Transition metal oxide loaded MCM catalysts for photocatalytic degradation of dyes

Transition metal oxide (TiO2, Pe(2)O(3), CoO) loaded MCM-41 and MCM-48 were synthesized by a two-step surfactant-based process. Nanoporous, high surface area compounds were obtained after calcination of the compounds. The catalysts were characterized by SEM, XRD, XPS, UV-vis and BET surface area analysis. The catalysts showed high activity for the photocatalytic degradation of both anionic and cationic dyes. The degradation of the dyes was described using Langmuir-Hinshelwood kinetics and the associated rate parameters were determined.

Transition metal oxide loaded MCM catalysts for photocatalytic degradation of dyes

Transition metal oxide (TiO2, Pe(2)O(3), CoO) loaded MCM-41 and MCM-48 were synthesized by a two-step surfactant-based process. Nanoporous, high surface area compounds were obtained after calcination of the compounds. The catalysts were characterized by SEM, XRD, XPS, UV-vis and BET surface area analysis. The catalysts showed high activity for the photocatalytic degradation of both anionic and cationic dyes. The degradation of the dyes was described using Langmuir-Hinshelwood kinetics and the associated rate parameters were determined.

Superconducting fluctuations and anomalous phonon renormalization much above superconducting transition temperature in Ca4Al2O5.7Fe2As2

Raman studies on Ca4Al2O5.7Fe2As2 superconductor in the temperature range of 5K to 300 K, covering the superconducting transition temperature T-c = 28.3 K, reveal that the Raman mode at similar to 230 cm(-1) shows a sharp jump in frequency by similar to 2% and linewidth increases by similar to 175% at T-o similar to 60 K. Below T-o, anomalous softening of the mode frequency and a large decrease by similar to 10 cm(-1) in the linewidth are observed. These precursor effects at T-0 (similar to 2T(c)) are attributed to significant superconducting fluctuations, possibly enhanced due to reduced dimensionality arising from weak coupling between the well separated (similar to 15 angstrom) Fe-As layers in the unit cell. A large blue-shift of the mode frequency between 300 K and 60 K (similar to 7%) indicates strong spin-phonon coupling in this superconductor. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4724206]

Road to Royalty - Transition of Potential Queen to Queen in the Primitively Eusocial Wasp Ropalidia marginata

Ropalidia marginata, a primitively eusocial wasp, is different from typical primitively eusocial species in having docile queens who cannot be using dominance to maintain reproductive monopoly and instead appear to use a pheromone from the Dufour's gland to do so. When a docile queen is removed from her colony, one of the workers (potential queen, PQ) becomes highly aggressive, and if the queen is not returned, gradually loses her aggression and becomes the new docile queen within a few days. We hypothesized that the decrease in aggression of the PQ with time since queen removal should be correlated with her change in ovaries and pheromone profile. Because the Dufour's gland hydrocarbon composition in R.marginata can be correlated with fertility, this also gave us an opportunity to test whether PQ is different from workers in her Dufour's gland hydrocarbons. In this study, we therefore trace the road to royalty in R.marginata, that is, the transition of the PQ during queen establishment, in terms of her ovaries, aggression, and Dufour's gland hydrocarbons. Our study focuses on queen establishment, which is important for understanding how reproductive conflict can be manifested and resolved.

