Wetting of gold by Bi2O3-B2O3 melts

The wetting of gold by Bi₂O₃-B₂O₃ melts has been studied by the sessile drop method, with the sample and substrate heated separately before being brought into contact. Only the melts containing 18.5 and 33.3 mol % B₂O₃ were found to have steady-state contact angles.     

Low temperature sintering of Li1.1Nb0.58Ti0.5O3-xBi2O3 dielectric with adjustable temperature coefficient

Ceramics of Li_1.1Nb_0.58Ti_0.5O₃-xBi₂O₃ with low sintering temperature have been prepared by the solid-solution reaction method using B₂O₃ (2 wt% added) as sintering aid. For all compounds, the sintering temperature achieves 900 °C. Microstructure and dielectric properties of Li_1.1Nb_0.58Ti_0.5O₃-2 wt% B₂O₃-xBi₂O₃ (LNT-B-xBi) ceramics have been investigated. The X-ray diffraction patterns indicate for higher Bi₂O₃ content (x = 0.1 mol%) that the material is composed by two phases identified as M-phase and Bi₄Ti₃O₁₂. The Li_1.1Nb_0.58Ti_0.5O₃ + 0.15 mol% Bi₂O₃ composition sintered at 900 °C with B₂O₃ addition exhibits attractive dielectric properties (ε _r = 59.68, tan δ = 1.2×10^?4 and a temperature coefficient of the relative permittivity near zero) at 1 MHz. It is also shown that the introduction of Bi₂O₃ can tune the temperature coefficient of the relative permittivity. All dielectric properties lead this system compatible to manufacture sliver based electrodes multilayer dielectric devices.     

Crystallization and properties of CaO-P2O2-B2O3 glasses

Glasses were prepared with compositions (50–0.5 x) CaO.(50–0.5 x) P₂O₅ · x B₂O₃ with B₂O₃ contents (x) from 0 to 45 mol%. The glass transformation temperature (T _g), dilatational softening temperature (T _D) and Vickers hardness (H _V) initially increased with x, but showed maxima at about x=20 for T _g and T _D and at about x=35 for H _V. The thermal expansion coefficient decreased with x, levelling off at about 35 mol% B₂O₃. The maximum tendency to crystallize occurred at around 25 mol% B₂O₃. Volume nucleation (and hence glass-ceramic formation) and surface nucleation were obtained for x between 15 and 25 mol%. The first phase to appear was BPO₄, which was probably homogeneously nucleated. Subsequently the 4CaO · P₂O₅ phase was heterogeneously nucleated on the BPO₄. For 10 x 35 only surface nucleation was observed. The kinetics of nucleation were investigated in the 20 mol% B₂O₃ glass. The changes in properties and crystallisation behaviour with B₂O₃ content were related to short-range structural information. Infrared spectra and literature data indicated a threedimensional network of B-O-B and B-O-P linkages in the glasses.     

Luminescence of bulk and thin-film single crystals of gadolinium gallium garnet excited by UV radiation

A difference between the luminescence spectra of bulk and thin-film single crystals of Gd₃Ga₅O₁₂ gadolinium gallium garnet excited by UV radiation from a deuterium lamp has been studied. The films were grown by liquid phase epitaxy from supercooled melts based on the PbO-B₂O₃ and Bi₂O₃-B₂O₃ solid solution systems.     

Glass formation and immiscibility in the TeO2-B2O3-Fe2O3-MnO system

The glass formation in the quaternary TeO₂-B₂O₃-MnO-Fe₂O₃ system and in its ternary systems was investigated. A range of liquid immiscible phases, located near to the binary TeO₂-B₂O₃ and B₂O₃-MnO systems was established. Using transmission electron microscopy, a trend to metastable liquid-phase separation in the single-phase glasses, located near to the boundary of immiscibility was observed. With an increase in the Fe₂O₃ and MnO content still in the process of cooling of the melts, it was possible for a fine glassy crystalline structure to be formed in them. It was shown that by changing the upper limit of the melting temperature and the cooling rate, the glassy crystalline structure and the Fe₃O₄ content could be modified.     

Dielectric properties of low-fitting Pb(Mg1/3Nb2/3)1−xTixO3-Bi2O3/Li2O ceramics

Dielectric properties of low-firing Pb(Mg_1/3Nb_2/3)_1–x Ti _x O₃-Bi₂O₃/Li₂O ceramics are studied in this work. With the addition of Bi₂O₃/Li₂O eutectic composition, the sintering temperature of PMN_1–x PT _x could be lowered to 900° C. Relaxor behaviour of PMN_1–x PT _x is enhanced by the incorporation of Bi₂O₃/Li₂O due to the substitution of Bi⁺³/Li⁺ into the PMN_1–x PT _x framework. Bi₂O₃/Li₂O eutectic composition is used as a fluxing agent, Curie shifter and depressor. Evaporation of Bi₂O₃/Li₂O and PbO during firing is checked and examined via energy dispersive spectrometry (EDS) and X-ray diffraction (XRD) is used to clarify the Curie shifting and depressing effect of Bi₂O₃/Li₂O.     

