Droplet Friction on Superhydrophobic Surfaces Scales With Liquid-Solid Contact Fraction.

It is generally assumed that contact angle hysteresis of superhydrophobic surfaces scales with liquid-solid contact fraction, however, its experimental verification has been problematic due to the limited accuracy of contact angle and sliding angle goniometry. Advances in cantilever-based friction probes enable accurate droplet friction measurements down to the nanonewton regime, thus suiting much better for characterizing the wetting of superhydrophobic surfaces than contact angle hysteresis measurements. This work quantifies the relationship between droplet friction and liquid-solid contact fraction, through theory and experimental validation. Well-defined micropillar and microcone structures are used as model surfaces to provide a wide range of different liquid-solid contact fractions. Micropillars are known to be able to hold the water on top of them, and a theoretical analysis together with confocal laser scanning microscopy shows that despite the spiky nature of the microcones droplets do not sink into the conical structure either, rendering a diminishingly small liquid-solid contact fraction. Droplet friction characterization with a micropipette force sensor technique reveals a strong dependence of the droplet friction on the contact fraction, and the dependency is described with a simple physical equation, despite the nearly three-orders-of-magnitude difference in liquid-solid contact fraction between the sparsest cone surface and the densest pillar surface.

Self-healable, Tolerant Superaerophobic Coating for Improving Electrochemical Hydrogen Production.

Gas-evolving electrodes often suffer from the blocking of catalytic active sites-due to unwanted and unavoidable adhesion of generated gas bubbles, which elevates the overpotential for the electrochemical hydrogen evolution reaction (HER)- by raising the resistance of the electrode. Here, a catalyst-free and self-healable superaerophobic coating having ultra-low bubble adhesion is introduced for achieving significantly depleted overpotentials of 209 and 506 mV at both low (50 mA cm-2) and high (500 mA cm-2) current densities, respectively, compared to a bare nickel-foam electrode. The optimized coating ensured an early detachment of the generated tiny (0.8 ± 0.1 mm) gas bubble-and thus, prevented the undesired rise in resistance of the coated electrode. The systematic association of physical (i.e., ionic interactions, H-bonding, etc.) cross-linkage, ß-amino ester type covalent cross-linkage and reinforced halloysite nano clay enables the design of such functional material embedded with essential characteristics-including improved mechanical (toughness of 63.7 kJ m-3, and tensile modulus of 26 kPa) property and chemical (extremes of pH (1 and 14), salinity, etc.) stability, rapid (<10 min) self-healing ability (even at alkaline condition) and desired bubble-wettability (bubble contact angle of 158.2 ± 0.2°) with ultralow force (4.2 ± 0.4 µN) of bubble adhesion.

Dual-Coating of Fluorinated Polydimethylsiloxane/Fluorinated SiO2 Nanoparticles for Superhydrophobic and High-Efficiency Bacteriostatic Surface.

A simple two-step spray method is used to prepare superhydrophobic and bacteriostatic surfaces, involving dual-coating with polydimethylsiloxane-normal-fluorine (PDMS-NF) or branched-fluorine (PDMS-BF) in combination with fluorinated silica nanoparticles (FSiO2 -NPs) using a spray technique. This approach has the potential to create surfaces with both water-repellent and antimicrobial properties, which could be useful in a variety of applications. It is noteworthy that the dual-coating on cotton fabric exhibited an impressive dual-scale roughness and achieved superhydrophobicity with a water contact angle of 158° and a hysteresis of less than 3°. Additionally, the coating was subjected to an ultra-high concentration of bacteria (109 CFU/mL) and was still able to inhibit more than 80 % of attachment, demonstrating its effectiveness as a bacteriostatic surface.

Cryopreservation of human semen by inherently-controlled icing probability: Or how the surface profile of superhydrophobic carbon soot coatings and the sperm volume affect the outcome of slow freezing?

