流化床化学气相沉积法制备近化学计量比的TiN粉体

doi:10.11949/0438-1157.20200077

摘要/Abstract

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

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

中图分类号:

TQ 134.1

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/表 9

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)

图2 制备TiN粉体的流化床反应器示意图

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

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)

图8 TiCl4-N2-H2体系在1000℃下反应不同时间后TiN种子粉体的表面形貌

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

参考文献 39

1	Nagakura S, Kusunoki T, Kakimoto F, et al. Lattice parameter of the non-stoichiometric compound TiN_x[J]. J. Appl. Cryst., 1975, 8(1): 65-66.
2	Liang H L, Jin X, Zhou D Y, et al. Thickness dependent microstructural and electrical properties of TiN thin films prepared by DC reactive magnetron sputtering[J]. Ceram. Int., 2015, 42(2): 2642-2647.
3	Liu M J, Dong Y Z, Wu Y M, et al. Titanium nitride nanocrystals on nitrogen-doped graphene as efficient electrocatalysts for oxygen reduction reaction[J]. Chem. J. Eur., 2013, 19(44): 14781-14786.
4	He P, Wang Y, Zhou H S. Titanium nitride catalyst cathode in a Li-air fuel cell with an acidic aqueous solution[J]. Chem. Commun., 2011, 47(38): 10701-10703.
5	Musthafa O T, Sampath S. High performance platinized titanium nitride catalyst for methanol oxidation[J]. Chem. Commun., 2008, 7(1): 67-69.
6	Gray B M, Hector A l, Jura M, et al. Effect of oxidative surface treatments on charge storage at titanium nitride surfaces for supercapacitor applications[J]. J. Mater. Chem. A., 2017, 5(9): 4550-4559.
7	Dong S M, Chen X, Cui G L, et al. One dimensional MnO₂/titanium nitride nanotube coaxial arrays for high performance electrochemical capacitive energy storage[J]. Energy Environ Sci., 2011, 4(9): 3502-3508.
8	Kim W M, Kim S H, Lee K S, et al. Titanium nitride thin film as an adhesion layer for surface plasmon resonance sensor chips[J]. Appl. Surf. Sci., 2012, 261(Complete): 749-752.
9	Wang Y, Yuan H Y, Lu X L, et al. All solid-state pH electrode based on titanium nitride sensitive film[J]. Electroanalysis, 2006, 18(15): 1493-1498.
10	Ishii S, Shinde S L, Jevasuwan W, et al. Hot electron excitation from titanium nitride using visible light[J]. ACS Photonics, 2016, 3(9): 1552-1557.
11	Ajikumar P L, Kamruddin M, Nithya R, et al. Surface nitridation of Ti and Cr in ammonia atmosphere[J]. Scr. Mater., 2004, 51(5): 361-366.
12	Wexler D, Calka A, Mosbah A Y. Ti-TiN hardmetals prepared by in situ formation of TiN during reactive ball milling of Ti in Ammonia[J]. J. Alloy Compd., 2000, 309(1/2): 201-207.
13	Lee K O, Cohen J J, Kenneth B. Fluidized-bed combustion synthesis of titanium nitride[J]. P. Combust. Inst., 2000, 28(1): 1373-1380.
14	Zhang H, Li F, Jia Q. Preparation of titanium nitride ultrafine powders by sol-gel and microwave carbothermal reduction nitridation methods[J]. Ceram. Int., 2009, 35(3): 1071-1075.
15	Luo M, Gao J Q, Zhang X, et al. Processing of porous TiN/C ceramics from biological templates[J]. Materials Letters, 2007, 61(1): 186-188.
16	Mosbah A, Calka A, Wexler D. Rapid synthesis of titanium nitride powder by electrical discharge assisted mechanical milling[J]. J. Alloy Compd., 2006, 424(1/2): 279-282.
17	石青娟. 非化学计量比TiN_x的制备及相稳定性研究[D]. 秦皇岛: 燕山大学, 2009.
	Shi Q J. Study of the preparation and phase stability of non-stoichiometric TiN_x[D]. Qinhuangdao: Yanshan University, 2009.
18	Song M, Xiang M Q, Yang Y F, et al. Synthesis of stoichiometric TiN from TiH₂ powder and its nitridation Mechanism[J]. Ceram. Int., 2018, 44(14): 16947-16952.
