A slip-spring framework to study relaxation dynamics of entangled wormlike micelles with kinetic Monte Carlo algorithm

[摘要] Hypothesis: Wormlike micelles (WLMs) formed due to the self-assembly of amphiphiles in aqueous solution have similar viscoelastic properties as polymers. Owing to this similarity, in this work, it is postulated that kinetic Monte Carlo (kMC) sampling of slip-springs dynamics, which is able to model the rheology of polymers, can also be extended to capture the relaxation dynamics of WLMs. Theory: The proposed modeling framework considers the following relaxation mechanisms: reptation, union-scission, and constraint release. Specifically, each of these relaxation mechanisms is simulated as separate kMC events that capture the relaxation dynamics while considering the living nature of WLMs within the slip-spring framework. As a case study, the model is implemented to a system of sodium oleate and sodium chloride to predict the linear rheology and the characteristic relaxation times associated with the individual relaxation mechanisms at different pH and salt concentrations. Findings: Linear rheology predictions were found to be in good agreement with experimental data. Furthermore, the calculated relaxation times highlighted that reptation contributed to a continuous increase in viscosity while union-scission contributed to the decrease in viscosity of WLM solutions at a higher salinity and pH. This manifests the proposed model's capability to provide insights into the key processes governing WLM's rheology. (c) 2021 Elsevier Inc. All rights reserved.

[发布日期] 2021-10-15

[关键词] Wormlike micelles;Slip-spring framework;Kinetic Monte Carlo;Relaxation dynamics;Linear rheology