The effect of B2O3, PbO and P2O5 on the sintering and machinability of fluormica glass–ceramics

Sintering, crystallization and machinability behavior of the SiO₂–Al₂O₃–MgO–K₂O–B₂O₃–F glasses were investigated. The optimum fluormica glass–ceramics with desirable sintering behavior and machinability were obtained by addition of PbO and P₂O₅ glass formers. Various parameters, e.g. the morphology of the mica crystal, relative intensity of the mica phase, the particle size distribution of chips obtained by drilling, microhardness, and the strength differences of glass–ceramics before and after drilling (Δσ) were investigated and compared with naked eye experiments.     

Enhancement of photoluminescence intensity of sintered CaAlSiN3:Eu2+ red phosphor-bismuthate glass composites

Wavelength converters in white light-emitting diodes are usually made by sintering of phosphor-glass powder compacts. An issue is that the sintering process usually results in the reduction of phosphor amount. In the present study, composites containing CaAlSiN₃:Eu²⁺ red phosphor and Bi₂O₃-B₂O₃-ZnO-Sb₂O₅ glass were fabricated by sintering method. Influences of CaAlSiN₃:Eu²⁺ phosphor content (10 vol%–30 vol%) and sintering temperature (410–430°C) on the residual amount of the phosphor phase and the resulting luminescence intensity of the composites were investigated. The change of CaAlSiN₃:Eu²⁺ content due to sintering was analyzed by X-ray diffraction. The interdiffusion between the CaAlSiN₃:Eu²⁺ and glass matrix was examine by scanning electron microscope equipped with energy dispersive X-ray spectrometry. This paper focuses on the change of luminescence intensity after sintering. It was found that although the content of phosphor CaAlSiN₃:Eu²⁺ reduces after sintering; the luminescent intensity of the composites anomalously increases. The optimum luminescence intensity is 14% higher than that of the as-mixed, unfired powder. It is proposed that the incorporation of Bi³⁺ ions from the glass matrix into the phosphor CaAlSiN₃:Eu²⁺ during sintering improves the luminescence ability of the phosphor particles.     

Preparation of machinable bioactive mica diopside-fluoroapatite glass-ceramics

Abstract

A fluorphlogopite based glass powder was added to a bioactive glass-ceramic in the system CaO-MgO-P₂O₅ (Fe₂O₃)-SiO₂ in order to improve its machinability. The sinterability of compacted mixtures, their crystallisation behaviour during sintering and their mechanical properties were evaluated and compared with the extreme ends compounds. According to results, fluoroapatite crystallised as a new phase only in the mixtures of the two glasses, its constituents originated by counter diffusion of two glasses components. Fracture toughness and microhardness of the best sample were higher than twice of the fluorphlogopite glass-ceramic composition. The machinability of samples was evaluated by naked eye observation and determination of brittleness factor.     

Influence of nucleation agents on crystallization and machinability of mica glass–ceramics

Effects of ZrO₂, La₂O₃, CeO₂, Yb₂O₃ and V₂O₅ on the crystallization kinetics, microstructure and mechanical properties of mica glass–ceramics were investigated by the differential scanning calorimetry (DSC), X-ray diffractometry (XRD), scanning electron microscopy (SEM) and microhardness tester. Results show that bulk crystallization can be obtained by introducing proper nucleation agents into the glass. Both Ozawa method and Kissinger method are suitable for analyzing the crystallization kinetics of mica glass–ceramic. The addition of nucleation agents has little influence on the value of n, keeping two-dimensional crystal growth mechanism. ZrO₂ and V₂O₅ are best nucleation agents in mica system. The increase of crystallization temperature is helpful for the increase of aspect ratio, and the microstructure of the glass–ceramics becomes interconnected, which contributes the improvement of the machinability of the glass–ceramics. Microhardness (H_v), cutting energy (μ¹) and machinability parameter (m) can be used for estimating the machinability of mica glass–ceramics.     

