论文标题

干燥胶体悬浮液的动态密度功能理论:硬球自由能功能的比较

Dynamic density functional theory for drying colloidal suspensions: Comparison of hard-sphere free-energy functionals

论文作者

Kundu, Mayukh, Howard, Michael P.

论文摘要

动态密度功能理论(DDFT)是一种预测包含一种或多种类型的胶体颗粒的干燥悬浮液的结构演化的有前途的方法。假定的自由能函数是DDFT的关键组成部分,该功能决定了模型的热力学,进而决定了由于浓度梯度而引起的密度通量。在这项工作中,我们比较了几种常用的自由能功能,用于干燥硬球悬浮液,包括基于理想气体,病毒式和bublousík-Mansoori-Carnahan-Starnahan-Starnahan-Starnahan-Starnahan-Starnahan-Starnahan-Starnahan-Starnahan-Starnahan-Starnahan-Starnahan-Starnahan-Starnahan-Starnahan-Starnahan-Starnahan-Starleland(BMCSL)方程,以及基于基础基于基本型号的加权密度近似值(FMT)。为了确定每个功能的准确性,我们在具有变化的初始高度和组成的干燥膜中对单组和两个组分硬球悬浮液进行建模,并比较DDFT预测的体积分数曲线与粒子基的Brownian Dynamics(BD)模拟。 FMT准确地预测了即使在高浓度下并且在形成明显的密度梯度时,单组分悬浮液的结构也可以预测,但状态和BMCSL方程在降低的计算成本下为较小的浓度提供了合理的近似值。在两个组分悬浮液中,与BD模拟相比,FMT和BMCSL彼此相似,但逐渐高估了按大小分层的程度。这项工作为在非平衡过程中选择软材料的热力学模型提供了有用的指导,例如溶剂干燥,溶剂冷冻和沉降。

Dynamic density functional theory (DDFT) is a promising approach for predicting the structural evolution of a drying suspension containing one or more types of colloidal particles. The assumed free-energy functional is a key component of DDFT that dictates the thermodynamics of the model and, in turn, the density flux due to a concentration gradient. In this work, we compare several commonly used free-energy functionals for drying hard-sphere suspensions including local-density approximations based on the ideal-gas, virial, and Boublík-Mansoori-Carnahan-Starling-Leland (BMCSL) equations of state as well as a weighted-density approximation based on fundamental measure theory (FMT). To determine the accuracy of each functional, we model one- and two-component hard-sphere suspensions in a drying film with varied initial heights and compositions, and we compare the DDFT-predicted volume-fraction profiles to particle-based Brownian dynamics (BD) simulations. FMT accurately predicts the structure of the one-component suspensions even at high concentrations and when significant density gradients develop, but the virial and BMCSL equations of state provide reasonable approximations for smaller concentrations at a reduced computational cost. In the two-component suspensions, FMT and BMCSL are similar to each other but modestly overpredict the extent of stratification by size compared to BD simulations. This work provides helpful guidance for selecting thermodynamic models for soft materials in nonequilibrium processes such as solvent drying, solvent freezing, and sedimentation.

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