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.     

Influence of heat treatment temperature on the properties of the lithium disilicate-fluorcanasite glass-ceramics

This study aims to investigate the influence of heat treatment temperatures on the mechanical properties and chemical solubility (CS) of lithium disilicate-fluorcanasite glass-ceramics and to develop new dental materials. The glasses and glass-ceramics were prepared using CaF₂-SiO₂-CaO-K₂O-Na₂O-Li₂O-Al₂O₃-P₂O₅-based glass system using a conventional melt quenching method followed by a two-stage crystallization process. This two-stage method involves two heating temperature steps: first at a constant temperature (T_S1) of 600°C and second step at varying temperatures (T_S2) of 650, 700, 750, and 800°C. The crystallization behavior, phase formation, microstructure, translucency characteristic, density, hardness, fracture strength, and CS were investigated. It was found that the lithium disilicate crystal acted as the main crystalline phase, and the crystalline phase of fluorcanasite occurred at the heat treatment temperatures of 750 and 800°C. In addition, it was found that density, hardness, fracture strength, and CS increased while the translucency values decreased with increasing heat treatment temperatures. Furthermore, the CS increased dramatically when the fluorcanasite phases occurred in the glass-ceramic samples. The maximum density values, Vickers hardness, fracture toughness, and flexural strength are 2.56 g/cm³, 6.73 GPa, 3.38 MPa.m^1/2, and 259 MPa, respectively. These results may offer a possibility to design a new material for dental applications based on lithium disilicate-fluorcanasite glass-ceramics.     

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/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.     

Crystallization-triggered bubbles in glass-ceramics

Bubbles appear sometimes in glass-ceramics and degrade most properties, especially light transmission and fracture strength. In this work, we deduced microstructural conditions that trigger bubble genesis during crystallization of bubble-free glasses. We related bubble formation to some microstructural parameters in two model glass compositions that exhibit internal crystallization: 1.07Na₂O.2CaO.3SiO₂ (1.07N2C3S) and Li₂O.2SiO₂ (L2S). In this way, we constructed bubble maps – experimental diagrams showing a region of bubble nucleation and growth in a crystal size versus crystallinity plot. Both glass-ceramics show bubbles having similar geometry that emerge from crystal/liquid interfaces and propagate into the residual liquid. These diagrams show that holes of the order of the crystal size tend to form in glass-ceramics containing a high-volume fraction crystallized (>50%) and relatively large crystal size (>10 μm). Mass spectroscopy experiments revealed that bubble formation in the 1.07N2C3S system is caused by O₂. We believe the knowledge generated by this work and resulting maps provide a very useful tool for the design of bubble-free glass-ceramics.     

Controlled nano-crystallization of IR frequency-doubling Cd4GeS6 crystal in chalcogenide glass

Crystallization of IR frequency-doubling nanocrystals in chalcogenide glasses is a promising approach to achieve novel nonlinear optical materials. However, controllable glass crystallization remains challenging. In this study, IR-transparent chalcogenide glass-ceramics containing novel Cd₄GeS₆ IR frequency-doubling nanocrystals (about 60-80 nm) are fabricated through controlled nano-crystallization. Nanocrystalline structure of the Cd₄GeS₆ nano-crystallized glass-ceramics is investigated in detail through X-ray diffractometer, field emission scanning electron microscope, and Raman scattering techniques. The structural similarity of [Cd₄GeS₆] polyhedron in the network structure of as-prepared glass is found to be responsible for the nucleation of Cd₄GeS₆ crystal. A unique microstructure of Cd₄GeS₆ nanocrystals embedded GeS₂ phase-separated structure is discovered in samples thermally treated at high temperatures (370°C and 380°C). This study would not only shed more light on glass crystallization mechanism but also provide a feasible approach for the design and fabrication of new IR frequency-doubling materials through glass crystallization.     

