Synthesis of Cu@ZnO Core−Shell Nanocomposite through Digestive Ripening of Cu and Zn Nanoparticles

The synthesis of colloids of copper and zinc nanoparticles by solvated metal atom dispersion (SMAD) is described. The as-prepared colloids with a large size distribution of the particles are transformed into colloidal nanoparticles of a narrow size distribution by the digestive ripening process which involves refluxing the colloid at or near the boiling point of the solvent in the presence of a passivating ligand. The copper nanoparticles of 2.1 ± 0.3 nm and zinc nanoparticles of 3.9 ± 0.3 nm diameters have thus been obtained. Digestive ripening of the as-prepared copper and zinc colloids together in the presence of a passivating agent gave Cu@ZnO core−shell nanoparticles, with an average diameter of 3.0 ± 0.7 nm. Particles synthesized in this manner were characterized by UV−visible spectroscopy, high-resolution electron microscopy, energy-filtered electron microscopy, and powder X-ray diffraction methods which confirm the core−shell structure.

Modeling of formation of gold nanoparticles by citrate method

Properties of nanoparticles are size dependent, and a model to predict particle size is of importance. Gold nanoparticles are commonly synthesized by reducing tetrachloroauric acid with trisodium citrate, a method pioneered by Turkevich et al (Discuss. Faraday Soc. 1951, 11, 55). Data from several investigators that used this method show that when the ratio of initial concentrations of citrate to gold is varied from 0.4 to similar to 2, the final mean size of the particles formed varies by a factor of 7, while subsequent increases in the ratio hardly have any effect on the size. In this paper, a model is developed to explain this widely varying dependence. The steps that lead to the formation of particles are as follows: reduction of Au3+ in solution, disproportionation of Au+ to gold atoms and their nucleation, growth by disproportionation on particle surface, and coagulation. Oxidation of citrate results in the formation of dicarboxy acetone, which aids nucleation but also decomposes into side products. A detailed kinetic model is developed on the basis of these steps and is combined with population balance to predict particle-size distribution. The model shows that, unlike the usual balance between nucleation and growth that determines the particle size, it is the balance between rate of nucleation and degradation of dicarboxy acetone that determines the particle size in the citrate process. It is this feature that is able to explain the unusual dependence of the mean particle size on the ratio of citrate to gold salt concentration. It is also found that coagulation plays an important role in determining the particle size at high concentrations of citrate.

Aerosol characteristics and radiative impacts over the Arabian Sea during the intermonsoon season: Results from ARMEX field campaign

During the second phase of the Arabian Sea Monsoon Experiment (ARMEX-II), extensive measurements of spectral aerosol optical depth, mass concentration, and mass size distribution of ambient aerosols as well as mass concentration of aerosol black carbon (BC) were made onboard a research vessel during the intermonsoon period (i.e., when the monsoon winds are in transition from northeasterlies to westerlies/ southwesterlies) over the Arabian Sea (AS) adjoining the Indian Peninsula. Simultaneous measurements of spectral aerosol optical depths (AODs) were made at different regions over the adjoining Indian landmass. Mean AODs (at 500-nm wavelength) over the ocean (similar to0.44) were comparable to those over the coastal land (similar to0.47), but were lower than the values observed over the plateau regions of central Indian Peninsula (similar to0.61). The aerosol properties were found to respond distinctly with respect to change in the trajectories, with higher optical depths and flatter AOD spectra associated with trajectories indicating advection from west Asia, and northwest and west-coastal India. On average, BC constituted only similar to2.2% to total aerosol mass compared to the climatological values of similar to6% over the coastal land during the same season. These data are used to characterize the physical properties of aerosols and to assess the resulting short-wave direct aerosol forcing. The mean values were similar to27 W m(-2) at the surface and -12 W m(-2) at the top of the atmosphere (TOA), resulting in a net atmospheric forcing of +15 W m(-2). The forcing also depended on the region from where the advection predominates. The surface and atmospheric forcing were in the range -40 to -57 W m(-2) and +27 to +39 W m(-2), respectively, corresponding to advection from the west Asian and western coastal India where they were as low as -19 and +10 W m(-2), respectively, when the advection was mainly from the Bay of Bengal and from central/peninsular India. In all these cases, the net atmospheric forcing (heating) efficiency was lower than the values reported for northern Indian Ocean during northern winter, which is attributed to the reduced BC mass fraction.

