Compositional dependence of bioactivity of glasses in the system CaO-SiO2-Al2O3: itsin vitro evaluation

In order to investigate fundamentally the effect of Al₂O₃ on the bioactivity of glasses and glass-ceramics, the compositional dependence of bioactivity of glasses in the system CaO-SiO₂-Al₂O₃ was studiedin vitro. It is already known that the essential condition for glasses and glass-ceramics to bond to living bone is the formation of an apatite layer on their surfaces in the body, and that the surface apatite layer can be reproduced even in an acellular simulated body fluid which has almost equal ion concentrations to those of the human blood plasma. In the present study, bioactivity of the glasses was evaluated by examining apatite formation on their surfaces in the simulated body fluid with thin-film X-ray diffraction, Fourier transform infrared reflection spectroscopy and scanning electron microscopic observation. Only CaO-SiO₂-Al₂O₃ glasses containing Al₂O₃ less than 1.5 mol % formed the surface apatite as well as Al₂O₃-free CaO-SiO₂ glasses, but CaO-SiO₂-Al₂O₃ containing Al₂O₃ more than 1.7 mol % did not form it as well as an SiO₂-free CaO-Al₂O₃ glass. This indicates that only a small amount of addition of Al₂O₃ to glass compositions suppresses the bioactivity of glasses and glass-ceramics by suppressing apatite formation on their surfaces in the body.     

Chemical reaction of bioactive glass and glass-ceramics with a simulated body fluid

Glass-ceramic A-W containing crystalline apatite and wollastonite in an MgO-CaO-SiO₂ glassy matrix bonds to living bone through an apatite layer which is formed on its surface in the body. The parent glass G of glass-ceramic A-W and glass-ceramic A, which has the same composition as glass-ceramic A-W but contains only the apatite, also bond to living bone through the surface apatite layer, whereas glass-ceramic A-W(Al), which contains the apatite and wollastonite in an MgO-CaO-SiO₂-Al₂O₃ glassy matrix, neither forms the surface apatite layer nor bonds to living bone. In the present study, in order to reveal the mechanism of formation of the surface apatite layer, changes in ion concentrations of a simulated body fluid with immersion of these four kinds of glass and glass-ceramics were investigated. Bioactive glass G and glass-ceramics A and A-W all showed appreciable increases in Ca and Si concentrations, accompanied by an appreciable decrease in P concentration, whereas non-bioactive glass-ceramic A-W(Al) hardly showed any element concentration change. It was speculated from these results that dissolution of the Ca(II) and Si(IV) ions from bioactive glass and glass-ceramics plays an important role in forming the apatite layer on their surfaces in the body.     

The stability of mother glass for porous glass-ceramics of the TiO2-SiO2 system

The stability of the glasses of TiO₂-SiO₂-Al₂O₃-B₂O₃-CaO-MgO and TiO₂-SiO₂-Al₂O₃-P₂O₅-CaO-MgO systems during formation has been investigated as a basic study on the preparation of porous glass-ceramics. The main factor affecting the stability of these glasses which are used as mother glasses of porous glass-ceramics was CaO content. The stability was remarkably improved by increasing the CaO content.The preparation of porous glass-ceramics with an appropriate amount of pore volume was possible from a glass containing CaO up to 30 mol%. The DTA trace of the glasses showed two distinct exothermic peaks in the ranges 30–130° C and 140–300° C above glass transition temperatures. The porous glass-ceramics of TiO₂-SiO₂ system containing more than 60 mol% TiO₂ and having a surface area larger than 400m²g^–1, a pore volume of 0.3–0.5 ml g^–1, and average pore radius between 1 and 20 nm were fabricated.     

