Effects of CaO/P2O5 ratio on the structure and elastic properties of SiO2–CaO–Na2O–P2O5 bioglasses

The evolution of elastic properties and structure upon the change of CaO/P₂O₅ ratio in SiO₂–CaO–Na₂O–P₂O₅ glasses (45S5-derived and 55S4-derived) at ambient conditions has been studied by using both Brillouin and Raman spectroscopy coupled with X-ray diffraction. Under the same SiO₂/Na₂O ratio, it is found that a decrease in CaO/P₂O₅ molar ratio has caused a more-polymerized silicate network via a net consumption of Q⁰, Q¹, and Q² species yet enriching in Q³ and Q⁴ species. Brillouin experiments revealed that all the bulk, shear and Young’s moduli of the glasses studied increases with the increase of CaO/P₂O₅ molar ratio. The unexpected variation trend in shear modulus can be correlated to the contribution from cohesion, the less-polymerized phosphate Q species, and density. Compared to the 45S5-derived, the more-polymerized 55S4-deived glass has a lower bulk but slightly higher shear modulus at the given CaO/P₂O₅ ratio.     

Characterisation of Ga2O3–Na2O–CaO–ZnO–SiO2 bioactive glasses

The structural role of Gallium (Ga) is investigated when substituted for Zinc (Zn) in a 0.42SiO₂–0.40–xZnO–0.10Na₂O–0.08CaO glass series, (where x = 0.08). Each starting material was amorphous, and the network connectivity (NC) was calculated assuming Ga acts as both a network modifier (1.23), and also as a network former. Assuming a network forming role for Ga the NC increased with increasing Ga concentration throughout the glass series (Control 1.23, TGa-1 2.32 and TGa-2 3.00). X-ray photoelectron spectroscopy confirmed both composition and correlated NC predictions. Raman spectroscopy was employed to investigate Q-structure and found that a shift in wavenumbers occurred as the Ga concentration increased through the glass series, from 933, 951 to 960 cm^?1. Magic angle spinning nuclear magnetic resonance determined a chemical shift from ?73, ?75 to ?77 ppm as the Ga concentration increased, supporting Raman data. These results suggest that Ga acts predominantly as a network former in this particular Zn-silicate system.     

Textural and structural studies of sol–gel derived SiO2–CaO–P2O5–MgO glasses by substitution of MgO for CaO

The partial substitution of MgO for CaO in the ternary SiO₂–CaO–P₂O₅ glass system was conducted by the sol–gel method and a comparison of the textural and structural properties was reported. The textural properties (specific surface area and pore size distribution) were obtained by N₂-adsorption measurement and the glasses structure was elucidated by Fourier transform infrared spectroscopy. It is observed that, in general, all synthesized glasses show high specific surface area and present porous nature in mesopore region. The presence of MgO in glass composition has little influence on its textural properties, however, with increasing MgO concentration the frequency of Si–O(s,asym) group shifts towards lower energy and the absorbance intensity ratio of Si–O–NBO(Q³)/Si–O–Si(s,sym)(Q⁴) declines, indicating the structure modification of MgO in glass composition.     

Effect of borosilicate glasses on the microwave dielectric properties of ZnO–Nb2O5–Ta2O5 system

(1 ? y)[0.5ZnNb₂O₆–0.5Zn₃Nb₂O₈]–yZnTa₂O₆ with y = 0.91 (ZNT) ceramic have been prepared by conventional solid state ceramic route. The effect of glass additives on the microstructure, densification, and microwave dielectric properties of the ZNT ceramic for low temperature co-fired ceramic applications was investigated. Different weight percentages of quenched glass such as ZnO–B₂O₃–SiO₂, BaO–B₂O₃–SiO₂, LiO–B₂O₃–SiO₂ and MgO–B₂O₃–SiO₂ were added to ZNT powder. The crystal structure of the ceramic–glass composites was studied by X-ray diffraction and microstructure by scanning electron microscopy. The microwave dielectric properties such as relative permittivity (ε_r), quality factor (Q_uxf) and co-efficient of temperature variation of resonant frequency (τ_f) of the ceramics have been measured in the frequency range 4–6 GHz. The 5 wt% ZnO–B₂O₃–SiO₂ added ZNT ceramic sintered at 900 °C showed: ε_r = 28.1, Q_uxf = 32820 GHz (at 4.92 GHz), and τ_f = ?7.7 ppm/^oC respectively.     

