Mechanical deformation of WC–Co composite micropillars under uniaxial compression

In this work, WC–Co micropillars machined by focused ion beam have been tested under uniaxial compression to investigate the stress–strain behavior and associated deformation mechanisms. The results indicate that yielding phenomena is evidenced by multiple strain bursts. Experimental data is found to fall within the bounds defined by the mechanical responses expected for an unconstrained Co-binder like model alloy and a bulk-like constrained binder region in WC–Co composites; capturing then local phase assemblage and crystal orientation effects.     

Investigation on plastic deformation mechanism of ultra-coarse cemented carbide based on energy analysis

Microstructure evolution and plastic deformation mechanisms of the ultra-coarse cemented carbide compressed at different temperatures were studied based on designed experiments and a proposed energy model. The cemented carbide compressed at high temperature exhibited larger strain, which resulted from the generation and movement of high density of dislocations in WC grain. The energies stored in WC and Co phases and dissipated by heat energy in the deformation were quantified. The larger energy stored in WC grain than that in Co phase indicates significant contribution of the hard matrix to deformation of the ultra-coarse cemented carbide.     

Ni3Al添加量对WC-Co硬质合金中WC晶粒形状的影响

采用粉末冶金制备技术,以粗WC粉末、Co粉和WC＋Ni3Al预合金粉末为原料制备出WC-40vol％（Co—Ni,Al）硬质合金。利用扫描电镜和透射电镜研究了不同NbAl含量对WC-40vol％（Co—Ni3Al）硬质合金中WC晶粒形状的影响规律。结果表明：W在Co粘结相中的固溶度接近25．4wt％,而W在Ni,Al粘结相中的固溶度接近9．5wt％,随着NbAl含量的增加,粘结相对W的固溶度减小,合金中的WC晶粒圆钝和细小;WC晶粒表面上出现明显的台阶。相应的,延长烧结时间,WC—Co—Ni3Al硬质合金具有与WC—Co硬质合金相同的WC生长行为,WC-40vol％（Co—Ni3Al）硬质合金中的WC晶粒表面上的台阶处出现明显的刻面。     

On the fatigue crack growth behavior of WC–Co cemented carbides: kinetics description,microstructural effects and fatigue sensitivity

The influence of microstructure and load ratio (R) on the fatigue crack growth (FCG) characteristics of WC–Co cemented carbides are studied. In doing so, five hardmetal grades with different combinations of binder content and carbide grain size are investigated. Attempting to rationalize microstructural effects, key two-phase parameters, i.e. binder thickness and carbide contiguity, are used. On the other hand, the effect of load ratio is evaluated from the FCG behavior measured under R values of 0.1, 0.4 and 0.7. Experimental results indicate that: (1) WC–Co cemented carbides are markedly sensitive to fatigue; and (2) their FCG rates exhibit an extremely large dependence on K_max. Furthermore, both fatigue sensitivity and relative prevalence of K_max over ΔK, as the controlling fatigue mechanics parameter, are found to be significantly dependent upon microstructure. As mean binder free path increases, predominance of static over cyclic failure modes diminishes and a transition from a ceramic-like FCG behavior to a metallic-like one occurs (conversely in relation to contiguity). Consequently, the trade-off between fracture toughness and FCG resistance becomes more pronounced with increasing binder content and carbide grain size. The observed behavior is attributed to the effective low ductility of the constrained binder and its compromising role as the toughening and fatigue-susceptible agent in hardmetals, the latter on the basis that cyclic loading degrades or inhibits toughening mechanisms operative under monotonic loading, i.e. crack bridging and constrained plastic stretching.     

