Multiscale landscaping of droplet wettability on fibrous layers of facial masks.

Liquid mobility is ubiquitous in nature, with droplets emerging at all size scales, and artificial surfaces have been designed to mimic such mobility over the past few decades. Meanwhile, millimeter-sized droplets are frequently used for wettability characterization, even with facial mask applications, although these applications have a droplet-size target range that spans from millimeters to aerosols measuring less than a few micrometers. Unlike large droplets, microdroplets can interact sensitively with the fibers they contact with and are prone to evaporation. However, wetting behaviors at the single-microfiber level remain poorly understood. Herein, we characterized the wettability of fibrous layers, which revealed that a multiscale landscape of droplets ranged from the millimeter to the micrometer scale. The contact angle (CA) values of small droplets on pristine fibrous media showed sudden decrements, especially on a single microfiber, owing to the lack of air cushions for the tiny droplets. Moreover, droplets easily adhered to the pristine layer during droplet impact tests and then yielding widespread areas of contamination on the microfibers. To resolve this, we carved nanowalls on the pristine fibers by plasma etching, which effectively suppressed such wetting phenomena. Significantly, the resulting topographies of the microfibers managed the dynamic wettability of droplets at the multiscale, which reduced the probability of contamination with impact droplets and suppressed the wetting transition upon evaporation. These findings for the dynamic wettability of fibrous media will be useful in the fight against infectious droplets.

Development of rapid and effective oil-spill response system integrated with oil collection, recovery and storage devices for small oil spills at initial stage: From lab-scale study to field-scale test.

In the present study, through the laboratory-to-field scale experiments and trials, we report the development and evaluation of an integrated oil-spill response system capable of oil collection, recovery (separation), and storage, for a timely and effective response to the initial stage of oil-spill accidents. With the laboratory-scale experiments, first, we evaluate that the water-surface waves tend to abate the oil recovery rate below 80% (it is above 95% for the optimized configuration without the waves), which is overcome by installing the hydrophilic (and oleophobic) porous structures at the inlet and/or near the water outlet of the separator. In the follow-up meso-scale towing tank tests with a scaled-up prototype, (i) we optimize the maneuverability of the assembled system depending on the speed and existence of waves, and (ii) evaluate the oil recovery performance (more than 80% recovery for the olive oil and Bunker A fuel oil). Although more thorough investigations and improvements are needed, a recovery rate of over 50% can be achieved for the newly enforced marine fuel oil (low sulfur fuel oil, LSFO) that was not targeted at the time of development. Finally, we perform a series of field tests with a full-scale system, to evaluate the rapid deployment and operational stability in the real marine environment. The overall floating balance and coordination of each functional part are sustained to be stable during the straight and rotary maneuvers up to the speed of 5 knots. Also, the collection of the floating debris (mimicking the spilled oil) is demonstrated in the field test. The present system is now being tested by the Korea Coast Guard and we believe that it will be very powerful to prevent the environmental damage due to the oil spills.

Highly stretchable and robust transparent conductive polymer composites for multifunctional healthcare monitoring.

Soft, stretchable, conductive thin films have propelled to the forefront of applications in stretchable sensors for on-skin health monitoring. Stretchable conductive films require high conformability, stretchability, and mechanical/chemical stability when integrated into the skin. Here, we present a highly stretchable, conductive, and transparent natural rubber/silver nanowire (AgNW)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) composite film. Overcoating the PEDOT:PSS layer results in outstanding mechanical robustness and chemical stability by suppressing the mechanical and chemical degradation of the nanowire networks. Moreover, the introduction of the organic surface modifier enhances the bonding strength between the natural rubber substrate and AgNW at the interface. The highly conformable composite films are integrated into multifunctional on-skin sensors for monitoring various human motions and biological signals with low-power consumption. We believe that the highly stretchable, robust, and conformable natural rubber/AgNW/PEDOT:PSS composite film can offer new opportunities for next-generation wearable sensors for body motion and physiological monitoring.

