Actinide(lanthanide)-noble metal alloy phases,preparation and properties

Actinide (AThCm)-noble metal phases with platinum, palladium, rhodium, and iridium (B)- and lanthanide-noble metal phases with platinum and palladium have been prepared by reduction of corresponding oxides or fluorides in the presence of noble metals by extremely purified hydrogen. Alloy phases of composition AB₂, AB₃, and/or AB₅ have been identified, most of which crystallize in the Cu₂Mg, Cu₃Au, Ni₃Ti, Cd₃Mg, Ni₅U, and Pt₅Sm types of structure. The lattice constants of isostructural series show a trend which also is known for the radii of the actinide elements. Analytical data, self-irradiation effects, magnetic data, nuclear γ resonance spectra, and thermal behaviour of selected alloy phases as well as the preparation of alloy phases of some other transition and main group elements, e.g., Zr, Hf, Nb, Ta, MgBa, are reported.     

Reduction reactivity of CuO-Cr2O3 mixed oxides with hydrogen and the effect of gamma pre-irradiation

The physico-chemical properties and parameters of CuO-Cr₂O₃ mixed oxides as well as their reactivity toward reduction with hydrogen have been investigated by means of various methods (X-ray analysis, electron spectroscopy for chemical analysis (ESCA), DTA, IR spectroscopy and scanning electron microscopy). A series of mixed oxides of various compositions in the range 0–100% of each component were prepared by calcinating the mass of coprecipitated basic carbonates in air. The reduction kinetics were studied by isothermal thermogravimetry in the temperature range 180–470 ° C. The effect of the origin of the oxides on the reactivity of the oxide system during its hydrogen reduction was proved by comparing its properties with those of a previously studied series of analogous mixed oxides, which were prepared from different precursors.The pre-irradiation of the system by ⁶⁰Co γ radiation results in a positive kinetic effect (an increase in the reduction rate) if the lowest dose applied is 2.57 × 10⁶ Gy. The magnitude of the radiation effect is greatly dependent on the composition of the mixed oxides.     

Untersuchungen in den Systemen Titan (Zirkonium,Hafnium)-Niob-Kohlenstoff

Zusammenfassung Die Aufteilung der Phasenfelder in den Dreistoffen: Titan (Zirkonium, Hafnium)-Niob-Kohlenstoff wird mit Hilfe gesinterter Proben bei je einer Temperatur ermittelt. Alle drei Systeme sind durch das Auftreten großer homogener Bereiche der Mischcarbide (Ti, Nb) C_1-x , (Zr, Nb) C_1-x und (Hf, Nb) C_1-x charakterisiert. Nb₂C löst wenig von dem Zweitcarbid. Eine thermodynamische Betrachtung führt zu einer Abschätzung der Stabilitätsdifferenz zwischen NbC_1-x und Nb₂C.

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The ternary systems: Ti(Zr, Hf)–Nb–C have been examined by means of sintered specimens. The equilibria of the above mentioned systems are characterized by the occurrence of a large domain of the respective solid solutions (Ti, Nb) C_1-x , (Zr, Nb)C_1-x and (Hf, Nb)C_1-x . Nb₂C dissolves very little of the second carbide. Thermodynamic considerations lead to an evaluation of the difference of stability between NbC_1-x and Nb₂C.

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Mit 6 Abbildungen     

Diffusion pack cementation of hafnium powder with halide activator on Ni–Ti shape memory alloy

The effect of a Hf chloride activator on the pack cementation of Hf powder on a Ni–Ti shape memory alloy wire was investigated. For this purpose, a Ni–Ti wire with a diameter of 0.5 mm was pack cemented in a powder mixture consisting of Hf and HfCl₄ powders at 1000 °C for 24 h. It was observed that Hf noticeably diffused into the Ni–Ti matrix with the aid of the HfCl₄ activator. The diffusion distance significantly increased as the amount of HfCl₄ activator increased. By the addition of 10 mass% HfCl₄, the martensite-to-austenite phase transformation start and finish temperatures increased from 12 to 142 °C and from 28 to 200 °C, respectively. The diffusion kinetics model was established based on Fick’s first law. It is suggested that 48 h of halide-activated pack cementation with 10 wt% HfCl₄ is necessary to increase the overall Hf content above 15 at.% throughout the Ni–Ti wire.     

