Between photocatalysis and photosynthesis: Synchrotron spectroscopy methods on molecules and materials for solar hydrogen generation

Energy research is to a large extent materials research, encompassing the physics and chemistry of materials, including their synthesis, processing toward components and design toward architectures, allowing for their functionality as energy devices, extending toward their operation parameters and environment, including also their degradation, limited life, ultimate failure and potential recycling. In all these stages, X-ray and electron spectroscopy are helpful methods for analysis, characterization and diagnostics for the engineer and for the researcher working in basic science.This paper gives a short overview of experiments with X-ray and electron spectroscopy for solar energy and water splitting materials and addresses also the issue of solar fuel, a relatively new topic in energy research. The featured systems are iron oxide and tungsten oxide as photoanodes, and hydrogenases as molecular systems. We present surface and subsurface studies with ambient pressure XPS and hard X-ray XPS, resonant photoemission, light induced effects in resonant photoemission experiments and a photo-electrochemical in situ/operando NEXAFS experiment in a liquid cell, and nuclear resonant vibrational spectroscopy (NRVS). (C) 2012 Elsevier B.V. All rights reserved.

Evolution of Nanocrystalline Ba2NaNb5O15 in 2BaO-0.5Na(2)O-2.5Nb(2)O(5)-4.5B(2)O(3) Glass System and Its Refractive Index and Band Gap Tunability

Monophasic Ba2NaNb5O15 was crystallized at nanometer scale (12-36 nm) in 2BaO-0.5Na(2)O-2.5Nb(2)O(5)- 4.5B(2)O(3) glass system. To begin with, optically transparent glasses, in this system, were fabricated via the conventional melt. quenching technique. The amorphous and glassy characteristics of the as-quenched samples were respectively confirmed by X-ray powder diffraction and differential thermal analyses. Nearly homogeneous distribution of Ba2NaNb5O15 (BNN) nanocrystals associated with tungsten bronze structure akin to their bulk parent structure was accomplished by subjecting the as-fabricated glasses to appropriate heat-treatment temperatures. Indeed transmission electron microscopy (TEM) carried out on these samples corroborated the presence of Ba2NaNb5O15 nanocrystals dispersed in a continuous glass matrix. The as-quenched glasses were similar to 75% transparent in the visible range of the electromagnetic spectrum. The optical band gap and refractive index were found to have crystallite size (at nanoscale) dependence. The optical band gap increased with the decrease in crystallite size. The refractive indices of the glass nanocrystal composites as determined by Brewster angle method were rationalized using different empirical models. The refractive index dispersion with wavelength of light was analyzed on the basis of the Sellmeier relations. At room temperature under UV excitation (355 nm) these glass nanocrystal composites displayed violet-blue emission which was ascribed to the defects states.

Autocatalytic duplex Ni-P/Ni-W-P coatings on AZ31B magnesium alloy

Autocatalytic duplex Ni-P/Ni-W-P coatings were deposited on AZ31B magnesium alloy using stabilizer free nickel carbonate bath. Some of the coated specimens were passivated in chromate solution with and without heat treatment. Plain Ni-P coatings were also prepared for comparison. Coatings were characterized for their surface morphology, composition and corrosion resistance. Energy dispersive analysis of X-ray (EDX) showed that the phosphorous content in the Ni-P coating is 6 wt.% and for Ni-W-P it reduced to 3 wt.% due to the codeposition of tungsten in the Ni-P coating. Marginal increase in P and W contents was observed on passivated coupons along with Cr (0.18 wt.%) and O (2.8 wt.%) contents. Field emission scanning electron microscopy (FESEM) examination of these coating surfaces exhibited the nodular morphology. Chromate passivated surfaces showed the presence of uniformly distributed bright Ni particles along with nodules. Potenfiodynamic polarization and electrochemical impedance spectroscopy (EIS) studies were carried out in deaerated 0.15 M NaCI solution to find out the corrosion resistance of the coatings. Among the coatings developed, duplex-heat treated-passivated (duplex-HIP) coatings showed lower corrosion current density (i(corr)) and higher polarization resistance (R-p) indicating the improved corrosion resistance. The charge transfer resistance (R-ct) value obtained for the duplex-HIP was about 170 times higher compared to that for Ni P coating. (c) 2013 Elsevier B.V. All rights reserved.

