Quantitative evaluation of normal and abnormal grain growth of cemented carbides during liquid phase sintering

The liquid-phase sintering (LPS) of cemented carbides prepared from submicronic powders induces a micro-structural evolution generally ascribed to normal and abnormal grain growth. Such phenomena can be prevented by small additions of inhibitors (Cr, V). Presently, the mechanisms controlling either the grain growth or its inhibition are not strictly identified. In the present work, the effects of major parameters on grain growth (initial WC grain size, liquid composition, liquid fraction) are studied by image analysis of specimens sintered at 1450°C up to 8h.The evolution of the mean intercept and intercept distribution of WC grains is analysed in terms of the possible mechanisms involved.     

Impact and dynamic deformation behavior of mechanically alloyed tungsten heavy alloy

93W-5.6Ni-l.4Fe tungsten heavy alloy was fabricated by mechanical alloying process using elemental powders of tungsten, nickel and iron, followed by sintering at temperatures of 1445~1485°C under hydrogen atmosphere. The tungsten heavy alloy sintered using mechanically alloyed powders showed finer tungsten particles about 5~18 μm with high density above 99% at shorter sintering time than that fabricated by conventional liquid-phase sintering process. Charpy impact energy of mechanically alloyed tungsten heavy alloy increased with increasing the matrix volume fraction and with decreasing the W/W contiguity. The high strain rate dynamic deformation behavior of tungsten heavy alloys using torsional Kolsky bar test exhibited different fracture modes dependent on microstructure. While the brittle intergranular fracture mode was dominant when the tungsten particles were contiguously interconnected in tungsten heavy alloys solid-state sintered below 1460°C, the ductile shear fracture mode was dominant when the tungsten particles were surrounded by ductile matrix phase in tungsten heavy alloys liquid-phase sintered above 1460°C.     

Experimental and simulation studies on grain growth in TiC and WC-based cermets during liquid phase sintering

The grain growth behaviors of TiC and WC particles in TiC-Ni, TiC-Mo₂C-Ni, WC-Co and WC-VC-Co alloys during liquid phase sintering were investigated for different Ni or Co contents and compared with the results of Monte Carlo simulations. In the experimental study, TiC-Ni and WC-Co alloys had a maximum grain size at a certain liquid volume fraction, while the grain size in TiC-Mo₂C-Ni and WC-VC-Co alloys increased monotonically with an increasing liquid volume fraction. These results mean that the grain growth of these alloys cannot be explained by the conventional mechanisms for Ostwald ripening, namely diffusion or reaction controlled processes. Monte Carlo simulations with different energy relationships between solidliquid interfaces predicted the effect of the liquid volume fraction on grain size similar to the experimental results. The contiguous boundaries between solid (carbide) particles appear to influence the grain growth behavior in TiC- and WC-based alloys during liquid phase sintering.     

Effect of microstructural parameters on the properties of W-Ni-Fe alloys

The aim of this research was to examine the effect of microstructural parameters on the tensile properties of dif- ferent compositions of tungsten heavy alloys. The microstructural parameters (grain size, connectivity, contiguity, and solid volume fraction) were measured and were found to have a significant effect on the tensile properties of tungsten-based heavy alloys. The microstructural parameters of W-Ni-Fe alloys are sufficiently different to present a range of me- chanical properties. It is concluded that the mechanical properties of tungsten heavy alloys largely depend on the micro- structural parameters and their ductility is particularly harmed when grains are contiguous.     

Effects of sintering conditions on mechanical properties of mechanically alloyed tungsten heavy alloys

