Adsorption of anionic dyes on a reversibly swelling cationic superabsorbent polymer

A cationic monomer 2-(methacryloyloxy)ethyl]trimethylammonium chloride was polymerized using N,N'-methylenebisacrylamide as the crosslinker to obtain a cationic superabsorbent polymer (SAP). This SAP was characterized by Fourier transform-infrared spectroscopy, and the equilibrium swelling capacity was determined by swelling in water. The SAP was subjected to cyclic swelling/deswelling in water and NaCl solution. The conductivity of the swelling medium was monitored during the swelling/deswelling and was related to the swelling/deswelling characteristics of the SAP. The adsorption of five anionic dyes of different classes on the SAP was carried out and was found to follow the first-order kinetics. The Langmuir adsorption isotherms were found to fit the equilibrium adsorption data. The dye adsorption capacity of the SAP synthesized in this study was higher than that obtained for other hydrogels reported in the literature. (c) 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

Removal of unwanted fluid

This work is concerned with the removal of unwanted fluid through the source-sink pair. The source consists of fluid issuing out of a nozzle in the form of a jet and the sink is a pipe that is kept some distance from the source pipe. Of concern is the percentage of source fluid sucked through the sink. The experiments have been carried in a large glass water tank. The source nozzle diameter is 6 mm and the sink pipe diameter is either 10 or 20 mm. The horizontal and vertical separations and angles between these source and sink pipes are adjustable. The flow was visualized using KMnO4 dye, planer laser induced fluorescence and particle streak photographs. To obtain the effectiveness (that is percentage of source fluid entering the sink pipe), titration method is used. The velocity profiles with and without the sink were obtained using particle image velocimetry. The sink flow rate to obtain a certain effectiveness increase dramatically with lateral separation. The sink diameter and the angle between source and the sink axes don't influence effectiveness as much as the lateral separation.

Study of Submerged Jet for Suction of Fluid

This paper deals with the study of a submerged jet for the suction of unwanted fluid. This submerged jet is caused by the fluid coming out from a source. The presence of a sink in front of this source facilitates the suction of the fluid depending upon the source and sink flow rates, the axial and lateral separations of the source and sink, and the angle between the axes of the source and sink. The main purpose is the determination of the sink flow rate for 100% removal of the source fluid as a function of these parameters. The experiments have been carried using a source nozzle 6 mm in diameter and two sizes for the sink pipe diameter: 10 mm and 20 mm. The main diagnostics used are flow visualization using dye and particle image velocimetry (PIV). The dependence of the required suction flow rate to obtain 100% effectiveness on the suction tube diameter and angle is relatively weak compared to the lateral separation. DOI: 10.1115/1.4007266]

Photocatalytic degradation with combustion synthesized WO3 and WO3-TiO2 mixed oxides under UV and visible light

The photocatalytic activity of commercial titanium dioxide under UV and visible radiation was improved by composites of tungsten trioxide (WO3) with TiO2. WO3 was prepared by solution combustion synthesis and the mixed oxides/composites of WO3-TiO2 were prepared in different weight ratios (0, 0.10, 0.15, 0.20, 0.25, 0.50, 0.75, and 1) by physical mixing. These catalysts were characterized by XRD, DRS, BET, SEM, TEM, pH drift method, TGA and photoluminescence. The photocatalytic activity varies with the WO3 loading in the composites. The optimum loading of WO3 in the composites was found to be 15 wt% for both UV and visible radiation. This loading showed faster dye degradation rate than commercial TiO2 (TiO2-C) and WO3 (WO3-C). The effect of initial concentrations of methylene blue (MB) and orange G (OG) and the effect of the functional group on dye degradation was studied with both anionic and cationic dyes with 15 wt% WO3-TiO2. (C) 2012 Elsevier B.V. All rights reserved.

Composite cyclodextrin-calcium carbonate porous microparticles and modified multilayer capsules: novel carriers for encapsulation of hydrophobic drugs

Novel composite cyclodextrin (CD)-CaCO3 spherical porous microparticles have been synthesized through Ca2+-CD complex formation, which influences the crystal growth of CaCO3. The CDs are entrapped and distributed uniformly in the matrix of CaCO3 microparticles during crystallization. The hydrophobic fluorescent molecules coumarin and Nile red (NR) are efficiently encapsulated into these composite CD-CaCO3 porous particles through supramolecular inclusion complexation between entrapped CDs and hydrophobic molecules. Thermogravimetric (TGA) and infrared spectroscopy (IR) analysis of composite CD-CaCO3 particles reveals the presence of large CDs and their strong interaction with calcium carbonate nanoparticles. The resulting composite CD-CaCO3 microparticles are utilized as sacrificial templates for preparation of CD-modified layer-by-layer (LbL) capsules. After dissolution of the carbonate core, CDs are retained in the interior of the capsules in a network fashion and assist in the encapsulation of hydrophobic molecules. The efficient encapsulation of the hydrophobic fluorescent dye, coumarin, was successfully demonstrated using CD-modified capsules. In vitro release of the encapsulated coumarin from the CD-CaCO3 and CD-modified capsules has been demonstrated.

