新型纳米晶硬质合金的研究现状及发展趋势

王倩玉; 秦明礼; 吴昊阳; 贾宝瑞; 曲选辉

doi:10.19591/j.cnki.cn11-1974/tf.2021040010

新型纳米晶硬质合金的研究现状及发展趋势

doi: 10.19591/j.cnki.cn11-1974/tf.2021040010

北京科技大学新材料技术研究院, 北京100083

基金项目: 国家自然科学基金资助项目（51774035）

详细信息

通讯作者:
E-mail: qinml@mater.ustb.edu.cn (秦明礼)

wuhaoyang@ustb.edu.cn (吴昊阳)

中图分类号: TG142.71
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出版历程
- 收稿日期: 2021-04-26
- 刊出日期: 2022-08-12

Research status and development trend of new nanocrystalline cemented carbides

Institute for Advanced Materials and Technology, University of Science and Technology Beijing, Beijing 100083, China

More Information

Corresponding author: E-mail: qinml@mater.ustb.edu.cn (QIN M L); wuhaoyang@ustb.edu.cn (WU H Y)

摘要

摘要: 纳米晶硬质合金以其优异的性能在电子信息、汽车制造、航空航天、国防军事等领域被广泛应用。本文概述了近年来纳米晶硬质合金的发展状况，包括新型粘结相纳米晶硬质合金、无粘结相纳米晶硬质合金、梯度纳米晶硬质合金以及涂层纳米晶硬质合金等一系列新型纳米晶硬质合金，展望了纳米晶硬质合金在各个领域的发展前景和研发重点，为现代硬质合金材料及技术的发展提供新思路。
- 纳米晶硬质合金 /
- 粘结剂 /
- 梯度 /
- 涂层 /
- 致密化
Abstract: Nanocrystalline cemented carbides have been widely used in the electronics information, automobile manufacturing, aerospace, national defense, and military industry due to the excellent performance. The development of nanocrystalline cemented carbides in recent years was summarized in this paper, including new binder phase nanocrystalline cemented carbides, binderless nanocrystalline cemented carbide, gradient nanocrystalline cemented carbides, and coating nanocrystalline cemented carbides. The development potential and research focus of the nanocrystalline cemented carbides in each field were prospected, providing the new ideas for the modern cemented carbide materials and technology.
- nanocrystalline cemented carbides /
- binders /
- gradient /
- coatings /
- densification

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图 1 全球硬质合金产量变化及区域分布图^[5]

Figure 1. Production change and regional distribution of the cemented carbides in the world^[5]

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图 2 纳米晶硬质合金制品：（a）刀具—医用牙钻切口；（b）微钻—PCB电路板钻孔工具；（c）切削刀具—切削飞机发动机采用的高温合金、钛合金；（d）切削刀具—切削汽车发动机采用的球磨铸铁

Figure 2. Nanocrystalline cemented carbide products: (a) cutting tools–cutting drill tooth for medicine; (b) micro drill–PCB circuit board drilling tool; (c) cutting tool–cutting superalloy and titanium alloys used in aircraft engines; (d) cutting tool–cutting nodular cast iron used in automobile engines

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图 3 不同Cu含量的WC–Fe–Cu硬质合金横向断裂强度^[19]（a）和WC–Ni样品场发射扫描电子显微形貌及能谱分析^[20]（b）

Figure 3. Transverse fracture strength of the WC–Fe–Cu cemented carbides with the different Cu contents^[19] (a) and the field emission scanning electron microscopy images and the energy spectrum analysis of the WC–Ni samples^[20] (b)

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图 4 超细晶无粘结相硬质合金产品^[39]：（a）RCCL机械密封环；（b）RCCFN超精密模具

Figure 4. Products of the ultrafine cemented carbides with unbonded phase^[39]: (a) RCCL mechanical seal ring; (b) RCCFN ultra-precision mold

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图 5 弥散颗粒增韧原理模型：（a）无增韧颗粒模型；（b）单个颗粒增韧模型；（c）整体颗粒增韧模型

Figure 5. Toughening principle models of the dispersed particles: (a) non-toughened particle model; (b) single particle toughening model; (c) whole particle toughening model