微量铁、钴元素对碳化钨形貌和粒度的影响

铁、钴元素大量用于硬质合金中 ,构成硬质合金的粘结相。而微量的铁、钴元素对碳化钨质量有什么影响 ,却报导甚少。通过试验发现 :钨加炭炉料中铁、钴含量分别超过约 0 .0 5 9%、0 .0 37%时 ,碳化后的碳化钨块发生严重收缩 ,难以磨碎和过筛 ,碳化钨的微观形貌也由类似球状变成棱角的多面体 ,费氏粒度变粗 ,影响到碳化钨的质量控制及一次投入产出合格率     

Implementation of an effective time-saving two-stage methodology for microstructural characterization of cemented carbides

Linear intercept on scanning electron microscopy micrographs is the most commonly used measurement method to determine carbide grain size and contiguity in WC–Co cemented carbides (hardmetals). However, it involves manual time-consuming measurements and is critically dependent on the quality of the micrographs as well as on the identification and definition of grain boundaries. In this study a two-stage methodology for microstructural characterization of hardmetals is presented. First, a digital semi-automatic image analysis procedure for grain size determination of the carbide phase is presented. It involves an experimental assessment of grain size on processed images corresponding to a series of WC–Co and WC–Ni cemented carbide grades with different microstructural characteristics. Obtained results are then compared to the values obtained by means of the linear intercept technique. A good correlation between the mean grain sizes determined following both measurement techniques was attained. Based on experimental findings, a series of empirical relations were found to correlate grain size distributions obtained following both methods. Second, an empirical relation for estimating carbide contiguity in WC–Co cemented carbides is proposed. This relation considers simultaneously the influence of the binder content and the experimentally determined mean grain size on contiguity. The proposed equation for contiguity estimation is based on extensive data collection from open literature. An excellent agreement was attained between contiguity values estimated from such equation and those obtained using the linear intercept technique. This validates the two-stage procedure as an effective time-saving methodology for microstructural characterization of WC–Co cemented carbides.     

WC粒度分布对WC-Co硬质合金力学性能影响的模拟分析

本文旨在建立基于WC-Co硬质合金真实微观组织的力学性能预测有限元分析方法,进而分析WC颗粒粒度分布对微区变形和力学行为的影响。实验设计和制备了具有Co含量相同,WC晶粒分布均匀和非均匀的两种WC-Co硬质合金,并进行维氏硬度测试和用SEM进行组织观测。通过对合金组织的SEM形貌照片进行WC颗粒边界的重构,建立WC和Co两相真实组织的二维有限元模型。通过有限元模拟对两种合金的弹性模量、泊松比和强度等力学性能进行预测和微观变形机理分析。有限元模拟结果表明均匀合金强度高于非均匀合金,与实验测试的硬度所揭示的规律相吻合。对微观变形机理分析揭示了均匀合金应力分布更均匀是强度较高的主要内在机理,而WC/WC邻接界面的应力集中是弱化力学性能的主要机制。     

超细WC-Co硬质合金及其磨损性能研究

采用低温化学镀方法在超细WC颗粒表面进行金属钴包覆,烧结包覆后的复合粉体制备新型硬质合金NYG（WC-3%Co）.研究了超细WC-Co硬质合金的力学性能、断口形貌和显微结构,在销盘式磨损试验机上进行干滑动磨损实验.结果表明,在硬质合金烧结过程中,沿WC晶界均匀分布的金属钴不仅起粘结剂作用,也起抑制剂作用阻碍晶粒的长大;新型硬质合金的抗弯强度、断裂韧性、硬度和耐磨性能均得到较大提高;在干滑动摩擦条件下,新型WC-Co硬质合金的失效以塑性变形及细小碳化钨相颗粒脱落为特征.     

Influence of microstructure on ultraprecision grinding of cemented carbides

The influence of microstructure on the ultraprecision grinding response of a series of cemented carbides for spherical mirrors was characterized by means of optical and laser interferometry, atomic force microscopy, scanning electron microscopy and X-ray diffraction. Surface roughness, form accuracy, grinding-induced residual stress and material removal behaviors were studied as a function of tungsten carbide (WC) grain size. In connection with the removal mechanisms in ultraprecision grinding, microindentations performed on each material showed similar deformation patterns, all in the plastic regime. The microstructure of WC-Co materials was found to have little influence on the nanometre surface roughness and submicron form accuracy. However, the X-ray stress measurements indicated that the microstructure of carbide materials had a significant influence on the grinding-induced residual stresses; i.e. an increase in grinding-induced residual compressive stress with an decrease in WC grain size. No grinding-induced cracks were observed in the ground cemented carbide surfaces. The material removal in ultraprecision grinding was considered to occur within the ductile regime. The formation of microgrooves and plastic flow regions via slip bands of WC grains along the cobalt binder without visible resultant microfracturing of WC grains were the dominant removal mechanisms.     

