Effect of Bi2O3 content on sintering and crystallization behavior of low-temperature firing Bi2O3–B2O3–SiO2 glasses

The sintering behavior of a Pb-free Bi₂O₃–B₂O₃–SiO₂ glass system was examined as a function of Bi₂O₃ content. The glass transition temperature and the crystallization temperature of the glasses decreased with different decreasing gradients as the Bi₂O₃ content increased. The change in temperature affected the sintering behaviors of the glasses. In the case of the 40 mol% Bi₂O₃ addition, large pore accompanied over-firing phenomenon was observed when the sample was sintered over the optimum sintering temperature. However, over-firing was not observed in the sample with 45 mol% of Bi₂O₃ because of the crystallized phases during sintering. When the Bi₂O₃ content was 50–55 mol%, the crystallization temperature became lower than the glass transition temperature, which resulted in the crystallization of glass and it hindered densification.     

Influence of Crystallization on the Conversion of Sm3+→Sm2+ in SrO–Bi2O3–K2O–B2O3 Glass‐Ceramics

Sm³⁺‐doped glass 13SrO–2Bi₂O₃–5K₂O–80B₂O₃ was fabricated by the conventional melt‐quenching technique. The glass‐ceramics were obtained by heating the as‐prepared glasses in air atmosphere at selected temperatures 550°C, 600°C, 615°C, and 650°C, respectively. The luminescence spectra of both Sm³⁺ and Sm²⁺ were detected in the ceramic heated at 650°C where crystalline phase is formed. The as‐prepared glass and the ceramics heated at 550°C, 600°C, and 615°C show only the emission due to Sm³⁺. In the sample heated at 650°C in air atmosphere, however, part of Sm³⁺ ions was converted to Sm²⁺, giving rise to sharp emission lines which are characteristic of Sm²⁺ in crystalline state. It is suggested that Sm²⁺ ions are located at Sr²⁺ site in the ceramic while Sm³⁺ ions are located at Bi³⁺ sites. The Sm²⁺‐doped glass‐ceramic has a high optical stability because the fluorescence intensity decreases by only about 8% of its initial value upon excitation at 488 nm Ar⁺ laser.     

Aerosol Codeposition of Ceramics: Mixtures of Bi2O3–TiO2 and Bi2O3–V2O5

Aerosol deposition (AD) is a promising method to apply ceramic films on a wide range of substrate materials. Until now, AD has mainly been performed using a single ceramic powder. In this work, mixtures of two different ceramic powders were prepared. The first mixture consisted of Bi₂O₃ and TiO₂ and the second consisted of Bi₂O₃ and V₂O₅, in stoichiometric ratios to form Bi₄Ti₃O₁₂ and Bi₄V₂O_11?δ, respectively. Aerosol codeposition produced films with homogeneously distributed particle fractions and thicknesses between 10 and 100 μm. Composite films were annealed to temperatures up to 750°C to enable an in situ calcination and attempted formation of the above‐mentioned compounds. Successful formation of Bi₄Ti₃O₁₂ was tracked by hot‐stage X‐ray diffraction (XRD), and confirmed by dielectric measurements. Formation of the intended Bi₄V₂O_11?δ, on the other hand, was not achieved, but rather BiVO₄, which was confirmed by XRD, EDX and electrical measurements. The bismuth deficiency occurred during spray deposition, and is attributed to powder/material characteristics. Additional insight about the AD process is gained by comparing mixtures of oxides with different relative hardness values. Aerosol codeposition of ceramics may be an interesting new technique for producing porous functional ceramics.     

