少钴/无钴WC材料制备研究进展

摘要: 针对我国钴资源稀缺及传统WC–Co硬质合金在腐蚀介质与高温环境下应用所存在的缺陷，总结了一系列性能良好的少钴/无钴WC材料，包括以其他金属或金属间化合物替代Co作为粘结剂的WC硬质合金，不添加任何粘结剂的纯WC材料以及由陶瓷相增强的WC复合材料，讨论了少钴/无钴WC材料的优缺点，并展望了其发展趋势。
- 硬质合金 /
- 碳化钨 /
- 研究进展 /
- 力学性能
Abstract: In view of the scarcity of cobalt resources in China and the deficiency of the traditional WC–Co cemented carbides serving in the corrosive medium and high temperature environments, a series of cobalt-less/cobalt-free WC-based materials with good performance was summarized, including the WC-based cemented carbides with other metals or intermetallic compounds instead of Co, the pure WC, and the WC composites reinforced by ceramic phases. The advantages and disadvantages of the cobalt-less/cobalt-free WC-based materials were discussed, and the development trend was forecasted.
- cemented carbides /
- tungsten carbides /
- research progress /
- mechanical properties

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图 1 球磨时间对烧结态WC–Co₈–Al₂合金硬度和横向断裂强度的影响^[5]

Figure 1. Hardness and TRS of the sintered WC–Co₈–Al₂ alloys with different milling times^[5]

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图 2 经不同时间球磨后烧结态WC–Co₈–Al₂合金X射线衍射图谱^[5]

Figure 2. XRD patterns of the sintered WC–Co₈–Al₂ alloys with different milling time^[5]

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图 3 经1380 ℃烧结WC–10Ni₃Al试样显微组织：（a）垂直于烧结压力方向截面；（b）平行于烧结压力方向截面^[8]

Figure 3. SEM images of the WC–10Ni₃Al specimens sintered at 1380 ℃: (a) vertical to the pressing direction; (b) parallel to the pressing direction^[8]

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图 4 烧结温度对WC–10Ni₃Al试样密度和横向断裂强度的影响^[8]

Figure 4. Effect of sintering temperature on the density and TRS of the WC–10Ni₃Al specimens^[8]

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图 5 烧结温度对WC–10Ni₃Al试样的硬度与断裂韧性的影响^[8]

Figure 5. Effect of sintering temperature on the hardness and fracture toughness of the WC–10Ni₃Al specimens^[8]

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图 6 WC–6Ni₃Al、WC–10Ni₃Al及YG8硬质合金刀片后刀面磨损量随切削时间的变化^[10]

Figure 6. Variation on the flank wear of WC–6Ni₃Al, WC–10Ni₃Al, and YG8 inserts with the cutting time^[10]

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图 7 经不同温度烧结的纯WC块体材料（原料粉末粒径：800 nm）的扫描电子显微形貌：（a）1750 ℃；（b）2000 ℃^[16]

Figure 7. SEM images of the WC bulk specimens (raw material particle size: 800 nm) at different sintering temperatures: (a) 1750 ℃; (b) 2000 ℃^[16]

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图 8 Al₂O₃体积分数对WC–Al₂O₃复合材料硬度（HV₁₀）、横向断裂强度以及断裂韧性的影响^[16]

Figure 8. Effect of Al₂O₃ volume fraction on the Vickers hardness (HV₁₀), fracture toughness, and TRS of the WC–Al₂O₃ composite materials^[16]

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图 9 WC–Al₂O₃材料中裂纹扩展与断面扫描电子显微形貌：（a）裂纹桥接；（b）穿晶断裂^[16]

Figure 9. SEM images of the crack propagation and fracture of the WC–Al₂O₃ composite materials: (a) crack-bridging; (b) transgranular fracture^[16]

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图 10 WC–Si₃N₄复合材料烧结显微组织^[22]

Figure 10. SEM images of the sintered WC–Si₃N₄ composite ^[22]

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图 11 烧结WC–Si₃N₄复合材料压痕裂纹形貌以及β-Si₃N₄晶须增韧机制^[22]：（a）压痕形貌；（b）裂纹扩展路径；（c）裂纹桥接；（d）晶须拔出

Figure 11. SEM images of the indentation cracks of the sintered WC–Si₃N₄ composites and the toughening mechanism of Si₃N₄ whisker^[22]: (a) indentation morphology; (b) crack propagation path; (c) crack bridging; (d) whisker pullout

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表 1 WC块体材料原料粒径、烧结温度与力学性能^[16]

Table 1. Raw material particle size, sintering temperature, and mechanical properties of the WC bulk specimens^[16]

粉末粒径 / nm	烧结温度 / ℃	密度 / (g·cm⁻³)	平均晶粒尺寸 / nm	硬度, HV₁₀ / GPa	横向断裂强度 / MPa	断裂韧性 / (MPa·m^1/2)
800	1750	15.65	800	24.81	1276.0	6.14
800	2000	15.60	2000	21.44	1429.0	6.62
200	1750	15.36	200	24.69	853.1	5.24
100	1900	15.39	100	25.20	861.7	4.48

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参考文献(23)

