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.     

Facile one-step solid-state reaction route to synthesize ordered mesoporous β-Zn2SiO4–SiO2 nanocomposites

Ordered crystalline mesoporous β-Zn₂SiO₄–SiO₂ nanocomposites were prepared by one-step solid-state reaction using mesoporous silica as both template and silica source. Zinc oxide formed by decomposition of zinc nitrate reacts with mesoporous silica and the β-Zn₂SiO₄ forms and disperses inside the silica walls. The obtained β-Zn₂SiO₄–SiO₂ nanocomposites possess hexagonal mesostructure with the β-Zn₂SiO₄ weight percentage below 40%. The β-Zn₂SiO₄ nanocrystals are surrounded by the non-crystalline silica of mesoporous walls. The non-crystalline silica acting as a binder to stick β-Zn₂SiO₄ nanocrystals plays a role in restraining the phase transformation from β-Zn₂SiO₄ to α-Zn₂SiO₄ and increasing the thermal stability of mesoporous β-Zn₂SiO₄. The crystalline mesoporous β-Zn₂SiO₄ may be a potential candidate for application as absorbents, for separation and as phosphors.     

Effect of ZrO2 crystallization on ion exchange properties in aluminosilicate glass

Ion exchange has the potential to improve the mechanical properties of glass ceramics. In this work, ZrO₂ nanocrystals embedded transparent glass ceramics were prepared and effect of the crystallization on ion-exchange properties was investigated. The crystallization of ZrO₂ did not affect the transmittance and Vickers hardness due to the small nanocrystal size and the low crystallinity, but significantly enhanced the ion exchange depth of layer (DOL). X-ray diffraction, high resolution transmission electron microscope, Raman spectra and nuclear magnetic resonance analysis demonstrated that with the crystallization of ZrO₂, the charge compensator (Na⁺) was released, which promoted the transformation of highly coordinated Al into [AlO₄]⁻ tetrahedral units and the formation of Na⁺ balanced non-bridging oxygens. These changes in structure of glass made the Na⁺ more mobile and increased the DOL upon the crystallization. Results reported here may be useful for the development of glass-ceramic materials suitable for chemical strengthening.     

Surface crystallized Mn-doped glass-ceramics for tunable luminescence

Monolithic luminescent glass-ceramic is highly desirable for solid-state lighting as it is stable and robust, while in practical light-emitting devices only a thin luminescent layer is used for more efficient excitation and light extraction. In this paper, Mn²⁺-doped glass and glass-ceramic with the composition of 60SiO₂-8Na₂O–20ZnO–12Ga₂O₃ were fabricated by the conventional melt-quenching technique. We observe that the crystallization of α-Zn₂SiO₄ nanocrystals takes place on the glass surface with controllable thickness after heat treatment. The glass samples show typical red emission peaking at λ = 620 nm that can be ascribed to the spin-forbidden ⁴T_1g(G) → ⁶A_1g(S) transition of Mn²⁺ (d⁵) located in the octahedral coordination site of the glass host. After surface crystallization this red emission is retained and a new green emission at 528 nm is observed through the control of the crystallization temperature and duration, thus offering tunable emission characteristics promising for the lighting application. This change in the visible emission is interpreted in terms of the change of coordination state of Mn²⁺ from octahedral in a glass matrix to tetrahedral in the surface precipitated α-Zn₂SiO₄ crystals.     

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 Glass Composition on the Refractive Index Change upon Photothermoinduced Crystallization

The influence of the main components (SiO₂, Al₂O₃, ZnO, and Na₂O) of a photothermorefractive glass matrix and Br^–ions on the change in the refractive index is studied in the course of photothermoinduced crystallization in glasses. The optimum concentrations of these components at which the change in the refractive index is maximum are determined. The regularities revealed are explained within the modern concepts of the structure of polychromatic glasses and the nature of the photothermorefractive effect.     

