1 高熵合金及其内涵
1.1 高熵合金的发展历程
1.2 高熵合金的定义
1.3 高熵合金的性能特点
2 航空用典型高熵合金体系研究现状
2.1 难熔高熵合金
表 1 典型难熔高熵合金的高温力学性能Table 1 High temperature mechanical properties of typical refractory high-entropy alloys |
| Alloy | Temperature/℃ | Yield strength/MPa | Fracture strain/% | Reference |
| NbMoTaW | 600 | 561 | [19] | |
| 800 | 552 | |||
| 1000 | 548 | |||
| 1200 | 506 | |||
| 1400 | 421 | |||
| 1600 | 405 | |||
| VNbMoTaW | 600 | 1246 | 13 | [19] |
| 800 | 862 | 17 | ||
| 1000 | 846 | 19 | ||
| 1200 | 735 | 7.5 | ||
| 1400 | 656 | |||
| 1600 | 477 | |||
| Hf0.25NbTaW0.5 | 1000 | 584 | >50 | [23] |
| 1200 | 577 | >50 | ||
| 1400 | 455 | >50 | ||
| C0.25Hf0.25NbTaW0.5 | 1000 | 868 | >50 | [23] |
| 1200 | 792 | >50 | ||
| 1400 | 749 | >50 | ||
| Re0.1Hf0.25NbTaW0.4Cr0.25 | 1000 | 811 | 26.5 | [24] |
| 1200 | 744 | 32.1 | ||
| 1450 | 759 | >35 | ||
| 1700 | 382 | >40 | ||
| AlMo0.5NbTiV | 800 | 637 | 13.6 | [25] |
| AlMo0.5NbTiVSi0.5 | 800 | 1428 | 7.8 | [25] |
| 1000 | 390 | >35 | ||
| AlMo0.5NbTiVSi0.1 | 1000 | 258 | >35 | [25] |
| AlMo0.5NbTiVSi | 1000 | 390 | >35 | [25] |
| MoNbTaTi | 600 | 592 | [26] | |
| HfNbTaTi | 600 | 472 | [26] | |
| TiNbMoTaW | 600 | 689 | 36 | [27] |
| 800 | 674 | 48.4 | ||
| 1000 | 620 | 36.9 | ||
| 1200 | 586 | 11.9 | ||
| (TiNbZr)89(AlTa)11 | 600 | 625 | 70 | [28] |
| 800 | 210 | 70 | ||
| HfMoTaTiZr | 800 | 1045 | 19 | [29] |
| 1000 | 855 | >30 | ||
| 1200 | 404 | >30 | ||
| HfMoNbTaTiZr | 800 | 1007 | 23 | [29] |
| 1000 | 814 | >30 | ||
| 1200 | 556 | >30 | ||
| AlNbTiV | 600 | 780 | 14.3 | [30] |
| 800 | 560 | >50 | ||
| AlNbTiVZr0.1 | 600 | 975 | 5.1 | [30] |
| 800 | 865 | >50 | ||
| AlNbTiVZr1.5 | 600 | 1195 | 0 | [30] |
| 800 | 180 | >50 | ||
| NbTaTiV | 700 | 667 | >40 | [31] |
| 800 | 580 | >40 | ||
| 900 | 540 | >40 | ||
| 1000 | 437 | >40 | ||
| HfMoScTaZr | 800 | 1118 | 35 | [32] |
| 1000 | 963 | >42 | ||
| 1200 | 498 | >42 | ||
| CrNbTiVZr | 600 | 795 | 0 | [33] |
| 800 | 440 | >50 | ||
| 1000 | 95 | >50 | ||
| AlCrNbTiVZr | 600 | 620 | 0 | [33] |
| 800 | 1250 | 0.3 | ||
| 1000 | 305 | >50 | ||
| AlMo0.5NbTa0.5TiZr | 800 | 1597 | 11 | [34] |
| 1000 | 745 | >50 | ||
| 1200 | 250 | >50 | ||
| Al0.4Hf0.6NbTaTiZr | 800 | 796 | >50 | [34] |
| 1000 | 298 | >50 | ||
| 1200 | 89 | >50 | ||
| VNbMoTa | 1000 | 811 | >25 | [35] |
| Nb45Mo15Ta20W10Ti10 | 1100 | 549 | >50 | [36] |
| 1100 | 516 | >40 | ||
| W30Ta30Mo15Nb15C10 | 1600 | 896 | >40 | [37] |
| MoNbWTaC | 1000 | 1270 | >20 | [38] |
| 1400 | 890 | >30 |
2.2 轻质高熵合金
表 2 典型轻质高熵合金的成分、制备方法和密度Table 2 Compositions,fabrication methods,and density of typical light weight high-entropy alloys |
| Type | Alloy | Preparation method | Density/ (g·cm−3) | Reference |
| Low-density LWHEAs | MgCaAlLiCu | Induction melting (IM) | 2.2 | [53] |
| Mg43 (MnAlZnCu)67 | IM | 2.4 | [53] | |
| Mg45.6 (MnAlZnCu)54.4 | Arc melting (AM) | 2.2 | [54] | |
| Mg30Al25Ti25Li15Si5 | Mechanical alloying (MA) | 1.71 | [55] | |
| Al50Ca5Cu5Ni10Si20Ti10 | IM | 3.3 | [53] | |
| AlLi0.5MgCu0.5Sn0.2 | AM | 3.91 | [54] | |
| Al20Li20Mg10Sc20Ti30 | MA | 2.67 | [56] | |
| Al65Cu5Cr5Si15Mn5Ti5 | IM | 3.73 | [57] | |