Thermal and optical properties of La2O3–Ga2O3– (Nb2O5 or Ta2O5) ternary glasses

La₂O₃–Ga₂O₃–M₂O₅ (M = Nb or Ta) ternary glasses were fabricated using an aerodynamic levitation technique, and their glass‐forming regions and thermal and optical properties were investigated. Incorporation of adequate amounts of Nb₂O₅ and Ta₂O₅ drastically improved the thermal stabilities of the glasses against crystallization. Optical transmittance measurements revealed that all the glasses were transparent over a wide wavelength range from the ultraviolet to the mid‐infrared. The refractive indices of the glasses increased and the Abbe number decreased upon substituting Ga₂O₃ with Nb₂O₅, and the decrease in the Abbe number was significantly suppressed when Ta₂O₅ was incorporated into the glass. As a result, excellent compatibility between high refractive index and lower wavelength dispersion was realized in La₂O₃–Ga₂O₃–Ta₂O₅ glasses. Analysis based on the single‐oscillator Drude–Voigt model provided more systematical information and revealed that this compatibility was due to an increase in the electron density of the glass.     

Effect of bulk and nanoparticle Bi2O3 on attenuation capability of radiation shielding glass

The aim of this study is to examine the effect of Bi₂O₃ concentration and particle size on Bi₂O₃ glass. The tested glasses had the composition of SiO₂–Bi₂O₃–CaO–MgO–B₂O₃–K₂O–Na₂O–ZnO. Ordinary glass was compared with glasses with 10% Bulk Bi₂O₃, 10% Bi₂O₃ Nanoparticles (NPs), 20% Bulk Bi₂O₃, and 20% Bi₂O₃ nanoparticles. The mass attenuation coefficients (MACs) of all the investigated glasses were determined between 0.0595 MeV and 1.41 MeV. The results demonstrated that increasing the Bi₂O₃ content in the glass matrix improved their shielding capability, as well as showing that the NPs provided greater attenuation than the bulk Bi₂O₃ at the same concentration. The percent increase in the MAC between the bulk and nano Bi₂O₃ was also calculated and analyzed. From the MAC values, the LAC of the glass was determined and similar results were found compared to the MAC figure. The HVL and MFP of the glass were then analyzed and the results demonstrated that the glass with Bi₂O₃ NPs attenuated the same amount of photons at a smaller thickness, making the NP shield more effective. The heaviness of the samples illustrated that all the tested samples have a smaller weight than pure lead, making them more desirable. The attenuation factor of the glass (Att. Factor %) showed that increasing the Bi₂O₃ content in the samples and increasing the thickness of the shields both improve the shielding capability of the glass. Lastly, the d_lead of the glasses was determined, indicating that the greatest reduction in thickness occurs near the K-absorption edge of bismuth. Overall, the glass with 20% Bi₂O₃ NPs demonstrated to have the greatest potential for radiation shielding applications.     

Thermal Stability,Optical Transmittance,and Refractive Index Dispersion of La2O3–Nb2O5–Al2O3 Glasses

La₂O₃–Nb₂O₅–Al₂O₃ high‐refractive‐index glasses were fabricated by containerless processing, and the glass‐forming region was determined. The thermal stability, density, optical transmittance, and the refractive index dispersion of these glasses were investigated. All the glasses were colorless and transparent in the visible to near infrared (NIR) region and had high refractive index with low wavelength dispersion. Some of these glasses were found to have significantly high glass‐forming ability. These results indicate that the ternary glasses are suitable for optical applications in the visible to NIR region. The effects of the substitution of Al₂O₃ for Nb₂O₅ on optical properties were discussed on the basis of the Drude–Voigt equation. It was suggested that the substitution of Al₂O₃ for Nb₂O₅ increased the molecular density and suppressed a decrease in the refractive index, even when both the average oscillator strength and inherent absorption wavelength decreased in La₂O₃–Nb₂O₅–Al₂O₃ glasses. These results are helpful for designing new optical glasses controlled to have a higher refractive index and lower wavelength dispersion.     