Anomalous enhancement of photoluminescence intensity of sintered YAG:Ce particles‐embedded glasses

For high‐power white LED applications, YAG:Ce‐based yellow phosphors were embedded in a low‐T_g Bi₂O₃–B₂O₅–ZnO–Sb₂O₅ glass by sintering route. Effects of sintering temperature (325‐390°C) on the microstructure and photoluminescence properties were investigated. X‐ray diffraction was used to measure the retained fraction of YAG:Ce phase after sintering. Scanning electron microscope and transmission electron microscope, equipped with energy‐dispersive X‐ray spectrometry, were used to examine the microstructure, including the element distribution across the phosphor–glass interface. Photoluminescence properties of the samples before and after sintering were compared. With the increasing sintering temperature, the retained fraction of YAG:Ce decreased from 83.3% to 82%. This effect tends to reduce the luminescence intensity of the samples after sintering. The increasing sintering temperature also enhances the diffusion of cations (esp. Bi) from glass matrix to YAG:Ce. This effect tends to increase the luminescence intensity of the YAG:Ce particles after sintering. When the sintering temperature was lower (325°C), the effect of YAG:Ce loss was dominant, thus the luminescence intensity was reduced after sintering. When the sintering temperature was higher (350‐390°C), the effect of solute dissolution was dominant, resulting in luminescence intensity anomalously higher than that before sintering. Similar result has not been reported in literatures. The maximum luminescence intensity of the sintered samples is 1.57 times as high as that of the samples before sintering.     

Lithium Disilicate Glass‐Ceramics by Heat Treatment of Lithium Metasilicate Glass‐Ceramics Obtained by Hot Pressing

Lithium disilicate glass‐ceramics are widely used as dental ceramics due to their machinability and translucency. In this study, lithium disilicate glass‐ceramic was fabricated through heat treatment of lithium metasilicate glass‐ceramics obtained by hot pressing of glass powder composed of SiO₂–Li₂O–P₂O₅–ZrO₂–Al₂O₃–K₂O–CeO₂ at low temperature. The crystalline phase, microstructure, and mechanical properties were investigated. The results indicated that lithium metasilicate glass‐ceramic with a relative density of higher than 99% was obtained after hot pressing, and glass‐ceramic with interlocked rod‐like Li₂Si₂O₅ crystals and good flexural strength (338 ± 20 MPa) was successfully obtained through heat treatment. The two‐step method was believed to be feasible in tailoring the microstructure and mechanical properties of lithium disilicate glass‐ceramics.     

Microstructure and mechanical properties of dental 3Y-TZP ceramics by using CaO-P2O5 glass as additive

This study investigated the effects of glass frits on the sintering and mechanical properties of dental 3Y-TZP ceramics. The glass frits, which consisted of MgO, CaO, Al₂O₃, SiO₂, and P₂O₅, were selected to lower the sintering temperature of zirconia via liquid phase sintering.The results of the experiment showed that these glass frit additives neither destroy the stability of the high temperature t-phase nor induce grain growth. All the mechanical properties and the relative densities were strongly correlated with the addition of glass frits. At lower sintering temperatures, the presence of glass additives resulted in an increase in mechanical properties. At higher sintering temperatures, the presence of glass additives decreased the mechanical properties.     

Influence of Al2O3 and B2O3 on Sintering and Crystallization of Lithium Silicate Glass System

This article reports on the effect of Al₂O₃ and B₂O₃ added as dopants on the preparation of glass‐ceramics (GCs) belonging to the lithium silicate glass system. The GCs are prepared by sintering route using glass powders. The reasons for the crystallization of the metastable crystalline phase lithium metasilicate (LS) are discussed and the impact of the dopants on the thermodynamics and kinetics of crystallization is investigated. The addition of dopants modifies the thermodynamic equilibrium of the system and this change is mainly entropy driven and also slowdown the kinetics of crystallization. Differential thermal analysis and hot‐stage microscopy are employed to investigate the glass‐forming ability, sintering, and crystallization behavior of the studied glasses. The crystalline phase assemblage studied under nonisothermal heating conditions in the temperature range of 800°C–900°C in air. Well sintered and dense glass‐ceramics are obtained after sintering of glass powders at 850°C–900°C for 1 h featuring crystalline phase assemblage dominated by lithium disilicate (LS₂).     

Effect of Al2O3 and K2O content on structure,properties and devitrification of glasses in the Li2O–SiO2 system

