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。     

高性能超细、纳米硬质合金及其制备过程中的关键技术问题

介绍了超细、纳米硬质合金的国内外研究、生产以及市场情况,主要应用领域,硬度、抗弯强度、断裂韧性、热硬度、热导率等力学、热物理性能和使用性能特点,湿磨过程中的研磨与分散、混合料制备过程中的控氧、粉末成形、烧结过程中WC晶粒长大的控制和粉尘控制等合金制备过程中存在的关键技术问题以及解决这些问题的主要途径.     

VC/Cr3C2添加剂与烧结温度对超细WC-12Co硬质合金的影响

为了有效控制烧结过程中WC晶粒的长大,获得高强度高硬度的超细硬质合金,采用扫描电镜、拉伸机和洛氏硬度仪研究了不同质量分数及配比的VC/Cr3C2晶粒长大抑制剂和烧结温度对超细WC-12Co硬质合金的显微组织及力学性能的影响,并结合试验结果分析了超细硬质合金中VC/Cr3C2晶粒长大抑制剂的作用机理.结果表明,添加适量VC/Cr3C2晶粒长大抑制剂的超细硬质合金中WC晶粒尺寸分布集中,不存在明显的组织缺陷,合金具有细而均匀的微观组织及优异的力学性能.当晶粒长大抑制剂(质量分数)为0.2%VC/0.5%Cr3C2,1450℃烧结制备WC-12Co超细硬质合金的抗弯强度为3710MPa,硬度(HRA)为91.5.VC/Cr3C2晶粒长大抑制剂的作用机理为:VC主要与WC反应生成(W,V)C固溶体聚集在WC/Co界面,降低WC/Co界面能,Cr3C2主要固溶在粘结相中,导致WC在粘结相中的溶解度降低,二者的综合作用减缓了粘结相中WC溶解-析出过程,从而抑制烧结过程中WC晶粒的长大.     

纳米材料在硬质合金中的应用

WC晶粒不断细化是硬质合金发展的一个重要特征。从硬质合金的纳米原料、纳米硬质合金、纳米材料助长或增强超粗晶硬质合金以及硬质合金的纳米涂层材料等4个方面论述了纳米材料在硬质合金中的应用,着重报道了中国在这些方面的优势。纳米粒径原料的制备是首要难题,1997年发明的"紫钨原位还原"技术利用传统工艺制备纳米、超细碳化钨粉末,碳化钨粉的粒径可小于20 nm。纳米硬质合金技术利用低压热等静压或热等静压,克服了烧结过程中WC异常长大的难题,制备100~200 nm纳米硬质合金,抗弯强度在5 000 MPa以上,使用性能优于亚微或超细晶硬质合金,已用于生产。利用"纳米颗粒溶解法"制备的超粗晶硬质合金晶粒度可达12μm;而含有纳米Co2W4C增强相的超粗晶硬质合金产品,使用寿命比普通合金产品提高了2~3倍。涂层材料纳米化,是硬质合金工具的一个发展方向,在耐磨性、硬度和抗裂纹扩展方面有明显优势,加工工件表面质量更好,工具使用寿命更长。     

超细(纳米)硬质合金的制备研究进展

随着电子信息产业、汽车制造业及相关行业的快速发展,超细(纳米)硬质合金的需求量逐年上升。超细(纳米)硬质合金制备的关键问题之一是如何控制WC晶粒的长大,着重论述原材料和烧结技术对高性能超细(纳米)硬质合金制备的影响。分析了超细(纳米)WC-Co复合粉末和硬质合金的关键制备方法及其优缺点,指出了复合粉末和超细(纳米)硬质合金制备过程中存在的主要问题及其解决方案。最后,对每种制备方法的发展潜力进行了展望,阐明了超细(纳米)硬质合金的发展趋势。     

纳米级碳化钨粉末的直接碳化制备

从WO3到WC的直接碳化反应一般遵从WO3→WO2.72→WO2→W→W2C→WC的顺序.细小的颗粒一般在直接碳化反应WO2.72→WO2的阶段产生,通过严格控制这个反应步骤可成功制得纳米WC粉末.大量的研究已证明,烧结碳化物的性能如硬度、强度主要受WC粉末粒子尺寸、Co含量及碳含量的影响.最细的工业级碳化物一般加入VC,Cr3C2,TaC来抑制晶粒的长大,烧结后可以获得晶粒约0.5μm的WC硬质合金.为了制备超硬的烧结碳化物,有必要开发纳米级WC粉末粒子及发展纳米WC粉末均匀分布的加工技术,阐明在从WO3到WC的反应过程中中间产品和WC晶粒增长,纳米晶的形核,中间产品形貌变化,及WC粒子的破碎和分级等现象.     

烧结工艺对WC-1.0TiC-3.1TaC-4.5Co硬质合金性能及微观组织的影响

采用传统粉末冶金法,分别用真空烧结和低压烧结工艺制备出一系列WC-1.0TiC-3.1TaC-4.5Co硬质合金样品。利用光学显微镜、扫描电镜与能谱仪对合金微观组织结构特征进行观察与分析。结果表明:提高真空工艺烧结温度或采用低压烧结工艺,能使合金内部的显微孔隙、钴池减少;低压烧结制备的合金WC晶粒度小于真空烧结制备的合金WC晶粒度,合金中易出现WC晶粒异常长大现象。     

超细（纳米）硬质合金的制备研究进展

随着电子信息产业、汽车制造业及相关行业的快速发展,超细（纳米）硬质合金的需求量逐年上升。超细（纳米）硬质合金制备的关键问题之一是如何控制WC晶粒的长大,着重论述原材料和烧结技术对高性能超细（纳米）硬质合金制备的影响。分析了超细（纳米）WC-Co复合粉末和硬质合金的关键制备方法及其优缺点,指出了复合粉末和超细（纳米）硬质...     

