Effect of ``dipolar-biasing'' on the tunability of tunneling magnetoresistance in transition metal oxide systems

We observe an unusual tunneling magnetoresistance (TMR) phenomenon in a composite of La2/3Sr1/3MnO3 with CoFe2O4 where the TMR versus applied magnetic field loop suggests a ``negative coercive field.'' Tracing its origin back to a ``dipolar-biasing'' of La2/3Sr1/3MnO3 by CoFe2O4, we show that the TMR of even a single composite can be tuned continuously so that the resistance peak or the highest sensitivity of the TMR can be positioned anywhere on the magnetic field axis with a suitable magnetic history of the sample. This phenomenon of an unprecedented tunability of the TMR should be present in general in all such composites. (C) 2012 American Institute of Physics.http://dx.doi.org/10.1063/1.4731206]

Modeling of Ascending/Descending Velocity of Metal Droplet Emulsified in Pb-Salt System

Metal-slag emulsion is an important process to enhance the reaction rate between the two phases; thus, it improves the heat and mass transfer of the process significantly. Various experimental studies have been carried out, and some system specific relations have been proposed by various investigators. A unified, theoretical study is lacking to model this complex phenomenon. Therefore, two simple models based on fundamental laws for metal droplet velocity (both ascending and descending) and bubble velocity, as well as its position at any instant of time, have been proposed. Analytical solutions have been obtained for the developed equations. Analytical solutions have been verified for the droplet velocity, traveling time, and size distribution in slag phase by performing high-temperature experiments in a Pb-salt system and comparing the obtained data with theory. The proposed model has also been verified with published experimental data for various liquid systems with a wide range of physical properties. A good agreement has been found between the analytical solution and the experimental and published data in all cases.

Self-Assembly and Catalytic Activity of Metal Nanoparticles Immobilized in Polymer Membrane Prepared via Layer-by-Layer Approach

Densely packed nanoparticles distributed in a stable and robust thin film is a highly preferred system for utilizing the various applications of nanoparticles. Here, we report covalent bond mediated layer-by-layer (LbL) self-assembled thin films of nanoparticles embedded in polymer membrane. Polymer with complementary functional group is utilized for fabrication of thin film via covalent bonding. UV-visible spectroscopy, atomic force microscopy (AFM) and scanning electron microscopy (SEM) were used to monitor the growth of LbL thin film. Subsequently, the composite thin film is used for catalysis of an organic electron transfer reaction of p-nitrophenol to p-aminophenol by sodium borohydride. The catalytic activity of these composite films is assayed multiple times, proving its applicability as a catalyst. The kinetic data obtained by monitoring reduction of p-nitrophenol suggest that the reaction rates are directly related to the sizes of the nanoparticle and porosity of the membrane.

Threshold voltage modeling under size quantization for ultra-thin silicon double-gate metal-oxide-semiconductor field-effect transistor

We report on the threshold voltage modeling of ultra-thin (1 nm-5 nm) silicon body double-gate (DG) MOSFETs using self-consistent Poisson-Schrodinger solver (SCHRED). We define the threshold voltage (V th) of symmetric DG MOSFETs as the gate voltage at which the center potential (Φ c) saturates to Φ c (s a t), and analyze the effects of oxide thickness (t ox) and substrate doping (N A) variations on V th. The validity of this definition is demonstrated by comparing the results with the charge transition (from weak to strong inversion) based model using SCHRED simulations. In addition, it is also shown that the proposed V t h definition, electrically corresponds to a condition where the inversion layer capacitance (C i n v) is equal to the oxide capacitance (C o x) across a wide-range of substrate doping densities. A capacitance based analytical model based on the criteria C i n v C o x is proposed to compute Φ c (s a t), while accounting for band-gap widening. This is validated through comparisons with the Poisson-Schrodinger solution. Further, we show that at the threshold voltage condition, the electron distribution (n(x)) along the depth (x) of the silicon film makes a transition from a strong single peak at the center of the silicon film to the onset of a symmetric double-peak away from the center of the silicon film. © 2012 American Institute of Physics.

Semiconductor-metal transition in semiconducting bilayer sheets of transition-metal dichalcogenides

Using first-principles calculations we show that the band gap of bilayer sheets of semiconducting transition-metal dichalcogenides (TMDs) can be reduced smoothly by applying vertical compressive pressure. These materials undergo a universal reversible semiconductor-to-metal (S-M) transition at a critical pressure. The S-M transition is attributed to lifting of the degeneracy of the bands at the Fermi level caused by interlayer interactions via charge transfer from the metal to the chalcogen. The S-M transition can be reproduced even after incorporating the band gap corrections using hybrid functionals and the GW method. The ability to tune the band gap of TMDs in a controlled fashion over a wide range of energy opens up the possibility for its usage in a range of applications.

