难熔高熵合金粉末制备技术及应用研究综述

赵宇敏; 施麒; 刘斌斌; 谭冲; 刘辛; 周舸; 丁忠耀; 秦奉

doi:10.7513/j.issn.1004-7638.2025.01.020

难熔高熵合金粉末制备技术及应用研究综述

doi: 10.7513/j.issn.1004-7638.2025.01.020

赵宇敏^{1, 2,},
施麒^2, ,,
刘斌斌³,
谭冲²,
刘辛²,
周舸¹,
丁忠耀⁴,
秦奉^{1, 2}

1.
沈阳工业大学材料科学与工程学院, 辽宁沈阳110870
2.
广东省科学院新材料研究所国家钛及稀有金属粉末冶金工程技术研究中心广东省金属强韧化技术与应用重点实验室, 广东广州 510650
3.
北京科技大学新金属材料国家重点实验室, 北京 100083
4.
稀美资源(广东)有限公司, 广东清远 513055

基金项目: 广东省重点领域研发计划资助(2018B090904004)；新金属材料国家重点实验室开放基金资助项目(2022-Z16)；广东省国际科技合作(2022A0505050025)；广州市重点研发计划(202206040001)；清远市科技计划项目(2021DZX028)；广东省科学院打造综合产业技术创新中心行动资金项目(2022GDASZH-2022010107）。

详细信息

作者简介:
赵宇敏，1998年出生，男，山西长治人，硕士研究生，从事金属粉体制备及增材制造研究，E-mail: 1252955839@qq.com

通讯作者:
施麒，1987年出生，男，浙江绍兴人，高级工程师，博士研究生，主要从事金属粉体制备及增材制造研究，E-mail: shiqi@gdinm.com

中图分类号: TF12
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- 被引次数: 0
出版历程
- 收稿日期: 2023-11-08
- 刊出日期: 2025-02-27

Research progress of preparation of refractory high entropy alloy powder

ZHAO Yumin^{1, 2
,},
SHI Qi^{2
, ,},
LIU Binbin³,
TAN Chong²,
LIU Xin²,
ZHOU Ge¹,
DING Zhongyao⁴,
QIN Feng^{1, 2}

1.
School of Materials Science and Engineering, Shenyang University of Technology, Shenyang 110870, Liaoning, China
2.
Institute of New Materials, Guangdong Academy of Sciences, National Engineering Research Center of Titanium and Rare Metal Powder Metallurgy, Guangdong Key Laboratory of Metal Strengthening and Toughening Technology and Application, Guangzhou 510650, Guangdong, China
3.
State Key Laboratory of Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083, China
4.
Ximei Resources (Guangdong) Co., LTD., Qingyuan 513055, Guangdong, China

摘要

摘要: 以增材制造为代表的近净成形工艺为难熔高熵合金复杂零部件制备提供了技术路径，同时也对其粉末提出了较高的性能要求。综述了难熔高熵合金成分设计准则以及各类元素对合金性能的影响，分析比较了其粉末制备的主要技术路线（机械合金化、等离子旋转电极雾化和射频等离子体球化）。指出了现有难熔高熵合金粉末在粉末冶金、激光熔覆、增材制造等领域的应用中存在的问题和解决办法。
- 难熔高熵合金 /
- 成分设计准则 /
- 粉末制备 /
- 增材制造
Abstract: The near-net forming process such as additive manufacturing provides technical paths for the preparation of complex parts of refractory high-entropy alloys, and also puts forward higher performance requirements for their powders. In this paper, the composition design criteria of refractory high-entropy alloys and the effects of various elements on the properties of alloys are reviewed. The main technical routes of powder preparation (mechanical alloying, plasma rotating electrode process and radio frequency plasma spheroidization) are analyzed and compared. In addition, the problems and solutions in the application of refractory high-entropy alloy powder in powder metallurgy, laser cladding, additive manufacturing and other fields had also been discussed.
- refractory high-entropy alloy /
- component design criteria /
- powder preparation /
- additive manufacturing

HTML全文

图 1 各参数与物相之间的关系^[11]

(a)δ, ΔH_mix和物相之间的关系；(b)δ, ΔH_mix, ΔS_mix和物相之间的关系

Figure 1. The relationship between the parameters and the phase^[11]

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图 2 气固流化技术^[24]

（a）气固流化原理；（b）粉体改性原理

Figure 2. Schematic diagram of gas-solid fluidization technology^[24]

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图 3 等离子旋转电极雾化制粉工艺原理^[24]