Tribology of steel/steel interaction in oil-in-water mulsion; a rationale for lubricity

Oil droplets are dispersed in water by an anionic urfactant to form an emulsion. The lubricity of this emulsion in steel/steel interaction is explored in a ball on flat nanotribometer. The droplet size and charge are measured using dynamic light scattering, while the substrate charge density is estimated using the pH titration method. These data are combined to calculate the DLVO forces for the droplets generated for a range of surfactant concentration and two oil to water volume ratios. The droplets have a clear bi-modal size distribution. The study shows that the smaller droplets which experience weak repulsion are situated (at the highest DLVO barrier) much closer to the substrate than thebigger droplets, which experience the same DLVO force, are. We suggest that the smaller droplets thus play a more important role in lubricity than what the bigger droplets do. The largest volume of such small droplets occurs in the 0.5 mM-1 mM range of surfactant concentration and 1% oil to water volume ratio, where the coefficient of friction is also observed to be the least. (C) 2010 Elsevier Inc. All rights reserved.

Dust Deposition on Single Cylinders

The inertial impaction of Lycopodium spores on single wires lying transverse to the direction of flow has been studied. The equations of particle motion in a potential flow field have been modified for the case when Stokes' law is inapplicable. Solutions to the above equations have been obtained by digital computation. Rec, the Reynolds number based on cylinder diameter, varied from 4 to 240; particle trajectories in a flow field at Rec = 10 have been determined for inertia parameter K = 1, 2, 4, 6, and 10. Ten trajectories were developed for the above cases by the numerical stepwise method. Experiments were performed by depositing Lycopodium spores on adhesive-coated wires of various diameters and at different velocities. The weight of dust deposited was determined with a microbalance. The experimental conditions were:. Wire diameters: 345, 457, 1500 μ. Particle diameter: 35 μ. Air velocities: 20-250 cm/sec. Inertia parameter: 1-60. The particle was considered as a point mass in the theoretical analysis. But in the experiments the ratio of particle size to wire size was not negligible (rp/rc = 0·1) and hence the effect of finite size of particle on collection efficiency due to the direct interception effect has been estimated. The effect of particle size distribution on collection efficiency has also been estimated. The experimental efficiencies obtained compare well with the calculated efficiencies at Rec = 10 when direct interception is taken into account.

Growth Mechanism of Cadmium Sulfide Nanocrystals

We investigate the growth kinetics of CdS nanocrystals in the quantum confinement regime using time-resolved small-angle X-ray scattering. In contrast to earlier reports for similar systems, we establish that the growth kinetics in this case follows the Lifshitz-Slyozov-Wagner theory, for not only growth of the average diameter of the nanocrystals but also the time dependence of the size distribution and the temperature dependence of the rate constant. This is the first rigorous example of the coarsening process in the quantum confinement (< 5 nm)regime. Ab initio studies for the reaction pathways provide a microscopic understanding of this finding.

Nanostructured Copper(II) oxide thin film for alcohol sensing

Nanostructured copper(II) oxide film was deposited using reactive DC magnetron sputtering. It has been characterized using XRD, EDAX, XPS, and FESEM. The grain size of copper oxide film was found to be 40-65 nm with size distribution. The entire study was divided into two parts. In the first part, the film has been studied for its response to alcohol at different temperatures to find the optimum sensing temperature, whereas in the second part, the film sensitivity to different alcohol concentrations were studied at fixed optimum operating temperature. The optimum temperature for the response of ethanol was observed to be 400 C,and the response for different concentrations was found to be almost linear.

The effect of cooling rate on the structure and properties of closed-cell aluminium foams

The application of different cooling rates as a strategy to enhance the structure of aluminium foams is studied. The potential to influence the level of morphological defects and cell size non-uniformities is investigated. AlSi6Cu4 alloy was foamed through the powder compact route and then solidified, applying three different cooling rates. Foam development was monitored in situ by means of X-ray radioscopy while foaming inside a closed mould. The macro-structure of the foams was analysed in terms of cell size distribution as determined by X-ray tomography. Compression tests were conducted to assess the mechanical performance of the foams and measured properties were correlated with structural features of the foams. Moreover, possible changes in the ductile brittle nature of deformation with cooling rate were analysed by studying the initial stages of deformation. We observed improvements in the cell size distributions, reduction in microporosity and grain size at higher cooling rates, which in turn led to a notable enhancement in compressive strength. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

A study of geotechnical properties of Cochin Marine Clays

Most of the Greater Cochin area, which is undergoing rapid industrialisation, consists of extremely soft marine clay calling for expensive deep foundations. This paper presents a study on the physical properties and engeering characteristics of Cochin marine clays. These marine clays are characterised by high Atterberg limits and natural water contents. They are moderately sensitive with liquidity indices ranging over 0.46 to 0.87.The grain size distribution shows almost equal fractions of clay and silt size with sand content varying around 20%. Use of a dispersing agent in carrying out grain size distribution test plays an important role. The fabric of these clays had been identified as flocculant. The pore water has low salinity which results in marginal changes in properties on washing.Consolidation test results showed a preconsolidation pressure of up to about 0.5 kg/cm2 with high compression indices. Compression index vs liquid limit yielded a correlation comparable to that of published data. The undisturbed samples have a much larger coefficient of secondary consolidation as a result of flocculant fabric. These clays have very low undrained shear strength.