Understanding the structural origin of crystalline phase transformations in nepheline (NaAlSiO4)‐based glass‐ceramics

Nepheline (Na₆K₂Al₈Si₈O₃₂) is a rock‐forming tectosilicate mineral which is by far the most abundant of the feldspathoids. The crystallization in nepheline‐based glass‐ceramics proceeds through several polymorphic transformations — mainly orthorhombic, hexagonal, cubic — depending on their thermochemistry. However, the fundamental science governing these transformations is poorly understood. In this article, an attempt has been made to elucidate the structural drivers controlling these polymorphic transformations in nepheline‐based glass‐ceramics. Accordingly, two different sets of glasses (meta‐aluminous and per‐alkaline) have been designed in the system Na₂O–CaO–Al₂O₃–SiO₂ in the crystallization field of nepheline and synthesized by the melt‐quench technique. The detailed structural analysis of glasses has been performed by ²⁹Si, ²⁷Al, and ²³Na magic‐angle spinning — nuclear magnetic resonance (MAS NMR), and multiple‐quantum MAS NMR spectroscopy, while the crystalline phase transformations in these glasses have been studied under isothermal and non‐isothermal conditions using differential scanning calorimetry (DSC), X‐ray diffraction (XRD), and MQMAS NMR. Results indicate that the sequence of polymorphic phase transformations in these glass‐ceramics is dictated by the compositional chemistry of the parent glasses and the local environments of different species in the glass structure; for example, the sodium environment in glasses became highly ordered with decreasing Na₂O/CaO ratio, thus favoring the formation of hexagonal nepheline, while the cubic polymorph was the stable phase in SiO₂–poor glass‐ceramics with (Na₂O+CaO)/Al₂O₃ > 1. The structural origins of these crystalline phase transformations have been discussed in the paper.     

Elucidating the Effect of Iron Speciation (Fe2+/Fe3+) on Crystallization Kinetics of Sodium Aluminosilicate Glasses

We report on the influence of Fe₂O₃ on the crystallization kinetics of nepheline (Na₂O·Al₂O₃·2SiO₂)‐based sodium aluminosilicate glasses. A series of glasses with varying Al₂O₃/Fe₂O₃ content were synthesized in the system 25Na₂O–(25–x) Al₂O₃–xFe₂O₃–50SiO₂ (x varies between 0 and 5 mol%) through melt‐quench technique. A systematic set of experiments were performed to elucidate the influence of iron speciation (Fe²⁺/Fe³⁺) on the crystallization kinetics of these glasses including: (1) obtaining the details of nonisothermal crystallization kinetics by differential scanning calorimetry, (2) determining the influence of heat treatment on the structure and iron coordination in glasses by X‐ray photoelectron spectroscopy and wet chemistry, and (3) following the crystalline phase evolution in glasses in air and inert environments by X‐ray diffraction and scanning electron microscopy. The crystallization of two polymorphs of NaAlSiO₄—carnegieite (orthorhombic) and nepheline (hexagonal)—was observed in all the glasses, wherein the incorporation of iron promotes the formation of nepheline over carnegieite while shifting the crystallization mechanism from surface to volume. The influence of environment (air versus inert) and iron content on the crystallization kinetics of these glasses is contextualized from the perspective of the devitrification problem usually observed in sodium‐ and alumina‐rich high level nuclear waste glasses.     

Structural dependence of crystallization in phosphorus-containing sodium aluminoborosilicate glasses

The article reports on the structural dependence of crystallization in Na₂O–Al₂O₃–B₂O₃–P₂O₅–SiO₂-based glasses over a broad compositional space. The structure of melt-quenched glasses has been investigated using ¹¹B, ²⁷Al, ²⁹Si, and ³¹P magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, while the crystallization behavior has been followed using X-ray diffraction and scanning electron microscopy combined with energy dispersive spectroscopy. In general, the integration of phosphate into the sodium aluminoborosilicate network is mainly accomplished via the formation of Al–O–P and B–O–P linkages with the possibility of formation of Si–O–P linkages playing only a minor role. In terms of crystallization, at low concentrations (≤5 mol.%), P₂O₅ promotes the crystallization of nepheline (NaAlSiO₄), while at higher concentrations (≥10 mol.%), it tends to suppress (completely or incompletely depending on the glass chemistry) the crystallization in glasses. When correlating the structure of glasses with their crystallization behavior, the MAS NMR results highlight the importance of the substitution/replacement of Si–O–Al linkages by Al–O–P, Si–O–B, and B–O–P linkages in the suppression of nepheline crystallization in glasses. The results have been discussed in the context of (1) the problem of nepheline crystallization in Hanford high-level waste glasses and (2) designing vitreous waste forms for the immobilization of phosphate-rich dehalogenated Echem salt waste.     

