Vratsanos Maria A, Xue Wangyang, Rosenmann Nathan D, Zarzar Lauren D, Gianneschi Nathan C
Department of Materials Science & Engineering, Northwestern University, Evanston, Illinois 60208, United States.
Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States.
ACS Cent Sci. 2023 Mar 8;9(3):457-465. doi: 10.1021/acscentsci.2c01194. eCollection 2023 Mar 22.
Herein, we present the direct observation via liquid-phase transmission electron microscopy (LPTEM) of the nucleation and growth pathways of structures formed by the so-called "ouzo effect", which is a classic example of surfactant-free, spontaneous emulsification. Such liquid-liquid phase separation occurs in ternary systems with an appropriate cosolvent such that the addition of the third component extracts the cosolvent and makes the other component insoluble. Such droplets are homogeneously sized, stable, and require minimal energy to disperse compared to conventional emulsification methods. Thus, ouzo precipitation processes are an attractive, straightforward, and energy-efficient technique for preparing dispersions, especially those made on an industrial scale. While this process and the resulting emulsions have been studied by numerous indirect techniques (e.g., X-ray and light scattering), direct observation of such structures and their formation at the nanoscale has remained elusive. Here, we employed the nascent technique of LPTEM to simultaneously evaluate droplet growth and nanostructure. Observation of such emulsification and its rate dependence is a promising indication that similar LPTEM methodologies may be used to investigate emulsion formation and kinetics.
在此,我们通过液相透射电子显微镜(LPTEM)直接观察了由所谓“茴香酒效应”形成的结构的成核和生长途径,这是无表面活性剂自发乳化的经典例子。这种液-液相分离发生在具有适当助溶剂的三元体系中,使得第三种组分的加入提取了助溶剂并使另一种组分不溶。与传统乳化方法相比,此类液滴尺寸均匀、稳定,且分散所需能量极小。因此,茴香酒沉淀过程是一种制备分散体的有吸引力、直接且节能的技术,尤其是在工业规模上制备的分散体。虽然该过程及所得乳液已通过众多间接技术(如X射线和光散射)进行了研究,但在纳米尺度上直接观察此类结构及其形成仍难以实现。在此,我们采用了新兴的LPTEM技术来同时评估液滴生长和纳米结构。对这种乳化及其速率依赖性的观察表明,类似的LPTEM方法有望用于研究乳液形成和动力学。