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2222材料工程  2021, Vol. 49 Issue (10): 1-17    DOI: 10.11868/j.issn.1001-4381.2020.000820
  综述 本期目录 | 过刊浏览 | 高级检索 |
高熵合金增材制造研究进展
魏水淼1, 马盼1,*(), 季鹏程1, 马永超2, 王灿1, 赵健1, 于治水1
1 上海工程技术大学 材料工程学院, 上海 201620
2 山推工程机械股份有限公司, 山东 济宁 272073
Research progress in high entropy alloys by additive manufacturing
Shui-miao WEI1, Pan MA1,*(), Peng-cheng JI1, Yong-chao MA2, Can WANG1, Jian ZHAO1, Zhi-shui YU1
1 School of Materials Engineering, Shanghai University of Engineering Science, Shanghai 201620, China
2 Shantui Construction Machinery Co., Ltd., Jining 272073, Shandong, China
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摘要 

基于不同的高熵合金（high-entropy alloys，HEAs）体系，综述了增材制造高熵合金的最新研究进展，阐述了不同成分高熵合金增材制造的快速凝固微观组织、偏析和析出行为，着重分析了增材制造高熵合金的力学性能、变形及强化机理。指出不同的高熵合金体系应选择适合的增材制造工艺，并且成型质量的影响因素还有待进一步研究，最后提出利用增材制造技术可以研发和制备出具有优异强度-塑性组合的高熵合金。
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魏水淼
马盼
季鹏程
马永超
王灿
赵健
于治水
关键词 ： 高熵合金,  增材制造,  微观组织,  强化机理    
Abstract：

Based on different high-entropy alloys (HEAs) systems, the latest research progress in additive manufactured high-entropy alloys was reviewed. The rapid solidification microstructure, segregation and precipitation behaviors of high-entropy alloys fabricated by additive manufacturing with different compositions were described. Especially, the analysis was focused on the mechanical properties, deformation and strengthening mechanisms. It was pointed out that the appropriate additive manufacturing process should be selected for different high-entropy alloy systems, and the influencing factors of forming quality need to be further studied. Finally, it was proposed that high-entropy alloys with both excellent strength and high plasticity can be developed and prepared by additive manufacturing technology.
Key words： high-entropy alloys (HEAs)    additive manufacturing    microstructure    strengthening mechanism
收稿日期: 2020-08-31      出版日期: 2021-10-14
中图分类号:  TG135  
通讯作者: 马盼     E-mail: mapan@sues.edu.cn
作者简介: 马盼(1986-), 女, 副教授, 博士, 研究方向为激光3D打印、高压凝固, 联系地址: 上海市松江区龙腾路333号行政楼1615(201620), E-mail: mapan@sues.edu.cn
引用本文:   
魏水淼, 马盼, 季鹏程, 马永超, 王灿, 赵健, 于治水. 高熵合金增材制造研究进展[J]. 材料工程, 2021, 49(10): 1-17.
Shui-miao WEI, Pan MA, Peng-cheng JI, Yong-chao MA, Can WANG, Jian ZHAO, Zhi-shui YU. Research progress in high entropy alloys by additive manufacturing. Journal of Materials Engineering, 2021, 49(10): 1-17.
链接本文:  
http://jme.biam.ac.cn/CN/10.11868/j.issn.1001-4381.2020.000820      或      http://jme.biam.ac.cn/CN/Y2021/V49/I10/1
Fig.1  SLM过程示意图[12]
Fig.2  LMD过程示意图[9]
Fig.3  EBM过程示意图[16]
Method Composition σy/MPa σuts/MPa εf/% Segregation Remark Reference
SLM FeCoCrNi 600 745 32 No [17]
SLM CoCrFeNi 572±7.5 691.0±15.9 17.9±0.9 No [18]
SLM FeCoCrNi 581.9 707.9 ≈20 [19]
Ink-extrusion CoCrFeNi 250±5 598±8 33.8±1.3 Sintering [20]
SLM FeCoCrNiC0.05 638 797 13.5 No [21]
SLM FeCoCrNiC0.05 638 795 13.5 Cr along dislocation networks Annealed at 400 ℃ for 3 h followed by water quenching [22]
SLM FeCoCrNiC0.05 787 950 10.3 C and Cr on grain boundaries Nano-scale Cr23C6 type carbides can precipitate under annealing at 1073 K for 0.5 h [23]
SLM 1.8%(atom fraction) N-doped FeCoNiCr 650 853 34 [24]
SLM FeCoCrNiSi0.05 701±14 907±25 30.8±2 No By remelting each layer after its initial laser scanning [25]
