Unveiling the evolution of early phase separation induced by P2O5 for controlling crystallization in lithium disilicate glass system

The nucleation and crystallization of glass-ceramics are typically influenced by early phase separation, which can impact glass properties. However, it has been challenging to characterize the nanoscale phase separation and understand the nucleation mechanism of lithium disilicate (L₂S) glass-ceramics, which has resulted in some controversy. Here, we raised the direct evidence of nanoscale clustering in the glassy phase prior to formal nucleation and crystallization by element distribution. Firstly, the amorphous Li₃PO₄ phase formed on the boundary between the phase separation area and residual glass matrix, and then nucleation tended to start on this phase boundary. Furthermore, the effect of phase-separation on nucleation and final crystallize products was illustrated. By sufficient phase-separation, the formation of desired Li₂Si₂O₅ and LiAlSi₄O₁₀ microcrystals was effectively motivated, which is prerequisite for high mechanical properties and transparency. We hope this work provides guidance to rationally understand the early phase separation in glass for subsequent controlling crystallization.     

Dual effect of ZrO2 on phase separation and crystallization in Li2O–Al2O3–SiO2–P2O5 glasses

ZrO₂ is an effective nucleation agent for low-expansion lithium–aluminum silicate (LAS) glass–ceramic (GC) with high Al₂O₃ content. However, the effect of ZrO₂ is still not fully understood in LAS glasses with low contents of Al₂O₃ and P₂O₅. In this work, the effect of ZrO₂ on the phase separation and crystallization of Li₂O–Al₂O₃–SiO₂–P₂O₅ glasses were investigated. The results revealed that ZrO₂ significantly increased T_g and the crystallization temperature of Li₂SiO₃ and Li₂Si₂O₅ crystals. Li₃PO₄ crystals precipitated preferentially in the glass containing 3.6-mol% ZrO₂, wherein Zr was stable in the network and no precipitation of ZrO₂ nanocrystals was observed. Moreover, the separation of phosphate-rich phases in the as-quenched glasses increased with the addition of ZrO₂. The findings of the study revealed a dual role of ZrO₂. First, ZrO₂ acted as a glass network former rather than a nucleation agent, increasing glass viscosity and the nucleation barrier of Li₂SiO₃ through its strong network connectivity. Second, as Zr preferentially combined with non-bridging oxygen to form Si–O–Zr linkages, a sufficient amount of charge-balancing Li⁺ ions existed in the network, which promoted the separation of phosphate-rich phases. It indicated that the incorporation of ZrO₂ contributes to the activation of the nucleation role of P₂O₅, thus contributing to the formation of nanocrystals and fine microstructure of GCs.     

Rapid preparation of low thermal expansion transparent LAS nanocrystalline glass by one-step thermoelectric treatment

The Li₂O–Al₂O₃–SiO₂ (LAS) glass ceramics are prepared by one-step thermoelectric treatment. The influence of thermoelectric treatments on LAS glass-ceramics were studied. The crystal phase composition and microstructure of the LAS glass-ceramics were investigated by DSC, SEM, XRD and FTIR. Moreover, the thermal expansion performance and light transmittance of LAS nanocrystalline glass were characterized. The results show that low-expansion transparent LAS nanocrystalline glass can be produced in a short time by thermoelectric treatment. The free energy of nucleation and the degree of polymerization of the glass network are reduced by the electric field. The key is that the electric field polarizes Ti and Zr ions at the crystallization temperature, so that the crystal nuclei repel the same poles. This allows uniform crystal distribution, promotes crystallization and reduces one-step crystallization of crystal agglomeration. This proves that the rapid preparation of nanocrystalline glass by the one-step method is feasible, and provides a reference for the future one-step processing of glass-ceramics.     

