Effect of CaO doping on the properties and crystallization behavior of Y2O3–Al2O3–SiO2 glass

Nowadays, Y₂O₃–Al₂O₃–SiO₂ (YAS) glass joining is considered to be a promising scheme for nuclear-grade continuous silicon carbide (SiC) fiber reinforced SiC matrix composites (SiC/SiC). CaO has great potential for nuclear applications since it has low reactivity and low decay rate under nuclear irradiation. In this paper, the effect of CaO doping on the structure, thermophysical properties, and crystallization behavior of YAS glass was systematically studied. As the CaO doping content increased, the number of bridge oxygens and the viscosity at high temperatures reduced gradually. After heat treatment at 1400 °C, the main phases in YAS glass were β-Y₂Si₂O₇, mullite, and SiO₂ (coexistence of crystalline and glass phases), while that with 3.0% CaO doping turned into a single glassy phase under the same treatment conditions. Moreover, a structural model and the modification mechanism were proposed, which provided a theoretical basis for the subsequent component design and optimization.     

Influence of Li2O–B2O3–SiO2 glass on the sintering behavior and microwave dielectric properties of BaO–0.15ZnO–4TiO2 ceramics

This paper reports the investigation of the performance of Li₂O–B₂O₃–SiO₂ (LBS) glass as a sintering aid to lower the sintering temperature of BaO–0.15ZnO–4TiO₂ (BZT) ceramics, as well as the detailed study on the sintering behavior, phase evolution, microstructure and microwave dielectric properties of the resulting BZT ceramics. The addition of LBS glass significantly lowers the sintering temperature of the BZT ceramics from 1150 °C to 875–925 °C. Small amount of LBS glass promotes the densification of BZT ceramic and improves the dielectric properties. However, excessive LBS addition leads to the precipitation of glass phase and growth of abnormal grain, deteriorating the dielectric properties of the BZT ceramic. The BZT ceramic with 5 wt% LBS addition sintered at 900 °C shows excellent microwave dielectric properties: ε_r=27.88, Q×f=14,795 GHz.     

Effects of CaO–B2O3–SiO2 glass additive on the microstructure and electrical properties of BCZT lead-free ceramic

Addition of CaO–B₂O₃–SiO₂ (CBS) glass was performed to lower the sintering temperature of lead-free Ba_0.85Ca_0.15Zr_0.1Ti_0.9O₃ (BCZT) ceramics. Orthorhombic and tetragonal phases coexisted in CBS-free BCZT ceramics. The BCZT ceramics transformed into a pseudo-cubic phase when sintered at 1300 °C with increasing CBS glass content. Additionally, the secondary phase, Ba₂TiSi₂O₈, was observed when CBS glass was added. The density initially increased, reached a maximum value with 2 wt% CBS glass, and then decreased rapidly with further increase in CBS glass content, which was consistent with the microstructure. The ɛ, T_c, P_r, and d₃₃ depend on microstructure, and the results agree with the density. Evident relaxation behavior was observed. Observed results were inferred to be dependent on the microstructure, phase structure, lattice distortion, and secondary phase. The sample with 2 wt% CBS glass showed the excellent performance, which could be a promising substitute to lead-free piezoelectric ceramics for lead-based materials.     

Effect of CuO addition on crystallization and thermal expansion properties of Li2O–ZnO–SiO2 glass-ceramics

A Li₂O-ZnO-SiO₂ (LZS) glass system was modified with CuO, and its phase development, microstructure evolution, crystallization kinetics and thermal expansion properties were investigated as a function of heat treatment temperature. As a result of the X-ray diffraction study and microstructure observation, lithium zinc silicate formed as the first crystalline phase with increasing heat treatment temperature. Silica polymorph developed as minor crystalline phase at higher temperatures. From the X-ray diffraction patterns, CuO addition led to a decrease in both the crystallization temperature of lithium zinc silicate phase and the volume fraction of quartz phase. According to the crystallization kinetics, the crystallization activation energy for lithium zinc silicates is almost equal to the diffusion activation energy of Zn²⁺ in glass, it suggests that the diffusion of network modifier Zn²⁺ dominates the crystallization of lithium zinc silicates. Additionally, CuO addition caused the transition of Zn²⁺ from network modifiers to network formers. From the thermal expansion coefficient measurements, two abrupt changes in slope of the thermal expansion curves were observed and attributed to the phase transitions of cristobalite and lithium zinc silicate, respectively. Comparison of the thermal expansion coefficient of two types of glass-ceramics revealed that CuO addition in the LZS system can partly inhibit the formation of cristobalite at high temperatures.     

