Programmable Liquid Adhesion on Bio‐Inspired Re‐Entrant Structures

Surfaces combining antispreading and high adhesion can find wide applications in the manipulation of liquid droplets, generation of micropatterns and liquid enrichment. To fabricate such surfaces, almost all the traditional methods demand multi‐step processes and chemical modification. And even so, most of them cannot be applied for some liquids with extremely low surface energy. In the past decade, multiply re‐entrant structures have aroused much attention because of their universal and modification‐independent antiadhesion or antipenetration ability. Unfortunately, theories and applications about their liquid adhesion behavior are still rare. In this work, inspired by the springtail skin and gecko feet in the adhered state, it is demonstrated that programmable liquid adhesion is realized on the 3D‐printed micro doubly re‐entrant arrays. By arranging the arrays reasonably, three different Cassie adhesion behaviors can be obtained: I) no residue adhesion, II) tunable adhesion, and III) absolute adhesion. Furthermore, various arrays are designed to tune macro/micro liquid droplet manipulation, which can find applications in the transportation of liquid droplets, liquid enrichment, generation of tiny droplets, and micropatterns.     

Emerging Applications of Superhydrophilic‐Superhydrophobic Micropatterns

Water on superhydrophilic surfaces spreads or is absorbed very quickly, and exhibits water contact angles close to zero. We encounter superhydrophilic materials in our daily life (e.g., paper, sponges, textiles) and they are also ubiquitous in nature (e.g., plant and tree leaves, Nepenthes pitcher plant). On the other hand, water on completely non‐wettable, superhydrophobic surfaces forms spherical droplets and rolls off the surface easily. One of the most well‐known examples of a superhydrophobic surface is the lotus leaf. Creating novel superhydrophobic surfaces has led to exciting new properties such as complete water repellency, self‐cleaning, separation of oil and water, and antibiofouling. However, combining these two extreme states of superhydrophilicity and superhydrophobicity on the same surface in precise two‐dimensional micropatterns opens exciting new functionalities and possibilities in a wide variety of applications from cell, droplet, and hydrogel microarrays for screening to surface tension confined microchannels for separation and diagnostic devices. In this Progress Report, we briefly describe the methods for fabricating superhydrophilic‐superhydrophobic patterns and highlight some of the newer and emerging applications of these patterned substrates that are currently being explored. We also give an outlook on current and future applications that would benefit from using such superhydrophilic‐superhydrophobic micropatterns.     

Flexible Transparent Hierarchical Nanomesh for Rose Petal‐Like Droplet Manipulation and Lossless Transfer

Precise manipulation of water is a key step in numerous natural and synthetic processes. Here, a new flexible and transparent hierarchical structure is determined that allows ultra‐dexterous manipulation and lossless transfer of water droplets. A 3D nanomesh is fabricated in one step by scalable electrospinning of low‐cost polystyrene solutions. Optimal structures are composed of a mesh of dense nanofiber layers vertically separated by isolated mesoporous microbeads. This results in a highly adhesive superhydrophobic wetting that perfectly mimics rose petal‐like structures. Structural–functional correlations are obtained over all key process parameters enabling robust tailoring of the wetting properties from hydrophilic to lotus‐like Cassie‐Baxter and rose‐like Cassie‐impregnating states. A mechanistic model of the droplet adhesion and release dynamics is obtained alongside the first demonstration of a mechanically induced transfer of microdroplets between two superhydrophobic coatings. This low‐temperature reaction‐free material structure demonstrates a facile means to fabricate impenetrable residue‐less rose petal‐like surfaces with superhydrophobic contact angles of 152 ± 2° and effective adhesion strength of 113 ± 20 μN. This is a significant step toward parallel, multistep droplet manipulation with applications ranging from flexible on‐paper devices to microfluidics and portable/wearable biosensors.     

