Glass transition and crystallization of ZnO-B2O3-SiO2 glass doped with Y2O3

The effect of Y₂O₃ on the glass transition kinetics, crystallization kinetics, phase separation and crystallization behavior of 60ZnO–30B₂O₃–10SiO₂ glass has been investigated by non-isothermal differential thermal analysis, scanning electron microscopy (SEM) and X-ray powder diffraction (XRD). The glass transition activation energies E_g calculated by using both Kissinger and Moynihan model decrease from 668?kJ/mol to 573?kJ/mol for Kissinger model, and 682?kJ/mol to 587?kJ/mol for Moynihan model with the increase of yttrium oxide doping content from 0 to 6?mol%. And the glass crystallization kinetics parameters, crystallization activation energy E_c and Avrami exponent n stands for crystal growth, are also obtained on the basis of several well developed equations. Increase of about 58?kJ/mol in Ec values obtained by different theoretical equations is caused by addition of 6?mol% yttrium oxide into 60ZnO–30B₂O₃–10SiO₂ glass, and the Avrami exponent (n close to 2) suggests that crystal growth in 60ZnO–30B₂O₃–10SiO₂ glass doped with or without yttrium is mainly one-dimensional growth of crystals. The results on the phase separation and crystallization behavior occurred at 893?K and 993?K respectively for base and doped glass, are well consistent with the glass transition and crystallization kinetics results. Hence, addition of yttrium oxide into 60ZnO–30B₂O₃–10SiO₂ glass decrease the glass transition activation energy while increase the crystallization activation energy of glass, thereby the stability of glass structure is improved. Phase separation phenomenon and crystallization behavior occurred at glass surface provide some useful information for preparing glass ceramics with micro- or nano-crystals in surface.     

Synthesis of Eu3+‐doped BaBi2Ta2O9 based glass‐ceramic nanocomposites: Optical and dielectric properties

In this paper we report for the first time synthesis of Eu³⁺‐doped transparent glass‐ceramics (TGC) with BaBi₂Ta₂O₉ (BBT) as the major crystal phase using the glass system SiO₂–K₂O–BaO–Bi₂O₃–Ta₂O₅ by melt quenching technique followed by controlled crystallization through ceramming heat treatment. DSC studies were conducted in order to determine a novel heat‐treatment protocol to attain transparent GCs by controlling crystal growth. The structural properties of the BBT GCs have been investigated using XRD, FE‐SEM, TEM and FTIR reflectance spectroscopy. Optical band gap energies of the glass‐ceramic samples were found to decrease with respect to the precursor glass. An increased intensity of emission along with increase in the average lifetime of Eu³⁺ was observed due to incorporation of Eu³⁺ ions into the low‐phonon energy BBT crystal site. The local field asymmetric ratios of all the samples were observed greater than unity. The dielectric constant (ε_r), dielectric loss, and dissipation factor values of both the base glass and ceramized samples were found to decrease with increase in frequency.     

Enhanced up-conversion luminescence of Tb3+-Yb3+ doped glass ceramics by doping Li+

Tb³⁺-Yb³⁺ co-doped transparent glass ceramics (GCs) containing Y₂Ti₂O₇ crystal phases were synthesized by the melt crystallization. The light transmittance of GCs in the visible region reached 78%, and the average grain size was 278 nm under the optimal heat treatment conditions (720 °C/2 h). The GCs exhibited greater up-conversion luminescence intensity than precursor glass, and the reason for this result was explained in accordance with the Judd-Ofelt theory. Moreover, the introduction of Li⁺ did not change the crystalline phase of GCs. The emission intensity of the green light of the 8% Li ⁺ doped GCs was significantly enhanced by nearly 4.48 times under 980 nm excitation. The XRD refinement results suggest that the enhanced luminescence intensity is correlated with the change of the Y₂Ti₂O₇ crystal lattice caused by Li⁺ doping. The relevant luminescence mechanism was elucidated. The results suggest that Li⁺ doped transparent GCs open novel avenues for green UC applications.     

