Effect of properties and crystallization behavior of BaO–ZnO–B2O3–SiO2 glass on the electrical conductivity of Cu paste

The extensive application of multilayer ceramic capacitors provides an attractive development for terminal electrode pastes. However, the growing requirement for advanced glass materials used in terminal electrode pastes is substantiated. Therefore, to advance the development of electrode pastes, better development and deeper exploration of glass powder are required. Here, a series of BaO–ZnO–B₂O₃–SiO₂ (BZBS) glasses were prepared by melt-quenching technique, which are used to investigate the effect of the introduction of BaO on structure and properties of the ZnO–B₂O₃–SiO₂ (ZBS) glass. With the introduction of BaO, the relative amount of [BO₄] was much less, which made the glass network structure loosen, decreased the glass transition temperature (T_g) and increased the coefficient of thermal expansion of the glass. The decreasing contact angle was observed on the surface of a barium titanate (BaTiO₃) substrate. When the BaO content was around 3–7 mol%, the stability of ZBS glass frit could be strengthened by inhibiting the precipitation of Zn₂SiO₄ crystal. In addition, to further characterize the effect of glass on terminal electrode paste, BZBS glass powder was adopted to prepare copper electrode paste, which was printed on the BaTiO₃ substrate and subsequently fired at 800°C for 10 min. With the related copper paste containing ZBS glass doped with 7 mol% BaO, the optimum value of acid resistance and sheet resistance (1.99 mΩ) were exhibited, at which the coated copper paste formed a dense conducting layer.     

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.     

Modification of glass network and crystallization of CaO–Al2O3–MgO–SiO2 based glass ceramics with addition of iron oxide

Modification of glass network and crystallization process of a CaO–Al₂O₃–MgO–SiO₂ (CAMS) based glass ceramic to form diopside through addition of iron oxide were investigated using differential thermal analysis (DTA), Raman spectrum, X-ray diffraction, SEM and EBSD techniques. The experimental results showed that addition of Fe₂O₃ led to remarkable reductions in both the glass transition temperature (Tg) and crystallization temperature (Tp) of the CAMS glass ceramic. At addition level below 5 wt%, the Tg and Tp temperatures were 651°C and 903°C, respectively, and the crystallization only occurred on the surface of the glass ceramic samples. Increasing the addition level to 10 wt% and 15 wt%, not only led to reduction in the Tg and Tp temperatures to 643-641°C and 892-876°C, respectively, but also promoted the formation of crystalline diopside throughout the CAMS samples. Based on the results of Raman spectrums, it was confirmed that Fe₂O₃ addition reduced the strength of glass connection as a result of chemical reactions between the isolated Si–O tetrahedron and Fe³⁺ ion, forming Fe³⁺O₄–SiO₄, which can be regarded as Q₂ unit. And this is the first experimental evidence that proving the approach of Fe³⁺ mending glass network. Microstructural examination also identified the formation of large numbers of spherical Fe-enriched regions within the CAMS glass matrix as a result of the amorphous phase separation due to the Fe₂O₃ addition. The interfaces between the Fe-enriched regions and the glass matrix acted as preferred nucleation sites for the diopside, facilitating the crystallization. Crystallographic analysis using EBSD technique determined the <001> as the most favorite growth direction for the diopside crystals in the CAMS based glass ceramic.     

Application of BaO–CaO–Al2O3–B2O3–SiO2 glass–ceramic seals in large size planar IT-SOFC

BaO–CaO–Al₂O₃–B₂O₃–SiO₂ (BCAS) glass–ceramics can be used as sealant for large size planar anode-supported solid oxide fuel cells (SOFCs). BCAS glass–ceramics after heat treatment for different times were characterized by means of thermal dilatometer, X-ray diffraction (XRD) and scanning electron microscopy (SEM). The results show that the coefficients of thermal expansion (CTE) of BCAS glass–ceramics are 11.4×10⁻⁶ K⁻¹, 11.3×10⁻⁶ K⁻¹ and 11.2×10⁻⁶ K⁻¹ after heated at 750 °C for 0 h, 50 h, and 100 h, respectively. The CTE of BCAS matches that of YSZ, Ni–YSZ and the interconnection of SOFC. Needle-like barium silicate, barium calcium silicate and hexacelsian are crystallized in the BCAS glass after heat-treatment for above 50 h at 750 °C. The glass–ceramics green tape prepared by aqueous tape casting can be directly applied in sealing the cell of SOFCs with 10 cm×10 cm. The open circuit voltage (OCV) of the cell keeps 1.19 V after running for 280 h at 750 °C and thermal cycling 10 times from 750 °C to room temperature. The maximum power density is 0.42 W/cm² using pure H₂ as fuel and air as oxidation gas. SEM images show no cracks or pores exist in the interface of BCAS glass–ceramics and the cell.     