Preparation and crystal data of the New Pyrochlores Pb2[M1.5Te0.5]O6.5 (M = Ti,Zr, Sn,Hf)

From mixtures of PbO, MO₂ (M = Ti, Zr, Hf), SnO, and TeO₂, four new oxides Pb₂[M_1.5Te_0.5]O_6.5 have been obtained as yellow powders giving X-ray diffraction patterns characteristic of cubic pyrochlores, S.G. Fd3 m (No. 227), Z = 8, and a/Å values from 10.3529(1) (M = Ti) to 10.7406(1) (M = Zr). The best R factors, from 0.0465 (M = Ti) to 0.0242 (M = Hf), were obtained for Pb in 16(c) positions, M and Te (3:1) randomly distributed in 16(d), oxygen atoms in 48(f) and in a half of the 8(a) sites, and x values for the oxygen positional parameter (origin at center, 3 m) from 0.436 (M = Ti) to 0.421 (M = Zr). For the compounds of Ti and Zr the angles of the coordination polyhedra around the metals are reported. For seven-coordinated Pb^II the stereochemical influence of the nonbonded electron pair is shown. Apparent interatomic distances agree with those calculated.     

A cyclopentadienyl ring exchange method for the attachment of early transition metal metallocene dichlorides to a polymer support

PMR and mass spectral analysis have been used to study the interchange of π-bonded cyclopentadienyl rings with σ-bonded cyclopentadienyl rings in the compounds (C₅H₅)₄M (M = Ti, Zr, Hf, Nb, Ta, Mo and W) and (C₅H₅)₃V or a-bonded benzylcyclopentadienyl rings in the compounds (C₆H₅CH₂C₅H₄) (C₅H₅)₂MC1 (M = Ti, Zr, Hf, Nb, Ta, Mo and W). As soon as the Cp₄M species are generated (indicated by a color change), the interchange occurs and the equilibrium is established. As reported, no such interchange was observed in (C₅H₅) ₄Mo in the PMR time scale; however, it does occur after a longer time. By using this interchange behavior of the cyclopentadienyl ring, metallocene dichlorides of Ti, Zr, Hf, V, Nb, Ta, Mo and W have been attached to polystyrene-divinylbenzene beads.     

Evidence for the formation of an antase-type VTi oxide solid-state solution

Samples of VTi oxides with V/Ti atomic ratios ranging from 0 to 0.01875 have been prepared by coprecipitation of VOCl₃ and TiCl₄, followed by calcination in air up to 700°C. The samples have been characterized by X-ray diffraction, UV-visible diffuse reflectance, FT-IR and ESR spectroscopy, scanning electron microscopy, and surface area measurements. The results provide evidence for the formation of a well crystallized anatase-type VTi oxide solid-state solution characterized by a small but significant unit cell expansion and by the incorporation of V as a tetravalent species.     

The influence of the transition metal and the heteroatomic-bridge on the action of metallocene/methyl aluminoxane catalysts in ethylene polymerization and on the properties of the polymer

This work reports a comparative study of the catalytic behaviour for a series of metallocenes derived from Ti, Zr, Hf and Nb, which after activation with methylaluminoxane can polymerize ethylene. Results show that the Zr metallocene with a  (CH₃)₂Si Bridge presents the highest activity, and the metallocenes based on Hf and Nb do not show any significant activity under the tested conditions.     

