Fabricating Super‐Hydrophobic Lotus‐Leaf‐Like Surfaces through Soft‐Lithographic Imprinting

Summary: A soft‐lithographic imprinting approach to fabricate super‐hydrophobic surfaces has been developed in this work. In this process, fresh lotus leaves were used as masters and PDMS stamps were prepared by replica molding against the lotus‐leaf surfaces. By using the stamps and an epoxy‐based azo polymer solution as “ink”, the mimicked lotus‐leaf surfaces made of the polymer were fabricated by pressing the featured faces of the stamps against “inked” substrates and drying under a proper condition after peeling off the stamps. The lotus‐leaf‐like surfaces show super‐hydrophobic characteristics with the water contact angle higher than 150° and contact angle hysteresis less than 3°.

SEM images of lotus‐leaf‐like papillary structures on the imprinted surface.     

Preparation and Characterisation of Super‐Hydrophobic Surfaces

The interest in highly water‐repellent surfaces has grown in recent years due to the desire for self‐cleaning surfaces. A super‐hydrophobic surface is one that achieves a water contact angle of 150° or greater. This article explores the different approaches used to construct super‐hydrophobic surfaces and identifies the key properties of each surface that contribute to its hydrophobicity. The models used to describe surface interaction with water are considered, with attention directed to the methods of contact angle analysis. A summary describing the different routes to hydrophobicity is also given.     

A Photocatalytically Active Lubricant‐Impregnated Surface

Lubricant impregnated surfaces (LISs) exhibit sliding angles below 5°. A LIS is presented that possesses photocatalytic activity as well as improved liquid repellency. In a single‐step reaction, the surface of photocatalytic mesoporous TiO₂ substrate is modified by grafting polydimethylsiloxane (PDMS) brush and the residual non‐bound PDMS serves as lubricant. Since the lubricant and the hydrophobic layer are chemically identical, the grafting PDMS layer is stably swollen by the lubricant PDMS, which inhibits direct contact of liquid drops to the solid substrate. Liquid drops such as water, methanol, and even low‐surface‐tension fluorocarbons, slide on the surface with tilt angles below 1°. The surface exhibits long‐term stable photocatalytic activity while retaining its liquid repellency. This photocatalytic activity allows photocatalytic chemistry, for example, decomposition of organics, on LIS to be carried out.     

Bioinspired construction on aluminum alloy surfaces with stable super‐hydrophobicity and their resulting wettability

The bioinspired leaf‐like super‐hydrophobic surfaces on aluminum alloy were fabricated by means of a facile method using anodic oxidation. The surface morphologies, compositions, and wettability were investigated with SEM, XPS, and contact angle measurement, respectively. The SEM showed hierarchical microstructures and nanostructures, the static contact angle was about 167.7 ± 1.2°, and sliding angle was 5°. The super‐hydrophobic phenomenon of the prepared surface was analyzed with Cassie theory, and it is found that only about 3% of the water surface is contacted with the metal substrate and the remaining 97% is contacted with the air cushion. Copyright © 2011 John Wiley & Sons, Ltd.     

Preparation of Cu-Coated Stainless Steel Surfaces for Superhydrophobic Investigation

Cu-coated stainless steel surfaces containing micro- and nanoscale binary structures with different surface roughness were successfully fabricated by means of a facile one-step electroless plating technology. The resulting surfaces were modified by the low free energy material HFTHTMS (HFTHTMS = (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane). The experimental results of wettability exhibit that such unmodified surfaces have a strong adhesive force to water droplets, and their contact angles increase with increasing surface roughness, whereas the modified surfaces by HFTHTMS show the superhydrophobic characteristic with contact angles higher than 150° and sliding angles lower than 5°.     

Super‐Hydrophobic PDMS Surface with Ultra‐Low Adhesive Force

Summary: Rough polydimethylsiloxane (PDMS) surface containing micro‐, submicro‐ and nano‐composite structures was fabricated using a facile one‐step laser etching method. Such surface shows a super‐hydrophobic character with contact angle higher than 160° and sliding angle lower than 5°, i.e. self‐cleaning effect like lotus leaf. The wettabilities of the rough PDMS surfaces can be tunable by simply controlling the size of etched microstructures. The adhesive force between etched PDMS surface and water droplet is evaluated, and the structure effect is deduced by comparing it with those own a single nano‐ or micro‐scale structures. This super‐hydrophobic PDMS surface can be widely applied to many areas such as liquid transportation without loss, and micro‐pump (creating pushing‐force) needless micro‐fluidic devices.

