过渡族金属碳化物在WC-Co硬质合金中的界面偏析与固溶行为

过渡族金属碳化物是最常见的硬质合金微观组织结构与性能调控添加剂,添加剂在硬质合金中赋存状态的研究是WC晶粒生长抑制机理研究的基础,也是硬质合金材料与工艺设计的基础。从基于第一性原理计算的理论研究、基于高分辨透射电镜和原子探针层析法的实验观察分析等2个方面,综述了过渡族金属碳化物在WC/β(钴基固溶体粘结相)相界偏析行为的研究现状。基于过渡族金属碳化物在硬质合金中晶界与相界的偏析行为、在硬质相与粘结相中的固溶行为,讨论了硬质合金中WC晶粒生长机理与晶粒生长抑制机理以及过渡族金属碳化物对硬质合金性能的影响机理,提出了硬质合金材料与工艺设计的建议。     

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%。     

WC-Co硬质合金的弹性性能

综述了WC-Co硬质合金弹性性能的预测模型,并计算了硬质合金不同Co含量时的弹性性能参数值,并对不同的模型的预测值与文献中的测量结果进行了比较。采用引入WC晶粒邻接度C的Golovchan模型计算的WC-Co硬质合金的弹性模量值,相比Voigt-Reuss模型和Hashin-Shtrikman模型,更接近于实测值。而泊松比的值相对偏低,但可以采用Hashin-Shtrikman模型的泊松比上限确定泊松比的值。另外,给出了弹性模量的实验测定方法标准。这为硬质合金重要弹性参数值的确定提供了实验测定和理论计算的依据。     

Wear-resistance and hardness: Are they directly related for nanostructured hard materials?

The major challenge in the field of cemented carbides and other hard materials is to obtain their better combination of hardness, wear-resistance and fracture toughness. It is well known that the dependence of abrasion wear on fracture toughness for WC–Co cemented carbides is represented by a relatively narrow band and it is hardly possible to “break away” out from it by the use of conventional approaches based on varying the WC mean grain size and Co content. Also, it is well known that the wear-resistance of conventional cemented carbides depends mainly on their hardness. The major objective of this paper is to establish what will happen with the wear-resistance of hard materials as a result of their nanostructuring when the hardness is nearly the same as for conventional WC–Co cemented carbides. The results obtained provide clear evidence that, if one enters the region of nanostructured materials with the mean grain size of less than 10 nm, traditional wisdom indicating that the wear-resistance is directly related to the hardness appears not to be valid. In some cases of such nanostructured materials, it can be possible to achieve the dramatically improved wear-resistance compared to that of conventional WC–Co cemented carbides at nearly the same level of hardness and fracture toughness. The abovementioned is based on considering hard nanomaterials of the following four types: (1) WC–Co cemented carbides with nanograin reinforced binder, (2) near-nano WC–Co cemented carbides, (3) cemented carbides of the W–C–Cr–Si–Fe system for hard-facing having a nanostructured Fe-based binder, and (4) CVD hard materials consisting of nanostructured W₂C grains embedded in a tungsten metal binder.     

Carbide grain growth in cemented carbides sintered with alternative binders

Cemented carbides are composites made of a hard refractory ceramic phase and a ductile binder, most commonly WC and Co, respectively. Since the use of cobalt in the hard metal industry is questioned by the new European regulation on chemicals, extensive research has been done to develop new grades based on a Co-Ni-Fe binder. With similar mechanical, physical properties and affinity to C and W, nickel and iron are the best candidates for an efficient binder in cemented carbides. As mechanical properties are strongly dependent on the materials microstructure, and especially on the WC grain size, understanding the effect of the binder on the final microstructure is crucial.In this work, the carbide grain growth behaviour of WC-M alloys (M = Co, Ni, Fe) with different carbon contents is discussed from qualitative and quantitative microstructural analyses. Whereas grain growth is more or less inhibited in WC-Fe alloys, increasing carbon content promotes grain growth in WC-Co and WC-Ni alloys, with a slight abnormal grain growth in case of Ni binder. Different mechanisms for grain growth are discussed, in relation with the observed morphology of WC grains after sintering.     

