Magnetocontrollable Droplet and Bubble Manipulation on a Stable Amphibious Slippery Gel Surface

Smart manipulation of liquid/bubble transport has garnered widespread attention due to its potential applications in many fields. Designing a responsive surface has emerged as an effective strategy for achieving controllable transport of liquids/bubbles. However, it is still challenging to fabricate stable amphibious responsive surfaces that can be used for the smart manipulation of liquid in air and bubbles underwater. Here, amphibious slippery surfaces are fabricated using magnetically responsive soft poly(dimethylsiloxane) doped with iron powder and silicone oil. The slippery gel surface retains its magnetic responsiveness and demonstrates strong affinity for bubbles underwater but shows small and switching resistance forces with the water droplets in air and bubbles underwater, which is the key factor for achieving the controllable transport of liquids/bubbles. On the slippery gel surface, the sliding behaviors of water droplets and bubbles can be reversibly controlled by alternately applying/removing an external magnetic field. Notably, compared with slippery liquid‐infused porous surfaces, the slippery gel surface demonstrates outstanding stability, whether in air or underwater, even after 100 cycles of alternately applying/removing the magnetic field. This surface shows potential applications in gas/liquid microreactors, gas–liquid mixed fluid transportation, bubble/droplet manipulation, etc.     

Filefish‐Inspired Surface Design for Anisotropic Underwater Oleophobicity

Surfaces with anisotropic wettability, widely found in nature, have inspired the development of one‐dimensional water control on surfaces relying on the well‐arranged surface features. Controlling the wetting behavior of organic liquids, especially the motion of oil fluid on surfaces, is of great importance for a broad range of applications including oil transportation, oil‐repellent coatings, and water/oil separation. However, anisotropic oil‐wetting surfaces remain unexplored. Here, the unique skin of a filefish Navodon septentrionalis shows anisotropic oleophobicity under water. On the rough skin of N. septentrionalis, oil droplets tend to roll off in a head‐to‐tail direction, but pin in the opposite direction. This pronounced wetting anisotropy results from the oriented hook‐like spines arrayed on the fish skin. It inspires further exploration of the artificial anisotropic underwater oleophobic surfaces: By mimicking the oriented hook‐like microstructure on a polydimethylsiloxane layer via soft lithography and subsequent oxygen‐plasma treatment to make the PDMS hydrophilic, artificial fish skin is fabricated which has similar anisotropic underwater oleophobicity. Drawn from the processing of artificial fish skin, a simple principle is proposed to achieve anisotropic underwater oleophobicity by adjusting the hydrophilicity of surface composition and the anisotropic microtextures. This principle can guide the simple mass manufacturing of various inexpensive high surface‐energy materials, and the principle is demonstrated on commercial cloth corduroy. This study will profit broad applications involving low‐energy, low‐expense oil transportation, underwater oil collection, and oil‐repellant coatings on ship hulls and oil pipelines.     

Bioinspired Continuous and Spontaneous Antigravity Oil Collection and Transportation

Liquids with low surface tension, such as petroleum, serve as the source of power for development of modern industry. Spontaneous and directional transportation of oily liquids in aqueous environment has drawn wide attentions owing to its scientific significance and practical prospect in marine petroleum exploitation and oil spill cleanup. Persistent effort has been made to the directional transportation of oil droplets under specific assistance. However, the spontaneous oriented movement of oil, especially the air/water two‐phase oil delivery is still identified as a big challenge. Here, a bioinspired superoleophobic pump has been fabricated through the assembly of a superoleophobic mesh and an oil column. Depending on the directional releases of surface energy, oil droplets can be continuously collected and pumped to centimeters high without additional driving forces. The antigravity oil delivery system can realize continuous oil flow under water, even the air/water two‐phase oil transportation. This work demonstrates a new mode of liquid transportation without external energy and should open a new way to design novel fluid delivery systems to realize diverse liquid transport.     

Droplets Crawling on Peristome‐Mimetic Surfaces

Controlling the mobility of liquids along surfaces is widely exploited in various technologies to achieve self‐lubrication, phase‐change heat transfer, and microfluidics. Despite commendable progress in directional liquid transport on peristome‐mimetic surfaces, liquid merely spreads directionally with a wetted trail remaining. It is a challenge to achieve directional contracting of spreading liquid at the rear side and ultimately unidirectional motion in bulk from one site to another. Here it is shown that liquids resting on the peristome‐mimetic surfaces can crawl directionally and rapidly in an inchworms‐like way under the action of sudden spontaneous bubbles levitation. Vacuuming or chemical reaction induces sudden nucleation, growth, coalescence (Ostwald ripening process), and rupture of bubbles in the asymmetric microcavities of the peristome‐mimetic surface with directional overpressure beneath the liquid, resulting in the guided contracting and spreading of the liquid. Bubbles regulate this new mode of liquid directional motion. The strategy offers opportunities for liquids directional motion for various applications, such as in microfluidic devices, oil–water separation, and water collection systems.     

