Article(id=1321927528739090692, tenantId=1146029695717560320, journalId=1220038251117760515, issueId=1321926982078681131, articleNumber=null, orderNo=null, doi=10.11868/j.issn.1001-4381.2024.000812, pmid=null, cstr=32421.14.j.issn.1001-4381.2024.000812, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=research-article, receivedDate=1733414400000, receivedDateStr=2024-12-06, revisedDate=null, revisedDateStr=null, acceptedDate=1734710400000, acceptedDateStr=2024-12-21, onlineDate=1793101683076, onlineDateStr=2026-10-27, pubDate=1771516800000, pubDateStr=2026-02-20, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1793101683076, onlineIssueDateStr=2026-10-27, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1793101683076, creator=13701087609, updateTime=1793101683076, updator=13701087609, issue=Issue{id=1321926982078681131, tenantId=1146029695717560320, journalId=1220038251117760515, year='2026', volume='54', issue='2', pageStart='1', pageEnd='311', issueExtLink='null', onlineDate='null', pubDate='1771516800000', pubDateStr='2026-02-20', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1793101552742, creator='13701087609', updateTime=1793101552742, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext=null, issueFiles=null, downloadFileDto=null}, startPage=258, endPage=267, ext={EN=ArticleExt(id=1321927529015914757, articleId=1321927528739090692, tenantId=1146029695717560320, journalId=1220038251117760515, language=EN, title=Effect of vanadium carbide on microstructure and properties of cemented carbide manufactured by binder jetting additive manufacturing, columnId=1220689384450478826, journalTitle=Journal of Materials Engineering, columnName=RESEARCH ARTICLE, runingTitle=null, highlight=null, articleAbstract=

The control of WC grain size homogeneity in cemented carbide produced by binder jetting additive manufacturing (BJAM) is crucial for optimizing its mechanical properties;however, related studies remain limited. This research investigates the effect of vanadium carbide (VC) addition on the microstructure and mechanical properties of WC-12Co cemented carbide to prevent abnormal WC grain growth. The results demonstrate that the addition of VC significantly improves the surface roughness of WC-12Co cemented carbides. Specifically, the addition of 0.5%(mass fraction, the same below) VC and 1.0%VC reduces the surface roughness by 21.49% and 17.77%, respectively. Compared to the plain WC-12Co carbide without VC, the average WC grain size in the cemented carbides with 0.5%VC and 1.0%VC decreases from 1.83 μm to 1.57 μm and 1.61 μm, respectively. VC effectively inhibits abnormal WC grain growth and promotes a more uniform distribution of WC grain sizes. Furthermore, the addition of 0.5%VC increases the Vickers hardness by 3.3% and the bending strength by around 3%. Additionally, VC incorporation significantly reduces the friction coefficient and the wear rate of the BJAMed carbides, enhancing their wear resistance. These findings suggest that VC addition offers a promising strategy for improving the performance of cemented carbides in additive manufacturing, providing a valuable technical route for further development in this field.

, authors=Xiaonan NI1, Yongxuan CHEN1, Wenxin YANG1, Zijian HU1, Feng JIN2, Xin DENG1, 2, authorsList=Xiaonan NI, Yongxuan CHEN, Wenxin YANG, Zijian HU, Feng JIN, Xin DENG, authorCompany=null, correspAuthors=Xin DENG, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1321927533235384606, articleId=1321927528739090692, tenantId=1146029695717560320, journalId=1220038251117760515, language=CN, title=碳化钒对黏结剂喷射增材制造硬质合金组织和性能的影响, columnId=1220689384622445292, journalTitle=材料工程, columnName=研究论文, runingTitle=null, highlight=null, articleAbstract=

黏结剂喷射增材制造硬质合金中WC晶粒尺寸的均匀化调控是决定硬质合金综合力学性能的关键,而相关研究却非常有限。通过添加碳化钒(VC)来抑制WC-12Co硬质合金中WC晶粒的异常生长,研究了VC含量对黏结剂喷射打印硬质合金显微组织和力学性能的影响。结果表明,添加VC能大幅改善硬质合金烧结件的表面粗糙度,添加0.5%(质量分数,下同)VC和1.0%VC可使硬质合金烧结件的表面粗糙度分别降低21.49%和17.77%。添加0.5%VC和1.0%VC之后,硬质合金烧结件中WC晶粒的D50由1.83 μm分别减小至1.57 μm和1.61 μm,显著抑制了硬质合金烧结件的WC晶粒生长,促使晶粒更细小,分布更均匀。添加0.5%的VC后,硬质合金烧结件的维氏硬度提升3.3%,抗弯强度提升约3.0%。此外,VC的添加还能显著降低硬质合金烧结件的摩擦因数和磨损率,提升硬质合金的耐磨性。本研究采用黏结剂喷射增材制造技术制备了含VC抑制剂的高性能硬质合金材料,为硬质合金增材制造工艺的发展提供了重要的技术路线和发展方向。

, authors=倪小南1, 陈永轩1, 杨温鑫1, 胡子健1, 金枫2, 邓欣1, 2, authorsList=倪小南, 陈永轩, 杨温鑫, 胡子健, 金枫, 邓欣, authorCompany=null, correspAuthors=邓欣, authorNote=null, correspAuthorsNote=