| Al80Li5Mg5Zn5Sn5 | IM | 3.05 | [57] | |
| Al80Li5Mg5Zn5Cu5 | IM | 3.08 | [57] | |
| AlLi0.5MgZn0.5Sn0.2 | IM | 3.22 | [57] | |
| AlLi0.5MgZn0.5Cu0.2 | IM | 3.69 | [57] | |
| AlMgZnCuSi | AM | 3.3 | [58] | |
| Mg33 (MnAlZnCu)77 | IM | 3.7 | [59] | |
| Al35Cu5Fe5Mn5Si30V10Zr10 | IM | 3.96 | [60] | |
| LWHEAs based on 3d transition elements | Al45Cu15Fe5Mn5Si5Ti5Zn20 | AM | 5.16 | [61] |
| Al60Cu10Fe10Cr5Mn5Ni5Mg5 | AM | 4.71 | [61] | |
| AlCrFeMnTi0.25 | AM | 5.87 | [61] | |
| Al1.5CrFeMnTi | MA+spark plasma sintering (SPS) | 5.79 | [62] | |
| Al2CrFeMnTi0.25 | MA+SPS | 5.37 | [62] | |
| Al3CrFeMnTi0.25 | MA+SPS | 4.91 | [62] | |
| AlFeCuCrMg1.7 | MA+vacuum hot pressing (VHP) | 4.93 | [63] | |
| Al2CrFeMnTi | MA+VHP | 5.1 | [63] | |
| Al1.5CrFeMnTi | AM | 5.31 | [64] | |
| Lightweight RHEAs | Al2NbTi3V2Zr0.4 | IM | 5.07 | [60] |
| Al2NbTi3V2Zr0.2 | AM | 5.06 | [61] | |
| Al2NbTi3V2Zr0.6 | AM | 5.31 | [61] | |
| Al2NbTi3V2 | MA+VHP | 5.02 | [63] | |
| Al2NbTi3V2Zr0.8 | MA+VHP | 5.18 | [63] | |
| Al2NbTi3V2Zr | MA+VHP | 5.21 | [63] | |
| AlTiVCr | AM | 5.06 | [65] | |
| Al20Cr10Nb15Ti20V25Zr10 | AM | 5.55 | [66] | |
| AlNbTiV | AM | 5.59 | [67-69] | |
| AlCr0.5NbTiV | AM | 5.71 | [68] | |
| AlCrNbTiV | AM | 5.82 | [68] | |
| AlCr1.5NbTiV | AM | 5.9 | [68] | |
| Al0.8NbTiV | AM | 5.61 | [69] | |
| Al0.8NbTiVCo0.2 | AM | 5.84 | [69] | |
| Al0.8NbTiVNi0.2 | AM | 5.84 | [69] | |
| AlNbTiZr | AM | 5.74 | [70] | |
| Ti30Al20V20Nb20Mo10 | AM | 5.88 | [71] | |
| Ti60 (AlVCr)40 | IM | 4.71 | [72] | |
| TiNbAl0.5V0.5 | AM | 5.94 | [73] |
2.2.1 低密度轻质高熵合金
2.2.2 3d过渡族轻质高熵合金
2.2.3 轻质难熔高熵合金
图 3 (Zr0.5Ti0.35Nb0.15)100-xAlx(x=10和20)轻质难熔高熵合金与其他高熵和非晶合金的室温比强度-拉伸应变(a)和比强度-密度(b)的对比[78]Fig.3 Comparison of room temperature specific strength-tensile strain (a) and specific strength-density (b) between (Zr0.5Ti0.35Nb0.15)100-xAlx (x=10 and 20) lightweight RHEAs and other HEAs and amorphous alloys[78] |
2.3 共晶高熵合金
表 3 典型共晶高熵合金的成分、相组成和形貌Table 3 Compositions,phase compositions,and morphologies of typical eutectic high-entropy alloys |
| Alloy | Phase composition | Eutectic morphology | Reference |
| AlCoCrFeNiNbx | BCC+HCP | Lamellar | [84] |
| Al1.2CrCuFeNi2 | FCC+B2 | Rod-shaped | [85] |
| AlCoCrCuFeNiMo0.4 | FCC+α | Lamellar | [86] |
| AlCrFeNiMo0.2 | FCC+B2 | Lamellar | [87] |
| AlCrFeNi | BCC+B2 | Lamellar | [87] |
| CoCrFeNiNb0.65 | FCC+Laves | Lamellar | [88] |
| AlCoCrFeNi2.1 | FCC+B2 | Lamellar | [89] |
| CoFeNi2V0.5Nb0.75 | FCC+Laves | Lamellar | [90] |
| CoFeNiVMo0.6 | FCC+IM | Lamellar | [91] |
| CoFeNi1.4VMo | FCC+IM | Lamellar | [91] |
| CoCrFeMnNbNi | FCC+Laves | Lamellar | [92] |
| Nb25Sc25Ti25Zr25 | HCP+BCC | Lamellar | [93] |
| CoCrFeNiZr0.5 | FCC+Laves | Lamellar | [94] |
| Al17Co14.3Cr14.3Fe14.3Ni40.1 | FCC+BCC | Lamellar | [95] |
| Al17Co28.6Cr14.3Fe14.3Ni25.8 | FCC+BCC | Lamellar | [95] |
| Al17Co14.3Cr14.3Fe28.6Ni25.8 | FCC+BCC | Lamellar | [95] |
| CoCrFeNiTa0.4 | FCC+Laves | Lamellar | [96] |
| CoCrFeNiNb0.45 | FCC+Laves | Lamellar | [97] |
| Co2Mo0.8Ni2VW0.8 | FCC+μ | Lamellar | [98] |
| Zr0.6CoCrFeNi2.0 | FCC+Ni7Zr2 | Lamellar | [99] |
