ABSTRACT
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.
Subject(s)
Fuel Oils , Petroleum Pollution , Bays , Laboratories , WaterABSTRACT
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.
ABSTRACT
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.
Subject(s)
Cellulose , Electricity , Humans , Electric Conductivity , ElectronicsABSTRACT
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.
ABSTRACT
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.
Subject(s)
Masks , Wettability , Physical PhenomenaABSTRACT
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.
ABSTRACT
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.
Subject(s)
Boehmeria , Fuel Oils , Hydrophobic and Hydrophilic Interactions , Sulfur , ViscosityABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
Subject(s)
Water Purification , Water , Lubricants , Lubrication , Oils/chemistry , Water/chemistryABSTRACT
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.
ABSTRACT
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 (â¼4 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.
ABSTRACT
Smart surfaces in nature have been extensively studied to identify their hierarchical structures in micro-/nanoscale to elucidate their superhydrophobicity with varying water adhesion. However, mimicking hybrid features in multiscale requires complex, multi-step processes. Here, we proposed a one-step process for the fabrication of hierarchical structures composed in micro-/nanoscales for superhydrophobic surfaces with tunable water adhesion. Hierarchical patterns were fabricated using a plasma-based selective etching process assisted by a dual scale etching mask. As the metallic mesh is placed above the substrate, it serves the role of dual scale etching masks on the substrate: microscale masks to form the micro-wall network and nanoscale masks to form high-aspect-ratio nanostructures. The micro-walls and nanostructures can be selectively hybridized by adjusting the gap distance between the mesh and the target surface: single nanostructures on a large area for a larger gap distance and hybrid/hierarchical structures with nanostructures nested on micro-walls for a shorter gap distance. The hierarchically nanostructured surface shows superhydrophobicity with low water adhesion, while the hybrid structured surface becomes become superhydrophobic with high adhesion. These water adhesion tunable surfaces were explored for water transport and evaporation. Additionally, we demonstrated a robust superhydrophobic surface with anti-reflectance over a large area.
ABSTRACT
Nanostructured glass with subwavelength hollow nanopillars of diameters of sub-65 nm was fabricated, showing high optical transmittance and ultralow diffuse reflectance. A simple process involving single-step plasma etching was used on a glass slide coated with a SiO2 sacrificial film. First, SiO2 nanodot structures were formed using plasma-induced anisotropic etching with CF4 plasma. The SiO2 nanodot array then became a secondary etching mask to form hollow nanopillars on the glass. The hollow structures formed at the upper part reaching up to the apex of the nanopillar had a lower solid fraction, while the lower part had a higher fraction. The refractive index (RI) gradually increased from 1.09 (near the value for air) to 1.42 (near the value for glass). Geometry-induced RI gradient enhanced light transmi, while it significantly reduced diffuse reflectance, particularly in the shorter wavelengths, thus suppressing the haziness or milky appearance of the nanostructured glass. Superhydrophilic and antifogging properties of nanostructured glasses and dental mirrored glasses were also demonstrated with water spraying and exhaled breath tests. Results showed that the wettability was enhanced in hydrophilicity and antifogging property by both the hydrophilic nature of the glass and the newly formed nanostructures. The nanostructured, superhydrophilic glass was also found to have easy cleaning nature against fine sand dust adhesion by simply blowing air or spraying water. Results of this study showed that such a hollow-pillared glass surface with gradient RI and special wettability could be applied in a variety of optical and optoelectronic applications requiring superwetting, such as optical windows for solar cell panels, display panels, light-emitting diodes, and medical devices even with curved surfaces.
ABSTRACT
This study explored the optimum conditions to achieve superhydrophobicity in polyethylene terephthalate (PET) in terms of crystallinity and microstructure. Surface superhydrophobicity was achieved by nanostructures induced by oxygen plasma etching and the recovery process of low surface energy through thermal aging of various PETs; semi-crystalline biaxial PET (B-PET) film, amorphous PET (A-PET) film, and semi-crystalline PET (F-PET) fabric. Under the anisotropic plasma etching, the nanostructures on the B-PET film were the longest, followed by the F-PET fabric, which developed a hierarchical micro/nanostructure, then the A-PET film. During thermal aging at 80 °C near T g, the plasma-treated A-PET film recovered its superhydrophobicity within 3 h, while the plasma-treated B-PET film did not exhibit superhydrophobicity. At 130 °C, higher than T g, the plasma-treated B-PET film recovered its superhydrophobicity within 1 h, but the plasma-treated A-PET film became opaque as its nanostructures deformed, decreasing its superhydrophobicity. The plasma-treated F-PET fabric exhibited faster recovery and greater superhydrophobicity than the plasma-treated B-PET film, due to its hierarchical micro/nanostructure. In addition, hydrophobic recovery during thermal aging was proved with a decrease in surface polar groups, lowering the surface energy using XPS analysis. Therefore, by designing the ratio of crystal to amorphous regions and surface micro/nanostructures, one can rapidly fabricate superhydrophobic PETs without additional surface finishing.
ABSTRACT
Nanostructured cellulose fabric with an air-bubble-enhanced anti-oil fouling property is introduced for quick oil-cleaning by water even with the surface fouled by oil before water contact under a dry state. It is very challenging to recover the super-hydrophilicity because once the surface is oil-fouled, it is hard to be re-wetted by water. Anti-oil-fouling under a dry state was realized through two main features of the nanostructured, porous fabric: a low solid fraction with high-aspect-ratio nanostructures significantly increasing the retracting forces, and trapped multiscale air bubbles increasing the buoyancy and backpressure for an oil-layer rupture. The nanostructures were formed on cellulose-based rayon microfibers through selective etching with oxygen plasma, forming a nanoscale open-pore structure. Viscous crude oil fouled on a fabric under a dry state was cleaned by immersion into water owing to a higher water affinity of the rayon material and low solid fraction of the high-aspect-ratio nanostructures. Air bubbles trapped in dry porous fibers and nanostructures promote oil detachment from the fouled sites. The macroscale bubbles add buoyancy on top of the oil droplets, enhancing the oil receding at the oil-water-solid interface, whereas the relatively smaller microscale bubbles induce a backpressure underneath the oil droplets. The oil-proofing fabric was used for protecting underwater conductive sensors, allowing a robot fish to swim freely in oily water.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
There are various fabrication methods for synthesizing nanostructures, among which plasma-based technology is strongly competitive in terms of its flexibility and friendly uses, economy, and safety. This review systematically discusses plasma techniques and the detailed interactions of charged particles, radicals, and electrons with substrate materials of, in particular, polymers for their nanostructuring. Applications employing a plasma-based nanostructuring process are explored to show the advantages and benefits that plasma treatment brings to many topical and traditional issues, and are specifically related to wettability, healthcare, or energy researches. A short perspective is also presented on strategic plans for overcoming the limitations in dimension from surface to bulk, lifetime of surface functions, and selectivity for interactions.