Effect of Silicon Carbide Additions on the Crystallization Behavior of a Magnesia-Lithia-Alumina-Silica Glass

Glass in the MgO-Li₂O-A1₂O₃-SiO₂ system was observed to crystallize readily at temperatures from 700° to 900°C. The primary crystalline phase evolved was Li₂Si₂O₅, and the secondary phase evolved was Li₂SiO₃. The glass was amorphous after heating in air at 1050°C for 30 min. The addition of 0.5 wt% SiC powder resulted in the crystallization of Li₂SiO₃ during heating in air at 1050°C for 30 min. It was suggested that the difference in crystallization behavior with Sic addition was due to dissolution of Sic into the oxide glass.     

Sintering and Crystallization of a Glass Powder in the Li2O–ZrO2–SiO2 System

Sintering and crystallization of a 23.12 mol% Li₂O, 11.10 mol% ZrO₂, 65.78 mol% SiO₂ glass powder was investigated. By means of thermal shrinkage measurements, sintering was found to start at about 650°C and completed in a very short temperature interval (Δ T similar/congruent 100°C) in less than 30 min. Crystallization took place just after completion of sintering and was almost complete at about 900°C in 20 min. Secondary porosity prevailed over the primary porosity during the crystallization stage. The glass powder compacts first crystallized into lithium metasilicate (Li₂SiO₃), which transformed into lithium disilicate (Li₂Si₂O₅), zircon (ZrSiO₄), and tridymite (SiO₂) after the crystallization process was essentially complete. The microstructure was characterized by fine crystals uniformly distributed and arbitrarily oriented throughout the residual glass phase.     

Crystallization Kinetics of Lithium Orthosilicate Glasses

The formation of crystalline Li₄SiO₄ and Li₂SiO₃ from lithium orthosilicate glasses has been studied by means of in situ high-temperature X-ray diffraction. The first phase that crystallizes from the glass could not be identified, but was followed by the transformation to crystalline orthosilicate and metasilicate. Orthosilicate formation was tracked at temperatures between 600° and 650°C, whereas at higher temperatures, the formation of a small amount of crystalline metasilicate occurs. The kinetics of the initial phase of both crystallization processes are described by the Avrami–Erofeev equation, resulting in activation energies of 90 kJ/mol for the formation of the unidentified phase, and 68 kJ/mol for the formation of Li₄SiO₄. The rate constant for the crystallization of the unidentified phase is 0.014 s⁻¹ at 510°C, equaling that of the orthosilicate formation at 630°C. After isothermal heat treatment for 100–800 s, depending on temperature, 80%–95% of the sample is crystallized and further crystallization is controlled by diffusion in both cases.     

Strength and Microstructure in Lithium Disilicate Glass-Ceramics

The effect of heat treatment on the microstructure of Li₂O-Al₂O₃·SiO₂ glass-ceramics which contain crystals of either Li₂SiO₃, Li₂Si₂O₅, or both was investigated quantitatively. Strength determinations for abraded rods were correlated with heat treatment on the basis of both size and distribution of crystals and the type and amount of crystal phases present. The presence of Li₂Si₂O₅ crystals enhanced the strength, whereas the presence of Li₂SiO₃ crystals did not change the strength of the abraded parent glass. The interrelation between strength and microstructure is discussed.     

Sol–Gel Preparation and Characterization of Lithium Disilicate Glass–Ceramic

A sol–gel process is described for preparation of crystalline lithium disilicate (Li₂Si₂O₅) from tetraethylorthosilicate and lithium ethoxide. The glass network structure and crystallinity resulting from heat treatment at temperatures from 150° to 900°C were investigated by nuclear magnetic resonance, X-ray diffraction, and differential scanning calorimetry/thermogravimetric analysis. Q³ structural units (SiO₄ tetrahedra with three bridging oxygen atoms) formed in the amorphous gel at a low temperature (≤150°C) persist to elevated temperature (≤500°C) and directly transform to crystalline Li₂Si₂O₅ at about 550°C. The heating schedule slightly affects the crystalline phase transformation.     

