化工学报 ›› 2020, Vol. 71 ›› Issue (6): 2743-2751.DOI: 10.11949/0438-1157.20200077
收稿日期:
2020-01-19
修回日期:
2020-03-22
出版日期:
2020-06-05
发布日期:
2020-06-05
通讯作者:
朱庆山
作者简介:
桑元(1994—),男,硕士研究生,基金资助:
Yuan SANG1,2(),Maoqiao XIANG1,Miao SONG1,2,Qingshan ZHU1,2()
Received:
2020-01-19
Revised:
2020-03-22
Online:
2020-06-05
Published:
2020-06-05
Contact:
Qingshan ZHU
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TiN0.96,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。
中图分类号:
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.
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.
图1 平均粒径为21.16 μm (a)和52.95 μm (b)的商用氮化钛粉体粒径分布图
Fig.1 Particle size distribution of commercial titanium nitride powder with average particle size of 21.16 μm (a) and 52.95 μm (b)
气体 | 气体流量/(ml/min) |
---|---|
Ar | 300 |
TiCl4 | 70 |
N2 | 70 |
H2 | 210 |
表1 实验中反应气体的流量
Table 1 Flow of reactant gases in experiment
气体 | 气体流量/(ml/min) |
---|---|
Ar | 300 |
TiCl4 | 70 |
N2 | 70 |
H2 | 210 |
图3 不同温度TiCl4-N2-H2体系在平衡状态下的Gibbs自由能变化(a)和平衡组分变化(b)
Fig.3 Gibbs free energy change (a) and equilibrium component change (b) of Ticl4-N2-H2 system at different temperatures
图4 TiCl4-N2-H2体系中不同进料比的TiCl4转化率(a)和理论能量消耗值(b)(1 cal=4.18 J)
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
图5 进料摩尔比为 n(TiCl4)∶n(N2)∶n(H2) = 1∶1∶3时不同温度下沉积产物中Cl元素含量
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
图6 不同粒径种子粉体流化压降曲线(a),平均粒径为21.16 μm的TiN种子粉体沉积后的宏观照片(b),平均粒径为21.16 μm种子粉体沉积后的SEM图(c),平均粒径为52.95 μm种子粉体沉积后的SEM图(d)
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)
图7 52.95 μm种子粉体沉积120 min前后的SEM图[(a)、(b)],沉积前后TiN种子的XRD谱图(c),沉积后种子中N和O含量与沉积时间的关系(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)
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