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摘要: 從加工方法、微觀結構以及各類性能三方面介紹了難熔高熵合金(Refractory high-entropy alloys，RHEAs)，最后對難熔高熵合金的發展和未來進行了展望。以MoNbTaVW為代表的難熔高熵合金在高溫下表現出優于傳統鎳基高溫合金的壓縮屈服強度，且屈服強度隨溫度的變化更加緩慢，高溫力學性能優異；以MoNbTaVW、MoNbTaTiZr、HfNbTiZr等為代表的難熔高熵合金，與商用高溫合金、難熔金屬、難熔合金以及工具鋼相比，展現出更優的耐磨性能。以W38Ta36Cr15V11合金為代表的難熔高熵合金在輻照后，除了析出小顆粒第二相外，不存在位錯環缺陷結構，抗輻照性能優異。提出了難熔高熵合金未來發展的兩大方向：建立高通量的實驗和計算方法繼續探索更多的難熔高熵合金組成和結構模型；探索多場耦合環境下難熔高熵合金的服役行為。Abstract: Alloying is one of the main ways to achieve desirable properties in materials. The design concept is based on one or two metal elements, supplemented with multiple trace elements to achieve altered or optimized properties. With the advancement in technology, the traditional alloy has evolved from simple to complex compositions, thus improving their properties and promoting the progress of civilization. High-entropy alloys (HEAs) are a new type of multi-master alloys that are popular in the recent two decades. Unlike conventional alloys, HEAs comprise multiple alloying elements according to the isoatomic or non-isoatomic ratios and have several unique properties, such as high strength and hardness, excellent wear and corrosion resistance, thermal stability, and irradiation resistance. Refractory high-entropy alloys (RHEAs), HEAs made of refractory metals, have attracted great attention because of their excellent high-temperature mechanical properties. This paper discusses RHEAs from three aspects: processing methods, microstructure, and properties. Finally, this work presents the development and future prospects of RHEAs. RHEAs represented by MoNbTaVW alloys show better compressive yield strengths at high temperatures and a slower change of yield strength with temperature than traditional Ni-based high-temperature alloys. Compared with commercial superalloys, refractory metals, refractory alloys, and tool steels, RHEAs, such as MoNbTaVW, MoNbTaTiZr, and HfNbTiZr, show excellent wear resistance. RHEAs represented by W38Ta36Cr15V11 have no dislocation ring defect structure and excellent anti-irradiation performance after irradiation, except for the precipitation of small particles in the second phase. In this paper, two directions of future development of RHEAs were proposed: (1) establishing high-throughput experimental and computational methods to continue exploring composition and structural models of RHEAs and (2) exploring the service behavior of RHEAs in a multi-field coupled environment.
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Key words:
- refractory high entropy alloys /
- processing methods /
- microstructure /
- phase composition /
- properties
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圖 9 鑄態TiZrHfNb、(TiZrHfNb)98O2和(TiZrHfNb)98N2的高能同步加速器X射線衍射圖（a）和電子背散射衍射圖（b），(TiZrHfNb)98O2沿[011]軸的球差矯正掃描電子顯微鏡高角度環形暗場圖（c）和原子序數對比度圖（d），以及相應的球差矯正掃描電子顯微鏡環形亮場圖（e），（e）中的插圖是有序間隙原子復合體的放大視圖[43]
Figure 9. Synchrotron high-energy X-ray diffraction (a) and the corresponding electron back-scattering diffraction patterns (b) of the as-cast TiZrHfNb, (TiZrHfNb)98O2 and (TiZrHfNb)98N2; scanning transmission electron microscope high-angle annular dark field images (c) for [011] axis, Z-contrast of the scanning transmission electron microscope high-angle annular dark field image (d) and the corresponding scanning transmission electron microscope-annular bright field image (e) that reveals the ordered oxygen complexes; the inset in (e) is an enlarged view of the ordered oxygen complexes[43]
