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.     

Hydrogen on WO3(001)

Ultraviolet photoemission measurements of the (001) surface of WO₃ show that after exposure to atomic hydrogen new states appear in the energy gap region at 2.3 and 0.9 eV below the Fermi energy. A peak at 2.2 eV was also produced by hydrogen ion bombardment. To investigate whether these surface effects were due to the formation of hydrogen tungsten bronze H_xWO₃, comparison was made with spectra from the electronically similar sodium bronze. The form of the spectra were different both in the valence band and energy gap regions indicating that hydrogen adsorption or loss of oxygen from the surface rather than formation of H_xWO₃ is the major effect.     

Metal-support interactions in systems palladium deposited on oxidized tungsten surfaces

The morphology of the palladium (Pd) overlayers on oxidized tungsten (W) tips has been studied by Field Emission Microscopy (FEM). The effect of thermal treatment on the interaction of Pd with the support and chemisorption of CO on variously treated Pd-containing samples has been investigated. The results are discussed in relation to complementary macroscopic experiments by synchrotron radiation excited photoelectron spectroscopy (SRPES) and thermally programmed desorption (TPD) of carbon monoxide (CO) on a polycrystalline W foil. A distinct influence of support pre-oxidation on the Pd layer growth has been demonstrated. Two types of oxidized supports have been used: tungsten with oxygen pre-adsorbed at room temperature (RT) and then heated to 700 K (WO_x/W (RT) system) and tungsten oxidized at 1300 K (WO_x/W (1300 K) system) in situ. The surface of WO_x/W (1300 K) sample is fully oxidized in contrast to WO_x/W (RT), where the presence of un-oxidized patches has been demonstrated by SRPES measurements. A Pd layer grows on the WO_x/W (RT) surface mostly on the densely populated planes (1 1 0) and (2 1 1) of the W tip. Heating of this system up to 700 K results in disaggregation of the original Pd layer. Pd clusters on the tungsten tip oxidized at 1300 K are localized on the atomically rough (1 1 1) plane. The observed differences in CO adsorption on the aforementioned types of investigated samples can be attributed to differences in the chemical nature of their surfaces.     

Thermochemistry of the cubic and hexagonal lithium tungsten bronze phases LixWO3

The enthalpies of formation of hexagonal WO₃, hexagonal and cubic Li_xWO₃ have been determined by solution calorimetry. The ambient-temperature materials h-Li_0.44WO₃ and c-Li_xWO₃ (x=0.51, 0.71) were prepared by n-butyl lithiation in hexane. The thermochemistries of the lithium insertion compounds were examined and related to structural features.     

Electrochemical lithium incorporation into WO3 and MoO3 thin films

The generally accepted mechanism of electrochromic phenomena into WO₃ thin films involves the simultaneous injection of cations and electrons to form a tungsten bronze M_xWO₃, e.g. H_xWO₃,Li_xWO₃. Electrochromic cells of the type ITO MO₃/LiClO₄(M) in propylene carbonate/Pt, where M = W or MO and MO₃ is an amorphous thin film have been used. Different amounts of charges have been injected through these cells by electrochemical means at room temperature. The variations of the MO₃ electrode potential with the injected charge are in good agreement with the assumption of the formation of Li_xMO₃ compounds. The free enthalpies of formation of these bronzes have been calculated. The behavior of thin film electrodes seems to be intermediate between amorphous and crystallized bulky materials. Some measurements of electrode potential have also been carried out with crystallized thin films of sputtered WO₃.     

Role of WO3 in structural and optical properties of WO3-Al2O3-PbO-B2O3 glasses

Glass samples of composition xAl₂O₃-20PbO-(80−x)B₂O₃ and xWO₃-xAl₂O₃-20PbO-(80−2x)B₂O₃ with x varying from 0% to 10% mole fraction are prepared by melt quench technique. The optical band gap decreases (from 3.21 to 2.37 eV) more for WO₃-Al₂O₃-PbO-B₂O₃ glasses with an addition of WO₃ content. The FTIR spectral studies have pointed out the conversion of structural units of BO₃ to BO₄ and WO₄ to WO₆ in these glasses. The increase in density from 4.51 to 5.80 g cm⁻³ for WO₃-Al₂O₃-PbO-B₂O₃ glasses is observed with an increase in WO₃ content. This is observed that the atomic structure changes more with the incorporation of WO₃. This is due to the formation of WO₆, WO₄ and BO₄ units.     

