Sintering of a Crystallizable CaO-B2O3-SiO2 Glass with Silver

Effects of Ag addition on sintering of a crystallizable CaO-B₂O₃-SiO₂ glass have been investigated at 700°–900°C in different atmospheres. With Ag content increasing in the range of 1–10 vol%, the softening point, the densification, the onset crystallization temperature, and the total amount of crystalline phase formed of the crystallizable glass are reduced when fired in air. A bloating phenomenon is observed when the crystallizable CaO-B₂O₃-SiO₂ glass doped with 1–10 vol% Ag is fired at 700°–900°C for 1–4 h. Fired in N₂ or N₂+ 1% H₂, however, the above phenomena disappear completely. It is thus believed that the diffusion of Ag into the crystallizable glass, which is caused by the oxidation of Ag in air, is the root cause for the above results observed.     

Crystallization of MgO-Al2O3-SiO2-ZrO2 Glasses

The crystallization of MgO-Al₂O₃-SiO₂-ZrO₂ glasses at 1000°C was studied. Isothermal heat treatments of a cordierite-based glass (2MgO.2Al₂O₃.5SiO₂= Mg₂Al₄Si₅O₁₈) with 7 wt% ZrO₂ produced surface crystallization of α-cordierite and tetragonal ZrO₂ ( t -ZrO₂). These phases advanced into the glass by cocrystallization of t -ZrO₂ rods in an α-cordierite matrix with a well-defined orientation relation. The t -ZrO₂ rods were unstable with respect to diffusional breakup (a Rayleigh instability) and decomposed into rows of aligned ellipsoidal and spheroidal particles. The t -ZrO₂ was very resistant to transformation to monoclinic symmetry. With a similar glass containing 15 wt% ZrO₂, surface crystallization of α-cordierite and t -ZrO₂ was accompanied by internal crystallization of t -ZrO₂ dendrites. Transformation of the dendrites to mono-clinic symmetry was observed under some conditions.     

Crystallization of a PbO-BaO-TiO2-Al2O3-SiO2 Glass

The phase development, microstructure development, and Curie temperature of PbO-BaO-TiO₂-Al₂O₃-SiO₂ glass- ceramics were investigated by X-ray diffractometry, electron microscopy, and dilatometry. The primary crystalline phase was perovskite titanate, which exhibited bulk nucle- ation. When the samples were heated at low temperatures, the Curie inversion was hindered and cubic perovskite was obtained. Increased heating temperature/time resulted in tetragonal perovskite. Growth of a surface layer due to the crystallization of the secondary crystalline phase PbO- Al₂O₃-2SiO₂ resulted in the coexistence of coarse and fine perovskite particles. The increase in the relative number of coarse-to-fine perovskite particles with the heating temperature/time was the major factor responsible for increased spontaneous deformation and higher Curie temperature of the perovskite phase. Substitution of barium for lead in the lead titanate phase probably occurred and is explained by the use of SiO₂ instead of B₂O₃ as the glass former in the present study.     

Microstructure and Kinetics of Crystallization of MgO-Al2O3−Si02 Glass-Ceramics

Quantitative X-ray diffraction and microscopy were used to study the morphology development and overall crystallization rate between 900° and 990°C of MgO-Al₂O₃−SiO₂ glasses with added ZrO, TiO₂, CaF₂, or CeO₂. Three basic stages of micro-structural development were distinguishable: I, an induction period, II, a spherulitic crystallization stage, and III, a final crystallization stage. The duration of the induction period, the crystallization rate of the high-quartz solid solution, and the microstructures varied markedly with prior nucleation treatment and the type of modifier present in a glass of nearly equal silica content. The roles of major (high-quartz ss , high cordierite) and of minor crystalline and liquid phases in textural development are discussed, and it is postulated that nucleants (ZrO₂, TiO₂) act also as growth-modifying "impurities" in crystal growth.     

