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.     

Elastic Moduli and Refractive Indices of Aluminosilicate Glasses Containing Y2O3, La2O3, and TiO2

Glasses in the system Al₂O₃-Y₂O₃-SiO₂, containing TiO₂ and La₂O₃, were investigated. Glasses of high refractive index and elastic modulus were developed. The observed Young's and shear moduli of these glasses show good agreement with theoretical values. Agreement was also found between the observed and calculated values of refractive index when the Appen's empirical coefficients were used.     

Effects of Glass Additions on (Zr,Sn)TiO4 for Microwave Applications

The effects of glass additions on the properties of (Zr,Sn)TiO₄ as a microwave dielectric material were investigated. The (Zr,Sn)TiO₄ ceramics with no glass addition sintered at 1360°C gave Q = 4900 and K = 37 at 7.9 GH_z. Several glasses, including SiO₂, B₂O₃, 5ZnO–2B₂O₃, and nine commercial glasses, were tested during this study. Among these glasses, (Zr,Sn)TiO₄ sintered with ZnO-B₂O₃–SiO₂ (Corning 7574) showed more than 20% higher density than that of pure (Zr,Sn)TiO₄ sintered at the same temperature. A 5-wt% addition of SiO₂, to (Zr,Sn)TiO₄, when sintered at 1200°C, gave the best Q : Q = 2700 at 9 GHz. Results of XRD analysis and scanning electron microscopy and the effect of glass content are also presented.     

Binary Titania-Silica Glasses Containing 10 to 20 Wt% TiO2

A series of glasses in the TiO₂-SiO₂ system was prepared by the flame hydrolysis boule process. Clear glasses containing as much as 16.5 wt% TiO₂ were obtained. More TiO₂ caused opacity due to phase separation and anatase/rutile crystallization during glass boule formation. Glasses in the 12 to ∼17 wt% TiO₂ range were metastable and showed structural rearrangements on heat treatment at temperatures as low as 750CEC (∼200° below the annealing point). These changes were accompanied by large changes in thermal expansion. Thermal treatment can be designed to produce almost any desired expansion between α_-200+700=−5 × 10^-7/°C and +10 × 10^-7/°C. Zero expansion between 0 and 550°C was obtained. Evidence that these changes are due to phase separation and anatase formation is presented. Viscosity data in the glass transition range, refractive index, and density are also presented.     

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.     

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.     

Properties and Structure of Glasses in the Binary Systems Alkali—TiO2

Glasses corresponding to mole formulas R₂TiO₃ and R₂Ti₂O₅ were prepared in 1- to 5-g quantities by quenching in a platinum crucible. K₂O, Rb₂O, and Cs₂O formed fairly stable glasses with TiO₂. On heat treatment, these glasses nucleated readily and formed opal-like glasses. Li₂O and Na₂O, however, did not form glasses with TiO₂ in 1-g quantities. Hygroscopicity increased with the alkali content and decreased with the increase in TiO₂ concentration. The refractive indices of the glasses ranged from 1.66 to 1.90. These facts indicate that TiO₂ is a glass former in its own right and that Ti⁴⁺ exists in sixfold coordination in these glasses.     

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.     

Enhanced Visible Light-Driven Photocatalytic Performance of La-Doped TiO2−xFx

La-doped TiO_{2− x} F _x (La–TiO_{2− x} F _x ) powders were prepared by the sol–gel method. X-ray diffraction results showed that La efficiently inhibited grain growth. X-ray photoelectron spectroscopy spectra revealed that La₂O₃ and O–Ti–F bonds have formed, the La₂O₃ maintained the high surface area of TiO_{2− x} F _x after calcination at a temperature above 500°C, while the O–Ti–F bonds increased the oxidation potential of the photogenerated hole in the valence band. The UV-vis spectroscopy of the La–TiO_{2− x} F _x showed that the presence of intraband gap states was likely responsible for its absorption of visible light. When the molar ratios of La and F to Ti were 1.5:100 and 5:100, respectively, and calcined at 500°C, the photocatalytic degradation rate of methylene blue over La–TiO_{2− x} F _x was about 1.5 times higher than that of F-doping TiO₂.     

