Effect of Reagent Addition Rate and Temperature on Synthesis of Gold Nanoparticles in Microemulsion Route

Nanoparticle synthesis in a microemulsion route is typically controlled by changing the water to surfactant ratio, concentration of precursors, and/or concentration of micelles. The experiments carried out in this work with chloroauric acid and hydrazine hydrate as precursors in water/AOT-Brij30/isooctane microemulsions show that the reagent addition rate can also be used to tune the size of stable spherical gold nanoparticles to some extent. The particle size goes through a minimum with variation in feed addition rate. The increase in particle size with an increase in reaction temperature is in agreement with an earlier report. A population balance model is used to interpret the experimental findings. The reduced extent of nucleation at low feed addition rates and suppression of nucleation due to the finite rate of mixing at higher addition rates produce a minimum in particle size. The increase in particle size at higher reaction temperatures is explained through an increase in fusion efficiency of micelles which dissipates supersaturation; increase in solubility is shown to play an insignificant role. The moderate polydispersity of the synthesized particles is due to the continued nucleation and growth of particles. The polydispersity of micelle sizes by itself plays a minor role.

On the evidence for the effect of bubble interference on cavitation noise

Cavitation-noise measurements from an axisymmetric body with ‘controlled’ generation of cavitation are reported. The control was achieved by seeding artificial nuclei in the boundary layer by electrolysis. It was possible to alter the number density of nuclei by varying the electrolysis voltage, polarity and the geometry of the electrode. From the observed trend of cavitation-noise data it is postulated that there exists an ‘interference effect’ which influences cavitation noise. When the nucleus-number density is high and cavitation numbers are low this effect is strong. Under these conditions the properties of cavitation noise are found to differ considerably from those expected based on theories concerning noise from single-spherical-bubble cavitation.

Synthesis and Microstructure of Laser Surface Alloyed Al–Sn–Si Layer on Commercial Aluminum Substrate

A new type of bearing alloy containing ultrafine sized tin and silicon dispersions in aluminum was designed using laser surface alloying and laser remelting techniques. The microstructures of these non-equilibrium processed alloys were studied in detail using scanning and transmission electron microscopy. The microstructures revealed three distinct morphologies of tin particles namely elongated particles co-existing with silicon, globular particles, and very fine particles. Our detailed analyses using cellular growth theories showed that the formation of these globular tin particles was due to the pinching off of the tin rich liquid in the inter-cellular space by the growth of aluminum secondary dendrite arms. Evidence of fine recrystallized aluminum grains at the top layer due to constrained solidification was shown. Thermal analyses suggested that melting of the spherical shaped tin particles was controlled by the binary aluminum-tin eutectic reaction, whereas non-spherical tin particles melted via the tin-silicon eutectic reaction.

Lubricity of an oil in water emulsion in metal cutting: The effect of hydrophilic/lypophilic balance of emulsifiers

A steel disc is cut using a single point tool. The coefficient of friction of the nascent cut surface is measured by a spherical steel pin situated in close proximity of the point of cutting. The tool, disc and the friction pin are immersed in an oil in water emulsion bath during the experiment. The purpose of the experiments conducted here is to record the effect of hydrophilic/lypophilic balance (HLB) of the emulsifier on the lubricity experienced in the cutting operation. The more lypophilic emulsifiers were found to give greater lubricity than what is recorded when the emulsifier is more hydrophilic. XPS and FTIR spectroscopy are used to explore the tribofilm generated on the nascent cut surface to indicate a possible rationale for the effect. (C) 2011 Elsevier B.V. All rights reserved.