Mechanical properties of WC–10Co cemented carbides sintered from nanocrystalline spray conversion processed powders

Mechanical properties and microstructures of nanocrystalline WC–10Co cemented carbides were investigated. The nanocrystalline WC–10Co cemented carbide powders were manufactured by reduction and carbonization of the nanocrystalline precursor powders which were prepared by spray drying process of solution containing ammonia meta-tungstate (AMT) and cobalt nitrate. The WC powders were about 100 nm in diameter mixed homogeneously with Co binder phase and were sintered at 1375 °C under a pressure of 1 mTorr. In order to compare the microstructures and mechanical properties with those of nanocrystalline WC–10Co, commercial WC powders in a diameter range of 0.57–4 μm were mixed with Co powders, and were sintered at the same conditions as those of nanocrystalline powders. TaC, Cr₃C₂ and VC of varying amount were added into nanocrystalline WC–10Co cemented carbides as grain growth inhibitors. To investigate the microstructure of Co binder phase in the WC–10Co cemented carbides, Co–W–C alloy was fabricated at the temperature of sintering process for the WC–10Co cemented carbides. The hardness of WC–10Co cemented carbides increased with decreasing WC grain size following a Hall–Petch-type relationship. The fracture toughness of WC–10Co cemented carbides increases with increasing HCP/FCC ratio of Co binder phase by HCP/FCC phase transformation.     

Creep behaviour of cemented carbides — Influence of binder content,binder composition and WC grain size

The high-temperature creep behaviour of cemented carbides was evaluated for a wide variety of binder contents, binder compositions and WC grain sizes at temperatures ranging from 700 °C to 950 °C. The creep behaviour was characterised using compressive high-temperature experiments. The results show that the above mentioned microstructural parameters as well as the binder composition have a significant influence on the samples' plastic deformation. Based on these findings, a structured creep behaviour control map may be established for future materials development, aiding in the design of new high performing cemented carbides for challenging technical applications.     

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.     

Thermodynamic calculation designed compositions,microstructure and mechanical property of ultra-fine WC-10Co-Cr3C2-TaC cemented carbides

The grain size of WC and the content of inhibitors are two critical factors responsible for mechanical properties of cemented carbides. Cr₃C₂ and TaC grain-growth inhibitors are added simultaneously to control the grain growth of ultra-fine WC-Co cemented carbides. The content of doping inhibitors should be controlled strictly, below the maximum solubility in the binder phase, to avoid the appearance of free carbides, which cause brittleness and thus have a negative influence on mechanical properties. In this work, several ultra-fine WC-10 wt%Co cemented carbides with various contents of Cr and Ta were designed and fabricated via combining thermodynamic calculations and key experiments. With the addition of Cr₃C₂ and TaC to a certain extent, the density, transverse rupture strength, hardness and fracture toughness of WC-Co cemented carbides are improved significantly. However, excessive Cr₃C₂ and TaC lead to the formation of M₇C₃ as well as coarse (Ta,W)C grains, which deteriorates the mechanical properties. Based on thermodynamic calculations, a favorable addition of inhibitors can be established, which enables an effective control of microstructure and mechanical properties.     

Examination of the wear properties of HVOF sprayed nanostructured and conventional WC-Co cermets with different binder phase contents

There has been an increase in interest of late regarding the properties of thermally sprayed WC-Co cermets with nanograin carbide particles. These powders have shown interesting properties in sintered components, giving high values of hardness (2200–2300 VHN) and improved wear properties. The method used for the processing for these materials—solution formation, spray drying and chemical conversion, rather than introduction of WC as solid particles to a molten binder—allows the formation of sub-100 nm WC particles as a hard second phase. The work presented here examined the effect of composition on the microstructure and wear properties of some nanostructured WC-Co materials. WC-Co cermets with 8, 10, 12, and 15% Co binder phase were deposited using a Sulzer Metco hybrid DJ HVOF thermal spray system. Optimization of deposition conditions was necessary because of the unique morphology of the powders (thick-shelled hollow spheres) to produce dense consolidated deposits. There is a higher degree of decarburization of the WC phase in the nanostructured materials compared with the conventional WC-Co. This dissolution of the hard phase is also noted to increase on decreasing binder phase content. The nanostructured WC-Co coatings have a lower wear resistance compared with the conventional WC-Co for abrasive wear and small particle erosion. The abrasive wear resistance of these nanostructured materials was found to increase on decreasing cobalt binder content. This trend in abrasive wear resistance is consistent with studies on conventional sized cermets and is believed to be more dependent upon proportion of binder phase content than degree of decarburization for the materials studied. The small particle erosion resistance of the nanostructured coatings was found to increase on increasing cobalt content.     