Enhanced visible emissions of Pr3+-doped oxyfluoride transparent glass-ceramics containing SrF2 nanocrystals

The Pr³⁺-doped oxyfluoride transparent glass and glass-ceramic (GC) with the composition of 41SiO₂ + 10Al₂O₃ + 25.5LiF + 23SrF₂ + 0.5Pr₂O₃ were prepared and investigated their optical and luminescence properties. The formation of SrF₂ nanocrystals in GC has been confirmed by X-ray diffraction (XRD) and transmission electron micrographs (TEM). The Fourier transform infrared spectroscopy (FT-IR) studies were used to examine the network structure characteristics of silicates in the glass matrices. The XRD and TEM results suggest that the Pr³⁺ ions are progressively incorporated into the SrF₂ nanocrystals in the GC with increase in time of thermal treatment at 650 °C, corresponding to the first crystallization temperature of the glass. The obtained visible emissions of Pr³⁺-doped GC are several times enhanced than that in the glass and the lifetime of the ³P₀ level of the Pr³⁺ ions in glass and GC are found to be 7 and 12 μs, respectively. Therefore, the enhanced visible emission and lifetimes in GC are due to the incorporation of Pr³⁺ ions into the lower phonon energy of SrF₂ nanocrystals in the GCs. Moreover, the smaller difference in ionic radius between the added trivalent ions (Pr³⁺) and Sr²⁺ induces the larger enhancement of luminescence intensity in the GC. Hence, these enhanced visible luminescence properties indicate that the present glass and GC could be useful for photonic device applications.     

Microstructure and ion-exchange properties of glass-ceramics containing ZnAl2O4 and β-quartz solid solution nanocrystals

Crystallization of glass has significant effects on glass structure and the resultant ion-exchange behaviors. In this work, transparent glass-ceramics (GCs) with sequential crystallization of ZnAl₂O₄ and β-quartz solid solution nanocrystals (NCs) were prepared, and effects of the crystallization on microstructure and ion-exchange properties were investigated. Compared with the specimen with simultaneous precipitation of ZnAl₂O₄ and β-quartz solid solution NCs, GCs with sequential crystallization of ZnAl₂O₄ and β-quartz solid solution NCs show smaller grain size and more uniform structure and higher transparency. Ion-exchange depth of layer (DOL) increases significantly with the crystallization of the specimens due to the reduction in content of zinc and five coordinated aluminum in the residual glass matrix. High residual compressive stress and Vickers hardness can be obtained after ion-exchange in KNO₃ molten salt.     

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).     

Enhanced energy storage properties of BaO-K2O-Nb2O5-SiO2 glass ceramics obtained through microwave crystallization

BaO-K₂O-Nb₂O₅-SiO₂ (BKNS) glass ceramics were prepared by microwave crystallization of transparent glass matrices and the effects of microwave treatment temperature on their dielectric performances, phase structure, microstructure and breakdown strength (BDS) were investigated systematically. X-ray diffraction results suggested that microwave treatment had no significant influence on the type of precipitated phases. The microstructure of the glass ceramics was remarkably optimized via microwave treatment. The dielectric constant and breakdown strength of microwave-treated samples were significantly improved as compared with conventional-heated samples at the same temperature. The maximum theoretical energy storage density of microwave-treatment samples at 750?°C reached 12.7?J/cm³, which was larger than that of the conventional-heated samples (8.6?J/cm³).     

Phase evolution and photoluminescence in Er3+ doped glass ceramics containing lutetium oxyfluoride nanocrystals

Crystalline phase evolution through merely adjusting composition was achieved in silicate glass ceramics containing Lu_nO_n-1F_n+2 (n = 5–10) nanocrystals. Orthorhombic or cubic phase nanocrystals were precipitated in the aluminosilicate glass matrix after thermal treatment together with varying the Na₂O/NaF ratio. Oxyfluoride nanocrystals with quasi-spherical shape show homogenous and dense distribution in glass matrix by transmission electron microscopy measurement. Intense upconversion and mid-infrared emissions were realized in these glass ceramics compared to the precursor glass, and the emission spectral shapes, relative emission intensity and fluorescence decay curves of Er³⁺ in cubic LuOF embedded samples exhibit remarkable differences due to the crystal phase dependent effect in glass ceramics. These results indicate that the crystallization and luminescence properties of oxyfluoride glass ceramics could be modified through the alteration of glass composition, which could be used for the development of novel glass ceramics and design of luminescent properties.     

