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.     

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.     

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.     

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.     

Preparation and characterization of alkali-free glass substrates with enhanced properties for TFT–LCDs applications

To obtain an alkali-free glass substrate with enhanced properties for thin-film transistor–liquid crystal displays (TFT–LCDs) applications, we chose a base glass composed of 3B₂O₃-15Al₂O₃-58SiO₂-22MgO-0.5SrO-1.5MgF₂ (mol%) for nucleation–crystallization. The results show that when the nucleation–crystallization processes of the base glass are 810 °C/6 h + 880 °C/6–9 h, the prepared GC/6–GC/9 glass-ceramics exhibit enhanced properties because of the precipitation of nano-sized cordierite. The transmittances in the visible range of the GC/6–GC/9 glass-ceramics exceed 85%, the densities are 2.564–2.567 g/cm³, thermal expansion coefficients are 2.934–3.059 × 10^-6/°C (25–300 °C), compressive strengths are 417–589 MPa, bending strengths are 141–259 MPa, Vickers hardnesses are 6.8–7.8 GPa, and strain points are approximately 735 °C. Considering these properties, the prepared GC/6–GC/9 glass-ceramics have good potential as candidate materials for alkali-free glass substrates. Additionally, these results demonstrate that it is feasible to improve the properties of alkali-free glass substrates by nucleation–crystallization.     

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%).     

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.     

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.     

Effects of Y2O3 addition on structure and properties of LZAS vitrified bond for CBN grinding tools application

The effects of Y₂O₃ addition on the structure and properties of Li₂O–ZnO–Al₂O₃–SiO₂ (LZAS) vitrified bonds were firstly investigated for CBN grinding tools application. Glasses and glass-ceramics were characterized using differential scanning calorimetry, X-ray diffractometry, scanning electron microscopy and infrared spectroscopy. The thermal expansion coefficient (TEC), microhardness, bending strength and chemical durability of the obtained products were also evaluated. Results showed that Y₂O₃ acted as the network former in the track of SiO₄ tetrahedrals. Introducing Y₂O₃ in the glasses increased the glass transition temperature and crystallization temperature. The crystallization of the main β-quartz_ss phase increased with increase of Y₂O₃ content. The morphology of the crystals was dependent on the Y₂O₃ content. The TEC (5.15×10⁻⁶/°C) of vitrified bond containing 1.0 mol% Y₂O₃ (Y1.0) was very close to the TEC (5.0×10⁻⁶/°C) of CBN grains. Moreover, Y1.0 vitrified bond exhibits a high microhardness (5.98 GPa), a high bending strength (202 MPa) and a good chemical durability (20 days, DR=2.8×10⁻⁹ g/cm² min), suggesting that it would be a promising material for CBN grinding tool.     

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.     

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.     

Remarkable photoluminescence enhancement and tuning in Eu/CdS co-doped chloroborosilicate glass-ceramics

The effect of heat treatment was studied on Eu/CdS co-doped chloroborosilicate glass having a new composition 37.8SiO₂–27B₂O₃–18BaO–3.6K₂O–3.6Al₂O₃–10BaCl₂ (mol%) recently developed in our group. The base glass has been proven to be a suitable host for various rare-earth ions and metallic nanoparticles, also upon controlled crystallization, because it has the potential to yield low-phonon energy (350 cm^?1) BaCl₂ crystals. The glasses were heat treated at 650 °C for several time durations. Transmission electron microscopy (TEM) revealed the presence of CdS quantum dots (QDs) and BaCl₂ crystals in the heat-treated glasses. X-ray diffraction studies confirmed the formation of glass-ceramics, with the presence of BaCl₂-based phases. When heat-treated, all the Eu/CdS co-doped glasses showed an intense enhancement in Eu³⁺/Eu²⁺ emissions up to 30 or 40 h of heat treatment, followed by a gradual decrease. The initial increase is due to the formation of low-phonon energy BaCl₂-based crystalline phases as well as the generation and growth of CdS QDs at elevated temperature. The subsequent decrease in PL intensity is attributed to the concentration quenching effect of the QDs. The rate of enhancement was significantly higher when glasses formed opaque glass-ceramics due to the change in environment of the Eu ions and scattering effect. The maximum intensity enhancement due to the CdS co-doping and glass crystallization was observed to be 400 times as compared to the non heat-treated glass containing the same amount of Eu. This enhancement is quite remarkable in rare-earth/semiconductor co-doped glasses and can be useful in various photonic applications.     

