Hans-Juergen Butt

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.

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.

Effect of capillary pressure and surface tension on the deformation of elastic surfaces by sessile liquid microdrops: An experimental investigation

Sessile liquid drops are predicted to deform an elastic surface onto which they are placed because of the combined action of the liquid surface tension at the periphery of the drop and the capillary pressure inside the drop. Here, we show for the first time the in situ experimental confirmation of the effect of capillary pressure on this deformation. We demonstrate micrometer-scale deformations made possible by using a low Youngs modulus material as an elastic surface. The experimental profiles of the deformed surfaces fit well the theoretical predictions for surfaces with a Youngs modulus between 25 and 340 kPa.

Dynamic effects on force measurements. I. Viscous drag on the atomic force microscope cantilever

When the atomic force microscope (AFM) is used for force measurements, the driving speed typically does not exceed a few microns per second. However, it is possible to perform the AFM force experiment at much higher speed. In this article, theoretical calculations and experimental measurements are used to show that in such a dynamic regime the AFM cantilever can be significantly deflected due to viscous drag force. This suggests that in general the force balance used in a surface force apparatus does not apply to the dynamic force measurements with an AFM. We develop a number of models that can be used to estimate the deflection caused by viscous drag on a cantilever in various experimental situations. As a result, the conditions when this effect can be minimized or even suppressed are specified. This opens up a number of new possibilities to apply the standard AFM technique for studying dynamic phenomena in a thin gap.

The Softer the Better: Fast Condensation on Soft Surfaces

Condensation on soft elastic surfaces differs significantly from condensation on hard surfaces. On polymeric substrates with varying cross-linking density, we investigate the nucleation and the growth of condensing water drops. With increasing softness of the substrates, we find (1) increasing nucleation density, (2) longer relaxation times for drop shape equilibration after merging of two drops, and (3) prevention of merging on very soft surfaces. These effects lead to higher surface coverage and overall condensed volume on soft surfaces.

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.

Forces between polystyrene surfaces in water-electrolyte solutions: Long-range attraction of two types?

A great deal of effort has recently been focused on the experimental studies of the phenomenon of long-ranged attraction between identically charged colloidal (polystyrene) particles immersed in an electrolyte. The theoretical validation suggested the need for revision of the existing and established colloidal theories assuming the observed attraction is of electrostatic origin. We, however, demonstrate that for a number of reasons (first of all hydrophobicity and roughnessof particles) the Derjaguin–Landau–Verwey–Overbeek (DLVO) behavior should not be expected for polystyrene surfaces. Indeed, the force measurements with an atomic force microscope-related set-up suggest that even within one pair of the interacting surfaces, attractive interaction of various types can be observed. There is usually a difference between the first approach and the later ones. The first approach is characterized by a short-range jump into a contact. Depending on conditions (electrolyte concentration, previous contacts of surfaces, etc.) there exists a late attraction of two types between polystyrene surfaces. The force of the first type is characterized by an abrupt jump from the maximum of a repulsive force, which is typically of longer-range than on the first approach. This is most likely due to submicroscopic bubbles trapped and/or formed due to previous contacts (and separation) of the surfaces. The attraction of the second type is weak and exponentially decaying.

Fluorescence Correlation Spectroscopy Directly Monitors Coalescence During Nanoparticle Preparation

Dual color fluorescence cross-correlation spectroscopy (DC FCCS) experiments were conducted to study the coalescence and aggregation during the formation of nanoparticles. To assess the generality of the method, three completely different processes were selected to prepare the nanoparticles. Polymeric nanoparticles were formed either by solvent evaporation from emulsion nanodroplets of polymer solutions or by miniemulsion polymerization. Inorganic nanocapsules were formed by polycondensation of alkoxysilanes at the interface of nanodroplets. In all cases, DC FCCS provided fast and unambiguous information about the occurrence of coalescence and thus a deeper insight into the mechanism of nanoparticle formation. In particular, it was found that coalescence played a minor role for the emulsion-solvent evaporation process and the miniemulsion polymerization, whereas substantial coalescence was detected during the formation of the inorganic nanocapsules. These findings demonstrate that DC FCCS is a powerful tool for monitoring nanoparticles genesis.

Tracer diffusion in silica inverse opals.

We employed fluorescence correlation spectroscopy (FCS) to study the diffusion of small fluorescence tracers in liquid filled silica inverse opals. The inverse opals consisted of a nanoporous silica scaffold spanning a hexagonal crystal of spherical voids of 360 nm diameter connected by circular pores of 70 nm diameter. The diffusion of Alexa Fluor 488 in water and of perylene-3,4,9,10-tetracarboxylic diimide (PDI) in toluene was studied. Three diffusion modes could be distinguished: (1) Free diffusion limited by the geometric constraints given by the inverse opal, where, as compared to the free solution, this diffusion is slowed down by a factor of 3-4, (2) slow diffusion inside the nanoporous matrix of the silica scaffold, and (3) diffusion limited by adsorption. On the length scale of the focus of a confocal microscope of roughly 400 nm diffusion was non-Fickian in all cases.

Solvent-Free Synthesis of Microparticles on Superamphiphobic Surfaces†

Polymeric and composite microspheres can be synthesized without solvents or process liquids by using superamphiphobic surfaces. In this method, the repellency of superamphiphobic layers to monomers and polymer melts and the extremely low adhesion to particles are taken advantage of.