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图 6 WC–TiC–Al₂O₃–GNPs横截面扫描电子显微形貌（a）和Ti、Al、W元素能谱分析（（b）～（d））^[71]

Figure 6. SEM micrographs of the WC–TiC–Al₂O₃–GNPs cross-section surfaces (a) and the EDS maps of Ti, Al, and W elements ((b)~(d))^[71]

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图 7 市场上的新型硬质合金刀具涂层^[10,75]：（a）多层涂层；（b）梯度涂层；（c）多层AlTiN/TiN纳米涂层

Figure 7. New cemented carbide tool coatings on the market^[10,75]: (a) multi-layer coating; (b) gradient coating; (c) multi-layer AlTiN/TiN nano-coating

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图 8 超细结构与微米结构的WC–Co涂层硬度和韧性比较^[76]（a）及三种不同涂层体系（不同碳化物粒径：2.5 μm，1.0 μm， 0.1 μm）的扫描电子显微断面形貌（（b）～（d））^[77]

Figure 8. Hardness and toughness of the WC–Co coatings with the ultra-fine structure and micro structure (a)^[76] and the cross section SEM images of three different coating systems (the different carbide particle size of 2.5 μm, 1.0 μm, and 0.1 μm) ((b)~(d))^[77]

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表 1 不同晶粒度WC硬质合金刀具的性能^[7]

Table 1. Properties of the WC cemented carbide tools with the different grain sizes^[7]

WC硬质合金刀具牌号	WC晶粒度 / μm	硬度，HRA	断裂韧性 / (MPa·m^1/2)	密度 / (g·cm⁻³)
YH6F	0.13	96.1	9.5	14.7
YU06	0.30	93.8	9.1	14.7
YF06	0.50	91.5	8.8	14.9
YL10	1.70	90.9	7.9	14.9

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表 2 按WC晶粒尺寸对硬质合金进行分类^[7]

Table 2. Categorization of cemented carbides by WC average grain size^[7]

类别	WC平均晶粒度 / μm
类别	瑞典山特维克公司	英国与德国标准协会
纳米	0.1～0.3	＜0.2
超细	0.3～0.5	0.2～0.5
亚微	0.5～0.9	0.5～0.8
细颗粒	1.0～1.3	0.5～1.3
中颗粒	1.4～2.0	1.3～2.5
中粗颗粒	2.1～3.4	—
粗颗粒	3.5～4.9	2.5～6.0
超粗颗粒	5.0～7.9	＞6.0
特粗颗粒	8.0～14.0	—

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表 3 硬质合金中常见粘结剂的分类及性能

Table 3. Classification and properties of the common binders in cemented carbides

分类	粘结相	性能
金属粘结剂	Co^[17]	对WC具有良好的润湿性和随温度变化的溶解度，有助于烧结；WC–Co硬质合金的硬度、耐腐蚀性、抗氧化性和高温性能与钴含量（质量分数）成反比；资源贫乏、对环境不友好。
	Fe^[18]	抑制WC晶粒生长，对环境友好；对WC的润湿性差，易生成脆性相W₃Fe₃C。
	Mn^[17]	提高对WC的润湿性；一种强的奥氏体稳定剂；Fe–Mn合金在晶体结构、熔化温度等方面表现出与Co相似的特性，并具有较高的强度和耐磨性；环保无毒、低成本。
	Cu^[19]	提高对WC的润湿性；降低WC–Fe合金的熔点；WC–Fe–Cu硬质合金比WC–Fe合金具有更好的致密化行为和更高的断裂韧性。
	Ni^[20]	对WC具有良好的润湿性，优异的耐腐蚀性/抗氧化性；对环境友好、低成本；此外，Ni还能通过防止碳化物颗粒团聚而形成具有细颗粒的均匀结构。
	Al^[21]	促进烧结过程，极大阻碍WC晶粒的生长。
	Mo^[20]	有利于抑制晶粒生长和增加断裂韧性，但对硬度没有明显影响；容易与碳形成碳化物，能起到一定的析出强化效应，还能改善合金耐热性能；Mo的添加量通常较低，过量添加会降低合金的抗氧化性。
	Cr^[17]	有利于抑制晶粒生长，并能显著提高材料的耐腐蚀性和抗氧化性；Cr的加入会增加合金的碳敏感性。
	高熵合金^[22]	具有高的硬度、断裂韧性、耐磨性和优异的耐高温软化性、耐腐蚀性和抗氧化性等潜在性能，是一种由等摩尔或近等摩尔比的多种主要元素组成的合金。
金属间化合物粘结剂	FeAl^[23]	对WC具有良好的润湿性；优良的耐腐蚀性/抗氧化性；优异的高温性能、耐磨性；低成本、低密度、对环境友好。
	Ni₃Al^[24]	对WC具有良好的润湿性；具有极快的加工硬化、高弹性模量、高硬度、高熔点、低密度；优异的耐腐蚀性/抗氧化性能和高温性能。
	TiAl₃/TiAl^[25]	TiAl₃/TiAl掺杂能抑制晶粒长大和诱发裂纹偏转，在不影响硬度的前提下，大幅度提高韧性。
	AlN^[26]	AlN的加入抑制了W₂C的形成，促进固溶相形成，减小晶粒尺寸，从而提高了合金的强度。

