超细、纳米晶WC-Co硬质合金烧结技术的研究现状

WC-Co硬质合金因高硬、耐磨而在切削、釆矿和耐磨零件等领域广泛应用。研究发现,当WC晶粒尺寸小于0.5μm时(即超细、纳米晶WC-Co硬质合金),与普通硬质合金相比,材料的硬度和强度显著提高,其韧性也同样会有所提升。因此,晶粒细化有助于改善硬质合金的力学性能,从而延长其使用寿命。长期以来,有关硬质合金性能改善方面的研究多关注于从粉体出发,即通过采用超细纳米粉体和合理烧结工艺来实现超细晶和纳米结构硬质合金的制备。然而,在合金制备过程中其致密性与晶粒长大之间往往存在较为复杂的交互作用,如何保证在烧结过程中致密化的同时抑制WC晶粒长大是提高合金性能以及保证合金质量稳定性的关键技术问题之一。本文主要阐述了高温液相烧结制备超细、纳米晶WC-Co硬质合金过程中有关致密化和晶粒长大机制之间的关联性,从烧结工艺与添加剂两方面介绍了近年来国内外的研究现状。烧结工艺具体分为常规烧结工艺(主要包括氢气烧结、真空烧结和热等静压烧结等)和快速烧结工艺(主要包括微波烧结、放电等离子烧结、高频感应热烧结等),对比了上述烧结工艺之间的不同以及总结了不同烧结工艺的优缺点。在添加剂方面,重点介绍了过渡族碳化物和稀土元素对硬质合金烧结过程中晶粒生长的抑制作用,并在此基础上阐述了超细、纳米晶WC-Co硬质合金烧结技术的未来发展趋势。     

纳米晶WC-Co硬质合金的研究现状

概述了国内外纳米晶硬质合金的发展现状.纳米晶WC-Co硬质合金制备的关键技术主要包括:优质纳米晶WC粉的制备和烧结过程中WC晶粒长大的控制.综述了优质纳米晶WC粉的特点和制备技术,以及目前国内外烧结过程中控制晶粒长大采取的主要措施:添加晶粒长大抑制剂、调整烧结工艺和开发新型烧结方法.列举了合金的实际应用领域,展望了纳米晶硬质合金的发展前景.     

烧结温度对WC-TiC-TaC-Co硬质合金性能的影响

采用不同温度下的低压烧结工艺制备WCTiC-TaC-Co硬质合金.结合金相显微镜、XRD及SEM等分析测试手段,研究了烧结温度对合金的微观组织和性能的影响.结果表明,低压烧结工艺下形成了WC+(WC-TiC-TaC)+γ三相合金;合金在1475℃下获得最优的综合性能,其密度、维氏硬度、抗弯强度及断裂韧性分别为:12.9...     

烧结保温时间对超粗晶WC-10Co硬质合金微观结构及性能的影响

超粗晶WC-Co硬质合金因耐磨性高和韧性好成为研究的一个热点,而致密度和晶粒的控制是获得优异性能的关键.采用轻度球磨法获得添加超细WC的复合粉末,通过真空烧结制备平均晶粒尺寸为8.3～8.8μm的超粗晶WC-10Co硬质合金,研究烧结保温时间对致密度、WC晶粒及力学性能的影响.结果表明:随着烧结保温时间从30 min增至120 min,致密度先增加后下降,Co在合金表面聚集氧化并使内部孔隙增多,部分WC晶粒聚集形成异常晶粒,这些缺陷结构阻碍了孔隙的消除;超细WC和球磨破碎细WC的先后溶解析出,使WC平均晶粒度先增加后减小,晶粒分布变宽.当烧结保温时间为60 min时,曲面类球状WC部分通过台阶生长机制转变为性能友好型的圆边六棱柱晶粒,抗弯强度和冲击韧性达到最高,分别为1733 MPa和28 kJ·m-2.此外,烧结过程中部分晶粒中原生缺陷难以完全消除,而较长的烧结保温时间下,多种缺陷的增多降低合金性能.     