Route to high Neel temperatures in 4d and 5d transition metal oxides

There are very few magnetic members among the 4d and 5d transition metal oxides. In the present work, we examine the recent observation of a high Neel temperature T-N in the 4d oxides SrTcO3 and CaTcO3. Considering a multiband Hubbard model, we find that T-N is larger in the limit of a large bandwidth and vanishingly small intra-atomic exchange interaction strength, contrary to our conventional understanding of magnetism. This is traced to specific aspects of the d(3) configuration at the transition metal site and the study reveals additional examples with high T-N.

Analysis of Strain Rates and Microstructural Evaluation during Metal Forming: Role of Surface Texture and Friction

The surface texture of a die plays an important role in friction during metal forming. In the present study, unidirectional and random surface finishes were produced on hardened steel plate surfaces. To understand the influence of surface texture on friction, experiments were conducted using Al-Mg alloy pins that slid against steel plates of different surface textures. In the sliding experiments, a high coefficient of friction was observed when the pins slid perpendicular to the unidirectional grinding marks and low friction occurred when the pins slid on the random surfaces. Finite element simulations were performed using the measured friction values to understand the stress and strain evolutions in the deforming material using dies with various friction. The numerical results showed that the states of stress and strain rates are strongly influenced by the friction at the interface and hence would influence the final material microstructure. To substantiate the numerical results, laboratory compression tests were conducted. Different surface textures were obtained in order to experience different friction values at different locations. A large variation in the microstructure at these locations was observed during experiments, verifying that surface texture and die friction significantly influence fundamental material formation behavior.

Bromenium-Catalysed Tandem Ring Opening/Cyclisation of Vinylcyclopropanes and Vinylcyclobutanes: A Metal-Free 3+2+1]/4+2+1] Cascade for the Synthesis of Chiral Amidines and Computational Investigation

We present a detailed study of a 3+2+1] cascade cyclisation of vinylcyclopropanes (VCP) catalysed by a bromenium species (Brd+?Xd-) generated in situ, which results in the synthesis of chiral bicyclic amidines in a tandem one-pot operation. The formation of amidines involves the ring-opening of VCPs with Br?X, followed by a Ritter-type reaction with chloramine-T and a tandem cyclisation. The reaction has been further extended to vinylcyclobutane systems and involves a 4+2+1] cascade cyclisation with the same reagents. The versatility of the methodology has been demonstrated by careful choice of VCPs and VCBs to yield bicyclo4.3.0]-, -4.3.1]- and -4.4.0]amidines in enantiomerically pure form. On the basis of the experimental observations and DFT calculations, a reasonable mechanism has been put forth to account for the formation of the products and the observed stereoselectivity. We propose the existence of a p-stabilised homoallylic carbocation at the cyclopropane carbon as the reason for high stereoselectivity. DFT studies at B3LYP/6-311+G** and M06-2X/6-31+G* levels of theory in gas-phase calculations suggest the ring-opening of VCP is initiated at the p-complex stage (between the double bond and Br?X). This can be clearly perceived from the solution-phase (acetonitrile) calculations using the polarisable continuum model (PCM) solvation model, from which the extent of the ring opening of VCP was found to be noticeably high. Studies also show that the formation of zero-bridge bicyclic amidines is favoured over other bridged bicyclic amidines. The energetics of competing reaction pathways is compared to explain the product selectivity.

Potential and electric field distribution in a ceramic disc insulator string with faulty insulators

Ceramic/Porcelain suspension disc insulators are widely used in power systems to provide electrical insulation and mechanically support for high-voltage transmission lines. These insulators are subjected to a variety of stresses, including mechanical, electrical and environmental. These stresses act in unison. The exact nature and magnitude of these stresses vary significantly and depends on insulator design, application and its location. Due to various reasons the insulator disc can lose its electrical insulation properties without any noticeable mechanical failure. Such a condition while difficult to recognize, can enhance the stress on remaining healthy insulator discs in the string further may lead to a flashover. To understand the stress enhancement due to faulty discs in a string, attempt has been made to simulate the potential and electric field profiles for various disc insulators presently used in the country. The results of potential and electric filed stress obtained for normal and strings with faulty insulator discs are presented.

Metal cholate hydrogels: versatile supramolecular systems for nanoparticle embedded soft hybrid materials

This work describes the formation of hydrogels from sodium cholate solution in the presence of a variety of metal ions (Ca2+, Cu2+, Co2+, Zn2+, Cd2+, Hg2+ and Ag+). Morphological studies of the xerogels by electron microscopy reveal the presence of helical nanofibres. The rigid helical framework in the calcium cholate hydrogel was utilised to synthesize hybrid materials (AuNPs and AgNPs). Doping of transition metal salts into the calcium cholate hydrogel brings out the possibility of synthesising metal sulphide nano-architectures keeping the hydrogel network intact. These novel gel-nanoparticle hybrid materials have encouraging application potentials.

