Promoted water transport across graphene oxide-poly(amide) thin film composite membranes and their antibacterial activity

Hybrid composite membranes have great potential for desalination applications since water transport can be favorably promoted by selective diffusion at the interface between matrix and reinforcement materials. In this paper, graphene oxide nano-sheets were successfully incorporated across 200nm thick poly(amide) films by interfacial polymerization to form novel thin-film composite membranes. The impact of the graphene oxide on the morphology, chemistry, and surface charge of the ultra-thin poly(amide) layer, and the ability to desalinate seawater was investigated. The graphene oxide nano-sheets were found to be well dispersed across the composite membranes, leading to a lower membrane surface energy and an enhanced hydrophilicity. The iso-electric point of the samples, key to surface charge repulsion during desalination, was found to be consistently shifted to higher pH values with an increasing graphene oxide content. Compared to a pristine poly(amide) membrane, the pure water flux across the composite membranes with 0.12wt.% of graphene oxide was also found to increase by up to 80% from 0.122 to 0.219L·μm·m-2·h-1·bar-1 without significantly affecting salt selectivity. Furthermore, the inhibitory effects of the composite membrane on microbial growth were evaluated and the novel composite membranes exhibited superior anti-microbial activity and may act as a potential anti-fouling membrane material.

Reflectance response of tapered optical fiber coated with graphene oxide nanostructured thin film for aqueous ethanol sensing

In this work, optical sensing performance of tapered multimode fiber tip coated with graphene oxide (GO) nanostructured thin film towards aqueous ethanol with different concentrations is investigated. The tapering process of the optical fiber is done by a glass processing machine. The multimode optical fiber tip is dip-coated with GO and annealed at 70 °C to enhance the binding of the nanomaterials to the silica fiber. FESEM, Raman microscopy and XRD analyses are performed to micro-characterize the GO thin films. The morphology of the GO is observed to be in sheets forms. The reflectance response of the GO coated fiber tip is compared with the uncoated tip. The measurements are taken using a spectrophotometer in the optical wavelength range of 550-720 nm. The reflectance response of the GO coated fiber tip reduced proportionally, upon exposure to ethanol with concentration range of 5-80%. The dynamic response of the developed sensor showed strong reversibility and repeatability when it is exposed to ethanol with concentrations of 5%, 20% and 40% in distilled water. At room temperature, the sensor shows fast response and recovery as low as 19 and 25 s, respectively. © 2014 Elsevier B.V.

The reduction of oxygen on iron(II) oxide/poly(3,4-ethylenedioxythiophene) composite thin film electrodes

© 2014 Elsevier Ltd. All rights reserved. Conducting polymers (CPs) are currently being investigated for use in many applications owing to their abilities to catalyze a wide range of electrochemical reactions and act as an effective electrode support for various inorganic and organic electrocatalyst materials. Here, we have found that the deposition of poly(3,4-ethylenedioxythiophene) (PEDOT) through the use of an established base-inhibited chemical vapor-phase polymerization (VPP) procedure using an iron(III) tosylate oxidant results in the co-deposition of electrocatalytic iron(II) oxide species within the film. The presence of these species accounts for the 2-electron reduction of hydrogen peroxide that occurs on these electrodes during the series 4-electron oxygen reduction reaction. Furthermore, this realization leads to the possibility of fabricating thin film inorganic/CP composites of various compositions through careful choice of oxidant in a facile, one-step process. A combination of in situ Raman (487.77 nm laser) and in situ UV-Vis spectroscopy was used to probe the oxidation state of PEDOT in the thin film composite electrodes while reducing oxygen in alkaline conditions. These measurements show that the 2-electron electroreduction of hydrogen peroxide (or HO2 -) occurs only on the iron(II) oxide species in a reaction that is facilitated by an effective electron transfer from the delocalized electron orbitals of the PEDOT matrix. This approach could potentially be used in situ to monitor the electrocatalyst/electrode interface quality of conducting polymer-supported electrocatalysts.

Hydrolysis of bis((trimethylsilyl)methyl)tin dihalides. Crystallographic and spectroscopic study of the hydrolysis pathway

The synthesis and characterization by multinuclear NMR spectroscopy of the diorganotin dihalides (Me₃SiCH₂)₂SnX₂ (1, X = Cl; 2, X = Br), the diorganotin dichloride water adduct (Me₃SiCH₂)₂SnCl₂·H₂O (1a), the dimeric tetraorganodistannoxanes [(Me₃SiCH₂)₂(X)SnOSn(Y)(CH₂SiMe₃)₂]₂ (3, X = Y = Cl; 4, X = Br, Y = OH; 5, X = Br, Y = F; 6, X = Y = OH; 8, X = Cl, Y = OH), and the molecular diorganotin oxide cyclo-[(Me₃SiCH₂)₂SnO]₃ (7) are reported. The structures in the solid state of compounds 1a, 3, 6, and 7 were determined by single-crystal X-ray analysis. In toluene solution, the hydroxy-substituted tetraorganodistannoxane 6 is in equilibrium with the diorganotin oxide 7 and water. The eight-membered diorganotin oxide cyclo-[(Me₃SiCH₂)₂SnO]₄ (7a) is proposed to be involved in this equilibrium. On the basis of the results of this and previous works, a general hydrolysis pathway is developed for diorganotin dichlorides containing reasonably bulky substituents.

