Controlling the microstructure and properties of lithium disilicate glass-ceramics by adjusting the content of MgO

In order to obtain lithium disilicate glass-ceramics for dental restoration with both high strength and high translucency, lithium disilicate glass-ceramics with different MgO contents were prepared by melt-casting and heat treatment method. The effects of MgO content on the crystallization temperature, microstructure and flexural strength of lithium disilicate glass-ceramics were investigated. The results indicate that Mg²⁺ exists in the form of [MgO₄] in the network of lithium disilicate glass-ceramics when the MgO content is 0.56 mol% (M0.56), which is beneficial to increasing the homogeneity and thermal stability of the glass system, and short rod-like lithium disilicate crystals can be formed after heat treatment at 840°C. Thus, the obtained lithium disilicate glass-ceramics exhibit excellent comprehensive performance, with the flexural strength being 312 ± 23 MPa, and the average transmittance of visible light being 37.3% (d = 1.62 mm). Especially, the glass-ceramic sample shows better translucency than the commercially available products. The research results are of great significance for developing high performance lithium disilicate glass ceramics and promoting its broad application in the field of dental restoration.     

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.     

Controlled precipitation of lithium disilicate (Li2Si2O5) and lithium niobate (LiNbO3) or lithium tantalate (LiTaO3) in glass-ceramics

In the present study, the crystallization principles and phenomena of base glasses from the system of SiO₂-Li₂O-P₂O₅-Al₂O₃-K₂O-Nb₂O₅ or Ta₂O₅ were investigated. Annealing parameters such as temperature and time were varied. Annealing the base glasses 10 min at temperatures <850 °C for Nb₂O₅ or Ta₂O₅ containing samples lead to the crystallization of Li₂SiO₃. At higher annealing temperatures or longer annealing times, Li₂SiO₃ disappeared and Li₂Si₂O₅ was the main crystal phase in all glass-ceramics. After the dissolution of Li₂SiO₃, the minor crystal phases of LiNbO₃ or LiTaO₃ were precipitated. Increasing the annealing temperatures as well as the annealing times lead to higher bending strengths up to about 676 MPa and CR-values of up to 100. Increasing the contents of Nb₂O₅ or Ta₂O₅ lead to higher CR-values. The radiopacities increased up to 355% compared to aluminum.     

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.     

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.     

Strengthening and toughening of a multi-component lithium disilicate glass-ceramic by ion-exchange

A multi-component lithium disilicate (LD) glass-ceramic with interlocking microstructure consisting of rod-like LD crystals and glassy matrix was ion-exchanged over wide temperature and time ranges in pure NaNO₃ or mixed NaNO₃ and KNO₃ baths below the glass transition temperature. Treatment temperature, time and salt bath dependences of surface characteristics and mechanical properties for the ion-exchanged glass-ceramic were investigated. It was found that the glass-ceramic with limited glassy matrix could be remarkably strengthened and toughened in NaNO₃ bath by adjusting the treatment temperature to a moderate level, at which Li⁺/Na⁺ exchange between the glassy matrix and the salt bath could form an ion-exchanged layer with larger depth and less stress relaxation. Furthermore, by using the mixed salt bath, the undesirable exchange of K⁺/Na⁺ in pure NaNO₃ bath could be limited; further enhanced strengthening effect was achieved. The results might renew the interest on strengthening LD glass-ceramics by traditional ion-exchange process.     

Machine learning predictions of Knoop hardness in lithium disilicate glass-ceramics

Predicting the effects of ceramic microstructures on macroscopic properties, such as the Knoop hardness, has long been a difficult task. This is particularly true in glass–ceramics, where multiple unique crystalline phases can overlap with a background glassy phase. The combination of crystalline and glassy phases makes it difficult to quantify the percent crystallinity and to predict properties that are the result of the chemical composition and microstructure. To overcome this difficulty and take the first step to build a system for characterizing glass-ceramics, we predict the Knoop hardness based on scanning electron microscopy images using two computational techniques. The first technique is a computer vision algorithm that allows for physical insights into the system because the features used in a predictive model are extracted from the images. The second technique is machine learning with convolutional neural networks that are trained through transfer learning, allowing for more accurate predictions than the first method but with the downside of being a black box. Discussion of the relative merits of the models is included.     

