Optical properties and crystallization of glasses in the system Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–MoO<Subscript>3</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript>

The purpose of this work is to study the optical properties and crystallization of glasses in the ternary system Bi₂O₃–MoO₃–B₂O₃. In order to verify the obtaining of bismuth borate crystal phases several glass compositions have been selected for crystallization. The obtained samples were characterized by X-ray diffraction, scanning electron microscopy and UV–Vis spectroscopy. The UV–Vis spectroscopy showed that the obtained glasses are transparent in the visible region. The values of optical band gap (E _opt) and changes in cut-off (λ_c) depending on composition are reported. It was established that the increase in the MoO₃ content led to decreasing the transmittance of the glasses. Moreover, the absorption edge shifts towards longer wavelength.     

Mechanical and acid-etching properties of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–ZnO–B<Subscript>2</Subscript>O<Subscript>3</Subscript> glass-containing ceramic fillers

The properties of the composite, having a complicated microstructure, are decided by many factors such as those of glass matrix, crystal phases, fillers, and holes. We investigated how the addition of ceramic fillers to the glass matrix affects the mechanical and etching properties of the glass composite by forming new crystal phases. Different amounts of two fillers, ZnO and Al₂O₃, were added to a glass frit consisting of Bi₂O₃–ZnO–B₂O₃. It was sintered at 550 °C for 30 min. Based on the results of this study, the porosity and degree of crystallization of the composites could be controlled by adjusting the content of the ZnO and Al₂O₃ fillers. Therefore, porosity and degree of crystallization formed by the reaction between a glass matrix and fillers influence the mechanical and etching properties of the composite.     

Spectroscopic characterisation of local structure in Y<Subscript>2</Subscript>O<Subscript>3</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses doped with gadolinium

Gadolinium doped bismuth borate glasses containing up to 30 mol% Y₂O₃ were prepared by fast melt quenching method. The effect of yttrium on the local order in 3B₂O₃ · Bi₂O₃ and B₂O₃ · Bi₂O₃ glass matrices, particularly on the bismuth sites, was investigated by infrared (IR) spectroscopy and electron paramagnetic resonance (EPR) of Gd³⁺ ions. The IR results show that the local structure is more ordered in the glass system with higher bismuth content and the progressive addition of yttrium increases the local disorder in both bismuth–borate glass matrices. The EPR results indicate that Gd³⁺ ions occupy both bismuth and yttrium sites and reflect the same structural disorder like that suggested by IR results.     

System ZnO ⋅ B<Subscript>2</Subscript>O<Subscript>3</Subscript>-CuO ⋅ B<Subscript>2</Subscript>O<Subscript>3</Subscript>

Differential thermal analysis and x-ray diffraction data indicate that the ZnO B₂O₃-CuO B₂O₃ join of the ternary system CuO-B₂O₃-ZnO is pseudobinary, with eutectic phase relations and a liquid-liquid miscibility gap in the composition range 25–35 mol % CuO.Translated from Neorganicheskie Materialy, Vol. 41, No. 3, 2005, pp. 339–340.Original Russian Text Copyright © 2005 by Kasumova, Bananyarly.This revised version was published online in April 2005 with a corrected cover date.This revised version was published online in April 2005 with a corrected cover date.     

Compositional dependence of the structural and dielectric properties of Li<Subscript>2</Subscript>O–GeO<Subscript>2</Subscript>–ZnO–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

(10Li₂O–20GeO₂–30ZnO–(40-x)Bi₂O₃–xFe₂O₃ where x = 0.0, 3, 6, and 9 mol%) glasses were prepared. A number of studies, viz. density, differential thermal analysis, FT-IR spectra, DC and AC conductivities, and dielectric properties (constant ε′, loss tan δ, AC conductivity, σ _ac, over a wide range of frequency and temperature) of these glasses were carried out as a function of iron ion concentration. The analysis of the results indicate that, the density and molar volume decrease with an increasing of iron content indicates structural changes of the glass matrix. The glass transition temperature T _g and onset of crystallization temperature T _x increase with the variation of concentration of Fe₂O₃ referred to the growth in the network connectivity in this concentration range, while glass-forming ability parameter ΔT decrease with increase Fe₂O₃ content, indicates an increasing concentration of iron ions that take part in the network-modifying positions. The FT-IR spectra evidenced that the main structural units are BiO₃, BiO₆, ZnO₄, GeO₄, and GeO₆. The structural changes observed by varying the Fe₂O₃ content in these glasses and evidenced by FTIR investigation suggest that the iron ions play a network modifier role in these glasses while Bi₂O₃, GeO₂, and ZnO play the role of network formers. The temperature dependence of DC and AC conductivities at different frequencies was analyzed using Mott’s small polaron hopping model and, the high temperature activation energies have been estimated and discussed. The dielectric constant and dielectric loss increased with increase in temperature and Fe₂O₃ content.     

