The effect of cobalt addition on sintering and microstructural behaviour of silver–tungsten (Ag–W) composite

The present investigation has been revealed that homogeneous silver-tungsten (Ag–W) composite powders doped with cobalt as sinter aid can be produced by the two-stage reduction of co-precipitated tungstate. The sintering of the powders has been studied using dilatometry and the results showed that the critical level for activated sintering is of the order of 0.3 mass percent cobalt with respect to the tungsten content of the compact powder. This critical level is equivalent to approximately six to seven atomic layer coverage of the tungsten particles by cobalt. The levels of cobalt addition above the critical amount leads to the formation of cobalt tungsten (CoW₃) intermetallic compound precipitates, which become trapped within the silver phase in the sintered composite material. Microstructural evaluation of sintered specimens has been carried out using optical and electron microscopy. Transmission electron microscopy results revealed the neck formation between adjacent tungsten particles along with the presence of silver around the tungsten particles. Energy dispersive X-ray (EDX) analysis also confirmed that amounts of cobalt was 0.3 mass percent, in the region containing the silver at the tungsten particle interface which agreed with the level of activated sintering.     

Pinched inlet gravitational split-flow thin fractionation of airborne particles and analysis of size dependent level of PCDD/Fs

Fine particles in air have a direct influence on human health because they carry toxic chemicals that can be deposited in the human lung when inhaled. Thus, particle size distribution and size dependent level of contamination of the airborne particles are important parameters for the study and assessment of environmental pollution. In this study, gravitational split-flow thin (SPLITT) fractionation (or GSF), a semi-preparative scale separation technique for particles, was applied for the continuous size sorting of airborne particles collected in urban area. About 2.0 g of airborne particles was fractionated into four different size intervals (<1.5, 1.5-2.5, 2.5-5.0, and >5.0 microm), and the collected fractions were examined by electron microscopy for particle size distribution and analyzed for the size dependent levels of polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs). It was found that more than 60% of particles including dissolved matters in weight were smaller than 5.0 microm and they contained more than 86% of the total PCDD/Fs amount in airborne particles.     

Analysis of powdered tungsten carbide hard-metal precursors and cemented compact tungsten carbides using laser-induced breakdown spectroscopy

Laser-induced breakdown spectroscopy (LIBS) has been applied to the direct analysis of powdered tungsten carbide hard-metal precursors and cemented tungsten carbides. The aim of this work was to examine the possibility of quantitative determination of the niobium, titanium, tantalum and cobalt. The investigated samples were in the form of pellets, pressed with and without binder (powdered silver) and in the form of cemented tungsten carbides. The pellets were prepared by pressing the powdered material in a hydraulic press. Cemented tungsten carbides were embedded in resin for easier manipulation.

Several lasers and detection systems were utilized. The Nd:YAG laser working at a basic wavelength of 1064 nm and fourth-harmonic frequency of 266 nm with a gated photomultiplier or ICCD detector HORIBA JY was used for the determination of niobium which was chosen as a model element. Different types of surrounding gases (air, He, Ar) were investigated for analysis. The ICCD detector DICAM PRO with Mechelle 7500 spectrometer with ArF laser (193 nm) and KrF laser (248 nm) were employed for the determination of niobium, titanium, tantalum and cobalt in samples under air atmosphere. Good calibration curves were obtained for Nb, Ti, and Ta (coefficients of determination r² > 0.96). Acceptable calibration curves were acquired for the determination of cobalt (coefficient of determination r² = 0.7994) but only for the cemented samples. In the case of powdered carbide precursors, the calibration for cobalt was found to be problematic.     

Integrated particle detection chip for environmental monitoring

This paper reports an integrated particle detection chip for low-cost and point-of-interest environmental monitoring; it consists of a micro virtual impactor and a micro corona discharger. With this system, airborne particles are introduced into the micro virtual impactor of the chip where they are classified according to their aerodynamic diameters. The particles are then charged and their number-concentration is detected in the micro corona discharger from the electrical current carried by the charged particles. The characteristics of each component were first analyzed, and the components were then integrated into a single chip. The micro virtual impactor was designed to have a cut-off diameter of 600 nm or 1.0 microm. Its classification characteristics were examined by classifying polydisperse particles-dioctyl sebacate particles ranging in diameter from 100 to 600 nm and carbon particles ranging in diameter from 0.6 to 10 microm. From the classification results, the cut-off diameter of the micro virtual impactor was measured to be either 550 nm or 1.1 microm. The micro corona discharger was fabricated based on a sharp silicon tip and a planar electrode and charged particles at 1.3 kV. Using the integrated particle detection chip comprising the micro virtual impactor and the micro corona discharger, the sensitivity for monodisperse particles-500 nm dioctyl sebacate in diameter-was measured to be 8 x 10(-7) pA/(particle cm(-3)).     

