Condensed Phase Relations in the Systems ZrO2-WO2-WO3 and HfO2-WO2-WO3

Phase relations for the systems ZrO₂–WO₂–WO₃ and HfO₂–WO₂–WO₃ from 1000° to 1700° C were determined by the quenching technique using sealed sample containers. In the system ZrO₂–WO₃, 1:2 compound, ZrW₂O₈ forms, having a cubic structure with a= 9.159 A. The ZrW₂O₈ melts incongruently at 1257°± 3°C to ZrO₂ and liquid and has a lower limit of stability at 1105°C, below which ZrO₂ and WO₃ coexist in equilibrium. One eutectic and one peritectic were established: at 1231°± 3°C and 74 mole % WO₃, and at 1257°± 3°C and 71 mole % WO₃, respectively. Along the join ZrO₂–WO₂, no compound formed. Two invariant points were determined: ZrO₂, WO₂, W, and liquid are in equilibrium at 1430°± 5°C and 76 mole % WO₂, whereas WO₂, W₁₈O₄₉, W, and liquid coexist at 1530°± 5°C and 89 mole % WO₂- Equilibrium relations in the system ZrO₂–WO₂–WO₃ were investigated at four temperatures. At 1200°C, a cubic phase with composition near W₂₀O₅₈ was found; it exists in equilibrium with ZrO₂, W₁₈O₄₉, W₂₀O₅₈, and WO₃. As the temperature increases, the liquid formed along the ZrO₂–WO₃ join extends into the ternary system, crosses the join ZrO₂–W₂₀O₅₈ at 1300°C, and crosses the join ZrO₂–W₁₈O₄₉ at 1400°C. The cubic phase can take more zirconium into its solid solution at 1300° than at 1200°C. At 1500°C, the system can no longer be treated as a simple ternary oxide system because of the presence of metallic tungsten, and equilibrium relations are presented on the basis of the system ZrO₂–W–WO₃. Phase equilibrium relations in the systems HfO₂–WO₃, HfO₂–WO₂, and HfO₂–WO₂–WO₃ in the temperature ranges studied are much like those in the corresponding zirconium system.     

Nb2O5 as efficient and recyclable photocatalyst for indigo carmine degradation

Heterogeneous photocatalysis is a significant green technology for application in water purification. The application of Nb₂O₅ catalyst for the photodegradation of contaminants is few reported in the literature. Thus, the Nb₂O₅ catalyst was characterized by SEM, FTIR, surface area and charge surface density. This catalyst was applied to degrade indigo carmine dye, which was compared with degradation catalyzed by TiO₂ and ZnO. Almost 100% of dye degradation occurred at 20, 45 and 90 min for TiO₂, ZnO and Nb₂O₅, respectively. The effect of Nb₂O₅ catalyst concentration, pH and ionic strength (μ) was investigated. The Nb₂O₅ activity increased at 0.7 g/L and for higher catalyst concentrations the degradation was kept constant. Degradation of indigo carmine dye catalyzed by Nb₂O₅ was improved at pH < 4.0 and μ = 0.05 mol/L. TiO₂, ZnO and Nb₂O₅ were recovered and re-applied in other nine reaction cycles. While TiO₂ and ZnO have an abrupt loss of their catalytic activity, Nb₂O₅ maintained 85% of catalytic activity after 10 reaction cycles.     

Medium-range order and physicochemical properties of (100 ? x)(0.5PbO · 0.5P2O5) · xTeO2 glasses in terms of the constant stoichiometry grouping concept

Glasses in the (100 − x)(0.5PbO · 0.5P₂O₅) · xTeO₂ section of the PbO-P₂O₅-TeO₂ system have been synthesized over the entire composition range for the first time and their properties (Raman spectra, refractive index n, density d, glass transition temperature T _g , and light scattering losses) have been investigated. It has been demonstrated that the Raman spectra can be represented as a superposition of constant spectral forms corresponding to constant stoichiometry groupings PbO · P₂O₅, TeO₂ · 2PbO · 2P₂O₅, TeO₂ · PbO · P₂O₅, 2TeO₂ · PbO · P₂O₅, and TeO₂. The existence of crystals of the corresponding stoichiometry has been predicted using the constant stoichiometry grouping concept. The diagram of the constant stoichiometry grouping contents (determined from the Raman spectra) in glasses of the system under investigation has made it possible to determine the partial properties of constant stoichiometry groupings, to calculate the dependences of the refractive index and density on the composition, and to refine the values of n and d for vitreous tellurium dioxide and lead metaphosphate. The practical importance of glasses in the system under consideration for the use in photonic devices has been discussed.     