Bioactivity of Fe2O3-containing CaO-SiO2 glasses: in vitro evaluation

In order to reveal conditions for obtaining bioactive and ferrimagnetic glass-ceramics useful as thermoseeds for hyperthermia treatment of cancer, the effects of additives on the bioactivity of an Fe₂O₃-CaO-SiO₂ glass were investigated by examining apatite formation on the surfaces of the glasses in a simulated body fluid with ion concentrations nearly equal to those in human blood plasma. A 3Fe₂O₃, 100CaO · SiO₂ (in weight ratio) glass did not form an apatite layer on its surface in the fluid, but glasses of the same compositions with 3Na₂O, B₂O₃ and/or P₂O₅ added (in weight ratio) formed an apatite layer. This indicates that bioactive and ferrimagnetic glass-ceramics could be obtained from Fe₂O₃-containing CaO-SiO₂ glasses with Na₂O, B₂O₃ and/or P₂O₅ added. Apatite formation on the surfaces of the glasses with the additives are interpreted in terms of the dissolution of the calcium and silicate ions from the glasses.     

Transparency of LiTaO3-SiO2-Al2O3 glass-ceramics in relation to their microstructure

The glasses with various compositions in the LiTaO₃-SiO₂-Al₂O₃ system were heated from room temperature to temperatures ranging from 750° to 1050° C at a rate of 5° C min^–1. From the glasses in the LiTaO₃-SiO₂ system no transparent glass-ceramic was obtained even when their LiTaO₃/SiO₂ mole ratios were as high as 2.33. The diameter and number of the LiTaO₃ crystal grains precipitated in the glasses were 5–15 m and 10⁸–10¹⁰ grains cm^–3, respectively. On the contrary, transparent glass-ceramics were obtained from the glasses containing Al₂O₃; their compositions covered a fairly large area in the LiTaO₃-SiO₂ -Al₂O₃ system, which encompasses the compositions with the LiTaO₃/SiO₂+AlO_1.5 mole ratio as low as 0.25. The diameter and number of the LiTaO₃ crystal grains precipitated in the transparent glass-ceramics were as small as 10–20 nm and as many as 10¹⁶–10¹⁸ grains cm^–3, respectively. High nucleation rates of the LiTaO₃ crystals in the Al₂O₃-containing glasses were interpreted in terms of structural inflexibility induced in the glass-network by the addition of Al₂O₃ to the LiTaO₃-SiO₂ system.     

Toughened glass-ceramics in the ZrO2-Al2O3-SiO2 system prepared by the sol-gel process

Monolithic glass-ceramics containing Al₂O₃ or TiO₂ were prepared in the ZrO₂-SiO₂ system by the sol-gel process from metal alkoxides. Tetragonal ZrO₂ was precipitated by heat treatment at 900–1200 °C and its crystal growth was increased by adding TiO₂ or Al₂O₃. Further heating at higher temperature resulted in the precipitation of zircon and monoclinic ZrO₂ which was transformed from tetragonal ZrO₂. The addition of Al₂O₃ had less effect on both the tetragonal-to-monoclinic ZrO₂ transformation and the precipitation of zircon. The fracture toughness increased as the size of tetragonal ZrO₂ particles increased and then decreased with the appearance of monoclinic ZrO₂ or zircon. The fracture toughness of the glass-ceramics was measured in the glass-forming regions of the ZrO₂-Al₂O₃-SiO₂ system. The fracture toughness was sensitively dependent on both Al₂O₃ and ZrO₂ content, of which the highest value achieved was 9 MPa m^1/2 for the 50ZrO₂·10Al₂O₃·40SiO₂ composition.     

