Implications of ideas on super-hydrophobicity for water repellent soil

Water repellence is an important factor in soil erosion due to its role in inhibiting the re-establishment of vegetation after fire and due to its enhancement of run-off. Water repellence is studied across a range of diverse disciplines, such as chemistry, materials, textiles and soil and reclamation science. In recent years many basic studies of water repellence of materials have focused on the role of the sub-mm surface topography of a material in modifying the intrinsic hydrophobicity imparted by the surface chemistry to create super-hydrophobicity. In this report, we first illustrate the types of hydrophobic effects created by a suitable coupling of small scale surface topography with surface chemistry using three examples of materials: an etched metal, a foam and a micro-fabricated pillar structure. These examples demonstrate the general applicability of the ideas and suggest that they could apply to a granular material, such as a fine sandy soil, particularly when the grains have become coated with a hydrophobic layer. This applicability is confirmed by contact angle measurements of droplets of water on hydrophobic sand. A theoretical model describing the application of these ideas to a loose-packed, but regular, array of uniform spherical grains is then presented and discussed. When the grains are in a dry initial state the effect of the surface is to increase the apparent water repellence as observed through the contact angle. However, when the spaces between the grains are initially filled with water, the effect is to provide greater wetting. To qualitatively confirm the enhancement of contact angle caused by the granular structure, model surfaces using 600 µm and 250 µm hydrophobic glass beads were created. On these surfaces, the contact angle of droplets of water was increased from 108° to 126° and 140°, respectively

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

A lichen protected by a super-hydrophobic and breathable structure

A species of lichen, Lecanora conizaeoides, is shown to be super-hydrophobic. It uses a combination of hydrophobic compounds and multi-layered roughness to shed water effectively. This is combined with gas channels to produce a biological analogue of a waterproof, breathable garment. The particular lichen grows mostly during wet seasons and is unusually resistant to acid rain [Hauck, M., 2003. The Bryotogist 106(2), 257-269; Honegger, R., 1998. Lichenologist 30(3),193-212]. The waterproof, breathable surface allows this lichen to photosynthesise when other species are covered with a layer of water. In addition, rainwater runs off the surface of the organism, reducing its intake of water from above and probably contributing to its resistance to acid rain

Water-repellent soil and its relationship to granularity, surface roughness and hydrophobicity: a materials science view

Considerable soil water repellency has been observed at a wide range of locations worldwide. The soil exhibiting water repellency is found within the upper part of the soil profile. The reduced rate of water infiltration into these soils leads to severe runoff erosion, and reduction of plant growth. Soil water repellency is promoted by drying of soil, and can be induced by fire or intense heating of soil containing hydrophobic organic matter. Recent studies outside soil science have shown how enhancement of the natural water repellency of materials, both porous and granular, by surface texture (i.e. surface roughness, pattern and morphology) into super-hydrophobicity is possible. The similarities between these super-hydrophobic materials and observed properties of water-repellent soil are discussed from a non-soil scientist, materials-based perspective. A simple model is developed for a hydrophobic granular surface and it is shown that this can provide a mechanism for enhancement of soil water repellency through the relative size and spacing of grains and pores. The model provides a possible explanation for why soil water repellency should be more prevalent under dry conditions than wet. Consequences for water runoff, raindrop splash and soil erosion are discussed

Dynamic wetting and spreading and the role of topography

Hoffman-de Gennes law, which relates the edge speed, ve, to the dynamic and equilibrium contact angles q and qe by ve µq(q2 -qe 2 ). When the liquid wets the surface completely and the equilibrium contact angle vanishes, the edge speed is proportional to the cube of the dynamic contact angle. When the droplets are non-volatile this law gives rise to simple power laws with time for the contact angle and other parameters in both the capillary and gravity dominated regimes. On a textured surface the equilibrium state of a droplet is strongly modified due to the amplification of the surface chemistry induced tendencies by the topography. The most common example is the conversion of hydrophobicity into superhydrophobicity. However, when the surface chemistry favors partial wetting, topography can result in a droplet spreading completely. A further, frequently over-looked consequence of topography is that the rate at which an out-of-equilibrium droplet spreads should also be modified. In this report, we review ideas related to the idea of topography induced wetting and consider how this may relate to dynamic wetting and the rate of droplet spreading. We consider the effect of the Wenzel and Cassie-Baxter equations on the driving forces and discuss how these may modify power-laws for spreading. We relate the ideas to both the hydrodynamic viscous dissipation model and the molecular-kinetic theory of spreading. This suggests roughness and solid surface fraction modified Hoffman-de Gennes laws relating the edge speed to the dynamic and equilibrium contact angle

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. 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

The superhydrophobicity of polymer surfaces: Recent developments

Superhydrophobicity is the extreme water repellence of highly textured surfaces. The field of superhydrophobicity research has reached a stage where huge numbers of candidate treatments have been proposed and jumps have been made in theoretically describing them. There now seems to be a move to more practical concerns and to considering the demands of individual applications instead of more general cases. With these developments, polymeric surfaces with their huge variety of properties have come to the fore and are fast becoming the material of choice for designing, developing, and producing superhydrophobic surfaces. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 49: 1203–1217, 201

