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

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The reaction products of gaseous ZrCl4 with ammonia were ZrCl4·2NH3 at 300 °C; ZrCl4·2NH3, ZrClN, and NH4Cl at 350–700 °C; ZrCl4·2NH3, ZrClN, ZrNx, Zr3N4, and NH4Cl at 750 °C; ZrClN, ZrNx, Zr3N4, and NH4Cl at 800–950 °C: ZrNx, Zr3N4, and NH4Cl at 1000–1050 °C; and ZrNx, NH4Cl, and HCl at 1100–1400 °C. The N/Zr atomic ratios, x, of the ZrNx formed was 1.28 at 1100 °C, 1.24 at 1200 °C, 1.18 at 1300 °C, and 1.12 at 1400 °C. The lattice constants of the ZrNx formed were shown. The reaction process of gaseous ZrCl4 with ammonia can be represented as follows: The reaction of gaseous ZrCl4 with ammonia to form ZrCl4·2NH3 occurs first. Above ca. 330 °C, the ZrCl4·2NH3 reacts with ammonia to form ZrClN. Above ca. 750 °C, the ZrClN reacts with ammonia to form ZrNx and Zr3N4. Above ca. 1000 °C, ZrNx. was also formed by the thermal decomposition of the Zr3N4. On heating the ZrNx(x=1.28), formed by the vapor-phase reaction, at temperatures higher than 700 °C in an argon atmosphere, the value of x decreased and became close to that of the stoichiometric nitride, being 1.03 at 1100–1300°C.
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