Theory of micellization

Nagarajan R. Theory of micelle formation quantitative approach to predicting micellar properties from surfactant molecular structure. Surface Sci Ser 1997 70 1-81. 

Tanford, C. (1974),Theory of micelle formation in aqueous solutions,/. Phys. Chem., 78, 24. 

Critical micelle concentration ( >cmc is expected to decrease strongly with diminished diblock asymmetry rc as low rc values favor easier creation of highly curved micelle interfaces. Theory of micelle formation [231,260] also indicates that the overall copolymer degree of polymerization Nc, as well as the anchor -homopolymer interaction parameter %AP have to be considered to explain properly the onset of micelle segregation as observed by Shull et al. [260]. Using this theory, experimenters are able to choose systems where only individual copolymers segregate. 

Scaling Theory of Micelles with Polyelectrolyte Corona. 78... 

It is usually observed that the critical micelle concentration for a surfactant is relatively sharp and characteristic. Although the detailed theory of micelle formation can become quite complex, the sharpness of the cmc can be explained conceptually in terms of the law of mass action. If Q denotes the total concentration of surfactant in solution, Q the fraction of surfactant present as free molecules, and Cm that in the aggregated state. Equation (15.3) may be written... 

M.D. Whitmore, J. Noolandi, Theory of micelle formation in block copolymer-homopolymer blends, Macromolecules 18 (1985) 657-665. 

The scaling theory of micelles formed by block copolymers with a nonionic soluble block has been developed in References 181-185. 

The first meaningfnl stndies on the kinetics of dynamic processes within micellar solutions, which looked at dissociation rates via temperature-jump (T-jump) and related techniqnes, were carried out in the 1960s. The first notable attempt at a complete theory of micellization kinetics was the work of Kresheck et al. [77], who proposed a stepwise surfactant aggregation model based on a monodisperse system, where all micelles have the same aggregation nnmber, n. However, this model found... 

The formation of ME systems can be explained with reference to the self-assembly theory of micelle and bilayer forming surfactant molecules where the volume of the surfactant is denoted v, its head group surface area a, and its... 

Pollard, M. L. and Radke, C. J., Density functional theory of micelle structuring in thin micellar liquid films, J. Chem. Phys., 8, 6979-6985 (1994). 

Two main approaches to the thermodynamic analysis of the micellization process have gained wide acceptance. In the phase separation approach the micelles are considered to form a separate phase at the CMC, whilst in the mass-action approach micelles and unassociated monomers are considered to be in association-dissociation equilibrium. In both of these treatments the micellization phenomenon is described in terms o.f the classical system of thermodynamics. Theories of micelle formation based on statistical mechanics have also been proposed [16Q-162] but will not be considered further. The application of the mass-action and phase-separation models to both ionic and non-ionic micellar systems will be briefly outlined and their limitations discussed. More recent developments in this field will be presented. 

In this section we consider the formation of micelles when AB diblock copolymers are placed in a solvent that is good for A but bad for B. Many of the theories specialize to the case when the solvent is the homopolymer A. First of all we review some basic theory of micelle formation. For a given number of copolymer chains in the solvent, there will exist a chemical equilibrium between isolated chains and all clusters of two or more chains. In dilute solution, where interactions between micelles and single copolymer chains may be neglected, one obtains the result... 

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