Preparation of ultrafine WC-Co cermets by combining pretreatment and consolidation with spark plasma sintering

Ultrafine-grained WC-Co bulk materials were prepared by a new method that contains pretreatrnent of the milled powder mixture and sub-sequent spark plasma sintering (SPS). Ball milling parameters and the pretreatment temperature have significant effects on the microstructure and properties of WC-Co cermets. The prepared cermets have a mean grain size of less than 0.5 μm even with a pretreatment temperature as high as 1300℃. The WC-10wt.%Co cermet bulk prepared by the optimized milling, pretreatment, and SPS processing achieves excellent mechanical properties with a Vickers hardness of HV 1643, a fracture toughness of 13.1 MPa-m1/2and a transverse rapture strength of 3100 MPa.     

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.     

纳米复合WC-6Co粉末的快速烧结

以液相复合-连续还原碳化方法制备的纳米复合WC-6Co粉末为原料，采用放电等离子烧结（SPS），制取了超细硬质合金。利用扫描电镜、维氏硬度仪、洛氏硬度仪、密度测试仪、MTS陶瓷测试系统等，观察烧结体显微结构，测试其硬度、密度、断裂强度、矫顽磁力、磁饱和度。结果表明采用放电等离子烧结获得的烧结体的硬度HVl≥19500MPa，断裂强度TRS≥2800MPa，平均晶粒度150nm～300nm。制备了高强度、高硬度的超细WC-6Co硬质合金。     

VC添加量对纳米晶硬质合金的制备及性能影响

以钨钴氧化物、炭黑和VC为原料,采用原位还原碳化法制备WC-Co复合粉末,将复合粉末进行放电等离子烧结致密化制备WC-Co硬质合金块体材料。研究了不同VC添加量的复合粉末和块体材料的相组成、显微组织和性能,结果表明:VC的添加量对复合粉末的相组成、合金的晶粒尺寸和性能具有重要的影响,原料中添加2.0%VC(质量分数)时可获得平均晶粒尺寸为101 nm,相组成仅为WC和Co且具有高硬度和良好韧性的硬质合金块体材料。     

燃烧合成-热压制备Al_2O_3-TiC-ZrO_2纳米复合陶瓷的力学性能与显微结构

以ＴｉＯ２,Ａｌ;Ｃ,纳米 ＺｒＯ２粒子为原料,利用燃烧合成－热压工艺制备了Ａｌ２Ｏ３－ＴｉＣ－ＺｒＯ２纳米复合陶瓷．添加ＺｒＯ２可使 Ａｌ２Ｏ３－ＴｉＣ断裂方式由沿晶断裂转变为穿晶断裂．ＺｒＯ２纳米粒子弥散于基体中,其周围产生的应力集中可引发位错,起到亚晶界的作甲,并可使位错钉扎、堆积,阻碍位错运动,从而使复合陶瓷的力学性能得到明显改善：抗弯强度为７０６ＭＰａ,提高幅度达１９．８％;断裂韧性为 ６．３ ＭＰａ·ｍ１／２,提高幅度１８．９％;洛氏硬度为 ９４．４．     

Synthesis of WC-Co composite powders with two-step carbonization and sintering performance study

In this study, WC-Co composite powder was synthesized by two-step carbonization method using W, Co and C as raw materials. X-ray diffraction (XRD) showed that the η phase (Co₆W₆C) was kept at 1100 °C for 1 h under vacuum, and it could be completely carbonized into WC-Co composite powders. The surface morphology of WC-Co composite powders was analyzed by scanning electron microscope (SEM). The effects of η phase and second phase (W phase) on WC morphology and Co phase distribution were investigated. Electron backscattered diffraction (EBSD) was used to analyze WC-10 wt% Co cemented carbide particle distribution. Comparison of transverse rupture strength, hardness and fracture toughness of two kinds of WC-10 wt% Co cemented carbides synthesized by WC-Co composite powders + WC and WC + Co respectively, the cemented carbide of composite powders + WC increases the fracture toughness from 11.4 ± 0.3 MPa·m^1/2 to 12.4 ± 0.3 MPa·m^1/2.     

