Conformation-Changing Aggregation in Hydroxyacetone: A Combined Low-Temperature FTIR, Jet, and Crystallographic Study

Aggregation in hydroxyacetone (HA) is studied using low-temperature FTIR, supersonic jet expansion, and X-ray crystallographic (in situ cryocrystallization) techniques. Along with quantum chemical methods (MP2 and DFT), the experiments unravel the conformational preferences of HA upon aggregation to dinners and oligomers. The O-H center dot center dot center dot O=C intramolecular hydrogen bond present in the gas-phase monomer partially opens upon aggregation in supersonic expansions, giving rise to intermolecular cooperatively enhanced O-H center dot center dot center dot O-H hydrogen bonds in competition with isolated O-H center dot center dot center dot O=C hydrogen bonds. On the other hand, low-temperature IR studies on the neat solid and X-ray crystallographic data reveal that HA undergoes profound conformational changes upon crystallization, with the HOCC dihedral angle changing from similar to 0 degrees in the gas phase to similar to 180 degrees in the crystalline phase, hence giving rise to a completely new conformation. These conclusions are supported by theoretical calculations performed on the geometry derived from the crystalline phase.

Two new 1D chains of Ni(2)Na(2) heterometallic double half-cubane building units: Synthesis, structures and variable temperature magnetic study

An equimolar mixture of Ni(NO(3))(2)center dot 6H(2)O and pyridine-2-aldehyde with two equivalents of NaN(3) in methanol in the presence of NaOMe resulted in the formation of light green precipitate which upon crystallization from dimethylformamide (DMF) yielded light green single crystals [{Ni(2)Na(2)(pic)(4)(N(3))(2)(H(2)O)(2)(MeOH)}center dot MeOH center dot 3H(2)O](n) (1) and [{Ni(2)Na(2)(pic)(4)(N(3))(2)(H(2)O)(4)}center dot 2DMF center dot H(2)O](n) (2) (pic = pyridine-2-carboxylate) at room temperature and high temperature (100 degrees C), respectively. Variable temperature magnetic studies revealed the existence of overall ferromagnetic behaviour with J approximate to + 10 cm(-1) and D approximate to -2 to -7 cm(-1) for 1 and 2, respectively. Negative D values as well as variation of D upon slight distortion of structure by varying reaction temperature were observed. The X-band Electron Paramagnetic Resonance (EPR) spectra of both 2 and 3 were recorded below 50 K. The structural distortion was also implicated from the EPR spectra. Density Functional Theory (DFT) calculations on both complexes were performed in two different ways to corroborate the magnetic results. Considering only Ni(2)(II) dimeric unit, results were J = + 20.65 cm(-1) and D = -3.16 cm(-1) for 1, and J = +24.56 cm(-1) and D = -4.67 cm(-1) for 2. However, considering Ni(2)(II)Na(2)(I) cubane as magnetic core the results were J = +16.35 cm(-1) (1), +19.54 cm(-1) (2); D = -3.05 cm(-1) (1), -4.25 cm(-1) (2).

Low temperature synthesis of layered NaxCoO2 and KxCoO2 from NaOH/KOH fluxes and their ion exchange properties

We report a low temperature synthesis of layered Na0×20CoO2 and K0×44CoO2 phases from NaOH and KOH fluxes at 400°C. These layered oxides are employed to prepare hexagonal HCoO2, LixCoO2 and Delafossite AgCoO2 phases by ion exchange method. The resulting oxides were characterised by powder X-ray diffraction, X-ray photoelectron spectroscopy, SEM and EDX analysis. Final compositions of all these oxides are obtained from chemical analysis of elements present. Na0×20CoO2 oxide exhibits insulating to metal like behaviour, whereas AgCoO2 is semiconducting.

Shape Transformation of ZnO Nanorods/Nanotubes at Low Temperature

We report the shape transformation of ZnO nanorods/nanotubes at temperatures (similar to 700 degrees C) much lower than the bulk melting temperature (1975 degrees C). With increasing annealing temperature, not only does shape transformation take place but the luminescence characteristics of ZnO are also modified. It is proposed that the observed shape transformation is due to surface diffusion, contradicting the previously reported notion of melting and its link to luminescence. Luminescence in the green-to-red region is observed when excited with a blue laser, indicating the conversion of blue to white light.

