Effect of Tungsten Oxide on the Crystallization Properties of Glasses of the B2O3–La2O3–Nb2O5 System

Glass Physics and Chemistry - The effect of tungsten oxide on the crystallization properties of glasses of the 37.5B2O3 22.5La2O3 (40 – x)Nb2O5 xWO3 (where x = 10, 15, 20, 30, 40 mol %)...     

Crystallization of Glasses in the K2O–Nb2O5–SiO2System

The changes in the structure and phase composition of glasses in the K₂O–Nb₂O₅–SiO₂system upon their heat treatment in the temperature range 700–800°C are studied by the small-angle X-ray scattering (SAXS) technique and X-ray powder diffraction. It is demonstrated that the crystallization is the primary process giving rise to microinhomogeneities in glasses due to heat treatment. Nanocrystals of an unidentified niobium-containing phase precipitate in glasses with the formation of regions with a decreased content of potassium and niobium oxides. An increase in the duration of heat treatment at the studied temperatures results in an increase in the size of nanocrystals without change in their phase composition. This is accompanied by the disappearance of diffusion zones, which leads to a decrease in the SAXS intensity in the range of small scattering angles and, correspondingly, to a decrease in the light scattering intensity.     

Effects of Bi2O3–Li2CO3 additions on dielectric and pyroelectric properties of Mn doped Pb(Zr0.9Ti0.1)O3 thick films

Pb(Zr_0.9Ti_0.1)O₃ pyroelectric thick films adding various amounts of the sintering aids Bi₂O₃–Li₂CO₃ have been deposited on the substrates Al₂O₃ by the screen-printing process, and the dependence of microstructure, dielectric and pyroelectric properties on the content of sintering aids has been studied. When the amount of Bi₂O₃–Li₂CO₃ increases from 0 wt% to 5.4 wt%, the sintering temperature of the thick films decreases from 1100 °C to 900 °C, and the grain size and the lattice constant decrease either, but the density and the dielectric constant increase. The Pb(Zr_0.9Ti_0.1)O₃ thick film with 5.4 wt% of Bi₂O₃–Li₂CO₃ sintered at 900 °C has the maximum pyroelectric coefficient 10.51×10^?8 C/cm^?2 K^?1 and the highest figure-of-merit 10.58×10^?5 Pa^?0.5.     

Formation of Al2O3–Nb2O5 composite oxide films on low-voltage etched aluminum foil by complexation–precipitation and anodizing

Niobium pentaoxide (Nb₂O₅) thin films were deposited on etched aluminum foils by complexation–precipitation followed by heat treatment. Then the Al₂O₃–Nb₂O₅ (Al–Nb) composite oxide films were formed by anodizing to increase the capacitance of anodized aluminum foils which are used in aluminum electrolytic capacitors. The composition and structure of niobium deposition layer were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD), and the microstructures and dielectric properties of anodic oxide films were investigated by scanning electron microscope (SEM) and electrochemical impedance spectroscopy (EIS) respectively. The results show that the niobium deposition layer after heat treatment existed in the form of crystalline Nb₂O₅. The aluminum foil with Nb₂O₅ coating can be anodized with higher efficiency and energy saving. Compared with that of normal anodized aluminum foils, the effective area of the anodized aluminum foils with Al–Nb composite oxide films had no apparent change. The specimens with Al–Nb composite oxide films anodized at 30 V exhibited about 20% higher specific capacitance than that of those with pure aluminum oxide films. It suggests that the method of complexation–precipitation is an effective way to increase the specific capacitance of anodized aluminum foils used in aluminum electrolytic capacitors.     

