High stability superhydrophobic glass-ceramic surface with micro–nano hierarchical structure

Inspired by the surface structure of lotus leaves, micro–nano hierarchical surface structures have been widely used for designing superhydrophobic surfaces. However, the conventionally designed superhydrophobic surface structures are fragile. In this study, a layer of micron-sized mullite whiskers was grown using molten salt on the surface of BaAl₂Si₂O₈ (BAS) glass ceramics. Subsquently, SiO₂ nanoparticles modified with 1H,1H,2H,2H-perfluorodecyltriethoxysilane were sprayed onto the whisker layer to form a superhydrophobic surface. The nanoparticles exhibit superhydrophobicity, which is protected by the whisker layer containing pores and bulges. This prohibits direct contact between the nanoparticles and external objects. Contact and rolling angle tests indicated that the surface contact angle of the micro–nano hierarchical structure is 158° and the rolling angle is less than 10°. The stability of the superhydrophobic surface was tested through ultraviolet light, long-time immersion in solutions with various pH values, water scouring, and sandpaper abrasion. The results showed that the contact angle is greater than 150°. This study is expected to provide a simple and effective method for fabricating superhydrophobic surfaces on ceramics on a large scale.     

Superhydrophobic durable coating based on UV‐photoreactive silica nanoparticles

Superhydrophobic surfaces can be obtained by tailoring both the chemistry and roughness topography, mimicking the Lotus leaf characteristics. Most of the synthetic superhydrophobic surfaces reported have been composed of micro and nanoparticles (NPs) embedded in polymer‐based coatings. The particles which tailor the topography are bonded to the base polymers by weak secondary forces. Consequently, the topography integrity is highly affected by handling and surface drag making them unsuitable for long term applications. This work is focused on promoting covalent bonding between the NPs and the base polymer to obtain durable superhydrophobic surfaces. The rough topography was achieved by ultraviolet (UV) curing of SiO₂ NPs containing a photoreactive benzophenone moiety in addition to methylated fumed silica NPs which can bind covalently to the polymer base coating, on UV radiation. The hydrophobic chemistry was obtained by fluoroalkylsilane top coating. Coating durability was evaluated using surface air drag and accelerated weathering conditions (UV radiation, humidity and temperature). Results indicated that the proposed approach resulted in superhydrophobic surfaces having high contact angle (>150°) and low sliding angle (<10°) with improved long term durability. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41122.     

Facile preparation of superhydrophobic polyester surfaces with fluoropolymer/SiO2 nanocomposites based on vinyl nanosilica hydrosols

A facile method to prepare superhydrophobic fluoropolymer/SiO₂ nanocomposites coating on polyester (PET) fabrics was presented. The vinyl nanosilica (V? SiO₂) hydrosols were prepared via one‐step water‐based sol‐gel reaction with vinyl trimethoxy silane as the precursors in the presence of the base catalyst and composite surfactant. Based on the V? SiO₂ hydrosol, a fluorinated acrylic polymer/silica (FAP/SiO₂) nanocomposite was prepared by emulsion polymerization. The FAP/SiO₂ nanocomposites were coated onto the polyester fabrics by one‐step process to achieve superhydrophobic surfaces. The results showed that silica nanoparticles were successfully incorporated into the FAP/SiO₂ nanocomposites, and a specific surface topography and a low surface free energy were simultaneously introduced onto PET fibers. The prepared PET fabric showed excellent superhydrophobicity with a water contact angle of 151.5° for a 5 μL water droplet and a water shedding angle of 12° for a 15 μL. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40340.     

Combined soft lithographic transfer‐printing and patterning method of highly fluorinated polymers as a facile surface treatment protocol

A combined soft lithographic transfer‐printing and patterning method of highly fluorinated polymers was investigated aiming to establish a facile surface treatment protocol for various substrates. Spin‐coated layers of poly(1H,1H,2H,2H‐perfluorodecyl methacrylate) (PFDMA) on patterned polydimethylsiloxane (PDMS) molds were transfer‐printed successfully on silicon, glass, aluminum substrates, resulting in the well‐controlled production of nano to micrometer‐scale periodic structures. With careful optimization of the dimension and density of the PFDMA patterns, it was possible to achieve a water contact angle as high as 175° on the transfer‐printed highly fluorinated polymer film. One of the advantages of the transfer‐patterning method is that highly fluorinated polymer films can be printed on curved surfaces while retaining their superhydrophobic and corrosion‐prevention character. In addition, the transfer‐printed PFDMA layers on the glass plates showed enhanced light transmission, which led to the extraction of 10% more light when they were applied to the emitting side of green organic light‐emitting devices. The micro‐patterned PFDMA surfaces also exhibited a significantly reduced level of bacterial adhesion when they were incubated in human bile juice. These results strongly suggest that the proposed facile transfer‐patterning protocol of highly fluorinated polymer films can be a suitable surface‐treatment technique for implantable electronic devices that exhibit improved device performance and anti‐biofouling nature. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45184.     

