熔盐法制备球形碳化钛纳米粉体的研究

李文靓; 郭赟; 杨亚东; 刘波; 辛亚男

doi:10.7513/j.issn.1004-7638.2023.04.002

熔盐法制备球形碳化钛纳米粉体的研究

doi: 10.7513/j.issn.1004-7638.2023.04.002

李文靓^{1, 2,},
郭赟^{1, 2},
杨亚东^{1, 2},
刘波^{1, 2},
辛亚男^{1, 2}

1.
攀钢集团研究院有限公司, 钒钛资源综合利用国家重点实验室, 四川攀枝花 617000
2.
成都先进金属材料产业技术研究院股份有限公司, 四川成都 610300

详细信息

作者简介:
李文靓，1993年出生，女，四川成都人，博士，通讯作者，研究方向为先进功能材料开发及应用，E-mail：wenjingli0610@126.com

中图分类号: TF823
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- 被引次数: 0
出版历程
- 收稿日期: 2023-03-27
- 刊出日期: 2023-08-30

Study on the preparation of spherical TiC nanopowder by molten salt method

Li Wenjing^{1, 2
,},
Guo Yun^{1, 2},
Yang Yadong^{1, 2},
Liu Bo^{1, 2},
Xin Yanan^{1, 2}

1.
Pangang Group Research Institute Co., Ltd., State Key Laboratory of Vanadium and Titanium Resources Comprehensive Utilization, Panzhihua 617000, Sichuan, China
2.
Chengdu Advanced Metal Materials Industry Technology Research Institute Co., Ltd., Chengdu 610300, Sichuan, China

摘要

摘要: 结合国家十四五战略部署，基于企业资源背景及下游市场需求，提出通过熔盐法短流程制备球形碳化钛纳米粉体，整个流程温度远低于传统工艺温度（1300 ℃），过程不使用易燃易爆还原剂，安全系数高，生产产品质量高、产量可控、生产周期较短且环保，具有一定工业推广性。研究了钛源碳源的选择及配比、熔盐比例，以及纳米颗粒的煅烧温度、保温时长对颗粒形貌和质量的影响。通过XRD和SEM对颗粒的物相组成、显微形貌进行了表征。结果表明，在NaCl-KCl混合盐摩尔比为1∶1的情况下，反应物以Ti/C摩尔比为1∶1配比，700 ℃保温2 h时开始有TiC生成，随温度升高，产物中目标产物的纯度逐步提高，900 ℃保温2 h可得到纯净的目标产物，无其余副产物生成，形貌为球形，粒径为80 nm左右。改变保温时长为5 h时，850 ℃即可得到纯净的目标产物，但粒径会适度增加到100 nm。从降低原料成本考虑，钛源比例为Ti∶TiO₂=9∶1时，900 ℃即可得到无杂质的碳化钛纳米颗粒，形貌均为球形颗粒，颗粒粒径为50～65 nm。
- 碳化钛 /
- 纳米粉体 /
- 熔盐法 /
- 煅烧温度 /
- 保温时间
Abstract: In combination with the national strategic deployment of the 14th Five-Year Plan, based on the enterprise resource background and the downstream market demand, this paper proposes to prepare spherical titanium carbide (TiC) nanopowder through the short process of molten salt method. The process does not use flammable and explosive reducing agent, and has high safety factor. The process produces products with high quality, controllable output, short production cycle and environmental protection, which has certain industrial popularization. The selection and proportion of titanium source and carbon source, the proportion of molten salt, the calcination temperature of nanoparticles, and the effect of holding time on the morphology and quality of nanoparticles were studied. The phase composition and microstructure of the particles were characterized by XRD and SEM. The results show that when the molar ratio of NaCl-KCl mixed salt is 1∶1, the reactants in the ratio of Ti/C molar ratio of 1∶1, and TiC begins to form when the temperature is kept at 700 ℃ for 2 h. With the increase of temperature, the purity of the target product in the product gradually increases. The temperature of holding at 900 ℃ for 2 h can obtain the pure target product, without the formation of other by-products. The morphology is spherical, and the particle size is about 80 nm. If the holding time is changed, when the holding time is 5 h, the pure target product can be obtained at 850 ℃, but the particle size will be moderately increased to 100 nm. From the perspective of reducing raw material costs, when the titanium source ratio is Ti∶TiO₂=9∶1, impurity free titanium carbide nanoparticles can be obtained at 900 ℃, with spherical morphology and particle size ranging from 50 to 65 nm.
- titanium carbide /
- nanopowder /
- molten salt method /
- calcination temperature /
- holding time

