Preparation of nearly-stoichiometric TiN powder by chemical vapor deposition in fluidized-bed

doi:10.11949/0438-1157.20200077

Abstract

Abstract:

The traditional gas-solid reaction process for preparing TiN powder has an insurmountable internal diffusion control process, which has caused great difficulties in preparing high-purity, positive stoichiometric ratio TiN powder. Herein, to address the issue, a fluidized bed chemical vapor deposition (FBCVD) process was developed to fabricate high quality TiN powders based on TiCl₄-N₂-H₂ system. The results showed that when the average particle size of TiN seeds was larger than 52.95 μm, they can realize long-term stable fluidization at 1000℃ even for 2 h and the obtained powders was nearly stoichiometric ratio TiN_0.96. In addition, the oxygen content of obtained TiN powders decreased about 40% compared with raw TiN seeds. Moreover, the growth of TiN was controlled by the Volmer-Weber growth mode, which provides a new horizon for preparing high quality TiN powder in industry.

Key words: fluidized-bed chemical vapor deposition, titanium nitride, powder, stoichiometric

摘要：

传统气-固反应工艺制备TiN粉体存在难以逾越的内扩散控制过程，导致制备高纯、正化学计量比的TiN粉体至今存在巨大困难。提出了流态化化学气相沉积工艺(FBCVD)制备高质量TiN粉体，即基于TiCl₄-N₂-H₂体系，在往复运动的TiN种子粉体上沉积新生高质量TiN粉体的新方法。实验发现，当TiN种子粉体粒径大于52.95 μm时，即使在1000℃沉积2 h也不会失流，同时在TiN种子粉体上获得了亚微米级的结节状新生TiN颗粒。通过氧氮分析仪和XRD分析发现，新方法显著提升了粉体的氮含量，获得了近化学计量比的TiN_0.96，且氧含量下降了约40%。此外，流化床中气相沉积TiN的生长模式为岛状生长模式，为工业中制备高质量TiN粉体提供了一种新的方法。

关键词: 流化床化学气相沉积, 氮化钛, 粉体, 化学计量比

CLC Number:

TQ 134.1

Yuan SANG, Maoqiao XIANG, Miao SONG, Qingshan ZHU. Preparation of nearly-stoichiometric TiN powder by chemical vapor deposition in fluidized-bed[J]. CIESC Journal, 2020, 71(6): 2743-2751.

桑元, 向茂乔, 宋淼, 朱庆山. 流化床化学气相沉积法制备近化学计量比的TiN粉体[J]. 化工学报, 2020, 71(6): 2743-2751.

Figures/Tables 9

Fig.1 Particle size distribution of commercial titanium nitride powder with average particle size of 21.16 μm (a) and 52.95 μm (b)

Fig.2 Schematic diagram of fluidized bed reactor for TiN powder synthesis

Table 1 Flow of reactant gases in experiment

气体	气体流量/(ml/min)
Ar	300
TiCl₄	70
N₂	70
H₂	210

Fig.3 Gibbs free energy change (a) and equilibrium component change (b) of Ticl4-N2-H2 system at different temperatures

Fig.4 Conversion rate of TiCl4 (a) and theoretical energy consumption (b) of different feed ratios in TiCl4-N2-H2 systemline 1—n(TiCl4)∶n(N2)∶n(H2) = 1∶0.5∶2； line 2—n(TiCl4)∶n(N2)∶n(H2) =1∶1∶3； line 3—n(TiCl4)∶n(N2)∶n(H2) = 1∶50∶2；line 4—n(TiCl4)∶n(N2)∶n(H2) = 1∶0.5∶200

Fig.5 Content of Cl in products deposited at different temperatures when feed molar ratio is n(TiCl4)∶n(N2)∶n(H2) =1∶1∶3

Fig.6 Fluidization pressure drop of TiN seeds with different particle size (a), macro photos (b) and SEM (c) of TiN seeds with average particle size of 21.16 μm after deposition, SEM of seeds with an average particle size of 52.95 μm after deposition (d)

Fig.7 SEM of 52.95 μm seeds before and after 120 min deposition [(a)—(b)], XRD patterns of TiN seeds before and after deposition (c), relationship between content of O/N in seeds and deposition time (d)

Fig.8 Surface morphology of TiN seeds after reaction of TiCl4-N2-H2 system at 1000℃ for different time

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