The restoration of initial functionality of human spermatozoa subjected to cryopreservation is challenging, because the deleterious intracellular icing and the occurrence of osmotic shocks due to prolonged exposure to increased concentrations of intracellular solutes are oppositely dependent on the cooling rate. This longstanding problem could be overcome if using superhydrophobic soot coatings delaying the heat transfer rate, reducing the ice formation probability and triggering balanced and timely dehydration of the cells, but the effect of their surface profile and sperm volume on the success rate of slow freezing is unclear. Here, we show for the first time that the two-factor freezing injury is entirely avoidable by tailoring the solid-to-gas voids (pores) fraction in the soot, leading to increased nucleation free energy barrier, presumable incipiency of ice crystals with controllable shape and size and hence, fully (100 %) recovered post-thaw sperm motility. It is demonstrated that the reason for such a unique scientific result is the selection of soot coatings with appropriate morphochemical features, hypothetically (not directly proven yet) inducing equilibrium among the solution composition and ice crystals formation, retarding the undesirable compression of liquid-filled "slush ice" channels surrounding the cytoplasm and impeding the ice recrystallization. The novel insights introduced in this article open endless horizon for customizing and revolutionizing the technical protocols in cryobiology.

Preparation of photoluminescent nano-biocomposite nacre from graphene oxide and polylactic acid.

Nano-biocomposites of inorganic and organic components wereprepared to produce long-persistent phosphorescent artificial nacre-like materials. Biodegradable polylactic acid (PLA), graphene oxide (GO), and nanoparticles (13-20 nm) of lanthanide-doped aluminate pigment (NLAP) were used in a simple production procedure of an organic/inorganic hybrid nano-biocomposite. Both polylactic acid and GO nanosheets were chemically modified to form covalent and hydrogen bonding. The high toughness, good tensile strength, and great endurance of those bonds were achieved by their interactions at the interfaces. Long-persistent and reversible photoluminescence was shown by the prepared nacre substrates. Upon excitation at 365 nm, the nacre substrates generated an emission peak at 517 nm. When ultraviolet light was shone on luminescent nacres, they displayed a bright green colour. The high superhydrophobicity of the generated nacres was obtained without altering their mechanical characteristics.

Study of the Antibacterial Activity of Superhydrophilic and Superhydrophobic Copper Substrates against Multi-Drug-Resistant Hospital-Acquired Pseudomonas aeruginosa Isolates.

The global spread of multidrug-resistant (MDR) hospital-acquired pathogens is a serious problem for healthcare units. The challenge of the spreading of nosocomial infections, also known as hospital-acquired pathogens, including Pseudomonas aeruginosa, must be addressed not only by developing effective drugs, but also by improving preventive measures in hospitals, such as passive bactericidal coatings deposited onto the touch surfaces. In this paper, we studied the antibacterial activity of superhydrophilic and superhydrophobic copper surfaces against the P. aeruginosa strain PA103 and its four different polyresistant clinical isolates with MDR. To fabricate superhydrophilic and superhydrophobic coatings, we subjected the copper surfaces to laser processing with further chemosorption of fluorooxysilane to get a superhydrophobic substrate. The antibacterial activity of superhydrophilic and superhydrophobic copper surfaces was shown, with respect to both the collection strain PA103 and polyresistant clinical isolates of P. aeruginosa, and the evolution of the decontamination of a bacterial suspension is presented and discussed. The presented results indicate the promising potential of the exploitation of superhydrophilic coatings in the manufacture of contact surfaces for healthcare units, where the risk of infection spread and contamination by hospital-acquired pathogens is extremely high.

Polyurethane Nanocomposite Coatings Coupled with Titanium-Based Conversion Layers for Enhanced Anticorrosion, Icephobic Properties, and Surface Protection.

This study examines the efficacy of icephobic polyurethane nanocomposite coatings in mitigating corrosion on an aluminum substrate. A titanium-based conversion coating is applied to modify the substrate, and the research focuses on optimizing the dual functionalities of icephobicity and anticorrosion within the polyurethane coatings while ensuring strong substrate adhesion. The coatings are formulated using fluoropolyol, isocyanate, and silica nanoparticles treated with polydimethylsiloxane. Surface properties are analyzed using contact angles, contact angle hysteresis measurements, and atomic force microscopy, and the coatings' icephobicity is evaluated through differential scanning calorimetry, freezing time delay, ice adhesion under impact and non-impact conditions, and ice accretion tests. The corrosion resistance and adhesive strength of the coatings are assessed using electrochemical impedance spectroscopy and cross-cut tests, respectively. Increasing the concentration of silica nanoparticles to 10 wt.% increases contact angles to 167°, although the 4 wt.% coating produces the lowest contact angle hysteresis (3° ± 0.5°) and ice nucleation temperature (-23 °C). The latter coating is then applied to a substrate pretreated with a titanium/cerium-based conversion coating. This prepared surface maintains an ice adhesion of about 15 kPa after 15 icing/de-icing cycles and provides approximately 90 days of surface protection (|Z|lf = 1.6 × 109 Ω·cm2). Notably, the impedance value exceeds that of untreated substrates, underscoring the effectiveness of the titanium/cerium-based conversion coating in enhancing both corrosion resistance and coating adhesion to the substrate.

