Observation of piezoelectric response on tungsten doped barium zirconium titanate ceramics

This study describes observation of piezoelectric response of Ba(Zr 0.10Ti 0.90.O3 ceramics modified with tungsten (BZT:2W) by the mixed oxide method. According to X ray diffraction analysis, the ceramics are free of secondary phases. Transmission electron microscopy (TEM) analyses reveals the absence of segregates in the grain boundaries indicates the high solubility of WO3 in the BZT matrix. The dielectric permittivity measured at a frequency of 10 KHz was equal to 6500 with dieletric loss of 0.15. A typical hysteresis loop was observed at room temperature. Electron Paramagnetic Resonance (EPR) analyses reveals that substitution of W6+ by Ti4+ causes distortion in the crystal structure changing lattice parameter. Polarization reversal was investigated by applying dc voltage through a conductive tip during the area scanning. Piezoelectric force microscopy images reveals that in-plane response may not change its sign upon polarization switching, while the out-of-plane response does. Copyright © 2010 American Scientific Publishers.

Microscopic and dielectric analyses of vanadium and tungsten modified barium zirconium titanate ceramics

Dielectric spectroscopy was used in this study to examine polycrystalline vanadium and tungstendoped BaZr 0.1Ti 0.90O 3 (BZT10:2V and BZT10:2W) ceramics obtained by the mixed oxide method. According to X-ray diffraction analyses, addition of vanadium and tungsten lead to ceramics free of secondary phases. SEM analyses reveal that both dopants result in slower oxygen ion motion and consequently lower grain growth rate. Temperature dependence dielectric study showed normal ferroelectric to paraelectric transition well above the room temperature for the BZT10 and BZT10:2V ceramics. However, BZT10:2W ceramic showed a relaxor-like behavior near phase transition characterized by the empirical parameter γ. Piezoelectric force microscopy images reveals that the piezoelectric coefficient is strongly influenced by type of donor dopant suggesting promising applications for dynamic random access memories and data-storage media. Copyright © 2010 American Scientific Publishers All rights reserved.

The role of Bi2O3 on the thermal, structural, and optical properties of tungsten-phosphate glasses

Glasses in the ternary system (70 - x)NaPO3-30WO 3-xBi2O3, with x = 0-30 mol %, were prepared by the conventional melt-quenching technique. X-ray diffraction (XRD) measurements were performed to confirm the noncrystalline nature of the samples. The influence of the Bi2O3 on the thermal, structural, and optical properties was investigated. Differential scanning calorimetry analysis showed that the glass transition temperature, Tg, increases from 405 to 440 C for 0 ≤ x ≤ 15 mol % and decreases to 417 C for x = 30 mol %. The thermal stability against devitrification decreases from 156 to 67 C with the increase of the Bi2O3 content. The structural modifications were studied by Raman scattering, showing a bismuth insertion into the phosphate chains by Bi-O-P linkage. Furthermore, up to 15 mol % of Bi 2O3 formation of BiO6 clusters is observed, associated with Bi-O-Bi linkage, resulting in a progressive break of the linear phosphate chains that leads to orthophosphate Q0 units. The linear refractive index, n0, was measured using the prism-coupler technique at 532, 633, and 1550 nm, whereas the nonlinear (NL) refractive index, n 2 was measured at 1064 nm using the Z-scan technique. Values of 1.58 ≤ n0 ≤ 1.88, n2 ≥ 10-15 cm 2/W and NL absorption coefficient, α2 ≤ 0.01 cm/GW, were determined. The linear and NL refractive indices increase with the increase of the Bi2O3 concentration. The large values of n0 and n2, as well as the very small α2, indicate that these materials have large potential for all-optical switching applications in the near-infrared. © 2012 American Chemical Society.

