Determination of the composition range suitable to the formation of WC–(V,W)Cx–Co materials

The phase equilibria of the system W–V–C–Co are determined experimentally in the composition range corresponding to small additions of VC_x in the cemented carbides WC–Co and to larger VC_x contents in the hard materials WC–(V,W)C_x–Co. The results are obtained from the microanalysis of the phase compositions in samples heat-treated at 1450 and 1200 °C. Two four-phase fields, {Cosolution+WC+(V,W)C_x+C} and {Cosolution+WC+(V, W)C_x+η}, are determined. The narrow domain between the two four-phase fields defines the composition range suitable to the formation of the hard materials WC–(V,W)C_x–Co. Some interfacial features important for the microstructure of the materials are underlined.     

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.     

The influence of carbon content on formation of carbo-nitride free surface layers in cemented carbides

To increase crack propagation resistance in cemented carbide cutting tools, it is sometimes of interest to create tough surface zones in the substrates. A way to do this is to use so-called gradient sintering in the manufacturing of the cutting tool. In this sintering process a nitrogen and titanium containing cemented carbide is sintered in a nitrogen free atmosphere. The difference in nitrogen activity between atmosphere and cutting tool during sintering will create an outward nitrogen diffusion. Due to thermodynamical coupling between nitrogen and titanium, this gives rise to an inward titanium diffusion, which creates a surface zone depleted of hard cubic carbo-nitrides, and enriched in ductile binder phase. By varying the carbon content of the material, the nitrogen activity is affected, and this in turn affects the surface zone formation.

In this report, Ti(C,N)–(Ti,W)C–WC–Co, Ti(C,N)–NbC–WC–Co, and Ti(C,N)–TaC–WC–Co cemented carbides were studied. All three materials were produced in series with varied carbon content, in order to study the effect of carbon on gradient surface zone formation.     

A novel (W–Al)–C–Co composite cemented carbide prepared by mechanical alloying and hot-pressing sintering

Novel cemented carbides (W_0.4Al_0.6)C_0.5–Co with different cobalt contents were prepared by mechanical alloying and hot-pressing technique. Hot-pressing technique as a common technique was performed to fabricate the bulk bodies of the hard alloys. The novel cemented carbides have good mechanical properties compared with WC–Co. The density and operation cost of the novel material were much lower than the WC–Co system. It was easy to process submicroscale sintering with the novel materials and obtain the rounded particles in the bulk materials. There is almost no η-phase in the (W_0.4Al_0.6)C_0.5–Co cemented carbides system although the carbon deficient obtains the astonishing value of 50%.     

Tailored sintering of VC-doped WC–Co cemented carbides by pulsed electric current sintering

WC–12 wt.% Co powder mixtures with 0, 0.45 or 0.9 wt.% VC additions were consolidated by solid state pulsed electric current sintering (PECS) for 2 min at 1080–1240 °C. The influence of the sintering condition and VC concentration on the densification, WC grain growth and mechanical properties of the cemented carbides were investigated. Finite element simulation revealed that the radial temperature gradient inside the sintering powder compacts could be homogenised using a carbon felt insulation surrounding the graphite die set-up.     

VC, Cr3C2 and NbC doped WC–Co cemented carbides prepared by pulsed electric current sintering

WC–12 wt.% Co grade cemented carbides doped with 0.9 wt.% VC, NbC or Cr₃C₂ grain growth inhibitor were consolidated by pulsed electric current sintering (PECS), also known as spark plasma sintering (SPS), in the solid state at 1240 °C for 2 min. The microstructure and properties of the PECS material grades are compared with those of pressureless sintered grades, liquid phase sintered at 1420 °C for 1 h. Microstructural and hardness characterization revealed that both the chemical composition and sintering technique play an important role on the WC grain growth and final mechanical properties. To obtain a nanometer sized WC–Co microstructure, it is essential to carefully select the grain growth inhibitor in addition to the application of a fast thermal densification cycle by means of spark plasma sintering.     

Rapid sintering of ultrafine WC–Ni cermets

Using high-frequency induction-heated sintering (HFIHS), cermets of WC–xNi (x = 8, 10, and 12 wt.%) were consolidated to a density of about 98%. The sintered samples had WC grain size of 300 nm. The hardness was significantly higher than that obtained with conventionally sintered WC–Co and WC–Ni cermets without a reduction in fracture toughness.     

Fundamentals of liquid phase sintering for modern cermets and functionally graded cemented carbonitrides (FGCC)

Metallurgical reactions and microstructure developments during sintering of modern cermets and functionally graded cemented carbonitrides (FGCC) were investigated by modern analytical methods such as mass spectrometer (MS), differential thermal analysis (DTA), differential scanning calorimeter (DSC), dilatometer (DIL), microscopy and analytical electronic microscopy with energy dispersive spectrometer (EDS). The complex phase reactions and phase equilibria in the multi-component system Ti/Mo/W/Ta/Nb/C,N-Co/Ni were studied. The melting behavior models in the systems of TiC–WC/MoC–Ni/Co, TiC–TiN–WC–Co and TiCN–TaC–WC–Co have been established. By an in-depth understanding of the mechanisms that govern the sintering processing and metallurgical reactions, new cermets and different types of FGCC with desired microstructures and properties were developed.     

