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.

Wave dispersion in a cellular composite with modulated microstructure

In this paper we report a modeling technique and analysis of wave dispersion in a cellular composite laminate with spatially modulated microstructure, which can be modeled by parameterization and homogenization in an appropriate length scale. Higher order beam theory is applied and the system of wave equations are derived. Homogenization of these equations are carried out in the scale of wavelength and frequency of the individual wave modes. Smaller scale scattering below the order of cell size are filtered out in the present approach. The longitudinal dispersion relations for different values of a modulation parameter are analyzed which indicates the existence of stop and pass band patterns. Dispersion relations for flexural-shear case are also analyzed which indicates a tendency toward forming the stop and pass bands for increasing values of a shear stiffness modulation parameter. The effect the phase angle (θ) of the incident wave indicates the existence more number of alternative stop bands and pass bands for θ = 45°.

Topology Optimization of Micromachined Structures with the Manufacturing Constraints of KOH Etching of (110) Silicon

The focus of this paper is on designing useful compliant micro-mechanisms of high-aspect-ratio which can be microfabricated by the cost-effective wet etching of (110) orientation silicon (Si) wafers. Wet etching of (110) Si imposes constraints on the geometry of the realized mechanisms because it allows only etch-through in the form of slots parallel to the wafer's flat with a certain minimum length. In this paper, we incorporate this constraint in the topology optimization and obtain compliant designs that meet the specifications on the desired motion for given input forces. Using this design technique and wet etching, we show that we can realize high-aspect-ratio compliant micro-mechanisms. For a (110) Si wafer of 250 µm thickness, the minimum length of the etch opening to get a slot is found to be 866 µm. The minimum achievable width of the slot is limited by the resolution of the lithography process and this can be a very small value. This is studied by conducting trials with different mask layouts on a (110) Si wafer. These constraints are taken care of by using a suitable design parameterization rather than by imposing the constraints explicitly. Topology optimization, as is well known, gives designs using only the essential design specifications. In this work, we show that our technique also gives manufacturable mechanism designs along with lithography mask layouts. Some designs obtained are transferred to lithography masks and mechanisms are fabricated on (110) Si wafers.

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.

Topology Optimization of Micromachined Structures with Surface Micromachining Manufacturing Constraints

Topology optimization methods have been shown to have extensive application in the design of microsystems. However, their utility in practical situations is restricted to predominantly planar configurations due to the limitations of most microfabrication techniques in realizing structures with arbitrary topologies in the direction perpendicular to the substrate. This study addresses the problem of synthesizing optimal topologies in the out-of-plane direction while obeying the constraints imposed by surface micromachining. A new formulation that achieves this by defining a design space that implicitly obeys the manufacturing constraints with a continuous design parameterization is presented in this paper. This is in contrast to including manufacturing cost in the objective function or constraints. The resulting solutions of the new formulation obtained with gradient-based optimization directly provide the photolithographic mask layouts. Two examples that illustrate the approach for the case of stiff structures are included.

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.

Trapped fermions in a synthetic non-Abelian gauge field

On increasing the coupling strength (lambda) of a non-Abelian gauge field that induces a generalized Rashba spin-orbit interaction, the topology of the Fermi surface of a homogeneous gas of noninteracting fermions of density rho similar to k(F)(3) undergoes a change at a critical value, lambda(T) approximate to k(F) [Phys. Rev. B 84, 014512 ( 2011)]. In this paper we analyze how this phenomenon affects the size and shape of a cloud of spin-1/2 fermions trapped in a harmonic potential such as those used in cold atom experiments. We develop an adiabatic formulation, including the concomitant Pancharatnam-Berry phase effects, for the one-particle states in the presence of a trapping potential and the gauge field, obtaining approximate analytical formulas for the energy levels for some high symmetry gauge field configurations of interest. An analysis based on the local density approximation reveals that, for a given number of particles, the cloud shrinks in a characteristic fashion with increasing.. We explain the physical origins of this effect by a study of the stress tensor of the system. For an isotropic harmonic trap, the local density approximation predicts a spherical cloud even for anisotropic gauge field configurations. We show, via a calculation of the cloud shape using exact eigenstates, that for certain gauge field configurations there is a systematic and observable anisotropy in the cloud shape that increases with increasing gauge coupling lambda. The reasons for this anisotropy are explained using the analytical energy levels obtained via the adiabatic approximation. These results should be useful in the design of cold atom experiments with fermions in non-Abelian gauge fields. An important spin-off of our adiabatic formulation is that it reveals exciting possibilities for the cold-atom realization of interesting condensed matter Hamiltonians by using a non-Abelian gauge field in conjunction with another potential. In particular, we show that the use of a spherical non-Abelian gauge field with a harmonic trapping potential produces a monopole field giving rise to a spherical geometry quantum Hall-like Hamiltonian in the momentum representation.

Structural and electrical properties of low pressure metalorganic chemical vapor deposition grown Eu2O3 films on Si(100)

Structural and electrical properties of Eu2O3 films grown on Si(100) in 500–600 °C temperature range by low pressure metalorganic chemical vapor deposition are reported. As-grown films also possess the impurity Eu1−xO phase, which has been removed upon annealing in O2 ambient. Film’s morphology comprises uniform spherical mounds (40–60 nm). Electrical properties of the films, as examined by capacitance-voltage measurements, exhibit fixed oxide charges in the range of −1.5×1011 to −6.0×1010 cm−2 and dielectric constant in the range of 8–23. Annealing has resulted in drastic improvement of their electrical properties. Effect of oxygen nonstoichiometry on the film’s property is briefly discussed.