邓欣(1971—),男,教授,博士,研究方向为金属及金属基复合材料增材制造研究,联系地址:广州市番禺区小谷围街广州大学城外环西路100号广东工业大学机电工程学院(510006),E-mail:
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ceramics:characterization,control,and challenges[J].Journal of the European Ceramic Society,2024,44(3):1361-1384., articleTitle=A review of defects in vat photopolymerization additive-manufactured ceramics:characterization,control,and challenges, refAbstract=null), Reference(id=1321927550029377938, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927528739090692, doi=null, pmid=null, pmcid=null, year=2021, volume=46, issue=null, pageStart=102128, pageEnd=null, url=null, language=null, rfNumber=[30], rfOrder=36, authorNames=MOSTAFAEI A, DE VECCHIS P R, KIMES K A, journalName=Additive Manufacturing, refType=null, unstructuredReference=MOSTAFAEI A, DE VECCHIS P R, KIMES K A,et al.Effect of binder saturation and drying time on microstructure and resulting properties of sinter-HIP binder-jet 3D-printed WC-Co composites[J].Additive Manufacturing,2021,46:102128., articleTitle=Effect of binder saturation and drying time on microstructure and resulting properties of sinter-HIP binder-jet 3D-printed WC-Co composites, refAbstract=null), Reference(id=1321927550121652627, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927528739090692, doi=null, pmid=null, pmcid=null, year=2024, volume=14, issue=6, pageStart=573, pageEnd=null, url=null, language=null, rfNumber=[31], rfOrder=37, authorNames=CABEZAS L, BERGER C, JIMÉNEZ-PIQUÉ E, journalName=Crystals, refType=null, unstructuredReference=CABEZAS L, BERGER C, JIMÉNEZ-PIQUÉ E,et al.Printing direction effects on the sliding contact response of a binder jetting 3D-printed WC-Co hardmetal[J].Crystals,2024,14(6):573., articleTitle=Printing direction effects on the sliding contact response of a binder jetting 3D-printed WC-Co hardmetal, refAbstract=null), Reference(id=1321927550205538708, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927528739090692, doi=null, pmid=null, pmcid=null, year=2019, volume=78, issue=null, pageStart=228, pageEnd=232, url=null, language=null, rfNumber=[32], rfOrder=38, authorNames=ENNETI R K, PROUGH K C, journalName=International Journal of Refractory Metals and Hard Materials, refType=null, unstructuredReference=ENNETI R K, PROUGH K C.Wear properties of sintered WC-12%Co processed via binder jet 3D printing (BJ3DP)[J].International Journal of Refractory Metals and Hard Materials,2019,78:228-232., articleTitle=Wear properties of sintered WC-12%Co processed via binder jet 3D printing (BJ3DP), refAbstract=null), Reference(id=1321927550302007701, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927528739090692, doi=null, pmid=null, pmcid=null, year=2021, volume=100, issue=null, pageStart=105639, pageEnd=null, url=null, language=null, rfNumber=[33], rfOrder=39, authorNames=MARIANI M, GONCHAROV I, MARIANI D, journalName=International Journal of Refractory Metals and Hard Materials, refType=null, unstructuredReference=MARIANI M, GONCHAROV I, MARIANI D,et al.Mechanical and microstructural characterization of WC-Co consolidated by binder jetting additive manufacturing[J].International Journal of Refractory Metals and Hard Materials,2021,100:105639., articleTitle=Mechanical and microstructural characterization of WC-Co consolidated by binder jetting additive manufacturing, refAbstract=null), Reference(id=1321927550398476694, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927528739090692, doi=null, pmid=null, pmcid=null, year=2014, volume=105, issue=6, pageStart=557, pageEnd=565, url=null, language=null, rfNumber=[34], rfOrder=40, authorNames=KAYTBAY S, EL-HADEK M, journalName=International Journal of Materials Research, refType=null, unstructuredReference=KAYTBAY S, EL-HADEK M.Wear resistance and fracture mechanics of WC-Co composites[J].International Journal of Materials Research,2014,105(6):557-565., articleTitle=Wear resistance and fracture mechanics of WC-Co composites, refAbstract=null)], funds=[Fund(id=1321927542148280682, 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sintered parts of 12G samples with different VC contents(a)12G00;(b)12G05;(c)12G10, figureFileSmall=6k6kiBizfdD7S3jQ9HlVKg==, figureFileBig=tc9s4SuIMJ6ygTIzCR1RQA==, tableContent=null), ArticleFig(id=1321927541707878757, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927528739090692, language=CN, label=图11, caption=不同VC含量12G样品烧结件的断裂横截面形貌(a)12G00;(b)12G05;(c)12G10, figureFileSmall=6k6kiBizfdD7S3jQ9HlVKg==, figureFileBig=tc9s4SuIMJ6ygTIzCR1RQA==, tableContent=null), ArticleFig(id=1321927541783376230, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927528739090692, language=EN, label=Fig.12, caption=Effect