Reducing the macroparticle content of cathodic arc evaporated TiN coatings

Cathodic arc evaporation (CAE) is a widely used technique for generating highly ionised plasma from which hard, wear-resistant PVD coatings can be deposited. A major drawback of this technique is the emission of micrometer-sized droplets of cathode material from the arc spot, which are commonly referred to as ‘macroparticles’. In this study, the effect of cathode poisoning was investigated as a method to reduce the number of macroparticles in PVD coatings. While the study focuses on the reduction of macroparticles in titanium nitride coatings, the outcomes and key findings can be broadly applied to the cathodic arc process, in particular, for the reduction of macroparticles in more advanced CAE coatings. The results support earlier findings that have shown that poisoning of the cathode can reduce the number of macroparticles emitted from the arc spot. The results of glow discharge optical emission spectroscopy (GD-OES) showed that the titanium content of the coatings varied little between the respective coatings despite changes in the deposition pressure from 0.1 to 1.2 Pa. The GD-OES results also showed the presence of oxide contamination at the surface of the coatings, which was significantly reduced with increasing deposition pressure. The coatings were also deposited onto high-speed steel twist drills to compare the metal-cutting performance when dry drilling a workpiece of cast iron. The results of the drill tests showed that tool life increased with a reduction in the number of macroparticles.

Effects of undoped and manganese-doped zinc oxide nanoparticles on the colour fading of dyed polyester fabrics

This paper describes the effects of applying coatings of an acrylic polymer containing nanoparticles of zinc oxide (ZnO) on the fading rate in artificial sunlight of polyester fabrics dyed with disperse dyes containing anthraquinone and benzopyran chromophores. Factors affecting the transparency and UV absorbance of the coatings are discussed. Removing the UV component of sunlight with ZnO nanoparticles markedly decreased the fading rate of the dyes, provided the polymer/ZnO film was not in direct contact with the fabric. When the treatment was applied directly to the fabrics, however, the protection against colour fading was different for the two dyes studied. Whereas the rate of colour fading of a benzopyran dye, of relatively low lightfastness, was decreased by the polymer-ZnO film, the treatment increased the fading rate of the dye of higher lightfastness, based on anthraquinone. This effect has been attributed to the generation of reactive oxygen species (ROS) when ZnO is exposed to UV. The effect of decreasing the photoactivity of ZnO by doping with manganese has been examined. For the benzopyran dye, the UV protection was greatly increased, whereas a much smaller improvement was found for the anthraquinone-based dye.

Inverse opal gas sensors : Zn(II)-doped tin dioxide systems for low temperature detection of pollutant gases

Focusing here on the effects of zinc doping in a nanocrystalline matrix of tin dioxide, inverse opal prototype sensors are presented and extensively studied as superior candidates for gas sensing applications. Courtesy of factors including controlled porosity, enhanced surface to volume ratio and homogeneous dispersion of species in the crystalline lattice assured by the sol–gel technique, prototype sensors were prepared with high dopant ratios in a range of new compositions. Exploiting their high sensitivities to low-gas concentrations at low working temperatures, and thanks to the presented templated sol–gel approach, the prepared sensors open up new frontiers in compositional control over the sensing oxide materials, consequently widening the possibilities available in on-demand gas sensor synthesis.

Polymer coatings containing nano particles of zinc oxide for the UV protection of dyed polyester fabrics

The useful life of many outdoor textile products is limited by degradation caused by exposure to sunlight, in particular by the ultra violet component (below 400 nm). The degradation results in fading of colours and also loss of physical properties, such as tear strength and abrasion resistance. Degradation can be decreased with UV absorbers, often used in conjunction with antioxidants or free radical quenchers. The protection afforded by these organic compounds is, however, limited as they are ultimately destroyed by the UV radiation they absorb.
An alternative approach is to coat fabrics with a polymer containing an inorganic UV absorber, such as zinc oxide. The inherent stability of zinc oxide would be expected to provide a protective effect over a much longer period than can be achieved with an organic UV absorber. A possible disadvantage of zinc oxide when applied in a polymer film is that absorption and scattering of visible light can produce hazy films and, hence, an unacceptable change in fabric appearance.
This poster paper examines the possibility of using nano particles of zinc oxide dispersed in acrylic polymers for protecting dyed polyester fabrics against sunlight fading. Factors affecting both UV absorbance and film clarity will be discussed. The possibility will also be examined that the protective effect may be reduced in some circumstances by reactive oxygen species, generated by the interaction of UV with zinc oxide in the presence of air and water.

