Investigations on doping induced changes in structural, electronic structure and magnetic behavior of spintronic Cr-ZnS nanoparticles

Dilute magnetic semiconducting Zn1-xCrxS (x = 0.00, 0.01, 0.03, 0.05, 0.07) nanoparticles were synthesized by the co-precipitation technique using thioglycerol as the capping agent. Powder X-ray diffraction studies showed that Zn1-xCrxS nanoparticles exhibit zinc blende structure with no secondary phase, indicating that Cr ions are substituted at the Zn sites. Photoluminescence and Raman studies show the incorporation of Cr in ZnS nanoparticles. X-ray absorption studies depict that the valence of Zn remains unchanged and maintained in the divalent state, upon doping with Cr. The M-H curves at room temperature indicate the presence of weak ferromagnetism at room temperature due to structural defects. The increase in ferromagnetism with increasing Cr content up to 3%, demonstrates the possibility of tailoring the weak ferromagnetism in ZnS by appropriate Cr doping. (C) 2015 Elsevier Ltd. All rights reserved.

FRP-Confined Clay Brick Masonry Assemblages under Axial Compression: Experimental and Analytical Investigations

Unreinforced masonry (URM) structures that are in need of repair and rehabilitation constitute a significant portion of building stock worldwide. The successful application of fiber-reinforced polymers (FRP) for repair and retrofitting of reinforced-concrete (RC) structures has opened new avenues for strengthening URM structures with FRP materials. The present study analyzes the behavior of FRP-confined masonry prisms under monotonic axial compression. Masonry comprising of burnt clay bricks and cement-sand mortar (generally adopted in the Indian subcontinent) having E-b/E-m ratio less than one is employed in the study. The parameters considered in the study are, (1) masonry bonding pattern, (2) inclination of loading axis to the bed joint, (3) type of FRP (carbon FRP or glass FRP), and (4) grade of FRP fabric. The performance of FRP-confined masonry prisms is compared with unconfined masonry prisms in terms of compressive strength, modulus of elasticity and stress-strain response. The results showed an enhancement in compressive strength, modulus of elasticity, strain at peak stress, and ultimate strain for FRP-confined masonry prisms. The FRP confinement of masonry resulted in reducing the influence of the inclination of the loading axis to the bed joint on the compressive strength and failure pattern. Various analytical models available in the literature for the prediction of compressive strength of FRP-confined masonry are assessed. New coefficients are generated for the analytical model by appending experimental results of the current study with data available in the literature. (C) 2014 American Society of Civil Engineers.

Experimentally validated Raman Monte Carlo simulation for a cuboid object to obtain Raman spectroscopic signatures for hidden material

In conventional Raman spectroscopic measurements of liquids or surfaces the preferred geometry for detection of the Raman signal is the backscattering (or reflection) mode. For non-transparent layered materials, sub-surface Raman signals have been retrieved using spatially offset Raman spectroscopy (SORS), usually with light collection in the same plane as the point of excitation. However, as a result of multiple scattering in a turbid medium, Raman photons will be emitted in all directions. In this study, Monte Carlo simulations for a three-dimensional layered sample with finite geometry have been performed to confirm the detectability of Raman signals at all angles and at all sides of the object. We considered a non-transparent cuboid container (high density polyethylene) with explosive material (ammonium nitrate) inside. The simulation results were validated with experimental Raman intensities. Monte Carlo simulation results reveal that the ratio of sub-surface to surface signals improves at geometries other than backscattering. In addition, we demonstrate through simulations the effects of the absorption and scattering coefficients of the layers, and that of the diameter of the excitation beam. The advantage of collecting light from all possible 4 angles, over other collection modes, is that this technique is not geometry specific and molecular identification of layers underneath non-transparent surfaces can be obtained with minimal interference from the surface layer. To what extent all sides of the object will contribute to the total signal will depend on the absorption and scattering coefficients and the physical dimensions. Copyright (c) 2015 John Wiley & Sons, Ltd.