of different VC contents on friction and wear of 12G sample sintered parts, figureFileSmall=3I/QqE3MWZGZkdxGd5L5nQ==, figureFileBig=nFJyotZRdyp9kCRKmBa5BA==, tableContent=null), ArticleFig(id=1321927541863068007, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927528739090692, language=CN, label=图12, caption=不同VC含量对12G样品烧结件摩擦磨损的影响, figureFileSmall=3I/QqE3MWZGZkdxGd5L5nQ==, figureFileBig=nFJyotZRdyp9kCRKmBa5BA==, tableContent=null), ArticleFig(id=1321927541938565480, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927528739090692, language=EN, label=Table 1, caption=

EDS results of surface scan of sample surface(mass fraction/%)

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SampleWCoCV
12G0081.2312.666.110
12G0577.9113.597.980.52
12G1078.3912.997.511.11
), ArticleFig(id=1321927542018257257, tenantId=1146029695717560320, journalId=1220038251117760515, articleId=1321927528739090692, language=CN, label=表1, caption=

样品表面的面扫描EDS结果(质量分数/%)

, figureFileSmall=null, figureFileBig=null, tableContent=
SampleWCoCV
12G0081.2312.666.110
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碳化钒对黏结剂喷射增材制造硬质合金组织和性能的影响
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倪小南 1 , 陈永轩 1 , 杨温鑫 1 , 胡子健 1 , 金枫 2 , 邓欣 1, 2
材料工程 | 研究论文 2026,54(2): 258-267
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材料工程 |研究论文 2026 , 54 (2) : 258 -267
碳化钒对黏结剂喷射增材制造硬质合金组织和性能的影响
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倪小南1, 陈永轩1, 杨温鑫1, 胡子健1, 金枫2, 邓欣1, 2
作者信息
  • 1.广东工业大学 机电工程学院,广州 510006
  • 2.广东金瓷三维技术有限公司,广东 佛山 528225
通讯作者:
邓欣(1971—),男,教授,博士,研究方向为金属及金属基复合材料增材制造研究,联系地址:广州市番禺区小谷围街广州大学城外环西路100号广东工业大学机电工程学院(510006),E-mail:
Effect of vanadium carbide on microstructure and properties of cemented carbide manufactured by binder jetting additive manufacturing
Xiaonan NI1, Yongxuan CHEN1, Wenxin YANG1, Zijian HU1, Feng JIN2, Xin DENG1, 2
Affiliations
  • 1.School of Electromechanical Engineering,Guangdong University of Technology,Guangzhou 510006,China
  • 2.Guangdong Metal Ceramic 3D Technology Co. ,Ltd. ,Foshan 528225,Guangdong,China
出版时间: 2026-02-20 doi: 10.11868/j.issn.1001-4381.2024.000812
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黏结剂喷射增材制造硬质合金中WC晶粒尺寸的均匀化调控是决定硬质合金综合力学性能的关键,而相关研究却非常有限。通过添加碳化钒(VC)来抑制WC-12Co硬质合金中WC晶粒的异常生长,研究了VC含量对黏结剂喷射打印硬质合金显微组织和力学性能的影响。结果表明,添加VC能大幅改善硬质合金烧结件的表面粗糙度,添加0.5%(质量分数,下同)VC和1.0%VC可使硬质合金烧结件的表面粗糙度分别降低21.49%和17.77%。添加0.5%VC和1.0%VC之后,硬质合金烧结件中WC晶粒的D50由1.83 μm分别减小至1.57 μm和1.61 μm,显著抑制了硬质合金烧结件的WC晶粒生长,促使晶粒更细小,分布更均匀。添加0.5%的VC后,硬质合金烧结件的维氏硬度提升3.3%,抗弯强度提升约3.0%。此外,VC的添加还能显著降低硬质合金烧结件的摩擦因数和磨损率,提升硬质合金的耐磨性。本研究采用黏结剂喷射增材制造技术制备了含VC抑制剂的高性能硬质合金材料,为硬质合金增材制造工艺的发展提供了重要的技术路线和发展方向。

硬质合金  /  碳化钒  /  黏结剂喷射  /  增材制造  /  显微结构  /  力学性能

The control of WC grain size homogeneity in cemented carbide produced by binder jetting additive manufacturing (BJAM) is crucial for optimizing its mechanical properties;however, related studies remain limited. This research investigates the effect of vanadium carbide (VC) addition on the microstructure and mechanical properties of WC-12Co cemented carbide to prevent abnormal WC grain growth. The results demonstrate that the addition of VC significantly improves the surface roughness of WC-12Co cemented carbides. Specifically, the addition of 0.5%(mass fraction, the same below) VC and 1.0%VC reduces the surface roughness by 21.49% and 17.77%, respectively. Compared to the plain WC-12Co carbide without VC, the average WC grain size in the cemented carbides with 0.5%VC and 1.0%VC decreases from 1.83 μm to 1.57 μm and 1.61 μm, respectively. VC effectively inhibits abnormal WC grain growth and promotes a more uniform distribution of WC grain sizes. Furthermore, the addition of 0.5%VC increases the Vickers hardness by 3.3% and the bending strength by around 3%. Additionally, VC incorporation significantly reduces the friction coefficient and the wear rate of the BJAMed carbides, enhancing their wear resistance. These findings suggest that VC addition offers a promising strategy for improving the performance of cemented carbides in additive manufacturing, providing a valuable technical route for further development in this field.

