Synthesis, characterization and spectroscopic investigation of Cr3+ doped wollastonite nanophosphor

This work explores the preparation of nanocrystalline Cr3+ (1-5 mol%) doped CaSiO3 phosphors by solution combustion process and study of its photoluminescence (PL) behavior. The nanopowders are well characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and Fourier transform infra-red (FTIR) spectroscopy. PXRD results confirm monoclinic phase upon calcination at 950 degrees C for 3 h. SEM micrographs indicates that the powder is highly porous and agglomerated. The TEM images show the powder to consist of spherical shaped particles of size similar to 30-60 nm. Upon 323 nm excitation, the emission profile of CaSiO3:Cr3+ exhibits a narrow red emission peak at 641 nm due to E-2 -> (4)A(2) transition and broad band at 722 nm due to T-4(2g) -> (4)A(2g). It is observed that PL intensity increases with increase in Cr3+ concentration and highest PL intensity is observed for 3 mol% doped sample. The PL intensity decreases with further increase in Cr3+ doping. This decrease in PL intensity beyond 3 mol% is ascribed to concentration quenching. Racah parameters are calculated to describe the effects of electron-electron repulsion within the crystal lattice. The parameters show 21% reduction in the Racah parameter of free ion and the complex, indicating the moderate nephelauxetic effect in the lattice. (C) 2014 Elsevier B.V. All rights reserved.

Detailed understanding of the excitation-intensity dependent photoluminescence of ZnO materials: Role of defects

The photoluminescence (PL) of ZnO is shown to be dependent on the excitation intensity (EI) of the laser, and the substantial shift observed in the band to band transition is attributed to the heating effect. In order to understand this phenomenon in detail, we investigate the EI dependent PL of various ZnO samples systematically from liquid nitrogen (LN) to room temperature by varying the laser power. Some of the samples exhibit substantial red shift in the band to band transition with increasing EI even in LN environment, negligible effect is observed for others. Hence, our results strongly suggest that the EI dependent PL is not a characteristic of all ZnO samples. This indicates that laser-induced heating effect is not the dominant factor that governs the shifts in the PL spectra. Rather, the defect level excitation accounts for such observation. (C) 2014 AIP Publishing LLC.

Polymorphic phase transition among the titania crystal structures using a solution-based approach: from precursor chemistry to nucleation process

Nanocrystalline titania are a robust candidate for various functional applications owing to its non-toxicity, cheap availability, ease of preparation and exceptional photochemical as well as thermal stability. The uniqueness in each lattice structure of titania leads to multifaceted physico-chemical and opto-electronic properties, which yield different functionalities and thus influence their performances in various green energy applications. The high temperature treatment for crystallizing titania triggers inevitable particle growth and the destruction of delicate nanostructural features. Thus, the preparation of crystalline titania with tunable phase/particle size/morphology at low to moderate temperatures using a solution-based approach has paved the way for further exciting areas of research. In this focused review, titania synthesis from hydrothermal/solvothermal method, conventional sol-gel method and sol-gel-assisted method via ultrasonication, photoillumination and ILs, thermolysis and microemulsion routes are discussed. These wet chemical methods have broader visibility, since multiple reaction parameters, such as precursor chemistry, surfactants, chelating agents, solvents, mineralizer, pH of the solution, aging time, reaction temperature/time, inorganic electrolytes, can be easily manipulated to tune the final physical structure. This review sheds light on the stabilization/phase transformation pathways of titania polymorphs like anatase, rutile, brookite and TiO2(B) under a variety of reaction conditions. The driving force for crystallization arising from complex species in solution coupled with pH of the solution and ion species facilitating the orientation of octahedral resulting in a crystalline phase are reviewed in detail. In addition to titanium halide/alkoxide, the nucleation of titania from other precursors like peroxo and layered titanates are also discussed. The nonaqueous route and ball milling-induced titania transformation is briefly outlined; moreover, the lacunae in understanding the concepts and future prospects in this exciting field are suggested.

