Crystallization Kinetics and Dielectric Properties of Fresnoite BaO–TiO2–SiO2 Glass–Ceramics

Nucleation and crystallization kinetics of fresnoite (Ba₂TiSi₂O₈) crystals in BaO–TiO₂–SiO₂ glasses have been explored for dielectric applications. The volume fractions crystallized at different temperatures and times were tracked by XRD analysis. The activation energy of crystallization was estimated from DTA results to be about 528 kJ/mol, which is consistent with the value obtained by XRD results. The Avrami parameter values calculated at different temperatures from DTA results were found to be between 3.2 and 3.9, indicating that the growth is three dimensional and the mechanism of growth is interface-controlled. Additionally, because of compositional similarities, the dielectric contrast between the glass (ɛ_r∼15) and the resulting glass–ceramic (ɛ_r∼18) was minimal.     

Degradation of Bioactive Polydimethylsiloxane–CaO–SiO2–TiO2 and Poly(tetramethylene oxide)–CaO–TiO2 Hybrids in a Simulated Body Fluid

It has been shown that polydimethylsiloxane (PDMS)–CaO–SiO₂–TiO₂ and poly(tetramethylene oxide) (PTMO)–CaO–TiO₂ hybrids form apatite on their surfaces in a simulated body fluid (SBF) and show mechanical properties similar to those of human cancellous bones. In the present study, changes, caused by soaking in SBF, were measured in the mechanical properties of PDMS–CaO–SiO₂–TiO₂ hybrids with different CaO and TiO₂ contents and PTMO–CaO–TiO₂ hybrids with different CaO contents. Significant decreases in the strength and strain at failure of the hybrids were observed for the PDMS–CaO–SiO₂–TiO₂ hybrids with high CaO or TiO₂ contents and PTMO–CaO–TiO₂ hybrids with a high CaO content after soaking in SBF for 4 w. This indicates that incorporation of a large amount of CaO component into the hybrids should result in the deterioration of the hybrids in the body environment.     

A Study of the Phase Relations of ZrO2–TiO2 and ZrO2–TiO2–SiO2

The phase relations of the systems ZrO₂–TiO₂ and ZrO₂–TiO₂–SiO₂ were investigated. X-ray diffraction techniques served as the principal means of analysis. The binary system ZrO₂–TiO₂ was found to be one of partial solid solutions with no intermediate compounds. A eutectic point was found to exist at 50 to 55 weight % ZrO₂ and 1600°C. A preliminary investigation of the ternary system ZrO₂–TiO₂–SiO₂, although not extensive, resulted in a better understanding of this system, with a fairly accurate location of some of its boundary lines. A eutectic point was located at 2% ZrO₂, 10% TiO₂, and 88% SiO₂ at approximately 1500°C.     

Immiscibility Area in the System TiO2–ZrO2–SiO2

A furnace for use in conjunction with the X-ray spectrometer was developed which was capable of heating small powdered specimens in air to temperatures as high as 1850°C. This furnace was also used for the heating and quenching of specimens in air from temperatures as high as 1850°C. An area of two liquids coexisting between 20 and 93 weight % TiO₂ above 1765°± 10°C. was found to exist in the system TiO₂–SiO₂, which is in substantial agreement with the previous work of other investigators. The area of immiscibility in the system TiO₂–SiO₂ was found to extend well into the system TiO₂–ZrO₂–SiO₂. The two liquids were found to coexist over a major portion of the TiO₂ (rutile) primary-phase area with TiO₂ (rutile) being the primary crystal beneath both liquids. The temperature of two-liquid formation in the ternary was found to fall about 80°C. with the first additions of ZrO₂ up to 3%. With larger amounts of ZrO₂ the change in the temperature of the boundary of the two-liquid area was so slight as to be within the limits of error of the temperature measurement. Primary-phase fields for TiO₂ (rutile), tetragonal ZrO₂, and ZrTiO₄ were found to exist in the system TiO₂–ZrO₂–SiO₂. SiO₂ as high cristobalite is known to exist in the system TiO₂–ZrO₂–SiO₂.     

Devitrification Kinetics and Mechanism of K2O–CaO–SrO–BaO–B2O3–SiO2 Glass-Ceramic

The devitrification kinetics and mechanism of a low-dielectric, low-temperature, cofirable K₂O–CaO–SrO–BaO–B₂O₃–SiO₂ glass-ceramic have been investigated. Crystalline phases including cristobalite (SiO₂) and pseudowollastonite ((Ca,Ba,Sr) SiO₃) are formed during firing. Activation energy analysis shows that the nucleation of the crystalline phases is controlled by phase separation of the glass. The crystallization kinetics of both cristobalite and pseudowollastonite obey Avrami-like behavior, and the results show an apparent activation energy close to that of the diffusion of alkaline and alkali ions in the glass, suggesting that diffusion is rate limiting. The above conclusion is further supported by analysis of measured growth rates.     

