高熵合金及其他高熵材料研究新进展

王晓鹏; 孔凡涛

doi:10.11868/j.issn.1005-5053.2019.000170

高熵合金及其他高熵材料研究新进展

doi: 10.11868/j.issn.1005-5053.2019.000170

王晓鹏^1,2,
孔凡涛^1, ,

1.
哈尔滨工业大学材料科学与工程学院，哈尔滨 150001
2.
哈尔滨工业大学分析测试中心，哈尔滨 150001

基金项目: 国家自然科学基金项目（51971074）

详细信息

通讯作者:
孔凡涛（1971—），男，博士，教授，主要研究方向为钛合金、钛铝合金及高熵金属间化合物材料，（E-mail）kft@hit.edu.cn

中图分类号: TG176
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- 被引次数: 0
出版历程
- 收稿日期: 2019-09-04
- 修回日期: 2019-11-06
- 网络出版日期: 2019-11-14
- 刊出日期: 2019-12-01

Resent development in high-entropy alloys and other high-entropy materials

Xiaopeng WANG^1,2,
Fantao KONG^{1
, ,}

1.
School of Materials Science and Engineering，Harbin Institute of Technology，Harbin 150001，China
2.
Center of Analysis and Measurement，Harbin Institute of Technology，Harbin 150001，China

摘要

摘要: 高熵材料是一类由多种元素以等摩尔比或近等摩尔比组成的新型多主元材料，打破了传统的材料设计理念。高熵材料以其独特的晶体结构特征，表现出许多不同于传统材料的组织和性能特点。目前国内外已经研发出多种高熵材料，在力学、物理和化学性能等方面具有独特的优势，在很多领域具有巨大的应用潜力，已经成为国际材料学术界的重要研究热点之一。本文从高熵材料的设计理念出发，主要综述了高熵合金、高熵陶瓷、高熵金属间化合物等高熵材料的最新研究进展，总结了不同高熵材料的结构特征、组织性能及强化机制，并对高熵材料的发展趋势进行了展望。高通量计算与制备将成为设计这类多主元材料的重要快捷手段，随着材料的进步，高熵材料成形加工技术必将快速发展以满足其多元化应用需求。
- 高熵材料 /
- 高熵合金 /
- 显微组织 /
- 性能 /
- 高熵金属间化合物
Abstract: High-entropy (HE) materials are defined as novel multi-principal materials that contain several principal elements (usually ≥ 5) in an (equa) equi-molar ratio, and the design concept of HE materials introduces a new way to improve the properties of materials. Due to their unique crystallographic structure characteristics, HE materials show many different characteristics of microstructures and properties compared with conventional materials .The HE materials have great potential applications in many fields. At present, many kinds of high-entropy materials were prepared with excellent properties in mechanics, physics or chemistry, such as high strength and elongation, distinguished thermal stability, wear resistance, magnetic, conductivity and corrosion resistance. This paper reviews the recent research and development of high-entropy alloys, high-entropy ceramics and high-entropy intermetallics, and summarizes their structure characteristics, microstructures, properties and strengthening mechanisms. In the future, high throughput calculation and preparation will be an important and fast way to design this kind of multi-component materials. With the development of materials, the forming and processing technologies of high entropy materials will develop rapidly to meet their diversified application needs.
- high-entropy materials /
- high-entropy alloys /
- microstructure /
- property /
- high-entropy intermetallics

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图 1 部分常见过渡元素高熵合金、316不锈钢、Inconel600和Incoloy800合金的拉伸性能对比^[4]　（a）屈服强度随温度变化；（b）抗拉强度随温度变化；（c）伸长率随温度变化

Figure 1. Tensile properties comparison of transition metal high entropy alloys，316 stainless steel，Inconel600 and Incoloy800 alloys^[4]　（a） yield strength vs temperature；（b） ultimate strength vs temperature；（c） tensile ductility vs temperature