Effects of CdF2 and WO3 additions on the microstructural and thermal properties of TeO2–CdF2–WO3 glass system

This paper presents microstructural characterization investigations and the crystallization behavior of some glasses in the ternary TeO₂–CdF₂–WO₃ system. Differential thermal analysis (DTA) showed that the glass forming ability of the ternary TeO₂–CdF₂–WO₃ system which is in between the values of 21 and 34, is lower than most of the studied tellurite glasses. It is possible to obtain amorphous glass structure for the compositions of 0.80TeO₂–0.10CdF₂–0.10WO₃ and 0.75TeO₂–0.10CdF₂–0.15WO₃. On the other hand, the 0.85TeO₂–0.10CdF₂–0.05WO₃ and 0.75TeO₂–0.15CdF₂–0.10WO₃ compositions do not form glass with conventional quenching techniques. During crystallization of these glasses, the formation of the alpha, delta and gamma TeO₂, WO₃ and CdTe₂O₅ phases were observed with the addition of a new unidentified phase. Three compositions of 0.85TeO₂–0.10CdF₂–0.05WO₃, 0.80TeO₂–0.10CdF₂–0.10WO₃ and 0.75TeO₂–0.10CdF₂–0.15WO₃ demonstrated two exothermic peaks in the DTA curves. SEM/EDS investigations confirmed the existence of the alpha, delta and gamma TeO₂, WO₃ and CdTe₂O₅ phases for the annealed glasses. The microstructure of the δ-TeO₂ phase was clearly observed in the as-cast 0.75TeO₂–0.10CdF₂–0.15WO₃ composition.     

Glass formation area and characterization studies in the CdO–WO3–TeO2 ternary system

The glass formation area in the CdO–WO₃–TeO₂ ternary system was determined and thermal and structural features of the ternary glasses were characterized by differential scanning calorimetry (DSC), X-ray diffraction (XRD) and Raman scattering methods and the variation of the glass properties and structural transformations were discussed in terms of the glass composition comparing with the literature. For all ternary glass samples, the glass transition (T_g) and crystallization (T_c/T_p) temperatures, glass stability (ΔT), activation enthalpy for glass transition (ΔH^*) and fragility parameter (m) values were calculated from the DSC thermograms. Density (ρ), molar volume (V_M) and oxygen molar volume (V_O) values and the refractive indices (n) at a wavelength of 632 nm were measured. Raman spectra of the glasses were interpreted in terms of the structural transformations on the glass network resulted by the changing WO₃ + CdO/TeO₂ ratio.     

Influence of Hydroxyl Group on IR Transparency of Tellurite-Based Glasses

A study of the glass properties with two opposite levels of hydroxyl content is presented for two different tellurite glass families with molar composition 70TeO₂-10Bi₂O₃-20ZnO and 80TeO₂-20Nb₂O₅. We show that melting tellurite-based glasses in a dried-oxidant atmosphere (relative humidity <1%) reduces drastically the OH impurities. The effect of reducing the OH content on the glass properties such as characteristic temperatures, crystallization stability (ΔT), density, and microhardness is investigated.     