Examination of evidence materials for environmental contamination using activation analysis

A unique application of forensic neutron activation analysis involving the analysis of trace levels of tungsten, cobalt and tantalum was presented as evidence in a murder trial. The evidence materials analyzed included the blous of the victim, bed sheets, a pair of pantyhose used in strangulation, head and public hair from the suspect, and several samples of raw materials used at a factory where the suspect was employed. The stalned areas of the fabrics analyzed showed trace levels of cobalt, tantalum, and tungsten which were not present in the fabric mattrices. The occupation of the suspect exposed him to fine dust particulates containing these trace elements. Although eyewitness accounts indicated that the suspect was in the neighborhood, there was, however, no evidence other that the neutron activation analysis results to indicate the probable presence of the suspect at the scence of the crime. A jury trial accepting neutron activation analysis findings resulted in a conviction.     

Concentration and particle-size distribution of uranium and some trace elements in airborne dust collected in Tsukuba

Uranium and some other trace elements were determined in the size-separated airborne dust collected in Tsukuba with an Andersen-type high-volume cascade impactor. The fission track method and the instrumental neutron activation method were applied to the determination of uranium and other elements, respectively. Selenium, antimony, arsenic and zinc were found to be rich in particulates of smaller size, while scandium, iron and cobalt showed a reverse trend, depending on their main origins, i.e. whether industrial or terrestrial. Uranium was distributed in both the larger and smaller particles to the same extent, suggesting that it is derived from both the terrestrial and artificial sources.     

Products of carbothermal reduction of tungsten oxides in argon flow

The investigation into carbothermal reduction of tungsten oxides has shown that this process involves several steps: WO₃ → WO_2.72 → WO₂ → W. The resulting oxide is rapidly reduced to tungsten metal at 950°C. The carbidization process has a diffusion mechanism. The staged character of carbothermal reduction of tungsten oxides and subsequent carbidization of tungsten are confirmed by scanning electron microscopy, which made it possible to determine the phase composition and size of the resulting particles.     

The Mechanical Properties and Rate of Electrodeposition of Co−W Alloys from a Boron−Gluconate Bath: Impact of Anodic Processes

The effects the anode material has on the rate of electrodeposition (current efficiency) and microhardness of Co–W alloys deposited from a boron–gluconate bath are studied in a broad range of bath ages Q (A h/L). We use nonconsumable (platinum and graphite) and consumable (tungsten, cobalt–tungsten) anodes. With the cobalt–tungsten double anode, the total concentration of W and Co species in the bath is maintained constant during electrodeposition. We find that, as Q increases, the anodic processes have a significant impact on both the rate of deposition and microhardness of the prepared coatings. Departing from the mechanism of induced codeposition in which the first stage is the formation of an intermediate species of the metal component that induces codeposition (Co), here we propose a model that takes into account the effects associated with the anodic processes. In this model, along with reduction at the cathode to give an alloy, this metal component can undergo oxidation at the anode.

     

Cobalt nanoparticles on charcoal: a versatile catalyst in the Pauson-Khand reaction,hydrogenation, and the reductive Pauson-Khand reaction

[formula: see text] Dispersions of nanometer-sized cobalt particles with very high stability were prepared in charcoal and analyzed by electron microscopy and X-ray analysis. The resulting cobalt nanoparticles on charcoal (CNC) were successfully used as a catalyst for the carbonylative cycloaddition of alkyne, alkene, and carbon monoxide (Pauson-Khand reaction), hydrogenation, and the reductive Pauson-Khand reaction.     

Physical properties of organic particulate UV absorbers used in sunscreens II. UV-attenuating efficiency as function of particle size

In this study the UV-attenuating properties of microparticles consisting of a benzotriazole derivative were investigated, which are used as absorbers for UV radiation in cosmetic sunscreens. The particles were micronized in presence of a dispersing agent by means of a ball milling process. According to the energy input different particle sizes were produced in the range of 0.16 to 4 microm. In order to study even smaller particles, the sample with particle size 0.16 microm was fractionated further by centrifugation. Particle sizes were measured using fiberoptic quasi-elastic light scattering (FOQELS) and laser diffractometry. The UV-attenuating properties of the dispersions with different particle sizes were assessed using UV spectroscopy. With decreasing particle size the efficiency of the UV extinction of the dispersion increases up to a particle size of 80 nm. For particles smaller than 80 nm the UV extinction decreases again indicating an optimum at 80 nm. From reflection spectroscopic measurements it was found that scattering makes about 10%, and absorption 90%, of the UV-attenuating effect of the particles, which are obtained at the end of the milling process.     

