Study on preparation of high-quality ultrafine TiB2 powder by short process melting method
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摘要: 基于企业生产研究背景与市场竞争优势，提出一种固液结合的短流程二硼化钛高端超细粉体的制备方法，利用廉价的钛源（二氧化钛）、硼源，无危险还原剂，采用短流程、低成本的方案制备出高产量、较短生产周期且无环境污染，具有一定工业推广性的固液结合的高端超细粉体--二硼化钛。研究了钛源、硼源的选择问题、熔融盐的比例问题、高端粉体的合成温度、Ti/B摩尔比、保温时间对TiB2粉体合成的影响。通过XRD和SEM对粉体的物相组成、显微形貌进行了表征。研究结果表明: 当选择摩尔比为1∶1 NaCl-KCl混合盐的情况下，反应物以TiO2/B为3∶10(摩尔比)配比，700 ℃保温2 h时开始有TiB2生成，随温度升高，产物中目标产物的纯度逐步提高，保温温度需达到950 ℃才可得到纯净的目标产物，无其余副产物生成，形貌为立方状，棱角分明，粒径为150 nm左右。若改变保温时长，当保温时长为5 h，900 ℃即可得到纯净的目标产物。Abstract: Based on research background and market competitive advantage of the enterprise production, a method of preparing high-quality ultrafine TiB2 powder with short process by melting method was proposed in this paper. This method is high yield, short production cycle and no environmental pollution, by which advanced ultrafine TiB2 powder with certain industrial extensibility was prepared using cheap titanium source, boron(B) source and nonhazardous reducing agent with short process and low cost. The effects of the selection of titanium and B sources, the proportion of molten salt, the synthesis temperature of high-quality powder, Ti/B molar ratio and holding time on the synthesis of TiB2 powder were studied. The phase composition and microstructure of the powder were characterized by XRD and SEM. The results show that when the molar ratio of NaCl/KCl mixed salt is 1∶1 and the molar ratio of TiO2/B is 3∶10, TiB2 begins to form when the reactant is kept at 700 ℃ for 2 h. With the increase of temperature, the purity of the target product in the product gradually improves. The pure target product can be obtained only when the holding temperature reaches 950 ℃ without other by-products. The morphology of powder is cubic, sharp edges and corners. The particle size is about 150 nm. If the holding time is changed, the pure target product can be obtained at 900 ℃ with 5 h of holding time.
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Key words:
- superfine TiB2 powder /
- melting method /
- TiO2 /
- boron powder
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图 1 不同温度保温2 h后产物TiB2及购买样品的XRD谱
Figure 1. XRD diagrams of TiB2 and purchased samples after holding for 2 h at different temperatures
图 3 不同温度保温2 h后产物TiB2的SEM形貌
Figure 3. SEM diagram of TiB2 after holding at different temperatures for 2 h
(a) 700 ℃；(b) 750 ℃；(c) 800 ℃；(d) 850 ℃；(e) 900 ℃；(f) 950 ℃
图 4 在850 ℃下不同保温时长（2、3、4、5 h）的TiB2产物XRD谱
Figure 4. XRD patterns of TiB2 products with different holding time (2, 3, 4, 5 h) at 850 ℃
图 5 在850 ℃下不同保温时长的TiB2产物SEM形貌
Figure 5. SEM morphology of TiB2 products with different holding time at 850 ℃
(a) 2 h；(b) 3 h；(c) 4 h；(d) 5 h
图 6 在900 ℃下不同保温时长(2、3、4、5 h)的TiB2产物XRD谱
Figure 6. XRD patterns of TiB2 products with different holding time (2, 3, 4, 5 h) at 900 ℃
图 7 在900 ℃下不同保温时长的TiB2产物SEM形貌
Figure 7. SEM morphology of TiB2 products with different holding time at 900 ℃
(a)2 h；(b)3 h；(c)4 h；(d)5 h
表 1 常见熔盐组成及性质
Table 1. Compositions and properties of common molten salts
熔盐 熔点/℃ 沸点/℃ 密度/(g·cm−3) NaCl 801 1407 1.55 KCl 770 1413 1.56 CaCl2 775 1935 2.15 NaCl-KCl 657 1.61 NaCl-CaCl2 504 Na2SO4 884 1404 2.68 
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表 2 试验所需试剂
Table 2. Reagents required for experiment
名称 化学式 纯度 特性 二氧化钛 TiO2 分析纯 粉体 硼粉 B 分析纯 粉体 无水乙醇 C2H5OH 分析纯 液体 氯化钠 NaCl 分析纯 固体颗粒 氯化钾 KCl 分析纯 固体颗粒
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