Fabrication and superhydrophobicity of fluorinated carbon fabrics with micro/nanoscaled two-tier roughness

Superhydrophobic carbon fabric with micro/nanoscaled two-tier roughness was fabricated by decorating carbon nanotubes (CNTs) onto microsized carbon fibers, using a catalytic chemical vapor deposition and subsequent fluorination surface treatment. The superhydrophobic surfaces are based on the regularly ordered carbon fibers (8-10 μm in diameter) that are decorated by CNTs with an average size of 20-40 nm. The contact angle of water significantly increases from 148.2 ± 2.1° to 169.7 ± 2.2° through the introduction of CNTs. This confirms that the wettability of carbon fabric changes from hydrophobicity to superhydrophobicity due to structural transformation. This finding sheds light on how the two-tier roughness surface induces superhydrophobicity of rough surfaces, and how the presence of CNTs reduces the area fraction of a water droplet in contact with the carbon surface with two-tier roughness.     

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.     

Growing carbon nanotubes on patterned submicron-size SiO2 spheres

Growing carbon nanotubes (CNTs) perpendicularly to the surface of submicron-size SiO₂ spheres by pyrolyzing iron(II) phthalocyanine (FePc) is reported for the first time in this paper. The large curvature isolates the nanotubes and forms unique structures. The density, lengths and morphology of CNTs on SiO₂ spheres can be controlled by varying the experimental conditions. A method of growing CNTs on patterned SiO₂ spheres on conducting surface by photolithography is further developed based on the selective growth of CNTs. This may offer an effective way to control the density of patterned, aligned CNTs on conducting substrates for various applications, particularly for field emission.     

Electrically conductive superhydrophobic octadecylamine-functionalized multiwall carbon nanotube films

Electrically conductive, superhydrophobic multiwall carbon nanotube (MWCNT) thin films were prepared by direct amination of MWCNTs with up to 14 wt.% of octadecylamine (ODA) by vacuum filtration method. The ODA-functionalized MWCNT films exhibit a high water contact angle of 165° and electrical conductivity of 860 S/m. The liquid–air–solid interface is directly observed from above the water droplet using an optical microscope. The observation indicates that the wettability state of the MWCNTs has changed from relatively hydrophilic to superhydrophobic state upon functionalization with ODA. The fundamental mechanisms responsible for the unusual combination of surface superhydrophobicity and high electrical conductivity of the MWCNT films are described and their implications are discussed.     

Facile fabrication of water repellent coatings from vinyl functionalized SiO2 spheres

Water repellent SiO₂ particulate coatings were prepared by a one-step introduction of vinyl groups on the coating surface. Rough surface structure and low surface energy could be directly obtained. Vinyl functionalized SiO₂ (vinyl-SiO₂) spheres with average diameter of 500 nm were first synthesized by a sol–gel method in aqueous solution using vinyltriethoxysilane as the precursor. The multilayer SiO₂ coating fabricated by dip-coating method was highly hydrophobic with a water contact angle of 145.7° ± 2.3°. The superhydrophobic SiO₂ coating with a water contact angle up to 158° ± 1.7° was prepared by spraying an alcohol mixture suspension of the vinyl-SiO₂ spheres on the glass substrate. In addition, the superhydrophobic SiO₂ coating demonstrated good stability under the acidic condition. However, it lost its hydrophobicity above 200°C because of the oxidation and degradation of vinyl groups.     

Fabrication of mechanically robust superhydrophobic aluminum surface by acid etching and stearic acid modification

The aluminium surface with multi-scale structure has been fabricated via a facile and rapid solution-phase etching method by HCl/H₂O₂ etchants. After modification with stearic acid solution, the wettability of the etched aluminum surface turns into superhydrophobicity with an optimal water contact angle of 160° ± 2° and a sliding angle of 4° ± 1°. The processing conditions, such as the etching time, modifier types and the concentration of H₂O₂ are investigated to determine their effects on the surface morphology and wettability. As a result, the obtained sample shows excellent anti-adhesion property and bouncing phenomenon of water droplet. It can withstand mechanical abrasion for at least 100 cm under 12.3 kPa, or hydrostatic pressure under 24 ± 1 kPa without losing its superhydrophobicity, suggesting superior mechanical durability. Moreover, the surface also remains superhydrophobicity even after contacting corrosive liquids or long-term exposure in air over 100 days. Such a mechanically durable superhydrophobic aluminum surface can provide a promising practical application in various fields.     