cemented carbide  /  vanadium carbide  /  binder jetting  /  additive manufacturing  /  microstructure  /  mechanical property
倪小南, 陈永轩, 杨温鑫, 胡子健, 金枫, 邓欣. 碳化钒对黏结剂喷射增材制造硬质合金组织和性能的影响. 材料工程, 2026 , 54 (2) : 258 -267 . DOI: 10.11868/j.issn.1001-4381.2024.000812
Xiaonan NI, Yongxuan CHEN, Wenxin YANG, Zijian HU, Feng JIN, Xin DENG. Effect of vanadium carbide on microstructure and properties of cemented carbide manufactured by binder jetting additive manufacturing[J]. Journal of Materials Engineering, 2026 , 54 (2) : 258 -267 . DOI: 10.11868/j.issn.1001-4381.2024.000812
硬质合金是由难熔金属碳化物与过渡金属通过粉末冶金工艺制备而成的陶瓷基复合材料,具有高强度、高硬度、耐腐蚀和高耐磨性等特点,在模具、刀具、石油钻井等领域具有重要应用[1-3]。传统粉末冶金技术虽为硬质合金的主流制备方法,但其加工时间长、设备投资大,且难以达到复杂零件所需的高精度[4-5]。此外,该技术对产品形状设计的自由度有限,加之硬质合金本身的加工难度和成本较高,促使业界寻求更先进的制备技术。近年来,增材制造技术(又称3D打印)作为一项革新性技术,因其不依赖模具、具有高设计自由度的特性而受到广泛关注[6-8]。金属材料增材制造中的选择性激光熔化(selective laser melting,SLM)、熔丝制造(fused filament fabrication,FFF)和黏结剂喷射(binder jetting,BJ)等3D打印技术,已被广泛用于硬质合金的制造,这些技术不仅缩短了工具制造时间,还实现了传统技术难以达到的轻量化和复杂化制造[9-11]。其中,BJ打印作为一种非激光、非热基的增材制造技术,通过使用黏结剂液体将粉末颗粒黏合,随后进行后处理如脱脂和烧结等工序,在降低金属内部热应力和提升制造效率方面展现出独特的潜力[12-14]。目前,尽管在硬质合金的增材制造方面已取得一定进展,但与传统技术相比,仍存在诸多挑战,包括裂纹,孔洞,表面粗糙度、密度、精度低,夹渣,多孔性和强度不足等问题[15]。此外,硬质合金中硬质相和黏结相的热物理性质差异大,导致使用增材制造技术成形的零件面临开裂风险,且难以达到高致密度。
近年来,硬质合金领域经历了显著的技术革新,旨在开发具备高硬度、高韧性且成本效益高的材料。研究者们聚焦于超细晶和超粗晶硬质合金两大体系,以平衡材料的硬度与韧性[16-17]。超粗晶硬质合金(WC晶粒尺寸8.0~14.0 μm),因其在高温高压环境下的卓越耐磨性、韧性和热稳定性,在地矿工具、机加工行业以及硬质合金冲压模具中表现出色[18]。相比之下,超细晶粒硬质合金(WC晶粒尺寸0.2~0.5 μm),凭借其高硬度、高强度和高耐磨性,在现代高速切削、少/无冷却液切削及难加工材料加工中展现出明显优势[19]。WC-Co硬质合金的性能优化涉及Co相尺寸及分布、WC晶粒尺寸、添加剂种类及外加载荷等多个关键因素[20-21]。Liu等[22]基于SLM法研究了Co含量对硬质合金致密化及显微组织的影响,分析指出,当Co含量低于12%(质量分数,下同)时,WC的团聚是WC晶粒生长的主要机制。陆腾轩等[5]研究了粉末挤出法制备硬质合金的工艺和显微结构,开发了硬质合金粉末挤出打印的蜡基有机黏结剂材料体系,且通过溶剂脱脂和热脱脂工艺可以有效去除打印件中的有机黏结剂。左锐等[23]研究了Cr含量对亚微晶WC-10%Co硬质合金晶界分布的影响,结果表明WC/WC的晶界总长度与Cr含量(0%、0.5%、1%)正相关,而小角度晶界与大角度晶界的占比则变化不大。晶粒抑制剂,如VC、Cr3C2、Mo2C、TaC、NbC等难熔金属化合物,在烧结过程中发挥着至关重要的作用,能够细化WC晶粒,促进晶粒尺寸均匀化,抑制Co相的马氏体转变,并与硬质合金中的杂质元素反应,降低界面处的偏聚,从而全面提升硬质合金的综合力学性能[24-25]。此外,添加抑制剂虽然能促进WC晶粒的细化,但需严格控制添加量,避免增加硬质合金的脆性[26]。