Fabrication of TiO2–SiO2 Photonic Crystals with Diamond Structure

Ceramic photonic crystals with diamond structure were fabricated using stereolithography and successive sintering. The green body of an epoxy resin incorporating 10 vol% TiO₂–SiO₂ was formed by stereolithography and then heated in air at 1100°–1400°C for 2 h. The sintered products maintained the diamond structure with a linear shrinkage ratio of about 57% and a porosity of 38%. The ceramic photonic crystal with eight unit cells showed a photonic band gap at the center frequency of 23.5 GHz. This fabrication method of three-dimensional (3D) ceramic photonic crystals is applicable to other 3D structural ceramics and does not require any molding techniques.     

The Ternary Systems BaO–TiO2–SnO2 and BaO-TiO2-ZrO2

An investigation of the ternary systems BaO-TiO₂-SnO₂ and BaO-TiO₂-ZrO₂ led to the discovery of two new compounds belonging to the system BaO-TiO₂. These compounds, Ba₂Ti₉-O₂₀ and Ba₂Ti₉O₂₀, are stabilized by minute additions of SnO₂ or ZrO₂. The known compound BaTi₂O₅ can be obtained only from the molten phase and decomposes below 1300°C. into Ba₂Ti₅O₁₂ and BaTiO₂. In these systems no ternary compounds are found. The ternary phase diagrams can be divided into regions with high and low dielectric losses, which are in accordance with the phase relations. Tables with crystallographic data of the new compounds are included.     

Determination of CaO–SiO2–MgO–Al2O3–CrOx Liquidus

In this work, the liquidus of synthetic CaO–SiO₂–MgO–Al₂O₃–CrO _x slags is evaluated in the industrially relevant compositional domain. Equilibrium experiments are carried out at 1500°C and partial oxygen pressure ( p _O2) 10^−11.04 atm, and at 1600°C and p _O2=10^−10.16 and 10^−9.36 atm. The studied basicities (CaO/SiO₂) are 1.2 and 0.5. Al₂O₃ levels range from 0 to 30 wt%. Oversaturated liquid is sampled and phase relations are measured with quantitative electron probe microanalysis–wavelength dispersive spectroscopy (EPMA–WDS). The results are compared with the commercially available FactSage thermodynamic databases. Qualitative agreement is always obtained. Also a good quantitative agreement is found at the higher basicity, especially for the spinel liquidus. A minor but systematic deviation can be observed for the eskolaite liquidus. At the lower basicity, the calculated phase diagram deviates strongly from the experimental results, probably due to missing ternary interactions in the database.     

Co-Additions of TiO2 and SiO2 Crystalline Fillers to Tailor the Properties of BaO–ZnO–B2O3–SiO2 Glass for Application to Barrier Ribs of Plasma Display Panels

The influence of co-additions of crystalline TiO₂ and SiO₂ fillers (10 wt% addition in total) to BaO–ZnO–B₂O₃–SiO₂ glass on resultant properties was investigated from the viewpoint of applying the material to the barrier ribs of plasma display panels. The substitution of SiO₂ for TiO₂ reduced the dielectric constant significantly, while it maintained high optical reflectance and appropriate coefficient of thermal expansion (CTE) in the case when TiO₂ alone was used. A 5–7.5 wt% SiO₂ addition with 2.5–5 wt% TiO₂ under the constraint of 10 wt% total fillers demonstrated an optical reflectance of about 55%, a CTE of about 8.3 × 10⁻⁶ K⁻¹ (compatible with glass panels), and a dielectric constant of about 7.5, which are promising properties for the barrier rib application.     

Effect of Glass Additions on BaO–TiO2–WO3 Microwave Ceramics

The effect of glass addition on the properties of BaO–TiO₂-WO₃ microwave dielectric material N-35, which has Q = 5900 and K = 35 at 7.2 GHz for samples sintered at 1360°C, was investigated. Several glasses including B₂O₃, SiO₂, 5ZnO–2B₂O₃, and nine other commercial glasses were selected for this study. Among these glasses, one with a 5 wt% addition of B₂O₃ to N-35, when sintered at 1200°C, had the best dielectric properties: Q = 8300 and K = 34 at 8.5 GHz. Both Q and K increased with firing temperature as well as with density. The Q of N-35, when sintered with a ZnO–B₂O₃ glass system, showed a sudden drop in the sintering temperature to about 1000°C. The results of XRD, thermal analysis, and scanning electron microscopy indicated that the chemical reaction between the dielectric ceramics and glass had a greater effect on Q than on the density. The effects of the glass content and the mixing process on the densification and microwave dielectric properties are also presented. Ball milling improved the densification and dielectric properties of the N-35 sintered with ZnO–B₂O₃.     