Encapsulation of cobalt phthalocyanine in zeolite-Y: Evidence for nonplanar geometry

Cobalt (11) phthalocyanine (CoPc) molecules have been encapsulated within the supercage of zeolite-Y. The square-planar complex, being larger than the almost spherical cage, is forced to adopt a distorted geometry on encapsulation. A comparative spectroscopic and magnetic investigation of CoPc encapsulated in zeolite-Y and in the unencapsulated state is reported. These results supported by molecular modeling have been used to understand the nature and extent of the loss of planarity of CoPc on encapsulation. The encapsulated molecule is shown to be the trans-diprotonated species in which the center of inversion is lost due to distortions required to accommodate the square complex within the zeolite. Encapsulation also leads to an enhancement of the magnetic moment of the CoPc. This is shown to be a consequence of the nonplanar geometry of the encapsulated molecule resulting in an excited high-spin state being thermally accessible.

Size-dependent and strain rate effects in quantum dot nanostructures with molecular dynamic simulations

Size and strain rate effects are among several factors which play an important role in determining the response of nanostructures, such as their deformations, to the mechanical loadings. The mechanical deformations in nanostructure systems at finite temperatures are intrinsically dynamic processes. Most of the recent works in this context have been focused on nanowires [1, 2], but very little attention has been paid to such low dimensional nanostructures as quantum dots (QDs). In this contribution, molecular dynamics (MD) simulations with an embedded atom potential method(EAM) are carried out to analyse the size and strain rate effects in the silicon (Si) QDs, as an example. We consider various geometries of QDs such as spherical, cylindrical and cubic. We choose Si QDs as an example due to their major applications in solar cells and biosensing. The analysis has also been focused on the variation in the deformation mechanisms with the size and strain rate for Si QD embedded in a matrix of SiO2 [3] (other cases include SiN and SiC matrices).It is observed that the mechanical properties are the functions of the QD size, shape and strain rate as it is in the case for nanowires [2]. We also present the comparative study resulted from the application of different EAM potentials in particular, the Stillinger-Weber (SW) potential, the Tersoff potentials and the environment-dependent interatomic potential (EDIP) [1]. Finally, based on the stabilized structural properties we compute electronic bandstructures of our nanostructures using an envelope function approach and its finite element implementation.

On a Novel Geometric Representation of Rotation

This paper presents a novel method of representing rotation and its application to representing the ranges of motion of coupled joints in the human body, using planar maps. The present work focuses on the viability of this representation for situations that relied on maps on a unit sphere. Maps on a unit sphere have been used in diverse applications such as Gauss map, visibility maps, axis-angle and Euler-angle representations of rotation etc. Computations on a spherical surface are difficult and computationally expensive; all the above applications suffer from problems associated with singularities at the poles. There are methods to represent the ranges of motion of such joints using two-dimensional spherical polygons. The present work proposes to use multiple planar domain “cube” instead of a single spherical domain, to achieve the above objective. The parameterization on the planar domains is easy to obtain and convert to spherical coordinates. Further, there is no localized and extreme distortion of the parameter space and it gives robustness to the computations. The representation has been compared with the spherical representation in terms of computational ease and issues related to singularities. Methods have been proposed to represent joint range of motion and coupled degrees of freedom for various joints in digital human models (such as shoulder, wrist and fingers). A novel method has been proposed to represent twist in addition to the existing swing-swivel representation.

Form, Content, and Magnetism in Iron Oxide Nanocrystals

Monodisperse iron oxide nanocrystals with spherical and cubic morphologies, of comparable dimensions, have been prepared by the thermal decomposition of FeOOH. The lattice spacings of both forms agree with that of magnetite, Fe(3)O(4). The two, however, exhibit very different blocking temperatures. Nanocrystals of cubic morphology are superparamagnetic above 190 K while the spherical nanocrystals at a lower temperature, 142 K. The higher blocking temperatures in particles of cubic morphology are shown to be a consequence of exchange bias fields. We show that in the present iron oxide nanocrystals the exchange bias fields originate from the presence of trace amounts of wustite, FeO. A Reitveld refinement analysis of the X-ray diffraction patterns shows that nanocrystals of cubic morphology have a higher FeO content. The higher FeO content is responsible for the larger exchange bias fields that in turn lead to a higher blocking temperature for nanocrystals with cubic morphology.

