Superomniphobic Surfaces Research Articles

Achieving Extreme Pressure Resistance to Liquids on a Super-Omniphobic Surface with Armored Reentrants.

Static repellency and pressure resistance toliquidsare essential for high-performance super-omniphobic surfaces. However, these two merits appear mutually exclusive in conventional designs because of their conflicting structural demands: Static liquid repellency necessitates minimal solid-liquid contact, which in turn inevitably undercuts the surface's ability to resist liquid invasion exerted by the elevated pressure. Here, inspired by the Springtail, these two merits can be simultaneously realized by structuring surfaces at two size scales, with a micrometric reentrant structure providing static liquid repellency and a nanometric reentrant structure providing pressure resistance, which dexterously avoids the dilemma of their structural conflicts. The nanometric reentrants are densely packed on the micrometric ones, serving as "armor" that prevents liquids invasion by generating multilevel energy barriers, thus naming the surface as the armored reentrants (AR) surface. The AR surface could repel liquids with verylow surface tensions, such as silicone oil (21mNm-1), and simultaneously resist great pressure from the liquids, exemplified by enduring the impact of low-surface-tension liquids under a high weber number (>400), the highest-pressure resistance ever reported. With its scalable fabrication and enhanced performance, our design could extend the application scope of liquid-repellent surfaces toward ultimateindustrial settings.

Fresnel Diffraction Strategy Enables the Fabrication of Flexible Superomniphobic Surfaces.

Doubly re-entrant surfaces inspired by springtails exhibit excellent repellency to low-surface-tension liquid. However, the flexible doubly re-entrant surfaces are difficult to fabricate, especially for the overhang of the structure. Herein, we demonstrate a simple Fresnel aperture diffraction modulation strategy in microscale lithography coupled with a molding process to obtain the flexible doubly re-entrant superomniphobic surfaces with nanoscale overhangs. The negative nanoscale overhang features were formed in a single-layer photoresist due to the fine-modulation of the optical intensity fluctuation of the Fresnel aperture diffraction. The as-prepared flexible non-fluorinated polydimethylsiloxane (PDMS) doubly re-entrant microstructure based on the Fresnel aperture diffraction (D-BF) surface (without any additional treatments) could repel ethanol droplets (21.8 mN m-1) in the Cassie-Baxter state. The robust nanoscale overhangs obtained by the molding process enable the maximum breakthrough pressure for the low-surface-tension ethanol droplets on the D-BF surfaces up to about 230 Pa, allowing ethanol liquids with Weber numbers up to 8.7 to fully bounce off. The fabricated non-fluorinated D-BF superomniphobic surface maintains outstanding liquid repellency after the surface wettability modification and deformation test.

Superomniphobic surfaces for easy-removals of environmental-related liquids after icing and melting

Superomniphobic surfaces for easy-removals of environmental-related liquids after icing and melting

One-Step Fabrication of Flexible Bioinspired Superomniphobic Surfaces.

Flexible superomniphobic doubly re-entrant (Dual-T) microstructures inspired by springtails have attracted growing attention due to their excellent liquid-repellent properties. However, the simple and practical manufacturing processes of the flexible Dual-T microstructures are urgently needed. Here, we proposed a one-step molding process coupled with the lithography technique to fabricate the elastomeric polydimethylsiloxane (PDMS) Dual-T microstructure surfaces with high uniformity. The angle between the downward overhang and the horizontal direction could reach 90° (vertical overhang). The flexible superomniphobic Dual-T microstructure surfaces, without fluorination treatment and physical treatments, could repel liquids with a surface tension lower than 20 mN m-1 in the Cassie-Baxter state. Owing to the excellent robustness of the one-step molding downward overhanging, the max breakthrough pressure of this surface could reach up to 164.3 Pa for ethanol droplets. Furthermore, the flexible superomniphobic Dual-T surface allowed impinging ethanol droplets to completely rebound at the Weber number up to 7.1 with an impact velocity of ∼0.32 m s-1. The Dual-T microstructure surface maintained excellent superomniphobicity even after surface oxygen plasma treatment and exhibited excellent structural robustness and recoverability to various large mechanical deformations.

