Enhanced photocatalytic efficiency of AuPd nanoalloy decorated ZnO-reduced graphene oxide nanocomposites

Inhibition of electron-hole pair recombination is the most desirable solution for stimulating photocatalytic activity in semiconductor nanostructures. To implement this, herein we study the photocatalytic efficiency of elemental Au, Pd and bimetallic AuPd nanoalloy decorated pristine and reduced graphene oxide (RGO) hybridized ZnO nanorods for degrading rhodamine 6G (R6G) dye. Fabrication of Au, Pd and AuPd nanoalloy on pristine and RGO modified ZnO nanorods is simple and more importantly surfactant or polymer free. AuPd nanoalloyed ZnO-RGO nanocomposites exhibit higher photocatalytic activity for degrading dye than both Au and Pd hybridized ones, indicating the promising potential of bimetallic nanoalloys over elemental components. A non-monotonic dependence on the composite composition was found by analyzing photodegradation efficiency of a series of ZnO-RGO-AuPd hybrid nanostructures with different weight percentages of RGO. The hybrid nanostructure ZnO-RGO (5 wt%)-AuPd (1 wt%) exhibits highest photodegradation efficiency (similar to 100% degradation in 20 min) with an improvement in rate constant (k) by a factor of 10 compared to that of the ZnO-RGO nanocomposite. The enhancement of the photocatalytic activity is attributed to the better separation of photogenerated charge carriers in photocatalysts thereby suggesting possible usefulness in a broad range of applications, such as sensing, photocatalysis and solar energy conversion.

Estimation of `drainable' storage - A geomorphological approach

Storage of water within a river basin is often estimated by analyzing recession flow curves as it cannot be `instantly' estimated with the aid of available technologies. In this study we explicitly deal with the issue of estimation of `drainable' storage, which is equal to the area under the `complete' recession flow curve (i.e. a discharge vs. time curve where discharge continuously decreases till it approaches zero). But a major challenge in this regard is that recession curves are rarely `complete' due to short inter-storm time intervals. Therefore, it is essential to analyze and model recession flows meaningfully. We adopt the wellknown Brutsaert and Nieber analytical method that expresses time derivative of discharge (dQ/dt) as a power law function of Q : -dQ/dt = kQ(alpha). However, the problem with dQ/dt-Q analysis is that it is not suitable for late recession flows. Traditional studies often compute alpha considering early recession flows and assume that its value is constant for the whole recession event. But this approach gives unrealistic results when alpha >= 2, a common case. We address this issue here by using the recently proposed geomorphological recession flow model (GRFM) that exploits the dynamics of active drainage networks. According to the model, alpha is close to 2 for early recession flows and 0 for late recession flows. We then derive a simple expression for drainable storage in terms the power law coefficient k, obtained by considering early recession flows only, and basin area. Using 121 complete recession curves from 27 USGS basins we show that predicted drainable storage matches well with observed drainable storage, indicating that the model can also reliably estimate drainable storage for `incomplete' recession events to address many challenges related to water resources. (C) 2014 Elsevier Ltd. All rights reserved.

Antiferromagnetism in Fe1+y Te and Superconductivity in K (x) Fe2Se2

Iron-based layered chalcogenides are interesting because of their structural magnetic and superconducting properties. Single crystals of the parent binary chalcogenides, Fe1+y Te, and intercalated ternary chalcogenides, K0.8Fe2Se2, are grown and investigated in detail. Single crystals are grown by modified horizontal Bridgman method. Fe1+y Te demonstrates an antiferromagnetic (AFM) transition at T (N) =67 K which is identified as a magnetostructural transition. By varying the concentration of excess Fe, we have tuned T (N) over a range of temperature from 67 to 57 K. The superconducting properties of K0.8Fe2Se2 crystals are explored by magnetization measurements. A superconducting transition is observed at T (C) =31 K. The lower critical field of K0.8Fe2Se2 is estimated from field variation of magnetization measurements.