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表 4 采用不同金属粘结剂制备的纳米晶硬质合金性能

Table 4. Properties of the nanocrystalline cemented carbides prepared with the different metal binders

材料	相对密度 / %	WC晶粒尺寸 / μm	硬度 / (kg·mm^‒2)	断裂韧性 / (MPa·m^1/2)
WC–8%Co^[30]（质量分数）	99.20	0.330	1945	13.30
WC–10%Co^[22]（质量分数）	—	0.150	1910	8.10
WC–15%Co^[28]（质量分数）	99.00	0.720	1470	12.33
WC–8%Ni^[30]（质量分数）	98.50	0.300	1948	13.00
WC–10%Ni^[20]（质量分数）	99.70	0.500	1783	17.27
WC–15%Fe–Ni^[31]（质量分数）	99.68	1.000	1488	15.10
WC–15%Fe–Ni–Co^[28]（质量分数）	99.00	0.680	1480	16.23
WC–5%Fe–Al^[23]（体积分数）	97.50	0.092	2549	9.60
WC–10%Fe–Al^[23]（体积分数）	98.20	0.097	2414	11.00
WC–10%Mo^[20]（质量分数）	99.60	1.000	2151	8.77
WC–5%Al^[21]（体积分数）	98.00	0.069	2700	7.10
WC–10%Al^[21]（体积分数）	98.00	0.154	2350	7.40
WC–15%Al^[21]（体积分数）	97.50	0.366	1700	11.90
WC–10%HEAs^[22]（质量分数）	—	0.150	2231	8.33
WC–20%HEAs^[22]（质量分数）	—	0.150	2358	12.10

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表 5 不同化合物对无粘结相硬质合金性能的影响

Table 5. Effect of the different compounds on the properties of BCC

化合物种类		作用
化合物种类		促进致密化	抑制晶粒生长	增韧
过渡金属碳化物	TiC^[44]	√	√	√
	TaC^[45]	√	√	√
	SiC^[46]	√	—	√
	VC^[47]	—	√	—
	Mo₂C^[48]	—	√	√
	Cr₃C₂^[17]	—	√	—
	NbC^[45]	—	√	—
	ZrC^[45]	—	√	√
	HfC^[49]	—	√	—
金属氧化物	Al₂O₃^[50]	√	√	√
	ZrO₂^[51]	√	—	√
	Y₂O₃^[52]	√	—	√
	La₂O₃^[53]	√	√	—
	MgO^[54]	—	—	√
其他化合物	Si₃N₄^[49]	—	—	√
其他化合物	TiB₂^[49]	—	—	√
注：表中“√”代表有作用，“—”代表无作用。

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表 6 不同晶粒生长抑制剂的作用^[4,35,58]

Table 6. Effect of the different grain growth inhibitors^[4,35,58]

