Kinetics and mechanisms of converting bioactive borate glasses to hydroxyapatite in aqueous phosphate solution

Borate bioactive glasses are receiving increasing attention as scaffold materials for bone repair and regeneration. In this study, the kinetics and mechanisms of converting three groups of sodium–calcium–borate glasses with varying CaO:B₂O₃ ratio to hydroxyapatite (HA) in 0.25 M K₂HPO₄ solution were investigated at 10–70 °C. Glass disks with the composition 2Na₂O·(2 − x)CaO·(6 + x)B₂O₃ (x = 0, 0.5, and 1.0) were immersed for up to 8 days in the potassium phosphate solution. The conversion kinetics to HA were monitored by measuring the weight loss of the glass, while X-ray diffraction, scanning electron microscopy, and Fourier transform infrared spectroscopy were used to study structural and compositional changes. All three groups of glasses formed HA on their surfaces, showing that the glasses were bioactive. At 10–37 °C, the conversion kinetics was well fitted by the contracting sphere model. Also, the contracting sphere model has a good fit for the early stage of conversion at 70 °C, whereas a three-dimensional (3D) diffusion model provided a good fit to the data of the later stage. The results of this study provide kinetic and structural data for the design of borate bioactive glasses for potential applications in bone tissue engineering.     

Conversion of melt-derived microfibrous borate (13-93B3) and silicate (45S5) bioactive glass in a simulated body fluid

Microfibrous bioactive glasses are showing a considerable capacity to heal soft tissue wounds, but little information is available on the mechanism of healing. In the present study, the conversion of microfibrous borate bioactive glass (diameter = 0.2–5 μm) with the composition designated 13-93B3 (5.5 Na₂O, 11.1 K₂O, 4.6 MgO, 18.5 CaO, 3.7 P₂O₅, 56.6 B₂O₃ wt%) was evaluated in vitro as a function of immersion time in a simulated body fluid (SBF) at 37 °C using structural and chemical techniques. Silicate 45S5glass microfibers (45 SiO₂, 24.5 Na₂O, 24.5 CaO, 6 P₂O₅ wt%) were also studied for comparison. Microfibrous 13-93B3 glass degraded almost completely and converted to a calcium phosphate material within 7–14 days in SBF, whereas >85 % of the silica remained in the 45S5 microfibers, forming a silica gel phase. An amorphous calcium phosphate (ACP) product that formed on the 13-93B3 microfibers crystallized at a slower rate to hydroxyapatite (HA) when compared to the ACP that formed on the 45S5 fibers. For immersion times >3 days, the 13-93B3 fibers released a higher concentration of Ca into the SBF than the 45S5 fibers. The fast and more complete degradation, slow crystallization of the ACP product, and higher concentration of dissolved Ca in SBF could contribute to the capacity of the microfibrous borate 13-93B3 glass to heal soft tissue wounds.     

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.     

Preparation of hollow hydroxyapatite microspheres

The preparation of hollow hydroxyapatite (HA) microspheres as potential drug-delivery vehicles was investigated. A lithium-calcium-borate (10Li₂O-15CaO-75B₂O₃) (mol%) glass, made by fusing the components at 1100°C for 1 h, was ground to a powder and passed through a flame at ∼1400°C to spheroidize the particles. The resulting glass microspheres (106–125 μm in diameter) were reacted in 0.25 M K₂HPO₄ solution for 5 days at 37°C and pH 10–12, resulting in the formation of porous, hollow microspheres of a calcium phosphate (Ca-P) material with external diameters similar to those of the original glass particles. Heat treatment at 600°C for 4 h partially converted the Ca-P material to HA, as confirmed by X-ray diffraction, and also increased the strength of the hollow microspheres.     

Surface degradation behaviour of sodium borophosphate glass in aqueous media: Some studies

The degradation behaviour of phosphate glass with nominal composition, 40Na₂O-10BaO-xB₂O₃-(50-x)P₂O₅, where 0 ≤ x ≤ 20 mol%, was studied in water, HCl and NaOH solutions at room temperature to 60°C for different periods extending up to 300 h. These glasses were synthesized by conventional melt-quench technique. Dissolution rates were found to increase with B₂O₃ content in the glass. The dissolution rates for the glass having 10 mol% B₂O₃ were found to be 0·002 g/cm² and 0·015 g/cm² in distilled water and 5% NaOH solution, respectively, at room temperature after 225 h of total immersion period, whereas it increased considerably to 0·32 g/cm² in 5% NaOH at 60°C after 225 h. However, glass samples with x = 15 and 20 mol% B₂O₃ were dissolved in 5% HCl solution after 5 h immersion. The degradation behaviour has been correlated with the structural features present in the glass. The optical microscopy of the corroded surface revealed that the corrosion mechanism were different in acid and alkali media.     

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.     