尽管目前已有不少关于硬质合金3D打印,以及异质相对硬质合金组织性能影响的研究,但关于抑制剂VC对BJ打印硬质合金影响的研究还鲜见报道。为此,本工作选取WC-12Co硬质合金粉末进行BJ打印研究,重点研究抑制剂VC对WC-12Co硬质合金的强化机制。通过探索硬质合金BJ打印烧结件的表面质量、微观组织演化和力学性能,旨在建立完整的BJ增材制造专用硬质合金复合材料体系和工艺流程,以期扩展硬质合金复杂结构的高效、精确制备方法,为其在现代制造业中的广泛应用提供数据支撑和理论指导。
WC-Co硬质合金粉末由自贡长城表面工程技术有限公司生产提供,VC由上海水田材料科技有限公司提供,纯度为99.99%。WC-12Co粉末的粒径范围为22~50 μm,D50=32.1 μm。晶粒抑制剂 VC具有不规则多边形形状,粒径范围为1~2 μm。WC-12Co和VC的粉末形貌如图1所示,从图中可以看出,WC-Co球形颗粒具有良好的圆整度,并且没有明显团聚现象发生。此外,在喷雾造粒预烧结之后得到的硬质合金具有一定强度,在后续的混合及打印过程中不易发生破碎现象。
本研究中,用于BJ打印的原料为含有WC-12Co硬质合金和抑制剂VC的复合粉体。该复合粉体通过放入球磨罐中进行机械混合而成,混合过程中以乙醇作为研磨介质,球料比为1∶2,球磨速度为180 r/min,球磨时间为1 h。混合充分后,使用筛网分离浆料中的硬质合金研磨球,然后将剩余的浆料放置在旋转蒸发仪中,蒸发出其中的无水乙醇。最后,将旋蒸处理后的粉体放置在烘箱中进行烘干,以备后续用于BJ打印。最终得到的复合粉体依据VC的含量(0%、0.5%、1%)分别命名为12G00、12G05、12G10,文中该硬质合金体系统一称为12G。
粉末的流动性及松装密度等物理性质是影响BJ打印中铺粉质量的关键因素。本研究使用2.5 mm孔径霍尔流速计,依据GB/T1482—2010标准测量WC-Co硬质合金球形粉末的流动性,在盛放硬质合金粉末的容器中随机取3处粉末倒入漏斗中,然后打开小孔并开始计时,记录粉末完全流出的时间,记录5次并取平均值。依据GB/T1479.1—2011标准测试粉末的松装密度,选用孔径5 mm的霍尔流速计漏斗,使用容积为25 cm3的量杯圆心正对漏斗中心,并使漏斗底部距量杯上表面25 cm。取出体积大于漏斗容积的粉末放到漏斗中,让粉末随自重落到量杯中,然后用平整的卡片刮去多余的粉末,用精密天平测出此时粉末与量杯的质量,最后通过公式ρ=(m1-m2)/V得出粉末的松装密度,其中,ρ为松装密度,g/cm3;m1为量杯与粉末的总质量,g;m2为量杯的质量,g;V为量杯的容积,cm3。取3处不同地方的粉末进行测试并取平均值。经测试,WC-12Co硬质合金粉末的性能参数为:理论密度16.33 g∙cm-3,松装密度5.15 g∙cm-3,松装相对密度35.93%,流动性良好。
本研究采用由广东金瓷三维技术有限公司生产的BJM460黏结剂喷射金属3D打印设备进行成形实验,该设备最大成形尺寸为460 mm×375 mm×300 mm。依据前期的预实验优化研究,实验中BJ打印工艺参数为:打印层厚55 μm、粉床填充量40%、黏结剂干燥时间10 s、黏结剂饱和度60%、漏斗筛网孔径300目。此外,本研究打印采用在常温常压下具有稳定物理化学性质以及良好喷射性能和润湿性能的水基黏结剂,水基黏结剂易于在脱脂-烧结过程中彻底脱除,因此广泛应用于金属、陶瓷等材料的3D打印成形中。
BJ打印样品需经过脱脂及烧结等后处理程序之后可获得最终致密烧结件,本研究中的脱脂工艺选用热脱脂法,脱脂气氛为真空+流动氩气,脱脂工艺的温度曲线如图2(a)所示。此外,采用气压烧结法对打印-脱脂件进行烧结致密化,烧结温度为1450 ℃,压强为2 MPa,烧结气氛为氩气,烧结温度曲线及压力曲线如图2(b)所示。
