纳米碳化钒对超细WC基硬质合金的影响

研究了在放电等离子烧结(SPS)条件下,纳米碳化钒(V8C7)对超细WC基硬质合金的相组成、微观组织及性能的影响。结果表明:超细WC基硬质合金主要由WC和Co3C两相组成,相对于未烧结的硬质合金材料,WC的衍射峰向小角度方向偏移;纳米碳化钒可以有效抑制超细WC基硬质合金中WC晶粒的长大,并且随着纳米碳化钒比表面积的增大而增强,添加比表面积为63.36m2/g的纳米V8C7后,硬质合金中大部分WC的晶粒尺寸0.5μm;纳米碳化钒对超细WC基硬质合金的性能具有重要影响,并且随着纳米碳化钒比表面积的增大而增加,添加比表面积为63.36m2/g的纳米V8C7后,超细WC基硬质合金具有较高的性能(相对密度99.7%,洛氏硬度93.4,断裂韧性12.7MPa.m1/2)。     

A novel sintering technique for fabrication of functionally gradient WC–Co cemented carbides

Functionally graded or functionally gradient WC–Co cemented carbides with Co and/or hardness gradients can potentially have great practical importance. In this article is described a novel sintering technique for fabrication of functionally gradient WC–Co cemented carbides. This technique includes (1) employing green carbide bodies with low (or high) carbon contents within the two-phase region of the W–Co–C phase diagram; (2) their pre-sintering in the solid state to obtain a certain green density and consequently gas permeability; (3) selective carburisation (or decarburisation) of their surface layer in a carburising (or decarburising) gas atmosphere; and (4) final liquid-phase sintering at tailored sintering conditions to obtain a Co drift (also known as ‘Co migration’) either from the surface towards the core or from the core towards the surface. The kinetics of Co drift between couples of model alloys with very similar WC mean grain sizes but different carbon contents were examined. The microstructure, hardness, Co contents, residual stresses and wear-resistance of the gradient cemented carbides with low-Co surface layers obtained by the selective surface carburisation of carbide green bodies with the original low carbon content were examined. Their surface layers were found to contain significantly less Co than the core resulting in a higher hardness of the surface layer. The surface layer is also characterised by high residual compressive stresses in both the carbide phase and binder phase, which results in an improved combination of hardness and fracture toughness. The microstructure, hardness and Co contents of gradient cemented carbide comprising high-Co surface layers obtained by selective surface decarburisation of carbide bodies with the original high carbon content were also examined. The surface layer of the gradient cemented carbide contains noticeably more Co than the core which is beneficial when using this functionally gradient carbide as a substrate for polycrystalline diamond coatings.     

A transmission electron microscopy study of WC-10Co cemented carbides with modified hard and binder phases

The alloy design of WC-10Co cemented carbide, modified with addition of a hard carbide phase, TiC, and with Ni and Mo in the binder phase, has been highlighted by the authors in a number of publications. The present article deals with the fine microstructural features of various phases in such cemented carbides. WC grains in all the investigated cemented carbide compositions appear to develop straight facets during sintering because of their anisotropic nature. In contrast, the TiC phase is characterized by its rounded shape. Dislocations are present in both WC and TiC grains, being of lesser density in the latter. The binder phase is always associated with stacking faults. The nature of the hard phase/binder interfaces has been found to be dependent on the binder phase chemistry. The observed changes in microstructures and mechanical properties have been correlated with the wettability and solubility of the hard phases in the binder melt, and with the different strengthening mechanisms in the binder phase.     

Quantitative fractography of WC-Co cermets by Auger spectroscopy

A general procedure has been developed to determine the area fraction occupied by the binder on the fracture surfaces of cemented carbides. The area fraction of binder on the fracture surface was obtained from the relative peak-to-peak height ratios of elements in the binder and the carbide content was measured by Auger spectroscopy on the fracture surface and an adjacent polished section and the volume fraction of binder present in the cermet. This procedure was employed to determine the area fraction of binder on the fracture surfaces of WC-Co cermets with different binder contents and carbide grain sizes. The average binder mean free path and the area fraction of binder together yield the amount of plastically deformed binder per unit area of fracture surface. The volume of deformed binder and its in situ yield strength were combined to obtain a term proportional to the amount of plastic work done per unit area of fracture surface. It is shown that the correlation between this plastic work term and the fracture toughness of the cermets is good, while correlation with binder mean free path alone is poor.     