High toughness transparent glass-ceramics with petalite and β-spodumene solid solution as two major crystal phases

Lithium aluminosilicate glass-ceramics are well known for good transparency, high fracture toughness, low thermal expansion, and good ion exchange ability. In this study, new transparent Li₂O-Al₂O₃-SiO₂ (LAS) glass-ceramics with petalite and β-spodumene solid solution as the major crystalline phases were invented for favorable mechanical properties and potential for application in the hollowware, tableware, container, and plate glass industries. Crystal phases are mainly influenced by the ratio of Al₂O₃ to SiO₂ concentrations. The concentration of SiO₂ required to form specific crystalline phases in the glass-ceramics is higher than that inferred from the ternary phase diagram. Al₂O₃ content is required to be sufficiently high for the formation of crystals, instead of balancing excess amounts of Li₂O in the glass. The average transmittances of 2.0 ± 0.1 mm thickness samples in visible light regions (400–700 nm) can reach more than 80% with crystal sizes of 20–40 nm. Transmittance is significantly decreased for heat treatments around 710°C, due to the high growth rate of β-spodumene solid solution crystals. Vickers hardness, indentation toughness, and crack probabilities of transparent LAS glass-ceramics are significantly improved compared with standard soda lime silicate glass, due to the crack bridging and deflection of crystal grains.     

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 microstructural evolution on the mechanical properties of lepidolite based glass-ceramics

In this paper, effect of microstructural evolution on mechanical property of lepidolite based glass-ceramics of MgO–Al₂O₃–SiO₂–Li₂O–R₂O–F(R=Na, K) system during the crystallization process has been studied. The results show that two distinct regions of strength dependence on grain size are found. The critical values of the flake diameter and aspect ratio of lepidolite are 1.8 and 4.6μm, respectively. The crystallization temperature (T_C) of critical point locates at 1060 °C. When T_C⩽1060 °C, the bending strength increases with heat-treatment temperature ascribing to the randomly oriented and interlocked lepidolite crystallites, which cause crack divert or blunt to limit the further development of the flaw size and increase the surface energy of fracture. While T_C> 1060 °C, the increased boundary shear stress arising from the mismatch of thermal coefficient between the lepidolite crystallite and the residual glass phase results in the decrease of strength.     

Role of MgO in lowering glass transition temperature and increasing hardness of lithium silicate glass and glass-ceramics

The effect of variation of MgO (1.5, 4.5 and 7.5 mol%) content on glass structure, crystallization behavior, microstructure and mechanical properties in a Li₂O–K₂O–Na₂O–CaO–MgO–ZrO₂–Al₂O₃–P₂O₅–SiO₂ glass system has been reported here. Increased amount of MgO enhanced the participation of Al₂O₃ as a glass network former along with [SiO₄] tetrahedra, reducing the amount of non-bridging oxygen (NBO) and increasing bridging oxygen (BO) amount in glass. The increased BO in glass resulted in a polymerized glass structure which suppressed the crystallization and subsequently increased the crystallization temperature, bulk density, nano hardness, elastic modulus in the glasses as well as the corresponding glass-ceramics. MgO addition caused phase separation in higher MgO (7.5 mol%) containing glass system which resulted in larger crystals. The nano hardness (～10 GPa) and elastic modulus (～127 GPa) values were found to be on a much higher side in 7.5 mol% MgO containing glass-ceramics as compared to lower MgO containing glass-ceramics.     

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.     

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.     

Crystallization,microstructure and mechanical behavior of titanium doped barium fluormica glass-ceramics

Crystallization, microstructure and mechanical behavior of TiO₂ doped barium fluorphlogopite glass-ceramics were systematically studied. TiO₂ was used as a doper nucleant in the BaO·4MgO·Al₂O₃·6SiO₂·2MgF₂ glass system. Melting technique was adopted to prepare the glass samples which were analyzed by differential thermal analysis (DTA), X-ray diffraction, scanning electron microscopy, and micro hardness indenter. The DTA study demonstrated that the crystallization exotherm of fluorphlogopite mica appeared in the temperature window of 886-903°C. In this investigation, four glass samples were prepared using 2 (MA1), 4 (MA2), 6 (MA3), and 8 (MA4) wt% of TiO_2. Glass transition (T_g) and peak crystallization (T_p) temperatures escalated with an increase in the TiO₂ content from 2 (MA1) to 4 wt% (MA2). However, beyond this value, T_g and T_p decreased with a surge in TiO₂ content from 6 (MA3) to 8 wt% (MA4). Nevertheless, with a gradual rise in the TiO₂ content, the crystals of the glass-ceramics became enlarged and subsequently exhibited mechanical properties, such as hardness, fracture toughness, and machinability. Therefore, in solid oxide fuel cell applications, TiO₂ is a promising nucleating agent to generate fluorphlogopite mica-based glass-ceramics.     

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.     

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.     

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.     