Imidazolium based ionic liquid type surfactant improves activity and thermal stability of lipase of Rhizopus oryzae

Lipase and surfactant together form a potent pair in various biotransformation, industrial application and biotechnological studies. The present investigation deals with changes in the activity, stability and structure of lipase from Rhizopus oryzae NRRL 3562 in presence of long chain ionic liquid-type imidazolium surfactant. Both the activity and stability were found to be enhanced in presence of the surfactant at low concentration (1-125 mu M) followed by inhibition at high concentration. The activity increased by 80% and thermal deactivation temperature raised by 2.5 degrees C. Investigations by ultraviolet-visible spectroscopy and circular dichroism revealed structural changes leading to rise in beta-sheet content and lowering of a-helix at low surfactant concentrations. Deactivation at high concentration correlated with greater structural changes depicted by spectroscopic studies. Isothermal titration calorimetric studies showed the binding to be spontaneous in nature involving non-covalent interactions. High negative value of entropy signifies exposure of hydrophobic domains and increase in structural rigidity, which correlates with active site being more accessible and rigid in presence of the surfactant. Application of these surfactants hold greater potential in the field of lipase based biotransformations, enzyme structural modifications and studies. (C) 2015 Elsevier B.V. All rights reserved.

Influence of fuel hydrogen fraction on syngas fueled SI engine: Fuel thermo-physical property analysis and in-cylinder experimental investigations

Hydrogen, either in pure form or as a gaseous fuel mixture specie enhances the fuel conversion efficiency and reduce emissions in an internal combustion engine. This is due to the reduction in combustion duration attributed to higher laminar flame speeds. Hydrogen is also expected to increase the engine convective heat flux, attributed (directly or indirectly) to parameters like higher adiabatic flame temperature, laminar flame speed, thermal conductivity and diffusivity and lower flame quenching distance. These factors (adversely) affect the thermo-kinematic response and offset some of the benefits. The current work addresses the influence of mixture hydrogen fraction in syngas on the engine energy balance and the thermo-kinematic response for close to stoichiometric operating conditions. Four different bio-derived syngas compositions with fuel calorific value varying from 3.14 MJ/kg to 7.55 MJ/kg and air fuel mixture hydrogen fraction varying from 7.1% to 14.2% by volume are used. The analysis comprises of (a) use of chemical kinetics simulation package CHEMKIN for quantifying the thermo-physical properties (b) 0-D model for engine in-cylinder analysis and (c) in-cylinder investigations on a two-cylinder engine in open loop cooling mode for quantifying the thermo-kinematic response and engine energy balance. With lower adiabatic flame temperature for Syngas, the in-cylinder heat transfer analysis suggests that temperature has little effect in terms of increasing the heat flux. For typical engine like conditions (700 K and 25 bar at CR of 10), the laminar flame speed for syngas exceeds that of methane (55.5 cm/s) beyond mixture hydrogen fraction of 11% and is attributed to the increase in H based radicals. This leads to a reduction in the effective Lewis number and laminar flame thickness, potentially inducing flame instability and cellularity. Use of a thermodynamic model to assess the isolated influence of thermal conductivity and diffusivity on heat flux suggests an increase in the peak heat flux between 2% and 15% for the lowest (0.420 MW/m(2)) and highest (0.480 MW/m(2)) hydrogen containing syngas over methane (0.415 MW/m(2)) fueled operation. Experimental investigations indicate the engine cooling load for syngas fueled engine is higher by about 7% and 12% as compared to methane fueled operation; the losses are seen to increase with increasing mixture hydrogen fraction. Increase in the gas to electricity efficiency is observed from 18% to 24% as the mixture hydrogen fraction increases from 7.1% to 9.5%. Further increase in mixture hydrogen fraction to 14.2% results in the reduction of efficiency to 23%; argued due to the changes in the initial and terminal stages of combustion. On doubling of mixture hydrogen fraction, the flame kernel development and fast burn phase duration decrease by about 7% and 10% respectively and the terminal combustion duration, corresponding to 90%-98% mass burn, increases by about 23%. This increase in combustion duration arises from the cooling of the near wall mixture in the boundary layer attributed to the presence of hydrogen. The enhancement in engine cooling load and subsequent reduction in the brake thermal efficiency with increasing hydrogen fraction is evident from the engine energy balance along with the cumulative heat release profiles. Copyright (C) 2015, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.