Thermal and dielectric properties of the LTCC composites based on the eutectic system BaO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript>

The low-temperature co-fired ceramic (LTCC) composites containing quartz based on the eutectic system BaO–Al₂O₃–SiO₂–B₂O₃ are fabricated at the sintering temperature below 980 °C. Preparation process and sintering mechanism were described and discussed, respectively. The results indicated that the addition of quartz to the eutectic system can availably improve dielectric properties of the LTCC composites. In addition, The LTCC composites with optimum compositions, which were obtained by the regulation of an Al₂O₃ content in the composite, can express excellent dielectric properties (permittivity: 5.94, 5.48; loss: 7 × 10⁻⁴, 5 × 10⁻⁴), considerable CTE values (11.7 ppm. °C⁻¹, 10.6 ppm. °C⁻¹) and good mechanical properties (128 MPa,133 MPa).     

Effect of sintering temperatures on properties of BaO–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript>–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> glass/silica composites for CBGA package

BaO–B₂O₃–SiO₂–Al₂O₃ (BBSA) glass/silica composites synthesized by solid-state reaction method were developed for CBGA packages, and the effects of sintering temperature (900–950 °C) on the phase transformation, microstructure, thermal, mechanical and electrical properties were investigated. XRD results show that the major phases quartz and cristobalite, and the minor phase BaSi₂O₅ are detected in BBSA composites. Furthermore, it was found that the quartz phase transforms to cristobalite phase at 930–940 °C. The formation of cristobalite phase with higher coefficient of thermal expansion (CTE) led to the increase of CTE value of BBSA composites. However, excessive cristobalite phase content would degrade the mechanical properties and the linearity of thermal expansion of the ceramics. BBSA composites sintered at 920 °C exhibited excellent properties: low dielectric constant and loss (ε_r = 6.2, tanδ = 10^?4 at 1 MHz), high bending strength (179 MPa), high CTE (12.19 ppm/°C) as well as superior linearity of the thermal expansion.     

Structure–property correlations in the SiO<Subscript>2</Subscript>–PbO–Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

SiO₂–PbO–Bi₂O₃ glasses having the composition of 35SiO₂–xPbO–(65−x)Bi₂O₃ (where x = 5, 10, 15, 20, 25, 35, 45; in mol%) have been prepared using the conventional melting and annealing method. Density, molar volume and Vickers microhardness of the prepared glasses were measured. Infrared (IR) and UV–visible spectroscopic techniques were used for structural studies of these glasses. Density as well as the microhardness increase systematically and, conversely, the molar volume decreases with increasing the lead oxide content. This behavior can be explained by the correlation with the glass structure. Increasing the lead oxide content (≥20 mol%) increases the network former PbO₄ groups which can play an important role in increasing the connectivity and compactness of the glass matrix via increasing the cross-linking with the other constituent silicate and bismuthate structural units. The increased compactness may explain, in turn, the increase of the density and microhardness. IR spectra reinforce the idea that bismuth participates in the glassy network predominantly as BiO₆ octahedral structural units. UV–VIS optical absorption spectra revealed UV-charge transfer absorption bands related to the contribution of Pb²⁺ ions in the region 350–385 nm; in addition to the extrinsic absorption of trace iron impurities in the range 220–290 nm. In the visible region, three optical bands in the ranges 415–435, 605–650 and 880–890 nm were correlated with the contribution of electronic transitions in Bi³⁺ ions. Calculation of the optical mobility gap and the width of the energy tail of glass from the UV–VIS absorption indicated a slight increase followed by a decrease in their values. The behavior change occurred at the glass in which PbO content is 20 mol% where lead oxide starts to participate into the glassy matrix as a network former. The combination of analytical FTIR and UV–visible spectroscopy provided a consistent picture of structure–property relations in this glass system.     