Preparation of transparent Bi2O3-ZnO-B2O3 glass by conventional sintering at low temperatures

Glass components fabricated by the sintering route have wide-ranging applications. However, one issue is that the crystallization tendency of glass powders often leads to residual pore-glass interfaces and crystal-glass interfaces, thereby causing strong light scattering and rendering the sintered glass opaque. This issue is particularly pronounced in glasses with a low glass transition temperature (T_g) due to their weak bonding and thus high crystallization tendency. In the present study, a Bi₂O₃-ZnO-B₂O₃ glass with a low T_g of 364°C was fabricated using the conventional sintering method to explore whether transparent glass materials can be obtained. The temperature range of crystallization of the glass powders was analyzed using differential scanning calorimetry. X-ray diffraction was employed to analyze the crystalline phases formed in the sintered glasses. The microstructure of the sintered glasses was examined using scanning electron microscopy. The optical transmittance of the sintered glasses was measured using ultraviolet-visible spectroscopy. The results show that transparent sintered glasses with the highest transmittance of 54% at the wavelength of 650 nm can be obtained by using a coarser initial particle size, lower forming pressure, and an appropriate sintering temperature/time (430°C/30 min). It is suggested that this combination of processing parameters can suppress glass crystallization while maintaining a low glass viscosity during sintering.     

Core–Shell Structure and Dielectric Properties of Ba0.991Bi0.006TiO3@Nb2O5–Co3O4 Ceramics

To meet the needs of future multilayer ceramic capacitors (MLCCs), thinner dielectric layers are necessary. To achieve this goal, the grain size and uniformity of the particles must be effectively controlled. In this study, we confirmed a core–shell particle structure by means of X‐ray diffraction, scanning electron microscopy, and energy‐dispersive spectroscopy. The dielectric properties of the ceramics were measured using an LCR meter. We found Ba_0.991Bi_0.006TiO₃ particles form a core that was coated with a homogeneous Nb₂O₅–Co₃O₄ layer (~9 nm). The relationship between core–shell structure and ε_r‐T curves of the Ba_0.991Bi_0.006TiO₃@Nb₂O₅–Co₃O₄ ceramics by different sintering temperature has been investigated. Dense, fine‐grained Ba_0.991Bi_0.006TiO@Nb₂O₅–Co₃O₄ ceramics were obtained by sintering at 1160°C. The ceramics met the X8R requirements, with a maximum dielectric constant of 2795, and a low dielectric loss at room temperature of 0.89%.     

Molten core fabrication of bismuth germanium oxide Bi4Ge3O12 crystalline core fibers

Optical fibers possessing a crystalline oxide core have significant potential for novel and useful electro‐ or nonlinear‐optic waveguides. Presently, however, their utility suffers from the slow speed and limited cladding materials afforded by conventional crystal‐fiber‐growth techniques. Described herein is the development of single phase bismuth germanium oxide crystalline core fibers using conventional glass fiber drawing. More specifically, fibers were fabricated and evaluated based on 2 embodiments of the molten core method. In a first approach, a Bi₄Ge₃O₁₂ single crystal was employed as the precursor and sleeved inside a borosilicate glass cladding. In the second approach, additional Bi₂O₃ was included along with the Bi₄Ge₃O₁₂ precursor single crystal. Glass clad fibers drawn from the precursor Bi₄Ge₃O₁₂ single crystal resulted in a polycrystalline core with various crystal morphologies (line‐like, dendrite‐like, and uniform grains) as will be discussed, while fibers drawn from the Bi₄Ge₃O₁₂ single crystal surrounded by Bi₂O₃ resulted in a more homogeneous microstructure. The eulytine crystal structure was crystallized using both approaches, with the formation of a secondary crystal phase using the second approach. More particularly, this work aims at showing that single phase and phase pure crystalline oxide core optical fibers can be achieved using conventional glass fiber draw processes, although further optimization is necessary for obtaining single crystalline core fibers.     

Coloration and Nonlinear Optical Properties of ZnTe Quantum Dots in ZnO–TeO2–P2O5 Glasses

ZnO–TeO₂–P₂O₅ glasses were prepared by melt‐quenching method. The color of the glass samples changed from colorless to pale red and dark red with increasing TeO₂ content. Coloration mechanism and nonlinear optical properties of ZnO–TeO₂–P₂O₅ glasses have been investigated. Raman spectra and transmission electron microscope measurements indicated the precipitation of ZnTe quantum dots in the glasses and ZnTe quantum dots are the origin of coloration. Z‐scan technique was used to examine the nonlinear optical properties of the glasses. The glass sample with 30 mol% TeO₂ exhibits large third‐order nonlinear optical susceptibility of 10^?11 esu.     

