Kinetics and mechanisms of the conversion of silicate (45S5), borate, and borosilicate glasses to hydroxyapatite in dilute phosphate solutions

Bioactive glasses with controllable conversion rates to hydroxyapatite (HA) may provide a novel class of scaffold materials for bone tissue engineering. The objective of the present work was to comprehensively characterize the conversion of a silicate bioactive glass (45S5), a borate glass, and two intermediate borosilicate glass compositions to HA in a dilute phosphate solution at 37°C. The borate glass and the borosilicate glasses were derived from the 45S5 glass by fully or partially replacing the SiO₂ with B₂O₃. Higher B₂O₃ content produced a more rapid conversion of the glass to HA and a lower pH value of the phosphate solution. Whereas the borate glass was fully converted to HA in less than 4 days, the silicate (45S5) and borosilicate compositions were only partially converted even after 70 days, and contained residual SiO₂ in a Na-depleted core. The concentration of Na⁺ in the phosphate solution increased with reaction time whereas the PO₄^3– concentration decreased, both reaching final limiting values at a rate that increased with the B₂O₃ content of the glass. However, the Ca²⁺ concentration in the solution remained low, below the detection limit of atomic absorption, throughout the reaction. Immersion of the glasses in a mixed solution of K₂HPO₄ and K₂CO₃ produced a carbonate-substituted HA but the presence of the K₂CO₃ had little effect on the kinetics of conversion to HA. The kinetics and mechanisms of the conversion process of the four glasses to HA are compared and used to develop a model for the process.     

Bioactive borate glass scaffolds: in vitro and in vivo evaluation for use as a drug delivery system in the treatment of bone infection

The objective of this work was to evaluate borate bioactive glass scaffolds (with a composition in the system Na₂O–K₂O–MgO–CaO–B₂O₃–P₂O₅) as devices for the release of the drug Vancomycin in the treatment of bone infection. A solution of ammonium phosphate, with or without dissolved Vancomycin, was used to bond borate glass particles into the shape of pellets. The in vitro degradation of the pellets and their conversion to a hydroxyapatite-type material in a simulated body fluid (SBF) were investigated using weight loss measurements, chemical analysis, X-ray diffraction, and scanning electron microscopy. The results showed that greater than 90% of the glass in the scaffolds degraded within 1 week, to form poorly crystallized hydroxyapatite (HA). Pellets loaded with Vancomycin provided controlled release of the drug over 4 days. Vancomycin-loaded scaffolds were implanted into the right tibiae of rabbits infected with osteomyelitis. The efficacy of the treatment was assessed using microbiological examination and histology. The HA formed in the scaffolds in vivo, resulting from the conversion of the glass, served as structure to support the growth of new bone and blood vessels. The results in this work indicate that bioactive borate glass could provide a promising biodegradable and bioactive material for use as both a drug delivery system and a scaffold for bone repair.     

Reaction of sodium calcium borate glasses to form hydroxyapatite

This study investigated the transformation of two sodium calcium borate glasses to hydroxyapatite (HA). The chemical reaction was between either 1CaO · 2Na₂O · 6B₂O₃ or 2CaO · 2Na₂O · 6B₂O₃ glass and a 0.25 M phosphate (K₂HPO₄) solution at 37, 75 and 200 °C. Glass samples in the form of irregular particles (125–180 μm) and microspheres (45–90 and 125–180 μm) were used in order to understand the reaction mechanism. The effect of glass composition (calcium content) on the weight loss rate and reaction temperature on crystal size, crystallinity and grain shape of the reaction products were studied. Carbonated HA was made by dissolving an appropriate amount of carbonate (K₂CO₃) in the 0.25 M phosphate solution. X-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy were used to characterize the reaction products. The results show that sodium calcium borate glasses can be transformed to HA by reacting with a phosphate solution. It is essentially a process of dissolution of glass and precipitation of HA. The transformation begins from an amorphous state to calcium-deficient HA without changing the size and shape of the original glass sample. Glass with a lower calcium content (1CaO · 2Na₂O · 6B₂O₃), or reacted at an elevated temperature (75 °C), has a higher reaction rate. The HA crystal size increases and grain shape changes from spheroidal to cylindrical as temperature increases from 37 to 200 °C. Increase in carbonate concentration can also decrease the crystal size and yield a more needle-like grain shape.     

