Reaction process of titanium tetrachloride with ammonia in the vapor phase and properties of the titanium nitride formed.

概要

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The reaction products of gaseous TiCl4 with ammonia were TiCl4·5NH3 at 200 °C, TiCl4·5NH3, TiClN, and NH4Cl at 250–400 °C, TiCl4·5NH3, TiClN, TiNx, and NH4Cl at 450–650 °C, TiNx and NH4Cl at 700–1000 °C, and TiNx, NH4Cl, and HCl at 1100–1400 °C. The N/Ti atomic ratio, x, of the TiNx formed was 1.21 at 700 °C, 1.16 at 800 °C, 1.13 at 900 °C, and 1.10 above 1000 °C. The lattice constants of the TiNx formed are shown. The reaction process can be represented as follows: The reaction of gaseous TiCl4 with ammonia occurs first to form TiCl4·5NH3. Above ca. 220 °C, the TiCl4·5NH3 decomposes to TiClN. Above ca. 430 °C, the TiClN reacts with ammonia to form TiNx. Above ca. 1100 °C, in addition to these reactions, the reaction of TiCl2, formed by the reduction of TiCl4 with hydrogen resulting from the thermal dissociation of ammonia, with ammonia occurs to form TiNx. On heating the TiNx, formed by the vapor-phase reaction, at temperatures higher than 500 °C in an argon atmosphere, the value of x decreased and became close to that of the stoichiometric nitride, being 1.02 at 900–1100 °C.
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