Surface properties of palladium catalysts supported on ternary ZrO2–Al2O3–WOx oxides prepared by the sol–gel method: Study of the chemical state of the support

The surface properties of Pd and Pd–Pt catalysts supported on binary ZrO₂–WOx and ternary ZrO₂–Al₂O₃–WOx oxides prepared by the sol–gel method were studied. Special attention was paid to the study of the texture of the catalysts as well as the chemical state of tungstated zirconia and tungstated zirconia promoted with alumina in the palladium catalysts. The catalysts were tested in the isomerization of n-hexane and were characterized by N₂ physisorption, XRD, TPR, Raman spectroscopy, XPS and FT-IR of adsorbed pyridine. The catalysts had bimodal pore size distributions with mesopores in the range 55–70 Å and macropores of 1000 Å in diameter. The catalysts had a surface WOx coverage (4.4–6.0 W nm^?2) lower than that of the theoretical monolayer (7.0 W nm^?2). A lower acidity of the ternary ZrO₂–Al₂O₃–WOx oxide as compared to the binary ZrO₂–WOx oxide was found. Higher activity in the isomerisation of n-hexane was obtained in the Pd–Pt catalysts supported on ternary ZrAlW oxides prepared by sol–gel that is correlated with the coexistence on the surface of W⁴⁺ (WO₂) or W⁰ and W⁶⁺ (Al₂(WO₄)₃) species, ZrO₂ in the tetragonal phase and a high amount of ZrOx suboxides species in a low oxidation state (Zr³⁺ and Zr²⁺).     

Synthesis,surface chemistry and electrocatalytic properties of oxygen-modified tungsten carbide in relation to the electrochemical hydrogen oxidation

The surface chemistry of tungsten carbide was studied using an indicator spectrophotometric method and X-ray photoelectron emission spectroscopy. The presence of WO₂, WO₃ and adsorbed polytungstate ions was identified on the surface of WC specimens. The electrocatalytic activity of oxygen-modified tungsten carbide was attributed to the WO₂ at their interface with WC. This conclusion is supported by the presence of some density of states of the 5d, 6s electrons at the Fermi level on the W⁴⁺ and by the relationship between exchange current density and concentration of the lattice O^2?. Insertion of oxygen atoms in the WC crystal lattice leads to a widening of the anodic range of potentials in which the WC maintains its electrochemical activity in hydrogen oxidation reaction.     

Structural and optical properties of WO3-ZnO-PbO-B2O3 glasses

Glass samples of compositions 20PbO-80B₂O₃ and xWO₃—(20−x) ZnO-20PbO-60B₂O₃ with x varying from 0% to 10% mole fraction are prepared by the melt quench technique. Decrease in the band gap from 2.86 to 2.16 eV for ZnO-PbO-B₂O₃ glasses with an increase in the WO₃ content has been observed and discussed. The FTIR spectral studies have pointed out the conversion of structural units of BO₃ to BO₄ and WO₄ to WO₆ with the presence of W-O-W vibration of tungsten and incorporation of ZnO₄ structural units of zinc in these glasses. The increase in density from 2.75 to 4.03 gcm⁻³ for ZnO-PbO-B₂O₃ glasses is observed with an increase in WO₃ content. Due to the formation of WO₆, WO₄ and BO₄ units, changes in the atomic structure with WO₃ composition are observed and discussed.     

Preparation and physical properties of CuxWO3

We report on the study of WO₃ doped with Cu using sol-gel (Cu_xWO₃^d) and impregnation (Cu_xWO₃ⁱ) methods. All materials are well crystallized and exhibit single phases whose crystallite size ranges from 17 to 100 nm depending on Cu amount and the preparation technique. The conductivity dependence on temperature demonstrates semiconductor behavior and follows the Arrhenius model, with activation energies, E_σ, commonly in the range 0.4-0.6 eV. Moreover, the thermopower study shows that Cu_xWO₃^d is mainly of p-type conductivity, whereas Cu_xWO₃ⁱ is n-type. The mechanism of conduction is attributed to a small polaron hopping. The doping process is found to decrease the interband transition down to 520 nm depending on the preparation conditions. The photoelectrochemical characterization confirms the conductivity type and demonstrates that the photocurrent J_ph increases with Cu-doping. Taking into consideration the activation energy, the flat band potential and the band gap energy, the band positions of each material are proposed according to the preparation method and Cu amount.     

Application of Black Pearl carbon-supported WO3 nanostructures as hybrid carriers for electrocatalytic RuSex nanoparticles

RuSe_x electrocatalytic nanoparticles were deposited onto hybrid carriers composed of Black Pearl carbon-supported tungsten oxide; and the resulting system's electrochemical activity was investigated during oxygen reduction reaction. The tungsten oxide-utilizing and RuSe_x nanoparticle-containing materials were characterized using transmission electron microscopy, X-ray diffraction and electrochemical diagnostic techniques such as cyclic voltammetry and rotating ring-disk voltammetry. Application of Black Pearl carbon carriers modified with ultra-thin films of WO₃ as matrices (supports) for RuSe_x catalytic centers results during electroreduction of oxygen in 0.5 mol dm⁻³ H₂SO₄ (under rotating disk voltammetric conditions) in the potential shift of ca. 70 mV towards more positive values relative to the behavior of the analogous WO₃-free system. Also the percent formation (at ring in the rotating ring-disk voltammetry) of the undesirable hydrogen peroxide has been decreased approximately twice by utilizing WO₃-modified carbon carriers. The results are consistent with the bifunctional mechanism in which oxygen reduction is initiated at RuSe_x centers and the hydrogen peroxide intermediate is reductively decomposed at reactive WO₃-modified Black Pearl supports. The electrocatalytic activity of the system utilizing WO₃-modified Black Pearl supports has been basically unchanged upon addition of acetic acid, formic acid or methyl formate to the sulfuric acid supporting electrolyte.     

