Mesoporous hydroxyapatite (HA) and iron(III)-doped HA (Fe-HA) are attractive materials for biomedical, catalytic, and environmental applications. In the present study, the nanopowders of HA and Fe-HA with a specific surface area up to 194.5 m2/g were synthesized by a simple precipitation route using iron oxalate as a source of Fe3+ cations. The influence of Fe3+ amount on the phase composition, powders morphology, Brunauer–Emmett–Teller (BET) specific surface area (S), and pore size distribution were investigated, as well as electron paramagnetic resonance and Mössbauer spectroscopy analysis were performed. According to obtained data, the Fe3+ ions were incorporated in the HA lattice, and also amorphous Fe oxides were formed contributed to the gradual increase in the S and pore volume of the powders. The Density Functional Theory calculations supported these findings and revealed Fe3+ inclusion in the crystalline region with the hybridization among Fe-3d and O-2p orbitals and a partly covalent bond formation, whilst the inclusion of Fe oxides assumed crystallinity damage and rather occurred in amorphous regions of HA nanomaterial. In vitro tests based on the MG-63 cell line demonstrated that the introduction of Fe3+ does not cause cytotoxicity and led to the enhanced cytocompatibility of HA.
Synthesis from mixed-anionic aqueous solutions is a novel approach to obtain active powders for bioceramics production in the CaO-SiO2-P2O5-Na2O system. In this work, powders were prepared using precipitation from aqueous solutions of the following precursors: Ca(NO3)2 and Na2HPO4 (CaP); Ca(NO3)2 and Na2SiO3 (CaSi); and Ca(NO3)2, Na2HPO4 and Na2SiO3 (CaPSi). Phase composition of the CaP powder included brushite CaHPO4‧2H2O and the CaSi powder included calcium silicate hydrate. Phase composition of the CaPSi powder consisted of the amorphous phase (presumably containing hydrated quasi-amorphous calcium phosphate and calcium silicate phase). All synthesized powders contained NaNO3 as a by-product. The total weight loss after heating up to 1000 °C for the CaP sample—28.3%, for the CaSi sample—38.8% and for the CaPSi sample was 29%. Phase composition of the ceramic samples after the heat treatment at 1000 °C based on the CaP powder contained β-NaCaPO4 and β-Ca2P2O7, the ceramic samples based on the CaSi powder contained α-CaSiO3 and Na2Ca2Si2O7, while the ceramics obtained from the CaPSi powder contained sodium rhenanite β-NaCaPO4, wollastonite α-CaSiO3 and Na3Ca6(PO4)5. The densest ceramic sample was obtained in CaO-SiO2-P2O5-Na2O system at 900 °C from the CaP powder (ρ = 2.53 g/cm3), while the other samples had densities of 0.93 g/cm3 (CaSi) and 1.22 (CaPSi) at the same temperature. The ceramics prepared in this system contain biocompatible and bioresorbable phases, and can be recommended for use in medicine for bone-defect treatment.
The development of magnesium calcium phosphate bone cements (MCPCs) has garnered substantial attention. MCPCs are bioactive and biodegradable and have appropriate mechanical and antimicrobial properties for use in reconstructive surgery. In this study, the cement powders based on a (Ca + Mg)/P = 2 system doped with Zn2+ at 0.5 and 1.0 wt.% were obtained and investigated. After mixing with a cement liquid, the structural and phase composition, morphology, chemical structure, setting time, compressive strength, degradation behavior, solubility, antibacterial activities, and in vitro behavior of the cement materials were examined. A high compressive strength of 48 ± 5 MPa (mean ± SD) was achieved for the cement made from Zn2+ 1.0 wt.%-substituted powders. Zn2+ introduction led to antibacterial activity against Staphylococcus aureus and Escherichia coli strains, with an inhibition zone diameter of up to 8 mm. Biological assays confirmed that the developed cement is cytocompatible and promising as a potential bone substitute in reconstructive surgery.
Powders based on β-tricalcium phosphate (β-TCP) containing sulphate groups at up to 12.0 mol.% were synthesised by chemical precipitation from aqueous solutions. The obtained materials were characterised by X-ray phase analysis, Fourier transform infrared spectroscopy, measurement of specific surface area, scanning electron microscopy, energy dispersive analysis, synchronous thermal analysis, mass spectra investigations and biological assays. It was established that during the synthesis, the obtained materials lose the sulphate groups in the course of heat treatment at 900 or 1200 °C. These groups stabilise low-temperature β-TCP, but when introduced at a high concentration, the sulphate groups contribute to the formation of hydroxyapatite during the heat treatment. Specific surface area of the powders proved to be in the range 81.7–96.5 m2/g. Results of biological assays showed cytocompatibility of both pure β-TCP and samples of sulphate-containing β-TCP. Additionally, matrix properties in the culture of MG-63 cells were revealed in all samples. Thus, the obtained materials are promising for biomedical applications.
Mesoporous hydroxyapatite (HA) is widely used in various applications, such as the biomedical field, as a catalytic, as a sensor, and many others. The aim of this work was to obtain HA powders by means of chemical precipitation in a medium containing a polymer—polyvinyl alcohol or polyvinylpyrrolidone (PVP)—with concentrations ranging from 0 to 10%. The HA powders were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, atomic emission spectroscopy with inductively coupled plasma, electron paramagnetic resonance, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). The specific surface area (SSA), pore volume, and pore size distributions were determined by low-temperature nitrogen adsorption measurements, and the zeta potential was established. The formation of macropores in powder agglomerates was determined using SEM and TEM. The synthesis in 10% PVP increased the SSA from 101.3 to 158.0 m2/g, while the ripening for 7 days led to an increase from 112.3 to 195.8 m2/g, with the total pore volume rising from 0.37 to 0.71 cm3/g. These materials could be classified as meso-macroporous HA. Such materials can serve as the basis for various applications requiring improved textural properties and may lay the foundation for the creation of bulk 3D materials using a technique that allows for the preservation of their unique pore structure.