Mason T G, Graves S M, Wilking J N, Lin M Y
Department of Chemistry and Biochemistry, California NanoSystems Institute, University of California-Los Angeles, Los Angeles, California 90095, USA.
J Phys Chem B. 2006 Nov 9;110(44):22097-102. doi: 10.1021/jp0601623.
Extreme osmotic compression of nanoemulsion droplets, achieved by ultracentrifugation, can create solidlike biliquid foams without causing significant droplet coalescence. Using small-angle neutron scattering (SANS), we probe the structure of a uniform silicone oil-in-water nanoemulsion stabilized by sodium dodecyl sulfate over a wide range of volume fractions, phi, up to and beyond the limit associated with maximal random jamming of spheres, phiMRJ = 0.64. Although some features in the structure can be understood at lower phi using simple predictions for hard spheres, the anionic repulsion and deformability of the droplet interfaces creates departures from these predictions at higher phi. For phi near and beyond phiMRJ, the effective structure factor, Seff, as a function of wavenumber, q, exhibits a primary peak that is subunity. We speculate that this striking feature is due to the deformation of the droplets into nonspherical shapes as the system begins to approach the limit of a random array of nanoscopic thin films, Plateau borders, and vertexes characteristic of a polyhedral foam.
通过超速离心实现的纳米乳液液滴的极端渗透压压缩,可以产生类似固体的双液泡沫,而不会导致明显的液滴聚并。使用小角中子散射(SANS),我们在很宽的体积分数范围内,即高达并超过与球体最大随机堵塞相关的极限(φMRJ = 0.64),探测了由十二烷基硫酸钠稳定的均匀水包硅油纳米乳液的结构。尽管在较低的φ值下,使用硬球的简单预测可以理解结构中的一些特征,但液滴界面的阴离子排斥和可变形性在较高的φ值下导致了与这些预测的偏差。对于接近和超过φMRJ的φ值,有效结构因子Seff作为波数q的函数,呈现出一个小于1的主峰。我们推测,这一显著特征是由于随着系统开始接近纳米级薄膜、普拉托边界和多面体泡沫特征顶点的随机阵列极限,液滴变形为非球形形状所致。