Neil J. Shirtcliffe

Progess in superhydrophobic surface development

Research into extreme water-repellent surfaces began many decades ago, although it was only relatively recently that the term superhydrophobicity appeared in literature. Here we review the work on the preparation of superhydrophobic surfaces, with focus on the different techniques used and how they have developed over the years, with particular focus on the last two years. We discuss the origins of water-repellent surfaces, examining how size and shape of surface features are used to control surface characteristics, in particular how techniques have progressed to form multi-scaled roughness to mimic the lotus leaf effect. There are notable differences in the terminology used to describe the varying properties of water-repellent surfaces, so we suggest some key definitions.

An introduction to superhydrophobicity

This paper is derived from a training session prepared for COST P21. It is intended as an introduction to superhydrophobicity to scientists who may not work in this area of physics or to students. Superhydrophobicity is an effect where roughness and hydrophobicity combine to generate unusually hydrophobic surfaces, causing water to bounce and roll off as if it were mercury and is used by plants and animals to repel water, stay clean and sometimes even to breathe underwater. The effect is also known as The Lotus Effect(®) and Ultrahydrophobicity. In this paper we introduce many of the theories used, some of the methods used to generate surfaces and then describe some of the implications of the effect.

Immersed superhydrophobic surfaces: Gas exchange, slip and drag reduction properties

Superhydrophobic surfaces combine high aspect ratio micro- or nano-topography and hydrophobic surface chemistry to create super water-repellent surfaces. Most studies consider their effect on droplets, which ball-up and roll-off. However, their properties are not restricted to modification of the behaviour of droplets, but potentially influence any process occurring at the solid-liquid interface. Here, we highlight three recent developments focused on the theme of immersed superhydrophobic surfaces. The first illustrates the ability of a superhydrophobic surface to act as a gas exchange membrane, the second demonstrates a reduction in drag during flow through small tubes and the third considers a macroscopic experiment demonstrating an increase in the terminal velocity of settling spheres.

Superhydrophobic copper tubes with possible flow enhancement and drag reduction.

The transport of a Newtonian liquid through a smooth pipe or tube is dominated by the frictional drag on the liquid against the walls. The resistance to flow against a solid can, however, be reduced by introducing a layer of gas at or near the boundary between the solid and liquid. This can occur by the vaporization of liquid at a surface at a temperature above the Leidenfrost point, by a cushion of air (e.g. below a hovercraft), or by producing bubbles at the interface. These methods require a continuous energy input, but a more recent discovery is the possibility of using a superhydrophobic surface. Most reported research uses small sections of lithographically patterned surfaces and rarely considers pressure differences or varying flow rates. In this work we present a method for creating a uniform superhydrophobic nanoribbon layer on the inside of round copper tubes of millimetric internal radius. Two types of experiments are described, with the first involving a simultaneous comparison of four tubes with different surface finishes (as received, as received with hydrophobic coating, nanoribbon, and nanoribbon with a hydrophobic coating) under constant flow rate conditions using water and water-glycerol mixtures. The results show that the superhydrophobic nanoribbon with a hydrophobic coating surface finish allows greater flow at low pressure differences but that the effect disappears as the pressure at the inlet of the tube is increased. The second experiment is a simple visual demonstration of the low-pressure behavior using two nominally identical tubes in terms of length and cross-section, but with one tube possessing a superhydrophobic internal surface finish. In this experiment a reservoir is allowed to feed the two tubes with open ends via a T-piece and it is observed that, once flow commences, it preferentially occurs down the superhydrophobic tube.

The use of high aspect ratio photoresist (SU-8) for super-hydrophobic pattern prototyping

In this work we present a reliable technique for the production of large areas of high aspect-ratio patterns and describe their use as model super-hydrophobic systems. The high thickness and straight sidewalls possible with SU-8 were used to generate dense patterns of small pillars. These photoresist patterns could be used directly, without the need for micromoulding. A method is given allowing resist thickness to be varied over a wide range and a bottom antireflective layer was used to simplify patterning on reflective substrates. This patterning technique allows rapid testing of wetting theories, as pattern size and depth can be varied simply and samples can be produced in sufficient numbers for laboratory use. We show how the static contact angle of water varies with pattern height for one sample-pattern and how static and dynamic contact angles vary with dimension using high aspect-ratio patterns.

Plastron properties of a superhydrophobic surface

Most insects and spiders drown when submerged during flooding or tidal inundation, but some are able to survive and others can remain submerged indefinitely without harm. Many achieve this by natural adaptations to their surface morphology to trap films of air, creating plastrons which fix the water-vapor interface and provide an incompressible oxygen-carbon dioxide exchange surface. Here the authors demonstrate how the surface of an extremely water-repellent foam mimics this mechanism of underwater respiration and allows direct extraction of oxygen from aerated water. The biomimetic principle demonstrated can be applied to a wide variety of man-made superhydrophobic materials.

Super-hydrophobic and super-wetting surfaces: Analytical potential?

Roughening or texturing surfaces provides super-liquid repellent or film forming properties without alteration of the surface chemistry. These surfaces are easy to produce, can amplify wetting properties and can be either “sticky” or “slippy” to liquids. Their use as water-repellent coatings is established, but their potential for use in microfluidics and sensor applications remains largely unfulfilled. This article explains several key ideas and suggests why there may be potential for analytical applications.

Terminal velocity and drag reduction measurements on superhydrophobic spheres

Super water-repellent surfaces occur naturally on plants and aquatic insects and are created in the laboratory by combining micro- or nanoscale surface topographic features with hydrophobic surface chemistry. When such types of water-repellent surfaces are submerged they can retain a film of air (a plastron). In this work, we report measurements of the terminal velocity of solid acrylic spheres with various surface treatments settling under the action of gravity in water. We observed increases in terminal velocity corresponding to drag reduction of between 5% and 15% for superhydrophobic surfaces that carry plastrons.

Electrowetting of liquid marbles

Electrowetting of water drops on structured superhydrophobic surfaces are known to cause an irreversible change from a slippy (Cassie–Baxter) to a sticky (Wenzel) regime. An alternative approach to using a water drop on a superhydrophobic surface to obtain a non-wetting system is to use a liquid marble on a smooth solid substrate. A liquid marble is a droplet coated in hydrophobic grains, which therefore carries its own solid surface structure as a conformal coating. Such droplets can be considered as perfect non-wetting systems having contact angles to smooth solid substrates of close to 180°. In this work we report the electrowetting of liquid marbles made of water coated with hydrophobic lycopodium grains and show that the electrowetting is completely reversible. Marbles are shown to return to their initial contact angle for both ac and dc electrowetting and without requiring a threshold voltage to be exceeded. Furthermore, we provide a proof-of-principle demonstration that controlled motion of marbles on a finger electrode structure is possible.

Critical conditions for the wetting of soils

The wettability of soil is of great importance for plants and soil biota and in determining whether flooding and soil erosion will occur. The analysis used in common measurements of soil hydrophobicity makes the assumption that water always enters soils if the average contact angle between the soil and water is 90° or lower; these tests have been used for decades. The authors show theoretically and experimentally that water cannot enter many soils unless the contact angle is considerably lower than this, down to approximately 50°. This difference generates serious errors in determining and modeling soil wetting behavior.