Nanoporous surface wetting behavior: the line tension influence

The aim of this work is to develop a physical model to describe the evolution of the apparent contact angle for four different liquids on nanotextured alumina surfaces with different pore radius. The nanoporous alumina templates were fabricated by anodization of Al foil in a 0.3 M oxalic acid solution. Scanning electron microscopy was used to characterize the morphology of the surfaces. The templates are approximately 400 nm in thickness and consist of a well-ordered hexagonal array of uniform radius pores spaced 105 nm apart with pore radii from 12 to 42 nm. The wettability of nanoporous alumina templates was investigated using contact-angle measurements. We measured the contact angles using four liquids: water, ethylene glycol, aniline, and a mixture of ethylene glycol and aniline. We developed a new theoretical model for the contact angle on nanoporous surfaces as a function of the pore radius. This model is based on energy considerations and involves liquid penetration into the nanopores driven by the capillarity (Laplace's law). Because the air is compressed inside the pores, this model also includes the effect of the line tension. This is important because the three-phase line length is greatly enhanced in our nanoporous structures. For example: for a millimeter-sized droplet, the three-phase line around the perimeter of the droplet is a few millimeters long, whereas the total three-phase line within the pores can reach several tens of meters. Using our model, the line-tension value for our nanopore samples is positive and ranges from 4 to 13 × 10(-9) N, which falls within the wide interval from 10(-11) to 10(-5) N quoted in the literature. Nanoporous surfaces may allow the effect of line tension to be visible for micro- to macrodroplets.