In situ crystallization and elastic properties of transparent MgO–Al2O3–SiO2 glass‐ceramic

Glass‐ceramics (GC) generally possess enhanced mechanical properties compared to their parent glasses. The knowledge of how crystallization evolves and affects the mechanical properties with increasing temperature is essential to optimize the design of the crystallization cycle. In this study, we crystallized a glass of the MgO–Al₂O₃–SiO₂ system with nucleating agents TiO₂ and ZrO₂. The crystallization cycle comprised a 48 hour nucleation treatment at the glass‐transition temperature followed by a 10 hour growth step at a higher temperature. During this cycle, the evolution of crystalline phases was followed by high‐temperature X‐ray diffraction (HTXRD), which revealed the presence of karooite (MgO·2TiO₂), spinel (MgO·Al₂O₃), rutile (TiO₂), sillimanite (Al₂O₃·SiO₂), and sapphirine (4MgO·5Al₂O₃·2SiO₂). The same heat treatment was applied for in situ measurement of elastic properties: elastic modulus, E, shear modulus, G, and Poisson's ratio, ν. The evolution of these parameters during the heating path from room temperature to the final crystallization temperature and during the nucleation and the crystallization plateaus is discussed. E and G evolve significantly in the first two hours of the growth step. At the end of the crystallization process, the elastic and shear moduli of the GC were approximately 20% larger than those of the parent glass.     

Fabrication and characterization of La2O3–Fe2O3–Bi2O3 nanopowders: Effects of La2O3 addition on structure,optical, and radiation-absorption properties

In this study, we fabricated and characterized six new nanopowders representing variations of La₂O₃–Fe₂O₃–Bi₂O₃, i.e., 100Bi₂O₃, 30Fe₂O₃–70Bi₂O₃, 3La₂O₃–27Fe₂O₃–70Bi₂O₃, 7La₂O₃–23Fe₂O₃–70Bi₂O₃, 10La₂O₃–20Fe₂O₃–70Bi₂O₃, and 20La₂O₃–10Fe₂O₃–70Bi₂O₃ (represented by 100B, 30F70B, 3L27F70B, 10L20F70B, and 20L10F70B, respectively). These nanopowders were prepared by the microwave-assisted hydrothermal synthesis method. Saponin extract from soapnuts was used as the nanoparticle capping agent. The structural, optical, and gamma radiation characteristics were measured, calculated, and analysed, respectively. The chemical structures of the nanocomposites influenced their optical and radiation shielding characteristics. The optical bandgaps of the 100B, 30F70B, 3L27F70B, 7L23F70B, 10L20F70B, and 20L10F70B nanopowders were 3.16, 3.13, 3.43, 3.45, 3.46, and 3.58 eV, respectively. The ranges of the mass attenuation coefficients of the nanopowders were computed, using XCOM, to be 0.0412–5.1624, 0.0401–4.5406, 0.0401–4.5285, 0.0401–4.5129, 0.0401–0.5015, and 0.0400–4.4156 cm²/g, respectively, and the ranges of mass energy absorption coefficients were found to be 0.0232–1.7525, 0.0228–1.5484, 0.0228–1.5598, 0.0288–1.5746, 0.0228–1.5853, and 0.0227–1.6192 cm²/g, respectively, for photon energies in the range of 0.1–10 MeV. The order of the dose rate trend was as follows: 30F70B < L27F70B < 7L23F70B < 10L20F70B < 20L10F70B. Analysis of the photon interaction parameters showed that the synthesized nanopowders could function well as fillers in radiation-shielding matrices.     

Hierarchical growth of BiOCl on SrO‐Bi2O3‐B2O3 glass‐ceramics for self‐cleaning applications

We have grown hierarchical structure of bismuth oxycloride (BiOCl) on SrO‐Bi₂O₃‐B₂O₃ (SBBO) transparent glass‐ceramic. SBBO glass‐ceramics were fabricated via conventional melt‐quenching technique while BiOCl was grown by etching the glass via HCl. Enhanced visible light driven photocatalytic activity and increasing hydrophobic feature were observed on BiOCl grown SBBO than as‐quenched SBBO glass‐ceramics. Contact angle analysis showed maximum contact angle of 130.7° on the surface of most BiOCl grown SBBO glass‐ceramic. Furthermore, under visible light illumination water contact angle decreased from 130.7° to 30.8°. Such photo‐induced hydrophilicity and catalytic performance in translucent glass‐ceramics lead self‐cleaning applications.     

