Commercially pure titanium was anodized in an electrolytic solution that was dissolved calcium and phosphorus compounds in water, and an AOFCP (anodic titanium oxide film containing Ca and P) was formed. It was found that sodium beta-glycerophosphate (beta-GP) and calcium acetate (CA) were suitable for the electrolytes to form the AOFCP having an equivalent Ca/P ratio to hydroxyapatite (HA). The AOFCP was characterized by scanning electron microscopy (SEM), an energy-dispersive X-ray microanalysis (EDX), and X-ray diffraction (XRD). Numerous micropores and microprojections were observed on the AOFCP by SEM. The composition of the AOFCP, which was measured by EDX, changed according to beta-GP and CA concentration, and the electrolytic voltage. Ca and P in the AOFCP seem to be incorporated into the TiO2 matrix from CA and beta-GP in the electrolyte during the anodic oxidation. Despite the existence of Ca and P in the AOFCP, no calcium phosphate peak was detected by XRD, and the AOFCP consisted of anatase and only a little rutile. The AOFCP, whose contents of Ca and P were low, had a high adhesive strength after soaking in a simulated body fluid for 300 days. When the AOFCP having an equivalent Ca/P ratio to HA was hydrothermally heated at 300 degrees C, HA crystals were precipitated on the AOFCP and completely covered the surface.

An anodic titanium oxide film containing Ca and P (AOFCP) was formed on commercially pure titanium which was anodized in an electrolytic solution of dissolved beta-glycerophosphate (beta-GP) and calcium acetate (CA). Hydroxyapatite (HA) crystals were precipitated by hydrothermally heating the AOFCP at 300 degrees C. After hydrothermal treatment, the film was characterized by scanning electron microscopy (SEM), energy-dispersive X-ray microanalysis (EDX), and tensile tests. The morphology, composition, and amount of HA crystals precipitated were significantly affected by the composition of the electrolytes. Near-stoichiometric HA crystals with high crystallinity were precipitated completely covering the AOFCP surface at specific electrolyte concentrations. The HA layers were thin at 1-2 microns in thickness. The adhesive strength of the film increased with decreasing electrolyte concentration and the maximum value was about 40 MPa. In vitro tests for 300 days suggested that the stability of the film was high. The high adhesive strength may result from the AOFCP existing as an intermediate layer between the HA layer and a titanium substrate. The intervention of the AOFCP may have prevented abrupt changes in Ca and P content at an HA coating-titanium interface as seen in a plasma-sprayed one. The porous TiO2 matrix of the AOFCP may be suitable for nucleation sites of HA crystals, as well as SiO2 matrix of silicate bioactive glasses or glass ceramics.

In a previous study a new method for forming thin hydroxyapatite (HA) layers on titanium was described. Titanium was anodized at 350 V in an electrolyte solution containing sodium beta-glycerophosphate and calcium acetate, and an anodic titanium oxide film containing Ca and P (AOFCP) was formed on the surface. Then numerous HA crystals were precipitated on the AOFCP during hydrothermal treatment in high-pressure steam at 300 degrees C. In this study three types of hydrothermally treated films differing in amounts of precipitated HA crystals and tensile adhesive strength, and untreated films were histologically and mechanically investigated in a transcortical rabbit femoral model for 8 weeks of implantation using light microscopy, scanning electron microscopy (SEM), and push-out tests. Machined titanium and HA ceramics served as control materials. The push-out shear strength and bone apposition of the AOFCP significantly increased after hydrothermal treatment, and were equivalent to those of HA ceramics, although the HA layer on the AOFCP was thin at 1-2 microns. From SEM observation of the pushed-out specimen, it was found that the thin HA layer had directly bonded to bone but the AOFCP had not. The push-out strength of the hydrothermally treated film resulted from the chemical bonding of the bone-HA layer interface, while that of the untreated film resulted from mechanical interlocking force between bone and the microprojections. There was a small difference in bone apposition but no significant difference in push-out strength with the amount of precipitated HA crystals on the treated films. Among the treated films, the film formed at the lowest electrolyte concentration showed the lowest bone apposition because of incomplete covering by the HA crystals, and showed the highest stability against mechanical failure because the adhesive strength was very high at about 38 mPa. Also, the hydrothermally untreated anodic oxide films, whose surfaces were rough as a result of the large microprojections, showed much higher push-out strength and bone apposition than titanium. The good hard-tissue compatibility may be attributed to the surface roughness and the possible inhibition of titanium ion release from the specimen.

By the previously described method of electrochemical and hydrothermal reaction, a thin hydroxyapatite (HA) layer of 1 microm thickness was formed on machined, grit-blasted, and titanium plasma-sprayed implants, the surfaces of which were equipped with a gap zone of 0.15 mm in depth. These implants, together with HA and titanium plasma-sprayed implants as control materials, were placed in dog mandibles for 4 weeks. Histomorphometrical comparison was performed to examine the effects of the thin HA layer and the surface topography on bone formation. The roughened implants, especially the grit-blasted implants, were surrounded with thin bone newly formed along the rough surfaces and showed higher bone apposition than the smooth implants. The gap zone of the HA plasma-sprayed implant was repaired with new bone that had vertically extended from the surrounding bone. The thin HA layer had as much osteoconduction as a plasma-sprayed HA coating but showed significantly different bone response. The results suggest that bone formation on an HA film is affected by degradation in living tissue that is related to the crystallinity and the chemical composition of the HA film itself.

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