Viscous behaviour of Bi2O3–B2O3–ZnO glass composites with ceramic fillers

Abstract

Variation in the viscous flow behaviour, nature and extent of glass fluidity in glass/filler composites are addressed with respect to various factors such as filler type, content, size, density and migration distance. The characterisation of a glass (Bi₂O₃–B₂O₃–ZnO) composite consisting of two different fillers (cordierite and willemite) was determined using hot stage microscopy, a differential scanning calorimeter and a flow button test. The microstructure was analysed using a scanning electron microscope. The apparent viscosity of the glass composites increased on increasing concentration and density of the filler. The variation in the viscosity is due to the diffusion of the glass matrix through channels in the cordierite filler of the composite. Based on the calculated migration distance of the filler in the glass matrix, the present work suggests that the interfacial behaviour and the density of the filler play a significant role in determining the viscous flow of the glass composites.     

Large third-order optical nonlinearity of ZnO–Bi2O3–B2O3 glass–ceramic containing Bi2ZnB2O7 nanocrystals

Homogeneous transparent optical glass–ceramics precipitated with unique nonlinear crystals are promising materials for photonic applications. We have utilized heat treatment method to prepare transparent ZnO–Bi₂O₃–B₂O₃ glass–ceramic containing Bi₂ZnB₂O₇ nonlinear nanocrystals. A large third-order nonlinear susceptibility χ⁽³⁾ of glass–ceramic is measured by Z-scan technique, which mainly attributed to unique [BiO₆] and [B₂O₅] units in Bi₂ZnB₂O₇ crystal structure and the quantum size effect of nanoparticles. The discovery is of great potential in the application of nonlinear optical integrated devices.     

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.     

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.     

Antibacterial and photocatalytic active transparent TiO2 crystallized CaO–BaO–B2O3–Al2O3–TiO2–ZnO glass nanocomposites

Transparent TiO₂ crystallized 5CaO–10BaO–65B₂O₃–Al₂O₃–20TiO₂–10ZnO (CBBATZ) glass nanocomposites were fabricated using melt-quenching technique followed by specific heat treatments. As-quenched glass samples were provided three different heat treatments at 630°C for 3, 5, and 10 hours in order to obtain different amounts of TiO₂ nanocrystals in the glass. The presence of rutile phase of TiO₂ nanocrystals in glass was confirmed by X-ray diffraction. The glass nanocomposite heat treated for 10 hours showed a hydrophobic nature with contact angle of 90.90°. Contact angle decreased from 90.90 to 22.20°, when irradiated under ultraviolet (UV) radiation for 45 minutes. This photoinduced hydrophilicity showed a photocatalytic and self-cleaning properties of glass nanocomposite. During photocatalytic ink test, the maximum change in color of Resurin (Rz) ink and 60% degradation in absorbance of ink within 150 minutes under UV radiation were found for glass nanocomposite heat treated at 10 hours. Also, 78% degradation in absorbance of methylene blue dye (pollutant) within 180 minutes under UV irradiation was found for glass naocomposite heat-treated at 10 hours. Antibacterial performance of transparent glass nanocomposite against Escherichia coli was evaluated as well. More than 95% of the bacterial cells were degraded with glass nanocomposite heat-treated at 10 hours. CBBATZ glass nanocomposite found to impart the antibacterial effect through generation of reactive oxygen species (ROS) in aqueous medium. ROS species which was confirmed in the bacterial cell through intracellular ROS generation kit. During evaluation of mechanical properties using nanoindentation technique, the values of hardness and reduced modulus increased by ~26% and 10%, respectively, for glass nanocomposite heat-treated at 10 hours as compared to as-quenched glass.     

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.     

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.     

