张太全;聂洪波;李文强;郑文庆;蔡晓康;

• 1:国家钨材料工程技术研究中心厦门钨业股份有限公司技术中心

摘要(Abstract)：

无粘结相硬质合金指以WC为主硬质相,粘结相Co或Ni含量低于质量分数为0.5%的WC基陶瓷材料。基于改善强韧性和抗氧化性,总结讨论了该类合金的成分和组织结构设计;也总结了其烧结方法和致密化机理、晶粒细化方法和机理及生产过程的控制难点;并指出该类合金及其应用的未来发展方向。

关键词(KeyWords)： 无粘结相硬质合金;性能设计;烧结致密化机理;晶粒细化机理;应用

Abstract:

Keywords:

基金项目(Foundation):

作者(Author): 张太全;聂洪波;李文强;郑文庆;蔡晓康;

Email:

DOI:

参考文献(References)：

• [1]TAKAHASHI T,FREISE E J.Determination of the slip systems in single crystals of tungsten monocarbide[J].Philosophical Magazine,1965,12(115):1-8.
• [2]KENEMITSU Y,NISHIMURA T,YOSHINO H,et al.Effect of hot isostatic pressing on binderless cemented carbide[J].International Journal of Refractory Metals&Hard Materials,1982,1(2):66-68.
• [3]SHUSHI I.Ultrafine particle binderless cemented carbide.Metal Powder Report,1992,47(4):32-33.
• [4]高建祥,范景莲.无粘结相WC基硬质合金研究进展[J].中国钨业,2011,26(6):22-26.GAO Jianxiang,FAN Jinglian.Research developments on the binderless WC-based cemented carbide[J].China Tungsten Industry,2011,26(6):22-26.
• [5]刘超.无粘结相硬质合金的发展与展望[J].中国材料进展,2016,35(8):622-628.LIU Chao.The development and prospect of binderless carbide[J].Materials China,2016,35(8):622-628.
• [6]Fraunhofer Institute for Ceramic Technologies and Systems IKTS.Nanoscaled hardmetals and WC ceramics[EB/OL].IKTS-817-W-15-9-22.[2015-09-22].https://www.ikts.fraunhofer.de/zh.html.
• [7]RICHTER V,RUTHENDORF M V.On hardness and toughness of ultrafine and nanocrystalline hard materials[J].International Journal of Refractory Metals&Hard Materials,1999,17(1/2/3):141-152.
• [8]EL-ESKANDARANY M S.Fabrication of nanocrystalline WC and nanocomposite WC-MgO refractory materials at room temperature[J].Journal of Alloys Compounds,2000,296(1):175-182.
• [9]ENGQVIST H,BOTTON G A,AXEN N,et al.Microstructure and abrasive wear of binderless carbides[J].Journal of the American Ceramic Society,2004,83(10):2491-2496.
• [10]KIM H C,OH D Y,JIANG G,SHON I J.Synthesis of WC and dense WC-5 vol.%Co hard materials by high frequency induction heated combustion[J].Materials Science&Engineering A,2004,368(1/2):10-17.
• [11]SUGIYAMA S,TAIMATSU H.Mechanical properties of WC-WB-W2B composites prepared by reaction sintering of B4C-W-WC powders[J].Journal of the European Ceramic Society,2004,24(5):871-876.
• [12]KIM H T,KIM J S,KWON Y S.Mechanical properties of binderless tungsten carbide by spark plasma sintering[C].Proceedings of the9th Russian-Korean International Symposium on Science and Technology,Korus:[s.n.],2005:458-461.
• [13]KIM H C,YOON J K,DOH J M,et al.Rapid sintering process and mechanical properties of binderless ultra fine tungsten carbide[J].Materials Science and Engineering A,2006,435/436(10):717-724.
• [14]KIM H C,SHON I J,YOON J K.One step synthesis and densification of ultra-fine WC by high-frequency induction combustion[J].International Journal of Refractory Metals&Hard Materials,2006,24(3):202-209.
• [15]KIM H C,KIM D K,WOO K D,et al.Consolidation of binderless WC-TiC by high frequency induction heating sintering[J].International Journal of Refractory Metals&Hard Materials,2008,26(1):48-54.
• [16]KIM H C,PARK H K,JEONG I K.Sintering of binderless WC-Mo2C hard materials by rapid sintering process[J].Ceramics International,2008,34(6):1419-1423.
• [17]SUGIYAMA S,KUDO D,TAIMATSU H.Preparation of WC-SiCwhisker composites by hot pressing and their mechanical properties[J].Materials Transactions Jim,2008,49(7):1644-1649.
• [18]MUKHOPADHYAY A,CHAKRAVARTY D,BASU B.Spark plasmasintered WC-ZrO2-Co nanocomposites with high fracture toughness and strength[J].Journal of the American Ceramic Society,2010,93(6):1754-1763.
• [19]SUN S,KAN Y,ZHANG G.Fabrication of nanosized tungsten carbide ceramics by reactive spark plasma sintering[J].Journal of the American Ceramic Society,2011,94(10):3230-3233.