Ellipsometric and mechanical characterization of nanostructured anodic oxide film formed on Ti-6Al-7Nb alloy

In this work, we grow TiO₂ nanotube layers by using the single-step direct anodization of Ti-6Al-7Nb alloy in aqueous electrolytes containing F^? ions. Nanotube layers are characterized by spectroscopic ellipsometry (SE) and field-emission gun scanning electron microscopy (FEG-SEM). We also use SE to monitor the anodization process for TiO₂ nanotube layers on biocompatible Ti-6Al-7Nb alloy. In addition, we study mechanical properties by nanoindentation.     

Effects of Ti and Zr Substituted on the Electrochemical Characteristics of MgNi-Based Alloy Electrodes

Mg-based hydrogen storage alloys MgNi, Mg0.9Ti0.1Ni, and Mg0.9Ti0.06Zr0.04Ni were successfully prepared by means of mechanical alloying （MA）. The structure and the electrochemical characteristics of these Mg-based materials were studied. The X-ray diffraction （XRD） result shows that the main phases of the alloys exhibit amorphous structure. The scanning electron microscopy （SEM） photograph shows that the particle size of Ti and Zr substituted alloys was about 2-4 μm in diameter. The cycle lives of the alloys were prolonged by adding Ti and Zr. After 50 charge-discharge cycles, the discharge capacity of Mg0.9Ti0.06Zr0.04Ni was 91.74% higher than that of MgNi alloy and 37.96% higher than that of Mg0.9Ti0.1Ni alloy. The main reason for the electrode capacity decay is the formation of Mg（OH）2 （product of Mg corrosion） at the surface of alloy. The potentiodynamic polarization result indicates that Ti and Zr doping improves the anticorrosion in an alkaline solution. The electrochemical impedance spectroscopy （EIS） results suggest that proper amount of Ti and Zr doping improves the electrochemical catalytic activity significantly.     

Synthesis,characterization and thermodynamic data of compounds with NZP structure

Data on synthesis, thermal behavior and thermodynamic properties for the NZP phosphates NaMe₂(PO₄)₃ and Na₅Me(PO₄)₃ (Me=Ti, Zr, Hf) are reported. The compounds were synthesized by sol-gel method and solid-state reactions and characterized by X-ray powder diffraction, IR spectroscopy, electron microprobe and chemical analysis. Their thermal behavior was studied by the DTA measurements. The heat capacities of the phosphates were measured between temperatures 7 and 650 K. The fractal dimensions for the phosphates were calculated. The obtained thermodynamic characteristics of these phosphates and also literature data for the compounds of NZP type structure are summarized.     

Olivine thermal diffusivity influencing factors

Titanium and its alloys are used in production of implants such as knee and hip prostheses due to their superior properties. Ti–Nb–Zr ternary alloys are preferred over other metallic implant materials due to the presence of non-toxic elements, high corrosion resistance, good biocompatibility, and proper mechanical properties. The aim of this work is to investigate the effect of zirconium addition on α → β phase transformation, microstructure, and mechanical behavior of Ti–16Nb alloy. In doing so, Ti–16Nb–xZr (x: 0, 5, 10, 15 mass%) alloys are produced by powder injection molding, which offers advantages such as low cost, net shape, and easy production of complicated parts for implant fabrication. X-ray diffraction analysis and scanning electron microscope images showed that zirconium behaves as a β stabilizer and according to differential thermal analysis, and it decreases α to β transition temperature approximately 30 °C. It is also revealed that increasing zirconium content caused finer microstructure and hardness of the alloy was raised from 336 HV_0.5 to 412 HV_0.5 while elastic modulus remains approximately steady between 103 and 110 GPa. It is concluded that Ti–Nb–Zr alloys have been found to be a good alternative to known metallic implant materials.     

Synthesis and Characterization of Uniformly Coated Particles of Nickel Basic Carbonateshell/Copper Oxalatecore

The coated system, i.e., nickel basic carbonate_shell/copper oxalate_core, were synthesized by heating dispersions, containing various amounts of the cores (copper oxalate particles), urea, and nickel sulfate for different intervals of time at 85 °C. These uniformly coated particles were obtained under narrow set of the experimental conditions. On heat treatment, the shell and core materials transformed independently into their respective oxides and ended up with coated particles composed of nickel oxide_shell/copper oxide_core. The above‐mentioned systems of particles were characterized by scanning electron microscopy (SEM), x‐ray diffractometry (XRD), Fourier transform infrared spectrometry (FTIR), and thermogravimetric/differential thermal analysis (TG/DTA).     