Thermodynamics and crystallization kinetics of REEs in CaO–SiO2–Ce2O3 system

Rare earth elements (REEs) have become increasingly important as ceramic materials. The RE-bearing slags contain massive REEs resources, whereas the lack of thermodynamic and kinetic data of REEs has brought great difficulties to efficient recovery of REEs from RE-bearing slags and the application in ceramics. According to the compositions of the RE-bearing slags in industrial production, the isothermal phase equilibria of CaO–SiO₂–Ce₂O₃ system at 1500°C and 1300°C were constructed by means of liquid-quenching method combined with a series of analyses, which provides the thermodynamic data for the equilibria of REEs. On this basis, the crystallization behaviors of the RE phase (Ce_9.33−xCa_x(SiO₄)₆O_2−0.5x) was investigated, and the temperature range in which the RE phase crystallized singly in RE-bearing slags with a selected compositions was acquired. CCT and TTT diagrams for CaO–SiO₂–Ce₂O₃ system were established to characterize the crystallization kinetics of the RE phase, and the favorable conditions for its crystallization and growth in RE-bearing slags were determined. In this study, the complete thermodynamic and kinetic basic data of REEs in CaO–SiO₂–Ce₂O₃ system are provided for RE-bearing slags.     

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.     

Bioactivity investigation of glass and glass ceramics in Li2O–SiO2–CaO–P2O5–CaF2 system

Abstract

Glass samples in Li₂O–SiO₂–CaO–P₂O₅–CaF₂ system with different contents of P₂O₅, CaO and CaF₂ in relative ratios responded to fluoroapatite (FA) composition (referred to P₂O₅ addition) have been prepared and heat treated at 550 and 750°C to obtain glass ceramics. Bioactivity of all samples has been proved in vitro by the presence of new layer of apatite-like phases formed after soaking in simulated body fluid (SBF). The development and the apatitic character of created layers have been demonstrated by Fourier transform infrared analysis. Scanning electron microscopy and electron probe microanalysis have demonstrated that the density and the thickness of new layer depend on P₂O₅ content, crystallisation temperature and immersion time. The bioactivity has been enhanced by P₂O₅ addition as well in the case of the base glasses as in the case of glass ceramics. The additional heat treatment appeared to inhibit the bioactive behaviour, though the longer SBF acting leads to the additional formation of apatite-like layer. The mechanical properties, expressed as Vicker hardness, have been found higher and increasing with P₂O₅ in glass ceramics treated at 750°C comparatively with base glass samples and the highest value of 7˙37 GPa has been achieved by 14 wt-%P₂O₅ addition. The same content of P₂O₅ in glass ceramics heat treated at 550°C resulted in a decrease in hardness to a minimum value from all samples. The increase and decrease in hardness responded to development and suppression of crystallisation respectively. The inhibition of crystallisation has been affected by the presence of 'amorphous' FA according to X-ray diffraction and differential thermal analysis results.     

Li2O—BaO—SiO2系统电极玻璃的研究

测定了Ｌｉ２Ｏ－ＢａＯ－ＳｉＯ２系统的玻璃形成范围和结晶相，得到了等水溶性和等膨胀系统曲线。这些图解指出高化学稳定性和低膨胀系数仅限于高ＳｉＯ２含量区，增加Ｌｉ２Ｏ含量，化学稳定性很快变坏。此外，还研究了玻璃电极的电阻和成分之间的关系。     

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.     

Crystallisation in SiO2 –Al 2 O 3 –ZnO– TiO 2 glass: process mechanism

Abstract

Devitrification of a frit based on the oxide system SiO₂–Al₂O₃–ZnO, using bulk glass as well as powdered glass samples with different particle sizes was studied. The following major crystalline phases were identified: gahnite (ZnAl₂O₄ ), α-quartz, cristobalite, and a solid solution exhibiting the β-quartz structure, which contained SiO₂ , Al₂O₃ , and ZnO and whose composition varied with temperature. Depending on the size of the glass (frit) samples, gahnite was found to devitrify directly from the initial glassy phase or from the solid solution with a β-quartz structure, which appeared to act as a precursor.     

