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.     

Formation of apatite nano-needles on novel gel derived SiO2-P2O5-CaO-SrO-Ag2O bioactive glasses

A novel SiO₂-P₂O₅-CaO-SrO-Ag₂O bioactive glass containing from 0 to 10 mol% Ag₂O was produced via the sol-gel method. The influence of silver content on in vitro hydroxyapatite (HA) formation, antibacterial and cell viability properties were investigated. The apatite shape and structure were evaluated by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction analysis (XRD). The results demonstrated that the rate of formation of crystalline HA on SiO₂-P₂O₅-CaO-SrO-Ag₂O bioactive glass containing 5% Ag₂O (BG-5A) was higher in comparison with other specimens. Formation of apatite nano-needles on the SiO₂-P₂O₅-CaO-SrO-5%Ag₂O surface in vitro, after 3 days soaking in SBF solution, demonstrated high bioactivity. The alkaline phosphatase (ALP) and 3-(4,5dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay evaluation methods illustrated that the presence of low silver (3% and 5% Ag₂O) had stimulating effect on promoting both differentiation and proliferation of G292 osteoblastic cells. Finally, results offer that specimen BG-5A is well candidate for bone tissue application with considerable high antibacterial potential, bioactivity and optimal cell viability.     

Influence of the sintering temperature on the structural feature and bioactivity of sol–gel derived SiO2–CaO–P2O5 bioglass

A sol–gel method was utilized to synthesize the gel with the composition of 58 mol% SiO₂–38 mol% CaO–4 mol% P₂O₅. The thermal properties were studied using thermogravimetric and differential thermal analysis (TG/DTA). Then the gels were sintered at 700, 900, 1000 and 1200 °C. The structure features were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), in addition in vitro assays were carried out in simulated body fluid (SBF). The results revealed that at sintering temperature above 900 °C, crystallization occurred and glass-ceramics with pseudowollastonite and wollastonite were formed. Furthermore with the increase of sintering temperature, the amount of pseudowollastonite decreased while that of wollastonite increased. In vitro tests indicated that the crystallization did not inhibit the samples bioactivity. After soaking in SBF, the formation of apatite was confirmed on glass and glass-ceramics surface, and the bioactivity of the glass-ceramics was based on the formed pseudowollastonite and wollastonite.     

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.     

Surface reactions of bioactive glasses in buffered solutions

In vitro bioactivity of glasses is usually measured in buffered solutions whereby a formation of a hydroxyapatite layer on the surface is taken as an indication of the bioactivity. In this work we compare the layer formation on three glasses in simulated body fluid, Tris buffer solution, sodium phosphate buffered saline and osteoblast medium. Two of the glasses are known bioactive glasses, 45S5 (45 wt.% SiO₂) and S53P4 (53 wt.% SiO₂), while the third is an experimental composition with a higher silica content (68 wt.% SiO₂). Plates of the glasses were immersed in the solutions at 37 °C for different times up to two weeks. The results showed clear differences between the layer developments on the three glasses in the different solutions. The results indicated that the relative order of the reactivity depended on the solution. Thus, results gained in different solutions for different glasses cannot be directly compared.     

Titania doped bioactive ceramics prepared by solid state sintering method

A bioactive ceramic in (48−x) SiO₂–36CaO–4P₂O₅–12Na₂O–xTiO₂ (where x= 0, 3.5, 7, 10.5 and 14 mol%) system was prepared by solid state sintering method. The in vitro bioactive properties of bodies were evaluated using stimulated body fluid under static condition at 37 °C. The formation of hydroxyl-carbonated apatite layer on the surface of samples was examined by XRD, FTIR, SEM and AAS. It was found that partial substitution of SiO₂ with TiO₂ produced a positive impact on the bioactivity of the specimens. Addition of TiO₂≤10.5 mol% to the system not only enhanced the bioactive properties but also accelerates the apatite forming process.     

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.     

Self-assembly of novel supramolecular silver(I) compound based on mixed ligands bipy/TST3−, H3TST = 2,4,6-tris (4-sulfophenylamino)-1,3,5-triazine

The novel supramolecular silver(I) compound with formula [Ag₆(TST)₂(bipy)₆(H₂O)₂]_n · 3nH₂O (1) based on assembly of Ag(I) and mixed ligand bipy/TST³⁻, bipy = 2,2′-bipyridine, H₃TST = 2,4,6-tris(4-sulfophenylamino)-1,3,5-triazine, has been prepared by hydrothermal method. In the solid-state structure of 1, two-dimensional layered polymeric structures extended with subunits [Ag₆(TST)₂(bipy)₆(H₂O)₂] interact each other in the form of π–π attractions between bipy, forming a three-dimensional supramolecular architecture. Compound 1 represents a Ag-containing polymeric compound possessing room-temperature luminescence.     