LMD CoCrFeNiNbx ≈410(Nb0.1) ≈690(Nb0.1) 55(Nb0.1) Laves phase was enriched in Nb As the Nb concentration increased, both yield and fracture strengths increased but tensile ductility decreased [26]
LMD CoCrFeNiMo0.2 500(77 K) 928(77 K) 60(77 K) [27]
LMD Ni2.1CoCrFeNb0.2 896 1127 17 Nb At 1250 ℃ for 1 h followed by water quenching，then at 650 ℃ aged for 96 h [28]
Table 1  增材制造CoCrFeNi系高熵合金
Method Grain size/ μm σy/MPa σuts/MPa εf/% Segregation Microstructural evolution Strengthening mechanism Reference
SLM ≈1 519 601 35 Mn is segregated at the boundary of weld pool After HIP, the Mn segregation disappeared Grain boundary strengthening [7]
SLM ≈12.9 510 609 34 Minor segregation of Mn along the melt pool boundaries Deformation induced twins Dislocation strengthening [30]
LMD 564(77 K) 891(77 K) 36(77 K) Mn, Cr When the strain increases to 18%, deformation twinning appears Grain boundary strengthening，dislocation strengthening [11]
LMD 3-4 710 (-130 ℃) 850 (-130 ℃) 40.2 (-130 ℃) Mn and Ni segregate into grain boundary Deformation induced twins Grain boundary strengthening，dislocation strengthening [9]
LMD 50-200 402(77 K) 878(77 K) 95(77 K) No Grain boundary strengthening，dislocation strengthening [8]
EBM ≈65 205±3 497±2 63±1 Mn and Ni segregate into the interdendrite Dislocation strengthening [33]
LMD 30-150 448 620 57 Fine BCC phase distributed at the grain boundaries of the FCC matrix Precipitation strengthening [10]
LMD 10 346 566 27.5 Mn and Ni segregate into grain boundary BCC phase appears in heat treatment Residual stress relief by heat treatment [31]
LMD ≈13 517 26 Mn and Ni segregate into grain boundary Deformation induced twins Grain boundary strengthening，dislocation strengthening [32]
Table 2  增材制造CoCrFeNiMn高熵合金
Method Addition Crystal structure σy/MPa σuts/MPa εf /% Strengthening mechanism Reference
LMD TiC FCC+TiC 385 723 32 Second-phase strengthening [37]
LMD WC FCC+Cr23C6 800 37 Grain boundary strengthening，precipitation strengthening [38]
SLM TiN FCC+TiN-particles 1036 12 Grain boundary strengthening，dislocation strengthening [39]
SLM TiN FCC+TiN-particles 1100 18 [40]
LMD CeO2 FCC+oxides [41]
LMD Al FCC+BCC 506 736 41.2 Grain boundary strengthening [42]
SLM C FCC+nano precipitate 829 989 24.3 Solution strengthening，dislocation strengthening，precipitation strengthening [43]
SLM C γ-austenite 900 30 Precipitation strengthening [44]
SLM C 741 874 39.7 Grain boundary strengthening，dislocation strengthening [45]
Table 3  增材制造CoCrFeNiMn高熵合金复合材料
Method Composition Mechanical property Segregation Crystal structure Reference
LMD Al0.3CoCrFeNi Tension and compression yield strength：194 MPa，tensile elongation 38% Grain boundary rich in Al FCC [14, 46]
SLM Al0.3CoCrFeNi Tensile strength：896 MPa，yield strength：730 MPa，elongation：29% FCC [47]
LMD Al0.3FeCoCrNi Tensile yield strength 410 MPa FCC，precipitation of L12 after HT [48]
SLM Al0.5CrFeCoNi Tensile strength：878 MPa，yield strength：540 MPa，elongation：18% Al and Ni rich in columnar intergranular BCC+FCC [49]
SLM Al0.5FeCoCrNi Tensile strength：721 MPa，yield strength：579 MPa，elongation：22% FCC [50]
LMD Al0.6CoCrFeNi Compression yield strength：400 MPa, compressive strength is 1420 MPa, tensile strength is 930 MPa Grain boundary rich in Al, Ni FCC/BCC [14, 46]
LMD AlxCoCrFeNi (0.3 < x < 0.7) FCC(x=0.3) FCC+B2(x=0.7) [51]
