Role of MgO on the HAp forming ability in phosphate based glasses

Phosphate-based glasses 45P₂O₅–30CaO–(25 ? x)Na₂O–xMgO for different compositions of x = 0, 1, 2.5, 5 and 10 mol% were prepared using the normal melt quench technique. To study the influence of MgO on phosphate glasses, a series of experimental analyses such as ultrasonic velocities, differential thermal analysis, X-ray diffraction, energy-dispersive X-ray spectroscopy, pH measurements, Fourier transform infrared spectroscopy, scanning electron microscopy and in vitro studies were carried out in all the prepared glasses. A maxima in ultrasonic parameters at x = 2.5 mol% of MgO content and a further decrease in the same with the addition of MgO content were observed in all glasses. The observed results indicate that structural compactness of glass network took place up to 2.5 mol% of MgO (PCNM2.5), beyond which a loose packing of atoms led to structural softening in glass network. The results obtained from X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy analyses in all glasses before and after in vitro studies revealed the existence of higher HAp-forming ability in PCNM2.5 glass.     

Surface behaviour of high MgO-containing glasses of the Si–Ca–P–Mg system in a synthetic physiological fluid

Two glasses of the Si–Ca–P–Mg system with low SiO₂ content (25 and 29 mol%) and high MgO contents (31 and 36 mol%, respectively) have been immersed in a Kokubo’s synthetic physiological solution for different times up to 30 days. The surface modifications of the glasses were observed by SEM and the changes in the surface composition followed by EDS. ICP was used to assess the evolution of ionic concentrations in the solution, namely Ca and P.It was observed that both glasses induced the precipitation of Ca–P rich layers on their surfaces, although these were poorly attached to the glass substrate. Ca and P ions required for the apatite formation were mainly provided by the composition of the glass, which was severely dissolved in the solution.The observed apatite-forming ability of these glasses, notwithstanding their high MgO content, suggests that further improvements at the surface and in the glasses can lead to attractive potentially bioactive materials.     

Effect of gallium addition on physical and structural properties of Ge–S chalcogenide glasses

GeS_2.5 chalcogenide glass was selected for studying effects of Ga addition on physical and structural properties. Glassy and partially crystallized samples of (100−x)GeS_2.5−xGa (5 mol% ≤ x ≤ 40 mol%) were prepared, and their thermal and optical properties were characterized. With increasing Ga content (x), values of T_g and optical band gap of glasses initially increased and then decreased, showing a maximal value at x = 25 mol%, that is, with stoichiometric composition of 85.7GeS₂·14.3Ga₂S₃. These changes were discussed and correlated to evolution of network structure, which was investigated by Raman spectra recorded in glassy matrices of (100−x)GeS_2.5−xGa (5 mol% ≤ x ≤ 40 mol%). This work contributes to understanding of composition–structure–property relationship of chalcogenide glasses.     

The effect of zinc substitution on the magnetism of magnesium ferrite nanostructures crystallized from borate glasses

Glasses in the system 51.7 B₂O₃/9.3 K₂O/1 P₂O₅/10.4 Fe₂O₃/(27.6–x) MgO/ x ZnO (with x=0, 5, 10, 13.8 and 20 mol%) were prepared by the conventional melt quenching method. The as prepared glass samples were thermally treated at 560 °C for 3 or 6 h. The effect of substituting MgO by ZnO in the glass network on the crystallized phase was studied. The resulting magnetic glass ceramics were characterized using X-ray diffraction (XRD), vibrating sample magnetometer (VSM) and transmission electron microscopy (TEM) including energy dispersive X-ray analysis (EDX). The substitution of Mg by Zn resulted in a larger lattice parameter of the precipitated crystals, while the crystallite size does not change significantly. TEM micrographs, recorded from extracted particles, showed the formation of small aggregates with about 30 nm in diameter. These agglomerates contain crystals with sizes in the range from 7 to 9 nm. EDX measurements proved the incorporation of Zn²⁺ ions into the crystal phase. Room temperature magnetic measurements of the samples with up to 10 mol% ZnO showed hysteresis loops which are characteristic for super paramagnetic (SPM) behavior. A magnetic contribution was not detected for samples with higher ZnO concentrations. The maximum magnetization varied with the composition of the glass ceramics to a great extent.     

