Surface composition of prepared tungsten carbide and its catalytic activity

The surface composition and electronic structure of carburized tungsten trioxide, which is prepared by heating WO₃ in carbon monoxide atmosphere at 700°C, are investigated using X-ray photoelectron spectroscopy (XPS). The relationship between the surface composition and the catalytic activity for methanol electro-oxidation is clarified. The formation of tungsten carbide at the surface enhances the catalytic activity. On the other hand, the presence of free carbon or tungsten trioxide in the surface layer reduces the activity remarkably. It is also shown that, the higher the electronic density of states near the Fermi level, the higher the catalytic activity. Additionally, the catalytic behavior of tungsten carbide for methanol electro-oxidation is mentioned.     

Ablation properties of carbon/carbon composites with tungsten carbide

The ablation properties and morphologies of carbon/carbon (C/C) composites with tungsten carbide (WC) filaments were investigated by ablation test on an arc heater and scanning electron microscopy. And the results were compared with those without tungsten carbide (WC) filaments tested under the same conditions. It shows that there is a big difference between C/C composites with and without WC filaments on both macroscopic and microscopic ablation morphologies and the ablation rates of the former are higher than the latter. It is found that the ablation process of C/C composites with WC filaments includes oxidation of carbon fibers, carbon matrices and WC, melting of WC and WO₃, and denudation of WC, WO₃ and C/C composites. Oxidation and melting of WC leads to the formation of holes in z directional carbon fiber bundles, which increases the coarseness of the ablation surfaces of the composites, speeds up ablation and leads to the higher ablation rate. Moreover, it is further found that the molten WC and WO₃ cannot form a continuous film on the ablation surface to prevent further ablation of C/C composites.     

Full potential calculation of structural, elastic properties and high-pressure phase of binary noble metal carbide: ruthenium carbide

We present in this paper the results of an ab initio theoretical study within the local density approximation (LDA) to determine in rock-salt (B1), cesium chloride (B2), zinc-blende (B3), and tungsten carbide (WC) type structures, the structural, elastic constants, hardness properties and high-pressure phase of the noble metal carbide of ruthenium carbide (RuC).The ground state properties such as the equilibrium lattice constant, elastic constant, the bulk modulus, its pressure derivative, and the hardness in the four phases are determined and compared with available theoretical data. Only for the three phases B1, B3, and WC, is the RuC mechanically stable, while in the B2 phase it is unstable, but in B3 RuC is the most energetically favourable phase with the bulk modulus 263 GPa, and at sufficiently high pressure (P_t=19.2 GPa) the tungsten carbide (WC) structure would be favoured, where ReC-WC is meta-stable.The highest bulk modulus values in the B3, B2, and WC structures and the hardnesses of H(B3)=36.94 GPa, H(B1)=25.21 GPa, and H(WC)=25.30 GPa indicate that the RuC compound is a superhard material in B3, and is not superhard in B1 and WC structures compared with the H(diamond)=96 GPa.     

Evidence of the surface layer in tungstated zirconia

We characterized the structure of tungstated zirconia (WO_x–ZrO₂) by combining X-ray diffraction, Raman spectroscopy and High Resolution Electron Microscopy (HREM) together with molecular simulations. Our results indicate that the structure of this material consists of metastable tetragonal ZrO₂ nanoparticles (<20 nm in diameter) covered by a few-nanometers thick low-crystallinity surface layer formed by tungsten oxospecies (WO_x). Although the X-ray diffraction pattern matched the spectra of the tetragonal ZrO₂ bulk phase the lattice fringes of the ZrO₂ nanoparticles observed by HREM were locally distorted, presumably as a result of the interaction with the surface WO_x layer. The local interplanar distances of the surface layer were close to those present in different bulk tungsten oxocompounds, and its variability was also an indication of the WO_x–ZrO₂ interaction. Molecular simulations corroborated our structural assignment. The results presented here are a direct evidence for the presence of a surface WO_x layer in the case of WO_x–ZrO₂. PACS 68.35.Bs; 81.05.Ys; 82.65.Dp     

The preparation of nanophase tungsten carbide powder with zeolite-X catalysts

The reduction–carburization of tungsten trioxide (WO₃) under carbon monoxide flow was studied in the temperature range of 300–750 °C. The reduction–carburization of WO₃ was improved by mechanically mixing with zeolite-HX, -NaX and -KX. The interaction between cation in zeolite-X and oxygen in WO₃ affected the improvement of the reduction–carburization of WO₃ to WC. Moreover, the improved reduction–carburization of WO₃ could lead to the decrease of reaction temperature. Because the particle size of WC is in contact with a reaction temperature, the nanophase WC can be prepared at low temperature. In particular, the particle size of WC was controlled by reaction temperature. The particle sizes of produced WC at 550, 650 and 700 °C were 25, 50 and 100 nm respectively.     

