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.     

Luminescence of Eu‐Doped Transparent LuPO4 Glass‐Ceramics

Dual valence Eu‐doped transparent glass‐ceramics containing LuPO₄ nanocrystals were fabricated by melt‐quenching technique in air atmosphere. Their luminescent properties were systematically investigated by excitation, emission spectra, and decay lifetime measurements. The prominent Stark splitting, low forced electric‐dipole ⁵D₀ – ⁷F₂ transition and long decay lifetimes of Eu^{3 +} emission for glass‐ceramics reveal the incorporation of Eu^{3 +} into LuPO₄ nanocrystals. The enhanced Eu^{2 +} emission and reduction mechanism of Eu^{3 +} to Eu^{2 +} after crystallization are discussed briefly. Our results indicate that transparent LuPO₄ glass‐ceramics may find applications in photonics.     

Fabrication of Sr0.5Ba0.5Nb2O6 Nanocrystallite‐Precipitated Transparent Phosphate Glass‐Ceramics

Transparent (Sr_0.5Ba_0.5)Nb₂O₆ (SBN50) nanocrystallite‐precipitated phosphate glass‐ceramics were prepared by a conventional glass‐ceramic process. x(SrO–BaO–2Nb₂O₅) ? (100–4x)P₂O₅ (xSBNP) glasses with a refractive index of 1.9–2.0 exhibited high water resistance owing to the presence of Q⁰ and Q¹ phosphate units. Both bulk and surface crystallization of the SBN50 phase were observed in 20SBNP and 21SBNP glass‐ceramics. Although the nominal content of SBN50 crystals in the 21SBNP glass was larger than that in the 20SBNP glass, the latter exhibited better crystallinity of SBN50 and a higher number density of precipitated SBN nanocrystallites. By tuning the two‐step heat‐treatment and the chemical composition, transparent SBN50‐precipitated glass‐ceramics were successfully obtained. Given that no remarkable increase of the relative dielectric constants was observed after crystallization of the SBN50 nanocrystallites, it is postulated that the relative dielectric constant of the bulk is mainly governed by the amorphous phosphate region, and that the contribution of precipitation of the SBN50 nanocrystallites to the dielectric constant is not very significant in this system.     

Structural Optimization and Improved Discharged Energy Density for Niobate Glass‐Ceramics by La2O3 Addition

The structural and dielectric properties were investigated in the La₂O₃ added glass‐ceramics based on complex niobates. With the addition of La₂O₃, the optimization of microstructure was observed which resulted in the improvement of breakdown strength for the glass‐ceramics. Besides, the dielectric constant was drastically enhanced because of the doping effect of La³⁺ in the A‐sites of both crystallographic structures. Due to the combined effects of both high breakdown strength and polarization difference, the maximum discharged energy density of 1.2 J/cm³ was achieved in the niobate glass‐ceramics with 2 mol% La₂O₃, suggesting dielectric glass‐ceramics of this composition could be the most attractive candidate for high‐energy density capacitors.     

Ultra High Energy‐Storage Density in the Barium Potassium Niobate‐Based Glass‐Ceramics for Energy‐Storage Applications

The barium potassium niobate‐based glass‐ceramics with high energy‐storage density, high discharge efficiency, and fast discharge speed have been prepared. It was found that dielectric breakdown strength decreases when the crystallization temperature increases. Glass‐ceramics have high energy‐storage density up to 14.58 ± 1.14 J/cm³ with high breakdown strength of 2382 ± 92 kV/cm. Discharge energy density and discharge efficiency of glass‐ceramic capacitor were achieved through a pulse charge–discharge circuit. The reduction of discharge efficiency with the increase of crystallization temperature is mainly caused by interfacial polarization.     

Effect of P2O5 on the Structural and Magnetic Properties of Magnetite‐Based Glass‐Ceramics

The specific morphology and magnetic properties of magnetite‐based glass‐ceramics obtained by crystallization of Fe‐containing borosilicate glassmelts in the presence of P₂O₅ as nucleating agent are investigated. We found that the distribution of the tiny nanoparticles of magnetite determines the low temperature response to magnetic field. The observed effects are discussed with respect to the following factors: (1) the existence of a multimodal size distribution of the tiny grains as revealed by Mössbauer spectroscopy, magnetometry, and high‐resolution electron microscopy; (2) the existence of a disordered layer at the grain surface which is driven by field in a magnetically ordered state; and (3) the interplay between the relaxation mechanisms in different temperature ranges.     