Environmentally friendly coloured materials: cellulose/titanium dioxide/inorganic pigment composite spherical microbeads prepared by viscose phase-separation method

In order to develop environmentally friendly coloured materials, cellulose composite spherical microbeads hybridised with titanium dioxide (TiO₂) particles and inorganic pigment were prepared by a phase-separation method using viscose and an aqueous solution containing sodium polyacrylate. Findings regarding the relationships between cellulose xanthate and the electronic characteristics of TiO₂ particles used in the cellulose/inorganic material composite sphering process are also reported. These findings suggest that the location of TiO₂ particles in cellulose microbeads is related to electrical repulsion between the xanthate (CSS⁻) group and TiO₂. The use of TiO₂ powder as colour pigment is limited, as its colour is white. The cellulose composite spherical microbeads covered with TiO₂ and Fe₂O₃ particles were developed by addition of iron oxide (Fe₂O₃). Their surfaces were viewed by laser microscope and using SEM images. These composite microbeads retained the photocatalytic property of TiO₂. Cellulose/TiO₂/Fe₂O₃ composite spherical microbeads with both colour function and photocatalytic properties were successfully prepared.     

Apatite Formation on Calcium Phosphate Invert Glasses in Simulated Body Fluid

Calcium phosphate invert glasses, which contain P₂O₇²⁻ and PO₄³⁻ ions, have been prepared via the addition of a small amount of TiO₂. The formation of bonelike calcium phosphate apatite on the surface of the phosphate invert glasses was examined in simulated body fluid (SBF) at a temperature of 37°C. Soaking for 20 d resulted in the deposition of leaflike apatite particles on 6CaO·3P₂O₅·TiO₂ invert glass (based on molar ratio). The glass had much-greater chemical durability against SBF, in comparison with a metaphosphate glass; P ions were not dissolved excessively from the 6CaO·3P₂O₅·TiO₂ glass, so the apatite formation was not suppressed.     

Formation of Nepheline Glass-Ceramics Using Nb2O5 as a Nucleation Catalyst

The crystallization of several Nb₂O₅-catalyzed glasses in the Na₂O.Al₂O.SiO₂ system was studied using DTA, X-ray diffraction, and electron microscopy. The Nb₂O₅ was an effective nucleation catalyst; fine-grained body-nucleated glass-ceramic materials containing hexagonal nepheline and NaNbO₃ were obtained. The crystallization sequence and final crystalline phases in these compositions were quite different from those found in the equivalent TiO₂ analogs. The addition of small amounts of carbides and nitrides at the expense of oxides in the initial glass batch markedly affected the final crystalline phases.     

Low-Temperature Atomic Layer-Deposited TiO2 Films with Low Photoactivity

Atomic layer deposition (ALD) has been successfully utilized for the conformal and uniform deposition of ultrathin titanium dioxide (TiO₂) films on high-density polyethylene (HDPE) particles. The deposition was carried out by alternating reactions of titanium tetraisopropoxide and H₂O₂ (50 wt% in H₂O) at 77°C in a fluidized bed reactor. X-ray photoelectron spectroscopy confirmed the deposition of TiO₂ and scanning transmission electron microscopy showed the conformal TiO₂ films deposited on polymer particle surfaces. The TiO₂ ALD process yielded a growth rate of 0.15 nm/cycle at 77°C. The results of inductively coupled plasma atomic emission spectroscopy suggested that there was a nucleation period, which showed the reaction mechanism of TiO₂ ALD on HDPE particles without chemical functional groups. TiO₂ ALD films deposited at such a low temperature had an amorphous structure and showed a much weaker photoactivity intensity than common pigment-grade anatase TiO₂ particles.     

Influence of TiO2 on Properties of Glasses in the System K2O–PbO–SiO2–TiO2 and Its Relation to Structure

By a progressive weight percent substitution of TiO₂ for SiO₂ at various rations of concentration of K₂O and PbO, the entire region of glass formation in the quaternary system K₂O–PbO–SiO₂–TiO₂ was covered with 51 glass compositions. The properties of these glasses were determined and studied with respect to the role of TiO₂ in the system. The results indicated that the dielectric constant increased progressively with increasing TiO₂ concentration whereas the dissipation factor showed an overall decrease, when measured at 1 Mc and 25°C. Density and the refractive index increased progressively with increasing TiO₂ concentration but deviated from the additive relation. Chemical durability, expansivity, and softening temperature vs. composition curves showed definite inflections. The effect of TiO₂ on oxygen packing indicated that Ti⁴⁺ strengthens the network in lower concentrations and weakens the network in higher concentrations in this system. It appears to be likely that Ti⁴⁺ changes its coordination number form 4 to 6.     