Clogged water bridges for fog harvesting.

Capillary water bridges clogged in the holes of mesh-type fog harvesters have previously been considered only as a drawback because they decrease fog-harvesting yield by hindering airflow in front of the clogged mesh in the usual wind conditions. In this study, we show that the role of a clogged water bridge may not be entirely negative and can contribute to increased fog harvesting by increasing the effective shade coefficient in a special condition with high fog inertia. As the fog speed close to the mesh or the plate increases, clogged mesh as well as the impermeable solid plate are found to produce high fog-harvesting efficiency owing to the high inertia of fog particles that impact the blocked wall. For fast fog speeds (∼4 m s-1) near the mesh, our results show that the fog-harvesting efficiency is proportional to the effective shade coefficient because fog flow circumventing the mesh is limited owing to high fog inertia. We analyzed the clogging effect on fog-harvesting performance by distinguishing between self-clogging and non-self-clogging patterns based on the water bridge stability clogged in mesh holes.

Spontaneous formation of aligned DNA nanowires by capillarity-induced skin folding.

Although DNA nanowires have proven useful as a template for fabricating functional nanomaterials and a platform for genetic analysis, their widespread use is still hindered because of limited control over the size, geometry, and alignment of the nanowires. Here, we document the capillarity-induced folding of an initially wrinkled surface and present an approach to the spontaneous formation of aligned DNA nanowires using a template whose surface morphology dynamically changes in response to liquid. In particular, we exploit the familiar wrinkling phenomenon that results from compression of a thin skin on a soft substrate. Once a droplet of liquid solution containing DNA molecules is placed on the wrinkled surface, the liquid from the droplet enters certain wrinkled channels. The capillary forces deform wrinkles containing liquid into sharp folds, whereas the neighboring empty wrinkles are stretched out. In this way, we obtain a periodic array of folded channels that contain liquid solution with DNA molecules. Such an approach serves as a template for the fabrication of arrays of straight or wrinkled DNA nanowires, where their characteristic scales are robustly tunable with the physical properties of liquid and the mechanical and geometrical properties of the elastic system.

Copper-Halide Polymer Nanowires as Versatile Supports for Single-Atom Catalysts.

Single-atom catalysts are heterogeneous catalysts with atomistically dispersed atoms acting as a catalytically active center, and have recently attracted much attention owing to the minimal use of noble metals. However, a scalable and inexpensive support that can stably anchor isolated atoms remains a challenge due to high surface energy. Here, copper-halide polymer nanowires with sub-nanometer pores are proposed as a versatile support for single-atom catalysts. The synthesis of the nanowires is straightforward and completed in a few minutes. Well-defined sub-nanometer pores and a large free volume of the nanowires are advantageous over any other support material. The nanowires can anchor various atomistically dispersed metal atoms into the sub-nanometer pores up to ≈3 at% via a simple solution process, and this value is at least twice as big as previously reported data. The hydrogen evolution reaction activity of -18.0 A mgPt -1 at -0.2 V overpotential shows its potential for single-atom catalysts support.

Nanotexturing of Conjugated Polymers via One-Step Maskless Oxygen Plasma Etching for Enhanced Tunable Wettability.

