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.     

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.     

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.     

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.     

Sol–Gel-Processed SiO2/TiO2/Methylcellulose Composite Materials for Optical Waveguides

SiO₂–TiO₂–methylcellulose (MC) composite materials processed by the sol-gel technique were studied for optical waveguide applications. Dense, crack-free and homogeneous films as thick as 2 μm were obtained via the organic binder MC-assisted sol–gel process and single coating with low-temperature treatment. Light waveguiding in such hybrid film was demonstrated at a wavelength of 650 nm. About 1.1 dB/cm or lower propagation loss for the SiO₂ (80 mol%)–TiO₂ (20 mol%)–MC (22 wt%) film can be achieved. The effects of thermal treatment on the structure and properties of the gel films were also investigated.     

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.     

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°.     

Nanostructure of TiO2 Nano-Coated SiO2 Particles

We characterized SiO₂–TiO₂ nano-hybrid particles, prepared using the sol–gel method, using high-resolution transmission microscopy. A few nanometer-ordered TiO₂ anatase crystallites could be observed on the monodispersed SiO₂ nanoparticle surface. The quantum size effect of the TiO₂ anatase crystallites is attributed to the blue shift of the absorption band. The rough surface of the SiO₂–TiO₂ nano-hybrid particles was derived from the developed growth planes of the TiO₂ anatase crystallites, grown from fully hydrolyzed Ti alkoxide that did not react with acetic acid during the crystallization process at 600°C thermal annealing.     

Phase Equilibria in the System CaO-TiO2–SiO2

Results of a study of phase equilibria in the system CaO–TiO₂–SiO₂ are presented. A prominent feature of the liquidus surface is a large two-liquid region which appears on the equilibrium diagram as a broad band extending from the SiO₂-CaO side to the SiO₂-TiO₂ side of the triangle. Evidence for the liquid immiscibility and the significance of the resulting large high-temperature liquidus region in silicate technology are discussed. Representative paths of crystallization of liquids in the system under equilibrium conditions are outlined. It is shown that solid solution in the system is virtually nonexistent except for the small-scale substitution of Ti⁴⁺ for Si⁴⁺ in wollastonite. Indices of refraction of glasses are given. Composition and temperature are listed for the twelve liquidus ternary invariant points.     

Liquid–Solid Equilibria in the System NiO–TiO2–SiO2 in the Temperature Range 1430° to 1660°C

Equilibrium relations in the system NiO–TiO₂–SiO₂ in air have been investigated in the temperature range 1430° to 1660°C. The most conspicuous feature of the phase relations is the existence of a cation-excess spinel-type phase, in addition to NiO and NiTiO₃, on the liquidus surface and at subsolidus temperatures down to 1430°C. Three invariant points have been located on the liquidus. There is a peritectic at 1540°C characterized by coexisting NiO ( ss ), spinel( ss ), cristobalite, and liquid of composition 47 wt% NiO, 29 wt% TiO₂, and 24 wt% SiO₂. Two eutectics are present, one at 1480°C, with spinel( ss ), NiTiO₃, cristobalite, and liquid (42 wt% NiO, 43 wt% TiO₂, and 15 wt% SiO₂), as the coexisting phases. The other is at 1490°C with NiTiO₃, rutile, cristobalite, and liquid (32 wt% NiO, 56 wt% TiO₂, and 12 wt% SiO₂). A liquid miscibility gap extends across the diagram from the two bounding binary systems NiO–SiO₂ and TiO₂–SiO₂.     

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.     

Dissolution of MgO in CaO–"FeO"–CaF2–SiO2 Slags under Static Conditions

The dissolution of MgO in CaO–"FeO"–CaF₂–SiO₂ slags has been studied in the temperature range 1573°–1673° K under static conditions. The concentration profiles of Mg in the product Mg_1-xFe_xO solid-solution layer as well as slag were determined by EDS analysis. From this, the diffusivities of MgO in the slag and the. interdiffusivities in solid solution were estimated. The dissolution of MgO in CaO–"FeO"–CaF₂–SiO₂ slags increased with CaF₂ content.     

