Pressure and Temperature Dependence of the Elastic Moduli of Na2O-TiO2-SiO2 Glasses

Ultrasonic interferometry was used to measure elastic-wave velocities and moduli in six Na₂O-TiO₂-SiO₂ glasses; three glasses contained 20 mol% TiO₂ and three 25 mol% TiO₂. The elastic moduli and their pressure derivatives varied systematically with the SiO₂/Na₂O molar ratio of the glasses. In the group of glasses which contained 20 mol% TiO₂, dK/dP ( K =bulk modulus) decreased linearly from 4.85 to 2.59 as the SiO₂/Na₂O ratio increased; in the other group, dK/dP decreased from 4.00 to 3.05. Similarly, dμ/dP (μ=shear modulus) decreased with the SiO₂/Na₂O ratio, but somewhat non-linearly. The extrinsic and intrinsic contributions to the temperature dependencies of the elastic moduli are evaluated in light of the measured pressure dependencies of these moduli.     

Activities and Structure of Some Melts in the System Na2SiO3-Na2Si2O5

Different structural models for melts between Na₂SiO₃ and Na₂Si₂O₅ were tested by comparison of activities computed from the models with activities determined from the calorimetric heat of fusion. Data were used from the liquidus curve of the phase diagram for the system Na₂SiO₃-Na₂Si₂O₅ (Kracek and Morey and Bowen). A group model involving (SiO₃)_x^2x- rings or chains, with a random distribution of (SiO_2.5)₂ pairs which bridge between rings or chains, gives activities in good agreement with those determined from the calorimetric heat of fusion.     

Crystallization of Beta NaFeO2 from a Glass Along the Na2SiO3-Fe2O3 Join

Fine-particle beta sodium ferrite (β-NaFeO₂), rather than α-Fe₂O₃, may be responsible for superparamagnetic behavior in a glass of composition (in mole fractions) 0.37Na₂O-0.26Fe₂O₃-0.37SiO₂. The 700°C isothermal section of the phase diagram of the Na₂O-Fe₂O₃-SiO₂ system is given, showing a three-phase field bounded by Na₂SiO₃-NaFeO₂-Fe₂O₃; there is no evidence for the existence (at 700°C) of compounds of molar composition 6Na₂O-4Fe₂O₃-5SiO₂ or 2Na₂O-Fe₂O₃-SiO₂. The Moessbauer spectrum of β-NaFeO₂ has an internal magnetic field of 487 kOe at room temperature.     

Sol–Gel Synthesis and Photocatalytic Activity of CeO2/TiO2 Nanocomposites

Uniform CeO₂ / TiO₂ composite nanoparticles with different Ce/Ti molar ratios have been successfully synthesized via the sol–gel method. The samples were characterized using differential thermal analysis (DTA), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and transmission electron microscopy (TEM). The surface state analysis by means of X-ray photoelectron spectroscopy (XPS) shows that the Ti element mainly exists as a chemical state of Ti⁴⁺, while the Ce element exists as a mixture of Ce³⁺ and Ce⁴⁺ oxidation states. The photocatalytic degradation of methyl orange (MeO) in CeO₂ / TiO₂ suspension was investigated. The results indicate that the CeO₂/TiO₂ nanocomposites show higher photocatalytic activity than pure TiO₂. Photodegradation of MeO can be improved by increasing the Ce/Ti molar ratio in the initial 15 min.     

Sol–Gel Synthesis and Characterization of Ag and Au Nanoparticles in SiO2, TiO2, and ZrO2 Thin Films

Silver and gold nanoparticles were synthesized by the sol–gel process in SiO₂, TiO₂, and ZrO₂ thin films. A versatile method, based on the use of coordination chemistry, is presented for stabilizing Ag⁺ and Au³⁺ ions in sol–gel systems. Various ligands of the metal ions were tested, and for each system it was possible to find a suitable ligand capable of stabilizing the metal ions and preventing gold precipitation onto the film surface. Thin films were prepared by spin-coating onto glass or fused silica substrates and then heat-treated at various temperatures in air or H₂ atmosphere for nucleating the metal nanoparticles. The Ag particle size was about 10 nm after heating the SiO₂ film at 600°C and the TiO₂ and ZrO₂ films at 500°C. After heat treatment at 500°C, the Au particle size was 13 and 17 nm in the TiO₂ and ZrO₂ films, respectively. The films were characterized by UV–vis optical absorption spectroscopy and X-ray diffraction, for studying the nucleation and the growth of the metal nanoparticles. The results are discussed with regard to the embedding matrix, the temperature, and the atmosphere of the heat treatment, and it is concluded that crystallization of TiO₂ and ZrO₂ films may hinder the growth of Ag and Au particles.     

