Effects of B2O3 substitution for Al2O3 on the crystallization and properties of translucent mica glass-ceramics

The effects of substituting Al₂O₃ with B₂O₃ on the structure, crystallization, mechanical properties, thermal properties and optical properties of translucent mica glass-ceramics were thoroughly investigated. The results demonstrated that the addition of 0.5 wt% B₂O₃ was optimum for glass precipitation, which increases the crystallinity of glass-ceramics and provides good translucency. When the content of B₂O₃ was greater than 0.5 wt%, both crystallinity and translucency decreased noticeably. The replacement of B₂O₃ for Al₂O₃ had no influence on the type of crystal phase and the precipitation of tetrasilicic fluoromica with non-stoichiometric ratio, while it did have an effect on the crystallinity and structure. The crystal sizes of glass-ceramics were in the nanoscale range and the transmittance test results indicated that they exhibit excellent translucency.     

Effect of substitution of ZrO2 by SnO2 on crystallization and properties of environment-friendly Li2O–Al2O3–SiO2 system (LAS) glass-ceramics

In this study, a transparent and environmentally friendly Li₂O–Al₂O₃–SiO₂ (LAS) glass-ceramic was prepared by melt-quenching and two-step heat treatment. The influence of the substitution amount of ZrO₂ by SnO₂ on the crystallization, microstructure, transparency, and mechanical properties of LAS glass and glass-ceramics was investigated by means of differential scanning calorimetry (DSC), X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), Ultraviolet–visible Spectrophotometer, three-point bending strength test, and microhardness test. The results indicate that the main crystalline phase of LAS glass ceramics was a β-quartz solid solution when heat treated at 780 °C for 2 h and 870 °C for 1.5 h. When the substitution amount of ZrO₂–SnO₂ increased from 0.4 mol% to 2.5 mol%, the grain size and thermal expansion coefficient of LAS glass-ceramics first decreased and then increased, and the crystallinity first increased and then decreased. When the substitution amount of ZrO₂–SnO₂ was 0.8 mol%, the transparency of the LAS glass-ceramics was maximum, the bending strength was 96 MPa, and the Vickers hardness was 10.9 GPa.     

Transparent Nd3+-Activated Glass-Ceramics in the Li2O–Al2O3–SiO2System: Physicochemical Aspects of Their Preparation and Optical Characteristics

The spectral–optical properties of transparent neodymium-activated lithium aluminosilicate glass-ceramics with titanium dioxide as a crystallization catalyst are investigated. The compositions of the initial glasses and the temperature–time schedules of heat treatment that provide a way of preparing highly homogeneous samples with low optical losses are determined. The most important parameters characterizing emission from the ⁴F_3/2metastable state of neodymium ions are obtained by analyzing the optical spectra of rare-earth ions in terms of the Judd–Ofelt theory. It is shown that the introduction of phosphorus oxide into the composition of glass-ceramics leads to a considerable increase in the stimulated emission cross section for the basic ⁴ F _3/2–⁴ I _11/2transition, even though the rare-earth activator is not incorporated into the crystalline phase. It is found that acceptable quantum yields of fluorescence with the retention of a high heat resistance of glass-ceramics can be achieved by decreasing the volume fraction of the crystalline phase. The lasing testing of the materials prepared is performed in a setup with a lamp pumping. The low lasing parameters can be associated with the specific features in the optical properties of glass-ceramics, primarily, with the revealed depolarization of polarized light due to the presence of microstresses at interfaces.     

Optical properties of transparent polycrystalline ruby (Cr:Al2O3) fabricated by high-pressure spark plasma sintering

Doped transparent ceramics with high optical quality can serve as materials for photonic applications such as laser gain media. In that regard, transparent polycrystalline alumina has potential for high-power applications due to its excellent physical and chemical properties, combined with unique doping possibilities. However, optical birefringence of Al₂O₃ crystals make achieving sufficiently high optical transmittance a processing challenge. In the present study, we demonstrated fabrication of highly transparent 0.5 at.% Cr:Al₂O₃ ceramics by high-pressure spark plasma sintering (HPSPS). The optical properties of these polycrystalline ruby ceramics were analyzed in order to assess possible laser operation (at 694.3 nm). The obtained ceramics exhibit high in-line transmittance (～72.5 % at 700 nm), equivalent to a scattering coefficient of 2.15 cm^?1, and characteristic ruby photoluminescence. The theoretically estimated lasing threshold and percentage of absorbed pump power indicate that such ruby ceramic lasers could operate at reasonable thresholds of 80?225 mW with short lengths of 0.5?5 mm. Thus, HPSPS is a promising method for producing laser-quality doped transparent ceramics for compact laser systems.     