Preparation and Anti-Icing Properties of Zirconia Superhydrophobic Coating.

Zirconia (ZrO2) is a ceramic material with high-temperature resistance and good insulating properties. Herein, for the first time, the surface of ZrO2 was modified with docosanoic acid (DCA) to improve its self-cleaning and hydrophobic properties. This surface modification transformed the surface of ZrO2 from hydrophilic to superhydrophobic. A two-step spraying method was used to prepare the superhydrophobic surface of ZrO2 by sequentially applying a primer and a topcoat. The primer was a solution configured using an epoxy resin as the adhesive and polyamide as the curing agent, while the topcoat was a modified ZrO2 solution. The superhydrophobic surface of ZrO2 exhibited a contact angle of 154° and a sliding angle of 4°. Scanning electron microscopy, X-ray diffraction, energy-dispersive X-ray spectroscopy, thermogravimetric analysis, and other analytical techniques were used to characterize the prepared zirconia particles and their surfaces. Moreover, results from surface self-cleaning and droplet freezing tests showed that DCA-modified ZrO2 can be well combined, and its coatings show good self-cleaning and anti-icing properties on TA2 bases.

Green Method for the Preparation of Durable Superhydrophobic Antimicrobial Polyester Fabrics with Micro-Pleated Structures.

To produce functional protective textiles with minimal environmental footprints, we developed durable superhydrophobic antimicrobial textiles. These textiles are characterized by a micro-pleated structure on polyester fiber surfaces, achieved through a novel plasma impregnation crosslinking process. This process involved the use of water as the dispersion medium, water-soluble nanosilver monomers for antimicrobial efficacy, fluorine-free polydimethylsiloxane (PDMS) for hydrophobicity, and polyester (PET) fabric as the base material. The altered surface properties of these fabrics were extensively analyzed using scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectrometry (XPS), thermogravimetric analysis (TGA), and water contact angle (WCA) measurements. The antimicrobial performance of the strains was evaluated using Gram-negative Escherichia coli and Gram-positive Staphylococcus aureus. After treatment, the fabrics exhibited enhanced hydrophobic and antimicrobial properties, which was attributed to the presence of a micro-pleated structure and nanosilver. The modified textiles demonstrated a static WCA of approximately 154° and an impressive 99.99% inhibition rate against both test microbes. Notably, the WCA remained above 140° even after 500 washing cycles or 3000 friction cycles.

A Simple and Sequential Strategy for the Introduction of Complexity and Hierarchy in Hydrogen-Bonded Organic Framework (HOF) Crystals for Environmental Applications.

Hydrogen-bonded organic frameworks (HOFs) are a new class of crystalline porous organic molecular materials (POMMs) with great potential for a diverse range of applications. HOFs face common challenges to POMMs, and in general to purely organic crystals, that is, the difficulty of integrating complexity in crystals. Herein, we propose a simple and sequential strategy for the formation of HOFs with hierarchical superstructures. The strategy is based on controlling the assembly conditions, avoiding the use of any surface functionalization or template, which allows to obtain hierarchical crystalline porous superstructures in an easy manner. As proof of concept, we obtained the first example of core-shell (HOF-on-HOF) crystals and HOFs with hierarchical superstructures having superhydrophobicity and trapping abilities for the capture of persistent water contaminants such as oils and microplastics. We expect that this strategy could serve as inspiration for the construction of more intricate multiscale structures that could greatly expand the library of HOF materials.

Room Temperature Hydroxyl Group-Assisted Preparation of Hydrophobicity-Adjustable Metal-Organic Framework UiO-66 Composites: Towards Continuous Oil Collection and Emulsion Separation.