Strategy toward fluorinated polyhedral oligomeric silsesquioxane wrapping nanoparticles for superomniphobic surfaces.

For engineering implementation of an ultralow-surface-energy hierarchically micro/nanostructured topography for superomniphobic surfaces, a strategy involving the design of a partially open-cage fluorinated polyhedral oligomeric silsesquioxane bearing an -OH pair (poc-F13POSS-2OH) and the subsequent wrapping of nanoparticles with poc-F13POSS-2OH as a result of weak-acid-triggered -OH protonation is developed. The poc-F13POSS-wrapped nanoparticle-based surfaces showed broad-spectrum superomniphobicity. This work has advanced the engineering of state-of-the-art superomniphobic solid surfaces/interfaces.

Water-Responsive Self-Repairing Superomniphobic Surfaces via Regeneration of Hierarchical Topography.

Superomniphobic surfaces that can self-repair physical damage are desirable for sustainable performance over time in many practical applications that include self-cleaning, corrosion resistance, and protective gears. However, fabricating such self-repairing superomniphobic surfaces has thus far been a challenge because it necessitates the regeneration of both low-surface-energy materials and hierarchical topography. Herein, a water-responsive self-repairing superomniphobic film is reported by utilizing cross-linked hydroxypropyl cellulose (HPC) composited with silica (SiO2) nanoparticles (HPC-SiO2) that is treated with a low-surface-energy perfluorosilane. The film can repair physical damage (e.g., a scratch) in approximately 10 s by regenerating its hierarchical topography and low-surface-energy material upon the application of water vapor. The repaired region shows an almost complete recovery of its inherent superomniphobic wettability and mechanical hardness. The repairing process is driven by the reversible hydrogen bond between the hydroxyl (-OH) groups which can be dissociated upon exposure to water vapor. This results in a viscous flow of the HPC-SiO2 film into the damaged region. A mathematical model composed of viscosity and surface tension of the HPC-SiO2 film can describe the experimentally measured viscous flow with reasonable accuracy. Finally, we demonstrate that the superomniphobic HPC-SiO2 film can repair physical damage by a water droplet pinned on a damaged area or by sequential rolling water droplets.

The benefits of being repellent

Materials Science The accumulation of foreign substances on a surface, whether it is dirt on a window or ice on an airplane wing, can lead to hazardous conditions. Many surfaces have been engineered to resist the accumulation of one type of fluid or matter in a particular state, but engineering broader resistivity has remained a challenge. For example, surfaces that repel water droplets may still be susceptible to fog accumulation. Dhyani et al. review the wetting performance and fouling resistance of different liquid-repellent coatings, focusing on superhydrophobic, superomniphobic, lubricant-infused, and liquid-like surfaces. Two key aspects are the performance of the surface to different foulants and the relevance of considering different length scales. Science , aba5010, this issue p. [eaba5010][1] [1]: /lookup/doi/10.1126/science.aba5010

Superwetting Shape Memory Microstructure: Smart Wetting Control and Practical Application.

Smart control of wettability on superwetting surfaces has aroused much attention in the past few years. Compared with traditional strategies such as adjusting the surface chemistry, regulating the surface microstructure is more difficult, though it can bring lots of new functions. Recently, it was found that, based on the shape memory effect of a shape memory polymer, the surface microstructure can be controlled more easily and precisely. Here, recent developments in the smart control of wettability on superwetting shape memory microstructures and corresponding applications are summarized. The primary concern is the superhydrophobic surfaces that have demonstrated numerous attractive functions, including controllable droplet storage, transportation, bouncing, capture/release, and reprogrammable gradient wetting, under variation of the surface microstructure. Finally, some achievements in wetting control on other superwetting surfaces (such as superomniphobic surfaces and superslippery surfaces) and perspectives on future research directions are also discussed.

