Salager Jean-Louis, Marquez Ronald, Rondón Miguel, Bullón Johnny, Graciaa Alain
Laboratorio FIRP, Universidad de Los Andes, Mérida 5101, Venezuela.
Universidad Industrial de Santander, Bucaramanga 680002, Colombia.
ACS Omega. 2023 Mar 2;8(10):9040-9057. doi: 10.1021/acsomega.3c00547. eCollection 2023 Mar 14.
Fundamental studies have improved understanding of molecular-level properties and behavior in surfactant-oil-water (SOW) systems at equilibrium and under nonequilibrium conditions. However, confusion persists regarding the terms "microemulsion" and "curvature" in these systems. Microemulsion refers to a single-phase system that does not contain distinct oil or water droplets but at least four different structures with globular domains of nanometer size and sometimes arbitrary shape. The significance of "curvature" in such systems is unclear. At high surfactant concentrations (typically 30 wt % or more), a single phase zone has been identified in which complex molecular arrangements may result in light scattering. As surfactant concentration decreases, the single phase is referred to as a bicontinuous microemulsion, known as the middle phase in a Winsor III triphasic system. Its structure has been described as involving simple or multiple surfactant films surrounding more or less elongated excess oil and water phase globules. In cases where the system separates into two or three phases, known as Winsor I or II systems, one of the phases, containing most of the surfactant, is also confusedly referred to as the microemulsion. In this surfactant-rich phase, the only curved objects are micellar size structures that are soluble in the system and have no real interface but rather exchange surfactant molecules with the external liquid phase at an ultrafast pace. The use of the term "curvature" in the context of these complex microemulsion systems is confusing, particularly when applied to merged nanometer-size globular or percolating domains. In this work, we discuss the terms "microemulsion" and "curvature", and the most simple four-dimensional spatiotemporal model is proposed concerning SOW equilibrated systems near the optimum formulation. This model explains the motion of surfactant molecules due to Brownian movement, which is a quick and arbitrary thermal fluctuation, and limited to a short distance. The resulting observation and behavior will be an average in time and in space, leading to a permanent change in the local microcurvature of the aggregate, thus changing the average from micelle-like to inverse micelle-like order over an extremely short time. The term "microcurvature" is used to explain the small variations of globule size and indicates a close-to-zero mean curvature of the surfactant-containing film surface shape.
基础研究增进了人们对表面活性剂 - 油 - 水(SOW)体系在平衡和非平衡条件下分子水平性质及行为的理解。然而,在这些体系中,“微乳液”和“曲率”这两个术语仍然存在混淆。微乳液是指一种单相体系,它不包含明显的油滴或水滴,而是至少有四种不同结构,具有纳米尺寸的球状区域,形状有时不规则。在这样的体系中,“曲率”的意义并不明确。在高表面活性剂浓度(通常为30 wt%或更高)下,已确定存在一个单相区,其中复杂的分子排列可能导致光散射。随着表面活性剂浓度降低,单相被称为双连续微乳液,在Winsor III三相体系中称为中间相。其结构被描述为涉及围绕或多或少拉长的过量油相和水相小球的简单或多个表面活性剂膜。当体系分离为两相或三相时,即Winsor I或II体系,其中一个含有大部分表面活性剂的相也被混淆地称为微乳液。在这个富含表面活性剂的相中,唯一的弯曲物体是胶束尺寸的结构,它们可溶于体系,没有真正的界面,而是以超快的速度与外部液相交换表面活性剂分子。在这些复杂的微乳液体系中使用“曲率”一词令人困惑,特别是当应用于合并的纳米尺寸球状或渗流区域时。在这项工作中,我们讨论了“微乳液”和“曲率”这两个术语,并针对接近最佳配方的SOW平衡体系提出了最简单的四维时空模型。该模型解释了由于布朗运动导致的表面活性剂分子运动,布朗运动是一种快速且任意的热涨落,且限于短距离。由此产生的观测和行为将是时间和空间上的平均值,导致聚集体局部微曲率的永久性变化,从而在极短的时间内将平均值从类似胶束的顺序改变为类似反胶束的顺序。术语“微曲率”用于解释小球尺寸的微小变化,并表示含表面活性剂膜表面形状的接近零的平均曲率。