Superhydrophobic Surface-Assisted Preparation of Microspheres and Supraparticles and Their Applications

Superhydrophobic surface(SHS) has been well developed, as SHS renders the property of minimizing the water/solid contact interface. Water droplets deposited onto SHS with contact angles exceeding 150°, allow them to retain spherical shapes, and the low adhesion of SHS facilitates easy droplet collection when tilting the substrate. These characteristics make SHS suitable for a wide range of applications. One particularly promising application is the fabrication of microsphere and supraparticle materials. SHS offers a distinct advantage as a universal platform capable of providing customized services for a variety of microspheres and supraparticles. In this review, an overview of the strategies for fabricating microspheres and supraparticles with the aid of SHS, including cross-linking process, polymer melting,and droplet template evaporation methods, is first presented. Then, the applications of microspheres and supraparticles formed onto SHS are discussed in detail, for example, fabricating photonic devices with controllable structures and tunable structural colors, acting as catalysts with emerging or synergetic properties, being integrated into the biomedical field to construct the devices with different medicinal purposes, being utilized for inducing protein crystallization and detecting trace amounts of analytes. Finally,the perspective on future developments involved with this research field is given, along with some obstacles and opportunities.

Robust,Flexible,and Superhydrophobic Fabrics for High-Efficiency and Ultrawide-Band Microwave Absorption

Microwave absorption(MA)materials are essential for protecting against harmful electromagnetic radiation.In this study,highly efficient and ultrawide-band microwave-absorbing fabrics with superhydrophobic surface features were developed using a facile dip-coating method involving in situ graphene oxide(GO)reduction,deposition of TiO_(2) nanoparticles,and subsequent coating of a mixture of polydimethylsiloxane(PDMS)and octadecylamine(ODA)on polyester fabrics.Owing to the presence of hierarchically structured surfaces and low-surface-energy materials,the resultant reduced GO(rGO)/TiO_(2)-ODA/PDMS-coated fabrics demonstrate superhydrophobicity with a water contact angle of 159°and sliding angle of 5°.Under the synergistic effects of conduction loss,interface polarization loss,and surface roughness topography,the optimized fabrics show excellent microwave absorbing performances with a minimum reflection loss(RL_(min))of47.4 dB and a maximum effective absorption bandwidth(EAB_(max))of 7.7 GHz at a small rGO loading of 6.9 wt%.In addition,the rGO/TiO_(2)-ODA/PDMS coating was robust,and the coated fabrics could withstand repeated washing,soiling,long-term ultraviolet irradiation,and chemical attacks without losing their superhydrophobicity and MA properties.Moreover,the coating imparts self-healing properties to the fabrics.This study provides a promising and effective route for the development of robust and flexible materials with microwave-absorbing properties.

Superhydrophobic Co/Fe sulfide nanoparticles and single-atoms doped carbon nanosheets composite air cathode for high-performance zinc-air batteries

Development of a high-performance bifunctional catalyst is essential for the actual implementation of zinc-air batteries in practical applications.Herein,a bifunctional cathode of Co_(3)S_(4)/FeS heterogeneous nanoparticles embedded in Co/Fe single-atom-loaded nitrogen-doped carbon nanosheets is designed.Cobalt-iron sulfides and single atomic sites with Co-N_(4)/Fe-N_(4)configurations are confirmed to coexist on the carbon matrix by EXAFS spectroscopy.3D self-supported super-hydrophobic multiphase composite cathode provides abundant active sites and facilitates gas–liquid-solid three-phase interface reactions,resulting in excellent electrocatalytic activity and batteries performance,i.e.,an OER overpotential(η_(10))of 260 mV,a half-wave potential(E_(1/2))of 0.872 V for ORR,aΔE of 0.618 V,and a discharge power density of 170 mW cm^(−2),a specific capacity of 816.3 mAh g^(−1).DFT analysis shows multiphase coupling of sulfide heterojunction through single-atomic metal doped carbon nanosheets reduces offset on center of electronic density of states before and after oxygen adsorption,and spin density of adsorbed oxygen with same spin orientation,leading to weakened charge/spin interactions between adsorbed oxygen and substrate,and a lowered oxygen adsorption energy to accelerate OER/ORR.