High Speed Imaging of Generation and Collapse of Multielectron Bubbles in Liquid Helium

We present experimental results on the generation and collapse of multielectron bubbles in liquid helium. By applying voltage pulses to a tungsten tip above the surface of the liquid, millimetre sized deformations were formed. Using high speed photography, we have imaged the disintegration of these deformations into bubbles of sizes ranging from ten to few hundred microns. At temperatures less than 2 K, the bubbles split into smaller bubbles and then disappeared in a time scale of few milliseconds. Smaller bubbles were formed at temperatures around 3 K, but were visible for more than hundreds of milliseconds. Although we have not been able to measure their charge directly, some of these bubbles responded to electric fields, implying these were indeed multielectron bubbles. With the existing theoretical picture, it is not possible to understand the strong dependence of the lifetime of multielectron bubbles on temperature.

Ferroelectric and optical properties of Ba5Li2Ti2Nb8O30 ceramics potential for memory applications

Giant grained (42 mu m) translucent Ba5Li2Ti2Nb8O30 ceramic was fabricated by conventional sintering technique using the powders obtained via solid state reaction route. These samples were confirmed to possess tetragonal tungsten bronze structure (P4bm) at room temperature. The scanning electron microscopy established the average grain size to be close to 20 mu m. The photoluminescence studies carried out on these ceramics indicated sharp emission bands around 433 and 578 nm at an excitation wavelength of 350 nm which were attributed to band-edge emission as the band gap was 2.76 eV determined by Kubelka-Munk function. The dielectric properties of these ceramics were studied over wide frequency range (100-1 MHz) at room temperature. The decrease in dielectric constant with frequency could be explained on the basis of Koops theory. The dielectric constant and the loss were found to decrease with increasing frequency. The Curie temperature was confirmed to be similar to 370 A degrees C based on the dielectric anomaly observed when these measurements were carried out over a temperature range of 30-500 A degrees C. This shows a deviation from Curie-Weiss behaviour and hence an indicator of the occurrence of disordering in the system, the gamma = 1.23 which confirms the diffuse ferroelectric transition. These ceramics at room temperature exhibited P-E hysteresis loops, though not well saturated akin to that of their single crystalline counterparts. These are the suitable properties for ferroelectric random access memory applications.

Neutron diffraction, Mossbauer effect and Electron Paramagnetic Resonance studies on multiferroic Pb(Fe2/3W1/3)O-3

Multiferroic Pb(Fe2/3W1/3)O-3 ceramics were synthesized via a modified two-stage Columbite method. Single phase formation was confirmed from the analysis of x-ray and neutron diffraction patterns recorded at room temperature. Structural analysis of the diffraction data reveals cubic phase (space group Pm-3m) for the title compound. Magnetic structure of the title compound at room temperature exhibits G-type antiferromagnetic structure. The Mossbauer spectroscopy and Electron Paramagnetic Resonance (EPR) studies were carried out at 300 K. The isomer shift and quadrupole splitting of the Mossbauer spectra confirms the trivalent state of iron (Fe3+). The Mossbauer spectra also suggest that the iron and tungsten are randomly distributed at the octahedral, B site. EPR spectra show a single broad line associated with Fe3+ ions. Both spectra clearly exhibit weak ferromagnetic behaviour of Pb(Fe2/3W1/3)O-3 ceramic at 300 K. Considering neutron diffraction, Mossbauer and EPR results together, it may be stated here that Pb(Fe2/3W1/3)O-3 exhibits antiferromagnetic behavior along with weak ferromagnetism at room temperature.

