The formation of nanoparticles of titanium oxides by homogeneous nucleation from highly supersaturated vapors was investigated by in situ Fourier transform IR spectroscopy and by observation of the resulting nanoparticles by transmission electron microscopy (TEM). Titanium metal was thermally evaporated in a specially designed chamber under a gaseous atmosphere of oxygen and argon. Nano particles nucleated and subsequently grew as they flew freely through the oxidizing gas atmosphere. Nascent nanoparticles of titanium oxides showed a broad IR absorption band at 10-20 mu m. Subsequently, the cooled nanoparticles showed a sharp crystalline anatase feature at 12.8 mu m. TEM observations showed the formation of spherical anatase nanoparticles. The IR spectral evolution showed that the titanium oxides nucleated as metastable liquid droplets, and that crystallization proceeded through secondary nucleation from the supercooled liquid droplets. This suggests that history of the titanium oxide nanoparticles, such as the temperature and oxidation that they experience after nucleation, determines their polymorphic form. (C) 2016 Elsevier B.V. All rights reserved.