Wettability is the affinity of a liquid for a solid surface. For energetic reasons, macroscopic drops of liquid form nearly spherical caps. The degree of wettability is then captured by the contact angle where the liquid-vapor interface meets the solid-liquid interface. As droplet volumes shrink to the scale of attoliters, however, surface interactions become significant, and droplets assume distorted shapes. In this regime, the contact angle becomes ambiguous, and a scalable metric for quantifying wettability is needed, especially given the emergence of technologies exploiting liquid-solid interactions at the nanoscale. Here we combine nanoscale experiments with molecular-level simulation to study the breakdown of spherical droplet shapes at small length scales. We demonstrate how measured droplet topographies increasingly reveal non-spherical features as volumes shrink. Ultimately, the nanoscale droplets flatten out to form layer-like molecular assemblies at the solid surface. For the lack of an identifiable contact angle at small scales, we introduce a droplet’s adsorption energy density as a new metric for a liquid’s affinity for a surface. We discover that extrapolating the macroscopic idealization of a drop to the nanoscale, though it does not geometrically resemble a realistic droplet, can nonetheless recover its adsorption energy if line tension is included.
A water drop on a superhydrophobic surface that is pinned by wire loops can be reproducibly cut without formation of satellite droplets. Drops placed on low-density polyethylene surfaces and Teflon-coated glass slides were cut with superhydrophobic knives of low-density polyethylene and treated copper or zinc sheets, respectively. Distortion of drop shape by the superhydrophobic knife enables a clean break. The driving force for droplet formation arises from the lower surface free energy for two separate drops, and it is modeled as a 2-D system. An estimate of the free energy change serves to guide when droplets will form based on the variation of drop volume, loop spacing and knife depth. Combining the cutting process with an electrofocusing driving force could enable a reproducible biomolecular separation without troubling satellite drop formation.
The coffee-ring effect, ubiquitously present in the drying process of aqueous droplets, impedes the performance of a myriad of applications involving precipitation of particle suspensions in evaporating liquids on solid surfaces, such as liquid biopsy combinational analysis, microarray fabrication, and ink-jet printing, to name a few. We invented the methodology of laser-induced differential evaporation to remove the coffee-ring effect. Without any additives to the liquid or any morphology modifications of the solid surface the liquid rests on, we have eliminated the coffee-ring effect by engineering the liquid evaporation profile with a CO2laser irradiating the apex of the droplets. The method of laser-induced differential evaporation transitions particle deposition patterns from coffee-ring patterns to central-peak patterns, bringing all particles (e.g. fluorescent double strand DNAs) in the droplet to a designated area of 100 μm diameter without leaving any stains outside. The technique also moves the drying process from the constant contact radius (CCR) mode to the constant contact angle (CCA) mode. Physical mechanisms of this method were experimentally studied by internal flow tracking and surface evaporation flux mapping, and theoretically investigated by development of an analytical model.
Controlling the wetting behaviour of liquids on surfaces is important for a variety of industrial applications such as water-repellent coatings and lubrication. Liquid behaviour on a surface can range from complete spreading, as in the ‘tears of wine’ effect, to minimal wetting as observed on a superhydrophobic lotus leaf. Controlling droplet movement is important in microfluidic liquid handling, on self-cleaning surfaces and in heat transfer. Droplet motion can be achieved by gradients of surface energy. However, existing techniques require either a large gradient or a carefully prepared surface to overcome the effects of contact line pinning, which usually limit droplet motion. Here we show that two-component droplets of well-chosen miscible liquids such as propylene glycol and water deposited on clean glass are not subject to pinning and cause the motion of neighbouring droplets over a distance. Unlike the canonical predictions for these liquids on a high-energy surface, these droplets do not spread completely but exhibit an apparent contact angle. We demonstrate experimentally and analytically that these droplets are stabilized by evaporation-induced surface tension gradients and that they move in response to the vapour emitted by neighbouring droplets. Our fundamental understanding of this robust system enabled us to construct a wide variety of autonomous fluidic machines out of everyday materials.
