Superhydrophobic conducting coatings based on silicone matrix and carbon nanotubes

Preparation of superhydrophobic conducting coatings based on silicone matrix and two types of carbon nanotubes, native and modified with alkyl groups, is described. The amount of carbon nanotubes per unit surface area was kept constant in all the samples, whereas the content of the polymer matrix was varied. The electrical conductivity, contact angle, and sliding angle were measured. The structure of the coatings was studied with an optical profilometer and a scanning electron microscope. The largest contact angle was 158.4° for the sample with 50 wt % content of native carbon nanotubes. For the samples with more than 20 wt % content of carbon nanotubes of both types, the sliding angle was less than 1°. Changes in the micro- and nanostructure of the coatings, observed with variation of the content of the polymer matrix in the samples, were studied. The relationship between the structural changes, on the one hand, and hydrophobic and water sliding properties of the conducting coatings, on the other hand, was demonstrated.     

Superhydrophobic Surfaces Produced by Carbon Nanotube Modified Polystyrene Composite Coating

The present work investigates the enhancement of water repellency on engineering materials surfaces using nanoscale roughness inherent in multi-walled carbon nanotubes (MWCNTs) together with a hydrophobic polystyrene coating via a simple spraying-based technique. The coatings show both a high contact angle and a small sliding angle for water droplets. The different surfaces obtained exhibit contact angles from 125° up to 153° depending on the preparation conditions. The observations of the topology by scanning electron microscopy reveal that the nanostructure created by the MWCNTs and the microstructure induced by the deposition of polystyrene particles forming a two-level structure that conceptually mimics the lotus leaf surface are necessary to create stable superhydrophobic surfaces.     

Percolation-dominated superhydrophobicity and conductivity for nanocomposite coatings from the mixtures of a commercial aqueous silica sol and functionalized carbon nanotubes

Superhydrophobic conductive nanocomposite coatings are prepared for the first time from the simple mixture of a commercial aqueous silica sol and functionalized multiwalled carbon nanotubes (MWNTs) by air-spraying at ambient conditions followed by fluorosilane treatment. The relationship between MWNT content and the structure and properties of the nanocomposite coatings is investigated systematically. An ultra-low threshold (<5 vol.%) for superhydrophobicity is observed, which suggests that MWNTs are superior to any other spherical fillers for the construction of superhydrophobic nanocomposite coatings. When the content of nanotubes is below the threshold, the surface roughness mainly caused by the silica nanoparticles is not enough for creating superhydrophobic surfaces. Only above the threshold, the multiscale hierarchical structure is enough for both high water contact angles (>165°) and extremely low sliding angles (<2°). The conductivity is also percolation dominated, while the threshold for conductivity is much higher than that for superhydrophobicity, which can be ascribed to the encapsulated structure and the agglomeration of nanotubes in the composite coatings during air-spraying. Moreover, the aqueous silica sols hold merits of great film-forming capability at relatively low calcination temperatures, and being free of organic solvents.     

Wettability characterization of transparent MgF<Subscript>2</Subscript> nanoparticle coatings with SiO<Subscript>2</Subscript> binder covered with fluoroalkylsilane self-assembled monolayers

SiO₂-added MgF₂ nanoparticle coatings with various surface roughness properties were formed on silica-glass substrates from autoclaved sols prepared at 100–180 °C. The samples were exposed to fluoro-alkyl silane (FAS) vapor to give hydrophobicity. All nanoparticle samples before FAS treatment had transmittances higher than 93% and such values were preserved even after FAS treatment. We examined root mean square roughnesses of the nanoparticle coatings with a Scanning Probe Microscope. We also examined their static and dynamic wettabilities with a contact angle meter and calculated their adhesive energies and surface free energies (SFEs). The surface roughness of the nanoparticle coating increased with the increase of the autoclave temperature. In addition, higher autoclave temperature caused increases in the sliding angle and decreases in the SFE. Interestingly, the higher the contact angle was, the larger the sliding angle was, although smaller sliding angle was expected with a larger contact angle.     