In-situ measurements of concentration and temperature during transient solidification of aqueous solution of ammonium chloride using laser interferometry

The variation in temperature and concentration plays a crucial role in predicting the final microstructure during solidification of a binary alloy. Most of the experimental techniques used to measure concentration and temperature are intrusive in nature and affect the flow field. In this paper, the main focus is laid on in-situ, non-intrusive, transient measurement of concentration and temperature during the solidification of a binary mixture of aqueous ammonium chloride solution (a metal-analog system) in a top cooled cavity using laser based Mach-Zehnder Interferometric technique. It was found from the interferogram, that the angular deviation of fringe pattern and the total number of fringes exhibit significant sensitivity to refractive index and hence are functions of the local temperature and concentration of the NH4Cl solution inside the cavity. Using the fringe characteristics, calibration curves were established for the range of temperature and concentration levels expected during the solidification process. In the actual solidification experiment, two hypoeutectic solutions (5% and 15% NH4Cl) were chosen. The calibration curves were used to determine the temperature and concentration of the solution inside the cavity during solidification of 5% and 15% NH4Cl solution at different instants of time. The measurement was carried out at a fixed point in the cavity, and the concentration variation with time was recorded as the solid-liquid interface approached the measurement point. The measurement exhibited distinct zones of concentration distribution caused by solute rejection and Rayleigh Benard convection. Further studies involving flow visualization with laser scattering confirmed the Rayleigh Benard convection. Computational modeling was also performed, which corroborated the experimental findings. (C) 2011 Elsevier Ltd. All rights reserved.

Pulsed plasma treatment of polluted gas using wet/low temperature corona reactors

pplication of pulsed plasma for gas cleaning is gaining prominence in recent years mainly from the energy consideration point of view. Normally, gas treatment is carried out, at or above room temperature, by a conventional dry type corona reactor. However, this treatment is still inadequate in the removal of certain stable gases present in the exhaust/flue gas mixture. The authors report some interesting results of the treatment of such stable gases with pulsed plasma at very low ambient temperature. Also reported in the paper is an improvement in DeNO/DeNOx efficiency using unconventional wet-type reactors, designed and fabricated by the authors, operating at different ambient temperatures. Apart from laboratory tests on simulated gas mixtures, field tests were also carried out on the exhaust gas of a 8 kW diesel engine. Further, an attempt was made to test the feasibility of a helical wire as a corona electrode in place of the conventional straight wire electrode. A comparative analysis of the various tests is presented together with a note on the energy consideration

Non-Thermal Plasma Applications at Very Low Temperature

Application of non-thermal plasma for gas cleaning is gaining prominence in the recent years. Normally, the gas treatment was carried out at or above room temperature, by the dry type plasma reactor. However, this treatment is still inadequate in the removal of certain stable gases present in the flue gas mixture. We propose the non-thermal plasma process at very low temperature, and report here some interesting results of treatment of NO or N2O with pulsed plasma below — 100°C ambient temperature. Direct methanol synthesis from CH4 and CO2 at very low temperature is also reported. A comparative analysis of the various tests are presented together with a note on the energy consideration

Pulsed plasma treatment of polluted gas using wet/low temperature corona reactors

Application of pulsed plasma for gas cleaning is gaining prominence in recent years mainly from the energy consideration point of view. Normally, gas treatment is carried out, at or above room temperature, by a conventional dry type corona reactor. However, this treatment is still inadequate in the removal of certain stable gases present in the exhaust/flue gas mixture. The authors report some interesting results of the treatment of such stable gases with pulsed plasma at very low ambient temperature. Also reported in the paper is an improvement in DeNO/DeNOx efficiency using unconventional wet-type reactors, designed and fabricated by the authors, operating at different ambient temperatures. Apart from laboratory tests on simulated gas mixtures, field tests were also carried out on the exhaust gas of a 8 kW diesel engine. Further, an attempt was made to test the feasibility of a helical wire as a corona electrode in place of the conventional straight wire electrode. A comparative analysis of the various tests is presented together with a note on the energy consideration