A one-step maskless oxygen plasma etching process is investigated to nanopattern conjugated polymer dodecylbenzenesulfonate doped polypyrrole (PPy(DBS)) and to examine the effects of nanostructures on the inherent tunable wettability of the surface and the droplet mobility. Etching characteristics such as the geometry and dimensions of the nanostructures are systematically examined for the etching power and duration. The mechanism of self-formation of vertically aligned dense-array pillared nanostructures in the one-step maskless oxygen plasma etching process is also investigated. Results show that lateral dimensions such as the periodicity and diameter of the pillared nanostructures are insensitive to the etching power and duration, whereas the length and aspect ratio of the nanostructures increase with them. X-ray photoelectron spectroscopy analysis and thermal treatment of the polymer reveal that the codeposition of impurities on the surface resulting from the holding substrate is the primary reason for the self-formation of nanostructures during the oxygen plasma etching, whereas the local crystallinity subject to thermal treatment has a minor effect on the lateral dimensions. Retaining the tunable wettability (oleophobicity) for organic droplets during the electrochemical redox (i.e., reduction and oxidization) process, the nanotextured PPy(DBS) surface shows significant enhancement of droplet mobility compared to that of the flat PPy(DBS) surface with no nanotexture by making the surface superoleophobic (i.e., in a Cassie-Baxter wetting state). Such enhancement of the tunable oleophobicity and droplet mobility of the conjugated polymer will be of great significance in many applications such as microfluidics, lab-on-a-chip devices, and water/oil treatment.

Rings, igloos, and pebbles of salt formed by drying saline drops.

It is well-known that evaporation of sessile drops with suspended particles like colloids and coffee powders can yield a variety of two-dimensional patterns depending on the particle shapes and internal flow patterns. Here we show that ordered three-dimensional structures can be built via evaporation of saline drops on highly hydrophobic substrates like pristine PP (polypropylene) with micropores and nanostructured low-surface-energy PP. On pristine PP having a high contact angle but a large contact angle hysteresis (CAH) with water, either rings or igloos of salt are formed depending on the salt concentration and evaporation rate. On nanostructured low-surface-energy PP having extreme water repellency with a very low CAH, pebbles of salt are formed regardless of salt concentration and evaporation rate. These observations lead us to conclude that combined effects of solubility, evaporation rate, and mobility of the contact line determine the final three-dimensional shape of the salt precipitate.

Dimensional Control of Highly Anisotropic and Transparent Conductive Coordination Polymers for Solution-Processable Large-Scale 2D Sheets.

Controlling the dimensional aspect of conductive coordination polymers is currently a key scientific interest. Herein, solution-based dimension control strategies are proposed for copper chloride thiourea (CuCl-TU) coordination polymers that enable centimeter-scale, 2D nanosheet formation for use as transparent electrodes. Despite the wide bandgap of CuCl-TU polymers (4.33 eV), through polaron-mediated electron transfer, the electrical conductivity of the 2D sheet at room temperature is able to reach 4.45 S cm-1 without intentional doping. This leads to a highly anisotropic electronic conductivity of up to the order of ≈103 differences, depending on the material orientation. Furthermore, by substituting alternative thiourea candidates, it is demonstrated that it is possible to predesign CuCl-TU structures with the desired functionality, stability, and porosity through dimensional control. These findings provide a blueprint to design next-generation transparent conducting materials that can operate at room temperature, thereby expanding their applicability to different fields.

Universal Stretchable Conductive Cellulose/PEDOT:PSS Hybrid Films for Low Hysteresis Multifunctional Stretchable Electronics.

Skin-attachable conductive materials have attracted significant attention for use in wearable devices and physiological monitoring applications. Soft, skin-like conductive films must have excellent mechanical and electrical characteristics with on-skin conformability, stretchability, and robustness to detect body motion and biological signals. In this study, a conductive, stretchable, hydro-biodegradable, and highly robust cellulose/poly(3,4-ethylene dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) hybrid film is fabricated. Through the synergetic interplay of a conductivity enhancer, nonionic fluorosurfactant, and surface modifier, the mechanical and electrical properties of the stretchable hybrid film are greatly improved. The stretchable cellulose/PEDOT:PSS hybrid film achieves a limited resistance change of only 1.21-fold after 100 stretch-release cycles (30% strain) with exceptionally low hysteresis, demonstrating its great potential as a stretchable electrode for stretchable electronics. In addition, the film shows excellent biodegradability, promising environmental friendliness, and safety benefits. High-performance stretchable cellulose/PEDOT:PSS hybrid films, which have high biocompatibility and sensitivity, are applied to human skin to serve as on-skin multifunctional sensors. The conformally mounted on-skin sensors are capable of continuously monitoring human physiological signals, such as body motions, drinking, respiration rates, vocalization, humidity, and temperature, with high sensitivity, fast responses, and low power consumption (21 µW). The highly conductive hybrid films developed in this study can be integrated as both stretchable electrodes and multifunctional healthcare monitoring sensors. We believe that the highly robust stretchable, conductive, biodegradable, skin-attachable cellulose/PEDOT:PSS hybrid films are worthy candidates as promising soft conductive materials for stretchable electronics.