Fabrication of self‐cleaning poly(vinylidene fluoride) membrane with micro/nanoscaled two‐tier roughness

Based on the “lotus effect” principle, smooth microreliefs of polyvinylidene fluoride (PVDF) membrane were prepared via thermally induced phase separation process. Hydroxyl groups were introduced into PVDF membrane by pretreatment with KOH/alcohol solution. Subsequently, these hydroxyl groups grafted with (CH₃)₂SiCl₂/CH₃SiCl₃ to form nano‐clusters, which were decorated on the microreliefs of PVDF membrane. Scanning Electronic Microscopy (SEM) and Atomic Force Microscope (AFM) analysis showed the micro‐ and nano‐scale structures, similar to lotus leaf, were successfully fabricated on the PVDF membrane surface. The water contact angle and sliding angle on the fabricated lotus‐leaf‐like PVDF membrane surface were 154 and 4°, respectively. Self‐cleaning test indicated that the lotus‐leaf‐like surface of PVDF membrane has excellent superhydrophobic and self‐cleaning properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Mimicking Lotus Leaf: Development of Micro‐Nanostructured Biomimetic Superhydrophobic Polymeric Surfaces by Ultrafine Powder Coating Technology

This study demonstrates the development of polymeric superhydrophobic surfaces by a solvent‐free ultrafine powder coating (UPC) technique for the first time. The developed surfaces exhibit lotus effect with water contact angles (CAs) of over 160° and sliding angle (SA) of less than 5°. It is evident that the higher CA and lower SA of the low‐energy surfaces are attributed to the appropriate surface textures of micro‐ and/or nano‐scales. AFM and SEM images revealed the unique double‐scale hierarchical (micro‐ and nano) structures on the developed superhydrophobic surfaces. As an additional advantage, these superhydrophobic UPC technology eliminates the use of toxic solvents that are responsible for the hazardous emissions of VOCs. Therefore, fabrication of polymeric superhydrophobic surfaces by solvent‐free PC technique has enormous opportunities for a revolutionary expansion in coating industry to save the surfaces from the intervention of moisture.

     

Nano‐sio2‐reinforced ultraviolet‐curing materials for three‐dimensional printing

As an additive manufacturing technology, ultraviolet (UV)‐curing three‐dimensional printing, which requires the use of a photocurable resin, is increasingly being used to produce customized end‐user parts of many complex shapes. In this study, to improve the strength and ductility of printing materials, nano‐SiO₂‐reinforced photocurable resins were prepared by a planetary ball mill; then, the morphology, photochemistry, thermal property, and mechanical properties of the nanocomposites were investigated and characterized. Transmission electron microscopy analysis indicated that the modified nano‐SiO₂ was well dispersed in the photocurable resin. The glass‐transition temperature increased from 67.2°C for the unfilled resin to 71.7 and 80.1°C for nanocomposites with nano‐SiO₂ contents of 0.3 and 0.7 wt %, respectively. The tensile strength and impact strength were increased by 46.7 and 165.3% for nanocomposites with 0.3 wt % nano‐SiO₂. The flexural modulus of the nanocomposites increased from 1.7 to 8.0 GPa when 0.7 wt % nano‐SiO₂ was added to the photocurable resin; this appeared to originate from the relatively high level of dispersion and the intimate combination of the nano‐SiO₂ with the matrix. The investigation of the physical and chemical properties of such UV‐curing materials showed that the low filler concentration (<1 wt %) of nano‐SiO₂ did not affect the processability of the nanocomposites. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42307.     