Crystallization of LiNbO3 and NaNbO3 in niobiosilicate glass–ceramics

Although glass–ceramics have been widely explored for their thermal stability and mechanical properties, they also offer unique symmetry-dependent properties such as piezoelectricity and pyroelectricity through controlled crystallization of a polar phase. This work examines crystallization of LiNbO₃ in a 35SiO₂–30Nb₂O₅–35Li₂O mol% composition and crystallization of LiNbO₃ and NaNbO₃ in a 35SiO₂–30Nb₂O₅–25Li₂O–10Na₂O mol% composition. Crystallization kinetics are examined using the Johnson–Mehl–Avrami–Kolmogorov (JMAK) theory where the Avrami exponent, n, is calculated to be 1.0–1.5. Microscopical analysis shows dendritic morphology, which when combined with the JMAK analysis, suggests diffusion-controlled one-dimensional growth. Adding Na₂O to the glass composition increases the inter-diffusivity of ions which causes LiNbO₃ to crystallize faster and lowers the activation energy of transformation from 1054 ± 217 kJ/mol in the ternary composition to 882 ± 212 kJ/mol. Time-temperature-transformation diagrams are presented which show that the temperature for maximum rate of transformation for LiNbO₃ is ∼650°C and for NaNbO₃ is ∼715°C.     

Crystallization characteristics of CaO–Al2O3–SiO2–Li2O–B2O3 mold flux with different values of w(CaO)/w(Al2O3)

The effect of C/A ratio (abbreviation of w(CaO)/w(Al₂O₃)) on the crystallization characteristics was investigated. With an increase in C/A ratio from 1.1 to 1.8, the crystallization ability first decreased and then increased; the crystallization ability is weakest and strongest with C/A ratios of 1.5 and 1.8, respectively. Increasing C/A ratio, the crystalline phase changed from LiAlO₂ and CaO·Al₂O₃ to LiAlO₂ and 3CaO·Al₂O₃. The Li⁺ ions in the slag took precedence over Ca²⁺ ions to participate in charge compensation because the mold flux contains Al3+ which is more advantageous for a monovalent cation, and LiAlO₂ formed preferentially over CaO·Al₂O₃. With a further increase in C/A ratio, 3CaO·Al₂O₃ formed from the combination of Ca²⁺ ions and Q_Al² units, and the precipitated amount of 3CaO·Al₂O₃ increased.     

Microstructure and characterization of interfacial phases of sapphire/sapphire joint bonded using Bi2O3–B2O3–ZnO glass

Bismuth borate zinc glass, 50Bi₂O₃–30B₂O₃–20ZnO (mol.%), was used as a braze intended to join sapphire. Thermal properties of the glass were all experimentally determined. The wettability of the glass on sapphire was investigated. The contact angle not greater than 11.3° was obtained in air at temperatures of ≥700 °C. Subsequently, sapphire was successfully joined to themselves at 700 °C for 20 min. The microstructure of the joint was studied and the interfacial phases were characterized. The results showed that the ZnAl₂O₄ phase was formed as a result of the reaction between the sapphire substrate and ZnO from the glass. The mechanical integrity of the joints was investigated. The joints with an average room shear strength of 70 MPa were achieved. The fracture analysis indicated that the fracture occurred within the glass interlayer rather than at the sapphire/glass interface, hence indicating a good bonding of the glass with sapphire.     

The impact of Nb2O5 on in-vitro bioactivity and antibacterial activity of CaF2–CaO–B2O3–P2O5–SrO glass system

This work consists of in vitro bioactivity (in SBF) and antibacterial studies (against S. aureus and E. coli bacteria) of Nb₂O₅ doped bioactive glasses. X-ray diffraction and scanning electron microscopy investigations indicated deposition of Nb-HAp (hydroxyapatite) crystalline layer on the samples after exposing to SBF. The spectroscopy investigations also indicated the deposition of HAp layer on these samples. The magnitude of HAp deposited on the glasses found to be relying on concentration of Nb₂O₅ dopant; this conclusion was drawn by determining weight loss of the glasses due to exposure to SBF and also by assessing the variation of pH of the remnant fluid as functions of Nb₂O₅content. The studies further indicated the maximal content of hydroxyapatite was deposited on the surface the glasses doped with 4.0 mol% of Nb₂O₅. The antibacterial studies (against E. coli and S. aureus bacteria) of these glasses indicated the maximal killing effect of bacteria of the samples admixed with 4.0 mol% of Nb₂O₅. This result is attributed to the occupancy of maximal fraction of Nb ions in NbO₆ structural units (confirmed by IR and Raman spectroscopic results) in this sample that paved the way for easy disintegration of the glass and to act on the bacteria. Overall, the results of bioactivity studies of Nb₂O₅ doped bioglasses indicated that the Nb₂O₅ not only enhanced bioactivity potential but also exhibited antimicrobial activity.     