Resonance raman detection and estimation in the aqueous phase using water dispersible cyclodextrin: reduced-graphene oxide sheets

Resonance Raman spectroscopy is a powerful analytical tool for detecting and identifying analytes, but the associated strong fluorescence background severely limits the use of the technique. Here, we show that by attaching beta-cyclodextrin (beta-CD) cavities to reduced graphene-oxide (rGO) sheets we obtain a water dispersible material (beta-CD: rGO) that combines the hydrophobicity associated with rGO with that of the cyclodextrin cavities and provides a versatile platform for resonance Raman detection. Planar aromatic and dye molecules that adsorb on the rGO domains and nonplanar molecules included within the tethered beta-CD cavities have their fluorescence effectively quenched. We show that it is possible using the water dispersible beta-CD: rGO sheets to record the resonance Raman spectra of adsorbed and included organic chromophores directly in aqueous media without having to extract or deposit on a substrate. This is significant, as it allows us to identify and estimate organic analytes present in water by resonance Raman spectroscopy.

A multifold reduction in the transition Reynolds number, and ultra-fast mixing, in a micro-channel due to a dynamical instability induced by a soft wall

A dynamical instability is observed in experimental studies on micro-channels of rectangular cross-section with smallest dimension 100 and 160 mu m in which one of the walls is made of soft gel. There is a spontaneous transition from an ordered, laminar flow to a chaotic and highly mixed flow state when the Reynolds number increases beyond a critical value. The critical Reynolds number, which decreases as the elasticity modulus of the soft wall is reduced, is as low as 200 for the softest wall used here (in contrast to 1200 for a rigid-walled channel) The instability onset is observed by the breakup of a dye-stream introduced in the centre of the micro-channel, as well as the onset of wall oscillations due to laser scattering from fluorescent beads embedded in the wall of the channel. The mixing time across a channel of width 1.5 mm, measured by dye-stream and outlet conductance experiments, is smaller by a factor of 10(5) than that for a laminar flow. The increased mixing rate comes at very little cost, because the pressure drop (energy requirement to drive the flow) increases continuously and modestly at transition. The deformed shape is reconstructed numerically, and computational fluid dynamics (CFD) simulations are carried out to obtain the pressure gradient and the velocity fields for different flow rates. The pressure difference across the channel predicted by simulations is in agreement with the experiments (within experimental errors) for flow rates where the dye stream is laminar, but the experimental pressure difference is higher than the simulation prediction after dye-stream breakup. A linear stability analysis is carried out using the parallel-flow approximation, in which the wall is modelled as a neo-Hookean elastic solid, and the simulation results for the mean velocity and pressure gradient from the CFD simulations are used as inputs. The stability analysis accurately predicts the Reynolds number (based on flow rate) at which an instability is observed in the dye stream, and it also predicts that the instability first takes place at the downstream converging section of the channel, and not at the upstream diverging section. The stability analysis also indicates that the destabilization is due to the modification of the flow and the local pressure gradient due to the wall deformation; if we assume a parabolic velocity profile with the pressure gradient given by the plane Poiseuille law, the flow is always found to be stable.

Ethylenediamine assisted synthesis of wurtzite zinc sulphide nanosheets and porous zinc oxide nanostructures: near white light photoluminescence emission and photocatalytic activity under visible light irradiation

