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从完全缠结的到部分缠结的蠕虫状胶束。

From well-entangled to partially-entangled wormlike micelles.

机构信息

Chemical Engineering, University of Michigan, Ann Arbor, MI 48109, USA.

Biomedical, Chemical, and Environmental Engineering, University of Cincinnati, Cincinnati, OH 45221, USA.

出版信息

Soft Matter. 2019 Jan 28;15(4):642-655. doi: 10.1039/c8sm02223b. Epub 2019 Jan 4.

Abstract

We combine mechanical rheometry, diffusing wave spectroscopy (DWS), and small angle neutron scattering (SANS) with a simulation model, the "pointer algorithm", to obtain characteristic lengths and time constants for wormlike micelle (WLM) solutions over a range of salt concentrations encompassing the transition from unentangled to entangled solutions. The solutions contain sodium lauryl ethylene glycol sulfate (SLE1S), cocamidopropyl betaine (CAPB), and NaCl. The pointer algorithm is extended to include relaxation of unentangled micelles, allowing micelle parameters to be extracted from the rheology of partially entangled solutions. DWS provides the data at high frequency needed to determine micelle persistence length accurately. From pointer algorithm fits to rheology, we observe a salt-induced rapid change in micellar length as the solution enters the well-entangled regime and a weaker growth with surfactant concentration consistent with mean-field theory. At a lower surfactant concentration, micelle length and persistence length from SANS are roughly consistent with values from rheology once the lower surfactant concentration used in SANS is accounted for. This is, to our knowledge, the first time that quantitative comparisons of structural features including micelle length are made between rheology and SANS. Finally, scaling laws for micelle diffusion and recombination times indicate that micelle kinetics are reaction controlled leading to mean-field recombination with surrounding micelles over the entire range of concentration of interest except at very low and very high surfactant concentrations where either short micelles or branched micelle clusters are dominant.

摘要

我们结合机械流变学、扩散波谱学 (DWS) 和小角中子散射 (SANS) 以及模拟模型“指针算法”,在涵盖无缠结到缠结溶液转变的一系列盐浓度范围内,获得了蠕虫状胶束 (WLM) 溶液的特征长度和时间常数。溶液中含有十二烷基聚氧乙烯醚硫酸钠 (SLE1S)、椰油酰胺丙基甜菜碱 (CAPB) 和 NaCl。指针算法扩展到包括无缠结胶束的弛豫,从而可以从部分缠结溶液的流变学中提取胶束参数。DWS 提供了在高频下确定胶束持久长度所需的数据。从指针算法对流变学的拟合中,我们观察到盐诱导的胶束长度快速变化,因为溶液进入完全缠结状态,并且随着表面活性剂浓度的增加,与平均场理论一致的胶束浓度较弱。在较低的表面活性剂浓度下,SANS 中的胶束长度和持久长度与流变学中的值大致一致,前提是考虑了 SANS 中使用的较低表面活性剂浓度。据我们所知,这是首次在流变学和 SANS 之间对包括胶束长度在内的结构特征进行定量比较。最后,胶束扩散和重组时间的标度定律表明,胶束动力学是反应控制的,导致在整个感兴趣的浓度范围内与周围胶束进行平均场重组,除了在非常低和非常高的表面活性剂浓度下,短胶束或支化胶束簇占主导地位。

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