Formation process of a strong water-repellent alumina surface by the sol-gel method

A novel strong water-repellent alumina thin film is fabricated by chemically adsorbing stearic acid (STA) layer onto the porous and roughened aluminum film coated with polyethyleneimine (PEI). The formation process and the structure of the strong water-repellent alumina film are investigated by means of contact angle measurement and atomic force microscope (AFM). Results show that the water contact angles for the alumina films increase with the increase of the immersion time in the boiling water, and meanwhile, the roughness of the alumina films increases with the dissolution of the boehmite in the boiling water. Finally, the strong water-repellent film with a high water contact angle of 139.1° is obtained when the alumina films have distinct roughened morphology with some papillary peaks and porous structure. Moreover, both the roughened structure and the hydrophobic materials of the STA endow the alumina films with the strong water-repellence.     

Fabrication of a superhydrophobic surface on a wood substrate

A layer of lamellar superhydrophobic coating was fabricated on a wood surface through a wet chemical process. The superhydrophobic property of the wood surface was measured by contact angle (CA) measurements. The microstructure and chemical composition of the superhydrophobic coating were analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FT-IR). An analytical characterization revealed that the microscale roughness of the lamellar particles was uniformly distributed on the wood surface and that a zinc stearate monolayer (with the hydrophobic groups oriented outward) formed on the ZnO surface as the result of the reaction between stearic acid and ZnO. This process transformed the wood surface from hydrophilic to superhydrophobic: the water contact angle of the surface was 151°, and the sliding angle was less than 5°.     

Fabrication of hydrophobic alumina aerogel monoliths by surface modification and ambient pressure drying

Hydrophobic crack-free alumina aerogel monoliths were fabricated by -Si(CH₃)₃ (trimethylsilyl substituent) modification of alcogels followed by an ambient pressure drying procedure. One-step solvent exchange and surface modification were simultaneously progressed by immersing alumina alcogels in trimethylmethoxysilane (TMMOS)/hexane solution. It is found that the hydrophobic property of alumina aerogels is affected by the contents of TMMOS from the measurements of contact angle and Fourier transform infrared spectrometry. Thermogravimetry/differential scanning calorimetry analyses reveal that the modified aerogels maintain their hydrophobic behavior up to a temperature of 260 °C. The structure and morphology of the obtained hydrophobic alumina aerogels were characterized by the measurements of N₂ physical adsorption and scanning electron microscopy, which showed that they were highly porous materials with narrow slit-like pore geometry and a high degree of pore size uniformity.     

Facile method to prepare stable superhydrophobic Co3O4 surface

A facile and novel method was developed to fabricate rough Co₃O₄ surface with hierarchical micro- and nanostructures by the combination of simple solid state reactions and coating process. After modification with stearic acid, a superhydrophobic surface with water contact angle of 155 ± 1.8° and sliding angle of 2° was obtained. The superhydrophobic Co₃O₄ surface remained superhydrophobic property in a wide pH range from 3 to 14. The superhydrophobic Co₃O₄ surface also showed excellent self-cleaning property and high stability in ambient environments.     

Superhydrophobic PEEK/PTFE composite coating

A simple and inexpensive method for forming a PEEK/PTFE superhydrophobic surfaces by controlling the topographical microstructures by adjusting the curing temperature has been proposed. The resulting porous surface, with ribbon-like randomly distributed double-scale structure and the lowest surface energy hydrophobic groups (-CF₃) has a water contact angle of 161°. PACS 06.60.Ei; 81.05.Rm; 81.20.Ev; 82.80.Pv     

Reversible switching of nanostructured cobalt hydroxide films from superhydrophobic to superhydrophilic state

Superhydrophobic cobalt hydroxide films with flower-like micro-nano structure prepared by chemical-bath deposition undergo a change in wettability from superhydrophobic to superhydrophilic state either by immersion in ethyl acetate or by heat treatment at 200°C and above. The superhydrophobicity of the film can be regained by immersion in an ethanolic solution of stearic acid. The superhydrophobicity is attributed to the combined effect of micro-nano binary surface morphology and the low surface energy of the self-assembled monolayer of stearic acid. It is proposed that switching from superhydrophobicity to superhydrophilicity is caused by removal of the adsorbed layer of stearic acid by solvent or heat treatment.     