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图 2 合金中元素间交互作用参数（Ω）和原子尺寸差（δ）与合金晶体结构之间的关系^[31]

Figure 2. Relationship between parameters Ω and δ for high entropy alloys^[31]

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图 3 常见高熵合金VEC与FCC、BCC相之间的关系^[20]

Figure 3. Relationship between VEC and the FCC，BCC phase stability for common HEA systems^[20]

Note on the legend： fully closed symbols for sole fcc phases；fully open symbols for sole bcc phase；top-half closed symbols for mixes fcc and bcc phases

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图 4 Nb₂₅Mo₂₅Ta₂₅W₂₅和V₂₀Nb₂₀Mo₂₀Ta₂₀W₂₀高熵合金与Inconel 718和Haynes 230高温合金不同温度下的屈服强度^[34]

Figure 4. Temperature dependence of yield stress of Nb₂₅Mo₂₅Ta₂₅W₂₅ and V₂₀Nb₂₀Mo₂₀Ta₂₀W₂₀ HEAs and two superalloys，Inconel 718 and Haynes^[34]

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图 5 TiZrHfNb、（TiZrHfNb） ₉₈O₂和（TiZrHfNb） ₉₈N₂与其他合金性能对比^[45]　（a）高熵合金室温拉伸性能曲线；（b）高熵合金强度和伸长率与典型高性能合金对比

Figure 5. RT tensile properties of TiZrHfNb，（TiZrHfNb） ₉₈O₂ and （TiZrHfNb） ₉₈N₂^[45]　（a）RT tensile properties curves of HEAs；（b） changes in strength and ductility HEAs，relative to several types of high-performance alloys

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图 6 （FeCoNiCr）₉₄Ti₂Al₄高熵合金显微组织与拉伸性能^[47]　（a）析出增强相与基体的界面高分辨TEM图；（b）FeCoNiCr高熵合金与析出相强化高熵高温合金拉伸性能

Figure 6. Microstructure and tensile properties of （FeCoNiCr）₉₄Ti₂Al₄ HEAs^[47]　（a）high-resolution TEM image showing the interface between one single nano-particle and fcc matrix，with relative FFT patterns；（b）tensile properties of alloys A，B，P1 and P2 at room temperature

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图 7 AlMo_0.5NbTa_0.5TiZr高熵高温合金晶粒内部的双相网篮层状结构^[52]

Figure 7. High magnification SEM/BSE images of a two-phase basket-weave lamellar structure in AlMo_0.5NbTa_0.5TiZr refractory high entropy superalloy^[52]

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图 8 Al_2.2CrCuFeNi₂共晶高熵合金的花朵状显微组织^[55]　（a）花朵状显微组织；（b）向日葵状显微组织；（c）菊花状显微组织

Figure 8. Flower-like microstructures in Al_2.2CrCuFeNi₂ eutectic high entropy alloy^[55]　（a） flower-like microstructures；（b） sunflower-like microstructure in region A in （a）；（c） chrysanthemum-like microstructure

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图 9 典型共晶高熵合金与NiAl基合金力学性能对比^[56]　（a）室温拉伸性能；（b）高温强度；（c）断裂应力与屈服应力之比

Figure 9. Comparison of mechanical properties between AlCoCrFeNi_2.1 EHEA and non-EHEAs，comprising NiAl-base alloys^[56]（a） room-temperature tensile properties；（b） high-temperature strength；（c） ratio of fracture stress to yield stress （proof stress）

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图 10 Sr₂₀Ca₂₀Yb₂₀（Li_0.55Mg_0.45）₂₀Zn₂₀高熵非晶合金杨氏模量和剪切模量与系列非晶合金比较^[72，75]

Figure 10. Comparison of Young’s modulus and shear modulus of a series of MGs and Sr₂₀Ca₂₀Yb₂₀（Li_0.55Mg_0.45）₂₀Zn₂₀ HEBMG^[72,75]

