Novel spherical hierarchical structures of GdOOH and Eu:GdOOH: rapid microwave-assisted synthesis through self-assembly, thermal conversion to oxides, and optical studies

We report a novel, rapid, and low-temperature method for the synthesis of undoped and Eu-doped GdOOH spherical hierarchical structures, without using any structure-directing agents, through the microwave irradiation route. The as-prepared product consists of nearly monodisperse microspheres measuring about 1.3 mu m in diameter. Electron microscopy reveals that each microsphere is an assembly of two-dimensional nanoflakes (about 30 nm thin) which, in turn, result from the assembly of crystallites measuring about 9 nm in diameter. Thus, a three-level hierarchy can be seen in the formation of the GdOOH microspheres: from nanoparticles to 2D nanoflakes to 3D spherical structures. When doped with Eu3+ ions, the GdOOH microspheres show a strong red emission, making them promising candidates as phosphors. Finally, thermal conversion at modest temperatures leads to the formation of corresponding oxide structures with enhanced luminescence, while retaining the spherical morphology of their oxyhydroxide precursor.

Dynamics of a driven magneto-martensitic ribbon

We investigate the dynamics of a sinusoidally driven ferromagnetic martensitic ribbon by adopting a recently introduced model that involves strain and magnetization as order parameters. Retaining only the dominant mode of excitation we reduce the coupled set of partial differential equations for strain and magnetization to a set of coupled ordinary nonlinear equations for the strain and magnetization amplitudes. The equation for the strain amplitude takes the form of parametrically driven oscillator. Finite strain amplitude can only be induced beyond a critical value of the strength of the magnetic field. Chaotic response is seen for a range of values of all the physically interesting parameters. The nature of the bifurcations depends on the choice of temperature relative to the ordering of the Curie and the martensite transformation temperatures. We have studied the nature of response as a function of the strength and frequency of the magnetic field, and magneto-elastic coupling. In general, the bifurcation diagrams with respect to these parameters do not follow any standard route. The rich dynamics exhibited by the model is further illustrated by the presence of mixed mode oscillations seen for low frequencies. The geometric structure of the mixed mode oscillations in the phase space has an unusual deep crater structure with an outer and inner cone on which the orbits circulate. We suggest that these features should be seen in experiments on driven magneto-martensitic ribbons. (C) 2014 Elsevier B. V. All rights reserved.

Exploring Cyclopentadienone Antiaromaticity: Charge Density Studies of Various Tetracyclones

A systematic study of six tetracyclones has been carried out using experimental and theoretical charge density analysis. A three pronged approach based on quantum theory of atoms in molecules (QTAIM), nucleus independent chemical shifts (NICS) criterion, and source function (SF) contributions has been performed to establish the degree of antiaromaticity of the central five-membered ring in all the derivatives. Electrostatic potentials mapped on the isodensity surface show that electron withdrawing substituents turn both C and O atoms of the carbonyl group more electropositive while retaining the direction of polarity.

Iodide Retention by Modified Kaolinite in the Context of Safe Disposal of High Level Nuclear Waste

Bentonite clay is identified as potential buffer in deep geological repositories (DGR) that store high level radioactive wastes (HLW) as the expansive clay satisfies the expected mechanical and physicochemical functions of the buffer material. In the deep geological disposal of HLW, iodine-129 is one of the significant nuclides, attributable to its long half-life (half life 1⁄4 1:7 × 107 years). However, the negative charge on the basal surface of bentonite particles precludes retention of iodide anions. To render the bentonite effective in retaining hazardous iodide species in DGR, improvement of the anion retention capacity of bentonite becomes imperative. The iodide retention capac-ity of bentonite is improved by admixing 10 and 20% Ag-kaolinite (Ag-K) with bentonite (B) on a dry mass basis. The present study produced Ag-kaolinite by heating silver nitrate-kaolinite mixes at 400°C. Marginal release of iodide retained by Ag-kaolinite occurred under extreme acidic (pH 1⁄4 2:5) and alkaline (pH 1⁄4 12:5) conditions. The swell pressure and iodide etention results of the B-Ag-K specimens bring out that mixing Ag-K with bentonite does not chemically modify the expansive clay; the mixing is physical in nature and Ag-K presence only contributes to iodide retention of the admixture. DOI: 10.1061/(ASCE)HZ.2153-5515.0000121. © 2012 American Society of Civil Engineers.

