Plastron Respiration Using Commercial Fabrics.

A variety of insect and arachnid species are able to remain submerged in water indefinitely using plastron respiration. A plastron is a surface-retained film of air produced by surface morphology that acts as an oxygen-carbon dioxide exchange surface. Many highly water repellent and hydrophobic surfaces when placed in water exhibit a silvery sheen which is characteristic of a plastron. In this article, the hydrophobicity of a range of commercially available water repellent fabrics and polymer membranes is investigated, and how the surface of the materials mimics this mechanism of underwater respiration is demonstrated allowing direct extraction of oxygen from oxygenated water. The coverage of the surface with the plastron air layer was measured using confocal microscopy. A zinc/oxygen cell is used to consume oxygen within containers constructed from the different membranes, and the oxygen consumed by the cell is compared to the change in oxygen concentration as measured by an oxygen probe. By comparing the membranes to an air-tight reference sample, it was found that the membranes facilitated oxygen transfer from the water into the container, with the most successful membrane showing a 1.90:1 ratio between the cell oxygen consumption and the change in concentration within the container.

Assembl y of Poly-3-Hexylthiophene Nano-Crystallites into Low Dimensional Structures Using Indandione Derivatives.

Conductive polymer poly-3-hexylthiophene (P3HT) needles were self-assembled using a second component (indandione derivatives) as a linking agent to enhance their long range alignment. The morphologies of the hybrid organic/organic materials were characterized by transmission electron microscopy (TEM). Both linear and branched structures could be produced, with the degree of branching depending upon the linker used. Incorporation of indandione derivatives broadened the UV absorbance band of P3HT without significant change to its photoluminescence. This hybrid material could open a promising avenue in photovoltaic applications due to its interesting morphologies and optical properties.

Wet adhesion and adhesive locomotion of snails on anti-adhesive non-wetting surfaces.

Creating surfaces capable of resisting liquid-mediated adhesion is extremely difficult due to the strong capillary forces that exist between surfaces. Land snails use this to adhere to and traverse across almost any type of solid surface of any orientation (horizontal, vertical or inverted), texture (smooth, rough or granular) or wetting property (hydrophilic or hydrophobic) via a layer of mucus. However, the wetting properties that enable snails to generate strong temporary attachment and the effectiveness of this adhesive locomotion on modern super-slippy superhydrophobic surfaces are unclear. Here we report that snail adhesion overcomes a wide range of these microscale and nanoscale topographically structured non-stick surfaces. For the one surface which we found to be snail resistant, we show that the effect is correlated with the wetting response of the surface to a weak surfactant. Our results elucidate some critical wetting factors for the design of anti-adhesive and bio-adhesion resistant surfaces.

Effect of particle size on droplet infiltration into hydrophobic porous media as a model of water repellent soil.

The wettability of soil is of great importance for plants and soil biota, and in determining the risk for preferential flow, surface runoff, flooding,and soil erosion. The molarity of ethanol droplet (MED) test is widely used for quantifying the severity of water repellency in soils that show reduced wettability and is assumed to be independent of soil particle size. The minimum ethanol concentration at which droplet penetration occurs within a short time (≤ 10 s) provides an estimate of the initial advancing contact angle at which spontaneous wetting is expected. In this study, we test the assumption of particle size independence using a simple model of soil, represented by layers of small (~0.2-2 mm) diameter beads that predict the effect of changing bead radius in the top layer on capillary driven imbibition. Experimental results using a three-layer bead system show broad agreement with the model and demonstrate a dependence of the MED test on particle size. The results show that the critical initial advancing contact angle for penetration can be considerably less than 90° and varies with particle size, demonstrating that a key assumption currently used in the MED testing of soil is not necessarily valid.

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 marbles.

Passive water control at the surface of a superhydrophobic lichen.