The effect of Al₂O₃ and K₂O content on structure, sintering and devitrification behaviour of glasses in the Li₂O–SiO₂ system along with the properties of the resultant glass–ceramics (GCs) was investigated. Glasses containing Al₂O₃ and K₂O and featuring SiO₂/Li₂O molar ratios (3.13–4.88) far beyond that of lithium disilicate (Li₂Si₂O₅) stoichiometry were produced by conventional melt-quenching technique along with a bicomponent glass with a composition 23Li₂O–77SiO₂ (mol.%) (L₂₃S₇₇). The GCs were produced through two different methods: (a) nucleation and crystallization of monolithic bulk glass, (b) sintering and crystallization of glass powder compacts.Scanning electron microscopy (SEM) examination of as cast non-annealed monolithic glasses revealed precipitation of nanosize droplet phase in glassy matrices suggesting the occurrence of phase separation in all investigated compositions. The extent of segregation, as judged from the mean droplet diameter and the packing density of droplet phase, decreased with increasing Al₂O₃ and K₂O content in the glasses. The crystallization of glasses richer in Al₂O₃ and K₂O was dominated by surface nucleation leading to crystallization of lithium metasilicate (Li₂SiO₃) within the temperature range of 550–900 °C. On the other hand, the glass with lowest amount of Al₂O₃ and K₂O and glass L₂₃S₇₇ were prone to volume nucleation and crystallization, resulting in formation of Li₂Si₂O₅ within the temperature interval of 650–800 °C.Sintering and crystallization behaviour of glass powders was followed by hot stage microscopy (HSM) and differential thermal analysis (DTA), respectively. GCs from composition L₂₃S₇₇ demonstrated high fragility along with low flexural strength and density. The addition of Al₂O₃ and K₂O to Li₂O–SiO₂ system resulted in improved densification and mechanical strength.     

The role of K2O on sintering and crystallization of glass powder compacts in the Li2O–K2O–Al2O3–SiO2 system

The effects of K₂O content on sintering and crystallization of glass powder compacts in the Li₂O–K₂O–Al₂O₃–SiO₂ system were investigated. Glasses featuring SiO₂/Li₂O molar ratios of 2.69–3.13, far beyond the lithium disilicate (LD-Li₂Si₂O₅) stoichiometry, were produced by conventional melt-quenching technique. The sintering and crystallization behaviour of glass powders was explored using hot stage microscopy (HSM), scanning electron microscopy (SEM), differential thermal (DTA) and X-ray diffraction (XRD) analyses. Increasing K₂O content at the expense of SiO₂ was shown to lower the temperature of maximum shrinkage, eventually resulting in early densification of the glass-powder compacts. Lithium metasilicate was the main crystalline phase formed upon heat treating the glass powders with higher amounts of K₂O. In contrast, lithium disilicate predominantly crystallized from the compositions with lower K₂O contents resulting in strong glass–ceramics with high chemical and electrical resistance. The total content of K₂O should be kept below 4.63 mol% for obtaining LD-based glass–ceramics.     

Suppression of phosphor‐glass reactions in YAG:Ce phosphor‐embedded glasses

For high‐power white LED applications, YAG:Ce‐based yellow phosphors were embedded in a low‐T_g Bi₂O₃–B₂O₅–ZnO–Sb₂O₅ glass (BiG) by sintering route. A high‐T_g silicate glass (SiG) was also used for comparison. Dense (porosity<2%) phosphor‐glass composites were obtained after sintered at 800°C (for SiG) and 325°C (for BiG). XRD quantitative analysis indicates that the loss of phosphor content is in the range of 2.5%‐22%, caused by partial dissolution of phosphor particles into the glass matrix during sintering. The element distribution across the interface and within the reaction zone between phosphor and glass was analyzed by TEM/SEM‐EDS. The intrinsic emission characteristic of YAG:Ce is nearly not altered, possibly resulted from the slight modification of the YAG phase during sintering. Thus the final emission intensity of the sintered body is mainly determined by the residual amount of the YAG:Ce phase. Replace the high‐T_g SiG glass by the low‐T_g BiG glass, prenitridize the YAG:Ce phosphor, and change the sintering atmosphere from air to N₂ suppress the loss of phosphor during sintering. Therefore, the resulting loss of emission intensity of the phosphor‐embedded glass material can be reduced to only about 1.8%.     

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.     

Structural and thermal characterization of CaO–MgO–SiO2–P2O5–CaF2 glasses

The influence of varying the CaO/MgO ratio on the structure and thermal properties of CaO–MgO–SiO₂–P₂O₅–CaF₂ glasses was studied in a series of eight glass compositions in the glass forming region of diopside (CaMgSi₂O₆)–fluorapatite [Ca₅(PO₄)₃F]–wollastonite (CaSiO₃) ternary system. The melt-quenched glasses were characterized for their structure by infrared spectroscopy (FTIR) and magic angle spinning (MAS)-nuclear magnetic resonance (NMR) spectroscopy. Silicon is predominantly present as Q² (Si) species, while phosphorus tends to coordinate in orthophosphate environment. The sintering and crystallization parameters of the glasses were obtained from differential thermal analysis (DTA) while crystalline phase fractions in the sintered glass–ceramics were analyzed by X-ray diffraction adjoined with Rietveld refinement. Diopside, fluorapatite, wollastonite and pseudowollastonite crystallized as the main crystalline phases in all the glass–ceramics with their content varying with respect to variation in CaO/MgO ratio in glasses. The implications of structure and sintering behaviour of glasses on their bioactivity were discussed.     

