Long term studies on the chemical stability of a superhydrophobic silicone nanofilament coating

We have performed extensive studies on the long term chemical stability of a superhydrophobic coating comprised of silicone nanofilaments. Durability was tested by immersion in various liquid media over a period of 6 months. The coating properties were monitored by static contact angle and sliding angle measurements. Changes in surface topography were examined by scanning electron microscopy. The coatings show an exceptional stability in organic solvents, neutral and mildly acidic aqueous solutions and mildly acidic detergent solutions. The superhydrophobic coating properties are stable for several days in mildly basic and strong acidic solutions but deteriorate fast under strong basic conditions.     

A Thin Liquid Film and Its Effects in an Atomic Force Microscopy Measurement

Recently, it has been observed that a liquid film spreading on a sample surface will significantly distort atomic force microscopy （AFM） measurements. In order to elaborate on the effect, we establish an equation governing the deformation of liquid film under its interaction with the AFM tip and substrate. A key issue is the critical liquid bump height yoc, at which the liquid film jumps to contact the AFM tip. It is found that there are three distinct regimes in the variation of yoc with film thickness H, depending on Hamaker constants of tip, sample and liquid. Noticeably, there is a characteristic thickness H^＊ physically defining what a thin film is; namely, once the film thickness H is the same order as H^＊, the effect of film thickness should be taken into account. The value of H^＊ is dependent on Hamaker constants and liquid surface tension as well as tip radius.     

Scanning probe studies of water nucleation on aluminum oxide and gold surfaces

The nucleation of nanoscale water at surfaces in humid environments is sensitive to several factors, including the details of the surface morphology, ability of the surface to hydrate and the presence of contaminants. Tapping mode atomic force microscopy was used to investigate the nucleation process as a function of relative humidity (RH) on passive aluminum and gold thin films. Films exposed to the ambient environment prior to RH exposure showed discrete structures with lateral sizes ranging from 10 to 100 nm only at RH > 70%. These structures formed preferentially at grain boundaries, triple points and regions with significant topography such as protruding grains. The morphology of the passive aluminum surface is permanently altered at the sites where discrete structures were observed; nodules with heights ranging from 0.5 to 2 nm persist even after reducing the RH to <2%. The gold surface does not show such a permanent change in morphology after reducing the RH. Passive aluminum films exposed to high RH immediately after growth (e.g. no ambient exposure) do not show discrete structures even at the highest RH exposures of 90%, suggesting a hydrophilic surface and the importance of surface hydrocarbon contaminants in affecting the distribution of the water layer.     

Fabrication of PECVD-grown fluorinated hydrocarbon nanoparticles and circular nanoring arrays using nanosphere lithography

Nanosphere lithography (NSL) masks were created by spin-coating of polystyrene particles onto silicon surfaces. Fluorinated hydrocarbon films were coated on the nanosphere lithography masks using plasma-enhanced chemical vapor deposition (PECVD) to obtain ordered arrays of fluorinated hydrocarbon. Atomic force microscope images show hexagonally ordered nanodots of dimension 225 ± 11 nm with a height of 23 ± 4 nm. Every hexagon encloses a circular ring of diameter 540 ± 24 nm having a height and width of 13.5 ± 0.6 nm and 203 ± 16 nm, respectively. FTIR analysis shows two distinct zones of atomic bonding of CH_x and CF_x in the plasma coated ordered fluorinated hydrocarbon films.     

Structures and properties of the polyacrylonitrile fabric coated with ZnO-Ag composites

The polyacrylonitrile (PAN) fabric coated with ZnO-Ag composite was achieved by hydrothermal synthesis techniques and photochemical method. The PAN fabrics coated with ZnO-Ag composite were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared (FT-IR), UV-vis spectrophotometer and fabric induced static tester, respectively. The SEM images revealed the formation of the coating aggregates on the fiber surface. The FT-IR spectra and XRD patterns revealed the chemical structures of the coatings on the PAN fabrics. The results of UV-vis test showed that there was an obvious increase in ultraviolet resistant properties after coating. The antistatic properties results revealed the improvement in the antistatic performance of coated fabrics, attributed to the superior electrical and optical properties of ZnO and Ag.     

