Department of Chemical & Biological Engineering, Northwestern University, Evanston, Illinois 60208, United States.
Advanced Photon Source, Argonne National Laboratory, Argonne, Illinois 60439, United States.
ACS Macro Lett. 2022 Apr 19;11(4):575-579. doi: 10.1021/acsmacrolett.1c00651. Epub 2022 Apr 7.
Wormlike micelles (WLMs) are ubiquitous viscoelastic modifiers that share properties with polymer solutions. While their macroscopic rheology is well-understood, their microscopic dynamics remain difficult to measure because they span a large range of time and length scales. In this work, we demonstrate the use of X-ray photon correlation spectroscopy to interrogate the segmental dynamics of inverse WLM solutions swollen with a rubidium chloride solution. We observe a diffusive scaling of the dynamics and extract a temperature-dependent diffusion coefficient, which we associate with the thermal interactions of the slow segmental dynamics near entanglement points. We probe this relaxation process across the unbranched to branched topological transition and find no microstructural evidence of branch formation in the slow mode. Instead, we observe that the dynamics become more homogeneous and prominent as the temperature is reduced and water content increases.
蠕虫状胶束(WLMs)是无处不在的粘弹性改性剂,它们具有与聚合物溶液相同的性质。虽然它们的宏观流变学已经得到很好的理解,但它们的微观动力学仍然难以测量,因为它们跨越了很大的时间和长度尺度。在这项工作中,我们展示了使用 X 射线光子相关光谱技术来研究反蠕虫状胶束溶液的分子动力学,这些溶液被氯化铷溶液溶胀。我们观察到动力学的扩散标度,并提取出与缠结点附近慢分子动力学的热相互作用相关的温度依赖性扩散系数。我们在无支化到支化拓扑转变的过程中探测这个弛豫过程,没有发现慢模中支化形成的微观结构证据。相反,我们观察到随着温度降低和含水量增加,动力学变得更加均匀和突出。