硼热/碳热还原法制备过渡金属二硼化物研究进展

doi:10.3969/j.issn.1001-1935.2025.02.015

耐火材料 ›› 2025, Vol. 59 ›› Issue (2): 170-176.DOI: 10.3969/j.issn.1001-1935.2025.02.015

硼热/碳热还原法制备过渡金属二硼化物研究进展

彭杰, 刘江昊, 张海军

武汉科技大学先进耐火材料全国重点实验室湖北武汉 430081

收稿日期:2024-06-28 出版日期:2025-04-15 发布日期:2025-04-14
通讯作者: 张海军,男,1970年生,教授。E-mail:zhanghaijun@wust.edu.cn
作者简介:彭杰:男,2001年生,硕士研究生。E-mail:PJ18674569275@163.com
基金资助:
国家自然科学基金项目(52072274,52272021,U23A20559,52232002)。

Research progress on synthesis of transition metal diborides by boro/carbothermal reduction method

Peng Jie, Liu Jianghao, Zhang Haijun

First author’s address:State Key Laboratory of Advanced Refractories,Wuhan University of Science and Technology,Wuhan 430081,Hubei,China

Received:2024-06-28 Online:2025-04-15 Published:2025-04-14

摘要/Abstract

摘要： 硼热/碳热还原法制备过渡金属二硼化物具有成本低、效率高且可以合成高纯度目标产物的优势。从硼热/碳热还原法的原理出发,综述了近年来硼热/碳热还原法制备ZrB₂、HfB₂、WB₂和高熵二硼化物粉体的研究现状,总结了过渡金属二硼化物结构陶瓷的研究进展及存在的问题,并对硼热/碳热还原法制备过渡金属二硼化物粉体及二硼化物结构陶瓷未来的发展进行展望。

关键词: 过渡金属二硼化物, 硼热/碳热还原法, ZrB₂, HfB₂, 高熵二硼化物, 结构陶瓷

Abstract: The preparation of transition metal diborides by the boro/carbothermal reduction method has the advantages of low cost,high efficiency and the ability to synthesize target products with high purity.Based on the principle of the boro/carbothermal reduction method,the current research status of the preparation of transition metal diborides such as ZrB₂,HfB₂,WB₂ and high-entropy diborides by the boro/carbothermal reduction method was reviewed.The research progress and existing problems of transition metal diboride structural ceramics were summarized.The development of transition metal diboride powders via the boro/carbothermal reduction method and diboride structural ceramics was looked ahead.

Key words: transition metal diborides, boro/carbothermal reduction method, ZrB₂, HfB₂, high entropy diborides, structural ceramics

中图分类号:

TQ134.1

彭杰, 刘江昊, 张海军. 硼热/碳热还原法制备过渡金属二硼化物研究进展[J]. 耐火材料, 2025, 59(2): 170-176.

Peng Jie, Liu Jianghao, Zhang Haijun. Research progress on synthesis of transition metal diborides by boro/carbothermal reduction method[J]. Refractories, 2025, 59(2): 170-176.