Modeling of Reactive Diffusion in Glass‐Ceramics

A model of reactive ion‐exchange diffusion in glassy materials (glasses and glass‐ceramics) has been developed. The model can be used to simulate the processes of ion‐exchange‐induced decrystallization of glass‐ceramics and ion‐exchange‐induced glass crystallization. Analysis of the model in dimensionless form resulted in determining a set of dimensionless complexes comprising dimensional parameters of the ion exchange system (diffusivity, rate constant of grain dissolution, initial size and composition of the crystalline grains, etc.). Numerical values of the complexes enable one, not solving the problem, to predict the composition and structure of glass‐ceramic subsurface layers produced in a certain glassy material and under given ion‐exchange conditions. It was shown that the developed model correctly describes experimental data on ion‐exchange‐induced glass‐ceramics decrystallization. It appears that the model can be used in developing a new technology of optical glass‐ceramics for photonic applications.     

Enhanced and Long‐Lived Near‐Infrared Luminescence of Er3+ Ions in Lead Borate Glass‐Ceramics Containing PbWO4 Nanocrystals

Lead tungstate PbWO₄ nanocrystals in transparent lead borate glass‐ceramics containing Er³⁺ ions were fabricated. Luminescence spectra at about 1530 nm due to main ⁴I_13/2–⁴I_15/2 laser transition of Er³⁺ ions were examined for glass samples before and after heat treatment. Near‐infrared luminescence of Er³⁺ ions in glass‐ceramics is enhanced and long‐lived in comparison to precursor glasses. It suggests that the Er³⁺ ions are partially incorporated into PbWO₄ crystalline phase.     

Ultra‐Low Fire Glass‐Free Li3FeMo3O12 Microwave Dielectric Ceramics

A new ultra‐low fire glass‐free microwave dielectric material Li₃FeMo₃O₁₂ was investigated for the first time. Single phase ceramics were obtained by the conventional solid‐state route after sintering at 540°C–600°C. The atomic packing fraction, FWHM of the A_g oxygen‐octahedron stretching Raman mode and Qf values of samples sintered at different temperatures correlated well with each other. The sample with a Lower Raman shift showed a higher dielectric constant. Interestingly, the system also showed a distinct adjustable temperature coefficient of resonant frequency (from ?84× 10^?6/°C to 25 × 10^?6/°C).     

Amorphization by Mechanical Milling for Making IR Transparent Glass‐Ceramics

In this article, we put forward the possibility to prepare amorphous powder from chalcogenide compositions usually located out of the glassy domain when synthesized via a conventional melt‐quenching technique. Both X‐ray diffraction and DSC techniques were used to demonstrate that the original Ge₁₅Ga₂₀S₆₅ composition can be prepared in the amorphous state by using mechanical milling starting from raw metallic elements. Subsequent hot‐pressing by spark plasma sintering in a graphite die above the glass transition temperature leads to sintered pellets presenting a high rate of nanocrystals of about 30 nm. These as‐made glass–ceramic materials present promising transparency in the infrared range.     

Effect of Microwave Processing on the Crystallization and Energy Density of BaO‐Na2O‐Nb2O5‐SiO2‐B2O3 Glass‐Ceramics

Barium sodium niobate (BNN) glass‐ceramics were successfully synthesized through a controlled crystallization method, using both a conventional and a microwave hybrid heating process. The dielectric properties of glass‐ceramics devitrified at different temperatures and conditions were measured. It was found that the dielectric constant increased with higher crystallization temperature, from 750°C to 1000°C, and that growth of the crystalline phase above 900°C was essential to enhancing the relative permittivity and overall energy storage properties of the material. The highest energy storage was found for materials crystallized conventionally at 1000°C with a discharge energy density of 0.13 J/cm³ at a maximum field of 100 kV/cm. Rapid microwave heating was found to not give significant enhancement in dielectric properties, and coarsening of the ferroelectric crystals was found to be critical for higher energy storage.     