Superhydrophobicity: Localized Parameters And Gradient Surfaces

The use of Cassie and Baxter's equation and that of Wenzel has been subject to some criticism of late. It has been suggested that researchers use these equations without always considering the assumptions that have been made and sometimes apply them to cases that are not suitable. This debate has prompted a reconsideration of the derivation of these equations using the concept of parameters for the Wenzel roughness and Cassie-Baxter solid surface fractions that are local to the three-phase contact lines. In such circumstances, we show the roughness and Cassie-Baxter solid fractions depend not only on the substrate material, but also on which part of the substrate is being sampled by the three-phase contact lines of a given droplet. We show that this is not simply a theoretical debate, but is one which has direct consequences for experiments on surfaces where the roughness or spatial pattern varies across the surface. We use the approach to derive formulae for the contact angle observed on a double length scale surface under the assumption that the small-scale features on the peaks of larger scale features are either wetted or non-wetted. We also discuss the case of curved and re-entrant surface features and how these bring the Young's law contact angle into the formula for roughness and the condition for suspending droplets without penetration into the surface. To illustrate the use of local parameters, we consider the case of a variation in Cassie-Baxter fraction across a surface possessing a homogeneous hydrophobic surface chemistry and discuss the conditions (droplet volume, surface hydrophobicity, gradient in superhydrophobicity and contact angle hysteresis) under which a droplet may be set into motion. We show that different contact angles on each side of a droplet of water placed on such a surface can generate sufficient lateral force for the droplet to move towards the region of the surface with the lowest contact angle. Using an electrodeposited copper surface with a radial gradient in superhydrophobicity we exemplify these ideas by showing experimentally that droplets enter into self-actuated motion and accumulate in the centre of the surface where the wettability is higher. In principle, paths can be defined and water droplets can be collected by creating such gradients in superhydrophobicity through changes in the lateral topography of the surface

Capillary origami: superhydrophobic ribbon surfaces and liquid marbles

In the wetting of a solid by a liquid it is often assumed that the substrate is rigid. However, for an elastic substrate the rigidity depends on the cube of its thickness and so reduces rapidly as the substrate becomes thinner as it approaches becoming a thin sheet. In such circumstances, it has been shown that the capillary forces caused by a contacting droplet of a liquid can shape the solid rather than the solid shaping the liquid. A substrate can be bent and folded as a (pinned) droplet evaporates or even instantaneously and spontaneously wrapped on contact with a droplet. When this effect is used to create three dimensional shapes from initially flat sheets, the effect is called capillary origami or droplet wrapping. In this work, we consider how the conditions for the spontaneous, capillary induced, folding of a thin ribbon substrate might be altered by a rigid surface structure that, for a rigid substrate, would be expected to create Cassie–Baxter and Wenzel effects. For smooth thin substrates, droplet wrapping can occur for all liquids, including those for which the Young’s law contact angle (defined by the interfacial tensions) is greater than 90° and which would therefore normally be considered relatively hydrophobic. However, consideration of the balance between bending and interfacial energies suggests that the tendency for droplet wrapping can be suppressed for some liquids by providing the flexible solid surface with a rigid topographic structure. In general, it is known that when a liquid interacts with such a structure it can either fully penetrate the structure (the Wenzel case) or it can bridge between the asperities of the structure (the Cassie–Baxter case). In this report, we show theoretically that droplet wrapping should occur with both types of solid–liquid contact. We also derive a condition for the transition between the Cassie–Baxter and Wenzel type droplet wrapping and relate it to the same transition condition known to apply to superhydrophobic surfaces. The results are given for both droplets being wrapped by thin ribbons and for solid grains encapsulating droplets to form liquid marble

Nano-scale superhydrophobicity: suppression of protein adsorption and promotion of flow-induced detachment

Wall adsorption is a common problem in microfluidic devices, particularly when proteins are used. Here we show how superhydrophobic surfaces can be used to reduce protein adsorption and to promote desorption. Hydrophobic surfaces, both smooth and having high surface roughness of varying length scales (to generate superhydrophobicity), were incubated in protein solution. The samples were then exposed to flow shear in a device designed to simulate a microfluidic environment. Results show that a similar amount of protein adsorbed onto smooth and nanometer-scale rough surfaces, although a greater amount was found to adsorb onto superhydrophobic surfaces with micrometer scale roughness. Exposure to flow shear removed a considerably larger proportion of adsorbed protein from the superhydrophobic surfaces than from the smooth ones, with almost all of the protein being removed from some nanoscale surfaces. This type of surface may therefore be useful in environments, such as microfluidics, where protein sticking is a problem and fluid flow is present. Possible mechanisms that explain the behaviour are discussed, including decreased contact between protein and surface and greater shear stress due to interfacial slip between the superhydrophobic surface and the liquid