Biomimetic Coating-free Superomniphobicity

Superomniphobic surfaces, which repel droplets of polar and apolar liquids, are used for reducing frictional drag, packaging electronics and foods, and separation processes, among other applications. These surfaces exploit perfluorocarbons that are expensive, vulnurable to physical damage, and have a long persistence in the environment. Thus, new approaches for achieving superomniphobicity from common materials are desirable. In this context, microtextures comprising “mushroom-shaped” doubly reentrant pillars (DRPs) have been shown to repel drops of polar and apolar liquids in air irrespective of the surface make-up. However, it was recently demonstrated that DRPs get instantaneously infiltrated by the same liquids on submersion because while they can robustly prevent liquid imbibition from the top, they are vulnerable to lateral imbibition. Here, we remedy this weakness through bio-inspiration derived from cuticles of Dicyrtomina ornata, soil-dwelling bugs, that contain cuboidal secondary granules with mushroom-shaped caps on each face. Towards a proof-of-concept demonstration, we created a perimeter of biomimicking pillars around arrays of DRPs using a two-photon polymerization technique; another variation of this design with a short wall passing below the side caps was investigated. The resulting gas-entrapping microtextured surfaces (GEMS) robustly entrap air on submersion in wetting liquids, while also exhibiting superomniphobicity in air. To our knowledge, this is the first-ever microtexture that confers upon intrinsically wetting materials the ability to simultaneously exhibit superomniphobicity in air and robust entrapment of air on submersion. These findings should advance the rational design of coating-free surfaces that exhibit ultra-repellence (or superomniphobicity) towards liquids.

Reliable and Robust Fabrication Rules for Springtail-Inspired Superomniphobic Surfaces.

We report a reliable and robust method for the fabrication of bioinspired superomniphobic surfaces with precise concave-cap-shaped micropillar arrays. This method includes silicon-based conventional microelectromechanical systems (MEMS) and polymer replication processes. We have elucidated two critical cases of fabrication rules for precise micromachining of a negative-shaped bioinspired silicon master. The fabricated polymeric structure replicated from the semipermanent silicon master based on the design rules exhibited high structural fidelity and robustness. Finally, we validated the superomniphobic properties, structural durability, and long-term stability of the fabricated bioinspired surfaces.

Passive Removal of Highly Wetting Liquids and Ice on Quasi-Liquid Surfaces.

Surfaces with ultralow adhesion to liquids and solids have attracted broad interests in both fundamental studies and engineering applications from passive removal of highly wetting liquids and water harvesting to anti-/de-icing. The current state-of-the-art superomniphobic surfaces (rely on air lubricant) and liquid-infused surfaces (rely on liquid lubricant) suffer from severe issues for liquid repellency and ice removal: air/liquid lubricant loss or topography damage. Here, we create a durable quasi-liquid surface by tethering flexible polymer on various solid substrates. The untethered end of the polymer has mobile chains that behave like a liquid layer and greatly reduce the interfacial adhesion between the surface and foreign liquids/solids. Such a quasi-liquid surface with a 30.1 nm flexible polymer layer shows ultralow contact angle hysteresis (≤1.0°) to liquids regardless of their surface tensions. The highly wetting perfluorinated liquids like FC72 and Krytox101, as well as complex fluids like urine and crude oil, can be repelled from the surface. Moreover, wind can remove accreted ice from the surface in harsh conditions due to the negligible ice adhesion. We have demonstrated that the quasi-liquid surface shows robust performances in repelling highly wetting liquids, harvesting water, and removing ice, respectively.

Improved dynamic stability of superomniphobic surfaces and droplet transport on slippery surfaces by dual-scale re-entrant structures

There has been substantial recent interest with respect to the broad potential applications of superomniphobic surfaces, but it remains enormously challenging to enhance the dynamic stability of such surfaces impacted by high-pressured droplets. Herein, a robust superomniphobic surface with dual-scale re-entrant structures (DRSs) has been designed and fabricated through a facile combination of magnetic particle-assisted self-assembly and a dip-coating technique. Compared to superomniphobic surfaces with single-scale re-entrant structures, this superomniphobic surface with DRSs shows highly improved repellency against the impact from different high-pressured droplets, a property which is furnished by the extension of three-phase contact lines, the increase in local geometric angles, and the formation of additional air pockets. Furthermore, the superomniphobic surface can serve as a platform to well maintain lubricating fluid so as to realize a photoresponsive slippery surface wherein near-infrared light can be used to manipulate various liquid droplets with a large range of volumes. Overall, this study provides a strategy for obtaining the robust superomniphobic and photoresponsive slippery surfaces through the DRS design, which provides a new insight into enhancing the dynamic stability of superomniphobic surfaces and also demonstrates the application of slippery surfaces for droplet manipulation.