Study of Al2O3 effect on structural change and phase separation in Na2O-B2O3-SiO2 glass by NMR

The effect of Al₂O₃ on the structure change and the phase separation in Na₂O-B₂O₃-SiO₂ glass was investigated using ¹¹B nuclear magnetic resonance (NMR), ²⁹Si MAS NMR, and ²⁷Al MAS NMR together with infrared absorption spectroscopy and field emission scanning electron microscopy (FE-SEM). The results show that the structure change from the introduction of Al₂O₃ contributes greatly to the inhibition of phase separation. First, the introduction of Al₂O₃ imparts an ionic character to the boron-oxygen network, resulting in the formation of B-O-Al-O-Si bonds and thus increases the compatibility of the silicon network with the boron-oxygen network. Second, the addition of Al₂O₃ causes the sodium ion to transfer from the boron-oxygen network to AlO₄ tetradedra, changing a number of four-coordinated borons into three-coordinated borons. As the bond energy of the four-coordinated boron is weaker than that of the three-coordinated boron, the -B-O-Si- bond with the four-coordinated boron in Na₂O-B₂O₃-SiO₂ glasses is easily broken and results in severe phase separation during heat treatment. However, the -B-O-Al- bond with the three-coordinated boron formed in Na₂O-B₂O₃-SiO₂-Al₂O₃ glasses is difficult to be broken due to the high bond energy. In addition, the silicon network in Na₂O-B₂O₃-SiO₂-Al₂O₃ glasses is also strengthened by the addition of Al₂O₃, which prevents [BO] groups from further aggregation. As a result, the tendency of the glass towards phase separation is greatly suppressed in the Na₂O-B₂O₃-SiO₂-Al₂O₃ system.     

Biomimetic apatite coating on biomorphous alumina scaffolds

Highly porous Al₂O₃ scaffolds were prepared from natural cellulosic sponges via pyrolysis and Al-vapour phase infiltration. Subsequent oxidation and sintering in air resulted in porous Al₂O₃ ceramics with an open cellular morphology and a total porosity of 95%. The Al₂O₃-sponges were immersed in highly supersaturated simulated body fluid (5 × SBF) solutions with different Mg²⁺ and HCO³⁻ concentrations. After soaking of the porous Al₂O₃ sponges for 4 days a homogeneous calcium phosphate layer with a thickness of approximately 2 μm and a Ca : P ratio of 1.62 (apatite) was found.     

Electrical and mechanical properties of alkali barium titanium alumino borosilicate glass-ceramics containing strontium or magnesium

The AC electrical data, measured in the frequency range 0.1 Hz–5 MHz, were used to study the electrical response of lithium barium titanium alumino borosilicate glass-ceramics containing strontium or magnesium. Complex plane plot from these electrical data for various glass ceramic samples reveal contributions from simultaneously operating polarization mechanisms to overall dielectric behaviour. The SrO/BaO or MgO/Al₂O₃ replacements resulted in the increase of the conductivity and dielectric constant of the corresponding glass-ceramic materials. The relationships between the crystalline phases formed and dielectric values of studied glass-ceramics are complicated. The complex impedance of the crystalline materials generally decreases with the addition of SrO instead of BaO and with increase of MgO at the expense of Al₂O₃. The obtained data were correlated to the internal microstructure, crystalline phases formed, glassy matrix and glass to crystal interface region. β-Spodumene together with varieties of Ba-containing phases [e. g. orthorhombic celsian—BaAl₂Si₂O₈, fresnoite—Ba₂(TiO)Si₂O₇], barium silicate Ba₂Si₃O₈, lithium borate—Li₆B₄O₉, lithium metasilicate—Li₂SiO₃ strontium titanate—SrTiO₃, and magnesium borate—MgB₄O₇ phases were mostly developed in the crystallized glasses. The microhardness characteristics of the crystalline glasses have been investigated by Knoop microhardness. The SrO/BaO or MgO/Al₂O₃ replacements resulted into decreasing the microhardness values. The obtained data of the glass-ceramic specimens were explained in relation to the crystalline phases, microstructure formed and the glassy matrix.     

