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。     

纳米复合碳化钨-钴材料的磁性能研究

超细晶碳化钨-钴(WC-Co)硬质合金是当今具有高强度、高硬度最佳综合性能的材料.通过测定WC-Co材料的磁性能来控制其制备工艺具有重要的理论意义和实用价值.本工作用喷雾热解-流态化连续还原碳化法制备了WC-Co纳米复合粉末,用等离子放电烧结(SPS烧结)技术制备了超细晶硬质合金,测试了不同钴含量样品的碳含量、密度和磁滞回线,由此计算了化合碳含量、钴平均自由程和碳化钨平均晶粒度,并与实测数据进行了比较.     

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.     

超细WC-Co硬质合金粉末的制备及其致密化研究

以超细碳化钨(WC)、氯化钴(CoCl2.6H2O)和柠檬酸钠(C6H5O7Na3.2H2O)为原料,水合肼(N2H4.H2O)为还原剂,使用液相还原法制备超细WC-Co硬质合金粉末,并通过低压烧结使其致密化,制得力学性能良好的WC-Co硬质合金。考察了反应体系温度对硬质合金粉包覆率、反应时间对包覆效果的影响,采用SEM、TEM、XRD等手段对硬质合金粉进行了表征,确定了制备超细WC-Co硬质合金粉的优化工艺条件,并对比了不同规格的WC-Co硬质合金烧结体的力学性能。结果表明,此方法制得的WC-Co硬质合金粉纯度高,粒径均匀,无团聚,低压烧结后所得硬质合金烧结体力学性能良好。     

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。     

基于超细晶硬质合金钻头的AFRP钻削性能

采用超细晶硬质合金钻头开展了芳纶纤维增强树脂基复合材料(Aramid Fiber Reinforce Polymer Composites,AFRP)的钻削实验,从钻削力、钻削温度、制孔质量、刀具磨损等方面对比分析了超细晶硬质合金钻头与普通硬质合金钻头的钻削性能。实验结果表明:芳纶纤维增强树脂基复合材料钻削过程中,钻削力随进给速度的增大而增大,随主轴转速的增大而减小,超细晶硬质合金钻头的钻削力比普通硬质合金钻头降低了40.6%以上;钻削温度随进给速度的增大而减小,随主轴转速的增大而增大,相对普通硬质合金钻头,采用超细晶硬质合金钻头的钻削温度降低了47~85℃;超细晶硬质合金钻头钻削产生的拉毛和热损伤明显少于普通硬质合金钻头;经过长时间的钻削,普通硬质合金钻头的橫刃和主切削刃出现了崩刃,后刀面出现了严重的磨料磨损;而超细晶硬质合金钻头由于高硬度和高耐磨性等特性,刀具的磨损相对较小,适合于芳纶纤维增强树脂基复合材料的高效低损伤加工。     

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...     

超细晶/纳米晶铝膜的研究现状

综述了超细晶/纳米晶铝膜的制备技术和制备工艺参数如衬底类型、氩气分压和靶功率等对铝膜结构性能的影响;介绍了目前超细晶/纳米晶铝膜的显微组织、铝薄膜及超薄铝薄膜的研究和其机械性能等研究方面的现状和进展,并展望了超细晶/纳米晶铝膜研究的发展前景.     

放电等离子烧结(SPS)制备金属材料研究进展

综述了放电等离子烧结(SPS)技术在制备纳米/超细晶、大块非晶、准晶、金属间化合物、功能梯度材料、多孔材料、硬质合金等多种金属材料中的应用情况.重点阐述烧结过程中的致密化机理,焦耳热生成机制,关于等离子活化效应的争议,电流、温度、位移量和应力分布的不均匀性及其影响,粉末的预处理工艺及其对性能的影响.并总结了SPS技术现存问题及发展趋势.     

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)。     

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.     

Research on Ultrafine Tungsten Carbide-Cobalt (WC-Co) Cemented Carbide Rods of Miniature Drills for Highly Integrated Printed Circuit Board (PCB)

Nanocrystalline tungsten carbide-cobalt (WC-Co) composite powders produced through spray thermal decomposition-continuous reduction and carburization technology were used to prepare φ3.25 mm×38 mm ultrafine tungsten carbide-cobalt (WC-Co) cemented carbide rods through vacuum sintering plus sinterhip technology. The microstructure, Vickers hardness, density and Rockwell A hardness (HRA), transverse rupture strength (TRS), saturated magnetization and coercivity force were tested. The results show that the average grain size of the sintering body prepared through vacuum sintering plus sinterhip technology was 430 nm; transverse rupture strength (TRS) was 3850 MPa; Vickers hardness was 1890 and Rockwell A hardness of sintering body was 93. High strength and high hardness ultrafine WC-Co cemented carbide rods used to manufacture printed circuit board (PCB) drills were obtained.     

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.     

Characterizations of WC–10Co nanocomposite powders and subsequently sinterhip sintered cemented carbide

Ultrafine WC–Co cemented carbides, combining high hardness and high toughness, are expected to find broad applications. In this study, WC–10Co–0.4VC–0.4Cr₃C₂ (wt.%) nanocomposite powders, whose average grain size was about 30 nm, were fabricated by spray pyrolysis-continuous reduction and carbonization technology. The as-prepared nanocomposite powders were characterized and analyzed by chemical methods, scanning electron microscopy (SEM), transmission electron microscopy (TEM), BET analysis and atomic force microscopy (AFM). Furthermore, “sinterhip” was used in the sintering process, by which ultrafine WC–10Co cemented carbides with an average grain size of 240 nm were prepared. The material exhibited high Rockwell A hardness of HRA 92.8, Vickers hardness HV₁ 1918, and transverse rapture strength (TRS) of 3780 MPa. The homogeneously dispersed grain growth inhibitors such as VC, Cr₃C₂ in nanocomposite powder and the special nonmetal–metal nanocomposite structure of WC–10Co nanocomposite powder played very important roles in obtaining ultrafine WC–10Co cemented carbide with the desired properties and microstructure. There was an abundance of triple junctions in the ultrafine WC–10Co cemented carbide; these triple junctions endowed the sintered specimen with high mechanical properties.     

WC-Co类硬质合金疲劳特性研究现状

综述了WC-Co类硬质合金疲劳裂纹的产生及扩展特性,指出WC-Co类硬质合金在使用时同时受多种疲劳的共同作用,但疲劳失效的主要形式是不同的,其中在中软岩石层中工作时的疲劳失效主要是由热疲劳引起的,在硬岩石层中工作时的疲劳失效主要是由冲击疲劳引起的.根据文献资料可归纳出:合金显微组织结构(晶粒度)、化学成分(Co量、总碳等)、纯净度(微量元素)和合金残余应力都是影响合金疲劳性能的主要因素,尤其认为Co粘结相的平均自由程是影响合金疲劳性能最主要的因素.     

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.     

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.     

Effect of Carbon Addition on Microstructure and Properties of WC-Co Cemented Carbides

Based on a unique method to synthesize WC-Co composite powder by insitu reactions of metal oxides and carbon, the effects of the carbon addition in the initial powders on the phase constitution, microstructure and mechanical properties of the cemented carbides were investigated. It is found that with a suitable carbon addition the pure phase constitution can be obtained in the sintered bulk from the composite powder. The mechanical properties of the cemented carbides depend on the phase constitution and the WC grain structure. To obtain the excellent properties of the WC-Co bulk, it is important to obtain the pure phase constitution from the appropriate carbon addition in the initial powders and a suitable grain size.