Evaporation of picoliter droplets on surfaces with a range of wettabilities and thermal conductivities.

The evaporation of picoliter water and ethanol droplets generated by drop-on-demand inkjet printing was investigated on substrates with apparent contact angles between 10^{∘} and 135^{∘} and thermal conductivities between 0.25 and 149 Wm^{-1}K^{-1}. Drying times were calculated from a diffusion-limited model for droplets with both pinned and moving contact lines as a function of droplet diameter and apparent contact angle. Droplets with a moving contact line take longer to dry on hydrophilic substrates than pinned droplets. The difference in drying times between evaporative modes vanishes at large apparent contact angles. Hence similar drying times are obtained for both modes on hydrophobic substrates. The predicted drying times for glass and silicon substrates were in good quantitative agreement with experimental data, suggesting that thermal effects are negligible for substrates of these base materials. However, on a PTFE substrate which has a lower thermal conductivity more relevant to inkjet printing, evaporative cooling reduces the evaporation rate causing drying times to be underpredicted by isothermal models.

Superhydrophobic hierarchical honeycomb surfaces.

Two-dimensional hexagonally ordered honeycomb surfaces have been created by solvent casting polybutadiene films under controlled humidity. Subsequent CF(4) plasmachemical fluorination introduces cross-linking and surface texturing, leading to hierarchical surfaces with roughness on both the 10 µm (honeycomb) and micrometer (texturing) length scales. For microliter droplets, these display high water contact angle values (>170°) in combination with low contact angle hysteresis (i.e., superhydrophobicity) while displaying bouncing of picoliter water droplets. In the case of picoliter droplets, it is found that surfaces which exhibit similar static contact angles can give rise to different droplet impact dynamics, governed by the underlying surface topography. These studies are of relevance to technological processes such as rapid cooling, delayed freezing, crop spraying, and inkjet printing.

Impact of picoliter droplets on superhydrophobic surfaces with ultralow spreading ratios.

The impact of picoliter-sized water droplets on superhydrophobic CF(4) plasma fluorinated polybutadiene surfaces is investigated with high-speed imaging. Variation of the surface topography by plasmachemical modification enables the dynamics of wetting to be precisely controlled. Final spreading ratios as low as 0.63 can be achieved. A comparison of the maximum spreading ratio and droplet oscillation frequencies to models described in the literature shows that both are found to be much lower than theoretically predicted.

On the predictions and limitations of the Becker-Döring model for reaction kinetics in micellar surfactant solutions.

We investigate the breakdown of a system of micellar aggregates in a surfactant solution following an order-one dilution. We derive a mathematical model based on the Becker-Döring system of equations, using realistic expressions for the reaction constants fit to results from Molecular Dynamics simulations. We exploit the largeness of typical aggregation numbers to derive a continuum model, substituting a large system of ordinary differential equations for a partial differential equation in two independent variables: time and aggregate size. Numerical solutions demonstrate that re-equilibration occurs in two distinct stages over well-separated timescales, in agreement with experiment and with previous theories. We conclude by exposing a limitation in the Becker-Döring theory for re-equilibration of surfactant solutions.

Complexes of surfactants with oppositely charged polymers at surfaces and in bulk.

Addition of surfactants to aqueous solutions of polyelectrolytes carrying an opposite charge causes the spontaneous formation of complexes in the bulk phase in certain concentration ranges. Under some conditions, compact monodisperse multichain complexes are obtained in the bulk. The size of these complexes depends on the mixing procedure and it can be varied in a controlled way from nanometers up to micrometers. The complexes exhibit microstructures analogous to those of the precipitates formed at higher concentrations. In other cases, however, the bulk complexes are large, soft and polydisperse. In most cases, the dispersions are only kinetically stable and exhibit pronounced non-equilibrium features. Association at air-water interfaces readily occurs, even at very small concentrations. When the surfactant concentration is small, the surface complexes are usually made of a surfactant monolayer to which the polymer binds and adsorbs in a flat-like configuration. However, under some conditions, thicker layers can be found, with bulk complexes sticking to the surface. The association at solid-water interfaces is more complex and depends on the specific interactions between surfactants, polymers and the surface. However, the behaviour can be understood if distinctions between hydrophilic surfaces and hydrophobic surfaces are made. Note that the behaviour at air-water interfaces is closer to that of hydrophobic than that of hydrophilic solid surfaces. The relation between bulk and surface complexation will be discussed in this review. The emphasis will be given to the results obtained by the teams of the EC-funded Marie Curie RTN "SOCON".

Mixtures of n-dodecyl-beta-D-maltoside and hexaoxyethylene dodecyl ether--surface properties, bulk properties, foam films, and foams.

