Mechanical properties of a metal-organic framework containing hydrogen-bonded bifluoride linkers

We report the mechanical properties of a framework structure, Cu2F(HF)(HF2)(pyz)(4)](SbF6)(2)](n) (pyz = pyrazine), in which Cu(pyz)(2)](2+) layers are pillared by HF2- anions containing the exceptionally strong F-H center dot center dot center dot F hydrogen bonds. Nanoindentation studies on single-crystals clearly demonstrate that such bonds are extremely robust and mechanically comparable with coordination bonds in this system.

Performance limits of transition metal dichalcogenide (MX2) nanotube surround gate ballistic field effect transistors

We theoretically analyze the performance of transition metal dichalcogenide (MX2) single wall nanotube (SWNT) surround gate MOSFET, in the 10 nm technology node. We consider semiconducting armchair (n, n) SWNT of MoS2, MoSe2, WS2, and WSe2 for our study. The material properties of the nanotubes are evaluated from the density functional theory, and the ballistic device characteristics are obtained by self-consistently solving the Poisson-Schrodinger equation under the non-equilibrium Green's function formalism. Simulated ON currents are in the range of 61-76 mu A for 4.5 nm diameter MX2 tubes, with peak transconductance similar to 175-218 mu S and ON/OFF ratio similar to 0.6 x 10(5)-0.8 x 10(5). The subthreshold slope is similar to 62.22 mV/decade and a nominal drain induced barrier lowering of similar to 12-15 mV/V is observed for the devices. The tungsten dichalcogenide nanotubes offer superior device output characteristics compared to the molybdenum dichalcogenide nanotubes, with WSe2 showing the best performance. Studying SWNT diameters of 2.5-5 nm, it is found that increase in diameter provides smaller carrier effective mass and 4%-6% higher ON currents. Using mean free path calculation to project the quasi-ballistic currents, 62%-75% reduction from ballistic values in drain current in long channel lengths of 100, 200 nm is observed.

Performance and reliability of Gd2O3 and stacked Gd2O3-Eu2O3 metal-insulator-metal capacitors

Gd2O3-based metal-insulator-metal capacitors have been characterized with single layer (Gd2O3) and bilayer (Gd2O3/Eu2O3 and Eu2O3/Gd2O3) stacks for analog and DRAM applications. Although single layer Gd2O3 capacitors provide highest capacitance density (15 fF/mu m(2)), they suffer from high leakage current density, poor capacitance density-voltage linearity, and reliability. The stacked dielectrics help to reduce leakage current density (1.2x10(-5) A/cm(2) and 2.7 x 10(-5) A/cm(2) for Gd2O3/Eu2O3 and Eu2O3/Gd2O3, respectively, at -1 V), improve quadratic voltage coefficient of capacitance (331 ppm/V-2 and 374 ppm/V-2 for Gd2O3/Eu2O3 and Eu2O3/Gd2O3, respectively, at 1 MHz), and improve reliability, with a marginal reduction in capacitance density. This is attributed to lower trap heights as determined from Poole-Frenkel conduction mechanism, and lower defect density as determined from electrode polarization model.

Exploring the color of transition metal ions in irregular coordination geometries: new colored inorganic oxides based on the spiroffite structure, Zn2-xMxTe3O8 (M = Co, Ni, Cu)

We describe the synthesis, crystal structures, and optical absorption spectra of transition metal substituted spiroffite derivatives, Zn2-xMxTe3O8 (M-II = Co, Ni, Cu; 0 < x <= 1.0). The oxides are readily synthesized by solid state reaction of stoichiometric mixtures of the constituent binaries at 620 degrees C. Reitveld refinement of the crystal structures from powder X-ray diffraction (XRD) data shows that the Zn/MO6 octahedra are strongly distorted, as in the parent Zn2Te3O8 structure, consisting of five relatively short Zn/M-II-O bonds (1.898-2.236 angstrom) and one longer Zn/M-II-O bond (2.356-2.519 angstrom). We have interpreted the unique colors and the optical absorption/diffuse reflectance spectra of Zn2-xMxTe3O8 in the visible, in terms of the observed/irregular coordination geometry of the Zn/M-II-O chromophores. We could not however prepare the fully substituted M2Te3O8 (M-II = Co, Ni, Cu) by the direct solid state reaction method. Density Functional Theory (DFT) modeling of the electronic structure of both the parent and the transition metal substituted derivatives provides new insights into the bonding and the role of transition metals toward the origin of color in these materials. We believe that transition metal substituted spiroffites Zn2-xMxTe3O8 reported here suggest new directions for the development of colored inorganic materials/pigments featuring irregular/distorted oxygen coordination polyhedra around transition metal ions.