Study of surface‐functionalized nano‐SiO2/polybenzoxazine composites

A series of the surface‐functionalized nano‐SiO₂/polybenzoxazine (PBOZ) composites was produced, and an attempt was made to improve the toughness of PBOZ material, without sacrificing other mechanical and thermal properties. A benzoxazine functional silane coupling agent was synthesized to modify the surface of nano‐SiO₂ particles, which were then mixed with benzoxazine monomers to produce the nano‐SiO₂‐PBOZ nanocomposites. The notched impact strength and the bending strength of the nano‐SiO₂‐PBOZ nanocomposites increase 40% and 50%, respectively, only with the addition of 3 wt % nano‐SiO₂. At the same load of nano‐SiO₂, the nano‐SiO₂‐PBOZ nanocomposites exhibit the highest storage modulus and glass‐transition temperature by dynamic viscoelastic analysis. Moreover, the thermal stability of the SiO₂/PBOZ nanocomposites was enhanced, as explored by the thermogravimetric analysis. The 5% weight loss temperatures increased with the nano‐SiO₂ content and were from 368°C (of the neat PBOZ) to 379°C or 405°C (of the neat PBOZ) to 426°C in air or nitrogen with additional 3 wt % nano‐SiO₂. The weight residue of the same nanocomposite was as high as 50% in nitrogen at 800°C. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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

Stable superhydrophobic surface based on low‐density polyethylene (LDPE)/ethylene–propylene–diene terpolymer (EPDM) thermoplastic vulcanizate (TPV) was successfully fabricated by using etched aluminum foil as template. The etched aluminum template consisted of micropores and step‐like textures, was obtained by the metallographic sandpaper sanding and the subsequent acid etching. The surface morphology and hydrophobic properties of the series molded TPV surfaces were researched by varying the weight ratio of the LDPE/EPDM TPV. The superhydrophobic LDPE/EPDM TPV surfaces exhibited the microstructures consisting of step‐like textures obtained via molding with etched aluminum template and a large number of fiber‐like structures resulted from the plastic deformation of LDPE matrix. The obtained TPV (LDPE/EPDM weight ratio = 70/30) surface exhibited the remarkable superhydrophobicity, with a contact angle of 152.0° ± 0.7° and a sliding angle of 3.1° ± 0.8°. The molded TPV surface had excellent environmental stability when the pH of water solution was in the range of 1 to 14; moreover, the surface also showed the excellent resistance to various organic solvents. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46241.     

Electrowetting-on-dielectric behavior of micro-nano hierarchical SiO2 layers decorated with noble metals

The performances of electrowetting-on-dielectric (EWOD) devices were investigated using micro-nano hierarchical structures of pristine and noble metal-decorated SiO₂ layers, with the entropy wetting model. The SiO₂ layers were prepared by an electrospray technique, and noble metals were decorated by UV irradiation. In addition, a thin Teflon coating was applied to enhance their initial hydrophobicity. The initial water contact angle (WCA) value of the Pd-decorated SiO₂ (Pd–SiO₂) and Ag-decorated SiO₂ (Ag–SiO₂) layers was 165°, while that of the Au-decorated SiO₂ (Au–SiO₂) and pristine SiO₂ layers was 154°. Different external voltages (up to 200 V) were used to investigate the EWOD behavior of the fabricated layers. In all cases, the WCA decreased with increasing applied voltage. Under 200 V (maximum applied voltage), WCA values of 129, 120, 115, and 102° were measured for pristine SiO₂, Pd–SiO₂, Ag–SiO₂, and Au–SiO₂ layers, respectively. Moreover, the EWOD properties of the noble metal-decorated layers were studied in the presence of dodecane oil. At 200 V, the WCAs of the Pd–SiO₂, Ag–SiO₂, Au–SiO₂, and layers were 134, 97 and 100°, respectively. Finally, we applied the entropy wetting model to further understand the results of the EWOD experiments.     

Facile generation of highly durable thiol-functionalized polyhedral oligomeric silsesquioxane based superhydrophobic melamine foam

In this study, a durable superhydrophobic/superoleophilic melamine foam was fabricated by a facile and rapid one-step thiol-ene click chemistry and Michael addition reaction, which demonstrated excellent robustness in oil/water separation. First, 1H, 1H, 2H-perfluoro-1-hexene reacted with thiol-functionalized polyhedral oligomeric silsesquioxane via the thiol-ene click chemistry to obtain a fluorinated thiol-functionalized polyhedral oligomeric silsesquioxane solution. Subsequently, the melamine foam was immersed to the solution system to form nanoaggregates on the melamine foam surface by the Michael addition reaction in the presence of ultraviolet light. The micro/nano rough structure and low surface energy of the nanoaggregates layer endowed the pristine melamine foam with superhydrophobicity; the water contact angle was greater than 150°. More importantly, the as-prepared melamine foam could withstand harsh conditions, such as a corrosive solution environment, strong ultraviolet light, mechanical compression, high and low temperature exposure, and ultrasonic washing. Driven by gravity, the as-prepared melamine foam could efficiently separate the oil/water mixtures and maintain 98% separation efficiency at high and low temperatures. In addition, it maintained the desirable absorption capability in different oil/organic solvents even after 15 absorption cycles. Accordingly, this facile, low-cost, and robust one-step method provides important support for the superhydrophobic oil/water separation field.     