Tunable Anisotropic Wettability of Rice Leaf‐Like Wavy Surfaces

Rice leaves can directionally shed water droplets along the longitudinal direction of the leaf. Inspired by the hierarchical structures of rice leaf surfaces, synthetic rice leaf‐like wavy surfaces are fabricated that display a tunable anisotropic wettability by using electrostatic layer‐by‐layer assembly on anisotropic microwrinkled substrates. The nanoscale roughness of the rice leaf‐like surfaces is controlled to yield tunable anisotropic wettability and hydrophobic properties that transitioned between the anisotropic/pinned, anisotropic/rollable, and isotropic/rollable water droplet behavior states. These remarkable changes result from discontinuities in the three‐phase (solid–liquid–gas) contact line due to the presence of air trapped beneath the liquid, which is controlled by the surface roughness of the hierarchical nanostructures. The mechanism underlying the directional water‐rolling properties of the rice leaf‐like surfaces provides insight into the development of a range of innovative applications that require control over directional flow.     

Gradient Quasi-Liquid Surface Enabled Self-Propulsion of Highly Wetting Liquids

Self-propulsion of highly wetting liquids is important in heat exchanger, air conditioning, and refrigeration systems. However, it is challenging to achieve such a spontaneous motion as these liquids tend to wet all the surfaces due to their ultralow surface tensions. Despite that extensive asymmetric surface structures and gradient chemical coatings are developed for directional droplet transport, they will be flooded and covered by these liquids. Here, this challenge is addressed by creating a gradient quasi-liquid surface to achieve the self-propulsion of droplets with surface tensions down to 10.0 mN m⁻¹. Such a surface engineered by tethering flexible polymers with gradient grafting density shows ultralow contact angle hysteresis (<1^o) to highly wetting liquids. Thus, the surface can simultaneously provide sufficient driving forces through the gradient wettability and negligible retention forces through the slippery boundary lubrication for spontaneous droplet movement. Moreover, continual self-propulsion of tiny droplets is achieved by spraying highly wetting liquids in simulated condensation conditions and demonstrates that adding temperature gradient can further accelerate the self-propulsion. The study provides a new paradigm to promote passive removal of highly wetting droplets, leading to potential impacts in enhancing condensation heat transfer regardless of surface orientations.     

Lubricant‐Infused Anisotropic Porous Surface Design of Reduced Graphene Oxide Toward Electrically Driven Smart Control of Conductive Droplets' Motion

The study of Nepenthes pitcher plants‐bioinspired anisotropic slippery liquid‐infused porous surfaces (SLIPS) is currently in its infancy. The factors that influence their anisotropic self‐cleaning and electric response of a drop's motion and the mechanism have not been fully elucidated. In order to address these problems, two new types of anisotropic slippery surfaces have been designed by using directional, porous, conductive reduced graphene oxide (rGO) films, and different lubricating fluids (conductive and nonconductive), which are used to study the influencing factors and the mechanism of anisotropic self‐cleaning and electric‐responsive control of a drop's motion. The results demonstrate the anisotropic self‐cleaning property of these two types of SLIPS is closely related to the interaction between liquid drops, lubricating fluids and dirt, and the conductive lubricating fluids filling the rGO porous film can reduce the response voltage of the electrically driven reversible control of a drop's slide. The uniqueness of this research lies in the use of two different lubricating fluids and graphene materials to prepare anisotropic SLIPS, identify the key factors to achieve an electrically driven system. These studies are essential for advancing the application of electronically responsive SLIPS in the fields of liquid directional transportation, microfluidics, microchips, and other related research.     