晶粒生长抑制剂	作用
VC	抑制WC晶粒生长。
Cr₃C₂	抑制WC晶粒生长，改善合金耐腐性能。
TaC	抑制WC晶粒生长，提高合金的红硬性、耐磨性能、抗氧化性能、高温强度、冲击韧性、抗热震性。
NbC	抑制WC晶粒生长，提高合金的红硬性和抗热冲击性能。
TiC	抑制WC晶粒生长，改善合金在高温下的化学稳定性、阻碍高温下铁基（钢铁）被加工件与硬质合金切削刀具之间的扩散行为。
Mo₂C	抑制WC晶粒生长，改善粘结相对含Ti(C,N)的润湿性。
ZrC	抑制WC晶粒生长。
HfC	抑制WC晶粒生长。

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表 7 添加不同晶粒生长抑制剂的无粘结相纳米晶硬质合金的性能

Table 7. Properties of the binderless nanocrystalline cemented carbides with the different grain growth inhibitors

材料	相对密度 / %	WC晶粒尺寸 / nm	硬度，HV	断裂韧性 / (MPa·m^1/2)
WC–1%VC^[47]（质量分数）	96.5	280	2795	4.2
WC–1%VC^[59]（质量分数）	99.8	272	2585	6.9
WC–1%Cr₃C₂^[59]（质量分数）	100.0	277	2605	7.2
WC–1%TaC^[45]（质量分数）	99.7	202	2570	6.9
WC–1%NbC^[45]（质量分数）	99.6	214	2540	6.6
WC–20%TiC^[44]（原子数分数）	98.5	200	2032	6.3
WC–20%TiC^[60]（原子数分数）	99.0	200	2240	7.5
WC–6%Mo₂C^[61]（质量分数）	99.0	250	2400	8.4
WC–1%Mo₂C^[45]（质量分数）	100.0	183	2630	6.6
WC–1%ZrC^[45]（质量分数）	98.8	236	2420	6.5

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表 8 无粘结相硬质合金的传统增韧方法及机理^{[35-39,45,49,61]}

Table 8. Traditional toughening methods and mechanism of binderless cemented carbide^{[35-39,45,49,61]}

增韧方法	机理	举例
颗粒弥散增韧	（1）扩展裂纹前的颗粒引起的裂纹偏转；（2）颗粒引起的裂纹桥接；（3）裂纹前缘与颗粒之间的相互作用；（4）由于基体和弥散颗粒的热膨胀系数不匹配以及（5）晶粒尺寸不匹配而产生的热残余应力场。	Al₂O₃、MgO、TiC、SiC、Mo₂C和ZrC颗粒
相变增韧	由硬质相基体中颗粒夹杂在断裂过程中的应力诱导相变而产生，主要取决于裂纹尖端拉伸应力场中亚稳四方氧化锆相向稳定单斜氧化锆相的转变。	ZrO₂
晶须增韧	（1）晶须拔出增韧：晶须在外界负载作用下从基质中拔出时，因界面摩擦而消耗掉一部分外界负载能量，从而达到增韧目的；（2）裂纹偏转增韧：当裂纹尖端遇到弹性模量大于基质的第二相时，裂纹将偏离原来的前进方向，沿两相界面或在基质内扩展。由于裂纹的非平面断裂比平面断裂具有更大的断裂表面，因此可吸收更多外界能量，从而起到增韧作用；（3）晶须桥接增韧：当基质断裂时，晶须可承受外界载荷并在断开的裂纹面之间起到桥梁连接作用。桥接的晶须可对基质产生使裂纹闭合的力，消耗外界载荷做功，从而提高材料韧性。	Al₂O₃、MgO、SiC、Si₃N₄、TiC和TiB₂晶须

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表 9 WC–12Co涂层性能^[77]

Table 9. Properties of the WC–12Co coatings^[77]

碳化物粒径 / μm	硬度，HV1	孔隙率 / %	厚度 / μm
2.5	991±61	2.5±0.9	533±23
1.0	1145±93	1.6±0.4	581±13
0.1	1210±36	1.0±0.2	566±8

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表 10 纳米金刚石涂层与微米金刚石涂层性能比较^[79]

Table 10. Performance comparison of the nano diamond coatings and micro diamond coatings^[79]

性能	晶粒尺寸 / nm	表面粗糙度 / nm	硬度 / GPa	摩擦系数	弹性模量 / GPa
纳米金刚石涂层	3～20	＜19	39～78	0.05～0.10	384
微米金刚石涂层	几十微米	粗糙	85～100	0.10	354～535

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