Tailoring resistive switching characteristics in WOx films using different metal electrodes

We have investigated the role of the metal/oxide junction interface on the resistive switching (RS) characteristics in WO_3+x films. The WO_x films are fabricated on Pt substrates by magnetron sputtering at room temperature. Top metal contact (Au or Al) is fabricated by using thermal evaporator. The thicknesses of WO_x films and top electrodes are 1 μm and 200 nm, respectively. It has been found that the bi-polar RS direction is dependent on the choice of top metal electrode, Au or Al. The sample with a Au top electrode shows clockwise (CW) RS mode whilst the sample with a Al top electrode shows counter-clockwise (CCW) RS mode. The on/off ratio is 10 times for Au/WO_x/Pt and 100 times for Al/WO_x/Pt. The bi-polar RS modes are modeled in terms of the difference in the electronegativity of the top and bottom electrodes.     

Electronically induced lattice distortion in WO3 and stability of ReO3 lattice

Structural phase transitions in WO₃ and the stability of cubic ReO₃ and M_xWO₃ lattices are attributed to the screening effect involving W or Re 5d and O 2p states on the lattice vibrations. The presence of the conduction electrons in ReO₃ or M_xWO₃ is shown to suppress this effect and to stabilize the cubic lattice.     

A structural analysis of W-Sb mixed oxide catalyst

An investigation on the structure of W-Sb mixed oxide catalyst, W₁₂Sb_xO_y (x = 1, 3, 5), is proposed. The W-Sb mixed oxide powders were prepared by the calcination of aqueous precursors, antimony tartrate and ammoniummetatungstate, and characterized with scanning electron microscope, X-ray diffractometer, and transmission electron microscope. At low content of Sb (x = 1), the W-Sb mixed oxide powder consisted of polyhedral particles, and their crystal structure was triclinic WO₃. At higher content (x = 3, 5), majority of the oxide powders were bar-shaped particles, consisting of triclinic WO₃ and tetragonal WO₃. With electron diffraction pattern and simulation, Sb incorporation into the cuboctahedral sites of perovskite-like WO₃ was proved and its effect on the phase transition from triclinic to tetragonal was discussed.     

Influence of space charges on the dielectric behaviour of (Li2B4O7)1−x(WO3)x-glasses

The dielectric behaviour of (Li₂B₄O₇)_1−x(WO₃)_x glass samples is to a large extent governed by space charges. A detailed analysis of the effective dielectric constant ϵ_eff and the loss tangent tan δ reveals the intrinsic dielectric properties of the materials. At large WO₃-contents (0.44<x<0.55) we find a characteristic temperature in ϵ(T) which coincides with a phase transition temperature in crystalline WO₃, suggesting a reconstruction of the local environment of many tungsten atoms near to their WO₃-crystalline state.     

Ultrasonic studies on alkali borate tungstate glasses

Longitudinal and shear ultrasonic wave velocities have been measured in different compositions of the glass system 20Li₂O-(80−x)B₂O₃-xWO₃ (0?x?12.5 mol%), at room temperature and at 4 MHz frequency. Elastic moduli, Debye temperature and Poisson's ratio have been obtained as a function of WO₃ content. Based on FTIR spectroscopy and theoretical bond compression model, quantitative analysis has been carried out in order to obtain more information about the structure of these glasses. The longitudinal ultrasonic wave velocity measurements showed a bend at about 2.5 mol% WO₃ content while shear ultrasonic wave velocity decreased monotonously with an increase of WO₃ content. Elastic moduli values decreased as WO₃ content increased from 0 to 2.5 mol%. Further increase of WO₃ beyond 2.5 mol% increased the elastic moduli values. It is suggested that these behaviours are mainly due to the presence of WO₃ in the network structure of these glasses as a network modifier when WO₃ content is between 0 and 2.5 mol%, and acts as a network former above 2.5 mol%.     

Silicon MOS structures with nonstoichiometric metal-oxide semiconductors

MOS structures are formed by oxidative annealing of tin, tungsten, palladium, nickel, and zinc thin films on silicon, and their high-frequency C-V characteristics are measured. The energy spectra of the density of surface states taken of SnO_{2 ? x} , WO_{3 ? x} and PdO_x nonstoichiometric oxides are found to have common features.     

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.     

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.     

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.