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Process impregnates polytetrafluoroethylene /PTFE/ with rhenium or molybdenum compounds. The refractory metals impregnated PTFE combines chemical inertness with electrical conductivity. They are useful for electro-chemical cells, chemical processing equipment, catalysts, electrostatic charge removal, RF gasketing, and cable shielding.
This paper presents a study of the synthesis and structural properties of the new pyrochlore-type Bi{sub 2-y}Sr{sub y}Ir{sub 2}O{sub 7} series. Ten compositions with 0.0{<=}y{<=}0.9 were prepared by solid-state reaction with thermal treatments at 873, 1073 and 1323 K under atmospheric pressure conditions. Structural refinements from X-ray powder diffraction data by the Rietveld method show that all compounds of the Bi{sub 2-y}Sr{sub y}Ir{sub 2}O{sub 7} solid solution crystallize in a {alpha}-pyrochlore structure. The main structural difference when bismuth is substituted by strontium concerns the x position of the O1 (x, (1/8), (1/8)). This substitution significantly increases the Bi/Sr-O1 distance and diminishes the Ir-O1 distance; this implies that the Ir-O1-Ir bond angle increases. With the Sr substitution, the IrO{sub 6} local configuration goes from a flattened trigonal antiprism, y<0.5, to an elongated one, y>0.5, passing through an octahedral array, y{approx}0.5. The electrical consequences of these structural changes observed in this system are qualitatively explained with electronic structure calculations, this behavior agrees very well with those observed in other pyrochlore systems A{sub 2}M{sub 2}O{sub 7} (A=rare earth cations or Tl{sup +}, Pb{sup 2+}, or Bi{sup 3+}, and M=Ru or Ir). -- Graphical abstract: Electrical behavior of the Bi{sub 2-y}Sr{sub y}Ir{sub 2}O{sub 7} solid solution. Display Omitted Highlights: {yields} Bi{sub 2-y}Sr{sub y}Ir{sub 2}O{sub 7} crystallizes in the {alpha}-pyrochlore structure. {yields} Local geometry of Ir goes from a flattened trigonal antiprism to an elongated one. {yields} Electrical resistivity increases with the Sr content in the solid solution. {yields} Electronic structure analysis relates resistivity with Sr disorder and bond strength.
Tungsten alloys (WA) have been introduced in an attempt to find safer alternatives to depleted uranium and lead munitions. However, it is known that at least one alloy, 91% tungsten-6% nickel-3% cobalt (WNC-91-6-3), causes rhabdomyosarcomas when fragments are implanted in rat muscle. This raises concerns that shrapnel, if not surgically removable, may result in similar tumours in humans. There is therefore a clear need to develop rapid and robust in vitro methods to characterise the toxicity of different WAs in order to identify those that are most likely to be harmful to human health and to guide development of new materials in the future. In the current study we have developed a rapid visual in vitro assay to detect toxicity mediated by individual WA particles in cultured L6-C11 rat muscle cells. Using a variety of techniques (histology, comet assay, caspase-3 activity, oxidation of 2'7'-dichlorofluorescin to measure the production of reactive oxygen species and whole-genome microarrays) we show that, in agreement with the in vivo rat carcinogenicity studies, WNC-91-6-3 was the most toxic of the alloys tested. On dissolution, it produces large amounts of reactive oxygen species, causes significant amounts of DNA damage, inhibits caspase-3, triggers a severe hypoxic response and kills the cells in the immediate vicinity of the alloy particles within 24 h. By combining these in vitro data we offer a mechanistic explanation of the effect of this alloy in vivo and show that in vitro tests are a viable alternative for assessing new alloys in the future.