Hydridoorganostannylene Coordination: Group 4 Metallocene Dichloride Reduction in Reaction with Organodihydridostannate Anions

Organodihydridoelement anions of germanium and tin were reacted with metallocene dichlorides of Group 4 metals Ti, Zr and Hf. The germate anion [Ar*GeH₂]⁻ reacts with hafnocene dichloride under formation of the substitution product [Cp₂Hf(GeH₂Ar*)₂]. Reaction of the organodihydridostannate with metallocene dichlorides affords the reduction products [Cp₂M(SnHAr*)₂] (M=Ti, Zr, Hf). Abstraction of a hydride substituent from the titanium bis(hydridoorganostannylene) complex results in formation of cation [Cp₂M(SnAr*)(SnHAr*)]⁺ exhibiting a short Ti–Sn interaction. (Ar*=2,6-Trip₂C₆H₃, Trip=2,4,6-triisopropylphenyl).     

Amorphous sol–gel SiO<Subscript>2</Subscript> film for protection of an orthorhombic phase alloy against high temperature oxidation

Silica coating derived by sol–gel processing was deposited on an orthorhombic phase Ti–22Al–26Nb alloy by dip-coating technique. Isothermal oxidation at 800 and 900 °C and cyclic oxidation at 900 °C in static air of the coated and uncoated specimens were performed to investigate the effect of the silica coating on the oxidation behavior of the Ti–22Al–26Nb alloy by thermogravimetry, SEM and XRD. The average parabolic rate constants of the coated specimens were lower than those of uncoated ones. Additionally, the present film exhibited a beneficial effect on the cyclic oxidation resistance of the alloy in air. TiO₂, Nb₂TiO₇ or AlNbO₄ were the main phases formed on the alloy. The thin film could inhibit the growth of the oxides. The possible mechanism of the thin film on the oxidation behavior of the alloy was discussed.     

Performance of bio-mortar under elevated temperatures

The microbially induced calcite precipitation was used to bind sand grains, yielding consolidated material known as bio-mortar. An aerobic, urease-active and nonpathogenic Sporosarcina pasteurii microorganism was used for the induction of calcite precipitation. Three different temperatures (250, 500 and 750 °C) were applied to examine the firing resistivity of bio-mortar. The results showed that the organic fiber of died bacterial cells completely dissociates at 500 °C, causing a moderate compressive strength reduction and mass loss increment in bio-mortar. The exposure of bio-mortar to 750 °C leads to a significant compressive strength regression, due to the thermal decomposition of CaCO₃ as confirmed by X-ray diffraction, Fourier transform infrared spectroscopy, thermogravimetric analysis and differential thermal analysis (TG and DTA) as well as scanning electron microscopy.

     

Photocatalytic Activity of Fibrous Ti/Ce Oxides Obtained by Hydrothermal Impregnation of Short Flax Fibers

Fibrous Ti/Ce oxide photocatalysts were prepared for the first time by a biomimetic solution process using short flax fibers (flax straw processing waste) as a biotemplate. Titanium polyhydroxy complex solutions with 3% and 5% cerium were used as precursors. Flax fibers were impregnated in an autoclave under hydrothermal conditions. Ti/Ce oxides were obtained from the biotemplate by annealing at 600 °C. The photocatalytic activity of the Ti/Ce oxides was studied by the adsorption and decomposition of the dye rhodamine B under UV irradiation. The photocatalytic decomposition of the dye was 50% and 75% faster for Ti/Ce oxides with 3% and 5% Ce, respectively, than for the analogous undoped fibrous TiO₂. The morphologies, textures, and structures of the photocatalysts were studied by scanning electron microscopy, low temperature N₂ adsorption/desorption, UV-Vis spectroscopy, and X-ray and XPS analytical methods. It was shown that the introduction of Ce into the precursor solution increased the surface irregularity of the Ti/Ce oxide crystallites compared to pure TiO₂. This effect scaled with the Ce concentration. Ce improved the UV light absorption of the material. The Ti/Ce oxides contained Ce⁴⁺/Ce³⁺ pairs that played an important role in redox processes and intensified the photocatalytic activity.     