Transition due to base roughness in a dense granular flow down an inclined plane

Particle simulations based on the discrete element method are used to examine the effect of base roughness on the granular flow down an inclined plane. The base is composed of a random configuration of fixed particles, and the base roughness is decreased by decreasing the ratio of diameters of the base and moving particles. A discontinuous transition from a disordered to an ordered flow state is observed when the ratio of diameters of base and moving particles is decreased below a critical value. The ordered flowing state consists of hexagonally close packed layers of particles sliding over each other. The ordered state is denser (higher volume fraction) and has a lower coordination number than the disordered state, and there are discontinuous changes in both the volume fraction and the coordination number at transition. The Bagnold law, which states that the stress is proportional to the square of the strain rate, is valid in both states. However, the Bagnold coefficients in the ordered flowing state are lower, by more than two orders of magnitude, in comparison to those of the disordered state. The critical ratio of base and moving particle diameters is independent of the angle of inclination, and varies very little when the height of the flowing layer is doubled from about 35 to about 70 particle diameters. While flow in the disordered state ceases when the angle of inclination decreases below 20 degrees, there is flow in the ordered state at lower angles of inclination upto 14 degrees. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4710543]

Effect of ``dipolar-biasing'' on the tunability of tunneling magnetoresistance in transition metal oxide systems

We observe an unusual tunneling magnetoresistance (TMR) phenomenon in a composite of La2/3Sr1/3MnO3 with CoFe2O4 where the TMR versus applied magnetic field loop suggests a ``negative coercive field.'' Tracing its origin back to a ``dipolar-biasing'' of La2/3Sr1/3MnO3 by CoFe2O4, we show that the TMR of even a single composite can be tuned continuously so that the resistance peak or the highest sensitivity of the TMR can be positioned anywhere on the magnetic field axis with a suitable magnetic history of the sample. This phenomenon of an unprecedented tunability of the TMR should be present in general in all such composites. (C) 2012 American Institute of Physics.http://dx.doi.org/10.1063/1.4731206]

Strain induced phase transition in CdSe nanowires: Effect of size and temperature

Using all-atom molecular dynamics simulation, we have studied the effect of size and temperature on the strain induced phase transition of wurtzite CdSe nanowires. The wurtzite structure transforms into a five-fold coordinated structure under uniaxial strain along the c axis. Our results show that lower temperature and smaller size of the nanowires stabilize the five-fold coordinated phase which is not a stable structure in bulk CdSe. High reversibility of this transformation with a very small heat loss will make these nanowires suitable for building efficient nanodevices. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4734990]

Glassy dynamics in a confined monatomic fluid

Molecular dynamic simulations of a strongly inhomogeneous system reveals that a single-component soft-sphere fluid can behave as a fragile glass former due to confinement. The self-intermediate scattering function, F-s(k,t), of a Lennard-Jones fluid confined in slit-shaped pores, which can accomodate two to four fluid layers, exhibits a two-step relaxation at moderate temperatures. The mean-squared displacement data are found to follow time-temperature superposition and both the self-diffusivity and late a relaxation times exhibit power-law divergences as the fluid is cooled. The system possesses a crossover temperature and follows the scalings of mode coupling theory for the glass transition. The temperature dependence of the self-diffusivity can be expressed using the Vogel-Fulcher-Tammann equation, and estimates of the fragility index of the system indicates a fragile glass former. At lower temperatures, signatures of additional relaxation processes are observed in the various dynamical quantities with a three-step relaxation observed in the F-s(k,t).

Nucleation-Growth Mode of Cubic-Tetragonal Transition with Coexistence of Phases over a Wide Temperature Interval in the High Temperature Ferroelectric Systems PbTiO3-BiMeO3:Me = Sc , and Zn1/2Ti1/2

Temperature dependent X-ray powder diffraction and dielectric studies have been carried out on tetragonal compositions of (1-x) PbTiO 3(x) BiMeO 3; Me similar to Sc and Zn 1/2 Ti 1/2. The cubic and the tetragonal phases coexist over more than 100 degrees C for 0.70 PbTiO 30.3 Bi ( Zn 1/2 Ti 1/2) O 3 and 0.66 PbTiO 30.34 BiScO 3. The wide temperature range of phase coexistence is shown to be an intrinsic feature of the system, and is attributed to the increase in the degree of the covalent character of the ( Pb +Bi ) O bond with increasing concentration of Bi at the Pb -site. The d-values of the {111} planes of the coexisting phases are nearly identical, suggesting this plane to be the invariant plane for the martensitic type cubic-tetragonal transformation occurring in these systems.

