This work continues a numerical kinetic modeling of temporal behavior of concentrations of surfactant monomers and aggregates in solutions with coexisting premicellar aggregates, spherical and cylindrical micelles started in the serial of our papers1-3. Our analysis is based on a discrete form of the Becker-Döring kinetic equations for surfactant aggregation in polar solvent with the Smoluchowsky diffusion model for the attachment rates of surfactant monomers to surfactant aggregates with matching the rates for spherical and large cylindrical micelles. Here we report the kinetic regularities of micellization and relaxation at arbitrary initial state of the micellar system, when final equilibrium state of the system can be considerably different from the initial one. Thus we consider the non-linear effects at self-aggregation which can not be described within the frameworks of linear relaxation approach. The results of our computations have been compared with the analytical ones (known in the limiting cases from solutions of the continuous Becker-Döring kinetic equation) and demonstrated a fair agreement even in the vicinity of the cmc2 where the analytical theory looses formally it applicability.
This work was supported by St. Petersburg State University (grant 11.37.183.2014) and grant RFBR 13-03-00991a.
References
1Babintsev, I.A.; Adzhemyan, L.Ts.; Shchekin A.K. J. Chem. Phys., 137, 044902 (2012).
2Babintsev, I.A.; Adzhemyan, L.Ts.; Shchekin A.K. Soft Matter, 10, 2619 (2014).
3Babintsev, I.A.; Adzhemyan, L.Ts.; Shchekin A.K. arXiv:1404.3818 [cond-mat.soft] (2014).
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