WC-Co硬质合金成分的磁性测定原理

推导了WC—Co硬质合金及其粘结相（γ相）的比饱和磁化强度4πσ。同γ相中钨和碳固溶度Xw、Xc及合金的真实钻含量Xco（质量分数）间的定量关系式：4πσ=4πσγ·XCo／（1—Xw—Xc）,4πσγ=2020-4408Xw＋28527Xc;提供了一种完全用磁性数据（Ms、4πσ）定量测定WC—Co硬质合金的碳含量和真实钴含量的实用方法,讨论了该方法的精度和应用范围。     

WC-Co硬质合金的强度

对两相 WC- Co硬质合金的研究表明 ,并非由钴含量 XCo而是由碳含量 XC 所决定的 相成分 (钨和碳在 相中的浓度 )才是制约 WC在 相中溶解—析出过程的决定性因素 ,因而也是影响 WC- Co合金 WC平均晶粒尺寸 LWC的重要因素。求得了相应于最大抗弯强度 σTRSmax的 LWC～ XCo反比关系式和最佳 相平均自由程 λ。 的取值范围。提出了在 相质量分数 X 增大引起 λ。 增大的情况下 λ 对应的合金结构由连续的 WC骨架向连续的 相网络的过渡的概念 ,从而较合理地解释了σTRSmax～λ 双支线关系和粗、细晶合金的σTRS～ XC关系。两相 WC- Co合金的强度取决于合金的钴含量、碳含量和WC平均晶粒尺寸并归因于 相平均自由程和 相中钨和碳固溶度的影响。在σTRS～λ 左支线范围内合金的断裂韧性 KIC同σTRS呈线性关系。在求得显微结构参数、成分和强度同磁性、密度和硬度的定量关系的基础上提出了无损鉴定两相 WC- Co硬质合金的结构、成分和强度的原理。     

碳含量对激光熔覆CoCrFeMnNiCx高熵合金涂层摩擦磨损和耐蚀性能的影响

采用激光熔覆技术在 45 钢基体上制备了不同碳含量(等摩尔比)的 CoCrFeMnNiC_x( x = 0,0. 03,0. 06,0. 09, 0. 12,0. 15)高熵合金涂层。 通过 X 射线衍射(XRD)、扫描电镜( SEM)、HVS-1000A 型显微硬度计、RST5000 型电化学工作站、UMT-2 型摩擦磨损试验机等表征和测试手段研究了不同碳含量对激光熔覆 CoCrFeMnNiC_x 高熵合金涂层物相结构、显微硬度、摩擦磨损及耐腐蚀性能的影响。 结果表明,当碳含量 x 由 0 逐渐增加至 0. 09 时,高熵合金相结构由 FCC 固溶体转变为 FCC 固溶体和 M23C6 相共存,合金微观组织变得细小;熔覆层硬度由 183. 20 HV_{0. 2} 增加至 223. 48 HV_{0. 2} ; 涂层的摩擦因数降低,耐磨性能变强;腐蚀电位由-469 mV 增大至-348 mV,腐蚀电流密度由 14. 95 μA·cm^-2 减小为 2. 29 μA·cm^-2 ,耐腐蚀性增强。 当碳含量 x 由 0. 09 逐渐增加至 0. 15 时,合金相结构再次转变为 FCC 固溶体,且合金微观组织恢复粗大状态;熔覆层硬度与耐腐蚀性降低,但耐磨性能却先减弱后增强。 合金在碳含量为 0. 09 时,硬度最高且耐腐蚀性能最强;在碳含量为 0. 15 时,耐磨性最强。     

WC-Ni硬质合金游离碳的无损测定原理

以三相 WC+ γ+石墨合金中各相含量同合金密度 d和比饱和磁化强度 4πσ的定量关系为基础 ,论述了用 d和 4πσ无损测定 WC- Ni系高碳硬质合金的游离碳的原理。用密度测定时的精度 (相对误差 )为 4‰ ,用比饱和磁化强度测定时的精度为 1%。     