Influence of the cemented carbide specification on the process force and the process temperature in grinding

Cemented carbides are hard and brittle materials. Their material properties are adjusted by their chemical composition, in particular their average hard phase grain size and their binder fraction. The research paper focusses on grinding of cemented carbides with cobalt (Co) as binder and tungsten carbide (WC) as hard phase material. Within the research paper, it is discussed if and to what extent the cemented carbide composition affects the occurring thermo-mechanical load collective in the grinding process. In particular, the influence of the average WC grain size and the cobalt fraction on the thermo-mechanical load collective is investigated and explained by the cemented carbide material properties. The results of the publication contribute to a knowledge-based design of cemented carbide grinding processes.     

气压烧结硬质合金性能的研究

选用一定条件的WC粉和Co粉,生产YG6、YG11、YG8顶锤3个牌号硬质合金试样．采用气压烧结和普遍真空烧结,对两种工艺进行对比,结果表明：气压烧结硬质含金孔隙等缺陷显著降低;密度、强度等物理性能大大提高,低粘合金更为明显,气压烧结硬质合金的磁力、Co磁更为均匀,组织更细。     

碳化钨/金属间化合物硬质合金的研究进展

对目前国内外以金属间化合物Ni3Al、FeAl、Fe3Al为粘结相的碳化钨基硬质合金的制备方法和性能特点进行了综合评述,重点介绍了硬质合金国家重点实验室在以Ni3Al为粘结相碳化钨基硬质合金方面的最新研究成果及应用情况。结果表明:均匀细小的金属间化合物预合金粉末的制备以及适当控制界面反应是粉末冶金法制备碳化钨/金属间化合物硬质合金的有效方法。碳化钨/金属间化合物硬质合金的研究方向应集中在界面问题、金属间化合物粘结相的韧化、制备工艺和综合性能评价体系的建立等几个方面。     

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.     

Carbide grain growth in cemented carbides sintered with alternative binders

Cemented carbides are composites made of a hard refractory ceramic phase and a ductile binder, most commonly WC and Co, respectively. Since the use of cobalt in the hard metal industry is questioned by the new European regulation on chemicals, extensive research has been done to develop new grades based on a Co-Ni-Fe binder. With similar mechanical, physical properties and affinity to C and W, nickel and iron are the best candidates for an efficient binder in cemented carbides. As mechanical properties are strongly dependent on the materials microstructure, and especially on the WC grain size, understanding the effect of the binder on the final microstructure is crucial.In this work, the carbide grain growth behaviour of WC-M alloys (M = Co, Ni, Fe) with different carbon contents is discussed from qualitative and quantitative microstructural analyses. Whereas grain growth is more or less inhibited in WC-Fe alloys, increasing carbon content promotes grain growth in WC-Co and WC-Ni alloys, with a slight abnormal grain growth in case of Ni binder. Different mechanisms for grain growth are discussed, in relation with the observed morphology of WC grains after sintering.     

Chemical mechanism of chemical mechanical polishing of tungsten cobalt cemented carbide inserts

To explore the chemical mechanism of tungsten‑cobalt cemented carbide inserts in H₂O₂-based polishing fluid. Before and after the YG8 cemented carbide inserts were corroded, surface phase, element and structure were characterized by XRD and SEM/EDS. The chemical mechanism of tungsten‑cobalt carbide inserts during chemical mechanical polishing (CMP) was analyzed. XPS was utilized to analyze the corrosion products formed on the surface of YG8 cemented carbide inserts during chemical reaction to determine the chemical reaction equation. In the H₂O₂ environment, the electrode potential of the Co layer at the boundary between the binder phase with larger crystal domains and the hard phase is greater than the electrode potential of the intermediate layer γ(Co-W-C solid solution) phase and WC, which creates a potential difference between the three, and occurs galvanic corrosion. The hard phase WC is protected as the cathode of the entire battery and has a tendency to stabilize. The Co layer at the phase boundary is the most anode feature to be corroded and dissolved first. The γ phase of the intermediate layer serves as the secondary anode feature and serves also as the cathode of the Co layer. When the Co layer at the phase boundary is corroded to a certain extent, a galvanic couple is formed between the γ phase and the testing phase WC to cause corrosion. In addition, the binder phase with smaller crystal domains directly forms galvanic corrosion with WC. The chemical products created on the surface of the blades are Co₃O₄ and WO₃. However, Co₃O₄ and WO₃ oxide films are small in size and have little effect on material removal during polishing. When the binder phase corrosion on the blades surface reaches a critical point, the stress exerted by the polishing abrasive is basically concentrated on the WC particle surface. The strength of the WC particles that have lost the supporting effect of the binder phase becomes low and the structure becomes brittle. Under the mechanical scratching and compressive stress of the abrasive particles of the polishing solution, the smaller WC particles are directly pulled out. The surface layer of the larger WC particles is broken into WC grains, and then the surface layer is mechanically removed.     

