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.

Spin injection into a metal from a topological insulator

We study a junction of a topological insulator with a thin two-dimensional nonmagnetic or partially polarized ferromagnetic metallic film deposited on a three-dimensional insulator. We show, by deriving generic boundary conditions applicable to electrons traversing the junction, that there is a finite spin-current injection into the film whose magnitude can be controlled by tuning a voltage V applied across the junction. For ferromagnetic films, the direction of the component of the spin current along the film magnetization can also be tuned by tuning the barrier potential V-0 at the junction. We point out the role of the chiral spin-momentum locking of the Dirac electrons behind this phenomenon and suggest experiments to test our theory.

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.

Effect of pouring temperature on cooling slope casting of semi-solid Al-Si-Mg alloy

Present trend of semi-solid processing is directed towards rheocasting route which allows manufacturing of near-net-shape cast components directly from the prepared semi-solid slurry. Generation of globular equi-axed grains during solidification of rheocast components, compared to the columnar dendritic structure of conventional casting routes, facilitates the manufacturing of components with improved mechanical properties and structural integrity. In the present investigation, a cooling slope has been designed and indigenously fabricated to produce semi solid slurry of Al-Si-Mg (A356) alloy and successively cast in a metallic mould. The scope of the present work discusses about development of a numerical model to simulate the liquid metal flow through cooling slope using Eulerian two-phase flow approach and to investigate the effect of pouring temperature on cooling slope semi-solid slurry generation process. The two phases considered in the present model are liquid metal and air. Solid fraction evolution of the solidifying melt is tracked at different locations of the cooling slope, following Schiel's equation. The continuity equation, momentum equation and energy equation are solved considering thin wall boundary condition approach. During solidification of the liquid metal, a modified temperature recovery scheme has been employed taking care of the latent heat release and change of fraction of liquid. The results obtained from simulations are compared with experimental findings and good agreement has been found.

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.

Microstructure and mechanical properties of oxidation resistant suction cast Nb-Si-Al alloy

In this paper, we report a significant improvement in mechanical and oxidation properties of near eutectic Nb-Si alloys by the addition of aluminum (Al) and control of microstructural length scale. A comparative study of two alloys Nb-18.79at%Si and Nb-12.3at%Si-9at%Al were carried out. The processing for microstructure refinements were carried out by vacuum suction casting in water cooled thick copper mould. It is shown that addition of Al suppresses Nb3Si phase and promotes beta Nb5Si3 phase under nonequilibrium solidification condition. The microstructural length scale and in particular eutectic spacing reduces significantly to 50-100 nm in suction cast ternary alloy. A detailed TEM study shows the presence of delta-Nb11Si4 phase in Nb matrix. The hardness of Nb solid solution can be increased as a consequence to a level observed in Nb3Si intermetallic due to the well oriented precipitates. Compression test yields the ultimate strength of 1.8 +/- 0.1 GPa and engineering strain of 2.3 +/- 0.03%. In comparison, the binary Nb-18.79 at% Si alloy possesses an ultimate strength of 1.35 +/- 0.1 GPa and strain of 0.2 +/- 0.01% when processed under identical conditions. The latter exhibits coarser microstructural length scale (300-400 nm) and a brittle behavior. The indentation fracture toughness of Al containing suction cast alloy shows a value of 20.2 +/- 0.5 MPa root m which represents a major improvement over bulk Nb-Si eutectic alloy. The detailed thermal studies confirm a multifold improvement in oxidation resistance up to 1000 degrees C. (C) 2012 Elsevier B.V. All rights reserved.

B-H Bond Activation Using an Electrophilic Metal Complex: Insights into the Reaction Pathway

A highly electrophilic ruthenium center in the RuCl(dppe)(2)]OTf] complex brings about the activation of the B H bond in ammonia borane (H3N center dot BH3, AB) and dimethylamine borane (Me2HN center dot BH3, DMAB). At room temperature, the reaction between RuCl(dppe)(2)]OTf] and AB or DMAB results in trans-RuH(eta(2)-H-2)(dppe)(2)]OTf] trans-RuCl(eta(2)-H-2)(dppe)(2)]OTf], and trans-RuH(Cl)(dppe)(2)], as noted in the NMR spectra. Mixing the ruthenium complex and AB or DMAB at low temperature (198/193 K) followed by NMR spectral measurements as the reaction mixture was warmed up to room temperature allowed the observation of various species formed enroute to the final products that were obtained at room temperature. On the basis of the variable-temperature multinuclear NMR spectroscopic studies of these two reactions, the mechanistic insights for B-H bond activation were obtained. In both cases, the reaction proceeds via an eta(1)-B-H moiety bound to the metal center. The detailed mechanistic pathways of these two reactions as studied by NMR spectroscopy are described.

