Aggregation processes in self‐associating polymer systems: Computer simulation study of micelles in the superstrong segregation regime

We present the results of extensive molecular dynamics and Monte Carlo studies of the self-organization in the solution of short polymer chains with strongly attracting head groups at their end. The formation of micelles (multiplets) is studied in detail. Both two dimensional (2d) and three-dimensional (3d) systems are considered. The off-lattice and lattice models under study incorporate physical factors which control micelle structure and growth in the so-called superstrong segregation regime. These factors include (i) conformational effects associated with short-range excluded-volume interaction between the tails of flexible-chain molecules and (ii) very strong attraction of head groups. Our computer simulations of 3d micelles, constructed a priori from chains with strong attraction of head groups (with the characteristic energy ≈ 10 kBT), show that size and shape of the micellar core depends crucially on the radius rc of the interaction of head-groups. If the value of rc is comparable with chain length, then micelles of nearly spherical shape emerges. The decrease of rc can induce a sharp polymorphic transition from the micellar core which is spheric in shape to a disk-like (bilayer-shaped) aggregate. Such molecular organization differs from the commonly held notion of a radially symmetric micellar core. On the other hand, these findings fall into line with a recent theory of the super strong segregation regime. When the starting configuration is a random one (i.e., no micelles were a priori formed) the type of final microstructures, emerging as a result of micellization in the superstrong segregation regime, also depends essentially on the radius of head-head attraction. In the case of three-dimensional systems and/or short range attractive potentials we always obtain many small spherically shaped aggregates which, once formed at initial stages of micellization, remain stable for all time scales. Such a behavior is due to both the strong head-head attraction and the screening (repulsive) action of micellar shells creating insurmountable potential barriers. As a result, we deal with kinetically “frozen-in” microstructures which are not reversible and cannot exchange molecules with one another. In dense systems, we observe the formation of a (quasi) periodic pattern of alternating microdomains.