碳化帆颗粒尺寸对纳米晶硬质合金组织和性能的影响

利用原位还原碳化反应制备纳米尺度的WC-Co复合粉体,应用放电等离子烧结(SPS)技术制备出纳米晶WC-Co硬质合金块体材料。分析了晶粒长大抑制剂碳化钒(VC)颗粒尺寸对纳米晶硬质合金的显微组织、晶粒尺寸及分布和力学性能的影响。结果表明:当VC的粒径减小到100 nm以下时,利用快速烧结技术可制备得到平均晶粒尺寸约为70 nm的致密WC-Co硬质合金块体材料,其物相纯净,晶粒尺寸分布均匀,维氏硬度为19.84 GPa,断裂韧性达到12.10 MPa·m1/2。     

Microstructure and properties of ultrafine WC-10Co composites with chemically doped VC

Vanadium carbide is the most effective grain growth inhibitor for ultrafine WC-Co composites due to its high solubility and mobility in the cobalt phase at relatively low temperatures;however,there are still some debates over the best way to introduce it into the WC-Co formulation.In this paper,the differences between admixed and chemically doped grain growth inhibitors on the microstructural development and properties of an ultrafine WC-10Co composite are discussed.The densification rate of chemically doped samples is slower in the early stage of sintering and the WC grain sizes of the sintered alloys are finer than those of admixed samples,leading to the increase of hardness and transverse rupture strength of the sintered alloys.The effectiveness of the chemically doped inhibitor is attributed to the formation of vanadium rich layers on the surfaces of tungsten carbide powders during reduction and carbonization,which alters the surface and interface energies of WC grains,impedes the contact with each other of WC grains and contributes to the resistance to W diffusion across the layer during sintering,resulting in the inhibition of nanosized particle coalescence.     

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.     

VC和碳含量对超细晶硬质合金室温和高温性能的影响

以原位还原碳化技术制备的WC-8Co复合粉和VC粉末为原料,采用低压烧结技术制备出超细晶硬质合金。系统研究了VC添加量和复合粉中碳含量对硬质合金的相组成、显微组织、室温和高温力学性能的影响。结果表明:硬质合金的晶粒尺寸、硬度和断裂韧性主要受VC添加量的影响,且随VC添加量的增加呈单调变化;抗弯强度随VC添加量的变化趋势与碳含量有关;压缩强度随温度的变化呈现先降低后升高的趋势;当WC-Co复合粉的碳含量为5.60%～5.68%(质量分数)、VC添加量不超过0.5%时,可分别制备出室温抗弯强度为4482MPa和600℃下抗压缩强度为4914MPa的高综合性能的超细晶硬质合金。基于微观组织特征的分析,结合弹-塑性有限元模型对应力分布的模拟,对超细晶硬质合金力学性能的变化规律及影响机理进行了分析。     

SPS烧结WC-5%Co纳米复合粉硬质合金

采用喷雾干燥、流态化床化学转化法生产的WC-5%Co纳米复合粉为原料,研究了放电等离子体烧结(SPS)对超细硬质合金显微结构和性能的影响,同时对SPS烧结、低压烧结、真空烧结等三种工艺进行了比较。结果表明:采用SPS烧结可以在较低的温度下实现超细硬质合金的固相烧结,使合金快速致密化,当1170℃保温6min、压力为50MPa时合金可以获得最好的力学性能;其显微硬度HV30、抗弯强度、断裂韧性分别为1870、3230MPa、10.96MPa/m1/2。低压烧结可促进颗粒在液相中重排,硬质合金压坯经8MPa、1410℃、保温45min烧结,也可以获得比较好的力学性能;而传统真空烧结,合金孔隙度比较高,晶粒不均匀,性能较差。     

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.     

含(W,Ti,Ta)C的超细硬质合金的性能及组织研究

本文在WC-8%Co(文中含量均为质量分数)、复合抑制剂(VC/Cr3C2)的基础上,添加不同配比的Cr3C2及(W,Ti,Ta)C,制备超细硬质合金。采用横向断裂强度检测、洛式硬度检测、SEM分析、TEM检测等方法,研究了Cr3C2和(W,Ti,Ta)C对超细硬质合金力学性能和组织结构的影响。结果表明:随着Cr3C2、(W,Ti,Ta)C的增加,晶粒大小没有显著变化,硬质合金的横向断裂强度减低,硬度提高。通过透射电镜观察,在WC-8%Co-4%(W,Ti,Ta)C-0.5%(VC/Cr3C2)硬质合金中发现了类似于孪晶的结构,并通过能谱证实了Cr3C2和(W,Ti,Ta)C的存在。WC-8%Co-4%(W,Ti,Ta)C硬质合金经1 390℃压力烧结后,硬度为93.8 HRA,抗弯强度为2 250 MPa,相对密度为99.7%。     

Effects of graphite on the microstructure and properties of ultrafine WC-11Co composites by spark plasma sintering

Ultrafine WC-11Co hard metals added with different proportions of graphite were prepared by spark plasma sintering at 40 MPa/1200°C for 5 min,and the influence of graphite as free carbon on the microstructure and mechanical properties were investigated.The XRD analysis showed that decarbonization could be prevented by adding graphite.Compact hard metals composed of finer and more homogeneous WC grains with little flaws can be achieved after 0 wt.% to 1.5 wt.% graphite was added.The hardness and fracture toughness increase initially with increasing graphite content,and with over 1.5 wt.% they descend due to coarse grains and more defects.Therefore,1.5 wt.% graphite is the optimal addition content in view of the hardness and transverse rupture toughness.Furthermore,the coercive force decreases while the saturated magnetic intensity increases with the increase of graphite content.     