RELATION OF ELECTRICAL CONDUCTIVITY TO CHEMICAL COMPOSITION OF GLASS*

The electrical conductivity of some glasses in the soda-lime-silica system was measured at 400 °C. with an apparatus which is described. The specific resistance at this temperature ranged from 0.06 to 5.0 × 10⁵ ohms per cc. Measurements were made on other glasses containing equivalent amounts of various oxides incorporated in a parent soda-lime-silica glass. It was found that an increase in resistance was produced by additions of MnO, ZnO, B₂O₃, Fe₂O₃, BaO, PbO, TiO₂, and K₂O, the resistances increasing in this order. A decreased resistance was produced by Na₂O, CaO, and Al₂O₃. Previously published data on the power factors of these glasses are reviewed.     

Transparent glazes with reduced concentration of B2O3

Na₂O?K₂O?CaO?B₂O₃?Al₂O₃?SiO₂ glasses low in B₂O₃ (14%) and highly resistant to crystallization and liquation under heating are synthesized. They are used for making transparent low-melting heat-resistant glazes with a low boron ion migration rate.     

Crystallization and Nonlinear Optical Properties of Potassium Niobium Silicate Glasses

The crystallization of the xK₂O · xNb₂O₅· (1 – 2x)SiO₂(x= 0.167–0.250) glasses and glasses close in composition to K₂O · Nb₂O₅· 4SiO₂at the ratio K₂O : Nb₂O₅ 1 is investigated. In high-silica glasses, the metastable phase separation followed by the bulk multiphase crystallization are observed at temperatures close to the glass transition point T _g. The nanostructured transparent glasses that exhibit the optical second harmonic generation (SHG) effect are formed at the early stages of phase separation. The surface crystallization of glasses with the precipitation of the KNbSi₂O₇noncentrosymmetric phase occurs at higher temperatures.     

Thermal behavior,structure, crystallization and solubility of the melt-derived SiO2–P2O5–Na2O–F-MO (M = Ca,Sr, Zn) glasses

In this work, phospho-silicate glasses with SiO₂–P₂O₅–Na₂O–F-MO (M = Ca, Sr, Zn) composition were prepared by using the conventional melt quenching technology. Structural, physical, and chemical property tests were used to analyze the effects of different SrO and ZnO content on the structure and properties of the glasses. The results showed that the glass stability varied nonlinearly as CaO was replaced by SrO, which was mainly related to the different positions of Sr²⁺ and Ca²⁺ ions breaking the network connection in the network structure, and the substitution of ZnO for CaO led to a continuous decrease in the stability of the glasses. The immersion experiment showed that SrO doping was more feasible than ZnO doping to improve the biological activity of the glasses, and the doping of ZnO promoted the dissolution of ions in the glasses. The obtained results indicated that the glass samples prepared in this paper have potential biological activity, which has potential applications in dental treatment.     

Impact of the cation field strength on physical properties and structures of alkali and alkaline-earth borosilicate glasses

The impact of the cation field strength (CFS) of the glass network-modifier cations on the structure and properties of borosilicate glasses (BS) were examined for a large ensemble of mixed-cation (R/2)M₍₂₎O–(R/2)Na₂O–B₂O₃–KSiO₂ glasses with M⁺ ={Li⁺, Na⁺, K⁺, Rb⁺} and M²⁺ ={Mg²⁺, Ca²⁺, Sr²⁺, Ba²⁺} from four series of {K, R} combinations of K = n(SiO₂)/n(B₂O₃) = {2.0, 4.0} and R =[n(M₍₂₎O) ?+ ?n(Na₂O)]/n(B₂O₃) = {0.75, 2.1}. Combined with results from La³⁺ bearing glasses enabled the probing of physical-property variations across a wide CFS range, encompassing the glass transition temperature (T_g), density, molar volume and compactness, as well as the hardness (H) and Young's modulus (E). We discuss the inferred composition–structure/CFS–property relationships. Each of T_g, H, and E revealed a non-linear dependence against the CFS and a strong T_g/H correlation, where each property is maximized for the largest alkaline-earth metal cations, i.e., Sr²⁺ and Ba²⁺, along with the high-CFS La³⁺ species. The ¹¹B MAS NMR-derived fractional BO₄ populations decreased linearly with the average M^z+/Na⁺ CFS within both K–0.75 glass branches, whereas the NBO-rich K–2.1 glasses manifested more complex trends. Comparisons with results from RM₂O–B₂O₃–KSiO₂ glasses suggested no significant “mixed alkali effect”.     

