Microstructure and mechanical properties of 90WC-8Ni-2Mo2C cemented carbide developed by conventional powder metallurgy

In this paper, the microstructure and mechanical properties of a WC-Ni based cemented carbide with the addition of 2 wt% Mo₂C, processed by conventional powder metallurgy, was investigated. With the addition of only Mo₂C in the WC-Ni alloy system, the wettability between the WC and Ni binder phase was improved, which was confirmed by the increased density, hardness, fracture toughness and flexure strength of the cemented carbide obtained, which is superior than those observed in WC-10Ni cemented carbides and similar to those observed in WC-Co and WC-Ni-TiC-Mo₂C cemented carbides. Microstructural examinations of the developed cemented carbide 90WC-8Ni-2Mo₂C indicated that there was no excessive grain growth of the WC particles during sintering, confirming that Mo₂C is a grain growth inhibitor as effective as other carbides such as VC, TiC, Cr₂O₃, showing that the addition of only Mo₂C is able to improve the overall mechanical properties of the WC-Ni alloy system without sacrificing the toughness.     

Effect of VC and NbC additions on microstructure and properties of ultrafine WC-10Co cemented carbides

The nanocomposite WC-Co powders were prepared through planetary ball milling method. Effects of grain growth inhibitor addition and the vacuum sintering parameters on the microstructure and properties of ultrafine WC-10Co cemented carbides were investigated using X-ray diffractometer, scanning electron microscope and mechanical property tester. The results show that VC and NbC additions can refine the WC grains, decrease the volume fraction of Co₃W₃C phase in ultrafine WC-10Co cemented carbides, and increase the hardness and fracture toughness of the base alloys. After sintering for 60 min at 1400 °C, the average grain size and hardness of ultrafine-grained WC-10Co-1VC cemented carbide are 470 nm and HRA 91.5, respectively. The fracture toughness of cemented carbide WC-10Co-1NbC alloy is over 7 MN·m^?3/2.     

Ni3Al添加量对WC-Co硬质合金中WC晶粒形状的影响

采用粉末冶金制备技术,以粗WC粉末、Co粉和WC＋Ni3Al预合金粉末为原料制备出WC-40vol％（Co—Ni,Al）硬质合金。利用扫描电镜和透射电镜研究了不同NbAl含量对WC-40vol％（Co—Ni3Al）硬质合金中WC晶粒形状的影响规律。结果表明：W在Co粘结相中的固溶度接近25．4wt％,而W在Ni,Al粘结相中的固溶度接近9．5wt％,随着NbAl含量的增加,粘结相对W的固溶度减小,合金中的WC晶粒圆钝和细小;WC晶粒表面上出现明显的台阶。相应的,延长烧结时间,WC—Co—Ni3Al硬质合金具有与WC—Co硬质合金相同的WC生长行为,WC-40vol％（Co—Ni3Al）硬质合金中的WC晶粒表面上的台阶处出现明显的刻面。     

Influence and effectivity of VC and Cr3C2 grain growth inhibitors on sintering of binderless tungsten carbide

For the production of hard, high temperature and abrasion resistant parts, like water-jet nozzles or pressing tools for forming glass lenses, binderless cemented carbide is used. In this work, the consolidation of tungsten carbide with additions of VC and Cr₃C₂ grain growth inhibitors is studied. Tungsten carbide powder dry or wet milled was consolidated by dry pressing, debindering and gas pressurized sintering and, alternatively, by spark plasma sintering. The effect of adding VC and Cr₃C₂ to binderless tungsten carbide on the grain growth was studied with contents being 0; 0.1; 0.3; 0.5; 0.7 and 1.0 wt.%. Samples with an ultrafine microstructure free of abnormal grain growth, a hardness of 25.5 GPa and a fracture toughness of 7.2 MPa·m^1/2 were archived by conventional sintering. Both carbides reduce grain growth, but with Cr₃C₂ a finer microstructure can be achieved at lower amounts. Compared to the same amount of Cr₃C₂, the addition of VC results in smaller grains but lower hardness and fracture toughness.     

Influence of consolidation process and sintering temperature on microstructure and mechanical properties of near nano- and nano-structured WC-Co cemented carbides

In this paper the influence of the consolidation process and sintering temperature on the properties of near nano- and nano-structured cemented carbides was researched. Samples were consolidated from a WC 9-Co mixture by two different powder metallurgy processes; conventional sintering in hydrogen and the sinter-HIP process. Two WC powders with different grain growth inhibitors were selected for the research. Both WC powders used were near nanoscaled and had a grain size of 150 nm and a specific surface area of 2.5 m²/g. Special emphasis was placed on microstructure and mechanical properties; hardness and fracture toughness of sintered samples. Consolidated samples are characterised by different microstructural and mechanical properties with respect to the sintering temperature, the consolidation process used and grain growth inhibitors in starting powders. Increasing sintering temperature leads to microstructure irregularities and inferior hardness, especially for samples sintered in hydrogen. The addition of Cr₃C₂ in the starting powder reduced a carbide grain growth during sintering, improved microstructural characteristics, increased Vickers hardness and fracture toughness. The relationship between hardness and fracture toughness is not linear. Palmqvist toughness does not change with regard to sintering temperature or the change of Vickers hardness.     

