抑制剂对WC-Co硬质合金涂层性能的影响

利用原位还原碳化反应合成的超细WC-12Co复合粉末作为原料, 分别添加1.0wt%晶粒长大抑制剂即VC、Cr₃C₂和NbC, 经团聚造粒和超音速火焰(HVOF)喷涂制备了超细结构的硬质合金涂层。研究了不同晶粒长大抑制剂对涂层的显微组织结构、物相、硬度、耐磨性能和耐蚀性能的影响。结果表明, 与未添加晶粒长大抑制剂涂层相比, 添加1.0wt% VC或Cr₃C₂制备的硬质合金涂层中WC颗粒的平均尺寸降低了约49%, 涂层硬度明显提高, 磨损速率降低了约52%~55%。添加1.0wt% NbC对制备涂层中WC颗粒尺寸的抑制作用不明显, Co粘结相中由于形成了(W, Nb)C化合物, 其耐蚀性获得显著提高, 但该化合物脆性大, 导致涂层耐磨性不及添加VC和Cr₃C₂制备的涂层。     

Elaboration, microstructure and reactivity of Cr3C2 powders of different morphology

Cr₃C₂ powders have been prepared by heat-treatment of metastable chromium oxides of controlled morphology in H₂---CH₄ atmosphere. Starting with these highly reactive oxides allows formation of Cr₃C₂ at 700 °C. The reaction is pseudomorphic and different grain shapes (needles, rods, spheres and polyhedra) have been obtained. The size distribution is narrow and the grain size is generally of the order of a few tens of micrometers, but the “spheres” are in fact made up of aggregates of small platelets about 1.5 μm wide and 0.7 μm thick. The oxidation in air of the carbides was studied by thermal analyses (TGA, DTG and DSC) and was found to proceed in four steps in the 250–700 °C range. The differences observed between the carbides are related to their morphology and texture.     

Effects of lower cobalt binder concentrations in sintering of tungsten carbide

Cemented tungsten carbides have received much attention because of their superior characteristics. Traditional cemented tungsten carbides usually contain 3–30 wt% binder phase. In this paper, WC with low Co concentration less than 3 wt% is studied using traditional powder metallurgy. The binder phase has tremendous effect on sinterability of WC. High sinterability and high hardness can be achieved for the WC (0.7 μm) with 0.5 wt% Co. Abnormal grain growth (AGG) is often observed in sintering WC with small amount of Co. It seems that AGG is affected by the concentration of Co and a range of Co concentrations may exist for the large amount of AGG. To control the grain size, VC is added to inhibit the grain growth of WC. It is observed that the hardness is affected by the amount of addition of VC. Controlling the ratio of C/W less than unity at low Co concentrations will result in the production of W₂C phase. The hardness of WC–Co is affected by the amount of W₂C phase in the sample and W₂C is stable during the normal cooling process.     

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。     

Electron microscopy and hardness study of a semi-solid processed 27 wt%Cr cast iron

A semi-solid processed 27 wt%Cr cast iron was studied by electron microscopy and its microstructure was related to the hardness. In the as-cast condition, the primary proeutectic austenite was round in shape while the eutectic M₇C₃ carbide was found as radiating clusters mixed with directional clusters. Growth in the [0 0 1]M₇C₃ with planar faces of {0 2 0}M₇C₃ and was usually observed with an encapsulated core of austenite. Destabilisation heat treatment followed by air cooling led to a precipitation of secondary M₂₃C₆ carbide and a transformation of the primary austenite to martensite in the semi-solid processed iron. Precipitation behaviour is comparable to that observed in the destabilisation of conventional cast iron. However, the nucleation of secondary M₂₃C₆ carbide on the eutectic M₇C₃ carbide was observed for the first time. Tempering after destabilisation led to further precipitation of carbide within the tempered martensite in the eutectic structure. The maximum hardness was obtained after destabilisation and tempering heat treatment due to the precipitation of secondary carbides within the martensite matrix and a possible reduction in the retained austenite.     