The effects of sintering conditions on the microstructural evolution and mechanical properties of mechanically alloyed tungsten heavy alloys were investigated. W, Ni and Fe powders were mechanically alloyed in a tumbler ball mill at a milling speed of 75 rpm, ball-to-powder ratio of 20∶1 and ball filling ratio of 15%. The mechanically alloyed powders were compacted and solid-state sintered at a temperature of 1300°C for 1 hour in a hydrogen atmosphere. The solid-state sintered tungsten heavy alloy was subsequently liquid-phase sintered at 1470°C with varying sintering times from 4 min to 90 min. The solid-state sintered tungsten heavy alloy showed fine tungsten particles of 3 μm in diameter and high relative density above 99%. The volume fraction of the W-Ni-Fe matrix phase was measured, as 11% and tungsten/tungsten contiguity was 0.74 in solid-state sintered tungsten heavy alloys. Mechanically alloyed and two-step sintered tungsten heavy alloys showed tungsten particles of 6–15 μm and a volume fraction of the W-Ni-Fe matrix phase of 16% and tungsten/tungsten contiguity of 0.40. The solid-state sintered tungsten heavy alloy exhibited a yield strength of about 1100 MPa due to its finer tungsten particles, while it showed low elongation and impact energy due to its large tungsten/tungsten contiguity. The yield strength of two-step sintered tungsten heavy alloys increased with the decreasing of tungsten particle size and volume fraction of the W-Ni-Fe matrix. This article is based on a presentation made in “The 4th International Conference on Fracture and Strength of Solid”, held at POSTECH, Pohang, Korea, August 16–18, 2000 under the auspices of Far East and Ocean Fracture Society (FEOFS)et al.     

Variation of WC grain shape with carbon content in the WC–Co alloys during liquid-phase sintering

WC–Co hard metals have faceted WC grains dispersed in a ductile cobalt-rich matrix. The effect of carbon (C) content on the shape of WC grain in the WC–Co metals during liquid-phase sintering is investigated in this work. The WC grain shape varies with the C content and, more importantly, the shape change occurs reversibly with the C content.     

An investigation into the effects of HIP after sintering of WC-ZrC-Co-Cr3C2 cemented carbides

The sintering behaviour of cemented carbides based on WC-ZrC-Co-Cr₃C₂ powder mixtures have been analyzed by dilatometric and calorimetric methods for different cobalt contents and WC/ZrC ratios. As expected, powder oxide reduction in these compositions is mainly of carbothermic nature. However, depending on the milling conditions, some highly stable Zr-rich oxides are retained in the binder phase after sintering. Hot isostatic pressing (HIP) cycles have been successfully applied for closing residual porosity after vacuum sintering. For a fixed amount of binder phase and a WC/ZrC ratio, the hardness of these materials depends on the amount of residual porosity and WC grain growth control. The best combination of hardness and toughness is found for alloys with 8 wt%Co and WC/ZrC wt. ratios of 6.46. HIP treatments induce the formation of a compact and well adhered layer mainly comprised of Zr oxides and WC grains. The cobalt binder phase migrates from this layer towards the sample bulk likely due to the loss of wettability on these Zr rich oxides. Hot hardness is higher for the alloy with higher WC/ZrC ratio suggesting that this property depends on both the volume fraction of (Zr_xW_1-x)C and WC phases and their degree of contiguity.     

TiMoCN based cermets Part II. Microstructure and room temperature mechanical properties

Cermets obtained by sintering powders of TiCN and Mo₂C with cobalt or nickel binder are studied in this paper. Different TiCN/Mo₂C ratios are used in order to vary the grain size. Morphology parameters such as grain size, contiguity, and phase ratios are related with fracture toughness and hardness. The hardness can be adequately modelled considering the hardness of each phase weighed by the respective volume fraction. The toughness is mainly controlled by the properties of the binder, in particular the binder flow stress and the size of binder regions.     

Densification and grain growth kinetics of boron carbide powder during ultrahigh temperature spark plasma sintering

Dense B₄C material was fabricated using spark plasma sintering (SPS), and the densification mechanisms and grain growth kinetics were revealed. The density, hardness, transverse flexure strength and toughness of samples were investigated and the model predictions were confirmed by SEM and TEM experimental observations. Results show that SPSed B₄C exhibits two sintering periods: a densification period (1800–2000 °C) and a grain growth period (2100–2200 °C). Based on steady-state creep model, densification proceeds by grain boundary sliding and then dislocation-climb-controlled mechanism. Grain growth mechanism is controlled by grain boundary diffusion at 2100 °C, and then governed by volume or liquid-phase diffusion at 2200 °C.     