Nucleating role of P2O5 in nepheline-based transparent glass-ceramics

The nepheline-based transparent glass-ceramics are promising candidates for cover glass applications in electronic displays owing to their superior mechanical properties (than glasses) and ability to be chemically strengthened. However, our poor understanding about the kinetic and thermodynamic drivers controlling their crystallization processes usually results in their opacification and development of large internal stresses. The present work focuses on the development of nepheline-based nanocrystalline transparent glass-ceramic designed in the Na₂O–Al₂O₃–SiO₂ ternary system nucleated with P₂O₅. The temporal evolution of the phosphate and nepheline nanocrystal formation has been followed using X-ray diffraction, scanning/transmission electron microscopy, and energy-dispersive spectroscopy. The incorporation of P₂O₅ in the glass structure leads to the phase separation resulting in the crystallization of nanocrystalline Na₃PO₄ as an intermediate phase; thus, acting as a nucleating site for volume crystallization of nepheline. The optimization of nucleation and growth profile in the designed composition results in the formation of a transparent glass-ceramic with high optical transmittance (91.5 ± 0.1%).     

Potential utilization of oil sludge incineration bottom ash for glass-ceramics: Crystallization kinetics,properties and toxicological evaluation

The bottom ash (OIBA) generated from the incineration of hazardous oil sludge is classified as a hazardous waste. In this work, the OIBA was applied as raw material to prepare SiO₂-Al₂O₃-CaO system glass-ceramics by melt-sintering with the addition of waste glass wool (GW). The effects of basicity (CaO/SiO₂ ratio, 0.52-1.05) and sintering temperature (900–1050 °C) on the crystallization kinetics, properties, microstructure, leaching concentrations of heavy metals and potential toxicity of glass-ceramics were investigated. The results showed that the crystallization pattern was two-dimensional crystallization, and with the decrease of basicity, the main crystalline phase evolved from gehlenite to diopside. And the glass-ceramics with basicity of 0.88 and sintering temperature of 950 °C exhibited the best comprehensive properties, including density (2.72 g/cm³), water absorption (0.06%), compressive strength (452.45 MPa) and chemical corrosion resistance. In addition, the reduction of heavy metal leaching concentration indicates that produced glass-ceramics showed excellent solidification effect on heavy metals, the low toxicity of glass-ceramics leaching solution to the wheat seeds and Artemia suggests the environmental protection characteristics of OIBA-based glass-ceramics. These findings proved that the glass-ceramics produced by OIBA and GW could be a promising method to dispose hazardous waste with preparing high value-added construction materials.     

Glass forming,crystallization, and physical properties of MgO-Al2O3-SiO2-B2O3 glass-ceramics modified by ZnO replacing MgO

This study focused on the glass forming, crystallization, and physical properties of ZnO doped MgO-Al₂O₃-SiO₂-B₂O₃ glass-ceramics. The results show that the glass forming ability enhances first with ZnO increasing from 0 to 0.5 mol%, and then weakens with further addition of ZnO which acted as network modifier. No nucleating agent was used and the crystallization of studied glasses is controlled by a surface crystallization mechanism. The predominant phase in glass-ceramics changed from α-cordierite to spinel/gahnite as ZnO gradually replaced MgO. The phase type did not change; however, the crystallinity and grain size in glass-ceramics increased when the glasses were treated from 1030 °C to 1100 °C. The introduction of ZnO can improve the thermal, mechanical, and dielectric properties of the glass-ceramics. The results reveal a rational mechanism of glass formation, crystal precipitation, and evolution between structure and performance in the xZnO-(20-x)MgO-20Al₂O₃-57SiO₂-3B₂O₃ (0 ≤ x ≤ 20 mol%) system.     

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.     

A novel Nd3+-doped MgO-Al2O3-SiO2-based transparent glass-ceramics: Toward excellent fluorescence properties