• [20]POETSCHKE J,RICHTER V,HOLKE R.Influence and effectivity of VC and Cr3C2grain growth inhibitors on sintering of binderless tungsten carbide[J].International Journal of Refractory Metals&Hard Materials,2012,31(3):218-223.
• [21]LIU C,NINO A,SUGIYAMA S,et al.Preparation of(W,Mo)C-SiC ceramics and their mechanical properties[J].Journal of the Japan Society of Powder and Powder Metallurgy,2012,59(8):484-488.
• [22]OUYANG C,ZHU S,QU H.VC and Cr3C2doped WC-MgOcompacts prepared by hot-pressing sintering[J].Materials and Design,2012,40:550-555.
• [23]GRASSO S,POETSCHKE J,RICHTER V,et al.Low-temperature spark plasma sintering of pure nano WC powder[J].Journal of the American Ceramic Society,2013,96(6):1702-1705.
• [24]ZHENG D H,LI X Q,LI Y Y.ZrO2(3Y)toughened WC composites prepared by spark plasma sintering[J].Journal of Alloys&Compound,2013,572(36):62-67.
• [25]ZHENG D H,LI X Q,LI Y Y.In-situ elongatedβ-Si3N4grains toughened WC composites prepared by one/two-step spark plasma sintering[J].Materials Science and Engineering A,2013,561:445-451.
• [26]REN X,PENG Z,PENG Y,et al.Ultrafine binderless WC-based cemented carbides with varied amounts of AlN nano-powder fabricated by spark plasma sintering[J].International Journal of Refractory Metals&Hard Materials,2013,41:308-314.
• [27]NINO A,TAKAHASHI N,SUGIYAMA S,et al.Effects of carbide grain growth inhibitors on the microstructures and mechanical properties of WC-SiC-Mo2C hard ceramics[J].International Journal of Refractory Metals&Hard Materials,2014,43(3):150-156.
• [28]KIM D,CHOI Y,KIM Y,et al.Characteristics of nanophase WCand WC-3 wt.%(Ni,Co,and Fe)alloys using a rapid sintering process for the application of frication stir processing tools[J].Advances in Materials Science and Engineering,2015,ID 343619:1-9.
• [29]REN X,PENG Z,WANG C,et al.Influence of nano-sized La2O3addition on the sintering behavior and mechanical properties of WC-La2O3composites[J].Ceramics International,2015,41(10):14811-14818.
• [30]REN X,PENG Z,WANG C,et al.Effect of ZrC nano-powder addition on the microstructure and mechanical properties of binderless tungsten carbide fabricated by spark plasma sintering[J].International Journal of Refractory Metals&Hard Materials,2015,48(1):398-407.
• [31]SHON I J.Mechanical properties and rapid sintering of binderless nanostructured TiC and WC by high frequency induction heated sintering[J].Journal of Ceramic Processing Research,2016,17(7)(11):707-711.
• [32]WANG J,ZUO D,ZHU L,et al.Effects and influence of Y2O3addition on the microstructure and mechanical properties of binderless tungsten carbide fabricated by spark plasma sintering[J].International Journal of Refractory Metals&Hard Materials,2018,71(11):167-174.
• [33]TAIMATSU H,SUGIYAMA S,KOMATSU M.Effects of Cr3C2and V8C7on the microstructure and mechanical properties of WC-SiCwhisker ceramics[J].Materials Transactions,2009,50(10):2435-2440.
• [34]HUANG S G,VANMEENSEL K,VAN DER BIEST O,et al.Binderless WC and WC-VC materials obtained by pulsed electric current sintering[J].International Journal of Refractory Metals&Hard Materials,2008,26(1):41-47.
• [35]GIRARDINI L,ZADRA M,CASARI F,A.Molinari.SPS,binderless WC powders,and the problem of sub carbide[J].Metal Powder Report,2008,63(4):18-22.
• [36]ZHAO J,HOLLAND T,UNUVAR C,et al.Sparking plasma sintering of nanometric tungsten carbide[J].International Journal of Refractory Metals&Hard Materials,2009,27(1):130-139.
• [37]NINO A,TAKAHASHI K,SUGIYAMA S,et al.Effects of carbon addition on microstructures and mechanical properties of binderless tungsten carbide[J].Materials Transactions,2012,53(8):1475-1480.
• [38]NINO A,MORIMURA K,SUGIYAMA S,et al.Effects of C and NbC additions on microstructure and mechanical properties of binderless WC ceramics[J].Key Engineering Materials,2017,749:205-210.
