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.

Preparation and characterization of biphasic calcium phosphate ceramics of desired composition.

A modified processing route for fabricating dense and porous biphasic calcium phosphate (BCP) ceramics of desired and reproducible phase composition (hydroxyapatite (HA)/beta-tricalcium phosphate (beta-TCP) ratio) has been developed. The principal idea of the route was combining a precipitation and a solid phase methods. First, a nonstoichiometric (slightly carbonated calcium-deficient) HA (CdHA) precipitate was synthesized by mixing a calcium carbonate (CaCO(3)) water suspension with an orthophosphoric acid (H(3)PO(4)) solution in abundance (related to the amount resulting in a stoichiometric HA) under definite conditions, and a powder of the precipitate was prepared and calcinated in air (860 degrees C, 1.5 h). In the second stage, a BCP ceramics of the composition determined by the calcium-deficiency in a calcinated powder (the acid abundance in a mixture) was processed by sintering powder compacts with or without a porosizer under appropriate conditions (1,200 degrees C, 2h). A calibrating dependence of the HA/beta-TCP ratio in the ceramics on the acid abundance has been plotted which enabled a controlled preparation of BCP ceramics. A correlation based on unresolved bands in nu(4)-PO (4) (3-) domain in IR-spectra of nanostructured BCP materials was found. Using the correlation, the process of CdHA --> beta-TCP transformation could be easily monitored. The density and microhardness of the BCP ceramics neglectly depended on the composition, however, the compressive strength did: the lower the HA/beta-TCP ratio, the higher the strength in the dense materials.

Preparation and properties of inhomogeneous hydroxyapatite ceramics.

Inhomogeneous ceramics of hydroxyapatite (HA) were prepared by sintering briquettes in which an inhomogeneous distribution of density was made by pressing HA powder into a die with rough walls. The resulting sample of such a ceramic is a hard thin shell with a loose core, and it is characterized by an inhomogeneous macro- and microstructure. It is a sintered conglomerate from HA grains containing grain boundary macropores in contact with the surface and micropores located inside the grains, part of which are also associated with the free surface. The highest value of microhardness is fixed on the surface of the sample. The radial distribution of microhardness in the (cylindrical) sample has an axisymmetric, nonmonotonic character and, on the whole, shows the decrease of microhardness (the increase of porosity) from the surface to the center. The highest values of microhardness, crushing strength, and fracture strength are close to those known for ceramics of moderate strength.

Possibilities for strengthening hydroxyapatite ceramics.

Some physics during heating and sintering of powder pressings of hydroxyapatite (HA) under conventional (usual) conditions have been studied. It is revealed that heating and firing of the pressings of a middle-dispersity powder are accompanied by release of gases. The gas release hinders and can stop the shrinkage (sintering). The microhardness is low and has a complicated distribution on the surface and in the volume of ceramics. A slight degassing (drying) of the pressing before sintering heightens the density and improves the microhardness characteristics of the ceramics. The shrinkage stop effect is eliminated in pressings of a fine powder. On the basis of the results, a technique and some methods for quality improvement of ceramics were proposed and approbated. They consisted of the manufacture of samples of a mixture of two powders with different dispersity, use of a press technique with two male dies, thermal treatment of pressing before sintering, and the choice of moderate sintering conditions. The resulting ceramics had a density close to the theoretical, almost homogeneous microhardness distribution in the sample and much higher values of microhardness and compressive strength.