Phase evolution and electrical properties of copper-electroded BaTi4O9 materials with BaO–ZnO–B2O3–SiO2 glass system in reducing atmosphere

BaTi₄O₉ (BT4) microwave dielectric ceramics using a copper electrode and containing 10 wt% BaO–ZnO–B₂O₃–SiO₂ (BZBS) glass frit were sintered under reducing atmosphere at 950 °C and were investigated on the phase evolutions, microstructures and dielectric properties of BT4 with various BaO/SiO₂ and ZnO/SiO₂ ratios of BZBS glasses. Experimental results show that the BaO/SiO₂ ratio contributes to wettability of glass with BaTi₄O₉ ceramics, and ZnO/SiO₂ ratio determines the densification of BaTi₄O₉ ceramics. The different Ba–Ti–O and Ba–Cu–O phases with various Ba/Ti and Ba/Cu ratios can be attributed to the contents of BaO in glass. Ba₄Ti₁₃O₃₀ and Ba₂Cu₃O_5+X may form when BaO contents are too high, and inducing copper diffusion due to the reactions of BaO and Cu, accompanying with degrading of the dielectric characteristics. If the ZnO contents of BZBS glasses were raised, a little bit of ZnSiO₃ and Ba₂Cu₃O_5+X phases appear without Cu diffusion due to non-reaction of ZnO and CuO. The high ZnO/SiO₂ ratio of glass reveals the lower softening point, indicating that the high ZnO glass could enhance the density and therefore increase the dielectric constant and quality factor.     

Effect of MgO addition on the properties of PbO –TiO2–B2O3 glass and glass–ceramics

Glass samples with composition of (50?X) PbO–X MgO–25 TiO₂–25B₂O₃ (where X=0, 5, 10 and 15 mol%) were prepared using conventional quenching technique. The amorphous nature of glass samples were confirmed by XRD. The glass transition temperature, T_g and crystallization temperature T_c were determined from the DTA. It has been observed that the addition of MgO enhances the T_g. The rise in T_g with MgO content may be attributed to the greater field strength of Mg²⁺ cation (as compared to Pb²⁺) which leads to the formation of stronger bonds. These glass samples were converted to glass–ceramics by following a two-stage heat treatment schedule. It was observed that there was good correlation between the density and CTE results of the glass–ceramics. The XRD results revealed the formation of tetragonal lead titanate as a major crystalline phase in the glass–ceramics. The addition of MgO to the glass contributes to the formation of MgB₄O₇. The dielectric constant for all the glass–ceramic samples was observed to be higher than that of corresponding glass samples. Further, with addition of MgO the room temperature dielectric constant for glass–ceramic samples increases up to 10 mol% of MgO and then decreases for 15 mol%. It has been further observed that the variation of dielectric constant of glass–ceramic samples with MgO content is exactly opposite to the variation of crystallite size of PbTiO₃ embedded in the glass ceramic-samples.     

Effect of ZnO on the crystallization behavior and properties of SiO2–CaO–Al2O3–Fe2O3 glass-ceramics prepared from simulated secondary slag after reduction of copper slag

The feasibility of preparing low-cost glass-ceramics from Zn-containing dust and secondary molten slag generated during the carbothermal reduction of copper slag was investigated. Analytical-grade agents, such as ZnO, Fe₂O₃, SiO₂, CaO, and Al₂O₃, were used to simulate the dust and secondary slag. The effect of ZnO content on the crystallization behavior, structure, and mechanical properties of the glass-ceramics was investigated through X-ray diffraction analysis, scanning electron microscopy-energy dispersive spectrometry, differential scanning calorimetry, Fourier transform infrared spectroscopy, and Raman spectroscopy. The results showed that with increased ZnO content from 0 to 6 wt%, the crystallization activation energy of base glass increased from 386.05 to 425.89 kJ/mol. Meanwhile, the average value of the crystal growth index increased from 1.91 to 4.10, and the highest crystallization rate of the glass-ceramics increased from about 1.44 to 23.11 mm³/min. The increased ZnO in glass-ceramics promoted the precipitation of gehlenite, but inhibit the crystallization of anorthite. When the ZnO content was 6 wt%, the comprehensive properties of the glass-ceramics were better; the flexural strength, microhardness, volume density, water absorption rate, and open porosity were 58.67 MPa, 738.35 HV, 2.92 g/cm³, 0.44% and 1.27%, respectively.     