Fabrication of transparent LaAlO3/t-ZrO2 nanoceramics through controlled amorphous crystallization

Transparent nanoceramics are attracting more and more interests recently, while it is practically difficult to prepare by conventional sintering process because of undesirable grain growth. In this study a new method of amorphous sintering followed by controlled crystallization (ASCC) was developed, and transparent LaAlO₃/t-ZrO₂ nanoceramics were prepared as examples. Glass powders from Al₂O₃-La₂O₃-ZrO₂ (ALZ) were synthesized, sintered, and then converted to nanoceramics by post-heat-treatment. The processes of hot pressing and controlled crystallization were investigated in detail. The heat-treatment performed at 1200 °C for 2 h produced a transparent LaAlO₃/t-ZrO₂ nanoceramic with an average grain size of 40 nm. Due to the nanoscale microstructure, the composite showed a transparency up to 55% at 800 nm (1 mm thick), Vickers hardness of 19.05 GPa, and fracture toughness of 2.64 MPa m^1/2, respectively. It is expected to be a promising candidate for window materials.     

Study on non-isothermal crystallization kinetics of the BaO-CaO-Al2O3-B2O3-SiO2 glass for IT-SOFCs sealing

The crystallization ability plays a key role in effecting thermal ability of sealing glass for intermediate temperature-solid oxide fuel cells (IT-SOFCs) to prevent fuel leakage during operation and insulate the cell stack from the external atmosphere. Herein, using differential thermal analysis (DTA) techniques, the growth mode of crystals precipitated in BaO-CaO-Al₂O₃-B₂O₃-SiO₂ (BCABS) sealing glass through the heat treatment was calculated in terms of non-isothermal crystallization kinetics for the first time. The calculated results showed that the average kinetic exponent n of the glass was approximatively 1, indicating that the crystal nucleuses became to form and further grew with one-dimensional mode from the surface inwards. Scanning electron microscope (SEM) observations clearly revealed that a large number of one-dimensional filamentous crystals have been formed on the interface between the sealing glass and the electrolyte after the heat treatment at 973?K for 100?h, which perfectly coincided with the theoretical calculations, and the glass was well combined with the electrolyte without any visible cracks or peeling at the interface. The one-dimensional growth of hexagonal BaAl₂Si₂O₈ crystals verified by X-ray diffraction (XRD) could effectively decelerate the decrease of thermal expansion coefficient of glass to ensure enhance the thermo-stability of the BCABS sealing glass for IT-SOFC.     

Optical Active Nano-Glass-Ceramics

This paper reviews the synthesis and characterization of several transparent glass-ceramics with optical active nanocrystals. Glass-ceramics containing ferroelectric Sr_xBa_1-xNb₂O₆ nanocrystals with an ellipsoidal shape show optical phase modulations in the presence of alternative electric fields. In the glass-ceramics with Ba₂TiSi₂O₈ (BTS) nanocrystals, BTS crystalline layers with a thickness of approximately 120 nm are formed at the surface and ellipsoidal-shaped crystallites with a diameter of 100–200 nm are dispersed in the glass matrix. Some TeO₂-based and GeO₂-based glasses show a prominent nanocrystallization. RE-doped CaF₂ nanocrystals are patterned in a spatially selected region by laser irradiations. The size, morphology, and dispersion state of nanocrystals should be carefully checked in each glass system and composition. The basic concept for the design of glass system and composition is also discussed. Some data on optical active performances in transparent glass-ceramics with nanocrystals were introduced.     