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.     

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.     

Crystallization and thermal expansion behavior of lithium zinc silicate sealing glass

Effect of heat treatment schedule on the crystallization and thermal expansion behavior of a lithium zinc silicate glass system was investigated by differential scanning calorimeter (DSC), X-ray diffraction, and linear thermal expansion test. Two well-defined crystallization exothermic peaks were observed from the DSC trace. According to the apparent activation energies and avrami parameter values calculated from the two crystallization exothermal peaks, the first crystallization exothermal peak was attributed to a combining surface and internal crystallization behavior, while the second one was found to be internal crystallization. Additionally, the phase evolution and the thermal expansion behavior with increasing heat treatment temperature were found to be closely related. Interestingly, it was found in comparison with previous reports that addition of CaO varies the phase composition of the resulting glass–ceramic in an opposite way to K₂O and the deep rooted reason has been discussed which may cast light on the modulation of properties of glass–ceramic involved crystalline phase of quartz or cristobalite. At last, average thermal expansion coefficient of 7.99–15.38×10⁻⁶ K⁻¹ in the temperature range of 25–400 °C has been obtained with different heat treatment schedules.     

Crystallization behavior and mechanical properties of high strength mica-containing glass-ceramics from granite wastes

The high-strength mica-containing glass-ceramics were prepared from granite wastes by bulk crystallization. The influences of SiO₂/Al₂O₃ molar ratio (S/A = 7.72, 9.62, 12.58, 17.82 and 29.67) on the crystallization behavior, microstructure, mechanical properties and machinability of glass-ceramics were investigated. The results demonstrated that the polymerization degree of the glass network decreased with the S/A ratio increasing, which further caused the decrease in glass transition temperature and crystallization temperatures. The increase in the S/A ratio promoted the precipitation of diopside, hectorite, kalsilite and tainiolite in glass-ceramics when the samples were heated at 750 °C, while inhibiting the precipitation of forsterite. For the glass-ceramics crystallized at 800 and 900 °C, the main crystalline phases transformed from diopside, forsterite, and nepheline to diopside, kalsilite, and tainiolite, with the S/A ratio increasing. As the SiO₂ gradually replaced Al₂O₃, the morphology of crystals changed from lamellar to granular, while the mean size of crystals reduced. The Vickers-Hardness values of glass-ceramics crystallized at 800 and 900 °C ascended with S/A ratio rising, and the values were above 6.30 GPa. The bending strength of most glass-ceramics is stable between 90 and 140 MPa, among which the maximum bending strength is 133.28 ± 14.81 MPa. The fracture toughness of the glass-ceramic crystallized at 800 and 900 °C declined, while that at 700 °C increased with a larger S/A ratio. Glass-ceramics after heat-treated at 900 °C with S/A ratio of 9.62 had the largest fracture toughness of 3.28 ± 0.15 MPa m^1/2. In preliminary tests of machinability, glass-ceramic after heat-treated at 900 °C with S/A ratio of 9.62 showed better results.     

Nano-to-microscale ductile-to-brittle transitions for edge cracking suppression in single-diamond grinding of lithium metasilicate/disilicate glass-ceramics

To suppress grinding-induced edge cracks in dental lithium metasilicate/disilicate glass-ceramics (LMGC/LDGC), this paper established a contact stress model for single-diamond grinding (SDG) to relate their crack generation and ductile-to-brittle transition (DBT) thresholds with the mechanical properties, diamond tool profiles and process variables. Nanoindentation, friction test and SDG were conducted to unravel material responses and dynamic diamond grit-workpiece interactions to determine the DBT thresholds. The nanoindentation revealed significant indentation size effects (ISEs) on the hardness and elastic moduli of the ceramics. SDG clearly elucidated their DBT behaviors, wherein edge cracks initiated at diamond peripheries when the concurrent contact stresses reached the DBT thresholds. Accordingly, the indicated critical cutting depths for DBT may be changed from the nanoscale to the microscale by increasing the tool radius and reducing the machining speed. This research contributes to edge crack suppression for ductile machining of brittle materials at large removal rates.     