Phase composition and magnetic properties of niobium-iron codoped TiO2 nanoparticles synthesized in Ar/O2 radio-frequency thermal plasma

Nanoparticles of Nb⁵⁺-Fe³⁺ codoped TiO₂ with various Nb⁵⁺ concentrations (Nb/(Ti+Fe+Nb)=0-10.0 at%) and Fe³⁺ (Fe/(Ti+Fe+Nb)=0-2.0 at%) were synthesized using Ar/O₂ thermal plasma. Dopant content, chemical valence, phase identification, morphology and magnetic properties were determined using several characterization techniques, including inductively coupled plasma-optical emission spectrometer, X-ray photoelectron spectroscopy, X-ray diffraction, UV-vis diffuse reflectance spectrometer, field-emission scanning electron microscopy, transmission electron microscopy and SQUID commercial instrument. The XRD revealed that all the plasma-synthesized powders were exclusively composed of anatase as major phase and rutile. The rutile weight fraction was increased by the substitution of Fe³⁺ for Ti⁴⁺ whereas it was reduced by the Nb⁵⁺ doping. The plasma-synthesized Nb⁵⁺-Fe³⁺ codoped TiO₂ powders had intrinsic magnetic properties of strongly paramagnetic and feebly ferromagnetic at room temperature. The ferromagnetic properties gradually deteriorated as the Fe³⁺ concentration was decreased, suggesting that the ferromagnetism was predominated by the phase composition as a carrier-mediated exchange.     

Catenated polysulfur ligands: the pentasulfides of di-η5-cyclopentadienyl-zirconium(IV) and -hafnium(IV)

The thiols Cp₂M(SH)₂, where M = Ti and Zr, react to form the complexes Cp₂MS₅ when treated with mono- and di-sulfur transfer reagents. Treatment of Cp₂MCl₂ with Li₂S₂ and sulfur gave Cp₂MS₅, M = Ti, Zr and Hf, in better yield. The new Zr and Hf complexes have a six-membered MS₅ ring in a chair conformation similar to the previously observed for M = Ti. Variable temperature NMR studies show that the barriers to MS₅ ring inversion decrease in the order Ti > Hf > Zr.     

Nano-titanium oxide doped with gold,silver, and palladium — synthesis and structural characterization

Nano-titania doped with noble metals (Au/TiO₂, Ag/TiO₂, Pd/TiO₂) has been synthesized by mild hydrolysis of the mixture of metal salts or complexes and titanium isopropoxide ((iPr-O)₄Ti). After thermal decomposition of the obtained precursors, nanomaterials were formed. Morphological characterization of the nanomaterials was provided by scanning electron microscopy (SEM) and stereological analysis, determining the BET specific surface area, and BJH nanoporosity (pore volume, pore size). It has been found that the structure of nanomaterials (size of nanoparticles and agglomerates) depended strongly on the method of the (iPr-O)₄Ti hydrolysis. A minor dependence on the kind of solvents and precursors of noble metals was observed. The presence of doping metal nanoparticles was confirmed by transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX). Nanomaterial phases were identified by X-ray diffraction (XRD). According to the XRD patterns, Ag/TiO₂ and Pd/TiO₂ products with doping metals in their oxidized form contain Ag-Ti and Pd-Ti phases. Peaks of the metal oxides Ag₂O and PdO are absent in the XRD patterns. The average size of TiO₂ nanoparticles is situated in the region of 20–60 nm, whereas metals are present as about 10–15 nm sized particles and fine nanoparticles.