Morphological and optical properties changes in nanocrystalline Si (nc-Si) deposited on porous aluminum nanostructures by plasma enhanced chemical vapor deposition for Solar energy applications

Photoluminescence (PL) spectroscopy was used to determine the electrical band gap of nanocrystalline silicon (nc-Si) deposited by plasma enhancement chemical vapor deposition (PECVD) on porous alumina structure by fitting the experimental spectra using a model based on the quantum confinement of electrons in Si nanocrystallites having spherical and cylindrical forms. This model permits to correlate the PL spectra to the microstructure of the porous aluminum silicon layer (PASL) structure. The microstructure of aluminum surface layer and nc-Si films was systematically studied by atomic force microscopy (AFM), transmission electron microscopy (TEM), Raman spectroscopy and X-ray diffraction (XRD). It was found that the structure of the nanocrystalline silicon layer (NSL) is dependent of the porosity (void) of the porous alumina layer (PAL) substrate. This structure was performed in two steps, namely the PAL substrate was prepared using sulfuric acid solution attack on an Al foil and then the silicon was deposited by plasma enhanced chemical vapor deposition (PECVD) on it. The optical constants (n and k as a function of wavelength) of the deposited films were obtained using variable angle spectroscopic ellipsometry (SE) in the UV-vis-NIR regions. The SE spectrum of the porous aluminum silicon layer (PASL) was modeled as a mixture of void, crystalline silicon and aluminum using the Cauchy model approximation. The specific surface area (SSA) was estimated and was found to decrease linearly when porosity increases. Based on this full characterization, it is demonstrated that the optical characteristics of the films are directly correlated to their micro-structural properties.     

Chemical modification of the surface of Fe<Subscript>75</Subscript>Si<Subscript>25</Subscript> alloy particles with stearic acid under high-energy ball-milling conditions

The morphology, phase composition and surface structure of Fe₇₅Si₂₅-alloy particles are studied by electron microscopy, X-ray diffraction analysis, and Mössbauer, Auger, IR (infrared) and X-ray photoelectron spectroscopy. The alloy particles used as fillers for the polyethylene matrix are produced by high-energy ball milling in an organic medium with the addition of stearic acid. The addition of stearic acid is shown to promote plasticization of the brittle Fe₇₅Si₂₅ alloy and the formation of a surface layer of no more than 1.5 nm thick, consisting of oxides based on iron and silicon, responsible for the chemisorption of stearic acid on the surface. Chemical modification of the surface of filler particles with an amphiphilic surfactant is carried out to enhance their adhesion in the polymer matrix.     

Microscale steps and micro-nano combined structures by anodizing aluminum

In this paper, we firstly present a novel microscale-step structure fabricated by anodizing aluminum in a mixture of 0.05-0.5 wt% NaCl (HCl), 2 wt% H₃PO₄ and 20 wt% ethanol under potentials of 1-40 V at room temperature. Then, we present two micro-nano combined structures by integrating the microsteps with nanopores through multi-step anodizations. The microstep-nanopore hierarchical structure was obtained by re-anodizing the sample in oxalic acid, and the regular nanopores can be realized on the microscale patterned aluminum surface. The two-layer porous structure was one layer of nanoporous anodic alumina and another layer of micropores by two-step anodization on sample's both sides. These two novel structures can be useful for surface engineering and high flux filtration, respectively. The current fabrication approach broadens the applications of aluminum anodization, and brings a new method for assembling micro-nano structures.     