Crystallization Kinetics of Lithia-Silica Glasses: Effect of Composition and Nucleating Agent

The kinetics of crystallization of a 25Li₂O · 75SiO₂ (wt%) glass doped with Pt, Cu, Au, TiO₂, and P₂O₅ were studied using nonisothermal techniques. The activation energy, E , and the frequency factor, v , for the overall crystallization process depended directly on the critical cooling rate for the glass formation, R_c , of these glasses. The crystallization kinetics of several other glasses in the lithia-silica system were also studied as a function of composition, critical cooling rate, and liquidus temperature, T_m. E and v for these glasses were more dependent on the liquidus temperature than on R_c .     

Preparation, Characterization, and Photocatalytic Activity of N, S-Codoped TiO2 Nanoparticles

The doping of titanium dioxide (TiO₂) with various metal or nonmetal elements has been considered as an effective strategy to extend the photoactive wavelength region to visible light. In this paper (nitrogen [N] and sulfur [S])-codoped anatase TiO₂ nanoparticles were prepared via a sol–gel route, followed by a heat treatment at elevated temperatures. The as-prepared samples were extensively characterized by X-ray diffraction, UV–Vis absorption spectroscopy, and X-ray photoelectron spectroscopy. The N, S-codoped TiO₂ nanoparticles showed a strong visible light absorption and exhibited an enhanced photocatalytic activity for the degradation of methylene blue as compared with the pure, N- or S-doped TiO₂ under either UV light or solar light irradiation.     

Formation and Properties of GeSe2–Ga2Se3–PbI2 Novel Chalcohalide Glasses

The glass-forming region of the GeSe₂–Ga₂Se₃–PbI₂ system was determined and homogeneous glasses were prepared. The maximum dissolvable PbI₂ can be up to 50 mol%. The structures of glasses were characterized by Raman spectroscopy. The thermal, optical, and some basic physical properties of the glasses were investigated. The results show that GeSe₂–Ga₂Se₃–PbI₂ glasses have a wide region of transmission window (0.7–16 μm) and high refractive index (∼2.5) with the addition of PbI₂. The glasses have good glass-forming ability and high glass transition temperatures. Consequently, these novel glasses may be promising candidate materials for infrared optics and nonlinear optical field.     

Physical Properties and Structure of Silica-Alumina-Europium Oxide Glasses

SiO₂–Al₂O3–Eu₂O₃ glasses were prepared for the composition 50siO₂·(50 – x )Al₂O_3·xEu₂O₃, and their density, sound velocity, and elastic modulus were measured. The chemical shift of the AIK a band emission spectra and the isomer shift of ¹⁵¹Eu by Mössbauer effect were obtained to determine the coordination states of Al³⁺ and Eu³⁺ ions in these glasses. It was found that the coordination number of Eu³⁺ ions was 12 and that the average coordination number of A1³⁺ ions was almost 5 in these glasses. By introducing Eu₂O₃, the packing of constituent ions was strongly enhanced and the elastic modulus increased in this system. The compositional dependence of the molar volume and elastic modulus were explained by these states of high coordination number for Eu³⁺ and low coordination number for Al³⁺ ions compared with those in the corresponding M₂O₃ crystals.     

Preparation of Titanium Dioxide Nanocrystallite with High Photocatalytic Activities

Anatase nanocrystalline titanium dioxide (TiO₂) with high photocatalytic activities was prepared by hydrothermal crystallization with the addition of acetic acid. The presence of acetic acid could arrest the growth of the nanocrystallites during the hydrothermal processes and be propitious to form nanocrystallites with round edges and corners. This morphology of (TiO₂) had more active sites in the photocatalytic process and showed high photocatalytic activity in the degradation of the methylene blue in the aqueous solution.     

Oxyfluoronitride Glasses with High Elastic Modulus and Low Glass Transition Temperatures

The preparation and properties of novel calcium aluminosilicate glasses containing both nitrogen and fluorine are reported. Nitrogen increases Young's modulus and microhardness of oxide glasses by ∼25%. However, one of the major disadvantages of the use of oxynitride glasses for high-stiffness applications is the fact that nitrogen also increases glass viscosity. Melting temperatures of the order of ∼1700°C are required to achieve sufficiently low viscosities for glass forming and drawing processes. Fluorine substitution for oxygen in Ca–Si–Al–O–N glasses yields significant decreases in glass transition temperature and glass melting temperature as well as increasing nitrogen solubility to levels much higher than that previously reported for glasses made by melting CaO, SiO₂, Si₃N₄, and Al₂O₃ powder mixtures. The important effect that N results in increased elastic modulus is not diminished by the addition of fluorine. Thus, it is possible to produce novel oxyfluoronitride glasses with a high elastic modulus but melting and working can be carried out at more conventional glass processing temperatures.