Characterization and analysis of CaO–SiO<Subscript>2</Subscript>–B<Subscript>2</Subscript>O<Subscript>3</Subscript> ternary system ceramics

The dielectric, thermal and mechanical properties of CaO–SiO₂–B₂O₃ ternary system ceramics by solid-phase method have been carried out and quantitive analysis been examined by X-ray diffraction (XRD) patterns. The results showed that the major crystalline phase of CaO–SiO₂–B₂O₃ ternary system ceramics was wollastonite (about 90 wt%) which existed at the temperature ranging from 950 to 1,100 °C. It is also observed that wollastonite could be transformed to pseudowollastonite at 1,200 °C. In addition, with increase in calcination temperature, the amount of wollastonite increases. When the sintering temperature is at 1,100 °C, the amount of wollastonite has a maximum value of 92.7 wt%. Accordingly, CaO–SiO₂–B₂O₃ ternary system ceramics achieved excellent properties at 1,100 °C, such as dielectric constant of 8.38, dielectric loss of 1.51 × 10⁻³ at 1 MHz, linear thermal-expansion coefficient (300 K) of 6.68 × 10⁻⁶/K, bending strength of 121.75 Mpa. Analysis of the mechanical and dielectric properties showed that the measured bending strength, dielectric constant and loss of CaO–SiO₂–B₂O₃ ternary system ceramics can be substantially modified and improved by controlling the sintering temperature, in particular due to the amount of wollastonite crystalline phase and size of grains.     

In vitro dissolution behavior of SiO<Subscript>2</Subscript>–MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–K<Subscript>2</Subscript>O–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–F glass–ceramic system

Herein, we report the results of the in vitro dissolution tests, which were carried out by immersing the selected glass-ceramic samples in artificial saliva (AS) for various time periods of up to 42 days. In our experiments, the SiO(2)-MgO-Al(2)O(3)-K(2)O-B(2)O(3)-F glass ceramics with different crystal morphology and crystal content were used and a comparison is also made with the baseline glass samples (without any crystals). The bioactivity of the samples was probed by measuring the changes in pH, ionic conductivity and ionic concentration of AS following in vitro dissolution experiments. High resistance of the selected glass-ceramic samples against in vitro leaching has been demonstrated by minimal weight loss (<1%) and insignificant density change, even after 6 weeks of dissolution in artificial saliva. While XRD analysis reveals the change in surface texture of the crystalline phase, FT-IR analysis weakly indicated the Ca-P compound formation on the leached surface. The experimental measurements further indicate that the leaching of F(-), Mg(2+) ions from the sample surface commonly causes the change in the surface chemistry. Furthermore, the presence of (Ca, P, O)-rich mineralized deposits on the leached glass-ceramic surface as well as the decrease in Ca(2+) ion concentrations in the leaching solutions (compared to that in the initial AS solution) provide evidences of the moderate bioactive or mild biomineralisation behaviour of investigated glass-ceramics.     

Influence of Bi substitution on microwave dielectric properties of BaO–La<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sm<Subscript>2</Subscript>O<Subscript>3</Subscript>–TiO<Subscript>2</Subscript> ceramics

The influences of Bi substitution on microwave dielectric properties of Ba₄(La_0.5Sm_0.5)_9.33Ti₁₈O₅₄ solid solutions were investigated. Dielectric ceramics with general formula Ba₄(La_(0.5−z)Sm_0.5Bi _z )_9.33Ti₁₈O₅₄, z = 0.0–0.2 were prepared by conventional solid state route. The structural analysis of all the samples was carried out by X-ray diffraction and scanning electron microscopy. The dielectric properties were investigated as a function of Bi contents using open-ended coaxial probe method in the frequency range 0.3–3.0 GHz at room temperature. Dielectric constant varies from 83 to 88 and loss tangent from 2.1 × 10⁻³ to 5.5 × 10⁻³ at 3 GHz with temperature coefficient of resonant frequency changing from 106.7 to −8.4 ppm/oC as Bi contents increases from z = 0.00–0.20. It has been found that dielectric constant and temperature coefficient of resonant frequency improve whereas loss tangent is adversely affected with increase in Bi substitution.     