Development and bioactivity evaluation of bioglasses with low Na2O content based on the system Na2O–CaO–MgO–P2O5–SiO2

Osteoconductive bioglasses, free of K(2)O and Al(2)O(3) and with content of Na(2)O lower than 10?mol%, were designed based on the ratio (SiO(2)?+?MgO)/(P(2)O(5)?+?CaO?+?Na(2)O) in the system Na(2)O-CaO-MgO-P(2)O(5)-SiO(2). The developed glasses have shown a strong potential for the formation of hydroxycarbonated apatite (HCA) in vitro. The particles of HCA aggregates tend to be of finer size with increasing the ratio of (SiO(2)?+?MgO)/(CaO?+?P(2)O(5)?+?Na(2)O) in the glass chemical composition indicating significant bioactivity. Critical size bone defects created in the femurs of albino adult female rats, and grafted with the glass particles for 12?weeks post implantation, were completely healed by filling with mineralized bone matrix without infection showing a strong potential for new bone formation in vivo. Osteoblasts and osteocytes were observed close to the surface of the granular implants with active areas of bone deposition, resorption and remodelling. The bioglass with lowest (SiO(2)?+?MgO)/(CaO?+?P(2)O(5)?+?Na(2)O) ratio has shown the highest bioactivity while the bioglass with the highest (SiO(2)?+?MgO)/(CaO?+?P(2)O(5)?+?Na(2)O) has shown the lowest bioactivity. The newly formed bone in vivo has shown a similar structure to that of the original bone as indicated by the histology and microstructural results. In addition, Ca/P molar ratio of the newly formed bone was found to be (~1.67), which is similar to that of the original bone.     

Fabrication and characterization of ZrO2–CaO–P2O5–Na2O–SiO2 bioactive glass ceramics

SiO₂–CaO–Na₂O–P₂O₅–ZrO₂ based bioactive glasses with different compositions of SiO₂ and yttrium stabilized ZrO₂ were prepared by the conventional melt quenching technique. The effects on the chemical–mechanical properties of bioactive glasses due to the addition of ZrO₂ by replacing SiO₂ were investigated. Microstructure and phase behavior were studied by scanning electron microscopy, energy-dispersive spectroscopy, and X-ray diffraction analysis. Compressive strength, porosity, Vickers hardness, and Young’s modulus were measured as mechanical properties. Bioactivity and cell viability were investigated by immersion in simulated body fluid and MTT assay analysis. Osteosarcoma cell proliferation on the specimen surfaces was examined by confocal laser scanning microscopy. The results showed that replacing SiO₂ with ZrO₂ helps the bioactive glass to be completely vitrified at comparatively lower sintering temperature than conventional Bioglass^®. The mechanical properties were also improved without compromising biocompatibility. Bioactive glass containing 10 wt% ZrO₂ and 35 wt% SiO₂ showed compressive strength of 399.71 MPa, Young's modulus of 22.3 GPa, Vicker’s hardness of 502.54 HV, and porosity of 26 vol%.     

Characterization of SiO2–Na2O–Fe2O 3–CaO–P2O 5–B 2O 3 glass ceramics

Bioactivity and magnetic properties were investigated in glass and glass ceramics based on the SiO₂–Na₂O–Fe₂O₃–CaO–P₂O₅–B₂O₃ system to find their suitability as thermoseed for hyperthermia treatment of cancer. The effect of change in compositions on bioactivity was examined in simulated body fluids. The glass ceramic samples exhibit Na₃CaSi₃O₈ and Na_3-XFe_XPO₄ phases. After dipping the glass ceramic samples in simulated body fluids silica hydrogel first forms, followed by an amorphous calcium phosphate layer. Magnetic and microwave resonance experiments further demonstrate the potential of these glass ceramics for possible use in hyperthermia.     

