Doris Vollmer

Candle Soot as a Template for a Transparent Robust Superamphiphobic Coating

In the Stick of It If a coating makes a surface nonstick, how do you stick the coating to the surface in the first place? For many nonstick coatings, this involves procedures to ensure good adhesion to the underlying surface though the use of surface roughening or intermediary layers. Deng et al. (p. 67, published online 1 December; see the cover) found a very simple route using little more than candle soot as a temporary sublayer that is coated with a silica shell and subsequently removed via calcination. Once top-coated with a semifluorinated silane, the resulting material possessed a low surface energy for water and also repelled oils, alchohols, and alkanes. While the coating could be damaged through mechanical wear, the remaining material continued to show superhydrophobic and superoleophobic behavior. Coatings that are highly resistant to water and to hydrocarbons can be made starting from candle soot. Coating is an essential step in adjusting the surface properties of materials. Superhydrophobic coatings with contact angles greater than 150° and roll-off angles below 10° for water have been developed, based on low-energy surfaces and roughness on the nano- and micrometer scales. However, these surfaces are still wetted by organic liquids such as surfactant-based solutions, alcohols, or alkanes. Coatings that are simultaneously superhydrophobic and superoleophobic are rare. We designed an easily fabricated, transparent, and oil-rebounding superamphiphobic coating. A porous deposit of candle soot was coated with a 25-nanometer-thick silica shell. The black coating became transparent after calcination at 600°C. After silanization, the coating was superamphiphobic and remained so even after its top layer was damaged by sand impingement.

Transparent, Thermally Stable and Mechanically Robust Superhydrophobic Surfaces Made from Porous Silica Capsules

Superhydrophobic surfaces are advantageous for a cost-effective maintenance of a variety of surfaces. The combination of micro and nano-sized roughness increases the contact angle of water such that water droplets cannot adhere but roll off. Therefore, superhydrophobic coatings are self-cleaning and anticorrosive. If the superhydrophobic surface were even transparent, the range of possible applications could be expanded to glass-based substrates such as goggles or windshields and, equally important, prevent an efficiency degradation of solar cells by pollution accumulation. Moreover mechanical robustness is also particularly critical because the dual scale roughness can easily be destroyed irreversibly leading to a rapid decrease of the contact angle and an increase of contact angle hysteresis. We use porous silica capsules as key components to build lotus leaf-like superhydrophobic surfaces. The latter are highly transparent as well as mechanically and thermally stable, see Fig. 1, left. When used as transparent coatings for organic solar cells they leave their performance unaffected, see Fig. 1, right.

How superhydrophobicity breaks down

A droplet deposited or impacting on a superhydrophobic surface rolls off easily, leaving the surface dry and clean. This remarkable property is due to a surface structure that favors the entrainment of air cushions beneath the drop, leading to the so-called Cassie state. The Cassie state competes with the Wenzel (impaled) state, in which the liquid fully wets the substrate. To use superhydrophobicity, impalement of the drop into the surface structure needs to be prevented. To understand the underlying processes, we image the impalement dynamics in three dimensions by confocal microscopy. While the drop evaporates from a pillar array, its rim recedes via stepwise depinning from the edge of the pillars. Before depinning, finger-like necks form due to adhesion of the drop at the pillar’s circumference. Once the pressure becomes too high, or the drop too small, the drop slowly impales the texture. The thickness of the air cushion decreases gradually. As soon as the water–air interface touches the substrate, complete wetting proceeds within milliseconds. This visualization of the impalement dynamics will facilitate the development and characterization of superhydrophobic surfaces.

Hollow Silica Spheres: Synthesis and Mechanical Properties

Core-shell polystyrene-silica spheres with diameters of 800 nm and 1.9 microm were synthesized by soap-free emulsion and dispersion polymerization of the polystyrene core, respectively. The polystyrene spheres were used as templates for the synthesis of silica shells of tunable thickness employing the Stöber method [Graf et al. Langmuir 2003, 19, 6693]. The polystyrene template was removed by thermal decomposition at 500 degrees C, resulting in smooth silica shells of well-defined thickness (15-70 nm). The elastic response of these hollow spheres was probed by atomic force microscopy (AFM). A point load was applied to the particle surface through a sharp AFM tip, and successively increased until the shell broke. In agreement with the predictions of shell theory, for small deformations the deformation increased linearly with applied force. The Youngs modulus (18 +/- 6 GPa) was about 4 times smaller than that of fused silica [Adachi and Sakka J. Mater. Sci. 1990, 25, 4732] but identical to that of bulk silica spheres (800 nm) synthesized by the Stöber method, indicating that it yields silica of lower density. The minimum force needed to irreversibly deform (buckle) the shell increased quadratically with shell thickness.

Design principles for superamphiphobic surfaces

To predict the properties of superamphiphobic layers we analyzed the wetting of a square and a hexagonal array of vertical pillars composed of spheres (radius R) partially sintered together. Apparent contact angles above 150° are obtained by pinning of a non-polar liquid surface at the underside of the top sphere resulting in a Fakir or Cassie state. Analytical equations are derived for the impalement pressure in the limiting case A0 ≫ R2, where A0 is the area of the regular unit cell containing a single pillar. The case of close pillars is investigated numerically. By balancing forces at the rim of a drop, we calculate the apparent receding contact angle. To describe drag reduction of a flowing liquid we calculate the apparent slip length. When considering pressure-induced flow through cylindrical capillaries of radius rc, significant drag reduction occurs only for thin capillaries. The mechanical stability with respect to normal forces and shear is analyzed. Nanoscopic silica glass pillars would be able to sustain the normal and shear stresses caused by capillary and drag forces. For a high impalement pressure and good mechanical stability A0 should be small and R (respectively the neck diameter) should be large, whereas a large A0 and a small R imply low contact angle hysteresis and high slip length.