Effect of Ta2O5 addition on the structure,crystallization mechanism,and properties of CaO–B2O3–SiO2 glasses for LTCC applications

CaO–B₂O₃–SiO₂–Ta₂O₅ (CBST) glass-ceramics, with different Ta₂O₅ content, (up to 6 mol%), have been prepared by using glass melt quenching followed by heat treatment between 800 and 880 °C. The Fourier Transform Infrared (FTIR) results showed that the stronger the attraction of Ta⁵⁺ to the oxygens in the BO₃^3? and SiO₃^2? structures, the more easily the B–O and Si–O bonds will be destroyed. The underlying reason is most probably the high field strength of Ta⁵⁺, which results in a weakening of the vibration intensities of the [BO₃] and [SiO₄] units. Moreover, the Differential Scanning Calorimetry (DSC) results showed that the softening point (T_g), crystallization starting temperature (T_c1), and exothermic crystallization peak temperature (T_p1), of the CaSiO₃ phase, shifted to higher values with the addition of Ta₂O₅. Also, the crystallization activation energy (E_a) and the glass stability factor (ΔT) of the CaSiO₃ phase increased, which indicated that the CaSiO₃ phase of the glass became inhibited by the addition of Ta₂O_5. It was, thus, obvious that there was a need of glass characterization. The results of the crystallization kinetics showed that the critical cooling rate decreased with the addition of Ta₂O₅, which indicated that the viscosity of the system had increased. The CBST glass-ceramics, containing 1 mol% Ta₂O_5, that were sintered at 875 °C for 15 min showed excellent dielectric properties: ε_r = 6.22 and tanδ = 1.19 × 10^?3 (1 MHz). To sum up, CaO–B₂O₃–SiO₂–Ta₂O₅ glass-ceramics are potential low temperature co-fired ceramic substrate materials.     

Thermal and crystallization behavior of SiO2-PbF2 glass system in the presence of ErF3 and Al2O3

Oxyfluoride glass-ceramics have been introduced as one of the best bulk hosts for upconversion process of rare-earth ions. However, less attention to the technological topics in the process of glass crystallization has hindered the development of them in industrial scale applications. In this research, SiO₂–PbF₂ glasses were investigated to clarify the ambiguous role of rare-earth ions and alumina content in the microstructure and crystallization behavior. Results indicated that Er³⁺ addition caused a liquid-liquid phase separation via nucleation and growth mechanism, which led to single phase crystallization of β-PbF₂:Er³⁺ solid solution. Moreover, Er³⁺ had a significant effect on the crystallite size, size distribution, and PbF₂ crystallization temperature. On the other hand, increasing Al₂O₃ content enhanced the transparency and thermal stability of glass samples, whereas it reduced the amount of fluorine loss and increased the dissolution of Er³⁺ in fluoride crystalline structure. These results address some of the most controversial issues about crystallization behavior of rare-earth-doped oxyfluoride glasses.     

Nepheline Crystallization in Nuclear Waste Glasses: Progress Toward Acceptance of High-Alumina Formulations

Historical data have been critically compiled and analyzed for investigating the quantity of nepheline (NaAlSiO₄) precipitated as a function of composition in simulated nuclear waste glasses. To understand compositional effects two primary methods were used: (1) investigating the Al₂O₃–SiO₂–Na₂O ternary while filtering for different B₂O₃ levels and (2) creating a quadrant system consisting of compositions reduced to two representations: (i) the nepheline discriminator (ND) which depends only on the SiO₂ content by weight normalized to the total weight of the Al₂O₃–SiO₂–Na₂O submixture and (ii) the optical basicity (OB) which contains contributions from all constituents in the glass. Nepheline precipitation is expected to be suppressed at high SiO₂ levels (ND > 0.62) or at low basicities (OB < 0.55–0.57). Changes in sodium aluminosilicate glass OB values due to additions of CaO and B₂O₃ correlate with the observed effects on nepheline formation. It is proposed that additional composition space is available for formulating high waste loading, high-Al₂O₃ nuclear waste glasses when consideration is given to location on the Al₂O₃–SiO₂–Na₂O submixture as well as OB.     