Crystallization of a Glass-Ceramic by Epitaxial Growth

The crystallization mechanism in a modified Li₂O-Al₂O₃-SiO₂glass containing P₂O₅ nucleating agent was investigated by transmission electron microscopy, X-ray diffraction, and differential thermal analysis. During an initial 1000°C treatment P₂0₅ and Li₂O react to precipitate Li₃PO₄ crystallites. At lower temperatures cristobalite, lithium metasilicate, and lithium disilicate crystallize by epitaxial growth on those Li₃PO₄crystallites. Crystallographic orientation relations for epitaxy were determined by electron diffraction, and lattice misfits were found to be in the range –5.3 to +3.8%. These results provide the first direct proof that glass-ceramics can crystallize by epitaxial growth on heterogeneous nuclei formed from intentionally added nucleating agents.     

Thermodynamic Properties of Alkali Silicates: Heat Capacity of Li2SiO3 and Lithium-Bearing Melts

The heat capacities of liquid Li₂SiO₃ and Li₂Si₃O₇ have been determined through drop calorimetry measurements to complement available data on lithium, sodium, and potassium silicate melts. The composition and temperature dependences of the heat capacity depends specifically on the nature of the alkali element, indicating that the temperature-induced structural changes that take place in the melts are specific. The properties of crystalline Li₂SiO₃ have also been determined above 298 K. The enthalpy of fusion at 1474 K is 71.3 ± 0.6 kJ/mol, in agreement with previous measurements. In contrast to other silicate compounds, and especially the isostructural crystal Na₂SiO₃, Li₂SiO₃ shows almost no premelting effects.     

Phase Equilibria in the System Li2O-CaO-SiO2

Phase relations in the system Li₂O-CaO-SiO₂ were studied by the quenching method. Four stable ternary compounds were found (Li₂Ca₃Si₆O_l6, Li₂Ca₄Si₄O₁₃, Li₂Ca₂Si₂O₇, and Li₂CaSiO₄) as well as phase Y , which is probably a metastable orthosilicate fairly close to Ca₂SiO₄ in composition. X-ray powder data are given for the new phases. Eleven subsolidus compatibility triangles and thirteen liquidus invariant points were located. Melting relations were determined for that part of the system bounded by Li₂SiO₃, Li₂CaSiO₄, Ca₂SiO₄, and SiO₂. The join Li₂SiO₃-CaSiO₃ is binary.     

Further Studies on Thermal Evolution of Glass-Forming Gels

Glasses of composition Na₂O·2SiO₂ containing iron oxide are obtained by the gel technique. The results show that the iron atoms accelerate the formation of the glass, whereas when they are present in low percentage (∼2%), the temperature necessary to obtain the glass phase is higher. During heat treatment at 250°C, two silicates are formed: Na₂SiO₃ and Na₄SiO₄. When the iron content is low, they change at 650°C into Na₂Si₂O₅, but when the iron content is higher (∼6%), this silicate does not form and the system becomes vitreous.     

Synthesis of Celsian (BaAl2Si2O8) from Solid Ba-Al-Al2O3-SiO2 Precursors: I, XRD and SEM/EDX Analyses of Phase Evolution

An intimate Ba-Al-Al₂O₃-SiO₂ powder mixture, produced by high-energy milling, was pressed to 3 mm thick cylinders (10 mm diameter) and hexagonal plates (6 mm edge-to-edge width). Heat treatments conducted from 300° to 1650°C in pure oxygen or air were used to transform these solid-metal/oxide precursors into BaAl₂Si₂O₈. Barium oxidation was completed, and a binary silicate compound, Ba₂SiO₄, had formed within 24 h at 300°C. After 72 h at 650°C, aluminum oxidation was completed, and an appreciable amount of BaAl₂O₄ had formed. Diffraction peaks consistent with hexagonal BaAl₂Si₂O₈, BaAl₂O₄, β-BaSiO₃, and possibly β-BaSi₂O₅ were detected after 24 h at 900°C. Diffraction peaks for BaAl₂O₄ and BaAl₂Si₂O₈ were observed after 35 h at 1200°C, although SEM analyses also revealed fine silicate particles. Further reaction of this silicate with BaAl₂O₄ at 1350° to 1650°C yielded a mixture of hexagonal and monoclinic BaAl₂Si₂O₈. The observed reaction path was compared to prior work with other inorganic precursors to BaAl₂Si₂O₈.     