Metal doped nanosized titania used for the photocatalytic degradation of rhodamine B dye under visible-light

Metal-doped anatase nanosized titania photocatalysts were successfully synthesized using a sal gel process. Different amounts of the dopants (0.2, 0.4, 0.6, 0.8 and 1.0%) of the metals (Ag, Ni, Co and Pd) were utilized. The UV-Vis spectra (solid state diffuse reflectance spectra) of the doped nanoparticles exhibited a red shift in the absorption edge as a result of metal doping. The metal-doped nanoparticles were investigated for their photocatalytic activity under visible-light irradiation using Rhodamine B (Rh B) as a control pollutant. The results obtained indicate that the metal-doped titania had the highest activity at 0.4% metal loading. The kinetic models revealed that the photodegradation of Rh B followed a pseudo first order reaction. From ion chromatography (IC) analysis the degradation by-products Rhodamine B fragments were found to be acetate, chloride, nitrite, carbonate and nitrate ions.

Black hole formation at the correspondence point

We study the process of bound state formation in a D-brane collision. We consider two mechanisms for bound state formation. The first, operative at weak coupling in the worldvolume gauge theory, is pair creation of W-bosons. The second, operative at strong coupling, corresponds to formation of a large black hole in the dual supergravity. These two processes agree qualitatively at intermediate coupling, in accord with the correspondence principle of Horowitz and Polchinski. We show that the size of the bound state and time scale for formation of a bound state agree at the correspondence point. The time scale involves matching a parametric resonance in the gauge theory to a quasinormal mode in supergravity.

Hydrodynamic energy harvesting using an ionic polymer-metal composite stack for underwater applications

Ionic Polymer Metal Composites (IPMCs) are a class of Electro-Active Polymers (EAPs) consisting of a base polymer (usually Nafion), sandwiched between thin films of electrodes and an electrolyte. Apart from fuel cell like proton exchange process in Nafion, these IPMCs can act both as an actuator and a sensor. Typically, IPMCs have been known for their applications in fuel cell technology and in artificial muscles for robots. However, more recently, sensing properties of IPMC have opened up possibilities of mechanical energy harvesting. In this paper, we consider a bi-layer stack of IPMC membranes where fluid flow induced cyclic oscillation allows collection of electronic charge across a pair of functionalized electrode on the surface of IPMC layers/stacks. IPMCs work well in hydrated environment; more specifically, in presence of an electrolyte, and therefore, have great potential in underwater applications like hydrodynamic energy harvesting. Hydrodynamic forces produce bending deformation, which can induce transport of cations via polymer chains of the base polymer of Nafion or PTFE. In our experimental set-up, the deformation is induced into the array of IPMC membranes immersed in electrolyte by water waves caused by a plunger connected to a stepper motor. The frequency and amplitude of the water waves is controlled by the stepper motor through a micro-controller. The generated electric power is measured across a resistive load. Few orders of magnitude increase in the harvested power density is observed. Analytical modeling approach used for power and efficiency calculations are discussed. The observed electro-mechanical performance promises a host of underwater energy harvesting applications.

Stabilization of diborane(4) by transition metal fragments and a novel metal to pi Dewar-Chatt-Duncanson model of back donation

The feasibility of using transition metal fragments to stabilize B2H4 in planar configuration by donating 2 electrons to the boron moiety is investigated. Building upon the existing theoretical and experimental data and aided by the isolobal analogy, the model transition metal complexes Cr(CO)(4)B2H4 (6), Mn(CO)-CpB2H4 (7), Fe(CO)(3)B2H4 (8) and CoCpB2H4 (9) are chosen to illustrate this unique bonding feature bond strengthening with pi-back donation. Other possible types of complexes with B2H4 and the metal fragment are also explored and the energies are compared. One of the low energy isomers wherein the planar B2H4 interacts with the metal fragment in an in-plane fashion represents a unique case study for the Dewar-Chatt-Duncanson model. In this complex the back-donation from the metal fills the p bonding orbital between the two boron atoms thus forming a B=B double bond.

Photoelectron spectromicroscopy study of metal-insulator transition in NaxWO3

We have investigated the validity of percolation model, which is quite often invoked to explain the metal-insulator transition in sodium tungsten bronzes, NaxWO(3) by photoelectron spectromicroscopy. The spatially resolved direct spectromicroscopic probing on both the insulating and metallic phases of high quality single crystals of NaxWO(3) reveals the absence of any microscopic inhomogeneities embedded in the system within the experimental limit. Neither any metallic domains in the insulating host nor any insulating domains in the metallic host have been found to support the validity of percolation model to explain the metal-insulator transition in NaxWO(3). The possible origin of insulating phase in NaxWO(3) is due to the Anderson localization of all the states near E-F. The localization occurs because of the strong disorder arising from random distribution of Na+ ions in the WO3 lattice.