Contribution of some transition metal oxides to crystallization and electro-thermal properties of glass-ceramics

Lithium di-silicate (LS₂) glass-ceramics modified with copper oxide using the formula: 34.83Li₂O–xCuO–(65.17-x)SiO₂ (where; x = 1, 2, 4 and 6 mol%) were prepared by melt-quenching followed by controlling heat-treatment. 6 mol% of MnO or Fe₂O₃ transition metal oxides was added instead of SiO₂ in the high CuO-content composition. The effect of the transition cations on phase formation, microstructure, density, thermal expansion, and electrical conductivity was investigated as a function of the controlled crystallization. Results show that up to 4 mol%, Cu⁺² was hosted in stable Li₂Si₂O₅ structure. This enhanced the crystal formation, including Li₂Si₂O₅ and its solid solution (ss), Li₂SiO₃, Li₂Cu₅(Si₂O₇)₂, CuMn₆SiO₁₂, LiFeSi₂O₆ (ss), and the orthosilicate Li₂FeSiO₄ (ss). The prepared materials had different density values ranged from 2.35 to 2.79 g/cm³ for glass and varied from 2.43 to 3.15 g/cm³ for glass–ceramics, whereas the α-values of glass-ceramics ranged in the 95–165 × 10⁻⁷/°C. The progress of electrical properties in glass-ceramics, as a function of composition, was studied. It was markedly improved by adding different transition cations especially, Fe⁺³. The study reveals that the incorporation of transition metal ions in LS₂ composition has a positive effect on the physical-chemical properties of the prepared glass-ceramics. Therefore, it constitutes to prepare future glass-ceramic applications as hermetic seals of metals as well solid electrolyte materials.     

LZS/Al2O3 nanostructured composites obtained by colloidal processing and spark plasma sintering

Li₂O-SiO₂-ZrO₂ (LZS) glass-ceramics have high mechanical strength, hardness, resistance to abrasion and chemical attack, but also a high coefficient of thermal expansion (CTE), which can be reduced adding alumina nanoparticles. The conventional glass-ceramic production is relatively complex and energy consuming, since it requires the melting of the raw materials to form a glass frit and a two-step milling process to obtain particle sizes adequate for compaction. This study describes the preparation of LZS glass-ceramics through a colloidal processing approach from mixtures of SiO₂ and ZrO₂ nanopowders and a Li precursor (lithium acetate obtained by reaction of the carbonate with acetic acid). Concentrated suspensions were freeze-dried to obtain homogeneous mixtures of powders that were pressed (100 MPa) and sintered conventionally and by spark plasma sintering. The effect of the alumina nanoparticles additions on suspensions rheology, sintering behavior and properties such as thermal expansion, thermal conductivity, hardness and Young’s modulus were evaluated.     

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.     

On the nature of the second-order optical nonlinearity of nanoinhomogeneous glasses in the Li2O-Nb2O5-SiO2 system

The submicroscopic structure of lithium niobium silicate glasses of the compositions 2xLiNbO₃ · (1 ? x)(Li₂O · 2SiO₂) (x = 0.40, 0.45, 0.50) and 30Li₂O · 25Nb₂O₅ · 45SiO₂ in the initial state and after heat treatment for different times at temperatures in the vicinity of the glass transition point T _g are investigated using X-ray powder diffraction, small-angle neutron scattering (SANS), synchrotron small-angle X-ray scattering (SAXS), and electron microscopy. A nanostructure with inhomogeneities ～40 Å in size is formed in glasses at the initial stages of phase separation at temperatures in the range 600–670°C. This structure is responsible for the appearance of the second-order optical nonlinearity. The SANS, SAXS, and electron microscopic data on the inhomogeneity size are in good agreement with each other. According to the X-ray diffraction, SANS, and SAXS data, the ordering of the glass structure and the difference between the density of inhomogeneities and the density of the matrix increase in the course of heat treatment. At the initial stage of amorphous phase separation, the glass decomposes into regions enriched in SiO₂ and regions with an increased content of lithium and niobium. An increase in the temperature or time of heat treatment results in the precipitation of LiNbO₃ ferroelectric crystals. The results obtained allow us, for the first time, to make the inference that nanoscale changes in the glass structure lead to considerable changes (by one order of magnitude and more) in the quadratic optical nonlinearity, which can be controlled by heat treatment. The origin of the second-order optical nonlinearity is associated with both the nanosized modulations of the polarizability due to the inhomogeneous glass structure and the polarity of structural nanoinhomogeneities from which the LiNbO₃ phase precipitates at the later stages of phase separation.