Study on the preparation of spherical TiC nanopowder by molten salt method
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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。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.
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Key words:
- 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
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
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 ℃
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 ℃
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
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
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
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
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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