BCC/B2基难熔高熵合金的组织与性能研究进展

doi:10.13251/j.issn.0254-6051.2025.04.002

摘要/Abstract

摘要： 难熔高熵合金是由高熔点的前过渡族元素混合而成的具有简单晶体结构的复杂成分合金。从其成分特点出发,将难熔高熵合金体系进行分类,详细综述了其成分、相组成、组织特性、性能(力学性能和功能性)。大多数难熔高熵合金以BCC/B2为基,具有优异的力学性能、良好的抗辐照性能、抗氧化性能、阻尼性能以及含能特性等,表现出作为结构功能一体化材料应用的巨大潜力,有望在核反应堆、航空航天、能源化工、机械电子等领域得到应用。尤其是一些难熔高熵合金具有高熔点、优异的高温组织稳定性和高温力学性能,展现出巨大的高温应用价值。此外,针对难熔高熵合金所面临的主要问题和挑战,对其发展和应用前景进行了展望。

关键词: 难熔高熵合金, 成分设计, 组织, 性能调控

Abstract: Refractory high entropy alloys, as complex-composition alloys with simple crystalline structures, consist of a mixture of early transition metals with high melting points. The refractory high-entropy alloy systems are classified based on the compositional characteristics, and the composition, phase constituents, microstructure and multiple properties (mechanical and functional) are reviewed in detail. Most of the refractory high entropy alloys are BCC/B2-based alloys and possess excellent mechanical properties, good irradiation resistance, prominent oxidation resistance, damping capability, energetic performance and so on, showing great potential for application as structural-functional integrated materials, and are expected to be applied in the fields of nuclear reactor, aerospace, energy and chemical industry and machinery and electronics. Particularly, some refractory high entropy alloys show great value for high-temperature applications due to the high melting point, excellent high-temperature microstructural stability and high-temperature mechanical properties. Finally, the main problems and challenges faced by refractory high entropy alloys are introduced, and the prospects for their development and application are prospected.

Key words: refractory high entropy alloys, composition design, microstructure, property modulation

中图分类号:

TG132.3⁺2

王镇华, 刘海洋, 王瑞, 高直, 唐丽娜, 王清. BCC/B2基难熔高熵合金的组织与性能研究进展[J]. 金属热处理, 2025, 50(4): 9-18.

Wang Zhenhua, Liu Haiyang, Wang Rui, Gao Zhi, Tang Lina, Wang Qing. Research progress on microstructure and properties of BCC/B2-based refractory high entropy alloys[J]. Heat Treatment of Metals, 2025, 50(4): 9-18.