Developing a straightforward and effective hydrophobic modification for metal-organic frameworks (MOFs) under mild conditions is meaningful for MOF applications. Here, a post-synthetic modification approach assisted with metal hydroxyl groups at room temperature is reported to induce hydrophobicity in the hydrophilic UiO-66. The bonding between Zr-OH in UiO-66 and n-tetradecylphosphonic acid (TDPA) is the vital force for the modifier TDPA. Superhydrophobic and superoleophilic composites were constructed for efficient oil-water separation by coating TDPA-modified UiO-66 (P-UiO-66) on commercial melamine sponges (MS) and filter papers (FP) with water contact angles of 153.2° and 155.6°, respectively. The P-UiO-66/MS composite could quickly and selectively absorb oily liquids up to 43 times its weight from water. The P-UiO-66/MS achieved continuous oil collection with high separation efficiencies (≥99.4 %). In addition, P-UiO-66/FP and P-UiO-66/MS showed high separation efficiencies for water-in-oil emulsions (≥98.5 %) and oil-in-water emulsions, respectively, with high resistance to low/high temperatures and acid/base conditions. The metal hydroxyl group-assisted post-synthetic modification strategy offers a facile and broad way to prepare hydrophobic MOFs for promising applications in environmental fields.

Superhydrophobic Thermoplastic Polyurethane Foam Fabricated by Phase Separation and Silica Coating for Oil-Water Separation.

Oil spills and the presence of oily wastewater have resulted in substantial ecological damage. Superhydrophobic polymer foam with selectivity and adsorption capacity is a promising candidate for efficient oil-water separation. In this study, a method that combines phase separation and silica coating to produce superhydrophobic thermoplastic polyurethane (TPU) foam is proposed. The TPU foam demonstrates superhydrophobicity with a water contact angle of 155.62°, and exhibits a maximum saturated adsorption capacity of 54.11 g g-1 . Furthermore, the foam can be utilized as a filter for oil-water separation, maintaining its filtration efficiency (41.2 m3  m2  h-1 ) even after ten filtration cycles.

A Superhydrophobic Trifluoromethyl-Containing Covalent Organic Framework Membrane for Efficient Oil/Water Separation.

Oily water caused in the process of industry leads to not only the waste of resources, but also environmental pollution. Membrane separation, as a facile and efficient separation technology, has attracted widespread attention in the field of oil/water separation. The development of membrane materials with high separation performance is one of the key elements to improve separation efficiency. In this work, a superhydrophobic membrane composited with a trifluoromethyl-containing covalent organic framework (COF) is prepared, which exhibits excellent performance on separations of oil/water mixtures and water-in-oil emulsions. For different composition of oil/water mixtures, the highest flux of oil is up to 32 000 L m-2  h-1 and oil/water separation efficiency is above 99%. Moreover, the high oil/water separation efficiency remains unchanged after successive cycles. This work provides a feasible scheme for the design of high-efficiency oil/water separation membranes.

A Novel Anti-Flashover Superhydrophobic Coating with Self-Assembly Characteristic of Surface Energy Differences.

Because of the versatility of superhydrophobic materials, they have attracted a lot of attention even in power electronics, transportation, engineering, and other fields. The volume fraction of fluorinated silicon oxide nanoparticles in superhydrophobic materials is one of the most important factors. Increasing the volume fraction will decrease the stability between the coating and the hydrophobic surface. Especially, the flashover voltage of the coating gradually decreases from 10 to 35 vol.%. Meanwhile, the flashover voltage dispersion of the coating increases drastically after 30 vol.%. In order to improve the electrical properties of the superhydrophobic coating, self-assembly of surface energy differences strategy is proposed in this work. A binary filling phase of the coating is introduced by 2D boron nitride nanosheets and silicon oxide nanoparticles. Although Hexagonal boron nitride with high surface energy and low roughness, it will be spontaneously assembled and wrapped by silicon oxide nanoparticle based on surface energy differences, which forming a low surface energy filled phase. Experiment results prove that the flashover voltage of the superhydrophobic coating is optimized by the binary filling phase coating. This method offers new ideas for the selection of filling phase and application of superhydrophobic materials.

Advances in Sol-Gel-Based Superhydrophobic Coatings for Wood: A Review.