稀土元素对硬质合金钴粘结相影响的研究

利用配备能谱仪（EDS）的透射电镜（TEM）、扫描电镜（SEM）和X射线衍射仪（XRD）对添加稀土元素前后的YT14硬质合金的钴粘结相进行了研究．结果表明，微量稀土元素加入后，钴粘结相中W、Ti元素的固溶量提高；钴粘结相中f．c．c－Co相的点阵常数和所占的体积分数均较未加稀土的合金增大了．根据实验结果对稀土元素强化硬质合金的机理进行了探讨．     

In-situ observation of hardmetal deformation processes by transmission electron microscopy. Part I: Deformation caused by bending loads

WC-based hardmetals have a unique combination of different properties including high hardness, fracture toughness, abrasion resistance, strength, fatigue resistance, etc. Such properties are achieved due to extraordinary features of tungsten carbide, which is characterized by a certain degree of plastic deformation before failure when loading. The major objective of this work is to examine hardmetal deformation processes leading to the formation and movement of crystallographic defects in a hardmetal lamella as a result of its in-situ bending directly in a transmission electron microscope. The deformation is found to result in the formation of different crystal lattice defects in the Co-based binder and WC grains. Mainly dislocations form in the tungsten carbide grains. The dislocations start moving when increasing the applied bending load. The deformation of the binder phase is found to result in the formation of mainly lamellae and stacking faults in the Co crystal lattice. As a result of the formation, interaction and movement of the crystal lattice defects in the WC phase and binder phase a significant rate of plastic deformation of the hardmetal lamella was achieved under bending loads without its breakage.     

WC-Ni硬质合金研究

研究以Ni替代Co作硬质合金粘结剂，通过在Ni中添加适量的金属添加剂，来提高和改善WC－Ni硬质合金性能，采用此方法生产出来的WC－Ni硬质合金的机械性能和使用性能完全可以达到WC—Co硬质合金的水平．     

Reprint of “Thermal fatigue behaviour of WC-20Co and WC-30(CoNiCrFe) cemented carbide”

Cemented carbides are used in many applications, such as drawing dies, cutting tools and hot rolls. In applications where cyclic temperature variations are present, an important factor that must be taken into account is thermal fatigue (TF). In this study, TF behaviour of two commercial cemented carbides was evaluated by means of a custom test configuration inducing a biaxial state of stress. At an early stage of the damage process, crack density is higher in WC-30(CoNiCrFe), while crack length is lower than WC-20Co. At a later stage cracking proceeds by propagation of existing cracks, partly reducing the difference between the two grades. The prevailing fracture modes are different in the two materials. In WC-20Co the main fractures occur at the WC/WC grain boundary and at WC/Co interface. In WC-30(CoNiCrFe) cracking proceeds by fracture of carbide particles and shear fracture of binder phase. A possible influence of oxidation on the TF crack propagation has been evidenced.     

用超合金作粘结相的硬质合金的TEM研究

用透射电子显微镜研究了由一种Ni基超合金作粘结相的硬质合金的组织结构。结果表明，烧结后合金的粘结相γ中分布着高度弥散的γ＇相。γ＇相质点在位错网络的结点上择优形核，形貌有粒状和片状两种，大小为10um数量级。观察表明，粘结相γ与WC的湿润性良好，因此用Ni基超合金作硬质合金的粘结相，不仅可节约战略物质Co，而且有可能使硬质合金的性能提高，使用范围扩大。