Cho Noah H, Riley John K, Richards Jeffrey J
Department of Chemical Engineering, Northwestern University, Evanston, Illinois 60208, United States.
Performance Materials & Coatings, The Dow Chemical Company, Collegeville, Pennsylvania 19426, United States.
J Phys Chem B. 2021 Oct 7;125(39):11067-11077. doi: 10.1021/acs.jpcb.1c06032. Epub 2021 Sep 22.
The rheology of wormlike micelle (WLM) solutions is tunable by engineering the micellar structure and topology. While much is known about how microscopic properties influence the rheological characteristics, questions remain regarding the quantification of fast relaxation processes, including Rouse and rotational modes. These fast processes are challenging to access using mechanical spectroscopy as bending modes dominate high-frequency mechanical measurements. In this work, we demonstrate the use of dielectric spectroscopy (DES) to directly interrogate these fast relaxation modes in solutions containing reverse WLMs. These consist of lecithin solutions in -decane swollen with water. We develop an equivalent circuit model that separates the fast spectral features from the low-frequency processes and show that this relaxation feature is consistent with a combination of high-frequency Rouse and rotational modes. Further, we show that the low-frequency response is not determined by polymer dynamics alone. These findings demonstrate the potential of DES measurements to describe WLM behavior and pave the way toward in situ measurements under steady and transient shear flow.
通过设计胶束结构和拓扑结构,蠕虫状胶束(WLM)溶液的流变学特性是可调节的。虽然人们对微观性质如何影响流变学特性已经了解很多,但关于快速弛豫过程(包括Rouse模式和旋转模式)的量化仍存在问题。使用机械光谱法获取这些快速过程具有挑战性,因为弯曲模式主导了高频机械测量。在这项工作中,我们展示了使用介电光谱法(DES)直接研究含有反向WLM的溶液中的这些快速弛豫模式。这些溶液由在癸烷中用水溶胀的卵磷脂溶液组成。我们开发了一个等效电路模型,将快速光谱特征与低频过程分离,并表明这种弛豫特征与高频Rouse模式和旋转模式的组合一致。此外,我们表明低频响应并非仅由聚合物动力学决定。这些发现证明了DES测量在描述WLM行为方面的潜力,并为在稳态和瞬态剪切流下的原位测量铺平了道路。