Nonlinear Optical Properties of Tungsten Lead-Pyrophosphate Glasses Containing Metallic Copper Nanoparticles

We have prepared heavy metal oxide glasses containing metallic copper nanoparticles with promising nonlinear optical properties which were determined by Z-scan and pump-probe measurements using femtosecond laser pulses. For the wavelengths within the plasmon band, we have observed saturable absorption and response times of 2.3 ps. For the other regions of the spectrum, reverse saturable absorption and lifetimes shorter than 200 fs were verified. The nonlinear refractive index is about 2.0 × 10-19 m2/W from visible to telecom region, thus presenting an enhancement effect at wavelengths near the plasmon and Cu+2 d-d band. © 2013 Springer Science+Business Media New York.

Low tungsten content of nanostructured material supported on carbon for the degradation of phenol

A comparative study using different mass proportions of WO3/C (1%, 5%, 10% and 15%) for H2O2 electrogeneration and subsequent phenol degradation was performed. To include the influence of the carbon substrate and the preparation methods, all synthesis parameters were evaluated. The WO3/C materials were prepared by a modified polymeric precursor method (PPM) and the sol-gel method (SGM) on Vulcan XC 72R and Printex L6 carbon supports, verifying the most efficient metal/carbon proportion. The materials were physically characterized by X-ray diffraction (XRD) and by X-ray photoelectron spectroscopy (XPS) techniques. The XRD and the XPS techniques identified just one phase containing WO3 and elevated oxygen concentration on carbon with the presence of WO3. The oxygen reduction reaction (ORR), studied by the rotating ring-disk electrode technique, showed that WO3/C material with the lowest tungsten content (1% WO3/C), supported on Vulcan XC 72R and prepared by SGM, was the most promising electrocatalyst for H2O2 electrogeneration. This material was then analyzed using a gas diffusion electrode (GDE) and 585mgL-1 of H2O2 was produced in acid media. This GDE was employed as a working electrode in an electrochemical cell to promote phenol degradation by an advanced oxidative process. The most efficient method applied was the photo-electro-Fenton; this method allowed for 65% degradation and 11% mineralization of phenol during a 2-h period. Following 12h of exhaustive electrolysis using the photo-electro-Fenton method, the total degradation of phenol was observed after 4h and the mineralization of phenol approached 75% after 12h. © 2013 Elsevier B.V.

Compressive strength of esthetic restorative materials polymerized with quartz-tungsten-halogen light and blue LED

Este estudo comparou a resistência à compressão de uma resina composta e de um compômero, fotoativados com luz halógena convencional de quarto-tungstênio (QTH) (XL 300, 3M/SPE) e LED azul (SmartLite PS; Dentsply/De Trey). Foram confeccionados 40 espécimes em forma de disco usando uma matriz bipartida de politetrafluoretileno (4,0 mm de diâmetro x 8,0 mm de altura) em que o material foi inserido incrementalmente. O tempo de polimerização de cada incremento foi de 40 s para a luz halógena convencional e de 10 s para o LED. Os espécimes foram aleatoriamente alocados em 4 grupos (n=10), de acordo com a fonte de luz e com o material restaurador. Depois de armazenadas em água destilada a 37°C ± 2°C por 24 h, a resistência à compressão dos espécimes foi testada em uma máquina universal de ensaios com célula de carga de 500 kgf a uma velocidade de carregamento de 0,5 mm/min. Os dados (em MPa) foram analisados estatisticamente por ANOVA e teste de Student-Newman-Keuls (p<0,05). Para a resina composta, a fotopolimerização com luz halógena não produziu diferença estatisticamente significante (p>0,05) em sua resistência à compressão quando comparada à fotopolimerização com LED. Contudo, a fotopolimerização do compômero com a luz halógena resultou em uma resistência à compressão significativamente maior que a feita o LED (p>0,05). A resina composta apresentou resistência à compressão significativamente maior que a do compômero, independente da fonte de luz. Concluiu-se que a resistência à compressão dos materiais fotopolimerizados com luz halógena e LED foi influenciada pela densidade de energia empregada e pela composição química dos materiais restauradores estéticos.