Application of a wax-based binder in PIM of WC–TiC–Co cemented carbides

A wax-based binder was developed for powder injection molding of WC–TiC–Co cemented carbides. The critical powder loading and the rheologic behavior of the feedstock were determined. It was found that the critical powder loading could achieve up to 62.5 vol% and the feedstock exhibited a pseudo-plastic flow behavior. The injection molding, debinding and sintering processes were studied. The dimensional deviation of the sintered samples could be controlled in the range of ±0.2% with the optimized processing parameters. The mechanical properties were better than or equivalent to those of the same alloy made by the conventional press-sintering process.     

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.     

Microstructure of model cermets with high Mo or W content

The microstructure of (mol%) TiC–18TiN–24Ni–(10–29)WC and TiC–18TiN–24Ni–(5–14)Mo₂C has been investigated using X-ray diffraction (XRD), optical microscopy (OM), scanning electron microscopy (SEM) and analytical electron microscopy (AEM). When the WC content in the raw materials was increased the W content in the outer rim of (Ti, W)(C, N) grains increased until it had a composition similar to that of the inner rim. If the WC content was high undissolved WC was present after sintering. When the Mo₂C content in the raw materials was increased, the volume fraction of inner rim increased and the Mo content in both inner and outer rim increased. Thermodynamical calculations on the Ti–W–C–N system suggest that the inner rim is formed during solid state sintering when there is an open porosity and thus a low nitrogen activity. The composition of the outer rim can be explained by the equilibrium at the sintering temperature if the volume fraction of undissolved Ti(C, N) cores is subtracted. Calculations on the Ti–Mo–C–N system show that (Ti, Mo)(C, N) decomposes into two phases with different Mo content and that the Ti(C, N) cores might be regarded as a stable phase.     

Effect of Mo addition on the microstructure and mechanical properties of ultra-fine grade TiC–TiN–WC–Mo2C–Co cermets

Effect of Mo addition on the microstructure and mechanical properties of ultra-fine grade TiC–TiN–WC–Mo₂C–Co cermets was studied in this work. Mechanical properties such as transverse rupture strength, fracture toughness and hardness were also measured. Results show that the microstructure exists in black core/grey rim structure and white core/grey rim structure, and the microstructure has an obvious trend to become finer with the increase of molybdenum content. When the added Mo exceeds 10%, ultra-fine TiC-based cermet with an average particle size of less than 0.5 μm is obtained, because of the formation of a Mo-rich rim and the improvement of the wettability between ceramic phase and metallic phase. The transverse rupture strength increases with the increase of Mo content, and the maximum values of the hardness and the fracture toughness were found with 10 wt% and 5 wt% Mo addition, respectively.     

Composition and properties of (Ti,W)C-WC-Co sintered carbides alloyed by MMT-process

Distribution of tantalum and molybdenum introduced into (Ti,W)C-WC-Co sintered carbides by the MMT-process has been studied. It is shown that Ta and Mo alloying elements do not change the WC phase composition, they melt into (Ti,W)C particles to form a layer of complex carbides and have a pronounced effect on the composition and state of interfaces. It is found that the alloying elements added to carbides by MMT-processes essentially prolong the fatigue fracture toughness of sintered carbides.     

Ultrafine hardmetals prepared by WC–10 wt.%Co composite powder

Ultrafine tungsten carbide–cobalt (WC–10 wt.%Co) composite powder was synthesized via spray-drying and direct reduction and carburization process in vacuum, which includes precursor preparation by spray-drying of a suspension of ammonium metatungstate (AMT) and cobalt carbonate (CoCO₃), calcination to evaporate volatile components, formation of tungsten–cobalt mixed oxide powder (CoWO₄/WO₃), ball-milling with carbon black, and subsequent direct reduction and carburization reaction in vacuum. The synthesis temperature of WC–10 wt.%Co composite powder without η or graphite phases is lower than 1000 °C. The calculated particle size by BET test is 0.29 μm. Coarse WC powder (FSSS: 0.9 μm) and Co powder (FSSS: 1.0 μm) (WC:Co = 9:1 in mass) were added into the obtained WC–10 wt.%Co composite powder with addition of 30 wt.%, 50 wt.% and 70 wt.%, respectively. Results show that the hardmetal fabricated from 70 wt.% (WC–10 wt.%Co composite powder) + 30 wt.% (90 wt.%WC + 10 wt.%Co coarse powder) mixed powders exhibits a fine microstructure as well as optimum mechanical properties.     

