Comparative Study on Microstructure and Mechanical Properties of Coarse-grained WC-based Cemented Carbides Sintered with Ultrafine WC or (W+C) as Additives

The effects of ultrafine WC(WC_(UF),0.5μm) or W(1μm) and C(0.3μm)(W+C)_(UF) additives on the densification,microstructure and mechanical properties of coarse-grained cemented carbides were compared systematically.Overall,the cemented carbides with WC_(UF)/(W+C)_(UF) additives are almost fully densification to be higher than 99%,and the average grain size is kept above 2.8μm.The WC_(UF) additive assists grains to(truncated)trigonal prism shape by two dimensional(2D) growth,whereas the(W+C)_(UF) additive assists grains to rounded shape by three dimensional(3D) growth,lowers WC contiguity and increases face-centered-cubic Co.The hardness and bending strength of(75WC_(C)-15WC_(UF))-10Co are 86.6 HRA and 2 272 MPa,respectively,both higher than those of(75WC_(C)-15(W+C)_(UF))-10Co,which could be ascribed to the enhanced densification and unblemished grains.However,the fracture toughness of the(75WC_(C)-15(W+C)_(UF))-10Co is 23.5 MPa·m^(1/2),higher than that of the(75WC_(C)-15WC_(UF))-10Co due to the uniform WC-Co structure and flexible binder phase.

Effects of Ta C on microstructure and mechanical properties of coarse grained WC-9Co cemented carbides

Coarse grained WC-9Co cemented carbides with 0-1.0% TaC(mass fraction) were fabricated by HIP-sintering and gas quenching. The effects of TaC on the microstructures and mechanical properties were investigated using scanning electron microscopy(SEM), energy dispersive X-ray analysis(EDS), X-ray diffractometry(XRD) and mechanical properties tests. The results show that the maximum values of hardness and strength are HV 1124 and 2466 MPa respectively when 0.4% TaC is added. When the content of TaC is more than 0.6%, the grain size of WC is no longer affected by the amount of TaC, and(W,Ta)C occurs as well. Moreover, the strength and fracture toughness increase and the(Ta+W) content decreases with the increase of TaC content. The dependence of(Ta+W) content on the mechanical properties indicates that(Ta+W) content in Co should be decreased as low as possible to improve the mechanical properties of coarse grained WC-TaC-9Co cemented carbides with the microstructure of WC+γ two phase regions.

Effect of VC and NbC additions on microstructure and properties of ultrafine WC-10Co cemented carbides

The nanocomposite WC-Co powders were prepared through planetary ball milling method.Effects of grain growth inhibitor addition and the vacuum sintering parameters on the microstructure and properties of ultrafine WC-10Co cemented carbides were investigated using X-ray diffractometer,scanning electron microscope and mechanical property tester.The results show that VC and NbC additions can refine the WC grains,decrease the volume fraction of Co3W3C phase in ultrafine WC-10Co cemented carbides,and increase the hardness and fracture toughness of the base alloys.After sintering for 60 min at 1 400℃,the average grain size and hardness of ultrafine-grained WC-10Co-1VC cemented carbide are 470 nm and HRA 91.5,respectively.The fracture toughness of cemented carbide WC-10Co-1NbC alloy is over 7 MN·m -3/2 .

Manufacture of the Ultrafine Grain WC/Co Cemented Carbides by Combined Sintering Processing

A new kind of sintering process, combined sintering process. i.e. vacuum sintering plus hot isolate pressure sintering (HIP), was introduced for producing ultrafine WC-10% Co (mass fraction. so as the follows) cemented carbides. The effects of some processing parameters on the microstructure and mechanical properties of the obtained cemented carbides were studied. The results show that the rapid shrinkage and the pronounced densification of tile cemented carbides took place during the vacuum sintering stage, which is intinaately correlated with the local liquid sintering occurred during this earl} sintering stage for the high surface activity of ultrafine WC-Co powder. The way of high pressure imposing. isothermal treatment cycle during ac.acuum sintering and HIP sintering stage directly influence the densitication of compacts and the mechanical properties of the produced WC-10%Co cemented carbides.