Raman spectroscopic investigation of sodium borosilicate glass structure

Raman spectra of sodium borosilicate glasses with a wide range of Na₂O/B₂O₃ ratios were systematically measured. Variations of the spectra with glass composition were studied to interpret the implied distribution of Na⁺ ions between silicate and borate units. When Na₂O/B₂O₃ is less than 1, all Na⁺ ions are associated with borate units as indicated by the absence of the 1100 cm⁻¹ band of Si-O⁻ non-bridging bond stretching. For the (1−x)Na₂O · SiO₂ ·xB₂O₃ glass withx≦0.4 the peak-height ratio of the 950 cm⁻¹ band to the 1080 cm⁻¹ band was used to analyse semiquantitatively the distribution of the Na⁺ ions between silicate and borate units. Sodium ions are divided between silicate and borate units approximately in proportion to the amount of SiO₂ and B₂O₃ present in these glasses. Some of the high sodium content glasses were crystallized and their spectra were compared with the bulk glass spectra. The distribution of Na⁺ ions in the glass was quite different from their distribution after crystallization. Spectra of high silica glasses that had been heat-treated for phase separation indicated exclusion of borate units from the silica network and the formation of borate groups. For high boron content glasses, no change was observed on heat treatment. Raman bands due to borate groups seem to be little affected by their environments. Also affiliated with the Department of Geosciences.     

Strontium oxide doped quaternary glasses: effect on structure,degradation and cytocompatibility

This preliminary study focuses on the effect of adding SrO to a Ti-containing quaternary phosphate glass system denoted by P₂O₅–Na₂O–CaO–TiO₂. The following four different glass compositions were manufactured: 0.5P₂O₅–0.17Na₂O–0.03TiO₂–(0.3−x)CaO–xSrO where x = 0, 0.01, 0.03 and 0.05. Structural characterisation revealed glass transition temperatures in the range 427–437°C and the presence of sodium calcium phosphate as the dominant phase in all the glasses. Degradation and ion release studies conducted over a 15-day period revealed that the Sr-containing glasses showed significantly higher degradation and ion release rates than the Sr-free glass. Cytocompatibility studies performed over a 7-day period using MG63 cells showed that the addition of 5 mol% SrO yielded glasses with cell viability nearly equivalent to that observed for quaternary TiO₂ glasses.     

Effect of pyrophosphate ions on the conversion of calcium–lithium–borate glass to hydroxyapatite in aqueous phosphate solution

The conversion of glass to a hydroxyapatite (HA) material in an aqueous phosphate solution is used as an indication of the bioactive potential of the glass, as well as a low temperature route for preparing biologically useful materials. In this work, the effect of varying concentrations of pyrophosphate ions in the phosphate solution on the conversion of a calcium–lithium–borate glass to HA was investigated. Particles of the glass (150–355 μm) were immersed for up to 28 days in 0.25 M K₂HPO₄ solution containing 0–0.1 M K₄P₂O₇. The kinetics of degradation of the glass particles and their conversion to HA were monitored by measuring the weight loss of the particles and the ionic concentration of the solution. The structure and composition of the conversion products were analyzed using X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy. For K₄P₂O₇ concentrations of up to 0.01 M, the glass particles converted to HA, but the time for complete conversion increased from 2 days (no K₄P₂O₇) to 10 days (0.01 M K₄P₂O₇). When the K₄P₂O₇ concentration was increased to 0.1 M, the product consisted of an amorphous calcium phosphate material, which eventually crystallized to a pyrophosphate product (predominantly K₂CaP₂O₇ and Ca₂P₂O₇). The consequences of the results for the formation of HA materials and devices by the glass conversion route are discussed.     