Solid State and Solution Mediated Multistep Sequential Transformations in Metal-Organic Coordination Networks

Sequential transformation in a family of metal-organic framework compounds has been investigated employing both a solid-state as well as a solution mediated route. The compounds, cobalt oxy-bis(benzoate) and manganese oxybis(benzoate) having a two-dimensional structure, were reacted with bipyridine forming cobalt oxy-bis(benzoate)-4,4'-bipyridine and manganese oxy-bis(benzoate)-4,4'-bipyridine, respectively. The bipyridine containing compounds appear to form sequentially through stable intermediates. For the cobalt system, the transformation from a two-dimensional compound, Co(H2O)(2)(OBA)] (OBA = 4,4'-oxy-bis(benzoate)), I, to two different three-dimensional compounds, Co(bpy)(OBA)]center dot bpy, II, (bpy = 4,4'-bipyridine) and Co(bpy)(0.5)(OBA)], III, and reversibility between II and III have been investigated. In the manganese system, transformation from a two-dimensional compound, Mn(H2O)(2)(OBA)], Ia, to two different three-dimensional compounds, Mn (bpy)(OBA)]center dot bpy, Ha and Ha to Mn(bpy)(0.5)(OBA)], Ilia, has been investigated. It has also been possible to identify intermediate products during these transformation reactions. The possible pathways for the formation of the compounds were postulated.

Investigations on micro-blast wave assisted metal foil forming for biomedical applications

The deformation dynamics of metal foils (<0.25 mm thick) subjected to micro-blast wave are presented in this paper. The energy of micro-blast wave emanating from the open end of a polymer tube is used to deliver micro-particles for bio-medical applications. In these experiments metal foils are used to transfer the energy of the micro-blast wave to the micro-particles. Using cubic root scaling law the over pressure of the blast wave at the open end of the polymer tube is estimated and using this peak plate over pressure is estimated. The finite element analysis is used to estimate the velocity profile of the deforming metal foils. The finite element analysis results are compared with experimental results for the maximum deformation and deformed shape. Based on the deformation velocity, metal foil to be used for experiments is selected. Among the materials investigated 0.1 mm thick brass foil has the maximum velocity of 205 m/s and is used in the experiments. It is found from finite element analysis that the particles deposited within a radius of 0.5 mm will leave the foil with nearly equal velocity (error < 5%). The spray cone angle which is the angle of deviation of the path of particles from the axis of the polymer tube is also estimated and found to be less than 7 degrees up to a radius of 0.75 mm. Illustrative experiments are carried out to deliver micro particles (0.7 mu m diameter tungsten) into plant tissues. Particle penetration depth up to 460 mu m was achieved in ground tissue of potato tuber. (C) 2012 Elsevier Ltd. All rights reserved.

Synthesis of a mixed-metal spinel, NiMn2O4, through site-selective substitution in MOF, (NiMn2){C6H3(COO)(3)}(2)]: synthesis, structure and magnetic studies

A mixed-metal metal-organic framework (MOF) compound NiMn2{C6H3(COO)(3)}(2)], I, is prepared hydrothermally by replacing one of the octahedral Mn2+ ions in Mn-3{C6H3(COO)(3)}(2)] by Ni2+ ions. Magnetic studies on I suggest antiferromagnetic interactions with weak canted antiferromagnetism below 8 K. On heating in flowing air I transforms to NiMn2O4 spinel at low temperature (T < 400 degrees C). The thermal decomposition of I at different temperatures results in NiMn2O4 with particle sizes in the nano regime. The nanoparticle nature of NiMn2O4 was confirmed using PXRD and TEM studies. Magnetic studies on the nanoparticles of NiMn2O4 indicate ferrimagnetism. The transition temperature of NiMn2O4 nanoparticles exhibits a direct correlation with the particle size. This study highlights the usefulness of MOF compound as a single-source precursor for the preparation of important ceramic oxides with better control on the stoichiometry and particle size.

Effect of Metal Ions (Ag, Co, Ni, and Pd) on the Visible Light Degradation of Rhodamine B by Carbon-Covered Alumina-Supported TiO2 in Aqueous Solutions

Metal-ion (Ag, Co, Ni, and Pd) doped TiO2 nanocatalysts were successfully embedded on carbon-covered alumina supports. The CCA-embedded catalysts were crystalline and had a high surface area compared to the free metal-ion doped titania nanocatalysts while they still retained the anatase phase of the core TiO2. These catalysts were photocatalytically active under solar light irradiation. Rhodamine B was used as a model pollutant and the reactivity followed a pseudo-first-order reaction kinetics. The reaction rate of the CCA-supported catalysts was Pd > Ag > Co > Ni. Among the ratios of the CCA:catalyst used, it was found that the 1:1 ratio had the fastest reaction rate, followed by the 1:2 ratio, while the 2:1 ratio exhibited the lowest reaction rate. The CCA/metal-ion doped titania were found to have photocatalytic activities comparable with those of CCA-supported titania.

New metal-organic precursors for MOCVD applications: Synthesis, characterization, crystal structure and thermal properties of mixed-ligand Mg(II) complexes

In an effort to develop new MOCVD precursors, mixed-ligand metal-organic complexes, bis (acetylacetonato-k(2)O,O') (2,2'-bipyridine-k(2)N,N') magnesium(II), and his (acetylacetonato-k(2)O,O') (1,10-phenanthroline-k(2)N,N') magnesium(II) were synthesized. Spectroscopic characterization and crystal structures confirmed them to be monomeric and stable complexes. Crystal structure analysis suggests in each of the magnesium(II) complexes, the metal center has a distorted octahedral coordination geometry. Thermo-gravimetric analysis (TGA/DTA) suggests that these complexes are volatile and thermally stable. The thermal characteristics of newly designed complexes make them attractive precursors for MOCVD applications. (c) 2012 Elsevier B.V. All rights reserved.