Spontaneous and Directional Transportation of Gas Bubbles on Superhydrophobic Cones

Understanding the behavior of gas bubbles in aqueous media and realizing their spontaneous and directional manipulation are of vital importance in both scientific research and industrial applications, owing to their significant influences on many processes, such as waste water treatment, gas evolution reactions, and the recovery of valuable minerals. However, the behaviors of gas bubbles in aqueous media are mainly dominated by the buoyant force, which greatly impedes gas bubble transportation to any other direction except upward. Consequently, the spontaneous and directional transportation of gas bubbles in aqueous media is still identified as a big issue. Here, superhydrophobic copper cones have been successfully fabricated by integrating low‐surface‐tension chemical coatings with conical morphology. The generated superhydrophobic copper cones are capable of transporting gas bubbles from their tip to the base spontaneously and directionally underwater, even when they are vertically fixed with tips pointing up. The present study will inspire people to develop novel strategies to achieve efficient manipulation of gas bubbles in practical applications.     

Lossless,Passive Transportation of Low Surface Tension Liquids Induced by Patterned Omniphobic Liquidlike Polymer Brushes

Surfaces enabling directional liquid transportation are of great interest for a wide range of applications such as water collection, microfluidics, and heat transfer systems. Surfaces capable of lossless, long-range passive transportation of low surface tension (LST) liquids using wettability patterned, liquidlike coatings with minimal contact angle hysteresis are reported. Lossless LST droplet travel distances over 150 mm are achieved, enabled by a two-phase transportation mechanism: morphological transformation from a bulge to a channel shape, followed by directional transportation along the asymmetrical wedge-shaped channel. The developed surfaces can split, merge, and precisely transport various low-surface tension liquids, including alcohols, alkanes, and solvents. The developed transportation strategy can also enhance LST liquid dropwise condensation through continuous removal of the condensate, even on horizontally positioned surfaces without the assistance of gravity.     

Ultrafast,Reversible Transition of Superwettability of Graphene Network and Controllable Underwater Oil Adhesion for Oil Microdroplet Transportation

Recently, reversible surface superwettability has attracted enormous interest, and methods to shorten the cycle time of transition have also garnered the attention of researchers. Herein, a superhydrophobic, open‐cell graphene network (OCGN) is fabricated via self‐assembly of graphene oxide and vapor ejection. Owing to the special open‐cell microstructure, the OCGNs can be transformed to be superhydrophilic rapidly within only 1 s by air plasma treatment. Moreover, the OCGNs with pure graphene composition have a high conductivity and show an ultrafast Joule heating rate of up to 20 °C s^?1 at a voltage of 20 V. By means of this property, for the first time an ultrafast recovery of the superhydrophobicity for OCGNs by self‐induced Joule heating with the shortest time of 1 min is reported. The mechanism of ultrafast, reversible transition is also explored specifically in this study. In addition, the superhydrophilic OCGNs show superoleophobicity in water and their underwater adhesion for oil droplets can be controlled by plasma treatment. Finally, the OCGNs with different oil adhesion properties are fabricated and the underwater oil microdroplet transportation is realized using OCGNs. Therefore, the OCGNs with smart surface can be an excellent candidate for achieving multifunctional superwettability of surfaces.     

Asymmetric Soft-Structure Functional Surface for Intelligent Liquids’ Distinction,Transportation, and Reaction Mixer

Structured surfaces have attracted wide attention because of their great potential in directional transport, liquid collection or separation, microfluidics, etc. However, it remains a big challenge to design a surface that can distinguish various liquids, utilize their inherent properties to control their transportation, and realize functional applications. Herein, it is presented an asymmetric soft-structure functional surface (ASFS) with arrayed curvature units that can make the Laplace pressure as a driving force to determine the preferential spreading direction and show abundant transport behaviors for liquids with different surface tensions. With good deformability, the proposed ASFS can directionally transport liquids along complex terrains, e.g., 1D-tilted, 2D-curved, and 3D-helical trajectories. It is also demonstrated that the ASFS can achieve synchronous or asynchronous liquid mixing by choosing appropriate liquids. Moreover, the intelligent response ability allows the ASFS to be a portable contact angle discriminator. This study proposes a new strategy to manipulate liquids via their intrinsic properties and opens new avenues for application-oriented liquid operation surfaces.     

Tunable Structural Color Surfaces with Visually Self‐Reporting Wettability

Functional materials with wettability of specific surfaces are important for many areas. Here, a new lubricant‐infused elastic inverse opal is presented with tunable and visually “self‐reporting” surface wettability. The elastic inverse opal films are used to lock in the infused lubricating fluid and construct slippery surfaces to repel droplets of various liquids. The films are stretchable, and the lubricating fluid can penetrate the pores under stretching, leaving the surface layer free of lubrication; the resultant undulating morphology of the inverse opal scaffold topography can reversibly pin droplets on the fluidic film rather than the solid substrate. This mechanical stimulation process provides an effective means of dynamically tuning the surface wettability and the optical transparency of the inverse opal films. In particular, as the adjustments are accompanied by simultaneous deformation of the periodic macroporous structure, the inverse opal films can self‐report on their surface status through visible structural color changes. These features make such slippery structural color materials highly versatile for use in diverse applications.     