Etched PDMS surface containing micro‐, submicro‐, and nano‐composite structures shows a self‐cleaning effect with water CA as high as 162° and SA lower than 5°.     

Effect of oxidized silicon (SiOx) surfaces functionalization on real‐time PCR by Lab‐on‐a‐chip microdevices

There is a great need to improve the biocompatibility of silicon‐based lab‐on‐chip substrate materials for reliable quantitative analysis of biological solutions. These advanced microdevice surfaces need not only be biocompatible but also have surfaces of defined wettability characteristics. The inhibition of biomolecular activity due to microdevice surface interaction is common and can result in inaccurate results or decreased reaction yields. In this work we investigate different techniques for the chemical functionalization of oxidized silicon (SiO_x) surfaces in order to: (i) obtain defined hydrophobic/hydrophilic surfaces; and (ii) increase the efficiency of performing Real‐Time Polymerase Chain Reaction (PCR) on a silicon‐based lab‐on‐chip. Silicon oxide surfaces are functionalized by grafting alkylic chain silanes and poly(ethylene glycol) (PEG) chains to the surfaces, rendering them hydrophobic or hydrophilic. Functionalized surfaces are characterized through contact angle and atomic force microscopy (AFM) measurements, showing stable hydrophobic surfaces with contact angles of 69–78° and layer thicknesses of 11–15 Å and hydrophilic surfaces displaying contact angles of 5–6° and thicknesses of 22–52 Å. PCR experiments carried out directly on bare silicon oxide lab‐on‐chip surfaces show low yields of DNA amplification. Hydrophobic surfaces decrease the inhibition of PCR. Hydrophilic surfaces are a major improvement on the bare silicon oxide exhibiting the same maximum reaction yield as obtained with a standard thermocycler. We have found that the best results are associated with PEG modified surfaces, which prove very suitable for the fabrication of reliable PCR silicon lab‐on‐chips. Copyright © 2011 John Wiley & Sons, Ltd.     

Preparation of Cu-Coated Stainless Steel Surfaces for Surperhydrophobic Investigation

Cu-coated stainless steel surfaces containing micro- and nanoscale binary structures having different surface roughness were successfully fabricated by means of a facile one-step electroless plating technology, and the resulting surfaces were modified by the low free energy material HFTHTMS (HFTHTMS = (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane). The experimental results of wettability exhibit that such unmodified surfaces have a strong adhesive force to water droplets, and their contact angles increase with increasing surface roughness, whereas the modified surfaces by HFTHTMS show the superhydrophobic characteristic with contact angles higher than 150° and sliding angles lower than 5°.     

Covalently Attached Liquids: Instant Omniphobic Surfaces with Unprecedented Repellency

Recent strategies to prepare “omniphobic” surfaces have demonstrated that minimizing contact angle hysteresis (CAH) is the key criterion for effectiveness. CAH is affected by chemistry and topography defects at the molecular and higher levels, thus most surfaces exhibit significant CAH. Preparative methods for stable coatings on smooth substrates with negligible CAH (<2°) for a broad range of liquids have not been reported. In this work, we describe a simple and rapid procedure to prepare omniphobic surfaces that are stable under pressure and durable at elevated temperatures. Consistent with theory, they exhibit sliding angles that decrease with liquid surface tension. Slippery omniphobic covalently attached liquid (SOCAL) surfaces are obtained through acid‐catalyzed graft polycondensation of dimethyldimethoxysilane. The smooth, stable, and temperature‐resistant coatings show extremely low CAH (≤1°) and low sliding angles for liquids that span surface tensions from 78.2 to 18.4 mN m^?1.     

