Cyclic-Oxidation Resistance of Protective Silicide Layers on Titanium

Titanium was powder siliconized and gas nitrided, in order to improve its cyclic-oxidation resistance. Siliconizing was performed in a pure-silicon powder at temperatures in the range of 800–1100° C for 3–48 h. Gas nitriding was carried out in pure N₂ at 1100° C/12 h. Cyclic-oxidation experiments with the siliconized and nitrided samples were conducted in air at 850 and 950° C for up to 560 h. It was found that the siliconized layers grew according to the parabolic law with the activation energy for siliconizing E_S being 47.2 kJ mol^–1. Powder siliconizing at 900–1100° C/3 h produced multi-phase layers, in which Ti₅Si₃ silicide predominated The siliconizing temperature of 800° C/3 h appeared to be insufficient, because it led to a non-uniform surface layer with a slight protective effect. The nitrided layers were composed of titanium nitride TiN and -Ti(N) intestitial solid solution. Measurement of the oxidation kinetics revealed that the titanium siliconized at 900–1100° C/3 h oxidized much more slowly than pure Ti, Ti–6Al–4V alloy and nitrided titanium. Microstructural investigation revealed the complex sub-structure of the scales on the siliconized samples which was composed of rutile+silica, rutile and nitrogen-rich sub-layers. The mechanism of high-temperature cyclic oxidation of the siliconized and nitrided titanium is discussed.