Finding hidden females in a crowd: Mate recognition in fig wasps

Multi-species mating aggregations are crowded environments within which mate recognition must occur. Mating aggregations of fig wasps can consist of thousands of individuals of many species that attain sexual maturity simultaneously and mate in the same microenvironment, i.e, in syntopy, within the close confines of an enclosed globular inflorescence called a syconium - a system that has many signalling constraints such as darkness and crowding. All wasps develop within individual galled flowers. Since mating mostly occurs when females are still confined within their galls,, male wasps have the additional burden of detecting conspecific females that are ``hidden'' behind barriers consisting of gall walls. In Ficus racemosa, we investigated signals used by pollinating fig wasp males to differentiate conspecific females from females of other syntopic fig wasp species. Male Ceratosolen fusciceps could detect conspecific females using cues from galls containing females, empty galls, as well as cues from gall volatiles and gall surface hydrocarbons. In many figs, syconia are pollinated by single foundress wasps, leading to high levels of wasp inbreeding due to sibmating. In F. racemosa, as most syconia contain many foundresses, we expected male pollinators to prefer non-sib females to female siblings to reduce inbreeding. We used galls containing females from non-natal figs as a proxy for non-sibs and those from natal figs as a proxy for sibling females. We found that males preferred galls of female pollinators from natal figs. However, males were undecided when given a choice between galls containing non-pollinator females from natal syconia and pollinator females from non-natal syconia, suggesting olfactory imprinting by the natal syconial environment. (C) 2013 Elsevier Masson SAS. All rights reserved.

Pulsed rf magnetron sputtered alumina thin films

Alumina thin films were deposited on titanium (Ti) and fused quartz by both direct and reactive pulsed rf magnetron sputtering techniques. X-ray diffraction, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy and atomic force microscopy were utilized to study the phases and surface morphology of the films. The as-deposited alumina thin films were amorphous. However, after annealing at 500 degrees C in vacuum, the crystalline peaks corresponding to the Theta (0), Delta (8) and Chi ()) alumina phases were obtained. The optical transmittance and reflectance as well as IR emittanc,e data were also evaluated for the thin films. The transmittance, e.g., (similar to 90%) of the bare quartz substrate was not changed even when the alumina thin films were deposited for an hour. However, further increase in deposition time (e.g., 7 h) of the alumina thin films showed only a marginal decrease (e.g., similar to 5%) in average transmittance of the bare quartz substrate. The direct and indirect optical band gaps and extinction coefficient of the alumina films were estimated from the transmittance spectra. The IR emittance of the Ti substrate (e.g., similar to 16%) was almost constant after depositing alumina thin films for an hour. Further increase in deposition time showed only a marginal increase (e.g., similar to 9%) in IR emittance value. Therefore, it is proposed that the alumina films developed in the present work can act as a protective cover for the Ti substrate while retaining the thermo-optical properties of the same. The nanohardness and Young's modulus of the alumina thin films were evaluated by the novel nanoindentation technique. The nanohardness was measured as similar to 6 GPa. Further, Young's modulus was evaluated as similar to 116 GPa. The magnitudes of the nanomechanical properties of the thin films were a little smaller than those reported in the literature. This was linked to the lack of crystalline phases in the as-deposited alumina thin films. (C) 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Study of liquid fuel transport in a small carburetted engine in the context of cold-start HC emission control

In the present study, a detailed visualization of the transport of fuel film has been performed in a small carburetted engine with a transparent manifold at the exit of the carburettor. The presence of fuel film is observed significantly on the lower half of the manifold at idling, while at load conditions, the film is found to be distributed all throughout the manifold walls. Quantitative measurement of the fuel film in a specially-designed manifold of square cross section has also been performed using the planar laser-induced fluorescence (PLIF) technique. The measured fuel film thickness is observed to be of the order of 1 nun at idling, and in the range of 0.1 to 0.4 mm over the range of load and speed studied. These engine studies are complemented by experiments conducted in a carburettor rig to study the state of the fuel exiting the carburettor. Laser-based Particle/Droplet Image Analysis (PDIA) technique is used to identify fuel droplets and ligaments and estimate droplet diameters. At a throttle position corresponding to idling, the fuel exiting the carburettor is found to consist of very fine droplets of size less than 15 mu m and large fuel ligaments associated with length scales of the order of 500 mu m and higher. For a constant pressure difference across the carburettor, the fuel consists of droplets with an SMD of the order of 30 mu m. Also, the effect of liquid fuel film on the cold start HC emissions is studied. Based on the understanding obtained from these studies, strategies such as manifold heating and varying carburettor main jet nozzle diameter are implemented. These are observed to reduce emissions under both idling and varying load conditions.