Robustα-Fe_(2)O_(3)/Epoxy Resin Superhydrophobic Coatings for Anti-icing Property

α-Fe_(2)O_(3)/epoxy resin composite superhydrophobic coating was prepared withα-Fe_(2)O_(3) nanoparticles and epoxy resin by spin coating method.The coating without epoxy resin has higher contact angle(CA)and lower ice adhesion strength(IAS),but the mechanical properties are poor.Theα-Fe_(2)O_(3)/epoxy resin composite superhydrophobic coating exhibits good mechanical durability.In addition,compared with the bare aluminum substrate,the Ecorr of the composite coating is positive and the Jcorr is lower.The inhibition efficiency of the composite coating is as high as 99.98%in 3.5 wt%NaCl solution.The difference in the microstructure caused by the two preparation methods leads to the changes in mechanical properties and corrosion resistance of composite superhydrophobic coating.

Superhydrophobic melamine sponge prepared by radiation-induced grafting technology for efficient oil-water separation

This paper presents a superhydrophobic melamine(ME)sponge(ME-g-PLMA)prepared via high-energy radiation-induced in situ covalent grafting of long-alkyl-chain dodecyl methacrylate(LMA)onto an ME sponge for efficient oil–water separation.The obtained ME-g-PLMA sponge had an excellent pore structure with superhydrophobic(water contact angle of 154°)and superoleophilic properties.It can absorb various types of oils up to 66–168 times its mass.The ME-g-PLMA sponge can continuously separate oil slicks in water by connecting a pump or separating oil underwater with a gravity-driven device.In addition,it maintained its highly hydrophobic properties even after long-term immersion in different corrosive solutions and repeated oil adsorption.The modified ME-g-PLMA sponge exhibited excellent separation properties and potential for oil spill cleanup.

Fabrication and anti-corrosion performance of superhydrophobic silane film on sintered NdFeB

An eco-friendly superhydrophobic protective film(DTMS/TEOS silane film)was fabricated on sintered NdFeB substrate through the utilization of electrochemically assisted deposition technology.The structure,properties,and film-forming mechanism of dodecyltrime-thoxysilane(DTMS)/tetraethoxysilane(TEOS)silane films were comprehensively analyzed using Fourier transform infrared spectroscopy(FT-IR),scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS),potentiodynamic polarization curves and electrochemical impedance spectroscopy(EIS).Based on the test results,it can be determined that this film has a superhydrophobic property with a hydrophobicity angle of 152°.This special property can be attributed to the long alkyl chains in the DTMS molecule,the rough morphology,and the low surface energy of the DTMS/TEOS silane film.The surface of sintered NdFeB is coated with a layered three-dimensional network silane film that forms through the condensation of silanol substances.This film provides excellent corrosion resistance to the sintered NdFeB substrate,reducing its corrosion current density to 2.02×10~(-6)A/cm~2.Moreover,the impact of film on the magnetic characteristics of sintered NdFeB was assessed and found to be minimal.

Characterization of Flame Retardancy and Oil-Water Separation Capacity of Superhydrophobic Silylated Melamine Sponges

A silylated melamine sponge(SMS)was prepared by two simple steps,namely,immersion and dehydration of a melamine sponge coated with methyltrichlorosilane.The silylated structure of SMS was characterized by FT-IR(Fourier-transform infrared)spectroscopy,SEM(Scanning electron microscopy)and in terms of water contact angles.Its oil-water absorption and separation capacities were measured by FT-IR and UV-visible spectrophoto-metry.The experimental results have shown that oligomeric silanol covalently bonds by Si-N onto the surface of melamine sponge skeletons.SMS has shown superhydrophobicity with a water contact angle exceeding 150°±1°,a better separation efficiency with regard to diesel oil(by 99.31%(wt/wt%)in oil-water mixture and even up to 99.99%(wt/wt%)for diesel oil in its saturated aqueous solution.Moreover,SMS inherited the intrinsicflame retardancy of the melamine sponge.In general,SMS has shown superhydrophobicity,high porosity,excellent selectivity,remarkable recyclability,and better absorption capacity for various oils and organic solvents,and a high separation efficiency for oil in saturated aqueous solutions.