Low Li2O content study in Li2O-Al2O3-SiO2 glass-ceramics

The price of lithium-containing minerals and other chemical materials continues to increase, resulting in an increase in the production cost of Li₂O-Al₂O₃-SiO₂ (LAS) system glass-ceramics. In the LAS glass-ceramics component, the reduction in the amount of Li₂O used can reduce the cost of the product. It is worthwhile to study whether it is possible to prepare glass-ceramics with low expansion properties under low Li₂O content. The effect of Li₂O content on the glass-ceramics of LAS system was studied. In this paper, spodumene was used as the main raw material, and TiO₂ and ZrO₂ were added as crystal nucleating agents to prepare transparent glass-ceramics with low expansion coefficient. The effects of the change of Li₂O content on the crystal phase and microstructure of glass-ceramics were investigated by XRD, DSC, FTIR and SEM. The results show that the main crystalline phase of the low expansion transparent glass-ceramics is β-quartz solid solution. When Li₂O content is in the range of 2.99 wt% to 4.13 wt%, low expansion glass ceramics can be prepared by an appropriate method. With the increase of Li₂O content, the average coefficient of thermal expansion (CTE) in the temperature range of 30 °C–300 °C shows a decreasing trend. When Li₂O content is in the range of 3.51 wt% to 4.13 wt%, the thermal expansion coefficient of the glass ceramics is extremely small, and even a negative expansion coefficient occurs.     

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 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.     

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.     

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.     

Thermo-magnetic properties of Fe2O3-doped lithium zinc silicate glass-ceramics for magnetic applications

The crystallization behaviour and thermo-magnetic characteristics of glass-ceramic based on the 15Li₂O–20ZnO–10CaO–55SiO₂ system doped with varied Fe₂O₃ additions (0.0125, 0.025, and 0.05 mol) are described in this work. In some cases, Al₂O₃ was also added to the iron-containing sample. Glasses were successfully prepared by melt-quenching technique and converted into glass-ceramics by controlled heat-treatment, using DTA, SEM, XRD, and VSM techniques. The density, thermal expansion coefficients (TCE), and magnetic characteristics of the glass-ceramic were examined. XRD results confirmed characteristic peaks for various phases like quartz, Li₂ZnSiO₄, wollastonite, Li₂Si₂O₅, ZnFe₂O₄, and β-spodumene. By doping Fe₂O₃ and Al₂O₃ with lowering annealing temperature, the particle size was reduce, resulting in glass-ceramics with a more uniform and dense microstructure. The density of glass-ceramics rises from 2.74 g/cm³ to 3.45 g/cm³, whereas the TCE values in average 14–78 × 10⁻⁷/°C with temperature range of 25–500 °C. The doped glass-ceramics have superior magnetic properties with saturation magnetization (0.143–0.548 emu/g), the coercivity force (65.116–86.359 G), and remanence magnetization (0.074–0.436 emu/g). Under an alternating magnetic field, the presence of the Zn-ferrite phase in the glass-ceramics improves their magnetic properties and increases their heat-generating capability. Certain features of the doped glass-ceramics control the extensive variety of possibilities for their usage in various magnetic applications particularly for cancer hyperthermia treatment.     

Effect of Li2O on the crystallization behavior of CaO-Al2O3-SiO2-Li2O-Ce2O3 mold slags

The effect of Li₂O on the crystallization properties of CaO-Al₂O₃-SiO₂-Li₂O-Ce₂O₃ slags was investigated. With increasing the Li₂O content, LiAlO₂ and CaCeAlO₄ were the main crystalline phases. LiAlO₂ formed for the charge compensating of Li⁺ ions to [AlO₄^5?]-tetrahedrons, and CaCeAlO₄ formed as a result of the charge balance of Ce³⁺ ions, Ca²⁺ ions, and [AlO₆^9?]-octahedrons. Increasing the content of Li₂O to 10%, the crystallization temperature was the highest, and the incubation time was the shortest. The crystallization ability was strong due to the three factors of strengthening the interaction between ions and ion groups, decreasing the polymerization degree, and increasing the melting temperature. Further increasing the content of Li₂O, the crystallization performance was obviously suppressed, because the melting temperature and the force between the cations and the anion groups decreased.     

Study of Li2O addition on crystallization behavior and thermal expansion properties of CaO-Al2O3–SiO2 (CAS) glass-ceramic and its application for joining SiC ceramic

Various glass-ceramics were prepared based on the CaO-Al₂O₃-SiO₂ system with the addition of Li₂O in an attempt to develop a suitable sealant for SiC ceramic. The effects of Li₂O content on crystallization behavior and thermal expansion properties were systematically investigated. The results revealed that the addition of Li₂O significantly reduced the crystallization activation energy of glass. Besides, as the Li₂O content increased, the precipitation of spodumene and wollastonite was promoted while the precipitation of anorthite was suppressed. By controlling the Li₂O content and crystallization treatment, the coefficient of thermal expansion (CTE) of glass-ceramic could be adjusted in a certain range, from 8.5 × 10^?6/°C to 2.8 × 10^?6/°C. When the content of Li₂O was 3 wt.%, the CTE of the formed glass-ceramic was well-matched with that of SiC ceramic. Furthermore, it was confirmed that this glass-ceramic possessed an excellent wettability and weldability to SiC ceramic.     