Chemical Strengthening of Glass-Ceramics in the System Li2O-Al2O3-SiO2

Fine-grained glass-ceramics containing a large proportion of β-spodumene solid-solution crystals were strengthened by immersion in molten sodium and potassium salt baths. An ion-exchange reaction placed sodium or potassium ions in lithium ion sites in the β-spodumene structure. The resultant "crowding" of the structure produced a surface compressive layer. In this system, strengths (modulus of rupture on abraded specimens) in excess of 100,000 psi were realized. In a similar manner, stuffed β-quartz solid-solution glass-ceramics derived from the crystallization of Li₂O-Al₂O₃-SiO₂ glasses containing an appropriate amount of nucleating agent were strengthened by K⁺-for-Li⁺ exchange. Stable β-quartz solid-solution glass-ceramics were strengthened by Na⁺-for-Li⁺ exchange, but no significant increase in strength was obtained in the metastable β-quartz materials.     

Microstructures and Crystallization Behavior of Gels in the System La2O3-SiO2,

Gels in the system La₂O₃,-SiO₂, were prepared by two methods, one based on the gelling of a commercial silica hydrosol and one based on the polymerization reaction of alkoxysilane. The microstructural changes and the variability in crystallization rates of the gels in relation to the methods of preparation, thermal treatment, and composition were investigated.     

The System Bi2O3-SiO2

The Bi₂O₃-rich side of the system Bi₂O₃-SiO₂ was studied with powder X-ray diffraction and differential thermal analysis. In the composition 6Bi₂O₃. x SiO₂, the metastable γ phase (bcc) was observed to exist over the range of 0 < x ≤ 1. In most of the compositions studied, metastable phases of water-quenched melts transformed into another metastable phase before reaching stable phases. A modification of the phase diagram is proposed.     

Secondary Grain Growth of Li2O-A12O3-SiO2-TiO2 Glass-Ceramics

The kinetics of secondary grain growth in a Ti0₂-nucleated β-spodumene solid-solution glass-ceramic was studied. The thermal stability of the grains was excellent. Grain growth followed the cube-root-of-time law. The activation energy of the grain boundary migration was 55 ± 10 kcal/mol. Grain growth inhibition due to Ti0₂ precipitates and the residual glassy phase was closely examined. The excellent thermal stability of the grains is due to grain growth inhibition by the residual glassy phase, not by rutile precipitates. It is suggested that the diffusion of A²⁺, and probably the simultaneous diffusion of Li⁺, through the residual glass is the rate-limiting process for the grain boundary migration.     

Sintering, Crystallization, and Properties of B2O3/P2O5-Doped Li2O·Al2O3·4SiO2 Glass-Ceramics

Sintering, crystallization, microstructure, and thermal expansion of Li₂O·Al₂O₃·4SiO₂ glass-ceramics doped with B₂O₃, P₂O₅, or (B₂O₃+ P₂O₅) have been investigated. On heating the glass powder compacts, the glassy phase first crystallized into high-quartz s.s., which transformed into β-spodumene after the crystallization process was essentially complete. The effects of dopants on the crystallization of glass to high-quartz s.s. and the subsequent transformation of high-quartz s.s. to β-spodumene were discussed. The major densification occurred only in the early stage of sintering time due to the rapid crystallization. All dopants were found to promote the densification of the glass powders. The effect of doping on the densification can fairly well be explained by the crystallization tendency. All samples heated to 950°C exhibited a negative coefficient of thermal expansion ranging from about −4.7 × 10^-6 to −0.1 × 10^-6 K^-1. Codoping of B₂O₃ and P₂O₅ resulted in the highest densification and an extremely low coefficient of thermal expansion.     

Fast Li+ Ion Conduction in Li2O-Al2O3-TiO2-SiO2-P2O5 Glass-Ceramics

Fast lithium ion conducting glass-ceramics have been successfully prepared from the pseudobinary system 2[Li_{1+ x} Ti₂Si _x P_{3− x} O₁₂]-AlPO₄. The major phase present in the glass-ceramics was LiTi₂P₃O₁₂ in which Ti⁴⁺ ions and P⁵⁺ ions were partially replaced by Al³⁺ ions and Si⁴⁺ ions, respectively. Increasing x resulted in a considerable enhancement in conductivity, and in a wide composition range extremely high conductivity over 10⁻³ S/cm was obtained at room temperature.     