Role of Co Content on Densification and Microstructure of WC–Co Cemented Carbides Prepared by Selective Laser Melting

WC–Co cemented carbides, well-known as the conventional tooling materials, have not been successfully produced by one step additive manufacturing processes such as selective laser melting(SLM) yet. The microstructure evolution as well as WC grain growth behavior has rarely been investigated in detail during SLM process. In this study, the WC–Co cemented carbides with different Co contents(12–32 wt%) were prepared by optimized SLM processes for comparative investigation of densification behavior, microstructure characterization and mechanical property. The increase in Co content in feedstock carbide granules can improve the densification behavior during SLM process. The SLM processed WC-12 Co shows larger average WC grain size and higher percentage of coarser WC grains as compared with both WC-20 Co and WC-32 Co. The microstructure characterization, combined with finite element simulation, shows the WC grain growth mechanisms include agglomeration and dissolution-deposition of WC during SLM process and agglomeration of WC is an important mechanism especially for WC–Co cemented carbides with Co content as low as 12 wt%. The comparison between horizontal(perpendicular to the SLM laser beam) and vertical(parallel to the SLM laser beam) cross sections of carbides shows that SLM process introduces a certain degree of microstructure and mechanical behavior anisotropy for WC-12 Co, WC-20 Co, and WC-32 Co.     

超粗晶WC-Co硬质合金的研究现状

超粗晶硬质合金是一类性能优异的新型合金,广泛用于采矿、凿岩、轧辊等领域,应用前景广阔。化学包覆法和纳米粉末溶解法是超粗晶WC-Co硬质合金制备的主要方法,介绍了超粗硬质合金原料WC颗粒平均粒度选择的动力学理论,碳含量对超粗合金中WC晶粒生长粗化的影响以及通过引入其它元素强化粘结相以提高合金寿命的探索结果。此外,分析了以合金硬度为常数时,晶粒尺寸与合金性能的关系,指出在保持合金硬度不变时,通过增大WC晶粒尺寸来提高合金的耐磨性和韧性是可行的。最后,展望了超粗晶合金的发展方向。     

超细WC-Co硬质合金及其磨损性能研究

采用低温化学镀方法在超细WC颗粒表面进行金属钴包覆,烧结包覆后的复合粉体制备新型硬质合金NYG（WC-3%Co）.研究了超细WC-Co硬质合金的力学性能、断口形貌和显微结构,在销盘式磨损试验机上进行干滑动磨损实验.结果表明,在硬质合金烧结过程中,沿WC晶界均匀分布的金属钴不仅起粘结剂作用,也起抑制剂作用阻碍晶粒的长大;新型硬质合金的抗弯强度、断裂韧性、硬度和耐磨性能均得到较大提高;在干滑动摩擦条件下,新型WC-Co硬质合金的失效以塑性变形及细小碳化钨相颗粒脱落为特征.     

Study of characteristics and properties of spark plasma sintered WC with the use of alternative Fe-Ni-Nb binder as Co replacement

Most of all WC-based cemented carbides use cobalt as binder due to the excellent strength and ductility that this combination provides. Motivators to find alternative binders have been related to factors such as the shortage and price oscillations of the cobalt and toxicity of the WC-Co system. In this work, Fe-Ni-Nb was used as alternative binder for WC sintered via spark plasma sintering (SPS) technique. The composites were sintered at different sintering temperatures (1100 °C, 1200 °C and 1300 °C). In addition, WC-Co was sintered at 1200 °C via SPS for comparison purposes. X-ray diffraction and Scanning electron microscopy (SEM) were employed as characterization methods to investigate the crystalline phase's formation, sintering effectiveness, porosity and phase distribution. Mechanical properties such as Vickers hardness, fracture toughness, nanohardness, elastic modulus and thermal properties (thermal expansion coefficient) were evaluated. The results demonstrate Fe-Ni-Nb as a viable alternative binder to cobalt in hardmetal applications.     