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图 1 不同温度保温2 h后产物TiC及购买样品的XRD谱

Figure 1. XRD spectra of TiC product and purchased samples at different temperatures for 2 h

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图 2 购买成品TiC的SEM形貌

Figure 2. SEM images of purchased TiC

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图 3 不同温度保温2 h后产物TiC的SEM形貌

Figure 3. SEM images of TiC product at different temperatures for 2 h

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图 4 在850 ℃下不同保温时长的TiC产物XRD谱

Figure 4. XRD spectra of TiC products with different calcination time at 850 ℃

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图 5 在850 ℃下不同保温时长的TiC产物SEM形貌

Figure 5. SEM images of TiC products with different calcination time at 850 ℃

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图 6 当钛源（Ti∶TiO₂）比例为5∶5时保温时长为2 h不同温度（900、950、1000 ℃）的TiC产物XRD谱

Figure 6. XRD patterns of TiC products calcinated at different temperatures for 2 h

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图 7 当钛源（Ti∶TiO₂）比例为5∶5时保温时长为2 h不同温度（900（a）、950（b）、1000(c) ℃）的TiC产物SEM图

Figure 7. SEM images of TiC products calcinated at different temperatures (900 (a), 950 (b), 1000 (c) ℃) for 2 h with a titanium source (Ti∶TiO₂) ratio of 5∶5

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图 8 当钛源（Ti∶TiO₂）比例为7∶3时保温时长为2 h不同温度（900、950、1000 ℃）的TiC产物XRD谱

Figure 8. XRD patterns of TiC products calcinated at different temperatures (900, 950, 1000 ℃) for 2 h with a titanium source (Ti∶TiO₂) ratio of 7∶3

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图 9 当钛源（Ti∶TiO₂）比例为7∶3时保温时长为2 h不同温度（900、950、1000 ℃）的TiC产物SEM形貌

Figure 9. SEM images of TiC products calcinated at different temperatures (900, 950, 1000 ℃) for 2 h with a titanium source (Ti∶TiO₂) ratio of 7∶3

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图 10 当钛源（Ti∶TiO₂）比例为9∶1时保温时长为2 h不同温度（900、950、1000 ℃）的TiC产物XRD谱

Figure 10. XRD patterns of TiC products calcinated at different temperatures (900, 950, 1000 ℃) for 2 h with a titanium source (Ti∶TiO₂) ratio of 9∶1

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图 11 当钛源（Ti∶TiO₂）比例为9∶1时保温时长为2 h不同温度（900、950、1000 ℃）的TiC产物SEM形貌

Figure 11. SEM images of TiC products calcinated at different temperatures (900, 950, 1000 ℃) for 2 h with a titanium source (Ti∶TiO₂) ratio of 9∶1

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参考文献(12)