低压烧结温度对一步法制备超细晶WC-Co基硬质合金组织及性能的影响

采用等离子球磨技术制得W-C-10Co-0.9VC-0.3Cr_3C_2纳米复合粉体,并利用单向模压成型法将其压制成生坯,再经低压烧结一步法制备成硬质合金。研究表明,等离子球磨3h所获得的复合粉体呈片层状形貌,并且成分分布均匀。在1 380℃及1 400℃烧结时,由于等离子球磨的特殊作用,VC、Cr_3C_2对WC晶粒长大抑制作用突显。1 380℃烧结制备的硬质合金,致密度为99.2%,WC平均晶粒尺寸为250nm,硬度和横向断裂强度分别为92.3HRA和2 443 MPa,具有最佳的WC晶粒尺寸与致密度配合,以及最佳的综合力学性能。     

Cr含量对WC-Co硬质合金显微组织和力学性能的影响

采用低压烧结技术制备了不同Cr含量的WC-8Co硬质合金,通过XRD、SEM和力学性能测试等手段分析了Cr含量对硬质合金物相、显微结构和合金的力学性能的影响。结果表明,当Cr含量<0.9%时,合金由WC+γ-(WC)相组成,添加量增至0.9%及以上时,组织中出现缺碳相Co3W3C;随着Cr含量的增加,WC晶粒不断细化,当添加量为0.6%时,合金的综合力学性能最佳,其抗弯强度、维氏硬度及断裂韧性分别为3885MPa、1632.4HV30、9.82MPa.m1/2。     

碳纳米管对硬质合金WC晶粒及强度的影响

以碳纳米管为增强相,WC-10Co硬质合金为基体,采用湿法球磨工艺将多壁碳纳米管(Multiwalled carbon nanotubes,MWCNTs)和WC-10Co硬质合金粉料充分混合,通过真空烧结制成CNTs增强的WC-10Co硬质合金试样。采用SEM观测MWCNT在硬质合金基体中的分布和烧结后硬质合金微观结构。SEM显示碳纳米管嵌插在WC晶粒之间,抑制WC晶粒生长,使WC晶粒得到细化。试样横向断裂强度达到1 780 MPa,对比未增强试样提高了7.8%。     

后续烧结对爆炸压实CuCr合金性能的影响

采用机械合金化工艺由Cu,Cr元素粉按重量比各半合成CuCr预合金粉,尔后爆炸压实工艺制坯,再加后续烧结制备了电触点材料CuCr合金,着重研究了后续烧结对爆炸实CuCr合金性能的影响,结果表明,真空烧结略微提高爆炸压实的CuCr合金的密度,而氢气烧结处理反而使其密度降低,真空烧结和氢气烧结都能显著降低CuCr合金硬度,而且氢气烧结降低得更明显,真空烧结和氢气烧结都显著提高CuCr合金的电导率,而且真空烧结提高更显著。     

粉末冶金法制备Al-Pb合金微观组织分析EI

采用机械合金化与真空热压烧结制备Al-Pb合金,并通过热挤压变形细化显微组织。XRD检测分析表明:Al,Pb衍射峰随机械合金化的进行不断宽化,晶粒尺寸减小。SEM分析表明:球磨15h后可以得到合金粉末,其具有Pb粒子弥散分布于Al基体的复相结构。再通过550℃/20MPa真空热压烧结1h,可制备出Al-Pb合金块体。适当的热挤压工艺能够细化组织,减小Pb颗粒的尺寸。其抗拉强度可达231.6MPa,延伸率为17.6%。     

微波烧结制备WC-TiC-Co硬质合金的组织和性能研究

以WC粉为基体,Co为粘结相,TiC颗粒为抑制剂,通过球磨、压制成型,微波烧结制备WC-TiC-Co硬质合金.结果表明,在1360℃微波烧结为液相烧结,Co与WC会发生反应生成η相(Co3W3C).随TiC含量升高,合金的晶粒逐渐变得均匀细小,合金的相对密度、硬度和抗弯强度均先升高后下降,硬度在0.5％TiC时达到最高值,相对密度和抗弯强度在1.0％TiC时达到最高值.     

纳米WC硬质合金制备新工艺

文章综述了制备纳米WC、WC Co粉体的几种方法。着重阐述了纳米WC Co硬质合金的烧结新工艺 :微波烧结、二阶段烧结、快速热等静压烧结和等离子体活化烧结等。与传统烧结方法相比 ,使用这些烧结新工艺制备的产品性能更优异 ,有很大的发展前景。     

