Structure and dynamics of an aqueous solution containing poly-(acrylic acid) and non-ionic surfactant octaethylene glycol n-decyl ether (C₁₀E₈) aggregates and their complexes investigated by molecular dynamics simulations.

Abstract

A detailed molecular dynamics simulation study of the self-assembly, intermolecular structure and thermodynamic behavior of an aqueous solution of non-ionic surfactant octa ethylene glycol n-decyl ether (C₁₀E₈) in the presence of a non-ionic polar polymer poly(acrylic acid) PAA is presented. The aggregation number N_agg and concentration of surfactant C_s in the simulation systems were varied in the range 0.01-0.32 M and 5 < N_agg < 101 (dilute to concentrated) with a dilute polymer concentration (C_p = 0.01 M). Lamellar aggregates of non-ionic surfactant in bulk aqueous solution are shown by molecular level computations for the first time. Spherical micellar aggregates and lamellar aggregates are formed at low and high N_agg, respectively. The transition from the spherical micelle phase to the lamellar phase in a binary solution is captured for the first time. A conformational transition from coiled to extended PAA chains adsorbed on the surfactant aggregate occurs at a particular value of N_agg, commensurate with the transition from spherical micelle aggregates to anisotropic lamellar aggregates. Formation of the surfactant aggregate in binary and ternary solutions and the polymer-surfactant complex in a ternary solution is enthalpically favored. Adsorption of PAA on the surfactant aggregate surface is driven by hydrogen bonds (HBs) between carboxylic acid groups of PAA and ethylene oxide groups of C₁₀E₈. A significant number of HBs occur between polar oxygens of C₁₀E₈ and hydroxyl oxygens of PAA. The results are in agreement with the limited available experimental data on this system.