Microwave-assisted synthesis of carbon-supported carbides catalysts for hydrous hydrazine decomposition

Microwave-assisted synthesis of carbon-supported Mo₂C and WC nanomaterials was studied. Two different routes were utilized to prepare MoO₃ (WO₃) - C precursors that were then subjected to microwave irradiation in an inert atmosphere. The effect of synthesis conditions, such as irradiation time and gas environment, was investigated. The structure and formation mechanism of the carbide phases were explored. As-synthesized nanomaterials exhibited catalytic activity for hydrous hydrazine (N₂H₄·H₂O) decomposition at 30–70 ^°C. It was shown that the catalyst activity significantly increases if microwave irradiation is applied during the decomposition process. Such conditions permit complete conversion of hydrazine to ammonia and nitrogen within minutes. This effect can be attributed to the unique nanostructure of the catalysts that includes microwave absorbing carbon and active carbide constituents.     

Oxidation of W(110): I. LEED study of the oxide formation at 1000 K

Oxidation of the (110) surface of a tungsten crystal in 2 × 10⁻³ torr of oxygen at 1000 K for 80 sec has revealed a LEED pattern which exhibits a complex variation with incident electron energy. A kinematic analysis has shown that the LEED patterns result from three pairs of twin related WO₃(111&#x0304;) nuclei, each facetted to pyramids exposing three well developed (100) type surfaces. Detailed analysis of the pattern has shown that the nuclei exhibit the same monoclinic symmetry at the surface as that existing in bulk WO₃. A pseudo-cubic lattice constant of 7.58 ± 0.1 Å was estimated from the electron energies at which Laue back reflexion beams were excited.     

Combustion synthesis of nano-sized tungsten carbide powder and effects of sodium halides

The synthesis of nano-size tungsten carbide powder has been investigated with a WO₃ + Mg + C + carbonate system using alkali halides. The effects of different types of alkali halides on combustion temperature and tungsten carbide formation were discussed. Sodium fluoride had a notable effect on the particle size of the product and the degree of transformation from the initial mixture. A small amount of ammonium carbonate activated the carburization of tungsten carbide by the gas phase carbon transportation. X-ray diffraction data and particle analysis showed that the final product synthesized from a WO₃–Mg–C–(NH₄)₂CO₃–NaF system contains pure-phase tungsten carbide with a particle size of 50–100 nm.     

Thermal spreading of WO3 onto zirconia support

This study focused on preparation of tungsten oxide supported on zirconia by thermal spreading. The prepared samples were characterized by infrared spectroscopy, UV-vis diffuse reflection spectroscopy, X-ray diffraction, and also by methanol dehydration reaction. It was observed that isolated octahedral tungsten dispersed species and dispersed polytungstate were formed on zirconia surface, although some WO₃ that remained after the thermal treatment could also be detected. The presence of these species led to an increase of the number of Lewis sites and the generation of Brönsted acid sites. High calcination temperatures promoted the creation of Brönsted sites as a consequence of polytungstate species formation. The activity on methanol dehydration was also determined by the concentration of these species, whereas the isolated WO_x species were found poorly active. The correlation observed between the catalytic performance and the tungsten dispersed species, as revealed by spectroscopic techniques, evidenced the occurrence of thermal spreading of WO₃ on ZrO₂. The results presented in this work show that WO₃ thermal spreading on ZrO₂ may be effectively accomplished as predicted by thermodynamics.     

Ab initio probing of the electronic band structure and Fermi surface of fluorine-doped WO<Subscript>3</Subscript> as a novel low-<Emphasis Type="Italic">T</Emphasis><Subscript><Emphasis Type="Italic">C</Emphasis></Subscript> superconductor

Ab initio calculations were performed to investigate the electronic structure and the Fermi surface of the newly discovered low-temperature superconductor: fluorine-doped WO₃. We find that F doping provides the transition of the insulating tungsten trioxide into a metallic-like phase WO_{3 − x} F _x , where the near-Fermi states are formed mainly from W 5d with admixture of O 2p orbitals. The cooperative effect of fluorine additives in WO₃ consists in change of electronic concentration as well as the lattice constant. At probing their influence on the near-Fermi states separately, the dominant role of the electronic factor for the transition of tungsten oxyfluoride into superconducting state was established. The volume of the Fermi surface gradually increases with the increase of the doping. In the sequence WO₃ → WO_2.5F_0.5 the effective atomic charges of W and O ions decrease, but much less, than it is predicted within the idealized ionic model—owing to presence of the covalent interactions W-O and W-F.     