Superhydrophobic polymer‐particle composite films produced using various particle sizes

Hydrophilic alumina (Al₂O₃) nanoparticles (25, 35, and 150 nm) are dispersed in different concentrations in solutions of a commercial hydrophobic poly(alkyl siloxane) (Silres BS‐290), and the suspensions are sprayed on glass surfaces. Static contact angles (θ_S), measured on surfaces of siloxane‐nanoparticle composite films that were prepared from dilute dispersions, increase rapidly with particle concentration. Composite films prepared from concentrated dispersions exhibit a maximum, constant θ_S (at saturation θ_S is 160°), which is not affected by the size of the particles. These films exhibit also very small contact angle hysteresis (5°), which is also independent of the particle size. Consequently, the same superhydrophobic character can be induced in siloxane films using nanoparticles, which can range from a few up to several tenths of nanometers. However, the particle size and more precisely the particle specific surface area affects dramatically the minimum critical particle concentration, which must be used in the dispersions to induce superhydrophobicity on the surface of the composite films, that is, to achieve θ_S = 150°. It is shown that critical particle concentration decreases exponentially with specific surface area. This result can be important for manufacturers of superhydrophobic surfaces who are interested in having a good control on the wettability of the composite films. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis and characterization of highly fluorinated poly(phthalazinone ether)s based on AB‐type monomers

Four different fluorinated methyl‐ and phenyl‐substituted 4‐(4‐hydroxyphenyl)‐2‐(pentafluorophenyl)‐phthalazin‐1(2H)‐ones, AB‐type phthalazinone monomers, have been successfully synthesized by nucleophilic addition–elimination reactions of methyl‐ and phenyl‐substituted 2‐((4‐hydroxy)benzoyl)benzoic acid with 1‐(pentafluorophenyl)hydrazine. Under mild reaction conditions, the AB‐type monomers underwent self‐condensation polymerization reactions successfully and gave fluorinated poly(phthalazinone ether)s with high molecular weights. Detailed structural characterization of the AB‐type monomers and fluorinated polymers was determined by ¹H NMR, ¹⁹F NMR, FTIR, and GPC. The solubility, thermal properties, mechanical properties, water contact angles, and optical absorption of the polymers were evaluated. The polymers had high T_gs varying from 337 to 349 °C and decomposition temperatures (T_{d, 25} wt %) above 409 °C. Tough, flexible films were cast from THF and chloroform solutions. The films showed excellent tensile strengths ranging from 70 to 85 MPa with good hydrophobicities with water contact angles higher than 95.5 °C. The polymers had absorption edges below 340 nm and very low absorbance per cm at higher wavelengths 500–2500 nm. These results indicate that the polymers are promising as high performance materials, for example, membranes and hydrophobic materials. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1761–1770     

聚苯硫醚超疏水复合涂层的制备与性能

利用工业原料聚苯硫醚微粉和疏水性二氧化硅纳米粉末,采用喷涂法在瓷砖表面制备了疏水复合涂层.研究了热处理温度、组分配比对涂层表面形貌、粗糙度和接触角的影响,发现随着热处理温度升高,涂层表面粗糙度增大,随着疏水性二氧化硅含量的增加,由于表面聚集的疏水性二氧化硅增多,涂层疏水性增强,在热处理温度为280℃、疏水性二氧化硅与聚苯硫醚质量比为1∶1时,可获得超疏水涂层,涂层的接触角大于150°,滚落角小于4°,pH值为1～14的水溶液在其表面都具有很高的接触角.超疏水涂层具有良好的自清洁效果,并且经落沙法实验测定,超疏水涂层耐刮伤性能良好.     

Thermo-responsive superhydrophobic paper using nanostructured cellulose stearoyl ester

Hydrophilic paper was rendered with hydrophobic and superhydrophobic property after the treatment with solutions and nanoparticles of cellulose stearoyl ester (CSE), respectively. Cellulose stearoyl ester with a degree of substitution of 2.99 was synthesized from cellulose using stearoyl chloride. By dip-coating paper in CSE solution of at least 3 mg/ml in toluene, paper became hydrophobic with stable water contact angles of more than 120°. After further spray-coating using CSE nanoparticles that were prepared from CSE solution via nanoprecipitation, paper surface became superhydrophobic with water contact angles of larger than 150°. These superhydrophobic surfaces also exhibited self-cleaning character. Furthermore, the superhydrophobic paper surfaces showed a temperature-responsive character and could be turned hydrophobic after a heat-treatment at 70 °C for 5 min.     