Investigation of dielectric relaxation, Jahn-Teller distortion, and magnetic ordering in Y substituted Pr1-xYxMnO3 (0.1 <= x <= 0.4)

We report structural, magnetic, and dielectric properties of the perovskite compound Pr1-xYxMnO3 (0.1 <= x <= 0.4) studied using dc magnetization, ac susceptibility, neutron powder diffraction, and dielectric techniques. These compounds crystallize in orthorhombic space group (Pnma) in the temperature range 5-300 K. The Mn-O-Mn bond angle decreases with the Y substitution along with an increase in the Jahn-Teller distortion. The Jahn-Teller distortion for Pr0.9Y0.1MnO3 shows an anomalous change near 50 K, below which it falls sharply. Neutron powder diffraction patterns of all reported compositions at low temperature constitute additional magnetic Bragg peaks that suggest magnetic ordering. Magnetic reflections were indexed in the nuclear lattice with the propagation vector k = (0, 0, 0). Rietveld refinement of powder patterns conform to A type antiferromagnetic ordering where moments are aligned ferromagnetically in a-c plane and coupled nearly antiferromagnetically along b-axis resulting in a net ferromagnetic component along the b-direction. The antiferromagnetic transition temperature was deduced from dc magnetization and ac susceptibility data. The transition temperature decreases by nearly 22 K (from 81 K to 59 K) as yttrium content (x) increases from 0.1 to 0.4. Measurements reveal strong frequency dispersion in dielectric constant and dielectric loss. Activation energy and relaxation time are estimated from the Arrhenius plot. It is further shown that relaxation behaviour is altered with yttrium doping concentration. (C) 2015 AIP Publishing LLC.

A unique strategy towards high dielectric constant and low loss with multiwall carbon nanotubes anchored onto graphene oxide sheets

Multiwall carbon nanotubes (MWNTs) were anchored onto graphene oxide sheets (GOs) via diazonium and C-C coupling reactions and characterized by spectroscopic and electron microscopic techniques. The thus synthesized MWNT-GO hybrid was then melt mixed with 50/50 polyamide6-maleic anhydride-modified acrylonitrile-butadiene-styrene (PA6-mABS) blend to design materials with high dielectric constant (30) and low dielectric loss. The phase morphology was studied by SEM and it was observed that the MWNT-GO hybrid was selectively localized in the PA6 phase of the blend. The 30 scales with the concentration of MWNT-GO in the blends, which interestingly showed a very low dielectric loss (< 0.2) making them potential candidate for capacitors. In addition, the dynamic storage modulus scales with the fraction of MWNT-GO in the blends, demonstrating their reinforcing capability as well.

Influence of initial degree of saturation on swell pressures of compacted Barmer bentonite specimens

Densely compacted bentonite or bentonite-sand mixture has been identified as suitable buffer in deep geological repositories as its exceptionally high swelling capacity enables tight contact between the waste canister and surrounding rock. The degree of saturation of the compacted bentonite buffer can increase upon ingress of groundwater from the surrounding rock mass or decrease from evaporation due to high temperature (50-210 degrees C) derived from the waste canister. Available studies indicate that the influence of initial moisture content or degree of saturation on the swell pressure or swell potential of compacted bentonites is unclear. Some studies suggest that initial degree of saturation has an influence, while others suggest that it does not have bearing on the swell pressure of compacted bentonites. This paper examines the influence of initial degree of saturation in montmorillonite voids (termed,S-r,S-MF) on swell pressure of compacted Barmer bentonite-sand mixtures (dry density range: 1.4-2 Mg/m(3)) from micro-structural considerations. The experimental results bring out that, constant dry density specimens that developed similar number of hydration layers upon wetting developed comparable swell pressures and were unaffected by variations in initial S-r,S-MF values. Comparatively, constant dry density specimens that developed dis-similar number of hydration layers upon wetting established different swell pressures and were responsive to variations in initial S-r,S-MF. (C) 2015 Elsevier Ltd. All rights reserved.

Evidence for phase transitions and pseudospin phonon coupling in K-0.9(NH4)(0.1)H2AsO4

This work reports a detailed temperature dependent Raman study on the mixed crystals of K-0.9(NH4)(0.1)H2AsO4 (KADA) from 5K to 300K in the spectral range of 60-1200cm(-1), covering tetragonal to orthorhombic structural phase transition accompanied by paraelectric to ferroelectric transition at T-c* similar to 60K. Multiple phase transitions below transition temperature (Tc* similar to 60K) are marked by the appearance of new modes, splitting of existing ones as well as anomalies in the self-energy parameters (i.e. mode frequencies and damping coefficient) of the phonon modes. Temperature independent behaviour of damping coefficient and abrupt jump in the mode frequency of some of the internal vibrations of AsO4 tetrahedra as well as external vibrations clearly signal long range ferroelectric ordering and proton ordering below T-c*. In addition, we observed that temperature dependence of many prominent phonon modes diverges significantly from their normal anharmonic behaviour below T-c* suggesting potential coupling between pseudospins and phonons. (C) 2015 Author(s).