Evolution of polyandry by reduction in progeny number variance in structured populations

When there is a variation in the quality of males in a population, multiple mating can lead to an increase in the genetic fitness of a female by reducing the variance of the progeny number. The extent of selective advantage obtainable by this process is investigated for a population subdivided into structured demes. It is seen that for a wide range of model parameters (deme size, distribution of male quality, local resource level), multiple mating leads to a considerable increase in the fitness. Frequency-dependent selection or a stable coexistence between polyandry and monandry can also result when the possible costs involved in multiple mating are taken into account.

Annealing effect on transport properties of Nd0.67Sr0.33MnO3 thin films

Annealing dependence of the lattice parameter, resistivity, magnetoresistance and thermopower have been studied on Nd0.87Sr0.33MnO3 thin films deposited on LaAlO3 and alumina substrates by pulsed laser ablation. Upon annealing at 800 degrees C and 1000 degrees C the lattice constant of the LaAlO3 film tends toward that of the bulk target due to reduction in oxygen vacancies. This results in a metal-insulator transition at temperatures which increase with progressive annealing along with a decrease in the observed low temperature MR. Using a magnon scattering model we estimate the e(g) bandwidth of the film annealed at 1000 degrees C and show that the magnon contribution to the resistivity is suppressed in a highly oxygen deficient film and gains prominence only upon subsequent annealing. We also show that upon annealing, the polaron concentration and the spin cluster size increases in the paramagnetic phase, using an adiabatic polaron hopping model which takes into account an exchange dependent activation energy above the resistivity peak.

Study of the growth of capped ZnO nanocrystals: A route to rational synthesis

We report the study of complex and unexpected dependencies of nanocrystal size as well as nanocrystalsize distribution on various reaction parameters in the synthesis of ZnO nanocrystals using poly(vinyl pyrollidone) (PVP) as a capping agent. This method establishes a qualitatively different growth mechanism to the anticipated Ostwald ripening behavior. The study of size-distribution kinetics and an understanding of the observed non-monotonic behaviors provides a route to rational synthesis. We used a simple, but accurate, approach to estimate the size-distribution function of nanocrystals from the UV-absorption spectrum. Our results demonstrate the accuracy and generality of this approach, and we also illustrate its application to various semiconducting nanocrystals, such as ZnO, ZnS, and CdSe, over a wide size range (1.8-5.3 nm).

Photocatalytic treatment of municipal wastewater using modified neodymium doped TiO2 hybrid nanoparticles

Photocatalytic degradation of municipal wastewater was investigated using reagent grade TiO2 and modified neodymium doped TiO2 hybrid nanoparticles. For the first time, surface modification of Nd3+ doped TiO2 hybrid nanoparticles were carried out with n-butylamine as surface modifier under mild hydrothermal conditions. The modified nanoparticles obtained were characterized by Powder XRD, FTIR, DLS, TEM, BET surface area, zeta potential and UV-Vis Spectroscopy. The characterization results indicated better morphology, particle size distribution and low agglomeration of the nanoparticles synthesized. It was found that photodegradation of wastewater using surface modified neodymium doped TiO2 nanoparticles was more compared to pure TiO2, which can be attributed to the doping and modification with n-butylamine.

Breakup of drops around the edges of Rushton turbine

A detailed experimental and simulation study has been carried out in the present work to understand drop breakup in regions around the edge of the Rushton turbine in agitated vessels. The effect of impeller speed, impeller size, interfacial tension, and the viscosities of the two phases is studied on drop breakup through their effect on dmax, the size of the largest drop in the system, and the whole size distribution. The measurements were carried out using Galai particle size analyser and optical microscope. Experimental analysis shows that the dmax, maximum stable drop diameter varies with impeller tip velocity to the power -1. The variation of dmax with interfacial tension is studied using different surfactants. The effect of viscosity ratio, achieved by changing the dispersed phase viscosity, on dmax is captured. For the same dmax values obtained from two different dispersed phases show that the wider drop size distribution is observed for higher dispersed phase viscosity.

A new model for the breakage frequency of drops in turbulent stirred dispersions

A model of drop breakage in turbulent stirred dispersions based on interaction of a drop with eddies of a length scale smaller than the drop diameter has been developed. It predicts that, unlike the equal breakage assumed by earlier models, a large drop reduces in size due to stripping of smaller segments off it through unequal breakage. It is only when the drop nears the value of the maximum stable drop diameter that it breaks into equal parts. This new model of drop breakage, coupled with the pattern of interaction of drops with eddies of different sizes existing in the vessel, has been used to evaluate not only the breakage frequency, but also the size distribution of the daughter droplets(which was hitherto assumed). The model has been incorporated in the population balance equation and the resulting cumulative size distributions compared with those availble in the literature.