Superhydrophobic polyurethane and silica nanoparticles coating with high transparency and fluorescence

A superhydrophobic surface was prepared by spin‐coating trimethylsiloxane functionalized SiO₂ (TMS‐SiO₂) solutions onto a precoated polyurethane (PU) layer. The superhydrophobic coatings showed high stability with time, and the prepared coatings remained superhydrophobicity even after 6 months. Furthermore, the as‐prepared surface showed high transparency with a transmittance above 70% in visible light region (400–800 nm). The transition of the composite surface from superhydrophobicity to hydrophilicity can be achieved by increasing the drying temperature. More interestingly, the surface showed excellent fluorescent property by the incorporation of fluorescent Europium (Eu) complex into the surface and without deteriorating the superhydrophobic and transparent properties. It was believed that the superhydrophobic surface with multifunction would broaden the applications of superhydrophobic materials. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation and hydrophobicities of biomorphic ZnO based on carbon derived from indicalamus leaf template

Abstract

Some plant leaves possess a superhydrophobicity because of the exclusive structures on their surfaces. Many methods were developed to imitate the leaf structures in order to obtain the superhydrophobic ZnO. However, it is difficult to simulate the natural complex structures through the traditional methods. In the present study, we used an indicalamus leaf as a template to fabricate a superhydrophobic biomorphic ZnO on a carbon substrate (ZnO/C). First, a carbon substrate with a leaf microstructure was obtained by sintering an indicalamus leaf in argon. The biomorphic ZnO/C was then obtained by immersing this carbon substrate into a Zn(NO₃)₂ solution and again sintering it. This ZnO/C exhibited superhydrophobicity after it was modified with fluorine silane. The water contact angle of the resulting product was 163°, which is similar to that of the indicalamus leaf (159°) and is much higher than that of smooth carbon covered with the same fluorine silane (114°).     

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.     

Fabrication of superhydrophobic transparent cyclic olefin copolymer (COC)-SiO2 nanocomposite surfaces

A superhydrophobic cyclic olefin copolymer (COC) nanocomposite coating was produced with a very simple and easy method. Self-cleaning superhydrophobic COC surfaces were obtained by only adding surface hydrophobized SiO₂ nanoparticles by dip coating method. The influence of concentration of SiO₂ and the coating temperatures on the wettability of the surfaces were investigated. The surface wettability of the coatings was examined with the contact angle measurements and the surface roughness and morphology were analyzed by using atomic force microscope and scanning electron microscopy analysis. Surfaces with certain amounts of COC and SiO₂ showed superhydrophobic character with high water contact angle of 169⁰. Also, the obtained superhydrophobic surfaces show superior water repellent, high transparency, and self-cleaning characteristics.     

Preparation and characterization of superhydrophobic conductive fluorinated carbon blacks

Superhydrophobic conductive carbon blacks were prepared by covalent bonding of perfluorocarbon and perfluoropolyether chains on the conductive carbon black surface. Perfluorodiacyl and perfluoropolyether peroxides were used as reagents for the chemical treatment. Their thermal decomposition produced respectively, perfluoroalkyl and perfluoropolyether radicals that directly bonded the polycyclic aromatic structure of carbon black surface. Measurements of contact angles with water on molded pellets made with carbon black powder demonstrated that water droplets were enduringly stable on the treated carbon blacks. Contact angle values were significantly high, exceeding the superhydrophobicity threshold. On the contrary, the droplets were adsorbed in few seconds by the native carbon black. Conductivity measurements showed that the covalent linkage of fluorinated chains weakly modified the electrical properties of the conductive carbon black, even if the surface properties changed so deeply. The relationship between the linkage of fluorinated chains and the variations of physical–chemical properties were studied combining electron spectroscopy, resistivity measurements, X-ray diffraction, scanning electron microscopy, surface area analysis and thermal gravimetric analysis. The superhydrophobic conductive carbon blacks were compared with a superhydrophobic carbon black obtained by direct fluorination of conductive carbon black with elemental fluorine, F₂.     