In-situ metal binder-phase formation to make WC-FeNi Cermets with spark plasma sintering from WC,Fe, Ni,and carbon powders

High-density WC-FeNi ceramic-metal (cermet) composites were fabricated using liquid-phase spark plasma sintering/field-assisted sintering technology (SPS/FAST) with in-situ formation of metal binder phase. The precursor materials were micron-sized powders of WC, Fe, Ni, and C. A low melting point from a eutectic reaction of the powders enabled the in-situ formation of FeNi alloy and facilitates liquid-phase sintering of the WC. The carbon powder was added to stabilize the formation of the binder phase. Electron backscatter diffraction (EBSD) was performed to measure grain size and orientation. The composite exhibited a 99% theoretical density and a microstructure consisting of rounded and contiguous WC grains. The average grain size is 10.5 μm. The composite has a maximum hardness of 16.1 GPa. This research provides a fast and cost-effective approach to fabricate hard metals.     

Anisotropic shrinkage during sintering of particle-oriented systems—numerical simulation and experimental studies

High shear rates involved in processes such as tape casting and injection molding result in anisotropic shrinkage during subsequent densification of the green bodies. Anisotropic shrinkage with more than 14% difference in the shrinkages between the casting and transverse directions was observed in tape cast alumina. To explain the measured shrinkage anisotropy in tape cast alumina and its variation as densification progresses, sintering of oriented ellipses is simulated. The simulated shrinkage anisotropy decreases as sintering progresses because of the increasing neck length in the particle-oriented direction. Similar trends were seen for experimental results on tape cast alumina. The decrease is more significant when surface diffusion dominates over grain boundary diffusion. Similar atomistic models were also used to simulate the sintering shrinkages in liquid-phase sintered alumina. Again, anisotropy decreases as sintering progresses. The predictions from solid state sintering models were then validated by sintering alumina with 500–1000 ppm of yttria. It is proposed that the addition of yttria lowers the grain boundary diffusion rate with respect to the surface diffusion and hence lowers the shrinkage anisotropy in accordance with the simulation model.     

相场法模拟不同形状的硬质颗粒对两相晶粒长大的影响

采用相场方法研究了不同颗粒体积分数及尺寸条件下不同形状的硬质颗粒对两相系统晶粒长大的影响,结果表明:球形颗粒大多处于三角晶界处,片状颗粒处于晶界处且沿晶界分布.不同形状的硬质颗粒对体积占优的α相晶粒长大无明显影响,对体积分数较小的β相晶粒长大的影响主要取决于颗粒数目.颗粒数目较少时,不同形状的硬质颗粒对β相晶粒长大无明显影响;颗粒数目较多时,片状颗粒比球形颗粒对β相晶粒长大的阻碍作用强烈.颗粒体积分数越大,颗粒对晶界的钉扎作用越强,稳态时晶粒的半径越小;颗粒尺寸越大,单个颗粒对晶界的钉扎作用越强,但总的钉扎作用越弱,稳态时晶粒的半径越大.     

Light scattering in MgO-doped alumina fabricated by spark plasma sintering

The microstructure and optical properties of MgO-doped alumina fabricated by spark plasma sintering were investigated. MgO doping to alumina exhibited no noticeable effect on the total forward transmission, but suppressed grain growth and enhanced in-line transmission. The analytical investigation of the scattering coefficients confirmed that MgO-doped alumina has the scattering characteristics of the homogeneous matrix dispersed with spherical scattering grains, and that the existing model of light scattering in an alumina polycrystal is valid within a limited range of the wavelength/grain size ratio. The investigation also led to experimental determination of the effective volume density of spherical scattering grains satisfying the Rayleigh–Gans theory.     

