermodynamic stability in micellar solutions. This concept was recently reported and applied to describe the behavior of several co-crystals." " Pharmaceutical co-crystals generally comprise a hydrophobic drug and a relatively hydrophilic co-former, thus, differential solubilization may be widely encountered. This finding has important implications for the characterization of co-crystal solution behavior and can lead to huge errors in the evaluation of co-crystal solubility and dissolution if not recognized. 

Finite amounts of glycerol (its viscosity is 945 cP at 25°C) can be dispersed in AOT/heptane or in CTAB/heptane + chloroform systems. The resulting solutions consist of thermodynamically stable, spherical droplets of glycerol stabilized by the surfactant [33,235]. The presence of glycerol within the micellar core results in a reduction of the surfactant mobility [137]. 

The reaction described in this example is carried out in miniemulsion.Miniemulsions are dispersions of critically stabilized oil droplets with a size between 50 and 500 nm prepared by shearing a system containing oil, water,a surfactant and a hydrophobe. In contrast to the classical emulsion polymerization (see 5ect. 2.2.4.2), here the polymerization starts and proceeds directly within the preformed micellar "nanoreactors" (= monomer droplets).This means that the droplets have to become the primary locus of the nucleation of the polymer reaction. With the concept of "nanoreactors" one can take advantage of a potential thermodynamic control for the design of nanoparticles. Polymerizations in such miniemulsions, when carefully prepared, result in latex particles which have about the same size as the initial droplets.The polymerization of miniemulsions extends the possibilities of the widely applied emulsion polymerization and provides advantages with respect to copolymerization reactions of monomers with different polarity, incorporation of hydrophobic materials, or with respect to the stability of the formed latexes. 

Menger et al. synthesized a Ci4H29-attached copper(II) complex 3 that possessed a remarkable catalytic activity in the hydrolysis of diphenyl 4-nitrophenyl phosphate (DNP) and the nerve gas Soman (see Scheme 2) [21], When 3 was used in great excess (ca. 1.5 mM, which is more than the critical micelle concentration of 0.18 mM), the hydrolysis of DNP (0.04 mM) was more than 200 times faster than with an equivalent concentration of the nonmicellar homo-logue, the Cu2+-tetramethylethylenediamine complex 9, at 25°C and pH 6 (Scheme 4). The DNP half-life is calculated to be 17 sec with excess 1.5 mM 3 at 25°C and pH 6. The possible reasons for the rate acceleration with 3 were the enhanced electrophilicity of the micellized copper(II) ion or the acidity of the Cu2+-bound water and an intramolecular type of reaction due to the micellar formation. On the basis of the pH(6-8.3)-insensitive rates, Cu2+-OH species 3b (generated with pK3 < 6) was postulated to be an active catalytic species. In this study, the stability constants for 3 and 9 and the thermodynamic pvalue of the Cu2+-bound water for 3a —> 3b + H+ were not measured, probably because of complexity and/or instability of the metal compounds. Therefore, the question remains as to whether or not 3b is the only active species in the reaction solution. Despite the lack of a detailed reaction mechanism, 3 seems to be the best detoxifying reagent documented in the literature. 

A special kind of stabilized emulsion in which the dispersed droplets are extremely small (<100 nm) and the emulsion is thermodynamically stable. These emulsions are transparent and can form spontaneously. In some usage a lower size-limit of about 10 nm is implied in addition to the upper limit see also Micellar Emulsion. In some usage the term microemulsion is reserved for a Winsor type IV system (water, oil, and surfactants all in a single phase). See also Winsor Type Emulsions. 

Ti icroemulsions are transparent thermodynamically stable colloidal dispersions containing high amounts of both water and hydrocarbons. The colloidal state is stabilized by a proper balance between a hydrophobic and a hydrophilic surfactant. Initially microemulsions were considered to be different from colloidal solutions (I, 2, 3, 4, 5) an opinion that is still held by some (6) although it is accepted generally that microemulsions belong to micellar systems (7, 8, 9, 10). 

This chapter deals almost exclusively with neat, or pure, diblock copolymer melts. Polymer blends are discussed in Chapter 9, micellar solutions in Chapter 12, and stabilized suspensions in Chapter 6. In the following, Section 13.2 briefly reviews the thermodynamics of block copolymers, and Section 13.3 describes the rheological properties and flow alignment of lamellae, cylinders, and sphere-forming mesophases of block copolymers. More thorough reviews of the thermodynamics and dynamics of block copolymers in the liquid state have been written by Bates and Fredrickson (1990 Fredrickson and Bates 1996). The processing of block copolymers and mechanical properties of the solid-state structures formed by them are covered in Folkes (1985). Biological applications are discussed in Alexandridis (1996). 

Microemulsions were initially considered to be a special case of emulsions, i.e., kinetically stable dispersions of two mutually immiscible solvents, although of an unusually high stability They are clear, seemingly one-phase systems and can be prepared without considerable input of mechanical energy. As they are thermodynamically stable, however, it is more plausible to conceive of microemulsions as being aggregated (micellar or swollen micellar) solutions [5],... 

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