板状WC晶粒WC-(Co-Ni)硬质合金的组织和性能

采用真空烧结法制备了板状WC晶粒WC-(Co-Ni)硬质合金,通过XRD、SEM、EDS等手段研究了Ni/(Ni+Co)比对硬质合金组织和性能的影响规律。结果表明:随着Ni/(Ni+Co)比的增大,硬质合金显微组织中板状WC晶粒的比例逐渐减少,硬质相颗粒的尺寸逐渐增大且平均长厚比逐渐减小。当Ni/(Ni+Co)比过大时,硬质合金中硬质相颗粒出现了团聚现象,使其力学性能显著降低。当Ni/(Ni+Co)比为0.3和0.5时,WC-(Co-Ni)硬质合金的综合力学性能较高,这与其硬质相颗粒较细和平均长厚比较大有关。当Ni/(Ni+Co)比为0.5时,WC-(5Co+5Ni)硬质合金具有较优的综合力学性能,其抗弯强度、硬度和断裂韧性分别为2 448 MPa、90.0HRA、21.2 MPa·m~(1/2)。     

1400℃放电等离子烧结制备MgO-B_(2)O_(3)增韧无金属黏结相WC硬质合金EI北大核心CSCD

为了降低无金属黏结相碳化钨(WC)硬质合金的烧结温度并获得较高的断裂韧度,采用MgO和B_(2)O_(3)协同增韧WC硬质合金。通过放电等离子烧结技术(SPS)在1400℃的较低温度下制备出致密的WC-MgO-B_(2)O_(3)硬质合金块体材料,研究MgO-B_(2)O_(3)对无金属黏结相WC硬质合金的烧结机理、微观组织演变以及力学性能的影响规律。结果表明:MgO-B_(2)O_(3)的添加促进了WC的烧结致密化,显著降低了无金属黏结相WC硬质合金的烧结温度。随着MgO-B_(2)O_(3)添加量的提高,组织中的部分第二相形貌发生显著改变,逐渐由短杆状转变为长杆状,再转变为聚集时的块状。当MgO-B_(2)O_(3)添加量达到8%(质量分数)时,块体材料具有较好的断裂韧度,为(9.45±0.37)MPa·m^(1/2),同时其硬度为(18.16±0.17)GPa。     

Spark plasma sintering on nanometer scale WC–Co powder

Nanometer scale WC–11Co powder was sintered by spark plasma sintering (SPS) process in order to improve the properties of the cemented carbides. Properties such as density and hardness were measured. The microstructures of sintered WC–11Co cemented carbides were observed. The grain size of WC in alloys was also obtained. The results showed that spark plasma sintering could lower the sintering temperature, increased the density and circumscribed the growth of grain size of WC. Besides, the hardness of the sintered cemented alloys that was dependent on the grain size and densification could also be improved by SPS. SPS was an effective method to get WC–11Co cemented carbides with fine grain size and good properties.     

纳米碳化钒对超细WC基硬质合金的影响

研究了在放电等离子烧结(SPS)条件下,纳米碳化钒(V8C7)对超细WC基硬质合金的相组成、微观组织及性能的影响。结果表明:超细WC基硬质合金主要由WC和Co3C两相组成,相对于未烧结的硬质合金材料,WC的衍射峰向小角度方向偏移;纳米碳化钒可以有效抑制超细WC基硬质合金中WC晶粒的长大,并且随着纳米碳化钒比表面积的增大而增强,添加比表面积为63.36m2/g的纳米V8C7后,硬质合金中大部分WC的晶粒尺寸0.5μm;纳米碳化钒对超细WC基硬质合金的性能具有重要影响,并且随着纳米碳化钒比表面积的增大而增加,添加比表面积为63.36m2/g的纳米V8C7后,超细WC基硬质合金具有较高的性能(相对密度99.7%,洛氏硬度93.4,断裂韧性12.7MPa.m1/2)。     

Microstructure development during sintering and heat-treatment of cemented carbides and cermets

WC based cemented carbides and Ti(C, N) based cermets are used in cutting tool applications. They are produced by liquid phase sintering, but much of the microstructure is formed already during solid state sintering, before the eutectic temperature has been reached. Changes in the microstructure during the sintering process have been followed with microscopy and microanalysis, in particular SEM and TEM including energy filtered transmission electron microscopy (EFTEM). It was found that part of the hard phases are dissolved in the solid binder, transported by diffusion and re-precipitated onto undissolved hard grains with a composition given by the equilibrium conditions (“inner rim”). For vacuum sintering of nitrogen containing materials, this means a low nitrogen activity due to the open porosity at this stage. After the liquid has formed, further dissolution and re-precipitation occur, but now the porosity is closed so the “outer rim” is formed with the nitrogen activity of the material. The solid solution of the binder (often by tungsten) is determined primarily by the carbon activity in the liquid phase. During cooling after sintering, tungsten and other metals dissolved in the binder re-precipitate onto hard grains so that depleted zones around these are formed, whereas dissolved carbon and nitrogen have time to leave the binder almost completely. Sintering or post-sintering heat-treatment of nitrogen containing materials in an atmosphere with a lower or higher nitrogen activity than in the material results in the formation of surface zones with a composition different from the bulk (“gradient sintering”). In the former case, a tough zone enriched in binder and depleted of cubic carbides is created, which is beneficial if the material is going to be coated with a wear resistant layer. In the latter case a hard surface zone rich in cubic carbo-nitrides and depleted of WC and binder may be obtained, improving the wear resistance of the material.     