参考文献

[1] Yeh J W, Chen S K, Lin S J, et al. Nanostructured high-entropy alloys with multiple principal elements: Novel alloy design concepts and outcomes[J]. Advanced Engineering Materials, 2004, 6: 299-303.
[2] Miracle D B, Senkov O N. A critical review of high entropy alloys and related concepts[J]. Acta Materialia, 2017, 122: 448-511.
[3] George E P, Raabe D, Ritchie R O. High-entropy alloys[J]. Nature Reviews Materials, 2019, 4: 515-534.
[4] 骆再斌, 范子泽, 彭振. 轻质高熵合金的研究进展[J]. 金属热处理, 2022, 47(4): 100-108.
Luo Zaibin, Fan Zize, Peng Zhen. Research progress of light-weight high-entropy alloys[J]. Heat Treatment of Metals, 2022, 47(4): 100-108.
[5] Ma Y, Zhou X Y, Hao J M, et al. A novel soft-magnetic B2-based multiprincipal-element alloy with a uniform distribution of coherent body-centered-cubic nanoprecipitates[J]. Advanced Materials, 2021, 33: 2006723.
[6] Wang Z H, Yuan J H, Wang Q, et al. Developing novel high-temperature soft-magnetic B2-based multi-principal-element alloys with coherent body-centered-cubic nanoprecipitates[J]. Acta Materialia, 2024, 266: 119686.
[7] Lei Z F, Wu Y, He J Y, et al. Snoek-type damping performance in strong and ductile high-entropy alloys[J]. Science Advances, 2020, 6: eaba7802.
[8] Wei P C, Liao C N, Wu H J, et al. Thermodynamic routes to ultralow thermal conductivity and high thermoelectric performance[J]. Advanced Materials, 2020, 32: 1906457.
[9] Senkov O N, Miracle D B, Chaput K J. Development and exploration of refractory high entropy alloys—A review[J]. Journal of Materials Research, 2018, 33(19): 3092-3128.
[10] Rao S I, Akdim B, Antillon E, et al. Modeling solution hardening in BCC refractory complex concentrated: NbTiZr, Nb_1.5TiZr_0.5 and Nb_0.5TiZr_1.5[J]. Acta Materialia, 2019, 168: 222-236.
[11] Senkov O N, Wilks G B, Scott J M, et al. Mechanical properties of Nb₂₅Mo₂₅Ta₂₅W₂₅ and V₂₀Nb₂₀Mo₂₀Ta₂₀W₂₀ refractory high entropy alloys[J]. Intermetallics, 2011, 19(5): 698-706.
[12] Senkov O N, Wilks G B, Miracle D B, et al. Refractory high-entropy alloys[J]. Intermetallics, 2010, 18: 1758-1765.
[13] Zhang J, Hu Y, Wei, Q, et al. Microstructure and mechanical properties of Re_xNbMoTaW high-entropy alloys prepared by arc melting using metal powders[J]. Journal of Alloys and Compounds, 2020, 827: 154301.
[14] Das S, Robi P S. Mechanical alloying of W-Mo-V-Cr-Ta high entropy alloys[J]. IOP Conference Series: Materials Science and Engineering, 2018, 346: 012047.
[15] Todai M, Nagase T, Hori T, et al. Novel TiNbTaZrMo high-entropy alloys for metallic biomaterials[J]. Scripta Materialia, 2017, 129: 65-68.
[16] Yao H W, Qiao J W, Gao M C, et al. NbTaV-(Ti, W) refractory high-entropy alloys: Experiments and modeling[J]. Materials Science and Engineering A, 2016, 674: 203-211.
[17] Zhang Y, Yang X, Liaw P K. Alloy design and properties optimization of high-entropy alloys[J]. JOM, 2012, 64: 830-838.
[18] Huang H L, Wu Y, He J M, et al. Phase-transformation ductilization of brittle high-entropy alloys via metastability engineering[J]. Advanced Materials, 2017, 29: 1701678.
[19] Komiya Y, Haginiwa D, Kogo Y, et al. Clarification of phase stability and oxidation mechanism for TiZrHfTaX (X=Ta, Cr) using thermodynamic calculation[J]. Materials Research Society Advances, 2022, 7: 841-847.
[20] Liu Y, Zhang Y, Zhang H, et al. Microstructure and mechanical properties of refractory HfMo_0.5NbTiV_0.5Si_x high-entropy composites[J]. Journal of Alloys and Compounds, 2017, 694: 869-876.