Plasma-induced graft polymerization on the surface of aramid fabrics with improved omniphobicity and washing durability

Durable superomniphobic surfaces are desirable for their practical applications, including self-cleaning, non-fouling, protective clothing and the separation of liquids. The plasma-induced polymerization of environmentally friendly C6 from a perfluoralkyl methlacrylate copolymer emulsion, AG-E081, was performed and a durable omniphobic fabric was achieved. C6 is an ecological alternative to C8 (eight CF2 groups) fluorinated compounds, and it was thereafter successfully incorporated into aramid fabric to achieve a durable superomniphobic surface. The fabric became water and oil repellent with an extremely high water contact angle of 180°. As tested by the water spray AATCC test and hydrocarbon resistance test, the as-prepared fabric gained 100° (ISO 5) and grade number 4 respectively. Furthermore, the fabrics also showed significantly improved washing durability after ten washing cycles. By scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR) and x-ray photoelectron spectroscopy (XPS) tests, it is indicated that the durable superomniphobicity can be attributed to the roughness and activation of the aramid surface by the plasma pre-treatment, which induces more adsorption and chemical graft of the C6 copolymer.

Superomniphobic Silk Fibroin/Ag Nanowires Membrane for Flexible and Transparent Electronic Sensor.

Superwetting surfaces that repel various liquids have been exciting for biomimetic research and have displayed versatile potential applications. Generally, superhydrophobic coatings can allow for droplet rolling off and antifouling, whereas it is a challenge to achieve superomniphobic surfaces with transparency, flexibility, and conductivity. Here, we adopt an effective and simple method to fabricate a superomniphobic, transparent, and flexible smart silk fibroin (SF) membrane by spray-coating long AgNWs dispersed in polydimethylsiloxane (PDMS), followed by treatment with vacuum drying. The resulting SF/AgNWs membranes are super-repellent to different liquids with low surface tension and water, and demonstrate high contact angles (CAs) more than 150° and low rolling-off angles (RAs) even less than 10°. Moreover, the obtained membranes display superior sensitivity under stretching and bending, as well as intact stability of high transparency, which can be considered as promising flexible sensing electronics to detect human motions under wet conditions.

Scalable Superomniphobic Surfaces

Superomniphobic surfaces that repel liquids of extremely low surface tension rely on carefully fabricated doubly re-entrant topographies, typically made by silicon deep reactive ion etching technology. However, previously published processes have depended on critically timed etching steps, which are difficult to downscale. We present a scalable process that eliminates the critically timed etching steps. It is based on the use of silicon-on-insulator wafers and a silicon oxide foot of the micropillar, which makes the isotropic silicon release step non-critical. The process allows easy downscaling of pillars from 20 $\mu \text{m}$ to 10 $\mu \text{m}$ and $5~\mu \text{m}$ . The downscaling increases the stability of the Cassie state. Based on the process, we are able to create superomniphobic surfaces that sustain perfluorohexane (FC-72), which has the lowest surface tension of the known liquids at room temperature ( $\gamma _{\text {lv}}=11.91$ mN/m at 20 °C), in the Cassie state at droplet diameters down to 200 micrometers. These are the smallest perfluorohexane droplets repelled to date. [2019-0207]

Slippery Liquid-Attached Surface for Robust Biofouling Resistance.

Materials for biodevices and bioimplants commonly suffer from unwanted but unavoidable biofouling problems due to the nonspecific adhesion of proteins, cells, or bacteria. Chemical coating or physical strategies for reducing biofouling have been pursued, yet highly robust antibiofouling surfaces that can persistently resist contamination in biological environments are still lacking. In this study, we developed a facile method to fabricate a highly robust slippery and antibiofouling surface by conjugating a liquid-like polymer layer to a substrate. This slippery liquid-attached (SLA) surface was created via a one-step equilibration reaction by tethering methoxy-terminated polydimethylsiloxane (PDMS-OCH3) polymer brushes onto a substrate to form a transparent "liquid-like" layer. The SLA surface exhibited excellent sliding behaviors toward a wide range of liquids and small particles and antibiofouling properties against the long-term adhesion of small biomolecules, proteins, cells, and bacteria. Moreover, in contrast to superomniphobic surfaces and liquid-infused porous surfaces (SLIPS) requiring micro/nanostructures, the SLA layer could be obtained on smooth surfaces and maintain its biofouling resistance under abrasion with persistent stability. Our study offers a simple method to functionalize surfaces with robust slippery and antibiofouling properties, which is promising for potential applications including medical implants and biodevices.