Effect of W addition on the electrical switching of VO2 thin films

Vanadium Oxide has been a frontrunner in the field of oxide electronics because of its metal-insulator transition (MIT). The interplay of different structures of VO2 has played a crucial role in deciding the magnitude of the first order MIT. Substitution doping has been found to introduce different polymorphs of VO2. Hence the role of substitution doping in stabilizing the competing phases of VO2 in the thin film form remains underexplored. Consequently there have been reports both discounting and approving such a stabilization of competing phases in VO2. It is reported in the literature that the bandwidth of the hysteresis and transition temperature of VO2 can be tuned by substitutional doping of VO2 with W. In this work, we have adopted a novel technique called, Ultrasonic Nebulized Spray Pyrolysis of Aqueous Combustion Mixture (UNSPACM) to deposit VO2 and W- doped VO2 as thin films. XRD and Raman spectroscopy were used to investigate the role of tungsten on the structure of VO2 thin films. Morphology of the thin films was found to be consisting of globular and porous nanoparticles of size similar to 20nm. Transition temperature decreased with the addition of W. We found that for 2.0 at % W doping in VO2, the transition temperature has reduced from 68 degrees C to 25 degrees C. It is noted that W-doping in the process of reducing the transition temperature, alters the local structure and also increases room temperature carrier concentration. (c) 2016 Author(s).

Investigation of the Mechanical Properties of Thin Films by Nanoindentation, Considering the Effects of Thickness and Different Coating-Substrate Combinations

In order to further investigate nanoindentation data of film-substrate systems and to learn more about the mechanical properties of nanometer film-substrate systems, two kinds of films on different substrate systems have been tested with a systematic variation in film thickness and substrate characteristics. The two kinds of films are aluminum and tungsten, which have been sputtered on to glass and silicon substrates, respectively. Indentation experiments were performed with a Nano Indent XP II with indenter displacements typically about two times the nominal film thicknesses. The resulting data are analyzed in terms of load-displacement curves and various comparative parameters, such as hardness, Young's modulus, unloading stiffness and elastic recovery. Hardness and Young's modulus are investigated when the substrate effects are considered. The results show how the composite hardness and Young's modulus are different for different substrates, different films and different film thicknesses. An assumption of constant Young's modulus is used for the film-substrate system, in which the film and substrate have similar Young's moduli. Composite hardness obtained by the Joslin and Oliver method is compared with the directly measured hardness obtained by the Oliver and Pharr method.

The application of B-P constitutive equations in finite element analysis of high velocity impact

We present in this paper the application of B-P constitutive equations in finite element analysis of high velocity impact. The impact process carries out in so quick time that the heat-conducting can be neglected and meanwhile, the functions of temperature in equations need to be replaced by functions of plastic work. The material constants in the revised equations can be determined by comparison of the one-dimensional calculations with the experiments of Hopkinson bar. It can be seen from the comparison of the calculation with the experiment of a tungsten alloy projectile impacting a three-layer plate that the B-P constitutive equations in that the functions of temperature were replaced by the functions of plastic work can be used to analysis of high velocity impact.

An Energy-Based Method for Analyzing Instrumented Spherical Indentation Experiments

Using dimensional analysis and finite element calculation, we studied spherical indentation in elastic-plastic solids with work hardening. We report two previously unknown relationships between hardness, reduced modulus, indentation depth, indenter radius, and work of indentation. These relationships, together with the relationship between initial unloading stiffness and reduced modulus, provide an energy-based method for determining contact area, reduced modulus, and hardness of materials from instrumented spherical indentation measurements. This method also provides a means for calibrating the effective radius of imperfectly shaped spherical indenters. Finally, the method is applied to the analysis of instrumented spherical indentation experiments on copper, aluminum, tungsten, and fused silica.