1.53 µm luminescence properties of Er3+-doped K–Sr–Al phosphate glasses

Trivalent erbium (Er³⁺)-doped K–Sr–Al phosphate glasses were prepared and studied their spectroscopic properties as a function of Er₂O₃ concentration. Judd–Ofelt analysis has been carried out for 1.0 mol% Er₂O₃-doped phosphate glass and in turn radiative properties have been evaluated for the excited levels of Er³⁺ ion. The radiative lifetime for the ⁴I_13/2 level was found to be higher for the present glass when compared to other Er³⁺-doped glasses. The Er³⁺-doped glasses exhibit intense near infrared emission at 1.53 µm corresponds to ⁴I_13/2→⁴I_15/2 transition as well as green emission at 546 nm corresponding to ⁴S_3/2→⁴I_15/2 under 980 nm and 488 nm excitations, respectively. The emission cross-section spectrum for 1.0 mol% of Er₂O₃-doped glass has been evaluated using McCumber theory. The gain cross-section has been evaluated as a function of population inversion, which revealed that the lasing action would be achieved at 1.53 µm for a population inversion about 40%. Decay curves for the ⁴I_13/2 level were measured and lifetimes have been determined for the studied glasses. The results indicate that the present glasses could be useful for laser as well as optical amplifiers at 1.53 µm.     

Effect of Al2O3 content on BaO–Al2O3–B2O3–SiO2 glass sealant for solid oxide fuel cell

The glass structure, wetting behavior and crystallization of BaO–Al₂O₃–B₂O₃–SiO₂ system glass containing 2–10 mol% Al₂O₃ were investigated. The introduction of Al₂O₃ caused the conversion of [BO₃] units and [BO₄] units to each other and it played as glass network former when the content was up to 10 mol%, accompanied by [BO₄] → [BO₃]. The stability of the glass improved first and then decreased as Al₂O₃ increased from 2 to 10 mol%, the glass with 5 mol% Al₂O₃ being the most stable one. The wetting behavior of the glasses indicates that excess Al₂O₃ leads to high sealing temperature. The glass containing 5 mol% Al₂O₃ characterized by a lower sealing temperature is suitable for SOFC sealing. Al₂O₃ improves the crystallization temperature of the glass. The crystal phases in the reheated glasses are mainly composed of Ba₂Si₃O₈, BaSiO₃, BaB₂O₄ and BaAl₂Si₂O₈. Al₂O₃ helps the crystallization of BaSiO₃ and BaAl₂Si₂O₈.     

Preparation and properties of Ge–Ga–La–S–AgI chalcogenide glass

Chalcogenide glasses of 65GeS₂–(25–x)Ga₂S₃–10AgI–xLa₂S₃ (x=0, 1, 3, and 5 mol%) were fabricated through the traditional melt-quenching method. The effects of addition of La₂S₃ on physical, thermal and optical properties of the glass system were investigated. The results showed that the fabricated glasses possess considerably high glass transition temperature, exhibit improved mechanical property and excellent infrared transmission. A redshift at the visible absorbing cut-off edge is observed with increasing of La₂S₃ content. The direct and indirect optical band gap values are also calculated. Raman spectra analysis indicated that the band at 265 cm⁻¹ decreased in amplitude and a new peak at 230 cm⁻¹ was detected manifesting the formation of La-S bond in the network. In addition, the mid-infrared emission at 3.74 µm of the glasses doped with Tm³⁺ ions was achieved. The results indicated that the glasses are promising materials for mid-infrared applications such as imaging, remote sensing and lasers.     

Gel-derived SiO2–CaO–P2O5 bioactive glasses and glass-ceramics modified by SrO addition

The effect of SrO substitution for CaO in two sol–gel glasses with different chemical compositions (mol%) A2Sr: (54−x)CaO–xSrO–6P₂O₅–40SiO₂ and S2Sr: (16−x)CaO–xSrO–4P₂O₅–80SiO₂ (x=0, 1, 3 and 5) stabilized at 700 °C on their structure (XRD, FTIR) and bioactive properties (SBF test) was investigated. Preliminary in vitro tests using human articular chondrocytes of selected A2Sr glass were also conducted. Moreover, the subject of this study was to detect the changes on material properties after heat treatment at 1300 °C. The results show that the effect of strontium substitution on structure, bioactivity and crystallization after treatment at both the above temperatures strongly depends on CaO/SiO₂ molar ratio. The presence of 3–5 mol% of strontium ions creates more expanded glass structure but does not markedly affect crystallization ability after low temperature treatment. Sintering at 1300 °C of A2 type glasses results in crystallization of pseudowollastonite, hydroxyapatite and also Sr-substituted hydroxyapatite for 3–5 mol% of SrO substitution. The increase of strontium concentration in silica-rich materials after sintering leads to appearance of calcium strontium phosphate instead of calcium phosphate. Bioactivity evaluation indicates that substitution of Sr for Ca delays calcium phosphate formation on the materials surface only in the case of silica-rich glasses treated at 700 °C. Calcium-rich glasses, after both temperature treatments, reveals high bioactivity, while crystal size of hydroxyapatite decreases with increasing Sr content. High temperature treatment of high-silica glasses inhibits their bioactivity. Preliminary in vitro tests shows Sr addition to have a positive effects on human articular chondrocytes proliferation and to inhibit cell matrix biomineralization.     