Effect of TiO2 on microphase development during phase separation and crystallization in Na2O–B2O3–SiO2 glass system

This study examines the incorporation of TiO₂ into sodium borosilicate glasses and its effect on the formation of glassy and crystalline microphases. Glasses in the composition range: 7Na₂O–23B₂O₃–(70 - X)SiO₂–XTiO₂ (where X = 0–14.6 mol.% TiO₂) which exhibit phase separation were investigated. Raman studies confirm the formation of two different TiO₂ coordinations depending on the molar content of TiO₂. Thermal properties of glasses are unaffected by TiO₂ addition. The domain size of microphase development in TiO₂-containing glass indicates competition between phase separation and crystallization. Enrichment of titanium on the interphase between glassy microphases reduces the mass transfer and consequently limits the growth rate of glassy phases. This competes with the formation of anatase for which a nucleation-controlled mechanism is proposed.     

Effect of Al2O3 content on BaO–Al2O3–B2O3–SiO2 glass sealant for solid oxide fuel cell

The glass structure, wetting behavior and crystallization of BaO–Al₂O₃–B₂O₃–SiO₂ system glass containing 2–10 mol% Al₂O₃ were investigated. The introduction of Al₂O₃ caused the conversion of [BO₃] units and [BO₄] units to each other and it played as glass network former when the content was up to 10 mol%, accompanied by [BO₄] → [BO₃]. The stability of the glass improved first and then decreased as Al₂O₃ increased from 2 to 10 mol%, the glass with 5 mol% Al₂O₃ being the most stable one. The wetting behavior of the glasses indicates that excess Al₂O₃ leads to high sealing temperature. The glass containing 5 mol% Al₂O₃ characterized by a lower sealing temperature is suitable for SOFC sealing. Al₂O₃ improves the crystallization temperature of the glass. The crystal phases in the reheated glasses are mainly composed of Ba₂Si₃O₈, BaSiO₃, BaB₂O₄ and BaAl₂Si₂O₈. Al₂O₃ helps the crystallization of BaSiO₃ and BaAl₂Si₂O₈.     

Investigating the effect of WO3 on the crystallization behavior of SiO2–B2O3 – Al2O3–Na2O – CaO–ZnO high VIS-NIR reflecting glazes

White glass enamels with high solar reflectance and containing different WO₃ concentrations have been prepared and characterized with regard to their optical, mechanical and microstructural characteristics. Upon addition of WO₃ to a glass containing SiO₂, B₂O₃, Al₂O₃, Na₂O, CaO, and ZnO, the crystallization of scheelite follows a crystallization mechanism of bulk type where scheelite grows in one-dimension in a patterned morphology dominated by the heating rate and the concentration of WO₃. Octahedral bipyramids and arrow-like crystals appeared in enamels containing WO₃ concentration above 6%. The presence of scheelite crystals with different orientations also leads to slight variations in hardness and Young modulus thus obtaining Hv values between 8 and 8.8 GPa and E values between 72 and 83 GPa. Similarly, the optical properties such as whiteness, brightness and solar reflectance increase with the presence of scheelite, and the highest solar reflectance occurs for the enamel containing arrow-like and bipyramidal crystals.     

Effect of a Bi–Cr–O synthetic multi-phase on the microstructure and electrical properties of ZnO–Bi2O3 varistor ceramics

ZnO–Bi₂O₃–MnO₂ (ZBM)-based varistors were fabricated via doping a novel synthetic multi-phase (SMP) additive produced by calcining the mixture of 18Bi₂O₃·Cr₂O₃ at a given temperature. The effects of the SMP on the microstructural and electrical properties of ZBM varistors were investigated. It was found that the SMP dopant was a compound crystalline phases including Bi–Cr–O phases (Bi_7.38Cr_0.62O_12+x and CrBi₁₈O₃₀) and small amounts of Bi₂O₃ rather than a synthesized polycrystal. The Bi–Cr–O phases were not emerged for samples with x=1, indicating that the amount of it is tiny and the small Bi₂O₃ may accelerate ZnO grain growth. With more SMP doping (x>1) in the ZBM ceramics, it acted as a barrier inhibiting grain growth. For samples with x=5, excellent electrical properties were obtained: the nonlinear coefficient α increased up to 50.19 corresponding to the highly barrier height of 2.62 eV; the leakage current I_L reduced to 0.3 μA. The dielectric constant ε_a is proportional to the ratio of the grain size d to the thickness of the depletion layer width t, which explained the ε_a increased at f=1 kHz for the samples with x=1 and 5. The improvement of the electrical properties can be explained by the oxygen absorption mechanism.     