Fabrication of Ketjen black-high density polyethylene superhydrophobic conductive surfaces

A Ketjen black-high density polyethylene (HDPE) superhydrophobic conductive surface was prepared by a single-step pressing method in which the Ketjen black was pressed into the HDPE leaving it partially exposed to form a superhydrophobic coating with high static water contact angle (～160^o), low sliding angle (～2.5^o), and low sheet resistance (10⁰–10² Ω/sq). The preparation conditions such as the pressing time and the amount of Ketjen black greatly influence the superhydrophobicity and conductivity. The simple pressing of Ketjen black onto the HDPE substrate provides hierarchically structured roughness, leading to the superhydrophobicity of the surface. The superhydrophobic conductive surface also can be obtained with other carbonaceous materials, such as other carbon blacks and nanotubes, and the superhydrophobicity is decided by whether it can produce hierarchically structure roughness.     

Preparation of a Superhydrophobic ZnO Film on ITO Glass via Electrodeposition Followed by Oxidation. Effect of the Deposition Time

This study investigates the fabrication of a stable superhydrophobic surface with low contact angle (CA) hysteresis using ZnO thin films prepared by cathodic electrodeposition and subsequent gaseous oxidation. The deposition time is a crucial factor in nanostructuring and producing surface roughness of the films. Cathodic electrodeposition for 60 s created a number of nanopillars, which exhibited the highest CA value, i.e., 167.9°. The rough ZnO surface displayed not only enhanced water repellency with low CA hysteresis but also excellent superhydrophobic stability. The application of the Cassie–Baxter model demonstrated that the ZnO nanostructure contributed to increasing the area of a water droplet in contact with air, leading to superhydrophobicity. Such a unique textured surface showed a great potential for the engineering of strong superhydrophobic coatings.     

The performance of superhydrophobic and superoleophilic carbon nanotube meshes in water–oil filtration

Vertically-aligned multi-walled carbon nanotubes (CNTs) were grown on stainless steel (SS) mesh by thermal chemical vapor deposition with a diffusion barrier of Al₂O₃ film. These three-dimensional porous structures (SS-CNT meshes) were found to be superhydrophobic and superoleophilic. Water advancing contact angles of 145–150° were determined for these SS-CNT meshes in air and oil (gasoline, isooctane). Oil, on the other hand, completely wet the SS-CNT meshes. This combined superhydrophobic and superoleophilic property repelled water while allowed the permeation of oil. Filtration tests demonstrated efficiencies better than 80% of these SS-CNT meshes as the filtration membranes of the water-in-oil emulsions. We have conducted quantitative analysis on the diameters of the oil droplets in both the feed emulsion and the filtrate. Then, we have evaluated the issue of water blockage and possible way to improve the filtration efficiency. Finally, the filtration and blockage mechanisms are proposed.     

Stable superhydrophobic surface of hierarchical carbon nanotubes on Si micropillar arrays

It is of great importance to construct a stable superhydrophobic surface with low sliding angle (SA) for various applications. We used hydrophobic carbon nanotubes (CNTs) to construct the superhydrophobic hierarchical architecture of CNTs on silicon micropillar array (CNTs/Si-μp), which have a large contact angle of 153° to 155° and an ultralow SA of 3° to 5°. Small water droplets with a volume larger than 0.3 μL can slide on the CNTs/Si-μp with a tilted angle of approximately 5°. The CNTs growing on planar Si wafer lose their superhydrophobic properties after exposing to tiny water droplets. However, the CNTs/Si-μp still show superhydrophobic properties even after wetting using tiny water droplets. The CNTs/Si-μp still have a hierarchical structure after wetting, resulting in a stable superhydrophobic surface.     