CO2 laser-assisted preparation of transparent Eu2Ti2O7 thin films

We present a laser-assisted preparation of transparent europium-titanate Eu₂Ti₂O₇ thin films with tailored structural and optical properties. We have evaluated the effects of the irradiation time on the structural and the optical properties of the films. This approach allows the preparation of nanocrystalline crack-free films and micro patterns. The amorphous thin films were prepared by a sol-gel method. The films were annealed by a CO₂ laser beam for various time intervals. The laser irradiation induced a crystallization process that resulted in the formation of Eu₂Ti₂O₇ nanocrystals. The nanocrystals regularly grew with increasing irradiation time reaching the size from 25?nm to 45?nm. A film of a thickness 480?nm exhibited an optical transmission of 91.9% that is close to the maximal theoretical limit. The film's refractive index at 632?nm was 2.26. A micrometric pattern was prepared by a direct laser writing followed by a wet chemical etching. Feasibility of the demonstrated approach, together with the high film's quality, and europium-titanate chemical resistivity open up many opportunities for advanced applications. The approach can be used for a preparation of protective coatings and integrated photonic devices such as planar optical waveguides and couplers.     

Effect of some nucleating agents on crystallizing phases and microstructure in Li2O–BaO–Al2O3–SiO2 system

Different concentrations of LiF and Cr₂O₃ were incorporated in Li, Ba aluminosilicate glass to establish their effects on the crystallization process. The kinetics of phase transformations, the final crystalline phase assemblages and the microstructures formed were found to be dependent on the types and concentration of the nucleant involved. Cr₂O₃ was found to increase the melting temperature and favor crystallization of β-spodumene ss hexacelsian and traces of monoclinic celsian. It also favors volume crystallization of finer grained microstructure. LiF was found to decrease the melting temperature and favor crystallization of β-spodumene ss and monoclinic celsian. LiF in low concentrations greatly facilitates the crystallization process, the β-eucryptite ss/β-spodumene ss transformation and hexacelsian/monoclinic celsian transformation. It also stimulates surface crystallization with holocrystalline coarse non-uniform textures. The effects of various Cr₂O₃ concentrations were discussed on the basis of the increased viscosity and separation of Cr₂O₃ and/or chromium spinel phases. The role of LiF was attributed to the role of fluorine ions in reducing the viscosity of the glasses, consequently facilitating crystallization of the structurally more complex silicate in addition to favoring reaching thermodynamic equilibrium.     

Non-isothermal crystallization kinetics of MgO–BaO–B2O3–Al2O3–SiO2 glass

5MgO–9BaO–33B₂O₃–33Al₂O₃–20SiO₂ (mol%) glass was prepared by the melt quenching method at 1823 K for 2 h. Dilatometry and differential scanning calorimetry (DSC) curves of the glass have been investigated. Fragility index F was used to estimate glass formability. The crystallization kinetics of the glass was described by the activation energy (E) for crystallization and numerical factors (n, m) depending on the nucleation process and growth morphology. XRD and SEM analysis were also used to describe the crystals’ types and morphology precipitated from the MgO–BaO–B₂O₃–Al₂O₃–SiO₂ glass. The results show that the effective activation energy of the crystallization process E was 45.19 kJ/mol, and n up to 4.05. Two crystals phases, i.e. Al₄B₂O₉ and Al₂₀B₄O₃₆ were observed in the crystallized samples. SEM results were consistent with crystallization kinetics.     

Preparation of surface-crystallized optical glass-ceramics SrO · 2B<Subscript>2</Subscript>O<Subscript>3</Subscript>

The physicochemical features of the phase formation upon crystallization of monolithic glasses of the strontium diborate stoichiometric composition are investigated. It is demonstrated that the first phase crystallizing on the surface of the SrO · 2B₂O₃ glass is the strontium borate Sr₄B₁₄O₂₅, which plays the role of a precursor for the subsequent crystallization of the SrB₄O₇ borate. The temperature corresponding to the maximum crystal nucleation rate on the surface and the time of complete “operation” of nuclei are determined using differential thermal analysis. The optical glass-ceramics prepared by the two-stage crystallization are surface-crystallized glasses in which the filling density of the surface is approximately equal to 30% and the content of the main phase SrB₄O₇ is as high as ∼ 70%. No second harmonic generation of neodymium laser radiation in the glass-ceramics is observed because of both the absence of the preferred orientation of SrB₄O₇ nonlinear optical crystals and the small crystal sizes (considerably smaller than the coherence length of the SrB₄O₇ crystal) in the direction perpendicular to the glass surface.     