Microscopic description of the evolution of the local structure and an evaluation of the chemical pressure concept in a solid solution

Extended x-ray absorption fine-structure studies have been performed at the Zn K and Cd K edges for a series of solid solutions of wurtzite Zn1-xCdxS samples with x = 0.0, 0.1, 0.25, 0.5, 0.75, and 1.0, where the lattice parameter as a function of x evolves according to the well-known Vegard's law. In conjunction with extensive, large-scale first-principles electronic structure calculations with full geometry optimizations, these results establish that the percentage variation in the nearest-neighbor bond distances are lower by nearly an order of magnitude compared to what would be expected on the basis of lattice parameter variation, seriously undermining the chemical pressure concept. With experimental results that allow us to probe up to the third coordination shell distances, we provide a direct description of how the local structure, apparently inconsistent with the global structure, evolves very rapidly with interatomic distances to become consistent with it. We show that the basic features of this structural evolution with the composition can be visualized with nearly invariant Zn-S-4 and Cd-S-4 tetrahedral units retaining their structural integrity, while the tilts between these tetrahedral building blocks change with composition to conform to the changing lattice parameters according to the Vegard's law within a relatively short length scale. These results underline the limits of applicability of the chemical pressure concept that has been a favored tool of experimentalists to control physical properties of a large variety of condensed matter systems.

Impacts of modern transitions on thermal comfort in vernacular dwellings in warm-humid climate of Sugganahalli (India)

Sugganahalli, a rural vernacular community in a warm-humid region in South India, is under transition towards adopting modern construction practices. Vernacular local building elements like rubble walls and mud roofs are given way to burnt brick walls and reinforced cement concrete (RCC)/tin roofs. Over 60% of Indian population is rural, and implications of such transitions on thermal comfort and energy in buildings are crucial to understand. Vernacular architecture evolves adopting local resources in response to the local climate adopting passive solar designs. This paper investigates the effectiveness of passive solar elements on the indoor thermal comfort by adopting modern climate-responsive design strategies. Dynamic simulation models validated by measured data have also been adopted to determine the impact of the transition from vernacular to modern material-configurations. Age-old traditional design considerations were found to concur with modern understanding into bio-climatic response and climate-responsiveness. Modern transitions were found to increase the average indoor temperatures in excess of 7 degrees C. Such transformations tend to shift the indoor conditions to a psychrometric zone that is likely to require active air-conditioning. Also, the surveyed thermal sensation votes were found to lie outside the extended thermal comfort boundary for hot developing countries provided by Givoni in the bio-climatic chart.

Electron microscopy of Ag-(Ni-O) core-shell nanowires

This report provides information about an electrodeposition based two-step synthesis methodology for producing core-shell Ag-(Ni-O) nanowires and their detailed structural and compositional characterization using electron microscopy technique. Nanowires were produced by employing anodic alumina templates with a pore diameter of 200 nm. In the first step of the synthesis process, nanocrystalline Ni-O was electrodeposited in a controlled manner such that it heterogeneously nucleated and grew only on the template pore walls without filling the pores from bottom upwards. This alumina template with pore walls coated with Ni-O was then utilized as a template during the electrodeposition of Ag in the second step. Electrodeposited Ag filled the template pores to finally produce Ag-(Ni-O) core-shell nanowires with an overall diameter of 200 nm.

TRANSIENT NATURAL CONVECTION FLOW IN A RECTANGULAR CAVITY FILLED WITH A POROUS MATERIAL WITH LOCALIZED HEATING FROM BELOW AND THERMAL STRATIFICATION

The transient natural convection flow with thermal stratification in a rectangular cavity filled with fluid saturated porous medium obeying Darcy's law has been studied. Prior to the time t* = 0, the flow in the cavity is assumed to be motionless and all four walls of the cavity are at the same constant temperature. At time t* = 0, the temperatures of the vertical walls are suddenly increased which vary linearly with the distance y and at the same time on the bottom wall an isothermal heat source is placed centrally. This sudden change in the wall temperatures gives rise to unsteadiness in the problem. The horizontal temperature difference induces and sustains a buoyancy driven flow in the cavity which is then controlled by the vertical temperature difference. The partial differential equations governing the transient natural convection flow have been solved numerically. The local and average Nusselt numbers decrease rapidly in a small time interval after the start of the impulsive change in the wall temperatures and the steady state is reached quickly. The time required to reach the steady state depends on the Rayleigh number and the thermal stratification parameter.

