Papers by Keyword: Oxide Reduction

Abstract: Tungsten trioxide (WO₃) is widely known for its technological importance in electrochromic sensors and catalytic devices. The incorporation of hydrogen into WO₃ can strongly influence the material's electrical, optical, and structural properties. This study investigates the evolution of different tungsten oxidation states and the mechanism of oxide reduction of polycrystalline WO₃ thin films induced by low-energy H₂⁺ irradiation at room temperature. The reduction investigation was conducted in situ using X-ray photoelectron spectroscopy (XPS) measurements around W 4f and O 1s core levels. The hydrogen-implanted film, which was irradiated with 5 keV H₂⁺ ions for 180 minutes, was subsequently characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy and secondary ion mass spectrometry (SIMS). During the initial phase of H₂⁺ irradiation, the W⁶⁺ oxidation state in WO₃ is reduced to W⁵⁺ and W⁴⁺, while the prolonged hydrogen bombardment leads to further reduction and the formation of W²⁺ and W⁰ states. SEM reveals crystallinity loss in the irradiated WO₃ sample, while Raman and XRD indicate a phase transformation from monoclinic to tetragonal after hydrogen bombardment. Our analysis shows that WO₃ reduction is confined to the surface while hydrogen-tungsten bronze (H_xWO₃) is formed in the bulk of the material.

Abstract: Microstructure of the powder metallurgy (PM) steels and especially mechanism of its formation differs significantly from the microstructure of the conventional steels even if composition will be exactly the same. The difference is not only connected to the presence of the pores, which are inalienable feature of the PM parts. Presence of the prior inter-particle boundaries, which can be contaminated by residual oxides, as well as microstructure heterogeneity are another characteristic features of the microstructure of PM steels. Microstructure heterogeneity is connected to the PM manufacturing process: powder mix, consisting of the base powder and additional alloying elements is compacted and then sintered. Fully prealloyed powder is not always possible to use in standard press & sintering route due to the solid solution strengthening of the ferrite resulting in bad powder compressibility. Hence, in order to provide good powder compressibility only pure iron or low-alloyed (typically <3 wt.%) powders are used. Required alloying elements and carbon (added as graphite) are further admixed in the powder form and are distributed during sintering by diffusion into iron particles at high temperatures. To assure satisfactory distribution of alloying elements, oxide layer, covering surface of the powder particles and hindering mass-transfer of the alloying elements, has to be removed first. This can be done by gaseous reducing agents as hydrogen and carbon monoxide. However, their cost and/or purity are of issue for modern alloyed PM steels. Admixed carbon, additionally to its function as alloying element, plays a role of effective reducing agent at higher temperatures. Paper summarizes the main features of microstructure formation during the whole sintering cycle (heating and isothermal sintering) and effect of alloying additives (different carbon sources, alloying elements) and processing parameters (sintering atmosphere composition, temperature profile) on the microstructure formation during conventional sintering process. Results indicate that for successful sintering of alloyed PM steels with homogeneous defect-free microstructure, hydrogen-rich atmospheres and high-temperature sintering are required.

Abstract: High energy ball milling has been used like alternative route for processing of materials. In the present paper, the reduction of tungsten oxide by aluminum in order to obtain metallic tungsten was studied using a SPEX type high energy mill. A powdered mixture of WO₃ and metallic aluminum, weighed according to the stoichiometric proportion with an excess 10% Al, was processed with hardened steel utensils using a 1:6 powder-to-ball ratio. The processing was carried out with milling jar temperature measurement in order to detect the reaction type. The temperature evaluation indicated the self-propagating reaction occurrence by fast increase of the jar temperature after a short milling time. The tungsten oxide reduction was verified by X-Ray Diffraction (XRD) analysis and the milling products were characterized by Scanning Electron Microscopy (SEM). The results were slightly different from the literature due to the mill type and milling parameters used in the work.

Abstract: Processing of W-Cu graded materials from attritor-milled W-CuO mixtures is described. The powder reduction steps are investigated by TG and XRD analyses and by microstructural observations (SEM, TEM). Sintering of reduced powder with different compositions is analysed by dilatometry. Sintering behaviour of the graded component processed by co-compaction of a 10/20/30wt%Cu multi-layer material is briefly discussed. Liquid Cu migration is observed and smoothes the composition gradient. Perspectives to control this migration are discussed.

Abstract: Powder grades pre-alloyed with 1.5-3 wt% chromium are suitable for PM steel components in high performance applications. These materials can be successfully sintered at the conventional temperature 1120 °C, although well-monitored sintering atmospheres with low oxygen partial pressures (<10-17-10-18 atm) are required to avoid oxidation. Mechanical properties of the Cralloyed PM grades are enhanced by a higher sintering temperature in the range 1120-1250 °C, due to positive effects from pore rounding, increased density and more effective oxide reduction. A material consisting of Astaloy CrM, which is pre-alloyed with 3 wt% Cr and 0.5 wt% Mo, and 0.6 wt% graphite obtains an ultimate tensile strength of 1470 MPa combined with an impact strength of 31 J at density 7.1 g/cm3, after sintering at 1250 °C followed by cooling at 2.5 °C/s and tempering.

Abstract: The mixtures NiO-WO3 were synthesized by the combustion of gels obtained by drying common solutions of nickel nitrate, polytungstic acid and citric acid. The X-ray diffractograms of oxide mixtures confirmed mutual interaction of oxides during synthesis leading to a new phase, NiWO4. The reduction of oxide mixtures in hydrogen atmosphere was investigated thermogravimetrically. The temperature of reduction of the oxide mixture lies between the temperatures of reduction of pure oxides and monotonously increases with the increase in WO3 mole fraction; however, the reduction itself is a multi-step process, preferably in the composition region rich in NiO. The X-ray diffractometry of metallic residues evidenced Ni-W alloys and tungsten excess to be the reduction products.