Tribological properties of micro‐ and nanoparticles‐filled poly(etherimide) composites

It has been found that nano‐ or microsized inorganic particles in general enhance the tribological properties of polymer materials. In the present study, 5 vol % nano‐TiO₂ or micro‐CaSiO₃ was introduced into a polyetherimide (PEI) matrix composite, which was filled additionally with short carbon fibers (SCF) and graphite flakes. The influence of these inorganic particles on the sliding behavior was investigated with a pin‐on‐disc testing rig at room temperature and 150°C. Experimental results showed that both particles could reduce the wear rate and the frictional coefficient (μ) of the PEI composites under the applied testing conditions. At room temperature, the microparticles‐filled composites exhibited a lower wear rate and μ, while the nano‐TiO₂‐filled composites possessed the lowest wear rate and μ at elevated temperature. Enhancement in tribological properties with the addition of the nano‐particles was attributed to the formation of transfer layers on both sliding surfaces together with the reinforcing effect. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1678–1686, 2006     

Transparent and durable SiO2‐containing superhydrophobic coatings on glass

We fabricated novel superhydrophobic coatings based on SiO₂ nanoparticles combined with NH₂‐terminated silicone (SN₂) or SN₂‐modified polyurethane (SN₂‐prePU) by alternately spin‐coating them onto glass slides. The final fabricated surface contained SN₂/SiO₂ or SN₂‐prePU/SiO₂ bilayers. The conditions of spin‐coating method were also explored. SN₂‐prePU with different SN₂/prePU molar ratios were synthesized to study the influence of SN₂ ratio on the water contact angles of ultimate spin‐coated surfaces. The surface was found to be tunable from hydrophobic to superhydrophobic by choosing SN₂‐prePU with different SN₂/prePU molar ratios or SN₂ content. Water droplets easily rolled off on these superhydrophobic surfaces. Surfaces coated with SN₂/SiO₂ bilayers showed better transparency, whereas surfaces coated with SN₂‐prePU(2 : 1)/SiO₂ bilayers exhibited better durability. Droplets of varied pH were prepared to test the anti‐wettability of the coatings. Results showed that the as‐coated surfaces had stable superhydrophobicity to droplets with pH values ranging from 1 to 14. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41500.     

Three‐dimensionally printed bioinspired superhydrophobic PLA membrane for oil‐water separation

A novel lotus‐leaf‐inspired superhydrophobic poly(lactic acid) (PLA) porous membrane was fabricated for oil‐water separation based on fused deposition modeling three‐dimensional printing and subsequent chemical etching and the decoration of polystyrene nanospheres. A superhydrophobic PLA fractal surface with a water contact angle of 151.7° and low water adhesion force of 21.8 μN was achieved. The membrane pore size could be easily adjusted from 40 to 600 μm via a computer‐aided design program to optimize separation performance. The maximal oil‐water separation efficiency of 99.4% was achieved with a pore size of 250 μm, which also exhibited a high flux of 60 kL m^?2 h^?1. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3700–3708, 2018     

Hierarchical superhydrophobic surfaces for oil–water separation via a gradient of ammonia content controlling of dopamine oxidative self-polymerization

Superhydrophobic three-dimensional porous materials have been considering as one of the most promising candidate absorbents for removal and collection of oil spills or organic contaminants from water. In this work, we report a novel and straightforward method for construction of hierarchical superhydrophobic surfaces on the commercial melamine sponge by controlling of the dopamine oxidative selfpolymerization via a gradient of ammonia content. The surface roughness of the sponge was enhanced by the deposited polydopamine coatings whose surfaces exhibited different morphologies at solutions of varied ethanol-ammonia ratios. Thereafter the low-surface free energy moieties were decorated on the surfaces by utilizing a secondary modification platform of polydopamine. Correspondingly, the obtained superhydrophobic melamine sponge achieved a water contact angle of 162.6° ± 1. Furthermore, the superhydrophobic sponge exhibited excellent absorption performances and extraordinary recyclabilities toward a variety of oils and organic solvents. These findings presented in this study offer an effective and versatile approach for oil spills and organic solvents containment removal and environmental remediation in more fundamental and practical fields. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48044.     