LMD AlxCoCrFeNi (x=0.3, 0.7) FCC(x=0.3) FCC+BCC(x=0.7) [52]
LMD Al0.85CoCrFeNi Compression yield strength：1400 MPa，elongation to failure：0.25 BCC rich in Fe, Cr BCC+B2 [14, 46]
LMD AlxCoCrFeNi (0.15 < x < 1.32) FCC(x≤0.37) BCC/B2(x≥1.16) [53]
LMD AlCoCrFeNi AlNi-rich matrix，FeCr- rich precipitates B2+BCC precipitates [54]
LMD AlCoCrFeNi Aged at 1200 ℃/168 h，compression yield strength：1.13 GPa，fracture stress：3.02 GPa，elongation：24.2% B2 rich in Al-Ni FCC rich in Fe-Cr B2 matrix+FCC precipitates after aging [55]
EBM AlCoCrFeNi Compression yield strength：1015 MPa，fracture strain 26.4%；tensile strength 1073.5 MPa，yield strength 769 MPa，elongation 1.2% B2 rich in Al-Ni BCC rich in Cr-Fe B2/BCC matrix+FCC precipitates [56-57]
SLM AlCoCrFeNi B2 rich in Al-Ni B2+A2+Fe-Cr precipitates [58]
SLM AlCoCrFeNi Cr B2/BCC [59]
Binder jetting AlCoCrFeNi Compression yield strength：(1461±23) MPa, elongation to failure：(31.46±2.1)% AlNi-rich B2 CrFe-rich BCC B2/BCC+FCC+σ phase [60]
LMD AlCoCrFeNi2.1 Compression yield strength is (711±23) MPa at 400 ℃ L12 phase is rich in Ni and deficient in Al L12+BCC [15]
LMD AlxFeCoCrNi2-x (0.3 < x < 1.7) γ+B2(x=0.7) A2+B2+L12(x=1) [61]
LMD AlCoxCr1-xFeNi (0 < x < 1) Ni+Al rich，Fe+Co rich BCC+B2 [62]
Table 4  增材制造AlxCoCrFeNi系高熵合金
Fig.4  激光沉积的AlxCoCrFeNi合金库的成分范围与粉末进料速率的函数关系[53]
Method Composition Crystal structure Segregation Mechanical property Reference
LMD TiZrNbMoV BCC Mo, Zr-rich precipitates [63]
LMD TiZrNbHfTa BCC [64]
LMD NbMoTaTi BCC Micro segregation between grain boundaries Compression strength 1301.83 MPa at 25 ℃ [65]
SLM WTaMoNb BCC [66]
LMD TiZrNbTa BCC [67]
LMD MoNbTaW BCC [68-69]
Table 5  增材制造难熔高熵合金
Method Composition Mechanical property Crystal structure Reference
SLM AlCrCuFeNi Compressive strength 2052.8 MPa, strain of 6.8% BCC [70]
SLM AlCrCuFeNix [71]
SLM AlCrCuFeNi3.0 Yield strength≈775 MPa, tensile strength ≈957 MPa, elongation≈14.3% B2+FCC [72]
LMD AlxCrCuFeNi2 (0 < x < 1.5) FCC+L12+BCC+B2 (x=1) [73-74]
SLM AlxCrCuFeNi2 BCC/B2(x=1) [75]
LMD AlxCoFeNiCu1-x (x=0.25, 0.5, 0.75) FCC(x=0.25, 0.5) FCC+BCC(x=0.75) [76]
SLM AlCoCuFeNi HT at 1000 ℃，compressive fracture strength of 1600 MPa, yield strength of 744 MPa, strain of 13.1% BCC(B2)+FCC(HT) [12]
SLM AlCoCrCuFeNi FCC+BCC [77]
SLM/EBM Co1.5CrFeNi1.5Ti0.5Mo0.1 SLM specimens yield strength：(773.0±4.2) MPa，tensile strength：1178.0 MPa，elongation：(25.8±0.6)% FCC [78]
LMD AlCrFeMoVx(x=0-1) BCC [79]
SLM AlCoFeNiSmTiVZr system FCC [80]
SLM Fe49.5Mn30Co10Cr10C0.5 Yield strength：710 MPa，tensile strength：1 GPa，elongation：28% FCC [81]
SLM Fe40Mn20Co20Cr15Si5 Yield strength of (530±40) MPa，ultimate tensile strength (≈1.1 GPa) and ductility (30%) ε+γ [82]
SLM Fe38.5Mn20Co20Cr15Si5Cu1.5 Ultimate tensile strength ≈1235 MPa, average yield strength is (665±13) MPa，ductility is 17.2% γ+ε [83]
SLM AlCrFeNiV Ultimate tensile strength≈1057.47 MPa and plastic strain≈30.3% FCC+L12 nano phase [84]
SLM AlCrFe2Ni2 Flexural strength is 2051 MPa BCC+FCC [85]
EBM Al0.5CrMoNbTa0.5 BCC [86]
SLM C0.12Al0.26CoFeMnNi Yield strength：500 MPa，tensile strength：800 MPa，elongation：41% [87]
SLM Ni6Cr4WFe9Ti Yield strength：742 MPa，tensile strength：972 MPa，elongation：12% γ+unknown phase [88]
Table 6  增材制造其他体系高熵合金
Fig.5  增材制造高熵合金力学性能强化机理
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