Nucleation and Crystallization of NaNbO3 from Glasses in the Na2O-Nb2O5-SiO2 System

Transparent glass-ceramics, in which the major phase was NaNbO₃, were obtained by heat treatment of glasses in the Na₂O-Nb₂O₅-SiO₂ system. The structure of the glass and the changes occurring during crystallization as a function of temperature and heating rate were examined by X-ray diffraction, transmission and replication electron microscopy, density, and other measurements. On heating, a rather abrupt formation of uniformly dispersed particles was observed. In the early stages of crystallization, these particles contained NaNbO₃ as loose, radially grown dendrites of identical crystal orientation which became dense during later stages of crystallization. The particle sizes ranged from 200 to 10,000 A, depending on the SiO₂ content of the glass. Transparency of the crystallized material was dependent on the particle size rather than on the amount of NaNbO₃ formed. The temperature at which crystallization occurred increased with the heating rate whereas the viscosity at crystallization decreased. For a given value of the rate of crystal formation per °C of temperature increase, the product (viscosity)ⁿ× (heating rate) was constant. The nucleation and growth phenomena which occurred in these glasses was attributed to microheterogeneities of higher Nb₂O₅ content which formed part of the glass structure.     

Differential Thermal Analysis on the Crystallization Kinetics of K2O-B2O3-MgO-Al2O3-SiO2-TiO2-F Glass

The crystallization kinetics of a glass based on one type of mica, NaMg₃AlSi₃O₁₀F₂, with the addition of a nucleating agent, TiO₂, has been studied using differential thermal analysis (DTA) under both isothermal and nonisothermal conditions. Two distinct crystallization exotherms in the DTA curve are observed and resolved that correspond to the initial formation of magnesium titanate (MgTi₂O₅) and the later formation of mica. The activation energy for precipitation of each crystalline phase has been evaluated, and the crystallization mechanism has been studied. The results indicate that the growth of mica is a two-dimensional process, controlled by the crystal-glass interface reaction. The average calculated values of activation energies are 256 ± 11 kJ/mol and 275 ± 6 kJ/mol for the precipitation of MgTi₂O₅ and mica from the glass matrix, respectively.     

Direct Observation of the Crystallization of Li2O-Al2O3-SiO2 Glasses Containing TiO2

The nucleation and crystallization of Li₂O-Al₂O₃-SiO₂ glasses containing TiO₂ were investigated using transmission electron microscopy of thin sections produced from bulk samples. Phase separation occurs during cooling from the melt, and on heating, a large number of titanium-aluminum crystals approximately 50 A in diameter are formed. These crystals are the heterogeneous nuclei for the crystallization of the remaining glass. Photomicrographs of various stages of crystallization show the development of the fine-grained glass-ceramic.     

Raman Spectroscopy of Heat-Treated B2O3-SiO2 Glasses

Raman spectra were measured on B₂O₃-SiO₂ glasses heat-treated at different temperatures and for different periods of time. It was found that the intensity ratio of the 810- and 475-cm⁻¹ bands depended on the thermal history and composition of glass. The intensity vs heat-treatment temperature curve exhibited a maximum in the glass-transition temperature range. High-temperature Raman spectra were measured on 0.5B₂O₃-0.5SiO₂ glass, both with increasing and decreasing temperature, between room temperature and 600°C. Above 300°C with increasing temperature, the intensity of the 810-cm⁻¹ band decreased, whereas the intensity of the 475-cm⁻¹ band increased. The changes reversed with decreasing temperature. The reversible change of the intensity of the two bands was interpreted as a reversible formation and decomposition of boroxy rings with temperature. The reaction becomes very sluggish below the glass transition so that the intensity ratio stayed constant below 300°C.     