Construction of Renewable Superhydrophobic Surfaces via Thermally Induced Phase Separation and Mechanical Peeling

We report a simple preparation method of a renewable superhydrophobic surface by thermally induced phase separation （TIPS） and mechanical peeling. Porous polyvinylidene fluoride （PVDF） membranes with hierarchical structures were prepared by a TIPS process under different cooling conditions, which were confirmed by scanning electron microscopy and mercury intrusion porosimetry. After peeling off the top layer, rough structures with hundreds of nanometers to several microns were obtained. A digital microscopy determines that the surface roughness of peeled PVDF membranes is much higher than that of the original PVDF membrane, which is important to obtain the superhydrophobicity. Water contact angle and sliding angle measurements demonstrate that the peeled membrane surfaces display super- hydrophobicity with a high contact angle （152°） and a low sliding angle （7.2°）. Moreover, the superhydrophobicity can be easily recovered for many times by a simple mechanical peeling, identical to the original superhydrophobicity. This simple preparation method is low cost, and suitable for large-scale industrialization, which may offer more opportunities for practical applications.

Recent Progress in Superhydrophobic Coatings Using Molecular Dynamics Simulations and Experimental Techniques

Superhydrophobic(SH)coatings are intended to resist a surface from cor­rosion and thereby increases the product life duration.It is also a promising solution to save cleaning costs and time by providing self-clean nature to the surface.This review article provides the most recent updates in design­ing SH surfaces and their characterizations adopted both in experimental and computational techniques.To gain a comprehensive perspective,the SH surfaces present in nature those are inspiring human beings to mimic such surfaces are introduced at the beginning of this article.Subsequently,different fabrication techniques undertaken recently to design artificial SH surfaces are briefly discussed.Recent progress in computations employed in the development of SH surfaces is then discussed.Next,the limitations in SH surfaces are addressed.Finally,perceptiveness of different strategies and their limitations are presented in the concluding remarks and outlook.Overall,this mini review article brings together and highlights the significant advancements in fabrication of superhydrophobic surfaces which may surely help the early-stage researchers/scientists to plan their work accordingly.

Superhydrophobic surface of Mg alloys:A review

In the present review,the formation of superhydrophobic(SHP)structures on the surface of Mg alloys was investigated.Different methods including hydrothermal technique,chemical and electrochemical deposition,conversion and polymer coating,and etching routes were discussed.The superhydrophobicity could form on the surface of Mg alloys by the application of different chemical,electrochemical,and physical methods followed by the immersion of these alloys in the solution containing modifying agents including fatty acids or long-chain molecules.The formed morphology,composition,and contact angle were reported and the effect of synthesis route on these characteristics was reviewed.

Femtosecond laser micro/nano fabrication for bioinspired superhydrophobic or underwater superoleophobic surfaces

The preparation of superhydrophobic or underwater superoleophobic interface materials has become a research hotspot because of their wide application in self-cleaning, drag reduction, oil-water separation, anti-oil pollution and so on. The unique wettability of organisms gives inspiration to design and create new interface materials. This review focuses on the recent research progress of femtosecond laser micro/nano fabrication for bioinspired superhydrophobic or underwater superoleophobic surfaces. This review starts with a presentation of the related background including the advantages of femtosecond laser and wettability theoretical basis. Then, organisms with unique wettability in nature, the preparation of superhydrophobic or underwater superoleophobic surfaces by femtosecond lasers on different materials, and their related important applications are introduced. Finally, the current challenges and future prospects with regard to this field are provided.

Superhydrophobicity of Bionic Alumina Surfaces Fabricated by Hard Anodizing

Bionic alumina samples were fabricated on convex dome type aluminum alloy substrate using hard anodizing technique. The convex domes on the bionic sample were fabricated by compression molding under a compressive stress of 92.5 MPa. The water contact angles of the as-anodized bionic samples were measured using a contact angle meter （JC2000A） with the 3μL water drop at room temperature. The measurement of the wetting property showed that the water contact angle of the unmodi- fied as-anodized bionic alumina samples increases from 90° to 137° with the anodizing time. The increase in water contract angle with anodizing time arises from the gradual formation of hierarchical structure or composite structure. The structure is composed of the micro-scaled alumina columns and pores. The height of columns and the depth of pores depend on the ano- dizing time. The water contact angle increases significantly from 96° to 152° when the samples were modified with self-assembled monolayer of octadecanethiol （ODT）, showing a change in the wettability from hydrophobicity to su- per-hydrophobicity. This improvement in the wetting property chemical modification. is attributed to the decrease in the surface energy caused by the