Self-assembled growth of C60 nanowhiskers on anodic porous alumina membranes

Unique structured claw-like C₆₀ nanowhiskers were fabricated on an anodic porous alumina membrane. Tips of the C₆₀ nanowhiskers are shaped like cusps, which directly extend into the nanopores of the alumina membrane. It is revealed that the surface stress of the alumina membrane with a highly ordered nanopore arrangement due to thermal treatment is responsible for self-assembled growth of the observed C₆₀ nanowhiskers. The ordering of the nanopore arrangement in the anodic porous alumina membrane helps to form the C₆₀ nanowhiskers along the nanopore channels. The shape and structure of the C₆₀ nanowhiskers are promising characteristics for applications in nanodevices such as field-emission tips and nanoprobes. PACS 61.46.+w; 61.48.+c; 33.20.Fb     

Thermal effect on superhydrophobic performance of stearic acid modified ZnO nanotowers

The thermal desorption of stearic acid on superhydrophobic zinc oxide nanotowers has been investigated. The stearic acid passivated zinc oxide nanotowers provide a very high contact angle of ∼173 ± 1.1° with a very low hysteresis of ∼1.4 ± 0.5° due to the presence of a binary structure composed of several nanosteps on each nanotower of height ∼700 nm that eventually reduces the area of contact between the drop and the nanotowers and trapping more air as revealed by the field emission scanning electron microscopy images. The superhydrophobic performance of these nanotowers, however, declines following annealing at elevated temperatures. Fourier transform infrared spectra show a reduction in the intensity of stearic acid -CH_n peaks at elevated temperatures revealing the cause of the decrease in contact angle and confirming the occurrence of thermal desorption at 184 °C. The corresponding activation energy for desorption determined from our data is 0.34 ± 0.05 eV. It is found that the stearic acid has completely disappeared at 350 °C, making the sample hydrophilic.     

Superhydrophobic and icephobic surfaces prepared by RF-sputtered polytetrafluoroethylene coatings

A superhydrophobic and icephobic surface were investigated on aluminum alloy substrate. Anodizing was used first to create a micro-nanostructured aluminum oxide underlayer on the alloy substrate. In a second step, the rough surface was coated with RF-sputtered polytetrafluoroethylene (PTFE or Teflon^®). Scanning electron microscopy images showed a “bird's nest”-like structure on the anodized surface. The RF-sputtered PTFE coating exhibited a high static contact angle of ∼165° with a very low contact angle hysteresis of ∼3°. X-ray photoelectron spectroscopy (XPS) results showed high quantities of CF₃ and CF₂ groups, which are responsible for the hydrophobic behavior of the coatings. The performance of this superhydrophobic film was studied under atmospheric icing conditions. These results showed that on superhydrophobic surfaces ice-adhesion strength was 3.5 times lower than on the polished aluminum substrate.     

Fabrication and anti-frosting performance of super hydrophobic coating based on modified nano-sized calcium carbonate and ordinary polyacrylate

Nano-sized calcium carbonate (CaCO₃) particles were modified by heptadecafluorodecyl trimethoxysilane under acidic water condition. An ordinary polyacrylate prepared via radical copolymerization of methyl methacrylate, butyl acrylate, acrylic acid and β-hydroxyethyl methacrylate was used as the binder to form hydrophobic coatings with the modified CaCO₃. Super hydrophobic coating with water contact angle of 155° was obtained from modified CaCO₃ and the polyacrylate at their weight ratio of 8/2 by a simple procedure. Based on surface analysis by scanning electron microscope (SEM) and X-ray photoelectron spectroscopy (XPS), the super hydrophobicity can be attributed to both the surface microstructure and surface enrichment of fluoroalkyl chains. Due to a low water sliding angle, carbon black powder on super hydrophobic surface was easily removed by rolling water droplet. Furthermore, the anti-frosting performance of different surfaces was investigated, which indicated that the frost formed on superhydrophobic surface was greatly retarded compared with that on bare copper surface. The surface kept super hydrophobicity even after freezing-thawing treatment for 10 times.     