参考文献

[1] 刘达.高熵过渡金属硼化物粉体制备[D].广州:华南理工大学,2020.
[2] MA T,ZHU P W,YU X H.Progress in functional studies of transition metal borides[J].Chinese Physics B,2021,30(10):108103.
[3] 陶强,马帅领,崔田,等.过渡金属硼化物的结构与性质[J].物理学报,2017,66(3):85-99.
[4] SI J J,YU J Q,LAN H H,et al.Chemical potential-modulated ultrahigh-phase-purity growth of ultrathin transition-metal boride single crystals[J].Journal of the American Chemical Society,2023,145(7):3994-4002.
[5] KNAPPSCHNEIDER A,LITTERSCHEID C,DZIVENKO D,et al.Possible superhardness of CrB₄[J].Inorganic Chemistry,2013,52(2):540-542.
[6] WELHAM N J.Formation of nanometric TiB₂ from TiO₂[J].Journal of the American Ceramic Society,2000,83(5):1290-1292.
[7] SHAHRIARI M,ZAKERI M,RAZAVI M,et al. Magnesiothermic synthesis of HfB₂-HfC-SiC nanocomposite by spark plasma technique[J].Ceramics International,2021,47(2):2172-2179.
[8] WEI T T,LIU Z T,REN D L,et al.Low temperature synthesis of TaB₂ nanorods by molten-salt assisted borothermal reduction[J].Journal of the American Ceramic Society,2018,101(1):45-49.
[9] 王晓玲,王周福,王玺堂,等.熔盐法合成二硼化钛纳米粉体研究[J].人工晶体学报,2014,43(5):1247-1251.
[10] BAO K,WEN Y,KHANGKHAMANO M,et al.Low-temperature preparation of titanium diboride fine powder via magnesiothermic reduction in molten salt[J].Journal of the American Ceramic Society,2017,100(5):2266-2272.
[11] 刘德磊.微波熔盐法合成过渡金属(IVB~VIB)硼化物固溶体研究[D].武汉:武汉科技大学,2022.
[12] WANG Y,YANG L X,LIU R J,et al.Molten salt synthesis of orthorhombic CrB and Cr₂AlB₂ ceramics[J].Ceramics International,2021,47(22):31772-31779.
[13] ZHOU Y Z,ZHU Q Q,XU L,et al.Effects of group-VB transition metals diborides substitution on HfB₂-based ceramics[J].Journal of the European Ceramic Society,2023,43(3):739-747.
[14] LIU D,FU Q G,CHU Y H.Molten salt synthesis,formation mechanism,and oxidation behavior of nanocrystalline HfB₂ powders[J].Journal of Advanced Ceramics,2020,9(1):35-44.
[15] TIAN X K,ZHOU C J,ZHANG L,et al.Preparation of ZrB₂-ZrO₂-SiC composite powder by carbothermal reduction from zircon[J].China’s Refractories,2023,32(1):25-29.
[16] LONG Y,LIU B,LIN S M,et al.Preparation of tungsten diboride by a combination of boro/carbothermal reduction process and spark plasma sintering[J].Journal of the European Ceramic Society,2022,42(13):5229-5237.
[17] SONBER J K,MURTHY T S R C,SUBRAMANIAN C,et al.Investigations on synthesis of HfB₂ and development of a new composite with TiSi₂[J].International Journal of Refractory Metals and Hard Materials,2010,28(2):201-210.
[18] LIU D L,JIAO B,ZHANG H J,et al.High-aspect-ratio single-crystalline (Hf_xZr_(1-x))B₂ micron-rods:low-temperature,highly-efficient synthesis and oriented growth mechanism[J].CrystEngComm,2022,24(24):4399-4407.
[19] WEN T Q,NING S S,LIU D,et al.Synthesis and characterization of the ternary metal diboride solid-solution nanopowders[J].Journal of the American Ceramic Society,2019,102(8):4956-4962.
[20] CSANÁDI T,AZIZPOUR A,VOJTKO M,et al.The effect of crystal anisotropy on fracture toughness and strength of ZrB₂ microcantilevers[J].Journal of the American Ceramic Society,2024,107(3):1669-1681.
[21] FENG L,FAHRENHOLTZ W G,HILMAS G E.Two-step synthesis process for high-entropy diboride powders[J].Journal of the American Ceramic Society,2020,103(2):724-730.
[22] 刘国昂,王海龙,方成,等.B₄C含量对(Ti_0.25Zr_0.25Hf_0.25Ta_0.25)B₂-B₄C陶瓷力学性能及抗氧化性能的影响[J].无机材料学报,2024,39(6):697-706.
[23] TANG Z Y,WEN Z H,LIU Y W,et al.Rapid experimental screening of high-entropy diborides for superior oxidation resistance[J].Advanced Functional Materials,2024,34(12):2312239.
[24] LIU D,LIU H H,NING S S,et al.Chrysanthemum-like high-entropy diboride nanoflowers:A new class of high-entropy nanomaterials[J].Journal of Advanced Ceramics,2020,9(3):339-348.
[25] GONG W L,WANG T Y,LUO W,et al.Synthesis and characterization of high-purity,high-entropy diboride ceramic powders by a liquid phase method[J].Materials,2023,16(23):7431.
[26] GAO Y,HUANG L,TONG Z M,et al.Low-temperature synthesis of high-entropy (Hf_0.2Ti_0.2Mo_0.2Ta_0.2Nb_0.2)B₂ powders combined with theoretical forecast of its elastic and thermal properties[J].Journal of the American Ceramic Society,2022,105(10):6370-6383.
[27] FENG L,FAHRENHOLTZ W G,HILMAS G E.Two-step synthesis process for high-entropy diboride powders[J].Journal of the American Ceramic Society,2020,103(2):724-730.
[28] HE J F,ZENG Y,HUANG Z,et al.Low temperature-rapid preparation of HfB₂-SiC powders by microwave/molten salt assisted boro/carbothermal reduction[J].Journal of the Ceramic Society of Japan,2021,129(8):528-534.
[29] GOLLA B R,MUKHOPADHYAY A,BASU B,et al.Review on ultra-high temperature boride ceramics[J].Progress in Materials Science,2020,111:100651.
[30] LI S L,SONG J X,CHE Y S,et al.Advances in molten salt synthesis of non-oxide materials[J].Energy & Environmental Materials,2023,6(2):e12339.
[31] WANG Z,LIU X,XU B S,et al.Fabrication and properties of HfB₂ ceramics based on micron and submicron HfB₂ powders synthesized via carbo/borothermal reduction of HfO₂ with B₄C and carbon[J].International Journal of Refractory Metals and Hard Materials,2015,51:130-136.
[32] LONG Y,ZHANG G H,LIN S M,et al.Microstructure and mechanical properties of WB₂-B₄C composites fabricated by boro/carbothermal reduction and SPS[J].Journal of the American Ceramic Society,2023,106(4):2539-2549.
[33] MA H B,LIU H L,ZHAO J,et al.Pressureless sintering,mechanical properties and oxidation behavior of ZrB₂ ceramics doped with B₄C[J].Journal of the European Ceramic Society,2015,35(10):2699-2705.
[34] FENG L,FAHRENHOLTZ W G,HILMAS G E,et al.Superhard single-phase (Ti,Cr)B₂ ceramics[J].Journal of the American Ceramic Society,2022,105(8):5032-5038.
[35] ZHANG W,ZHANG Y,GUO W M,et al.Powder synthesis,densification,microstructure and mechanical properties of Hf-based ternary boride ceramics[J].Journal of the European Ceramic Society,2021,41(7):3922-3928.
[36] SILVESTRONI L,GILLI N,SANGIORGI A,et al.Multi-phase (Zr,Ti,Cr)B₂ solid solutions:Preparation,multi-scale microstructure,and local properties[J].Journal of Advanced Ceramics,2023,12(2):414-431.
[37] DEMIRSKYI D,SUZUKI T S,YOSHIMI K,et al.High-temperature reactive synthesis of the Zr-Ta multiboride with a supercomposite structure[J].Journal of the American Ceramic Society,2022,105(11):6989-7002.
[38] JIN W L,PANG J,KOU Q,et al.Synthesis of a (Ti,Mo)B₂ coating by electro-codeposition in NaCl-KCl-AlCl₃-MoO₃ melt containing TiB₂ nanoparticles[J].Journal of the American Ceramic Society,2023,106(2):860-866.
[39] MARUMO T,KOIDE N,ARAI Y,et al.Characterization of carbon fiber-reinforced ultra-high temperature ceramic matrix composites fabricated via Zr-Ti alloy melt infiltration[J].Journal of the European Ceramic Society,2022,42(13):5208-5219.
[40] GILD J,KAUFMANN K,VECCHIO K,et al.Reactive flash spark plasma sintering of high-entropy ultrahigh temperature ceramics[J].Scripta Materialia,2019,170:106-110.
[41] FENG L,MONTEVERDE F,FAHRENHOLTZ W G,et al.Superhard high-entropy AlB₂-type diboride ceramics[J].Scripta Materialia,2021,199:113855.
[42] NAUGHTON-DUSZOVÁ A,MEDVED D,DAKOVÁ L,et al.Highly wear resistant dual-phase (Ti-Zr-Nb-Hf-Ta)C/(Ti-Zr-Nb-Hf-Ta) B₂ high-entropy ceramics[J].Advances in Applied Ceramics:Structural,Functional and Bioceramics,2023,122(3/4):107-118.
[43] YANG Y,BI J Q,SUN K N,et al.Novel (Hf_0.2Zr_0.2Ta_0.2V_0.2Nb_0.2)B₂ high entropy diborides with superb hardness sintered by SPS under a mild condition[J].Ceramics International,2022,48(20):30859-30867.
[44] 魏红康,邓翔宇,汪长安,等.反应热压烧结制备SiC/ZrB₂复相陶瓷及其性能表征[J].人工晶体学报,2014,43(3):550-554.
[45] 曾渊,梁峰,刘江昊,等.微波熔盐辅助硼热/碳热还原法制备ZrB₂-SiC复合粉[J].机械工程材料,2018,42(4):31-34+57.
[46] WANG H L,LEE S H,FENG L.The processing and properties of (Zr,Hf)B₂-SiC nanostructured composites[J].Journal of the European Ceramic Society,2014,34(15):4105-4109.