碳含量对超细晶WC-12%Co硬质合金组织及性能的影响

经混料、压形、热等静压烧结制备了8组不同碳含量的WC-12%Co硬质合金,采用金相显微镜、扫描电镜、硬度计、电子万能力学试验机分析了碳含量对合金微观组织及力学性能的影响。结果表明:碳含量为5.26%~5.42%的WC-12%Co硬质合金处于WC+γ二相区;当碳含量小于等于5.22%时,合金出现絮状、针状脱碳相;当碳含量大于等于5.46%时,合金出现黑色絮状的渗碳相,伴有粗晶、粗晶聚集及钴偏析现象。随着碳含量逐渐增加,WC晶粒逐渐长大,结晶趋于完整,晶粒边缘趋于平直化,晶界变得更加清晰,当碳含量达到5.54%时,WC晶粒边缘出现圆角。碳含量为5.26%~5.42%的合金处于WC、Co二相区,综合力学性能较优,硬度维持在1 777~1 695 kg/mm^(2),抗弯强度为3 357~3 290 MPa。

WC/Co硬质合金界面特征分布

利用电子背散射衍射、五参数分析、重叠极图迹线分析和近重位点阵分析等方法研究不同热处理状态WC/Co硬质合金中的WC/WC晶界与WC/Co相界等界面特征分布。结果表明:经高温烧结后油淬的样品,生成了比例为4.5%的WC/WCΣ2晶界,具有{10-10}/{10-10}界面匹配特征的Σ2晶界的比例约为2.6%;该样品中的Co主要为面心立方结构,具有{10-10}_(WC)/{001}_(Co),{10-10}_(WC)/{110}_(Co)和{11-20}_(WC)/{110}_(Co)等界面匹配特征的界面是WC/Co相界的主要部分。经800℃回火后气氛保护随炉缓冷的样品,其WC/WCΣ2晶界比例及特征与油淬样品十分接近;该样品中的Co主要为六方结构,具有{10-10}_(WC)/{10-10}_(Co)和{11-20}_(WC)/{11-20}_(Co)等界面匹配特征的界面是WC/Co相界的主要部分。

Effects of Phosphorus Additions on Microwave Sintering Properties of Uitrafine WC-10Co Cemented Carbides

Using the microwave sintering technology, the effects of phosphorus （P） additions on the microstructure and properties of the ultrafine WC-10Co alloys were investigated. The experimental results show that with only 0.3wt% P additions, full density WC-10Co cermets were obtained at temperature of 1250℃, which is 70 ℃ lower than that of the undoped counterparts. Lower sintering temperature can result in finer WC grain growth; therefore, the P-doped WC-10Co alloys exhibited higher hardness than the undoped ones. But at the same time, P doping could lead to sacrifice of fracture toughness ofWC-10Co cemented carbides.

γ-PHASE IN WC-Co CEMENTED CARBIDES

The allotropic transformation process of the γ-phase in WC-Co cemented carbides has been explored.Theconcepts of γ-grain and the γ-domain have been proposed forward:The γ-domain is the residual FCC-typeβ-Co grain that failed to transform when cooling alloy sample and γ-base is the HCP-type x-Co transformedmainly by means of diffusion,the outline of the γ-grain is consistent with the newly fromed β-Co grain formedat high temperature.The quantity and distribution of γ-grain domain are related to the cooling rate after sinter-ing and influence the alloys properties.

Material Removal Behavior and Surface Integrity in Grinding of UltrafineGrained WC-Co Materials

