I. V. Fadeeva

Solid solution formation at the sintering of hydroxyapatite–fluorapatite ceramics

Abstract Fluorhydroxyapatite ceramics are increasingly studied for the use as biomaterials due to their good integration ability in the bone tissue and higher resorption resistance compared to the common hydroxyapatite (HA) ceramics. This study is aimed at the X-ray diffraction investigation of the interaction between HA and fluorapatite (FA) particulates in the sintering temperature range up to 1300 °C. The lattice parameters were calculated in dependence of both the FA content in the powder mixtures and the sintering temperature. From those data, the solid solution formation is concluded, at least in the temperature range from 1200 to 1300 °C. Energy-dispersive X-ray microanalysis confirmed the fluorine distribution to be almost uniform in the sintered at 1300 °C ceramics.

Environment Effect on the Strength of Hydroxy- and Fluorohydroxyapatite Ceramics

The effect of partial fluoride-ion substitution for hydroxy groups on the stability of hydroxyapatite ceramics toward delayed fracture is studied in three media: air, water, and a solution modeling saliva. The stability toward delayed fracture is assessed in dynamic fatigue tests. The results are used to evaluate the exponent in the relation between the rate of subcritical crack propagation and the stress intensity factor, which characterizes the stability of the material toward delayed fracture. The composition of the environment is found to have a significant effect on the resistance to delayed fracture and the average strength of the material. The introduction of fluorine into hydroxyapatite ceramics slightly enhances their stability to delayed fracture and, in addition, notably increases their average strength.

Stabilization of Carbonate Hydroxyapatite by Isomorphic Substitutions of Sodium for Calcium

Carbonate hydroxyapatite (CHA) is an analogue of the mineral component of bone tissue. Synthetic CHA is thermally unstable: it readily decomposes with carbon oxide evolution when sintered to ceramics. Its thermal stability has been studied as affected by partial isomorphic substitution of sodium for calcium intended to compensate a possible charge imbalance induced by CO32− groups. Investigative tools were thermogravimetry and FTIR spectroscopy of the condensed vapor produced by heating CHA samples doped with 0.4 and 0.8 wt % sodium. Sodium does not improve the thermal stability of CHA: weight loss on heating increases with increasing sodium level; evolution of carbon oxides occurs at lower temperatures and more intensively. Sodium enhances the generation of B-type defects (CO32− → PO43− substitutions); these defects are thermodynamically less stable than AB-type defects (2CO32− → PO43−, OH− substitutions), which are characteristic of sodium-free CHA.

Effect of the concentration of carbonate groups in a carbonate hydroxyapatite ceramic on its in vivo behavior

Carbonate-substituted hydroxyapatites containing up to 9 wt % of carbonate groups were synthesized and fabricated in the form of porous granules with a view to developing materials for use in bone tissue repairs. The use of sintering additives forming a liquid phase allowed the granule sintering temperature to be reduced by 400–450°C. It was found that the carbonate groups enter into the structure of the ceramic by a mixed AB-type substitution; the microstructure of the granules depends substantially on the concentration of the carbonate groups; introduction of 6 wt % of carbonate groups into apatite ensures high biological properties of the granules in experiments in vivo.

Hydroxyapatite of platelet morphology synthesized by ultrasonic precipitation from solution

Hydroxyapatite (HA) synthesis by precipitation with urea from aqueous solutions of calcium nitrate and ammonium hydrogenphosphate is studied. Ultrasonication during the synthesis decreases the size of platelet HA crystals from several micrometers to 200–300 nm. At low calcium concentrations in solution, the crystallizing phase is carbonate-hydroxyapatite, whereas at high calcium concentrations, octacalcium phosphate (OCP) precedes hydroxyapatite crystallization.

Phase Development During Setting and Hardening of a Bone Cement Based on α-Tricalcium and Octacalcium Phosphates

In this study, the phase development in the cement system α-TCP–OCP with phosphoric acid as a setting liquid was studied. The most promising formulation of α-TCP (60 wt%) and OCP (40 wt%) is proposed. This cement has the following characteristics: setting time 10 min, pH = 6.7, the compressive strength about 30 MPa, and high dissolution rate in an isotonic solution; the final wt% composition of α-TCP/DCPD/HA/OCP equals 27/38/20/15. Energy dispersive X-ray diffraction techniques were used for in situ monitoring of the processes taking place in the cement in real time.