WC-Co硬质合金的显微结构参数

通过X射线衍射分析 (XRD) ,扫描电镜 (SEM)体视学测量和磁性与密度测试 ,并依据碳化钨(WC)基合金维氏硬度HV与γ相平均自由程λ间的Hall Petch型关系式和HV的“混合物规则”进行验证 ,探讨了两相WC Co硬质合金显微结构参数间的定量关系。结果表明 ,γ相平均自由程λ与WC晶粒邻接度CWC 间存在反向对应关系 ,与γ相体积分数fγ 和WC平均晶粒尺寸LWC 间存在正向对应关系 :λ =1 0 5× 10 - 5·(1-CWC) 3 7=8 74× 10 - 2 ·(f- 1γ - 1) - 0 79·L0 79WC ,说明fγ 和LWC对λ～CWC关系的影响处在测量误差范围内 ,因而用CWC(或λ)、fγ 和LWC中任意两个参数都能准确表征两相WC Co硬质合金的结构特征 ;合金的比矫顽磁力HSC与γ相平均自由程λ间存在定量关系 :HSC=4 0 5× 10 - 7 λ。讨论了用磁性和密度测定值无损鉴定两相WC Co硬质合金显微结构参数的可行性。     

WC-Co梯度硬质合金的制备及渗碳对其组织的影响

采用光学金相检测、扫描电镜分析、能谱分析等方法对WC-6Co硬质合金渗碳处理后的成分和梯度组织结构进行分析.结果表明:对硬质合金渗碳处理后可形成显微组织和钨、钴含量的梯度分布,其特征是合金表层和次表层的η相已经完全消失,属正常的WC γ两相组织,合金的芯部依然是含η相的三相组织,中间形成了一个富钴层;碳原子的扩散和液相钴的流动是形成梯度的原因;在各渗碳温度下,合金的梯度结构厚度均随渗碳时间的增加而增加;在渗碳时间和渗碳温度相同的情况下,合金的梯度层厚度均随合金初始总碳含量的增加而增厚.渗碳处理后外表面的WC晶粒可能会产生一定的粗化现象.     

WC—Co硬质合金硬度的磁性评估原理

实验结果和理论分析表明 ,基于与合金的显微结构参数和成分的密切对应关系 ,烧结态的两相 WC- Co硬质合金的比矫顽磁力 HSC同γ相平均自由程λγ 和平均硬度 HV间存在确定的对应关系 :HSC=2 .31- 1.5 0 / (1- 192λγ ) ,HV =5 70 4 +2 397/(1- 1.2 3HSC)。根据上述关系式用 HSC测定值能够有效地无损鉴定烧结态两相 WC— Co合金的γ相平均自由程和间接评估平均硬度。导出了一定钴含量 w Co的两相 WC— Co硬质合金的最高抗弯强度σ。TRS所对应的最佳γ相平均自由程λ。γ=3.15× 10 — 7/ (0 .92 0 -w Co)和最佳比矫顽磁力 H。SC=2 .31- 1.5 0 / (1- 0 .10 8/ 0 .892 - w Co)。根据 HSC与 HV和断裂韧性 Kl C及在 λγ 低于 λ。γ 的情况下同 σTRS的定量关系 :Kl C=31.3- 2 7.1HSC,σTRS=4 .5 4× 10 3- 3.93× 10 3HSC,用 H。SC能够有效地间接评估合金的最佳综合力学性能 HV。 、K。l C和 σ。TRS。     

WC碳量对高钴硬质合金性能与硬质相晶粒度的影响

本文通过选用碳含量不同的WC原料配制成4组WC-22%Co高钴硬质合金,采用物理性能检测、光学金相等分析方法,对比研究了不同碳含量WC对WC-22%Co高钴硬质合金烧结后的性能和硬质相粒度的影响。结果表明:在所有方案中,原料WC中碳质量分数为5.97%时,合金抗弯强度最高,达到2 590 MPa,但合金金相组织不均匀,粗大WC晶粒数量较多,WC粒度分布最宽;随着原料WC碳含量的增加,合金金相组织趋于均匀化,粗大晶粒数量逐渐减少且WC晶粒粒径离差系数同步减小,并在WC碳质量分数为6.14%时WC晶粒粒径离差系数出现最小值,为0.475 7。     