Estimated immiscibility isotherms of the Li2O-Al2O3-SiO2 system

Using the immiscibility temperature estimation method, recently developed by the present author and Tomozawa, immiscibility isotherms of the Li₂O-Al₂O₃-SiO₂ system were estimated. High reliability of the estimated immiscibility isotherms was confirmed by observing the morphologies of phase-separated glasses, and also by comparing the estimated and observed immiscibility temperatures at several compositions. The determined immiscibility isotherms revealed that, in the Li₂O-Al₂O₃-SiO₂ system, only composition regions near the Li₂O-SiO₂ and Al₂O₃-SiO₂ binary edges are phase-separable. In composition regions where base glasses for commercial glass-ceramics are located, the immiscibility temperatures were much lower than the glass transition temperatures, implying that no phase separation actually occurs. Accordingly the phase separation in practical glasses for producing glass-ceramics may be attributed to increased immiscibility resulting from various additives.     

Morphology and luminescent properties of Al<Superscript>3+</Superscript>/Mg<Superscript>2+</Superscript>-doped Y<Subscript>2</Subscript>O<Subscript>3</Subscript>:Eu<Superscript>3+</Superscript> phosphor

Al³⁺/Mg²⁺ doped Y₂O₃:Eu phosphor was synthesized by the glycine-nitrate solution combustion method. In contrast to Y₂O₃:Eu which showed an irregular shape of agglomerated particles (the mean particle size >10 μm), the morphology of Al³⁺/Mg²⁺ doped Y₂O₃:Eu crystals was quite regular. Al³⁺/Mg²⁺ substituting Y³⁺ in Y₂O₃:Eu resulted in an obvious decrease of the particle size. Meanwhile, higher the Al³⁺/Mg²⁺ concentration, smaller the particle size. In particular, the introduction of Al³⁺ ion into Y₂O₃ lattice induced a remarkable increase of PL and CL intensity. While, for Mg²⁺ doped Y₂O₃:Eu samples, their PL and CL intensities decreased. The reason that causes the variation of PL and CL properties for Al³⁺ and Mg²⁺ doped Y₂O₃:Eu crystals was concluded to be related to sites of Al³⁺ and Mg²⁺ ions inclined to take and the difference of ion charge.     

Keimbildung und kristallwachstum des reaktions-produktes bei festkörperreaktionen: bildung von MgCr2O4 aus den oxiden

If MgO single crystals react with gaseous Cr₂O₃ at temperatures much lower than the eutectic temperature in the system MgOMgCr₂O₄ the epitaxial formation of the spinel MgCr₂O₄ on {001} MgO proceeds by nucleation and crystal growth within a quasi-liquid phase which can be described as a supersaturated solution of spinel in MgO. On a thin coherent spinel layer containing sufficient pores and gaps a quasi-liquid film is formed; this is the matrix for the spinel crystal growth. On thick spinel layers the existence of a Cr₂O₃ film, e.g. an adsorption film, which is a solution of spinel and from which the spinel crystal growth occurs, is discussed.     

Synthesis,characterization and evaluation of bioactivity and antibacterial activity of quinary glass system (SiO2–CaO–P2O5–MgO–ZnO): In vitro study

Bioactive glasses in the systems SiO₂–CaO–P₂O₅–MgO (BGZn0) and SiO₂–CaO–P₂O₅–MgO–ZnO (BGZn5), were prepared by sol–gel method and then characterized. Surface reactivity was studied in simulated body fluid (SBF) to determine the effect of zinc (Zn) addition as a trace element. The effect of Zn addition to the glass matrix on the formation of apatite layer on the glass surface was investigated through X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT–IR) and scanning electron microscopy (SEM). Also, inductively coupled plasma–optical emission spectroscopy (ICP–sOES) was used to determine the concentrations of released ions in SBF solution after different time intervals in SBF solution. The antibacterial activity of Zn containing glass against Pseudomonas aeruginosa was measured by the halo zone test. The presence of Zn in glass composition improved chemical durability, slowed down the formation rate of Ca–P layer and decreased the size of crystalline apatite particles. Zn containing glass exhibited an excellent antibacterial activity against P. aeruginosa which could demonstrate its ability to treat bone infection.     