Enhanced corrosion resistance of micro-arc oxidation coated magnesium alloy by superhydrophobic Mg-Al layered double hydroxide coating

To further enhance the corrosion resistance of the porous micro-arc oxidation(MAO) ceramic layers on AZ31 magnesium alloy, superhydrophobic Mg-Al layered double hydroxide(LDH) coating was fabricated on MAO-coated AZ31 alloy by using in-situ growth method followed by surface modification with stearic acid. The characteristics of different coatings were investigated by XRD, SEM and EDS. The effect of the hydrothermal treatment time on the formation of the LDH coatings was studied. The results demonstrated that the micro-pores and cracks of MAO coating were gradually sealed via in-situ growing LDH with prolonging hydrothermal treating time. Electrochemical measurement displayed that the lowest corrosion current density, the most positive corrosion potential and the highest impedance modulus were observed for superhydrophobic LDH/MAO coating compared with those of MAO coating and LDH/MAO coating. Immersion experiment proved that the superhydrophobic LDH/MAO coating with the active anti-corrosion capability significantly enhanced the long-term corrosion protection for MAO coated alloy.

Fabrication of corrosion-resistant superhydrophobic coating on magnesium alloy by one-step electrodeposition method

A one-step electrodeposition method was used to construct a superhydrophobic coating on the surface of magnesium alloy.Using magne-sium nitrate and ethanol solution of stearic acid as electrolyte,four groups of electrolytes with different ratios of stearic acid and magnesium nitrate were designed to explore the influence of electrolyte to the process.The contact angles of the four coating samples were 136.4±5.8°,152.7±2.8°,156.2±4.9°and 155.1±4.4°The addition of magnesium nitrate in the solution increased the hydrogen evolution reaction in the electrodeposition process,which was not conducive to electrodeposition process.During the deposition process,the sample prepared in a molar ratio of stearic acid to magnesium nitrate of 10:1 had the best corrosion resistance,and its corrosion circuit density was 3.74×10^(−8)A/cm^(2),far lower than the corrosion current density of the magnesium alloy substrate.

Modeling Superhydrophobic Contact Angles and Wetting Transition

It is well known that surface roughness has a very important effect on superhydrophobicity.The Wenzel and Cassie-Baxter models,which correspond to the homogeneous and heterogeneous wetting respectively,are currently primary instructions for designing superhydrophobic surfaces.However,the particular drop shape that a drop exhibits might depend on how it is formed. A water drop can occupy multiple equilibrium states,which relate to different local minimal energy.In some cases,both equilibrium states can even co-exist on a same substrate.Thus the apparent contact angles may vary and have different values.We discuss how the Wenzel and Cassie-Baxter equations determine the homogeneous and heterogeneous wetting theoretically. Contact angle analysis on hierarchical surface structure and contact angle hysteresis has been put specific attention.In particular, we study the energy barrier of transition from Cassie-Baxter state to Wenzel state,based on existing achievement by previous researchers,to determine the possibility of the transition and how it can be interpreted.It has been demonstrated that surface roughness and geometry will influence the energy required for a drop to get into equilibrium,no matter it is homogeneous or heterogeneous wetting.

Corrosion resistance and anti-soiling performance of micro-arc oxidation/graphene oxide/stearic acid superhydrophobic composite coating on magnesium alloys

Magnesium(Mg)alloys,the lightest metal construction material used in industry,play a vital role in future development.However,the poor corrosion resistance of Mg alloys in corrosion environments largely limits their potential wide applications.Therefore,a micro-arc oxidation/graphene oxide/stearic acid(MAO/GO/SA)superhydrophobic composite coating with superior corrosion resistance was fabricated on a Mg alloy AZ91D through micro-arc oxidation(MAO)technology,electrodeposition technique,and self-assembly technology.The composition and microstructure of the coating were characterized by scanning electron microscopy,X-ray diffraction,energy dispersive spectroscopy,and Raman spectroscopy.The effective protection of the MAO/GO/SA composite coating applied to a substrate was evaluated using potentiodynamic polarization,electrochemical impedance spectroscopy tests,and salt spray tests.The results showed that the MAO/GO/SA composite coating with a petal spherical structure had the best superhydrophobicity,and it attained a contact angle of 159.53°±2°.The MAO/GO/SA composite coating exhibited high resistance to corrosion,according to electrochemical and salt spray tests.