The absorption spectra of nonlinear laser crystals Y{sub 1-x}Yb{sub x}Al{sub 3}(BO{sub 3}){sub 4} grown from bismuth-lithium-molybdate and potassium-molybdate solution-melts are comparatively studied by high-resolution Fourier spectroscopy. The differences observed in the fine structure of the absorption spectra are correlated with the variations in the solution-melt composition and in the concentrations of bismuth and molybdenum impurities in the crystals. It is shown that the concentration of the molybdenum impurity (the main factor hindering lasing in the UV spectral region) in the single crystals grown from the bismuth-lithium-molybdate solutions is more than an order of magnitude smaller than in the crystals grown using the potassium-molybdate solution-melt. The described method can be used for express analysis of the quality of UV laser crystals and for improving the solution-melt technologies of growth of laser crystals and crystals used for generation of the fourth harmonic of Nd:YAG laser radiation. (active media)
Single crystals of KNbO{sub 3} (KN), KTaO{sub 3} (KT), and KTa{sub 1-x}Nb{sub x}O{sub 3} (x=0.44, KTN) have been prepared by hydrothermal synthesis in highly concentrated KOH mineralizer solutions. The traditional problems of inhomogeneity, non-stoichiometry, crystal striations and crystal cracking resulting from phase transitions associated with this family compounds are minimized by the hydrothermal crystal growth technique. Crystals of good optical quality with only minor amounts of metal ion reduction can be grown this way. Reactions were also designed to provide homogeneous distribution of tantalum and niobium metal centers throughout the KTN crystal lattice to maximize its electro-optic properties. Synthesis was performed at relatively low (500-660 {sup o}C) temperatures in comparison to the flux and Czochralski techniques. This work represents the largest crystals of this family of compounds grown by hydrothermal methods to date. -- Graphical Abstract:
TiO{sub 2}-anatase and SiO{sub 2} supported oxorhenate catalysts were prepared by an original and simple technique based on the oxidative dispersion of metallic rhenium under dry conditions. The dispersion process of the supported oxorhenate phase as a function of the rhenium coverage and the support properties are discussed on the base of in situ characterization. The structures of the as prepared catalysts were found to be comparable to those of materials prepared using the incipient wetness impregnation technique. The absence of water in the preparation technique has made it possible to highlight the role of the hydration level on the rhenium oxide volatilization. The as-prepared Re/TiO{sub 2} catalysts were found to be effective for the direct conversion of methanol to methylal. - Graphical Abstract: Evolution of the 900-1000 cm{sup -1} region of the Raman spectrum of a mixture of metal rhenium with anatase TiO{sub 2} K03 upon heating in pure O{sub 2}. Highlights: > Supported rhenium catalysts can be easily prepared from metal Re. > This dry process is mainly a CVD immediately followed by rhenium deposition. > Hydration of the oxorhenate phase is dependent on the support.
Refractory oxide-metal joining and blend-uniting to produce compound ceramics of uniform or gradient composition
The Group VIA-Re binary systems are characterized by the presence of several intermediate phases. The u phase is present in all of the systems, but the a-Mn phases occur in only the Mo-Re and W-Re systems. The occurrence of these intermediate phases appears to be governed largely by electronic factors and is predictable on the basis of electron/atom ratio. The thermionic work functions of the intermediate phase materials were experimentally determined. function and the screening of the outermost electrons in the Group VIA metals was found. A correlation between the work As might be expected for purely metallic substances, the work functions were relatively high, in the range 4. 5 to 5. 0 eV, and in each case were bracketed by the work functions of the pure constituents. A discontinuous change in the average work function with composition is proposed, based on a thermodynamical treatment of the electron vapor.
New niobium oxynitrides containing either magnesium or silicon were prepared at 1000 deg. C by ammonia nitridation of oxide precursors obtained via the citrate route. The products had rock-salt type crystal structures. Crystallinity was improved by annealing in 0.5 MPa N{sub 2} and the final compositions were (Nb{sub 0.95}Mg{sub 0.05})(N{sub 0.92}O{sub 0.08}) at 1500 deg. C and (Nb{sub 0.87}Si{sub 0.09{open_square}0.04})(N{sub 0.87}O{sub 0.13}) at 1200 deg. C. The magnesium and oxide ions partially co-substitute the niobium and nitride ions in the octahedral sites of the {delta}-NbN lattice, respectively. Silicon ions were also successfully doped together with oxide ions into the rock-salt type NbN lattice. The Si doped product exhibited relatively large displacement at the octahedral sites and was accompanied by a small amount of cation vacancies. Superconductivity was improved by annealing to obtain critical temperatures/volume fractions of T{sub c}=17.6 K/100% for Mg- and T{sub c}=16.2 K/95% for the Si-doped niobium oxynitrides. - Graphical Abstract: Doped silicon ions substituting Nb in (Nb{sub 0.87}Si{sub 0.09{open_square}0.04})(N{sub 0.87}O{sub 0.13}) introduced a large displacement at the 4a site mainly because of the accompanied vacancy. The silicon ions may also be slightly shifted from the regular octahedral 4a site (green) towards the interstitial tetrahedral site (red) statistically in the rock-salt type lattice. Highlights: > New superconducting niobium oxynitrides containing either magnesium or silicon were prepared. > Their annealed products had chemical compositions of (Nb{sub 0.95}Mg{sub 0.05})(N{sub 0.92}O{sub 0.08}) and (Nb{sub 0.87}Si{sub 0.09{open_square}0.04})(N{sub 0.87}O{sub 0.13}) in the rock-salt type structure. > Their superconductivities were T{sub c}/volume fraction=17.6 K/100% and 16.2 K/95%, respectively.