Influence of WC addition on the microstructure and mechanical properties of NbC–Co cermets

NbC–24.5 wt.% Co cermets with up to 30 wt.% WC were obtained by solid state hot pressing at 1300 °C under a pressure of 45 MPa for 10 min and pressureless liquid phase sintering at 1360 °C for 60 min. The effect of WC addition on the microstructure and mechanical properties of NbC–Co based cermets was investigated. The hot pressed cermets exhibited interconnected and irregular niobium carbide (NbC) or (Nb,W)C grains, whereas the shape of the NbC grains changed from faceted with rounded corners to spherical, as the WC content increased in the pressureless sintered cermets. The undissolved WC increased with increasing WC addition. A clear core/rim structure was observed in the hot pressed cermets with 10–30 wt.% WC additions, whereas this structure was gradually eliminated when pressureless sintering. The hardness remains nearly constant whereas the fracture toughness slightly increases with increasing WC addition. The dissolution of WC in the Co binder and NbC grains, as well as the formation of a solid solution (Nb,W)C phase were supported by thermodynamic calculations.     

Grain and phase boundary segregation in WC-Co with TiC, ZrC, NbC or TaC additions

The microstructure of interfaces in WC-Co based cemented carbides with TiC, ZrC, NbC or TaC additions was analysed using energy dispersive X-ray analysis in a transmission electron microscope and using atom probe tomography. Segregation to WC/WC grain boundaries and WC/(M,W)C phase boundaries corresponding to between 0.4 and 1.2 atomic layers of close packed monolayers of Co was observed in all the materials. In addition to Co, Ti, Zr and Nb, but not Ta, segregate to the WC/WC grain boundaries. Segregation was also observed for B, P, Fe and Cr, but not Ni, to the boundaries. These are impurities that originate from the material production. Segregation of Ti, Zr, Nb and Ta to WC/binder phase boundaries was observed. If formation of a MC phase at the interface is assumed, the segregation corresponded to a thickness less than a monolayer.     

EFFECTS OF SIZE COMBINATION AND CONTACTING STATE OF RAW POWDER PARTICLES ON SPARK PLASMA SINTERED ULTRAFINE CEMENTED CARBIDES

本文采用亚微米WC粉和纳米Co粉、亚微米WC粉和高能球磨后具有纳米晶组织的微米级Co粉这两种具有不同粒径匹配的混合粉末作为原料粉末，利用放电等离子烧结（SPS）技术制备超细晶WC-10Co硬质合金。对不同原料粉末的SPS过程及烧结试样的显微组织和性能进行了系统的对比分析。实验结果表明，以两种混合粉末为原料均获得了平均晶粒尺寸在200nm以下的超细硬质合金材料，其中，采用亚微米WC粉和高能球磨的微米级Co粉利用SPS技术制备的材料相对密度达到98%以上，硬度达到HRA94.5，断裂韧性达到13.50MPa•m1/2，表明具有优良的综合性能。而采用亚微米WC粉和纳米Co粉利用SPS技术制备出的超细晶硬质合金的组织均匀性和性能较差。根据SPS技术的特殊烧结机理，对采用不同粒径匹配和结合状态的WC和Co混合粉末的SPS致密化机制进行了分析。     

Ultrafine WC-0.5Co-xTaC cemented carbides prepared by spark plasma sintering

Ultrafine (below 500 nm) tungsten carbide (WC) - 0.5 wt% cobalt (Co) cemented carbides were prepared by spark plasma sintering (SPS), containing varied tantalum carbide (TaC) contents, at 1500 °C under 50 MPa. The sintering behavior and microstructure of these materials were investigated. It was found that adding TaC could get a rapid shrinkage period during sintering and make a finer microstructure with a more narrowing range of the grain-size distribution. Adding inadequate or excessive amount of TaC, however, not only lower the sinterability but also get a result against the finer microstructure. Moreover, the (Ta,W)C solid-solution phase (formed by the part dissolution of WC in TaC grains) was mainly gathered at the WC grain boundary, and Co film was found. Benefiting from the ultrafine and homogeneous microstructure, these materials maintained excellent hardness and improved fracture toughness.     

Microstructure and mechanical properties of WC–10Co cemented carbide containing VC or (Ta,Nb)C and fracture toughness evaluation using different models

This article describes a study on WC–10Co cemented carbides with different percent of grain growth inhibitors. Samples were prepared by the conventional powder metallurgy method, using WC and Co powder and different concentrations of VC and (Ta, Nb)C powder. All samples were processed using a hot isostatic press (HIP) and the effect of grain growth inhibitors on the microstructure and mechanical properties were investigated. Additionally, microstructure and powder particle morphology were examined using scanning electron microscopy (SEM) and electron dispersive spectroscopy (EDS). The specimen's microstructure proved that the addition of VC is more effective at suppressing grain growth than (Ta, Nb)C. Besides the microstructure observations, hardness, transverse rupture strength (TRS) and indentation fracture toughness (IFT) were evaluated. Due to the brittleness of the cemented carbides, fracture toughness was evaluated using different IFT models. The IFT values were determined by measuring the lengths of the cracks generated at the corners of a Vicker's indentation.