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.     

Effect of carbide and nitride addition on the strength of sintered TiC-Mo2C-Ni carbides

The effect of TaC, VC, Cr₃C₂, NbC, and TiN additives on the strength and hardness of sintered TiC-Mo₂C-Ni hard metals was studied. The additive powder was mixed separately with the TiC-Mo₂C-Ni base powder. The powder mixtures were then compacted and sintered in a vacuum. Experimental results showed that the transverse rupture strength of sintered hard metals was effectively promoted by adding the VC and TiN powders, respectively. However, no additives increased the hardness value of the base materials.     

Effect of carbide additions on grain growth in TiC−Ni cermets

The growth of carbide particles in TiC-XC-2 vol.% Ni and TiC-XC-30 vol.% Ni alloys, where X=Zr, Cr, W, Ta and Mo, was fitted to an equation of the form d³-d_o ³=Kt. The grain growth behavior during liquid phase sintering at 1673K decreased markedly with the addition of Mo₂C or WC, changed little for TaC, and increased with the addition of ZrC or Cr₃C₂. The grain contiguity decreased with increasing Ni content in the TiC−Mo₂C−Ni alloy and was greater in the alloys with smaller growth rate constant. Consequently, the effect of carbide addition on the grain growth of 2 vol.% Ni alloys was found to be similar to that of 30 vol.% Ni alloys. The grain growth mechanism could be explained by the effect of contiguous carbide grain boundaries in restricting the overall grain growth, as well as the area of the solid/liquid interfaces in the alloy by the usual solution/reprecipitation model.     

Grain growth simulation with the second phase particle pinning for heat-affected zone of microalloyed steel welds

The second phase particle dispersed in microaUoyed steel has different effects on grain growth depending on their size and volume fraction of the second phase particles which will change during welding thermal cycles.The particle coarsening and dissolution kinetics model was analyzed for continuous heating and cooling.In addition,based on experimental data,the coupled equation of grain growth was established by introdacing limited size of grain growth with the consideration of the second phase particles pinning effects.Using Monte Carlo method based on experimental data model,the grain growth simulation for heat-affected zone of microalloyed steel welds was achieved.The calculating results were well in agreement with that of experiments.     

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.     

超细硬质合金中晶粒非均匀长大机理

采用市售的粒度为0.8μm的WC粉末和粒度为1.6μm的Co粉制备了WC-10%Co超细硬质合金,通过金相显微镜﹑扫描电子显微镜观察了不同烧结温度下制备的试样WC晶粒形貌,对超细晶粒硬质合金非均匀长大现象及机理进行了研究。结果表明:粉末湿磨后的粗大颗粒在烧结过程中起晶核作用,是引起晶粒非均匀长大的关键因素。固相烧结时,烧结体中细小颗粒受到张力的作用发生旋转,当其取向与邻近的大颗粒取向一致时,形成共格界面,以粗大晶粒为核心以并合的方式非均匀长大;液相烧结时,细小晶粒溶解并优先地在大晶粒的某些低能量晶面如(0001)和(1010)面析出,引起晶粒异常长大。本研究中,当烧结温度达到1 410℃时,WC晶粒可异常长大为接近20μm的粗大晶粒。     

不同烧结温度下超细合金烧结体的密度、钴磁和晶粒度

本文研究了钴质量分数为10.5%的超细硬质合金在不同的烧结温度下的致密度、钴磁、晶粒长大等方面的变化趋势。研究结果表明:含量为10.5%的超细硬质合金,当烧结温度达到1 350℃时合金已基本致密化;在经典的WC-Co伪二元状态图表明的固相烧结阶段,随着温度升高,钴磁降低,晶粒长大以并合方式为主,可能存在少许的溶解-析出现象;在液相烧结阶段,钴磁达到稳定值后基本不变,晶粒长大以溶解-析出为主。     

纳米WC—Co复合粉的烧结特征

对纳米 WC— Co复合粉的烧结特征以及怎样充分利用这一特征来控制合金晶粒长大进行了介绍。指出 ,由喷雾转化法生产的纳米 WC— Co复合粉是一种预合金粉 ,它的烧结应该属于超固相线液相烧结范畴。与传统的液相烧结相比 ,超固相线液相烧结时 ,合金的微观结构和性能对烧结温度、工艺参数及合金成分更为敏感 ,因此必须对这些参数进行严格控制     

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.     

Effects of LaB6 addition on the microstructure and mechanical properties of ultrafine grained WC-10Co alloys

The ultrafine grain WC-10Co alloys were prepared by the planetary ball milling method and low pressure sintering. The effects of LaB₆ addition on the microstructure and mechanical properties of the based alloys were investigated by X-ray diffraction, scanning electron microscope and mechanical property testing. It has been shown that the grain growth and regularization of WC particles occur simultaneous with the addition of LaB₆. Adding suitable amount of LaB₆ improves the density, hardness and fracture toughness of the ultrafine WC-10Co alloys, and decreases the volume fraction of Co₃W₃C phase in ultrafine WC-10Co alloys.     