| Nb0.74CoCrFeNi2.0 | FCC+(Co,Ni)2Nb | Lamellar | [99] |
| Hf0.55CoCrFeNi2.0 | FCC+Ni7Hf2 | Lamellar | [99] |
| Ta0.65CoCrFeNi2.0 | FCC+(Co,Ni)2Ta | Lamellar | [99] |
| Ni25Fe25.3Cr15Co10V10Mn10Nb9.7 | FCC+Laves | Lamellar | [100] |
| Al9Cr12Fe20V12Ni47 | FCC+BCC | Needle-shaped | [101] |
| Al1.05CoCrFeNi3Ti0.2 | FCC+BCC | Lamellar | [102] |
| Al0.75CoCrFeNi3Ti0.5 | FCC+BCC | Petal-shaped | [102] |
| Ni49Fe28Al17V6 | FCC+B2 | Lamellar | [103] |
| CoCrFeNiNb0.45 | FCC+HCP | Lamellar | [104] |
2.4 航空航天典型结构材料与高熵合金对比分析
表 4 镍基高温合金、钛合金与典型高熵合金的对比Table 4 Comparison of Ni-based superalloys,titanium alloys and typical high-entropy alloys |
| Alloy | Density/(g·cm−3) | Temperature bearing capacity/℃ | Mechanical property | Advantage | Limitation |
| Ni-based superalloys | 8.2-9.0 | 600-1100 | High high-temperature strength | High- temperature stability,high oxidation/creep resistance | High density,high cost |
| Titanium alloys | 4.3-4.8 | 300-600 | Moderate specific strength | Light weight,corrosion resistance | Limited service temperature (<600 ℃) |
| RHEAs | >8.0 | 1000-1600 | High high-temperature strength, exceptional resistance to heat softening | Applications demanding elevated temperature | Large density,brittleness,fabrication |
| LWHEAs | ≤6.0 | 300-800 | High specific strength | Light weight,high specific strength | Limited high-temperature stability |
| EHEAs | 6.5-8.5 (depends on the matrix elements) | 700-1000 | Excellent synergy of strength and ductility | Good casting ability | Limited chemical compositions |
3 高熵合金的国际研发态势与战略规划
3.1 北美地区
表 5 美国国防部高级研究计划局ULTIMATE专项部分资助项目[111]Table 5 Partial projects of ULTIMATE program funded by advanced research projects agency-energy[111] |
| Project | Project undertaker | Funding amount/104 USD |
| Computationally guided oxide dispersion-strengthened refractory HEAs via additive manufacturing | Raytheon Technologies | 120 |
| High-throughput computational guided development of refractory complex concentrated alloys-based composite | West Virginia University | 109 |
| High entropy rare-earth oxide (HERO) coatings for refractory alloys | University of Virginia | 103 |
| Designing novel multicomponent niobium alloys for high temperature:integrated design,rapid processing and validation approach | The University of Utah | 369 |
| Concurrent design of a multimaterial niobium alloy system for next-generation turbine applications | QuesTek Innovations | 315 |
| Additive manufacturing of ultrahigh temperature refractory metal alloys | University of Wisconsin-Madison | 110 |
| Rapid design and manufacturing of high-performance materials for turbine blades applications above 1300 degrees celsius | National Energy Technology Laboratory | 118 |
| Design and manufacturing of ultrahigh temperature refractory alloys | Pennsylvania State University | 401 |
| Development of niobium-based alloys for turbine applications | Oak Ridge National Laboratory | 110 |
| Ultra-high performance metallic turbine blades for extreme environments | Boeing Company | 183 |
| Research content | Expected time | Expected funds |