The nature of the surface film on steel treated with cerium and lanthanum cinnamate based corrosion inhibitors

The corrosion inhibition mechanisms of new cerium and lanthanum cinnamate based compounds have been investigated through the surface characterisation of the steel exposed to NaCl solution of neutral pH. Attenuated Total Reflectance-Fourier Transform Infrared (ATR-FTIR) spectroscopy was used to identify the nature of the deposits on the metal surface and demonstrated that after accelerated tests the corrosion product commonly observed on steel (i.e. lepidocrocite, γ-FeOOH) is absent. The cinnamate species were clearly present on the steel surface upon exposure to NaCl solution for short periods and appeared to coordinate through the iron. At longer times the Rare Earth Metal (REM) oxyhydroxide species are proposed to form as identified through the bands in the 1400–1500 cm⁻¹ region. These latter bands have been previously assigned to carbonate species adsorbed onto REM oxyhydroxide surfaces. The protection mechanism appears to involve the adsorption of the REM–cinnamate complex followed by the hydrolysis of the REM to form a barrier oxide on the steel surface.

New insights into the fundamental chemical nature of ionic liquid film formation on magnesium alloy surfaces

Ionic liquids (ILs) based on trihexyltetradecylphosphonium coupled with either diphenylphosphate or bis(trifluoromethanesulfonyl)amide have been shown to react with magnesium alloy surfaces, leading to the formation a surface film that can improve the corrosion resistance of the alloy. The morphology and microstructure of the magnesium surface seems critical in determining the nature of the interphase, with grain boundary phases and intermetallics within the grain, rich in zirconium and zinc, showing almost no interaction with the IL and thereby resulting in a heterogeneous surface film. This has been explained, on the basis of solid-state NMR evidence, as being due to the extremely low reactivity of the native oxide films on the intermetallics (ZrO₂ and ZnO) with the IL as compared with the magnesium-rich matrix where a magnesium hydroxide and/or carbonate inorganic surface is likely. Solid-state NMR characterization of the ZE41 alloy surface treated with the IL based on (Tf)₂N− indicates that this anion reacts to form a metal fluoride rich surface in addition to an organic component. The diphenylphosphate anion also seems to undergo an additional chemical process on the metal surface, indicating that film formation on the metal is not a simple chemical interaction between the components of the IL and the substrate but may involve electrochemical processes.

Stability of oxide films formed on mild steel in turbulent flow conditions of alkaline solutions at elevated temperatures

In the industries involving alkaline solutions in different process streams, the nature and stability of oxide films formed on the metallic surfaces determine the rates of erosion–corrosion of the equipment. In the present study the characteristics of the oxide films formed on AISI 1020 steel in a 2.75 M sodium hydroxide solution at temperatures up to 175°C, have been investigated by employing electrochemical techniques of cyclic voltammetry and chronoamperometry. The experiments were carried out in an autoclave system based upon a ‘rotating cylinder electrode’ geometry to determine the effects of turbulence on the stability of the films. The results suggest that little protection is afforded in the active region (at about −0.8 V_SHE). In the passive region at low potentials (−0.6 V to −0.4 V_SHE), it appears the films are compact and more stable, and therefore provide good protection. At higher potentials (>−0.4 V_SHE) in the passive region, the results suggest that film formation and dissolution occur simultaneously and the increase in temperature and turbulence causes a breakdown of the passive film resulting in a situation similar to nonprotective magnetite growth.

Synthesis of high surface area amorphous tin-zinc oxides by a sol-gel method

A new method to synthesize conducting oxide nanoparticles with low photocatalytic activity was investigated. Initially, the preparation of amorphous ZnO-SnO2 solid solution nanoparticles was studied using a sol-gel technique. It was found that X-ray amorphous nanopowders with low photocatalytic activity were produced when the precipitates were heat treated below 500 °C. However, FT-IR data showed that the sample may not be an oxide semiconductor. A mixture of ZnO and SnO2 crystalline nanoparticles was also produced at 800 °C and found to have much reduced photoactivity than commercial ZnO nanoparticles having a similar specific surface area.

Electrophoretic deposition of YSZ thin-film electrolyte for SOFCs utilizing electrostatic-steric stabilized suspensions obtained via high energy ball milling

This manuscript describes a facile alternative route to make thin-film yttria-stabilized zirconia (YSZ) electrolyte by liquid-phase assisted electrophoretic deposition utilizing electrostatic-steric stabilized YSZ suspension followed by sintering. Very fine YSZ particles in ball-milled suspension facilitate their sustained dispersion through electrostatic mechanism as evidenced by their higher zeta potentials. Binder addition into the ball-milled suspension is also demonstrated to contribute complementary steric hindrance effects on suspension stability. As the consequence, the film quality and sinterability improve in the sequence of film made from non ball-milled suspension, film made from ball-milled suspension and film made from ball-milled suspension with binder addition. The specific deposition mechanisms pertaining to each suspension are also postulated and discussed below. A very thin dense electrolyte layer of ∼10 μm can be achieved via electrophoretic deposition route utilizing ball-milled suspension and binder addition. This in turn, makes the electrolyte resistance a more negligible part of the overall cell resistance. Further on, we also tested the performance of SOFC utilizing as-formed 10 μm YSZ electrolyte i.e. YSZ-NiO|YSZ|LSM (La0.8Sr0.2MnO3-δ), whereby a maximum power density of ∼850 mW cm−2 at 850 °C was demonstrated.