Department of Chemical and Biological Engineering, Illinois Institute of Technology , Chicago, Illinois 60616, United States.
Langmuir. 2016 May 17;32(19):4837-47. doi: 10.1021/acs.langmuir.6b00561. Epub 2016 May 6.
Thin liquid films containing surfactant micelles or other nanocolloidal particles are considered to be the key structural elements of foams containing gas and liquid. We report here the experimental results and theoretical modeling for the phenomenon of the stratification (stepwise thinning) of a foam film formed from a nonionic micellar solution. The film stratification phenomenon was experimentally observed by reflected light microinterferometry. We observed that the stepwise layer-by-layer decrease of the film thickness is due to the appearance and growth of a dark spot of one layer less than the film thickness in the film. The dark spot expansion is driven by the diffusion of the dislocation (or vacancy) in the micellar lattice. The vacancies from the meniscus diffuse and condense into the dark spot, leading to its expansion inside the film. We experimentally observed the expansion of the dark spot at various film thicknesses (i.e., the number of micellar layers) and at different film sizes. We also measured the contact angle between the film and the meniscus; we used the data to estimate the structural film interaction energy barrier and the apparent diffusion coefficient. We used the two-dimensional diffusion model to model the dynamics of the dark spot expansion with consideration to the apparent diffusion coefficient and the film size. The model predictions are in good agreement with the experimental observations. On the basis of this model, we carried out a parametric study depicting the effects of the film thickness (or the number of micellar layers) and film area on the rate of the dark spot expansion. We also generalized the model previously proposed by Kralchevsky et al. [ Langmuir 1990 , 6 , 1180 - 1189 ], incorporating the effects of the film size, film thickness, and apparent diffusion coefficient to predict the dark spot expansion rate.
含有表面活性剂胶束或其他纳米胶体颗粒的薄液膜被认为是含有气液的泡沫的关键结构单元。我们在这里报告了非离子胶束溶液形成的泡沫膜分层(逐步变薄)现象的实验结果和理论建模。通过反射光微干涉法实验观察到了膜分层现象。我们观察到,膜厚度的逐步逐层减少是由于在膜中出现并生长出一个比膜厚度少一层的暗斑。暗斑的扩展是由位错(或空位)在胶束晶格中的扩散驱动的。来自弯月面的空位扩散并凝聚到暗斑中,导致其在膜内扩展。我们在各种膜厚度(即胶束层数)和不同膜尺寸下实验观察到暗斑的扩展。我们还测量了膜与弯月面之间的接触角;我们使用这些数据来估计结构膜相互作用能垒和表观扩散系数。我们使用二维扩散模型来模拟暗斑扩展的动力学,考虑到表观扩散系数和膜尺寸。模型预测与实验观察结果吻合良好。在此模型的基础上,我们进行了参数研究,描述了膜厚度(或胶束层数)和膜面积对暗斑扩展速率的影响。我们还推广了 Kralchevsky 等人提出的模型[Langmuir, 1990, 6, 1180-1189],将膜尺寸、膜厚度和表观扩散系数的影响纳入其中,以预测暗斑扩展速率。