Temperature-Induced Reversible First-Order Single Crystal to Single Crystal Phase Transition in Boc-gamma(4)(R)Val-Val-OH: Interplay of Enthalpy and Entropy

Crystals of Boc-gamma y(4)(R)Val-Val-OH undergo a reversible first-order single crystal to single crystal phase transition at T-c approximate to 205 K from the orthorhombic space group P22(1)2(1) (Z' = 1) to the monoclinic space group P2(1) (Z' = 2) with a hysteresis of similar to 2.1 K. The low-temperature monoclinic form is best described as a nonmerohedral twin with similar to 50% contributions from its two components. The thermal behavior of the dipeptide crystals was characterized by differential scanning calorimetry experiments. Visual changes in birefringence of the sample during heating and cooling cycles on a hot-stage microscope with polarized light supported the phase transition. Variable-temperature unit cell check measurements from 300 to 100 K showed discontinuity in the volume and cell parameters near the transition temperature, supporting the first-order behavior. A detailed comparison of the room-temperature orthorhombic form with the low-temperature (100 K) monoclinic form revealed that the strong hydrogen-bonding motif is retained in both crystal systems, whereas the non-covalent interactions involving side chains of the dipeptide differ significantly, leading to a small change in molecular conformation in the monoclinic form as well as a small reorientation of the molecules along the ac plane. A rigid-body thermal motion analysis (translation, libration, screw; correlation of translation and libration) was performed to study the crystal entropy. The reversible nature of the phase transition is probably the result of an interplay between enthalpy and entropy: the low-temperature monoclinic form is enthalpically favored, whereas the room-temperature orthorhombic form is entropically favored.

Absolute/Convective Instability Transition in a Backward Facing Step Combustor: Fundamental Mechanism and Influence of Density Gradient

Hydrodynamic instabilities of the flow field in lean premixed gas turbine combustors can generate velocity perturbations that wrinkle and distort the flame sheet over length scales that are smaller than the flame length. The resultant heat release oscillations can then potentially result in combustion instability. Thus, it is essential to understand the hydrodynamic instability characteristics of the combustor flow field in order to understand its overall influence on combustion instability characteristics. To this end, this paper elucidates the role of fluctuating vorticity production from a linear hydrodynamic stability analysis as the key mechanism promoting absolute/convective instability transitions in shear layers occurring in the flow behind a backward facing step. These results are obtained within the framework of an inviscid, incompressible, local temporal and spatio-temporal stability analysis. Vorticity fluctuations in this limit result from interaction between two competing mechanisms-(1) production from interaction between velocity perturbations and the base flow vorticity gradient and (2) baroclinic torque in the presence of base flow density gradients. This interaction has a significant effect on hydrodynamic instability characteristics when the base flow density and velocity gradients are colocated. Regions in the space of parameters characterizing the base flow velocity profile, i.e., shear layer thickness and ratio of forward to reverse flow velocity, corresponding to convective and absolute instability are identified. The implications of the present results on understanding prior experimental studies of combustion instability in backward facing step combustors and hydrodynamic instability in other flows such as heated jets and bluff body stabilized flames is discussed.

Modeling non-stationarity in intensity, duration and frequency of extreme rainfall over India

Significant changes are reported in extreme rainfall characteristics over India in recent studies though there are disagreements on the spatial uniformity and causes of trends. Based on recent theoretical advancements in the Extreme Value Theory (EVT), we analyze changes in extreme rainfall characteristics over India using a high-resolution daily gridded (1 degrees latitude x 1 degrees longitude) dataset. Intensity, duration and frequency of excess rain over a high threshold in the summer monsoon season are modeled by non-stationary distributions whose parameters vary with physical covariates like the El-Nino Southern Oscillation index (ENSO-index) which is an indicator of large-scale natural variability, global average temperature which is an indicator of human-induced global warming and local mean temperatures which possibly indicate more localized changes. Each non-stationary model considers one physical covariate and the best chosen statistical model at each rainfall grid gives the most significant physical driver for each extreme rainfall characteristic at that grid. Intensity, duration and frequency of extreme rainfall exhibit non-stationarity due to different drivers and no spatially uniform pattern is observed in the changes in them across the country. At most of the locations, duration of extreme rainfall spells is found to be stationary, while non-stationary associations between intensity and frequency and local changes in temperature are detected at a large number of locations. This study presents the first application of nonstationary statistical modeling of intensity, duration and frequency of extreme rainfall over India. The developed models are further used for rainfall frequency analysis to show changes in the 100-year extreme rainfall event. Our findings indicate the varying nature of each extreme rainfall characteristic and their drivers and emphasize the necessity of a comprehensive framework to assess resulting risks of precipitation induced flooding. (C) 2014 Elsevier B.V. All rights reserved.