Stainless steel sandwich

The Cambridge University's Gordon Laboratory, in collaboration with Fibertech and the Defence Science and Technology Laboratory in the UK, has developed a novel melt spun fiber bore called 'Fibrecore', fabricated entirely from stainless steel with thin faceplates. Fibrecore is typically manufactured by 5mm-long and 70μm thick stainless steel fibers, produced by a melt overflow process. Its entirely metallic construction allows spot welding and tungsten inert gas welding without difficulty. Fibrecore exhibits different energy absorption mechanisms such as core cushioning, core-faceplate delamination, and plastic faceplate deformation, often in a concertina-like fashion. Its low-cost, high structural efficiency and good energy absorption characteristics make it attractive for a range of commercial and military applications. Such applications being evaluated include vehicle body panels, exhaust system noise reduction, low cost filters, and lightweight physical protection. In addition to these characteristics, Fibrecore exhibits properties such as corrosion protection, vibrational damping, and thermal insulation, which also extend its applications.

Microfabrication and application of reservoir pins for liquid transfer in biotechnology

Microarraying involves laying down genetic elements onto a solid substrate for DNA analysis on a massively parallel scale. Microarrays are prepared using a pin-based robotic platform to transfer liquid samples from microtitre plates to an array pattern of dots of different liquids on the surface of glass slides where they dry to form spots diameter < 200 μm. This paper presents the design, materials selection, micromachining technology and performance of reservoir pins for microarraying. A conical pin is produced by (i) conventional machining of stainless steel or wet etching of tungsten wire, followed by (ii) micromachining with a focused laser to produce a microreservoir and a capillary channel structure leading from the tip. The pin has a flat end diameter < 100 μm from which a 500 μm long capillary channel < 15 μm wide leads up the pin to a reservoir. Scanning electron micrographs of the metal surface show roughness on the scale of 10 μm, but the pins nevertheless give consistent and reproducible spotting performance. The pin capacity is 80 nanolitres of fluid containing DNA, and at least 50 spots can be printed before replenishing the reservoir. A typical robot holds can hold up to 64 pins. This paper discusses the fabrication technology, the performance and spotting uniformity for reservoir pins, the possible limits to miniaturization of pins using this approach, and the future prospects for contact and non-contact arraying technology.

A porous bulk metallic glass with unidirectional opening pores

Porous Zr-based bulk metallic glass (PMG) with unidirectional opening pores is prepared by electrochemical etching of tungsten wires of the W/bulk metallic glass (BMG) composites. The porosity and pore size can be controlled by adjusting the tungsten wires. The PMG showed no measurable loss in thermal stability as compared to the monolithic Zr-based BMG by water quenching and is more ductile and softer than the pore-free counterpart. The specific surface area of the PMGs is calculated to be 0.65, 3.96, and 10.54 m(2)/kg for 20, 60, and 80 vol % porosity, respectively. (c) 2007 The Electrochemical Society.

Microstructure and high-temperature wear and oxidation resistance of laser clad gamma/W2C/TiC composite coatings on gamma-TiAl intermetallic alloy

There are very strong interests in improving the high-temperature wear resistance of the y-TiAl intermetallic alloy, especially when applied as tribological moving components. In this paper, microstructure, high-temperature dry sliding wear at 600 degrees C and isothermal oxidation at 1000 degrees C on ambient air of laser clad gamma/W2C/TiC composite coatings with different constitution of Ni-Cr-W-C precursor mixed powders on TiAl alloy substrates have been investigated. The results show that microstructure of the laser fabricated composite coatings possess non-equilibrium microstructure consisting of the matrix of nickel-base solid solution gamma-NiCrAl and reinforcements of TiC, W2C and M23C6 carbides. Higher wear resistance than the original TiAl alloy is achieved in the composite coatings under high-temperature wear test conditions. However, the oxidation resistance of the laser clad gamma/W2C/TiC composite coatings is deceased. The corresponding mechanisms resulting in the above behaviors of the laser clad composite coatings are discussed. (c) 2006 Elsevier B.V. All rights reserved.

钨球打钢靶数值仿真研究

通过对钨球垂直撞击钢靶的数值仿真，获得了模拟钨球撞击钢板的整个物理图象，并给出了多种人们所关心的侵彻过程和物理场的演化数据，仿真结果与试验数据有较好的一致性。