High-temperature plastic flow behaviour in the binder of WC-Co cemented carbides

Co-rich solid solution alloys regarded as the composition of binder phasesat elevated temperatures in WC-Co cemented carbides were fabricated and the high-temperature deformation behaviour of the alloys was investigated. The logarithmic relationship between flow stress and strain rate is expressed by a single straight line with the slope of 0.15 at a constant temperature in all strain rate range examined, unlike in cemented carbides showing the sigmoidal behaviour. The solid solution hardening due to the addition of Cr₃C₂ and VC is negligible in the Co-9WC-lCr₃C₂-0.5VC alloy and the mutual relation in flow stress is different between the cemented carbides and their binder phases in region I. The plastic flow in region I in WC-Co cemented carbides cannot be explained by the flow stress or flow behaviour in the binder phase.     

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.     

Sintering characteristics and microstructure of WC-Co-VC/Cr<Subscript>3</Subscript>C<Subscript>2</Subscript> ultrafine cemented carbides

The sintering characteristics, microstructure, and mechanical properties of ultrafine WC-12%Co-0.2%VC/0.5%Cr₃C₂ cemented carbides were investigated. Dilatometric and differential thermal analyses (DTA) indicate that the compacts start to shrink at 600°C, the shrinkage rate peak is at 1190°C, and the liquid formation temperature is lower than the W-C-Co eutectic temperature (1330°C). Microstructure analysis results show that the cemented carbides with fine and homogeneous microstructure were obtained when sintered at 1430°C. Continuous and discontinuous grain growth was suppressed due to the synergistic action of VC/Cr₃C₂. The transverse rupture strength (TRS) of the samples reaches 4286 MPa, with the hardness HRA 92.1. The fine and homogeneous microstructure, alloy strengthening, and different phase constitutions of binder in the cemented carbides result in high hardness and TRS. Continuous and discontinuous grain growth was observed in the cemented carbide sintered at 1450°C, which results in significant decreases of hardness and TRS. It indicates that VC/Cr₃C₂ additions in the cemented carbides can only suppress the grain growth at a certain temperature.     

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。     

Synthesis of Cr-doped APT in the evaporation and crystallization process and its effect on properties of WC-Co cemented carbide alloy

WC grain size has significant effect on WC-Co cemented carbide alloy properties. In order to inhibit WC grain growth during sintering process, grain growth-inhibitor Cr₃C₂ is usually added to tungsten carbide powder in advance through mechanical milling. While, homogeneous distribution of Cr₃C₂ in the tungsten carbide powder is difficult to achieve and result in abnormal growth of WC grains. For this purpose of growth-inhibitor uniform distribution, (CH₃COO)₃Cr is added into ammonium tungstate solution during evaporation and crystallization process to prepare Cr-doped APT powder, which can be used as precursor for ultrafine-grained WC-Co cemented carbide alloy preparation. Compared with conventional APT powder, the Cr-doped APT has smaller particle size and bulk density, moreover, chromium is evenly distributed within it. The Cr-doped APT is then used to produce Cr-doped tungsten powder, which also has smaller particle size than that of conventional tungsten powder. Cr-doped tungsten powder is subsequently prepared into tungsten carbide powder and WC-Co cemented carbide alloy through carbonization and sintering process, respectively. Compared with conventional WC-Co cemented carbide alloy, the obtained WC-Co cemented carbide alloy has smaller mean WC grain size (0.36 μm), and more uniform microstructure. Furthermore, the phenomenon of WC grain abnormal growth during sintering process is not observed, because the grain growth-inhibitor Cr₃C₂ is well dispersed in tungsten carbide and cobalt composite powder. Results show that the obtained WC-Co cemented carbide alloy presents better mechanical properties (HRA, bending strength, coercive force) than those of conventional WC-Co cemented carbide alloy. Accordingly, the novel addition of (CH₃COO)₃Cr during the evaporation and crystallization process is the key factor of ultrafine-grained WC-Co cemented carbide alloy production.     