Properties and microstructure of VC/Cr3C2-doped WC/Co cemented carbides

This paper deals with the effects of codoped VC/Cr3C2 and sintering temperature on the magnetic and mechanical properties of ultra-fine grained WC-12%Co alloys. Results show that the synergistic action of doped VC/Cr3C2 in optimal proportion enhances both the hardness and transverse rupture strength (TRS) of the alloys, with more homogeneous microstructure. When the alloy is sintered at 1430℃ and with 0.5% Cr3C2/0.2% VC, the TRS reaches 3786 MPa, the hardness is 91.7 HRA and the grain size srnaller than 0.6 μm. The numerical analyses on grain growth during the sintering process show that both VC precipitating on the WC grain boundary and Cr3C2 dissolving in the Co phase decrease the solid/liquid interfacial energy γ, the process of dissolution and reprecipitation is greatly retarded and the coarsening of WC grains is inhibited.     

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.     

Effect of Al2O3 ceramic binder on mechanical and microstructure properties of spark plasma sintered WC-Co cermets

This study investigates how the partial replacement of Co with Al₂O₃ ceramic binder has an effect on the sintering behaviour, microstructure, and final mechanical properties of WC-Co cermets via spark plasma sintering. To examine this, three batches (WC-6 wt%Co, WC-3 wt%Co-3 wt%Al₂O_3, and WC-6 wt%Al₂O₃) were mixed through high energy ball mill, and sintering was carried out at temperatures of 1350 °C and 1600 °C. The results showed nearly full dense WC-Co cermets at different temperatures. It was shown that WC-6 wt%Al₂O₃, in comparison to reference WC-6 wt%Co cermet, not only led to the rise in sintering temperature from 1350 °C to 1600 °C, but also reduced its strength and toughness. But replacing some part of Co with alumina (WC-3 wt%Co-3 wt%Al₂O₃) exhibited the combination of high strength (1095 MPa), hardness (17.62 GPa), and fracture toughness (19.46 MPa·m^1/2).     

Er掺杂强韧化Al_2O_3/TiAl复合材料

以Ti、Al、TiO2为起始原料,以Er2O3为掺杂剂,原位热压合成了Er掺杂Al2O3/TiAl复合材料。通过XRD、SEM分析及力学性能测试,研究了不同Er2O3引入量对合成Al2O3/TiAl复合材料微观结构和力学性能的影响。结果表明:复合材料主要由TiAl、Ti3 Al、Al2 O3相和少量Al10 Er6 O24相组成,含Er相主要分布在基体相晶界处;掺杂0.01 mol Er2 O3制得的复合材料,经1250℃保温2 h真空热压烧结后表观断裂韧性达到最大值(10.41 MPa.m1/2),经1300℃保温2 h真空热压烧结后弯曲强度达到最大值(456.06 MPa);当Er2O3掺杂量增加到0.02 mol时,复合材料的弯曲强度和表观断裂韧性均呈减小趋势。微观结构分析表明,掺杂0.01 mol Er2O3的复合材料断口毛糙,颗粒尺寸变小,增强相分布较均匀,表明适量的Er2O3掺杂可细化复合材料晶粒尺寸,提高增强颗粒分布均匀度,起到增强增韧的效果。     

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。     

WC-Co based cemented carbides with large Cr3C2 additions

Five model alloys based on WC-16.6 vol% Co with different amounts of Cr₃C₂ (0–12 vol%) substituting WC were studied. Their microstructures were characterised with X-ray diffraction, scanning electron microscopy and transmission electron microscopy in combination with energy dispersive X-ray analysis. Thermodynamic calculations on the C-Co-Cr-W system were carried out using the Thermo-Calc software. The microstructures were related to previously published results on properties (magnetic coercivity, hardness, transverse rupture strength and indentation fracture toughness) of these materials. The aim of this work was to investigate whether the positive effect of small Cr₃C₂ additions on grain refinement and various properties remains also for large Cr₃C₂ additions. For Cr₃C₂ additions larger than 2 vol%, the most obvious effect on the microstructure was the formation of a chromium- and cobalt-rich M₇C₃ carbide. The Cr/Co ratio of this phase depends on the amount of Cr₃C₂ substituting WC. Some large WC grains were present in the WC-Co material, but not in the materials with Cr₃C₂ additions. Apart from this, no major changes of the WC grain size with Cr₃C₂ content were observed. The partial replacement of tough binder by presumably brittle M₇C₃ carbide might explain the lower toughness of these materials.