Solid-state field-assisted ion exchange of Ag in lithium aluminum silicate glass-ceramics: A superfast processing route toward stronger materials with antimicrobial properties

Lithium-aluminum-silicate glass-ceramics (LAS) are of pivotal relevance in various applications as they combine excellent mechanical and functional properties. Due to their use in medical devices and cooking articles, antimicrobial properties are obviously of interest.Herein, we report the solid-state field-assisted (Ag→Li,Na) ion exchange in LAS glass-ceramics containing β-quartz and β-spodumene solid solutions. The ion-exchange is extremely rapid and deep silver penetration (>100 μm) can be achieved within a few minutes (<5 min), this being proportional to the treating time and applied current. The elemental profiles are characterized by a relatively complex shape which reflects the different alkali mobility in the different phases. The ion exchange initiates structural modifications involving: (i) β→α transition in spodumene; (ii) formation of lattice microstrain and quartz cell expansion; (iii) substantial changes in the IR absorption spectra. The obtained materials possess improved resistance to crack formation and antimicrobial activity against Staphylococcus aureus.     

The effect of lithium fluoride on the thermal stability and thermoluminescence properties of borosilicate glass and glass-ceramics

The oxyfluoride glass and glass-ceramics from the LiF-B₂O₃-SiO₂ system are developed. The stable glass can be produced in the range of 20–40 mol% LiF. The effect of LiF admixture on the thermal stability of the glass as well as the thermoluminescence (TL) properties such as glow curves shape is studied. The results show that the increase of lithium fluoride content in the borosilicate glass causes efficiency enhancement of the thermoluminescence signal. We have clearly stated that the process of controlled crystallization of the oxyfluoride glasses can lead again to increased intensity of the TL process. The glass-ceramics with 40 mol% LiF reveals similar level of TL signal to commercially used doped LiF material and can be considered as active material for alpha and beta radiation detectors.     

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 glass-ceramics from red mud in the aluminium industries

The feasibility of recycling red mud and fly ash in the aluminium industries by producing glasses and glass-ceramics has been investigated. The crystallization behavior of glass-ceramics mostly produced from red mud and fly ash was studied by DTA, XRD, optical microscopy techniques. According to DTA curve, nucleation experiments were carried out at various nucleation temperatures at the same crystallization temperature of 900 °C for 2 h, and crystallization experiments were performed at the same nucleation temperature of 697 °C for 2 h followed by crystallization at various temperatures. The nucleation results show that optimum nucleation temperature is near 697 °C, and the crystallization experiments show that the crystallization at a high temperature of over 900 °C results in denser grain size. The major crystallized phases were gehlenite (Ca₂Al₂SiO₇), and augite (Ca(Fe,Mg)Si₂O₆). The XRD results show that with the increase of crystallization temperature, the amount of gehlenite increases, and augite decreases, which is the result of augite transformation into gehlenite.     

Physicochemical surface characterizations of four dental CAD/CAM lithium disilicate-based glass ceramics on HF etching: An XPS study

The surfaces of four lithium disilicate glass ceramics (LDGC) were characterized at the nanolevel. The goal was to detect the chemical alteration of the surface on etching with hydrofluoric acid (HF). The four LDGC tested were Celtra Duo, IPS e.max CAD, Straumann n!ce and Vita Suprinity. Four blocks of each LDGC were sectioned to ∼ 1 mm thicknesses. The requirement for firing, or not, was carried out following the manufacturer’s recommendations. The samples were then divided into two groups: a control and an etched group. Etching was carried out using a solution of 5% HF for 20 s, rinsed for 20 s and dried for 10 s, using an air jet. The atomic percentages of the first atomic layers were probed using X-ray photoelectron spectroscopy (XPS) in the survey mode (n = 12). The oxygen and silicon peaks (O1s and Si2p) were then analyzed in the high resolution mode. The samples were also characterized using scanning electronic microscopy at high magnification (60 k). XPS showed the amounts of the major elements, Si, O and Li, were changed on etching. For all samples, trace elements, such as P, Zn, Y, Na and Sr, disappeared on glassy phase dissolution. Zr and Al percentages varied, based on the LDGC analyzed. High resolution spectra of the O1s and Si2p peaks showed that the chemical environments were qualitatively different in all samples. Acid etching, using 5% HF for 20 s, modified not only the topographic structure, but also the chemical composition of the LDGC surface.     