Preparation and anti‐icing property of a lotus‐leaf‐like superhydrophobic low‐density polyethylene coating with low sliding angle

A lotus‐leaf‐like superhydrophobic low‐density polyethylene (LDPE) coating with low sliding angle was prepared by a facile method. The water contact angle and sliding angle of the as‐prepared superhydrophobic LDPE coating were 156 ± 1.7° and 1°, respectively. The anti‐icing property of the as‐prepared LDPE coating with low sliding angle was investigated in a climatic chamber with a working temperature of ?5°C. The results showed that the superhydrophobic LDPE coating with low sliding angle can largely prevent ice formation on the surface, showing excellent anti‐icing property. The as‐prepared superhydrophobic LDPE coating with good anti‐icing property will be perfectly desirable for outdoor equipments to reduce ice formation on their surfaces in cold seasons. This work will provide a new way to fabricate anti‐icing coating and thus find applications in a variety of fields. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Preparation and properties of core–shell nanosilica/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) latex

A core–shell nanosilica (nano‐SiO₂)/fluorinated acrylic copolymer latex, where nano‐SiO₂ served as the core and a copolymer of butyl acrylate, methyl methacrylate, and 2,2,2‐trifluoroethyl methacrylate (TFEMA) served as the shell, was synthesized in this study by seed emulsion polymerization. The compatibility between the core and shell was enhanced by the introduction of vinyl trimethoxysilane on the surface of nano‐SiO₂. The morphology and particle size of the nano‐SiO₂/poly(methyl methacrylate–butyl acrylate–2,2,2‐trifluoroethyl methacrylate) [P(MMA–BA–TFEMA)] core–shell latex were characterized by transmission electron microscopy. The properties and surface energy of films formed by the nano‐SiO₂/P(MMA–BA–TFEMA) latex were analyzed by Fourier transform infrared spectroscopy, differential scanning calorimetry, thermogravimetric analysis, scanning electron microscopy/energy‐dispersive X‐ray spectroscopy, and static contact angle measurement. The analyzed results indicate that the nano‐SiO₂/P(MMA–BA–TFEMA) latex presented uniform spherical core–shell particles about 45 nm in diameter. Favorable characteristics in the latex film and the lowest surface energy were obtained with 30 wt % TFEMA; this was due to the optimal migration of fluorine to the surface during film formation. The mechanical properties of the films were significantly improved by 1.0–1.5 wt % modified nano‐SiO₂. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Water‐dispersible conducting polyaniline/nano‐SiO2 composites without any stabilizer

A water‐dispersible conducting polyaniline/ nano‐SiO₂ composite, with a conductivity of 0.071 S cm^?1 at 25°C, was prepared by the oxidative polymerization of aniline in the presence of amorphous nano‐SiO₂ particles. And the structure, morphology, thermal stability, conductivity, and electroactivity of this composite were also investigated. This composite has been steadily dispersed in the aqueous solution for about 10–36 h without the need for any stabilizer. It would significantly impulse the commercial applications of conducting polyaniline/nano‐SiO₂ composite as fillers for antistatic and anticorrosion coatings. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

耐腐蚀超疏水超亲油不锈钢网的制备及其在油水分离过程中的应用

以不锈钢网为基底,通过化学刻蚀法制备微米级粗糙表面,通过一步浸泡法将st9ber法制得的疏水亲油纳米Si O2颗粒沉积到粗糙的不锈钢网表面,制备了具有微纳二级粗糙结构的超疏水超亲油不锈钢网。利用扫描电子显微镜(SEM)、傅里叶变换红外光谱仪(FT-IR)和接触角测量仪(CA)表征了超疏水超亲油不锈钢网的表面形貌、化学组成和润湿性能,并将其用于油水分离过程中。结果表明,疏水亲油纳米Si O2颗粒成功的沉积到不锈钢网表面;水滴在超疏水超亲油不锈钢网上的接触角最大为151°,煤油的接触角为0°;制备的超疏水超亲油不锈钢网不仅能高效的分离不同种类油和水的混合物,还能高效的分离油和腐蚀性液体(强酸或强碱水溶液)的混合物,其耐腐蚀特性可满足复杂环境下的油水分离要求。     

One‐step fabrication of fluoropolymer transparent films with superhydrophobicity by dry method

Fluoropolymer transparent thin films were deposited on different substrates by one‐step vacuum evaporation method, which exhibit superhydrophobic property with water contact angle (CA) greater than 150°. Polytetrafluoroethylene (PTFE) film with network structure shows high oleophobicity with oil CA of 138°, whereas polytetrafluoroethylene‐perfluoropropylvinylethers (PFA) film with particle structure is superoleophilicity with oil CA near 0°. It is believed that different conformation of  CF₂ groups at the surface lead to this different surface activity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011