Characterization and catalytic properties of MoO3–V2O5/Nb2O5 catalysts

The influence of molybdenum oxide on the dispersion of vanadium oxide supported on niobia was investigated. A series of MoO₃–V₂O₅/Nb₂O₅ catalysts with varying MoO₃ content ranging from 1% to 5% (w/w) with fixed V₂O₅ content were prepared by impregnation of previously prepared 5 wt% V₂O₅/Nb₂O₅ with requisite amounts of ammonium molybdate solution. X-ray diffraction patterns indicate the presence of β-(Nb,V)₂O₅ phase with the addition of MoO₃ up to a loading of 3 wt%. Temperature-programmed reduction (TPR) results suggest that the reducibility is decreasing with MoO₃ loading. The results of temperature programmed desorption (TPD) of ammonia suggest that the acidity of the catalysts increased with the addition of MoO₃. The catalytic properties of the catalysts in the ammoxidation of 3-picoline were correlated with the characterization data.     

Dual effect of ZrO2 on phase separation and crystallization in Li2O–Al2O3–SiO2–P2O5 glasses

ZrO₂ is an effective nucleation agent for low-expansion lithium–aluminum silicate (LAS) glass–ceramic (GC) with high Al₂O₃ content. However, the effect of ZrO₂ is still not fully understood in LAS glasses with low contents of Al₂O₃ and P₂O₅. In this work, the effect of ZrO₂ on the phase separation and crystallization of Li₂O–Al₂O₃–SiO₂–P₂O₅ glasses were investigated. The results revealed that ZrO₂ significantly increased T_g and the crystallization temperature of Li₂SiO₃ and Li₂Si₂O₅ crystals. Li₃PO₄ crystals precipitated preferentially in the glass containing 3.6-mol% ZrO₂, wherein Zr was stable in the network and no precipitation of ZrO₂ nanocrystals was observed. Moreover, the separation of phosphate-rich phases in the as-quenched glasses increased with the addition of ZrO₂. The findings of the study revealed a dual role of ZrO₂. First, ZrO₂ acted as a glass network former rather than a nucleation agent, increasing glass viscosity and the nucleation barrier of Li₂SiO₃ through its strong network connectivity. Second, as Zr preferentially combined with non-bridging oxygen to form Si–O–Zr linkages, a sufficient amount of charge-balancing Li⁺ ions existed in the network, which promoted the separation of phosphate-rich phases. It indicated that the incorporation of ZrO₂ contributes to the activation of the nucleation role of P₂O₅, thus contributing to the formation of nanocrystals and fine microstructure of GCs.     

Thermal Stability and Crystallization Kinetics of MgO–Al2O3–B2O3–SiO2 Glasses

To support commercialization of the MgO–Al₂O₃–B₂O–SiO₂-based low-dielectric glass fibers, crystallization characteristics of the relevant glasses was investigated under various heat-treatment conditions. The study focused on the effects of iron on the related thermal properties and crystallization kinetics. Both air-cooled and nucleation-treated samples were characterized by using the differential thermal analysis/differential scanning calorimeter method between room temperature and 1200°C. A collected set of properties covers glass transition temperature (T_g), maximum crystallization temperature (T_p), specific heat (ΔC_p), enthalpy of crystallization (ΔH_cryst), and thermal stability (ΔT=T_p—T_g). Using the Kinssiger method, the activation energy of crystallization was determined. Crystalline phases in the samples having various thermal histories were determined using powder X-ray diffraction (XRD) and/or in situ high-temperature XRD method. Selective scanning electron microscope/energy-dispersive spectroscopy analysis provided evidence that crystal density in the glass is affected by the iron concentration. Glass network structures, for air-cooled and heat-treated samples, were examined using a midinfrared spectroscopic method. Combining all of the results from our study, iron in glass is believed to function as a nucleation agent enhancing crystal population density in the melt without altering a primary phase field. By comparing the XRD data of the glasses in two forms (bulk versus powder), the following conclusions can be reached. The low-dielectric glass melt in commercial operation should be resistant to crystallization above 1100°C. Microscopic amorphous phase separation, possibly a borate-enriched phase separating from the silicate-enriched continuous phase can occur only if the melt is held at temperatures below 1100°C, that is, below the glass immiscibility temperature. The study concludes that neither crystallization nor amorphous phase separation will be expected for drawing fibers between 1200°C and 1300°C in a commercial operation.     