Tailoring local density of optical states to control emission intensity and anisotropy of quantum dots in hybrid photonic-plasmonic templates

We report results of controlled tuning of the local density of states (LDOS) in versatile, flexible, and hierarchical self assembled plasmonic templates. Using 5 nm diameter gold (Au) spherical nanoantenna within a polymer template randomly dispersed with quantum dots, we show how the photoluminescence intensity and lifetime anisotropy of these dots can be significantly enhanced through LDOS tuning. Finite difference time domain simulations corroborate the experimental observations and extend the regime of enhancement to a wider range of geometric and spectral parameters bringing out the versatility of these functional plasmonic templates. It is also demonstrated how the templates act as plasmonic resonators for effectively engineer giant enhancement of the scattering efficiency of these nano antenna embedded in the templates. Our work provides an alternative method to achieve spontaneous emission intensity and anisotropy enhancement with true nanoscale plasmon resonators. (C) 2015 AIP Publishing LLC.

Decreasing intensity of monsoon low-frequency intraseasonal variability over India

Understanding the changing nature of the intraseasonal oscillatory (ISO) modes of Indian summer monsoon manifested by active and break phase, and their association with extreme rainfall events are necessary for probabilistic estimation of flood-related risks in a warming climate. Here, using ground-based observed rainfall, we define an index to measure the strength of monsoon ISOs and show that the relative strength of the northward-propagating low-frequency ISO (20-60 days) modes have had a significant decreasing trend during the past six decades, possibly attributed to the weakening of large-scale circulation in the region during monsoon season. This reduction is compensated by a gain in synoptic-scale (3-9 days) variability. The decrease in low-frequency ISO variability is associated with a significant decreasing trend in the percentage of extreme events during the active phase of the monsoon. However, this decrease is balanced by significant increasing trends in the percentage of extreme events in the break and transition phases. We also find a significant rise in the occurrence of extremes during early and late monsoon months, mainly over eastern coastal regions. Our study highlights the redistribution of rainfall intensity among periodic (low-frequency) and non-periodic (extreme) modes in a changing climate scenario.

Molecular dynamics insight to phase transition in n-alkanes with carbon nanofillers

The present work aims to investigate the phase transition, dispersion and diffusion behavior of nanocomposites of carbon nanotube (CNT) and straight chain alkanes. These materials are potential candidates for organic phase change materials(PCMs) and have attracted flurry of research recently. Accurate experimental evaluation of the mass, thermal and transport properties of such composites is both difficult as well as economically taxing. Additionally it is crucial to understand the factors that results in modification or enhancement of their characteristic at atomic or molecular level. Classical molecular dynamics approach has been extended to elucidate the same. Bulk atomistic models have been generated and subjected to rigorous multistage equilibration. To reaffirm the approach, both canonical and constant-temperature, constant-pressure ensembles were employed to simulate the models under consideration. Explicit determination of kinetic, potential, non-bond and total energy assisted in understanding the enhanced thermal and transport property of the nanocomposites from molecular point of view. Crucial parameters including mean square displacement and simulated self diffusion coefficient precisely define the balance of the thermodynamic and hydrodynamic interactions. Radial distribution function also reflected the density variation, strength and mobility of the nanocomposites. It is expected that CNT functionalization could improve the dispersion within n-alkane matrix. This would further ameliorate the mass and thermal properties of the composite. Additionally, the determined density was in good agreement with experimental data. Thus, molecular dynamics can be utilized as a high throughput technique for theoretical investigation of nanocomposites PCMs. (C) 2015 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.

ABSOLUTE/CONVECTIVE INSTABILITY TRANSITION IN A BACKWARD FACING STEP COMBUSTOR: FUNDAMENTAL MECHANISM AND INFLUENCE OF DENSITY GRADIENT

Hydrodynamic instabilities of the flow field in lean premixed gas turbine combustors can generate velocity perturbations that wrinkle and distort the flame sheet over length scales that are smaller than the flame length. The resultant heat release oscillations can then potentially result in combustion instability. Thus, it is essential to understand the hydrodynamic instability characteristics of the combustor flow field in order to understand its overall influence on combustion instability characteristics. To this end, this paper elucidates the role of fluctuating vorticity production from a linear hydrodynamic stability analysis as the key mechanism promoting absolute/convective instability transitions in shear layers occurring in the flow behind a backward facing step. These results are obtained within the framework of an inviscid, incompressible, local temporal and spatio-temporal stability analysis. Vorticity fluctuations in this limit result from interaction between two competing mechanisms - (1) production from interaction between velocity perturbations and the base flow vorticity gradient and (2) baroclinic torque in the presence of base flow density gradients. This interaction has a significant effect on hydrodynamic instability characteristics when the base flow density and velocity gradients are co-located. Regions in the space of parameters characterizing the base flow velocity profile, i.e. shear layer thickness and ratio of forward to reverse flow velocity, corresponding to convective and absolute instability are identified. The implications of the present results on prior observations of flow instability in other flows such as heated jets and bluff-body stabilized flames is discussed.

