Drying Liquid Coatings with an Evaporation Mask: Theory and Experiments.

We report a study of the spatially varying thickness of dried films of polymer solutions resulting from a nonuniform evaporation flux. The controlled heterogeneity of the evaporation flux is imposed by placing a solid mask above the evaporating film spread on a solid substrate. At the end of drying, a depression has formed under the mask, together with overthicknesses extending from the edge of the mask and over distances that may be larger than its size. By considering the flows induced in a vertically homogeneous film, we obtain analytical solutions for the thickness profiles during drying using a linear approximation in the limits of either gravity or capillarity-driven flows. We demonstrate that gravity can play a role in the deformations of the films, even if their initial thicknesses are 1 order of magnitude smaller than the capillary length. In addition, we examine two possible reference states for the linear approximation, i.e., far from the mask in the film of decreasing thickness and increasing viscosity, or under the mask where no evaporation occurs. We further compare these results with experimental ones obtained by drying thin films of polymer solutions under a mask. Both the extent and amplitude of the thickness heterogeneities of the dry film are quantitatively predicted by the linear analysis for a reference state under the mask. Our results therefore provide new insight on the patterns resulting from evaporation masks and can be generalized to minimize thickness heterogeneities in any situation in which the evaporation flux is nonuniform.

New Platform for Gravitational Microfluidic Using Ferrofluids.

Among the large variety of microfluidic platforms, surface devices are a world apart. Electrowetting systems are used to control the displacement of droplets among predetermined pathways. More confidential, superhydrophobic surfaces are more and more described as new elements to guide spherical droplet reactors. As such, they can exhibit confinement properties analogous to channel-based microfluidics. In this article, we describe a new strategy to use superhydrophobic surfaces as a permanently tilted microfluidic platform, on which droplets containing iron oxide nanoparticles are guided with permanent magnets. These droplets are fed with water through a capillary tube until their weight exceeds the magnetic field force. Thus, the volume at which the droplet rolls off the surface is only governed by the initial quantity of magnetic nanoparticles and the tilting angle of the surface. This phenomenon provides a strategy for droplet dilution in a simple and reproducible manner, which is not that easy in microchannels, and a key advantage of open systems. As a proof of concept, we used this platform to prepare magnetic filaments by a salting-out process already described in large batches. By reducing salt concentration on the platform, we are able to control the electrostatic attractive interactions between iron oxide nanoparticles coated with poly(acrylic acid) and a positively charged polyelectrolyte [poly(diallyldimethylammonium chloride)]. The formation of nanostructured filaments was conducted in 2 min while more than 30 min was required for dialysis. Our results also illustrate the power of microfluidic reaction processes because such magnetic filaments could not be obtained through direct batch dilution because of mixing issues. Such microfluidic platforms could be useful for the efficient and simple dilution of systems where reactivity is controlled by concentration.

Experimental studies of the transmission of light through low-coverage regular or random arrays of silica micropillars supported by a glass substrate.

The transmission of light through low-coverage regular and random arrays of glass-supported silica micropillars of diameters 10-40 µm and height 10 µm is studied experimentally. Angle-resolved measurements of the transmitted intensity are performed at visible wavelengths by either a goniospectrophotometer or a multimodal imaging (Mueller) polarimetric microscope. It is demonstrated that for the regular arrays, the angle-resolved measurements are capable of resolving many of the densely packed diffraction orders that are expected for periodic structures of lattice constants 20-80 µm, but they also display features ("halos" and fringes) that are due to the scattering and guiding of light in individual micropillars or in the supporting glass slides. These latter features are also found in angle-resolved measurements on random arrays of micropillars of the same surface coverage. Finally, we perform a comparison of direct measurements of haze in transmission for our patterned glass samples with what can be calculated from the angle-resolved transmitted intensity measurements. Good agreement between the two types of results is found, which testifies to the accuracy of the angle-resolved measurements that we report.

Swelling Dynamics of Surface-Attached Hydrogel Thin Films in Vapor Flows.

Hydrogel coatings absorb water vapor, or other solvents, and, as such, are good candidates for antifog applications. In the present study, the transfer of vapor from the atmosphere to hydrogel thin films is measured in a situation where water vapor flows alongside the coating which is set to a temperature lower than the ambient temperature. The effect of the physico-chemistry of the hydrogel film on the swelling kinetics is particularly investigated. By using model thin films of surface-grafted polymer networks with controlled thickness, varied cross-links density, and varied affinity for water, we were able to determine the effect of the film hygroscopy on the dynamics of swelling of the film. These experimental results are accounted for by a diffusion-advection model that is supplemented with a boundary condition at the hydrogel surface: we show that the latter can be determined from the equilibrium sorption isotherms of the polymer films. Altogether, this paper offers a predictive tool for the swelling kinetics of any hydrophilic hydrogel thin film.

Wetting against the nap - how asperity inclination determines unidirectional spreading.

We have carried out wetting experiments on textured surfaces with high aspect ratio asperities in the Wenzel state. When inclination is imparted to the asperities, we observe a strictly unidirectional spreading opposite to the direction in which the asperities point. The advancing contact angle decreases markedly as inclination increases. A crude numerical analysis successfully accounts for this behaviour, highlighting the interplay between Gibbs pinning at the top of the structures and imbibition along the valleys between them. In Gibbs pinning non-linearities play a major role and we find that simple line averaging - i.e. a rule of mixture - cannot account for this evolution except for weak surface perturbations, i.e. large inclinations.

