This paper reports studies on time-resolved laser induced breakdown spectroscopy (LIBS) of plasmas induced by IR nanosecond laser pulses on the titanium oxides TiO and TiO2 (anatase). LIBS excitation was performed using a CO2 laser. The laser-induced plasma was found strongly ionized yielding Ti+, O+, Ti2 +, O 2 +, Ti3 +, and Ti4 + species and rich in neutral titanium and oxygen atoms. The temporal behavior of specific emission lines of Ti, Ti+, Ti2 + and Ti3 + was characterized. The results show a faster decay of Ti3 + and Ti 2 + ionic species than that of Ti+ and neutral Ti atoms. Spectroscopic diagnostics were used to determine the time-resolved electron density and excitation temperatures. Laser irradiation of TiO 2-anatase induces on the surface sample the polymorphic transformation to TiO2-rutile. The dependence on fluence and number of irradiation pulses of this transformation was studied by micro-Raman spectroscopy. © 2013 Elsevier B.V.

We gratefully acknowledge the support received in part by the DGICYT (MICINN, Spain) Projects: CTQ2008-05393/BQU and CTQ2010- 15680/BQU for this research. M.S. thanks CAM (Geomateriales S2009/ MAT 1629) for a contract.

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