Hardness properties and microscopic investigation of crack–crystal interaction in SiO<Subscript>2</Subscript>–MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–K<Subscript>2</Subscript>O–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–F glass ceramic system

In view of the potential engineering applications requiring machinability and wear resistance, the present work focuses to evaluate hardness property and to understand the damage behavior of some selected glass–ceramics having different crystal morphologies with SiO₂–MgO–Al₂O₃–K₂O–B₂O₃–F composition, using static micro-indentation tests as well as dynamic scratch tests, respectively. Vickers hardness of up to 5.5 GPa has been measured in glass–ceramics containing plate like mica crystals. Scratch tests at a high load of 50 N in artificial saliva were carried out in order to simulate the crack–microstructure interaction during real-time abrasion wear and machining operation. The experimental observations indicate that the novel “spherulitic-dendritic” shaped crystals, similar to the plate like crystals, have the potential to hinder the scratching induced crack propagation. In particular, such potential of the ‘spherulitic-dendritic’ crystals become more effective due to the larger interfacial area with the glass matrix as well as the dendritic structure of each mica plate, which helps in crack deflection and crack blunting, to a larger extent. While modest damage tolerant behavior is observed in case of ‘spherulitic-dendritic’ crystal containing material, severe brittle fracture of plate like crystals were noted, when both were scratched at 50 N load.     

Variable—Range hopping in Fe<Subscript>2</Subscript>O<Subscript>3</Subscript>-Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>-K<Subscript>2</Subscript>B<Subscript>4</Subscript>O<Subscript>7</Subscript> glasses

The dc conductivity of the glasses in the Fe₂O₃-Bi₂O₃-K₂B₄O₇ system was studied at temperatures between 223 and 393 K. At temperatures from 300 to 223 K, T^–1/4 (T is temperature) dependence of the conductivity was found, however, both Mott variable-range hopping and Greaves intermediate range hopping models are found to be applicable. Mott and Greaves parameters analysis gave the density of states at Fermi level N (E_F) = 3.13 × 10²⁰–21.01 × 10²⁰ and 1.93 × 10²¹–16.39 × 10²¹ cm^–3eV^–1 at 240 K, respectively. The variable-range hopping conduction occurred in the temperature range T = 300–223 K, since W_D was found to be large (W_D = 0.08–0.14 eV for these glasses) and dominated the conduction at T < 300 K.     

Compositional dependence of some physical properties of ZnO–PbO–P<Subscript>2</Subscript>O<Subscript>5</Subscript> glasses

Six glasses of the chemical composition 10ZnO–xPbO–(90−x) P₂O₅ were prepared. With an increase in PbO content a non-monotonous step like increase in the density, in the glass transition temperature, and in the refractive index was observed. From the Raman and IR spectra studied the evidence is given for the phosphate network depolymerization as PbO content increases. Increase in PbO content leads also to an increase in refractive index (n) up to n = 1.74, for x = 55, and to an increase in the glass transition temperature (T _g) from T _g = 270 °C (x = 30) to T _g = 360 °C (x = 55).

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Characterization of microstructure and properties of Al–Al<Subscript>3</Subscript>Zr–Al<Subscript>2</Subscript>O<Subscript>3</Subscript> composite

Aluminium-based metal matrix composite strengthened by in situ Al₂O₃ and Al₃Zr particles were synthesized by powder metallurgy route. Phase analysis by X-ray diffraction and scanning electron microscopy revealed that the reaction between Al and ZrO₂ produced Al₂O₃ and Al₃Zr phases in the sintered composites. The hardness of the composite is a strong function of sintering temperature as well as the volume fraction of reinforcements. The dry sliding wear test results clearly indicated that increasing the volume fraction of zirconia particles in the composite improved the wear resistance. Microcutting, ploughing, delamination and oxidation were the main mechanisms of wear.     

The effect of Fe contents on the local structure and crystallization behavior of SiO<Subscript>2</Subscript>–CaO–P<Subscript>2</Subscript>O<Subscript>5</Subscript>–Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> glasses

The glass and glass ceramics containing SiO₂–CaO–Fe₂O₃–P₂O₅ were prepared by sol–gel method. The influence of the Fe contents on the crystallization and local structure of the glass and glass ceramics was systematically investigated. The crystal structure of the glass ceramics was identified by XRD characterization. Hematite phase can be precipitated from the glass matrix in all glass ceramics with various Fe contents, and the crystallographic parameters of hematite were determined by XRD Rietveld refinement. The crystallization kinetics of the glasses was investigated in detail. Relative low activation energies were obtained at low Fe contents. The local structure evolution of the glass and glass ceramics has been studied in-depth by means of FTIR and Mössbauer spectroscopy. Fe element is present both as network former and network modifier which significantly influenced the crystallization activation energies of the glasses. The results of this work may be of great significance for the material design and practical applications of bioactive magnetic glass ceramics for hyperthermia.     