Preparation of fully dense and magnetically controllable CaO-Al2O3-SiO2-Na2O-Fe3O4 glass ceramics by hot pressing

Fully dense and magnetically controllable glass ceramics was successfully synthesized by method of hot pressing using CaO-Al₂O₃-SiO₂-Na₂O glass powder and Fe₃O₄ powder as raw materials. The influences of sintering temperature and time, content and particle size of Fe₃O₄, as well as particle size of glass powder on the densification and magnetic properties of samples were investigated. It was found that the saturation magnetization gradually increased with increasing magnetite content. In addition, the samples containing smaller size magnetite particles had a higher coercivity. However, for samples using smaller size glass powder, magnetite particles could partially dissolve into the glass matrix, which led to the decrease of saturation magnetization and the increase of coercivity. It was also concluded that the precipitation of crystalline phase from smaller size glass powder caused the decrease of degree of densification, and after decreasing the sintering temperature, the degree of densification of product was enhanced.     

Dielectric Properties of Ultra‐Low Sintering Temperature Al2O3–BBSZ Glass Composite

Ceramic composites of B₂O₃–Bi₂O₃–SiO₂–ZnO (BBSZ) glass mixed with Al₂O₃ (10–50 vol%) were sintered at 450°C, and their microstructural and dielectric properties investigated. Dense structures were obtained when the Al₂O₃ content was lower than 30 vol%. Raman, XRD, and FESEM showed the existence of a secondary phase, Bi₂₄Si₂O₄₀, in all samples. The dielectric properties of the composite with 30 vol% addition of Al₂O₃ showed good dielectric properties with ε_r of 14.8 and 20.8 and 32.5 at 100 kHz and 100 MHz and 1 GHz, respectively. The tanδ values at the same frequencies were 0.004 and 0.006 and 0.016. The results show that BBSZ glass with different amounts of Al₂O₃ exhibit widely applicable relative permittivity values and affordable loss and are thus promising candidates for ultra‐low sintering temperature applications.     

Differences in microstructure and mechanical properties between Y-TZP and AL2O3-doped Y-TZP/bioglass ceramics

Y-TZP (YZ) and Al₂O₃-doped Y-TZP (AYZ) bioceramics with addition of different contents of a refractory bioglass were fabricated. The influence of the glass addition and sintering temperature on the densification behavior, microstructure, and mechanical properties of YZ and AYZ was studied. The developed ceramics contained small amounts of ZrSiO₄ and Ca₂P₂O₇ phases within the ZrO₂ matrix. The incorporation of glass to YZ promoted the ZrO₂ phase partitioning and enhanced the ZrO₂ grain growth at all the sintering temperatures, whereas the glass addition in AYZ prevented the Y₂O₃ redistribution between ZrO₂ grains and limited the ZrO₂ grain growth at 1300–1400°C. The hardness of the samples with glass was not significantly altered by using either YZ or AYZ. A slight increase in the fracture toughness with increasing glass content was found for YZ, while the fractured toughness of AYZ decreased by the glass addition. The more pronounced ZrO₂ phase partitioning of YZ with glass decreased the flexural strength, whereas AYZ maintained almost unaltered its flexural strength at a high level by the glass incorporation.     

Effects of Sb2O3 on the microstructure and electrical properties of ZnO–Bi2O3-based varistor ceramics fabricated by two-step solid-state reaction route

In this work, the ZnO–Bi₂O₃–Cr₂O₃–Co₂O₃–MnO₂ varistors doped with different content of Sb₂O₃ were prepared by two-step solid-state reaction route, including a pre-calcining of the mixtures of nanosized ZnO and the other additives at an optimized temperature, followed by a consequent sintering process at different temperatures. Meanwhile, the effects of Sb₂O₃ on the sintering temperature, microstructure and electrical properties of the objective varistors were investigated. It was found the densification temperature went up in a proper range and the content of pyrochlore phase, spinel phase and β-Bi₂O₃ phase increased with the increasing content of Sb₂O₃, while the grain size of ZnO–Bi₂O₃-based varistor reduced. The results demonstrated that at the same sintering temperature, the second particles increased with the increasing amount of Sb₂O₃, which was helpful to control the grain growth, leading to a higher breakdown voltage. However, the decrease of α-Bi₂O₃ phase (melting point of α-Bi₂O₃ phase is 825 °C), which is the main component of the liquid Bi₂O₃ phase in the sample during sintering process, leads to the increase of the sintering temperature of the green pallet. As a result, the ZnO varistor doped with 3.0 mol% Sb₂O₃ sintered at 1000 °C exhibited the highest breakdown voltage of 1863.3 V/mm. By contrast, the ZnO varistor without Sb₂O₃ doping sintered at 900 °C had the optimum nonlinear coefficient of 59.8.     