1400℃放电等离子烧结制备MgO-B_(2)O_(3)增韧无金属黏结相WC硬质合金EI北大核心CSCD

为了降低无金属黏结相碳化钨(WC)硬质合金的烧结温度并获得较高的断裂韧度,采用MgO和B_(2)O_(3)协同增韧WC硬质合金。通过放电等离子烧结技术(SPS)在1400℃的较低温度下制备出致密的WC-MgO-B_(2)O_(3)硬质合金块体材料,研究MgO-B_(2)O_(3)对无金属黏结相WC硬质合金的烧结机理、微观组织演变以及力学性能的影响规律。结果表明:MgO-B_(2)O_(3)的添加促进了WC的烧结致密化,显著降低了无金属黏结相WC硬质合金的烧结温度。随着MgO-B_(2)O_(3)添加量的提高,组织中的部分第二相形貌发生显著改变,逐渐由短杆状转变为长杆状,再转变为聚集时的块状。当MgO-B_(2)O_(3)添加量达到8%(质量分数)时,块体材料具有较好的断裂韧度,为(9.45±0.37)MPa·m^(1/2),同时其硬度为(18.16±0.17)GPa。     

Brazing of carbon–carbon composites to Nimonic alloys

Industrially produced C_f/C ceramic composites have been brazed to Nimonic alloys using a TiCuSil filler metal. Ιn order to accommodate the different linear coefficients of expansion between ceramic and metal as well as to provide compatibility between the surfaces to be joined, the C_f/C surface was metallized through the deposition of a chromium layer. Subsequent heat treatments were carried out to develop intermediate layers of chromium carbides. Crack-free joints have been produced and shear tests show that failure occurs within the composite. At the C_f/C-filler interface a layered structure of the metallic elements is observed. Titanium is depleted from the filler zone and interacts with the carbon to form carbides. In the filler region, Ag and Cu rich regions are formed.     

Mechanical properties of WC-based hardmetals bonded with iron alloys – a review

Growing concerns over the use of cobalt as binder for WC-based hardmetals has directed research efforts towards finding a suitable alternative binder offering comparable or even superior properties than those found in WC–Co hardmetals. Complete substitution of cobalt by iron alloys has been extensively explored in several studies with significant improvements in mechanical properties of WC bonded with Fe alloys when carbon content addition is strictly controlled in powder composition. Asides from the commonly studied hardness and fracture toughness properties, transverse rupture strength property of this composites has also been observed to hold future promise with further development in the microstructural parameters such as porosity during sintering. This article reviews the progress in the mechanical properties of WC–Fe alloys hardmetals.     

Mechanisms of Fatigue in Cemented Carbides at Elevated Temperatures

Cemented carbides are mainly used as cutting tools in various fields of application. In nearly all industrial uses they have to resist wear and concurrent complex thermomechanical loading, often including alternating mechanical loads at high temperatures. It has been shown that cemented carbides suffer lifetime‐limiting fatigue under cyclic loads at 25 °C caused by subcritical crack growth. Present investigations show that strong, temperature‐dependent fatigue effects occur in cemented carbides at elevated temperatures. TEM investigations revealed temperature‐dependent processes that are responsible for the changes in the fatigue behavior: at low temperatures a phase transformation of the Co‐binder phase and at higher temperatures oxidation in the cracks and brittle–ductile transitions of cubic carbides.     

Mechanical properties of titanium diboride based cermets

Mechanical properties of titanium diboride (TiB₂) cermets critically depend on the composition of the binder phase. Both, fracture toughness and hardness are substantially increased by avoiding the formation of extremely brittle secondary borides which form during sintering by chemical reactions between TiB₂ and the metallic additives. Fractographic observations of TiB₂ cermets without secondary borides show the presence of ductile ligaments of the binder phase bridging the advancing crack tip. The powder metallurgy processing route applied to these materials allows modification of the binder phase structure from the ferritic iron-aluminium phase to Fe-Ni-Al austenite by changing the aluminium content of the powder mixtures. The highest toughness values have been obtained for the TiB₂ cermets with an austenitic binder phase. X-ray diffraction analyses of the fracture surfaces of such samples show that the binder phase is metastable exhibiting stress induced martensitic transformation during fracture. This new family of materials presents an outstanding combination of hardness and toughness, comparable to those obtained with commercial grades of tungsten carbide (WC) hardmetals.     

Crack propagation behavior of cermets and cemented carbides under repeated thermal shocks by the improved quench test

In this study, an improved quench testing method for thermal shock resistance has been proposed. Repeated thermal shock tests were performed on cemented carbides to show the advantages of the new proposed method that would enable us to estimate an intrinsic relationship between the crack propagation rate and the stress intensity factor under repeated thermal shocks. The cyclic thermal fatigue crack propagation behavior and fracture toughness values were shown to be independent of the specimen heights and the cooling media employed. We then evaluated the thermal crack propagation behavior for cermets and cemented carbides by using this method, and discussed the differences between both materials in the crack growth behavior on the basis of their microstructures.     