Electronic properties of electrolyte/anodic alumina junction during porous anodizing

The growth of porous oxide films on aluminum (99.99% purity), formed in 4% phosphoric acid was studied as a function of the anodizing voltage (23-53 V) using a re-anodizing technique and transmission electron microscopy (TEM) study. The chemical dissolution behavior of freshly anodized and annealed at 200 °C porous alumina films was studied. The obtained results indicate that porous alumina has n-type semiconductive behavior during anodizing in 4% phosphoric acid. During anodising, up to 39 V in the barrier layer of porous films, one obtains an accumulation layer (the thickness does not exceed 1 nm) where the excess electrons have been injected into the solid producing a downward bending of the conductive and valence band towards the interface. The charge on the surface of anodic oxide is negative and decreases with growing anodizing voltage. At the anodizing voltage of about 39 V, the charge on the surface of anodic oxide equals to zero. Above 39 V, anodic alumina/electrolyte junction injects protons from the electrolyte. These immobile positive charges in the surface layer of oxide together with an ionic layer of hydroxyl ions concentrated near the interface create a field, which produces an upward bending of the bands.     

Deposition of superhydrophobic nanostructured Teflon-like coating using expanding plasma arc

A novel approach was used to grow nanostructured Teflon-like superhydrophobic coatings on stainless steel (SS). In this method Teflon tailings were pyrolyzed to generate fluorocarbon precursor molecules, and an expanding plasma arc (EPA) was used to polymerize these precursors to deposit Teflon-like coating. The coating shows super hydrophobic behavior with water contact angle (WCA) of 165°. The coating was observed to be uniform. It consists of nanostructured (∼80-200 nm) features, which were confirmed by scanning electron microscopy. The chemical bond state of the film was determined by XPS and FTIR, which indicate the dominance of -CF₂ groups in the deposited coating. The combination of nanofeature induced surface roughness and the low surface energy imparted by Teflon-like coating is responsible for the observed superhydrophobic nature.     

Enhanced in vitro biocompatibility of ultrafine-grained biomedical NiTi alloy with microporous surface

Bulk ultrafine-grained Ni_50.8Ti_49.2 alloy (UFG-NiTi) was successfully fabricated by equal-channel angular pressing (ECAP) technique in the present study, and to further improve its surface biocompatibility, surface modification techniques including sandblasting, acid etching and alkali treatment were employed to produce either irregularly roughened surface or microporous surface or hierarchical porous surface with bioactivity. The effect of the above surface treatments on the surface roughness, wettability, corrosion behavior, ion release, apatite forming ability and cytocompatibility of UFG-NiTi alloy were systematically investigated with the coarse-grained NiTi alloy as control. The pitting corrosion potential (E_pit) was increased from 393 mV (SCE) to 704 mV (SCE) with sandblasting and further increased to 1539 mV (SCE) with following acid etching in HF/HNO₃ solution. All the above surface treatment increased the apatite forming ability of UFG-NiTi in varying degrees when soaked them in simulated body fluid (SBF). Meanwhile, both sandblasting and acid etching could promote the cytocompatibility for osteoblasts: sandblasting enhanced cell attachment and acid etching increased cell proliferation. The different corrosion behavior, apatite forming ability and cellular response of UFG-NiTi after different surface modifications are attributed to the topography and wettability of the resulting surface oxide layer.     