Generally, glass-ceramics have superior properties compared to their parent glasses. Here, we prepared a novel Nd³⁺-doped MgO-Al₂O₃-SiO₂-based transparent glass-ceramics with excellent fluorescence properties. The effects of Nd₂O₃ content on the structure and properties of glass-ceramics were studied, aiming to provide a key guidance for preparing this transparent glass-ceramics. The results revealed that the glass stability increased originally and then decreased with increasing Nd₂O₃ content, so did the variation of wavenumbers in infrared spectra. And these glass-ceramics are mainly composed of cordierite with residual glassy phase. The three phenomenological intensity parameters (Ω_2,4,6) and radiative properties were estimated by Judd-Ofelt theory, and the values of Ω₂ first decreased and then increased with increasing Nd₂O₃ content. Three main emission peaks ascribed to the transitions from ⁴F_3/2 to ⁴I_9/2, ⁴I_11/2, ⁴I_13/2 at 898, 1057, 1330  nm were observed, respectively. The branching ratios for ⁴F_3/2→⁴I_11/2 transition increased as the Nd₂O₃ content raised, and the fluorescence lifetimes of the ⁴F_3/2 level were found to increase first and then decrease with Nd₂O₃ content (from 181 to 726 μs). The excellent fluorescence properties indicate that this novel glass-ceramics can be used as a potential solid-state optical functional material for 1.06 μm laser emission.     

Effect of metastable phase on the crystallization and mechanical properties of MgO-Al2O3-SiO2 glass-ceramics without nucleating agents

Glass-ceramics without nucleating agents usually undergo surface crystallization, which deteriorates the overall performance of the products. In this paper, we evaluated the effects of the metastable MgAl₂Si₃O₁₀ crystalline phase on the crystallization behavior of a MgO–Al₂O₃–SiO₂ (MAS) glass without nucleating agents and mechanical properties of the glass-ceramics obtained. The results demonstrated that the precipitation of metastable MgAl₂Si₃O₁₀ crystallites promotes the crystallization mechanism transformed from surface crystallization into volume crystallization with two-dimensional crystal growth. Furthermore, the grain size of MgAl₂Si₃O₁₀ near the surface of the prepared glass-ceramics was larger than that of MgAl₂Si₃O₁₀ inside, which helps to generate compressive stress and improves its mechanical properties. The glass-ceramics containing metastable MgAl₂Si₃O₁₀ phase exhibited an enhanced hardness in the range of 7.6 GPa–9.5 GPa for indentation loads ranging from 2.94 N to 98 N, and indentation size effect behavior was observed in Vickers hardness tests of both MAS glass and glass-ceramics. The load-independent hardness values for MAS glass and glass-ceramics were reliably evaluated by the modified proportional specimen resistance (MPSR) model of 7.1 GPa and 7.6 GPa, respectively, with a high correlation coefficient of more than 0.9999. This work reveals the unexploited potential of the metastable phase in improving the crystallization ability and mechanical properties of glass-ceramics.     

Influence of Al2O3/SiO2 ratio in multicomponent LNAS glasses and glass-ceramics on the crystallization behavior,microstructure and mechanical performance

Transparent glass-ceramics containing eucryptite and nepheline crystalline phases were prepared from alkali (Li, Na) aluminosilicate glasses with various mole substitutions of Al₂O₃ for SiO₂. The relationships between glass network structure and crystallization behavior of Li₂O–Na₂O–Al₂O₃–SiO₂ (LNAS) glasses were investigated. It was found that the crystallization of the eucryptite and nepheline in LNAS glasses significantly depended on the concentration of Al₂O₃. LNAS glasses with the addition of Al₂O₃ from 16 to 18 mol% exhibited increasing Q⁴ (mAl) structural units confirmed by NMR and Raman spectroscopy, which promoted the formation of eucryptite and nepheline crystalline phases. With the Al₂O₃ content increasing to 19–20 mol%, the formation of highly disordered (Li, Na)₃PO₄ phase which can serve as nucleation sites was inhibited and the crystallization mechanism of glass became surface crystallization. Glass-ceramics containing 18 mol% Al₂O₃ showed high transparency ～84% at 550 nm. Moreover, the microhardness, elastic modulus and fracture toughness are 8.56 GPa, 95.7 GPa and 0.78 MPa m^1/2 respectively. The transparent glass-ceramics with good mechanical properties show high potential in the applications of protective cover of displays.     

Effect of MgO/Al2O3 ratio on the crystallization behaviour of Li2O–MgO–Al2O3–SiO2 glass-ceramic and its wettability on Si3N4 ceramic

The composition governs the crystallization ability, the type and content of crystal phases of glass-ceramics. Glass-ceramic joining materials have generated more research interest in recent years. Here, we prepared a novel Li₂O–MgO–Al₂O₃–SiO₂ glass-ceramic for the application of joining Si₃N₄ ceramics. We investigated the influence of the MgO/Al₂O₃ composition ratio on microstructure and crystallization behaviour. The crystallization kinetics demonstrated that the glasses had excellent crystallization ability and high crystallinity. β-LiAlSi₂O₆ and Mg₂SiO₄ were precipitated from the glass-ceramics, and the increase of MgO concentration was conducive to the precipitation of Mg₂SiO₄. Among the glass-ceramic samples, the thermal expansion coefficient of LMAS2 glass-ceramic was 3.1 × 10^?6/°C, which was very close to that of Si₃N₄ ceramics. The wetting test showed that the final contact angle of the glass droplet on the Si₃N₄ ceramic surface was 32° and the interface was well bonded.     