Inconel 600合金中不同类型晶界处铬的浓度

应用TEM、EDS和EBSD等技术研究了Inconel 600合金在715℃时效过程中不同类型晶界处碳化物的结构、形貌和晶界附近Cr浓度的分布。结果表明,不同类型晶界处碳化物的结构和形貌有较大的不同：在Σ3_c晶界析出的碳化物很少,在Σ3_i晶界析出不规则形状的M₂₃C₆碳化物,在Σ9晶界析出较大的M₂₃C₆碳化物颗粒,在Σ27晶界随机析出粗大的M₇C₃碳化物颗粒。富Cr碳化物在晶界的析出使晶界附近贫铬,在相同的时效条件下晶界的Σ值越高其附近贫铬越严重。随着时效时间的延长各晶界附近贫铬区的宽度不同程度地增大,时效15 h贫铬区的深度最大,时效50 h后深度不同程度地减小。     

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)。     

微量Ce元素对高铬高钴型马氏体耐热钢力学性能的影响

在不同条件下对X20Co高钴高铬型马氏体耐热钢进行热处理,用光学显微镜、扫描电镜、X射线衍射仪以及拉伸实验等手段进行表征,研究了微量Ce元素对其微观组织和力学性能的影响。结果表明,在X20Co钢的淬火过程中,添加质量分数为50×10^-6 Ce元素能促进M₆C型碳化物沿晶析出,阻碍晶界迁移,使奥氏体晶粒细化;在回火过程中能抑制M₂₃C₆型碳化物沿晶界聚集长大。同时,添加50×10^-6 Ce元素对X20Co高钴高铬型马氏体耐热钢的室温硬度、室温强度、高温瞬时拉伸强度没有显著的影响,但是使其室温韧性、塑性和高温塑性显著改善。     

WC-氧化石墨烯/Ni复合熔覆层的制备及形成机制

采用真空熔覆技术制备了WC-氧化石墨烯(GO)/Ni复合熔覆层,运用扫描电镜、能谱仪、X射线衍射仪观察并分析在不同温度下熔覆层内显微形貌的变化与物相组成。结果表明:在ZG45表面制备了组织致密、与基体形成良好冶金熔合的WC-GO/Ni复合熔覆层;熔覆层的微观结构组成从表面至基体依次是约1.5 mm厚的复合层、360 μm左右的过渡层、50 μm左右的扩散熔合层和100 μm左右的扩散影响层,其主要组成相有Cr₇C₃、FeNi₃、WC、Cr₂₃C₆、Ni₃Si、C、Fe₇W₆、γ-Ni固溶体等,FeNi₃、Fe₇W₆分散在冶金熔合带,扩散影响区主要组织为珠光体;复合区的物相尺寸小于界面区的物相尺寸,熔覆层形成过程中复合区的金属颗粒变化先于界面区,凝固时熔化不完全的颗粒表面长出团簇物(Cr₇C₃/Cr₂₃C₆),随着保温长大逐渐变成针状物镶嵌在Ni基固溶体中。      

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.     

Microstructural evolution of Alloy 690 during sensitization at 700 °C

A structural characterization of sensitized Alloy 690 has been carried out. Alloy 690 was solution annealed (SA; 1100 °C for 30 min, water quenched, WQ) and sensitized at 700 °C for 5, 12, 24, 36, 48 and 72 h, followed by water quenched. Techniques employed included scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray diffraction and corrosion weight-loss tests. It was found that the cubic Cr_0.19Fe_0.7Ni_0.11 phase was the main component in all the conditions. In addition, a grain refinement was observed when the aging time was increased; but after 48 h of aging, a discrete, semicontinuous network of Cr₂₃C₆ precipitates was detected by X-ray diffraction, in addition to the NiCrO₄, Ni₉S₈ and (Fe,Ni)₉S₈ phases found by TEM at the grain boundaries, making this alloy more susceptible to intergranular attack (IGA). After 72 h of aging, chromium continues diffusing, “back-filling” the prior depletion profile, recovering the IGA resistance.     

TEM study on precipitation and transformation of secondary carbides in 16Cr–1Mo–1Cu white iron subjected to subcritical treatment

High chromium white irons solidify with a substantially austenitic matrix supersaturated with chromium and carbon. The subcritical heat treatment can destabilize the austenite by precipitating chromium-rich secondary carbides and other special carbides. In the as-cast condition the eutectic carbides are (Fe,Cr)₇C₃ and (Fe_4.3Cr_2.5Mo_0.1)C₃. The initial secondary carbide precipitated is (Fe,Cr)₂₃C₆ after heat-treating at 853 K for 10 h. There are MoC, Fe₂MoC and -carbide precipitating, and (Fe,Cr)₂₃C₆ transforms to M₃C after 16 h at 853 K. The -carbide and (Fe,Cr)₂₃C₆ accomplish transformation to M₃C and the matrix changes from martensitic to pearlitic after 22 h at 853 K. Thereby, in the subcritical heat treatment process, the initial secondary carbide precipitated is (Fe,Cr)₂₃C₆, followed by -carbide, MoC and Fe₂MoC. In addition, there are two in situ transformations from (Fe,Cr)₂₃C₆ and -carbide to M₃C carbides.     