Effect of Al2O3 content on BaO–Al2O3–B2O3–SiO2 glass sealant for solid oxide fuel cell

The glass structure, wetting behavior and crystallization of BaO–Al₂O₃–B₂O₃–SiO₂ system glass containing 2–10 mol% Al₂O₃ were investigated. The introduction of Al₂O₃ caused the conversion of [BO₃] units and [BO₄] units to each other and it played as glass network former when the content was up to 10 mol%, accompanied by [BO₄] → [BO₃]. The stability of the glass improved first and then decreased as Al₂O₃ increased from 2 to 10 mol%, the glass with 5 mol% Al₂O₃ being the most stable one. The wetting behavior of the glasses indicates that excess Al₂O₃ leads to high sealing temperature. The glass containing 5 mol% Al₂O₃ characterized by a lower sealing temperature is suitable for SOFC sealing. Al₂O₃ improves the crystallization temperature of the glass. The crystal phases in the reheated glasses are mainly composed of Ba₂Si₃O₈, BaSiO₃, BaB₂O₄ and BaAl₂Si₂O₈. Al₂O₃ helps the crystallization of BaSiO₃ and BaAl₂Si₂O₈.     

Persistent luminescence of Eu/Dy-doped Sr2MgSi2O7 glass-ceramics processed by aerodynamic levitation

Glass beads of the Sr₂MgSi₂O₇ stoichiometric composition and a non-stoichiometric composition with higher SiO₂/SrO ratio doped with Eu₂O₃/Dy₂O₃ were prepared through aerodynamic levitation coupled to CO₂ laser heating. The glass beads were subsequently treated at 1100 ºC to produce glass-ceramics with Sr₂MgSi₂O₇: Eu²⁺, Dy³⁺ as the main crystalline phase. The doped glasses exhibit red emissions; after crystallisation, the corresponding glass-ceramics emit blue light under UV excitation. The starting glass composition considerably affects the crystallisation process, resulting in Sr₂MgSi₂O₇ glass-ceramics with very different microstructures which, in turn, have a significant influence on the luminescence properties. The photoluminescence emission spectra of the glass-ceramics under UV light show a broadband emission (λ = 400–500 nm) with a main peak assigned to the typical Eu²⁺ transition under excitation at 365 nm. Both the intensity of the emission and the persistence time significatively increase on decreasing temperature. Glass-ceramics from the non-stoichimetric glass composition co-doped with 1Eu₂O₃/0.5Dy₂O₃ (mol%.) provided the longest persistence times.     

Y3Al5O12–SiO2 Glasses: Structure and Polyamorphism

Aerodynamic levitation and CO₂ laser melting have been used to synthesize the yttrium aluminosilicate glasses zY₂O₃–yAl₂O₃–xSiO₂ with z/y = 3/5 corresponding to the YAG (Y₃Al₅O₁₂) composition and x between ~5 and ~45 mol%. The low‐ and high‐density (LDA inclusion and HDA matrix) polyamorphic phases in glasses with less than ~14 mol% SiO₂ were identified with backscattering electron imaging. Polarized and depolarized Raman spectra show the formation of various Qⁿ SiO₄ species whose relative populations change smoothly as the SiO₂ content is altered. The AlOs (s = 4–6) and YOz (z = 6–9) polyhedra formed in the YAG glass are preserved upon silica additions while the terminal oxygens of the Q²AlO₄ tetrahedra are gradually bridged to the Qⁿ‐SiO₄ species. The low‐frequency Boson Peak overlaps with the vibrational spectrum and its maximum is redshifted with increasing silica content. Micro‐Raman spectra measured for the LDA and HDA amorphous phases are found to be similar to the spectra of the bulk glass indicating common structural characteristics. The stability of the LDA phase against crystallization appears to be lower than that of the HDA phase. The crystallinity on certain inclusions consisted of YAG microcrystals and a new unidentified microcrystalline phase within Y₄Al_2(1?x)Si_2xO_(9+x) solid solution.     

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.     

Effect of TiO2 on crystallization and mechanical properties of MgO–Al2O3–SiO2 glasses containing P2O5

MgO–Al₂O₃–SiO₂ glass-ceramics have been widely used in military, industrial, and construction applications. The nucleating agent is one of the most important factors in the production of glass-ceramics as it can control the crystallization temperature or the grain size. In this study, we investigated the effect of replacing P₂O₅ with different amounts of TiO₂ on the crystallization, structure, and mechanical properties of an MgO–Al₂O₃–SiO₂ system. The crystallization and microstructure were investigated by differential scanning calorimetry, Raman spectroscopy, X-ray diffraction, scanning electron microscopy, and transmission electron microscopy. The mechanical properties were investigated by measuring the Vickers hardness, Young's modulus, and fracture toughness. The results showed that adding TiO₂ favored the precipitation of fine grains and significantly increased the Vickers hardness, Young's modulus, and fracture toughness of the glasses. Introducing an appropriate amount of TiO₂ can make a glass structure more compact, promote crystallization, and improve the mechanical properties of MgO–Al₂O₃–SiO₂ glass-ceramics.