Crystallization of Bismuth Borosilicate-Based Dielectric Thick Films on a LiZn Ferrite Substrate

The compatibility and crystallization of dielectric thick films, consisting of a bismuth borosilicate glass and crystalline cordierite, on a LiZn ferrite substrate were investigated by focusing on phase development and microstructural changes. Significant diffusion of Li and Fe from the substrate to the dielectric was confirmed as unexpected crystalline phases such as Li₂Al₂Si₃O₁₀ and Fe₂O₃ were found in the thick films fired at 850°C. The crystallization was believed to be initiated from the film interface and developed further toward the film surface as evidenced from cross-sectional microstructures of the films with additional firings. The degree of crystallization and the relative contents of the observed phases were dependent on the ratio between the glass and cordierite and the number of refirings.     

Grain-Boundary-Phase Crystallization and Strength of Silicon Nitride Sintered with a YSlAlON Glass

Densifying silicon nitride with a YSiAlON glass additive produced 99% dense materials by pressureless sintering. Subsequent heat-treating led to nearly complete crystallization of the amorphous intergranular phase. Transmission electron microscopy revealed that for heat treatments at 1350°C, only β-Y₂Si₂O₇ was crystallized at the grain boundaries. At a higher temperature of 1450°C, primarily YSiO₂N and Y₄Si₂O₇N₂ in addition to small amounts of Y₂SiO₅ were present. Al existed only in high concentrations in residual amorphous phases, and in solid solution with Si₃N₄ and some crystalline grain-boundary phases. In four-point flexure tests materials retained up to 73% of their strengths, with strengths of up to 426 MPa, at 1300°C. High-strength retention was due to nearly complete crystallization of the intergranular phase, as well as to the high refractoriness of residual amorphous phases.     

Phase Relations in the System Al2O3─Ce2Si2O7 in the Temperature Range 900° to 1925°C in Inert Atmosphere

Equilibrium relationships in the system Al₂O₃-Ce₂Si₂O₇ in inert atmosphere have been investigated in the temperature range 900° to 1925°C. A simple eutectic reaction was found at 1375°C and 51 mol% Ce₂Si₂O₇. A high-low polymorphic transformation in Ce₂Si₂O₇ was observed at 1274°C. New XRD patterns are suggested for both polymorphs of cerium pyrosilicate. The melting point of Ce₂Si₂O₇ was found to be 1788°C. A value for ΔH°_m,Ce2Si2O7 of 36.81 kJ/mol was calculated from the initial slope of the experimentally determined liquidus in equilibrium with the pyrosilicate phase.     

Crystallization of Li2O · Al2O3· 6SiO2 Glasses Containing Niobium Pentoxide as Nucleating Dopant

Niobium pentoxide (T form, orthorhombic system) was utilized to promote devitrification in Li₂O · Al₂O₃· 6SiO₂ glasses. Two or more mole percentage of this nucleating dopant enhanced crystallization in these glasses. Glasses containing 4.0 and 8.0 mol% T-Nb₂O₅ exhibited a high tendency to form dispersed TT-Nb₂O₅ (monoclinic system) precipitates during the glass quenching process. The crystallization process in glasses containing 2.0 or 4.0 mol% T-Nb₂O₅ occurred as microphase separation, followed by the formation of dispersed TT-Nb₂O₅ crystalline precipitates (760°C), followed by β-quartz solid-solution ( ss ) formation (850° to 900°C) heterogeneously nucleated from the precipitates. β-quartz( ss ) transformed to β-spodumene( ss ), along with a polymorphic transition from the TT-Nb₂O₅ to M-Nb₂O₅ (tetragonal system) crystalline phase.     

Phase Equilibria in the System Si3N4-SiO2-BeO-Be3N2

The 1780°C isothermal section of the reciprocal quasiternary system Si₃N₄-SiO₂-BeO-Be₃N₂ was investigated by the X-ray analysis of hot-pressed samples. The equilibrium relations shown involve previously known compounds and 8 newly found compounds: Be₆Si³N₈, Be₁₁Si₅N₁₄, Be₅Si²N₆, Be₉Si₃N₁₀, Be₈SiO₄N₄, Be₆O₃N₂, Be₈O₅N₂, and Be₉O₆N₂. Large solid solubility occurs in β-Si₃N₄, BeSiN₂, Be₉Si₃N₁₀, Be₄SiN₄, and β-Be₃N₂. Solid solubility in β-Si₃N₄ extends toward Be₂SiO₄ and decreases with increasing temperature from 19 mol% at 1770°C to 11.5 mol% Be₂SiO₄ at 1880°C. A 4-phase isotherm, liquid +β-Si₃N₄ ( ss )Si₂ON₂+ BeO, exists at 1770°C.     