The aim of our study was to modify the basis compound ss-TaON, which crystallizes in the monoclinic baddeleyite-type, by incorporation of appropriate dopant ions, in order to obtain anion-deficient cubic fluorite-type phases, which are of interest as solids with mobile nitrogen ions. For this purpose, scandium-doped tantalum oxide nitrides were prepared by ammonolysis of amorphous oxide precursors. An unexpected variety of phases with different structural features was observed: bixbyite-type phases of general composition Sc{sub x}Ta{sub 1-x}(O,N){sub y} with 0.33{<=}x{<=}1 and 1.7{<=}y{<=}1.9, yellow colored metastable anatase-type phases such as Sc{sub 0.1}Ta{sub 0.9}O{sub 1.2}N{sub 0.8} or Sc{sub 0.15}Ta{sub 0.85}O{sub 1.3}N{sub 0.7} and, additionally, anosovite-type phases Sc{sub x}Ta{sub 3-x}O{sub 2x}N{sub 5-2x} with 0{<=}x{<=}1.05. Selected phases were investigated by UV/vis spectroscopy. Anatase- and anosovite-type compounds show brilliant colors. In the anatase-type phase, a possible anion ordering was examined by theoretical methods. Additionally, energy calculations on phase stability were performed for Sc{sub x}Ta{sub 1-x}O{sub 1+2x}N{sub 1-2x} in the baddeleyite, rutile, and anatase structure types with varying amounts of dopants. - Graphical abstract: New anatase- and bixbyite-type phases obtained as single-phase samples in the system Sc-Ta-O-N.
CBMM is a fully integrated company, from the mine to the end line of the production chain, supplying different niobium products to the world market: ferroniobium, nickelniobium, niobium pentoxide and high purity metallic niobium. This high purity metallic niobium has long been known to exhibit superconductivity below 9.25 Kelvin. This characteristic has the potential to bring technological benefits for many different areas such as medicine, computing and environment. This paper presents the raw material requirements as well as CBMM experience on producing high purity niobium ingots. The results prove that CBMM material can be the best solution for special applications such as low cost superconductive radiofrequency cavities.
Thermionic work function of refractory metallic compounds and electronic and crystal structure - emissivity measurement and diode fabrication
We report on a one-step hydrothermal growth of one-dimensional (1D) WO{sub 3} nanostructures, using urea as 1D growth-directing agent and a precursor free of metals other than tungsten. By decreasing the pH of the starting solution, the size of the nanostructures was reduced significantly, this development being accompanied by the realization of phase pure hexagonal WO{sub 3} nanorods (elimination of monoclinic impurity phase) and a red shift in optical absorption edge. Surface analyses indicated the presence of reduced tungsten species in the WO{sub 3} nanostructures, which increased two-fold in a hydrated WO{sub 3} phase obtained with further decrease in pH. We suggest that oxygen vacancies are responsible for this defect state in WO{sub 3}, while protons are responsible or contribute significantly to the same in the hydrated phase. - Graphical abstract: The figure illustrates the role of pH in morphological and absorption edge evolution of WO{sub 3} (hydrate) as well as the variation in the concentration of defect electrons between anhydrous and hydrated WO{sub 3}. Highlights: Black-Right-Pointing-Pointer WO{sub 3} nanorods prepared in a one step procedure. Black-Right-Pointing-Pointer HCl (aq) enables phase pure WO{sub 3} nanorods. Black-Right-Pointing-Pointer HCl (aq) induces significant reduction in dimension of and red shift in absorption edge of nanorods. Black-Right-Pointing-Pointer W{sup 5+} detected in hydrothermal WO{sub 3} phase, the concentration of which increases in the hydrated phase. Black-Right-Pointing-Pointer W{sup 5+} from the two phases due to different positive defects.