On the Formation of Intercarbide and Interface Surfaces in WC–Co Cemented Carbides. Review

Based on the analysis of published studies, thermodynamic functions describing the processes of the formation of intercarbide and interface surfaces during the solid- and liquid-phase sintering of WC–Co cemented carbides. At present a certain progress in studies of the structure and composition of intercarbide WC/WC and interface WC/Co surfaces is attained, the technologies are developed that allow affecting the composition and structure of these surfaces. It is noted that the composition and structure of intercarbide and interface surfaces (Ti, W, Ta)C–WC–Co and (Ti, W, Nb)C–WC–Co of cemented carbides are not adequately investigated. The studies on the influence of the composition and structure of intercarbide and interface surfaces on physico-mechanical properties of cemented carbides and their operational characteristics remained urgent.     

硬质合金粉末挤出打印中增材制造工艺及其显微结构

粉末挤出打印(PEP)是基于传统金属注塑成型和3D打印相结合的新型增材制造技术,具有打印材料范围广、打印成本低等巨大优势。以WC-13Co硬质合金的PEP增材制造为核心,以热塑性打印材料为重点研究对象,开发打印原料的材料体系,研究打印原料的均匀性、流变性能、成形性能、黏结剂的脱除工艺以及烧结工艺对打印件显微结构及力学性能的影响机制。独立开发了硬质合金PEP打印专用的有机黏结剂材料体系,通过EDS分析黏结剂在打印坯体中分散均匀性。采用两步法脱脂工艺可以完全脱除打印坯体中的黏结剂,并结合真空烧结,在1450 ℃下保温60 min,成功制备高性能硬质合金打印件。研究结果发现打印件线收缩率为17.8%,WC晶粒尺寸分布均匀,维氏硬度1410HV₃₀。本研究采用PEP增材制造技术制备了高性能、打印件尺寸可控的硬质合金材料,为硬质合金的增材制造探索出一条有效的技术路线。     

Fabrication of Functionally Gradient Cemented Carbide with Ultrafine Grains

At present, the functionally gradient cemented carbide (FGCC) substrate with enrich cobalt on surface is mainly formed from medium grained WC grains. In order to further improve the properties of gradient cemented carbides, the ultrafine powder was chosen in this study and the functionally gradient cemented carbide with ultrafine grains was prepared by a two-step process, where the cemented carbide is first lower pressure pre-sintered and then subjected to a gradient sintering. The results show that it is possible to form gradient layer with enriched cobalt on surface by this method and also the grain growth can be inhibited by low pressure pre-sintering. Ultrafine grain gradient cemented carbide was fabricated after the gradient sintering, the thickness of gradient layer was about 43μm and the average grain size of WC is about 0.42μm. The formational mechanism of the functionally gradient cemented carbide with ultrafine grains are discussed through analyzing the influence of ultrafine microstructure, which was obtain by lower pressure pre-sintering, on atomic diffusion and grain growth during gradient sintering process.     

Investigation of WC–Co alloy properties based on thermodynamic calculation and Weibull distribution

The influence of alloy composition and sintering temperature on the mechanical properties and reliability of WC–Co cemented carbides was studied theoretically and experimentally. For the first time, through a hybrid approach of thermodynamic calculations and Weibull distribution, the comprehensive performance of ultrafine WC–Co cemented carbides with different C contents and inhibitor type was investigated in detail. The carbon content of WC–10?wt-% Co–0.5?wt-% Cr cemented carbides was carefully controlled within the range of 5.38?5.52?wt-%. The contents of Cr and V are chosen to be in the range of 0–1?wt-%. It is found that WC–10?wt-% Co–0.5?wt-% Cr alloys with 5.46?wt-% C or 5.5?wt-% C show excellent mechanical properties and high reliability. WC–10?wt-% Co alloys with 0.5?wt-% Cr and 0.4?wt-% Cr–0.2?wt-% V demonstrate high mechanical property and reliability. The results of this study can be used to design process parameters during the manufacture of WC–Co cemented carbides.