The effect of foreign ions on the reactivity of the CaO-SiO2-Al2O3-Fe2O3 system: Part II: Cations

The subject of this paper is the effect of foreign cations on the reactivity of the CaO-SiO₂-Al₂O₃-Fe₂O₃ system. One reference mixture and eighteen modified mixtures, prepared by mixing the reference sample with 1% w/w of chemical grade MnO₂, CuO, V₂O₅, PbO, CdO, ZrO₂, Li₂O, MoO₃, Co₂O₃, NiO, WO₃, ZnO, Nb₂O₅, CrO₃, Ta₂O₅, TiO₂, BaO₂ and H₃BO₃ were studied. The effect on the reactivity is evaluated on the basis of the free lime content in samples sintered at 1200 and 1450 °C. At 1200 °C, the reactivity of the mixture is greatly increased in the presence of Cu and Li oxides. Based on their effect at 1450 °C, the added elements can be divided into three groups. W, Ta, Cu, Ti and Mo show the most positive effect, decreasing the free CaO (fCaO) content by 30-60%, compared with the pure sample. Cr and B cause an increase of fCaO content, while the rest of the elements exhibit a marginal positive effect. According to their volatility at 1450 °C, the added compounds can be subdivided into three groups of low (Ti⁴⁺, Cu²⁺, Mo⁶⁺, W⁺⁶, V⁵⁺, Zn²⁺, Zr⁴⁺), moderate (Cr⁶⁺, Co³⁺, Ni²⁺, Mn⁴⁺) and high volatility (Cd²⁺, Pb²⁺). All burned samples, analyzed by means of X-ray diffraction, have a final mineralogical composition, which corresponds to the structure of a typical clinker.     

Raman investigations of NH3 adsorption on TiO2, Nb2O5, and Nb2O5/TiO2

A study has been carried out of the interactions of NH₃ with TiO₂, Nb₂O₅, and Nb₂O₅/TiO₂. Raman spectroscopy was used to characterize the structure of the adsorbed NH₃ and perturbations of species present at the surface of the adsorbent. On each oxide, NH₃ adsorbs predominantly at Lewis acid sites. Hydrogen-bonding occurs between the adsorbed NH₃ and OH groups present on the surface of TiO₂. A small concentration of NH ₄ ⁺ is observed, consistent with the relatively low concentration of Brønsted acid sites compared to Lewis acid sites on each of the samples investigated. Exposure of Nb₂O₅/TiO₂ to NH₃ at temperatures up to 500°C does not result in partial reduction of the supported niobia.     

Understanding the structure,thermal, and optical properties in Al2O3-incorporated La2O3-TiO2-Nb2O5 glasses

Glasses in the 30La₂O₃-40TiO₂-30Nb₂O₅ system are known to have excellent optical properties such as refractive indices over 2.25 and wide transmittance within the visible to mid-infrared (MIR) region. However, titanoniobate glasses also tend to crystallize easily, significantly limiting their applications in optical glasses due to processing challenges. Therefore, the 30La₂O₃-40TiO₂-(30−x) Nb₂O₅-xAl₂O₃ (LTNA) glass system was successfully synthesized using a aerodynamic containerless technique, which improves glass thermal stability and expands the glass-forming region. The effects of Al₂O₃ on the structure, thermal, and optical properties of base composition glasses were investigated by XRD, DSC, NMR, Raman spectroscopy, and optical measurements. DSC results indicated that as the content of Al₂O₃ increased, the thermal stability of the glasses and glass-forming ability increased, as the 30La₂O₃-40TiO₂-25Nb₂O₅-5Al₂O₃ (Nb-Al-5) glass obtained the highest ΔT value (103.5°C). Structural analysis indicates that the proportion of [AlO₄] units increases gradually and participates in the glass network structure to increase connectivity, promoting more oxygen to become bridging oxygen and form [AlO₄] tetrahedral linkages to [TiO₅] and [NbO₆] groups. The refractive index values of amorphous glasses remained above 2.1 upon Al₂O₃ substitution, and a transmittance exceeding 65% in the visible and mid-infrared range. The crystallization activation energies of 30La₂O₃-40TiO₂-30Nb₂O₅ (Nb-Al-0) and Nb-Al-5 glasses were calculated to be 611.7 and 561.4 kJ/mol, and the Avrami parameters are 5.28 and 4.96, respectively. These results are useful to design new optical glass with good thermal stability, high refractive index and low wavelength dispersion for optical applications such as lenses, endoscopes, mini size lasers, and optical couplers.     