Effect of ZnO/K2O ratio on the crystallization sequence and microstructure of lithium disilicate glass-ceramics

The effect of ZnO/K₂O (Z/K) ratio on the crystallization sequence and microstructure of lithium disilicate (Li₂Si₂O₅: LS2) glass-ceramics was carefully investigated for the SiO₂-Li₂O-K₂O-ZnO-P₂O₅ system. The Z/K ratios of precursor glasses were varied from 0 to 3.5 while the nucleating agent of P₂O₅ and glass modifiers of ZnO plus K₂O were fixed to have 1.5 and 4.5 mol% relative to LS2, respectively. For the samples prepared by two-stage heat treatments of 500 °C for 1 h and 800 °C for 2 h in air, the LS2 nucleation rate was increased with increasing the Z/K ratio due to the variation in crystallization sequence from type II (Li₂SiO₃: LS) to type I (LS + LS2) in addition to an amorphous phase separation in base glass. Consequently, with increasing the Z/K ratio, the LS2 crystalline phase within the glass matrix continuously changed from larger acicular ones to smaller equiaxed ones.     

Statistical mechanical model for the formation of octahedral silicon in phosphosilicate glasses

Unlike ambient pressure silicate glasses, some phosphosilicate glasses contain sixfold-coordinated silicon (Si⁶) units even when prepared at ambient pressure. The variation in the fraction of Si⁶ with composition remains a topic of interest, both for technological applications of phosphosilicate glasses and for fundamental understanding of the glass structure. In this work, we use statistical mechanical modeling to predict the composition–structure relationships in Na₂O–P₂O₅–SiO₂ and CaO–P₂O₅–SiO₂ glasses. This is achieved by accounting for the enthalpic and entropic contributions to the interactions between each pairwise modifier ion and structural unit. The initial enthalpy parameters are obtained based on experimental structural data for binary Na₂O–SiO₂, CaO–SiO₂, Na₂O–P₂O₅, and CaO–P₂O₅ glasses, which can then be transferred to predict the structure of mixed former glasses. This approach has previously been used to predict the short-range structure of borosilicate and aluminoborate glass systems. However, here we show that the formation of Si⁶ must be specifically included to make accurate predictions of the composition–structure relationships in phosphosilicate glasses. After incorporating the formation mechanism of Si⁶ in the statistical mechanics model, we find an excellent agreement between model predictions and experimental structure data for Na₂O–P₂O₅–SiO₂ and CaO–P₂O₅–SiO₂ glasses.     

The effects of SiO2 and K2O on glass forming ability and structure of CaOTiO2P2O5 glass system

The effects of SiO₂ and K₂O were investigated on the glass forming ability (GFA) and structural characteristics of CaOTiO₂P₂O₅ system. Differential thermal analyzer (DTA), X-ray diffraction (XRD), scanning electron microscopy (SEM), FT-IR and ³¹P magic angle spinning NMR methods were applied for characterizations of the system.Unwanted crystallization in the initial three components base glass composition was observed by adding SiO₂ and crystalline phases such as TiP₂O₇, rutile (TiO₂) and cristobalite (SiO₂) were formed in it.The results showed that K₂O prevents crystallization of glasses and promotes the formation of glass. FT-IR and X-ray diffraction showed that the addition of K₂O caused the formation of phosphate–silicate network as POSi, and formation of isolated droplet phases (rich of Si and P) separated from the phosphate matrix.The optimum amounts of SiO₂ and K₂O in phosphate structure were respectively 6 and 2 wt.%, 0 in accordance with glass forming ability (GFA) parameters. Despite addition of SiO₂ along with K₂O; the ³¹P MAS NMR and infrared spectrums of glasses show that no Q² sites were in the phosphate network. The Q¹ and the pyrophosphate groups was the predominant structural unit in these glasses.     