Self-Healable Conductive Hydrogels with High Stretchability and Ultralow Hysteresis for Soft Electronics.

Stretchable sensors based on conductive hydrogels have attracted considerable attention for wearable electronics. However, their practical applications have been limited by the low sensitivity, high hysteresis, and long response times of the hydrogels. In this study, we developed high-performance poly(vinyl alcohol) (PVA)/poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) based hydrogels post-treated with NaCl, which showed excellent mechanical properties, fast electrical response, and ultralow hysteresis properties. The hydrogels also demonstrated excellent self-healing properties with electrical and mechanical properties comparable to those of the original hydrogel and more than 150% elongation at break after the self-healing process. The high performance of the optimized hydrogels was attributed to the enhanced intermolecular forces between the PVA matrix and PEDOT:PSS, the favorable conformational change of the PEDOT chains, and an increase in localized charges in the hydrogel networks. The hydrogel sensors were capable of tracking large human motion and subtle muscle action in real time with high sensitivity, a fast response time (0.88 s), and low power consumption (<180 µW). Moreover, the sensor was able to monitor human respiration due to chemical changes in the hydrogel. These highly robust, stretchable, conductive, and self-healing PVA/PEDOT:PSS hydrogels, therefore, show great application potential as wearable sensors for monitoring human activity.

Fatigue-free, electrically reliable copper electrode with nanohole array.

Design and fabrication of reliable electrodes is one of the most important challenges in flexible devices, which undergo repeated deformation. In conventional approaches, mechanical and electrical properties of continuous metal films degrade gradually because of the fatigue damage. The designed incorporation of nanoholes into Cu electrodes can enhance the reliability. In this study, the electrode shows extremely low electrical resistance change during bending fatigue because the nanoholes suppress crack initiation by preventing protrusion formation and damage propagation by crack tip blunting. This concept provides a key guideline for developing fatigue-free flexible electrodes.

Water harvest via dewing.

Harvesting water from humid air via dewing can provide a viable solution to a water shortage problem where liquid-phase water is not available. Here we experimentally quantify the effects of wettability and geometry of the condensation substrate on the water harvest efficiency. Uniformly hydrophilic surfaces are found to exhibit higher rates of water condensation and collection than surfaces with lower wettability. This is in contrast to a fog basking method where the most efficient surface consists of hydrophilic islands surrounded by hydrophobic background. A thin drainage path in the lower portion of the condensation substrate is revealed to greatly enhance the water collection efficiency. The optimal surface conditions found in this work can be used to design a practical device that harvests water as its biological counterpart, a green tree frog, Litoria caerulea , does during the dry season in tropical northern Australia.

Unclogged Janus Mesh for Fog Harvesting.