Synthesis and properties of oxetane‐based polysiloxanes used for cationic UV curing coatings

The polysiloxanes end‐capped with oxetane group (PSiO‐H and PSiO‐L) were synthesized via hydrosilylation reaction based on α,ω‐dihydrogen‐terminated polydimethylsiloxanes with a higher (0.23%, PDSi‐H) and lower (0.12%, PDSi‐L) hydrogen amount. The molecular structures were characterized by FT‐IR and ¹H NMR spectroscopy. The polysiloxanes were added into a commercial oxetane‐based resin, 3,3′‐(oxydi(methylene)) bis(3‐ethyloxetane) (DOX), as an additive to prepare a series of cationic UV curable formulations. The photo‐DSC results showed that the maximum photopolymerization rate decreased while the oxetane conversion increased with the polysiloxane content increasing. The surface hydrophobic property of cured films was improved having the water contact angles of 97° and 99° compared with 82° of the cured DOX film with only 1 wt% PSiOs, respectively. The dynamic mechanical thermal analysis results showed that both the storage modulus on the rubbery plateau region and the glass transition temperature decreased with increasing PSiO‐H loading. Moreover, the decrease became more obvious as PSiO‐L was added instead of PSiO‐H due to its lower concentration of oxetane group. The thermal stability of cured films was enhanced by the addition of PSiOs from the thermogravimetric analysis. And the DOX/PSiO‐H film possessed higher thermal degradation temperatures than DOX/PSiO‐L film. Copyright © 2011 John Wiley & Sons, Ltd.     

Fabrication of Biomimetic Super‐Amphiphobic Surfaces Through Plasma Modification of Benzoxazine Films

Summary: In this study, a method for producing super‐amphiphobic surfaces through plasma modification of benzoxazine films is presented. Microroughening and fluorination of the benzoxazine films occurs during the plasma treatment process and a rugged surface with a micro/nano binary structure is formed. The combined effect of low surface energy and substrate roughness results in high advancing contact angles (157° for water, 152° for diiodomethane) and low contact angle hysteresis.

SEM image of a cross‐linked polybenzoxazine film treated with Ar plasma (7 min) heated to 200 °C (1 h) and treated with CF₄ plasma for 30 s.     

A novel superhydrophobic surface based on low‐density polyethylene/ethylene‐propylene‐diene terpolymer thermoplastic vulcanizate

A novel superhydrophobic surface based on low‐density polyethylene (LDPE)/ethylene‐propylene‐diene terpolymer (EPDM) thermoplastic vulcanizate (TPV) was successfully fabricated where the etched aluminum foil was used as template. The etched aluminum template, consisted of countless micropores and step‐like textures, was obtained by metallographic sandpaper sanding and the subsequent acid etching. The surface morphology and the hydrophobic properties of the molded TPV surface were researched by using field emission scanning electron microscope and contact angle meter, respectively. From the microstructure observation of the superhydrophobic LDPE/EPDM TPV surface, the step‐like textures obtained via molding with etched aluminum foil template and a large number of fiber‐like structures resulted from the plastic deformation of LDPE matrix could be found obviously. The obtained TPV surface exhibited remarkable superhydrophobicity, with a contact angle of 152.0° ± 0.7° and a sliding angle of 3.1° ± 0.8°.     

Stimuli‐responsive antifouling polyisobutylene‐based biomaterials via modular surface functionalization

This article demonstrates a new, modular approach to surface functionalization that harnesses chain entanglement. A layer of functionalized polyisobutylene, (PIB)‐ω, where ω = ‐OH, ‐thymine (T), ‐hexaethylene glycol (HEG), poly(ethylene glycol) (‐PEG‐OH), methoxy‐functionalized poly(ethylene glycol) (‐PEG‐OCH₃), and ‐tetraethylene glycol‐α‐lipoate (TEG‐αL) was adhered to PIB‐based thermoplastic elastomer (TPE) surfaces. X‐ray photoelectron spectroscopy (XPS) at angles ranging from 20° to 75° showed decreasing polar group concentration with increasing penetration depth, confirming segregation of polar groups toward the surface. Water contact angle (WCA) of the PIB‐based TPE dropped from 95° to 79°?83° upon coating, and soaking in water for 24 h further decreased the WCA. Dynamic WCA measurements showed 40–30° receding angles, showing that stimulus from an aqueous environment elicits enrichment of polar groups on the surface. Fibrinogen (Fg) adsorption on the various surfaces was quantified using surface plasmon resonance (SPR). Static and dynamic WCA did not vary significantly among TPE + PIB‐ω surfaces, but there were dramatic differences in Fg adsorption: 256 ng/cm² was measured on the native TPE, which dropped to 40 and 22 ng/cm² on PIB‐PEG‐OCH₃ and PIB‐PEG‐OH‐coated surfaces. PIB‐TEG‐αL‐coated surfaces presented the lowest Fg adsorption with 14 ng/cm². © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 1742–1749     

