Djerdjev Alex M, Beattie James K
School of Chemistry, University of Sydney, New South Wales 2006, Australia.
Langmuir. 2008 Aug 5;24(15):7711-7. doi: 10.1021/la800140s. Epub 2008 Jun 21.
The time dependence of the dynamic mobility and the ultrasonic attenuation of octane and decane oil-in-water emulsions stabilized by sodium dodecyl sulfate (SDS) was measured. The emulsions grew to larger droplets due to Ostwald ripening. The growth rate measured by attenuation depends on the surfactant concentration and the polydispersity of the emulsion. At surfactant concentrations below the critical micelle concentration (cmc) of SDS, the growth was linear with time and the rate was dependent on the polydispersity of the drops; the rate was several times faster than that predicted on the basis of a diffusion growth mechanism. Above the cmc, however, as the droplets grew in size there was a point at which the rate of growth increased, which corresponds to the droplet size at which depletion forces due to the surfactant micelles become significant. Under these conditions both the electroacoustic dynamic mobility and the acoustic attenuation spectra displayed characteristics of flocs: a large decrease in the phase lag at higher frequencies in the dynamic mobility spectrum and a decrease in the attenuation coefficient at low-megahertz frequencies with an increase at higher frequencies. This depletion flocculation enhancement in ripening rates in the presence of SDS micelles provides another, alternative, and self-consistent mechanism for the effect of surfactant micelles on Ostwald ripening.
测量了由十二烷基硫酸钠(SDS)稳定的辛烷和癸烷水包油乳液的动态迁移率和超声衰减的时间依赖性。由于奥斯特瓦尔德熟化,乳液会长大成更大的液滴。通过衰减测量的生长速率取决于表面活性剂浓度和乳液的多分散性。在表面活性剂浓度低于SDS的临界胶束浓度(cmc)时,生长与时间呈线性关系,且速率取决于液滴的多分散性;该速率比基于扩散生长机制预测的速率快几倍。然而,在cmc以上,随着液滴尺寸的增大,生长速率会在某一点增加,这对应于表面活性剂胶束引起的耗尽力变得显著时的液滴尺寸。在这些条件下,电声动态迁移率和声衰减谱都显示出絮凝物的特征:动态迁移率谱中高频处的相位滞后大幅降低,以及在低兆赫兹频率下衰减系数降低,在高频下增加。在存在SDS胶束的情况下,这种耗尽絮凝对熟化速率的增强为表面活性剂胶束对奥斯特瓦尔德熟化的影响提供了另一种、替代的且自洽的机制。