Preparation and characterization of Li<Subscript>2</Subscript>O–CaO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–P<Subscript>2</Subscript>O<Subscript>5</Subscript>–SiO<Subscript>2</Subscript> glasses as bioactive material

The aim of the present investigation was to study the role of Al₂O₃ in the Li₂O–CaO–P₂O₅–SiO₂ bioactive glass for improving the bioactivity and other physico-mechanical properties of glass. A comparative study on structural and physico-mechanical properties and bioactivity of glasses were reported. The structural properties of glasses were investigated by X-ray diffraction, Fourier transform infrared spectrometry, scanning electron microscopy and the bioactivity of the glasses was evaluated by in vitro test in simulated body fluid (SBF). Density, compressive strength, Vickers hardness and ultrasonic wave velocity of glass samples were measured to investigate physical and mechanical properties. Results indicated that partial molar replacement of Li₂O by Al₂O₃ resulted in a significant increase in mechanical properties of glasses. In vitro studies of samples in SBF had shown that the pH of the solution increased after immersion of samples during the initial stage and then after reaching maxima it decreased with the increase in the immersion time. In vitro test in SBF indicated that the addition of Al₂O₃ up to 1.5 mol% resulted in an increase in bioactivity where as further addition of Al₂O₃ caused a decrease in bioactivity of the samples. The biocompatibility of these bioactive glass samples was studied using human osteoblast (MG-63) cell lines. The results obtained suggested that Li₂O–CaO–Al₂O₃–P₂O₅–SiO₂-based bioactive glasses containing alumina would be potential materials for biomedical applications.     

Preparation,structure and microwave dielectric properties of 3MgO–Al<Subscript>2</Subscript>O<Subscript>3</Subscript>–3TiO<Subscript>2</Subscript> ceramics

3MgO–Al₂O₃–3TiO₂ (MAT) ceramics were prepared by a conventional solid-state reaction method. The crystal structure, sintering behavior and microwave dielectric properties of ceramics were investigated using X-ray diffraction, scanning electron microscopy and network analyzer. MAT ceramics contained the coexistence of three phases, including MgAl₂O₄, MgTiO₃ and MgTi₂O₅. The ceramics sintered at 1350 °C for 4 h presented excellent comprehensive performances with relative permittivity (ε _r ) of 15.4, quality factor (Q × f) of 91,000 GHz and temperature coefficient of resonant frequency (τ _f ) about ?55.1 ppm/°C.     

Synthesis,bioactivity and preliminary biocompatibility studies of glasses in the system CaO–MgO–SiO<Subscript>2</Subscript>–Na<Subscript>2</Subscript>O–P<Subscript>2</Subscript>O<Subscript>5</Subscript>–CaF<Subscript>2</Subscript>

New compositions of bioactive glasses are proposed in the CaO–MgO–SiO₂–Na₂O–P₂O₅–CaF₂ system. Mineralization tests with immersion of the investigated glasses in simulated body fluid (SBF) at 37°C showed that the glasses favour the surface formation of hydroxyapatite (HA) from the early stages of the experiments. In the case of daily renewable SBF, monetite (CaHPO₄) formation competed with the formation of HA. The influence of structural features of the glasses on their mineralization (bioactivity) performance is discussed. Preliminary in vitro experiments with osteoblasts’ cell-cultures showed that the glasses are biocompatible and there is no evidence of toxicity. Sintering and devitrification studies of glass powder compacts were also performed. Glass-ceramics with attractive properties were obtained after heat treatment of the glasses at relatively low temperatures (up to 850°C).     

Preparation and properties of antioxidative BaO–B<Subscript>2</Subscript>O<Subscript>3</Subscript>–SiO<Subscript>2</Subscript> glass-coated Cu powder for copper conductive film on LTCC substrate

In this study, uniform BaO–B₂O₃–SiO₂ glass coatings on micro Cu powders with different glass/Cu ratio were prepared by sol–gel method. The pastes prepared with the glass-coated Cu powders were screen printed on low temperature co-fired ceramic (LTCC) substrate. Then the dry films on substrate were binder-burned-out at 400 °C in air and co-fired at 910 °C in N₂ atmosphere. During the binder-burning-out process, the oxidization of the films with 9 and 11 wt% glass was slight because of the improvement of oxidization resistance of the glass-coated Cu powders. Moreover, the sintered film with 9 wt% glass coating showed no crystal phase of copper oxide and had small sheet resistance of 1.3 mΩ/□, which can be used as good conductive thick film on LTCC substrate for microelectronic packaging.