[21] Lin C M, Juan C C, Chang C H, et al. Effect of Al addition on mechanical properties and microstructure of refractory Al_xHfNbTaTiZr alloys[J]. Journal of Alloys and Compounds, 2015, 624: 100.
[22] Qiao D X, Jiang H, Chang X X, et al. Microstructure and mechanical properties of VTaTiMoAl_x refractory high entropy alloys[J]. Materials Science Forum, 2017, 898: 638-642.
[23] Senkov O N, Woodward C, Miracle D B. Microstructure and properties of aluminum-containing refractory high-entropy alloys[J]. Journal of Metals, 2014, 66: 2030-2042.
[24] Wang Q, Han J C, Liu Y F, et al. Coherent precipitation and stability of cuboidal nanoparticles in body-centered-cubic Al_0.4Nb_0.5Ta_0.5TiZr_0.8 refractory high entropy alloy[J]. Scripta Materialia, 2021, 190: 40-45.
[25] Jin D M, Wang Z H, Yuan J H, et al. High-strength and energetic Al₂Ti₆Zr₂Nb₃Ta₃ high entropy alloy containing a cuboidal BCC/B2 coherent microstructure[J]. Journal of Alloys and Compounds, 2023, 931: 167546.
[26] Senkov O N, Senkova S V, Woodward C. Effect of aluminum on the microstructure and properties of two refractory high-entropy alloys[J]. Acta Materialia, 2014, 68: 214-228.
[27] Liu X F, Tian Z L, Zhang X F, et al. “Self-sharpening” tungsten high-entropy alloy[J]. Acta Materialia, 2020, 186: 257-266.
[28] Li T, Liu T W, Zhao S T, et al. Ultra-strong tungsten refractory high-entropy alloy via stepwise controllable coherent nanoprecipitations[J]. Nature Communications, 2023, 14: 3006.
[29] Jiang H, Jiang L, Lu Y P, et al. Microstructure and mechanical properties of the W-Ni-Co system refractory high-entropy alloys[J]. Materials Science Forum, 2015, 816: 324-329.
[30] Senkov O N, Senkova S V, Woodward C, et al. Low-density, refractory multi-principal element alloys of the Cr-Nb-Ti-V-Zr system: Microstructure and phase analysis[J]. Acta Materialia, 2013, 61: 1545-1557.
[31] Wu Y D, Cai Y H, Wang T, et al. A refractory Hf₂₅Nb₂₅Ti₂₅Zr₂₅ high-entropy alloy with excellent structural stability and tensile properties[J]. Materials Letters, 2014, 130: 277-280.
[32] Senkov O N, Scott J M, Senkova S V, et al. Microstructure and elevated temperature properties of a refractory TaNbHfZrTi alloy[J]. Journal of Materials Science, 2012, 47: 4062-4074.
[33] Cui D C, Zhang Y Y, Liu L X, et al. Oxygen-assisted spinodal structure achieves 1.5 GPa yield strength in a ductile refractory high-entropy alloy[J]. Journal of Materials Science and Technology, 2023, 157: 11-20.
[34] Wang L, Ding J, Chen S S, et al. Tailoring planar slip to achieve pure metal-like ductility in body-centred-cubic multi-principal element alloys[J]. Nature Communications, 2023, 22: 950-957.
[35] Senkov O N, Woodward C F. Microstructure and properties of a refractory NbCrMo_0.5Ta_0.5TiZr alloy[J]. Materials Science and Engineering A, 2011, 529: 311-320.
[36] Yang C, Aoyagi K, Bian H K, et al. Microstructure evolution and mechanical property of a precipitation-strengthened refractory high-entropy alloy HfNbTaTiZr[J]. Materials Letters, 2019, 254: 46-49.
[37] Han Z D, Chen N, Zhao S F, et al. Effect of Ti additions on mechanical properties of NbMoTaW and VNbMoTaW refractory high entropy alloys[J]. Intermetallics, 2017, 84: 153-157.
[38] Wang Q, Li Z, Pang S J, et al. Coherent precipitation and strengthening in compositionally complex alloys: A review[J]. Entropy, 2018, 20: 878.
[39] Pan J Y, Dai T, Lu T, et al. Microstructure and mechanical properties of Nb₂₅Mo₂₅Ta₂₅W₂₅ and Ti₈Nb₂₃Mo₂₃Ta₂₃W₂₃ high entropy alloys prepared by mechanical alloying and spark plasma sintering[J]. Materials Science and Engineering A, 2018, 738: 362-366.