A gap theorem for Ricci-flat 4-manifolds

Let (M, g) be a compact Ricci-fiat 4-manifold. For p is an element of M let K-max(P) (respectively K-min(p)) denote the maximum (respectively the minimum) of sectional curvatures at p. We prove that if K-max(p) <= -cK(min)(P) for all p is an element of M, for some constant c with 0 <= c < 2+root 6/4 then (M, g) is fiat. We prove a similar result for compact Ricci-flat Kahler surfaces. Let (M, g) be such a surface and for p is an element of M let H-max(p) (respectively H-min(P)) denote the maximum (respectively the minimum) of holomorphic sectional curvatures at p. If H-max(P) <= -cH(min)(P) for all p is an element of M, for some constant c with 0 <= c < 1+root 3/2, then (M, g) is flat. (C) 2015 Elsevier B.V. All rights reserved.

Effect of sputtering parameters on the structure, microstructure and magnetic properties of Tb-Fe films

The effect of sputtering parameters such as gas pressure and power on the structure, microstructure and magnetic properties of sputtered Tb-Fe thin films was investigated. X-ray diffraction and transmission electron microscopy studies showed that all the films were amorphous in nature irrespective of the sputtering parameters. A fine island kind of morphology was observed at low sputtering power whereas large clusters were seen at higher sputtering power. While the composition of Tb-Fe films remained constant with increasing sputtering power, the magnetic behaviour was found to change from superparamagnetic to ferromagnetic. On the other hand, the increase in argon gas pressure was found to deplete the iron concentration in Tb-Fe thin films, which in turn reduced the anisotropy and Curie temperature. Annealing of the films at 773 K did not result in any crystallization and the magnetic properties were also found to remain unchanged. (C) 2015 Elsevier B.V. All rights reserved.

A rhodamine-based `turn-on' Al3+ ion-selective reporter and the resultant complex as a secondary sensor for F- ion are applicable to living cell staining

A newly designed fluorescent aluminum(III) complex (L'-Al; 2) of a structurally characterized non-fluorescent rhodamine Schiff base (L) has been isolated in pure form and characterized using spectroscopic and physico-chemical methods with theoretical density functional theory (DFT) support. On addition of Al(III) ions to a solution of L in HEPES buffer (1 mM, pH 7.4; EtOH-water, 1 : 3 v/v) at 25 degrees C, the systematic increase in chelation-enhanced fluorescence (CHEF) enables the detection of Al(III) ions as low as 60 nM with high selectivity, unaffected by the presence of competitive ions. Interestingly, the Al(III) complex (L'-Al; 2) is specifically able to detect fluoride ions by quenching the fluorescence in the presence of large amounts of other anions in the HEPES buffer (1 mM, pH 7.4) at 25 degrees C. On the basis of our experimental and theoretical findings, the addition of Al3+ ions to a solution of L helps to generate a new fluorescence peak at 590 nm, due to the selective binding of Al3+ ions with L in a 1 : 1 ratio with a binding constant (K) of 8.13 x 10(4) M-1. The Schiff base L shows no cytotoxic effect, and it can therefore be employed for determining the intracellular concentration of Al3+ and F-ions by 2 in living cells using fluorescence microscopy.

Rheological Behavior of Al-7Si-0.3Mg Alloy at Mushy State

In recent years, semisolid manufacturing has emerged as an attractive option for near net shape forming of components with aluminum alloys. In this class of processes, the key to success lies mainly in the understanding of rheological behavior of the semi-solid slurry in the temperature range between liquidus and solidus. The present study focuses on the non-Newtonian flow behavior of the pseudo plastic slurry of Al-7Si-0.3Mg alloy for a wide shear range using a high-temperature Searle-type rheometer. The rheological behavior of the slurry is studied with respect to relevant process variables and microstructural features such as shear rate, shear duration, temperature history, primary particle size, shape, and their distribution. The experiments performed are isothermal tests, continuous cooling tests, shear jump tests, and shear time tests. The continuous cooling experiments are aimed toward studying the viscosity and shear stress evolution within the slurry matrix with increasing solid fraction at a constant shear rate. Three different cooling rates are considered and their effect on flow behavior of the slurry was studied under iso-shear condition. Descending shear jump experiments are performed to understand the viscous instability of the slurry.