Impedance spectroscopic studies on microwave synthesized NaPO3-V2O5 glasses containing SO42- ions

Impedance spectroscopic studies on modified phospho-vanadate glasses containing SO42- ions have been carried out over wide range of frequency. Modulated DSC studies suggest that the addition of alkali salt makes the glass less rigid and more fragile. The frequency dependent impedance data has been used to calculate d.c conductivity and activation energies. These values are comparable with the other ionic liquids. The conductivity and relaxation phenomenon was rationalized using universal a.c conductivity power law and modulus formalism. The activation energies for relaxation mechanism was also determined using imaginary parts of electrical modulus peaks which were close to those of the d.c conductivity implying the involvement of similar energy barriers in both the processes. Kohlrausch-William-Watts (KWW) stretched exponent beta, is temperature insensitive and power law (s) exponent is temperature dependent. The enhanced conductivity in these glasses is attributed to the depolymerised structure in which migration of Na+ ions proceeds in an expanded network comprising SO42- ions in the interstitials. The effect of structure on activation energy is well supported by abinitio DFT computations. (C) 2015 Elsevier B.V. All rights reserved.

Zinc acetylacetonate hydrate adducted with nitrogen donor ligands: Synthesis, spectroscopic characterization, and thermal analysis

We report synthesis, spectroscopic characterization, and thermal analysis of zinc acetylacetonate complex adducted by nitrogen donor ligands, such as pyridine, bipyridine, and phenanthroline. The pyridine adducted complex crystallizes to monoclinic crystal structure, whereas other two adducted complexes have orthorhombic structure. Addition of nitrogen donor ligands enhances the thermal property of these complexes as that with parent metal-organic complex. Zinc acetylacetonate adducted with pyridine shows much higher volatility (106 degrees C), decomposition temperature (202 degrees C) as that with zinc acetylacetonate (136 degrees C, 220 degrees C), and other adducted complexes. All the adducted complexes are thermally stable, highly volatile and are considered to be suitable precursors for metal organic chemical vapor deposition. The formation of these complexes is confirmed by powder X-ray diffraction, Fourier transform infrared spectroscopy, mass spectroscopy, and elemental analysis. The complexes are widely used as starting precursor materials for the synthesis of ZnO nanostructures by microwave irradiation assisted coating process. (c) 2015 Elsevier B.V. All rights reserved.

Low temperature FTIR, Raman, NMR spectroscopic and theoretical study of hydroxyethylammonium picrate

A combined experimental (infrared, Raman and NMR) and theoretical quantum chemical study is performed on the charge-transfer complex hydroxyethylammonium picrate (HEAP). The infrared (IR) spectra for HEAP were recorded at various temperatures, ranging from 16 K to 299 K, and the Raman spectrum was recorded at room temperature. A comparison of the experimental IR and Raman spectra with the corresponding calculated spectra was done, in order to facilitate interpretation of the experimental data. Formation of the HEAP complex is evidenced by the presence of the most prominent characteristic bands of the constituting groups of the charge-transfer complex e.g., NH3+, CO- and NO2]. Vibrational spectroscopic analysis, together with natural bond orbital (NBO) and theoretical charge density analysis in the crystalline phase, was used to shed light on relevant structural details of HEAP resulting from deprotonation of picric acid followed by formation of a hydrogen bond of the N-H center dot center dot center dot OC type between the hydroxyethylammonium cation and the picrate.C-13 and H-1 NMR spectroscopic analysis are also presented for the DMSO-d(6) solution of the compound revealing that in that medium the HEAP crystal dissolves forming the free picrate and hydroxyethylammonium ions. Finally, the electron excitation analysis of HEAP was performed in an attempt to determine the nature of the most important excited states responsible for the NLO properties exhibited by the compound. (C) 2015 Elsevier B.V. All rights reserved.