Some lichens have a super-hydrophobic upper surface, which repels water drops, keeping the surface dry but probably preventing water uptake. Spore ejection requires water and is most efficient just after rainfall. This study was carried out to investigate how super-hydrophobic lichens manage water uptake and repellence at their fruiting bodies, or podetia. Drops of water were placed onto separate podetia of Cladonia chlorophaea and observed using optical microscopy and cryo-scanning-electron microscopy (cryo-SEM) techniques to determine the structure of podetia and to visualise their interaction with water droplets. SEM and optical microscopy studies revealed that the surface of the podetia was constructed in a three-level structural hierarchy. By cryo-SEM of water-glycerol droplets placed on the upper part of the podetium, pinning of the droplet to specific, hydrophilic spots (pycnidia/apothecia) was observed. The results suggest a mechanism for water uptake, which is highly sophisticated, using surface wettability to generate a passive response to different types of precipitation in a manner similar to the Namib Desert beetle. This mechanism is likely to be found in other organisms as it offers passive but selective water control.

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.

Dynamic wetting and spreading and the role of topography.

The spreading of a droplet of a liquid on a smooth solid surface is often described by the Hoffman-de Gennes law, which relates the edge speed, v(e), to the dynamic and equilibrium contact angles θ and θ(e) through [Formula: see text]. 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 overlooked 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. We also consider the spreading of small droplets and stripes of non-volatile liquids in the capillary regime and large droplets in the gravity regime. In the case of small non-volatile droplets spreading completely, a roughness modified Tanner's law giving the dependence of dynamic contact angle on time is presented. We review existing data for the spreading of small droplets of polydimethylsiloxane oil on surfaces decorated with micro-posts. On these surfaces, the initial droplet spreads with an approximately constant volume and the edge speed-dynamic contact angle relationship follows a power law [Formula: see text]. As the surface texture becomes stronger the exponent goes from p = 3 towards p = 1 in agreement with a Wenzel roughness driven spreading and a roughness modified Hoffman-de Gennes power law. Finally, we suggest that when a droplet spreads to a final partial wetting state on a rough surface, it approaches its Wenzel equilibrium contact angle in an exponential manner with a time constant dependent on roughness.

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.

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.

Quantification of surface-bound proteins by fluorometric assay: Comparison with quartz crystal microbalance and amido black assay.

Protein adsorption is of major and widespread interest, being useful in the fundamental understanding of biological processes at interfaces through to the development of new materials. A number of techniques are commonly used to study protein adhesion, but few are directly quantitative. Here we describe the use of Nano Orange, a fluorometric assay, to quantitatively assess the adsorption of bovine fibrinogen and albumin onto model hydrophilic (OH terminated) and hydrophobic (CH3 terminated) surfaces. Results obtained using this method allowed the calibration of previously unquantifiable data obtained on the same surfaces using quartz crystal microbalance measurements and an amido black protein assay. Both proteins were found to adsorb with higher affinity but with lower saturation levels onto hydrophobic surfaces. All three analytical techniques showed similar trends in binding strength and relative amounts adsorbed over a range of protein concentrations, although the fluorometric analysis was the only method to give absolute quantities of surface-bound protein. The versatility of the fluorometric assay was also probed by analyzing protein adsorption onto porous superhydrophobic and superhydrophilic surfaces. Results obtained using the assay in conjunction with these surfaces were surface chemistry dependent. Imbibition of water into the superhydrophilic coatings provided greater surface area for protein adsorption, although the protein surface density was less than that found on a comparable flat hydrophilic surface. Superhydrophobic surfaces prevented protein solution penetration. This paper demonstrates the potential of a fluorometric assay to be used as an external calibration for other techniques following protein adsorption processes or as a supplemental method to study protein adsorption. Differences in protein adsorption onto hydrophilic vs superhydrophilic and hydrophobic vs superhydrophobic surfaces are highlighted.

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 Bryologist 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.

Porous materials show superhydrophobic to superhydrophilic switching.

Switching between superhydrophobicity and superhydrophilicity in porous materials was predicted theoretically and demonstrated experimentally with the example of thermally induced contact angle change; tunability of this system was also demonstrated.