WC-Co-Re cemented carbides: Structure,properties and potential applications

Cemented carbides of the WC-Co-Re system represent a new class of hard materials having a significantly increased Young's modulus, hot hardness and high temperature creep resistance. The WC-Co-Re phase diagram was evaluated and compared with the corresponding WC-Co phase diagram. Physical and mechanical properties of such composites were measured at room and elevated temperatures and compared with those of conventional WC-Co cemented carbides. Microstructures of the WC-Co-Re cemented carbides at different carbon contents, binder contents and WC grain sizes were examined. Rhenium being dissolved in the Co-based binder is found to be a very strong grain growth inhibitor with respect to WC coarsening during liquid-phase sintering. The Young's modulus, hot hardness and high temperature creep resistance of the WC-Co-Re cemented carbides are greater than those of conventional WC-Co cemented carbides. Due to their unique properties the WC-Co-Re materials can find applications in use in high-pressure high-temperature components for synthesis of diamond and c-BN and cutting Ni-based super alloys and other heat-generating workpiece materials.     

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.     

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 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.     

Effect of chromium and carbon contents on the sintering of WC-Fe-Ni-Co-Cr multicomponent alloys

WC-Fe-Ni-Co-Cr cemented carbides have been obtained by liquid phase sintering from WC-Fe-Ni-Co-Cr₃C₂ powder mixtures. Taking the 40wt%Fe-40wt%Ni-20wt.%Co alloy as a reference, new binder phases has been prepared by introducing controlled amounts of Cr and C, via Cr₃C₂ and C black powders respectively. As described for WC-Co-Cr materials, Cr additions are observed to reduce the eutectic temperatures of the WC-Fe-Ni-Co system. First liquids detected on heating exhibit wide temperature melting ranges, which become narrower and are displaced to higher temperatures on repeated heating and cooling cycles. Apart from the decarburization associated to the carbothermal reduction of powder oxides, this phenomenon could be also associated to the homogeneization of the chemical composition of these multicomponent binder phases, which is faster as C content decreases. Correlation between experimental melting and solidification temperature ranges and those predicted by Thermocalc® is better as Cr content increases. Experimental C windows, defined in this work by the absence of free C or η phases, are located at C contents higher than those estimated by Thermocalc®. Although the 40wt.%Fe-40wt.%Ni-20wt.%Co alloy is austenitc, BCC phases are partially stabilized at low C and high Cr contents. Although these compositions are free from η phases or free C, a precipitation of Cr-rich carbides is found at the WC-metal interface. These precipitates are not observed in the alloy with 0.75 wt% Cr (i.e. 5 wt% of the nominal metal content) and 5.39 wt%C. This C content is 0.17 wt% higher than that predicted for precipitation of M₇C₃.     

Influence of microstructure on hardness and thermal conductivity of hardmetals

Hardmetals or cemented carbides are used in a wide range of applications due to their excellent mechanical properties. WC-Co hardmetals with the same room temperature hardness can be obtained by different combinations of the WC grain size and cobalt content. However, the thermal conductivity of such hardmetal grades is not equal. Applications such as cutting may require a certain combination of hardness and thermal conductivity, which means that a targeted adjustment is desirable. In this study a wide range of hardmetal grades was studied in respect of microstructure, hardness and thermal conductivity in the temperature range between 20 °C and 1000 °C. Results show that thermal conductivity is considerably influenced by Co content, WC grain size and Cr₃C₂ content. Furthermore, hardmetal grades with the same hardness at room temperature retain hardness very differently at elevated temperatures. For the selection of hardmetal grades for high temperature applications these findings help to choose the right composition in regard to Co content and WC grain size.     

Grain growth inhibition in ultrafine hardmetals

Ultrafine and nanoscaled hardmetals show mechanical properties like hardness and bending strength which lie way above conventional fine or submicron grained hardmetals. To achieve such fine microstructures very fine WC starting powders as well as grain growth inhibitors such as Cr₃C₂ or VC are needed. To study the grain growth inhibition in ultrafine hardmetals investigations on samples made from nearly nanoscaled WC and Co starting powders with and without the addition of Cr₃C₂ were done. For studying the dissolution behaviour of Cr₃C₂ and the evolution of density, magnetic properties and lattice parameters of WC during sintering, interrupted sintering experiments were carried out. Thermal analysis techniques including TG-MS and DSC were used, to link the observed changes to expected reactions. The results show that grain growth inhibitors greatly influence the sintering behaviour already way below the eutectic melting of WC-Co. Especially dissolution of Cr₃C₂ and homogenous distribution of Cr within the samples already starts below 800 °C with the reduction of W surface oxides and the creation and spreading of Cr oxides. The findings are relevant for optimising sintering regime, composition (amount of grain growth inhibitors) as well as the microstructure and mechanical properties.     