Dielectric response of tungsten modified Ba(Ti0.90Zr0.10)O3 ceramics obtained by mixed oxide method

The electrical response of Ba(Ti0.90Zr0.10)O3 (BZT) ceramics obtained by the mixed oxide method as a functionof tungsten content was investigated. According to X-ray diffraction analysis the single phase BZT1W (1wt.% W doped BZT) and BZT2W (2 wt.% W doped BZT) ceramics, crystallized in a perovskite structure, wereobtained. It is also shown that tungsten substituted ceramics can be sintered at a reduced temperature whencompared to the undoped BZT. Electron paramagnetic resonance (EPR) analyses reveals that substitution ofTi4+ by W6+ causes distortion in the crystal structure changing lattice parameter. Substitution of W6+ on B-siteof ABO3 perovskite BZT ceramics shifted the phase transition to lower temperatures up to a tungsten contentof 2 wt.% leading to a relaxor-like behaviour.Keywords: donor dopant; ceramics; dielectric response; mixed oxide method

Direct determination of chromium in empty medicine capsules by tungsten coil atomic emission spectrometry

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TUNGSTEN ISOTOPIC COMPOSITIONS IN STARDUST SiC GRAINS FROM THE MURCHISON METEORITE: CONSTRAINTS ON THE s-PROCESS IN THE Hf-Ta-W-Re-Os REGION

We report the first tungsten isotopic measurements in stardust silicon carbide (SiC) grains recovered from the Murchison carbonaceous chondrite. The isotopes (182,183,184,186)Wand (179,180)Hf were measured on both an aggregate (KJB fraction) and single stardust SiC grains (LS+ LU fraction) believed to have condensed in the outflows of low-mass carbon-rich asymptotic giant branch (AGB) stars with close-to-solar metallicity. The SiC aggregate shows small deviations from terrestrial (= solar) composition in the (182)W/(184)Wand (183)W/(184)Wratios, with deficits in (182)W and (183)W with respect to (184)W. The (186)W/(184)W ratio, however, shows no apparent deviation from the solar value. Tungsten isotopic measurements in single mainstream stardust SiC grains revealed lower than solar (182)W/(184)W, (183)W/(184)W, and (186)W/(184)W ratios. We have compared the SiC data with theoretical predictions of the evolution of W isotopic ratios in the envelopes of AGB stars. These ratios are affected by the slow neutron-capture process and match the SiC data regarding their (182)W/(184)W, (183)W/(184)W, and (179)Hf/(180)Hf isotopic compositions, although a small adjustment in the s-process production of (183)W is needed in order to have a better agreement between the SiC data and model predictions. The models cannot explain the (186)W/(184)W ratios observed in the SiC grains, even when the current (185)W neutron-capture cross section is increased by a factor of two. Further study is required to better assess how model uncertainties (e. g., the formation of the (13)C neutron source, the mass-loss law, the modeling of the third dredge-up, and the efficiency of the (22)Ne neutron source) may affect current s-process predictions.

Syntheses and structures of molybdenum and tungsten complexes capable of epoxidaton and copper coordination polymers and dendrimers