[40] Bu Y Q, Wu Y, Lei Z F, et al. Local chemical fluctuation mediated ductility in body-centered-cubic high-entropy alloys[J]. Materials Today, 2021, 46: 28-34.
[41] Senkov O N, Crossman B, Rao S I, et al. Mechanical properties of an Al₁₀Nb₂₀Ta₁₅Ti₃₀V₅Zr₂₀ A2/B2 refractory superalloy and its constituent phases[J]. Acta Materialia, 2023, 254: 119017.
[42] Guo N N, Wang L, Luo L S, et al. Microstructure and mechanical properties of refractory MoNbHfZrTi high-entropy alloy[J]. Materials and Design, 2015, 81: 87.
[43] 张平, 蒋丽, 杨金学, 等. 核用难熔高熵合金的研究进展[J]. 材料导报, 2022, 36(14): 5-26.
Zhang Ping, Jiang Li, Yang Jinxue, et al. Research progress in refractory high entropy alloys for nuclear applications[J]. Materials Reports, 2022, 36(14): 5-26.
[44] Sadeghilaridjani M, Muskeri S, Pole M, et al. High-temperature nano-indentation creep of reduced activity high entropy alloys based on 4-5-6 elemental palette[J]. Entropy, 2020, 22: 230.
[45] Kareer A, Waite J, Li B, et al. Short communication: ‘Low activation, refractory, high entropy alloys for nuclear applications’[J]. Journal of Nuclear Materials, 2019, 526: 151744.
[46] Chang S, Tseng K K, Yang T Y, et al. Irradiation-induced swelling and hardening in HfNbTaTiZr refractory high-entropy alloy[J]. Materials Letters, 2020, 272: 127832.
[47] Lu Y P, Huang H F, Gao X Z, et al. A promising new class of irradiation tolerant materials: Ti₂ZrHfV_0.5Mo_0.2 high-entropy alloy[J]. Journal of Materials Science and Technology, 2019, 35(3): 369-373.
[48] Ei-Atwani O, Li N, Li M, et al. Outstanding radiation resistance of tungsten-based high-entropy alloys[J]. Science Advances, 2019, 5: eaav2002.
[49] Byggmästar J, Nordlund K, Djurabekova F. Modeling refractory high-entropy alloys with efficient machine-learned interatomic potentials: Defects and segregation[J]. Physical Review B, 2021, 104: 104101.
[50] Lu C Y, Niu L L, Chen N J, et al. Enhancing radiation tolerance by controlling defect mobility and migration pathways in multicomponent single-phase alloys[J]. Nature Communications, 2016, 7: 13564.
[51] Xiao Y F, Kuang W H, Xu Y F, et al. Microstructure and oxidation behavior of the CrMoNbTaV high-entropy alloy[J]. Journal of Materials Research, 2019, 34: 301-308.
[52] Müeller F, Gorr B, Christ H J, et al. On the oxidation mechanism of refractory high entropy alloys[J]. Corrosion Science, 2019, 159: 108161.
[53] Chang C H, Titus M S, Yeh J W. Oxidation behavior between 700 and 1300 ℃ of refractory TiZrNbHfTa high-entropy alloys containing aluminum[J]. Advanced Engineering Materials, 2018, 20: 1700948.
[54] Gorr B, Mueller F, Christ H J, et al. High temperature oxidation behavior of an equimolar refractory metal-based alloy 20Nb-20Mo-20Cr-20Ti-20Al with and without Si addition[J]. Journal of Alloys and Compounds, 2016, 688: 468-477.
[55] Gorr B, Müeller F, Azim M, et al. High-temperature oxidation behavior of refractory high-entropy alloys: Effect of alloy composition[J]. Oxidation of Metals, 2017, 88: 339-349.
[56] 赵太霖, 牛犇, 王清, 等. 阻尼合金研究进展[J]. 材料工程, 2024, 52(6): 109-121.
Zhao Tailin, Niu Ben, Wang Qing, et al. Research progress in damping alloys[J]. Journal of Materials Engineering, 2024, 52(6): 109-121.
[57] 崔小龙, 黄晋英, 刘进明, 等. 材料阻尼测试中影响因素研究[J]. 煤矿工程, 2016, 37(1): 58-60.
Cui Xiaolong, Huang Jinying, Liu Jinming, et al. Material damping test analysis of influencing factors[J]. Coal Mine Machinery, 2016, 37(1): 58-60.
[58] Zhang Z R, Zhang H, Tang Y, et al. Microstructure, mechanical properties and energetic characteristics of a novel high-entropy alloy HfZrTiTa_0.53[J]. Materials and Design, 2017, 133: 435-443.