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)。     

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.     

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.     

超细碳化钨-钴硬质合金的原子力显微镜研究

以液相复合-连续还原碳化方法制备的纳米碳化钨-钴复合粉末为原料,采用低压烧结制备了性能优良的超细碳化钨-钴硬质合金.运用原子力显微镜(AFM)对超细碳化钨-钴硬质合金的表面形貌进行了观察、缺陷和粒度分析,同时对合金的力学性能进行了测试.结果表明,采用低压烧结获得的烧结试样的洛氏硬度HRA≥93.5,抗弯强度TRS≥3300MPa,平均晶粒度＜220nm.制备了具有高强度、高硬度的超细碳化钨-钴硬质合金.纳米碳化钨-钴复合粉末制备的超细硬质合金组织结构均匀,但局部仍然存在着组织缺陷,分析了产生缺陷的机理.     

Mechanical properties of WC/Co cemented carbide with larger WC grain size

The mechanical properties of WC/Co cemented carbide with WC grain size of up to 30 μm are investigated through compressive and transverse rupture tests, because it is now to produce WC/Co cemented carbide of which grain sizes are from 20 to 30 μm. From testing specimens with a WC grain size of 3–30 μm and Co content of 5–20 wt.%, it is found that WC/Co cemented carbide with larger WC grains (20–30 μm) exhibit ductility, whereas smaller-grained materials are characteristically brittle.     

Complex carbide powders for plasma spraying

Various carbide-containing powders are used for plasma spraying. Most of these consist of tungsten carbide. Very frequently the tungsten carbide is mixed with cobalt to produce coatings similar to cemented carbides. The powders can be made by agglomeration of the carbides and the metal matrix powders or by coating the carbides with the matrix metal. As in cemented carbides, cobalt and nickel form the metal binder of the coatings. The coating metals can be increased to 20% of the total weight. Further metal matrix powders can be added also. The W₂C, WC, W₂C-WC eutectic phases and mixtures of them are used as tungsten carbide. The carbon content is very important and can be controlled better in coated particles than in an agglomerated powder. In the case of WCCo the carbon content has to correspond to MC to avoid the embrittling η phase and to achieve a strength of the coating comparable with that of cemented carbides. In addition to the composition, shape and grain size distribution of the powders, the spraying conditions are very important for the properties of the coating. Coated carbide powders are less sensitive to spraying conditions. When it is possible to control the carbon content in carbides better during spraying it will be feasible to use complex carbides also.Titanium carbide forms a solid solution with WC over a wide range of composition and forms mixed crystals with tantalum carbide and niobium carbide. These binary and ternary mixed carbide crystals, sometimes containing additional tungsten carbide, are used in cemented carbides to increase the wear resistance. By spraying these cobalt- or nickel-coated complex carbide powders similar properties of the coatings can be achieved. Spraying conditions and the shape, grain size and grain size distribution of the powders are important. Results will be given.     

Cu部分代Co超细硬质合金研究

基于Cu与Co相同的晶型结构和相似的原子结构,采用共沉淀方法,制备Cu部分代Co的WC—10Co硬质合金,研究Cu对材料的组织和力学性能的影响。实验结果表明,通过Cu—Co共沉淀方式将cu加入粘接相中,形成Co（Cu）固溶体,在液相烧结过程中Cu均匀地分布在Co中,可以降低WC在粘接相中的溶解度,有效阻碍WC颗粒的溶解...     

Grain size effect on wear resistance of WC-Co cemented carbides under different tribological conditions

The grain-size dependence of wear resistance of WC-Co cemented carbides(with mean WC grain sizes of 2.2 μm,1.6 μm,0.8 μm and 0.4 μm,respectively) was investigated under different tribological conditions.The results showed that the grain size had opposite effects on wear resistance of the cemented carbides in dry sliding wear and microabrasion tests.In the former condition,with decrease of WC grain size hence the increase of hardness,plastic deformation,fracture,fragmentation and oxidation were all mitigated,leading to a drastic decrease in the wear rate.In the latter condition,pull-out of WC grains after Co removal dominated the wear,so that the hardness of cemented carbide was not a core factor.As a result,the wear resistance of the cemented carbide generally showed a decreasing trend with decrease of the grain size,except for a slight increase in the ultrafine-grained cemented carbide.Single-pass scratching of the cemented carbides under various loads indicated the same failure mechanism as that in the sliding wear tests.Furthermore,the reasons for severe surface oxidation of the coarse-grained cemented carbides were disclosed.     

Preparation of nanomaterials from metalorganic compounds of tungsten and molybdenum

We have studied the sequence of phase transformations of the thermolysis products of tungsten- and molybdenum-containing metalorganic compounds and examined the influence of various phases on the formation of nanocrystalline carbide materials and the possibility of controlling the particle size of forming phases. We have obtained WC and WC/Co materials ranging in crystallite size from 13 to 26 nm and high-porosity (up to 80%) molybdenum, nickel-molybdenum, and titanium-molybdenum materials ranging in strength from 5 to 26 MPa.     

Chemical Processing of Nanostructured Cemented Carbide

Chemical processing is becoming a vital component in the economic development of advanced engineering materials. Our research group on chemical processing has been focussed on the development of process to produce nanophase cemented carbide. It is a much more direct route for making WC/Co than traditional processing methods, and offers the potential for lower cost production of novel materials with homogeneous nanophase microstructures and improved properties. This paper addresses the scientific and technical issues relating to the chemical processing of nanophase WC/Co composite powder and their sintering.