Surface characteristic and cell response of CVD SiC coating for carbon/carbon composites used for hip arthroplasty

SiC coatings were applied on carbon/carbon composites by chemical vapor deposition for potential application in hip arthroplasty. The surface morphology, roughness, and wettability of the coatings were evaluated by scanning electron microscopy, laser confocal scanning microscope, and video‐based contact angle measuring device, respectively. The bonding strength between the coatings and carbon/carbon composites was analyzed by scratch testing. The cell responses to coatings were studied by analyzing the cell morphology and cell proliferation. The results showed that SiC coatings showed spherical morphology with a roughness of R_a = 1.0 ± 0.2 µm and a contact angle of 64.7 ± 4.0°. The coatings had lower surface roughness and better surface hydrophilicity compared with those of the uncoated carbon/carbon composites. A strong shear strength averaging 120.0 MPa between the coating and carbon/carbon composites was achieved. The cell culture experiments showed that cell spreading was improved, and cell proliferation was increased with the SiC coatings. It was demonstrated that CVD‐SiC‐coated carbon/carbon composites were good candidates as artificial hip joint materials. Copyright © 2012 John Wiley & Sons, Ltd.     

Superhydrophobic surfaces formed using layer-by-layer self-assembly with aminated multiwall carbon nanotubes

A convenient and simple route to functionalized multiwall carbon nanotubes (MWNTs) using the reaction of the amine (NH) groups of polyethyleneimine (PEI) with MWNTs in N,N-dimethylformamide (DMF) at 50 degrees C is described. The product functionalized MWNTs (MWNT-NH-PEI) contain 6-8% by weight PEI based on elemental analysis, thermal gravimetric analysis, and titration. The products form stable emulsions in water below pH 9 and can be derivatized to form alkylated MWNTs that are dispersible in organic media. Such MWNT-NH-PEI nanoparticles can also be used in covalent or ionic layer-by-layer assembly to form nanocomposite thin films on functionalized polyethylene (PE) films and powders. Such nanocomposite films were analyzed by contact angle analysis, atomic force microscopy (AFM), and confocal Raman microscopy. These analyses show that these superhydrophilic surfaces have micro/nanoroughness with a roughly uniform distribution of MWNT nanoparticles. Superhydrophobic PE films can be formed either from ionic layer-by-layer self-assembly of MWNT-NH-PEIs and poly(acrylic acid) or from covalent layer-by-layer self-assembly of MWNT-NH-PEIs and Gantrez if the final graft is acrylated with a mixed anhydride prepared from ethyl chloroformate and octadecanoic acid. The resulting octadecylated surface produced by five covalent layer-by-layer deposition steps has a water contact angle of 165 degrees and a sliding angle of less than 5 degrees. The corresponding surface produced by five ionic layer-by-layer deposition steps has a water contact angle of 155 degrees but exhibits water pinning. The ionically assembled nanocomposite graft is labile under acidic conditions. The covalently assembled graft is more chemically robust.     

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.     

柱状结构阵列碳纳米管膜的超疏水性研究

浸润性是固体表面的重要性质之一 .决定固体表面的浸润性的两个主要因素中 ,化学性质是内因 ,而几何结构形貌也是不可缺少的重要因素 .通过改变固体表面的粗糙度可以改变其浸润性 [1～ 5] .通常 ,人们用水接触角的大小来衡量固体表面水的浸润性 ,水与固体表面的接触角大于 1 5     

Functionalized carbon nanotubes containing isocyanate groups

Functionalized carbon nanotubes containing isocyanate groups can extend the nanotube chemistry, and may promote their many potential applications such as in polymer composites and coatings. This paper describes a facile method to prepare functionalized carbon nanotubes containing highly reactive isocyanate groups on its surface via the reaction between toluene 2,4-diisocyanate and carboxylated carbon nanotubes. Fourier-transformed infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) confirmed that reactive isocyanate groups were covalently attached to carbon nanotubes. The content of isocyanate groups were determined by chemical titration and thermogravimetric analysis (TGA).     

Plasma polymerized allylamine coated quartz particles for humic acid removal

Nowadays, titanium is a very commonly used biomaterial for the preparation of orthopedic and dental implants. Its excellent mechanical and biochemical bulk properties are nevertheless counterbalanced by its propensity to long term degradation in physiological conditions and its weak osseointegrative capacities. In this context, surface modifications can significantly hinder titanium weaknesses. The approach considered in this work relies on the preparation of thin composite coatings based on tantalum oxide and carbon nanotubes by sol-gel process. Tantalum is particularly interesting for its high biocompatibility and bioactivity, as well as its strong resistance to bio-corrosion. Carbon nanotubes are exploited to reinforce the compactness and homogeneity of the coatings, and can act as a favorable factor to strengthen the interaction with bone components by biomimicry. The composite layers are further modified with specific organophosphonic acid molecular films, able to chemically bind the tantalum oxide surface and improve the hydroxyapatite formation process. The characteristics and the qualities of these hybrid inorganic/organic coatings are evaluated by XPS, SEM, TEM, peeling tests, contact angle measurements, and electrochemical characterizations (free potential, polarization curves).     