Phase Equilibria in the System Na2SiO3-Li2SiO3

Phase equilibria were studied for the system Na₂SiO_:rLi₂SiO₃. The 2 end-member metasilicates show limited mutual solid solubility with the (Na_2-χLi_χ)SiO₃ solid solutions being particularly extensive at solidus temperatures (0 x 1.06). Ordering of the latter solid solution occurs at the NaLiSiO_;) composition with a_supercellx= 6a_subcell During cooling of the solid solutions, metastable phase transformations occur; a twinned monoclinic metastable phase, low (Na, Li)₂SiO₃, has been characterized.     

Phase Relations in the Pseudobinary System Na2TiSi4O11-Na2Ti2Si2O9

The quenching technique was used to study subliquidus and subsolidus phase relations in the pseudobinary system Na₂ Ti₂Si₂ O₁₁-Na₂ Ti₂ Si₂ O₉. Both narsarukite (Na₂TiSi₄O₁₁) and lorenzenite (Na₂Ti₂Si₂O₉) melt incongruently. Narsarsukite melts at 911°±°C to SiO₂+liquid, with the liquidus at 1016°C. Lorenzenite melts at 910°±5°C to Na₂ Ti₆ O₁₃+liquid; Na₂ Ti₆ O₁₃ reacts with liquid to form TiO₂ and is thus consumed by 985°±5°C. The liquidus occurs at 1252°C.     

Preparation of TiO2 Nanoparticles on Different SiO2 Supports by the Adsorption Phase Technique

The influence of supports on the preparation of TiO₂ nanoparticles by the adsorption phase technique is studied in detailed. Series temperature experiments of two types of supports (named as SiO₂ A and B) were used. Energy-dispersive analysis by X-ray indicates that the concentration of TiO₂ on both supports decreases with temperature increasing. TiO₂ quantity on SiO₂ A decreases sharply between 40° and 60°C, whereas the temperature range for SiO₂ B is between 30° and 50°C. X-ray diffraction (XRD) shows that grain size of TiO₂ particles on two SiO₂ surfaces is all below 7 nm. It is also shown by XRD that particles on SiO₂ A decrease sharply as in the quantity curve of TiO₂, but particles on SiO₂ B all change gradually and TiO₂ particles on SiO₂ B are more uniform in transmission electron spectroscopy. The similarly of both supports is considered to be the reason for the similar changes in Ti concentration, and the different characteristics of the internal/external surface lead to variant quantity and grain size, as well as characteristics of TiO₂.     

Phases in the System Ba2SiO4-Ca2SiO4

The system Ba₂SiO₄-Ca₂SiO₄ was studied by heating mixtures of Ba₂SiO₄ and Ca₂SiO₄ at 1723 K. Six distinct phases resulted; they were examined by both X-ray diffraction and differential thermal analysis. The phases β -(Ba_0.05Ca_1.95)SiO₄ and α-(Ba_0.15Ca_1.85)SiO₄ are isostructural with corresponding high-temperature modifications of Ca₂SiO₄. The X phase (Ba_0.48Ca_1.52SiO₄) is orthorhombic, is a pure phase rather than a solid solution, and is defined for the first time in the present work. The T phase (Ba_1.31Ca_0.69SiO₄) is hexagonal and interpreted in terms of a unit cell with a doubled c parameter, in contrast with literature data.     

The System KAlSiO4–Mg2SiO4–KAlSi2O6

Schairer's study (1954) on phase relations in the system KalSi₂O₆–Mg₂SiO₄–SiO₂ was extended to include the system KalSiO₄–Mg₂SiO₄–KalSi₂O₆. It is shown that this join is ternary; however, the relatively high vapor pressure of the condensed phases prohibits study by the usual quenching techniques. The apparent intersection of the (KalSiO₄–Mg₂SiO₄–SiO₃) join with the primary phase volume of spinel is attributed to loss of the alkali-silicate constituents by vapor transport. This results in the effective bulk composition being moved away from this join toward the primary phase volume of spinel in the system K₂O–MgO–Al₂O₃–SiO₂.     

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.     

Photoactive and Adsorptive Niobium-Doped Anatase (TiO2) Nanoparticles: Influence of Hydrothermal Conditions on their Morphology, Structure, and Properties

Anatase-type TiO₂ nanoparticles with adsorptivity and improved photocatalytic activity for the decomposition of methylene blue (MB) in its aqueous solution, which contained up to 10 mol% niobium by forming solid solutions with niobium oxide, were directly synthesized from precursor solutions of TiOSO₄ and NbCl₅ under three hydrothermal conditions in the absence and presence of urea and aqueous ammonia at 180°C for 5 h. The influence of the hydrothermal conditions on the crystallite growth, morphology, specific surface area, adsorptivity, and photocatalytic activity of niobium-doped TiO₂ was investigated. The crystallite growth of anatase was enhanced by the presence of the niobium component. The 10 mol% niobium-doped TiO₂ that was prepared under the hydrothermal condition in the presence of urea had fine crystallites (11 nm) and high specific surface areas (135 m²/g), which showed the most enhanced photocatalytic activity and the highest adsorptivity. The hydrothermal treatment under weak basic conditions and formation of solid solutions with niobium oxide brought about a considerable increase in the adsorption of MB for the anatase-type TiO₂.     