Effect of MgO addition on the properties of PbO –TiO2–B2O3 glass and glass–ceramics

Glass samples with composition of (50?X) PbO–X MgO–25 TiO₂–25B₂O₃ (where X=0, 5, 10 and 15 mol%) were prepared using conventional quenching technique. The amorphous nature of glass samples were confirmed by XRD. The glass transition temperature, T_g and crystallization temperature T_c were determined from the DTA. It has been observed that the addition of MgO enhances the T_g. The rise in T_g with MgO content may be attributed to the greater field strength of Mg²⁺ cation (as compared to Pb²⁺) which leads to the formation of stronger bonds. These glass samples were converted to glass–ceramics by following a two-stage heat treatment schedule. It was observed that there was good correlation between the density and CTE results of the glass–ceramics. The XRD results revealed the formation of tetragonal lead titanate as a major crystalline phase in the glass–ceramics. The addition of MgO to the glass contributes to the formation of MgB₄O₇. The dielectric constant for all the glass–ceramic samples was observed to be higher than that of corresponding glass samples. Further, with addition of MgO the room temperature dielectric constant for glass–ceramic samples increases up to 10 mol% of MgO and then decreases for 15 mol%. It has been further observed that the variation of dielectric constant of glass–ceramic samples with MgO content is exactly opposite to the variation of crystallite size of PbTiO₃ embedded in the glass ceramic-samples.     

Synthesis and in vitro bioactivity assessment of injectable bioglass−organic pastes for bone tissue repair

The aim of this work was to study the bioactivity of systems based on a clinically tested bioactive glass (BG) particulates (mol%: 4.33 Na₂O−30.30 CaO−12.99 MgO−45.45 SiO₂−2.60 P₂O₅−4.33 CaF₂) and organic carriers. The cohesiveness of injectable bone graft products is of high relevance when filling complex volumetric bone defects. With this motivation behind, BG particulates with mean sizes within 11−14 μm were mixed in different proportions with glycerol (G) and polyethylene glycol (PEG) as organic carriers and the mixtures were fully injectable exhibiting Newtonian flow behaviors. The apatite forming ability was investigated using X-ray diffraction and field emission scanning electron microscopy under secondary electron mode after immersion of samples in simulated body fluid (SBF) for time durations varying between 12 h and 7 days. The results obtained revealed that in spite of the good adhesion of glycerol and PEG carriers to glass particles during preparation stage, they did not hinder the exposure of bioactive glass particulates to the direct contact with SBF solution. The results confirmed the excellent bioactivity in vitro for all compositions expressed by high biomineralization rates with the formation of crystalline hydroxyapatite being identified by XRD after 12 h of immersion in SBF solution.     

Effect of Bi2O3 content on sintering and crystallization behavior of low-temperature firing Bi2O3–B2O3–SiO2 glasses

The sintering behavior of a Pb-free Bi₂O₃–B₂O₃–SiO₂ glass system was examined as a function of Bi₂O₃ content. The glass transition temperature and the crystallization temperature of the glasses decreased with different decreasing gradients as the Bi₂O₃ content increased. The change in temperature affected the sintering behaviors of the glasses. In the case of the 40 mol% Bi₂O₃ addition, large pore accompanied over-firing phenomenon was observed when the sample was sintered over the optimum sintering temperature. However, over-firing was not observed in the sample with 45 mol% of Bi₂O₃ because of the crystallized phases during sintering. When the Bi₂O₃ content was 50–55 mol%, the crystallization temperature became lower than the glass transition temperature, which resulted in the crystallization of glass and it hindered densification.     

