Oxidation of Nanometer‐Sized Titanium Nitride and Micrometer‐Sized Titanium Particles with Titanium Nitride Traces up to 1473 K in Air

This study compares the oxidation behaviour of TiN particles (nanometer‐sized to micrometer‐sized) to titanium particles with traces of titanium nitride (micrometer‐sized) regarding the similarities of the formation of the products. These particles were investigated between 323 K and 1473 K in air using high‐temperature X‐ray diffraction, SEM, and the methods of thermal analysis (TG and DSC). The oxidation of the nanometer‐sized TiN particles forms anatase and rutile in two partially overlapping successive steps, whereas the anatase transforms completely to rutile at higher temperatures. The investigated titanium particles directly transform to rutile. Traces of TiN in titanium particles induce the formation of traces of anatase phase which similar to the oxidation of TiN particles transforms to rutile phase. A Jander model for three‐dimensional diffusion was utilized for describing the oxidation kinetics of the both oxidation steps occurring with TiN. A least squares fit procedure gives good agreement of the calculated curves to measured TG and DSC curves and adequate approximation to intensities of X‐ray measurements. The amount of TiN oxidized to anatase was found to be about 46 %. The kinetic parameters were determined: for the first step of TiN oxidation, the pre‐exponential factor was 1.33 · 106 μm2/s and the activation energy was 180.5 kJ/mol as well as for the second step 5.51 · 103 μm2/s and 197.6 kJ/mol, respectively.

[1]  A. V. Vorontsov,et al.  Air detoxification with nanosize TiO2 aerosol tested on mice. , 2010, Journal of hazardous materials.

[2]  M. Diamanti,et al.  Effect of thermal oxidation on titanium oxides' characteristics , 2009 .

[3]  A. Gromov,et al.  Combustion of the “Ti–TiO2” and “Ti–Al” powdery mixtures in air , 2008 .

[4]  J. Ferreira,et al.  Dynamically Controlled Formation of TiN by Combustion of Ti in Air , 2007 .

[5]  V. Ramaswamy,et al.  Characterization of nanocrystalline anatase titania: an in situ HTXRD study , 2005 .

[6]  N. Eisenreich,et al.  On the Mechanism of Low Temperature Oxidation for Aluminum Particles down to the Nano-Scale , 2004 .

[7]  Stergios Logothetidis,et al.  Room temperature oxidation behavior of TiN thin films , 1999 .

[8]  H. Theliander,et al.  Kinetic study of the direct causticization reaction involving titanates and titanium dioxide , 1997 .

[9]  J. Nicholls,et al.  Hot Salt Corrosion of titanium aluminides , 1997 .

[10]  Katsuyuki Kawamura,et al.  Molecular Dynamic Simulation in Titanium Dioxide Polymorphs: Rutile, Brookite, and Anatase , 1996 .

[11]  M. Metikoš-huković,et al.  Electrochemical and thermal oxidation of TiN coatings studied by XPS , 1995 .

[12]  A. Rahmel,et al.  Cyclic-oxidation behavior of TiAl and of TiAl alloys , 1993 .

[13]  N. Eisenreich,et al.  Thermal expansion, transitions, sensitivities and burning rates of HMX , 1992 .

[14]  O. Inal,et al.  Kinetics of layer growth and multiphase diffusion in ion- nitrided titanium , 1989 .

[15]  N. Eisenreich,et al.  Difference thermal analysis of crystalline solids by the use of energy-dispersive X-ray diffraction , 1983 .

[16]  M. Billy,et al.  Oxidation mechanism of titanium nitride in oxygen , 1979 .

[17]  M. Billy,et al.  Oxidation of titanium nitride in oxygen: Behavior of TiN0.83 and TiN0.79 plates , 1979 .

[18]  L. Iyengar,et al.  Thermal Expansion of Rutile and Anatase , 1970 .

[19]  C. Basch,et al.  Oxidation Kinetics of Single Crystal Titanium Nitride by Optical Measurements , 1969 .

[20]  P. G. Wahlbeck,et al.  Reinvestigation of the Phase Diagram for the System Titanium–Oxygen , 1966 .

[21]  C. Houska.  THERMAL EXPANSION AND ATOMIC VIBRATION AMPLITUDES FOR TiC, TiN, ZrC, ZrN, AND PURE TUNGSTEN , 1963 .

[22]  A. Münster,et al.  Über die Oxydation der Titannitrids , 1957 .

[23]  A. Münster.  Eigenschaften und Anwendungen von Titannitrid und Titancarbid , 1957 .

[24]  K. Hauffe.  Reaktionen in und an festen Stoffen , 1955 .

[25]  O. Kubaschewski,et al.  Oxidation of metals and alloys , 1953 .

[26]  H. O. Nicolaus.  Titan und Titanlegierungen , 1951 .