Controllable High‐Speed Electrostatic Manipulation of Water Droplets on a Superhydrophobic Surface

Biological processes and technological applications cannot work without liquid control, where versatile water droplet manipulation is a significant issue. Droplet motion is conventionally manipulated by functionalizing the target surface or by utilizing additives in the droplet, still, with uncontrolled limitation on superhydrophobic surfaces since droplets are either unable to move fast or are difficult to stop while moving. A controllable high‐speed “all‐in‐one” no‐loss droplet manipulation, that is, in‐plane moving and stopping/pinning in any direction on a superhydrophobic surface, with electrostatic charging is demonstrated. The experimental results reveal that the transport speed can vary from zero to several hundreds of millimeters per second. Controlled dynamic switching between the onset moving state and the offset pinning state of a water droplet can be achieved by out‐of‐plane electrostatic charging. This work opens the possibility of droplet control techniques in various applications, such as combinatory chemistry, biochemical, and medical detection.     

Robust Flower‐Like TiO2@Cotton Fabrics with Special Wettability for Effective Self‐Cleaning and Versatile Oil/Water Separation

Inspired by the hierarchical structure of the mastoid on the micrometer and nanometer scale and the waxy crystals of the mastoid on natural lotus surfaces, a facile one‐step hydrothermal strategy is developed to coat flower‐like hierarchical TiO₂ micro/nanoparticles onto cotton fabric substrates (TiO₂@Cotton). Furthermore, robust superhydrophobic TiO₂@Cotton surfaces are constructed by the combination of hierarchical structure creation and low surface energy material modification, which allows versatility for self‐cleaning, laundering durability, and oil/water separation. Compared with hydrophobic cotton fabric, the TiO₂@Cotton exhibits a superior antiwetting and self‐cleaning property with a contact angle (CA) lager than 160° and a sliding angle lower than 5°. The superhydrophobic TiO₂@Cotton shows excellent laundering durability against mechanical abrasion without an apparent reduction of the water contact angle. Moreover, the micro/nanoscale hierarchical structured cotton fabrics with special wettability are demonstrated to selectively collect oil from oil/water mixtures efficiently under various conditions (e.g., floating oil layer or underwater oil droplet or even oil/water mixtures). In addition, it is expected that this facile strategy can be widely used to construct multifunctional fabrics with excellent self‐cleaning, laundering durability, and oil/water separation. The work would also be helpful to design and develop new underwater superoleophobic/superoleophilic materials and microfluidic management devices.     

Multifunctional Janus Microplates Arrays Actuated by Magnetic Fields for Water/Light Switches and Bio‐Inspired Assimilatory Coloration

Smart dynamic regulation structured surfaces, inspired by nature, which can dynamically change their surface topographies under external stimuli for convertible fluidic and optical properties, have recently motivated significant interest for scientific research and industrial applications. However, there is still high demand for the development of multifunctional dynamically transformable surfaces using facile preparation strategies. In this work, a type of Janus high‐aspect‐ratio magnetically responsive microplates array (HAR‐MMA) is readily fabricated by integrating a flexible laser scanning strategy, smart shape‐memory‐polymer‐based soft transfer, and a simple surface treatment. By applying external magnetic field, instantaneous and reversible deformation of Janus HAR‐MMA can be actuated, so surface wettability can be reversibly switched between superhydrophobic (158°) and hydrophilic (40°) states, based on which a novel magnetically responsive water droplet switch can be realized. Moreover, inspired by the biological assimilatory coloration of chameleons, dynamically color conversion can be skillfully realized by applying different colors on each side of the Janus HAR‐MMA. Finally, as a proof‐of‐concept demonstration in light manipulation, a HAR‐MMA is applied as an optical shutter actuated by external magnetic field with eximious controllability and repeatability. The developed multifunctional HAR‐MMA provides a versatile platform for microfluidic, biomedical, and optical applications.     