Phase development and sintering behaviour of biphasic HA-TCP calcium phosphate materials prepared from hydroxyapatite and bioactive glass

The composites of hydroxyapatite (HA) with 2.5 and 5 wt% of a double oxide (50 mol% CaO and 50 mol% P₂O₅) glass were prepared using the conventional powder mixing and sintering method. The addition of the glass significantly enhanced the decomposition process of HA into alpha tricalcium phosphate (α-TCP) for bodies sintered at 1,300 and 1,350 °C and β-TCP phases for the ones sintered at 1,200, 1,250 and 1,300 °C. Microstructural characteristics, phase development and thermal behaviour were studied by SEM, XRD and STA. The effects of TCP phase content and phase transformation from β-TCP to α-TCP on the sintering are discussed. The characterizations revealed considerable content of TCP in the form of large semi-islands due to important reactions between the fine HA and the glass mixed powders.     

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.     

Characterization of sintered titanium/hydroxyapatite biocomposite using FTIR spectroscopy

Fourier transform infrared (FTIR) spectroscopy was employed to characterize the phase changes of hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂, HA) in a titanium/HA biocomposite during sintering. The effects of sintering temperature and the presence of Ti on the decomposition of HA were examined. It was observed that pure HA was stable in argon atmosphere at temperatures up to 1,200°C, although the dehydroxylation of pure HA was promoted by the increase in sintering temperature. In the Ti/HA system, on the other hand, the presence of Ti accelerated dehydroxylation and the decomposition of HA was detected at a temperature as low as 800°C. Tetracalcium phosphate (Ca₄P₂O₉, TTCP) and calcium oxide (CaO) were the dominant products of the decomposition, but no tricalcium phosphate (Ca₃(PO₄)₂, TCP) was detected due to phosphorus diffusion and possible reactions during the thermal process. The main decomposed constituents of HA in Ti/HA system at high temperatures (≥1,200°C) would be CaO and amorphous phases.     

A study on the phase transformation of the nanosized hydroxyapatite synthesized by hydrolysis using in situ high temperature X-ray diffraction

The biodegradable hydroxyapatite (HA) was synthesized by hydrolysis and characterized using high temperature X-ray diffraction (HT-XRD), differential thermal analysis and thermogravimetry (DTA/TG), and scanning electron microscopy (SEM). The in situ phase transformation of the HA synthesized from CaHPO₄·2H₂O (DCPD) and CaCO₃ with a Ca / P = 1.5 in 2.5 M NaOH_(aq) at 75 °C for 1 h was investigated by HT-XRD between 25 and 1500 °C. The HA was crystallized at 600 °C and maintained as the major phase until 1400 °C. The HA steadily transformed to the α-tricalcium phosphate (α-TCP) which became the major phosphate phase at 1500 °C. At 700 °C, the minor CaO phase appeared and vanished at 1300 °C. The Na⁺ impurity from the hydrolysis process was responsible for the formation of the NaCaPO₄ phase, which appeared above 800 °C and disappeared at 1200 °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.     

Macroporous calcium phosphate glass-ceramic prepared by two-step pressing technique and using sucrose as a pore former

Macroporous calcium phosphate glass-ceramic with an initial glass composition of 60CaO ⋅ 30P₂O₅⋅ 3TiO₂⋅ 7Na₂O in mol% was successfully prepared by sintering the mixture compact consisting of calcium phosphate glass and sucrose powders, which was formed using a two-step pressing technique. After burning off the sucrose phase, a 3D interconnected macroporous structure was formed in the sintered body, in which the skeleton consisting of the calcium phosphate glass-ceramic (including β -calcium pyrophosphate and β -tricalcium phosphate as the crystalline phases) was transformed from the initial glass during the sintering. The macropores with several hundred microns in diameter and the large interconnection size (∼ 100 μ m), which result from the controllably large-sized sucrose particles and the hot-pressing at a little higher temperature than the sucrose’s melting point, are believed to meet the requirements for cell adhesion and bone tissue regeneration well. Moreover, in vitro dissolution behavior study indicates that the calcium phosphate glass-ceramic is soluble to an acetic acid solution of pH 5–7. These, together with the simplicity and feasibility of the innovative fabrication method itself, show that the formed porous glass-ceramic has a promising potential for application to a scaffold for bone tissue engineering.     

Dielectric and microstructural behaviour of strontium titanate borosilicate glass ceramic system

65(SrO·TiO₂)−35(2SiO₂·B₂O₃) wt% glass was synthesized. Differential thermal analysis study shows one exothermic peak which shifts towards higher temperature with increasing heating rate. Glass ceramics prepared by controlled crystallization of strontium titanate borosilicate glass produce uniform distribution of crystallites in a glassy matrix. Attempt was made to crystallize strontium titanate phase in this glass ceramic. Different phases precipitated out during ceramization have been identified by X-ray diffraction. It appears that due to high reactivity of SrO with B₂O₃, strontium borate crystallizes as principal phase followed by TiO₂ (rutile) and Sr₃Ti₂O₇ phases. Dielectric constant of these glass ceramics was observed to be more or less temperature independent over wide range of temperatures with low values of dielectric constant and dissipation factor.     