| A specific search strategy to explore Refractory HEAs and high entropy ceramics (HECs) for two-to-three DoD-relevant high-temperature structural applications | 1 year | 106 USD |
| Develop new synthesis methodologies for establishing HEA materials libraries | 3 years | 5×106 USD |
| Develop post-synthesis thermomechanical processing techniques | 2 years | 3×106 USD |
| Design an autonomous materials research (AMR) platform for HEAs | 5 years | 107 USD |
| Establish high-temperature, high-throughput tests | 2-10 years | 6×106-107 USD |
| Establish a database and common data schema and infrastructure for high-throughput HEA data | 1 year | 106 USD |
| Develop validated machine learning (ML) models for phase and properties predictions | 3-10 years | 107 USD |
| Engage in Feedstock Production and Scalability Research | Sustained investment | 106 USD/year |
3.2 欧洲地区
表 7 德国科学基金复杂成分合金-高熵合金专项部分资助项目[113]Table 7 Partial projects funded by the special program for complex composition alloys-high-entropy alloys of German research foundation[113] |
| Project | Project undertaker |
| Design and mechanical properties of compositionally complex alloys from twinning-induced towards bidirectional transformation-induced plasticity | Max Planck Institute for Sustainable Materials and Ruhr University Bochum |
| Phase stability,precipitation kinetics,nanoscale elemental distributions and their effect on tensile properties in refractory TiZrNbHfTa BCC high-entropy alloys | Ruhr University Bochum |
| Polycrystalline high entropy superalloys (PHESA)-combining novel strengthening mechanisms in compositionally complex CoNiCr-based superalloys with a large fraction of multicomponent intermetallic precipitates | University of Erlangen-Nurnberg |
| Tailored precipitation (B2,L21) strengthened,compositionally complex FeAlCr (Mn,Co,Ni,Ti) alloys for high temperature applications | Ruhr University Bochum,University of Erlangen-Nurnberg,and RWTH Aachen University |
| Mechanical properties and hydrogen tolerance of particle-reinforced CCA produced by additive manufacturing | Max Planck Institute for Sustainable Materials and University of the Bundeswehr Munich |
| Development of refractory metal-based CCAs with improved mechanical properties | University of Siegen and Karlsruhe Institute of Technology |
| Thermomechanical properties and microstructure of FCC and BCC high-entropy alloys | University of Muenster and Technical University of Darmstadt |
| Deformation mechanisms in FCC and BCC high entropy alloys under various conditions | Ruhr University Bochu and Karlsruhe Institute of Technology |
3.3 亚洲地区
4 高熵合金的工程化应用前景与挑战
图 6 钢、镍基高温合金、FCC-HEAs和BCC-HEAs(主要为难熔高熵合金)发展可持续性对比[118] (a)售价;(b)供应风险;(c)供应受限归一化脆弱性;(d)内含能;(e)用水量;(f)矿盐金属比;(g)人体健康损害;(h)人权压力;(i)劳工权益压力Fig.6 Sustainability comparison of steels,Ni-based superalloys,FCC-HEAs,and BCC-HEAs (mainly refractory HEAs) [118] (a) mass price;(b) supply risk;(c) normalized vulnerability to supply restriction;(d) embodied energy;(e) water usage;(f) rock to metal ratio;(g) human health damage;(h) human rights pressure;(i) labor rights pressure |