Effects of TiO2 addition on dielectric and energy storage properties of BaO-K2O-Nb2O5-SiO2 glass ceramics

In this work, 25.6BaO-6.4K₂O-32Nb₂O₅-36SiO₂-xTiO₂ (0 ≤ x ≤10 mol%) (BKNST) glass ceramics were synthesized by conventional melts and controllable crystallization method. The effects of different TiO₂ addition on the phase composition, dielectric and energy storage properties of BKNS glass ceramics were systematically evaluated. With the TiO₂ concentration increasing, a growing content of Ba₂TiO₄ phase was observed in the glass ceramics. The microstructures appeared to be homogenous and uniform with very low porosity through the addition of TiO₂, for which the maximal breakdown strength of 2112 kV/cm and the corresponding energy storage density of 9.48 J/cm³ were obtained with x = 7.5. The extremely low dielectric loss of less than 1‰ (25 °C, 100 kHz) and the obviously improved microstructure contributed to the increased breakdown strength. In addition, the discharge power density of the glass-ceramic capacitor (x = 7.5) was investigated using the RLC charge-discharge circuit and a relatively high value of 16 MW/cm³ at 300 kV/cm was obtained.     

The System Bi2O,—B2O3

The phase diagram for the system Bi₂O₃-B₂O₃ has been determined experimentally. The melting point of Bi₂O₃ has been redetermined as 825° C with an estimated overall uncertainty of about ±3°C, and the molal heat of fusion of Bi₂O₃, calculated from the slope of the liquidus curve, is 2050 cal per mole. The system contains a body-centered cubic phase of approximate composition 12Bi₂O₃·B₂O₃, which melts incongruently at 632°C. Four congruently melting compounds exist in the system: 2Bi₂O₃· B₂O₃·5B₂O₃, Bi₂O₃·3B₂O₃, and Bi₂O₃·4B₂O₃, with melting points, respectively, of 675°, 722°, 708°, and 715°C. The Bi₂O₃·4B₂O₃ compound exhibits a sluggish transformation at 696°C. Compositions containing up to 97.5 wt% (85 mole %) Bi₂O₃ can be partly or totally quenched to glass. Indices of the quenched glasses are greater than 1.74. A region of liquid immiscibility extends at 709°C from almost pure B₂O₃ to 19.0 mole % Bi₂O₃. The extent of immiscibility theoretically calculated agrees with the experimentally determined value when 1.20 A is used for the ionic radius of Bi³⁺.     

Synthesis,characterization and demonstration of self-cleaning TiO2 coatings on glass and glazed ceramic tiles

An effort was made not only to demonstrate the performance of the self-cleaning coatings on building materials such as ceramic glazed tiles and glass windows, but also to understand the fundamental issues that are still alive in the field of self-cleaning surfaces based on photocatalysis. Nano TiO₂ transparent thin films were generated by dip, spray and flow coating method. The present results indicate that the inconsistent results in the self-cleaning studies may be due to the effect of aggregation of model pollutant (methylene blue) dye on TiO₂ surface. The effect of aliovalent metal ion (Ni²⁺, Fe³⁺, Nb⁵⁺) doping on phase formation, polymorphic transition, visible light absorbance and optical transparency of TiO₂ film were investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS) and UV visible absorption spectroscopy. The improved visible light activity of doped TiO₂ thin film was correlated to the Ti(Ni/Fe)O₃ phase formation, UV and visible light absorbance, variation in the optical energy band gap and the probable light scattering associated with grain size.     

Structural and Optical Properties of Erbium and Ytterbium Codoped Germanoniobophosphate Glasses

A series of glasses with compositions of 20Na₂O–30Nb₂O₅–(5?y?z)Al₂O₃–30P₂O₅–(15?x)TiO₂–xGeO₂–yEr₂O₃–zYb₂O₃, where x = (0; 5; 10; 15), y = (0; 1), z = (0; 2) mol%, were investigated with respect to their structural, optical, and luminescence properties. The coordination of the germanium(IV) ion is normally reported as being mainly tetrahedral. However, results of this study suggest that the germanium(IV) ion may have an octahedral coordination and that TiO₂ is substituted. This proposition can be done mainly by ³¹P MAS‐NMR spectroscopy, which spectra show predominantly pyrophosphate chains in the different glasses, without changes in their polymerization after substitution. A similar coordination of germanium can also be identified by the photoluminescence behavior of the different codoped samples, which shows similar erbium(III) emission decay lifetimes (5 ms), and Judd–Ofelt intensity parameters. It was found that the upconversion emission process involved 1.5 photons. Regarding the thermal behavior, it is noted that the glasses containing higher proportions of GeO₂ exhibit higher thermal stability and are therefore more resistant to devitrification when compared to compositions containing more TiO₂.     