Physical and spectroscopic properties of multi-component Na2O–PbO–Bi2O3–SiO2 glass ceramics with Cr2O3 as nucleating agent

Transparent glass ceramics, synthesized from melt quenching followed by heat treatment, of the composition 10Na₂O–30PbO–10Bi₂O₃–(50 − x)SiO₂:xCr₂O₃ (mol%), where 0 ⩽ x ⩽ 0.5, were characterized with XRD, DTA, SEM and EDS. Physical and spectroscopic studies, viz., optical absorption, electron paramagnetic resonance (EPR), FTIR and Raman were investigated. The characterization of the host glass ceramic has revealed that the formation of a major phase of sodium silicate along with two minor phases such as lead silicate and bismuth oxide. By integrating Cr₂O₃ to the host glass additional crystal phases viz., NaCrO₂, Na₂Cr₂O₇ and Pb(CrO₄) which are the complexes of Cr³⁺ and Cr⁶⁺ ions were also developed. As the concentration of nucleating agent is increased, a part of the Cr⁶⁺ ions is found to reduce in to Cr³⁺ ions. Spectroscopic studies have revealed that with an increase in the concentration of Cr₂O₃ from 0.1 to 0.5 mol%, there is a gradual increase in the intensity of vibrational modes of various asymmetric structural units of silicate, bismuthate and chromate in the glass ceramic network at the expense of symmetrical structural units. The analysis of the results of these studies has indicated that in the samples containing higher concentration of Cr₂O₃, chromium ions exists predominantly in Cr³⁺ state and occupy the octahedral positions in glass ceramic matrix and such glass ceramic samples are suitable for lasing action.     

Low-temperature firing and microwave dielectric properties of MgTiO3 ceramics with Bi2O3–V2O5

The effects of Bi₂O₃–V₂O₅ additive on the microstructures, the phase formation and the microwave dielectric properties of MgTiO₃ Ceramics were investigated. The Bi₂O₃–V₂O₅ addition lowered the sintering temperature of MgTiO₃ ceramics effectively from 1400 to 875 °C due to the liquid-phase effect. The microwave dielectric properties were found to strongly correlate with the amount of Bi₂O₃–V₂O₅ addition. The saturated dielectric constant decreased and the maximum Qf values increased with the increasing V₂O₅ content, which is attributed to the variation of the second phase including Bi₂Ti₂O₇, Bi₄V_1.5Ti_0.5O_10.85 and BiVO₄. At 875 °C, MgTiO₃ ceramics with 5.0 mol% Bi₂O₃–7 mol% V₂O₅ gave excellent microwave dielectric properties: ε_r = 20.6,Qf = 10420 GHz (6.3 GHz).     

Mechanochemical synthesis of SnO-B2O3 glassy anode materials for rechargeable lithium batteries

The xSnO·(100 ? x)B₂O₃ (0 ≦ x ≦ 80) glasses were successfully prepared by a mechanical milling technique. The glass with 40 mol% SnO showed the maximum glass transition temperature of 347°C. The SnO-B₂O₃ milled glasses consisted of both BO₃ and BO₄ units, and the fraction of BO₄ units was maximized at the composition of 50 mol% SnO. The electrochemical properties of the milled glasses were examined using a simple three electrodes cell with a conventional liquid electrolyte. The glasses with high SnO content exhibited high charge capacities more than 1100 mAh g^?1 and discharge capacities more than 700 mAh g^?1 at the first cycle. The SnO-B₂O₃ milled glasses proved to work as anode materials for rechargeable lithium batteries.     

Surface crystallization and second-order optical non-linearity in Gd2O3–Bi2O3–B2O3 glasses

Some ternary Gd₂O₃–Bi₂O₃–B₂O₃ glasses are prepared, and crystallization behavior and second harmonic intensity are examined to develop new non-linear optical crystallized glasses. The glasses with Gd₂O₃ contents of 8–14 mol% have large densities of over 6 g/cm³ and large refractive indices of ∼1.9. Transparent surface crystallized glasses consisting of two kinds of crystalline phases with different morphologies, i.e. plate shape and needle shape crystals, are fabricated by heat-treatment at temperatures between glass transition and crystallization temperatures. From second harmonic generation microscope observations, micro-Raman scattering spectra and XRD analyses, plate shape crystals are determined to be non-linear optical Gd_xBi_1−xBO₃ and needle shape crystals are Bi₃B₅O₁₂ having no second-order optical non-linearity. Since crystallized glasses consisting of Gd_xBi_1−xBO₃ crystals exhibit relatively strong SHGs, they have a high potential for application to light control devices.     