Precipitation of calcium apatite from boroaluminophosphate glass

For fabricating glass ceramics containing calcium apatite as the major phase, a series of glasses of composition 50[xCaO-(1−x)P₂O₅]-25Al₂O₃-25B₂O₃ (mol%; 0.667 <x< 0.773) were heat-treated at various temperatures. X-ray diffraction and DTA study indicated that calcium apatite is precipitated at about 725°C from all glasses but it is decomposed to β-tricalcium phosphate at about 900°C. AlPO₄ is found as the major phase for the lower CaO content. Dependence of the precipitated phases on the glass composition is tentatively interpreted in relation to the glass structure.     

Synthesis and dissolution behaviour of CaO/SrO-containing sol–gel-derived 58S glasses

The effect of the substitution of strontium for calcium in the tertiary the SiO₂–CaO–P₂O₅ sol–gel bioactive glass 58S (60SiO₂·36CaO·4P₂O₅, mol%) on its structure and its chemical durability on soaking in simulated body fluids was investigated. 58S was selected as a starting composition, and substitution for calcium was carried out from 0 to 100% with an increment of 25%. A novel phosphate source of diethylphosphatoethyltriethoxysilane, which consists of Si and P connected with ethylene group, was used in this work. XRD and FTIR showed that the gels obtained following drying at 130 °C had a typical sol–gel structure, where a continuous amorphous silica gel network and surface bound mineral salts of Ca(NO₃)₂ and Sr(NO₃)₂. Once the gels were heat stabilised to decompose nitrates and incorporate the cations into the network, samples containing Sr formed a strontium silicate crystalline phase. With increasing levels of Sr in the composition, the overall crystallinity of the glass–ceramic increased, while, at the maximum substitution of 100% SrO, macroscopic phase separation was observed, characterised by needle-like crystals of strontium apatite (Sr₅(PO₄)₃OH) and strontium silicate (Sr₂SiO₄) phases in addition to amorphous regions. Dissolution experiments in Tris-buffered solution showed Sr successfully released into the media even though it existed as a crystalline phase in the glass–ceramic. Further, the glass–ceramics induced nucleation and growth of carbonated hydroxyapatite (HA) on their surface suggesting potential bioactivity of the materials. At higher substitutions (75 and 100% SrO for CaO), HA nucleation was not found to occur this may have been due to low amount of phosphate released from the original glass–ceramic as a result of it being locked up in the strontium apatite phase.     

Near net-shape fabrication of hydroxyapatite glass composites

Near net-shape fabrication of hydroxyapatite (HA) glass composites has been attempted by infiltrating a glass into porous HA performs. Main efforts were put to develop glasses that are chemically compatible with HA at elevated temperatures. After extensive investigations in the phosphate and borosilicate systems, glasses of (50-55)SiO₂-(20-25)B₂O₃-(10-20)Li₂O-(0-6)CaO (wt%) composition were successfully developed. The glass shows good chemical compatibility with HA at elevated temperatures. Dense HA/glass composites can be fabricated at 850–950 C by the melt infiltration process. Investigations demonstrated a good near net-shape capability of the process, where the linear shrinkage induced by the infiltration process is less than 0.1%. Preliminary mechanical tests showed that the fracture strength and toughness of the infiltrated HA/glass composite are comparable with dense HA.     

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.     

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.     

Synthesis of nanoparticle zinc phosphate dihydrate by solid state reaction at room temperature and its thermochemical study

Nanoparticle zinc phosphate dihydrate was prepared by solid-state reaction at ambient temperature from Na₃PO₄·12H₂O and ZnSO₄·7H₂O, and characterized by X-ray, Raman, FT-IR spectra and TEM. Thermochemical study was performed by a RD496-III microcalorimeter at 298.15 K. The results reveal that the obtained product is Zn₃(PO₄)₂·2H₂O with spherical shape and particle size is between 40–50 nm. The standard enthalpy value for above reaction is calculated as − 45.793 kJ·mol^− 1. The standard enthalpy of formation for zinc phosphate dihydrate is recommended as − 3788.607 kJ·mol^− 1.     

Effect of 1 wt% CoO addition on dielectric and microstructural behaviour of (SrO·TiO2)-(2SiO2·B2O3) glass and glass ceramic

Glass of the nominal composition 64 wt%(SrO·TiO₂)·35 wt%(2SiO₂·B₂O₃)-1 wt%(CoO) was prepared. The glass samples were subjected to heat treatment at 900 and 950 C. The phase progression in these glass ceramics from X-ray diffraction studies shows the formation of Sr₂B₂O₅ as primary crystalline phase followed by rutile (TiO₂), Sr₃Ti₂O₇, SrB₂Si₂O₈ and Sr₃B₂SiO₈ as secondary phases. The first DTA exothermic peak of glass corresponds to the crystallization of Sr₂B₂O₅, rutile and Sr₃Ti₂O₇ phase while second crystallization peak may be assigned to the formation of SrB₂Si₂O₈ and Sr₃B₂SiO₈ phases. From microstructure studies we find that strontium borate grows with larger grain size whereas the other phases like Sr₃Ti₂O₇, TiO₂ appear smaller in size. Cobalt oxide content in the strontium titanate borosilicate glass ceramic gives the thermal stability to dielectric behaviour and decreases the dielectric loss. Paper presented at the poster session of MRSI AGM VI, Kharagpur, 1995