含Nb2O5和La2O3系统玻璃形成区

用新的玻璃形成区探索方法研究了La     

Preparation and properties of a high-entropy amorphous oxide with high refractive index by containerless solidification

A non-proportional high-entropy oxide glass disc: 25LaO_3/2-25TiO₂–25NbO_5/2-(25-x) WO₃-xZrO₂(x = 0, 5, 10) was formed using containerless solidification technology. In optical tests, the 25LaO_3/2-25TiO₂–25NbO_5/2-20WO₃–5ZrO₂(x = 5) disc had the highest refractive index (2.53) and the highest visible transmittance (84%). In addition, the refractive index of amorphous materials prepared from La₂O₃, TiO₂, Nb₂O₅, WO_3, and ZrO₂ were all greater than 2.1, which is considered as a high refractive index. The results suggest that these components can provide a specific reference for optical glass material selection in future research.Furthermore, based on the concept of performance synergy in high-entropy materials, our research group developed a high-entropy amorphous oxide in equal proportion, 20LaO_3/2-20TiO₂–20NbO_5/2-20WO₃–20ZrO₂ (Qi Xiwei, 2019). The structure has a high refractive index (2.22) and a high Abbe coefficient (61), which ensures that the lens has sufficient clarity when it is ultra-thin. By comparing the results of the two systems, we found that all non-proportional high-entropy systems are unable to simultaneously show both a high Abbe value and a high refractive index. This phenomenon further indicates the necessity of preparing high-entropy amorphous oxide in equal proportion.     

Effect of Niobium Oxide on the Structure and Properties of Melt‐Derived Bioactive Glasses

The effects of adding Nb₂O₅ on the physical properties and glass structure of two glass series derived from the 45S5 Bioglass^® have been studied. The multinuclear ²⁹Si, ³¹P, and ²³Na solid‐state MAS NMR spectra of the glasses, Raman spectroscopy and the determination of some physical properties have generated insight into the structure of the glasses. The ²⁹Si MAS NMR spectra suggest that Nb⁵⁺ ions create cross‐links between several oxygen sites, breaking Si–O–Si bonds to form a range of polyhedra [Nb(OM)_6?y(OSi)_y], where 1 ≤ y ≤ 5 and M = Na, Ca, or P. The Raman spectra show that the Nb–O–P bonds would occur in the terminal sites. Adding Nb₂O₅ significantly increases the density and the stability against devitrification, as indicated by ΔT(T_x ? T_g). Bioglass particle dispersions prepared by incorporating up to 1.3 mol% Nb₂O₅ by replacing P₂O₅ or up to 1.0 mol% Nb₂O₅ by replacing SiO₂ in 45S5 Bioglass^® using deionized water or solutions buffered with HEPES showed a significant increase in the pH during the early steps of the reaction, compared using the rate and magnitude during the earliest stages of BG45S5 dissolution.     

Glass Formation and Characterization Studies in the TeO2–WO3–Na2O System

Glass formation behavior of the TeO₂–WO₃–Na₂O system was studied by using conventional melt‐quenching technique. A wide glass formation range was determined for the first time in the literature and thermal, physical, and structural characterization of sodium‐tungsten‐tellurite glasses were realized using differential scanning calorimetry (DSC) and Fourier transform infrared (FTIR) spectroscopy techniques. Glass transition (T_g) and crystallization (T_c/T_p) temperatures, glass stability (?T), density (ρ), molar volume (V_M), oxygen molar volume (V_O), and oxygen packing density (OPD) values and structural transformations in the glass network were investigated according to the equimolar substitution of TeO₂ by Na₂O+WO₃ and changing Na₂O or WO₃ at constant TeO₂.     