Pressure-induced phase transition in Bi2Se3 at 3 GPa: electronic topological transition or not?

In recent years, a low pressure transition around P similar to 3 GPa exhibited by the A(2)B(3)-type 3D topological insulators is attributed to an electronic topological transition (ETT) for which there is no direct evidence either from theory or experiments. We address this phase transition and other transitions at higher pressure in bismuth selenide (Bi2Se3) using Raman spectroscopy at pressure up to 26.2 GPa. We see clear Raman signatures of an isostructural phase transition at P similar to 2.4 GPa followed by structural transitions at similar to 10 GPa and 16 GPa. First-principles calculations reveal anomalously sharp changes in the structural parameters like the internal angle of the rhombohedral unit cell with a minimum in the c/a ratio near P similar to 3 GPa. While our calculations reveal the associated anomalies in vibrational frequencies and electronic bandgap, the calculated Z(2) invariant and Dirac conical surface electronic structure remain unchanged, showing that there is no change in the electronic topology at the lowest pressure transition.

Intensity Distribution Design for Laser-Induced Thermal Loading Based on Numerical Simulation

To accomplish laser-induced thermal loading simulation tests for pistons,the Gaussian beam was modulated into multi-circular beam with specific intensity distribution.A reverse method was proposed to design the intensity distribution for the laser-induced thermal loading based on finite element(FE) analysis.Firstly,the FE model is improved by alternating parameters of boundary conditions and thermal-physical properties of piston material in a reasonable range,therefore it can simulate the experimental resul...

Stability of ZrTiCuNiBe Bulk Metallic Glass Upon Isothermal Annealing Near the Glass Transition Temperature

The stability of Zr41Ti14Cu12.5Ni10Be22.5 bulk metallic glass (BMG) upon isothermal annealing near the glass transition temperature has been investigated by using x-ray diffraction, differential scanning calorimetry, and the pulse echo overlap method. The density, elastic constants, and thermodynamic parameters as well as their annealing time dependence have been determined. The microstructural and properties changes of the annealed BMG were checked by acoustic measurement. Obvious structural and property changes were observed with prolonged annealing of the BMG near the glass transition temperature.

Carbon transition efficiency and process cost in high-rate, large-area deposition of diamond films by DC arc plasma jet

A new DC plasma torch in which are jet states and deposition parameters can be regulated over a wide range has been built. It showed advantages in producing stable plasma conditions at a small gas flow rate. Plasma jets with and without magnetically rotated arcs could be generated. With straight are jet deposition, diamond films could be formed at a rate of 39 mu m/h on Mo substrates of Phi 25 mm, and the conversion rate of carbon in CH4 to diamond was less than 3%. Under magnetically rotated conditions, diamond films could be deposited uniformly in a range of Phi 40 mm at 30 mu m/h, with a quite low total gas flow rate and high carbon conversion rate of over 11%. Mechanisms of rapid and uniform deposition of diamond films with low gas consumption and high carbon transition efficiency are discussed.

Thermal fatigue on pistons induced by shaped high power laser. Part II: Design of spatial intensity distribution via numerical simulation

In the laser induced thermal fatigue simulation test on pistons, the high power laser was transformed from the incident Gaussian beam into a concentric multi-circular pattern with specific intensity ratio. The spatial intensity distribution of the shaped beam, which determines the temperature field in the piston, must be designed before a diffractive optical element (DOE) can be manufactured. In this paper, a reverse method based on finite element model (FEM) was proposed to design the intensity distribution in order to simulate the thermal loadings on pistons. Temperature fields were obtained by solving a transient three-dimensional heat conduction equation with convective boundary conditions at the surfaces of the piston workpiece. The numerical model then was validated by approaching the computational results to the experimental data. During the process, some important parameters including laser absorptivity, convective heat transfer coefficient, thermal conductivity and Biot number were also validated. Then, optimization procedure was processed to find favorable spatial intensity distribution for the shaped beam, with the aid of the validated FEM. The analysis shows that the reverse method incorporated with numerical simulation can reduce design cycle and design expense efficiently. This method can serve as a kind of virtual experimental vehicle as well, which makes the thermal fatigue simulation test more controllable and predictable. (C) 2007 Elsevier Ltd. All rights reserved.