A titania layer with ordered nanostructures is expected to be of high photocatalytic activity due mainly to its high specific surface area. In the present work, large-area films with ordered titania nanorods were deposited on titanium substrates through a solution approach. The nanorods, with the phase composition of a mixture of anatase and rutile, grew on top of a condensed anatase interlayer along mainly the rutile [001]-axis. The photocatalytic activity was evaluated by decomposing rhodamine B in water and compared with the general sol-gel derived titania films and a commercial DP-25 titania coating. It is found that the as-deposited titania nanorods exhibited extremely high initial photocatalytic activity but declined to a poor value after the consumption of beneficial oxidative peroxo complexes coordinated to Ti(IV). A subsequent thermal treatment eliminated such complexes but at the same time improved the crystallinity of the titania nanorods. The photocatalytic activity of the thermally treated titania nanorods was stable and significantly higher than that of the sol-gel derived film and commercial DP-25 coating.
Commercially pure titanium was treated with a H(2) O(2)/3mM TaCl(5) solution at 80 degrees C for various periods and a titania gel layer was formed on the surface. This gel remained amorphous when heating for 1 h below 200 degrees C and transformed to anatase after heating between 300 degrees and 600 degrees C. The anatase titania gel layers were found to be bioactive as to deposit carbonate ion-incorporated apatite within 1 day of immersion in the Kokubo solution, whereas the amorphous layers did not deposit apatite within 7 days. The apatite particles were found to nucleate preferentially inside the cracks prevailing in the thicker gel layers of 1-h chemically treated specimens. After immersing for 2 days, the titanium specimens were almost completely covered by apatite. Elimination of peroxide radicals from the titania gel and formation of anatase upon subsequent heating are considered to be responsible for the enhanced ability of apatite deposition.
Commercially pure titanium specimens are subjected to three different treatments, and their bioactivity are evaluated by immersing the specimens in a simulated body fluid (SBF, Kokubo's recipe) for various periods up to 7 days, with particular attention being paid to the differences in apatite deposition between surfaces open to SBF and surfaces in contact with the container's bottom. The treatment with a H(2)O(2)/HCl solution at 80 degrees C for 30 min followed by heating at 400 degrees C for 1 h produces an anatase titania gel layer on the specimen surface. This gel layer deposits apatite both on the contact and on open surfaces, and apatite deposition ability does not change with pre-staking in distilled water. The treatment with a NaOH solution at 60 degrees C for 3 days produces a sodium titanate gel layer. This gel layer can deposit apatite only on the contact surface, and the apatite deposition ability is completely lost after 1 day of pre-staking in distilled water. It is concluded, therefore, that the bioactivity of the titania gel originates from the favorable structure of the gel itself while the bioactivity of the sodium titanate gel depends heavily on ion release from the gel. The third treatment, a simple heat treatment at 400 degrees C for 1 h, produces a dense (not porous) oxide layer on the specimen surface. The specimens can deposit apatite on the contact surface after only 3 days of staking in SBF, but they cannot deposit apatite on the open surface for up to 2 months of staking. The implications of such apatite deposition behavior have been discussed in relation to the environments of titanium implants in bone as well as to the methodology of the SBF staking experiment.
Surface modification of titanium and its alloys to induce apatite deposition within a short period is of practical importance in clinical applications. In this study, titanium substrates were treated with hydrogen peroxide solutions at low temperatures to yield titania layers consisting of anatase and rutile. Those titania layers, regardless of the fraction of anatase and rutile, were bioactive to induce deposition of apatite in Kokubo's simulated body fluid within 24 h. The bioactivity was attributed to both the epitaxial effect and the abundant Ti–OH group of the titania layer.
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