[1]	Sun J L, Zhao J, Huang Z F, et al. A review on binderless tungsten carbide: development and application. Nano-Micro Lett, 2020, 12(1): 12 doi: 10.1007/s40820-019-0348-z
[2]	Zheng J, Zhao Z W, Liu X F, et al. Effect of nano-composite grain inhibitors on composition and microtructure of WC‒TiC‒Co cemented carbide prepared by microwave method. Powder Metall Ind, 2018, 28(4): 21 郑娟, 赵志伟, 刘晓芳, 等. 纳米复合抑制剂对微波法制备WC‒TiC‒Co硬质合金组成和微观结构的影响. 粉末冶金工业, 2018, 28(4): 21
[3]	Chen Q W, Deng Y, Jiang S, et al. Functionally graded cemented carbides of WC‒TiC‒Co with cubic rich surface. Powder Metall Technol, 2020, 38(1): 36 陈巧旺, 邓莹, 姜山, 等. 表层富立方相WC‒TiC‒Co功能梯度硬质合金. 粉末冶金技术, 2020, 38(1): 36
[4]	Chang L F, Jiang Y, Wang W, et al. Ultrafine WC‒0.5Co‒xTaC cemented carbides prepared by spark plasma sintering. Int J Refract Met Hard Mater, 2019, 84(1): 1
[5]	Ma N, Zhang K K, Yin D Q, et al. Synthesis and characterization of nanostructured WC–Co/Al powder prepared by mechanical alloying. J Nanomater, 2016, 2016(Special issue): 9080684
[6]	Li Y Y, Zhang J B, Li X Q, et al. Research on WC–6Co–1.5Al hardmetals prepared by spark plasma sintering. Powder Metall Technol, 2006, 24(3): 199 doi: 10.3321/j.issn:1001-3784.2006.03.009 李元元, 张建兵, 李小强, 等. SPS烧结制备WC–6Co–1.5Al硬质合金的研究. 粉末冶金技术, 2006, 24(3): 199 doi: 10.3321/j.issn:1001-3784.2006.03.009
[7]	Tumanov A V, Gostev Y V, Panov V S, et al. Wetting of TiC–WC system carbides with molten Ni₃Al. Sov Powder Metall Met Ceram, 1986, 25(1): 428
[8]	Li X Q, Chen J, Zheng D H, et al. Preparation and mechanical properties of WC–10Ni₃Al cemented carbides with plate-like triangular prismatic WC grains. J Alloys Compd, 2012, 544(1): 134
[9]	Li X Q, Zhang M A, Zheng D H, et al. The oxidation behavior of the WC–10wt. % Ni₃Al composite fabricated by spark plasma sintering. J Alloys Compd, 2015, 629(1): 148
[10]	Liu X, Liang L, Xu X, et al. Cutting forces and wear resistance of WC–Ni₃Al cemented carbides in machining austenitic stainless steel // 10th International Conference on Progress of Machining Technology (ICPMT2012). Tsubame, 2012: 39.
[11]	Kim H C, Shon I J, Yoon J K, et al. One step synthesis and densification of ultra-fine WC by high-frequency induction combustion. Int J Refract Met Hard Mater, 2006, 24(3): 202 doi: 10.1016/j.ijrmhm.2005.04.004
[12]	Zhang J X, Zhang G Z, Zhao S X, et al. Binder-free WC bulk synthesized by spark plasma sintering. J Alloys Compd, 2009, 479(1): 427
[13]	Zheng D H, Li X Q, Li Y Y, et al. Zirconia-toughened WC with/without VC and Cr₃C₂. Ceram Int, 2014, 40(1): 2011 doi: 10.1016/j.ceramint.2013.07.111
[14]	Huang B, Chen L D, Bai S Q. Bulk ultrafine binderless WC prepared by spark plasma sintering. Scr Mater, 2006, 54(3): 441 doi: 10.1016/j.scriptamat.2005.10.014
[15]	Zheng D H, Li X Q, Li Y Y, et al. ZrO₂ (3Y) toughened WC composites prepared by spark plasma sintering. J Alloys Compd, 2013, 572(1): 62
[16]	Zheng D H, Li X Q, Ai X, et al. Bulk WC–Al₂O₃ composites prepared by spark plasma sintering. Int J Refract Met Hard Mater, 2012, 30(1): 51 doi: 10.1016/j.ijrmhm.2011.07.003
[17]	Kim H C, Kim D K, Woo K D, et al. Consolidation of binderless WC–TiC by high frequency induction heating sintering. Int J Refract Met Hard Mater, 2008, 26(1): 48 doi: 10.1016/j.ijrmhm.2007.01.006
[18]	Sun J L, Zhao J, Gong F, et al. Development and application of WC-based alloys bonded with alternative binder phase. Crit Rev Solid State Mater Sci, 2019, 44(3): 211 doi: 10.1080/10408436.2018.1483320
[19]	Dong W, Zhu S, Wang Y, et al. Infuence of VC and Cr₃C₂ as grain growth inhibitors on WC–Al₂O₃ composites prepared by hot press sintering. Int J Refract Met Hard Mater, 2014, 45(1): 223
[20]	Radajewski M, Schimpf C, Krüger L. Study of processing routes for WC–MgO composites with varying MgO contents consolidated by FAST/SPS. J Eur Ceram Soc, 2017, 37(5): 2031 doi: 10.1016/j.jeurceramsoc.2017.01.005
[21]	Sun J L, Zhao J, Ni X Y, et al. Fabrication of dense nano-laminated tungsten carbide materials doped with Cr₃C₂/VC through two-step sintering. J Eur Ceram Soc, 2018, 38(9): 3096 doi: 10.1016/j.jeurceramsoc.2018.02.037
[22]	Zheng D H, Li X Q, Li Y Y, et al. In-situ elongated β-Si₃N₄ grains toughened WC composites prepared by one/two-step spark plasma sintering. Mater Sci Eng A, 2013, 561(1): 445
[23]	Kim H D, Han B D, Park D S, et al. Novel two-step sintering process to obtain a bimodal microstructure in silicon nitride. J Am Ceram Soc, 2002, 85(1): 245