We are interested in the syntheses of new complexes and in their characterization by single crystal X-ray diffraction techniques. Once we understand the structures, studies aimed at understanding uses of these complexes in the field of catalytic epoxidation using complexes soluble in water and syntheses of thin films (not assessed) were conducted. The syntheses, characterization and catalytic properties of a series of mononuclear, dinuclear and tetranuclear molybdenum and tungsten oxo complexes are described. The syntheses and structural characterization of two copper coordination polymers with 3,5-dihydroxylbenzoate ligand, and five paddlewheel shaped copper dendrimers coordinated with Fréchet-type dendrons are also detailed. The background of this dissertation is outlined in Chapter 1. Chapter 2 describes the syntheses, and characterization of two new mononuclear molybdenum(VI) and tungsten(VI) oxo complexes, MoO2Cl2(OPPh2CH2OH)2, and WO2Cl2(OPPh2CH2OH)2, bearing hydrophilic phosphine oxide ligand. The catalytic properties of these complexes for the epoxidation of cis-cyclooctene were also studied. Two new dinuclear molybdenum(VI) and tungsten(VI) oxo complexes Mo2O4Cl2[(HOCH2)PhPOO]2, and (CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2, bearing organophosphinate ligand are described in Chapter 3 and 4. Chapter 4 and 5 describes the syntheses and characterization of tetranuclear molybdenum(V) oxo complexes bearing various organophosphinate ligands. The catalytic abilities of these complexes for the epoxidation of cis-cyclooctene in the presence of hydrogen peroxide as oxidant were explored as well. Various spectroscopic methods, such as IR, UV-vis, and NMR are used to characterize the nature of these complexes. Crystal structures of compounds MoO2Cl2(OPPh2CH2OH)2, WO2Cl2(OPPh2CH2OH)2, Mo2O4Cl2[(HOCH2)PhPOO]2, (CH3O)2(O)W(μ-O)(μ-O2PPh2)2W(O)(CH3O)2, and Mo4(µ3-O)4(µ-O2PR2)4O4 (R=Ph, Me, ClCH2, o-C6H4(CH2)2) are also presented. The syntheses, and structural characterization of three copper(II) coordination polymers bearing 3,5-dihydroxybenzoate ligand are described in Chapter 6. Two copper(II) coordination polymers, [Cu2(3,5-dhb)2(pyridine)4]n, and [Cu2(3,5-dhb)4]n were afforded based on different amount of pyridine used in the reaction. The structures of these complexes are further built into 2D or 3D networks via inter or intra hydrogen bonds. The syntheses and structural characterization of the zinc(II) monomer, Zn(3,5-dhb)2(pyridine)2 is also described in this Chapter. Chapter 7 describes the syntheses, and characterization of five dendronized dicopper complexes bearing different generations of Fréchet-type dendrons. The structures of 3,5- bis(benzoyloxl)benzoic acid, 3,5-(PhCOO)2PhCOOH (G1), Cu2(3,5-dhb)4(THF)2, Cu2(G1)4(pyridine)2, and Cu2(G1)4(CH3OH)2 were characterized unambiguously by single X-ray diffraction. In addition, all compounds were characterized by FT-IR, UV-vis spectroscopy and elemental analyses.

The Testing and Concentration of a Tungsten Ore

At the present time the principal uses for tungsten lie in the manufacture of ferro-alloys and tungsten steels. Due to it’s hardening and strengthening characteristics it holds an important position among steel hardening metals. The great rush for it’s production during the World War years clearly points to it’s importance in the manufacture of armament.

Deformation Studies of Tungsten-Gold Contacts at the Nanometer Scale.

The deformation behavior of atomically clean, nanometer sized tungsten / gold contacts was studied at room temperature in ultra-high vacuum. An instrument that combines atomic force microscopy (AFM), scanning tunneling microscopy (STM), and field ion microscopy (FIM) into a single experimental apparatus was designed, constructed, and calibrated. A cross-hair force sensor having a spring constant of - 442 N/m was developed and its motion was monitored during indentation experiments with a differential interferometer. Tungsten tips of controlled size (12.8 nm < tip radius < 2 1.6 nm) were first shaped and characterized using FIM and then indented into a Au (1 10) single crystal to depths ranging from 1.5 nrn to 18 nm using the force sensor. Continuum mechanics models were found to be valid in predicting elastic deformation during initial contact and plastic zone depths despite our small size regime. Multiple discrete yielding events lasting < 1.5 ms were observed during the plastic deformation regime; at the yield points a maximum value for the principal shear stress was measured to be 5 + 1 GPa. During tip withdrawal, "pop-out" events relating to material relaxation within the contact were observed. Adhesion between the tip and sample led to experimental signatures that suggest neck formation prior to the break of contact. STM images of indentation holes revealed various shapes that can be attributed to the (1 1 1 ) (1 10) crystallographic slip system in gold. FIM images of the tip after indentation showed no evidence of tip damage