Direct ink writing of highly bioactive glasses

Direct ink writing (DIW), or Robocasting, is an additive manufacturing technique that offers the opportunity to create patient specific bioactive glass scaffolds and high strength scaffolds for bone repair. The original 45S5 Bioglass^® composition crystallises during sintering and until now, robocast glass scaffolds contained at least 51.9 mol% SiO₂ or B₂O₃ to maintain their amorphous structure. Here, ICIE16 and PSrBG compositions, containing <50 mol% SiO₂, giving silicate network connectivity close to that of 45S5, were robocast and compared to 13–93 composition. Results showed Pluronic F-127 can be used as a universal binder regardless of glass reactivity and that particle size distribution affected the ink “printability”. Scaffolds with interconnects of 150 μm (41–43% porosity) had compressive strengths of 32–48 MPa, depending on the glass composition. Robocast scaffolds from these highly reactive bioactive glasses promise greatly improved bone regeneration rates compared with existing bioactive glass scaffolds.     

Structural characterization of TiO2–P2O5–CaO glasses by spectroscopy

The structure of glasses with composition x TiO₂·(65 ? x) P₂O₅·35 CaO (x = 0–30 mol%) has been studied and their glass transition temperature, Raman and NMR spectra have been analysed.For TiO₂-free glass two phosphate species have been identified as Q² and Q³. Increasing TiO₂ content in glass compositions results in the disappearance of the Q³ and Q² species and in the formation of, mainly, pyrophosphate structure, Q¹.In calcium titanophosphate glass with higher TiO₂ content the structure consists of a distorted Ti octahedral linked to pyrophosphate unit through P–O–Ti bonds. In these glass series the structural cohesion increases with TiO₂, although a depolymerization in the original P–O–P network occurs.The study of these glasses and the understanding of their structural characteristics can give a valuable contribution for the clarification of their degradation behaviour namely in biological environments.     

Effect of neodymium ions on upconversion fluorescence studies of oxyfluorosilicate glasses for optoelectronic devices

Effect of Nd₂O₃ concentrations on optical properties and upconversion studies were investigated for oxyfluorosilicate glasses with composition of SiO₂-Al₂O₃-Na₂CO₃-SrF₂-CaF₂. The Judd-Ofelt (JO) intensity parameters, Ω_λ (λ = 2, 4 and 6) as well as radiative properties for the ⁴F_3/2 level of Nd³⁺ ion have been evaluated from the absorption spectra of 1.0 mol% Nd₂O₃-doped glass. For all the glass samples, the strong NIR emissions were observed at 891, 1058 and 1330 nm and have been attributed to ⁴F_3/2 → ⁴I_{9/2, 11/2, 13/2} transitions respectively. The stimulated emission cross-section for the ⁴F_3/2 → ⁴I_11/2 transition is evaluated and found to be 4.24 × 10^–20 cm². From the decay curves, experimental lifetimes (τ_exp) of the ⁴F_3/2 level have been determined and are found to be 363, 340, 205, 134, 122 and 54 μs for 0.1, 0.5, 1.0, 1.5, 2.0 and 3.0 mol% Nd³⁺ ions doped glasses, respectively. By exciting the prepared glass samples at 808 nm, the upconversion of infrared light into blue, green, yellow and red emission have also observed. These results indicate that the present glasses could be useful for opto-electric devices and solid state laser applications.     

Intermediate-temperature conductivity of B-site doped Na0.5Bi0.5TiO3-based lead-free ferroelectric ceramics

Na_0.5Bi_0.5TiO₃ (NBT) based oxide-ion conductor ceramics have great potential applications in intermediate-temperature solid oxide fuel cells (SOFCs) and oxygen sensors. Na_0.5Bi_0.49Ti_1−xMg_xO_3−δ ceramics with x=0, 0.01, 0.02, 0.03, 0.05 and 0.08 were prepared by conventional solid-state reaction. XRD measurement and SEM analysis revealed the formation of pure perovskite structures without secondary phase. MgO doping greatly decreased the sintering temperature and inhibited grain growth. AC impedance spectroscopy measurement was adopted to measure the total conductivity, which was found to increase with MgO doping content ranging from 0 to 3 mol% and subsequently to decrease. High oxygen ionic conductivity σ_t=0.00629 S/cm was achieved for sample doped with 3 mol% MgO at 600 °C in air atmosphere.     

Fabrication of highly insulating foam glass made from CRT panel glass

We prepared low-density foam glasses from cathode-ray-tube panel glass using carbon and MnO₂ as the foaming agents. We investigated the influence of the carbon and MnO₂ concentrations, the glass-powder preparation and the foaming conditions on the density and homogeneity of the pore structure and the dependence of the thermal conductivity on the foam density. The results show that the moderate foaming effect of the carbon is greatly improved by the addition of MnO₂. A density as low as 131 kg m⁻³ can be achieved with fine glass powder. The foam density has a slight dependence on the carbon and MnO₂ concentrations, but it is mainly affected by the foaming temperature and the time. The thermal conductivity of the foam-glass samples is lower than that of commercial foam glasses with the same density. The lowest value was determined to be 42 mW m⁻¹ K⁻¹ for a foam glass with a density of 131 kg m⁻³. A further improvement in the closed porosity could potentially decrease the thermal conductivity even further, and thus our approach has great potential in terms of a thermal insulation material.     