纳米硬质合金制备技术的研究

研究了 WC-Co纳米硬质合金的制备技术。采用强化球磨、添加晶粒长大抑制剂和低温加压烧结工艺 ,获得了 WC晶粒度接近 2 0 0 nm的硬质合金。研究了 VC和Cr3 C2 两种抑制剂加入量对合金组织、WC晶粒度和性能的影响以及抑制晶粒长大的机理。研究结果表明 ,添加 VC和 Cr3 C2 晶粒长大抑制剂十分有效的抑制了晶粒的长大 ,合金中的 WC晶粒度随抑制剂加入量的增加而细化。但过多的抑制剂不仅会导致碳化物在 WC/Co晶界上大量析出 ,而且也会增加孔隙度 ,结果增加了合金脆性 ,降低了合金的强度 ,其有害影响 VC比 Cr3 C2 更大。采用加压烧结可消除合金中的孔隙提高合金的强度。     

Pressureless sintering of internally synthesized SiC-TiB2 composites with improved fracture strength

SiC-TiB₂ particulate composites were fabricated by converting TiO₂ to TiB₂ through the reaction between TiO₂, B₄C and C. The presence of initially very fine, in-situ created, TiB₂ particles increased driving force for sintering and enabled fabrication of a dense composite utilizing pressureless sintering and the liquid phase created between Al₂O₃ and Y₂O₃ additives. The effect of volume fraction of the in-situ formed TiB₂ on density, microstructure and flexural strength was discussed. It was found that the presence of TiB₂ particles suppressed the growth of SiC grains and enhanced fracture strength. The fracture strength of samples containing 12 vol% TiB₂ was more than 30% higher than that of the monolithic SiC. The effect of SiC grain size on fracture strength was also analyzed.     

The effect of contiguity on growth kinetics in liquid-phase sintering

Experimental and mathematical consideration of microstructural coarsening during liquid-phase sintering has resulted in kinetic laws which define grain size to the third power as being proportional to the isothermal sintering time. Despite thoseprior efforts, the situations typical to liquid-phase sintering are poorly treated by the current models because the models assume a structure consisting of widely separated spherical grains (zero contiguity). No experiment had been completed to quantify the effect of contiguity on the growth kinetics. In order to do this, the contiguity and growth rates of tungsten grains in a liquid matrix at 1,750K were measured in sintered heavy alloys of 78,83, 88,93 and 98 wt.% Wbalanced with 70Ni-30Fe. The observed grain growth rates were compared with the theoretical predictions of the LSW theory and volume fraction modified theories. By modifying the volume fraction effect with a contiguity term, a model was produced that closely followed the experimental results.     

Microstructure,grain size distribution and grain shape in WC–Co alloys sintered at different carbon activities

The properties of cemented carbides strongly depend on the WC grain size and it is thus crucial to control coarsening of WC during processing. The aim of this work was to study the effect of sintering at different carbon activities on the final microstructure, as well as the coarsening behavior of the WC grains, including the size distribution and the shape of WC grains. These aspects were investigated for five WC–Co alloys sintered at 1410 °C for 1 h at different carbon activities in the liquid, in the range from the graphite equilibrium (carbon activity of 1) to the eta (M₆C) phase equilibrium (carbon activity of 0.33). The grain size distribution was experimentally evaluated for the different alloys using EBSD (electron backscatter diffraction). In addition, the shape of the WC grains was evaluated for the different alloys. It was found that the average WC grain size increased and the grain size distribution became slightly wider with increasing carbon activity. Comparing the two three-phase (WC–Co–eta and WC–Co–graphite) alloys a shape change of the WC grains was observed with larger grains having more planar surfaces and more triangular shape for the WC–Co–graphite alloy. It was indicated that in alloys with a relatively low volume fraction of the binder phase the WC grain shape is significantly affected by impingements. Moreover, after 1 h of sintering the WC grains are at a non-equilibrium state with regards to grain morphology.     

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.     

复合添加Cr_3C_2/NbC对超细晶WC-10%Co硬质合金组织和性能的影响

采用真空烧结方式制备超细晶WC-10%Co硬质合金,研究了复合添加晶粒长大抑制剂Cr3C2/NbC对合金组织及性能的影响。结果表明:在1400℃烧结条件下,添加剂的组成为0.4%Cr3C2+0.3%NbC时(文中含量均为质量分数),合金具有最好的综合力学性能,抗弯强度可达1951MPa、硬度1615HV30;WC平均晶粒尺寸为490nm。经SEM观察并通过EDS发现,抑制剂Cr3C2/NbC固溶到粘结相Co中,改变界面能,限制WC晶粒的长大;同时,也会降低WC在粘结相Co中的溶解度,从而起到细化晶粒的作用。     

Real-time observation of grain nucleation and growth during solidification of aluminium alloys

The crystallisation kinetics of liquid aluminium–titanium alloys with microscopic TiB₂ particles added to refine the grain size in the solidified material was studied by X-ray diffraction measurements at a synchrotron source. Real-time observation of the formation and growth of individual grains reveals the central role played by the added TiB₂ particles during solidification. Prior to the main transformation, weak reflections of a metastable TiAl₃ phase were detected. This observation finally pinpoints the highly debated mechanism responsible for enhanced grain nucleation in Al–Ti–B alloys.     

Macrosegregation induced sedimentation in liquid phase sintered Ni–W alloys

In this study, liquid phase sintering of Ni–W alloys containing a low W solid volume fraction was conducted. A solid-plus-liquid (mushy) zone forms at the compact bottom. A liquid head above this zone demonstrates macrosegregation. With increasing sintering time, macrosegregation is reduced concurrent with a decrease in the volume fraction of W particles and mushy-zone sedimentation.     

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。     

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。