Direct Measurement of Relative Partial Molar Enthalpy of SiO2 in SiO2–M2O (M=Li, Na, K, Cs) Binary and SiO2–CaO–Al2O3 Ternary Melts

The relative partial molar enthalpies, Δ _SiO2, of SiO₂ in SiO₂–M₂O (M = Li, Na, K and Cs) binary and SiO₂–CaO–Al₂O₃ternary melts were directly measured by drop-solution calorimetry at 1465 K and 1663 K. Δ _SiO2 changes from exothermic to endothermic as silica content increases, confirming the tendency toward immisciblity seen from activity measurements. It is concluded that Δ _SiO2 is negative due to acid-base reactions and charge-coupled substitutions when the melt is composed of fewer Q ⁴ and more Q ³ and Q ² species, but positive due to structural strain when the melt is composed of mostly Q ⁴ species. The Δ _SiO2 obtained by calorimetry is a useful measure of basicity, when comparing different alkali and alkaline earth oxides.     

Fluoride Model Systems: II, The Binary Systems CaF2–BeF2, MgF2–BeF2, and LiF–MgF2

Data obtained by quenching, thermal, and high-temperature X-ray techniques are presented for the three binary systems CaF₂–BeF₂, MgF₂–BeF₂, and LiF–MgF₂. The systems CaF₂–BeF₂ and MgF₂–BeF₂ are presented as weakened models of the systems ZrO₂–SiO₂ and TiO₂–SiO₂, respectively. The compound CaBeF₄ is a model of ZrSiO₄ (zircon). New data obtained for the system LiF–MgF₂ explain many discrepancies among the results of previous authors. Solid solution is almost complete between LiF and MgF₂ at elevated temperatures, but a small gap occurs at the eutectic (735°C.) with extensive exsolution at lower temperatures.     

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.     

Effects of the Addition of Different Types of Fillers on the Properties of BaO–ZnO–B2O3–SiO2 Glass Composites for Application to Barrier Ribs of Plasma Display Panels

Various types of crystalline ceramic fillers (TiO₂, ZrO₂, Al₂O₃, MgO, and cordierite) were added to BaO–ZnO–B₂O₃–SiO₂ (BZBS) glass (5–20 wt%), and the resultant dielectric constant, coefficient of thermal expansion (CTE), and optical reflectance were investigated for the application of the composites to the barrier ribs in plasma display panels. All the investigated fillers were partially dissolved into the glass at the fabrication temperature (575°C), and the residual fillers were aligned along the boundaries of sintered glass frits. By considering all aspects of the properties, the addition of TiO₂ fillers of about 10 wt% to BZBS glass was the most desirable of the types of fillers investigated. The addition of TiO₂ filler (10 wt%) yielded 61% in optical reflectance, 8.3 × 10⁻⁶ K^–1 in coefficient of thermal expansion, and 15.5 in dielectric constant, which were properties comparable with the currently used Pb-based barrier ribs.     

Quaternary System Al2O3–CaO–MgO–SiO2: I, Study of the Crystallization Volume of Al2O3

Compatibility relations of Al₂O₃ in the quaternary system Al₂O₃–CaO–MgO–SiO₂ were studied by firing and quenching followed by microstructural and energy-dispersive X-ray examination. A projection of the liquidus surface of the primary phase volume of Al₂O₃ was constructed in terms of the CaO, SiO₂, and MgO contents of the mixtures recalculated to 100 wt%. Two invariant points, where four solids coexist with a liquid phase, were defined, and the positions of the isotherms were tentatively established. The effect of SiO₂, MgO, and CaO impurities on Al₂O₃ growth also was studied.     

Preparation and Physical Properties of Radiofrequency-Sputtered Amorphous Films in the System AlPO4–TiO2

Amorphous films in the system AlPO₄–TiO₂ were prepared by an rf-sputtering method, and their physical properties, such as density, refractive index, and thermal expansion coefficient, and the infrared absorption spectra were measured. The thermal expansion coefficient increased linearly with increasing TiO₂ content. The results of the molar refractivity and the infrared absorption spectra indicated that the coordination number of titanium ions in these films is higher than that in SiO₂–TiO₂ glasses with a negative thermal expansion, in which Ti⁴⁺ ions are tetrahedrally coordinated. In order to confirm the coordination state of the titanium ions in these amorphous films, titanium K -band emission spectra were obtained by X-ray emission spectroscopy, revealing sixfold coordination. The higher coordination state of Ti⁴⁺ was considered to account for these amorphous films not exhibiting negative thermal expansion, as in the SiO₂–TiO₂ system.