New tungstate fluorophosphate glasses

A new class of tungstate fluorophosphate glasses was identified in the NaPO₃-BaF₂-WO₃ ternary system. The variation of several physical properties was determined with respect to chemical composition. Characteristic temperatures, density and refractive index increase as tungsten oxide content increases. The optical transmission range and specially the energy bandgap depend of the WO₃ amount. No crystallization could be observed for the most WO₃ concentrated vitreous samples (?20% molar). Color and optical properties of the glasses depend of the melting time because of the presence of reduced tungsten species like W⁵⁺ and W⁴⁺. In addition, photodarkening is observed in tungsten rich glass samples under UV laser illumination and this phenomenon can be reversible by heat treatment near the glass transition temperature.     

X-ray diffraction studies of bismuth tungstate catalysts

Bismuth tungstate catalysts with Bi/W ratios 2/3, 1/1, 2/1, and 6/1 have been investigated after various heat treatments by room temperature X-ray analysis. The activity and selectivity of Bi₂WO₆ catalyst are suggested to be connected with the presence of corner sharing W—O octhedra in the bulk of the solid that give rise to tetragonal pyramidal W—O sites at the surface. The very low activity of Bi₂(WO₄)₃ is attributed to edge-shared octahedral coordination of W while the same of Bi₆WO₁₂ is due to tetrahedral coordination of W. The inactivity of Bi₂W₂O₉ may be associated with its typically low oxidation power. The promoting influence of Bi₂O₃ is to enforce a structural situation on W—O so that W may be present in a tetragonal pyramidal 5-configuration.     

Crystal growth and structure of KBi(WO4)2 single crystals

Potassium bismuth tungstate [KBi(WO₄)₂] single crystals have been grown by the top‐seeded solution growth technique. Bulk crystal with dimensions up to several centimeters is obtained for the first time. Several self‐flux systems have been used for the growth from the solution and the experiments using K₂W₂O₇ as a solvent are detailed. Powder and single crystal X‐ray diffraction of this crystal are reported. The structure refinement shows that KBi(WO₄)₂ crystallizes in the monoclinic space group C2/c, with a=10.837(3), b=10.586(3), c=7.622(2)Å, β=130.860(3)°, V=661.4(3)ų, and Z=4. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Raman and luminescence studies of alkali borate tungstate glasses

Raman and luminescence spectroscopy were used to determine the structure of alkali borate tungstate glasses: M₂O(B₂O₃)₂·xWO₃, M = Li or Na (0 < x < 1). Raman scattering results showed the dominant tungstate species in these photochromic glasses to be tetrahedral WO₄⁼. At high concentrations of WO₃, WO₃·H₂O, and W₂O₇⁼ are also present. Luminescence measurements provided evidence for an octahedral WO₃ structure not identified by the Raman results. The results also revealed a possible change in the structure of the glasses similar to that observed in alkali borate glasses and associated with the “borate anomaly”. In addition, preliminary measurements are reported on the variation of the band gap, density, index of refraction, and the elastic coefficient C₁₁ determined by Brillouin scattering with composition.     

Study of some K2W2O7–KGd1−xLnx(WO4)2 systems to be used for flux growth of doped KGd(WO4)2 single crystals

High-temperature solutions of the systems K₂W₂O₇–KGd_1−xLn_x(WO₄)₂ (x=0.05, 0.10, 0.20 and 0.50; Ln=Er, Eu and Ho) were investigated. The solubility curves were plotted for each x value and each dopant and the concentration and temperature regions of crystallization of the low-temperature monoclinic phase were determined. The distribution coefficients were determined for gadolinium and for the dopants. The data obtained were compared with the distribution coefficients in the case of double doping of KGd(WO₄)₂ with erbium and neodymium.     

Growth and characterization of KBi(WO4)2 single crystals

Potassium bismuth tungstate [KBi(WO₄)₂] single crystals with dimensions up to 20 mm × 15 mm × 15 mm have been successfully grown by using the top‐seeded solution growth technique and K₂W₂O₇ as solvent. Experiments show that this crystal is unstable in a strong acid or alkali environment and has a blue fluorescence emission. The density, hardness, melting point, absorption edge, transparency range, prominent Raman shift frequency are 7.57 g/cm³, 238 kg/mm², 800 °C, 380 nm, 400–5450 nm, 868 cm^–1 respectively. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The role of coordination and valance states of tungsten ions on some physical properties of Li2O–Al2O3–ZrO2–SiO2 glass system