Preparation of transparent Mn-doped CaF2 glass-ceramics from silicon-manganese slag: Dependence of colour-controllable change on slag addition and crystallization behavior

Silicon-manganese slag was firstly used to prepare the transparent colour-controlled glass-ceramics containing Mn-doped CaF₂ nanocrystals. The maximum utilization ratio of slag reaches to 27.04 wt%, and the colour of the samples trended red-brown to red light as the added slag content increased. The transparent glass-ceramics could be prepared when crystallized between 650 and 710 °C for 2 h, and had a minimum transmittance of 67.95 % at a wavelength of 780 nm. Increasing the content of added slag caused the emission spectrum to shift, demonstrating the ability to control the colour of the transparent glass-ceramics, and also enhanced the fluorescence intensity. The crystallization behaviour conversely has little effect on the colour change, but can increase the fluorescence intensity. In general, this work provides a new approach for the comprehensive utilization of silicon-manganese slag for applications in optical engineering.     

Glass-ceramics for joining oxide-based ceramic matrix composites (Al2O3f/Al2O3-ZrO2) operating under direct flame exposure

This work focuses on the joining processes of oxide-based ceramic matrix composites (Al₂O_3f /Al₂O₃-ZrO₂), which are used as radiant tube furnace components in the steel industry. These components have to operate in harsh environments, and under high temperatures, and they therefore have to resist corrosion, humidity, and combustion. Two glass-ceramics systems, which have Y₂Ti₂O₇ as their main crystalline phase, as well as specific and optimized properties to withstand severe operating conditions, including temperatures of 900 °C, are here proposed as joining materials. The adhesion of the glass-ceramics to the composite was found to be excellent after mechanical and thermal tests in which they were in direct contact with a 900 °C flame and thermal cycling of between 400 °C and 900 °C.     

Lithium concentration effect on crystallization kinetics and spectral properties of Cr-doped Li2O–K2O–Al2O3–B2O3 glass-ceramics

Alkali-aluminaborate glass-ceramics doped with Cr ions are synthesized by volume crystallization. According to non-isothermal DSC method three parallel processes occur in material: 2D Avrami-Yerofeev nucleation, 2D and 3D crystallization. During the heat treatment, the LiAl₇B₄O₁₇ crystalline phase is formed. With Li₂O content rising crystallinity of the material increases from 27 to 69% and the crystalline field strength Dq/B of Cr³⁺ increases from 2.25 to 3.55. The photoluminescence spectra possess intense bands at 685, 700, and 715 nm for glass with 6.8 mol.% Li₂O and higher and its decay kinetics is described by the sum of two exponentials. The maximum luminescence QY obtained is 50% at 16.1 mol.% Li₂O. The highest conversion efficiency of the 532 nm LED luminescence obtained by glass-ceramics with chromium is 10%. Thus, Cr-doped alkali-alumina-borate glass-ceramics are a promising material for use in the design of radiation sources for the red and NIR spectral regions.     

Sintering behavior,structure and dielectric properties of CuO-ZnO-MgO-B2O3 glass-ceramics for ULTCC applications

High performance ultra-low temperature co-fired ceramic (ULTCC) materials were prepared from CuO- MgO- ZnO- Al₂O₃- B₂O₃- Li₂O glass-ceramics. The sintering behaviors, crystalline phase evolution, microstructure and dielectric properties, as well as their compatibility with Ag and Al electrodes, were investigated. With the suitable substitution of MgO for ZnO, the dielectric properties of glass-ceramics were improved. It is mainly associated with the fine microstructure, highly crystallinity, and decrease in tetrahedral distortion in the crystal lattice. All the glasses completed the densification at 575–600 °C, and ZnB₄O₇ is the only crystalline phase precipitated from the glasses. Moreover, the glass-ceramic with 1 wt% MgO sintered at 575 °C for 5 h, exhibited low relative permittivity ~ 7.1 and low dielectric loss ~ 6.40 × 10^?4. And the glass-ceramic with 4 wt% MgO sintered at 600 °C for 5 h, also displayed low relative permittivity ~ 7.1 and low dielectric loss ~ 5.77 × 10^?4. Both two glasses have good sintering compatibility with silver and aluminum electrodes, which provided high potential for ULTCC application.     