Dual enzyme responsive and targeted nanocapsules for intracellular delivery of anticancer agents

We report the fabrication of dual enzyme responsive hollow nanocapsules which can be targeted to deliver anticancer agents specifically inside cancer cells. The enzyme responsive elements, integrated in the nanocapsule walls, undergo degradation in the presence of either trypsin or hyaluronidase leading to the release of encapsulated drug molecules. These nanocapsules, which were crosslinked and functionalised with folic acid, showed minimal drug leakage when kept in pH 7.4 PBS buffer, but released the drug molecules at a rapid rate in the presence of either one of the triggering enzymes. Studies on cellular interactions of these nanocapsules revealed that doxorubicin loaded nanocapsules were taken up by cervical cancer cells via folic acid receptor medicated endocytosis. Interestingly the nanocapsules were able to disintegrate inside the cancer cells and release doxorubicin which then migrated into the nucleus to induce cell death. This study indicates that these nanocapsules fabricated from biopolymers can serve as an excellent platform for targeted intracellular drug delivery to cancer cells.

Analysis of cracked and un-cracked semicircular rings under symmetric loading

Edge cracked specimens have been widely utilized for fracture testing. Edge cracked semicircular disk (ECSD) specimen has now been well characterized with regard to its form factor and weight function. This paper presents a modified semicircular ring version of this specimen to enhance the form factor in general while retaining other desirable features. The efficacy of the modified design is proved by combining theory of elasticity solutions with finite element results to arrive at the optimum design geometry. New insights emerging from this work are used to theoretically re-examine the arch-tension and the four-point bend specimens. (C) 2014 Elsevier Ltd. All rights reserved.

Exploiting oriented attachment in stabilizing La3+-doped gallium oxide nano-spindles

Retaining the morphology of gallium oxide nanostructures during structural transformations or after doping with lanthanide ions is not facile. Here we report on the sonochemical synthesis of nearly monodisperse similar to 550 nm long nano-spindles of undoped and La-doped alpha-GaOOH. The transformation of as-prepared undoped and La-doped alpha-GaOOH powders into the corresponding undoped and La-doped Ga2O3 phases (alpha and beta) was achieved by carrying out controlled annealing at elevated temperatures under optimized conditions. The formation of gallium oxide nano-spindles is explained by invoking the phenomenon of oriented attachment, as amply supported by electron microscopy. Interestingly, the morphology of the gallium oxide nano-spindles remained conserved even after doping them with more than 1.4 at% of La3+ ions. Such robust structural stability could be attributed to the oriented attachment-type growth observed in the nano-spindles. The as-prepared samples and the corresponding annealed ones were thoroughly characterized by powder X-ray diffraction (PXRD), electron microscopy (SEM, TEM, and STEM-EDS) and X-ray photoelectron spectroscopy (XPS). Finally, photoluminescence from the single-crystalline undoped and La-doped beta-Ga2O3 was explored.

Throwing light on platinized carbon nanostructured composites for hydrogen generation

In the present study, we have synthesised carbon nanoparticles (CNPs) through a relatively simple process using a hydrocarbon precursor. These synthesised CNPs in the form of elongated spherules and/or agglomerates of 30-55 nm were further used as a support to anchor platinum nanoparticles. The broad light absorption (300-700 nm) and a facile charge transfer property of CNPs in addition to the plasmonic property of Pt make these platinized carbon nanostructures (CNPs/Pt) a promising candidate in photocatalytic water splitting. The photocatalytic activity was evaluated using ethanol as the sacrificial donor. The photocatalyst has shown remarkable activity for hydrogen production under UV-visible light while retaining its stability for nearly 70 h. The broadband absorption of CNPs, along with the Surface Plasmon Resonance (SPR) effect of PtNPs singly and in composites has pronounced influence on the photocatalytic activity, which has not been explored earlier. The steady rate of hydrogen was observed to be 20 mu mol h(-1) with an exceptional cumulative hydrogen yield of 32.16 mmol h(-1) g(-1) observed for CNPs/Pt, which is significantly higher than that reported for carbon-based systems.