Early Stages of Crystallization in Canasite-Based Glass Ceramics

Previous work by Miller et al . (2000–2004) has demonstrated that canasite-based glass ceramics have potential for use as biocompatible glass ceramics in hard-tissue augmentation. Several compositional modifications with respect to the stoichiometric formula (K₂Na₄Ca₅Si₁₂O₃₀F₄) were studied and biocompatibility in simulated body fluid was reported. However, the mechanism(s) of crystallization were not investigated in detail. The purpose of this study was to examine the early stages of nucleation and growth in four glass compositions using X-ray diffraction and transmission electron microscopy. In stoichiometric compositions (CAN1), laths of predominantly frankamenite homogeneously nucleate throughout the glass at ∼700°C without the presence of a nucleating phase. However, in Na₂O-deficient compositions (CAN2), CaF₂ particles (650°C) act as nucleating sites for canasite laths (700°C). In CaO-rich compositions (CAN3), CaF₂ particles (650°C) once again act as nucleating sites but for xonotlite (700°C) rather than canasite laths. Instead, frankamenite and canasite crystallize to become the dominant phases at >700°C. In P₂O₅-modified compositions (CAN4), CaF₂ and fluorapatite, present on cooling, act as nucleating agents for canasite (750°C).     

Kinetics and Mechanism of Hot Corrosion of γ-Y2Si2O7 in Thin-Film Na2SO4 Molten Salt

γ-Y₂Si₂O₇ is a promising candidate material both for high-temperature structural applications and as an environmental/thermal barrier coating material due to its unique properties such as high melting point, machinability, thermal stability, low linear thermal expansion coefficient (3.9 × 10⁻⁶/K, 200°–1300°C), and low thermal conductivity (<3.0 W/m·K above 300°C). The hot corrosion behavior of γ-Y₂Si₂O₇ in thin-film molten Na₂SO₄ at 850°–1000°C for 20 h in flowing air was investigated using a thermogravimetric analyzer (TGA) and a mass spectrometer (MS). γ-Y₂Si₂O₇ exhibited good resistance against Na₂SO₄ molten salt. The kinetic curves were well fitted by a paralinear equation: the linear part was caused by the evaporation of Na₂SO₄ and the parabolic part came from gas products evolved from the hotcorrosion reaction. A thin silica film formed under the corrosion scale was the key factor for retarding the hot corrosion. The apparent activation energy for the corrosion of γ-Y₂Si₂O₇ in Na₂SO₄ molten salt with flowing air was evaluated to be 255 kJ/mol.     

Preparation of Rapidly Quenched Glasses in Pseudobinary Systems Composed of Lithium Ortho-Oxosalts

Twin-roller quenching was attempted for 15 pseudobinary systems combining two chosen from the lithium ortho-oxosalts, i.e. Li₃BO₃, Li₄SiO₄, Li₄GeO₄, Li₃PO₄, Li₂SO₄, and Li₂WO₄. Glassy flakes were obtained in almost all systems. Glass formation was easier in systems containing large amounts of Li₃BO₃ or Li₂WO₄ compared to those containing Li₄GeO₄ or Li₃PO₄. Glass transition, crystallization, and liquidus temperatures were determined. Infrared spectra revealed that the glasses consisted of Li⁺ ions and discrete ortho-oxoanions only .     

Estimate of Enthalpies of Formation and Fusion of Cordierite

The enthalpies of solution in molten 2PbO·B₂O₃ at 690°±2°C of cordierite, Mg₂Al₄Si₅O₁₈, and of a glass of cordierite composition were determined. From these data, the enthalpy of formation of cordierite from the component oxides is -16.1±1.7 kcal/mol and its heat of fusion +54.0±2.0 kcal/mol.     

Studies in Lithium Oxide Systems: XI, Li2O–B2O3–P2O5

The glassforming region in the system was roughly outlined and liquidus data were obtained for the three joins LiPO₃-BPO₄, Li₄P₂O₇-BPO₄, and Li₃PO₄-Li₂B₄O₇. Compatibility relations for the ternary subsystems Li₄P₂O₇-BPO₄-P₂O₅ and Li₂O-Li₃PO₄-Li₂B₈O₁₃ were established. Two ternary compounds with the probable compositions 22Li₂O - 11B₂O₃ - 13P₂O₅ and 2Li₂O 3B₂O₃ P₂O₅ were detected.