Highly transparent polycrystalline Gd2O3 ceramic attained via ZrO2 stabilization effect

The transition from the cubic to monoclinic phase of Gd₂O₃ at high temperatures poses a significant challenge to the preparation of transparent Gd₂O₃ materials. In this work, we presented a straightforward yet effective method for fabricating transparent Gd₂O₃ ceramics. Via ZrO₂ stabilization effect for phase structure, highly transparent Gd₂O₃ ceramics were successfully fabricated by vacuum sintering at 1850 °C for 8 h. The effect of different Zr (0 ∼ 13 at%) concentrations on phase transition, grain growth, fracture mode and optical properties of Gd₂O₃ transparent ceramics was investigated. As the Zr content increases, the transition from the cubic (C) to monoclinic (M) phase is effectively suppressed, which is crucial for achieving Gd₂O₃ transparent ceramics. Moreover, the results indicate that the addition of ZrO₂ has a significant effect on grain growth by not only impeding the migration of grain boundaries but also affecting the phase composition. In addition, the 11 at% Zr-doped Gd₂O₃ ceramic exhibits the best optical properties, of which transmittance is about 76% at 850 nm and about 80% in the 2.5 µm ∼ 6 µm mid-infrared range. This work provides an illustrative example for the development of other ceramics with phase transition. The obtained Zr-doped Gd₂O₃ transparent ceramics with high optical quality are potential candidates for optical window, scintillator host and mid-infrared transmission materials.     

Highly transparent LiAlON ceramic prepared by reaction sintering and post hot isostatic pressing

A highly transparent polycrystalline LiAlON ceramic with the size of Φ57?mm?×?6?mm was successfully fabricated by reaction sintering (1750?°C, 20?h) and post hot isostatic pressing (HIP, 1850?°C, 3?h, 180?MPa) using AlN, Al₂O₃ and LiAl₅O₈ powders. Related mechanism on the reaction sintering and densification were studied via the analysis of phase and microstructural evolution. High transparency was resulted from full elimination of Al₂O₃ secondary phase and residual pores. It has excellent optical transparency from the visible to middle infrared (IR) bands with the maximum transmittance of ～ 85.5%. The flexural strength and Vikers hardness reach ～303?MPa and ～15.0?GPa, respectively.     

Fabrication and characterization of highly transparent ZrO2-doped Tm2O3 ceramics

Highly transparent polycrystalline Tm₂O₃ ceramics were successfully fabricated by vacuum sintering at temperatures from 1650 to 1850 °C for 8 h using commercial Tm₂O₃ and ZrO₂ (1 at%) powders as starting materials. It is the first time that ZrO₂ was reported as a sintering additive to prepare Tm₂O₃ transparent ceramics. The effects of sintering temperature on the optical transmittance and microstructure of Tm₂O₃ transparent ceramics were studied. The desired Tm₂O₃ ceramics with relative density of 99.8% and an average grain size of approximately 9.7 μm were obtained at 1800 °C and the in-line transmittance reached 75% at 880 nm and fluctuated around 80% from 2100 to 2400 nm, respectively. This study demonstrated that Tm₂O₃ transparent ceramics with higher in-line transmittance and smaller grain size could be prepared by using ZrO₂ as sintering additive at a relatively lower vacuum sintering temperature compared to those already reported in open literatures.     

Optical and Microwave Dielectric Properties of Zn‐Doped MgAl2O4 Transparent Ceramics Fabricated by Spark Plasma Sintering

(Mg_1?xZn_x)Al₂O₄ transparent ceramics were fabricated by spark plasma sintering technique at 1325°C for 10 min. A small mount of Zn²⁺ addition to MgAl₂O₄ ceramics was very effective to the performance improvement, while further increase in Zn‐doped content would give rise to the optical transmittance deterioration. The optical and microwave dielectric properties of MgAl₂O₄ transparent ceramics were improved by Zn substitution for Mg. The in‐line transmittance of the (Mg_1?xZn_x)Al₂O₄ (x = 0.02) ceramics can be as high as 70% at λ = 550 nm and 86.5% at λ = 2000 nm, respectively. The dielectric constant ε_r of (Mg_1?xZn_x)Al₂O₄ just varied from 8.32 to 8.54, however, the Q × f value increased significantly up to a maximal value of 66,000 GHz at x = 0.02. Moreover, the τ_f of (Mg_1?xZn_x)Al₂O₄ transparent ceramics changed from ?74 to ?65.5 ppm/°C. With the increasing of Zn‐doped content, the average grain size and the porosity increased, which was the primary reason for the change in optical and microwave dielectric properties.