Synthesis of composite biomaterials in the hydroxyapatite-calcite system

New medical engineering processes for repair of human bone tissue damaged upon diseases or injury are based on implanting porous scaffolds made of bio� compatible materials with cultivated osteoforming cells into the defect site [1–5]. With time, this struc� ture is replaced by bone tissue formed de novo. Apart from biocompatibility with the body, the requirements to the scaffold material include also time coherence between the resorption and the formation of a new bone tissue. Materials based on calcium phosphates, especially hydroxyapatite (HA), which is analogous in the chemical and phase composition to the mineral component of bone tissue, is best suited for this pur� pose. However, HA is the calcium phosphate most resistant to resorption. The resorption kinetics can be controlled by introducing a second, more soluble phase to the HA. To this end, composite materials in the HA–tricalcium phosphate system were developed [4, 5]; however, these materials still suffer from a num�

Silicon-containing hydroxylapatite nanopowders

Silicon-substituted hydroxylapatite nanopowders containing 0.14–1.4 wt % Si have been synthesized by the heterophase reaction between calcium hydroxide, diammonium hydrogen phosphate, tetraethoxysilane, and water and by precipitation from aqueous solutions of calcium nitrate, diammonium hydrogen phosphate, and tetraethoxysilane. The products have been characterized by specific surface area (SBET) measurements, X-ray powder diffraction, chemical analysis, and IR spectroscopy. The phase composition of the products depends on the synthesis method. The heterophase reaction yields nanopowders with SBET = 20–24 m2/g in which the main crystalline phase is silicon-substituted hydroxylapatite. The product synthesized by precipitation from solution has an SBET of up to 73 m2/g and an increased tricalcium phosphate content, which crystallizes from the amorphous phase during heat treatment.

The Bone Building Blues: Self-hardening copper-doped calcium phosphate cement and its in vitro assessment against mammalian cells and bacteria

A blue calcium phosphate cement with optimal self-hardening properties was synthesized by doping whitlockite (β-TCP) with copper ions. The mechanism and the kinetics of the cement solidification process were studied using energy dispersive X-ray diffraction and it was found out that hardening was accompanied by the phase transition from TCP to brushite. Reduced lattice parameters in all crystallographic directions resulting from the rather low (1:180) substitution rate of copper for calcium was consistent with the higher ionic radius of the latter. The lower cationic hydration resulting from the partial Ca→Cu substitution facilitated the release of constitutive hydroxyls and lowered the energy of formation of TCP from the apatite precursor at elevated temperatures. Addition of copper thus effectively inhibited the formation of apatite as the secondary phase. The copper-doped cement exhibited an antibacterial effect, though exclusively against Gram-negative bacteria, including E. coli, P. aeruginosa and S. enteritidis. This antibacterial effect was due to copper ions, as demonstrated by an almost negligible antibacterial effect of the pure, copper-free cement. Also, the antibacterial activity of the copper-containing cement was significantly higher than that of its precursor powder. Since there was no significant difference between the kinetics of the release of copper from the precursor TCP powder and from the final, brushite phase of the hardened cement, this has suggested that the antibacterial effect was not solely due to copper ions, but due to the synergy between cationic copper and a particular phase and aggregation state of calcium phosphate. Though inhibitory to bacteria, the copper-doped cement increased the viability of human glial E297 cells, murine osteoblastic K7M2 cells and especially human primary lung fibroblasts. That this effect was also due to copper ions was evidenced by the null effect on viability increase exhibited by the copper-free cements. The difference in the mechanism of protection of dehydratases in prokaryotes and eukaryotes was used as a rationale for explaining the hereby evidenced selectivity in biological response. It presents the basis for the consideration of copper as a dually effective ion when synergized with calcium phosphates: toxic for bacteria and beneficial for the healthy cells.

Preparation of octacalcium phosphate from calcium carbonate powder

We have studied a process for the preparation of apatite precursors through calcium carbonate conversion into dicalcium phosphate dihydrate, which is then hydrolyzed to octacalcium phosphate. The process enables the preparation of both phase-pure octacalcium phosphate and calcium phosphate mixtures with variable dicalcium phosphate dihydrate : octacalcium phosphate and hydroxyapatite : octacalcium phosphate ratios.