Crystallization behavior of BaO–CaO–SiO2–B2O3 glass sealant and adjusting its thermal properties for oxygen transport membrane joining application

In this work, the thermal stability of a BaO–CaO–SiO₂–B₂O₃ glass sealant, named “H”, was investigated by differential scanning calorimetry (DSC). The crystallization behavior of glass H as the sealant matrix was investigated by a combination of experimental X-ray diffraction (XRD) analysis and thermodynamic simulation with the FactSage package. A good agreement was found between the Rietveld refinement of XRD experiments and the FactSage simulation. Particular attention was also given to the influence of the Sr₂SiO₄ filler added to the glass matrix “H” on the thermal expansion and microstructures of glass-Sr₂SiO₄ composites by means of dilatometry and scanning electron microscopy (SEM). The reinforced 20 wt% Sr₂SiO₄ composite (HS2S20) showed excellent properties and, thus, its joining performance was investigated using SrTi_0.75Fe_0.25O_3-δ (STF25) and Aluchrom as promising oxygen transport membrane (OTM) and counterpart, respectively. The joining behaviors were investigated by comparing different joining temperatures. 920 °C is the best joining temperature for HS2S20 sealant.     

Effect of TiO2 on crystallization and mechanical properties of MgO–Al2O3–SiO2 glasses containing P2O5

MgO–Al₂O₃–SiO₂ glass-ceramics have been widely used in military, industrial, and construction applications. The nucleating agent is one of the most important factors in the production of glass-ceramics as it can control the crystallization temperature or the grain size. In this study, we investigated the effect of replacing P₂O₅ with different amounts of TiO₂ on the crystallization, structure, and mechanical properties of an MgO–Al₂O₃–SiO₂ system. The crystallization and microstructure were investigated by differential scanning calorimetry, Raman spectroscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The mechanical properties were investigated by measuring the Vickers hardness, Young's modulus, and fracture toughness. The results showed that adding TiO₂ favored the precipitation of fine grains and significantly increased the Vickers hardness, Young's modulus, and fracture toughness of the glasses. Introducing an appropriate amount of TiO₂ can make a glass structure more compact, promote crystallization, and improve the mechanical properties of MgO–Al₂O₃–SiO₂ glass-ceramics.     

Effect of Ta2O5 addition on the structure,crystallization mechanism,and properties of CaO–B2O3–SiO2 glasses for LTCC applications

CaO–B₂O₃–SiO₂–Ta₂O₅ (CBST) glass-ceramics, with different Ta₂O₅ content, (up to 6 mol%), have been prepared by using glass melt quenching followed by heat treatment between 800 and 880 °C. The Fourier Transform Infrared (FTIR) results showed that the stronger the attraction of Ta⁵⁺ to the oxygens in the BO₃^3? and SiO₃^2? structures, the more easily the B–O and Si–O bonds will be destroyed. The underlying reason is most probably the high field strength of Ta⁵⁺, which results in a weakening of the vibration intensities of the [BO₃] and [SiO₄] units. Moreover, the Differential Scanning Calorimetry (DSC) results showed that the softening point (T_g), crystallization starting temperature (T_c1), and exothermic crystallization peak temperature (T_p1), of the CaSiO₃ phase, shifted to higher values with the addition of Ta₂O₅. Also, the crystallization activation energy (E_a) and the glass stability factor (ΔT) of the CaSiO₃ phase increased, which indicated that the CaSiO₃ phase of the glass became inhibited by the addition of Ta₂O_5. It was, thus, obvious that there was a need of glass characterization. The results of the crystallization kinetics showed that the critical cooling rate decreased with the addition of Ta₂O₅, which indicated that the viscosity of the system had increased. The CBST glass-ceramics, containing 1 mol% Ta₂O_5, that were sintered at 875 °C for 15 min showed excellent dielectric properties: ε_r = 6.22 and tanδ = 1.19 × 10^?3 (1 MHz). To sum up, CaO–B₂O₃–SiO₂–Ta₂O₅ glass-ceramics are potential low temperature co-fired ceramic substrate materials.     