Porous fungus-like ZnO nanostructures have been synthesized by simple thermal annealing of the hydrothermally synthesized sheet-like ZnS(en)(0.5) complex precursor in air at 600 degrees C. Structural and morphological changes occurring during ZnS(en)(0.5) -> ZnS -> ZnO transformations have been observed closely by annealing the as-synthesized precursor at 100-600 degrees C. Wurtzite ZnS nanosheets and ZnS-ZnO composites are obtained at temperatures of 400 degrees C and 500 degrees C, respectively. Thermal decomposition and oxidation of the ZnS(en) 0.5 nanosheets have been confirmed by differential scanning calorimetry and thermo-gravimetric analysis. The visible light driven photocatalytic degradation of methylene blue dye has been demonstrated in the synthesized samples. ZnS-ZnO composite shows the highest dye degradation efficiency of 74% due to the formation of surface complex as well as higher visible light absorption as a result of band-gap narrowing effect. The porous ZnO nanostructures show efficient visible photoluminescence (PL) emission with a colour coordinate of (0.29, 0.35), which is close to that of white light (0.33, 0.33). The efficient visible PL emission as well as visible light driven photocatalytic activity of the materials synthesized in the present work might be very attractive for their applications in future optoelectronic devices, including in white light emitting devices.

Unsteady separation and vortex shedding from a laminar separation bubble over a bluff body

Boundary layers are subject to favorable and adverse pressure gradients because of both the temporal and spatial components of the pressure gradient. The adverse pressure gradient may cause the flow to separate. In a closed loop unsteady tunnel we have studied the initiation of separation in unsteady flow past a constriction (bluff body) in a channel. We have proposed two important scalings for the time when boundary layer separates. One is based on the local pressure gradient and the other is a convective time scale based on boundary layer parameters. The flow visualization using a dye injection technique shows the flow structure past the body. Nondimensional shedding frequency (Strouhal number) is calculated based on boundary layer and momentum thicknesses. Strouhal number based on the momentum thickness shows a close agreement with that for flat plate and circular cylinder.

Combining indentation and diffusion couple techniques for combinatorial discovery of high temperature shape memory alloys

We demonstrate the possibility of accelerated identification of potential compositions for high-temperature shape memory alloys (SMAs) through a combinatorial material synthesis and analysis approach, wherein we employ the combination of diffusion couple and indentation techniques. The former was utilized to generate smooth and compositionally graded inter-diffusion zones (IDZs) in the Ni-Ti-Pd ternary alloy system of varying IDZ thickness, depending on the annealing time at high temperature. The IDZs thus produced were then impressed with an indenter with a spherical tip so as to inscribe a predetermined indentation strain. Subsequent annealing of the indented samples at various elevated temperatures, T-a, ranging between 150 and 550 degrees C allows for partial to full relaxation of the strain imposed due to the shape memory effect. If T-a is above the austenite finish temperature, A(f), the relaxation will be complete. By measuring the depth recovery, which serves as a proxy for the shape recovery characteristic of the SMA, a three-dimensional map in the recovery temperature composition space is constructed. A comparison of the published Af data for different compositions with the Ta data shows good agreement when the depth recovery is between 70% and 80%, indicating that the methodology proposed in this paper can be utilized for the identification of promising compositions. Advantages and further possibilities of this methodology are discussed.

Tripodal Bile Acid Architectures Based on a Triarylphosphine Oxide Core Obtained by Copper-Catalysed 1,3]-Dipolar Cycloaddition: Synthesis and Preliminary Aggregation Studies

We report the synthesis and aggregation behaviour of new water-soluble, bile acid derived tripodal architectures based on a core derived from triphenylphosphine oxide. We employed the well-established copper-catalysed 1,3]-dipolar cycloaddition (CuAAC) for the construction of these tripodal molecules. The aggregation behaviour of these molecules in aqueous media was studied by different analytical methods such as dye solubilisation, dynamic light scattering, NMR and AFM. These molecular architectures also offer an additional advantage in aiding understanding of the influence of the nature of the bile acid backbone and of the configuration at the steroid C-3 position in these architectures; to the best of our knowledge this has not been reported in the literature. The unique gelation properties of the -derivatives were explained through molecular modelling studies and the mechanical behaviour of these gels was studied by rheology experiments.

Quantum-Confined ZnO Nanoshell Photoanodes for Mesoscopic Solar Cells

We present a photoanode for dye-sensitized solar cell (DSC) based on ZnO nanoshell deposited by atomic layer deposition at 150 degrees C on a mesoporous insulating template. An ultrathin layer of ZnO between. 3 and 6 nm, which exhibits quantum confinement effect, is found to be sufficient to transport the photogenerated electrons to the external contacts and exhibits near-unity collection efficiency. A 6 nm ZnO nanoshell on a 2.5 mu m mesoporous nanoparticle Al2O3 template yields photovoltaic power conversion efficiency (PCE) of 4.2% in liquid DSC. Perovskite absorber (CH3NH3PbI3) based solid state solar cells made with similar ZnO nanostructures lead to a high PCE of 7%.