Janus membranes with asymmetric surface wettability have been extensively utilized in various fields, including fog harvesting, because of their novel liquid transport properties. However, Janus membranes have an inherent disadvantage in terms of aerodynamic efficiency in harvesting fog because of the clogged water bridges caused by the small pore size. In the present work, we applied Janus wettability to mesh geometry with systematically varying hole sizes. For a clogged mesh with a small hole size, capillary water transport to the mesh back via the wettability gradient in the direction of fog flow helps harvest more fog by enhancing water drainage, similarly to the Janus membrane. The advantage of the capillary water transport extends to a clog-free mesh with larger hole sizes but more preferably to a Janus mesh with a superhydrophilic back, which presents the highest level of fog-harvesting yield because of the fast shedding frequency and short onset time. In contrast, a Janus mesh with a superhydrophobic front, which also has a wettability gradient along the fog flow, produces a lower fog-harvesting performance, particularly at slow fog speeds, because of the dropwise deposition of large water drops that locally disturb fog flow around a protruding water surface. On the other hand, the other type of Janus mesh with a superhydrophilic front is observed to minimize this disadvantage in the local fog flow by virtue of the filmwise deposition. It is also found that some Janus treatments can help protect mesh holes from clogging up by either forming a thin water meniscus or resisting water transport through the mesh holes.

Hygroscopic ramie fabrics for recovering highly viscous low sulfur fuel oil.

Low sulfur fuel oils (LSFOs) with less than 0.5% sulfur content have been mandated for marine vessels by the International Maritime Organization since 2020. However, owing to the low dispersibility and high viscosity of LSFOs, their oceanic spills are difficult to clean using conventional response systems. In this study, we propose a superhydrophilic and hygroscopic ramie to clean spilled LSFO. To this end, a raw ramie fiber, which is intrinsically hydrophobic, was treated using a mild alkali to remove its waxy, rough, and gummy veneer and reveal a smooth surface. This substantially improved its hygroscopic nature, superhydrophilicity, and water-retention, while preserving its mechanical durability in dry and wet environments. The hygroscopic ramie exhibited underwater superoleophobicity and self-cleaning abilities against highly adhesive LSFOs. Two proofs-of-concept are demonstrated in this study-an oil-proof glove for maximizing oil repellency and a direct oil-scooping device for simple and continuous recovery of spilled oil with high efficiency.

Stretchable and Conductive Cellulose/Conductive Polymer Composite Films for On-Skin Strain Sensors.

Conductive composite materials have attracted considerable interest of researchers for application in stretchable sensors for wearable health monitoring. In this study, highly stretchable and conductive composite films based on carboxymethyl cellulose (CMC)-poly (3,4-ethylenedioxythiopehe):poly (styrenesulfonate) (PEDOT:PSS) (CMC-PEDOT:PSS) were fabricated. The composite films achieved excellent electrical and mechanical properties by optimizing the lab-synthesized PEDOT:PSS, dimethyl sulfoxide, and glycerol content in the CMC matrix. The optimized composite film exhibited a small increase of only 1.25-fold in relative resistance under 100% strain. The CMC-PEDOT:PSS composite film exhibited outstanding mechanical properties under cyclic tape attachment/detachment, bending, and stretching/releasing tests. The small changes in the relative resistance of the films under mechanical deformation indicated excellent electrical contacts between the conductive PEDOT:PSS in the CMC matrix, and strong bonding strength between CMC and PEDOT:PSS. We fabricated highly stretchable and conformable on-skin sensors based on conductive and stretchable CMC-PEDOT:PSS composite films, which can sensitively monitor subtle bio-signals and human motions such as respiratory humidity, drinking water, speaking, skin touching, skin wrinkling, and finger bending. Because of the outstanding electrical properties of the films, the on-skin sensors can operate with a low power consumption of only a few microwatts. Our approach paves the way for the realization of low-power-consumption stretchable electronics using highly stretchable CMC-PEDOT:PSS composite films.

Slippery, Water-Infused Membrane with Grooved Nanotrichomes for Lubricating-Induced Oil Repellency.