Periclase solid solutions containing Li+1 and R+3 ions

Recent work on phase equilibria diagrams has shown that periclase can take R⁺³ (Cr⁺³, Al⁺³, and Fe⁺³) in solid solution at elevated temperatures. In order to retain electrical neutrality, 2R⁺³ and a vacancy replaces 3Mg⁺² in the periclase lattices. When Li⁺¹ is added to MgO/R₂O₃ compositions, one Li⁺¹ and one R⁺³ replaces 2 Mg⁺² to form a solid solution which is stable at room temperature. These periclase solid solutions are more stable under conditions of temperature fluctuations and hydration than periclase/R₂O₃ solid solutions without lithia.     

Effect of magnesia on structure, degradability and in vitro bioactivity of CaO-MgO-P2O5-SiO2 system ceramics

CaO-MgO-P₂O₅-SiO₂ system ceramics with various magnesia contents (0, 5, 10 and 20 mol%) were successfully prepared by sintering the sol-gel-derived powder compacts. The ceramic degradation was evaluated through the weight loss in the tris-(hydroxymethyl)-aminomethane and hydrochloric acid (Tris-HCl) buffer solution, and their ability to form apatite was determined by soaking in simulated body fluid (SBF). Results indicated that the ceramics structure was greatly influenced by magnesia contents. New crystal phases of Ca₂MgSi₂O₇ and SiO₂ were formed when magnesia was added and with an increase of magnesia concentration the phase of Ca₂MgSi₂O₇ increased with a simultaneous decline of β-CaSiO₃. In addition, studies showed that magnesia played an important role in affecting the degradability and apatite forming ability of CaO-MgO-P₂O₅-SiO₂ system ceramics. It is observed that with increasing magnesia concentration, the ceramic degradability gradually decreased and the formation of apatite on samples was delayed.     

Preparation of porous glass-ceramics of the TiO2-SiO2 system

Porous glass-ceramics of the TiO₂-SiO₂ system of high titania content have been prepared by heat treatment and subsequent acid leaching of phase-separated glasses of the TiO₂-SiO₂-Al₂O₃-B₂O₃-CaO-MgO (or -Na₂O) system. The porous glass-ceramics obtained in the study had a surface area of 100 to 300 m²g^–1, with an average pore radius of 3 to 9 nm. The ceramics which contained a large amount of anatase and rutile were expected to be applied in the field of photocatalysts.     

Influence of alumina content on the nucleation crystallization and microstructure of barium fluorphlogopite glass-ceramics based on 8SiO2·YAl2O34MgO2MgF2BaO Part I Nucleation and crystallization behaviour

The effect of varying the aluminium oxide content on the nucleation and crystallization behaviour of barium containing glasses based on 8SiO₂·YAl₂O₃4MgO2MgF₂BaO was investigated in order to develop novel, high strength, machinable glass-ceramics. Nine glasses were synthesized and characterized by Differential Scanning Calorimetry (DSC) Combined Differential Thermal Analysis Thermal Gravimetric Analysis (DTA/TGA), X-ray diffraction (XRD) and dilatometry. The glass transition temperature (T _g) and first peak crystallization temperature (Tp1) reduced with reducing alumina content. Glasses with Y > 1.5 exhibited a second peak crystallization temperature (Tp2). Tp1 was shown to correspond to the crystallization of barium fluorphlogopite (BaSi₆Al₂Mg₆F₂O₁₉) and Tp2 to the crystallization of cordierite (Mg₂Al₂Si₅O₁₈). The thermal expansion coefficient (TEC) was insensitive to alumina content. All the glasses exhibited an optimum nucleation temperature just above T _g, which was thought to be a result of amorphous phase separation (APS). DTA/TGA showed the glasses to undergo weight loss corresponding to silicon tetrafluoride volatilization from the surface, which resulted in a fluorphlogopite deficient surface layer.     