• [39]ASADA N,YAMAMOTO Y,SHIMATANI K,et al.Particle size of fine grain WC by the‘continuous direct carburizing process’[J].Metal Powder Report,1990,45(1):60-64.
• [40]DONG Y,ZHANG L,WANG C,et al.In situ reactive synthesis and plasma-activated sintering of binderless WC ceramics[J].Advances in Applied Ceramics,2017,116(5):267-271.
• [41]EL-ESKANDARANY M S,SOLIMAN H M A,OMORIC M.Influence of nanocrystalline ZrO2additives on the fracture toughness and hardness of spark plasma activated sintered WC/ZrO2nanocomposites obtained by mechanical mixing method[J].Open Journal of Composite Materials,2012,2:1-7.
• [42]VINITSKII I M.Relation between the properties of monocarbides of groups IV-V transition metals and their carbon content[J].Soviet Powder Metallurgy&Metal Ceramics,1972,11(6):488-493.
• [43]ZACHARIEV Z.New superhard ternary borides in composite materials.Institute of Polymers,Bulgarian Academy of Sciences,Bulgaria.Edited by John Cuppoletti.Metal,Ceramic and Polymeric Composites for Various Uses,July 20,2011:61-77.
• [44]WARD Jet.Waterjet university-precision and quality.WARDjet,Retrieved[EB/OL].[2017-02-10].https://wardjet.com/waterjet/university/precision-quality.
• [45]CHEBOTAREVA N P,IL'CHENKO N I,GOLODETS G I.Kinetics and mechanism of oxidation of hydrogen on carbides of transition metals of groups IV-VI[J].Theoretical&Experimental Chemistry,1977,12(2):154-162.
• [46]UPADHYAYA G S.Cemented tungsten carbides:production,properties,and testing[M].Materials Science and Process Technology Series.Norwich:Noyes Publications,1998:18-19.
• [47]GNESIN B A,GURZHIYANTS P A.Refsicoat heat resistant material and high-temperature electric heaters using said material:US6770856[P/OL].[2004-08-03].
• [48]VOITOVICH V B,SVERDEL V V,VOITOVICH R F,et al.Oxidation of WC-Co,WC-Ni and WC-Co-Ni hard metals in the temperature range 500-800℃[J].International Journal of Refractory Metals&Hard Materials,1996,14(4):289-295.
• [49]刘祥庆,林涛,郭志猛,等.无粘结剂硬质合金的研究进展[J].粉末冶金技术,2007,25(4):293-296.LIU Xiangqing,LIN Tao,GUO Zhimeng,et al.Research progress of binderless cemented carbide[J].Powder Metallurgy Technology,2007,25(4):293-296.
• [50]李仁琼,刘铁梅.工艺参数对无粘结相硬质合金性能的影响[J].硬质合金,2005,22(1):23-26.LI Renqiong,LIU Tiemei.Effects of processing parameters on the properties of non-bond cemented carbide[J].Cemented Carbide,2005,22(1):23-26.
• [51]RICHTER V,HOLKE R,RUTHENDORF M,et al.Properties of binderless hardmetal densified by sinter-HIP,hot pressing and SPS[C].Proceedings of the Powder Metallurgy World Congress&Exhibition 2004(Euro PM2004),Vienna:[s.n.],2004:573-577.
• [52]周腾,夏铁锋,高立新,等.超细无粘结相WC基陶瓷的研究进展[J].硬质合金,2014,31(2):120-124.ZHOU Teng,XIA Tiexin,GAO Lixin,et al.Technical progress of binderless WC-based nanostructured cemented carbide[J].Cemented Carbide,2014,31(2):120-124.
• [53]张国珍,王澈,张久兴,等.配碳量对放电等离子烧结无粘结剂纳米WC硬质合金的影响[J].稀有金属与硬质合金,2005,33(2):12-15.ZHANG Guozhen,WANG Che,ZHANG Jiuxing,et al.Effects of mixed carbon content on spark plasma sintering of binder-free nanostructured WC cemented carbides[J].Rare Metals and Cemented Carbides,2005,33(2):12-15.
• [54]张立,陈述,黄方杰,等.微量钴对无金属粘结相WC硬质合金烧结致密化与WC晶粒生长行为的影响[J].硬质合金,2011,28(5):271-275.ZHANG Li,CHEN Shu,HUANG Fangjie,et al.Effects of small amount of cobalt addition on densification and WC grain growth during sintering of binderless cemented tungsten carbide[J].Cemented Carbide,2011,28(5):271-275.
• [55]邹洪伟,叶金文,刘颖,等.原料粉末碳,氧含量对无粘结相硬质合金性能的影响[J].功能材料,2010,41(1):90-93.ZOU Hongwei,YE Jinwen,LIU Yin,et al.The influence of quality of ultrafine powder on microstructure and properties of binderless tungsten carbide[J].Journal of Functional Materials,2010,41(1):90-93.
• [56]ANDERSON L.Ceramic cutting insert of polycrystalline tungsten carbidep:US6634837[P].2003-10-21.
• [57]KODASH V Y,GEVORKIAN E P.Tungsten carbide cutting tool materials:US6617271[P].2003-09-09.