Martula DS, Hasegawa T, Lloyd DR, Bonnecaze RT
Department of Chemical Engineering, The University of Texas at Austin, Austin, Texas, 78712
J Colloid Interface Sci. 2000 Dec 15;232(2):241-253. doi: 10.1006/jcis.2000.7179.
A comprehensive simulation of the coarsening mechanism coalescence-induced coalescence (CIC) is developed to predictthe growth rate of inviscid droplets in a viscous matrix fluid. In CIC, the shape relaxations of coalescing droplets establish flow fields that drive other droplets into contact, thus creating a cascade of coalescence events. It is believed that CIC is responsible for droplet growth in some demixed polymer solutions, such as isotactic polypropylene (iPP) and diphenyl ether (DPE). A cascade of coalescence events is simulated using a three-dimensional molecular dynamics-like simulation of a dispersed two-phase isopycnic fluid system. The coalescence-induced flow is driven mostly by the strong gradients in curvature at the neck of a coalescing pair of droplets, and the flow is modeled analytically by approximating it as due to a ring of point forces. The resultant velocity of each droplet in the suspension is calculated by superimposing all of the coalescence-induced flow fields and applying Faxen's Law. The mean droplet size grows like t(xi), where t is the coarsening time and xi a growth exponent that increases with increasing minority phase volume fraction varphi. Good agreement with experimental values of xi (0.22<xi<0.47) is obtained for a phase-separated iPP-DPE solution for varphi>/=0.23. It is also shown that the droplet size distribution broadens for semidilute suspensions (varphi</=0.42) but remains relatively narrow for highly concentrated suspensions (varphi>/=0.54). A phenomenological kinetic theory of coalescence is proposed. It is believed that in nondilute emulsions, CIC can account for coarsening that has been attributed previously to more traditional coalescence mechanisms. Copyright 2000 Academic Press.
开展了对聚并诱导聚并(CIC)粗化机制的全面模拟,以预测粘性基体流体中无粘性液滴的生长速率。在CIC中,聚并液滴的形状弛豫建立了驱动其他液滴接触的流场,从而引发一系列聚并事件。据信,CIC是某些相分离聚合物溶液(如全同立构聚丙烯(iPP)和二苯醚(DPE))中液滴生长的原因。使用分散两相等密度流体系统的三维分子动力学类模拟来模拟一系列聚并事件。聚并诱导的流动主要由聚并液滴对颈部强烈的曲率梯度驱动,并且通过将其近似为由点力环引起的流动来进行解析建模。通过叠加所有聚并诱导的流场并应用法克森定律来计算悬浮液中每个液滴的合成速度。平均液滴尺寸〈a〉的增长类似于t(xi),其中t是粗化时间,xi是随少数相体积分数varphi增加而增大的生长指数。对于varphi≥0.23的相分离iPP - DPE溶液,xi的模拟值(0.22<xi<0.47)与实验值吻合良好。还表明,对于半稀悬浮液(varphi≤0.42),液滴尺寸分布变宽,但对于高浓度悬浮液(varphi≥0.54),液滴尺寸分布仍相对较窄。提出了一种聚并的唯象动力学理论。据信,在非稀乳液中,CIC可以解释先前归因于更传统聚并机制的粗化现象。版权所有2000年学术出版社。