SiO2–PbO–CaO–ZrO2–TiO2–(B2O3–K2O), A New Zirconolite Glass–Ceramic System: Crystallization Behavior and Microstructure Evaluation

Zirconolite (CaZrTi₂O₇) is a mineral that has a high containment capacity for actinides and lanthanides and is considered to be a good candidate for the immobilization of radioactive wastes. The glass–ceramic technique seems to be a very suitable and convenient method to produce zirconolite crystals by precipitating them in a specific glass matrix. In this study, development of a new zirconolite-based glass–ceramic belonging to SiO₂–PbO–CaO–ZrO₂–TiO₂–(B₂O₃–K₂O) system was investigated. The presence of PbO, together with B₂O₃ and K₂O, allowed the preparation of a X-ray diffraction (XRD) amorphous glass with a relatively high concentration of ZrO₂ and TiO₂, which was successfully converted to a glass–ceramic containing 34 wt% of zirconolite after heating at 770°C for 4 h. Differential thermal analysis, XRD, scanning electron microscope, and energy dispersive X-ray spectroscopy were used to determine the crystallization conditions, identify the crystallized phases, determine their compositions and quantities and observe and analyze the microstructures. The zirconolite crystals showed a platelet morphology with a monoclinic structure characterized by a =1.246 nm, b =0.7193 nm, c =1.128 nm, and β=100.508°.     

Corrosion Behaviors of Zirconia Refractory by CaO–SiO2–MgO–CaF2 Slag

In this work the corrosion behaviors of zirconia refractory (partially MgO-stabilized zirconia) was investigated in CaO–SiO₂–MgO–CaF₂ slag with varying CaF₂ content at 1873 K. To figure out the corrosion mechanism, the characteristics of present slag at high temperature were examined in terms of melting temperature and vaporization behaviors. Corrosion experiment and melting temperature measurement were carried out by heating microscope (HM) and the vaporization phenomenon was investigated by thermo gravimetry–differential scanning calorimetry. After experiment, the corroded interfaces of zirconia refractory by slag were analyzed by scanning electron microscope-energy dispersive spectroscopy and electron probe microanalysis. With an addition of CaF₂, three different layers were formed at the interface of slag and zirconia refractory. Furthermore, the corrosion behaviors of zirconia refractory were found to be continuously accelerated with an increase of CaF₂ which facilitated the dissolution of intermediate compound. On the other hand, melting temperature of CaO–SiO₂–MgO–CaF₂ slag showed no continuous decrease with an increase of CaF₂. Also, considerable vaporization of fluoride gas was occurred in high CaF₂ containing slag during HM experiment which might cause a gradual change of slag composition and also environmental pollution. From the results, present study suggested that a proper amount of CaF₂ should be added when it is used for enhancing refining capacity of slag in order not to cause any severe damage of zirconia-based refractory by slag.     

Role of Cuspidine (3CaO.2SiO2.CaF2) in the System CaO–SiO2–CaF2

Cuspidine is a well-defined ternary compound with a stability field in the subsystem CaF₂–CaSiO₃–Ca₂SiO₄. Cuspidine is easily formed by solid-state reactions in the subsystem mentioned and is stable above its apparently congruent fusion point if heated in welded platinum containers. Above 1450° decomposition and the formation of a mixture of CaF₂ and Ca₂SiO₄ is observed. Cuspidine also is easily formed by secondary reactions in solid mixtures of the subsystem CaF₂–CaSiO₃ and in ternary mixtures of these with free SiO₂ if heated in open crucibles. The existence of double compounds of CaF₂ and CaSiO₃ is not confirmed.     

Chemical Interactions Promoting the ZrO2 Tetragonal Stabilization in ZrO2–SiO2 Binary Oxides

Metastable tetragonal ZrO₂ phase has been observed in ZrO₂–SiO₂ binary oxides prepared by the sol–gel method. There are many studies concerning the causes of ZrO₂ tetragonal stabilization in binary oxides such as Y₃O₂–ZrO₂, MgO–ZrO₂, or CaO–ZrO₂. In these binary oxides, oxygen vacancies cause changes or defects in the ZrO₂ lattice parameters, which are responsible for tetragonal stabilization. Since oxygen vacancies are not expected in ZrO₂–SiO₂ binary oxides, tetragonal stabilization should just be due to the difficulty of zirconia particles growing in the silica matrix. Furthermore, changes in the tetragonal ZrO₂ crystalline lattice parameters of these binary oxides have recently been reported in a previous paper. The changes of the zirconia crystalline lattice parameters must result from the chemical interactions at the silica–zirconia interface (e.g., formation of Si–O–Zr bonds or Si–O⁻ groups). In this paper, FT-IR and ²⁹Si NMR spectroscopy have been used to elucidate whether the presence of Si–O–Zr or Si–O⁻ is responsible for tetragonal phase stabilization. Moreover, X-ray diffraction, Raman spectroscopy, and transmission electron microscopy have also been used to study the crystalline characteristics of the samples.     