Effects of ions dissolved from bioactive glass-ceramic on surface apatite formation

Non-bioactive glass-ceramic A-W(Al) containing apatite and wollastonite in a MgO–CaO–SiO₂–Al₂O₃ glassy matrix did not form an apatite layer on its surface in a simulated body fluid with ion concentrations nearly equal to those of human blood plasma and also in the fluids with small amounts of the calcium and silicate ions added individually, but formed the apatite layer in the fluid with the calcium and silicate ions added simultaneously. This indicates that the calcium and silicate ions dissolved from bioactive glass-ceramic A-W containing the apatite and wollastonite in a MgO–CaO–SiO₂ glassy matrix play a cooperative and important role in forming an apatite layer on its surface in the body, to give the glass-ceramic bioactivity. The calcium ion might increase the degree of the supersaturation of the surrounding body fluid, and the silicate ion might provide favourable sites for nucleation of the apatite on the surfaces of glass-ceramic.     

In vitro biocompatibility study of calcium phosphate glass ceramic scaffolds with different trace element doping

Porous calcium phosphate based glass ceramics (CaO-P₂O₅-Na₂O) containing different trace elements (2.0 mol% Mg, Sr and Zn respectively) were prepared by coating polyurethane foams with sol-gel derived glass slurry. After heat treatment at suitable temperatures, main phase catena hexaphosphate (Ca₄P₆O₁₉) and minor phase calcium pyrophosphate (β-Ca₂P₂O₇) crystallized from the glass matrix. These scaffolds were soaked in simulated body fluid (SBF) to determine the solubility and apatite formation, and mouse MC3T3-E1 cells were used to investigate the bioactivity and biocompatibility. The Sr doped scaffold showed a higher degradability than those samples containing Zn or Mg, inducing the formation of an apatite layer with a high (Sr + Ca)/P molar ratio of 1.64, whereas only some discontinuous CaP layers and spare apatite agglomerates were found on the scaffolds doped with Mg ((Mg + Ca)/P = 1.12) and Zn ((Zn + Ca)/P = 1.55) respectively. In vitro cell culture, a high degree of cell adhesion and spreading was achieved on the samples containing Sr or Zn, while only a few cells adhered to the Mg doped sample. These results implied that the bioactivity and biocompatibility of the scaffolds were not only strongly associated with the apatite forming ability, but also related with the Ca/P molar ratios of the deposits.     

Preparation and studies on surface modifications of calcium-silico-phosphate ferrimagnetic glass-ceramics in simulated body fluid

The structure and magnetic behaviour of 34SiO₂–(45 − x) CaO–16P₂O₅–4.5 MgO–0.5 CaF₂ − x Fe₂O₃ (where x = 5, 10, 15, 20 wt.%) glasses have been investigated. Ferrimagnetic glass-ceramics are prepared by melt quench followed by controlled crystallization. The surface modification and dissolution behaviour of these glass-ceramics in simulated body fluid (SBF) have also been studied. Phase formation and magnetic behaviour have been studied using XRD and SQUID magnetometer. The room temperature Mössbauer study has been done to monitor the local environment around Fe cations and valence state of Fe ions. X-ray photoelectron spectroscopy (XPS) was used to study the surface modification in glass-ceramics when immersed in simulated body fluid. Formation of bioactive layer in SBF has been ascertained using X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). The SBF solutions were analyzed using an absorption spectrophotometer. The magnetic measurements indicated that all these glasses possess paramagnetic character and the [Fe²⁺/Fe³⁺] ions ratio depends on the composition of glass and varied with Fe₂O₃ concentration in glass matrix. In glass-ceramics saturation magnetization increases with increase in amount of Fe₂O₃. The nanostructure of hematite and magnetite is formed in the glass-ceramics with 15 and 20 wt.% Fe₂O₃, which is responsible for the magnetic property of these glass-ceramics. Introduction of Fe₂O₃ induces several modifications at the glass-ceramics surface when immersed in SBF solution and thereby affecting the surface dissolution and the formation of the bioactive layer.