Catalytic Reduction of NO with NH3 over V2O5-MnOX/TiO2-Carbon Nanotube Composites

Abstract  

A series of V₂O₅–MnO_X/TiO₂-CNTs, V₂O₅/TiO₂-CNTs, and MnO_X/TiO₂-CNTs catalysts were synthesized via solvothermal method and their NO_X removal activities were studied. A catalytic performance improvement was observed over catalysts prepared by mechanical mixing MnO_X/TiO₂-CNTs and V₂O₅/TiO₂-CNTs. XRD, SEM, EDS, TPD, TPR, and BET were employed to analyze the improvement which is ascribed to the separation of Mn and V as well as the increase in reducibility and acidic strength.     

Studies in Lithium Oxide Systems: I, Li2O B2O3–B2O3

Phase relationships in the system Li₂O, B₂O₃-B₂O₃ were studied by the quenching method using twenty compositions. The crystalline phases encountered were (a) Li₂O, B₂O₃, which melts congruently at 849°± 2°C., (b) Li₂O.-2B₂O₃, which melts congruently at 917°± 2°C., (c) a new compound, 2Li₂O-5B₂O₃, which melts incongruently at 856°± 2°C. and dissociates below 696°± 4°C., (d) Li₂O.3B₂O₃, which melts incongruently at 834°± 4°C. and dissociates below 595°± 20°C., and (e) probably Li₂O.4B₂O₃, which melts incongruently at 635°± 10°C. Reactions were sluggish at temperatures near 600°C., resulting in metastable relations. Hence phase equilibrium data relating to the lower stability limit of Li₂O.3B₂O₃ and to the upper stability limit of Li₂O.4B₂O₃ are considered to be tentative. Properties of the glasses and crystalline phases were studied. The refractive index of the glasses increased with the addition of Li₂O up to 22%, but further additions up to 40% had no substantial effect. Glasses containing less than 30% Li₂O were water soluble. Limited data on the density and thermal expansion of the glasses are presented. Li₂OB₂O₃ was euhedral, lath-shaped, length-fast, biaxial negative (2V = 27°), with n_α= 1.540, n_β= 1.612, n_γ= 1.616. Li₂O.2B₂O₃ was uniaxial negative, with n_e= 1.560, n_w= 1.605. Li₂O.3B₂O₃ was biaxial negative (2V = 75° to 80°), with n_α= 1.576, n_β= 1.602, n_γ= 1.605. X-ray powder diffraction data for the five crystalline compounds are presented. Thermal expansion data for Li₂O-B₂O₃ and Li₂O.2B₂O₃ and limited data on the fluorescent properties of the compounds are given. X-ray diffraction data are also presented for Li₂O.B₂O₃.4H₂O and Li₂O.-5B₂O₃. 10H₂O. Li₂O B₂O₃ was obtained by heating the first hydrate at 450° to 680° C. X-ray diffraction showed Li₂O.4B₂O₃ and Li₂O-3B₂O₃ to be the crystalline products obtained during heating the decahydrate at 500°C. and 600°C., respectively.     

Preparation and improved photochemical properties of V-doped Nb2Te4O13

Mixed oxides combining d⁰-and p-cations with stereoactive lone pair electrons exhibit excellent polarization abilities for potential photoelectric applications. This work reports the photochemical properties of V-doped Te–Nb mixed oxide Nb₂Te₄O₁₃, which has the typical framework constructed by NbO₆ (d⁰-) octahedra, TeO₄, and TeO₃ (p-) polyhedra. The samples were prepared using the sol-gel method, which resulted in the final nanoparticles. The luminescence spectra, lifetimes of photoinduced electrons and holes, and conductivity properties of the samples were characterized. Nb₂Te₄O₁₃ has an indirect transition with a band energy of 2.98 eV V⁵⁺-doping shows a narrowing effect on the band gap, enhancing the harvest of the optical absorption in the visible light region. Photocatalysis tests were conducted via the photodegradation of RhB solutions under visible-light irradiation. V⁵⁺-doping depresses the intrinsic luminescence efficiency, while it significantly enhances photodegradation. It is suggested that the induced redox couples V^5+/4+ and defects are responsible for the improvements of photocatalysis of Nb₂Te₄O₁₃. This work offers an effective method to modify photochemical properties via redox couples and defects induced by impurity ion doping.