Improvement in structural,dielectric and energy-storage properties of lead-free niobate glass-ceramic with Sm2O3

Phase evolution, microstructure, dielectric performance, polarization, breakdown strength as well as energy-storage behaviors for the lead-free niobates glass-ceramics with Sm₂O₃ were systematically investigated. Two crystallographic structures of tetragonal tungsten bronze and orthorhombic perovskite complex phases were obtained and Sm³⁺ entered into the crystalline phases. The optimal microstructure of the glass-ceramic was obtained with Sm₂O₃ of 2 mol%. Both dielectric constant and polarizability were enhanced with increasing Sm₂O₃. The breakdown strength and energy-storage behaviors of the glass-ceramics were also improved by increased Sm₂O₃. The highest breakdown field of 21.2 kV/mm, the highest charged (0.74 J/cm³) and discharged energy density (0.45 J/cm³) were obtained in the glass-ceramic with 2 mol% Sm₂O₃. It is due to the reduced interfacial polarization in this particular composition.     

Characterization,in vitro bioactivity and biological studies of sol-gel synthesized SrO substituted 58S bioactive glass

Bioactive glasses (BGs) are considered as a high potential candidate in bone repair and replacement. In the present study, sol–gel derived BGs based on 60% SiO₂-(36%-x) CaO-4%P₂O₅-x SrO (where x = 0, 5 and 10 mol%) quaternary system were synthesized and characterized. The effect of Sr substitutions on bioactivity, proliferation, alkaline phosphatase activity of osteoblast cell line MC3T3-E1 and antibacterial activity were investigated. Dried gels were stabilized at 700 °C to eliminate the nitrates and prevent the crystallization of bioactive glasses. X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy results confirmed the formation of hydroxycarbonate apatite on the BG surfaces. The 3-(4,5dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide and alkaline phosphate activity results showed that 5% SrO increased both differentiation and proliferation of MC3T3-E1 cells, while 10% SrO resulted in a decrease in bioactivity. Live/Dead and DAPI/Actin staining exhibited viable cell and the morphology of actin fibers and nuclei of MC3T3 cells treated with BG-0 and BG-5. The result of antibacterial test showed that strontium substituted 58S BG exhibited antibacterial effect against methicillin-resistant Staphylococcus aureus bacteria. Taken together, results suggest that 58S BG with 5 mol% SrO is a good candidate for bone tissue engineering with maximum cell proliferation and ALP activity, good bioactivity and high antibacterial efficiency.     

Microstructural characterization and crystallization kinetics of (1 − x)TeO2–xK2O (x = 0.05, 0.10, 0.15, 0.20 mol) glasses

Microstructural characterization and crystallization kinetics of (1 − x)TeO₂–xK₂O (x = 0.05, 0.10, 0.15, and 0.20 in molar ratio) glasses were investigated using DTA, XRD, Raman spectroscopy, optical microscopy and SEM techniques. Whereas only one exothermic peak was observed for the 0.95TeO₂–0.05K₂O and 0.90TeO₂–0.10K₂O glasses, two crystallization peaks were present on the DTA plots of the 0.85TeO₂–0.15K₂O and 0.80TeO₂–0.20K₂O glasses. On the basis of the XRD and Raman spectrophometry investigations, α-TeO₂, γ-TeO₂ and K₂Te₄O₉ crystal phases were present in the (1 − x)TeO₂–xK₂O (x = 0.05, 0.10, 0.15, and 0.20 in molar ratio) glass samples heated above the peak crystallization temperatures, T_p. SEM/EDS investigations of (1 − x)TeO₂–xK₂O (x = 0.05, 0.10, 0.15, and 0.20 in molar ratio) glasses heated above T_p revealed the presence of distinct TeO₂-rich and K₂Te₄O₉ in the 0.95TeO₂–0.05K₂O and triangular wedge-shaped crystalline regions in the 0.90TeO₂–0.10K₂O, 0.85TeO₂–0.15K₂O and 0.80TeO₂–0.20K₂O glasses. DTA analyses were carried out at different heating rates and the Avrami constant for the 0.95TeO₂–0.05K₂O glass was calculated as 0.94, an indication of surface crystallization also confirming SEM results. On the other hand, the n values were between 1.7 and 1.87 for the exothermic peaks of the 0.80TeO₂–0.10K₂O, 0.85TeO₂–0.15K₂O and 0.80TeO₂–0.20K₂O glasses, indicating one-dimensional crystalline growth mechanisms for these glasses. Activation energies for one-dimensional crystal growth mechanisms in these crystals determined from the modified Kissinger plots were found to vary between 550 and 650 kJ/mol.     

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.     

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.     

Processing of transparent glass-ceramics by nanocrystallisation of LaF3

Transparent glass-ceramics have been prepared by heat-treating oxyfluoride glasses in the Na₂O–Al₂O₃–SiO₂–LaF₃ system. The nanocrystallisation of LaF₃ was achieved by controlling time and temperature parameters. Glasses and glass-ceramics were characterised by dilatometry, DTA, XRD and TEM. The mean crystal size (<20 nm) and the crystal fraction increase with the temperature of heat treatment, while they reach a maximum at about 20 h at a temperature close to T_g. The crystallisation of phases containing glass modifier elements as well as F anions leads to the increase in the viscosity of the remaining glass matrix. Phase separation occurs in glass-ceramics depending on the glass composition which affects nanocrystallisation.     