Preparation of superhydrophobic membranes by electrospinning of fluorinated silane functionalized poly(vinylidene fluoride)

Fluorinated silane functionalized poly(vinylidene fluoride) (PVDF) is synthesized by graft polymerization of 3-trimethoxylpropyl methylacrylate with PVDF followed by coupling of fluorinated silanes. Flat membrane prepared using this functionalized PVDF has a water contact angle of 140°. Superhydrophobic PVDF membrane with a contact angle larger than 150° is prepared by the electrospinning of the fluorinated silane functionalized PVDF. The morphologies of the membranes are characterized using scanning electron microscopy. The surface composition of the membranes is analyzed using FTIR and the contact angles and water drops on the surface of the membrane are measured using video microscopy.     

Atomic force microscopy study of thermal stability of silver selenide thin films grown on silicon

Silver selenide thin films were grown on silicon substrates by the solid-state reaction of sequentially deposited Se and Ag films of suitable thickness. Transmission electron microscopy and particle-induced X-ray emission studies of the as-deposited films showed the formation of single phase polycrystalline silver selenide from the reaction of Ag and Se films. Atomic force microscopy images of the as-deposited and films annealed at different temperatures in argon showed the film morphology to evolve into an agglomerated state with annealing temperature. The results indicate that when annealed above 473 K, silver selenide films on silicon become unstable and agglomerate through holes generated at grain boundaries.     

Anti-icing performance of superhydrophobic surfaces

This article studies the anti-ice performance of several micro/nano-rough hydrophobic coatings with different surface chemistry and topography. The coatings were prepared by spin-coating or dip coating and used organosilane, fluoropolymer or silicone rubber as a top layer. Artificially created glaze ice, similar to the naturally accreted one, was deposited on the nanostructured surfaces by spraying supercooled water microdroplets (average size ∼80 μm) in a wind tunnel at subzero temperature (−10 °C). The ice adhesion strength was evaluated by spinning the samples in a centrifuge at constantly increasing speed until ice delamination occurred. The results show that the anti-icing properties of the tested materials deteriorate, as their surface asperities seem to be gradually broken during icing/de-icing cycles. Therefore, the durability of anti-icing properties appears to be an important point for further research. It is also shown that the anti-icing efficiency of the tested superhydrophobic surfaces is significantly lower in a humid atmosphere, as water condensation both on top and between surface asperities takes place, leading to high values of ice adhesion strength. This implies that superhydrophobic surfaces may not always be ice-phobic in the presence of humidity, which can limit their wide use as anti-icing materials.     

Structural characterization of nc-Si films grown by low-energy PECVD on different substrates

The knowledge and control of the structural details (texture, crystallite environment and size) of nanocrystalline silicon films is a prerequisite for their proper application in various technological fields. To this purpose, nanocrystalline silicon films grown by low energy plasma enhanced chemical vapour deposition (LEPECVD) on different kinds of substrates were submitted to a systematic characterization using Raman spectroscopy, X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). The results showed how the difference in substrate morphology is responsible for a deep difference in the film structural properties, particularly in the case of high silane dilutions.     

The effect of nitrogen incorporation on surface properties of silicon oxynitride films

In order to investigate the surface heterogeneity of silicon oxynitride films, we observed the nanoscale variation of the surface potential by Kelvin probe force microscopy (KFM), the molecular bonding characteristics by Fourier transform infrared spectrometry (FTIR), and the wetting behavior by contact angle measurement. Nitrogen incorporation into silicon oxynitride films influenced the decrease in the surface potential and the polar component of the surface free energy. We present the first correlation between the nanoscale measurement of the surface potential and the macroscopic measurement of the surface free energy in silicon oxynitride films grown by a standard plasma‐enhanced chemical vapor deposition (PECVD) technique. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Revealing of water surface pollution with liquid marbles

Floating of “liquid marbles” on the surface of water contaminated with organic compounds was studied. Marbles were obtained with spreading of hydrophobic polyvinylidene fluoride particles on the surface of water droplets. Marbles floated stably on the water surface, whereas they were destroyed on the water surfaces contaminated with silicon oil and kerosene. Limiting conditions of floating were studied experimentally with the water/alcohol mixtures.     