Microstructure and ion-exchange properties of transparent glass-ceramics containing Zn2TiO4/α-Zn2SiO4 nanocrystals

Transparent glass-ceramics have particular properties compared with their precursor glasses, and have promising potential applications in many fields. Titanium-relative phases are frequently employed as nucleation agents for crystallization of glass-ceramics, and rarely been precipitated as functional nanocrystalline phases in glass-ceramics. In this work, transparent glass-ceramics containing Zn₂TiO₄ and/or α-Zn₂SiO₄ nanocrystals are investigated. It turns out that Vickers hardness of these glass-ceramics increases with the precipitation of Zn₂TiO₄ and α-Zn₂SiO₄ nanocrystals. Despite the blocking effect of nanocrystals precipitated in the glass-ceramics, structural and compositional modification of the residual glass induced by the precipitation of these nanocrystalline phases facilitates the K-Na ion-exchange, leading to the enhanced depth of layer and further improved Vickers hardness of the glass-ceramics.     

Effect of P2O5 on the Nonisothermal Sinter‐Crystallization Process of a Lithium Aluminum Silicate Glass

Dense (~98.5%), lithium aluminum silicate glass‐ceramics were obtained via the sinter‐crystallization of glass particle compacts at relatively low temperatures, that is, 790–875°C. The effect of P₂O₅ on the glass‐ceramics' sinter‐crystallization behavior was evaluated. We found that P₂O₅ does not modify the surface crystallization mechanism but instead delays the crystallization kinetics, which facilitates viscous flow sintering. Our glass‐ceramics had virgilite (Li_xAl_xSi_3‐xO₆; 0.5 < x < 1), a crystal size <1 μm, and a linear thermal expansion coefficient of 2.1 × 10^?6°C^?1 in the temperature range 40–500°C. The overall heat treatment to obtain these GCs was quite short, at ~25 min.     

Influence of Cr2O3, LiF, CaF2 and TiO2 nucleants on the crystallization behavior and microstructure of glass-ceramics based on blast-furnace slag

Glass-ceramics based on blast-furnace slag (56.78 wt%) were prepared by mixing quartz sand, dolomite, limestone, clay as other batch constituents.The nucleating agents Cr₂O_3, LiF, CaF₂ and TiO₂ were added to the batches to study their effects on the crystallization, phase assemblages, and microstructure. Glass-ceramics were obtained by single and double heat-treatment schedules and examined by DTA, XRD and polarizing microscope. The presence of Cr₂O_3, TiO_2, CaF₂ and LiF was found to enhance the crystallizability of the glass. Cr₂O₃ and TiO₂ are much better than LiF and CaF₂ in promoting homogeneous nucleation and the formation of extremely fine-grained microstructure of aluminous pyroxene and magnetite.     

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.     

Chalcogenide glasses with embedded ZnS nanocrystals: Potential mid‐infrared laser host for divalent transition metal ions

Chalcogenide glasses (ChGs) containing II‐VI chalcogenide (ChG) nanocrystals such as ZnS/Se have recently been intensively studied as promising mid‐infrared nonlinear optics and laser materials, yet preparation of pure‐phase II‐VI nanocrystals embedded in ChGs via controlled crystallization is still very challenging. In this study, a new system of ChGs and glass ceramics (GCs), viz., (100?x)As₂S₃–xZnSe (x = 0 ~ 30 mol%), is synthesized, and its physical and optical properties including density, molar volume, microhardness, glass transition temperature, glass network structure, transmission, and refractive index are comprehensively characterized. Significantly, it is initially demonstrated that pure ZnS nanocrystals can be precipitated in GCs simply by a thermal treatment process. The composition and thermal treatment temperature dependencies of crystallization are studied using X‐ray diffraction spectroscopy, and the morphology of the nanocrystals by high‐resolution transmission electron microscope. The ChG GCs with embedded ZnS nanocrystals retaining good transparency can be a potential host laser material for divalent transition metals (e.g., Cr²⁺/Fe²⁺, etc.), and thus used for ultrabroadband tunable continuous or ultra‐short‐pulsed mid‐infrared fiber lasers.