Influence of the cemented carbide specification on the process force and the process temperature in grinding

Cemented carbides are hard and brittle materials. Their material properties are adjusted by their chemical composition, in particular their average hard phase grain size and their binder fraction. The research paper focusses on grinding of cemented carbides with cobalt (Co) as binder and tungsten carbide (WC) as hard phase material. Within the research paper, it is discussed if and to what extent the cemented carbide composition affects the occurring thermo-mechanical load collective in the grinding process. In particular, the influence of the average WC grain size and the cobalt fraction on the thermo-mechanical load collective is investigated and explained by the cemented carbide material properties. The results of the publication contribute to a knowledge-based design of cemented carbide grinding processes.     

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.     

我国钛合金的发展现状──评第八届全国钛合金学术交流会

探讨了淬火热处理对ＷＣ－ｃｏ硬质合金性能影响的机理。查明了淬火既改变ＷＣ－ＣＯ合金γ相的成分和合金的应力状态，也改变合金的显微结构参数（其变化程度与ＷＣ的平均晶粒度有关）。考查了Ｗｅ－Ｃｏ合金淬火效果在合金制品实际应用过程中的稳定性从而指出了ＷＣ－Ｃｏ合金淬火热处理的实用意义。     

晶粒长大抑制剂对超细WC-9%Co硬质合金性能的影响

在复合抑制剂(VC/Cr3C2)的基础上,添加了不同配比的TaC,研究了TaC对超细WC-9%Co硬质合金组织结构和力学性能的影响。结果表明:添加不同配比的TaC制备的WC-9%Co硬质合金的硬度随着TaC质量分数的增加先增大后减小;TaC的加入降低了W在Co相中的固溶度,从而抑制了晶粒长大。在本实验范围内,在复合抑制剂(VC/Cr3C2)质量分数为0.6%的基础上添加质量分数0.3%的TaC,经1 390℃真空烧结后,制备的超细WC-9%Co硬质合金硬度为93.5 HRA,TRS为2 370 MPa,致密度为99.5%,磁饱和强度为13.29 G.cm3/g,矫顽磁力为31.86 kA/m,此时具有较佳的综合力学性能。     

含板状WC晶粒硬质合金的强韧化机制研究

通过加入2.5%板状WC晶种,制备含板状WC晶粒硬质合金,研究其强韧化机制。结果表明:WC晶粒的各向异性和形状改变诱导的Hall-Petch硬化是硬质合金硬度增加的主要原因。加入板状晶种后,裂纹在扩展过程中出现了明显的穿晶断裂和Co相桥接,增加了裂纹偏转,硬质合金的抗弯强度大大提高。不同Co含量和初始WC粉体粒度制备的含板状WC晶粒硬质合金,穿晶断裂、Co相桥接和裂纹偏转对抗弯强度增加的贡献不同。     

超细晶硬质合金显微组织参数与力学性能定量关系的研究

对超细晶WC-Co硬质合金的复相显微组织进行了系统的定量化表征和分析,获得了WC晶粒尺寸d_(WC),Co相平均自由程L_(Co)和WC晶粒邻接度C_(WC-WC)等显微组织参数与力学性能的定量关系,模型预测结果与实验测定结果符合很好.结果表明,当C_(WC-WC)基本相同时,超细晶硬质合金的硬度分别与d_(WC)~(-1/2)和L_(Co)~(-1/2)成线性正比关系,断裂韧性K_(IC)分别与d_(WC)~(-1/2)和L_(Co)~(-1/2)成确定性函数关系.在Co含量一定、WC平均晶粒尺寸基本相同的情况下,随着C_(WC-WC)的增大,超细晶硬质合金的横向断裂强度降低,且当C_(WC-WC)>0.5时,硬质合金的强度随C_(WC-WC)增加显著下降.