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乳液稳定性,从稀乳液到浓乳液——液滴变形的作用

Emulsions stability, from dilute to dense emulsions -- role of drops deformation.

作者信息

Sanfeld Albert, Steinchen Annie

机构信息

Thermodynamique-Systèmes Chimiques Complexes-UMR 6171-Faculté des Sciences de Saint Jérôme-Bd Escadrille Normandie-Niemen, 13397 Marseille Cedex 20-France.

出版信息

Adv Colloid Interface Sci. 2008 Jul 1;140(1):1-65. doi: 10.1016/j.cis.2007.12.005. Epub 2008 Jan 11.

DOI:10.1016/j.cis.2007.12.005
PMID:18313631
Abstract

The present paper starts with a review of fundamental descriptions based on physico-chemical laws derived for emulsions with a special interest for eventual evidences of drops deformation. A critical analysis of theories and experiments is given that leads the authors to propose new static and dynamic models for the approach to flocculation and coalescence of two deformable drops in dense and dilute environments of other neighboring drops. The model developed is based on an old paper by Albers and Overbeek for W/O dense emulsions with non-deformable particles, that has been improved recently first by Sengupta and Papadopoulos and then by Mishchuk et al. to account for all the interaction forces (electrostatic, van der Waals and steric). The basic idea here rests in the assumption that the flat surface area of the two coalescing drops, interacting in the field of other particles, increases when the distance between the particles decreases according to an exponential law with a characteristic length related to the disjoining force in the inter-particle film and to the capillary pressure that opposes flattening. The difficulty lies, indeed, in manifold interpretations on experimental observations so that no clear conclusion can be derived on mechanisms responsible for the deformation of droplets. This is why, from a pure theoretical and physical point of view, according to rather complicated models, we propose a much more simple approach that permits to define a capillary length as part of virtual operations. In a static approach, this length is based on analogy with electricity, namely repulsion leads to flatness while attraction to hump. Therefore this brings us to a definition of a length depending on the maximum value of the disjoining pressure in competition with the capillary pressure. Gravity also promotes flocculation, therefore we compare the maximum values of the surface forces acting between the surfaces of two floculating particles to gravity. Finally, considering that in most publications on emulsions foams and colloidal systems, much attention is paid on the role of the drainage in the stability process, we devote the last section to the drainage between flattened drops. We first describe briefly Taylor's approach and extend Reynolds revisited formulae taking into account the viscous friction, the disjoining pressure, the film elasticity and the wetting angle weighting the capillary pressure through the characteristic length. Our calculated values are compared to some experimental data. In conclusion to make this long paper as useful as possible for research purposes, we have the hope that our understanding of emulsion stability is not only based on knowledge of numerous theoretical and experimental works sometimes controversial given in a critical way but that it gives a new approach based on an interpretation of the drop deformation in terms of a characteristic length linked to a deformation number analogous to a Bond number.

摘要

本文首先回顾了基于物理化学定律对乳液的基本描述,特别关注液滴变形的最终证据。对理论和实验进行了批判性分析,这使作者提出了新的静态和动态模型,用于研究在其他相邻液滴的密集和稀疏环境中两个可变形液滴的絮凝和聚结过程。所开发的模型基于阿尔伯斯和奥弗贝克关于不可变形颗粒的W/O密集乳液的一篇旧论文,该论文最近首先由森古普塔和帕帕多普洛斯改进,然后由米舒克等人改进,以考虑所有相互作用力(静电、范德华力和空间位阻)。这里的基本思想基于这样一个假设:在其他颗粒的场中相互作用的两个聚结液滴的平坦表面积,会随着颗粒间距离的减小而增加,其增加规律符合指数定律,该指数定律中的特征长度与颗粒间薄膜中的分离力以及阻碍变平的毛细压力有关。实际上,难点在于对实验观察结果有多种解释,以至于无法就导致液滴变形的机制得出明确结论。这就是为什么从纯粹的理论和物理角度出发,根据相当复杂的模型,我们提出了一种更为简单的方法,该方法允许将毛细长度定义为虚拟操作的一部分。在静态方法中,这个长度基于与电学的类比,即排斥导致变平,而吸引导致隆起。因此,这使我们得出一个取决于分离压力与毛细压力竞争时的最大值的长度定义。重力也促进絮凝,因此我们将两个絮凝颗粒表面之间作用的表面力的最大值与重力进行比较。最后,考虑到在大多数关于乳液、泡沫和胶体系统的出版物中,人们非常关注排水在稳定性过程中的作用,我们在最后一节专门讨论扁平液滴之间的排水问题。我们首先简要描述泰勒的方法,并扩展雷诺重新审视的公式,同时考虑粘性摩擦、分离压力、薄膜弹性以及通过特征长度加权毛细压力的接触角。我们将计算值与一些实验数据进行了比较。总之,为了使这篇长文对研究尽可能有用,我们希望我们对乳液稳定性的理解不仅基于对众多有时存在争议的理论和实验工作的批判性了解,而且还基于一种新的方法,该方法基于根据与类似于邦德数的变形数相关的特征长度对液滴变形的解释。

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