界面反应对Cu35Ni25Co25Cr15多主元合金/金刚石复合材料磨损性能的影响

金刚石超硬磨具在高端芯片加工、3C陶瓷等领域发挥的作用日益重要,粘结相与金刚石的界面结合情况在很大程度上影响了金刚石超硬复合材料的力学和磨损性能。为了研究粘结相和金刚石的界面结合情况,采用放电等离子烧结方法制备了Cu₃₅Ni₂₅Co₂₅Cr₁₅多主元合金/金刚石复合材料,通过热力学计算和实验研究了粘结相和金刚石颗粒的界面反应。结果表明：烧结过程中,金属粘结相中的Cr元素与金刚石在界面处发生了化学反应,生成Cr-C化合物,且Cr-C化合物层的厚度随着烧结温度的升高而增加。当烧结温度达到950℃时,Cr-C化合物反应层均匀连续,厚度大约为1.1μm。复合材料粘结相与金刚石颗粒的粘结系数随着Cr-C化合物层厚度的增加而增大。摩擦磨损测试表明,在900℃和950℃烧结的样品表面,粘结相在摩擦过程中首先被磨除,金刚石随后露出,而Cr-C界面反应层有助于保持对金刚石颗粒的把持能力,提高复合材料的磨削性能。因此,适当的界面反应可提升金刚石复合材料的服役性能。     

Mechanics and mechanisms of fatigue in a WC–Ni hardmetal and a comparative study with respect to WC–Co hardmetals

There is a major interest in replacing cobalt binder in hardmetals (cemented carbides) aiming for materials with similar or even improved properties at a lower price. Nickel is one of the materials most commonly used as a binder alternative to cobalt in these metal-ceramic composites. However, knowledge on mechanical properties and particularly on fatigue behavior of Ni-base cemented carbides is relatively scarce. In this study, the fatigue mechanics and mechanisms of a fine grained WC–Ni grade is assessed. In doing so, fatigue crack growth (FCG) behavior and fatigue limit are determined, and the attained results are compared to corresponding fracture toughness and flexural strength. An analysis of the results within a fatigue mechanics framework permits to validate FCG threshold as the effective fracture toughness under cyclic loading. Experimentally determined data are then used to analyze the fatigue susceptibility of the studied material. It is found that the fatigue sensitivity of the WC–Ni hardmetal investigated is close to that previously reported for Co-base cemented carbides with alike binder mean free path. Additionally, fracture modes under stable and unstable crack growth conditions are inspected. It is evidenced that stable crack growth under cyclic loading within the nickel binder exhibit faceted, crystallographic features. This microscopic failure mode is rationalized on the basis of the comparable sizes of the cyclic plastic zone ahead of the crack tip and the characteristic microstructure length scale where fatigue degradation phenomena take place in hardmetals, i.e. the binder mean free path.     

研发硬质合金的集成计算材料工程

用于研发硬质合金的集成计算材料工程是将微观(10~(-10)10~(-8)m)、细观(10~(-8)10~(-4)m)、介观(10~(-4)10~(-2)m)和宏观(10~(-2)10 m)等多尺度计算模拟和关键实验集成到硬质合金设计开发的全过程中,通过成分-工艺-结构-性能的集成化分析,把硬质合金的研发由传统经验式提升到科学设计,从而大大加快硬质合金材料的研发速度,降低研发成本.本文详细阐述了第一性原理计算、CALPHAD方法、相场模拟和有限元模拟等计算模拟方法及各种微结构表征和性能测定的实验方法,论述了其在硬质合金研发中所发挥的具体作用.基于集成计算材料工程,提出了从用户需要、设计制备和工业生产的3个层面研发硬质合金的具体框架.通过应用实例,展示了集成计算材料工程在新型硬质合金研发中的强大功能,为新型硬质合金的设计和开发提供了新模式.     

Microstructure development during sintering and heat-treatment of cemented carbides and cermets

WC based cemented carbides and Ti(C, N) based cermets are used in cutting tool applications. They are produced by liquid phase sintering, but much of the microstructure is formed already during solid state sintering, before the eutectic temperature has been reached. Changes in the microstructure during the sintering process have been followed with microscopy and microanalysis, in particular SEM and TEM including energy filtered transmission electron microscopy (EFTEM). It was found that part of the hard phases are dissolved in the solid binder, transported by diffusion and re-precipitated onto undissolved hard grains with a composition given by the equilibrium conditions (“inner rim”). For vacuum sintering of nitrogen containing materials, this means a low nitrogen activity due to the open porosity at this stage. After the liquid has formed, further dissolution and re-precipitation occur, but now the porosity is closed so the “outer rim” is formed with the nitrogen activity of the material. The solid solution of the binder (often by tungsten) is determined primarily by the carbon activity in the liquid phase. During cooling after sintering, tungsten and other metals dissolved in the binder re-precipitate onto hard grains so that depleted zones around these are formed, whereas dissolved carbon and nitrogen have time to leave the binder almost completely. Sintering or post-sintering heat-treatment of nitrogen containing materials in an atmosphere with a lower or higher nitrogen activity than in the material results in the formation of surface zones with a composition different from the bulk (“gradient sintering”). In the former case, a tough zone enriched in binder and depleted of cubic carbides is created, which is beneficial if the material is going to be coated with a wear resistant layer. In the latter case a hard surface zone rich in cubic carbo-nitrides and depleted of WC and binder may be obtained, improving the wear resistance of the material.     