Study of lithium–zinc borophosphate glasses

Mixed lithium–zinc borophosphate glasses were prepared and studied in three compositional series xLi₂O–(50−x)ZnO–50P₂O₅, xLi₂O–(50−x)ZnO–10B₂O₃–40P₂O₅ and xLi₂O–(50−x)ZnO–20B₂O₃–30P₂O₅ with x = 0, 10, 20, 30, 40 and 50 mol% Li₂O. The obtained glasses were characterized by the measurements of the density (ρ), molar volume (V _M), glass transition temperature (T _g) and thermal expansion coefficient (α). For the investigation of structural changes ¹¹B and ³¹P MAS NMR and Raman spectroscopy were applied. The replacement of zinc by lithium in borophosphate glasses slightly decreases V _M and T _g, while α increases. In Li–Zn metaphosphate glasses the compositional dependence of T _g reveals a minimum, while at the borophosphate series T _g decreases monotonously with increasing Li₂O content. Chemical stability of Li–Zn borophosphate glasses is very good for glasses with x = 0–30 mol% Li₂O. Spectral studies showed in the glass series with 10 mol% B₂O₃ only the presence of BO₄ sites. In the glasses with 20 mol% B₂O₃ the presence of BO₃ and two BO₄ sites was revealed in ZnO-rich glasses and only one BO₄ site in Li₂O-rich glasses; the number of BO₃ groups decreases with increasing Li₂O content which is ascribed to the formation of P–O–Zn covalent bonds in ZnO-rich glasses.     

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).     

Hollow hydroxyapatite microspheres as a device for controlled delivery of proteins

Hollow hydroxyapatite (HA) microspheres were prepared by reacting solid microspheres of Li₂O–CaO–B₂O₃ glass (106–150 μm) in K₂HPO₄ solution, and evaluated as a controlled delivery device for a model protein, bovine serum albumin (BSA). Reaction of the glass microspheres for 2 days in 0.02 M K₂HPO₄ solution (pH = 9) at 37°C resulted in the formation of biocompatible HA microspheres with a hollow core diameter equal to 0.6 the external diameter, high surface area (~100 m²/g), and a mesoporous shell wall (pore size ≈13 nm). After loading with a solution of BSA in phosphate-buffered saline (PBS) (5 mg BSA/ml), the release kinetics of BSA from the HA microspheres into a PBS medium were measured using a micro bicinchoninic acid (BCA) protein assay. Release of BSA initially increased linearly with time, but almost ceased after 24–48 h. Modification of the BSA release kinetics was achieved by modifying the microstructure of the as-prepared HA microspheres using a controlled heat treatment (1–24 h at 600–900°C). Sustained release of BSA was achieved over 7–14 days from HA microspheres heated for 5 h at 600°C. The amount of BSA released at a given time was dependent on the concentration of BSA initially loaded into the HA microspheres. These hollow HA microspheres could provide a novel inorganic device for controlled local delivery of proteins and drugs.     

Crystal structure and methane oxidation on perovskite-type (La<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Nd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>)CoO<Subscript>3</Subscript> synthesized using citric acid

Perovskite-type (La_1−x Nd _x )CoO₃ was synthesized using citric acid at 700 °C. The Rietveld method indicated that the crystal structure changed from a rhombohedral to an orthorhombic system at x = 0.4. The Co–O distance of the rhombohedral structure connected continuously with the average Co–O(2) distance of the orthorhombic structure, and the Co–O–Co angle of the rhombohedral structure and the Co–O(2)–Co angle of the orthorhombic structure were continuous. The average particle size of the samples was approximately 55 nm. CH₄ oxidation started above 300 °C, and the temperature corresponding to the 50% conversion (T _1/2) of CH₄ increased linearly with increases in x. It is considered that the amount of adsorbed oxygen decreased in response to the steric hindrance, and that T _1/2 increased as a result.     