A series of Li₂O–Al₂O₃–ZrO₂–SiO₂ glasses doped with different concentrations of WO₃ (0 to 5.0 mol.%) have been synthesized. Differential thermal analysis of the samples indicated increasing glass forming ability with the increasing concentration of WO₃ in the glass matrix. A variety of spectroscopic (optical absorption, IR, Raman and ESR) and dielectric properties (over a range of frequency and temperature) of these glasses have been investigated. The optical absorption and ESR spectral studies have pointed out that a part of tungsten ions do exist in W⁵⁺ state in addition to W⁶⁺ state especially in the samples containing low concentration of WO₃. The IR and Raman spectral studies have suggested that there is a decreasing degree of disorder in the glass network with increase in the concentration of WO₃. The values of dielectric parameters viz., dielectric constant, loss and ac conductivity at any frequency and temperature are observed to decrease as the concentration of WO₃ is increased. Such changes have been attributed to decrease of redox ratio or decreasing proportions of W⁵⁺ ions that act as modifiers in the glass network. The quantitative analysis of the results of ac conductivity and dielectric properties have indicated an increase in the insulating character of the glasses with the concentration of WO₃; this is attributed to the presence of tungsten ions largely in W⁶⁺ ions that participate in the glass network forming with WO₄ structural units.     

Continuous-wave laser operation of disordered double tungstate and molybdate crystals doped with ytterbium

Several ytterbium doped disordered doubles tungstate and molybdate crystals, NaGd(WO₄)₂, NaLa(WO₄)₂, NaLa(MoO₄)₂ and LiGd(MoO₄)₂, were grown with sufficient Yb-doping and optical quality. The crystal field splitting of the Yb³⁺ multiplets and the lifetimes are similar to the biaxial monoclinic double tungstates but the peak absorption cross sections are roughly one order of magnitude lower. Room temperature cw laser operation was achieved under Ti:sapphire and diode laser pumping. The polarization dependence of the laser emission and possible power scaling were studied. The slope efficiency achieved with the best sample, Yb:LiGd(MoO₄)₂, was 64.5%. The maximum output power obtained was 900 mW for Yb:NaLa(MoO₄)₂ pumped in the absorption maximum. The laser tunability was studied with an intracavity Lyot filter and the tuning ranges (FWHM up to 33 nm) achieved indicate interesting potential for mode-locked femtosecond operation.     

Growth of single-crystalline sodium titanate and sodium tungstate one-dimensional nanostructures: Bio-inspired approach using oyster shell

Using oyster shell, single-crystalline Na₂Ti₆O₁₃ and Na₂W₄O₁₃ one-dimensional nanostructures (ODNS) were simply synthesized from granular TiO₂ and WO₃ particles by thermal heating at 700 °C. The oyster shell was used as a source of both sodium and carbon dioxide, which have an effect on unidirectional growth of single-crystalline Na₂Ti₆O₁₃ and Na₂W₄O₁₃ from TiO₂ and WO₃. The growth of sodium metal oxide ODNS from metal oxide particles was reproduced by replacing oyster shell with chemical reagents (NaCl, CaCO₃) or gas (CO₂), allowing identification of the main factors for the growth of ODNS. The characteristics of biological material (i.e., oyster shell) lend certain advantages in the fabrication of sodium metal oxide ODNS: (a) low processing temperature with high yield; (b) an eco-friendly method; and (c) no requirement of additional processes such as separation or washing. This work suggests a new approach for using biological material for the crystal growth of nanostructured materials.     

Thermal and optical properties of TeO2–BaO–SrO–Nb2O5 based glasses: New broadband Raman gain media

We systematically added WO₃ (up to 10 mol%) and P₂O₅ (up to 16 mol%) in TeO₂–BaO–SrO–Nb₂O₅ (TBSN) glass system and studied thermal and optical properties of the resultant glasses. The dependences of the additive concentration on glass transition (T_g) and crystallization (T_x) temperatures are presented. The TBSN glass added with ⩾4 mol% WO₃ and P₂O₅ showed high stability against crystallization. The changes in optical band gap energy due to WO₃ and P₂O₅ addition was studied using UV–VIS–NIR absorption spectrometry. The WO₃ addition shifted the optical band gap to longer wavelengths, whereas P₂O₅ addition shifted that to shorter wavelengths. Effects of the WO₃ and P₂O₅ addition on the Raman spectra of TBSN glass are clarified. New Raman bands due to WO₄ and PO₄ tetrahedra formed in the resultant glasses broadened their Raman spectra. Present glasses are characterized by higher thermal stability and wider Raman spectra, therefore, they are promising candidates for fiber Raman amplifiers in photonics systems.     