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.     

The impact of Nb2O5 on in-vitro bioactivity and antibacterial activity of CaF2–CaO–B2O3–P2O5–SrO glass system

This work consists of in vitro bioactivity (in SBF) and antibacterial studies (against S. aureus and E. coli bacteria) of Nb₂O₅ doped bioactive glasses. X-ray diffraction and scanning electron microscopy investigations indicated deposition of Nb-HAp (hydroxyapatite) crystalline layer on the samples after exposing to SBF. The spectroscopy investigations also indicated the deposition of HAp layer on these samples. The magnitude of HAp deposited on the glasses found to be relying on concentration of Nb₂O₅ dopant; this conclusion was drawn by determining weight loss of the glasses due to exposure to SBF and also by assessing the variation of pH of the remnant fluid as functions of Nb₂O₅content. The studies further indicated the maximal content of hydroxyapatite was deposited on the surface the glasses doped with 4.0 mol% of Nb₂O₅. The antibacterial studies (against E. coli and S. aureus bacteria) of these glasses indicated the maximal killing effect of bacteria of the samples admixed with 4.0 mol% of Nb₂O₅. This result is attributed to the occupancy of maximal fraction of Nb ions in NbO₆ structural units (confirmed by IR and Raman spectroscopic results) in this sample that paved the way for easy disintegration of the glass and to act on the bacteria. Overall, the results of bioactivity studies of Nb₂O₅ doped bioglasses indicated that the Nb₂O₅ not only enhanced bioactivity potential but also exhibited antimicrobial activity.     

Antibacterial activity of organomontmorillonites and organovermiculites prepared using chlorhexidine diacetate

Organoclays with antibacterial activity were prepared from cation exchanged Ag⁺, Cu^2 + and Zn^2 + forms of montmorillonite and vermiculite using five concentrations of chlorhexidine diacetate. The samples were characterized by X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). The antibacterial activity against Enterococcus faecalis, Escherichia coli and Pseudomonas aeruginosa was evaluated by finding the minimum inhibitory concentration (MIC). All prepared organomontmorillonites and organovermiculites showed the best antibacterial activity against an E. coli bacterial strain.     

Orientated crystallization of fresnoite glass-ceramics by using a thermal gradient

The glass with chemical composition (mol%) 33.33 BaO, 16.66 TiO₂, 50.00 SiO₂ was prepared by a conventional melt-quenching method. The glass-ceramics with a Ba₂TiSi₂O₈ crystal was prepared by crystallization of the glasses using a hot stage. The crystals are shown highly orientated along the c-axis perpendicular to the hot surface of the sample. Crystallization was controlled by a diffusion process with surface nucleation. The activation energy for crystallization was about 518 kJ/mol. The mechanism of oriented crystallization was considered in the present paper.     

Preparation of infrared transparent YAG-based glass-ceramics with nano-sized crystallites

Transparent YAG-based glass-ceramics were prepared by a novel method called amorphous sintering followed by controlled crystallization (ASCC) from the compositions of 62.5Al₂O₃–(37.5 ? x)Y₂O₃–xLa₂O₃ (in molar ratio, x = 5, 7, 10 and 20). The stability of the YAG glass was improved by the incorporation of La₂O₃, which increased the activation energy for crystallization. With 10 mol% La₂O₃, bulk YAG glass was prepared by hot-pressing and showed an infrared transmittance of 66%. The YAG glass was converted into glass-ceramics by post annealing at 875 °C for 5 h for controlled crystallization. The obtained glass-ceramic sample showed a crystallite size of 20–50 nm and an infrared transmittance of 60%. With increasing annealing time, the crystallites grew up quickly, resulting in a significant decrease in transparency. In the hot-pressed glass, nano-sized YAG nuclei (～5 nm) were found, which were probably responsible for the crystallization behavior observed at temperatures (e.g. 875 °C) below the onset crystallization temperature.     

Flame-spraying synthesis of aluminate glasses in the Al2O3–La2O3 system

The paper deals with the synthesis and characterisation of binary aluminate glasses in the La₂O₃–Al₂O₃ system with Al₂O₃ contents changing between 74.6 and 86.9 mol% (48–65 wt.%), and of ternary glasses with 75.7 mol% Al₂O₃ doped with 1 mol% of Nd₂O₃ or Er₂O₃. Six binary and two ternary compositions were prepared. Flame synthesis facilitated the preparation of X-ray amorphous microspheres in the systems with 58 wt.% Al₂O₃, and with eutectic composition in the pseudobinary LaAlO₃–LaAl₁₁O₁₈ system doped with Er. Other systems contained low fractions of crystalline LaAlO₃ perovskite, regardless of the composition. The diameter of prepared microspheres ranged between 2 and 10 μm. They were transparent for visible light, as well as in the IR wavenumber range from 1300 to 4000 cm^?1.