The alkali treated titanium was hydrothermally treated in water and 10 mM CaHPO4 solution (nominal concentration) at 80-180 degrees C to crystallize the titanate hydrogel layer and calcify the alkali treated titanium. Surface structure and elemental composition of the samples were analyzed by scanning electron microscopy, energy dispersive x-ray analysis, x-ray photoelectron spectroscopy, x-ray diffraction and Raman spectroscopy. Porous titanate hydrogel layer is formed on titanium after the alkali treatment. For the hydrothermal treatment in water, the hydrogel layer is crystallized as anatase TiO2 with nanoporous or nanofibrous structure at 100 and 120 degrees C, and the layer is converted to anatase nanoparticles at 150 and 180 degrees C. For the hydrothermal treatment in the CaHPO4 solution, hydroxyapatite nanocrystallites are deposited at the samples surface at 80-120 degrees C, but only anatase nanoparticles are formed at 150 and 180 degrees C. The growth of hydroxyapatite nanocrystallites is influenced by pH and temperature variations of the solution. The present alkali-hydrothermal treatment can avoid higher temperatures involved in the traditional alkali-heat treatments, which is applicable for bioactive surface modification of the thermally sensitive titanium alloys. The results also show that Raman spectroscopy is a useful technique to analyze the microstructure of TiO2 and apatite films. (C) 2016 Elsevier B.V. All rights reserved.