ZrB<sub>2</sub>与ZrC单相粉末及ZrB<sub>2</sub>-ZrC复合粉末制备现状

任金翠; 李欣沂; 吴义胜

doi:10.13801/j.cnki.fhclxb.20231108.002

ZrB₂与ZrC单相粉末及ZrB₂-ZrC复合粉末制备现状

doi: 10.13801/j.cnki.fhclxb.20231108.002

西安建筑科技大学　材料科学与工程学院，西安 710055

基金项目: 国家自然科学基金(51902242)；陕西省自然科学基础研究计划项目(2020JQ-668)；陕西省高校科协青年人才托举计划项目(20200422)

详细信息

通讯作者:
任金翠，博士，副教授，硕士生导师，研究方向为高温陶瓷材料　E-mail: renjincui@xauat.edu.cn

中图分类号: TQ174.75；TB332
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- 被引次数: 0
出版历程
- 收稿日期: 2023-08-14
- 修回日期: 2023-10-14
- 录用日期: 2023-11-02
- 网络出版日期: 2023-11-10
- 刊出日期: 2024-03-01

Preparation status of ZrB₂, ZrC single-phase powders and ZrB₂-ZrC composite powder

School of Materials Science and Engineering, Xi'an University of Architecture & Technology, Xi'an 710055, China

Funds: National Natural Science Foundation of China (51902242); Natural Science Basic Research Project of Shaanxi Province (2020JQ-668); Shaanxi University Science and Technology Association Youth Talent Lifting Program Project (20200422)

摘要

摘要: 随着科学技术的飞速发展及日益增长的技术需求，不仅能够承受高温同时可以在高温下依然保持高强度、高抗氧化性等优异性能的超高温陶瓷材料成为主要研究趋势。ZrB₂和ZrC由于具有高熔点、良好的导电导热性、低密度、较低的热膨胀系数等，同时在高温下具有高强度和良好的抗氧化性等优点，成为非常有潜力的超高温结构陶瓷材料。目前ZrB₂、ZrC单相粉末已经很难满足航空航天领域中极端条件的要求，因此ZrB₂-ZrC复合粉末的制备研究受到广泛关注。本文对ZrB₂、ZrC单相粉末及ZrB₂-ZrC复合粉末的合成原理及制备方法进行了综述，分析了目前ZrB₂、ZrC单相粉末及ZrB₂-ZrC复合粉末制备研究中存在的局限，对其未来研究方向进行了展望。
- ZrB₂粉末 /
- ZrC粉末 /
- ZrB₂-ZrC复合粉末 /
- 合成原理 /
- 制备方法
Abstract: With the rapid development of science and technology and the increasing technical demand, ultra-high temperature ceramic materials can not only withstand high temperatures but also maintain high strength and high oxidation resistance at high temperatures, making them become the main research trend. ZrB₂ and ZrC have become very potential ultra-high temperature structural ceramic materials because of their high melting point, good electrical and thermal conductivity, low density, low thermal expansion coefficient, and high strength and good oxidation resistance at high temperatures. However, ZrB₂ and ZrC single-phase powders are difficult to meet the requirements of extreme conditions in aerospace field, so preparing ZrB₂-ZrC composite powders has been widely concerned. The synthesis mechanism and preparation methods of ZrB₂ and ZrC single-phase powders and ZrB₂-ZrC composite powder are reviewed. The limitations of current preparation and application of ZrB₂ and ZrC single-phase powders and ZrB₂-ZrC composite powder are analyzed, the future research direction is prospected.
- ZrB₂ powder /
- ZrC powder /
- ZrB₂-ZrC composite powder /
- synthesis mechanism /
- preparation methods

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图 1 ZrB₂和ZrC晶体结构^[3-5]

Figure 1. ZrB₂ and ZrC crystal structures^[3-5]

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图 2 碳热还原1750℃下制备ZrB₂粉末SEM图像^[20]

Figure 2. SEM image of ZrB₂ powder prepared by carbothermal reduction at 1750℃^[20]

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图 3 不同温度和$ p_{\text{CO}} $压力下ZrO₂碳热还原反应${{\Delta G}}$变化图^[28]

Figure 3. Change diagram of carbon-thermal reduction reaction △G of ZrO₂ under different temperatures and $ p_{\text{CO}} $ pressures^[28]

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图 4 常规1600℃热处理1.5 h (a)与两步热处理(b)制备的ZrB₂粉末的SEM图像^[31]

Figure 4. SEM images of ZrB₂ powders prepared by1.5 h heat treatment at 1600℃ (a) and two-step heat treatment (b)^[31]

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图 5 不同碳源炭黑(a)、石墨(b)在氩气气氛中合成的ZrB₂的SEM图像^[33]

Figure 5. SEM images of ZrB₂ synthesized in argon atmosphere with different carbon sources carbon black (a), graphite (b)^[33]

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图 6 ZrO₂-B₂O₃-Mg系统的TG-DSC曲线^[35]

Figure 6. TG-DSC curves of ZrO₂-B₂O₃-Mg system^[35]

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图 7 ZrO₂-B₂O₃-Mg系统反应示意图^[35]

Figure 7. Schematic diagram of ZrO₂-B₂O₃-Mg system reaction^[35]

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图 8 ZrO₂-Mg-Na₂CO₃体系的TG-DSC曲线^[36]

Figure 8. TG-DSC curves of ZrO₂-Mg-Na₂CO₃ system^[36]