Effect of binder-phase modification and Cr3C2 addition on properties of WC-IOC0 cemented carbide

For production of fine-grained and corrosion-resistant tungsten carbide (WC) based cemented carbides, addition of chromium carbide (Cr₃3C₂) in small amounts is standard practice. No systematic study, however, has been made of the effects of large additions (maximum 6 wt % ) of Cr₃C₂ as a substitute for tungsten carbide. This study focuses on the effect of hard-phase substitution by C₃C₂ in WC-1OCo cemented carbide. An attempt is also made to modify the binder metal cobalt by partial or complete substitution of nickel. Specimens were prepared using the standard liquid-phase sintering process and were tested for sintered porosity, mechanical properties, corrosion resistance, and microstructural parameters. Results confirm the findings of earlier workers regarding grain refinement and improvement of mechanical properties upon the addition of small amounts (<2 wt%) of Cr₃C₂. Modification of the binder phase improves indentation fracture toughness and corrosion resistance. Addition of Cr₃C₂ independent of the binder type improves corrosion resistance.     

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

采用Cr3C2、VC掺杂超细WC为原料和无压真空烧结工艺,通过合金微观组织结构的观察与分析,研究了添加质量分数为0.3%的Co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。结果表明,微量Co的存在加速了WC的烧结致密化过程,与此同时也导致了WC晶粒明显的各向异性非连续晶粒长大。在上述研究基础上,提出了一种无金属粘结相WC硬质合金的低成本制备工艺,探讨了超细硬质合金中WC晶粒生长机制,提出了超细硬质合金的质量改进建议。     

粗晶碳化钨粒度对WC-Co合金晶粒度的影响

选用供应态分别为30μm和12μm的二种粗颗粒WC粉末,研究不同方法表征的粉末粒度与合金晶粒度的关系。结果表明:三种粉末粒度测定方法给出的结果都呈现粒度越粗合金的晶粒度也越粗的规律。粗颗粒WC的研磨态粒度与合金的晶粒度相当接近,金相法测得的12μmWC的晶粒分布与所制备的合金的晶粒度的一致性比30μmWC制备的合金要好。粗晶WC研磨态的Fsss粒度可以用于评价粗晶WC晶粒度,也可以预测WC-Co合金的晶粒度。     

WC-Co-(Ni)-(Cr)硬质合金在中性溶液中的腐蚀行为

以WC粉、Co粉、Ni粉及Cr3C2粉为原料,采用粉末冶金方法制备了3组不同粘结相成分的WC-Co-(Ni)-(Cr)硬质合金,通过极化曲线测试和浸泡实验研究了3组合金在中性溶液中的腐蚀行为,并采用扫描电镜、能谱分析、X射线光电子能谱(XPS)和EBSD等手段对其腐蚀机理进行了探讨。结果表明,WC-Co和WC-Co-Cr硬质合金在中性溶液中主要发生粘结相Co的腐蚀,浸泡产生的腐蚀产物主要是Co(OH)2;添加Cr将提高WC-Co硬质合金在中性溶液中的耐腐蚀性能,这可能与Cr的添加明显降低了粘结相中密排六方Co的含量有关;同时添加Ni和Cr可进一步提高WC-Co合金在中性溶液中的耐腐蚀性能,在pH=7的Na2SO4溶液中浸泡480 h后,WC-Co-Ni-Cr合金发生很少量的腐蚀。     

Tungsten carbide platelet-containing cemented carbide with yttrium containing dispersed phase

A fine and platelet tungsten carbide patterned structure with fine yttrium containing dispersed phase was observed in liquid phase sintered WC-20% Co-1%Y2O3 cemented carbide with ultrafine tungsten carbide and nano yttrium oxide as starting materials. By comparing the microstructures of the alloy prepared by hot-press at the temperature below the eutectic melting temperature and by conventional liquid phase sintering, it is shown that hexagonal and truncated trigonal plate-like WC grains are formed through the mechanism of dissolution-precipitation （recrystallization） at the stage of liquid phase sintering. Yttrium in the addition form of oxide exhibits good ability in inhibiting the discontinuous or inhomogeneous WC grain growth in the alloy at the stage of solid phase sintering.     