Influence of synthesis methods on tungsten dispersion, structural deformation, and surface acidity in binary WO3-ZrO2 system

WO3-ZrO2 catalysts were synthesized by precipitating the aqueous solutions of zirconium oxynitrate and ammonium metatungstate with ammonium hydroxide. The white slurry precipitate was treated under three different conditions. In the as-made materials, the amorphous phase was formed in the aged and refluxed samples, while well-crystallized tetragonal and monoclinic phases were obtained in the hydrothermally treated sample. The real amount of tungsten loaded in the samples was similar for the three samples, independently of the treatments; however, the tungsten surface atomic density in the annealed WO3-ZrO2 samples varied between 6 and 9 W atoms/nm2. Two different contrast types of aggregates were determined by scanning electron microscopy, the white particles which are rich in W, and the gray ones which are rich in zirconium; both of them were formed in the calcined solids prepared under aging or reflux condition. A very high dispersion of tungsten species on the zirconia surface was achieved in the hydrothermally treated sample. The degree of the interaction between WO(x) and ZrO2 surface strongly modified the Zr-O bond lengths and bond angles in the structure of tetragonal zirconia as proved by X-ray diffraction analysis and the Rietveld refinement. The catalyst obtained under hydrothermal condition exhibited the highest dispersion of tungsten species in the zirconia, which in turn causes strong structural deformation of the tetragonal ZrO2 phase responsible of the strongest surface acidity and, consequently, the optimum catalytic activity for n-hexane isomerization.     

Control over structural-dimensional characteristics of tungsten disulfide particles in aerosol-assisted chemical vapor deposition

Solutions of ammonium thiotungstate in dimethylformamide were used to synthesize spherical tungsten disulfide particles with average radius of 500–100 nm by the method of aerosol-assisted chemical vapor deposition. Nanoparticles with composition close to stoichiometric tungsten disulfide are formed at pyrolysis temperatures not lower than 800°C. It was found that the average particle radius linearly decreases as the reagent concentration in solution becomes lower, and the nebulizer power has no effect within the range under study on the size characteristics and structure of the particles obtained. It was demonstrated that the particles have a layered structure that is formed in all probability by S–W–S packets, which must provide high antifriction properties of the material in its use as a high-temperature solid lubricant. The results obtained indicate that the size of tungsten disulfide particles can be controlled in a wide range in the course of the aerosol-assisted chemical vapor deposition. This may be of interest for developing a technology for creating high-temperature wear-resistant antifriction coatings.     

Hollow-fiber flow/hyperlayer field-flow fractionation for the size characterization of airborne particle fractions obtained by SPLITT fractionation

Hollow-fiber flow field-flow fractionation (HF FlFFF) was applied for the separation and size characterization of airborne particles which were collected in a municipal area and prefractionated into four different-diameter intervals >5.0, 2.5-5.0, 1.5-2.5, <1.5 microm) by continuous split-flow thin (SPLIIT) fractionation. Experiments demonstrated the possibility of utilizing a hollow-fiber module for the high-performance separation of supramicron-sized airborne particles at steric/hyperlayer operating mode of HF FlFFF. Eluting particles during HF FlFFF separation were collected at short time intervals (approximately 10 s) for the microscopic examination. It showed that particle size and size distributions of all SPLITT fractions of airborne particles can be readily obtained using a calibration and that HF FlFFF can be utilized for the size confirmation of the sorted particle fraction during SPLITT fractionation.     

Superoxide Complex [W4O12（O2^-）]： A Theoretical Study

Extensive DFT calculations are performed to optimize the geometric structures of O-rich tungsten oxide clusters, to simulate the PES spectra, and to analyze the chemical bonding. The ground-state structure of W4O14^- is best considered as W4O12（O2^-）, containing a side-on bound superoxide ligand. The current study indicates that the extra electron in W4O12^- is capable of activating dioxygen by non-dissociative electron transfer （W 5d → O2 π^＊）, and the anionic clusters can be viewed as models for reduced defect sites on tungsten oxide surfaces for the chemisorption of O2.     

Substrate changes associated with the chemistry of self-assembled monolayers on silicon

Alkylsiloxane self-assembled monolayers (SAMs) are used in the semiconductor industry and, more recently, as proxies for organics adsorbed on airborne mineral dust and on buildings and construction materials. A number of methods have been used for removing the SAM from the substrate after reaction or use, particularly plasmas or piranha (H2SO4/H2O2) solution. However, when the substrates are reused to make new SAMs, the impact of the cleaning methods on the chemistry of subsequently formed SAMs on the surface is not known. Here we report atomic force microscopy, X-ray photoelectron spectroscopy, Auger electron spectroscopy, and Fourier transform infrared studies of changes in a silicon substrate upon repetitive deposition and removal of SAMs by these two methods. It is shown that a thicker layer of silicon oxide is formed, and the surface becomes irregular and roughened, particularly after the piranha treatment. This layer of silica impacts the structure of the SAMs attached to it and can serve as a reservoir for trace gases that adsorb on it, potentially contributing to the subsequent reactions of the SAM. The implications for the use of such surfaces as a proxy for reactions of organics on airborne dust particles and on structures in the boundary layer are discussed.     