Non-thermal plasma applications at Very Low Temperature

Application of non-thermal plasma for gas cleaning is gaining prominence in the recent years. Normally, the gas treatment was carried out at or above room temperature, by the dry type plasma reactor. However, this treatment is still inadequate in the removal of certain stable gases present in the flue gas mixture. We propose the non-thermal plasma process at very low temperature, and report here some interesting results of treatment of NO or N2O with pulsed plasma below — 100°C ambient temperature. Direct methanol synthesis from CH4 and CO2 at very low temperature is also reported. A comparative analysis of the various tests are presented together with a note on the energy consideration

Evidence for low temperature glassy behavior in La0.5Sr0.5CoO3

We report the observed low temperature spin glass like feature in the optimally doped La0.5Sr0.5CoO3 ferromagnetic system. The characteristic of glassy behavior has been identified by noting (i) the frequency-dependent shift of the low temperature hump position in the out of phase ac susceptibility component; (ii) evolution of freezing temperature with dc biasing field that adheres to de Almeida-Thouless relation; (iii) memory effect; and (iv) sluggish magnetic relaxation. The results of magnetic measurements demonstrate that neither the inter-cluster interaction nor the spin disorder at the interface between ferromagnetic clusters is responsible for the manifestation of such collective glassy behavior. Rather, it is believed to arise from a distinct cluster glass like phase that possibly coexists with the dominant ferromagnetic phase. (C) 2012 American Institute of Physics. [doi:10.1063/1.3684610]

Effect of natural convection on oscillating flow in a pipe with cryogenic temperature difference across the ends

The effect of natural convection on the oscillatory flow in an open-ended pipe driven by a timewise sinusoidally varying pressure at one end and subjected to an ambient-to-cryogenic temperature difference across the ends, is numerically studied. Conjugate effects arising out of the interaction of oscillatory flow with heat conduction in the pipe wall are taken into account by considering a finite thickness wall with an insulated exterior surface. Two cases, namely, one with natural convection acting downwards and the other, with natural convection acting upwards, are considered. The full set of compressible flow equations with axissymmetry are solved using a pressure correction algorithm. Parametric studies are conducted with frequencies in the range 5-15 Hz for an end-to-end temperature difference of 200 and 50 K. Results are obtained for the variation of velocity, temperature. Nusselt number and the phase relationship between mass flow rate and temperature. It is found that the Rayleigh number has a minimal effect on the time averaged Nusselt number and phase angle. However, it does influence the local variation of velocity and Nusselt number over one cycle. The natural convection and pressure amplitude have influence on the energy flow through the gas and solid. (C) 2011 Elsevier Ltd. All rights reserved.

Near-Room-Temperature Colossal Magnetodielectricity and Multiglass Properties in Partially Disordered La2NiMnO6

We report magnetic, dielectric, and magnetodielectric responses of the pure monoclinic bulk phase of partially disordered La2NiMnO6, exhibiting a spectrum of unusual properties and establish that this compound is an intrinsically multiglass system with a large magnetodielectric coupling (8%-20%) over a wide range of temperatures (150-300 K). Specifically, our results establish a unique way to obtain colossal magnetodielectricity, independent of any striction effects, by engineering the asymmetric hopping contribution to the dielectric constant via the tuning of the relative-spin orientations between neighboring magnetic ions in a transition-metal oxide system. We discuss the role of antisite (Ni-Mn) disorder in emergence of these unusual properties.

Modeling of room temperature current-voltage measurements on homo-junction HgCdTe diodes exhibiting nonequilibrium effects

HgCdTe mid wave infrared (MWIR) n(+)/nu/p(+) homo-junction photodiodes with planar architecture are designed, fabricated, and measured at room temperature. An improved analytical I-V model is reported by incorporating trap assisted tunneling and electric field enhanced Shockley-Read-Hall generation recombination process due to dislocations. Tunneling currents are fitted before and after the Auger suppression of carriers with energy level of trap (E-t), trap density (N-t), and the doping concentrations of n(+) and nu regions as fitting parameters. Values of E-t and N-t are determined as 0.79 E-g and similar to 9 x 10(14) cm(-3), respectively, in all cases. Doping concentration of nu region was found to exhibit nonequilibrium depletion from a value of 2 x 10(16) to 4 x 10(15) cm(-3) for n(+) doping of 2 x 10(17) cm(-3). Pronounced negative differential resistance is observed in the homo-junction HgCdTe diodes. (C) 2012 American Institute of Physics. [doi:10.1063/1.3682483]