On‐Demand Liquid Transportation Using Bioinspired Omniphobic Lubricated Surfaces Based on Self‐Organized Honeycomb and Pincushion Films

In this work, on‐demand control of liquids is realized by using elastic, patterned omniphobic surfaces. This paves the way for novel microfluidics, as well as liquid harvesting, transportation, and manipulation technologies. Inspired by the lubricating properties of pitcher plants, microstructured 1,2‐polybutadiene honeycomb and pincushion films obtained by self‐organization are fluorinated by the ene‐thiol reaction and infused with fluorinated lubricant to obtain omniphobic liquid‐repellent surfaces. Unlike conventional bioinspired omniphobic surfaces, the liquid repellency of the fabricated surface can be programmed by changing the surface microstructures via patterning of the film. Furthermore, the elasticity of the omniphobic film is suitable for controlling the repellency through external stimuli. The method presented here for the fabrication of lubricant‐infused omniphobic microstructured surfaces is also simple, cost‐effective, and can be scaled for large area fabrication.     

Overcoming Limitations in Surface Geometry-Driven Bubble Transport: Bidirectional and Unrestricted Movement of an Underwater Gas Bubble Using a Magnetocontrollable Nonwetting Surface

The movement of underwater gas bubbles significantly affects the core processes of a variety of applications in water electrolysis, heat transfer, optofluidics, and other fields. To maneuver the motion of bubbles, surface geometry-driven transport is widely applied by employing asymmetric nonwetting surfaces, which induce Laplace pressure based on the bubble radius differences in confined states. Although this method has successfully demonstrated bubble manipulations in various geometries, it has inevitably shown some critical limitations; gas bubbles move unidirectionally from tip to root direction and cease their movements upon reaching unconfined states. This unidirectional and local bubble transport restrains the method's applicability to many fields, and overcoming this obstacle still remains an enormous challenge. Herein, a magnetocontrollable lubricant-infused surface (MCLIS) is introduced as a key solution to this issue. MCLISs manipulate the adhesion of gas bubbles by controlling magneto-responsive microwire alignments and rendering two reversible adhesion states, sticky (upright) and slippery (laying wires). This unique characteristic of MCLISs enables the bidirectional and geometry-unrestricted transportation of bubbles by the wire geometry-gradient force (F_wgg) generated at sticky–slippery interfaces. Furthermore, this novel magnetic responsive surface supports anti-buoyancy transport and presents promising applications in microreactors and optical laser shutters in aqueous media.     

Phototunable Underwater Oil Adhesion of Micro/Nanoscale Hierarchical‐Structured ZnO Mesh Films with Switchable Contact Mode

Controllable surface adhesion of solid substrates has aroused great interest both in air and underwater in solving many challenging interfacial science problems such as robust antifouling, oil‐repellent, and highly efficient oil/water separation materials. Recently, responsive surface adhesion, especially switchable adhesion, under external stimulus in air has been paid more and more attention in fundamental research and industrial applications. However, phototunable underwater oil adhesion is still a challenge. Here, an approach to realize phototunable underwater oil adhesion on aligned ZnO nanorod array‐coated films is reported, via a special switchable contact mode between an unstable liquid/gas/solid tri‐phase contact mode and stable liquid/liquid/solid tri‐phase contact mode. The photo‐induced wettability transition to water and air exists (or does not) in the micro/nanoscale hierarchical structure of the mesh films, playing important role in controlling the underwater oil adhesion behavior. This work is promising in the design of novel interfacial materials and functional devices for practical applications such as photo‐induced underwater oil manipulation and release, with loss‐free oil droplet transportation.     