Study of H/D exchange rates to derive the strength of intramolecular hydrogen bonds in halo substituted organic building blocks: An NMR spectroscopic investigation

Rates of hydrogen/deuterium (H/D) exchange determined by H-1 NMR spectroscopy are utilized to derive the strength of hydrogen bonds and to monitor the electronic effects in the site-specific halogen substituted benzamides and anilines. The theoretical fitting of the time dependent variation of the integral areas of H-1 NMR resonances to the first order decay function permitted the determination of HID exchange rate constants (k) and their precise half-lives (t(1/2)) with high degree of reproducibility. The comparative study also permitted the unambiguous determination of relative strength of hydrogen bonds and the contribution from electronic effects on the HID exchange rate. (C) 2015 Elsevier B.V. All rights reserved.

Conductometric Sensing of H-2 by Chromium Niobate

Investigations on chromium niobate (CrNbO4) have shown that the material responds to a wide hydrogen concentration range of 0.01%-0.40% at 613 K. The conductivity of CrNbO4 is independent of oxygen partial pressure and offers to be a promising candidate for monitoring H-2 in radioactive spent fuel storage facilities. Reduction of metal ions to lower valence states during hydrogen sensing was evidenced by X-ray photoelectron spectroscopic studies.

Solution processible Cu2SnS3 thin films for cost effective photovoltaics: Characterization

Thin films of Cu2SnS3 (CTS) were deposited by the facile solution processed sol-gel route followed by a low-temperature annealing. The Cu-Sn-thiourea complex formation was analysed using Fourier Transform Infrared spectrophotometer (FTIR). The various phase transformations and the deposition temperature range for the initial precursor solution was determined using Thermogravimetric analysis (TGA) and Differential Scanning Calorimetry (DSC). X-Ray Diffraction (XRD) studies revealed the tetragonal phase formation of the CTS annealed films. Raman spectroscopy studies further confirmed the tetragonal phase formation and the absence of any deterioratory secondary phases. The morphological investigations and compositional analysis of the films were determined using Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) respectively. Atomic Force Microscopy (AFM) was used to estimate the surface roughness of 1.3 nm. The absorption coefficient was found to be 10(4) cm(-1) and bandgap 1.3 eV which qualifies CTS to be a potential candidate for photovoltaic applications. The refractive index, extinction coefficient and relative permittivity of the film were measured by Spectroscopic ellipsometry. Hall effect measurements, indicated the p type nature of the films with a hole concentration of 2 x 10(18) cm(-3), electrical conductivity of 9 S/cm and a hole mobility of 29 cm(2)/V. The properties of CTS as deduced from the current study, present CTS as a potential absorber layer material for thin film solar cells. (C) 2015 Elsevier B.V. All rights reserved.

Electronic and Magnetic Properties of Yttrium-doped Silicon Carbide Nanotubes: Density Functional Theory Investigations

The electronic structure of yttrium-doped Silicon Carbide Nanotubes has been theoretically investigated using first principles density functional theory (DFT). Yttrium atom is bonded strongly on the surface of the nanotube with a binding energy of 2.37 eV and prefers to stay on the hollow site at a distance of around 2.25 angstrom from the tube. The semi-conducting nanotube with chirality (4, 4) becomes half mettalic with a magnetic moment of 1.0 mu(B) due to influence of Y atom on the surface. There is strong hybridization between d orbital of Y with p orbital of Si and C causing a charge transfer from d orbital of the Y atom to the tube. The Fermi level is shifted towards higher energy with finite Density of States for only upspin channel making the system half metallic and magnetic which may have application in spintronic devices.