Glasses for laser joining of zirconia ceramics

Laser joining of ZrO₂ ceramics using glasses and glass ceramics as sealing components requires optimized systems. The ternary systems SiO₂–BaO–B₂O₃ and BaO–SrO–SiO₂ were selected as a basis for development of suitable glass compositions for the laser joining process. Additives such as CaO, TiO₂, Al₂O₃, and MgO were used to control the crystallization processes and hence the thermal expansion coefficients during glass synthesis. The glass viscosity, the strength of the ceramic-glass-ceramic joint, and the joint tightness are other important glass properties which were optimized for the laser process. For glass G018-345, this yielded strengths of up to 225 MPa (Weibull modulus of m = 8.6) and He leak rates of up to 4.3 × 10⁻⁵ mbar l s⁻¹. Because of the varying viscosities obtained, the optimized glass systems could be used selectively in a temperature range of 700–900 °C.     

Structural,optical, and spectroscopic properties of Er3+-doped TeO2–ZnO–ZnF2 glass-ceramics

Transparent fluorotellurite glass-ceramics have been obtained by heat treatment of precursor Er-doped TeO₂–ZnO–ZnF₂ glasses. ErF₃ nanocrystals nucleated in the glass-ceramics have a typical size of 45 ± 10 nm. Based on the Judd-Ofelt theory, the main radiative parameters for the ⁴I_13/2 → ⁴I_15/2 transition have been obtained. The split of the absorption and emission bands and the reduction of the Ω₂ parameter, as compared to the glass, confirm the presence of Er³⁺ ions in a crystalline environment in glass-ceramic samples. The analysis of the ⁴I_13/2 decays suggests that a fraction of Er³⁺ ions remains in a glass environment while the rest forms nanocrystals. For the glass-ceramics, intense red and green upconversion emissions were observed with an enhancement of the ⁴F_9/2 → ⁴I_15/2 red one compared to the glass sample. The temporal evolution of the red emission together with the excitation upconversion spectra suggests that energy transfer processes are responsible for the enhancement of the red emission.     

Tuning the interfacial reaction between CaO–SrO–Al2O3–B2O3–SiO2 sealing glass–ceramics and Cr-containing interconnect: Crystalline structure vs. glass structure

In this paper, Al₂O₃ was added to CaO–SrO–B₂O₃–SiO₂ sealing system to tailor the structure of sealing glass–ceramics and glass–ceramics/metal interfacial reaction. The addition of alumina in glasses contributes to increasing fraction of bridging oxygen in silica tetrahedral as well as the change in boron environment from three-fold to four-fold (BO₄ → BO₃). The devitrification tendency of glasses also decreases with increasing Al₂O₃ content. The condensed glass structure and increasing residual glass content play opposite roles on the interfacial reaction, consequently resulting in a maximum fraction of Cr⁶⁺ in reaction couples between Cr₂O₃ and glass containing 6 mole% Al₂O₃ at 700 °C. In addition, the good bonding can be observed at the interface between Cr-containing interconnect (Crofer 22APU) and glass containing 4 mole% Al₂O₃, held at 700 °C for 100 h. The reported results support the suitability of the prepared glass–ceramics as sealing materials for SOFC applications.     

Low-temperature reactive hot-pressing of cerium-doped titanate composite ceramics and their aqueous stability

Reactive hot-pressing was scarcely applied to fabricate titanate ceramic waste forms designed for immobilizing high-level radioactive waste (HLW). However, compared with non-reactive processes, there is an advantage of producing high-density ceramics at reduced temperatures by reactive hot-pressing. Ce^IV-doped titanate composite ceramics with relative densities in excess of 99% were prepared by reactive hot-pressing at temperature as low as 1150 °C and pressure of 30 MPa for 1–4 h. The results show that low-temperature densification of the composite ceramics might be attributed to the plastic deformation under hot-pressing condition. In addition, aqueous stability testing was carried out using the standard MCC-1 static leach test method. The results demonstrate that the normalized elemental leach rate of Ca, Ce and Zr were fairly constant in a low value below 5 × 10⁻² g m⁻² d⁻¹, 7 × 10⁻⁶ g m⁻² d⁻¹ and 6 × 10⁻⁶ g m⁻² d⁻¹ after 21 d.