抑制剂对WC-15wt%Co硬质合金性能的影响

研究了抑制剂的不同种类和添加量对WC-15wt%Co硬质合金性能的影响。添加抑制剂可以抑制烧结过程中的晶粒长大及非均匀长大,提高合金的各项性能。在原始WC粉末粒度较粗的合金中添加一定量的VC/Cr3C2,也可以制取WC晶粒度达到亚微米级的合金。     

A threshold stress for high-temperature plastic flow in WC-CO cemented carbides

The logarithmic relationship between flow stress and strain rate in WC-Co cemented carbides is represented by a signoidal curve at a constant temperature and is divided into three regions, as in superplastic metals. The flow stress in region I has no dependence on both carbide grain size and binder content, indicative of the presence of a threshold stress for high-temperature plastic flow in cemented carbides. The threshold stress estimated by extrapolating the plot of ε^m against σ to zero strain rate has a strong dependence on temperature. The logarithmic plot of the effective stress compensated by the threshold stress against strain rate shows a single straight line for region I and region II at a constant temperature, which suggests that the regions I and II are controlled by the same deformation process i.e. the grain boundary sliding in WC/WC boundaries. A small addition of Cr₃C₂ and VC gives rise to the outstanding increase in flow stress in region I and subsequently results in the marked increase in the threshold stress. The origin of the threshold stress in WC-Co cemented carbides is closely related to the impurity elements or the intensional additives such as Cr₃C₂ and VC.     

Vacuum sintering of WC-8 wt.% Co hardmetals from WC powders with different dispersity

The effect of sintering temperature and particle size of tungsten carbide WC on phase composition, density and microstructure of hardmetals WC-8 wt.% Co has been studied using X-ray diffraction, scanning electron microscopy and density measurements. The sintering temperature has been varied in the range from 800 to 1600 °C. The coarse-grained WC powder with an average particle size of 6 μm, submicrocrystalline WC powder with an average particle size of 150 nm and two nanocrystalline WC powders with average sizes of particles 60 and 20 nm produced by a plasma-chemical synthesis and high-energy ball milling, respectively, have been used for synthesis of hardmetals. It is established that ternary Co₆W₆C carbide phase is the first to form as a result of sintering of the starting powder mixture. At sintering temperature of 1100-1300 °C, this phase reacts with carbon to form Co₃W₃C phase. A cubic solid solution of tungsten carbide in cobalt, β-Co(WC), is formed along with ternary carbide phases at sintering temperature above 1000 °C. Dependences of density and microhardness of sintering hardmetals on sintering temperature are found. The use of nanocrystalline WC powders is shown to reduce the optimal sintering temperature of the WC-Co hardmetals by about 100 °C.     

氧化钨的形貌结构对纳米WC粉末均匀性的影响

研究了在传统氢还原工艺制备纳米碳化钨粉末过程中不同氧化钨的形貌结构对纳米W/WC粉末均匀性的影响,并对粉末及其WC-Co烧结体的性能进行了表征。结果表明,用具有疏松、多孔形貌结构的细小氧化钨颗粒更容易制备出结构较疏松、分散性较好的纳米W粉和WC粉。晶粒聚集和异常粗大颗粒的产生,主要与碳化过程中团聚纳米钨粉颗粒因烧结合并增粗有关。     

放电等离子烧结压力对超细WC-Co硬质合金性能的影响

通过分析放电等离子烧结致密化过程,确定了致密化温度;研究了SPS烧结过程中压力对WC-Co硬质合金致密化、显微组织及性能的影响。结果表明,放电等离子烧结粉末在1 130℃时,达到最大收缩率;烧结压力的增加,样品的致密度、硬度增加;断裂韧性的变化集中在11.5~12.1 MPa.m1/2之间,和硬度的变化呈现相反的趋势;烧结压力相对较小时,样品WC晶粒较粗大且不均匀;在40 MPa和55 MPa时,晶粒相对较小且分布均匀。要得到高性能、高致密度的样品,合理的烧结温度在1 200℃以上,烧结压力为40 MPa。     

Sintering behavior and mechanical properties of Cr3C2 doped ultra-fine WC-Co cemented carbides: Experment guided with thermodynamic calculations

The influence of Cr₃C₂ doping on the sintering process and mechanical properties of WC-Co cemented carbides was studied. Using differential thermal analysis of green powders and thermodynamic calculations, the disappearing temperature of solid-state binder phase in the ultra-fine WC-Co cemented carbides with different amounts of Cr₃C₂ dopant was first investigated and then verified to descend with the increase of Cr content. Based on these investigations, the sintering temperatures of three alloys with 0.3, 0.5 and 0.65 wt% Cr were selected to high by 50 °C than the phase disappearing temperature of solid-state binder. Compared with the commercial sample with the sintering temperature at 1410 °C for Cr₃C₂ doped WC-Co cemented carbides, the optimized sintering temperatures lead to finer microstructures and better mechanical properties, such as transverse rupture strength and hardness. In addition, the reliability for the performance of WC-Co cemented carbides prepared with the optimized sintering schedule is significantly improved in comparison with the commercial sample. The strategy from the present work can be used to design sintering process parameters during the manufacture of ultrafine WC-Co cemented carbides.     