Influence of Cr3+ on yellowish-green UC emission and energy transfer of Er3+/Cr3+/Yb3+ tri-doped zinc silicate glasses

In this paper, we study the influence of Cr³⁺ on yellowish-green upconversion (UC) emission and the energy transfer (ET) of Er³⁺/Cr³⁺/Yb³⁺ tri-doped in SiO₂–ZnO–Na₂O–La₂O₃ (SZNL) zinc silicate glasses under excitation of the 980 nm laser diode (LD). The influence of Cr³⁺ on enhancing the red UC emission of Er³⁺/Cr³⁺/Yb³⁺ tri-doped in SiO₂–ZnO–Na₂O–La₂O₃ zinc silicate glasses under the excitation of 980nm LD was also investigated. The ET processes between Yb³⁺, Cr^3+, and Er³⁺, together with the combination of Yb³⁺-Cr³⁺-Er³⁺, which led to the green UC emission intensity of Er³⁺/Cr³⁺/Yb³⁺ tri-doped in SiO₂–ZnO–Na₂O–La₂O₃ zinc silicate glasses bands centered at ~546 nm have been significantly enhanced. By increasing the concentration of Cr³⁺ from 0 up to 5 mol.%, we can locate the Commission Internationale de l'éclairage (CIE) 1931 (x; y) chromaticity coordinates for UC emissions of Er³⁺/Cr³⁺/Yb³⁺ tri-doped in the central position of the yellowish-green color region of CIE 1931 chromaticity diagram. Besides, the ET processes between the Yb³⁺, Cr³⁺, and Er³⁺ are also proposed and discussed.     

Reduction of crystallization ability of sodium zinc phosphate glass under X-ray radiation

The effect of X-ray radiation on the crystallization ability of maximally homogenized sodium zinc phosphate glass with a minimal light scattering value of V _v = 4 × 10^?6 cm^?1 has been investigated. The crystallization kinetics of the sodium zinc phosphate glass of the 33.9P₂O₅ · 56.6ZnO · 9.5Na₂O (mol % from analysis) composition under the conditions of homogeneous nucleation and X-ray radiation have been studied. It has been demonstrated that the crystallization properties of phosphate glasses are more sensitive to the synthesis method than those of silicate glasses. It has been established that sodium zinc phosphate glass crystals represent the main crystalline phase precipitated in the glass of the above composition. The main parameters of nucleation have been determined in glass without preliminary radiation, including stationary nucleation rate I _st, nonstationary nucleation time ??, and nucleation activation energy E _??. It have been found that the effect of the CuK _?? X-ray radiation leads to the slowing down or even cessation of the nucleation of crystals in glass (the result depends on the change in the radiation intensity along the sample depth) in the case when radiation takes place immediately during the nucleation thermal treatment of the sample in a high-temperature chamber of the X-ray device. The kinetics of sodium zinc phosphate crystallization in the samples upon their pretreatment by CuK _?? X-ray irradiation has been investigated. It has been shown that the rate of crystal nucleation in glasses exposed to X-ray radiation is lower than that in glasses without preliminary irradiation.     

Diffusion of cations in sodium-potassium and sodium-barium silicate melts

Diffusion coefficients of sodium and potassium ions in molten glasses with the composition (25 ? x)Na₂O · xK₂O · 75SiO₂ have been determined by the sectioning method with measurement of the residual activity ²²Na and ⁴²K isotopes. Diffusion of sodium and ¹³³Ba ions has been studied in melts of the (30 ? x)Na₂O · xBaO · 5Ga₂O₃ · 65SiO₂ system. It has been found that the concentration dependences of diffusion characteristics in melts containing alkali and alkaline-earth cations principally differ from the regularities diffusion in dialkali melts.