In‐Air Bubble Phobicity and Bubble Philicity Depending on the Interfacial Air Cushion: Toward Bubbles Manipulation Using Superhydrophilic Substrates

Bubbles, a typical air‐in‐liquid system including both underwater and in‐air bubbles, are important phenomena involved in our daily life and engineering fields. So far, the fundamental and dynamics for in‐air bubbles largely remain unclear. Here, two typical in‐air wetting states of the bubble are revealed: the bubble‐phobic state in which a bubble with a perfect spherical shape stays on the liquid surface but without coalescence with the liquid; and the bubble‐philic state in which a bubble on the liquid substrate gives a quasi‐hemispherical shape. It is proposed that the bubble phobicity is a typical high‐energy state where the air cushion at the bubble/liquid interface plays a crucial role in preventing their coalescence by generating an energy barrier. By applying an external force to overcome the energy barrier, the bubble will distort and finally be stabilized in a bubble‐philic state. It is demonstrated that superhydrophilic substrates enable manipulating bubbles in air: a superhydrophilic surface with microscale hairy textures shows robust in‐air repellence to the bubbles, while a hemispherical bubble is capable of transport directionally in air on a superhydrophilic conical fiber. Here, the concept of superwetting into air‐in‐air system (liquid films) is promoted, which may open a new perspective in surface and interface chemistry.     

An Innovative Design by Single‐Layer Superaerophobic Mesh: Continuous Underwater Bubble Antibuoyancy Collection and Transportation

Underwater bubbles are unavoidable in the natural world and industrial production. Understanding the behavior of underwater bubbles and manipulating gas bubbles are vital important to both fundamental scientific research and industrial application. Although there has been some progress in controlling underwater bubbles, continuous underwater bubble collection and transportation remain challenging targets. Herein, inspired by the mechanism of water spider's gas storage, a strategy to collect and transport underwater gas bubble is demonstrated by design of a single‐layer underwater superaerophobic mesh (USM) assembled with a quartz tube. Gas bubbles supplied by a syringe pump penetrate the mesh pore and then gather to form a gas column in the quartz tube. Collapse occurs when the gas column reach the maximum storage height/pressure. Under a continuous supply of gas bubbles, the change of pressure becomes a cyclic process, which acts in a pump‐like manner to transport bubbles continuously from the water to the gas phase in the USM device assembled with an asymmetric U‐tube. This novel gas collection and transport system provides a new inspiration for developing new technologies for applications in pipes, sensors, gas collection, and environment protection.     

Bioinspired Self‐Propulsion of Water Droplets at the Convergence of Janus‐Textured Heated Substrates

Controlled propulsion of liquid droplets on a solid surface offers viable applications in fog harvesting, heat transfer, microfluidics, and microdevice technologies. A prerequisite for the propulsion of liquid droplets is to break the wetting symmetry of a droplet and contact‐line pinning on the surface by harnessing surface energy gradient. Here, a series of Janus‐textured substrates is constructed to investigate the self‐propulsion of Leidenfrost droplets. It is found that the self‐propulsion of droplets occurs only on two special Janus‐textured substrates. Those are nanostructured silicon substrate bounded by smooth silicon substrate and the nanowire‐decorated microstructured silicon substrate bounded by micropillars with smooth surfaces. The difference in roughness between the two sides of the Janus‐textured substrates creates various numbers and sizes of vapor bubbles. The vapor bubbles cause the droplets to become turbulent, and a pressure gradient is generated. The sufficiently large pressure gradient propels the Leidenfrost droplet to move directionally. The propulsion direction is always toward areas with low roughness.     

Omniphobic “RF Paper” Produced by Silanization of Paper with Fluoroalkyltrichlorosilanes

The fabrication and properties of “fluoroalkylated paper” (“R^F paper”) by vapor‐phase silanization of paper with fluoroalkyl trichlorosilanes is reported. R^F paper is both hydrophobic and oleophobic: it repels water (θ_app^H2^O>140°), organic liquids with surface tensions as low as 28 mN m^‐1, aqueous solutions containing ionic and non‐ionic surfactants, and complex liquids such as blood (which contains salts, surfactants, and biological material such as cells, proteins, and lipids). The propensity of the paper to resist wetting by liquids with a wide range of surface tensions correlates with the length and degree of fluorination of the organosilane (with a few exceptions in the case of methyl trichlorosilane‐treated paper), and with the roughness of the paper. R^F paper maintains the high permeability to gases and mechanical flexibility of the untreated paper, and can be folded into functional shapes (e.g., microtiter plates and liquid‐filled gas sensors). When impregnated with a perfluorinated oil, R^F paper forms a “slippery” surface (paper slippery liquid‐infused porous surface, or “paper SLIPS“) capable of repelling liquids with surface tensions as low as 15 mN m^‐1. The foldability of the paper SLIPS allows the fabrication of channels and flow switches to guide the transport of liquid droplets.