两相WC-Co硬质合金的成分

由理论分析和实验数据推导了两相WC-Co硬质合金γ相磁饱和与钨浓度的关系及合金成分与合金密度和磁饱和的定量关系。结果表明,兼用密度和磁饱和测量值用解析法能精确计算WC-Co合金的成分;两相区下限合金碳含量及WC+γ两相区碳含量宽度不仅和真实钴含量有关,还取决于两相区下限γ相中的钨浓度。     

含碳量对WC-13Co硬质合金组织和性能的影响

采用粉末冶金方法制备了不同碳含量的WC-13Co细晶粒硬质合金。采用X射线衍射、SEM、自动钴磁仪、矫顽磁力测量仪等分析方法,研究了含碳量对细晶粒WC-13Co硬质合金表面组织及性能的影响。结果表明,随着含碳量的增加,合金中石墨相逐渐增多,WC颗粒长大;烧结后含0.2%C的WC-13Co硬质合金只存在(WC+γ)相,抗弯强度达到最大值3 730 MPa,断口中存在很多韧窝;随着碳含量的增加,合金的硬度下降,矫顽磁力降低,而磁性钴含量不断升高,但均小于原始钴含量。     

Synthesis of WC-Co composite powders with two-step carbonization and sintering performance study

In this study, WC-Co composite powder was synthesized by two-step carbonization method using W, Co and C as raw materials. X-ray diffraction (XRD) showed that the η phase (Co₆W₆C) was kept at 1100 °C for 1 h under vacuum, and it could be completely carbonized into WC-Co composite powders. The surface morphology of WC-Co composite powders was analyzed by scanning electron microscope (SEM). The effects of η phase and second phase (W phase) on WC morphology and Co phase distribution were investigated. Electron backscattered diffraction (EBSD) was used to analyze WC-10 wt% Co cemented carbide particle distribution. Comparison of transverse rupture strength, hardness and fracture toughness of two kinds of WC-10 wt% Co cemented carbides synthesized by WC-Co composite powders + WC and WC + Co respectively, the cemented carbide of composite powders + WC increases the fracture toughness from 11.4 ± 0.3 MPa·m^1/2 to 12.4 ± 0.3 MPa·m^1/2.     

TaC、Cr_3C_2对WC-Co硬质合金组织和性能的影响

研究了添加：TaC、Cr3C2对WC－10Co合金组织结构和性能影响，讨论了相关机理。结果表明，少量添加TaC（2－m％）、Cr3C2（0．44m％）可导致WC－10Co合金的WC晶粒明显细化’WC邻接度下降，γ相平均自由程减小，但强韧性有所下降；Cr3C2助长WC－10Co合金WC晶粒断续长大；TaC－WC固溶体耐碱蚀性差；合金断口中沿WC—WC品界脆断比例增加，TaC－WC固溶体晶粒倾向于穿晶劈裂。工艺中控制TaC、Cr3C2添加量、确保WC～Cr3C2粉碳化完善以及同时添加TaC、Cr3C2对确保合金材质至关重要。     

硬质合金的硬度和矫顽力及其相互关系

探讨了硬质合金的硬度、矫顽力同合金显微结构和成分的关系，得到了两相高碳ＷＣ－Ｃｏ硬质合金的比矫顽力Ｈｓｃ，和维氏硬度ＨＶ间关系的实验规律；Ｈｓｃ＝１．１６＋「（１８９７／ＨＶ）－３．３１」＾－１。论述了有关物理基础，讨论了用Ｈｓｃ对ＷＣ－Ｃｏ合金的ＨＶ进行评估的可能性。     