Nanofold‐decorated surfaces from the electrodeposition of di‐alkyl‐cyclopentadithiophenes

This work describes the synthesis and subsequent electrodeposition of 4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene (cyclopentadithiophene) monomers di‐substituted with alkyl chains. Each monomer was electropolymerized in solution to observe their capacity at creating well‐structured, rough surfaces. The length of the alkyl chain substituent has a significant influence on the overall surface morphology and wetting behavior after electropolymerization. In the case of nonsubstituted cyclopentadithiophene monomers or those with short alkyl (methyl and ethyl) substituents, the polymerization proceeds readily, forming rough surfaces that follow the Wenzel regime of wetting. In these cases, the surfaces were decorated with globular agglomerates and woven mat features. The measured surface roughness decreases with alkyl chain length as steric hindrance caused by the alkyl substituents limits electropolymerization. As the alkyl chain substituent increases to propyl chain length and beyond, the increase in steric hindrance is so significant that the surface morphology formed during electrodeposition is primarily due to π‐stacking interactions between very short oligomers formed in solution. With propyl and butyl substituents, nanofold morphology is observed, leading to surfaces with much higher contact angles with water (~132°) that follow the Cassie‐Baxter regime of wetting. This type of surface morphology has only been demonstrated one other time and with the use of fluorinated constituents. This work exposes a mild, fluorine‐free synthetic route to creating nanofold‐decorated surfaces.     

Multiple levels hydrophobic modification of polymeric substrates by UV‐grafting polymerization with TFEMA as monomer

The hydrophobic solid surface modification with fluorine‐containing monomers has received tremendous attention because of its unique structure and excellent property. However, these hydrophobic films normally suffer from two major problems: one is weak interface interaction between fluoropolymers and substrates, and the other is the high cost of fluorine‐containing monomers. Herein, with the aim of feasible industrial application, a facile in situ UV photo‐grafting method is reported, which could ensure the formation of chemical bonds between fluoropolymer‐grafted layer and substrate with a low cost commercial 2,2,2‐trifluoroethyl methacrylate (TFEMA) as monomer. With low‐density polyethylene (LDPE) film as a model substrate, four kinds of poly‐TFEMA‐grafted layer are fabricated on LDPE films with different surface morphologies: polymer brush, polymer network, crosslinked nanoparticles, and a micro‐ and nanoscale hierarchical structure. The experimental results showed that the water contact angles (CAs) of the LDPE films grafted with polymer brush, polymer network, and crosslinked nanoparticles were (103 ± 2)°, (95 ± 2)°, and (122 ± 2)°, respectively, which were much higher than that of LDPE film. The introduction of micro‐ and nanoscale hierarchical structures can dramatically improve the surface roughness, which will further enhance the film hydrophobicity, and the water CA can reach as high as (140 ± 1)°. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1059–1067     

Tailoring of multifunctional cellulose fibres with “lotus effect” and flame retardant properties

This research aimed to create multifunctional cellulose fibres with water- and oil-repellent, self-cleaning, and flame retardant properties. A sol mixture of fluoroalkyl-functional siloxane, organophosphonate and methylol melamine resin was applied to cotton fabric by the pad-dry-cure method. Successful coating was verified by atomic force microscopy and Fourier transform infrared spectroscopy. The functional properties of the coated fibres were investigated using the static contact angles of water and n-hexadecane, the water sliding angles, the vertical test of flammability, the limiting oxygen index, and simultaneous thermal analysis. The results reveal that a homogeneous composite inorganic–organic polymer film formed on the cotton fabric surface exhibited the following properties: static contact angle of water of 150° and of n-hexadecane of 128°, water sliding angle of 10°, limiting oxygen index of 34 %, and high thermal stability. These results demonstrate the synergistic activity of the compounds in the coating, which resulted in the creation of a “lotus effect” on the fabric surface as well as excellent flame retardancy and thermal stability.