Investigations of aerosol black carbon from a semi-urban site in the Indo-Gangetic Plain region

Long-term (2009-2012) data from ground-based measurements of aerosol black carbon (BC) from a semi-urban site, Pantnagar (29.0 degrees N, 79.5 degrees E, 231 m amsl), in the Indo-Gangetic Plain (IGP) near the Himalayan foothills are analyzed to study the regional characterization. Large variations are seen in BC at both diurnal and seasonal scales, associated with the mesoscale and synoptic meteorological processes, and local/regional anthropogenic activities. BC diurnal variations show two peaks (morning and evening) arising from the combined effects of the atmospheric boundary layer (ABL) dynamics and local emissions. The diurnal amplitudes as well as the rates of diurnal evolution are the highest in winter season, followed by autumn, and the lowest in summer-monsoon. BC exhibits nearly an inverse relation with mixing layer depth in all seasons; being strongest in winter (R-2 = 0.89) and weakest (R-2 = 0.33) in monsoon (July-August). Unlike BC, co-located aerosol optical depths (AOD) and aerosol absorption are highest in spring over IGP, probably due to the presence of higher abundances of aerosols (including dust) above the ABL (in the free troposphere). AOD (500 nm) showed annual peak (>0.6) in May-June, dominated by coarse mode, while fine mode aerosols dominated in late autumn and early winter. Aerosols profiles from CALIPSO show highest values close to the surface in winter/autumn, similar to the feature seen in surface BC, whereas at altitudes > 2 km, the extinction is maximum in spring/summer. WRF-Chem model is used to simulate BC temporal variations and then compared with observed BC. The model captures most of the important features of the diurnal and seasonal variations but significantly underestimated the observed BC levels, suggesting improvements in diurnal and seasonal varying BC emissions apart from the boundary layer processes. (C) 2015 Elsevier Ltd. All rights reserved.

Investigations into the structural and down-shifting and up-conversion luminescence properties of Ba2Na1-3xErxNb5O15 (0 <= x <= 0.06) nanocrystalline phosphor synthesized via sol-gel route

The present work deals with the structural and efficient down-shifting (DS) and up-conversion (UC) luminescence properties of erbium ion (Er3+) doped nanocrystalline barium sodium niobate (Ba2Na1-3xErxNb5O15, where x = 0, 0.02, 0.04 and 0.06) powders synthesized via novel citrate-based sol-gel route. The monophasic nature of the title compound was confirmed via x-ray powder diffraction followed by FT-IR studies. High-resolution transmission electron microscopy (HRTEM) facilitated the establishment of the nanocrystalline phase and the morphology of the crystallites. The Kubelka-Munk function, based on diffused reflectance studies and carried out on nano-sized crystallites, was employed to obtain the optical band-gap. The synthesized nanophosphor showed efficient DS/PL-photoluminescence and UC luminescence properties, which have not yet been reported so far in this material. The material emits intense DS green emission on excitation with 378 nm radiation. Interestingly, the material gives intense UC emission in the visible region dominated by green emission and relatively weak red emission on 976 nm excitation (NIR laser excitation). Such a dual-mode emitting nanophosphor could be very useful in display devices and for many other applications.

Investigations on the physical origin of lateral photovoltage in PbS-colloidal quantum dot/Si heterojunctions

Restricted area heterojunctions, an array of lead sulfide colloidal quantum dots (PbS-CQDs) and crystalline silicon, are studied with a non-destructive remote contact light beam induced current (RC-LBIC) technique. As well as getting good quality active area images we observed an anomalous unipolar signal response for the PbS-CQD/n-Si devices and a conventionally expected bipolar signal profile for the PbS-CQD/p-Si devices. Interestingly, our simulation results consistently yielded a unipolar and bipolar nature in the signals related to the PbSCQD/n-Si and PbS-CQD/p-Si heterostructures, respectively. In order to explain the physical mechanism involved in the unipolar signal response of the PbS-CQD/n-Si devices, we propose a model based on the band alignment in the heterojunctions, in addition to the distribution of photo-induced excess majority carriers across the junction. Given that the RC-LBIC technique is well suited to this context, the presence of these two distinct mechanisms (the bipolar and unipolar nature of the signals) needs to be considered in order to have a better interpretation of the data in the characterization of an array of homo/heterojunctions.