Department of Statistical Physics, Faculty of Physics, St Petersburg State University, Ulyanovskaya 1, Petrodvoretz, St Petersburg 198504, Russia.
J Chem Phys. 2012 Jul 28;137(4):044902. doi: 10.1063/1.4737130.
A numerical description of micellization and relaxation to an aggregate equilibrium in surfactant solution with nonionic spherical micelles has been developed on the basis of a discrete form of the Becker-Döring kinetic equations. Two different models for the monomer-aggregate attachment-detachment rates have been used, and it has been shown that the results are qualitatively the same. The full discrete spectrum of characteristic times of micellar relaxation and first relaxation modes in their dependence on equilibrium monomer concentration have been found with using the linearized form of the Becker-Döring kinetic equations. Overall time behavior of surfactant monomer and aggregate concentrations in micellization and relaxation at large initial deviations from final equilibrium has been studied with the help of nonlinearized discrete Becker-Döring kinetic equations. Comparison of the computed results with the analytical ones known in the limiting cases from solutions of the linearized and nonlinearized continuous Becker-Döring kinetic equation demonstrates general agreement.
已基于 Becker-Döring 动理论的离散形式，发展了关于含有非离子球形胶束的表面活性剂溶液中的胶束化和弛豫到聚集平衡的数值描述。已使用两种不同的单体-胶束附着-脱附速率模型，结果表明它们在质上是相同的。使用 Becker-Döring 动理论线性化形式，找到了胶束弛豫的完整离散特征时间谱以及它们对平衡单体浓度的第一弛豫模式。借助非线性离散 Becker-Döring 动理论，研究了在远离最终平衡的初始较大偏差下，表面活性剂单体和胶束在胶束化和弛豫过程中的总时间行为。与已知线性化和非线性化连续 Becker-Döring 动理论解的极限情况下的分析结果的比较表明，总体上是一致的。
