中国超细晶硬质合金及原料制备技术进展

超细晶硬质合金是WC晶粒度≤0.5μm的硬质合金,这类合金具有高强度和高硬度的优异性能。目前由超细晶硬质合金制备的高效刀具已经广泛用于航空航天、核能、汽车、发电设备、新能源和电子通讯等现代制造业。主要对中国超细晶硬质合金原料(例如超细碳化钨粉、钴粉、复合粉)和超细晶硬质合金制备技术、性能及表征方法作了系统的阐述。最后对超细晶硬质合金制备技术进行了展望。     

Complex carbide powders for plasma spraying

Various carbide-containing powders are used for plasma spraying. Most of these consist of tungsten carbide. Very frequently the tungsten carbide is mixed with cobalt to produce coatings similar to cemented carbides. The powders can be made by agglomeration of the carbides and the metal matrix powders or by coating the carbides with the matrix metal. As in cemented carbides, cobalt and nickel form the metal binder of the coatings. The coating metals can be increased to 20% of the total weight. Further metal matrix powders can be added also. The W₂C, WC, W₂C-WC eutectic phases and mixtures of them are used as tungsten carbide. The carbon content is very important and can be controlled better in coated particles than in an agglomerated powder. In the case of WCCo the carbon content has to correspond to MC to avoid the embrittling η phase and to achieve a strength of the coating comparable with that of cemented carbides. In addition to the composition, shape and grain size distribution of the powders, the spraying conditions are very important for the properties of the coating. Coated carbide powders are less sensitive to spraying conditions. When it is possible to control the carbon content in carbides better during spraying it will be feasible to use complex carbides also.Titanium carbide forms a solid solution with WC over a wide range of composition and forms mixed crystals with tantalum carbide and niobium carbide. These binary and ternary mixed carbide crystals, sometimes containing additional tungsten carbide, are used in cemented carbides to increase the wear resistance. By spraying these cobalt- or nickel-coated complex carbide powders similar properties of the coatings can be achieved. Spraying conditions and the shape, grain size and grain size distribution of the powders are important. Results will be given.     

A novel rapid route for synthesizing WC–Co bulk by in situ reactions in spark plasma sintering

A novel rapid route for preparing WC–Co cemented carbides bulk, which integrated the synthesis of the composite powder by in situ reactions and subsequent consolidation in the spark plasma sintering (SPS) system, was proposed. The phase configurations both in the synthesized composite powder and in the sintered bulk were analyzed in details. It was shown that the obtained WC–Co bulk has a homogeneous and fine-grained structure and good combined mechanical properties. As compared with the conventional methods, the present preparation route has been remarkably simplified. Particularly, with the greatly reduced temperature and time in the preparation procedures, it is effective to control the grain coarsening during the processes. By taking into account the characteristics of the SPS technology, the formation mechanism of the WC–Co composite by in situ reduction and carbonization reactions was proposed.     

纳米WC硬质合金制备新工艺

文章综述了制备纳米WC、WC Co粉体的几种方法。着重阐述了纳米WC Co硬质合金的烧结新工艺 :微波烧结、二阶段烧结、快速热等静压烧结和等离子体活化烧结等。与传统烧结方法相比 ,使用这些烧结新工艺制备的产品性能更优异 ,有很大的发展前景。     

Characterizations of WC–10Co nanocomposite powders and subsequently sinterhip sintered cemented carbide

Ultrafine WC–Co cemented carbides, combining high hardness and high toughness, are expected to find broad applications. In this study, WC–10Co–0.4VC–0.4Cr₃C₂ (wt.%) nanocomposite powders, whose average grain size was about 30 nm, were fabricated by spray pyrolysis-continuous reduction and carbonization technology. The as-prepared nanocomposite powders were characterized and analyzed by chemical methods, scanning electron microscopy (SEM), transmission electron microscopy (TEM), BET analysis and atomic force microscopy (AFM). Furthermore, “sinterhip” was used in the sintering process, by which ultrafine WC–10Co cemented carbides with an average grain size of 240 nm were prepared. The material exhibited high Rockwell A hardness of HRA 92.8, Vickers hardness HV₁ 1918, and transverse rapture strength (TRS) of 3780 MPa. The homogeneously dispersed grain growth inhibitors such as VC, Cr₃C₂ in nanocomposite powder and the special nonmetal–metal nanocomposite structure of WC–10Co nanocomposite powder played very important roles in obtaining ultrafine WC–10Co cemented carbide with the desired properties and microstructure. There was an abundance of triple junctions in the ultrafine WC–10Co cemented carbide; these triple junctions endowed the sintered specimen with high mechanical properties.     