Dielectric properties and microstructure of TiO2 modified (ZnMg)TiO3 microwave ceramics with CaO–B2O3–SiO2

The low-fired (ZnMg)TiO₃–TiO₂ (ZMT–TiO₂) microwave ceramics using low melting point CaO–B₂O₃–SiO₂ as sintering aids have been developed. The influences of Mg substituted fraction on the crystal structure and microwave properties of (Zn_1−x Mg _x )TiO₃ were investigated. The result reveals that the sufficient amount of Mg (x ≥ 0.3) could inhibit the decomposition of ZnTiO₃ effectively, and form the single-phase (ZnMg)TiO₃ at higher sintering temperatures. Due to the compensating effect of rutile TiO₂ (τ_f = 450 ppm/°C), the temperature coefficient of resonant frequency (τ_f) for (Zn_0.65Mg_0.35)TiO₃–0.15TiO₂ with biphasic structure was adjusted to near zero value. Further, CaO–B₂O₃–SiO₂ addition could reduce the sintering temperature from 1150 to 950 °C, and significantly improve the sinterability and microwave properties of ZMT–TiO₂ ceramics, which is attributed to the formation of liquid phases during the sintering process observed by SEM. The (Zn_0.65Mg_0.35)TiO₃–0.15TiO₂ dielectrics with 1 wt% CaO–B₂O₃–SiO₂ sintered at 950 °C exhibited the optimal microwave properties: ε ≈ 25, Q × f ≈ 47,000 GHz, and τ_f ≈ ± 10 ppm/°C.     

Evaluation of hydroxyapatite microspheres made from a borate glass to separate protein mixtures

A hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂), transformed from a calcium-containing borate glass, has been investigated for its protein adsorption and chromatographic characteristics. Microspheres of the borate glass were transformed into HA by reacting them with a 0.25 M phosphate (K₂HPO₄) solution for 24 h at 37 °C (pH 9.0). The HA microspheres with a diameter of 45–90 μm were hand packed into a steel column (4.6 mm × 80 mm) and used to separate a binary protein mixture of bovine serum albumin (BSA) and lysozyme. HA microspheres, with a diameter <45 μm, were used for separating a protein mixture of BSA, myoglobin, and lysozyme. These microspheres had a diameter that was 20–30 times larger than commercial HA column packing spherical particles, 2–3 μm, but these microspheres had a six times larger surface area and a more uniform spherical shape. These advantages compensated for their larger size and the separation results were comparable to those commercially available HA columns in the separation of the proteins studied. These unique HA microspheres, made from microspheres of a borate glass, are considered to be useful as packing materials for protein separation in chromatography.     

Glasses and glass-ceramics in the SrO–TiO2–Al2O3–SiO2–B2O3 system and the effect of P2O5 additions

The glass formation abilities of various compositions in SrO–TiO₂–Al₂O₃–SiO₂, SrO–TiO₂–B₂O₃–SiO₂, SrO–TiO₂–Al₂O₃–B₂O₃, and SrO–TiO₂–Al₂O₃–SiO₂–B₂O₃ systems were studied. Many new compositions were found to be suitable for the casting of crack-free, optically clear glasses of different color and with glass transition temperatures ranging from 595 to 775 °C. The crystallization behavior, structure, and thermal expansion behavior of selected glasses were analyzed by DTA, XRD, dilatometry, and heat treatment. The effect of P₂O₅ on the glass structure and crystallization behavior was also studied. P₂O₅ played a dual role depending on composition. In some glasses it acted as a nucleating agent while in others it suppressed crystallization. Heat treatment of borate and borosilicate glasses transformed them into glass-ceramics while comparable SrO–TiO₂–Al₂O₃–SiO₂ glasses showed a lower tendency to crystallize and form glass-ceramics under the same conditions.     