Elastic properties of quaternaryTeO2–ZnO–Nb2O5–Gd2O3 glasses

Tellurite glass systems in the form 75TeO₂–15ZnO–(10−x)Nb₂O₅–xGd₂O₃ (x=0.0, 0.5, 1.0, 1.5, 2.0, 2.5 mol%) have been prepared by the melt quenching technique. Both longitudinal and shear ultrasonic velocities were measured by using the pulse-echo method at 5 MHz frequency and at room temperature. Elastic moduli (longitudinal modulus, shear modulus, Young׳s modulus, Bulk modulus), Poisson׳s ratio, Debye temperature, micro-hardness and softening temperature have been calculated. Quantitative analysis of elastic moduli based on the number of bond per unit volume, average crosslink and number of vibrating atoms per unit volume has been achieved.     

Al2O3–cyanate ester hybrid thick films through aerosol deposition and resin infiltration

Al₂O₃–cyanate ester hybrid thick films had high Al₂O₃ contents over 75 vol.% were fabricated as 3D integrated substrates. The Al₂O₃–cyanate ester hybrid thick films were completed by resin infiltration of the cyanate ester into the porous Al₂O₃ thick films deposited by aerosol deposition (AD). Al₂O₃ particles were packed as high-density layers in the porous Al₂O₃ thick films by controlling the carrier gas flow rate using AD at room temperature. As dielectric substrate materials, the Al₂O₃–cyanate ester hybrid thick films had dielectric constant of 7.6 and quality (Q) factor of 390, and both were nearly independent of the measuring frequency.     

Phase equilibria of CaO–SiO2–CaF2–P2O5–Ce2O3 system and formation mechanism of britholite

Recently, the sustainable utilization of REE-bearing slag for the recovery and application of rare-earth elements (REEs) has attracted considerable attention. However, a limited amount of thermodynamic data and crystal information for REE systems has been reported, which greatly limits the utilization of REE-bearing slag. In this study, the isothermal phase diagram of the CaO–SiO₂–CaF₂(30 wt%)-P₂O₅(10 wt%)-Ce₂O₃ system was constructed to provide phase equilibria data for the REEs in REE-bearing slag. The formation mechanism of britholite (Ca_5-xCe_x[(Si,P)O₄]₃F) in the quinary system was found: it evolved from Ca₅(PO₄)₃F, when a Ce³⁺ replaced a Ca²⁺, there would be a SiO₄^4? instead of a PO₄^3?. The phase equilibria and formation mechanism of REEs in the CaO–SiO₂–CaF₂–P₂O₅–Ce₂O₃ system are supplied to provide the data required for sustainable utilization of REE-bearing slag.     

Ion implantation effects on the characteristics of β-Ga2O3 epilayers grown on sapphire by MOCVD

In this study, the Si-ions implantation technique with different doses from 1 × 10¹⁴ to 1 × 10¹⁵ cm^?2 and dose energy 30, 40 and 50 keV was used to tune the electrical properties in unintentionally doped (UID) β-Ga₂O₃ epilayers grown on the sapphire substrates by metalorganic chemical vapor deposition (MOCVD). A high quality UID β-Ga₂O₃ epilayers were fabricated using the optimized growth parameters of MOCVD. The UID and Si-ions implanted β-Ga₂O₃ epilayers were examined and results were compared with the help of X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy, and transmission electron microscopy. Si-ions implantation parameters were also simulated by stopping and range of ions in matter software (SRIM) and actual Si-ions concentration was measured by secondary ions mass spectroscopy. The electrical properties of the implanted β-Ga₂O₃ epilayers were measured by transmission length method and Hall measurements. The sheet resistivity for the β-Ga₂O₃epilayers with Si-ion dose of 1 × 10¹⁴, 6 × 10¹⁴ and 1 × 10¹⁵ cm^?2 were found as 2.047, 0.158 and 0.144 Ω cm, respectively measured by Hall measurements and the electron carrier concentrations for the above doses were 4.39 × 10¹⁸, 6.86 × 10¹⁸ and 7.98 × 10¹⁹ cm^?3. From the above results, the ion implantation was demonstrated to effectively reduce the resistivity with the high carrier concentrations.     