Water/oil repellency and drop sliding behavior on carbon nanotubes/carbon paper composite surfaces

The study examines the water/oil repellency and the sliding behavior of carbon papers (CPs) decorated with carbon nanotube (CNT) forest, prepared by using a catalytic chemical vapor deposition. The topography showed that CNTs with 20-40 nm grown on CPs form a hierarchical nano/submicron scale roughness. The CNT-CP composite surface with a thin fluoro-silica coating exhibits excellent water/oil repellency (contact angle >150°) with low sliding angles (SAs), i.e., SA: ∼6° and ∼18° for water and ethylene glycol (EG) droplets, respectively. Taking into account Young-Duprè’s equation incorporated with the Cassie parameter, the work of adhesion (W_ad) between droplets and CP surface is significantly reduced because the decoration of CNTs offers an air cushion to repel the drop penetration. The appearance of CNTs contributes area fractions in contact with air, 7.4% and 14.1%, to resist water and EG drops, respectively. The analysis of W_ad confirms that the smaller the W_ad value, the smaller the SA value reached, thus favoring the self-cleaning effect.     

Fabrication of superhydrophobic surfaces with non-aligned alkyl-modified multi-wall carbon nanotubes

Films of superhydrophobic multi-wall carbon nanotubes (MWCNTs) have been obtained by using alkyl-modified MWCNTs (MWCNT(COOC₁₈H₃₇)_n) and a simple and effective preparation method. The films show both a high contact angle and a small sliding angle for water droplets. A particular characteristic is that on the superhydrophobic surface the alkyl-modified MWCNTs are not intentionally aligned, thus avoiding the preparation techniques using aligned carbon nanotubes to produce the same effect.     

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.     

Facile fabrication of superhydrophobic raspberry‐like SIO2/polystyrene composite particles

A facile and novel strategy was reported on the fabrication of raspberry‐like SiO₂/polystyrene (SiO₂/PS) composite particles by emulsion polymerization in the presence of vinyl‐functionalized silica (vinyl‐SiO₂) particles, which were prepared via a one‐step sol–gel process using vinyltriethoxysilane as the precursor. The submicron vinyl‐SiO₂ particles were used as the core, and nanosized PS particles were then adsorbed onto the vinyl‐SiO₂ particles to form raspberry‐like composite particles during the polymerization process. The composition, morphology, and structure of the vinyl‐SiO₂ particles and the SiO₂/PS hybrid particles were characterized by thermogravimetric analysis, nuclear magnetic resonance, Fourier transform infrared spectroscopy, transmission electron microscopy, and scanning electron microscopy. Superhydrophobic surface can be constructed by directly depositing the raspberry‐like SiO₂/PS composite particles on glass substrate, and the water contact angle can be adjusted by the styrene/SiO₂ weight ratio. In addition, the superhydrophobic film possessed a strong adhesive force to pin water droplet on the surface even when the film was turned upside down. POLYM. COMPOS., 2013. © 2012 Society of Plastics Engineers     

Synthesis and field emission properties of carbon nanotubes/nanofibers grown on pyrolyzed polyaniline–SiO2 substrates

Pyrolyzed polyaniline–SiO₂ substrates with the rough surface containing some holes were prepared by the pyrolysis of polyaniline–SiO₂ composites at temperature of 900 °C. Carbon nanotubes/nanofibers (CNTs/CNFs) were grown on the rough surface and inside the holes using a CVD method with a xylene–ferrocene mixture as a carbon and catalyst precursor source. The structural and morphological properties of CNTs were characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The results indicated that the SiO₂ content of the substrates was responsible to the diameter and electron field emission properties of CNTs.