DTA and X-Ray Analysis Study of Nucleation and Crystallization of MgO-Al2O3-SiO2 Glasses Containing ZrO2, TiO2, and CeO2

Crystallization sequences of glasses with compositions in the tridymite primary phase field of the MgO-Al₂O₃-SiO₂ system were studied by DTA, X-ray diffraction, and other techniques. Crystallization was catalyzed by the addition of 7 wt% of either ZrO₂ or TiO₂. Up to 10 wt% CeO₂ was also added to some glasses. Metastable solid solutions with the high-quartz structure exhibiting varying lattice parameters commonly occurred at low temperatures, transforming into a high cordierite at higher temperatures. Depending on the composition and heat treatment, other phases also appeared, e.g. Ce₂Ti₂O₄ (Si₂O₇). The rate of crystallization was markedly dependent on the catalyst. Colloidal precipitation of the catalyst accompanied by bulk crystallization of the glass was observed with ZrO₂, but no crystalline TiO₂ was detected. In the presence of CeO₂, TiO₂ was a more effective catalyst than ZrO₂. Although CeO₂ lowered the melting temperatures of the glass-ceramics, it increased the stability of the glasses and inhibited volume nucleation, causing coarse structures to form on crystallization.     

Kinetics of Solid-State Reaction of Bi2O3 and Fe2O3

Solid-state reactions of equimolar mixtures of Bi₂O₃ and Fe₂O₃ from 625° to 830°C and their kinetics were investigated. The reaction rates were determined from the integrated X-ray diffraction intensities of the strongest peaks of the reactants and products. The activation energy for the formation of BiFeO₃ was 96.6±9.0 kcal/mol; that for a second-phase compound, Bi₂Fe₄O₉, which formed above 675°C, was 99.4±9.0 kcal/mol. Specific rate constants for these simultaneous reactions were obtained. The preparation of single-phase BiFeO₃ from the stoichiometric mixture of Bi₂O₃ and Fe₂O₃ is discussed.     

Eletrical Properties of Glasses in the System PbO-Al2O3-B2O3-SiO2

Glasses in the system Pb0–Al₂O₃-B₂O₃-SiO₂ are chemically stable over a wide composition range and have very desirable electrical characteristics such as high electrical resistivities and activation energies for conduction. Variations in these electrical properties were studied as a function of composition changes within the system, the object being to identify the role of the constituent oxides in achieving the highest activation energy and resistivity values consistent with moderate preparation temperatures. Measurements were made in the temperature range 25° to 400°C on carefully prepared glass disks in which the individual oxide components or different oxide ratios such as PbO/SiO₂, Al₂O₃/SiO₂, and B_sO₃/SiO₁ were systematically varied. The activation energy and resistivity values obtained ranged from 1.2 to 1.6 ev and 10° to 10¹⁴ ohm-cm, with dielectric constants ranging from 9 to 19 and densities from 4.30 to 4.50 g/cmY. Indications were that, for the composition range studied, the behavior manifested was basically that of the binary PbO-SO₂ glass with additions of Al₂O₃ or B₂O₃, even in small concentrations, sharply increasing the activation energy for conduction while lowering the density.     

Thermochemistry of Glasses in the Y2O3-Al2O3-SiO2 System

Enthalpies of drop solution in molten 2PbO-B₂O₃ at 1078 K were measured for glasses along the 2YAlO₃-3SiO₂ and return ½Y₃Al₅O₁₂-3SiO₂ joins. The onset glass transition temperature increases slightly with increasing silica content and Y/Al. Enthalpies of mixing were calculated on the basis of amorphous end members. Strongly negative heats of mixing support the absence of miscibility gaps except possibly for very high silica content, consistent with experimental phase analyses, which indicate much narrower miscibility gaps compared with the phase diagrams calculated on the basis of previous data and the CALPHAD formalism.     

Surface and Bulk Crystallization of Glass-Ceramic in the Na2O-CaO-ZnO-PbO-Fe2O3-Al2O3-SiO2 System Derived from a Goethite Waste

A goethite waste from zinc hydrometallurgical processes has been used to produce a glass-ceramic in the Na₂O-CaO-ZnO-PbO-Fe₂O₃-Al₂O₃-SiO₂system. The surface and bulk microstructure of this glass-ceramic have been studied by using scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The surface was comprised of crystalline and glassy areas. Two different types of crystalline growth and two morphologies were observed in the crystallized and glassy zones, respectively. The bulk microstructure was composed of a homogeneously distributed dendritic network comprised of small crystallites of magnetite. A glassy matrix was observed surrounding the magnetite network. Further heat treatment produced the precipitation of a nonstoichiometric zinc ferrite with magnetite crystals, being the nucleating agents of the secondary phase.