Micro‐/Nanostructured Interface for Liquid Manipulation and Its Applications

Understanding the relationship between liquid manipulation and micro‐/nanostructured interfaces has gained much attention due to the wide potential applications in many fields, such as chemical and biomedical assays, environmental protection, industry, and even daily life. Much work has been done to construct various materials with interfacial liquid manipulation abilities, leading to a range of interesting applications. Herein, different fabrication methods from the top‐down approach to the bottom‐up approach and subsequent surface modifications of micro‐/nanostructured interfaces are first introduced. Then, interactions between the surface and liquid, including liquid wetting, liquid transportation, and a number of corresponding models, together with the definition of hydrophilic/hydrophobic, oleophilic/olephobic, the definition and mechanism of superwetting, including superhydrophobicity, superhydrophilicity, and superoleophobicity, are presented. The micro‐/nanostructured interface, with major applications in self‐cleaning, antifogging, anti‐icing, anticorrosion, drag‐reduction, oil–water separation, water collection, droplet (micro)array, and surface‐directed liquid transport, is summarized, and the mechanisms underlying each application are discussed. Finally, the remaining challenges and future perspectives in this area are included.     

Facile Fabrication of Eco‐Friendly Durable Superhydrophobic Material from Eggshell with Oil/Water Separation Property

Most superhydrophobic surfaces are fragile and even lose their functions under harsh conditions especially in outdoor applications. In this study, we have demonstrated a facile strategy for fabricating eco‐friendly and mechanical durable superhydrophobic material from eggshell. The as‐prepared superhydrophobic materials possess not only excellent self‐cleaning property and under oil superhydrophobicity, but also high‐efficient oil/water separation capability. More importantly, the obtained materials show outstanding and mechanical durable water repellency, which can maintain superhydrophobicity after 360 cm abrasion length of sandpaper. In addition, the materials also show durable superhydrophobic toward strong acidic/alkali solutions, UV irradiation, and water droplet impact, which demonstrates the outstanding chemical and environmental stability. This facile fabrication of the mechanical durable superhydrophobic materials and the utilization of daily garbage will provide the new ideas for engineering materials and accelerate the real application of the super‐repellent materials.

     

Nanofur for Biomimetic Applications

Many plants and insects possess multi‐functional surfaces covered by dense nanohair. Such a nanofur is of high interest for various biomimetic applications like self‐healing, air retention, and oil/water separation. Here, we introduce a highly scalable and competitive molding technique for the fabrication of biomimetic nanofur. With this method, we pull nanofur out of flat polycarbonate and tune its wettability from hydrophilic to superhydrophobic. By mechanically structuring these samples we create various devices suitable for microfluidics. The nanofur can be also used for the fabrication of self‐healing surfaces inspired by pitcher plants as well as for air‐retaining surfaces mimicking the water fern Salvinia minima. Finally, we utilize the nanofur for oil/water separation and the cleaning of oil spills.     

Dual‐Layer Superamphiphobic/Superhydrophobic‐Oleophilic Nanofibrous Membranes with Unidirectional Oil‐Transport Ability and Strengthened Oil–Water Separation Performance

Thin porous membranes with unidirectional oil‐transport capacity offer great opportunities for intelligent manipulation of oil fluids and development of advanced membrane technologies. However, directional oil‐transport membranes and their unique membrane properties have seldom been reported in research literature. Here, it is proven that a dual‐layer nanofibrous membrane comprising a layer of superamphiphobic nanofibers and a layer of superhydrophobic oleophilic nanofibers has an unexpected directional oil‐transport ability, but is highly superhydrophobic to liquid water. This novel fibrous membrane is prepared by a layered electrospinning technique using poly(vinylidene fluoride‐hexafluoropropylene) (PVDF‐HFP), PVDP‐HFP containing well‐dispersed FD‐POSS (fluorinated decyl polyhedral oligomeric silsesquioxanes), and FAS (fluorinated alkyl silane) as materials. The directional oil‐transport is selective only to oil fluids with a surface tension in the range of 23.8–34.0 mN m^–1. By using a mixture of diesel and water, it is further proven that this dual‐layer nanofibrous membrane has a higher diesel–water separation ability than the single‐layer nanofiber membranes. This novel nanofibrous membrane and the incredible oil‐transport ability may lead to the development of intelligent membrane materials and advanced oil–water separation technologies for diverse applications in daily life and industry.     