Morphology controlled synthesis of wurtzite ZnS nanostructures through simple hydrothermal method and observation of white light emission from ZnO obtained by annealing the synthesized ZnS nanostructures

A controllable synthesis of phase pure wurtzite (WZ) ZnS nanostructures has been reported in this work at a low temperature of similar to 220 degrees C using ethylenediamine as the soft template and by varying the molar concentration of zinc to sulphur precursors as well as by using different precursors. A significant reduction in the formation temperature required for the synthesis of phase pure WZ ZnS has been observed. A strong correlation has been observed between the morphology of the synthesized ZnS nanostructures and the precursors used during synthesis. It has been found from Scanning Electron Microscope (SEM) and Transmission Electron Microscope (TEM) image analyses that the morphology of the ZnS nanocrystals changes from a block-like to a belt-like structure having an average length of similar to 450 nm when the molar ratio of zinc to sulphur source is increased from 1 : 1 to 1 : 3. An oriented attachment (OA) growth mechanism has been used to explain the observed shape evolution of the synthesized nanostructures. The synthesized nanostructures have been characterized by the X-ray diffraction technique as well as by UV-Vis absorption and photoluminescence (PL) emission spectroscopy. The as-synthesized nanobelts exhibit defect related visible PL emission. On isochronal annealing of the nanobelts in air in the temperature range of 100-600 degrees C, it has been found that white light emission with a Commission Internationale de I'Eclairage 1931 (CIE) chromaticity coordinate of (0.30, 0.34), close to that of white light (0.33, 0.33), can be obtained from the ZnO nanostructures obtained at an annealing temperature of 600 degrees C. UV light driven degradation of methylene blue (MB) dye aqueous solution has also been demonstrated using as-synthesized nanobelts and similar to 98% dye degradation has been observed within only 40 min of light irradiation. The synthesized nanobelts with visible light emission and having dye degradation activity can be used effectively in future optoelectronic devices and in water purification for cleaning of dyes.

Effect of thermal annealing on dual photoluminescence emission characteristics of chemically synthesized uncapped Mn2+ doped ZnS quantum dots

Dual photoluminescence (PL) emission characteristics of Mn2+ doped ZnS (ZnS:Mn) quantum dots (QDs) have drawn a lot of attention recently. However, here we report the effect of thermal annealing on the PL emission characteristics of uncapped ZnS:Mn QDs of average sizes similar to 2-3 nm, synthesized by simple chemical precipitation method by using de-ionized (DI) water at room temperature. As-synthesized samples show dual PL emissions, having one UV PL band centred at similar to 400 nm and the other in the visible region similar to 610 nm. But when the samples are isochronally annealed for 2 h at 100-600 degrees C temperature range in air, similar to 90% quenching of Mn2+ related visible PL emission intensity takes place at the annealing temperature of 600 degrees C. X-ray diffraction data show that the as-synthesized cubic ZnS has been converted to wurtzite ZnO at 600 degrees C annealing temperature. The nanostructural properties of the samples are also determined by transmission electron micrograph, electron probe micro-analyser and UV-vis spectrophotometry. The photocatalytic property of the annealed ZnS:Mn sample has been demonstrated and photo-degradation efficiency of the as-synthesized and 600 degrees C annealed ZnS:Mn sample has been found out to be similar to 35% and similar to 61%, respectively, for the degradation of methylene blue dye under visible light irradiation. The synthesized QDs may find significant applications in future optoelectronic devices. (C) 2014 Elsevier B.V. All rights reserved.

Synthesis and photocatalytic performance of quasi-fibrous ZnO

The combustion of oxidizer zinc nitrate and fuel oxalic acid results in quasi-fibrous zinc oxide. The processing parameters including oxidizer to fuel ratio, time and temperature were optimized for the resultant crystal structure and morphology. Pure hexagonal phase formation does not depend on the fuel ratio, but a stoichiometric ratio of oxidizer to fuel at 450 degrees C and 30 min results in highly crystalline ZnO with 3 mu m length and 0.5 mu m width. This quasi-fiber originates from partial fusion of near spherical, similar to 60 nm particles during the rapid rate of reaction in the combustion process. Transmission electron microscopic analysis confirms the anisotropic primary particle orientation and pore distribution within the developed quasi-fibrous particles. The degradation of methyl orange was assessed by degrading the dye in the presence of the synthesized ZnO (2.95 eV) under both UV and visible light. Quasi-fibrous zinc oxide exhibits effective photocatalytic efficiency under visible light irradiation.