Figure 3. Schematic diagram of atomizing pulverization process with plasma rotating electrod^[24]

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图 4 (a)TaNbTiZr棒材^[27]；(b)PREP制备的粉末SEM形貌及插入的粒径分布^[27]；(c)TaNbTiZr棒材和PREP制备粉末XRD谱^[27]

Figure 4. (a) TaNbTiZr bar^[27]; (b) SEM image of powder prepared by PREP and particle size distribution of insertion^[27]; (c) XRD pattern of TaNbTiZr rod and PREP powder preparation^[27]

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图 5 (a) 金属原料粉末^[29]；(b)喷雾造粒粉末^[29]；(c)等离子体球化后难熔高熵合金粉末SEM形貌及其粒径分布^[29]

Figure 5. (a) SEM images of four different metal raw material powders^[29]; (b) SEM images after spray granulation, insertion grout photos^[29]; (c) SEM images and particle size distributions of HEA powders after plasma spheroidization^[29]

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图 7 氢化破碎和等离子体处理后的粉末形貌^[30]

(a)氢化破碎后的不规则粉体；(b)等离子体处理后的球形粉末

Figure 7. Morphology of powder after hydrogenation crushing and plasma treatment^[30]

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图 6 难熔高熵合金粉末纳米压痕加载-卸载曲线^[29]

Figure 6. Loading and unloading nanoindentation curve of HEA powder inserted into indentation photograph^[29]

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图 8 射频等离子球化前后粉末的SEM形貌^[31]

(a)研磨粉末；(b) (a)的放大图像；(c)等离子处理后的球形粉末；(d) (c)的放大图像

Figure 8. Morphology observed by SEM^[31]

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图 9 (a) NbMoTaTi难熔高熵合金的缺陷^[37] ；(b) NbMoTi合金激光熔覆沉积成形的纵表面^[37]

Figure 9. (a) Defect diagram of NbMoTaTi refractory high entropy alloy^[37]；(b)Longitudinal surface of NbMoTi alloy formed by laser cladding deposition^[37]

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图 10 直接沉积和重熔沉积单道熔道表面SEM形貌和能谱 (EDX) 元素分布 ^[41]

(a)单道沉积熔道SEM；(b)重熔沉积单道熔道表面SEM； (c)单道沉积熔道元素分布； (d)重熔沉积单道熔道元素分布

Figure 10. SEM image and EDX element distribution of direct deposition and remelting deposition single-pass fuse surface^[41]

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表 1 Ti_（65-x）Ta₂₅Nb₁₀Zr_x（x=0、5、10、15、20）难熔高熵合金的ΔS_mix、ΔH_mix、Ω、δ数值^[15]

Table 1. Values of ΔS_mix, ΔH_mix, Ω and δ of Ti_(65-x) Ta₂₅Nb₁₀Zr_x (x=0, 5, 10, 15, 20) refractory high entropy alloy^[15]

合金名称	ΔS_mix /(J·mol⁻¹·K⁻¹)	ΔH_mix /(kJ·mol⁻¹)	Ω	δ/%	VEC
Ti₆₅Ta₂₅Nb₁₀	7.12	1.17	14.3	0	4.35
Ti₆₀Ta₂₅Nb₁₀Zr₅	8.59	1.31	15.5	1.9	4.35
Ti₅₅Ta₂₅Nb₁₀Zr₁₀	9.44	1.45	15.4	2.6	4.35
Ti₅₀Ta₂₅Nb₁₀Zr₁₅	10.04	1.59	15	3.12	4.35
Ti₄₅Ta₂₅Nb₁₀Zr₂₀	10.46	1.73	14.4	3.48	4.35

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表 2 难熔高熵合金粉末三种制粉方法比较

Table 2. Comparison of three milling methods of refractory high entropy alloy powder

制粉方法	优点	缺点
MA	工艺简单，成本较低，粉末晶粒细小	引入杂质，粉末呈片状，流动性较差
PREP	粉末球形度高，几乎无空心粉，氧含量低	原材料需要熔锭棒材，细粉收得率低
RFPS	粉末球形度高，流动性好，内部缺陷少，粒度可控	原料不规则粉末制备可能引入碳、氧等杂质元素

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表 3 样品成分^[40]

Table 3. Compositions of samples

元素	S1/%	S2/%	S3/%	平均值/%	方差
W	27.6	24.76	24.45	25.46	1.65
Ta	28.09	29.49	27.06	28.21	0.99
Nb	21.61	20.97	21.93	21.50	0.16
Mo	23.05	24.79	26.67	24.84	2.19

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