[1]	Liu Yang, Zhang Haodong, Yuan Suiyan, et al. Study on the mechanical properties of titanium carbide silicon ceramic materials[J]. Modern Salt Chemical Industry, 2021,(5):74−75. (刘洋, 张浩东, 原遂严, 等. 碳化钛硅陶瓷材料力学性能研究[J]. 现代盐化工, 2021,(5):74−75. Liu Yang, Zhang Haodong, Yuan Suiyan, et al. Study on the mechanical properties of titanium carbide silicon ceramic materials[J]. Modern Salt Chemical Industry, 2021, (5): 74-75
[2]	Liu Ping'an, Zeng Lingke, Shui Anze, et al. Research progress in the preparation and application of ultrafine titanium carbide powder[J]. Weapon Materials Science and Engineering, 2006,29(5):82−85. (刘平安, 曾令可, 税安泽, 等. 超细碳化钛粉体的制备及应用研究进展[J]. 兵器材料科学与工程, 2006,29(5):82−85. Liu Ping'an, Zeng Lingke, Shui Anze, et al. Research progress in the preparation and application of ultrafine titanium carbide powder[J]. Weapon Materials Science and Engineering, 2006, 29 (5): 82-85
[3]	Xu Benping. Current status and latest progress in chemical phase analysis of vanadium and titanium in vanadium and titanium materials[J]. China Inorganic Analytical Chemistry, 2014,4(2):18−23. (徐本平. 钒钛物料中钒钛化学物相分析现状及最新进展[J]. 中国无机分析化学, 2014,4(2):18−23. Xu Benping. Current status and latest progress in chemical phase analysis of vanadium and titanium in vanadium and titanium materials[J]. China Inorganic Analytical Chemistry, 2014, 4 (2): 18-23
[4]	Bandar Almangour, Min-seok Baek, Dariusz Grzesiak, et al. Strengthening of stainless steel by titanium carbide addition and grain refinement during selective laser melting [J]. Materials Science & Engineering A , 2017: S0921509317315.
[5]	Kattamis T Z, Suganuma T. Solidification processing and tribological behavior of particulate TiC-ferrous matrix composites[J]. Materials Science and Engineering A, 1990,128(2):241−252. doi: 10.1016/0921-5093(90)90232-R
[6]	Sen Wei, Xu Baoqiang, Yang Bin, et al. Preparation of titanium carbide powder by vacuum carbothermal reduction method[J]. Chinese Journal of Non Ferrous Metals:English Edition, 2011,21(1):185−190. (森维, 徐宝强, 杨斌, 等. 真空碳热还原法制备碳化钛粉末[J]. 中国有色金属学报:英文版, 2011,21(1):185−190. Sen Wei, Xu Baoqiang, Yang Bin, et al. Preparation of titanium carbide powder by vacuum carbothermal reduction method[J]. Chinese Journal of Non Ferrous Metals: English Edition, 2011, 21 (1): 185-190
[7]	Wang Zhi, Yuan Zhangfu, Guo Zhancheng. Exploration of a new process for direct preparation of titanium alloy by molten salt electrolysis[J]. Non-ferrous Metals, 2003,55(4):32-43. (王志, 袁章福, 郭占成. 熔盐电解法直接制备钛合金新工艺探讨[J]. 有色金属, 2003,55(4):32-43. Wang Zhi, Yuan Zhangfu, Guo Zhancheng. Exploration of a new process for direct preparation of titanium alloy by molten salt electrolysis[J]. Non-ferrous Metals, 2003, 55 (4): 4
[8]	Hao Xian, Liang Feng, Li Hongxia, et al. Progress in the preparation of nano titanium carbide and its application in energy storage[J]. Material Introduction, 2021,35(S01):11-18. (郝娴, 梁峰, 李红霞, 等. 纳米碳化钛的制备及在储能领域的应用研究进展[J]. 材料导报, 2021,35(S01):11-18. Hao Xian, Liang Feng, Li Hongxia, et al. Progress in the preparation of nano titanium carbide and its application in energy storage[J]. Material Introduction, 2021, 35 (S01): 8
[9]	Wang Jinshu, Xing Pengfei, Li Lili, et al. Preparation and characterization of N doped nano TiO₂ by mechanochemical method[J]. Journal of Beijing University of Technology, 2006,32(7):633−637. (王金淑, 邢朋飞, 李莉莉, 等. 机械化学法N掺杂纳米TiO₂的制备与表征[J]. 北京工业大学学报, 2006,32(7):633−637. Wang Jinshu, Xing Pengfei, Li Lili, et al. Preparation and characterization of N doped nano TiO₂ by mechanochemical method[J]. Journal of Beijing University of Technology, 2006, 32 (7): 633-637
[10]	Luo Xuming, Chen Yiming, Mu Yufeng. Self propagating high-temperature synthesis of non stoichiometric titanium carbide based cermets[J]. Material Development and Application, 1995,(5):20−23. (罗序明, 陈一鸣, 母育锋. 自蔓延高温合成非化学计量碳化钛基金属陶瓷[J]. 材料开发与应用, 1995,(5):20−23. Luo Xuming, Chen Yiming, Mu Yufeng. Self propagating high-temperature synthesis of non stoichiometric titanium carbide based cermets[J]. Material Development and Application, 1995, (5): 20-23
[11]	Lv Yanan, Chen Dong. Study on atomic diffusion behavior during the formation of titanium carbide particles[J]. Iron Steel Vanadium Titanium, 2021,42(3):143−147. (吕亚男, 陈栋. 碳化钛颗粒形成过程中原子扩散行为研究[J]. 钢铁钒钛, 2021,42(3):143−147. Lv Yanan, Chen Dong. Study on atomic diffusion behavior during the formation of titanium carbide particles[J]. Iron Steel Vanadium Titanium, 2021, 42 (3): 143-147
[12]	Zhou Yanli. Research on the salt separation process of sodium chloride and potassium chloride wastewater[J]. Hebei Chemical Industry, 2021,44(1):136−138. (周艳丽. 氯化钠氯化钾废水分盐工艺研究[J]. 河北化工, 2021,44(1):136−138. Zhou Yanli. Research on the salt separation process of sodium chloride and potassium chloride wastewater[J]. Hebei Chemical Industry, 2021, 44 (1): 136-138