Syntheses of Spinon Thermal Conductivity Materials in Sr–Cu–O System by Glass‐Ceramics Technique

We have synthesized spinon thermal conductivity materials in Sr–Cu–O system by glass‐ceramics technique. The materials are promising for active control of thermal energy in microelectronic devices because of high and anisotropic thermal conduction, its controllability, and electric insulation. Nevertheless, research on these materials has been limited to that concerning theoretical perspectives and investigation of physical properties using large single crystals. In this study, we adopt glass‐ceramics technique to synthesize these materials: We prepared melt‐quenched multicomponent oxides including SrO and CuO, and checked its glass‐forming ability and crystallization behaviors by heating. As a result, we have found that SrCuO₂ and Sr₁₄Cu₂₄O₄₁, known as the spinon thermal conductivity materials, are synthesized using SrO–CuO–?Li₂O–?Al₂O₃?–Ga₂O₃ system. This synthesis process for the system will provide practical application of the spinon thermal conductivity materials.     

Enhanced Thermostability,Thermo‐Optics,and Thermomechanical Properties of Barium Gallo‐Germanium Oxyfluoride Glasses and Glass‐Ceramics

Serial substitutions of BaF₂ for BaO in BaO–Ga₂O₃–GeO₂ glasses were performed, and the effects of the substitutions on the glass properties were investigated. The glass transition temperature, density, refractive index, thermo‐optics coefficient, and figure of merit for thermal shock decreased with the replacement of oxygen by fluorine. On the other hand, the glass‐forming ability increased. Fluorine substitution removed the absorption band of hydroxyl near 2.9 μm. Raman scattering spectroscopy was used to characterize the fluorogermanate glasses. The crystallization process of the glass‐ceramics under different heat‐treatment conditions was also investigated using differential scanning calorimetry, X‐ray diffraction, scanning electron microscopy, and atomic force microscopy. The thermal and mechanical properties were improved by controlling the crystal size of the near‐ and middle‐infrared transparent glass‐ceramics.     

共沉淀-焙烧法制备球形铝酸锶粉体

以碳酸氢铵、硫酸铝铵和硝酸锶为原料,采用共沉淀法制备了化学组成为SrCO3•2Al(OH)3•7H2O的前体,此前体在较低温度下可合成SrAl2O4粉体。利用红外光谱（FTIR）、扫描电镜（SEM）及能量散射分光光谱（EDS）、X射线衍射（XRD）和热分析（TG-DSC）表征了前体及其热处理产物的特征。结果表明,锶铝物质的量比和pH值对粉体成分和颗粒形貌有显著影响,n(Sr)∶n(Al)=1∶1.6、pH=7.6条件下制备了球形前体,此前体在1 100 ℃于空气气氛中焙烧2 h获得了单分散、球形SrAl2O4粉体,合成温度较传统高温固相法低约400 ℃。     

Structural and Kinetic Analysis of BaCl2 Nanocrystals in Fluorochlorozirconate Glass‐Ceramics

The presence of BaCl₂ nanocrystals and the crystallographic phase that they adopt controls the optical behavior of fluorochlorozirconate glass‐ceramics. We have used in situ X‐ray diffraction heating experiments and ex situ transmission electron microscopy to follow the BaCl₂ nanocrystal nucleation and growth processes as a function of heating rate and isothermal hold temperature. The BaCl₂ nanocrystals nucleate with the hexagonal crystal structure and grow as spherical particles to a size of ~10 to 20 nm. They then undergo a structural transformation to the orthorhombic phase and their shape changes to rounded disks, with diameters ranging from 150 to 250 nm, and thicknesses ranging from 80 to 120 nm. The change in size results from Ostwald ripening of the hexagonal BaCl₂ nanocrystals to form the orthorhombic BaCl₂ nanocrystals.     

Microwave Dielectric Properties of Novel Glass‐Free Low‐Firing Li2CeO3 Ceramics

Novel glass–free low temperature firing microwave dielectric ceramics Li₂CeO₃ with high Q prepared through a conventional solid‐state reaction method had been investigated. All the specimens in this paper have sintering temperature lower than 750°C. XRD studies revealed single cubic phase. The microwave dielectric properties were correlated with the sintering conditions. At 720°C/4 h, Li₂CeO₃ ceramics possessed the excellent microwave dielectric properties of ε_r = 15.8, Q × f = 143 700 (GHz), and τ_f  = ?123 ppm/°C. Li₂CeO₃ ceramics could be excellent candidates for glass‐free low‐temperature co‐fired ceramics substrates.     