Effect of BaO substitution for CaO on the structural and thermal properties of SiO2–B2O3–Al2O3–CaO–Na2O–P2O5 bioactive glass system used for implant coating applications

The present study replaced 3.30 and 9.00 mol.% BaO for CaO in a SiO₂–B₂O₃–Al₂O₃–CaO–Na₂O–P₂O₅ bioactive glass system used for implant coating applications. Variations of the glass structure, thermal properties, cytotoxicity, and radiopacity of glasses were studied. As demonstrated by the results, upon adding barium oxide to the glass structure, the weight density increased significantly, while a slight decrease in oxygen density was determined. Introducing barium oxide into glass composition did not cause any considerable change in the spectra of FTIR and Raman. It was demonstrated that the amount of bridging oxygen in the glass structure remained quite unaffected. The hot stage microscopy evaluations revealed further shrinkage of barium-containing frits due to lower viscosity and hence, higher viscous flow of these glasses. By substituting barium oxide for calcium oxide and increasing its concentration, the glass transition temperature (T_g) and the dilatometric softening temperature (T_d) decreased, while the thermal expansion coefficient increased. Moreover, upon substituting 9 mol.% barium oxide for calcium oxide, a 30 °C reduction in maximum sintering temperature (T_ms) of the glass was obtained, whereas the shrinkage rate was increased 1.7 times. It was indicated that the sintering process of barium-incorporated glasses would easily proceed without any phase crystallization. The barium-incorporated glasses exhibited more radiopacity. Additionally, no cytotoxic effect was caused by the substitution, and the Ba-containing glasses could be used for biomedical applications and implant coating as well.     

Effect of ZnO on the structural,physio-mechanical properties and thermal shock resistance of Li2O–Al2O3–SiO2 glass-ceramics

The composition of lithium aluminosilicate (LAS) with different zinc oxide-magnesium oxide (ZnO–MgO) contents that ranged from 0 to 1.45 wt percent (wt%) was investigated to determine the thermal shock resistance properties of the glass-ceramics. The LAS glasses were melted in an alumina crucible at 1550 °C for 5 h, and the green compact samples were then heat-treated at 1100 °C for 3.5 h. The presence of zinc oxide (ZnO) in the compositions did not change the major crystal phase of β-spodumene. However, the addition of ZnO shifted the pronounced peak to a lower angle and increased the percentage of crystallinity from 55% to 59%. Additionally, the function of ZnO in LAS glass-ceramics as the network modifier was confirmed through Fourier Transform Infrared Spectroscopy (FTIR) analysis. The physio-mechanical properties were improved when 1.45 wt% ZnO was added to the LAS glass-ceramics. The results showed increased density (2.42 g/cm³), low porosity (0.85%), high flexural strength (125.23 MPa), and low coefficient of thermal expansion (25–800 °C) (CTE_{(25–800 °C)}) value of 1.73 × 10^?6 °C^?1. Meanwhile, the thermal shock resistance properties evaluation of the LAS glass-ceramics at different ZnO contents were conducted at different thermal shock temperatures of 200 °C, 500 °C, and 800 °C. The critical temperature of the LAS specimens with 1.45 wt% ZnO demonstrated the ability to withstand a thermal shock at 800 °C while preserving 87% of their initial strength of 108.40 MPa, exemplifying the best LAS glass-ceramics properties for rapid high-temperature change applications.     

Influence of nucleating agents on crystallization and electrical properties of SiO2–MgO–MgF2–K2O mica glass-ceramics

The effects of adding ZrO₂ and TiO₂ at the expense of MgF₂ on the crystallization, microstructure, mechanical properties, thermal properties and electrical properties of mica glass-ceramics based on the SiO₂–MgO–MgF₂–K₂O system were investigated by the differential scanning calorimetry (DSC), X-ray powder diffraction (XRD), scanning electron microscopy (SEM), microhardness tester and resistivity tester. The electrical properties were discussed emphatically. The results showed that the additions of ZrO₂ and/or TiO₂ at the expense of MgF₂ effectively increase the viscosity, the glass transition temperatures (T_g) and the crystallization temperatures (T_p) of the glasses. The crystallization activation energy (E_c) of the amorphous glasses varied with the nucleating agents was discussed in depth. It was discovered that the nucleating agents had no effect on the crystal phase type but had a certain effect on the crystallinity and microstructure. Tetrasilicic fluoromica and enstatite were precipitated at different crystallization temperatures. Due to the non-stoichiometric ratio of tetrasilicic fluoromica crystal, the prepared glass-ceramics had high dielectric constant (24.4–34.3) and volume resistivity (>2 × 10¹¹ Ω cm) at 25 ^°C, and the dielectric loss was almost zero.