Proton Conduction in Metal-Organic Frameworks and Related Modularly Built Porous Solids

Proton-conducting materials are an important component of fuel cells. Development of new types of proton-conducting materials is one of the most important issues in fuel-cell technology. Herein, we present newly developed proton-conducting materials, modularly built porous solids, including coordination polymers (CPs) or metalorganic frameworks (MOFs). The designable and tunable nature of the porous materials allows for fast development in this research field. Design and synthesis of the new types of proton-conducting materials and their unique proton-conduction properties are discussed.

Strain localization effect on system reliability based design of bridge abutments under earthquake loading

The component and system reliability based design of bridge abutments under earthquake loading is presented in the paper. Planar failure surface has been used in conjunction with pseudo-dynamic approach to compute seismic active earth pressures on an abutment. The pseudo-dynamic method, considers the effect of phase difference in shear waves, soil amplification along with the horizontal seismic accelerations, strain localization in backfill soil and associated post-peak reduction in the shear resistance from peak to residual values along a previously formed failure plane. Four modes of stability viz. sliding, overturning, eccentricity and bearing capacity of the foundation soil are considered in the analysis. The series system reliability is computed with an assumption of independent failure modes. The lower and upper bounds of system reliability are also computed by taking into account the correlations between four failure modes, which is evaluated using the direction cosines of the tangent planes at the most probable points of failure.

Influence of strain localization on reliability based design of bridge abutments using pseudo-dynamic method

The paper focuses on reliability based design of bridge abutments when subjected to earthquake loading. Planar failure surface has been used in conjunction with pseudo-dynamic approach to compute the seismic active earth pressures on the bridge abutment. The proposed pseudo dynamic method, considers the effects of strain localization in the backfill soil and associated post-peak reduction in the shear resistance from peak to residual values along a previously formed failure plane, phase difference in shear waves and soil amplification along with the horizontal seismic accelerations. Four modes of stability viz. sliding, overturning, eccentricity and bearing capacity of the foundation soil are considered for the reliability analysis. The influence of various design parameters on the seismic reliability indices against four modes of failure is presented, following the suggestions of Japan Road Association, Caltrans Bridge Design Specifications and U.S Department of the Army.

Thermal Rearrangement of Azido Ketones into Oxazoles via Azirines: One-Pot, Metal-Free Heteroannulation to Functionalized 1,3-Oxazoles

alpha-Azidoacetophenones were converted into 2-aryl-1,3-oxazole-4-carbaldehydes through rearrangement of the carbon framework upon exposure to DMF/POCl3. The unprecedented rearrangement occurs via alkenyl azides and 2H-azirines. A mechanism for this unusual reaction was proposed and evidenced.

Safety Assessment of a Masonry Arch Bridge: Field Testing and Simulations

The safety of an in-service brick arch railway bridge is assessed through field testing and finite-element analysis. Different loading test train configurations have been used in the field testing. The response of the bridge in terms of displacements, strains, and accelerations is measured under the ambient and design train traffic loading conditions. Nonlinear fracture mechanics-based finite-element analyses are performed to assess the margin of safety. A parametric study is done to study the effects of tensile strength on the progress of cracking in the arch. Furthermore, a stability analysis to assess collapse of the arch caused by lateral movement at the springing of one of the abutments that is elastically supported is carried out. The margin of safety with respect to cracking and stability failure is computed. Conclusions are drawn with some remarks on the state of the bridge within the framework of the information available and inferred information. DOI: 10.1061/(ASCE)BE.1943-5592.0000338. (C) 2013 American Society of Civil Engineers.

A novel piezoelectric ZnO nanogenerator on flexible metal alloy substrate

In this paper, we report a novel piezoelectric ZnO nanogenerator on flexible metal alloy substrate (Phynox alloy) for energy harvesting and sensing applications. The vertically aligned ZnO nanowires are sandwiched between Au electrodes. The aligned growth of ZnO nanowires have been successfully synthesized on Au coated metal alloy substrate by hydrothermal method at low temperature (95 +/- 1 degrees C). The as-synthesized vertically aligned ZnO nanowires were characterized using FE-SEM. Further, PMMA is spin coated over the aligned ZnO nanowires for the purpose of their long term stability. The fabricated nanogenerator is of size 30mm x 6mm. From energy harvesting point of view, the response of the nanogenerator due to finger tip impacts ranges from 0.9 V to 1.4V. Also for sensing application, the maximum output voltage response of the nanogenerator is found to be 2.86V due to stainless steel (SS) ball impact and 0.92 V due to plastic ball impact.

Identification of source of heavy metal contamination in a site - a case study

Accidental spills and improper disposal of industrial effluent/sludge containing heavy metals onto the open land or into subsurface result in soil and water contamination. Detailed investigations are carried out to identify the source of contamination of heavy metals in an industrial suburb near Bangalore in India. Detailed investigation of ground water and subsurface soil analysis for various heavy metals has been carried out. Ground water samples were collected in the entire area through the cluster of borewells. Subsurface soil samples were collected from near borewells which were found to contain heavy metals. Water samples and soils samples (after acid digestion) were analysed as per APHO-standard method of analysis. While the results of Zn, Ni and Cd showed that they are within allowable limits in the soil, the ground water and soils in the site have concentration of Cr+6 far exceeding the allowable limits (up to 832 mg/kg). Considering the topography of the area, ground water movement and results of chromium concentration in the borewells and subsurface it was possible to identify the origin, zone of contamination and the migration path of Cr+6. The results indicated that the predominant mechanism of migration of Cr+6 is by diffusion.

Ratiometric, reversible, and parts per billion level detection of multiple toxic transition metal ions using a single probe in micellar media

We present the selective sensing of multiple transition metal ions in water using a synthetic single probe. The probe is made up of pyrene and pyridine as signaling and interacting moiety, respectively. The sensor showed different responses toward metal ions just by varying the medium of detection. In organic solvent (acetonitrile), the probe showed selective detection of Hg2+ ion. In water, the fluorescence quenching was observed with three metal ions, Cu2+, Hg2+, and Ni2+. Further, just by varying the surface charge on the micellar aggregates, the probe could detect and discriminate the above-mentioned three different toxic metal ions appropriately. In neutral micelles (Brij 58), the probe showed a selective interaction with Hg2+ ion as observed in acetonitrile medium. However, in anionic micellar medium (sodium dodecyl sulfate, SDS), the probe showed changes with both Cu2+ and Ni2+. under UV-vis absorption spectroscopy. The discrimination between these two ions was achieved by recording their emission spectra, where it showed selective quenching with Cu2+.

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.

Common-mode voltage eliminated three-level inverter using a three-level flying-capacitor inverter and cascaded H-bridge

This paper proposes a new 3 level common mode voltage eliminated inverter using an inverter structure formed by cascading a H-Bridge with a three-level flying capacitor inverter. The three phase space vector polygon formed by this configuration and the polygon formed by the common-mode eliminated states have been discussed. The entire system is simulated in Simulink and the results are experimentally verified. This system has an advantage that if one of devices in the H-Bridge fails, the system can still be operated as a normal 3 level inverter mode at full power. This inverter has many advantages like use of single DC-supply, making it possible for a back to back grid-tied converter application, improved reliability etc.

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.