Responses of pre-crystallized and crystallized zirconia-containing lithium silicate glass ceramics to diamond machining

This paper reports on the responses of pre-crystallized and crystallized zirconia-containing lithium silicate glass ceramics (ZLS) to diamond machining in simulated dental milling and adjusting processes. Machining mechanics, tool wear and tribological characteristics, and surface and subsurface damage were investigated. Machining forces and coefficients of friction were measured using a force sensor and high-speed data acquisition system. Diamond tool wear and debris adhesion, and machining-induced surface and subsurface damage were examined using field emission scanning electron microscopy. The results show that both tangential and normal forces of crystallized ZLS were significantly higher than those of pre-crystallized ZLS (p < 0.05) while these forces for both materials significantly increased with the material removal rate (p < 0.05). Coefficients of friction in machining of crystallized ZLS were significantly higher than those in machining of pre-crystallized ZLS. In spite of the minimum wear of applied diamond tools in machining both materials, more crystallized ZLS debris adhesion on tool surfaces was observed. The principal removal mechanisms in machining of both materials were primary fracture and minor plastic deformation of pre-crystallized and crystallized ZLS. However, there was more severe fracture in machining of pre-crystallized ZLS than in machining of crystallized ZLS. Although machining-induced subsurface edge chipping damage in both materials remarkably increased with the feed rate (p < 0.05), such damage was significantly severer in pre-crystallized ZLS than in crystallized ZLS (p < 0.05). These microstructure-property-processing relations provide practical guidance of process selection for high-quality fabrication of ZLS materials.     

Effect of CuO addition on crystallization and thermal expansion properties of Li2O–ZnO–SiO2 glass-ceramics

A Li₂O-ZnO-SiO₂ (LZS) glass system was modified with CuO, and its phase development, microstructure evolution, crystallization kinetics and thermal expansion properties were investigated as a function of heat treatment temperature. As a result of the X-ray diffraction study and microstructure observation, lithium zinc silicate formed as the first crystalline phase with increasing heat treatment temperature. Silica polymorph developed as minor crystalline phase at higher temperatures. From the X-ray diffraction patterns, CuO addition led to a decrease in both the crystallization temperature of lithium zinc silicate phase and the volume fraction of quartz phase. According to the crystallization kinetics, the crystallization activation energy for lithium zinc silicates is almost equal to the diffusion activation energy of Zn²⁺ in glass, it suggests that the diffusion of network modifier Zn²⁺ dominates the crystallization of lithium zinc silicates. Additionally, CuO addition caused the transition of Zn²⁺ from network modifiers to network formers. From the thermal expansion coefficient measurements, two abrupt changes in slope of the thermal expansion curves were observed and attributed to the phase transitions of cristobalite and lithium zinc silicate, respectively. Comparison of the thermal expansion coefficient of two types of glass-ceramics revealed that CuO addition in the LZS system can partly inhibit the formation of cristobalite at high temperatures.     

Role of vanadium oxide on the lithium silicate glass structure and properties

The structural role of V in 28Li₂O–72SiO₂ (in mol%) lithium silicate glass doped with 0.5 mol% V₂O₅ was assessed using ²⁹Si and ⁵¹V Nuclear Magnetic Resonance (NMR), Fourier-transform infrared (FTIR), and X-ray photoelectron (XPS) spectroscopy techniques. Despite the low amount of V₂O₅ used, the structural information obtained or deduced from the statistical analysis of the NMR data could explain the evolution of glass properties after V₂O₅ addition. The XPS results indicated that all vanadium exists in 5+ oxidation state. Both the ²⁹Si NMR and FTIR data point toward an increase in the polymerization of the silicate network, caused by the V₂O₅ acting as network former, capable to form various tetrahedral units (for n = 0, 1, and 2) in the glasses. These units, which are similar to phosphate units, scavenge the Li⁺ ions and cause the silicate network to polymerize. However, in an overall balance, the entire glass network is depolymerized due to the additional nonbridging oxygens contributed by the vanadium polyhedra. The addition of vanadium causes the network to expand and increases the ionic conductivity.