Sintering behavior and characteristics study of BaTiO3 with 50 wt% of B2O3-Bi2O3-SiO2-ZnO glass

The thermal analysis of B₂O₃-Bi₂O₃-SiO₂-ZnO (BBSZ) glass with different particle sizes and LiF addition was researched to study its temperature behavior. Next the composites with 50 wt% BaTiO₃–50 wt% BBSZ glass were prepared for shrinkage, microstructures and dielectric properties investigations. The differently treated BBSZ glass showed that the smaller glass particles clearly decreased its softening and crystallization temperatures. LiF addition had the same but much weaker effect.The composites showed two-stage shrinkage related to the softening of the glass and new phase generation of Bi₂₄Si₂O₄₀ at 385–450 °C, and Bi₄BaTi₄O₁₅ over 680 °C. The microstructures of the composites sintered at 720 °C showed Bi₄BaTi₄O₁₅, BaTiO₃ and Bi₂₄Si₂O₄₀ with residual ZnO phase. LiF addition increased the amount of Bi₄BaTi₄O₁₅, thus increasing the loss value. However the particle size of the glass did not effect to the dielectric properties of the composites showing permittivity of 248–256 and loss of 0.013 at 100 kHz.     

Phase Evolution of SiO2–Al2O3–ZnO–CaO–ZrO2–TiO2‐Based Glass with Added Y‐PSZ Particles

Yttria partially stabilized zirconia Y‐PSZ/glass‐ceramic composites were prepared by reaction sintering using powder mixtures of a SiO₂–Al₂O₃–ZnO–CaO–ZrO₂–TiO₂‐based glass and yttria partially stabilized zirconia (Y‐PSZ). The glass crystallized during sintering at temperatures of 1173, 1273, and 1373 K to give a glass‐ceramic matrix for high‐temperature protecting coatings. With the increasing firing time, the added zirconia reacted with the base glass and a glass‐ceramic material with dispersed zircon particles was prepared in situ. Furthermore, the added zirconia changed the crystallization behavior of the base glass, affecting the shape, amount, and distribution of zircon in the microstructure. The bipyramid‐like zircon grains with imbedded residual zirconia particles turned out to have two growth mechanisms: the inward growth and the outward growth, and its rapid growth was mainly dominated by the later one. For comparison, the referenced glass‐ceramic was prepared by sintering using exclusive glass granules and its crystallization behavior at 1173–1373 K was examined as well. Scanning electron microscopy (SEM), energy dispersive X‐ray spectroscopy (EDS), transmission electron microscopy (TEM), and X‐ray diffraction (XRD) were used to characterize the crystallization behavior of the base glass and the phase evolution of the Y‐PSZ/glass‐ceramic composites.     

Crystallization Kinetics and Dielectric Properties of a Low‐Fire CaO–Al2O3–SiO2 Glass + Alumina System

The crystallization kinetics and dielectric properties of a low‐dielectric, low‐temperature, cofirable ceramic system comprised of CaO–Al₂O₃–SiO₂ (CAS) glass and alumina have been investigated. Crystalline phases including pseudowollastonite (CaSiO₃), anorthite (CaAl₂Si₂O₈) and cristobalite (SiO₂) are formed during firing the pure CAS glass. The crystallization kinetics of both pseudowollastonite and cristobalite exhibit Avrami‐like behavior, and the results show apparent activation energies close to that of diffusion of alkali ions in the glass. With added alumina content greater than a critical value, the above crystalline phases are completely suppressed but more anorthite is formed. This result is attributed to the rapid dissolution kinetics of alumina into the CAS glass. As the degree of crystallization increases with firing time, the dielectric loss of the composite decreases significantly, however, with dielectric constant remaining relatively unchanged.     