Effect of surface roughness and chemical composition on the wetting properties of silicon-based substrates

The article reports on the wetting properties of silicon-based materials as a function of their roughness and chemical composition. The investigated surfaces consist of hydrogen-terminated and chemically modified atomically flat crystalline silicon, porous silicon and silicon nanowires. The hydrogenated surfaces are functionalized with 1-octadecene or undecylenic acid under thermal conditions. The changes occurring upon surface functionalization are characterized using Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) spectroscopy and water contact angle measurements. By increasing the surface roughness, the static water contact angle increases. The combination of high surface roughness with chemical functionalization with water repellent coating (1-octadecene) enables reaching superhydrophobicity (water contact angle greater than 150°) for silicon nanowires.     

Superhydrophobic bionic surfaces with hierarchical microsphere/SWCNT composite arrays

Superhydrophobic bionic surfaces with hierarchical micro/nano structures were synthesized by decorating single-walled or multiwalled carbon nanotubes (CNTs) on monolayer polystyrene colloidal crystals using a wet chemical self-assembly technique and subsequent surface treatment with a low surface-energy material of fluoroalkylsilane. The bionic surfaces are based on the regularly ordered colloidal crystals, and thus the surfaces have a uniform superhydrophobic property on the whole surface. Moreover, the wettability of the bionic surface can be well controlled by changing the distribution density of CNTs or the size of polystyrene microspheres. The morphologies of the synthesized bionic surfaces bear much resemblance to natural lotus leaves, and the wettability exhibited remarkable superhydrophobicity with a water contact angle of about 165 degrees and a sliding angle of 5 degrees.     

Superoleophobic surfaces through control of sprayed-on stochastic topography

The liquid repellency and surface topography characteristics of coatings comprising a sprayed-on mixture of fluoroalkyl-functional precipitated silica and a fluoropolymer binder were examined using contact and sliding angle analysis, electron microscopy, and image analysis for determination of fractal dimensionality. The coatings proved to be an especially useful class of liquid repellent materials due to their combination of simple and scalable deposition process, low surface energy, and the roughness characteristics of the aggregates. These characteristics interact in a unique way to prevent the buildup of binder in interstitial regions, preserving re-entrant curvature across multiple length scales, thereby enabling a wide range of liquid repellency, including superoleophobicity. In addition, rather than accumulating in the interstices, the binder becomes widely distributed across the surface of the aggregates, enabling a mechanism in which a simple shortage or excess of binder controls the extent of coating roughness at very small length scales, thereby controlling the extent of liquid repellence.     

Chitosan-mediated synthesis of carbon nanotube-gold nanohybrids

Metal-nanotube nanohybrids were produced by in situ synthesis and stabilization of gold nanoparticles on chitosan-functionalized carbon nanotubes. The formation of gold nanoparticles from tetrachloroauric acid was observed after only a few minutes of contact with the functionalized nanotubes, at room temperature. These results suggest that adsorption of chitosan at the surface of carbon nanotubes permits smooth reduction of the metallic salt and efficient anchoring of gold nanoparticles to the nanotubes.

     

二氧化硅纳米颗粒/硅树脂复合超疏水功能涂层的制备和性能研究

将二氧化硅纳米颗粒和硅树脂制成混合液,采用喷涂法(spray-coating)制备出了具备超疏水性的复合涂层.研究了二氧化硅、硅树脂不同含量配比对涂层疏水性能的影响,结果表明复合涂层的接触角随二氧化硅含量的增加而增加.在二氧化硅含量大于3%(质量分数)时,涂层显现超疏水性;当二氧化硅含量为3%(质量分数)、硅树脂含量为7%(质量分数)时,涂层与水的接触角达到151.6°,滚动角接近0°.通过扫描电子显微镜(SEM)观察涂层表面的微观结构,发现超疏水性的涂层具备微-纳复合阶层结构,类球状突起粒径在5μm左右,类球状突起上分布纳米团聚颗粒,直径约为50 nm.这种类似荷叶表面的微(纳复合阶层结构,结合硅树脂的低表面能,使得复合涂层具备了超疏水性能.     