Analysis of size quantization and temperature effects on the threshold voltage of thin silicon film double-gate metal-oxide-semiconductor field-effect transistor (MOSFET)

In this paper, we analyze the combined effects of size quantization and device temperature variations (T = 50K to 400 K) on the intrinsic carrier concentration (n(i)), electron concentration (n) and thereby on the threshold voltage (V-th) for thin silicon film (t(si) = 1 nm to 10 nm) based fully-depleted Double-Gate Silicon-on-Insulator MOSFETs. The threshold voltage (V-th) is defined as the gate voltage (V-g) at which the potential at the center of the channel (Phi(c)) begins to saturate (Phi(c) = Phi(c(sat))). It is shown that in the strong quantum confinement regime (t(si) <= 3nm), the effects of size quantization far over-ride the effects of temperature variations on the total change in band-gap (Delta E-g(eff)), intrinsic carrier concentration (n(i)), electron concentration (n), Phi(c(sat)) and the threshold voltage (V-th). On the other hand, for t(si) >= 4 nm, it is shown that size quantization effects recede with increasing t(si), while the effects of temperature variations become increasingly significant. Through detailed analysis, a physical model for the threshold voltage is presented both for the undoped and doped cases valid over a wide-range of device temperatures, silicon film thicknesses and substrate doping densities. Both in the undoped and doped cases, it is shown that the threshold voltage strongly depends on the channel charge density and that it is independent of incomplete ionization effects, at lower device temperatures. The results are compared with the published work available in literature, and it is shown that the present approach incorporates quantization and temperature effects over the entire temperature range. We also present an analytical model for V-th as a function of device temperature (T). (C) 2013 AIP Publishing LLC.

Modelling of metal-slag emulsion

Many industrial processes involve reaction between the two immiscible liquid systems. It is very important to increase the efficiency and productivity of such reactions. One of the important processes that involve such reactions is the metal-slag system. To increase the reaction rate or efficiency, one must increase the contact surface area of one of the phases. This is either done by emulsifying the slag into the metal phase or the metal into the slag phase. The latter is preferred from the stability viewpoint. Recently, we have proposed a simple and elegant mathematical model to describe metal emulsification in the presence of bottom gas bubbling. The same model is being extended here. The effect of slag and metal phase viscosity, density and metal droplet size on the metal droplet velocity in the slag phase is discussed for the above mentioned metal emulsification process. The models results have been compared with experimental data.

Black hole formation in fuzzy sphere collapse

We study the collapse of a fuzzy sphere, that is a spherical membrane built out of D0-branes, in the Banks-Fischler-Shenker-Susskind model. At weak coupling, as the sphere shrinks, open strings are produced. If the initial radius is large then open string production is not important and the sphere behaves classically. At intermediate initial radius the backreaction from open string production is important but the fuzzy sphere retains its identity. At small initial radius the sphere collapses to form a black hole. The crossover between the later two regimes is smooth and occurs at the correspondence point of Horowitz and Polchinski.

Establishing a Relation between the Mass and the Spin of Stellar-Mass Black Holes

Stellar mass black holes (SMBHs), forming by the core collapse of very massive, rapidly rotating stars, are expected to exhibit a high density accretion disk around them developed from the spinning mantle of the collapsing star. A wide class of such disks, due to their high density and temperature, are effective emitters of neutrinos and hence called neutrino cooled disks. Tracking the physics relating the observed (neutrino) luminosity to the mass, spin of black holes (BHs) and the accretion rate ((M) over dot) of such disks, here we establish a correlation between the spin and mass of SMBHs at their formation stage. Our work shows that spinning BHs are more massive than nonspinning BHs for a given (M) over dot. However, slowly spinning BHs can turn out to be more massive than spinning BHs if (M) over dot at their formation stage was higher compared to faster spinning BHs.

On the mechanism of metal nanoparticle synthesis in the brust-schiffrin method

Brust-Schiffrin synthesis (BSS) of metal nanoparticles has emerged as a major breakthrough in the field for its ability to produce highly stable thiol functionalized nanoparticles. In this work, we use a detailed population balance model to conclude that particle formation in BSS is controlled by a new synthesis route: continuous nucleation, growth, and capping of particles throughout the synthesis process. The new mechanism, quite different from the others known in the literature (classical LaMer mechanism, sequential nucleation-growth-capping, and thermodynamic mechanism), successfully explains key features of BSS, including size tuning by varying the amount of capping agent instead of the widely used approach of varying the amount of reducing agent. The new mechanism captures a large body of experimental observations quantitatively, including size tuning and only a marginal effect of the parameters otherwise known to affect particle synthesis sensitively. The new mechanism predicts that, in a constant synthesis environment, continuous nucleation-growth-capping mechanism leads to complete capping of particles (no more growth) at the same size, while the new ones are born continuously, in principle leading to synthesis of more monodisperse particles. This prediction is validated through new experimental measurements.

Graphene composites containing chemically bonded metal oxides

Composites of graphene involving chemically bonded nano films of metal oxides have been prepared by reacting graphene containing surface oxygen functionalities with metal halide vapours followed by exposure to water vapour. The composites have been characterized by electron microscopy, atomic force microscopy and other techniques. Magnetite particles chemically bonded to graphene dispersible in various solvents have been prepared and they exhibit fairly high magnetization.