超细WC-Co硬质合金的制备与性能研究

利用高能球磨法制备纳米级WC-Co混合粉末,采用脉冲电流烧结技术进行烧结。用能谱分析仪(EDX)对球磨后的粉末进行成分分析,用X射线衍射(XRD)对比分析球磨前后WC-Co混合粉末的衍射峰变化,用透射电子显微镜(TEM)和扫描电子显微镜(SEM)对所制备的粉末及烧结材料进行了组织形貌观察,并测定了烧结试样的硬度。结果表明:随着球磨时间的延长,WC-Co纳米粉末的粒度逐渐变小,当球磨时间超过30h后获得了粒度为100nm以下的WC-Co纳米粉末。脉冲电流烧结后获得超细WC-Co硬质合金,与传统的WC-Co硬质合金相比,超细WC-Co硬质合金具有更高的硬度(HRA92.5～94)和耐磨性。另外通过实验获得了最佳的烧结工艺参数。     

含WB烧结硬质合金的组织结构和性能研究

将不同含量的WB粉末添加到传统成分的WC-Co粉末中,利用低压烧结技术制备了系列含WB的WC-Co型硬质合金,并对其物相组成、组织结构和力学性能进行了系统表征分析。研究发现,在低压烧结过程中WB与Co发生反应,生成了具有超高硬度的WCoB相,由此降低了粘结相Co对WC晶粒的隔离,增加了WC晶粒间的接触度,引起合金韧性下降。添加WB制备的硬质合金材料其摩擦系数更低,随WB添加量的增加,硬度和耐磨性明显提高,当WB添加量为30%(质量分数)时,制备的硬质合金材料的硬度达到19 000 MPa,其磨损速率仅为传统WC-Co硬质合金1/10。然而,添加WB的WC-Co合金的断裂韧性约为传统WC-Co硬质合金的83%~91%。     

Additive manufacturing of WC-13%Co by selective electron beam melting: Achievements and challenges

Additive manufacturing is a powerful tool for rapid prototyping and fabricating metal articles having a complicated geometry. This method is known to be used almost solely for the manufacture of articles consisting of pure metals and alloys. In the present work the possibility of obtaining dense carbide articles by a single-step process of additive manufacturing based on selective electron beam melting was evaluated. A new technology for fabricating cemented carbide granules suitable for selective electron beam melting was developed. It includes conventional granulating WC-Co powders followed by solid-state pre-sintering and preliminary screening of the granules. After that their liquid-phase sintering and final screening are carried out to obtain a desired fraction needed for the additive manufacturing process. Results of experiments on selective electron beam melting at different scan rates and current values indicated that it was possible to obtain non-porous carbide articles of complex geometry from WC-Co granules initially containing 13 wt% Co. The selective electron beam melting process led to the evaporation of some liquid Co and very intense local WC grain growth resulting in peculiar microstructures of the cemented carbide articles comprising layers with medium-coarse and abnormally large WC grains. A near-surface layer of the cemented carbide articles obtained by additive manufacturing is characterized by a high roughness comparable with the mean size of the original WC-Co granules.     

Effects of nano-alumina on mechanical properties and wear resistance of WC-8Co cemented carbide by spark plasma sintering

The effects of adding different nano-alumina on the structure, mechanical properties and wear resistance of WC-8Co cemented carbide during spark plasma sintering (SPS sintering) were investigated. The results show that the nano-alumina is dissolved in the Co phase, which results in a larger proportion of FCC-Co in the γ phase on the surface of the WC-Co cemented carbide. Under the scanning electron microscope, it is observed that the grains of cemented carbide are refined, and when the addition amount is 0.5 wt%, the effect of WC grain refinement is the most significan. The hardness, flexural strength and fracture toughness showed a trend of increasing first and then decreasingwith nano-alumina added. The peak value is reached when the nano-alumina content is 0.5 wt%, Which means that the alloy has the best combination of mechanical properties, that is, hardness reaches 1716 HV₃₀, bending strength reaches 2728 MPa, and fracture toughness is 12.95 MPa·m^1/2. Adding nano-alumina is beneficial to improve the wear resistance of cemented carbide. As a matter of course, when the content of nano-alumina is 0.5 wt%, the friction coefficient is the lowest, the wear rate is the smallest, and the wear resistance is the best.