Field-emission properties of transparent tungsten oxide nano-urchins

The field-emission properties of transparent tungsten oxide nano-urchin (NU) films deposited on conducting glass substrates were examined. The novel crystalline tungsten oxide NUs consisted of nanowires added to a spherical shell. The WO_2.72 NUs showed better field-emission properties than the WO₃ NUs with a low turn-on field of approximately 5.8 V/μm and a current density as high as 1.3 mA/cm² at 7.2 V/mm. The WO _x NUs films could be used in FE applications using a large-area glass substrate without the need for a catalyst and a mechanical rubbing or lift-up process. These results have implications for the enhancement of FE properties by further tuning the WO _x phases.     

Thermally-induced morphological transition in WOx deposited on a ZrO2(1 0 0) substrate

A combined atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS) study of tungsten oxide model catalysts is presented. The model catalysts were prepared by applying the real preparation method to a ZrO₂(1 0 0) single crystal support. AFM imaged several granular structures of scattered dimensions on the surface of ZrO₂(1 0 0) in the as prepared samples. After heating, at low loading the tungsten species rearranged into small WO_x particles strongly interacting with the substrate. At high tungsten content large WO₃ aggregates also formed. XPS analysis confirmed these changes. The estimated surface density of the interacting W-containing species closely matched that of real catalysts.     

First principles study of the structural,electronic, mechanical and superconducting properties of WX (X=C,N)

The structural, electronic, mechanical and superconducting properties of tungsten carbide (WC) and tungsten nitride (WN) are investigated using first principles calculations based on density functional theory (DFT). The computed ground state properties, such as equilibrium lattice constant and cell volume, are in good agreement with the available experimental data. A pressure induced structural phase transition is observed in both tungsten carbide and nitride, from a tungsten carbide phase (WC) to a zinc blende phase (ZB), and from a zinc blende phase (ZB) to a wurtzite phase (WZ). The electronic structure reveals that these materials are metallic at ambient conditions. The calculated elastic constants obey the Born-Huang criteria, suggesting that they are mechanically stable at normal and high pressure. Also, the superconducting transition temperature is estimated for the WC and WN in stable structures at atmospheric pressure.     

Surface composition modification of tungsten higher oxide under He<Superscript>+</Superscript> ion bombardment

The surface reduction of higher oxide WO₃ under irradiation by He⁺ ions with the energies 1 and 3 keV in a high vacuum is investigated by X-ray photoelectron spectroscopy. It is found that lower WO₂ and intermediate WO _x (2 < x < 3) oxides form first in WO₃ surface layers under He⁺ ion bombardment, and with an increase in the irradiation dose metallic tungsten forms. It is shown that the degree of irradiated oxide surface metallization increases with an increase in the energy of the bombarding He⁺ ions. A comparison of WO₃ oxide surface composition modification under He⁺ and Ar⁺ ion irradiation is presented.     

Synthesis of tungsten carbide nanoparticles in WO3 pyrolysis in a plasma arc

Synthesis of tungsten carbides is investigated in the process of WO₃ pyrolysis in a dc electric arc during dispersion of a composite electrode (graphite-WO₃) in a helium medium at 25 Torr. The synthesized material is analyzed by high-resolution transmission electron microscopy. The interplanar spacings of nanocrystallites are measured directly by using both TEM images and electron diffractometry. The size distribution functions of nanoparticles containing tungsten are measured. It is shown that W, WC, W₂C, and WO₃ nanoparticles can be obtained in the conditions of the present experiments. The content of these compounds in the synthesized material was quantitatively assessed. It is shown that the W₂C content forms the dominant portion of nanoparticles in the synthesized material.     

Phase transformation during surface ablation of cobalt-cemented tungsten carbide with pulsed UV laser

Surface ablation of cobalt-cemented tungsten carbide hard metal has been carried out in this work using a 308 nm, 20 ns XeCl excimer laser. Surface microphotography and XRD, as well as an electron probe have been used to investigate the transformation of phase and microstructure as a function of the pulse-number of laser shots at a laser fluence of 2.5 J/cm². The experimental results show that the microstructure of cemented tungsten carbide is transformed from the original polygonal grains of size 3 μm to interlaced large, long grains with an increase in the number of laser shots up to 300, and finally to gross grains of size 10 μm with clear grain boundaries after 700 shots of laser irradiation. The crystalline structure of the irradiated area is partly transformed from the original WC to βWC_1-x, then to αW₂C and CW₃, and finally to W crystal. It is suggested that the undulating ‘hill–valley’ morphology may be the result of selective removal of cobalt binder from the surface layer of the hard metal. The formation of non-stoichiometric tungsten carbide may result from the escape of elemental carbon due to accumulated heating of the surface by pulsed laser irradiation. Received: 13 July 2000 / Accepted: 27 October 2000 / Published online: 10 January 2001     

Rapid anisotropic diffusion of lithium in electrochromic thin films based on the hexagonal tungsten bronze structure