Carbon nanofiber reinforced aluminum matrix composite fabricated by combined process of spark plasma sintering and hot extrusion

Spark plasma sintering and hot extrusion processes have been employed for fabricating carbon nanofiber (CNF)-aluminum (Al) matrix bulk materials. The Al powder and the CNFs were mixed in a mixing medium of natural rubber. The CNFs were well dispersed onto the Al particles. After removal of the natural rubber, the Al-CNF mixture powders were highly densified. From the microstructural viewpoint, the composite materials were observed by optical, field-emission scanning electron, and high-resolution transmission electron microscopies. The CNFs were found to be located on every grain boundary and aligned with the extrusion direction of the Al-CNF bulk materials. Some Al carbides (Al4C3) were also observed at the surface of the CNFs. This carbide was created by a reaction between the Al and the disordered CNF. The CNFs and the formation of Al4C3 play an important role in the enhancement of the mechanical properties of the Al-CNF bulk material. The CNFs can also be used for engineering reinforcement of other matrix materials such as ceramics, polymers and more complex matrices.     

超细碳化钨-钴硬质合金的原子力显微镜研究

以液相复合-连续还原碳化方法制备的纳米碳化钨-钴复合粉末为原料,采用低压烧结制备了性能优良的超细碳化钨-钴硬质合金.运用原子力显微镜(AFM)对超细碳化钨-钴硬质合金的表面形貌进行了观察、缺陷和粒度分析,同时对合金的力学性能进行了测试.结果表明,采用低压烧结获得的烧结试样的洛氏硬度HRA≥93.5,抗弯强度TRS≥3300MPa,平均晶粒度＜220nm.制备了具有高强度、高硬度的超细碳化钨-钴硬质合金.纳米碳化钨-钴复合粉末制备的超细硬质合金组织结构均匀,但局部仍然存在着组织缺陷,分析了产生缺陷的机理.     

高分散多壁碳纳米管增强铝基复合材料的制备(英文)

采用机械合金化技术制备高分散多壁碳纳米管(MWCNTs)-铝(Al)复合材料。将纯度99%的铝粉和质量分数2%的MWCNTs经超声和水平球磨处理使Al颗粒与MWCNTs间产生机械键合力。场发射SEM观察表明,MWCNTs分散在Al薄片的表面,随球磨时间的不同,颗粒大小和形貌各异。采用加压烧结手段将混合粉末加工成块体材料,其微观硬度测试表明,加入MWCNTs后Al基体的机械性能得到提高。     

Production and mechanical properties of metallic glass-reinforced Al-based metal matrix composites

Al-based metal matrix composites were synthesized through powder metallurgy methods by hot extrusion of elemental Al powder blended with different amounts of metallic glass reinforcements. The glass reinforcement was produced by controlled milling of melt-spun Al₈₅Y₈Ni₅Co₂ glassy ribbons. The composite powders were consolidated into highly dense bulk specimens at temperatures within the supercooled liquid region. The mechanical properties of pure Al are improved by the addition of the glass reinforcements. The maximum stress increases from 155 MPa for pure Al to 255 and 295 MPa for the samples with 30 and 50 vol.% of glassy phase, respectively. The composites display appreciable ductility with a strain at maximum stress ranging between 7% and 10%. The mechanical properties of the glass-reinforced composites can be modeled by using the iso-stress Reuss model, which allows the prediction of the mechanical properties of a composite from the volume-weighted averages of the components properties.     

Cutting Performance of WC-Co Alloys Modified by Nano-Additives

In this paper,the microstructure of WC-Co alloys with and without nano-additives was characterized by scanning electron microscopy(SEM) and transmission electron microscopy(TEM).The hardness and fracture toughness was tested by using a Vickers hardness tester and a universal testing machine.The cutting test was carried out at different feed velocities(250 r/min and 320 r/min),and the contact pairs are cutting tools and 45# steel bars.Results showed that the hardness and fracture toughness of WC-Co cemented carbides with nano-additives are higher than that of WC-Co cemented carbides without nano-additives,and they are increased 10.21% and 19.69%,respectively.The flank worn width and crater width of cutting tools decrease greatly with the addition of nano-additives.For the nano-modified specimen with WC grain size of 7 μm,both the flank worn width and crater width are the minimum after the cutting process.And there are little built-up layers and some pile-up regions on the flank face leading to high cutting performance for the nano-modified cemented carbides.There are some melted regions on the flank face of cutting tools without nano-additives,and the WC grains on the cross section of alloys without nano-additives show severe fragmentation.The wear type of WC-Co is flank wear,and the wear mechanism is abrasive,adhesion and oxidation wear.     