Economic tradeoffs in mitigation, due to different atmospheric lifetimes of CO2 and black carbon

Tradeoffs are examined between mitigating black carbon (BC) and carbon dioxide (CO2) for limiting peak global mean warming, using the following set of methods. A two-box climate model is used to simulate temperatures of the atmosphere and ocean for different rates of mitigation. Mitigation rates for BC and CO2 are characterized by respective timescales for e-folding reduction in emissions intensity of gross global product. There are respective emissions models that force the box model. Lastly there is a simple economics model, with cost of mitigation varying inversely with emission intensity. Constant mitigation timescale corresponds to mitigation at a constant annual rate, for example an e-folding timescale of 40 years corresponds to 2.5% reduction each year. Discounted present cost depends only on respective mitigation timescale and respective mitigation cost at present levels of emission intensity. Least-cost mitigation is posed as choosing respective e-folding timescales, to minimize total mitigation cost under a temperature constraint (e.g. within 2 degrees C above preindustrial). Peak warming is more sensitive to mitigation timescale for CO2 than for BC. Therefore rapid mitigation of CO2 emission intensity is essential to limiting peak warming, but simultaneous mitigation of BC can reduce total mitigation expenditure. (c) 2015 Elsevier B.V. All rights reserved.

Phase space path integral approach to harmonic oscillator with a time-dependent force constant

The quantum statistical mechanical propagator for a harmonic oscillator with a time-dependent force constant, m omega(2)(t), has been investigated in the past and was found to have only a formal solution in terms of the solutions of certain ordinary differential equations. Such path integrals are frequently encountered in semiclassical path integral evaluations and having exact analytical expressions for such path integrals is of great interest. In a previous work, we had obtained the exact propagator for motion in an arbitrary time-dependent harmonic potential in the overdamped limit of friction using phase space path integrals in the context of Levy flights - a result that can be easily extended to Brownian motion. In this paper, we make a connection between the overdamped Brownian motion and the imaginary time propagator of quantum mechanics and thereby get yet another way to evaluate the latter exactly. We find that explicit analytic solution for the quantum statistical mechanical propagator can be written when the time-dependent force constant has the form omega(2)(t) = lambda(2)(t) - d lambda(t)/dt where lambda(t) is any arbitrary function of t and use it to evaluate path integrals which have not been evaluated previously. We also employ this method to arrive at a formal solution of the propagator for both Levy flights and Brownian subjected to a time-dependent harmonic potential in the underdamped limit of friction. (C) 2015 Elsevier B.V. All rights reserved.

Polypyridyl iron(II) complexes showing remarkable photocytotoxicity in visible light

Iron(II) complexes of polypyridyl ligands (B), viz. Fe(B)(2)]Cl-2 (1 and 2) of N, N, N-donor 2-(2-pyridyl)-1,10-phenanthroline (pyphen in 1) and 3-(pyridin-2-yl)dipyrido3,2-a:2',3'-c]phenazine (pydppz in 2), are prepared and characterized. They are 1:2 electrolytes in aqueous DMF. The diamagnetic complexes exhibit metal to ligand charge transfer band near 570 nm in DMF. The complexes are avid binders to calf thymus DNA giving binding constant (K (b)) values of similar to 10(6) M-1 suggesting significant intercalative DNA binding of the complexes due to presence of planar phenanthroline bases. Complex 2 exhibits significant photocytotoxicity in immortalized human keratinocyte cells HaCaT and breast cancer cell line MCF-7 giving IC50 values of 0.08 and 13 mu M in visible light (400-700 nm). Complex 2 shows only minor dark toxicity in HaCaT cells but is non-toxic in dark in MCF-7 cancer cells. The light-induced cellular damage follows apoptotic pathway on generation of reactive oxygen species as evidenced from the dichlorofluorescein diacetate (DCFDA) assay.

Reynolds averaged Navier-Stokes simulations of compressible mixing layers of similar and dissimilar gases: Performance of k- turbulence model

The issue of growth rate reduction of high speed mixing layer with convective Mach number is examined for similar and dissimilar gases using Reynolds averaged Navier-Stokes (RANS) methodology with k- turbulence model. It is observed that the growth rate predicted using RANS simulations closely matches with that predicted using model free simulations. Velocity profiles do not depend on the modelled value of Pr-t and Sc-t; while the temperature and species mass fraction distributions depend heavily on them. Although basic k- turbulence model could not capture the reduced growth rate for the mixing layer formed between similar gases, it predicts very well the reduced growth rate for the mixing layer for the dissimilar gases. It appears that density ratio changes caused by temperature changes for the dissimilar gases have profound effect on the growth rate reduction.