Joining MgAl2O4 ceramics using ZnO–Al2O3–SiO2 glass ceramic with precipitated ZnAl2O4

In this work, crystallization, thermal expansion and wetting behavior of ZnO–Al₂O₃–SiO₂ (ZAS) glass were first investigated. The results showed that ZnAl₂O₄ was precipitated from ZAS glass after crystallization treatment. Crystallization increased the coefficient of thermal expansion (CTE) of ZAS glass ceramic due to the high CTE of ZnAl₂O₄. In addition, ZAS glass exhibited good wettability on the surface of MgAl₂O₄ substrate. On this basis, ZAS glass was used to join MgAl₂O₄ ceramic, and the microstructure and mechanical properties of joints obtained with different cooling methods were investigated. The flexural strength of joints was related to the content of ZnAl₂O₄ crystals in the brazing seams. Additional nucleation and crystallization treatment during cooling process improved the crystallinity of brazing seam, resulting in better matching of the CTE of brazing seam with that of MgAl₂O₄ ceramic. The maximum flexural strength of joints reached 201 MPa, which was equivalent to the strength of MgAl₂O₄ ceramic.     

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.     

Effects of La2O3–B2O3 on the flexural strength and microwave dielectric properties of low temperature co-fired CaO–B2O3–SiO2 glass–ceramic

The La₂O₃–B₂O₃ (LB) addition, synthesized using the traditional solid-state reaction process, was chosen as a novel sintering aid of the low temperature co-fired CaO–B₂O₃–SiO₂ (CBS) glass–ceramic. The effects of LB on the flexural strength and microwave dielectric properties have been investigated. The LB addition promotes the crystallization of the CaSiO₃ but high amount of the LB addition leads to the formation of more pores. The CBS sample with 4 wt% LB addition sintered at 850 °C for 15 min shows good properties: flexural strength = 193 MPa, ?_r = 6.26 and loss = 9.96 × 10^?4 (10 GHz).     

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.     

Growth mechanism of house-of-cards aggregates of alumina platelets containing Na2O–B2O3–SiO2 glass flux

Porous alumina bodies, intended for use as heat-insulating refractory materials, were fabricated by a high-temperature evaporation method and characterized. A series of flux systems was used by adding a third component to Na₂O–B₂O₃ glass in addition to boric acid and sodium carbonate. When SiO₂ was added as the third component, the primary alumina particles grew anisotropically, forming a plate-like shape, and the house-of-cards structure was self-organized. The anisotropic growth of alumina platelets was promoted by the solid solution of Si⁴⁺ ions in the flux on the α-Al₂O₃ surface. Furthermore, the bonding between the alumina platelets was strengthened by the high-SiO₂-concentration flux. Our typical alumina body had a porosity of 71.5%, a compressive strength of 3.7 MPa, a shrinkage rate of 2.6% when reheated at 1700 °C, and a thermal conductivity of 0.24 W m⁻¹•K⁻¹ at 1000 °C. Thus, the present alumina bodies are expected to find application as high-performance heat-insulating refractory materials.     

Microstructure evolution during air bonding of Al2O3 to Al2O3 joints using bismuth–borate–zinc glass

Alumina ceramics with 95 wt.% purity were sealed together using a bismuth based glass, 40Bi₂O₃–40B₂O₃–20ZnO (mol.%). The wettability of the glass on the Al₂O₃ substrate was investigated. The results showed a contact angle of ≤36.5° was achieved when the temperature was ≥630 °C. Subsequently, sealing cycles were performed at temperatures of 520–700 °C for 30 min. The dependence of microstructure evolution of the joints on temperature was investigated. Bi₂₄B₂O₃₉ was detected to be the product in the joints sealed at 530–580 °C, while ZnAl₂O₄ was identified to be the main product when sealing at temperature of ≥650 °C due to the reaction between the Al₂O₃ substrate and ZnO from the glass. The influence of dwelling time at 700 °C on microstructure evolution of the joints was also studied. The results showed that the size of ZnAl₂O₄ increased with increasing holding time.     

Effect of P2O5 on evolution of microstructure of MgO–Al2O3–SiO2 glass ceramics

Abstract

MgO–Al₂O₃–SiO₂ (MAS) cordierite based glass ceramics were prepared by volume crystallisation. X-ray diffraction, Scanning electron microscopy and Energy diffraction scanning were used to investigate crystallisation behaviour and the influence of P₂O₅ on microstructure MAS based glass ceramics. The results showed that P⁵⁺ could promote the phase separation of MAS glass and that the glass was divided into two areas, such as Mg₄Al₂Ti₉O₂₅ and the containing P⁵⁺ area at <900°C. Mg₄Al₂Ti₉O₂₅ and Mg₃(PO₄)₂ in the area were both advantageous to the precipitation of μ cordierite, which further transformed to α cordierite due to P⁵⁺ in the residual glassy phase. However, P⁵⁺ inhibited the presence of cordierite when the heat treatment temperature was >900°C.     