Facile Fabrication of Robust Ice‐Phobic Polyurethane Sponges

Bio‐inspired superhydrophobicity is a promising anti‐icing (or deicing) strategy, but a superhydrophobic surface may lose its anti‐icing capability once the deposited water freezes. Herein, it is shown that ice can be readily and repeatedly removed from the surface of superhydrophobic polyurethane sponges via a simple mechanical squeezing process. The sponges are fabricated through a mussel‐inspired process and subsequent deposition of Ag nanoparticles. The resulting sponges are able to shed off the ice layers formed on their surfaces up to 90 times, exhibiting robust icephobic properties among the reported superhydrophobic surfaces. The mechanism for the excellent icephobicity is investigated by a highly sensitive microelectrobalance and a fluorescent labeling method. It is revealed that the icephobicity is attributed to low ice adhesion of the superhydrophobic sponges, as well as mechanical durability of their surface textures. The present findings provide a facile strategy to fabricate robust icephobic surfaces for various technological applications.     

Desert Beetle‐Inspired Superwettable Patterned Surfaces for Water Harvesting

With the impacts of climate change and impending crisis of clean drinking water, designing functional materials for water harvesting from fog with large water capacity has received much attention in recent years. Nature has evolved different strategies for surviving dry, arid, and xeric conditions. Nature is a school for human beings. In this contribution, inspired by the Stenocara beetle, superhydrophilic/superhydrophobic patterned surfaces are fabricated on the silica poly(dimethylsiloxane) (PDMS)‐coated superhydrophobic surfaces using a pulsed laser deposition approach with masks. The resultant samples with patterned wettability demonstrate water‐harvesting efficiency in comparison with the silica PDMS‐coated superhydrophobic surface and the Pt nanoparticles‐coated superhydrophilic surface. The maximum water‐harvesting efficiency can reach about 5.3 g cm^?2 h^?1. Both the size and the percentage of the Pt‐coated superhydrophilic square regions on the patterned surface affect the condensation and coalescence of the water droplet, as well as the final water‐harvesting efficiency. The present water‐harvesting strategy should provide an avenue to alleviate the water crisis facing mankind in certain arid regions of the world.     

Super‐Hydrophobic Surfaces: From Natural to Artificial

Super‐hydrophobic surfaces, with a water contact angle (CA) greater than 150°, have attracted much interest for both fundamental research and practical applications. Recent studies on lotus and rice leaves reveal that a super‐hydrophobic surface with both a large CA and small sliding angle (α) needs the cooperation of micro‐ and nanostructures, and the arrangement of the microstructures on this surface can influence the way a water droplet tends to move. These results from the natural world provide a guide for constructing artificial super‐hydrophobic surfaces and designing surfaces with controllable wettability. Accordingly, super‐hydrophobic surfaces of polymer nanofibers and differently patterned aligned carbon nanotube (ACNT) films have been fabricated.     

A Droplet‐Based High‐Throughput SERS Platform on a Droplet‐Guiding‐Track‐Engraved Superhydrophobic Substrate

A novel droplet‐based surface‐enhanced Raman scattering (SERS) sensor for high‐throughput real‐time SERS monitoring is presented. The developed sensors are based on a droplet‐guiding‐track‐engraved superhydrophobic substrate covered with hierarchical SERS‐active Ag dendrites. The droplet‐guiding track with a droplet stopper is designed to manipulate the movement of a droplet on the superhydrophobic substrate. The superhydrophobic Ag dendritic substrates are fabricated through a galvanic displacement reaction and subsequent self‐assembled monolayer coating. The optimal galvanic reaction time to fabricate a SERS‐active Ag dendritic substrate for effective SERS detection is determined, with the optimized substrate exhibiting an enhancement factor of 6.3 × 10⁵. The height of the droplet stopper is optimized to control droplet motion, including moving and stopping. Based on the manipulation of individual droplets, the optimized droplet‐based real‐time SERS sensor shows high resistance to surface contaminants, and droplets containing rhodamine 6G, Nile blue A, and malachite green are successively controlled and detected without spectral interference. This noble droplet‐based SERS sensor reduces sample preparation time to a few seconds and increased detection rate to 0.5 µ L s^?1 through the simple operation mechanism of the sensor. Accordingly, our sensor enables high‐throughput real‐time molecular detection of various target analytes for real‐time chemical and biological monitoring.     