Due to the excellent combination of wear resistance and fracture toughness,the ultrafine-grained WC-Co composites can significantly improve the durability and reliability of industrial tools.However,the grinding of ultrafine-grained WC-Co remains a challenge.In order to provide an experimental basis for improving grinding quality of ultrafine-grained WC-Co,a series of surface grinding experiments on ultrafine-grained WC-Co hardmetals were conducted by diamond wheel under various grinding conditions,and the material removal behavior and surface integrity in grinding of ultrafine-grained WC-Co materials were characterized by means of scanning electron microscopy(SEM),X-ray microstress analyzer and surface roughness analyzer in this paper.The results indicate that the material removal behavior in grinding of ultrafine-grained WC-Co materials is determined not only by the abrasive grain size on the wheel,but also by the depth of cut.The roughness values of ground surface increase with increasing grit size of diamond wheel,and increase initially,then decrease with increase in depth of cut.Grinding causes the residual compressive stress in the surface layer of ground cemented carbides under various grinding conditions;the magnitude of residual surface stress increases with increasing grit size of diamond wheel,and isn't changed obviously along with the change of depth of cut.

复合添加Cr_(3)C_(2)/VC/TaC的WC-12%Co超细晶硬质合金的组织和性能研究

研究了复合添加不同含量的Cr_(3)C_(2)、VC、TaC三种晶粒长大抑制剂对WC-12%Co超细晶硬质合金组织及性能的影响。结果表明,与采用Cr_(3)C_(2)+VC组合晶粒长大抑制剂的合金相比,采用Cr_(3)C_(2)+VC+TaC组合晶粒长大抑制剂的合金的综合力学性能呈降低趋势,但导热性能更好。采用Cr_(3)C_(2)+VC+TaC组合晶粒长大抑制剂的合金的组织和力学性能取决于晶粒长大抑制剂的抑制效果,而不是其添加总量,优化三种抑制剂的配比是提升合金性能的关键。

Effects of cubic carbides and La additions on WC grain morphology,hardness and toughness of WC-Co alloys

Effects of Cr3C2,VC and La2O3 additions on the WC grain morphology,hardness and toughness of WC-10Co alloys were investigated.To intensify the grain growth driving force,nano W and nano C,instead of the conventionally used WC,were used as the starting materials.To obtain a three-dimensional WC grain morphology,the natural sinter skins of the alloys were observed directly by scanning electron microscopy.It is shown that the additions have a strong ability in regulating the WC grain morphological and grain size distribution characteristics and the combinations of hardness and toughness.Due to the formation of regular and homogeneous triangular platelet WC grains,WC-10Co-0.6Cr3C2-0.06La2O3 alloy shows an excellent combination of hardness and toughness.The morphological regulation mechanism,the relationship between the WC grain morphology and the properties were discussed.

Cr_(3)C_(2)/VC复合抑制剂比例对WC-10%Co超细晶硬质合金微观结构和力学性能的影响

本文以WC-10%Co为研究对象,添加质量分数1.0%的Cr_(3)C_(2)/VC复合抑制剂,在1410℃下烧结1 h,制备了WC-10%Co-Cr_(3)C_(2)/VC超细晶硬质合金,研究了Cr_(3)C_(2)/VC复合抑制剂比例对物相组成、WC晶粒尺寸和粒度分布、WC三维形貌及力学性能的影响。结果表明:随Cr_(3)C_(2)含量的减少和VC含量的增加,WC平均晶粒尺寸先快速后缓慢减小,WC粒度分布不断变窄;WC形貌由三棱柱向台阶三棱柱转变,WC(0001)晶面上的台阶数量不断增加,这些台阶会显著降低合金的断裂韧性和抗弯强度;WC-10%CoCr_(3)C_(2)/VC超细晶硬质合金的硬度先快速后缓慢增加,而断裂韧性和抗弯强度先快速后缓慢降低;当w(Cr_(3)C_(2))∶w(VC)=4∶1时,WC-10%Co-0.8%Cr_(3)C_(2)-0.2%VC硬质合金具有最优的综合性能,其维氏硬度、断裂韧性和抗弯强度分别为17.05 GPa、9.26 MPa·m^(1/2)和3650 MPa。

超粗晶WC-Co硬质合金制备技术及发展趋势

超粗晶硬质合金因其独特的组织特征,表现出良好的抗冲击性、耐磨性、抗热疲劳性等优势,在凿岩、冲压模具、热轧辊领域具有极大的发展潜力,在硬质合金领域备受关注。本文概述了超粗晶硬质合金的特点及增韧机理,介绍了目前粗颗粒WC原料粉末和超粗晶硬质合金的制备工艺,以及超粗晶硬质合金性能强化方法的探索情况,最后对超粗晶硬质合金的发展趋势提出了几点思考。