Effects of MgO on properties of Li2O–Al2O3–SiO2 glass–ceramics for LTCC applications

Li₂O–Al₂O₃–SiO₂ (LAS) glass–ceramics for low temperature co-fired ceramics (LTCC) application were prepared by melting method, and the effects of MgO on the sinterability, microstructure, dielectric property, thermal expansion coefficient (CTE) and mechanical character of this glass–ceramics have been studied. The X-ray diffraction images represent that the main phase is β-spodumene solid solutions. And some ZrO₂ and CaMgSi₂O₆ phases in LAS glass–ceramics are detected. The LAS glass–ceramics without additive (MgO) sintered at 800° had the dielectric properties: dielectric constant (ε_r) of 5.3, dielectric loss (tanδ) of 2.97 × 10^?3 at 1 MHz, CTE value of 1.06 × 10^?6 K^?1, bulk density of 2.17 g/cm³, and flexural strength of 73 MPa. 5.5 wt% MgO-added LAS glass–ceramic achieves densification at 800° exhibited excellent properties: low dielectric constant and loss (ε_r = 7.1, tanδ = 2.02 × 10^?3 at 1 MHz), low CTE (2.89 × 10^?6 K^?1), bulk density = 2.65 g/cm³ as well as high flexural strength (145 MPa). The results indicate that the addition of MgO is helpful to improve the dielectric and mechanical properties. The formation of CaMgSi₂O₆ crystal phase with higher CTE leads to the increase of CTE value of LAS glass–ceramics due to the increasing MgO content, and the increase of CTE is favourable for matching with silicon (3.1 × 10^?6 K^?1). The prepared LAS glass–ceramics have the potential for LTCC application.     

Ti K-edge XANES study of the local environment of titanium in bioresorbable TiO2–CaO–Na2O–P2O5 glasses

Ti K-edge XANES (X-ray absorption near edge structure) spectroscopy has been used to study the local coordination of titanium in biocompatible and bioresorbable TiO₂–CaO–Na₂O–P₂O₅ glasses. Both conventional melt-quenched glasses of composition (TiO₂) _x (CaO)_0.30(Na₂O)_(0.20−x)(P₂O₅)_0.50, where x = 0.01, 0.03 and 0.05, and sol–gel derived (TiO₂)_0.25(CaO)_0.25(P₂O₅)_0.50 glass have been studied. The results show that in all the materials studied, titanium is surrounded by an octahedron of oxygen atoms. Further analysis reveals that the TiO₆ site in the amorphous samples is not heavily distorted relative to that in rutile, anatase or CaSiTiO₅. The spectra from the (TiO₂)_0.25(CaO)_0.25(P₂O₅)_0.50 sol–gel samples reveal greater distortion in the TiO₆ site in the dried gel compared to the heat-treated sol–gel glass. The XANES spectra from melt-quenched glass samples soaked in distilled water for various times do not shown any evidence of degradation of the titanium site over periods of up to 14 days.     

The influence of phosphorus precursors on the synthesis and bioactivity of SiO2–CaO–P2O5 sol–gel glasses and glass–ceramics

Bioactive glasses and glass–ceramics of the SiO₂–CaO–P₂O₅ system were synthesised by means of a sol–gel method using different phosphorus precursors according to their respective rates of hydrolysis—triethylphosphate (OP(OC₂H₅)₃), phosphoric acid (H₃PO₄) and a solution prepared by dissolving phosphorus oxide (P₂O₅) in ethanol. The resulting materials were characterised by differential scanning calorimetry and thermogravimetry, X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy coupled with energy dispersive X-ray spectroscopy and by in vitro bioactivity tests in acellular simulated body fluid. The different precursors significantly affected the main steps of the synthesis, beginning with the time required for gel formation. The most striking influence of these precursors was observed during the thermal treatments at 700–1,200 °C that were used to convert the gels into glasses and glass–ceramics. The samples exhibited very different mineralisation behaviours; especially those prepared using the phosphoric acid, which had a reduced onset temperature of crystallisation and an increased resistance to devitrification. However, all resulting materials were bioactive. The in vitro bioactivity of these materials was strongly affected by the heat treatment temperature. In general, their bioactivity decreased with increasing treatment temperature. For crystallised samples obtained above 900 °C, the bioactivity was favoured by the presence of two crystalline phases: wollastonite (CaSiO₃) and tricalcium phosphate (α-Ca₃(PO₄)₂).     