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图 9 老化凝胶的前驱体不同温度1000℃ (a)、1300℃ (b)、1500℃ (c)热处理2 h的SEM图像^[43]

Figure 9. SEM images of the precursor of the aging gel after heat treatment at different temperatures 1000℃ (a), 1300℃ (b), 1500℃ (c) for 2 h^[43]

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图 10 新生凝胶的前体不同温度1300℃ (a)、1500℃ (b)热处理2 h得到的 ZrB₂粉末SEM图像^[43]

Figure 10. SEM images of ZrB₂ powders obtained by heat treatment for 2 hat different temperatures 1300℃ (a) and 1500℃ (b)^[43]

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图 11 八水合氧氯化锆、柠檬酸、乙二醇体系下反应示意图^[47]

Figure 11. Reaction schematic diagram of zirconia (ZrOCl₂·8H₂O) with citric acid (C₆H₈O₇·H₂O) and ethylene glycol (C₂H₆O₂)^[47]

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图 12 1500℃ (a)和1800℃ (b)下热处理制备ZrC粉末的SEM图像^[52]

Figure 12. SEM images of ZrC powders prepared at 1500℃ (a) and 1800℃ (b)^[52]

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图 13 在不同温度1500℃ (a)、1600℃ (b)下煅烧生成的ZrC粉末的FE-SEM图像^[54]

Figure 13. FE-SEM images of ZrC powders produced by calcination at different temperatures 1500℃ (a), 1600℃ (b)^[54]

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图 14 熔盐与反应物生成ZrB₂粉末传质机制^[60]

Figure 14. Mass transfer mechanism of ZrB₂ powder formed by molten salt and reactants^[60]

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图 15 1200℃下获得的50ZrC-50ZrB₂复合粉末的FE-TEM图像^[70]

Figure 15. FE-TEM images of 50ZrC-50ZrB₂ composite powders obtained at 1200℃^[70]

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表 1 ZrB₂粉末的合成原理

Table 1. Principle of synthesis of ZrB₂ powder

Method	Raw materials	Reaction equation
Carbothermal reduction	ZrO₂, B₂O₃/H₃BO₃, C	$ \text{Zr}\text{O}_{\text{2}}\text{ + }\text{B}_{\text{2}}\text{O}_{\text{3}}\text{ + 5C}\to\text{Zr}\text{B}_{\text{2}}\text{ + 5CO} $ $ \text{Zr}\text{O}_{\text{2}}\text{ + 2}\text{H}_{\text{3}}\text{B}\text{O}_{\text{3}}\text{ + 5C = Zr}\text{B}_{\text{2}}\text{ + 5CO + 3}\text{H}_{\text{2}}\text{O} $
Borothermal reduction	ZrO₂, B	$ \text{Zr}\text{O}_{\text{2}}\text{ + 4B = Zr}\text{B}_{\text{2}}\text{ + }\text{B}_{\text{2}}\text{O}_{\text{2}} $
Boron/carbothermal reduction	ZrO₂, B₄C, graphite/carbon black	$ \text{2Zr}\text{O}_{\text{2}}\text{ + }\text{B}_{\text{4}}\text{C + 3C}\to\text{2Zr}\text{B}_{\text{2}}\text{ + 4CO} $
Magnesiothermic reduction	ZrO₂, B₂O₃, Mg	$ \text{2Zr}\text{O}_{\text{2}}\text{ + }\text{B}_{\text{2}}\text{O}_{\text{3}}\text{ + 5Mg}\to\text{Zr}\text{B}_{\text{2}}\text{ + 5MgO} $

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表 2 ZrB₂和ZrC粉末制备工艺及其优缺点

Table 2. Preparation of ZrB₂ and ZrC powders and their advantages and disadvantages

Preparation	Introduce	Advantages	Disadvantages
Self-propagation high-temperature synthesis	The mixture of raw materials uses the high temperature and heat generated by the chemical reaction to make the reaction proceed spontaneously and obtain the desired product	Energy saving, rapid response, high efficiency, high purity of the generated powder, less pollution^[37]	The reaction speed is too fast, resulting in unsatisfactory mixing uniformity of raw materials, the reactant conversion is incomplete, more impurities
Sol-gel methed	The raw materials are first mixed and heated according to the ratio to form a stable sol, and then the sol is dried into a gel and ground into a powder to prepare the precursor powder, and the product is obtained after high temperature heat treatment in a tube furnace	Small particle size and good dispersion, low reaction temperature	High cost, cumbersome process, long production cycle, organic materials are not good for human health
Liquid phase precursor method	The precursor solution is prepared from raw materials in proportion, and then dried and heat-treated at high temperature in a tube furnace to obtain the required product	The raw materials are fully mixed, simple equipment, short process cycle	Pollution of organic raw materials during heat treatment
Plasma process	The raw material is injected at the top of the plasma torch, rapidly heated in the plasma area, cooled at high speed after flying out of the plasma flame, and finally condensed into a very fine spherical powder	The product has high purity and uniform dispersion	High equipment requirements, high preparation cost
Molten salt method	Molten salt with low melting point is used to provide liquid phase environment for the reactants, so that the reactants are mixed evenly, and the diffusion and migration rate of each reaction component is accelerated to produce products	Low synthesis temperature, short reaction time, the shape and size of the product can be controlled by controlling the synthesis temperature and the type of molten salt	The process of removing molten salt impurities is complicated, not suitable for mass production

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