超细WC和细WC/Co添加对WC-10Co硬质合金微观结构与力学性能的影响

在粒径为0.5μm的超细碳化钨(WC)粉体表面包覆钴(Co)纳米颗粒获得细WC/Co,将细WC/Co、粗WC和Co粉通过球磨混合均匀,压制成型后在1420℃下真空烧结1 h,得到WC-10Co硬质合金。借助扫描电子显微镜、透射电子显微镜、万能试验机等对比研究细WC/Co和超细WC对WC-10Co硬质合金微观形貌和力学性能的影响。结果表明:相比于超细WC,细WC/Co促进合金的致密化,并形成双晶结构。添加细WC/Co和超细WC制备的硬质合金的平均晶粒度分别为2.18μm和3.57μm。细WC/Co的添加会降低晶粒生长速度并抑制细晶完全溶解,而粗晶通过缺陷辅助生长及溶解-析出生长机制生长为表面阶梯状的缺角三棱柱形;硬质合金的硬度和断裂韧度得到提升,二者分别为1131HV 30和22.1 MPa·m^(1/2),而在1131HV 30同等硬度下,其断裂韧度比线性拟合的断裂韧度高27.7%。机理分析认为,超细WC的添加会导致异常晶粒产生,不利于性能;而细WC/Co的添加能够同时形成双晶结构和均匀的钴相分布结构,降低晶粒缺陷,提升综合力学性能。

Mo添加对WC-Ni硬质合金微结构及性能的影响

采用X射线衍射(XRD)、扫描电子显微镜(SEM)和性能检测等方法研究了不同Mo添加量对WC-Ni-Mo硬质合金的WC粒度、硬度、摩擦磨损和耐腐蚀性能的影响。结果表明:在研究的成分范围内(w(Mo)=1.5%~2.0%),WC的平均晶粒尺寸基本不随Mo添加量的变化而变化;随Mo添加量的增加,WC-Ni-Mo硬质合金的硬度略微有所下降,而摩擦磨损性能得到提升。Mo质量分数为2%的WC-Ni-Mo硬质合金在酸性溶液中的耐腐蚀能力要高于Mo质量分数为1.5%的合金,并且具有更好的电化学稳定性。总体来看,WC-8.0%Ni-2.0%Mo合金的综合性能优于WC-8.5%Ni-1.5%Mo硬质合金。

添加纳米Ti(C,N)对粗晶WC-8Co硬质合金微观组织和力学性能的影响

将粒度为0.2μm的Ti(C,N)纳米粉末添加到粗晶WC-8Co硬质合金中,采用低压烧结技术制备了WC-xTi(C,N)-8Co系列硬质合金。利用XRD、SEM和EDS研究了添加纳米Ti(C,N)的硬质合金试样的物相组成和微观组织,并分析和讨论了合金的钴磁、矫顽磁力、洛氏硬度和抗弯强度等性能。结果表明,添加纳米Ti(C,N)烧结后的合金均出现了典型的Ti(C,N)芯-环结构,提高了硬质合金的硬度。然而,微量的Ti(C,N)添加会导致合金的力学性能下降,当添加量达到5%时,合金的综合力学性能最好,但当添加量达到15%以上时,基体出现脱碳相,导致合金的抗弯强度大幅下降。