Contact angle hysteresis, adhesion, and marine biofouling

Adhesive and marine biofouling release properties of coatings containing surface-oriented perfluoroalkyl groups were investigated. These coatings were prepared by cross-linking a copolymer of 1H,1H,2H,2H-heptadecafluorodecyl acrylate and acrylic acid with a copolymer of poly(2-isopropenyl-2-oxazoline) and methyl methacrylate at different molar ratios. The relationships between contact angle, contact angle hysteresis, adhesion, and marine biofouling were studied. Adhesion was determined by peel tests using pressure-sensitive adhesives. The chemical nature of the surfaces was studied by using X-ray photoelectron spectroscopy. Resistance to marine biofouling of an optimized coating was studied by immersion in seawater and compared to previous, less optimized coatings. The adhesive release properties of the coatings did not correlate well with the surface energies of the coatings estimated from the static and advancing contact angles nor with the amount of fluorine present on the surface. The adhesive properties of the surfaces, however, show a correlation with water receding contact angles and contact angle hysteresis (or wetting hysteresis) resulting from surface penetration and surface reconstruction. Coatings having the best release properties had both the highest cross-link density and the lowest contact angle hysteresis. An optimized coating exhibited unprecedented resistance to marine biofouling. Water contact angle hysteresis appears to correlate with marine biofouling resistance.     

Surface control and cryogenic durability of transparent CNT coatings on dip-coated glass substrates

Transparent carbon nanotube (CNT) coatings were deposited on boro-silicate glass substrates by dip-coating. Ultraviolet-visible (UV) spectra, surface resistance measurement, and the wettability tests were used to investigate the optical transmittance and electrical properties of these CNT coatings. The changes in electrical and optical properties of these coatings were observed to be functions of the number of dip-coating cycles. The surface resistance of the CNT coated substrates decreased dramatically as the number of dip-coatings was increased, whereas the increases in the CNT layer thickness beyond that for the first dipping cycle had little effect on the transparent-properties. Static contact angle measurements proved to be an effective means for evaluating the surface morphology of CNT coatings. The interfacial durability of the CNT coatings on a glass substrate was much better than that of ITO coatings over the temperature range from -150°C to +150°C.     

Influence of nanoscale particle roughness on the stability of pickering emulsions

The wetting behavior of solid surfaces can be altered dramatically by introducing surface roughness on the nanometer scale. Some of nature's most fascinating wetting phenomena are associated with surface roughness; they have inspired both fundamental research and the adoption of surface roughness as a design parameter for man-made functional coatings. So far the attention has focused primarily on macroscopic surfaces, but one should expect the wetting properties of colloidal particles to be strongly affected by roughness, too. Particle wettability, in turn, is a key parameter for the adsorption of particles at liquid interfaces and for the industrially important use of particles as emulsion stabilizers; yet, the consequence of particle roughness for emulsion stability remains poorly understood. In order to investigate the matter systematically, we have developed a surface treatment, applicable to micrometer-sized particles and macroscopic surfaces alike, that produces surface coatings with finely tunable nanoscale roughness and identical surface chemistry. Coatings with different degrees of roughness were characterized with regard to their morphology, charging, and wetting properties, and the results were correlated with the stability of emulsions prepared with coated particles of different roughness. We find that the maximum capillary pressure, a metric of the emulsions' resistance to droplet coalescence, varies significantly and in a nonmonotonic fashion with particle roughness. Surface topography and contact angle hysteresis suggest that particle roughness benefits the stability of our emulsions as long as wetting occurs homogeneously (Wenzel regime), whereas the transition toward heterogeneous wetting (Cassie-Baxter regime) is associated with a loss of stability.     

Synthesis and properties of zinc–nickel–carbon nanotube composite coatings

Composite electrochemical coatings modified with carbon nanotubes were produced on the basis of the zinc–nickel alloy. The functional properties (friction coefficient, protective capacity) of the composite coatings were studied in comparison with zinc–nickel alloys without a dispersed phase. It was found that, upon inclusion of carbon nanotubes particles into zinc–nickel deposits, their sliding friction coefficient decreases by a factor of 1.3–1.4 and the range of passive-state potentials becomes two times wider.     

Enhanced field emission from multiwall carbon nanotube films by secondary growth

We have studied nickel, gold, and ferritin coatings on catalytically grown multiwall carbon nanotubes as well as the generation of secondary nanotubes by resubmitting the decorated nanotubes to the chemical vapor deposition process. Nickel layers sputtered on nanotubes show a stronger interaction with the nanotube walls than gold coatings. At ambient temperature this results in a metal film that is more homogeneous for Ni than for Au. Surface mass transport at elevated temperatures leads to a transformation of the coating to nanoscale clusters on the nanotube surface. The resulting Au clusters are spherelike with a very small contact area with the nanotube whereas the Ni clusters are stretched along the tube axis and have a large contact area. Secondary nanotubes were established by growing nanotubes directly on the walls of primary nanotubes. Thin Ni layers or ferritin served as catalysts. We compared the field emission properties of samples with and without secondary nanotubes. The presence of secondary nanotubes enhances the field emission substantially.