Flexible skin-attachable strain-gauge sensors are an essential component in the development of artificial systems that can mimic the complex characteristics of the human skin. In general, such sensors contain a number of circuits or complex layered matrix arrays. Here, we present a simple architecture for a flexible and highly sensitive strain sensor that enables the detection of pressure, shear and torsion. The device is based on two interlocked arrays of high-aspect-ratio Pt-coated polymeric nanofibres that are supported on thin polydimethylsiloxane layers. When different sensing stimuli are applied, the degree of interconnection and the electrical resistance of the sensor changes in a reversible, directional manner with specific, discernible strain-gauge factors. The sensor response is highly repeatable and reproducible up to 10,000 cycles with excellent on/off switching behaviour. We show that the sensor can be used to monitor signals ranging from human heartbeats to the impact of a bouncing water droplet on a superhydrophobic surface.
Wetting and dewetting are both fundamental modes of motion of liquids on solid surfaces. They are critically important for processes in biology, chemistry, and engineering, such as drying, coating, and lubrication. However, recent progress in wetting, which has led to new fields such as superhydrophobicity and liquid marbles, has not been matched by dewetting. A significant problem has been the inability to study the model system of a uniform film dewetting from a nonwetting surface to a single macroscopic droplet-a barrier that does not exist for the reverse wetting process of a droplet spreading into a film. We report the dewetting of a dielectrophoresis-induced film into a single equilibrium droplet. The emergent picture of the full dewetting dynamics is of an initial regime, where a liquid rim recedes at constant speed and constant dynamic contact angle, followed by a relatively short exponential relaxation of a spherical cap shape. This sharply contrasts with the reverse wetting process, where a spreading droplet follows a smooth sequence of spherical cap shapes. Complementary numerical simulations and a hydrodynamic model reveal a local dewetting mechanism driven by the equilibrium contact angle, where contact line slip dominates the dewetting dynamics. Our conclusions can be used to understand a wide variety of processes involving liquid dewetting, such as drop rebound, condensation, and evaporation. In overcoming the barrier to studying single film-to-droplet dewetting, our results provide new approaches to fluid manipulation and uses of dewetting, such as inducing films of prescribed initial shapes and slip-controlled liquid retraction.
Microfluidic chips provide unparalleled control over droplets and jets, which have advanced all natural sciences. However, microfluidic applications could be vastly expanded by increasing the per-channel throughput and directly exploiting the output of chips for rapid additive manufacturing. We unlock these features with in-air microfluidics, a new chip-free platform to manipulate microscale liquid streams in the air. By controlling the composition and in-air impact of liquid microjets by surface tension-driven encapsulation, we fabricate monodisperse emulsions, particles, and fibers with diameters of 20 to 300 μm at rates that are 10 to 100 times higher than chip-based droplet microfluidics. Furthermore, in-air microfluidics uniquely enables module-based production of three-dimensional (3D) multiscale (bio)materials in one step because droplets are partially solidified in-flight and can immediately be printed onto a substrate. In-air microfluidics is cytocompatible, as demonstrated by additive manufacturing of 3D modular constructs with tailored microenvironments for multiple cell types. Its in-line control, high throughput and resolution, and cytocompatibility make in-air microfluidics a versatile platform technology for science, industry, and health care.
- Proceedings of the National Academy of Sciences of the United States of America
- Published over 7 years ago
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.
Hierarchically structured, superoleophobic surfaces displaying one of the lowest contact angle hysteresis ever reported are developed by Anish Tuteja and co-workers on page 5838. These surfaces allow droplets of the extremely low surface tension liquid, n-heptane, to bounce and roll off at tilt angles ≤ 2°.
This paper describes a facile method for the preparation of porous gelatin beads with uniform pore sizes using a simple fluidic device and their application as supporting materials for cell culture. An aqueous gelatin droplet containing many uniform toluene droplets, produced in the fluidic device, is dropped into liquid nitrogen for instant freezing and the small toluene droplets evolve into pores in the gelatin beads after removal of toluene and then freeze-drying. The porous gelatin beads exhibit a uniform pore size and monodisperse diameter as well as large open pores at the surface. Fluorescence microscopy images of fibroblast-loaded gelatin beads confirm the attachment and proliferation of the cells throughout the porous gelatin beads.