As the focus of architecture, furniture, and other fields, wood has attracted extensive attention for its many advantages, such as environmental friendliness and excellent mechanical properties. Inspired by the wetting model of natural lotus leaves, researchers prepared superhydrophobic coatings with strong mechanical properties and good durability on the modified wood surface. The prepared superhydrophobic coating has achieved functions such as oil-water separation and self-cleaning. At present, some methods such as the sol-gel method, the etching method, graft copolymerization, and the layer-by-layer self-assembly method can be used to prepare superhydrophobic surfaces, which are widely used in biology, the textile industry, national defense, the military industry, and many other fields. However, most methods for preparing superhydrophobic coatings on wood surfaces are limited by reaction conditions and process control, with low coating preparation efficiency and insufficiently fine nanostructures. The sol-gel process is suitable for large-scale industrial production due to its simple preparation method, easy process control, and low cost. In this paper, the research progress on wood superhydrophobic coatings is summarized. Taking the sol-gel method with silicide as an example, the preparation methods of superhydrophobic coatings on wood surfaces under different acid-base catalysis processes are discussed in detail. The latest progress in the preparation of superhydrophobic coatings by the sol-gel method at home and abroad is reviewed, and the future development of superhydrophobic surfaces is prospected.

A harsh environment resistant robust Co(OH)2@stearic acid nanocellulose-based membrane for oil-water separation and wastewater purification.

Traditional membranes are inefficient in treating highly toxic organic pollutants and oily wastewater in harsh environments, which is difficult to meet the growing demand for green development. Herein, the Co(OH)2@stearic acid nanocellulose-based membrane was prepared by depositing Co(OH)2 on the nanocellulose-based membrane (NBM) through chemical soaking method, which enables efficient oil/water mixtures separation and degradation of pollutants by photocatalysis in harsh environments. The Co(OH)2@stearic acid nanocellulose-based membrane (Co(OH)2@stearic acid NBM) shows good photocatalytic degradation performance for methylene blue pollutants in harsh environment, and has significant degradation rate (93.66%). At the same time, the Co(OH)2@stearic acid NBM with superhydrophobicity and superoleophilicity also exhibits respectable oil/water mixtures separation performance (n-Hexane, dimethyl carbonate, chloroform and toluene) under harsh environment (strong acid/strong alkali), which has an excellent oil-water mixtures separation flux of 87 L·m-2·h-1 (n-Hexane/water) and oil-water mixture separation efficiency of over 93% (n-Hexane/water). In addition, this robust Co(OH)2@stearic acid NBM shows good self-cleaning and recycling performance. Even though seven oil-water separation tests have been carried out under harsh environment, it can still maintain respectable oil-water mixture separation rate and flux. The multifunctional membrane has excellent resistance to harsh environments, oil-water separation and pollutant degradation can be performed even in harsh environments, which provides a convenient way to treat sewage under harsh conditions efficiently and has great potential in practical application.

Superhydrophobic and Conductive Wire Membrane for Enhanced CO2 Electroreduction to Multicarbon Products.

Gas-liquid-solid triple-phase interfaces (TPI) are essential for promoting electrochemical CO2 reduction, but it remains challenging to maximize their efficiency while integrating other desirable properties conducive to electrocatalysis. Herein, we report the elaborate design and fabrication of a superhydrophobic, conductive, and hierarchical wire membrane in which core-shell CuO nanospheres, carbon nanotubes (CNT), and polytetrafluoroethylene (PTFE) are integrated into a wire structure (designated as CuO/F/C(w); F, PTFE; C, CNT; w, wire) to maximize their respective functions. The realized architecture allows almost all CuO nanospheres to be exposed with effective TPI and good contact to conductive CNT, thus increasing the local CO2 concentration on the CuO surface and enabling fast electron/mass transfer. As a result, the CuO/F/C(w) membrane attains a Faradaic efficiency of 56.8 % and a partial current density of 68.9 mA cm-2 for multicarbon products at -1.4 V (versus the reversible hydrogen electrode) in the H-type cell, far exceeding 10.1 % and 13.4 mA cm-2 for bare CuO.

Cost-Effective Fabrication of Micro-Nanostructured Superhydrophobic Polyethylene/Graphene Foam with Self-Floating, Optical Trapping, Acid-/Alkali Resistance for Efficient Photothermal Deicing and Interfacial Evaporation.