Unidirectional Wetting Properties on Multi‐Bioinspired Magnetocontrollable Slippery Microcilia

Here, a smart fluid‐controlled surface is designed, via the rational integration of the unique properties of three natural examples, i.e., the unidirectional wetting behaviors of butterfly's wing, liquid‐infused “slippery” surface of the pitcher plant, and the motile microcilia of micro‐organisms. Anisotropic wettability, lubricated surfaces, and magnetoresponsive microstructures are assembled into one unified system. The as‐prepared surface covered by tilted microcilia achieves significant unidirectional droplet adhesion and sliding. Regulating by external magnet field, the directionality of ferromagnetic microcilia can be synergistically switched, which facilitates a continuous and omnidirectional‐controllable water delivery. This work opens an avenue for applications of anisotropic wetting surfaces, such as complex‐flow distribution and liquid delivery, and extend the design approach of multi‐bioinspiration integration.     

Superamphiphobic Bionic Proboscis for Contamination‐Free Manipulation of Nano and Core–Shell Droplets

Manipulation of nanoliter droplets is a key step for many emerging technologies including ultracompact microfluidics devices, 3D and flexible electronic printing. Despite progress, contamination‐free generation and release of nanoliter droplets by compact low‐cost devices remains elusive. In the present study, inspired by butterflies' minute manipulation of fluids, the authors have engineered a superamphiphobic bionic proboscis (SAP) layout that surpasses synthetic and natural designs. The authors demonstrate the scalable fabrication of SAPs with tunable inner diameters down to 50 µ m by the rapid gas‐phase nanotexturing of the outer and inner surfaces of readily available hypodermic needles. Optimized SAPs achieve contamination‐free manipulation of water and oil droplets down to a liquid surface tension of 26.56 mN m^?1 and a volume of 10 nL. The unique potential of this layout is showcased by the rapid and carefully controlled in‐air synthesis of core‐shell droplets with well‐controlled compositions. These findings provide a new low‐cost tool for high‐precision manipulation of nanoliter droplets, offering a powerful alternative to established thermal‐ and electrodynamic‐based devices.     

Hierarchical Structured Multifunctional Self‐Cleaning Material with Durable Superhydrophobicity and Photocatalytic Functionalities

Self‐cleaning materials, which are inspired and derived from natural phenomena, have gained significant scientific and commercial interest in the past decades as they are energy‐ and labor‐saving and environmentally friendly. Several technologies are developed to obtain self‐cleaning materials. The combination of superhydrophobic and photocatalytic properties enables the efficient removal of solid particles and organic contaminations, which could reduce or damage the superhydrophobicity. However, the fragility of the nanoscale roughness of the superhydrophobic surface limits its practical application. Here, a hierarchical structure approach combining micro‐ and nanoscale architectures is created to protect the nanoscale surface roughness from mechanical damage. Glass beads of 75 µm are partially embedded into a low‐density polyethylene film. This composite surface is coated with silicone nanofilaments (SNFs) via the droplet‐assisted growth and shaping approach, providing the nanoscale surface roughness as well as the support for the photocatalyst with enlarged surface area. TiO₂ nanoparticles, which serve as the photocatalyst, are synthesized in situ on SNFs through a hydrothermal reaction. The self‐cleaning effect is proved using wettability measurements for various liquids, degradation of organic contamination under UV light, and antibacterial tests. The enhanced mechanical durability of the hierarchical structure of the composite material is verified with an abrasion test.     