Self-replicating cracks: a collaborative fracture mode in thin films.

Straight cracks are observed in thin coatings under residual tensile stress, resulting into the classical network pattern observed in china crockery, old paintings, or dry mud. Here, we present a novel fracture mechanism where delamination and propagation occur simultaneously, leading to the spontaneous self-replication of an initial template. Surprisingly, this mechanism is active below the standard critical tensile load for channel cracks and selects a robust interaction length scale on the order of 30 times the film thickness. Depending on triggering mechanisms, crescent alleys, spirals, or long bands are generated over a wide range of experimental parameters. We describe with a simple physical model, the selection of the fracture path and provide a configuration diagram displaying the different failure modes.

Finite size effects on textured surfaces: recovering contact angles from vagarious drop edges.

A clue to understand wetting hysteresis on superhydrophobic surfaces is the relation between receding contact angle and surface textures. When the surface textures are large, there is a significant distribution of local contact angles around the drop. As seen from the cross section, the apparent contact angle oscillates as the triple line recedes. Our experiments demonstrate that the origin of these oscillations is a finite size effect. Combining side and bottom views of the drop, we take into account the 3D conformation of the surface near the edge to evaluate an intrinsic contact angle from the oscillations of the apparent contact angle. We find that for drops receding on axisymmetric textures the intrinsic receding contact angle is the minimum value of the oscillation while for a square lattice it is the maximum.

Role of kinks in the dynamics of contact lines receding on superhydrophobic surfaces.

We have investigated the depinning of the contact line on superhydrophobic surfaces with anisotropic periodic textures. By direct observation of the contact line conformation, we show that the mobility is mediated by kink defects. Full 3D simulations of the shape of the liquid surface near the solid confirm that kinks account for the measured wetting properties. This behavior, which is similar to the Peierls-Nabarro mechanism for dislocations, may open perspectives for the optimization of wetting hysteresis by design.

Controlled angular redirection of light via nanoimprinted disordered gratings.

Enhanced control of diffraction through transparent substrates is achieved via disordered gratings in a silica sol-gel film. Tailoring the degree of disorder allows tuning of the diffractive behavior from discrete orders into broad distributions over large angular range. Gratings of optical quality are formed by silica sol-gel nanoimprint lithography and an optical setup for the measurement of continuous diffraction patterns is presented. Sound agreement is found between measurements and simulation, validating both the approach for redirection of light and the fabrication process. The disordered gratings are presented in the context of improved interior daylighting and may furthermore be suited to a wide variety of applications where controlled angular redirection of light is desired.

Digital Microfluidics─How Magnetically Driven Orientation of Pillars Influences Droplet Positioning.

Interfaces between a water droplet and a network of pillars produce eventually superhydrophobic, self-cleaning properties. Considering the surface fraction of the surface in interaction with water, it is possible to tune precisely the contact angle hysteresis (CAH) to low values, which is at the origin of the poor adhesion of water droplets, inducing their high mobility on such a surface. However, if one wants to move and position a droplet, the lower the CAH, the less precise will be the positioning on the surface. While rigid surfaces limit the possibilities of actuation, smart surfaces have been devised with which a stimulus can be used to trigger the displacement of a droplet. Light, electron beam, mechanical stimulation like vibration, or magnetism can be used to induce a displacement of droplets on surfaces and transfer them from one position to the targeted one. Among these methods, only few are reversible, leading to anisotropy-controlled orientation of the structured interface with water. Magnetically driven superhydrophobic surfaces are the most promising reprogramming surfaces that can lead to the control of wettability and droplet guidance.

Towards a passive limitation of particle surface contamination in the Columbus module (ISS) during the MATISS experiment of the Proxima Mission.

Future long-duration human spaceflight calls for developments to limit biocontamination of the surface habitats. The MATISS experiment tests surface treatments in the ISS's atmosphere. Four sample holders were mounted with glass lamella with hydrophobic coatings, and exposed in the Columbus module for ~6 months. About 7800 particles were detected by tile scanning optical microscopy (×3 and ×30 magnification) indicating a relatively clean environment (a few particles per mm2), but leading to a significant coverage-rate (>2% in 20 years). Varied shapes were displayed in the coarse (50-1500 µm2) and fine (0.5-50 µm2) area fractions, consistent with scale dices (tissue or skin) and microbial cells, respectively. The 200-900 µm2 fraction of the coarse particles was systematically higher on FDTS and SiOCH than on Parylene, while the opposite was observed for the <10 µm2 fraction of the fine particles. This trend suggests two biocontamination sources and a surface deposition impacted by hydrophobic coatings.

All-silica nanofluidic devices for DNA-analysis fabricated by imprint of sol-gel silica with silicon stamp.

We present a simple and cheap method for fabrication of silica nanofluidic devices for single-molecule studies. By imprinting sol-gel materials with a multi-level stamp comprising micro- and nanofeatures, channels of different depth are produced in a single process step. Calcination of the imprinted hybrid sol-gel material produces purely inorganic silica, which has very low autofluorescence and can be fusion bonded to a glass lid. Compared to top-down processing of fused silica or silicon substrates, imprint of sol-gel silica enables fabrication of high-quality nanofluidic devices without expensive high-vacuum lithography and etching techniques. The applicability of the fabricated device for single-molecule studies is demonstrated by measuring the extension of DNA molecules of different lengths confined in the nanochannels.