Grain size effect on wear resistance of WC-Co cemented carbides under different tribological conditions

The grain-size dependence of wear resistance of WC-Co cemented carbides(with mean WC grain sizes of 2.2 μm,1.6 μm,0.8 μm and 0.4 μm,respectively) was investigated under different tribological conditions.The results showed that the grain size had opposite effects on wear resistance of the cemented carbides in dry sliding wear and microabrasion tests.In the former condition,with decrease of WC grain size hence the increase of hardness,plastic deformation,fracture,fragmentation and oxidation were all mitigated,leading to a drastic decrease in the wear rate.In the latter condition,pull-out of WC grains after Co removal dominated the wear,so that the hardness of cemented carbide was not a core factor.As a result,the wear resistance of the cemented carbide generally showed a decreasing trend with decrease of the grain size,except for a slight increase in the ultrafine-grained cemented carbide.Single-pass scratching of the cemented carbides under various loads indicated the same failure mechanism as that in the sliding wear tests.Furthermore,the reasons for severe surface oxidation of the coarse-grained cemented carbides were disclosed.     

Spark plasma sintering on nanometer scale WC–Co powder

Nanometer scale WC–11Co powder was sintered by spark plasma sintering (SPS) process in order to improve the properties of the cemented carbides. Properties such as density and hardness were measured. The microstructures of sintered WC–11Co cemented carbides were observed. The grain size of WC in alloys was also obtained. The results showed that spark plasma sintering could lower the sintering temperature, increased the density and circumscribed the growth of grain size of WC. Besides, the hardness of the sintered cemented alloys that was dependent on the grain size and densification could also be improved by SPS. SPS was an effective method to get WC–11Co cemented carbides with fine grain size and good properties.     

Sintering,thermal stability and mechanical properties of ZrO2-WC composites obtained by pulsed electric current sintering

ZrO₂-WC composites exhibit comparable mechanical properties as traditional WC-Co materials, which provides an opportunity to partially replace WC-Co for some applications. In this study, 2 mol.% Y₂O₃ stabilized ZrO₂ composites with 40 vol.% WC were consolidated in the 1150°C–1850°C range under a pressure of 60 MPa by pulsed electric current sintering (PECS). The densification behavior, microstructure and phase constitution of the composites were investigated to clarify the role of the sintering temperature on the grain growth, mechanical properties and thermal stability of ZrO₂ and WC components. Analysis results indicated that the composites sintered at 1350°C and 1450°C exhibited the highest tetragonal ZrO₂ phase transformability, maximum toughness, and hardness and an optimal flexural strength. Chemical reaction of ZrO₂ and C, originating from the graphite die, was detected in the composite PECS for 20 min at 1850°C in vacuum.     

Research on Ultrafine Tungsten Carbide-Cobalt (WC-Co) Cemented Carbide Rods of Miniature Drills for Highly Integrated Printed Circuit Board (PCB)

Nanocrystalline tungsten carbide-cobalt (WC-Co) composite powders produced through spray thermal decomposition-continuous reduction and carburization technology were used to prepare φ3.25 mm×38 mm ultrafine tungsten carbide-cobalt (WC-Co) cemented carbide rods through vacuum sintering plus sinterhip technology. The microstructure, Vickers hardness, density and Rockwell A hardness (HRA), transverse rupture strength (TRS), saturated magnetization and coercivity force were tested. The results show that the average grain size of the sintering body prepared through vacuum sintering plus sinterhip technology was 430 nm; transverse rupture strength (TRS) was 3850 MPa; Vickers hardness was 1890 and Rockwell A hardness of sintering body was 93. High strength and high hardness ultrafine WC-Co cemented carbide rods used to manufacture printed circuit board (PCB) drills were obtained.     

Dense pure binderless WC bulk material prepared by spark plasma sintering

The phases, microstructures and mechanical properties of binderless WC bulk materials prepared by the spark plasma sintering technique were investigated systematically. The addition of carbon was added to eliminate the impurity phase W₂C. The relative density, Vickers hardness and grain size increase obviously with increasing sintering temperature, but increase weakly with increasing pressure or sintering time. The high relative density of 99·1%, HV30 of 27·5 GPa and fracture toughness K_IC of 4·5 MPa m^1/2 of pure binderless WC bulk with a grain size of 400 nm was obtained by sintering the WC powders with a particle size of 200 nm and the addition of 0·63 wt-%C at 1800°C for 6 min under 70 MPa.     