CO_xM_(4—x)异金属四面体簇羰基化合物的量子化学研究

本文对十个CO_xM_(4-x)异金属四面体簇合物体系进行了量化计算(DV-X_a方法)。结果表明:CO_xM_(4-x)异金属簇与Co_4四面体簇化学键相似,但其他金属(M)的引入,使四面体簇价带收缩,Co的3d能级展宽,体系费米能级升高。在Co与Fe、Ru等ⅦB族元素形成的双金属簇中,Co在簇中所占比例愈大,贡献的电荷就愈多;而在Co与Mo、W等ⅥB族元素形成的四面体簇中,Mo、W为电荷主要提供者。     

Magnetic properties of transition metal films and islands on W(110)

In this contribution we report on magnetic phenomena of iron and cobalt islands on a W(110). In our experiment we employed the technique of magnetic circular dichroism in photoemission from the Fe and Co 3p semi core levels. Using highly circularly polarized synchrotron radiation in the soft X-ray region our photoemission data clearly show a remanent ferromagnetic effect for cobalt island on tungsten. The phase transition from the epitaxial iron and cobalt film to the island structure was additionally studied with LEED and atomic force microscopy.     

Enrichment adsorption of a labile substance to the surface of particular mineral particles in river water as investigated by SEM-EDX and dilute-acid extraction/ICP-MS.

The selective enrichment behavior of a labile substance, such as hydroxides, to the surface of particular mineral particles in river water was clarified by scanning electron microscopy/energy dispersive X-ray microanalysis (SEM-EDX). Individual particles other than diatom collected on a 0.45 microm filter from the Fuji and Sagami rivers, central Japan, were analyzed by SEM-EDX and classified into seventeen groups according to the chemical composition and shape. Phosphorus, sulfur, chlorine, manganese and copper detected in each particle collected on the 0.45 microm filter could be successfully used as effective indicators of labile substance secondarily formed and adsorbed afresh in river water, because the detection frequencies of such elements are quite low, or negligible, in fresh mineral particles derived from igneous rocks. The labile substance adsorbed on mineral particles collected on the 0.45 microm filter was also evaluated by dilute-acid leaching, followed by inductively coupled plasma mass spectrometry (ICP-MS). Almost all parts of the manganese detected in individual particles were those adsorbed afresh as hydroxides together with iron and aluminum. Also, anionic elements, such as phosphorus, sulfur and chlorine, formed complexes with the hydroxides and/or were incorporated in them. Mg and/or Ca-rich aluminosilicate groups were the most effective adsorbers of such labile species. However, Si-rich and Na-, K- and Na-Ca rich aluminosilicates did not significantly adsorb the labile substance. Consequently, the remarkable selectivity was clarified in the adsorption process of labile substance to individual mineral particles in river water.     

Electrodeposition of Co–W coatings from boron gluconate electrolyte with a soluble tungsten anode

Conditions were determined in which an active anodic dissolution of tungsten is observed in a borongluconate electrolyte used to obtain Co–W coatings (pH ~6.5) and the nature of critical currents of transition to the passivation was found, which makes it possible to use the tungsten anode as a soluble electrode. The anodic dissolution of tungsten occurs under these conditions with a current efficiency of 90–100%, which, in contrast to the case of a graphite anode, does not lead to an additional oxidation of the electrolyte components and polymerization in solution; in combination with the decrease in the concentration of tungstate ions, this reduces the electrolyte performance. It was shown that the use of a soluble tungsten anode in obtaining nanocrystalline cobalt–tungsten coating can improve the electrolyte performance due to the rise in the current efficiency of electrodeposition and to the increase in the microhardness of the coatings in comparison with the case of an insoluble graphite anode.     

Effect of polar solvents on the optical properties of water-dispersible thiol-capped cobalt nanoparticles

We were able to stabilize cobalt nanoparticles dispersible in water by optimizing the synthetic procedure using small polar thiol containing compounds as the capping agents. The nanoparticles were found to be spherical. The optical properties of the cobalt nanoparticles were investigated by monitoring the changes in the surface plasmon resonance (SPR) spectrum in various polar solvents. The extent of solvent dependence of the SPR spectrum was found to be dependent on the nature of the capping agent, the size of the cobalt nanoparticles, as well as the nature of the solvent. The Drude model was applicable for the particles capped with mercaptopropionic acid, while the effect of variations in the free electron density in the particles at different solvents became predominant in the nanoparticles capped with mercaptoethanol. The absorption spectra of the Co nanoparticles were simulated with the help of the classical Mie theory, and the results supported the effect of free electron density due to different capping agents on the spectra of the particles.