Preparation and characterization of slice-like Cu2(OH)3NO3 superhydrophobic structure on copper foil

Superhydrophobic structure was prepared on copper foil via a facile solution-immersion method. Thus slice-like Cu₂(OH)₃NO₃ crystal was prepared on the surface of the copper foil by sequential immersing in an aqueous solution of sodium hydroxide and cupric nitrate. And the superhydrophobic structure was obtained by modifying the slice-like Cu₂(OH)₃NO₃ crystal with 1H,1H,2H,2H-perfluorodecyltriethoxysilane (FAS-17). The morphologies, chemical compositions and states, and hydrophobicity of the surface-modifying films on the copper foil substrates were analyzed by means of scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), and water contact angle measurement. Moreover, the thermal stability of the slice-like structure was also evaluated using thermogravimetric analysis (TGA). It was found that roughening of the copper foil surface helped to increase the hydrophobicity to some extent, but no superhydrophobicity was obtained unless the slice-like Cu₂(OH)₃NO₃ crystal formed on the Cu substrate was modified with 1H,1H,2H,2H-perfluorodecyltriethoxysilane. Besides, the superhydrophobicity of the FAS-17-modified slice-like Cu₂(OH)₃NO₃ structure was closely related to the surface morphology. And this hydrophobic structure retained good superhydrophobic stability at elevated temperature and in long-term storage as well, which should be critical to the application of Cu-matrix materials in engineering.     

Modification of alumina barrier-layer through re-anodization in an oxalic acid solution with fluoride additives

A new simple method for modification of the porous alumina barrier-layer is described and characterized by the voltammetric, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and electrochemical impedance spectroscopy (EIS) techniques. The method is based on re-anodization of porous alumina under galvanostatic conditions in the anodizing bath that, in addition to conventional anodization solution components, contains fluoride salts: (NH₄)₂SiF₆ or NH₄F. During first few minutes of alumina re-anodization, the sharp drop of anodizing voltage was observed, which is indicative of chemical/electrochemical transformations of the alumina barrier-layer. As a result, the scalloped structure of the barrier-layer changes drastically, becoming smooth and finely grained. Upon re-anodization, a significant loss of insulating ability of the barrier-layer and considerable increase in its capacitance were observed, while the variation of the constant phase element was found to be consistent with the oxide film morphology transformations observed by microscopy techniques. All these changes intensify with fluoride concentration increase. Curiously, (NH₄)₂SiF₆ exhibited about three-fold stronger effect on the barrier-layer properties than NH₄F, thus allowing us to hypothesize about possible chemical break up of SiF₆²⁻ anion and the formation of the AlF₃ phase inside the alumina pores.     

Hybrid photonic surface-plasmon-polariton ring resonators for sensing applications

We introduce a hybrid photonic surface plasmon ring resonator which consists of a silicon nitride (Si₃N₄) dielectric traveling-wave ring resonator vertically coupled to a thin layer of metallic strip ring resonator made of Silver (Ag) on top. The cladding is assumed to be porous alumina on top of the metal layer, which provides more surface area for the adsorption of target molecules and their efficient interaction with the surface plasmon wave excited at the metal-cladding interface. Simulations show that this hybrid structure has a large refractive index sensitivity due to the excitation of surface plasmon waves and also a relatively narrow resonance linewidth due to the large quality factor of the photonic ring resonator. The Finite Element method is used to systematically design the hybrid structure and to investigate the performance of the hybrid resonator as a refractive index sensor. The proposed structure is very compact and can be implemented on a chip in an integrated platform. Thus, it can be used for lab-on-a-chip sensing applications and is capable of being spectrally and spatially multiplexed for muti-analyte sensing.     

Fabrication and surface characterization of biomimic superhydrophobic copper surface by solution-immersion and self-assembly

Biomimic superhydrophobic surfaces with contact angle greater than 150° and low sliding angle on copper substrate were fabricated by means of a facile solution immersion and surface self-assembly method. The scanning electron microscopy showed a nanoneedle structure copper surface with sporadic flower-like aggregates after treatment with sodium hydroxide and potassium persulfate solution. X-ray photoelectron spectroscopy and X-ray diffraction results confirmed that the formed nanoneedles were crystallized Cu(OH)₂. And the hydrophilic Cu(OH)₂ surface can be further modified into superhydrophobic through surface self-assembly with dodecanoic acid.