Work

Calcium-Regulated Self-Assembly of Zwitterionic/Cationic Surfactant–Counterion Complexes: Molecular Dynamics Insights into the Suppression of Wormlike Micelle Growth

Year: 2026

Type: article

Abstract: Wormlike micelles provide the structural basis for the viscoelasticity of clean fracturing fluids, yet the molecular mechanism by which calcium-containing brine regulates their growth remains insufficiently understood. In this work, all-atom molecular dynamics simulations were performed to investigate the calcium-regulated self-assembly of an EAHSB/EHAC/NaPts surfactant–counterion system. In the absence of Ca2+, dispersed surfactant and counterion molecules first formed small spherical aggregates, which subsequently fused into larger micelles, rod-like intermediates, and finally wormlike micelles. Increasing the local surfactant/counterion loading further promoted one-dimensional micellar growth and network-like association. When Ca2+ was introduced, the assembly process became slower and the final aggregate morphology shifted from elongated wormlike micelles to smaller spherical aggregates. Radial distribution functions and coordination-number analysis show that Ca2+ redistributes charged-group correlations within the mixed surfactant/counterion assemblies. Hydration analysis indicates enlarged polar hydration shells, whereas hydrophobic-tail hydration and gauche-defect probabilities reveal enhanced tail exposure and looser chain packing. These results demonstrate that Ca2+ suppresses wormlike micelle growth through coupled electrostatic redistribution, interfacial hydration, and hydrophobic-chain disorder, thereby favoring high-curvature spherical aggregates over extended wormlike networks.

Source: Molecules

DOI: 10.3390/molecules31142490