Solar evaporation is one of the most attractive and sustainable approaches to address worldwide freshwater scarcity. Unfortunately, it is still a crucial challenge that needs to be confronted when the solar evaporator faces harsh application environments. Herein, a promising polymer molding method that combines melt blending and compression molding, namely micro extrusion compression molding, is proposed for the cost-effective fabrication of lightweight polyethylene/graphene nanosheets (PE/GNs) foam with interconnected vapor escape channels and surface micro-nanostructures. A contact angle of 155 ± 2°, a rolling angle of 5 ± 1° and reflectance of ≈1.6% in the wavelength range of 300-2500 nm appears on the micro-nanostructured PE/GNs foam surface. More interestingly, the micro-nanostructured PE/GNs foam surface can maintain a robust superhydrophobic state under dynamic impacting, high temperature and acid-/alkali solutions. These results mean that the micro-nanostructured PE/GNs foam surface possesses self-cleaning, anti-icing and photothermal deicing properties at the same time. Importantly, the foam exhibits an evaporation rate of 1.83 kg m-2 h-1 under 1 Sun illumination and excellent salt rejecting performance when it is used as a self-floating solar evaporator. The proposed method provides an ideal and industrialized approach for the mass production of solar evaporators suitable for practical application environments.

PTFE/EP Reinforced MOF/SiO2 Composite as a Superior Mechanically Robust Superhydrophobic Agent towards Corrosion Protection, Self-Cleaning and Anti-Icing.

Organic resin cross-linking ZIF-67/SiO2 superhydrophobic (SHPB) multilayer coating was successfully fabricated on metal substrate. The perfluoro-octyl-triethoxy silane (POTS) modified ZIF-67 and SiO2 coating was applied on primary coated polytetrafluoroethylene (PTFE) and epoxy resin (EP) via spray coating method. Here, we present that the robust superhydrophobicity can be realized by structuring surfaces at two different length scales, with a nanostructure design to provide water repellence and a microstructure design to provide durability. The as-fabricated multilayer coating displayed superior water-repellence (CA=167.4°), chemical robustness (pH=1-14) and mechanical durability undergoing 120th linear abrasion or 35th rotatory abrasion cycle. By applying different acidic and basic corrosive media and various weathering conditions, it can still maintain superior-hydrophobicity. To get a better insight of interaction between inhibitor molecules and metal surface, density functional theory (DFT) calculations were performed, showing lower energy gap and increased binding energy of ZPS/SiO2 /PTFE/EP (ZPS=ZIF-67+POTS) multilayer coating compared to the ZIF-67/SiO2 /PTFE/EP, thereby supporting the experimental findings. Additionally, such coatings may be useful for applications such as anti-corrosion, self-cleaning, and anti-icing multi-functionalities.

Plasmonic heating of protected silver nanowires for anti-frosting superhydrophobic coating.

Atmospheric frosting and icing pose significant problems for critical and common-use infrastructures. Passive anti-frosting and anti-icing strategies that require no energy input have been actively sought, with no viable and permanent solutions known yet. Bioinspired superhydrophobic (SH) materials have been considered promising path to explore; however, the outcome has been less than compelling because of their low resistance to atmospheric humidity. In most cases, condensing water on an SH surface eventually leads to mechanical locking of ice instead of ice removal. Hybrid strategies involving some form of limited energy input are being increasingly considered, each with its own challenges. Here, we propose the application of plasmonic heating of silver nanowires (AgNWs) for remote frost removal, utilizing an SH hybrid passive-active system. This novel system comprises a durable nanocomposite covered with a hydrophobized mesh of AgNWs, protected against environmental degradation by a tin oxide (SnO2) shell. We demonstrate the frost removal ability at -10 °C and 30% RH, achieved by a combination of plasmonic heating of AgNWs with a non-sticking behavior of submicrometric droplets of molten frost on the SH surface. Heating was realized by illuminating the mesh with low-power blue laser light. Adjustment of the nanowire (NW) and shell dimensions allows the generation of surface plasmon resonance in illuminated NWs at a wavelength overlapping the emission maximum of the light used. In environmental stability tests, the nanostructures exhibited high atmospheric, mechanical, and thermal stability. The narrow-wavelength absorption of the structure in the blue light range and the reflective properties in the infrared range were designed to prevent protected surfaces from overheating in direct sunlight.