Aspects of the metrology of contiguity measurements in WC based hard materials

Contiguity is thought to be of significant importance regarding the properties of WC–Co hardmetals and other multiphase hard materials. Contiguity is an estimate of the degree of contact between adjacent grains in two phase materials. It is straightforward to define and, in principle, relatively easy to measure. However, published values of contiguity, generally expressed as a function of the volume fraction of the Co phase in WC–Co, show considerable scatter. Possible reasons for this scatter are discussed; in particular various aspects of the measurement process are examined in order to recommend suitable measurement metrology that will contribute to minimising uncertainties in the measurement process. Furthermore, the consequences of uncertainty in contiguity measurements for the use of published models relating contiguity to microstructural variables is also discussed.     

Haynes 230合金热变形组织演化规律研究

采用Thermecmastor-Z型热模拟机对Haynes230合金进行变形温度为950~1250 ℃,应变速率为0.001～10 s-1范围内的高温压缩试验,并利用OM和TEM分析研究了热变形组织演化特征和动态再结晶形核机制。结果表明：动态再结晶晶粒尺寸和体积分数随着变形温度的升高而增大和增多,随着应变速率的升高而变小和减少;晶界弓出是合金动态再结晶的主要形核机制,项链组织在热变形组织演化过程中起着重要作用;动态再结晶稳态晶粒尺寸Dss与Z参数之间符合幂函数关系     

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.     

稀土La在纳米晶（W, Ni, Fe, La）复合粉末烧结过程中的作用机理

采用溶胶-喷雾干燥法制备纳米晶(W,Ni,Fe,La)复合粉末,研究了粉末在烧结过程中La对抑制鼓泡和晶粒长大的作用机理,通过XRD与SEM分析了La在烧结过程中的相转变规律和在合金中的存在形式,讨论了稀土La对合金液相烧结过程中扩散的影响。结果表明:稀土La在纳米复合粉末中主要以La2WO6与La4W2O15的形式存在。经液相烧结后,稀土La主要以二次相颗粒的形式分布于粘结相中,生成高温下能稳定存在的La4W2O15相,该相对杂质元素Ca、O具有很好的亲和力,起到晶界净化和晶内净化的作用。同时二次相颗粒存在于粘结相中,抑制了W在粘结相中的扩散,降低了W在粘结相中的溶解度,使得液相烧结溶解-析出过程减慢,从而抑制液相烧结阶段的晶粒长大和鼓泡现象。     

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.     

Additive manufacturing of WC-13%Co by selective electron beam melting: Achievements and challenges

Additive manufacturing is a powerful tool for rapid prototyping and fabricating metal articles having a complicated geometry. This method is known to be used almost solely for the manufacture of articles consisting of pure metals and alloys. In the present work the possibility of obtaining dense carbide articles by a single-step process of additive manufacturing based on selective electron beam melting was evaluated. A new technology for fabricating cemented carbide granules suitable for selective electron beam melting was developed. It includes conventional granulating WC-Co powders followed by solid-state pre-sintering and preliminary screening of the granules. After that their liquid-phase sintering and final screening are carried out to obtain a desired fraction needed for the additive manufacturing process. Results of experiments on selective electron beam melting at different scan rates and current values indicated that it was possible to obtain non-porous carbide articles of complex geometry from WC-Co granules initially containing 13 wt% Co. The selective electron beam melting process led to the evaporation of some liquid Co and very intense local WC grain growth resulting in peculiar microstructures of the cemented carbide articles comprising layers with medium-coarse and abnormally large WC grains. A near-surface layer of the cemented carbide articles obtained by additive manufacturing is characterized by a high roughness comparable with the mean size of the original WC-Co granules.     

Abnormal grain growth in Al–3.5Cu

Significant abnormal grain growth has been observed in an Al–3.5 wt.% Cu alloy at temperatures where the volume fraction of small CuAl₂ particles was less than about 0.01. The initial fine-grained material had a weak crystallographic texture and there was no indication that any special boundaries were involved in the abnormal growth. Island grains isolated within the abnormal grains also showed no indication of special orientation relationships with their surrounding grains. Measurements indicated that the island grains initially had a size advantage over other matrix grains. The fraction of pinning phase was much lower at abnormal grain boundaries than at boundaries in the fine-grained matrix into which they were growing. A variety of simulations were made, including attempts to model that difference in pinning phase distribution, but none of these were successful in predicting abnormal grain growth.