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图 11 高熵金属二硼化物晶体结构模型^[89]

Figure 11. Crystal structure model of high-entropy metal diborides^[89]

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图 12 Mg_0.2Co_0.2Ni_0.2Cu_0.2Zn_0.2O高熵氧化物陶瓷XRD图谱　（a），N组分固溶体计算构型熵与第N组元的摩尔百分比的函数（b），预期最大构型熵的等摩尔组成（c~g）^[90]

Figure 12. X-ray diffraction analysis for a composition series Mg_0.2Co_0.2Ni_0.2Cu_0.2Zn_0.2O　（a），calculated configurational entropy in an N-component solid solutions as a function of mol% of the N^th component（b），and partial phase diagrams showing the transition temperature to single phase as a function of composition （solvus） in the vicinity of the equimolar composition where maximum configurational entropy is expected（c-g）

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图 13 L1₂结构高熵金属间化合物晶体结构模型^[95]　（a）第I类高熵金属间化合物；（b）第II类高熵金属间化合物；（c）第Ⅲ类高熵金属间化合物

Figure 13. Crystal structure model of L1₂ structure high entropy intermetallics^[95]　（a） I type high entropy intermetallics；（b） II type high entropy intermetallics；（c） III type high entropy intermetallics

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图 15 D0₁₉结构高熵金属间化合物晶体结构模型^[95]　（a）第I类高熵金属间化合物；（b）第II类高熵金属间化合物；（c）第Ⅲ类高熵金属间化合物

Figure 15. Crystal structure model of D0₁₉ structure high entropy intermetallics^[95]　（a） I type high entropy intermetallics；（b） II type high entropy intermetallics；（c） III type high entropy intermetallics

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图 14 B2结构高熵金属间化合物晶体结构模型^[95]　（a）第I类高熵金属间化合物；（b）第II类高熵金属间化合物

Figure 14. Crystal structure model of B2 structure high entropy intermetallics^[95]　（a） I type high entropy intermetallics；（b） II type high entropy intermetallics

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表 1 过渡元素高熵合金拉伸性能及晶体结构^{[3-4，6，24-29，31]}

Table 1. Tensile properties and crystal structure of transition metal high entropy alloys^{[3-4，6，24-29，31]}

Alloy composition	Microstructure and processing	T/℃	σ_0.2/MPa	σ_b/MPa	δ/%	HV
Al_0.3CoCrFeNi	FCC + L1₂，as-cast	23	310	525	44	480
Al_0.5CoCrCu_0.5FeNi₂	FCC + L1₂，as-cast	23	215	489	39
Al_0.5CoCrCu_0.5FeNi₂	FCC + L1₂，as-cast	500	215	248	6
AlCoCrCuFeMo_0.6Ni	BCC，as-cast	23	1880^C	2820^C	1.4^C	496
Al₂₀TiVCrMnFeCoNiCu	BCC + FCC，as-cast	23	1465^C	2010^C	2.4^C	560
AlCoCrFeNiTi_0.5	BCC，as-cast	23	2260^C	3140^C	22^C	200
Al_0.5CoCrCuFeNi	FCC + L1₂，as-cast	23	360	707	19	208
	FCC + FCC， HT + cold rolling	23	650	790	25	399
		300	460	600	6	420
		400	500	590	4	440
		500	430	450	2	490
		600	270	310	3	460
		700	170	190	13	450
Al_0.5CrCuFeNi₂	FCC + FCC， Cold rolling + annealing	23	704	1088	5.6
AlCoCrCuFeNi	BCC + FCC + B2 + L1₂，as-cast	20	790	790	0.2	440
		600	551	648	0.4
		700	350	360	4.7
		800	161	180	12.1
		900	88	100	30
		1000	37	44	77
AlCoCrFeNb_0.25Ni	FCC + BCC，as-cast	23	1959^C	3008^C	10.5^C
Al_xCoCrFeMnNi	BCC + FCC，as-cast	23	800	1150	6	400
CoCrFeMnNi	FCC， Cold rolling + annealing	–196	571	1099	72
		23	362	651	51	170
		400	267	493	32
		600	241	423	42
		800	127	145	51
CoCrFeNi	FCC， Cold rolling + annealing	–196	473	1170	50
		–70	328	917	44
		23	273	714	38	200
		200	215	582	34	115
		400	195	496	28
CoCrMnNi	FCC， Cold rolling + annealing	–196	499	1283	62
		–70	357	1006	54
		23	280	699	43
		200	215	582	36
		400	186	555	28
CoFeMnNi	FCC， Cold rolling + annealing	–196	300	835	48
		–70	210	656	44
		23	175	551	41
		200	135	488	36
		400	116	465	37
CuCoNiCrFe	FCC，as-cast	23	230^C			133
TiZrNbMoV_x	As-cast	23	1500^C	3500^C	20^C
*Superscript C represents compression mechanical properties，and the rest are tensile mechanical properties.