Preparation and corrosion resistance of superhydrophobic coatings on AZ31 magnesium alloy

In order to improve the corrosion resistance of the Mg alloys, the superhydrophobic coatings on AZ31 Mg alloy wereprepared by a two-step process of micro-arc oxidation treatment and superhydrophobic treatment in stearic acid ethanol solution. Theeffects of voltages, frequencies and treatment time on the contact angle of the superhydrophobic treated sample were investigated.The results showed that with increasing the voltage, frequency and treatment time, all of the contact angles of the superhydrophobictreated sample increased first, and then decreased, reaching the maximum values at 350 V, 1000 Hz and 5 min, respectively. Theoptimal superhydrophobic coating was mainly composed of MgO and Mg2SiO4 phases, with the pore diameter of ～900 nm, thethickness of ～6.86 μm and the contact angle of 156.96°. The corrosion current density of the superhydrophobic AZ31 sampledecreased by three orders of magnitude, and the amount of hydrogen evolution decreased by 94.77% compared with that of the AZ31substrate sample.

Preparation and photocatalytic property of Fe_(2)O_(3)/ZnO composites with superhydrophobicity

A facile approach was developed to construct Fe_(2)O_(3)-modified ZnO micro/nanostructures with excellent superhydrophobicity and photocatalytic activities.The effects of stearic acid(SA)and Fe_(2)O_(3) on the morphological characteristics,water contact angle(WCA),and photocatalytic degradation were investigated.Superhydrophobicity results showed that WCA increased from 144°±2°to 154°±2°when the weight of SA increased from 5 to 20 mg because of the formation of a hierarchical or rough structure.Furthermore,Fe_(2)O_(3)-modified ZnO micro/nanostructure surfaces before and after SA treatment(20 mg)were chosen to evaluate the photodegradation of methylene blue(MB)dye under the support of visible light.MB degraded after 80 min of irradiation,and its photodegradation efficiencies were 91.5%at the superhydrophobic state and 92%at the hydrophilic state.This improvement in photocatalytic activity at both states might be attributed to an increase in surface area and improvement in charge carrier separation.

Recent progress in superhydrophobic and superamphiphobic coatings for magnesium and its alloys

Superhydrophobic coatings are projected as a practical approach to tackle the weak aqueous corrosion resistance of Mg/Mg alloys.The present review provides the most recent updates in this area.The various low surface energy treatments reported are presented first,followed by the methods employed for developing hierarchical surface micro/nanostructuring.Reported works in different application areas,including anti-corrosion,biomedical and anti-icing are systematically discussed.Concise descriptions of self-healing characteristics and long-term durability of the superhydrophobic surfaces provided.Reports on superamphiphobic surfaces also deliberated.

Underwater gas self-transportation along femtosecond laser-written open superhydrophobic surface microchannels(<100μm)for bubble/gas manipulation

Underwater transportation of bubbles and gases has essential applications in manipulating and using gas,but achieving this function at the microscopic level remains a significant challenge.Here,we report a strategy to self-transport gas in water along a laser-induced open superhydrophobic microchannel with a width less than 100μm.The femtosecond laser can directly write superhydrophobic and underwater superaerophilic microgrooves on the polytetrafluoroethylene(PTFE)surfaces.In water,the single laser-induced microgroove and water medium generate a hollow microchannel.When the microchannel connects two superhydrophobic regions in water,the gas spontaneously travels from the small region to the large area along this hollow microchannel.Gas self-transportation can be extended to laser-drilled microholes through a thin PTFE sheet,which can even achieve anti-buoyancy unidirectional penetration.The gas can overcome the bubble’s buoyance and spontaneously travel downward.The Laplace pressure difference drives the processes of spontaneous gas transportation and unidirectional bubble passage.We believe the property of gas self-transportation in the femtosecond laser-structured open superhydrophobic and underwater superaerophilic microgrooves/microholes has significant potential applications related to manipulating underwater gas.