Phonon anomalies and structural transition in spin ice Dy2Ti2O7: a simultaneous pressure-dependent and temperature-dependent Raman study

We revisit the assignment of Raman phonons of rare-earth titanates by performing Raman measurements on single crystals of O18 isotope-rich spin ice Dy2Ti2O718 and nonmagnetic Lu2Ti2O718 pyrochlores and compare the results with their O16 counterparts. We show that the low-wavenumber Raman modes below 250 cm-1 are not due to oxygen vibrations. A mode near 200 cm-1, commonly assigned as F2g phonon, which shows highly anomalous temperature dependence, is now assigned to a disorder-induced Raman active mode involving Ti4+ vibrations. Moreover, we address here the origin of the new Raman mode, observed below TC similar to 110 K in Dy2Ti2O7, through a simultaneous pressure-dependent and temperature-dependent Raman study. Our study confirms the new mode to be a phonon mode. We find that dTC/dP = + 5.9 K/GPa. Temperature dependence of other phonons has also been studied at various pressures up to similar to 8 GPa. We find that pressure suppresses the anomalous temperature dependence. The role of the inherent vacant sites present in the pyrochlore structure in the anomalous temperature dependence is also discussed. Copyright (c) 2012 John Wiley & Sons, Ltd.

High Temperature Phase Transition Studies and Dielectric Properties of Sr2SbMnO6

Sr2SbMnO6 (SSMO) ceramics were, fabricated using the nanocrystalline powders obtained via molten salt synthesis (MSS) method. High temperature X-ray diffraction studies confirmed the structural phase transition (room temperature tetragonal (I4/mcm) to the cubic phase (Pm-3m)) temperature to be around 736K. The discontinuity in the phase transition indicated its first order nature reflecting the presence of ferroelectric-like distortions in SSMO prepared from MSS which seemed to be unique as it was not observed so far in the case of SSMO prepared using solid-state reaction method. The dielectric behavior of SSMO was studied in the 300-950 K temperature range at high frequencies (MHz range) in order to suppress the of space charge and related effects that dominate at such higher temperatures and mask the real phase transition.

Semiconductor-metal transition in semiconducting bilayer sheets of transition-metal dichalcogenides

Using first-principles calculations we show that the band gap of bilayer sheets of semiconducting transition-metal dichalcogenides (TMDs) can be reduced smoothly by applying vertical compressive pressure. These materials undergo a universal reversible semiconductor-to-metal (S-M) transition at a critical pressure. The S-M transition is attributed to lifting of the degeneracy of the bands at the Fermi level caused by interlayer interactions via charge transfer from the metal to the chalcogen. The S-M transition can be reproduced even after incorporating the band gap corrections using hybrid functionals and the GW method. The ability to tune the band gap of TMDs in a controlled fashion over a wide range of energy opens up the possibility for its usage in a range of applications.

Optimal Control of Markov Processes with Age-Dependent Transition Rates

We study optimal control of Markov processes with age-dependent transition rates. The control policy is chosen continuously over time based on the state of the process and its age. We study infinite horizon discounted cost and infinite horizon average cost problems. Our approach is via the construction of an equivalent semi-Markov decision process. We characterise the value function and optimal controls for both discounted and average cost cases.

Route to high Neel temperatures in 4d and 5d transition metal oxides

There are very few magnetic members among the 4d and 5d transition metal oxides. In the present work, we examine the recent observation of a high Neel temperature T-N in the 4d oxides SrTcO3 and CaTcO3. Considering a multiband Hubbard model, we find that T-N is larger in the limit of a large bandwidth and vanishingly small intra-atomic exchange interaction strength, contrary to our conventional understanding of magnetism. This is traced to specific aspects of the d(3) configuration at the transition metal site and the study reveals additional examples with high T-N.