Effect of Ca/Si ratio on the microstructures and properties of CaO–B2O3–SiO2 glass-ceramics

CaO–B₂O₃–SiO₂ glass-ceramics were synthesized by sol–gel method, and the effect of Ca/Si ratio on the microstructures, electrical properties and mechanical characteristics of this ternary system was investigated. The results showed that the increase of CaO content is favorable for the crystallization of CaO–B₂O₃–SiO₂ system and formation of the desired glass-ceramics. The bending strength of the sintered glass-ceramics increases with CaO content by increasing of crystalline phases. When the Ca/Si ratio increases, the dielectric constant (ε _r) decreases and loss (tanδ) increases gradually. The thermal expansion coefficient (TEC) enhances by increasing CaO contents due to the formation of other crystal phases with large TEC value. The glass-ceramics exhibit low dielectric constant and loss (ε _r < 4.7, tanδ < 5 × 10^-4 at 1 MHz), high resistivity (ρ > 10¹² Ω · cm), as well as excellent mechanical properties (σ ≈ 160 MPa, α ≈ 3.6 × 10⁻⁶/°C).     

Facile route to obtain a highly bioactive SiO2–CaO–Na2O–P2O5 crystalline powder

This work describes a facile method to obtain highly bioactive crystalline powders of the SiO₂–CaO–Na₂O–P₂O₅ system using a simple route: solid state reaction. Success in obtaining the highly bioactive crystal phase of interest (sodium calcium silicate Na₂Ca₂Si₃O₉ containing phosphorus) involves heating the starting reactant powder mixture under an oxidizing atmosphere for 480 min in the temperature range 950–1000 °C. Despite a significant loss of phosphorus at heat treatment temperatures above 950 °C, the resulting Na₂Ca₂Si₃O₉ crystal phase is thermally stable up to 1100 °C. Longer treatment times favor the formation of a secondary phase (sodium calcium phosphate NaCaPO₄), which, according to recent studies, further increases the bioactivity of a similar material. Finally, in vitro bioactivity tests in acellular simulated body fluid (SBF) of a powder containing only the Na₂Ca₂Si₃O₉ phase has shown behavior similar to that of Biosilicate® — an ~ 99.5% crystalline glass–ceramic whose outstanding characteristics of interaction with living tissue have already been reported in the literature.     

Effect of TiO2 on the sintering temperature and dielectric properties of Li2O–MgO–ZnO–B2O3–SiO2 ceramic composites for LTCC applications

Journal of Materials Science: Materials in Electronics - The effects of injecting TiO2 to a Li2O–MgO–ZnO–B2O3–SiO2 (LMZBS) microwave dielectric composite on sinterability,...     

Electrical and physical properties of Na2O–CaO–MgO–SiO2 glass doped with NdF3

The structure of soda-calcia-magnesia-silicate glasses doped with rare-earth fluoride (NdF₃) was investigated by Fourier transform infrared spectrometer. The density and microhardness have been investigated in order to study the effect of doping NdF₃ on the physical properties of the studied glasses. The results showed that the density of glasses increases with the increase in NdF₃ contents. While, the increase of NdF₃ contents led to decrease the microhardness values of the studied samples. The AC electrical properties of samples were measured in the frequency interval 100 Hz up to 1 MHz. The increase of NdF₃ doping generally increases the conductivity and dielectric constants of the samples slightly. The obtained experimental data from samples were discussed based on the internal structure of the glass and the distribution of its constituents, connectivity and number of free charges or broken bonds.     

Fabrication of CaO–NaO–SiO2/TiO2 scaffolds for surgical applications

A series of titanium (Ti) based glasses were formulated (0.62 SiO₂?C0.14 Na₂O?C0.24 CaO, with 0.05?mol% TiO₂ substitutions for SiO₂) to develop glass/ceramic scaffolds for bone augmentation. Glasses were initially characterised using X-ray diffraction (XRD) and particle size analysis, where the starting materials were amorphous with 4.5???m particles. Hot stage microscopy and high temperature XRD were used to determine the sintering temperature (~700?°C) and any crystalline phases present in this region (Na₂Ca₃Si₆O₁₆, combeite and quartz). Hardness testing revealed that the Ti-free control (ScC??2.4?GPa) had a significantly lower hardness than the Ti-containing materials (Sc1 and Sc2 ~6.6?GPa). Optical microscopy determined pore sizes ranging from 544 to 955???m. X-ray microtomography calculated porosity from 87 to 93?% and surface area measurements ranging from 2.5 to 3.3?SA/mm³. Cytotoxicity testing (using mesenchymal stem cells) revealed that all materials encouraged cell proliferation, particularly the higher Ti-containing scaffolds over 24?C72?h.