Mixtures of the two non-ionic surfactants hexaoxyethylene dodecyl ether (C(12)E(6)) and n-dodecyl-beta-D-maltoside (beta-C(12)G(2)) were studied with regard to surface properties, bulk properties, foam films, and foams. The reason for studying a mixture of an ethylene oxide (C(i)E(j)) and a sugar (C(n)G(m)) based surfactant is that despite being non-ionic, these two surfactants behave quite differently. Firstly, the physico-chemical properties of aqueous solutions of C(n)G(m) surfactants are less temperature-sensitive than those of C(i)E(j) solutions. Secondly, the surface charge density q(0) of foam films stabilized by C(n)G(m) surfactants is pH insensitive down to the so-called isoelectric point, while that of foam films stabilized by C(i)E(j) surfactants changes linearly with the pH. The third difference is related to interaction forces between solid surfaces. Under equilibrium conditions very high forces are needed to expel beta-C(12)G(2) from between thiolated gold surfaces, while for C(12)E(6) low loads are sufficient. Fourthly, the adsorption of C(12)E(6) and beta-C(12)G(2) on hydrophilic silica and titania, respectively, is inverted. While the surface excess of C(12)E(6) is large on silica and negligible on titania, beta-C(12)G(2) adsorbs very little on silica but has a large surface excess on titania. What is the reason for this different behaviour? Under similar conditions and for comparable head group sizes, it was found that the hydration of C(i)E(j) surfactants is one order of magnitude higher but on average much weaker than that of C(n)G(m) surfactants. Moreover, C(n)G(m) surfactants possess a rigid maltoside unit, while C(i)E(j) surfactants have a very flexible hydrophilic part. Indeed, most of the different properties mentioned above can be explained by the different hydration and the head group flexibilities. The intriguing question of how mixtures of C(i)E(j) and C(n)G(m) surfactants would behave arises organically. Thus various properties of C(12)E(6)+beta-C(12)G(2) mixtures in aqueous solution have been studied with a focus on the 1:1 mixture. The results are compared with those of the single surfactants and are discussed accordingly.

Emergent properties in optically bound matter.

Sub-micron particles have been observed to spontaneously form regular two-dimensional structures in counterpropagating evanescent laser fields. We show that collective properties of large numbers of optically-trapped particles can be qualitatively different to the properties of small numbers. This is demonstrated both with a computer model and with experimental results. As the number of particles in the structure is increased, optical binding forces can be sufficiently large to overcome the optical landscape imposed by the interference fringes of the laser beams and impose a different, competing structure.

Wetting, mixing, and phase transitions in Langmuir-Gibbs films.

Millimolar bulk concentrations of the surfactant cetyltrimethylammonium bromide (CTAB) induce spreading of alkanes, H(CH(2))(n)H (denoted C(n)) 12< or =n< or =21, on the water surface, which is not otherwise wet by these alkanes. The novel Langmuir-Gibbs film (LGF) formed is a liquidlike monolayer comprising both alkanes and CTAB tails. Upon cooling, an ordering transition occurs, yielding a hexagonally packed, quasi-2D crystal. For 11< or =n< or =17 this surface-frozen LGF is a crystalline monolayer. For 18< or =n< or =21 the LGF is a bilayer with a crystalline, pure-alkane, upper monolayer, and a liquidlike lower monolayer. The phase diagram and film structure were determined by x-ray, ellipsometry, and surface tension measurements. A thermodynamic theory accounts quantitatively for the observations.

Lattice model for the wetting transition of alkanes on aqueous surfactant solutions.

Droplets of alkanes on aqueous solutions of the cationic surfactants C(n)TAB (CH3(CH2)(n-1)N+ (CH3)3Br-) exhibit a first-order wetting transition as the concentration of the surfactant is increased. A theoretical model is presented in which the surface free energy is broken down into a long-range dispersion interaction and a short-range interaction described by a 2D lattice gas, taking into account the interaction between oil and surfactant molecules. The model provides quantitative agreement with the observed wetting transitions and the variation in composition of the wetting film with bulk surfactant concentration. The behavior of oil drops on large reservoirs of dilute surfactant is discussed.

Motion of liquids on surfaces.

The macroscopic manipulation of liquids is a core component to the development of microfluidic devices. Although the Marangoni effect has been described for well over a century, actively tuning such surface tension effects is a more recent achievement. This Highlight compares recently reported electro- and photochemical methods in which this liquid manipulation has occurred. One such method, electrocapillarity as utilised by Prins et al., is shown in the picture.

Molecular-Level Control over Surface Order in Self-Assembled Monolayer Films of Thiols on Gold.

Long-chain omegahydroxyalkanethiols [HS(CH(2))nOH] coordinate to gold surfaces through the sulfur atom and produce ordered, hydrophilic monolayers in which the hydroxyl groups are exposed at the outer surface. Coadsorption of two omega-hydroxyalkanethiols of different chain lengths n resulted in the formation of a monolayer having a disordered surface region that was markedly less hydrophilic than the homogeneous, hydroxylic surface formed from either pure compound. By controlling the composition of the monolayer, it was also possible to control simultaneously the degree of order in the surface and its hydrophilicity. In the monolayers containing a mixture of alkanethiol components, these components apparently did not phase-segregate into macroscopic islands, but were dispersed on a molecular scale. assistance and many useful discussions.