Viscosity Studies of System CaO–MgO–Al2O3–SiO3: IV, 60 and 65% SiO2

In this final paper of a series on viscosity in the system CaO—MgO-Al₂O₃SiO₂ data are presented for melts containing 60 and 65% SiO₂. There also are diagrammatic presentations of the systems of isokoms at intervals on planes parallel to the zero alumina, zero lime, and zero magnesia faces of the tetrahedron, the apices of which represent 100% of each of the four oxides that make up the system.     

Crystallization and Dielectric Properties of SrO–BaO–Nb2O5–SiO2 Tungsten-Bronze Glass-Ceramics

The crystallization and dielectric properties of SrO–BaO–Nb₂O₅–SiO₂ glass-ceramics have been investigated. Glass-ceramics that contain strontium barium niobate (SBN) as a primary crystalline phase, which has a tungsten bronze structure, are produced. The formation of crystalline secondary phases also has been studied. The SBN phase shows evidence of both surface nucleation and bulk nucleation, and the crystals have an average composition of Sr_0.47Ba_0.53Nb₂O₆. The dendritic morphology of the SBN crystals has been examined. The SBN content and composite dielectric constant each has been studied as a function of heating temperature/time. The highest SBN content and dielectric constant obtained in the present study are 42 vol% and 180, respectively. The dielectric constant of the glass-ceramics is determined primarily by the SBN content and the residual glass phase. The dielectric constant of the randomly oriented SBN crystal in the glass-ceramics is calculated, using dielectric mixture rules, to be ∼400.     

Sintering and Crystallization of CaO–Al2O3–ZrO2–SiO2 Glasses Containing Different Amount of Al2O3

In this work several complementary techniques have been employed to carefully characterize the sintering and crystallization behavior of CaO–Al₂O₃–ZrO₂–SiO₂ glass powder compacts after different heat treatments. The research started from a new base glass 33.69 CaO–1.00 Al₂O₃–7.68 ZrO₂–55.43SiO₂ (mol%) to which 5 and 10 mol% Al₂O₃ were added. The glasses with higher amounts of alumina sintered at higher temperatures (953°C [lower amount] vs. 987°C [higher amount]). A combination of the linear shrinkage and viscosity data allowed to easily find the viscosity values corresponding to the beginning and the end of the sintering process. Anorthite and wollastonite crystals formed in the sintered samples, especially at lower temperatures. At higher temperatures, a new crystalline phase containing ZrO₂ (2CaO·4SiO₂·ZrO₂) appeared in all studied specimens.     

Structure of Na2O–CaO–P2O5–SiO2 Glass–Ceramics with Multimodal Porosity

We have investigated the evolution of the structure of nano–macro porous CaO–Na₂O–P₂O₅–SiO₂ bioactive glass–ceramics by Fourier transform infrared (FTIR) and Raman spectroscopies, and X-ray diffraction (XRD). A controlled devitrification, followed by a chemical leaching treatment is used to produce a multimodal distribution of nano/macro pores that are expected to improve cell attachment. Data show that the leaching process removes the sodium- and calcium-containing crystalline phases that are formed during the ceramming heat treatment. The primary Si–O peaks in the infrared spectra blue shift with leaching, indicating that the sample becomes SiO₂ rich. In parallel, the fraction of nonbridging oxygen decreases. These results suggest a restructuring of the glass network far below the glass transition temperature. The stresses from leaching, capillary forces, and subsequent restructuring develop and grow, eventually producing cracks in the sample.     

Calcium Hexaluminate and Its Stability Relations in the System CaO–Al2O3–SiO2

By a combination of solid-state sintering and quenching experiments the validity of calcium hexaluminate as a stable phase and the extent of its primary field in the system CaO–Al₂O₃–SiO₂ have been established. The size of the primary field is considerably reduced from that suggested by earlier work. The anorthite-corundum-calcium hexaluminate invariant point has been relocated at 28.0% CaO, 39.7% Al₂O₂, and 32.3% SiO₂ and at 1405°± 5°C.