Surface and bulk crystallization in Nd2O3–Al2O3–SiO2–TiO2 glasses

Neodymium aluminosilicate (Nd₂O₃–Al₂O₃–SiO₂; NdAS) glasses have been investigated for the effect of concentration of TiO₂ on the crystallization mechanism and for the effect of surface condition on crystal growth. NdAS glasses with 0–10 wt.% TiO₂ were heat-treated for nucleation and crystal growth and were examined for phase separation and morphology of surface crystals as well as for crystal growth rate. All the glasses exhibit surface crystallization, however, the glass having 8 wt.% TiO₂ also exhibits internal crystallization after a two-stage heat treatment. Surface crystallization was dependent on the condition of the glass surface and the amount of TiO₂. The crystal growth on the cut surface was faster than on the fractured surface and the growth rate in surface increased with increasing TiO₂. The phase separation found in NdAS glasses containing above 8 wt.% TiO₂, was confirmed to be an important factor controlling the internal crystallization process in Nd₂O₃–Al₂O₃–SiO₂–TiO₂ glasses.     

Low temperature production of glass ceramics in the anorthite–diopside system via sintering and crystallization of glass powder compacts

The production of glass ceramics (GCs) with theoretical anorthite–diopside (An–Di) weight ratios of 60/40, 50/50 and 45/55 via sintering and crystallization of glass powder compacts was investigated at different temperatures between 800 and 950 °C. The investigated compositions are located in the cross-section of the ternary fluorapatite–An–Di system close to An–Di binary joint, with constant fluorapatite content of 4.8 wt.%. Two different groups of glass powders, with mean particle size of 2 and 10 μm, were used. The experimental results showed that sintering is almost complete at 800 °C, preceding crystallization, which takes place via surface crystallization mechanism. The properties values of the produced GCs, which are the best for the composition close to An–Di eutectic line, are discussed with respect to the evolution of crystalline phases and the microstructure over increasing firing temperature. Under the technology perspective, the investigated processing route is significantly superior in comparison to the attempts reported in earlier studies.     

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.     

Crystallisation and characterisation of dielectric glass ceramics in Li2O–Al2O3–SiO2 system

Abstract

Glass ceramics in the Li₂O–Al₂O₃–SiO₂ system have been synthesised to produce bulk materials grown in a glass phase via quenching followed by controlled crystallisation. The crystallisation and microstructure of Li₂O–Al₂O₃–SiO₂ (LAS) glass–ceramic with nucleating agents (B₂O₃ and/or P₂O₅) are investigated by differential thermal analysis, X-ray diffraction and scanning electron microscopy and the effects of B₂O₃ and P₂O₅ on the crystallisation of LAS glass are also analysed. The introduction of both B₂O₃ and P₂O₅ promotes the crystallisation of LAS glass by decreasing the crystallisation temperature and adjusting the crystallisation kinetic parameters, allows a direct formation of β spodumene phase and as a result, increases the crystallinity of the LAS glass ceramic. Microstructural observations show that the randomly oriented, nanometre sized crystalline is found with residual glass concentrated at crystallite boundaries. Furthermore, it is interesting that codoping of B₂O₃ and P₂O₅ creates not much effect on the crystallisation temperature. The dielectric properties of the glass–ceramics formed through controlled crystallisation have a strong dependence on the phases that are developed during heat treatment. The dielectric constant is continuously increased and the dielectric loss is decreased with addition of additives where mobile alkali metal ions (e.g. Li⁺) are incorporated in a crystal phase and minimise the residual glass phase.     

BaO—SrO—TiO2—SiO2系统压电微晶玻璃的研究

本文采用高梯温定向微晶化工艺制备了BaO-SrO-TiO_2-SiO_2系统晶粒定向微晶玻璃压电材料。运用差热分析法研究了该系统玻璃表面定向析晶机理,讨论了组成、微观结构与压电性能的关系。该材料无老化、去极化现象,介电常数ε_(33)~T/ε_0=10—12,压电系数d_(33)=10—16×10~(-12)C/N,压电优值因子d_h·g_(?)=1600—2600×10~(-15)m~2/N,因此,该材料属新型复合压电材料,特别适用于水听器应用。     

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.     

Preparation and characterization of crednerite glass–ceramics in the MnO·CuO·SiO2 system

Nanoscale crednerite (CuMnO₂) was prepared in the system MnO·CuO·SiO₂, using glass–ceramics technique for the first time. Based on obtained data from differential thermal analysis (DTA), the prepared samples were heat-treated at 700 and 800 °C for 2 h. The presence of crystalline phases after and before heat treatment was investigated by X-ray diffraction analysis. Crystallization of crednerite (CuMnO₂), manganese silicate (Mn₂SiO₄) and traces of cuprite (Cu₂O) and cristobalite (SiO₂) phases were recognized. Transmission electron microscopy showed nanoscale crystals in the range 5–10 nm. The prepared glass–ceramics showed ferrimagnetic properties with wide range coercivity from 53 to 2217 Hci and magnetization saturation from 0.21708 to 1.2 emu/g. From IR reflection data; the reflection intensity of the light is high in the range of orange–red color and violet–blue colors and low in the range of green color.