Ultrasonic study and physical properties of some borate glasses

The structure of the glass system (75−x)B₂O₃–xBi₂O₃–25Li₂O, where x=5, 10, 15, and 20 mol% was investigated by using pulse-echo technique. Elastic properties of the glass system have been calculated together with Poisson’s ratio and Debye temperature from the measured densities as well as longitudinal and shear ultrasonic velocities at room temperature. Ultrasonic velocity measurements were taken at 4 MHz. Estimated parameters based on Makishima–Mackenzie theory and bond compression model were calculated in order to analyse the experimental elastic moduli. Addition effect of Bi₂O₃ on the elastic moduli was investigated in terms of the number of network bonds and the mean cross-link density of the glass systems. The average atomic ring size of the network was also calculated and it was found that it depends on the concentration of the modifiers. Composition dependence of the elastic moduli and Poisson’s ratio from one hand and the trend of both the ring diameter and the packing density from the other hand showed structural change at x=15 mol%.     

MoO3 and Sb2O3 effects on bubble formation in silicate glass coatings during sintering

Small additions (0.25–0.5 mol%) of MoO₃ were effective in preventing bubble defects from forming in silicate glass powder coatings during sintering, without changing the glass transition temperature or molten viscosity. Surface tension was reduced to a similar linear degree as predicted by Kucuk's model, by approximately 20 mN/m per mol% MoO₃. MoO₃ increases the temperature where open porosity is sealed in the coating, allowing gas to escape before bubbles form. Sb₂O₃, a common fining agent used in industrial glass melts, does not significantly affect surface tension but produced higher bubble size and volume due to reduction above 1050 °C. Bonded OH groups in the glass frit were identified as a source of gas for bubble growth.     

Influence of Ga3+ ions on spectroscopic and dielectric features of multi component lithium lead boro bismuth silicate glasses doped with manganese ions

Multi-component glasses of the chemical composition 19.5Li₂O–20PbO–20B₂O₃–30SiO–(10 − x)Bi₂O₃–0.5MnO:xGa₂O₃ with 0 ≤ x ≤ 5.0 have been synthesized. Spectroscopic (optical absorption, IR, Raman and ESR) and dielectric properties were investigated. Optical absorption and ESR spectral studies have indicated that managanese ions do exist in Mn³⁺ state in addition to Mn²⁺ state in the samples containing low concentration of Ga₂O₃. The IR and Raman studies indicated increasing degree of disorder in the glass network with the concentration of Ga₂O₃ up to 3.0 mol%. The dielectric constant, loss and ac conductivity are observed to increase with the concentration of Ga₂O₃ up to 3.0 mol%. The quantitative analysis of the results of dielectric properties has indicated an increase in the insulating strength of the glasses as the concentration of Ga₂O₃ is raised beyond 3.0 mol%. This has been attributed to adaption of gallium ions from octahedral to tetrahedral coordination.     

Mixed cation effect in xR2O-(40 − x)Na2O-50B2O3-10Bi2O3 (R = Li, K) glasses

Mass density, glass transition temperature and ionic conductivity are measured in xLi₂O-(40 − x)Na₂O-50B₂O₃-10Bi₂O₃ and xK₂O-(40 − x)Na₂O-50B₂O₃-10Bi₂O₃ glass systems with 0 ≤ x ≤ 40 mol%. The strength of the mixed alkali effect in T_g, dc electrical conductivity and activation energy has been determined in each glass system. The magnitudes of the mixed alkali effect in T_g for the mixed Li/Na glass system are much smaller than those in the mixed K/Na glasses. The impact of mixed alkali effect on dc electrical conductivity in mixed Li/Na glass system is more pronounced than in the K/Na glass system. The results are explained based on dynamic structure model.     

Phase evolution of electron-beam evaporated Pb(Zr,Ti)O3 thin films

Solid phase reactions among electron-beam deposited PbO, ZrO₂ and TiO₂ in the thin film state as distinct from those occurring in the bulk state are described under varied annealing conditions leading to growth of perovskite PZT phase. Loss of PbO by direct high temperature (700 °C) anneal led to the growth of cubic A₂B₂O_7−x pyrochlore as well as an AB₃O₇ phase of monoclinic structure. A lower temperature initial anneal at 600 °C in O₂ ambient minimises PbO loss through phase transformation to tetragonal Pb₃O₄ and better crystallised oxide phases partially react to form pyrochlore as well as perovskite PZT. This partial reaction is kinetically driven as it goes to completion in ∼4 h resulting in transformation of pyrochlore to perovskite phase. At high temperature (800 °C) A₂B₂O_7−x phase converts to PZT perovskite and the AB₃O₇ dissociate to yield TiO₂ secondary phase inclusion in the PZT film.     