在完成BJ打印、固化、脱脂、烧结等步骤后,将得到的硬质合金打印烧结件进行性能表征。样品的尺寸变化采用线收缩率和平均收缩率进行评价,采用奥林巴斯工业激光共焦显微镜LEXT OLS4100精确测量硬质合金的表面粗糙度值。根据GB/T 4340.1—2009标准,采用HXD-10000TM/LCD型维氏硬度计3D打印硬质合金烧结件的上表面(沿垂直于打印轴方向)进行硬度测试。硬度测试的条件:压头为二面角136°的金刚石正棱锥体,压头的载荷等级为30 N,保压时间为15 s。使用金相光学显微镜对样件抛光面进行观察,以初步观察抛光面的划痕以及孔隙分布情况。采用 Hitachi SU8220场发射扫描电子显微镜在180~2000倍的放大范围内对样品抛光面进行显微结构观察,显示分辨率为0.8 nm。
根据ASTM-C373标准,采用阿基米德排水法来测量硬质合金烧结件的相对密度。具体步骤为:将烧结后的样品放入去离子水中煮沸2~3 h以去除表面的附着物和杂质,然后静置10~15 min,在精密天平上测出样品浮重,再将样品表面的水珠擦除,然后测量湿重。随后将样品放置于干燥箱中烘干,再测量样品的干重,重复以上步骤5次,并计算平均值。相对密度的计算公式见式(1),(2):
ρ=ρ1ρ2-ρ3
d=ρρth×100%
式中:ρ为硬质合金打印烧结件的实际密度,g/cm3;ρth为硬质合金的理论密度,g/cm3;ρ1、ρ2和ρ3分别为干重、湿重和浮重,g;d为硬质合金的相对密度。
采用电子万能试验机(SHIMAZDU AGS-X-50KND)进行抗弯性能测试,测试遵循GB/T 3851—2015/IS0 3327:2009标准,选择B型标准抗弯样条,尺寸为20 mm×6.5 mm×5.25 mm。在测试过程中,跨距为14.5 mm,施压形变速率为0.1 mm/min。采用安东帕球盘摩擦试验机(THT),遵循ONORM M 8125—1994标准,在常温条件下进行摩擦磨损实验。
在本研究中,对不同VC含量的3种硬质合金材料进行了BJ打印、脱脂和烧结工艺处理。随后,对硬质合金打印生坯件、脱脂件以及烧结件的尺寸、密度和表面粗糙度进行对比分析。图3展示了12G00硬质合金生坯件、脱脂件、烧结件的形貌,与生坯件相比,脱脂件收缩率相对较小,外形变化不明显。然而,与打印生坯尺寸相比,烧结件的收缩率明显更大。
图4展示了WC-12Co硬质合金烧结件的收缩率以及3种WC-12Co硬质合金打印生坯、脱脂件、烧结件的相对密度。图中X、Y、Z 3个方向分别对应水平铺粉方向、喷嘴水平运动方向、打印厚度方向。由图4(a)可知,添加VC的硬质合金展现出更大的尺寸收缩率,且随着VC含量的升高,烧结件尺寸收缩率有所提高,这反映出添加了VC的硬质合金打印件及脱脂件的相对密度有所降低。各类硬质合金在厚度方向(Z)收缩率明显高于水平方向(X、Y)的收缩率,这主要是由于打印过程中存在层层堆积效应、各向异性烧结行为、黏结剂渗透不均匀以及应力和变形等因素的不同,最终导致在烧结过程中厚度方向产生了较大的收缩[27]。
从图4(b)中可以明显看到,硬质合金打印生坯件的相对密度范围为35%~42%,这一数值比粉末的松装相对密度最大高出7%左右。这主要是因为粉末在打印过程中经过辊子压实,并且喷射了黏结剂,导致其密度略微增加。BJ打印硬质合金经过脱脂处理后,相对密度与生坯密度相比都略有下降,降低了约1.0%,这主要是由于脱脂过程中大部分黏结剂被去除,导致脱脂件内部孔隙增多,相对密度也随之降低。但值得注意的是,加入少量的VC对打印生坯和脱脂件的相对密度影响并不显著。此外,3种硬质合金在经过烧结处理后的相对密度均达到了97%左右,比生坯及脱脂件的相对密度提升了1倍以上,反映出硬质合金BJ打印件在烧结过程中产生了较大的尺寸收缩。
进一步地,采用激光共聚焦显微镜测定了WC-12Co硬质合金BJ打印烧结件正表面(平行于打印粉床)的粗糙度。图5展示了3种硬质合金烧结件的表面三维形貌,从图中可以观察到,在添加0.5%VC后,硬质合金烧结件的表面粗糙度由5.49 μm降至4.31 μm,降低了约21.49%,当添加1.0%VC后,表面粗糙度降至4.52 μm,降幅为17.77%。因此可知,VC的添加有助于降低硬质合金烧结件的表面粗糙度,这是由于VC能起到抑制晶粒长大的作用,同时VC的添加改变了WC与Co相的界面结构,改善了烧结过程中的合金相互作用,进而降低硬质合金烧结件的表面粗糙度。而当VC含量过高时,可能会导致烧结过程中产生更多的过渡相或不均匀区域,这可能导致材料的脆性增加,烧结过程中出现表面缺陷,进而增大表面粗糙度。