TiCp/Cr15高铬铸铁复合材料的制备与性能

以TiC_p粉末和水雾化Cr15高铬铸铁粉末为原料,采用粉末冶金液相烧结技术制备TiC_p增强高铬铸铁复合材料。研究了TiC_p含量对高铬铸铁的物相组成、显微组织和力学性能的影响。研究结果表明,全致密的TiC_p增强高铬铸铁基体复合材料的构成相为TiC、M₇C₃型碳化物、马氏体和少量奥氏体;随着TiC_p添加量增大,金属基体逐步呈孤岛状,并在其中析出越来越多的M₇C₃型碳化物,同时TiC_p逐步呈连续网状分布;同时,其硬度稳步提升,而抗弯强度和冲击韧性降低。当TiC_p添加量为20wt%时烧结态复合材料具有最佳综合力学性能。此时硬度为HRC 66.8 ,冲击韧性为6.86 J/cm2,抗弯强度为1 343.10 MPa。当TiC_p添加量为25wt%时硬度达到最大值HRC 67.20 。      

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.     

基于超细晶硬质合金钻头的AFRP钻削性能

采用超细晶硬质合金钻头开展了芳纶纤维增强树脂基复合材料(Aramid Fiber Reinforce Polymer Composites,AFRP)的钻削实验,从钻削力、钻削温度、制孔质量、刀具磨损等方面对比分析了超细晶硬质合金钻头与普通硬质合金钻头的钻削性能。实验结果表明:芳纶纤维增强树脂基复合材料钻削过程中,钻削力随进给速度的增大而增大,随主轴转速的增大而减小,超细晶硬质合金钻头的钻削力比普通硬质合金钻头降低了40.6%以上;钻削温度随进给速度的增大而减小,随主轴转速的增大而增大,相对普通硬质合金钻头,采用超细晶硬质合金钻头的钻削温度降低了47~85℃;超细晶硬质合金钻头钻削产生的拉毛和热损伤明显少于普通硬质合金钻头;经过长时间的钻削,普通硬质合金钻头的橫刃和主切削刃出现了崩刃,后刀面出现了严重的磨料磨损;而超细晶硬质合金钻头由于高硬度和高耐磨性等特性,刀具的磨损相对较小,适合于芳纶纤维增强树脂基复合材料的高效低损伤加工。     

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.     

硬质合金粉末挤出打印中增材制造工艺及其显微结构

粉末挤出打印(PEP)是基于传统金属注塑成型和3D打印相结合的新型增材制造技术,具有打印材料范围广、打印成本低等巨大优势。以WC-13Co硬质合金的PEP增材制造为核心,以热塑性打印材料为重点研究对象,开发打印原料的材料体系,研究打印原料的均匀性、流变性能、成形性能、黏结剂的脱除工艺以及烧结工艺对打印件显微结构及力学性能的影响机制。独立开发了硬质合金PEP打印专用的有机黏结剂材料体系,通过EDS分析黏结剂在打印坯体中分散均匀性。采用两步法脱脂工艺可以完全脱除打印坯体中的黏结剂,并结合真空烧结,在1450 ℃下保温60 min,成功制备高性能硬质合金打印件。研究结果发现打印件线收缩率为17.8%,WC晶粒尺寸分布均匀,维氏硬度1410HV₃₀。本研究采用PEP增材制造技术制备了高性能、打印件尺寸可控的硬质合金材料,为硬质合金的增材制造探索出一条有效的技术路线。     

热作模具钢DM的高温稳定性和热疲劳性能

研究了热作模具钢DM的高温稳定性和热疲劳性能。结果表明,DM钢在620℃热稳保温过程中马氏体板条内的薄片状M₃C型碳化物逐渐向条块状M₇C₃型碳化物转变,在板条的边界生成M₇C₃、M₂₃C₆型碳化物。DM钢的短循环周次热疲劳性能受控于位错重排和湮灭,长循环周次热疲劳性能受控于碳化物的粗化程度。DM钢中M₃C、M₇C₃、M₆C型碳化物的生成自由能分别为27765.5 J/mol、3841.5 J/mol、-7138.1 J/mol,表明在热稳保温与热疲劳试验过程中碳化物的演变机理一致,发生了M3C→M7C3→M6C类型演变。     

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.     

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.