The chemical diffusion coefficient of lithium in oxidized potassium hexatungstate and reduced hexagonal potassium tungsten bronze films was measured by the galvanostatic transient method. Two-dimensional anisotropic diffusion was found in the hexagonal hexatungstates, while no appreciable anisotropy was observed in samples with the potassium hexagonal tungsten bronze structure. The chemical diffusion coefficients along the c-axis in thin films of the tungstates K_0.33WO_3.165 and K_0.3WO_3.15 (about 6000 Å thick) are about 10^?10 cm²/s, while those along the a-axis are about 10^?7 cm²/s. This latter value is about the same to those measured in a potassium hexagonal tungsten bronze single crystal of composition K_0.28WO₃ which was grown electrochemically. It is most likely that the presence of the additional oxygen atoms in the tunnels within the hexatungstate structure is responsible for the large decrease in the rate of motion of lithium along the c-axis that leads to the anisotropy in the macroscopic diffusion coefficient in this crystal structure.     

Pd/WO<Subscript>3</Subscript>/C nanocomposite with APTMS-functionalized tungsten oxide nanosheet for formic acid electrooxidation enhancement

A Pd/WO₃/C nanocomposite with 3-aminopropyltrimethoxysilane (APTMS)-functionalized tungsten oxide nanosheets (Pd/WO₃/C-APTMS) was synthesized and applied as the efficient anode catalyst for direct formic acid fuel cells (DFAFCs). The mechanism for synthesizing the nanocomposite is as follows: initially, [PdCl₄]^2? was assembled onto the tungsten oxide nanosheets modified with APTMS. Following this, Pd nanoparticles were reduced via traditional impregnation reduction of [PdCl₄]^2? with NaBH₄. The transmission electron microscope (TEM) images revealed that the Pd nanoparticles were uniformly dispersed on WO₃ nanosheets and were approximately 2.7 nm in size. The electrochemical test results showed that enhanced electrocatalytic activity for the formic acid oxidation reaction (FAOR) was obtained on the Pd/WO₃/C catalyst compared with Pd/C. The higher electrocatalytic activity might be attributed to the uniform distribution of Pd with smaller particles. Furthermore, it is likely that the improvement in catalytic stability for the Pd/WO₃/C catalyst is due to the hydrogen spillover effect of WO₃ particles. These results indicate that this novel Pd/WO₃/C-APTMS nanocomposite exhibits promising potential for use as an anode electrocatalyst in DFAFCs.     

n型有序多孔硅基氧化钨室温气敏性能研究

利用电化学腐蚀方法制备了n型有序多孔硅, 并以此为基底用直流磁控溅射法在其表面溅射不同厚度的氧化钨薄膜. 利用X射线和扫描电子显微镜表征了材料的成分和结构, 结果表明, 多孔硅的孔呈柱形有序分布, 溅射10 min的WO₃薄膜是多晶结构, 比较松散地覆盖在整个多孔硅的表面. 分别测试了多孔硅和多孔硅基氧化钨在室温条件下对二氧化氮的气敏性能, 结果表明, 相对于多孔硅, 多孔硅基氧化钨薄膜对二氧化氮的气敏性能显著提高. 对多孔硅基氧化钨复合结构的气敏机理分析认为, 多孔硅和氧化钨薄膜复合形成的异质结对良好的气敏性能起到主要作用, 氧化钨薄膜表面出现了反型层引起了气敏响应时电阻的异常变化. 关键词： 有序多孔硅 氧化钨薄膜 二氧化氮 室温气敏性能     

Electronic structure and lattice dynamics of Li2Ni(WO4)2

We combined spectroscopic ellipsometry and Raman scattering measurements to explore the electronic structure and lattice dynamics in Li₂Ni(WO₄)₂. The optical absorption spectrum of Li₂Ni(WO₄)₂ measured at room temperature presents a direct optical band gap at 2.25 eV and two bands near 5.2 and 6.0 eV, which are attributed to charge-transfer transitions from oxygen 2p states to nickel 3d or tungsten 5p states. The Raman scattering spectrum of Li₂Ni(WO₄)₂ measured at room temperature presents seventeen phonon modes at approximately 112, 143, 193, 222, 267, 283, 312, 352, 387, 418, 451, 476, 554, 617, 754, 792, and 914 cm⁻¹. When the temperature is decreased to 20 K, the frequency, linewidth, and normalized intensity of all phonon modes exhibited almost no temperature dependence. Upon cooling across 13 K, which is the antiferromagnetic phase transition temperature, the oxygen octahedra stretching mode at 914 cm⁻¹ exhibited a softening and an increase in intensity, thus suggesting a coupling between the magnetic and lattice degrees of freedom. The spin-phonon coupling constant was estimated to be 0.94 mRy/Ų, indicating a weak spin-phonon interaction in Li₂Ni(WO₄)₂.