硬质合金的WC晶粒形貌主要以梯形与三角形呈现,图6为硬质合金BJ打印烧结件显微结构的低倍和高倍SEM图,WC晶粒的棱角形貌清晰可见,WC/WC和WC/Co界面分明。在图6(a)中,发现未添加VC抑制剂的WC-12Co硬质合金中WC晶粒出现了明显的异常长大现象,并且存在粗晶粒WC聚集现象。然而,当在WC-12Co硬质合金中加入0.5%和1.0%的VC后,可以看到WC晶粒明显细化并呈现均匀分布,且异常长大的WC晶粒数量明显减少,如图6(b),(c)所示。因此得出,在12G硬质合金中加入WC晶粒生长抑制剂可以有效抑制BJ打印硬质合金烧结件中WC晶粒的异常长大和粗晶粒WC聚集现象。
为了进一步探究VC对12G硬质合金打印烧结件中WC晶粒异常长大的抑制作用,对12G00、12G05、12G10打印烧结件的WC晶粒尺寸分布进行了定量对比分析,如图7所示,当VC添加量为0%时,WC晶粒D50为1.83 μm,最大WC晶粒尺寸将近10 μm,说明12G00中会出现WC晶粒异常长大现象;当添加0.5%和1.0%的VC后,BJ打印烧结件中WC晶粒的D50分别为1.57 μm和1.61 μm,最大WC晶粒尺寸为5 μm,相比于不添加VC的12G00的WC晶粒D50各降低16.5%与12.1%,晶粒细化效果显著。由此可见VC的添加有利于抑制WC晶粒的异常长大,同时促进最终烧结件显微结构的均匀化,这对于BJ增材制造专用硬质合金材料体系设计具有关键意义。
在本研究中,VC是通过机械混合的方式分布于硬质合金球形粉体外围,为了验证VC在烧结过程中是否形成偏聚,采用EDS分别对12G硬质合金烧结件显微结构中元素的分布进行了整体面扫描分析,具体元素分布如图8所示。表1详细列出了图8中各硬质合金面扫描EDS的数据结果,可以观察到,V元素随着液相钴扩散均匀分散于整个硬质合金显微结构中,并且添加V元素的含量与实验添加量基本一致,并未发现VC偏聚现象,证明该烧结过程可以有效消除VC的起始偏聚。
对于3D打印的材料,内部常存在较多缺陷,主要包括气孔、表面粗糙和分层现象3类缺陷,其中气孔和表面粗糙缺陷广泛存在于3D打印的生坯件、脱脂件及烧结件中,而分层现象主要存在于烧结件中[28]。X射线计算机断层扫描(X-CT)技术是对3D打印缺陷表征和定量分析的主要手段,通过可视化缺陷形状,可有效解析缺陷形成机理并建立缺陷与力学性能的映射关系[29]。本研究采用的SEM显微图像和激光共聚焦测量表面粗糙度的方法,虽不能全面可视化BJ打印硬质合金的内部缺陷,但能客观快捷地评价BJ打印质量。
图9展示了BJ打印硬质合金烧结件的粗晶粒WC团聚现象及在烧结过程中显微结构的演化过程。对于BJ打印技术,为确保打印过程中的高质量铺粉,所使用的硬质合金粉体需要球形度较好且粒度在十几至几十微米,而使用这种粉体进行BJ打印得到的生坯内部常存在两类孔隙缺陷:一是微米级别的粉体内部孔隙,这一类孔隙的尺寸相对较小,其在液相烧结过程中易被液相Co填充并消除;二是硬质合金球形粉体堆积形成的,在粉体搭接区域的几十微米及以上的第二类孔隙,在烧结过程中钴液相不断填充这些孔隙区域时会形成较大面积的富钴相区域,而WC晶粒在这些较大的钴相区域中由于缺少相邻WC晶粒的限制作用,故WC晶粒可以更为快速地生长,因而形成WC晶粒的异常长大现象[30-31]。
抑制剂的作用机理主要包括:降低WC在液相中的溶解度,抑制其溶解析出过程;吸附在WC晶粒表面,减少溶解析出的动力;沿WC/WC界面偏析,阻碍WC界面迁移,防止WC颗粒发生聚集长大[25]。具体而言,VC抑制剂与Co具有较低的共晶温度,优先溶解于液相中,降低了WC的溶解度,从而抑制了WC的异常长大。WC晶粒异常生长以及大量存在的粗晶粒WC会降低硬质合金的力学性能,而本研究开发的在球形硬质合金粉体颗粒之间添加VC的方法可以有效抑制WC晶粒的异常长大,对提升增材制造硬质合金的显微结构均匀性及相应的力学性能起到积极促进作用。
经过烧结处理后,不同VC含量对12G硬质合金的硬度和抗弯强度产生了显著影响。如图10所示,12G00烧结件的硬度超过了1250HV30。在加入0.5% VC后,硬度提升约3.3%,达到1291HV30,高于近期相关研究中未添加抑制剂BJ打印硬质合金得到的硬度值[32-33],这说明由于VC的加入使得WC晶粒发生明显细化,从而使硬质合金硬度得到有效提升。在继续添加VC至1.0%后,硬度达到1273HV30,略低于12G05,这主要是由于高VC含量导致硬质合金致密度有一定下降。另一方面,对于抗弯强度,随着VC含量从0%增加至0.5%,抗弯强度从2051 MPa上升至2112 MPa,升幅约3.0%,当VC含量进一步增加至1.0%时,抗弯强度略有下降至2087 MPa。这表明适量添加VC可使12G硬质合金获得更细小和均匀的显微结构,因而可以有效提升抗弯强度。
