Dipartimento di Fisica e Astronomia, Università di Padova, via Marzolo 8, I-35131 Padova, Italy.
Consiglio Nazionale delle Ricerche, Istituto dei Sistemi Complessi, via Madonna del Piano 10, I-50019 Sesto Fiorentino, Italy.
J Chem Phys. 2021 Dec 7;155(21):214905. doi: 10.1063/5.0072374.
A mean-field kinetic model suggests that the relaxation dynamics of wormlike micellar networks is a long and complex process due to the problem of reducing the number of free end-caps (or dangling ends) while also reaching an equilibrium level of branching after an earlier overgrowth. The model is validated against mesoscopic molecular dynamics simulations and is based on kinetic equations accounting for scission and synthesis processes of blobs of surfactants. A long relaxation time scale is reached with both thermal quenches and small perturbations of the system. The scaling of this relaxation time is exponential with the free energy of an end cap and with the branching free energy. We argue that the subtle end-recombination dynamics might yield effects that are difficult to detect in rheology experiments, with possible underestimates of the typical time scales of viscoelastic fluids.
平均场动态度量模型表明,由于在早期过度生长后,需要减少游离端盖(或悬垂端)的数量,同时达到分支的平衡水平,因此,蠕虫状胶束网络的弛豫动力学是一个漫长而复杂的过程。该模型通过介观分子动力学模拟进行了验证,并基于考虑了胶束状表面活性剂的断裂和合成过程的动力学方程。通过对系统进行热淬火和小扰动,达到了较长的弛豫时间尺度。该弛豫时间的标度与端盖的自由能以及分支自由能呈指数关系。我们认为,末端再结合动力学的微妙变化可能会导致流变学实验难以检测到的影响,从而可能低估了粘弹性流体的典型时间尺度。