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表 2 部分难熔高熵合金组织结构、密度及力学性能^{[4，11，34-41]}

Table 2. Mechanical properties，density and crystal structure of some refractory high-entropy alloys^{[4，11，34-41]}

Alloy composition	Microstructure and processing	ρ/（g•cm^–3）	T/℃	σ_0.2/MPa	δ/%
Al_0.4Hf_0.6NbTaTiZr	BCC	9.05	23	1841	10
			800	796	> 50
			1000	298	> 50
AlMo_0.5NbTa_0.5TiZr	BCC + B2	7.40	23	2000	10
			800	1597	11
			1000	745	> 50
			1200	255	> 50
Al_0.25NbTaTiV	BCC	8.80	23	1330	> 50
Al_0.5NbTaTiV	BCC	8.46	23	1012	> 50
AlNbTaTiV	BCC	7.89	23	991	> 50
Al_0.3NbTa_0.8Ti_1.4V_0.2Zr_1.3	BCC	7.78	25	1965	5
			800	678	> 50
			1000	166	> 50
AlNb_1.5Ta_0.5Ti_1.5Zr_0.5	BCC	6.88	25	1280	3.5
			800	728	30
			1000	403	> 50
AlNbTiV	BCC	5.59	22	1020	5
			600	810	12
			800	685	> 50
			1000	158	> 50
HfMoNbTiZr	BCC	8.69	23	1575	9
			800	825	> 50
			1000	635	> 50
			1200	187	> 50
HfNbTaTiZr	BCC	9.94	23	929	> 50
			600	675	> 50
			800	535	> 50
			1000	295	> 50
			1200	92	> 50
	BCC， Cold rolling + HT		25	1145^T	9.7^T
HfNbTiVZr	BCC	8.06	25	1170	30
HfNbTiZr	BCC	8.40	25	879^T	14.5^T
MoNbTaVW	BCC	12.36	23	1246	1.7
			600	862	13
			800	846	17
			1000	842	19
			1200	735	7.5
			1400	656	18
			1600	477	13
NbTiVZr	BCC	6.5	25	1105	> 50
			600	248	> 50
			800	187	> 50
			1000	58	> 50
NbTiV₂Zr	BCC	6.38	25	918	> 50
			600	571	> 50
			800	240	> 50
			1000	72	> 50
CrNbTiVZr	BCC + Laves	6.52	25	1298	3
			600	1230	20
			800	615	> 50
			1000	259	> 50
CrNbTiZr	BCC + Laves	6.67	23	1280
CrMo_0.5NbTa_0.5TiZr	BCC + Laves	8.23	23	1595	5
			800	983	5.5
			1000	546	> 50
			1200	170	> 50
TiZrHfNbCr	BCC + Laves	8.24	23	1375
*Superscript T represents tensile mechanical properties，and the rest are compression mechanical properties.

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