图11展示了硬质合金抗弯强度测试后断口显微形貌。从图可知,12G00断口表面显示出较大的WC晶粒形貌,WC晶粒呈现明显的脆性解理断裂,表明此类WC晶粒对硬质合金力学性能具有负面影响。12G05样品的断口显示出WC晶粒细化和均匀化的特征,这有助于提高硬质合金的强度。
为了进一步评估BJ打印12G硬质合金的表面质量及其力学性能,对其进行了摩擦磨损测试,图12展示了不同VC含量下12G硬质合金BJ打印烧结件的摩擦性能测试结果。
当VC添加量从0%上升至0.5%时,摩擦因数从0.71下降至0.65,而当VC添加量继续上升至1.0%时,摩擦因数反而上升至0.68。摩擦因数越高,摩擦阻力越大,测试过程中产生的热量就越多,耐磨性就可能会降低。此外,从图中的WC-12Co硬质合金的磨损率来看,加入0.5%VC后可以明显降低磨损率,这与VC引起WC晶粒显著细化有直接关联,WC晶粒的细化导致更高的硬度,样品硬度越高,耐磨性越强,磨损率越低[34]。相反,不加入VC的12G硬质合金烧结件硬度较低,且有较高的摩擦因数,这意味着在测试过程中测试件受到的摩擦力越大,产生的热量就越多,耐磨性就变得越差。
(1)VC能有效提升黏结剂喷射增材制造硬质合金的SLM成形质量,VC在不显著影响硬质合金烧结件收缩率和致密度的情况下,可以显著改善硬质合金SLM构件的表面质量。未添加VC的硬质合金烧结件粗糙度为5.49 μm,添加0.5%VC和1.0%VC之后,硬质合金烧结件的表面粗糙度分别降低21.49%和17.77%。
(2)添加VC能显著抑制黏结剂喷射增材制造硬质合金打印-烧结件的WC晶粒的生长,使晶粒尺寸更细小,分布更均匀。在未添加VC时,WC晶粒D50为1.83 μm,最大WC晶粒尺寸将近10 μm;添加0.5%VC和1.0%VC之后,BJ打印烧结件中WC晶粒的D50分别为1.57 μm和1.61 μm,最大WC晶粒尺寸为5 μm,晶粒尺寸得到显著细化。
(3)适量的VC能有效提升WC-12Co硬质合金的力学性能,未添加VC的硬质合金烧结件的维氏硬度和抗弯强度分别为1250HV30和2051 MPa,添加0.5%VC使硬质合金烧结件的维氏硬度提升3.3%,抗弯强度提升约3.0%。此外,VC能有效降低硬质合金烧结件的摩擦因数和磨损率,显著强化耐磨性能。
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2026年第54卷第2期
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doi: 10.11868/j.issn.1001-4381.2024.000812
  • 接收时间:2024-12-06
  • 首发时间:2026-10-27
  • 出版时间:2026-02-20
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  • 收稿日期:2024-12-06
  • 录用日期:2024-12-21
基金
2019佛山市科技创新团队项目(FS0AA-KJ919-4402-0023)
阳江市引进创新科研团队项目(RCZX2024003)
作者信息
    1.广东工业大学 机电工程学院,广州 510006
    2.广东金瓷三维技术有限公司,广东 佛山 528225

通讯作者:

邓欣(1971—),男,教授,博士,研究方向为金属及金属基复合材料增材制造研究,联系地址:广州市番禺区小谷围街广州大学城外环西路100号广东工业大学机电工程学院(510006),E-mail:
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https://castjournals.cast.org.cn/joweb/clgc/CN/10.11868/j.issn.1001-4381.2024.000812
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2种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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