Self-Healable Superomniphobic Surfaces for Corrosion Protection.

Corrosion-protective surfaces are of the utmost relevance to ensure long-term stability and reliability of metals and alloys by limiting their interactions with corrosive species, such as water and ions. However, their practical applications are often limited either by the inability to repel low surface tension liquids such as oils and alcohols or by poor mechanical durability. Here, a superomniphobic surface is reported that can display very high contact angles for both high and low surface tension liquids as well as for concentrated acids and bases. Such extreme repellency allowed for approximately 20% of the corrosion rate compared to the conventional superhydrophobic corrosion protective coatings. Furthermore, the superomniphobic surface can autonomously repair mechanical damage at an elevated temperature (60 °C) within a short period of time (60 s), and the surface can restore its intrinsic corrosion protection performance. Such superomniphobic surfaces thus offer a wide range of potential applications, including pipelines, with sustainable corrosion protection and rust inhibitors for steel in reinforced concrete.

Superomniphobic Surfaces with Improved Mechanical Durability: Synergy of Hierarchical Texture and Mechanical Interlocking.

Due to their unique functionality, superomniphobic surfaces that display extreme repellency toward virtually any liquid, have a wide range of potential applications. However, to date, the mechanical durability of superomniphobic surfaces remains a major obstacle that prevents their practical deployment. In this work, a two-layer design strategy was developed to fabricate superomniphobic surfaces with improved durability via synergistic effect of interconnected hierarchical porous texture and micro/nano-mechanical interlocking. The improved mechanical robustness of these surfaces was assessed through water shear test, ultrasonic washing test, blade scratching test, and Taber abrasion test.

Multifaceted design optimization for superomniphobic surfaces.

Superomniphobic textures are at the frontier of surface design for vast arrays of applications. Despite recent substantial advances in fabrication methods for reentrant and doubly reentrant microstructures, design optimization remains a major challenge. We overcome this in two stages. First, we develop readily generalizable computational methods to systematically survey three key wetting properties: contact angle hysteresis, critical pressure, and minimum energy wetting barrier. For each, we uncover multiple competing mechanisms, leading to the development of quantitative models and correction of inaccurate assumptions in prevailing models. Second, we combine these analyses simultaneously, demonstrating the power of this strategy by optimizing structures that are designed to overcome challenges in two emerging applications: membrane distillation and digital microfluidics. As the wetting properties are antagonistically coupled, this multifaceted approach is essential for optimal design. When large surveys are impractical, we show that genetic algorithms enable efficient optimization, offering speedups of up to 10,000 times.

Superomniphobic Papers for On‐Paper pH Sensors

AbstractPaper‐based superomniphobic surfaces are of great interest because paper is flexible, inexpensive, lightweight, breathable, and recyclable. Prior reports on paper‐based superomniphobic surfaces have failed to demonstrate high mobility with low surface tension liquids. In order to overcome this issue, in this work, superomniphobic papers are developed through growth of nanofilaments on inherent microfibers of papers without noticeably altering their microscale features (i.e., diameter and distance of the microfibers). These superomniphobic papers display very low roll‐off angle, indicative of ultra‐high droplet mobility, even with low surface tension liquids. Here, a facile method is also developed to control the motion and adhesion of the droplets on the superomniphobic paper. Utilizing such liquid mobility in a controlled manner on these superomniphobic papers, a simple on‐paper pH sensor is fabricated. It is anticipated that this on‐paper, simple, and rapid detection methodology can also be extended to the colorimetric sensing of protein and chemical assays. Further, these superomniphobic papers have potential applications in water–oil separation and enhanced weight‐bearing capacity.