Effect of the Cr content on the sintering behaviour of TiCN–WC–Ni–Cr3C2 powder mixtures

In TiCN–W–Cr–Ni cermets produced by liquid phase sintering melting occurs at lower temperatures as their Cr content increases. For low Cr additions (up to 4 wt.%) eutectic temperatures are close to those found in the TiC–WC–Ni system. For 8 wt.% Cr and above, temperatures are similar to those found in the Cr–Ni–C system. The precipitation of M₇C₃ carbides is observed to start at 8 wt.% Cr in samples sintered at 1425 °C for 1 h. This sets a limit for the Cr solubility in the binder phase of these cermets around 18 wt.%. The dissolution of WC and Cr₃C₂ particles starts at temperatures as low as 1150 °C, but that the homogenization of the binder phase is only achieved after melting. The carbonitride phase exhibits the typical precipitation of inner and outer rims onto Ti(C,N) cores. However, a fine precipitation of Ni-rich particles is found inside Ti(C,N) cores, likely related to coalescence phenomena.     

Effect of milling conditions and binder phase content on liquid phase sintering of heat treatable WC-Ni-Co-Cr-Al-Ti cemented carbides

The binder phase of WC based cemented carbides has been alloyed by adding two different aluminium compounds, AlN and TiAl₃, to mixtures comprised of WC, Ni, Co and Cr₃C₂ powders. A more efficient alloying effect is obtained by TiAl₃ additions likely due to its higher dissolution rate during liquid phase sintering. Shrinkage and melting phenomena are strongly affected by the energy of the milling process and the amount of metallic additions. The use of higher milling rotation speed induces higher oxidation of the powder mixtures and the subsequent formation of a higher volume fraction of alumina particles after sintering. Densification and WC grain growth are hindered by increasing the Al addition. Thus, full densification of alloys with higher Al additions require the use of HIP after standard vacuum sintering cycles. As-HIPed WC-Ni-Co-Cr-Al-Ti samples present a binder phase with precipitation of gamma prime similar to that found in as-cast Ni superalloys. The size, volume fraction and morphology of these precipitates has been modified by applying a standard solution treatment (1150 °C-2 h) followed by fast air cooling and subsequent aging at 600 °C and different dwelling times. Age hardening effects have been confirmed in the composition consisting of WC-12 wt% Co-12 wt% Ni-1.7 wt% Cr₃C₂-5 wt% TiAl₃ after 100 h at this temperature.     

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.     

Fracture toughness of cemented carbides obtained by electrical resistance sintering

The unique combination of hardness, toughness and wear resistance exhibited by WC-Co cemented carbides (hardmetals) has made them a preeminent material choice for extremely demanding applications, such as metal cutting/forming tools or mining bits, in which improved and consistent performance together with high reliability are required. The high fracture toughness values exhibited by hardmetals are mainly due to ductile ligament bridging and crack deflection (intrinsic to carbides). In this work two WC-Co grades obtained by using the electric resistance sintering technique are studied. The relationships between the process parameters (cobalt volume fraction, sintering current and time, die materials, etc.), the microstructural characteristics (porosity, cobalt volume fraction, carbide grain size, binder thickness and carbide contiguity) and mechanical properties (Vickers hardness and fracture toughness) are established and discussed. Also the presence of microstructural anisotropy and residual stresses is studied. The sintering process at 7 kA, 600 ms and 100 MPa, in an alumina die, followed by a treatment of residual stress relief (800 °C, 2 h in high vacuum), allows to obtain WC-Co pellets with the best balance between an homogeneous microstructure and mechanical behaviour.     