Substrate temperature influence on the properties of nanostructured ZnO transparent ultrathin films grown by PLD

Zinc oxide films of 40 nm thickness have been deposited on glass substrates by pulsed laser deposition using an excimer XeCl laser (308 nm) at different substrate temperatures ranging from room temperature to 650 °C. Surface investigations carried out by using atomic force microscopy have shown a strong influence of temperature on the films surface topography. UV-VIS transmittance measurements have shown that our ZnO films are highly transparent in the visible wavelength region, having an average transmittance of ∼90%. The optical band gap of the films was found to be 3.26 eV, which is lower than the theoretical value of 3.37 eV. Besides the normal absorption edge related to the transition between the valence and the conduction band, an additional absorption band was also recorded in the wavelength region around 364 nm (∼3.4 eV). This additional absorption band may be due to excitonic, impurity, and/or quantum size effects. Photoreduction/oxidation in ozone of the ZnO films lead to larger conductivity changes for higher deposition temperature. In conclusion, the ozone sensing characteristics as well as the optical properties of the ZnO thin films deposited by pulsed laser deposition are strongly influenced by the substrate temperature during growth. The sensitivity of the films towards ozone might be enhanced significantly by the control of the films deposition parameters and surface characteristics.     

Structural and electrical properties of zinc oxides thin films prepared by thermal oxidation

We report on zinc oxide (ZnO) thin films (d = 55-120 nm) prepared by thermal oxidation, at 623 K, of metallic zinc films, using a flash-heating method. Zinc films were deposited in vacuum by quasi-closed volume technique onto unheated glass substrates in two arrangements: horizontal and vertical positions relative to incident vapour. Depending on the preparation conditions, both quasi-amorphous and (0 0 2) textured polycrystalline ZnO films were obtained. The surface morphologies were characterized by atomic force microscopy and scanning electron microscopy. By in situ electrical measurements during two heating-cooling cycles up to a temperature of 673 K, an irreversible decrease of electrical conductivity of as flash-oxidized Zn films was revealed. The influence of deposition arrangement and oxidation conditions on the structural, morphological and electrical properties of the ZnO films is discussed.     

Investigation of GaN layer grown on different low misoriented sapphire by MOCVD

GaN layer on c-plane misoriented sapphire, grown by metal organic chemical vapor deposition, has been studied. It was observed that the random and non-uniform distribution of the step was caused by the step reconstruction for GaN grown on 0° sapphire by atomic force microscopy. The image quality parameter analysis of electron back-scatter diffraction indicated that the strains were reduced for GaN grown on 0.2° and 0.3° sapphire, and optical and electrical properties were improved. The electroluminescence intensity of LED grown on 0.2° and 0.3° sapphire was 2 times as that of 0° sapphire.     

Tip-induced local anodic oxidation on p-GaAs surface with non-contact atomic force microscopy

Nano-sized oxide structures resulted from localized electrochemical oxidation induced by a negatively biased atomic force microscopy (AFM) tip operated with the non-contact mode were fabricated on p-GaAs(1 0 0) surface. The geometrical characteristics of the oxide patterns and their dependences on various fabrication parameters, e.g., the anodization time, the biased voltages, the tip scanning rates, as well as the formation mechanism and relevant growth kinetics are investigated. Results indicate that the height of the protruded oxide dots grow exponentially as a function of time in the initial stage of oxidation and soon reaches a maximum height depending linearly with the anodized voltages, in according with the behaviors predicted by space charge limited local oxidation mechanism. In addition, selective micro-Auger analysis of the anodized region reveals the formation of Ga(As)O_x, indicating the prominent role played by the field-induced nanometer-size water meniscus in producing the nanometer-scale oxide dots and bumps on p-GaAs(1 0 0) surface.     

Sliding tribological properties of untreated and PIII-treated PETP

Poly(ethylene terephthalate) (PETP) was treated by plasma immersion ion implantation (PIII or PI³) in nitrogen. The surface changes were characterised by XPS and water contact-angle measurements. Sliding tribological properties of untreated and nitrogen PIII-treated PETP against conventional low carbon structural steel S235 were studied under dry and water-lubricated conditions by a pin-on-disc tribometer.XPS results suggested the evolution of surface composition and bonding towards those of amorphous hydrogenated carbon-nitride. Water contact-angle decreased implying increased surface wettability. At a very low Pv factor (0.0075 MPa m s⁻¹) for the nitrogen PIII-treated PETP the dry friction coefficient was smaller than, while the lubricated friction coefficient was similar to, the corresponding value of the untreated variant. At higher Pv factors (near 0.1 MPa m s⁻¹), however, both the dry and lubricated friction coefficients were higher for the treated sample than for the untreated variant, suggesting an increased adhesion component of friction for the nitrogen PIII-treated PETP in this region.     