Energy‐Efficient Oil–Water Separation of Biomimetic Copper Membrane with Multiscale Hierarchical Dendritic Structures

Membrane‐based materials with special surface wettability have been applied widely for the treatment of increasing industrial oily waste water, as well as frequent oil spill accidents. However, traditional technologies are energy‐intensive and limited, either by fouling or by the inability of a single membrane to separate all types of oil–water mixtures. Herein, a biomimetic monolayer copper membrane (BMCM), composed of multiscale hierarchical dendritic structures, is cleverly designed and successfully fabricated on steel mesh substrate. It not only possesses the ability of energy‐efficient oil–water separation but also excellent self‐recovery anti‐oil‐fouling properties (<150 s). The BMCM even keeps high separation efficiency (>93%) after ten‐time cycling tests. More importantly, it retains efficient oil–water separation capacity for five different oils. In fact, these advanced features are benefited by the synergistic effect of chemical compositions and physical structures, which is inspired by the typical nonwetting strategy of butterfly wing scales. The findings in this work may inspire a facile but effective strategy for repeatable and antipollution oil–water separation, which is more suitable for various applications under practical conditions, such as wastewater treatment, fuel purification, separation of commercially relevant oily water, and so forth.     

Highly Stretchable Superhydrophobic Composite Coating Based on Self‐Adaptive Deformation of Hierarchical Structures

With the rapid development of stretchable electronics, functional textiles, and flexible sensors, water‐proof protection materials are required to be built on various highly flexible substrates. However, maintaining the antiwetting of superhydrophobic surface under stretching is still a big challenge since the hierarchical structures at hybridized micro‐nanoscales are easily damaged following large deformation of the substrates. This study reports a highly stretchable and mechanically stable superhydrophobic surface prepared by a facile spray coating of carbon black/polybutadiene elastomeric composite on a rubber substrate followed by thermal curing. The resulting composite coating can maintain its superhydrophobic property (water contact angle ≈170° and sliding angle <4°) at an extremely large stretching strain of up to 1000% and can withstand 1000 stretching–releasing cycles without losing its superhydrophobic property. Furthermore, the experimental observation and modeling analysis reveal that the stable superhydrophobic properties of the composite coating are attributed to the unique self‐adaptive deformation ability of 3D hierarchical roughness of the composite coating, which delays the Cassie–Wenzel transition of surface wetting. In addition, it is first observed that the damaged coating can automatically recover its superhydrophobicity via a simple stretching treatment without incorporating additional hydrophobic materials.     

Bioinspired Mechanically Robust Metal‐Based Water Repellent Surface Enabled by Scalable Construction of a Flexible Coral‐Reef‐Like Architecture

Mechanical robustness is a central concern for moving artificial superhydrophobic surfaces to application practices. It is believed that bulk hydrophilic materials cannot be use to construct micro/nanoarchitectures for superhydrophobicity since abrasion‐induced exposure of hydrophilic surfaces leads to remarkable degradation of water repellency. To address this challenge, the robust mechanical durability of a superhydrophobic surface with metal (hydrophilic) textures, through scalable construction of a flexible coral‐reef‐like hierarchical architecture on various substrates including metals, glasses, and ceramics, is demonstrated. Discontinuous coral‐reef‐like Cu architecture is built by solid‐state spraying commercial electrolytic Cu particles (15–65 µm) at supersonic particle velocities. Subsequent flame oxidation is applied to introduce a porous hard surface oxide layer. Owing to the unique combination of the flexible coral‐reef‐like architecture and self‐similar manner of the fluorinated hard oxide surface layer, the coating surface retains its water repellency with an extremely low roll‐off angle (<2°) after cyclic sand‐paper abrasion, mechanical bending, sand‐grit erosion, knife‐scratching, and heavy loading of simulated acid rain droplets. Strong adhesion to glass, ceramics, and metals up to 34 MPa can be achieved without using adhesive. The results show that the present superhydrophobic coating can have wide outdoor applications for self‐cleaning and corrosion protection of metal parts.