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.     

Reactive sintering study of a novel cemented carbide hard alloy (W0.5Al0.5)C0.5-Ni

Cemented carbides hard alloy (W_0.5Al_0.5)C_0.5-13.3 vol% Ni was successfully prepared by reactive sintering of carbon, nickel powder and W_0.5Al_0.5 alloy powder. The novel cemented carbide hard alloy has superior mechanical properties. The influence of sintering time and temperature on the microstructure, mechanical properties and density of the specimens are well described. Interestingly, both sintering time and temperature have amazing influence on the mechanical properties, density and microstructure of the specimen. During the reactive sintering process, Ni was the binder phase for sintering (W_0.5Al_0.5)C_0.5-Ni cemented carbide, and it also accelerated the reaction rate of synthesizing (W_0.5Al_0.5)C_0.5. The reactive sintering is a good method for preparing cemented carbide hard alloy (W_0.5Al_0.5)C_0.5-Ni. Another phenomenon is that no WNi/W₃Ni₃C/NiC_x type phases are found in the bulk specimens, although it was prepared by reactive sintering the carbon, nickel powder and W_0.5Al_0.5 alloy powder directly and the carbon vacancy reach to the astonished 50% value.     

Microstructure and Properties of HVOF-Sprayed WC-(W,Cr)<Subscript>2</Subscript>C-Ni Coatings

The composition WC-(W,Cr)₂C-Ni is one of the standard compositions used for the preparation of thermally sprayed coatings by high velocity oxy-fuel (HVOF) spraying. Surprisingly, this composition has been poorly investigated in the past. Frequent use of commercial designations WC-‘CrC’-Ni, WC-Cr₃C₂-Ni, and WC-NiCr indicates the insufficient knowledge about the phase compositions of these powders and coatings. The properties of these coatings differ significantly from those of WC-Co and WC-CoCr coatings. In this paper, the results of different series of experiments conducted on HVOF-sprayed WC-(W,Cr)₂C-Ni coatings are compiled and their specific benefits pointed out. The focus of this study is on the analysis of the microstructures and phase compositions of the feedstock powders and coatings. Unlike WC-Co and Cr₃C₂-NiCr, WC-(W,Cr)₂C-Ni is not a simple binary hard phase—binder metal composite. The phase (W,Cr)₂C with unknown physical and mechanical properties appears as a second hard phase, which is inhomogeneously distributed in the feedstock powders and coatings. As examples of coating properties, the oxidation resistance and dry sliding wear properties are compared with those of WC-10%Co-4%Cr coatings.     

A short and facile process to synthesize WC-Co cemented carbides

WC-Co cemented carbides are widely used in the fields of military, aerospace, mining and cutting industry etc. In this paper, a new two-step method for the preparation of WC-Co cemented carbides was proposed. First, the mixture of yellow tungsten trioxide (WO₃) and cobaltic oxide (Co₂O₃) were reduced by carbon black to remove all the oxygen. Then, the carbothermic reduction products were precisely mixed with an appropriate amount of carbon black to directly prepare WC-Co cemented carbides. The effects of C/WO₃ ratio on the phase composition, morphological evolution, particle size and mechanical properties of products are investigated. The experimental results revealed that when the C/WO₃ molar ratio was above 2.7, all oxygen in the raw material mixture were removed by carbon black and a mixture of W₂C and η-phase were obtained after the first step of carbothermic reduction at 1150 °C for 2 h; then, the mixture of carbothermic reduction product and an appropriate content of carbon black was compacted, and the green compact was first carbonized at 1200 °C for 2 h and then sintered at 1450 °C for 4 h to prepare cemented carbides. With the increase of C/WO₃ ratio at the first stage, the content of η-phase with a low melting point increased, which resulted in the large grain size of WC in the finally prepared cemented carbide. Compared with the traditional method of preparing cemented carbides, the cemented carbides prepared by the current method showed a higher hardness and toughness. Furthermore, the addition of a proper content of the VC in the second stage can significantly inhibit the grain growth of WC and further increase the hardness of cemented carbides.