We have used X-ray absorption spectroscopy at the Cu K-edge to investigate the electrochemical conversion reaction of 20 nm size 85 wt% CuF{sub 2}-15 wt% MoO{sub 3} nanocomposite under in situ conditions. The nanocomposite was prepared by high energy milling. Upon discharge, the lithiation reaction with the nanocomposite resulted in the formation of nanophase metallic Cu, which is consistent with the conversion of CuF{sub 2} into Cu and LiF. Based on XANES and Fourier transforms of EXAFS spectra, we show that the discharge process proceeded via the formation of highly dispersed Cu particles. Based on the coordination number of the first shell of Cu, the average size of the Cu particles was estimated to be in the 1-3 nm range in the fully discharged state. -- Graphical Abstract: Comparison of Fourier transform of in situ Cu K-edge EXAFS spectra for a fully discharged CuF{sub 2{center_dot}}MoO{sub 3} nanocomposite in a nonaqueous Li cell with that of a Cu foil. Quantitative analysis of the Fourier transforms confirmed that the discharge mechanism for the nanocomposite proceeds via the reaction CuF{sub 2}+2Li{yields}Cu+2LiF. The discharge product of Cu is in the form of highly dispersed nanoparticles. Display Omitted
Double perovskite compounds (Sr{sub 2-x}Eu{sub x})FeMoO{sub 6} (0{<=}x{<=}0.3) were prepared by solid-state reaction at high temperature. Crystal structure, magnetic and transport properties of the compounds were investigated. The crystal structure of the compounds changes from an I4/m lattice to an Fm3-bar m lattice around x=0.1. The unit-cell volume decreases with the doping level in both the I4/m lattice and the Fm3-bar m lattice. The resistivity of the compounds shows a metal-semiconductor transition, and the transition temperature T{sub M-S} increases with the doping level. However, Curie temperature (T{sub C}) of the compounds exhibits a weak dependence on the doping level. The saturation magnetization (M{sub S}) at 100 K varies almost linearly with the anti-site defect concentration and agrees well with the simple FIM model. In contrast to the Ce-, Pr-, Nd- and Sm-doped Sr{sub 2}FeMoO{sub 6}, the difference of M{sub S} of (Sr{sub 2-x}Eu{sub x})FeMoO{sub 6} between 5 and 100 K indicates that the moment of Eu{sup 3+} is antiparellel to that of Fe{sup 3+} at low temperature. - Graphical abstract: Temperature dependence of saturation magnetization of (Sr{sub 1.8}Eu{sub 0.2})FeMoO{sub 6} (filled circle) and (Sr{sub 1.8}Nd{sub 0.2})FeMoO{sub 6} (open circle).
