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材料柔韧性对疏水物体间水的干燥转变的作用:热力学分析

The role of material flexibility on the drying transition of water between hydrophobic objects: a thermodynamic analysis.

作者信息

Altabet Y Elia, Debenedetti Pablo G

机构信息

Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544, USA.

出版信息

J Chem Phys. 2014 Nov 14;141(18):18C531. doi: 10.1063/1.4898366.

Abstract

Liquid water confined between hydrophobic objects of sufficient size becomes metastable with respect to its vapor at separations smaller than a critical drying distance. Macroscopic thermodynamic arguments predicting this distance have been restricted to the limit of perfectly rigid confining materials. However, no material is perfectly rigid and it is of interest to account for this fact in the thermodynamic analysis. We present a theory that combines the current macroscopic theory with the thermodynamics of elasticity to derive an expression for the critical drying distance for liquids confined between flexible materials. The resulting expression is the sum of the well-known drying distance for perfectly rigid confining materials and a new term that accounts for flexibility. Thermodynamic arguments show that this new term is necessarily positive, meaning that flexibility increases the critical drying distance. To study the expected magnitude and scaling behavior of the flexible term, we consider the specific case of water and present an example of drying between thin square elastic plates that are simply supported along two opposite edges and free at the remaining two. We find that the flexible term can be the same order of magnitude or greater than the rigid solution for materials of biological interest at ambient conditions. In addition, we find that when the rigid solution scales with the characteristic size of the immersed objects, the flexible term is independent of size and vice versa. Thus, the scaling behavior of the overall drying distance will depend on the relative weights of the rigid and flexible contributions.

摘要

当液态水被限制在足够大尺寸的疏水物体之间时,在小于临界干燥距离的间距下,相对于其蒸汽而言会变得亚稳。预测这个距离的宏观热力学论据一直局限于完全刚性的限制材料的极限情况。然而,没有材料是完全刚性的,在热力学分析中考虑这一事实是很有意义的。我们提出一种理论,将当前的宏观理论与弹性热力学相结合,以推导出限制在柔性材料之间的液体的临界干燥距离的表达式。所得表达式是完全刚性限制材料的著名干燥距离与一个考虑柔性的新项之和。热力学论据表明,这个新项必然是正的,这意味着柔性会增加临界干燥距离。为了研究柔性项的预期大小和标度行为,我们考虑水的具体情况,并给出一个在沿两条相对边简支而在其余两条边自由的薄方形弹性板之间干燥的例子。我们发现,对于环境条件下具有生物学意义的材料,柔性项的大小可能与刚性解相同或更大。此外,我们发现,当刚性解与浸没物体的特征尺寸成比例时,柔性项与尺寸无关,反之亦然。因此,整体干燥距离的标度行为将取决于刚性和柔性贡献的相对权重。

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