超细/纳米晶WC基硬质合金制备技术研究发展现状

超细/纳米晶WC基硬质合金具有超高强度、硬度和韧性等优点,在汽车、航空航天、国防军工等领域有着重要应用。然而,超细/纳米级WC粉末粒度小、活性大,控制超细/纳米级WC粉末在烧结过程中的快速长大粗化成为一个巨大的挑战。为了获得超细/纳米晶WC基硬质合金,从原料粉末制备、新型烧结技术开发、晶粒长大抑制剂添加和新型硬质合金设计等方面综述最新的研究进展,分析优化的制粉和烧结工艺获得的WC粉末的粒度以及烧结后合金的力学性能,并对比各种晶粒生长抑制剂对WC基硬质合金微观结构和性能的影响,比较新型的烧结方法,如低压热等静压烧结(Sinter-HIP)、放电等离子体烧结(SPS)和微波烧结(MS)对WC基硬质合金微观结构和性能的影响,阐述典型的新型纳米级硬质合金的微观结构和性能,包括无黏结剂硬质合金和高熵黏结相的硬质合金,并展望超细/纳米晶WC基硬质合金的发展前景和研究重点,以期为现代超细/纳米晶硬质合金材料及技术的发展提供新的途径。

WC-Ni基硬质合金的光固化增材制造

采用光固化增材制造(3D打印)技术制备WC-Ni基硬质合金,研究了浆料配比和增材制造工艺参数对浆料流变性能和固化性能的影响以及WC-Ni基硬质合金的性能。结果表明:当浆料固含量为40%(体积分数)、分散剂为ZN-1344且加入量为粉体质量的2%时,WC-Ni浆料的流变性能满足增材制造工艺需求,当剪切速率为100 s^(-1)时,浆料黏度为2.718 Pa·s;该浆料的最大单层固化厚度可达144μm,对应工艺参数为0.01 mm线间距、90%激光功率和2 000 mm/s扫描速度;采用响应曲面法拟合数据获得的浆料单层固化厚度计算模型,计算值与实际值误差为3.4%,可起理论预测作用;光固化增材制造WC-15%Ni硬质合金的密度和相对密度最高,分别为13.51 g/cm^(3)和96.5%,加入1%晶粒长大抑制剂Cr_(3)C_(2)后,硬质合金维氏硬度显著提高,达到945 HV_(30),接近同等Ni含量但不含有Cr_(3)C_(2)的传统硬质合金硬度。

Microstructures and properties of WC-20Co-1Y_2O_3 cemented carbide by hot-press and liquid phase sintering

Ultrafine tungsten carbide and fine cobalt as well as nano yttrium oxide powders were used as the raw materials. The effects of hot-press below the eutectic temperature and conventional liquid phase sintering on the structures and properties of WC-20Co-1Y2O3 cemented carbide were studied. It is shown that hot-pressed alloy has the character of isotropic properties and microstructure with homogeneous and ultrafine WC grains. However, the ultrafine and fully-densified structure is developed at the cost of the presence of large amount of cobalt-lake （unevenly distributed binder phase）, and thus lower strength. Yttrium oxide in the alloy cannot play the role of grain growth inhibitor fully when cemented carbide with high content of cobalt and ultrafine raw materials is sintered at high liquid phase sintering temperature. Peculiar platelet-enhanced bi-model structure is formed in WC-20Co-1Y2O3 cemented carbide by conventional liquid phase sintering, which points out that yttrium oxide in the alloy facilitates the formation of plate-like WC grain.

钴粉粒度和成分对亚微米晶WC-10Co硬质合金组织和性能的影响

研究了原料钴粉的粒度、成分对亚微米晶WC-10Co硬质合金物理力学性能的影响。结果表明:在烧结工艺相同的情况下,钴粉越细,其表面能越高,熔化温度越低,合金致密化的时间越长,同时钴蒸气挥发时间也相应增加;随着钴粉粒度减小,合金密度增大,硬度、矫顽磁力降低,抗弯强度先增大后减小,当钴粉粒度为0.73μm时达最大。钴粉中Cl含量也是影响硬质合金孔隙的重要因素之一,当Cl含量达到550×10^(-6)时,合金内部出现大量孔隙。为得到优异性能的亚微米晶硬质合金,需严格控制原材料成分,同时调整生产工艺,缩短球磨时间,降低烧结温度。以FSSS粒度为0.73μm、Cl含量为171×10^(-6)的钴粉制备的亚微米晶WC-10Co硬质合金抗弯强度达4231N/mm^(2),硬度达91.8HRA,密度达14.45g/cm3,矫顽磁力达19.1kA/m。