Synthesis of uniformly dispersed carbon nanotube reinforcement in Al powder for preparing reinforced Al composites

In order to obtain homogeneously dispersed carbon nanotube (CNT) reinforcement with well structure in Al powder, a novel and simple approach was developed as a means of overcoming the limits of traditional mixing methods. This process involves the even deposition of Ni catalyst onto the surface of Al powder by impregnation route with a low Ni content (0.5 wt.%) and in situ synthesis of CNTs in Al powder by chemical vapor deposition. The in situ synthesized CNTs with well-crystallized bamboo-like structure in the composite powders can obviate the reaction with Al below 1000 °C. The feasibility of fabricating CNT/Al composites with high mechanical properties using the as-prepared composite powders was proved by our primary test, which indicated that the compressive yield stress and elastic modulus of 1.5 wt.%-CNT/Al composites synthesized by hot extrusion are 2.2 and 3.0 times as large as that of the pure Al matrix.     

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。     

Recent developments on WC-based bulk composites

In order to achieve improved properties and performance with WC-based cemented carbides, research efforts have been directed towards the development of nanostructured cemented carbides. With the recent development of ‘spray conversion process’ for synthesizing nanosized powders and the advent of spark plasma sintering technique, it has been possible to successfully develop bulk nanostructured cemented carbides, possessing improved hardness and wear resistance. On a different note, realisation of the fact that the presence of metallic binder phase is deleterious towards certain applications of WC-based cermets has led to a recent surge of interest towards the development of novel ‘binderless’ WC-based ceramics by replacing the metallic binder phase with ceramic sinter-additives. More recently, it has been possible to develop dense WC-based ceramic composites without considerable deterioration of fracture toughness in the absence of the metallic binder phase. In the above perspective, the present review focuses mainly on the recent research results concerned with the processing and characterisation of nanostructured WC-based cermets and binderless WC-based ceramic composites.     

Synthesis and Characterizations of Nanocrystalline WC-Co Composite Powders by a Unique Ball Milling Process

In order to explore the high efficiency of fabricating nanocrystalline WC-Co composite powders, this paper presented a unique high energy ball milling process with variable rotation rate and repeatious circulation, by which nanocrystalline WC-10Co-0.8VC-0.2Cr3C2 (wt pct) composite powders with mean grain size of 25 nm were prepared in 32 min, and the quantity of the powders for a batch was as much as 800 grams. The as-prepared powders were analyzed and characterized by chemical analysis, X-ray diffraction (XRD), transmission electron microscopy (TEM) and differential thermal analysis (DTA). The results show that high energy ball milling with variable rotation rates and repeatious circulation could be used to produce nanocrystalline WC-Co powder composites with high efficiency. The compositions of the powders meet its specifications with low impurity content. The mean grain size decreases, lattice distortion and system energy increase with increasing the milling time. The morphology of nanocrystalline WC     

Effect of milling time,MWCNT content,and annealing temperature on microstructure and hardness of Fe/MWCNT nanocomposites synthesized by high-energy ball milling

Nanocrystalline pure Fe and Fe/MWCNT nanocomposites powders with 0.25, 0.5, 1, and 10 wt% MWCNT contents were synthesized by high-energy ball milling (HEBM). The as-milled powders were cold-compacted and annealed at 400 °C and 600 °C for 1 h in Ar atmosphere. The effect of ball milling on pristine MWCNT and Fe/MWCNT composite powders was also investigated as a function of milling time up to 20 h. The physical properties of MWCNT were imaged by scanning electron microscopy (SEM) and transmission electron microscopy (TEM) before and after HEBM. The structural damage of MWCNT as a function of milling time and MWCNT content was studied using Raman spectroscopy. The structural characterization of MWCNT and Fe/MWCNT composites was conducted by X-ray diffraction (XRD) as a function of milling time, MWCNT content, and annealing temperature. The chemical properties of the synthesized composite powders were investigated using X-ray photoelectron spectroscopy (XPS). The microhardness test was performed to assess the effect of milling time, annealing temperature, and MWCNT content on the mechanical properties. The results indicated that after the ball milling process, the structure of MWCNT was destroyed, and the formation of the amorphous carbon phase was observed, which was confirmed by XRD and TEM analyses. In addition, decreased defect and carbon intensity ratios (I_D/I_G) were calculated from the Raman results with longer ball milling processes, which is attributed to the destruction of carbon bonds. The XPS results confirmed the presence of FeC bonds as a result of the formation of carbide phases. A fine dispersion of precipitated carbides determined by TEM is found to promote the grain size stability below 100 nm in the nanocrystalline Fe matrix. The results from the micro-hardness tests showed that Orowan particle strengthening resulting from the carbide formation, as well as grain size hardening, is an important contributor to strengthening in Fe/MWCNT composites.