19	Drygaś M, Czosnek C, Paine R T, et al. Two-stage aerosol synthesis of titanium nitride TiN and titanium oxynitride TiO_xN_y nanopowders of spherical particle morphology[J]. Chem. Mater., 2006, 18(13): 3122-3129.
20	Bang J H, Suslick K S. Dual templating synthesis of mesoporous titanium nitride microspheres[J]. Adv. Mater., 2009, 21(31): 3186-3190.
21	Yoo J B, Yoo H J, Jung H J, et al. Titanium oxynitride microspheres with the rock-salt structure for use as visible-light photocatalysts[J]. J. Mater. Chem. A., 2016, 4(3): 869-876.
22	Berge L M, Gruner W. Investigation of the effect of a nitrogen-containing atmosphere on the carbothermal reduction of titanium dioxide[J]. Int. J. Refract. Met. H., 2002, 20(3): 235-251.
23	戴遐明, 李庆丰. 粉体的气、固相合成[J]. 中国粉体技术, 2000, 10(6): 15-20.
	Dai X M, Li Q F. Vapor and solid synthesis of powders[J]. China Powder Science and Technology, 2000, 10(6): 15-20.
24	刘志宏, 张淑英, 刘智勇. 化学气相沉积制备粉体材料的原理及研究进展[J]. 粉末冶金材料科学与工程, 2009, 14(6): 359-363.
	Liu Z H, Zhang S Y, Liu Z Y. Principle and research development of powder materials prepared by chemical vapor deposition[J]. Mater. Sci. Eng. Powder. Metall., 2009, 14(6): 359-363.
25	Shin D H, Yong C H, Uhm H S. Production of nanocrystalline titanium nitride powder by atmospheric microwave plasma torch in hydrogen/nitrogen gas[J]. J. Am. Ceram. Soc., 2005, 88(10): 2736-2739.
26	Wen Q, Qian W Z, Nie J Q, et al. 100 mm long, semiconducting triple-walled carbon nanotubes[J]. Adv. Mater., 2010, 22(16): 1867-1871.
27	刘马林. 流化床-化学气相沉积技术在先进核燃料制备中的应用进展[J]. 化工进展, 2019, 38(4): 1646-1653.
	Liu M L. Research activities on FB-CVD technology application in advanced nuclear fuel fabrication[J]. Chem. Ind. & Eng. Pro., 2019, 38(4): 1646-1653.
28	Du J, Dutta S, Ydstie B E. Modeling and control of solar-grade silicon production in a fluidized bed reactor[J]. AIChE J., 2014, 60(5): 1740-1751.
29	Luo X, Wu S, Yang Y, et al. Deposition characteristics of titanium coating deposited on SiC fiber by cold-wall chemical vapor deposition[J]. Mater. Chem. Phys., 2016, 184: 189-196.
30	Slavens G J. Vapor-phase reactions to prepare titanium nitride powder[R]. Report of Investigations. United States: Bureau of Mines, 1992.
31	He S Y, Sun H Y, Hu C Q, et al. Direct reduction of fine iron ore concentrate in a conical fluidized bed[J]. Powder Technology, 2017, 313: 161-168.
32	Geldart D. Types of gas fluidization[J]. Powder Technology, 1973, 7(5): 285-292.
33	郭慕孙, 李洪钟. 流态化手册[M]. 北京: 化学工业出版社, 2008: 110.
	Guo M S, Li H Z. Handbook of Fluidization[M]. Beijing: Chemical Industry Press, 2008: 110.
34	Lei C, Zhu Q S, Li H Z. Experimental and theoretical study on the fluidization behaviors of iron powder at high temperature[J]. Chemical Engineering Science, 2014, 118: 50-59.
35	Roberts G C, Nenes A. A continuous-flow streamwise thermal-gradient CCN chamber for atmospheric measurements[J]. Aerosol. Sci. Technol., 2005, 39(3): 206-221.
36	Zhu L P, Ohashi M, Yamanaka Y. Novel synthesis of TiN fine powders by nitridation with ammonium chloride[J]. Materials Research Bulletin, 2002, 37(3): 475-483.
37	Koch R, Hu D Z, Das A K. Compressive stress in polycrystalline Volmer-Weber films[J]. Phys. Rev. Lett., 2005, 94(14): 146101.
38	Eichfeld S M, Colon V O, Nie Y F. Controlling nucleation of monolayer WSe2 during metal-organic chemical vapor deposition growth[J]. 2D Mater, 2016, 3(2): 025015.
39	张军, 张磊, 李国栋, 等. 化学气相沉积ZrB₂涂层的微观形貌及晶粒择优生长[J]. 材料研究学报, 2017, 31(3): 168-174.
	Zhang J, Zhang L, Li G D, et al. Micro-morphology and preferential growth of ZrB₂ coating prepared by chemical vapor deposition[J]. Chinese Journal of Materials Research, 2017, 31(3): 168-174.

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