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.     

The Join Ca2SiO4-CaMgSiO4

New data obtained on the join Ca₂SiO₄-CaMgSiO₄ established a limit of crystalline solubility of Mg in α-Ca₂SiO₄ corresponding to the composition Ca_1.90Mg_0.10SiO₄ at 1575°C. The α-α'Ca₂SiO₄ inversion temperature is lowered from 1447° to 1400°C by Mg substitution in the lattice. α'-Ca₂SiO₄ takes Mg into its lattice up to the composition Ca_1.94Mg_0.06SiO₄ at 1400°C and to Ca_1.96Mg_0.04SiO₄ at 900°C. A new phase (T) reported previously by Gutt, with the approximate composition Ca_1.70Mg_0.30SiO₄, was stable between 979° and 1381°C, and should be stable at liquidus temperatures in multicomponent systems involving CaO–MgO–SiO₂.     

Equilibria of SiF4 with SiO2, Be2SiO4, and BeO in Molten Li2BeF4

Equilibrium partial pressures of SiF₄ were measured for the reactions 2SiO₂( c )+2BeF₂( d )⇋SiF₄( g )+Be₂SiO₄( c ) (log P _siF4(mm) = [8.790 - 7620/ T ] ±0.06(500°–640°C)) and Be₂SiO₄( c ) +2BeF₂( d )⇋SiF₄( g ) +4BeO( c )(log P _siF4(mm) = [9.530–9400/T] ±0.04 (700°–780°C)), wherein BeF₂ was present in solution with LiF as molten Li₂BeF₄. The solubility of SiF₄ was low (∼0.04 mol kg^-1 atm^-1) in the melt. The results for the first equilibrium were combined with available thermochemical data to calculate improved Δ H_f and Δ G_f values for phenacite (–497.57 ±2.2 and –470.22±2.2 kcal, respectively, at 298°K). The few measurements above 700°C for the second equilibrium are consistent with the temperature of the subsolidus decomposition of phenacite to BeO and SiO₂ and with the heat of this decomposition as determined by Holm and Kleppa. Below 700°C, the pressures of SiF₄ generated showed an increasing positive deviation from the expression given for the equilibrium involving Be₂SiO₄ and BeO. This deviation might have been caused by the formation of an unidentified phase below 700°C which replaced the BeO; it more likely resulted from a metastable equilibrium involving BeO and SiO₂.     

Effect of Small Additions of Al2O3 and Ga2O3 on the Immiscibility Temperature of Na2O-SiO2 Glasses

Alumina and gallia were substituted separately for Na₂O in amounts of 0.2, 0.5, 1.0, 1.5, 2.0, and 3.0 wt% in three Na₂O-SiO₂ glass compositions (82, 84, and 86 wt% SiO₂) within the immiscibility region. The immiscibility regions for each system extend to ∼1.5 mol% of the added oxide. In general, the addition reduced the immiscibility temperature ( T _m), but at the edge of the immiscibility region (82% SiO₂) the Na₂O loss effect initially increased T _m. A structural model of the miscibility of Al₂O₃ added to silicate glasses is presented.     

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.     

Glass Formation and Properties of Glasses in the System Na2O-B2O3-SiO2-TiO2

An investigation was made of the effect of TiO₂ on the glassforming region and on the physical properties of glasses in the system Na₂O-B₂O₃-SiO₂TiO₂. Glasses containing up to 45 mole % TiO₂ may be formed with an alkali content of 30 mole %. At lower alkali contents (10 mole % Na₂O) glasses may be formed containing up to 22 mole % TiO₂. The way in which the coefficient of linear thermal expansion and the transformation and softening temperatures are affected by TiO₂ additions has been determined.     

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.     

Sodium Transport in the Na2O-H2O-SiO2 Glass System

The variation with water content of dc conductivity and Na diffusion coefficient for the Na₂O · 4siO₂ and Na₂O · 2SiO₂ glass systems was found to be similar to that of the Na₂O.3SiO₂ series reported earlier. The conductivity was estimated for the ternary system Na₂O-H₂O-SiO₂ by combining the present results with the previous data on the Na₂O · 3SiO₂ system. When the conductivity of those glasses with a constant [Na₂O] + [H₂O] content was plotted against water content, a pronounced mixed "alkali" effect was demonstrated. The Haven ratio, calculated by comparison of the dc conductivity to the Na diffusion coefficient at 100°C for each of the three glass systems, was found to increase toward unity with increasing water content. This suggests that the addition of water reduces the number of sodium charge carriers. The subsequent increase in conductivity beyond the minimum with the introduction of larger amounts of water is, probably, due to an increase in the mobility of the Na⁺ ions.