Pressure-less joining of SiCf/SiC composites by Y2O3–Al2O3–SiO2 glass: Microstructure and properties

In this study, Y₂O₃–Al₂O₃–SiO₂ (YAS) glass was prepared from Y₂O₃, Al₂O₃, and SiO₂ micron powders. Thermal expansion coefficient of as-obtained YAS glass was about 3.9 × 10⁻⁶, matching-well with that of SiC_f/SiC composites. SiC_f/SiC composites were then brazed under pressure-less state by YAS glass and effects of brazing temperature on microstructures and properties of resulting joints were investigated. The results showed that glass powder in brazed seam sintered and precipitated yttrium disilicate, cristobalite, and mullite crystals after heat treatment. With the increase in temperature, joint layer gradually densified and got tightly bonded to SiC_f/SiC composite. The optimal brazing parameter was recorded as 1400 °C/30 min and shear strength of the joint was 51.7 MPa. Formation mechanism of glass-ceramic joints was proposed based on combined analysis of microstructure and fracture morphology of joints brazed at different temperatures. Thermal shock resistance testing of joints was also carried out, which depicted decline in shear strength with the increase of thermal shock times. The strength of the joint after three successive thermal shock cycles at 1200 °C was 35.6 MPa, equivalent to 69% of that without thermal shock.     

The formation mechanism of pores and unbonding in the Al2O3/Al2O3 joints brazed by 50Bi2O3–35B2O3–15ZnO glass

50Bi₂O₃–35B₂O₃–15ZnO (mol. %) glass referred to as Bi50 glass, was used to braze Al₂O₃ ceramics. The phase transformations and wettability of the Bi50 glass on Al₂O₃ substrates at different temperatures were investigated. The results showed that the chemical compatibility of Bi50 glass and Al₂O₃ substrates at 650 °C was excellent. However, Al₂O₃/Al₂O₃ joints having a considerable volume fraction of pores and unbonding were obtained when the joining procedures were carried out by a one-step brazing method. Based on the experiments and simulation results, the prime determinants responsible for the presence of the pores and unbonding within the brazing joints can be divided into two aspects: (i) the intrinsic causes leading to the formation of closed pores (ii) the external factors causing the failure of pores and glass separation. Ultimately, an advanced joining procedure named two-step brazing was proposed, and joints nearly free of defects were acquired.     

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.     

Colloidal processing of Al2O3-doped zirconia ceramics with CaO–P2O5–SiO2 glass as additive

Well-dispersed concentrated aqueous suspensions of Al₂O₃-doped Y-TZP (AY-TZP), AY-TZP with 5.4 vol% of CaO–P₂O₅–SiO₂ (CaPSi) glass (AY-TZP5) and 10.5 vol% CaPSi glass (AY-TZP10), with ammonium polyacrylate (NH₄PA) dispersant were prepared to produce slip cast compacts. The rheological properties of 35 and 40 vol% slips were studied. The densification, microstructure as well as hardness and fracture toughness were investigated as a function of CaPSi glass content at 1300°C-1500°C. The optimum NH₄PA concentration of 35 vol% AY-TZP5 and AY-TZP10 slips at pH ~9 was found to be about 43% and 67% greater than that of AY-TZP slips; this behavior was related to the greater amounts of Ca²⁺ ions leached out from the CaPSi glass surface. The viscosity of stabilized 40 vol% slips with NH₄PA attained a minimum value at 5.4 vol% CaPSi glass addition, and resulted in a more dense packing of cast samples. AY-TZP5 can be sintered at a lower temperature (1300°C) compared to that of AY-TZP. AY-TZP5 exhibited a fine microstructure of tetragonal ZrO₂ (grain sizes below 0.3 µm), and ZrSiO₄–Ca₂P₂O₇ particles homogeneously distributed within the zirconia matrix. It presented similar fracture toughness and a slightly lower hardness compared to those of AY-TZP.