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%).     

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.     

Microstructural development during crystallization firing of a dental-grade nanostructured lithia-zirconia glass-ceramic

The microstructural development during crystallization firing of a commercially-available dental-grade nanostructured lithia-zirconia glass-ceramic (Vita Suprinity® PC) was unraveled using a wide battery of ex-situ and in-situ characterization techniques. It was found that the milling blocks are slightly crystallized glass-ceramics, with a complex chemical composition and consisting of partially de-polymerized glass plus lithium silicate (Li₂SiO₃) nanocrystals. It was also found that during crystallization firing the glassy matrix first reacts with part of the Li₂SiO₃ to form lithium disilicate (Li₂Si₂O₅) at ～810?820 °C, and then lithium orthophosphate (Li₃PO₄) precipitates from the glass. This results in glass-ceramics with abundant nanocrystals embedded in a sparse zirconosilicate glass matrix (containing many other cations subsumed) that, due to its high viscosity, inhibited crystal growth. Therefore, these dental glass-ceramics are not reinforced with zirconia (ZrO₂) crystals unless over-fired above ～890 °C and at the expense of its singular nanostructure. Finally, this study opens doors for optimizing the clinical performance of these dental glass-ceramics via microstructural tailoring.     

Phase and microstructural evolution in lithium silicate glass-ceramics with externally added nucleating agent

Development of lithium disilicate-based glass-ceramics critically depends on use of nucleating agent in the glass matrix. The present study reports the effect of externally added nucleating agent Li₃PO₄ in Li₂O–K₂O–MgO–ZnO–ZrO₂–Al₂O₃–SiO₂ system which is compared with a reference composition (GC1) (SiO₂:Li₂O = 2.16:1) prepared with in situ formed Li₃PO₄. For externally added Li₃PO₄, two compositions were studied. In one case (GC2) before addition of Li₃PO₄, SiO₂:Li₂O ratio in glass was maintained as 2.87:1 and in another case (GC3) SiO₂:Li₂O ratio in glass was maintained same as reference GC1 that is, 2.16:1. The glasses were characterized by using MAS-NMR spectroscopy. Sintering and crystallization behavior of the glass-ceramics was characterized by using XRD, SEM, DTA. Due to in situ formation of Li₃PO₄, GC1 resulted in a dense sample with finer crystals of lithium disilicate. In GC2 and GC3, externally added lithium phosphate, which was in the form of ultrafine aggregated particles, formed flower-like colonies of radially outward crystals. Higher SiO₂:Li₂O ratio in GC2 resulted in lithium disilicate crystals and high viscous glass causing large air entrapment and so less densification. GC3 with higher lithia in glass showed higher densification than GC2 but only lithium metasilicate crystals were formed.     

Microstructure,cytocompatibility, and chemical durability of chemically strengthened LAS (Li2O-Al2O3-SiO2) glass-ceramic materials

The K⁺-Na⁺ ion exchange was used to strengthen LAS glass-ceramic materials prepared by hot-pressing sintering. The microstructure, cytocompatibility, and chemical durability of the chemically strengthened LAS glass-ceramics were characterized. The XRD results showed that the K⁺-Na⁺ ion exchange mainly occurred between the glass phase of the LAS glass-ceramics and molten salt baths. The ion-exchange process was mainly responsible for the improved chemical durability of the LAS glass-ceramics. The dissolution in acetic acid was significantly reduced from 72 to 15 μg·cm^?2 after the ion-exchange treatment, which was attributed to residual compressive stress and increased contents of Q³ and Q⁴ structural units in the surface region of the LAS glass-ceramics. In addition, the chemically strengthened LAS glass-ceramic samples exhibited good biocompatibility determined by the CCK-8 process using the L929 cell line, having a promising potential as dental restorative materials.     

