The modification of the composition of apatite materials can be made by several processes corresponding to ion exchange reactions which can conveniently be adapted to current coatings and ceramics and are an alternative to setting up of new synthesis methods. In addition to high temperature thermal treatments, which can partly or almost totally replace the monovalent OH- anion of stoichiometric hydroxyapatite by any halogen ion or carbonate, aqueous processes corresponding to dissolution-reprecipitation reactions have also been proposed and used. However, the most interesting possibilities are provided by aqueous ion exchange reactions involving nanocrystalline apatites. These apatites are characterised by the existence on the crystal surface of a hydrated layer of loosely bound mineral ions which can be easily exchanged in solution. This layer offers a possibility to trap mineral ions and possibly active molecules which can modify the apatite properties. Such processes are involved in mineralised tissues and could be used in biomaterials for the release of active mineral species.
Calcium phosphate coatings on dental implants enhance integration of the material. Resorption of the ceramic coatings has raised some concern about the behavior of the bone-implant interfaces after the coating disappearance. Substitution of the OH- ions by fluoride in the hydroxylapatite (HA) lattice makes the calcium phosphate more stable. We investigated the degradation rate of dental implants with 50- and 100-microm coatings of HA, fluorapatite (FA), or fluorhydroxylapatite (FHA). The implants were inserted in dog jaws and retrieved for histological analysis after 3, 6, and 12 months. The thickness of the calcium phosphate coatings was evaluated using an image analysis device. A relative resorption index and its standard deviation were studied. HA and FA coatings (even at 100-microm thickness) were almost totally degraded within the implantation period. In contrast, the FHA coatings did not show significant degradation during the same period. The standard deviation showed that the resorption process for FHA with thicknesses of 50 or 100 microm was the same. Such a difference was not observed between the 50- and 100-microm thick coatings of FA and HA. In conclusion, the FHA coatings showed good integration in the bone tissue and lasted much longer than classic calcium phosphate coatings.
The decomposition of bioactive plasma sprayed apatite layers and the weakness of their interface with the metallic substrate limit the longevity of orthopaedic prostheses. Analysis of the coating and of the metal-apatite different techniques (EDS, XPS, IR) indicates alterations of the apatite composition which can be related to several chemical reactions occurring either in the plasma or on the surface of the implant. EDS shows a calcium-rich layer on the apatite side of the interface whereas after dissolution of the apatite, XPS indicates that phosphorus atoms are incorporated in the metal surface. Depending on the rate of decomposition, calcium oxide may possibly form and weaken the apatite-metal interface. Fluorohydroxyapatite coating, have proven to decompose less and differently and to be more effective than hydroxyapatite coatings.
The hydroxyapatite Ca10(PO4)6OH2 (HAP) was plasma sprayed onto titanium alloy substrate. The samples having thickness of about 150 µm ware sprayed in a way to obtain two different content of crystalline HAP: 25 an 30 %. The coatings ware subsequently submitted to laser treatment with the CO2 laser. The treatment was carried out with different laser powers and scanning velocities and resulting thereof sample surface temperatures and the kinetics of the thermal fields ware monitored with a pyrometer. The XRD method enabled verification of the crystallinity state of HAP, content of amorphous calcium phosphate and the content of foreign phases. Optical microscope was used to check the microstructure and the depth of laser modified zone.
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