硼热/碳热还原法制备过渡金属二硼化物研究进展

Research progress on synthesis of transition metal diborides by boro/carbothermal reduction method

PDF

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 6

编辑推荐

Metrics

本文评价

[1]	马昭蕊, 孙小飞, 刘广华, 赵世贤, 丛鹤地, 王刚. SiC气凝胶材料表面ZrB₂陶瓷涂层的制备及抗氧化性能研究[J]. 耐火材料, 2025, 59(2): 144-148.
[2]	刘苗伟, 贾全利, 彭西高, 张小会, 张子英, 王海梅, 王佳. 硼/碳热还原结合热压烧结原位制备ZrB₂陶瓷及其性能研究[J]. 耐火材料, 2024, 58(5): 381-386.
[3]	王兴国, 陈滨, 李欣, 长世伦, 徐晨, 杨建红. 以蔗糖为碳源制备亚微米级TiB₂粉体的研究[J]. 耐火材料, 2024, 58(5): 405-409.
[4]	陈滨, 王兴国, 李欣, 吴纪清, 唐健, 杨建红. TiO₂晶型对微波加热制备TiB₂粉体的影响[J]. 耐火材料, 2024, 58(1): 44-47.
[5]	周超杰, 张磊, 赵飞, 贾全利, 刘新红, 钟香崇. 锆英石碳热还原制备ZrB₂-ZrO₂-SiC复合粉体[J]. 耐火材料, 2022, 56(1): 20-23.
[6]	陈若愚,黑大千,汪瑜凡,周倩波,刘欣雅,肖七巧,冯阳春,贾文宝. 有机泡沫浸渍法制备多孔结构陶瓷研究现状[J]. , 2018, 52(6): 475-480.