Processing and microstructure of non-oxide ceramic fibres

Research and development efforts on high-temperature, oxidation-resistant fibres have increased over the past decade due to the demand for light-weight, stiff and strong composite materials in aerospace applications. Varieties of ‘high-performance’, continuous, non-oxide fibres with low-density, high tensile strength and tensile modulus have been developed either from organic precursors or via chemical vapour deposition for fabrication of ceramic matrix composites. Fibres derived from polymer precursors (e.g. Nicalon, Tyranno, HPZ) are small in diameter (compared to CVD monofilaments) and are ideally suited for ceramic composites. Processing, microstructural stability and mechanical properties of these newly developed SiC and Si₃N₄ base fibres are briefly reviewed in this paper.     

Biomimetic synthesis of cellular SiC based ceramics from plant precursor

A novel biomimetic approach in designing and fabricating engineering ceramic materials has gained much interest in recent times. Following this approach, synthesis has been made of dense Si-SiC duplex ceramic composites and highly porous SiC ceramics in the image of the morphological features inherent in the caudex stem of a local monocotyledonous plant. The process route involves making of a carbonaceous biopreform and its subsequent reaction with an infiltrating silicon melt to yield the biomorphic Si-SiC ceramic composites with flexural strength and Young’s modulus of 264 MPa and 247 Gpa, respectively and loss in weight of only ∼9% during oxidative heating up to 1200°C in flowing air. The Si-SiC composites were transformed into porous (49 vol.%) SiC ceramics with complete preservation of microcellular anatomy of the parent plant, by depleting residual silicon phase in channel pores through reaction with carbon. SiC based materials so derived can be used in structural applications and in designing high temperature filters and catalyst supports.     

Nanostructured ceramics for biomedical implants

Recent progress in the synthesis, characterization, and biological compatibility of nanostructured ceramics for biomedical implants is reviewed. A major goal is to develop ceramic coating technology that can reduce the friction and wear in mating total joint replacement components, thus contributing to their significantly improved function and longer life span. Particular attention is focused on the enhancement of mechanical properties such as hardness, toughness, and friction coefficient and on the bioactivity as they pertain to the nanostructure of the material. The development of three nanostructured implant coatings is discussed: diamond, hydroxyapatite, and functionally graded metalloceramics based on the Cr-Ti-N ternary system. Nanostructured diamond produced by chemical vapor deposition (CVD) techniques and composed of nano-size diamond grains have particular promise because of the combination of ultrahigh hardness, improved toughness over conventional microcrystalline diamond, low friction, and good adhesion to titanium alloys. Nanostructured processing applied to hydroxyapatite coatings is used to achieve the desired mechanical characteristics and enhanced surface reactivity and has been found to increase osteoblast adhesion, proliferation, and mineralization. Finally, nanostructured metalloceramic coatings provide continuous variation from a nanocrystalline metallic bond at the interface to the hard ceramic bond on the surface and have the ability to overcome adhesion problems associated with ceramic hard coatings on metallic substrates.     

高性能WC合金的研究进展

WC合金具有高硬度、高强度、高耐磨性、强抗腐蚀性等一系列优点,作为一种不可缺少的工具材料已经得到了广泛的应用.结合近几年来WC合金的研究状况,重点讨论其在制备工艺、改性处理等方面的发展动态及其优缺点,并展望了WC合金的发展趋势.     

A Dielectric Sensing Approach for Controlling Matrix Composition During Oxide-Oxide Ceramic Composite Processing

Continuous fiber reinforced ceramic matrix composites (CMC’s) made from aluminum oxide fibers and matrices are usually fabricated using a tape casting process. In this process, ceramic slurry consisting of the oxide powder, a polymeric binder and a solvent is infiltrated into a woven ceramic fiber mat. After evaporation of some of the solvent, the resulting flexible tapes can be stacked and sintered to create a composite component. Because the fraction of ceramic powder in the slurry can vary during processing, in-situ compositional sensors are required for on-line feedback control to limit property variations in the composite material. Since the dielectric properties of the slurry components are distinctly different, the effective permittivity of the slurry depends upon its composition. Here, a non-contact capacitance probe has been used to explore the possibility of capacitance sensing for compositional control. Results indicate that the removal of solvent during a precision drying step may be monitored by this approach. The feasibility of monitoring changes in the slurry’s composition during infiltration of the fiber mat is also discussed.