Redundancy resolution using a tractrix and its application to real-time simulations of hyper-redundant manipulators, snakes and tying of knots

To realistically simulate the motion of flexible objects such as ropes, strings, snakes, or human hair,one strategy is to discretise the object into a large number of small rigid links connected by rotary or spherical joints. The discretised system is highly redundant and the rotations at the joints (or the motion of the other links) for a desired Cartesian motion of the end of a link cannot be solved uniquely. In this paper, we propose a novel strategy to resolve the redundancy in such hyper-redundant systems.We make use of the classical tractrix curve and its attractive features. For a desired Cartesian motion of the `head'of a link, the `tail' of the link is moved according to a tractrix,and recursively all links of the discretised objects are moved along different tractrix curves. We show that the use of a tractrix curve leads to a more `natural' motion of the entire object since the motion is distributed uniformly along the entire object with the displacements tending to diminish from the `head' to the `tail'. We also show that the computation of the motion of the links can be done in real time since it involves evaluation of simple algebraic, trigonometric and hyperbolic functions. The strategy is illustrated by simulations of a snake, tying of knots with a rope and a solution of the inverse kinematics of a planar hyper-redundant manipulator.

A near-singular, flexure jointed, moment sensitive Stewart platform based fore-torque sensor

A force-torque sensor capable of accurate measurement of the three components of externally applied forces and moments is required for force control in robotic applications involving assembly operations. The goal in this paper is to design a Stewart platform based force torque sensor at a near-singular configuration sensitive to externally applied moments. In such a configuration, we show an enhanced mechanical amplification of leg forces and thereby higher sensitivity for the applied external moments. In other directions, the sensitivity will be that of a normal load sensor determined by the sensitivity of the sensing element and the associated electronic amplification, and all the six components of the force and torque can be sensed. In a sensor application, the friction, backlash and other non-linearities at the passive spherical joints of the Stewart platform will affect the measurements in unpredictable ways. In this sensor, we use flexural hinges at the leg interfaces of the base and platform of the sensor. The design dimensions of the flexure joints in the sensor have been arrived at using FEA. The sensor has been fabricated, assembled and instrumented. It has been calibrated for low level loads and is found to show linearity and marked sensitivity to moments about the three orthogonal X, Y and Z axes. This sensor is compatible for usage as a wrist sensor for a robot under development at ISRO Satellite Centre.

Characterization of phase transformation behaviour and microstructural development of electroless Ni-B coating

Phase transformation behaviour of amorphous electroless Ni-B coating with a targeted composition of Ni-6wt% B is characterized in conjunction with microstructural development and hardness. Microscopic observations of the as-deposited coating display a novel microstructure which is already phase separated at multiple length scales. Spherical colonies of similar to 5 mu m consist of 2-3 mu m nodular regions which are surrounded by similar to 2-3 mu m region that contains fine bands ranging from 10 to 70 nm in width. The appearance of three crystalline phases in this binary system at different stages of heat treatment and the concomitant variation in hardness are shown to arise from nanoscale fluctuations in the as-deposited boron content from 4 to 8 wt%. High temperature annealing reveals continuous crystallization up to 430 degrees C, overlapping with the domain of B loss due to diffusion into the substrate. The implications of such a microstructure for optimal heat treatment procedures are discussed. (C) 2011 Elsevier B.V. All rights reserved.

Evolution of crystallinity of free gold agglomerates and shape transformation

We report the shape evolution of free gold agglomerates with different morphologies that transform to ellipsoidal and then to spherical shapes during the heating cycle. The shape transformation is associated with a structural transition from polycrystalline to single crystalline. The structural transition temperature is shown to be dependent on the final size of the particles and not on the initial morphologies of the agglomerates. It is also shown that the transition occurs well below the melting temperature which is in contrast with the melt-freeze process reported in the literature.

