Study of structure of calcium phosphate materials by means of electron spin resonance.

Structure of γ-irradiated calcium phosphates synthesized in different conditions was studied by means of ESR. It has been shown that amorphous and nanocrystalline calcium phosphates have qualitatively different ESR spectra. The new paramagnetic center in hydroxyapatite (HA) has been found. It consists of four protons of water molecules located in the parallelogram vertexes and the free electron formed in HA by γ-irradiation. This center is thermally stable up to 300 °C, when the water molecules release from the HA crystal lattice.

Structural and compositional features of amorphous calcium phosphate at the early stage of precipitation.

Precipitates formed at an early stage (during the first 6 h) of the hydroxyapatite crystallization of a solution were studied. A nitrous synthesis was used (0.583M (NH(4))(2)HPO(4) and 0.35 M Ca(NO(3))(2).4H(2)O solutions at pH 11-12, 21 degrees C, fast mixing, lyophilization of aliquots). Although XRD patterns indicated an amorphous calcium phosphate (ACP), IR spectra revealed apatite nanocrystals in the precipitates. Some amount of free calcium was found in the mother solution by mass spectrometrical analysis of the aliquots. This amount considerably decreased as the synthesis proceeded, however, the decrease had a slight effect on the crystallinity of the precipitates. A new suggestion on the nature of delayed crystallization (under conditions as those in the present study) was proposed. The free calcium adsorbed by the nanoparticles from the solution formed a shell around a particle because the calcium diffusion into the bulk was poor at the low synthesis temperature. As such, the encapsulation delayed the crystallization of the nanoparticles. Evidence for this suggestion was given. New possibilities were proposed for preparation of bioactive materials of desired composition based on the structural and compositional peculiarities of the X-ray diffraction-amorphous calcium phosphates.

Thermal impurity reactions and structural changes in slightly carbonated hydroxyapatite.

Lattice and surface impurity reactions and structural changes induced by them in slightly carbonated hydroxyapatite (SCHA) treated at 25-1100 degrees C were comprehensively studied. The SCHA was processed by a conventional wet synthesis at a high possible temperature(96 degrees C) using ammonium containing parent reagents. IR-spectroscopy, XRD, TG-DTA technique and mass spectrometric thermal analysis (MSTA) were employed for characterization of the samples. NH4+ with H3O+ in cationic-and CO3(2-) (A- and B-positions) with HPO4(2-) in anionic sites, and H2O, CO3(2-)(HCO3(-)) NO3(-), NxHy on the surface of particles were found and considered as impurity groups. Complicated changes in lattice constants of theSCHA stepwise annealed in air (for 2 h) were revealed; the changes were associated with reactions of the impurity groups. Filling the hexed sites with hydroxyl ions above 500 degrees C was shown to happen partly due to lattice reactions but was mainly owing to hydrolysis of the SCHA by water molecules in air. Decomposition of CO3(2-) groups proceeded through both thermal destruction and reactions with some of the impurity ions. The decarbonation in A-sites occurred at much lower temperatures (450-600 degrees C) than in B-sites (700-950 degrees C) and was first revealed to happen in two stages: due to an impurity reaction around 500 degrees C, and then through thermal destruction at 570 degrees C. A redistribution of CO3(2-) ions, decreasing in amount on the whole, was observed upon annealing above 500 degrees C. To avoid possible erroneous conclusions from TG-data, a sensitive method was shown to be required for monitoring gaseous decomposition products (such as the MSTA in this study), in case several impurity groups were present in a SCHA.