Hardness and elastic properties of Bi2O3-based glasses

The hardness and elastic properties of 20PbO · xBi₂O₃ · (80 – x)B₂O₃ glasses with x = 20–60 were evaluated through usual Vickers indentation and nanoindentation tests. The glass transition temperature (T _g = 295–421°C), Vickers hardness (H _v = 2.9–4.5 GPa), true hardness (H = 1.5–3.8 GPa) and Young's modulus (E = 24.4–72.6 GPa) decreased monotonously with increasing Bi₂O₃ content. This compositional trend demonstrates that the strength of Bi–O chemical bonds in these glasses is considerably weak compared with B–O bonds and plastic deformations under indentation loading occur easily. The elastic recovery after unloading was about 45% for the glasses with x = 20–50, and the Poisson's ratio was 0.27 for the glass with x = 20. The fracture toughness was evaluated to be 0.37–0.88 MPam^1/2 from the values of H _v and E, and it was proposed that not only weak Bi–O bonds but also boron coordination polyhedra (BO₃ or BO₄) and their arrangements affect on crack formation. From the temperature dependence of Vickers hardness up to the glass transition region, it was suggested that the glasses with high Bi₂O₃ contents belong to the category to fragile glass-forming liquids.     

Low-temperature ageing map for 3mol% Y2O3-ZrO2

The ageing behaviour of 3mol% Y₂O₃-ZrO₂ at 100–500° C in a water-containing atmosphere was studied. A critical grain size of ～ 0.37 μm and a lower temperature limit of ～80°C for retaining the tetragonal symmetry were deduced from the kinetic study. An “ageing map” constructed on the grain size (G) against ageing temperature (T) plot is proposed to describe the low-temperature ageing behaviour of 3mol% Y₂O₃-ZrO₂.     

Immiscibility in the TeO2-B2O3 system

Experimental investigations have been carried out to study the phase separation process in the TeO₂-B₂O₃ system. It was found that the phase diagram is of a eutectic-like type (monotectic invariant reaction), with a wide region of stable and metastable phase separation. During the cooling of the melts two phases are obtained. One has a high TeO₂ content and is a transparent glass. The other, richer in B₂O₃, is opaque and in structure constitutes a complicated microheterogeneous system.     

Preparation of B2O3-P2O5-SiO2 coating films by the sol-gel method

ThexB₂O₃ · (20-x) P₂O₅ · 80SiO₂ (in mol%) glass films withx=0, 10 and 20 have been prepared from metal alkoxides by carrying out the coating in a dry atmosphere. These coating films have shown a larger value of load at scratch and a smaller shrinkage during heat-treatment by replacing P₂O₅ in the films with B₂O₃. It has been found that B₂O₃ more effectively reduces the glass transition temperature of SiO₂ glass than P₂O₅. The concentrations of sodium ions, which migrated from soda-lime-silica glass substrates during the film formation, were higher in phosphosilicate and borophosphosilicate films than in borosilicate and pure silica films. This finding should be ascribed to the gettering effects of phosphorus for sodium ions.     

Phase equilibrium relations in the binary system Bi2O3-ZnO

Phase equilibria in the binary system Bi₂O₃-ZnO were studied by quenching technique. Heat-treated compositions were subjected to X-ray diffraction for phase identification, and differential thermal analysis, optical and scanning electron microscopy were used to determine the solid-liquid equilibria occurring in this system. The data thus obtained revealed that incorporation of a small amount of ZnO to the high-temperature face-centered cubic lattice of Bi₂O₃ leads to the formation of a body-centered cubic solid solution (-Bi₂O₃), which extends up to a composition of 2.2 mol% ZnO at a temperature near 750°C. On cooling, the -Bi₂O₃ solid solution undergoes a eutectoid transformation at a temperature of 710°C to yield the low-temperature monoclinic polymorph of Bi₂O₃ (-Bi₂O₃) and Bi₃₈ZnO₅₈. The eutectoid occurs at a composition of 1.8 mol% ZnO. The compound Bi₃₈ZnO₅₈ has a crystal structure analogous to the body-centered cubic -Bi₂O₃ solid solution and melts incongruently at a temperature near 753 ± 2°C to yield -Bi₂O₃ and liquid. A binary eutectic occurs between Bi₃₈ZnO₅₈ and ZnO at a composition near 25 ± 1.0 mol% ZnO with a melting temperature of 738 ±2°C. Based on the data obtained in this study, a revised phase diagram of the binary system Bi₂O₃-ZnO is proposed.