Malijevský Alexandr
Department of Physical Chemistry, Institute of Chemical Technology, Prague, 166 28 Praha 6, Czech Republic and Institute of Chemical Process Fundamentals, Academy of Sciences, 16502 Prague 6, Czech Republic.
J Chem Phys. 2014 Nov 14;141(18):184703. doi: 10.1063/1.4901128.
Any solid surface is intrinsically rough on the microscopic scale. In this paper, we study the effect of this roughness on the wetting properties of hydrophilic substrates. Macroscopic arguments, such as those leading to the well-known Wenzel's law, predict that surface roughness should amplify the wetting properties of such adsorbents. We use a fundamental measure density functional theory to demonstrate the opposite effect from roughness for microscopically corrugated surfaces, i.e., wetting is hindered. Based on three independent analyses we show that microscopic surface corrugation increases the wetting temperature or even makes the surface hydrophobic. Since for macroscopically corrugated surfaces the solid texture does indeed amplify wetting there must exist a crossover between two length-scale regimes that are distinguished by opposite response on surface roughening. This demonstrates how deceptive can be efforts to extend the thermodynamical laws beyond their macroscopic territory.
在微观尺度上,任何固体表面本质上都是粗糙的。在本文中,我们研究了这种粗糙度对亲水性基底润湿特性的影响。宏观理论,比如那些推导出著名的文泽尔定律的理论,预测表面粗糙度会增强这类吸附剂的润湿特性。我们使用一种基本度量密度泛函理论来证明,对于微观波纹表面,粗糙度会产生相反的效果,即阻碍润湿。基于三项独立分析,我们表明微观表面波纹会提高润湿温度,甚至使表面具有疏水性。由于对于宏观波纹表面,固体纹理确实会增强润湿,所以在两个长度尺度 regime 之间必然存在一个转变点,这两个 regime 对表面粗糙度的响应相反。这表明,试图将热力学定律扩展到其宏观领域之外的努力可能会有多么具有欺骗性。