Evidence for a threshold in the biosolubility of aluminosilicate vitreous fibers

Two series of aluminosilicate glasses have been synthesized with the nominal composition (64 − x) SiO₂–x Al₂O₃–36 Na₂O/CaO with x varying from 9 to 19 mol%. They have been corroded in static conditions in a solution that mimics in a simplified manner the intracellular medium of the lung alveolar macrophages (37 °C, pH 4.6, citric acid). The original and corroded glasses have been studied by ²⁷Al and ²⁹Si MAS NMR. Both series display a sharp increase in the silicon dissolution rate with the alumina content. The glass network dissolves extremely slowly, whereas the release of excess sodium is very fast, for the glasses with low alumina content. On the opposite, the glasses with high alumina content dissolve much more rapidly in a nearly congruent manner. The crossover between the two behaviors occurs for x = 13, which corresponds to 33% of aluminum in the glass-former network. The sharp crossover from slow to fast network dissolution is explained in terms of connectivity of the silica sub-network. Above a certain amount of alumina, the silicon sub-network is no more percolating and the corroded glass breaks up into colloids. The sharpness of the transition and the relatively low alumina content required for fast dissolution are related to a structural feature of the aluminosilicate glasses, namely the aluminum self-avoidance that decreases the connectivity of the silica sub-lattice.     

IR study of Pb-Sr titanate borosilicate glasses

The infrared spectra (IR) of various glass compositions in the glass system, [(Pb _x Sr_1−x )O·TiO₂]-[2SiO₂·B₂O₃]-[BaO·K₂O]-[La₂O₃], were recorded over a continuous spectral range (400–4000 cm⁻¹) to study their structure systematically. IR spectrum of each glass composition shows a number of absorption bands. These bands are strongly influenced by the increasing substitution of SrO for PbO. Various bands shift with composition. Absorption peaks occur due to the vibrational mode of the borate network in these glasses. The vibrational modes of the borate network are seen to be mainly due to the asymmetric stretching relaxation of the B-O bond of trigonal BO₃ units. More splitting is observed in strontium-rich composition.     

Crystallization characteristic and properties of some zinc containing soda lime silicate glasses

The crystallization behaviour of some soda lime silicate glasses modified by ZnO/CaO replacement to give the composition (Na₂O)₂·CaO_1−x ·(ZnO) _x ·3SiO₂ (x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0) have been investigated using differential scanning calorimetry (DSC) and X-ray diffraction analysis (XRD). The thermal expansion coefficients and AC electrical properties in the frequency range 40 Hz–5 MHz of the obtained crystalline products were determined. Two forms of sodium calcium silicate (Na₄CaSi₃O₉ & Na₂Ca₂Si₃O₉), sodium metasilicate-Na₂SiO₃, two types of sodium zinc silicate (Na_1.31Zn_0.655Si_1.345O₄ & Na₂ZnSiO₄) and α-quartz phases were mostly developed in the crystallized glasses using various heat-treatment processes. The coefficient of thermal expansion of the obtained glass–ceramic materials are between 120 × 10⁻⁷°K⁻¹ and 168 × 10⁻⁷°K⁻¹ in the 25°–600 °C temperature range. The increase of frequency generally resulted in the increase of the conductivity and decrease the dielectric constant together with the loss tangent of the glass–ceramic materials.     

Development of nano-macroporous soda-lime phosphofluorosilicate bioactive glass and glass-ceramics

We have extended the usefulness of bioactive glass-ceramics for the repair and reconstruction of hard tissues by introducing F ions that are known to be beneficial, especially in dentistry. Nano-macro multimodal porosity in soda-lime phosphofluorosilicate bulk samples was introduced by the recently developed melt-quench-heat-etch method. The choice of starting glass composition is based on 48SiO₂–2.7P₂O₅–xCaF₂–yCaO–zNa₂O where x = 0, 1, 4, 8, 10, 12, and (y + z) = 49.3 − x (mol%). The effect of thermal and chemical treatment on the microstructure of samples is characterized by SEM, XRD and EDX. We find the formation of many crystalline phases, but mainly sodium calcium silicate, calcium phosphate, fluorapatite and calcium silicate. The bioactivity of soda-lime phosphofluorosilicate glass-ceramics is assessed by monitoring the formation of hydroxyl apatite (HA) layer: fluorapatite phase accelerates the rate of HA layer formation; the initial composition and multi-modal porosity are other key parameters that impact the formation of HA. The present porous glass-ceramics should be superior candidates for use in dental bone regeneration.