Lithium concentration effect on crystallization kinetics and spectral properties of Cr-doped Li2O–K2O–Al2O3–B2O3 glass-ceramics

Alkali-aluminaborate glass-ceramics doped with Cr ions are synthesized by volume crystallization. According to non-isothermal DSC method three parallel processes occur in material: 2D Avrami-Yerofeev nucleation, 2D and 3D crystallization. During the heat treatment, the LiAl₇B₄O₁₇ crystalline phase is formed. With Li₂O content rising crystallinity of the material increases from 27 to 69% and the crystalline field strength Dq/B of Cr³⁺ increases from 2.25 to 3.55. The photoluminescence spectra possess intense bands at 685, 700, and 715 nm for glass with 6.8 mol.% Li₂O and higher and its decay kinetics is described by the sum of two exponentials. The maximum luminescence QY obtained is 50% at 16.1 mol.% Li₂O. The highest conversion efficiency of the 532 nm LED luminescence obtained by glass-ceramics with chromium is 10%. Thus, Cr-doped alkali-alumina-borate glass-ceramics are a promising material for use in the design of radiation sources for the red and NIR spectral regions.     

Solid-state formation of lithium ferrites from mechanicallyactivated Li2CO3–Fe2O3 mixtures

The formation of lithium ferrites (LiFe₅O₈ and LiFeO₂) from mechanically activated mixtures of Li₂CO₃–Fe₂O₃ has been studied using thermal analysis (TGA, DSC), evolved gas analysis (TG/FT-IR), X-ray powder diffraction (XRD), scanning electron microscopy (SEM) and particle size analysis. It is shown that mechanical activation of the precursors considerably enhances the reactivity of the solid system analysed and makes it possible to obtain reaction products with a much lower expense of thermal energy. In particular, lithium ferrites can be obtained at temperatures at least 160 °C lower than those necessary in the absence of mechanical activation. Moreover, both the microstructure and the allotropic ratio of the products, as well as the reaction path, are affected by mechanical activation.     

Synthesis and characterization of corrosion-resistant and biocompatible Al2O3–TiB2 nanocomposite films on pure titanium

Alumina is widely used as a coating on a metal implant due to its favorable mechanical and biological properties. In this research, in order to improve mechanical and biological properties of alumina, a composition of nanoparticles of alumina (instead of microparticles) and titanium diboride micro powder is introduced. The atmospheric plasma spray (APS) technique was applied to deposit Al₂O₃–TiB₂ on the pure titanium substrate. The properties of Al₂O₃–TiB₂ nanocomposite coatings with various weight percent of TiB₂ (20, 30 and 40 wt%) were experimentally studied. The characteristics of nanocomposite films of TiB₂ (20, 30 and 40 wt%) were analyzed using Field Emission Scanning Electron Microscopy (FE-SEM), energy dispersive electron spectroscopy (EDX) and X-Ray Diffraction (XRD) tests. The XRD spectra exhibited that in addition to alumina and titanium diboride, the films contained titania. Thickness and morphology of the films were calculated from FE-SEM images and the thickness of the optimized coating (Al₂O₃-30 wt% TiB₂) was about 30–45 μm. Also, the roughness, corrosion resistance, hardness and cytotoxicity (MTT) tests were studied. The highest of hardness and roughness of the samples were obtained from Al₂O₃-30 wt% TiB₂. According to the obtained results from the polarization test, Al₂O₃-30 wt% TiB₂ coating had the highest corrosion resistance (222558.9962 Ω cm²). Therefore, the toxicity of Al₂O₃-30 wt% TiB₂ was investigated as the optimized coating and the results confirmed its non-toxicity and biocompatibility.