Effect of Li2O on melt crystallization of CaO–SiO2–CaF2 based glasses

This paper presents the effects of Li₂O on the kinetics and structural aspects of the Cuspidine (Ca₄Si₂F₂O₇) crystallization behavior of CaO–SiO₂–CaF₂ glass (basicity 1.7). In order to elucidate the crystallization characteristics during differential scanning calorimetry (DSC) measurements, the kinetic parameters have been determined using the Johnson-Mehl-Avrami-Kolmogorov (JMAK) equation. The crystallization rate constant and negative activation energy thus calculated indicated that the limiting step of crystallization was nucleation. Also, Raman spectroscopy and Solid-state MAS NMR spectroscopy analyses indicated that lithium could interact with fluorine, thereby disturbing the interaction between calcium and fluorine. This retards Cuspidine nucleation at the initial stage of melt crystallization. These findings on CaO–SiO₂–CaF₂-based glass lubricants can be used to optimize essential properties such as viscosity and crystallization temperature during continuous casting of steels.     

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.     

Influence of heat-treatment protocols on mechanical behavior of lithium silicate dental ceramics

In this work, three different commercial lithium silicate (LS) glass-ceramics for computer aided design/computer aided machining systems, CeltraDuo-Dentsply (LS-C), E-MaxCAD-Ivoclar (LS-E), and Suprinity-Vita (LS-S), were comparatively characterized. Following the protocols recommended by the manufacturers, the glass-ceramics were heat-treated under low vacuum and characterized by X-ray diffraction, scanning electron microscopy, hardness, fracture toughness, Young's modulus, and flexural strength. Rietveld refinement indicated that the materials “as-received” present mostly amorphous phase and Li₂SiO₃ as secondary crystalline phase in LS-E and LS-S specimens, while LS-C specimens also present Li₂Si₂O₅ and Li₃PO₄ as crystalline phases. All “as-received” glass-ceramics present hardness, fracture toughness, and Young's modulus of around 647-678 HV, 1.15-1.40 MPa.m^1/2, and 82-92 GPa, respectively. After heat treatment, the LS-C and LS-S specimens presented decreasing of amorphous phase associated to Li₂SiO₃ and Li₂Si₂O₅ grains with low aspect ratio, while LS-E indicates a reduction of amorphous phase and Li₂Si₂O₅ elongated grains. Fracture toughness and Young's modulus increase about 10% due to the crystallization of residual amorphous phase for all materials. Moreover, crystallographic and microstructural characteristics are responsible for the higher flexural strength of LS-E (327 MPa), regarding LS-C and LS-S. However, the glass-ceramics LS-E present lower Weibull modulus (m = 5.4) comparatively to LS-C (m = 9) and LS-S (m = 6).     

Effect of ZnO on the crystallization behavior and properties of SiO2–CaO–Al2O3–Fe2O3 glass-ceramics prepared from simulated secondary slag after reduction of copper slag

The feasibility of preparing low-cost glass-ceramics from Zn-containing dust and secondary molten slag generated during the carbothermal reduction of copper slag was investigated. Analytical-grade agents, such as ZnO, Fe₂O₃, SiO₂, CaO, and Al₂O₃, were used to simulate the dust and secondary slag. The effect of ZnO content on the crystallization behavior, structure, and mechanical properties of the glass-ceramics was investigated through X-ray diffraction analysis, scanning electron microscopy-energy dispersive spectrometry, differential scanning calorimetry, Fourier transform infrared spectroscopy, and Raman spectroscopy. The results showed that with increased ZnO content from 0 to 6 wt%, the crystallization activation energy of base glass increased from 386.05 to 425.89 kJ/mol. Meanwhile, the average value of the crystal growth index increased from 1.91 to 4.10, and the highest crystallization rate of the glass-ceramics increased from about 1.44 to 23.11 mm³/min. The increased ZnO in glass-ceramics promoted the precipitation of gehlenite, but inhibit the crystallization of anorthite. When the ZnO content was 6 wt%, the comprehensive properties of the glass-ceramics were better; the flexural strength, microhardness, volume density, water absorption rate, and open porosity were 58.67 MPa, 738.35 HV, 2.92 g/cm³, 0.44% and 1.27%, respectively.