Clustering Based Large Margin Classification: A Scalable Approach using SOCP Formulation

This paper presents a novel Second Order Cone Programming (SOCP) formulation for large scale binary classification tasks. Assuming that the class conditional densities are mixture distributions, where each component of the mixture has a spherical covariance, the second order statistics of the components can be estimated efficiently using clustering algorithms like BIRCH. For each cluster, the second order moments are used to derive a second order cone constraint via a Chebyshev-Cantelli inequality. This constraint ensures that any data point in the cluster is classified correctly with a high probability. This leads to a large margin SOCP formulation whose size depends on the number of clusters rather than the number of training data points. Hence, the proposed formulation scales well for large datasets when compared to the state-of-the-art classifiers, Support Vector Machines (SVMs). Experiments on real world and synthetic datasets show that the proposed algorithm outperforms SVM solvers in terms of training time and achieves similar accuracies.

Instabilities of soft elastic microtubes filled with viscous fluids: Pearls, wrinkles, and sausage strings

A linear stability analysis is presented to study the self-organized instabilities of a highly compliant elastic cylindrical shell filled with a viscous liquid and submerged in another viscous medium. The prototype closely mimics many components of micro-or nanofluidic devices and biological processes such as the budding of a string of pearls inside cells and sausage-string formation of blood vessels. The cylindrical shell is considered to be a soft linear elastic solid with small storage modulus. When the destabilizing capillary force derived from the cross-sectional curvature overcomes the stabilizing elastic and in-plane capillary forces, the microtube can spontaneously self-organize into one of several possible configurations; namely, pearling, in which the viscous fluid in the core of the elastic shell breaks up into droplets; sausage strings, in which the outer interface of the mircrotube deforms more than the inner interface; and wrinkles, in which both interfaces of the thin-walled mircrotube deform in phase with small amplitudes. This study identifies the conditions for the existence of these modes and demonstrates that the ratios of the interfacial tensions at the interfaces, the viscosities, and the thickness of the microtube play crucial roles in the mode selection and the relative amplitudes of deformations at the two interfaces. The analysis also shows asymptotically that an elastic fiber submerged in a viscous liquid is unstable for Y = gamma/(G(e)R) > 6 and an elastic microchannel filled with a viscous liquid should rupture to form spherical cavities (pearling) for Y > 2, where gamma, G(e), and R are the surface tension, elastic shear modulus, and radius, respectively, of the fiber or microchannel.

Combustion synthesis, characterization and Raman studies of ZnO nanopowders

Spherical shaped ZnO nanopowders (14-50 nm) were synthesized by a low temperature solution combustion method in a short time <5 min. Rietveld analysis show that ZnO has hexagonal wurtzite structure with lattice constants a = 3.2511(1) angstrom, c = 5.2076(2) angstrom, unit cell volume (V) = 47.66(5) (angstrom)(3) and belongs to space group P63mc. SEM micrographs reveal that the particles are spherical in shape and the powders contained several voids and pores. TEM results also confirm spherical shape, with average particle size of 14-50 nm. The values are consistent with the grain sizes measured from Scherrer's method and Williamson-Hall (W-H) plots. A broad UV-vis absorption spectrum was observed at similar to 375 nm which is a characteristic band for the wurtzite hexagonal pure ZnO. The optical energy band gap of 3.24 eV was observed for nanopowder which is slightly lower than that of the bulk ZnO (3.37 eV). The observed Raman peaks at 438 and 588 cm(-1) were attributed to the E(2) (high) and E(1) (LO) modes respectively. The broad band at 564 cm(-1) is due to disorder-activated Raman scattering for the A(1) mode. These bands are associated with the first-order Raman active modes of the ZnO phase. The weak bands observed in the range 750-1000 cm(-1) are due to small defects. (C) 2011 Elsevier B.V. All rights reserved.