Recovery of WC and Co from cemented carbide scraps by remelting and electrodissolution

A novel method was proposed in this study to recycle WC and Co from cemented carbide scraps by remelting and electrodissolution. WC was recrystallized and purified through melting process. The WC that embedded in alloy was independent of each other and thus was easily separated by electrodissolution. The effects of dissolving parameters were investigated, and the results indicated that the maximum dissolving rate was 0.045 g·h⁻¹·cm⁻² and the anodic passivation was not found even at 500 A·m⁻² of current density. In addition, the temperature and concentration of HCl were irrelevant to the rate and the current efficiency of the electrolysis. The SEM showed that the final WC powder was 5–20 μm in particle size with a regular shape, and the Co was directly recycled from the cathode at the same time.     

复合添加Cr_3C_2/NbC对超细晶WC-10%Co硬质合金组织和性能的影响

采用真空烧结方式制备超细晶WC-10%Co硬质合金,研究了复合添加晶粒长大抑制剂Cr3C2/NbC对合金组织及性能的影响。结果表明:在1400℃烧结条件下,添加剂的组成为0.4%Cr3C2+0.3%NbC时(文中含量均为质量分数),合金具有最好的综合力学性能,抗弯强度可达1951MPa、硬度1615HV30;WC平均晶粒尺寸为490nm。经SEM观察并通过EDS发现,抑制剂Cr3C2/NbC固溶到粘结相Co中,改变界面能,限制WC晶粒的长大;同时,也会降低WC在粘结相Co中的溶解度,从而起到细化晶粒的作用。     

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 1400 °C, 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.     

Grain and phase boundary segregation in WC-Co with TiC, ZrC, NbC or TaC additions

The microstructure of interfaces in WC-Co based cemented carbides with TiC, ZrC, NbC or TaC additions was analysed using energy dispersive X-ray analysis in a transmission electron microscope and using atom probe tomography. Segregation to WC/WC grain boundaries and WC/(M,W)C phase boundaries corresponding to between 0.4 and 1.2 atomic layers of close packed monolayers of Co was observed in all the materials. In addition to Co, Ti, Zr and Nb, but not Ta, segregate to the WC/WC grain boundaries. Segregation was also observed for B, P, Fe and Cr, but not Ni, to the boundaries. These are impurities that originate from the material production. Segregation of Ti, Zr, Nb and Ta to WC/binder phase boundaries was observed. If formation of a MC phase at the interface is assumed, the segregation corresponded to a thickness less than a monolayer.     

Deposition effects of WC particle size on cold sprayed WC-Co coatings

The WC particle size and its influence on the deposition of Co-based cermets are examined. Micron and nanostructured powders with similar Co content were employed. Varying the WC particle size influenced significantly the deposition efficiency of the coating process. Micrometer-structured WC-Co feedstocks did not permit coating build up when processed under comparable or elevated thermal spray parameters used for the nanostructured WC-Co feedstocks. In addition, micrometer-structured WC-Co coatings exhibited a conjoint erosion and deposition effect on the surface. Fine WC particles (< 1 μm) were observed near the substrate interface and larger WC particles (1-2 μm) in the vicinity of the coating surface. These observations indicate the existence of a critical WC particle size for deposition by the cold spray method and that the size criteria arises due to the formation and cohesion mechanisms within the coating layer.Nanostructured test specimens displayed (i) a dense microstructure with little presence of porosity, (ii) a crack free interface between the coating and substrate that indicated good adhesion, and (iii) no observable phase changes. The XRD patterns of each powder and their respective coatings did not have observable peak differences but the diffraction peak broadening of coatings indicated that there was grain refinement during the coating process. Furthermore, all nanostructured as-sprayed WC-Co coatings exhibited Vickers hardness values above HV1000. The nanostructured WC-Co coatings demonstrated adhesive strengths that exceeded the limits of the glue (60 MPa).