Two-micron lasing is obtained for the first time on the {sup 3}F{sub 4} {yields} {sup 3}H{sub 6} transition of Tm{sup 3+} ions in diode-pumped crystals of mixed sodium - lanthanum - gadolinium tungstate Tm:NaLa{sub 1/2}Gd{sub 1/2}(WO{sub 4}){sub 2} (C{sub Tm} = 3.6 at %) (3.6Tm : NLGW) and molybdate Tm:NaLa{sub 1/3}Gd{sub 2/3}(MoO{sub 4}){sub 2} (C{sub Tm} = 4.8 at %) (4.8Tm : NLGM). For the 3.6Tm : NLGW crystal, the quasi-cw laser output power exceeded 200 mW and the slope efficiency (with respect to absorbed pump power) for the {pi}- and {sigma}-polarisations at wavelengths of 1908 and 1918 nm was 34% and 30%, respectively. The laser wavelength of this crystal was continuously tuned within the spectral range of 1860 - 1935 nm. For the 4.8Tm : NLGM crystal, the slope efficiency for the {pi}- and {sigma}-polarisations at wavelengths of 1910 and 1918 nm was 27% and 23%, respectively, and the laser wavelength was tunable within the spectral range of 1870 - 1950 nm. (lasers)
Structure determination of the fully intercalated phase Li{sub 12}Mo{sub 5}O{sub 17} and of the deintercalated oxide Li{sub 5}Mo{sub 5}O{sub 17} has been carried out by electron microscopy and neutron powder diffraction. The reversible topotactic transformation between the ordered rock salt structure of the former and the ribbon structure of the latter (closely related to that of Li{sub 4}Mo{sub 5}O{sub 17}) is explained on the following basis: both structures can be described as strips built up as an assembly of infinite ribbons of MoO{sub 6} octahedra that are five octahedra thick, and that differ by slight displacements of the octahedral ribbons. We show that the electrochemical behavior of the Li{sub x}Mo{sub 5}O{sub 17} system is based on two sorts of Li{sup +} sites; those that are located within the strips between the ribbons, and those that are located at the border of the strips. The high rate of Li intercalation in this oxide and its reversibility are discussed in terms of its peculiar structure. -- Graphical abstract: Structure determination of the fully intercalated phase Li{sub 12}Mo{sub 5}O{sub 17} and of the deintercalated oxide Li{sub 5}Mo{sub 5}O{sub 17} has been carried out by electron microscopy and neutron powder diffraction. The reversible topotactic transformation between the ordered rock salt structure of the former and the ribbon structure of the latter is explained on the following basis: both structures can be described as strips built up as an assembly of infinite ribbons of MoO{sub 6} octahedra that are five octahedra thick, and that differ by slight displacements of the octahedral ribbons. We show that the electrochemical behavior of the Li{sub x}Mo{sub 5}O{sub 17} system is based on two sorts of Li{sup +} sites; those that are located within the strips between the ribbons, and those that are located at the border of the strips. The high rate of Li intercalation in this oxide and its reversibility are discussed in terms of its peculiar structure. Research highlights: {yields} Electron microscopy and neutron powder diffraction structure determination {yields} We have explained the reversible topotactic transformation between an ordered rock salt structure and a ribbon structure {yields} We show that the electrochemical behavior of the Li{sub x}Mo{sub 5}O{sub 17} system is based on two sorts of Li{sup +} sites {yields} The high rate of Li intercalation in this oxide and its reversibility are discussed in terms of its peculiar structure.
EDM is a known process for machining of hard and brittle materials. Due to its noncontact and nearly forceless behaviour, it has been introduced into micro manufacturing and through constant development it is now an important means for producing high-precision micro geometries. One restriction of EDM is its limitation to electrically conducting materials.Today many applications, especially in the biomedical field, make use of the benefits of ceramic materials, such as high strength, very low wear and biocompatibility. Common ceramic materials such as Zirconium dioxide are, due to their hardness in the sintered state, difficult to machine with conventional cutting techniques. A demand for the introduction of EDM to these materials could so far not be satisfied because of their nonconductive nature.At the Chemnitz University of Technology and the Fraunhofer IWU, investigations in the applicability of micro-EDM for the machining of nonconductive ceramics are being conducted. Tests are undertaken using micro-EDM drilling with Tungsten carbide tool electrodes and ZrO{sub 2} ceramic workpieces. A starting layer, in literature often referred to as 'assisting electrode' is used to set up a closed electric circuit to start the EDM process. Combining carbon hydride based dielectric and a specially designed low-frequency vibration setup to excite the workpiece, the process environment can be held within parameters to allow for a constant EDM process even after the starting layer is machined. In the experiments a cylindrical 120 {mu}m diameter Tungsten carbide tool electrode and Y{sub 2}O{sub 3}- and MgO- stabilized ZrO{sub 2} worpieces are used. The current and voltage signals of the discharges within the different stages of the process (machining of the starting layer, machining of the base material, transition stage) are recorded and their characteristics compared to discharges in metallic material. Additionally, the electrode feed is monitored. The influences of the process parameters are analysed with regard to the discharge type, electrode wear and process speed.Using the found parameters, micro geometries can be successfully machined into nonconductive Y{sub 2}O{sub 3}- and MgO- stabilized ZrO{sub 2} ceramic by means of micro-EDM.