On the structure of tungstate–tellurite glasses

A continuous network model of xWO₃–(1 − x)TeO₂ glasses is developed, based on quantum-chemical calculation and Raman spectra analysis, in order to relate the structural and vibrational properties with glass composition. The tungstate–tellurite glass network is shown to be formed mainly by structural units of three types, TeO₄ trigonal bipyramids, OTeO₂ trigonal pyramids, and WO₆ octahedra with OW double bonds. Most of the W atoms are found to be incorporated into single OWO₅ octahedra, with no more than several percents of these atoms occurring in 2[OWO₅] paired tungstate centers. The structural and vibrational properties of tungstate–tellurite glasses of several compositions are analyzed by application of the model and a novel interpretation of the Raman spectra is suggested.     

On the preparation of tungsten oxides by chemical transport with TeCl4

The Tungsten oxides WO₃, W₂₀O₅₉, W₁₈O₄₉ and WO₂ have been transported by TeCl₄ in monocrystalline Form. W₃O is not a equilibrium phase of the system, and therefore it is impossible to obtain this phase by CTR. The value of the lower phase boundary of tungsten trioxide is 2.96.     

Dielectric properties,conductivity, UV–visible and infrared spectroscopy of PbO P2O5 NaF glasses containing WO3

Homogeneous (50P₂O₅–(30 ? x)PbO–20NaF–xWO₃ where x = 0.0, 5, 10 and 15 mol%) glasses were synthesized using a melt-quenching method. The short range structures of the phosphate samples were examined by Fourier transform infrared spectroscopy. The infrared spectral studies have pointed out the existence of conventional PO₄, WO₄ and WO₆ structural units in the glass network, the number of WO₄ tetrahedra decreases as WO₃ concentration increases. The optical transmittance and reflectance spectrum of the glasses have been recorded in the wavelength range of 190–1100 nm. The values of the optical band gap E_op for all types of electronic transitions and refractive index have been determined and discussed. The real and imaginary parts ε₁ and ε₂ of the dielectric constant have been determined. The type of electronic transitions in the present glass system is indirectly allowed and the high values for the refractive index and dispersion are recorded due to the high polarizability of tungsten ions. The results of refractive indices as determined reveal the homogeneity of samples and were found to depend on the glass composition. The electrical properties of the glasses were investigated by ac conductivity from 0.12 to 100 kHz for temperatures ranging from room temperature to 600 K. The study of dielectric properties suggested increase in the insulating character of the glass system with increase in the content of WO₃. The ac conductivity in the high temperature region seems to be connected mainly with the polarons involved in the process of transfer from W⁴⁺ to W⁵⁺ ions.     

Glass formation and structure of glasses in the ZnO―Bi2O3―WO3―MoO3 system

The glass formation region in the ternary ZnO―Bi₂O₃―WO₃ system is determined by melt quenching technique (cooling rates 10¹-10² K/s). New original glasses are obtained in a narrow concentration range with high WO₃ content (60-75 mol%). Homogeneous glasses of the composition (100 − x)[0.2ZnO·0.3Bi₂O₃·0.5WO₃]xMoO₃, were obtained between 20 and 60 mol% MoO₃. Characterization of the amorphous samples was made by x-ray diffraction (XRD), differential thermal analysis (DTA) and infrared spectroscopy (IR). The thermal stability of glasses decreases with the increasing of MoO₃ content. The glass transition temperature, T_g, varies between 340-480 °C, while the crystallization temperature, T_x, varies between 388-531 °C. The tungstate glasses possess higher crystallization temperature (T_x over 500 °C) in comparison with the other vanadate and molybdate non-traditional glasses. The glass network is realized by transformation of three-dimensional structure of WO₃ into a layered one, consisting mainly of WO₆ units. We supposed that the network of quaternary glasses is built up by MoO₄, MoO₆ and WO₆. At low concentration ZnO and Bi₂O₃ facilitate the disorder in the supercooled melts, while at high concentration stimulate crystallization processes. These oxides belong to the intermediate ones.     