Superhydrophobic surfaces by hybrid raspberry-like particles.

Surface roughness on different length scales is favourable for superhydrophobic behaviour of surfaces. Here we report (i) an improved synthesis for hybrid raspberry-like particles and (ii) a novel method to obtain superhydrophobic films of good mechanical stability. Polystyrene spheres with a diameter of 400 nm-1 microm are decorated with silica colloids < 100 nm in size, thus introducing surface asperities on a second length scale. To improve mechanical resistance, we then coated the polystyrene core and attached silica colloids with a smooth silica shell of 10 nm to 40 nm thickness. All three steps of this synthesis procedure can be sensitively tuned so that the average size and number of the silica colloids as well as the morphology of the resulting raspberry particles can be predicted. As the particles disperse in water, either monolayers can be prepared by dip coating or multilayers by drop casting. Although mechanically stable, the shells are porous enough to allow for leakage of molten or dissolved polystyrene from the core. In tetrahydrofuran vapour polystyrene bridges form between the particles that render the multilayer-film stable. Leaked polystyrene that masks some asperities can be removed by plasma cleaning. Surface roughness on larger scales can be tuned by the drying procedure. The films are hydrophobized by silanization with a semi-fluorinate silane.

How Water Advances on Superhydrophobic Surfaces

Superliquid repellency can be achieved by nano- and microstructuring surfaces in such a way that protrusions entrap air underneath the liquid. It is still not known how the three-phase contact line advances on such structured surfaces. In contrast to a smooth surface, where the contact line can advance continuously, on a superliquid-repellent surface, the contact line has to overcome an air gap between protrusions. Here, we apply laser scanning confocal microscopy to get the first microscopic videos of water drops advancing on a superhydrophobic array of micropillars. In contrast to common belief, the liquid surface gradually bends down until it touches the top face of the next micropillars. The apparent advancing contact angle is 180°. On the receding side, pinning to the top faces of the micropillars determines the apparent receding contact angle. Based on these observations, we propose that the apparent receding contact angle should be used for characterizing superliquid-repellent surfaces rather than the apparent advancing contact angle and hysteresis.

Super liquid-repellent gas membranes for carbon dioxide capture and heart–lung machines

In a gas membrane, gas is transferred between a liquid and a gas through a microporous membrane. The main challenge is to achieve a high gas transfer while preventing wetting and clogging. With respect to the oxygenation of blood, haemocompatibility is also required. Here we coat macroporous meshes with a superamphiphobic—or liquid repellent—layer to meet this challenge. The superamphiphobic layer consists of a fractal-like network of fluorinated silicon oxide nanospheres; gas trapped between the nanospheres keeps the liquid from contacting the wall of the membrane. We demonstrate the capabilities of the membrane by capturing carbon dioxide gas into a basic aqueous solution and in addition use it to oxygenate blood. Usually, blood tends to clog membranes because of the abundance of blood cells, platelets, proteins and lipids. We show that human blood stored in a superamphiphobic well for 24 h can be poured off without leaving cells or adsorbed protein behind.

Liquid drops impacting superamphiphobic coatings.

The dynamics of liquid drops impacting superamphiphobic coatings is studied by high-speed video microscopy. Superamphiphobic coatings repel water and oils. The coating consists of a fractal-like hydrophobized silica network. Mixtures of ethanol-water and glycerin-water are chosen to investigate the influence of interfacial tension and viscosity on spreading and retraction dynamics. Drop spreading is dominated by inertia. At low impact velocity, the drops completely rebound. However, the contact time increases with impact velocity, whereas the restitution coefficient decreases. We suggest that the drop temporarily impales the superamphiphobic coating, although the drop completely rebounds. From an estimate of the pressure, it can be concluded that impalement is dominated by depinning rather than sagging. With increasing velocity, the drops partially pin, and an increasing amount of liquid remains on the coating. A time-resolved study of the retraction dynamics reveals two well-separated phases: a fast inertia-dominated phase followed by a slow decrease of the contact diameter of the drop. The crossover occurs when the diameter of the retracting drop matches the diameter of the drop before impact. We suggest that the depth of impalement increases with impact velocity, where impalement is confined to the initial impact zone of the drop. If the drop partially pins on the coating, the depth of impalement exceeds a depth, preventing the whole drop from being removed during the retraction phase.

Effect of Nanoroughness on Highly Hydrophobic and Superhydrophobic Coatings

The effect of nanoroughness on contact angles and pinning is investigated experimentally and numerically for low-energy surfaces. Nanoroughness is introduced by chemical vapor deposition of tetraethoxysilane and was quantified by scanning force microscopy. Addition of a root-mean-square roughness of 2 nm on a flat surface can increase the contact angle after fluorination by a semifluorinated silane by up to 30°. On the other hand, nanoroughness can improve or impair the liquid repellency of superhydrophobic surfaces that were made from assembled raspberry particles. Molecular dynamics simulations are performed in order to gain a microscopic understanding on how the length and the surface coating density of semifluorinated silanes influence the hydrophobicity. Solid-liquid surface free energy computations reveal that the wetting behavior strongly depends on the density and alignment of the semifluorinated silane. At coating densities in the range of experimental values, some water molecules can penetrate between the semifluorinated chains, thus increasing the surface energy. Combining the experimental and numerical data exhibits that a roughness-induced increase of the contact angle competes with increased pinning caused by penetration of liquid into nanopores or between neighboring semifluorinated molecules.