Preparation of machinable cordierite/mica composite by low-temperature sintering

In order to fabricate machinable cordierite/mica composite at low temperatures, the mica-composition glass powder was mixed with the conventional magnesia, alumina and silica powders which are raw materials of cordierite, compacted and fired in a sealed platinum container. By the addition of the 40 mass% mica-composition glass powder, machinable cordierite/mica composite was obtained. The machinability was caused by the interlocking microstructure of mica developed in the composite. In the firing process, mica crystallized at about 730 °C, cordierite was suddenly formed at 1050–1100 °C and the densification progressed markedly at 1000–1100 °C. The formation and sintering of cordierite were strongly promoted by a small amount of gaseous fluorine and/or fluorides. It was considered that fluorine and fluorides such as AlF₃ evaporated from the mica-composition glass at >800 °C and gaseous HF was formed in the sealed platinum container by the reaction of fluorine with water evaporated from the glass.     

The structures and dielectric properties of Ba0.80Sr0.20TiO3/Pb0.82La0.18TiO3 composite thick films with addition of PbO–B2O3 glass

Sol–gel derived Ba_0.80Sr_0.20TiO₃ (BST) and Pb_0.82La_0.18TiO₃ (PLT) powders and a low-melting PbO–B₂O₃ glass powder were mixed to prepare paste. The composite thick films (∼40 μm) were fabricated by screen-printing the paste onto the Al₂O₃ substrates with screen-printed silver bottom electrode and then sintered at the low temperature 650–800 °C, respectively. X-ray diffraction (XRD), transmission microscope (TEM), scanning electron microscope (SEM) and an impedance analyzer were used to analyze the structures, microstructures and dielectric properties of the powders and the composite thick films. The results show that the composite thick films containing sol–gel derived Ba_0.80Sr_0.20TiO₃ and Pb_0.82La_0.18TiO₃ perovskite phases have been fabricated by using the PbO–B₂O₃ glass as a sintering aid. Compared to conventional sintering at ≥1200 °C, high densification of the composite thick films is achieved at temperature as low as 800 °C by the “wetting” and “infiltration” of the liquid phase on the particles. The homogenization of the BST and PLT perovskite phase in the composite thick films is evitable by controlling the sintering temperature and time. The formation of the small amount of pyrochlore phase in composite thick films sintered at 800 °C is resulted from both the volatilization of PbO and the interaction between the PLT and PbO–B₂O₃ glass. The relative dielectric properties of the composite thick films exhibit good temperature-stable behavior, and the variation of the relative dielectric constant is less than 10% in the temperature range 0–300 °C.     

Densification and biocompatibility of sintering 3.0 mol% yttria-tetragonal ZrO2 polycrystal ceramics with x wt% Fe2O3 and 5.0 wt% mica powders additive

The densification and biocompatibility of sintered 3.0 mol% yttria-tetragonal zirconia polycrystal (3Y-TZP) ceramics, with X wt% Fe₂O₃ and 5.0 wt% mica powders (denoted by 3Y-TZP: X-5.0 wt% mica) have been studied. When the pellets of 3Y-TZP: X-5.0 wt% mica were sintered at 1300 °C for 1 h, the relative shrinkage increases from 19.20–19.43% with the X increased from 0.3 to 1.0. The relative shrinkage of pellets containing 1.0 wt% Fe₂O₃ (X=1.0) increased from 19.43–19.59% when sintering temperatures were raised from 1300 °C to 1450 °C. X-ray diffraction results show that the pellets of 3Y-TZP: X-5.0 wt% mica sintered at 1400 °C for 1 h only contained single phase of tetragonal ZrO₂ (t-ZrO₂). When the sintering temperature was higher than 1400 °C, the Vickers microhardness was greatest in the pellets with X=0.5. Within pellets with the same Fe₂O₃ content, the dominant wavelength (λ_d) was only slightly different for pellets sintered at 1300 °C and those sintered at 1450 °C. The results of the materials were evaluated in vitro cytotoxicity tests reveals that the powders and sintered pellets are safe materials. The oral mucosa irritation tests did not find erythema or histopathological change including normal epithelium, and was free from leucocyte infiltration, vascular congestion and oedema.