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Ultrasonic velocity in sodium borate glasses

Ultrasonic velocities in sodium borate glasses are measured as a function of composition at a frequency of 10 MHz and at a temperature of 298 K by making use of the ultrasonic pulse echo overlap method. Elastic properties of these glasses are analysed in terms of the elastic internal energy due to deformation; elastic resistances of the network-former, B₂O₃, and the modifier, Na₂O, are obtained as a function of composition from the plot ofMV ² againstx ₂, whereM is the molar mass of sodium borate glasses,V the velocity of sound andx ₂ the mole fraction of Na₂O. The elastic resistances of B₂O₃ and Na₂O are as follows: (i) forx ₂<0.33, the elastic resistance of B₂O₃ is smaller than that of Na₂O; (ii) atx ₂=0.33, the elastic resistances of B₂O₃ and Na₂O are equal; (iii) forx ₂>0.33, the elastic resistance of B₂O₃ is greater than that of Na₂O; (iv) atx ₂≈0.15, the elastic resistances of B₂O₃ and Na₂O become respectively maximal and minimal; (v) atx ₂≈0.23, the elastic resistances of B₂O₃ and Na₂O become respectively minimal and maximal; (vi) abovex ₂=0.36, the elastic resistance of Na₂O becomes negative.     

Structure and dielectric/piezoelectric properties of LiNbO3-doped BiScO3–PbTiO3 ceramics with morphotropic phase boundary composition

0.02LiNbO₃–0.98{(1 − x)BiScO₃–xPbTiO₃} (2LN–BS–xPT) ceramics near the morphotropic phase boundary (MPB) were investigated. MPB region of 2LN–BS–xPT ceramics was identified to be in the composition of 0.62 < x ≤ 0.64. The coexistence of the tetragonal domain structure and a polar microdomain structure was observed by transmission electron microscope for x = 0.64. It is found that 2LN–BS–xPT ceramics (x = 0.64) showed good piezoelectric and ferroelectric properties with piezoelectric constant d ₃₃ about 505 pC/N, planar electromechanical coupling factors k _p about 0.47, and remnant polarization P _r about 40 μC/cm², respectively, while T _max is about ~350–400 °C. The high-temperature relaxation behavior was also studied in 2LN–BS–xPT ceramics. Effects of thermal depoling on the piezoelectric properties of 2LN–BS–xPT ceramics indicated good thermal stability before 300 °C for x = 0.62 and 0.64.     

Glasses formation,characterization, and crystal-structure determination in the Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>–Sb<Subscript>2</Subscript>O<Subscript>3</Subscript>–TeO<Subscript>2</Subscript> system prepared in an air

A glass-forming domain is found and studied within Bi₂O₃–Sb₂O₃–TeO₂ system. The glasses composition were obtained in pseudo-binary xSbO_1.5, (1−x)TeO₂ for 0.05 ≤ x ≤ 0.20. The constitution of glasses in the system Sb₂O₃–TeO₂ was investigated by DSC, Raman, and Infrared spectroscopy. The influence of a gradual addition of the modifier oxides on the coordination geometry of tellurium atoms has been elucidated based Infrared and Raman studies and showed the transition of TeO₄, TeO₃₊₁, and TeO₃ units with increasing Sb₂O₃ content. XRD results reveal the presence of three crystalline: γ-TeO₂, α-TeO₂, and SbTe₃O₈ phases during the crystallization process. The density of glasses has been measured. The investigation in the ternary system by the solid state reaction using XRD reveals the existence of a solid solution Bi_1−x Sb_1−x Te_2x O₄ isotopic to BiSbO₄ with 0 ≤ x ≤ 0.1.