Two orders of magnitude increase in metal piezoresistor sensitivity through nanoscale inhomogenization

Metal-based piezoresistive sensing devices could find a much wider applicability if their sensitivity to mechanical strain could be substantially improved. Here, we report a simple method to enhance the strain sensitivity of metal films by over two orders of magnitude and demonstrate it on specially designed microcantilevers. By locally inhomogenizing thin gold films using controlled electromigration, we have achieved a logarithmic divergence in the strain sensitivity with progressive microstructural modification. The enhancement in strain sensitivity could be explained using non-universal tunneling-percolation transport. We find that the Johnson noise limited signal-to-noise ratio is an order of magnitude better than silicon piezoresistors. This method creates a robust platform for engineering low resistance, high gauge factor metallic piezoresistors that may have profound impact on micro and nanoscale self-sensing technology. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4761817]

Metal and Alloy Nanoparticles by Amine-Borane Reduction of Metal Salts by Solid-Phase Synthesis: Atom Economy and Green Process

A new solid state synthetic route has been developed toward metal and bimetallic alloy nanoparticles from metal salts employing amine-boranes, as the reducing agent. During the reduction, amine-borane plays a dual role: acts as a reducing agent and reduces the metal salts to their elemental form and simultaneously generates a stabilizing agent in situ which controls the growth of the particles and stabilizes them in the nanosize regime. Employing different amine-boranes with differing reducing ability (ammonia borane (AB), dimethylamine borane (DMAB), and triethylamine borane (TMAB)) was found to have a profound effect on the particle size and the size distribution. Usage of AB as the reducing agent provided the smallest possible size with best size distribution. Employment of TMAB also afforded similar results; however, when DMAB was used as the reducing agent it resulted in larger sized nanoparticles that are polydisperse too. In the AB mediated reduction, BNHx polymer generated in situ acts as a capping agent whereas, the complexing amine of the other amine-boranes (DMAB and TMAB) play the same role. Employing the solid state route described herein, monometallic Au, Ag, Cu, Pd, and Ir and bimetallic CuAg and CuAu alloy nanoparticles of <10 nm were successfully prepared. Nucleation and growth processes that control the size and the size distribution of the resulting nanoparticles have been elucidated in these systems.

Tuning the Sensitivity of a Metal-Based Piezoresistive Sensor Using Electromigration

We report a simple method to enhance the piezoresistive sensitivity of a gold film by more than 30 times and demonstrate it using a microcantilever resonator. Our method depends on controlled electromigration that we use to tune the resistance and sensitivity of the piezoresistive sensor. We attribute the enhancement in strain sensitivity to the creation of an inhomogeneous conduction medium at a predefined location by directed and controlled electromigration. We understand this phenomenon with tunneling-percolation model, which was originally hypothesized to explain nonuniversal percolation behavior of composite materials. 2012-0174]

Theoretical-experimental study of shock wave-assisted metal forming process using a diaphragmless shock tube

The use of high-velocity sheet-forming techniques where the strain rates are in excess of 10(2)/s can help us solve many problems that are difficult to overcome with traditional metal-forming techniques. In this investigation, thin metallic plates/foils were subjected to shock wave loading in the newly developed diaphragmless shock tube. The conventional shock tube used in the aerodynamic applications uses a metal diaphragm for generating shock waves. This method of operation has its own disadvantages including the problems associated with repeatable and reliable generation of shock waves. Moreover, in industrial scenario, changing metal diaphragms after every shot is not desirable. Hence, a diaphragmless shock tube is calibrated and used in this study. Shock Mach numbers up to 3 can be generated with a high degree of repeatability (+/- 4 per cent) for the pressure jumps across the primary shock wave. The shock Mach number scatter is within +/- 1.5 per cent. Copper, brass, and aluminium plates of diameter 60 mm and thickness varying from 0.1 to 1 mm are used. The plate peak over-pressures ranging from 1 to 10 bar are used. The midpoint deflection, circumferential, radial, and thickness strains are measured and using these, the Von Mises strain is also calculated. The experimental results are compared with the numerical values obtained using finite element analysis. The experimental results match well with the numerical values. The plastic hinge effect was also observed in the finite element simulations. Analysis of the failed specimens shows that aluminium plates had mode I failure, whereas copper plates had mode II failure.

Metal-Ion Metathesis in Metal-Organic Frameworks: A Synthetic Route to New Metal-Organic Frameworks

A porous metalorganic framework, Mn(H3O)(Mn4Cl)(3)(hmtt)(8)] (POST-65), was prepared by the reaction of 5,5',10,10',15,15'-hexamethyltruxene-2,7,12-tricarboxylic acid (H(3)hmtt) with MnCl2 under solvothermal conditions. POST-65(Mn) was subjected to post-synthetic modification with Fe, Co, Ni, and Cu according to an ion-exchange method that resulted in the formation of three isomorphous frameworks, POST-65(Co/Ni/Cu), as well as a new framework, POST-65(Fe). The ion-exchanged samples could not be prepared by regular solvothermal reactions. The complete exchange of the metal ions and retention of the framework structure were verified by inductively coupled plasmaatomic emission spectrometry (ICP-AES), powder X-ray diffraction (PXRD), and BrunauerEmmettTeller (BET) surface-area analysis. Single-crystal X-ray diffractions studies revealed a single-crystal-to-single-crystal (SCSC)-transformation nature of the ion-exchange process. Hydrogen-sorption and magnetization measurements showed metal-specific properties of POST-65.