Optical properties of KGd(WO4)2 single crystals studied by Brillouin spectroscopy

The results of a study of KGd(WO₄)₂ single crystals by Brillouin scattering method are presented. The Brillouin spectra for the acoustic phonons propagating in the [100], [010], [001], [110] and [101] directions, taken in 90° and 180° scattering geometry at room temperature have been recorded. Using the Brillouin spectroscopy the refractive indices for some directions of KGd(WO₄)₂ crystals were determined. The refractive indices were also calculated for the same directions by the rotation transformation of the principal optical axes of the optical indicatrix to the crystallographic directions of KGd(WO₄)₂ crystals. Moreover, some anomalies of the acoustic phonons propagating connected with birefringence of KGd(WO₄)₂ crystals were discussed. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Kinetics of crystal growth of strontium tungstate from solutions in sodium tungstate melts by continuous cooling

The crystallisation kinetics of strontium tungstate from unstirred saturated solutions in sodium tungstate melts was studied by continuous cooling from initial crystallisation temperatures T₀ = 1000° to 800°C to room temperature at cooling rates R_T = 0.67° to 3.3°C min⁻¹. The main crystal growth was diffusion rate-controlled; the final crystal growth was rate-controlled by the development rate of excess solute concentration. The estimated diffusion rate constant (k_D) values increased with cooling rates and initial crystallisation temperatures. They are higher than the rate constants for diffusion-controlled growth of calcium tungstate from sodium tungstate melts, but very much smaller than those for strontium tungstate from lithium chloride melts.     

Bulk crystallisation of (00l) oriented fresnoite Sr2TiSi2O8 in glass-ceramics of the Sr-Ti-Si-K-B-O system

This paper shows that glass-ceramics containing highly surface and bulk preferentially oriented fresnoite Sr₂TiSi₂O₈ crystals can be synthesised by a simple isothermal heat treatment of suitable glass compositions in the Sr-Ti-Si-K-B-O system. For all tested compositions, crystallisation starts from the free surfaces of the specimens and propagates to bulk with time. If most of these compositions lead to (00l) preferential orientation at the specimens' surfaces, bulk crystal texture is very composition dependent. The effects of variation in K₂O and B₂O₃ contents on the crystallisation have been studied. It is shown that low K₂O and high B₂O₃ contents are required to keep the (00l) orientation from the surface into the bulk. This result seems to be explained by the viscosities of the initial and residual glasses at the temperature of crystallisation: a low viscosity leads to a fine and homogeneous microstructure with small and strongly (00l) bulk oriented crystals.     

Effect of foreign phases on the growth of NaBi(WO4)2 crystals

Single crystals of NaBi(WO₄)₂ (NBW) have been grown by Czochralski technique, employing differently synthesized starting charge and different axial temperature gradients. The causes behind inherent problems related to compositional changes and associated lowering in crystallization temperature have been probed by analyzing XRD and DTA patterns of post growth residual charge. Presence of low melting phases viz. Na₂WO₄ and hitherto unreported compound Na₅Bi(WO₄)₄ is thought to be responsible for the observed decrease in crystallization temperature. This problem was tackled by segregating pure phase material through re‐crystallization, under high axial temperature gradient. The use of re‐crystallized charge enabled transformation of almost the entire charge into a single crystal of high transparency. The effect of starting charge synthesis and temperature gradient on the optical transmission characteristics of NBW crystal has also been investigated. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Reflection spectra of NaClO<Subscript>3</Subscript>, NaBrO<Subscript>3</Subscript>, and LiIO<Subscript>3</Subscript> gyrotropic crystals in the vacuum UV region

The reflection spectra in the fundamental-absorption region, 5–25 eV (250–40 nm), of optically active crystals with cubic symmetry (NaClO₃, NaBrO₃) and uniaxial optically active crystal (LiIO₃) have been investigated. It is shown that the reflection spectra of cubic crystals have a similar structure, which is determined by the electronic transitions in the XO₃ group. The comparison of these spectra with the corresponding spectrum of lithium iodide made it possible to determine the type of transition in the spectra of cubic crystals. Using the projection operator method, it was shown that the sign of optical rotation of cubic crystals with symmetry T is independent of the screw axis sign. Possible reasons for the unprecedentedy large optical rotation of lithium iodide crystal in the optical axis direction are considered.     

Investigations on the crystallisation of potassium molybdenum bronzes from flux melts

Results are presented to identify the fields of primary crystallisation of red and blue potassium molybdenum oxide bronzes K_0.30MoO₃ and K_0.33MoO₃ in the ternary system K₂MoO₄–MoO₃–MoO₂. Starting from crystal growth experiments for the preparation of bronze crystals by electrolytic reduction the binary marginal systems K₂MoO₄–MoO₃ as well as MoO₃–MoO₂ and further pseudo‐binary sections have been investigated by differential thermo‐analysis, hot‐stage microscopy, and by quenching experiments under inert gas. We succeeded in determining phase transition temperatures in the binary section Mo₄O₁₁–K₂Mo₂O₇. Temperature and composition ranges have been found in this section to crystallise red and blue potassium molybdenum oxide bronzes. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)