Water, abundant and ubiquitous in nature, is an easy yet powerful resource for the creatures to survive by putting together with their topologies interfacing their living environment. Here, a slippery, water-infusing surface (SWIS) that retains a thick and stable water layer on the membrane is presented, robustly maintaining the oil repellency against the pressure and friction of immiscible liquids. Inspired by the plant trichome structures and their function, grooved nanotrichome, formed on the fibrous membrane by the oxygen plasma etching, induces robust water lubrication on the SWIS. SWIS membrane repels and separates highly viscous and adhesive oils in air and underwater by preventing oils from adhering to the lubricating surface. Repeated tests both in air and underwater confirm the antiadhesion and self-cleaning properties of the SWIS. The SWIS oil scooper, fixed on a frame with a handle, successfully collects spilled oil on a pilot-scale oil spill site and a real ocean oil spill site by simply scooping and recovering the oil. In addition, SWIS membrane is expected to help protect environments with further applications such as oil-wastewater treatment and oil separation in food.

Hydrodynamics of writing with ink.

Writing with ink involves the supply of liquid from a pen onto a porous hydrophilic solid surface, paper. The resulting linewidth depends on the pen speed and the physicochemical properties of the ink and paper. Here we quantify the dynamics of this process using a combination of experiment and theory. Our experiments are carried out using a minimal pen, a long narrow tube that serves as a reservoir of liquid, which can write on a model of paper, a hydrophilic micropillar array. A minimal theory for the rate of wicking or spreading of the liquid is given by balancing the capillary force that drives the liquid flow and the resistance associated with flow through the porous substrate. This allows us to predict the shape of the front and the width of the line laid out by the pen, with results that are corroborated by our experiments.

Direct recovery of spilled oil using hierarchically porous oil scoop with capillary-induced anti-oil-fouling.

The pitcher plant has evolved its hierarchically grooved peristome to enhance a water-based slippery system for capturing insects with oil-covered footpads. Based on this, we proposed a hierarchically porous oil scoop (HPOS) with capillary-induced oil peel-off ability for repeatable spilled oil recovery. As the HPOS scoops oil-water mixture, water passes through the hole while the oil is confined within a curved geometry. The filter in HPOS has three levels of porous structures; (1) 3D-printed mesh structure with sub-millimeter scale hole to filter out oil from an oil-water mixture, (2) internal micropore in fibers enhancing capillarity and water transport, (3) O2 plasma-induced high-aspect-ratio nanopillar structures imposing anti-oil-fouling property with capillary-induced oil peeling. As the oil-contaminated HPOS makes contact with water, water meniscus rises and peels off the oil immediately at the air-water interface. The oil-peel-off ability of the HPOS would prevent pores from clogging by oils for reuse. The study demonstrated that the HPOS recovers highly viscous oil (up to 5000 mm2·s-1) with a high recovery rate (>95%), leaving the filtered water with low oil content (<10 ppm), which satisfies the discharge criterion of 15 ppm.

Wrinkled, dual-scale structures of diamond-like carbon (DLC) for superhydrophobicity.

We present a simple two-step method to fabricate dual-scale superhydrophobic surfaces by using replica molding of poly(dimethylsiloxane) (PDMS) micropillars, followed by deposition of a thin, hard coating layer of a SiO(x)-incorporated diamond-like carbon (DLC). The resulting surface consists of microscale PDMS pillars covered by nanoscale wrinkles that are induced by residual compressive stress of the DLC coating and a difference in elastic moduli between DLC and PDMS without any external stretching or thermal contraction on the PDMS substrate. We show that the surface exhibits superhydrophobic properties with a static contact angle over 160 degrees for micropillar spacing ratios (interpillar gap divided by diameter) less than 4. A transition of the wetting angle to approximately 130 degrees occurs for larger spacing ratios, changing the wetting from a Cassie-Cassie state (C(m)-C(n)) to a Wenzel-Cassie state (W(m)-C(n)), where m and n denote micro- and nanoscale roughness, respectively. The robust superhydrophobicity of the Cassie-Cassie state is attributed to stability of the Cassie state on the nanoscale wrinkle structures of the hydrophobic DLC coating, which is further explained by a simple mathematical theory on wetting states with decoupling of nano- and microscale roughness in dual scale structures.