Crystallization behavior,microstructure and dielectric properties of lead titanate glass ceramics in the presence of Bi2O3 as a nucleating agent

The crystallization behavior of PbO–TiO₂–B₂O₃–SiO₂ glasses in the presence of Bi₂O₃ as a nucleating agent were studied utilizing XRD, DTA, SEM. The glass samples heat treated in the range of 557–630 °C for different soaking times, all developed PbTiO₃ (PT) with perovskite structure. It was found that the addition of 0.5–1.0 mol% Bi₂O₃ resulted in the formation of homogenous, nano-structured glass ceramics with a mean crystallite size of 20–25 nm and PbTiO₃ as the major crystalline phase. The dielectric constant and dissipation factors for the prepared glass ceramics were in ～140–400 and ～0.04–0.4 ranges respectively.     

Joining of Porous Alumina with a CaO–Al2O3–SiO2 Glass‐Ceramic

A CaO–Al₂O₃–SiO₂ (CAS)‐based glass interlayer was developed for joining of porous alumina membrane tubes with dense alumina in this work. The results indicated that the interfacial microstructure of the joint was highly sensitive to the quench rate from the joining temperature, which rendered crystallization of CaTiSiO₅ at a fast quench rate but CaAl₂Si₂O₈ at a slow quench rate due to the interfacial reaction between the CAS glass interlayer and the substrate. An extra crystallization treatment during quench, i.e., dwelling at 800°C–900°C for 2 h, produced a multiphase interlayer consisting of LiAlSi₂O₆, CaTiSiO₅, and CaAl₂Si₂O₈. All joints were evaluated by the thermal shock test. The results showed that the LiAlSi₂O₆‐containing joint interlayer had much lower thermal shock resistance than those without LiAlSi₂O₆.     

Study on crystallization behaviors of As–Se–Bi chalcogenide glasses

The crystallization behaviors of As–Se–Bi chalcogenide glasses were investigated by differential scanning calorimetry (DSC) and X‐ray diffraction (XRD). Three models were used to study the glass transition behavior and the activation energy. Results showed thermal stability of glass against crystallization decreased with Bi addition in As–Se–Bi system. The mechanism of crystal growth in glasses was also studied by the Avrami exponent n. For B0, B2.5, and B5, n values are 3.12, 1.59, and 2.21 (low temperature) and 4.61 (high temperature), respectively. The thermal stability of glass is in good agreement with glass network structure. It was found that glass network structures closely associated with the Bi content and As/Se ratio were studied by X‐ray diffraction and Raman spectroscopy. And the different ratios lead to the change in Bi₂Se₃ crystalline orientation.     

Preparation and electrical properties of ZnO‐Bi2O3‐based multilayer varistors with base metal nickel inner electrodes

In this study, ZnO‐Bi₂O₃‐based multilayer varistors (MLVs) cofired with nickel (Ni) inner electrodes were prepared by tape‐casting method. Samples were sintered in pure nitrogen (N₂) to keep Ni from being oxidized, and then reoxidized in air to obtain the nonlinear properties (reduction‐reoxidation method). The EDAX results showed that Ni inner electrodes are stable and have no evident migration into ZnO‐Bi₂O₃‐based ceramics when sintered in N₂. The influence of reoxidation temperature on microstructures and nonlinear properties of samples were studied. Samples reoxidized at the temperatures lower than 650°C showed poor nonlinear properties. After reoxidized in air at 700°C for 2 hours, samples exhibited nonlinear properties of V_1 mA=16.3 V, α=26.5, I_L=0.68 μA. At the reoxidation temperature higher than 750°C, the oxidation of Ni inner electrodes deteriorated the nonlinear properties of samples. It demonstrated that ZnO‐Bi₂O₃‐based MLVs with base metal Ni inner electrodes proposed in this work are suitable for reduction‐reoxidation method. The replacement of noble metals Pt or Ag/Pd alloys by base metal Ni is expected to lower the cost of ZnO‐Bi₂O₃‐based MLVs.