Powellite‐Rich Glass‐Ceramics: A Spectroscopic Study by EPR and Raman Spectroscopy

The aim of this study was to better understand the incorporation of rare‐earth elements in glass‐ceramics of nuclear interest. We synthesized glass‐ceramics from glasses in the system SiO₂–B₂O₃–Na₂O–CaO–Al₂O₃–MoO₃–Gd₂O₃ by various heat treatments. Gadolinium is used both as a spectroscopic probe and as a minor actinide surrogate. Glass‐ceramics contain only one crystalline phase in the bulk: powellite (CaMoO₄). This phase can incorporate Gd³⁺ and Na⁺ ions by substitutions on the Ca site. We demonstrated that the charge compensation by Na⁺ favors the incorporation of rare‐earth elements. Moreover, the incorporated elements do not seem to be randomly distributed into the powellite structure.     

Er3+ Ions‐Doped Germano‐Gallate Oxyfluoride Glass‐Ceramics Containing BaF2 Nanocrystals

Er³⁺ ions‐doped germano‐gallate oxyfluoride glass‐ceramic containing BaF₂ nanocrystals was prepared through conventional melt quenching and subsequent thermal treatment method. X‐ray diffraction patterns and transmission electron microscope images confirmed the formation of BaF₂ nanocrystals in glass‐ceramics. Preferential incorporation of Er³⁺ ions into the BaF₂ nanocrystals were confirmed by the absorption spectra and emission spectra, and enhanced upconversion emission and infrared emission were observed. Relatively high transmittance in the mid‐infrared region indicated great potential of this germano‐gallate oxyfluoride glass‐ceramics as host materials for the efficient mid‐infrared emission from rare‐earth ions.     

Magnetic Properties of Iron Phosphate Glass and Glass‐Ceramics

Magnetic properties of crystallized iron phosphate glasses and relationship between structural and magnetic properties modifications that occur during crystallization have been investigated. Iron phosphate glass exhibits the spin‐glass (SG) behavior and represents a prototype of solid with disordered spatially distributed magnetic moments. Glass of the composition 43Fe₂O₃–57P₂O₅ (wt%) was heat‐treated in air at 893, 923, and 1073 K for 24 h. The samples were studied using X‐ray diffraction, Raman spectroscopy, and dc magnetic measurements. The magnetic measurements show dominant antiferromagnetic (AF) interactions for all samples. The starting glass exhibits SG behavior, whereas magnetic behavior of samples heat‐treated at 893 and 923 K, which contain Fe₃(P₂O₇)₂ crystalline phase embedded in glass matrix, is ascribed to a mixture of superparamagnetism and SG behavior. In the sample heat‐treated at 1073 K, several peaks in the magnetization curves were observed which correspond to the various crystalline phases present in the sample: Fe₃(P₂O₇)₂, Fe₄(P₂O₇)₃ and Fe(PO₃)₃. Hysteresis loops show paramagnetic behavior at 300 K. Small curvature is present at low temperature (5 K) that can be ascribed to the AF ordering in the samples.     

Europium(III)‐Doped MgAl2O4 Spinel Nanophosphor Prepared by CO2 Laser Co‐Vaporization

Photoluminescent nanoparticles (NPs) are of specific interest for biomedical applications, bioimaging, and cell tracking. Here, we report on the synthesis of europium(III)‐doped MgAl₂O₄ spinel NPs by the CO₂ laser co‐vaporization of a homogeneous raw powder mixture consisting of micrometer‐sized MgAl₂O₄ and Eu₂O₃ (2 and 4 mol%, respectively). The resulting NPs are spherically shaped, show a narrow size distribution (mean diameter: ~30 nm), and are well dispersed. The as‐prepared NPs are highly crystalline and consist of MgAl₂O₄ with small amounts of the secondary phases MgO (~10 mass%) and Eu₂O₃ (<0.5 mass%). The photoluminescence spectra of the doped spinel nanopowders show an intense red emission (λ_em = 615 nm) resulting from the ⁵D₀→⁷F₂ transition with a maximum intensity at an excitation wavelength of 470 nm.