Penetration range and backscattering ratio of low-energy electrons in metals

The accuracy of the Ashley's optical-data model [J.C. Ashley, J. Electron Spectrosc. Relat. Phenom. 50 (1990) 323] for describing the energy loss rate and inelastic mean free path of low-energy electrons in Al and Cu has been examined through the use of Ashley's model for calculating the electron penetration range. The latter has also been calculated using the empirical expressions reported by Iskef et al. [Phys. Med. Biol. 28 (1983) 535] and Gryzinski excitation function. The resulting range of penetration is used for determining the electron backscattering coefficients via the use of Vicanek and Urbassek theory [Phys. Rev. B 44 (1991) 7234] where the transport cross-sections are obtained from Rouabah et al. [Appl. Surf. Sci. 255 (2009) 6217] approximation. Besides the electron backscattering coefficients have been calculated from Monte Carlo simulation in which the inelastic scattering processes are handled using Ashley dielectric approach. It is found that the use of Ashley's optical model via Monte-Carlo method gives backscattering coefficients more accurate than those obtained via Vicanek and Urbassek theory. This confirms the accuracy of Ashley's optical model and shows that the Monte-Carlo method is much more accurate and precise than the Vicanek and Urbassek semi-empirical approach.     

Phase-contrast scanning force microscopy and chemical heterogeneity of GR polysulfone ultrafiltration membranes

The surfaces of three commercial urea formaldehyde polysulfone membranes from Dow Denmark^TM (GR51, GR61 and GR81) are characterised both topographically and chemically. Their topography is studied by scanning force microscopy to obtain the corresponding pore-size distributions, which are in fair agreement with nominal molecular weight cut-offs. The composition of the surfaces of the membranes is analysed by X-ray photoelectron spectroscopy. The resulting percentage content of nitrogen, which could be attributed probably to an additive used in the manufacturing process, is shown to correlate with the portion of the total surface with different viscoelastic properties as investigated by using phase-contrast scanning force microscopy. Both parameters are increasing for membranes with decreasing molecular weight cut-off. Also, the additive seems to be more sparsely distributed for the membranes with bigger pores, according to fractal analysis. Finally, all the membranes are very similarly wettable. Received: 22 May 2001 / Accepted: 30 May 2001 / Published online: 25 July 2001     

Thermal stability of SiGe films on an ultra thin Ge buffer layer on Si grown at low temperature

The thermal stability of SiGe films on an ultra thin Ge buffer layer on Si fabricated at low temperature has been studied. The microstructure and morphology of the samples were investigated by high-resolution X-ray diffraction, Raman spectra and atomic force microscopy, and using a diluted Secco etchant to reveal dislocation content. After thermal annealing processing, it is observed that undulated surface, threading dislocations (TDs) and stacking faults (SFs) appeared at the strained SiGe layer, which developed from the propagation of a misfit dislocation (MD) during thermal annealing, and no SFs but only TDs formed in strain-relaxed sample. And it is found that the SiGe films on the Ge layer grown at 300 °C has crosshatch-free surface and is more stable than others, with a root mean square surface roughness of less than 2 nm and the threading dislocation densities as low as ∼10⁵ cm⁻². The results show that the thermal stability of the SiGe films is associated with the Ge buffer layer, the relaxation extent and morphology of the SiGe layer.     

Stable superhydrophobic surfaces over a wide pH range

A stable superhydrophobic surface was fabricated by solidifying poly(epoxy-terminated polydimethylsiloxane-co-bisphenol A) [P(ETPDMS-co-BPA)] copolymer on a rough substrate. The low surface energy of the copolymer and the geometric structure at micrometer scale of the surface contribute to the superhydrophobic property. The as-prepared surface shows stable superhydrophobicity over a wide pH range (1-14) and the wettability is excellent stable to heating, water, corrosive solution and organic solvent treatments. The procedure is simple and time-saving as well as utilizing non-fluorine-containing compounds.