圖 12 不同條件下MoTaWNbV和Inconel 718的體積損失（左）和磨損率（右）的對比圖[55]，用鋼球和氧化鋁球進行400 m （a）和1000 m （b）滑動距離測試
Figure 12. Comparative diagrams of the volume loss (left) and the wear rate (right) of MoTaWNbV versus Inconel 718 under different conditions[55]，tested with both an alumina and a steel ball for sliding distances of 400 m (a), 1000 m (b)
圖 13 MoTaNbZrTi合金磨損表面收集的碎片的掃描電子顯微鏡圖，用鋼球（a, b, c）和氧化鋁球（d, e, f）分別滑動（a和d）400 m；（b和e）1000 m和（c和f）2000 m[57]
Figure 13. Scanning electron microscope images of the debris collected from the worn surface of MoTaNbZrTi tested with a steel ball (a, b, c) and an alumina ball (d, e, f) for the sliding distances of (a and d) 400 m; (b and e) 1000 m; and (c and f) 2000 m[57]
圖 14 HfNbTiZr合金在500 mN恒定載荷下劃痕形貌的掃描探針顯微鏡圖（a）和對應的3D圖（b），純Nb和C103以及（a）中所示的橫截面輪廓（c）[58]
Figure 14. Scanning probe microscopy image showing the topography of the scratch track of the HfNbTiZr alloy under a constant load testing at 500 mN (a), the corresponding 3D view (b), and cross-section profiles (c) as indicated in the pure Nb and C103 alloy as well as (a)[58]
圖 15 在1300℃下氧化10 h的RHEAs外部氧化膜橫截面的背散射電子圖像[21]。（a）NbCrMoTiAl0.5；（b）NbCrMoVAl0.5；（c）NbCrMoTiVAl0.5；（d）NbCrMoTiVAl0.5Si0.3
Figure 15. Backscattered electron microscopy images showing the cross sections of the outer oxide scales of the RHEAs oxidized at 1300 ℃ for 10 h[21]: (a) NbCrMoTiAl0.5; (b) NbCrMoVAl0.5; (c) NbCrMoTiVAl0.5; (d) NbCrMoTiVAl0.5Si0.3
久色视频表 1 近幾年難熔高熵合金的結構特征及制備工藝
Table 1. Structural characteristics and preparation technology of refractory high-entropy alloys in recent years
Phase structure Elemental composition Preparation technology BCC WMoNbTa[11] As-cast WMoNbTaV[11] As-cast TaNbHfZrTi[14-15] Hot isostatic pressing NbTiVTa[16] As-cast NbTiVTaAl0.25[16] As-cast NbTiVTaAl0.5[16] As-cast NbTiVTaAl[16] As-cast TiZrNbMoVx(x=0~3)[17] As-cast NbTiVZr[18-19] Hot isostatic pressing HfNbTiZr[20] Annealed NbCrMoTiAl0.5[21] As-cast NbCrMoVAl0.5[21] As-cast NbCrMoTiVAl0.5[21] As-cast AlNb1.5Ta0.5Ti1.5Zr0.5[22] Hot isostatic pressing Al0.3NbTa0.8Ti1.4V0.2Zr1.3[22] Hot isostatic pressing Al0.4Hf0.6NbTaTiZr[22-23] Hot isostatic pressing AlNbTiV[24] Annealed HfMoTaTiZr[25] As-cast HfMoNbTaTiZr[25] As-cast TaNbHfZr[26] As-cast NbMoCrTiAl[27] Mechanical alloying and spark plasma sintering WMoNbTa[5] Mechanical alloying and spark plasma sintering WMoNbTaV[5] Mechanical alloying and spark plasma sintering MoNbTaTiV[28] As-cast MoNbTaTiW[29] As-cast HfMoTiWZr[30] As-cast AlCrMoTi[31] As-cast AlMoNbTi[31] As-cast BCC+Laves CrNbTiZr[18-19] Hot isostatic pressing CrNbTiVZr[18-19] Hot isostatic pressing TiZrHfNbV[32] Annealed TiZr0.5NbCr0.5[33] As-cast TiZr0.5NbCr0.5Mo[33] As-cast TiZr0.5NbCr0.5V[33] As-cast AlCrMoTiW[34] As-cast AlCrMoTaTi[35] As-cast BCC+B2 AlMo0.5NbTa0.5TiZr[36-37] Hot isostatic pressing Al0.5Mo0.5NbTa0.5TiZr[38] Hot isostatic pressing Al0.25NbTaTiZr[38] Hot isostatic pressing B2 AlNbTa0.25TiZr0.25[38] Hot isostatic pressing BCC+HCP HfTaTiZr[39] As-cast HfTa0.4TiZr[39] As-cast HfTa0.5TiZr[39] As-cast HfTa0.6TiZr[39] As-cast FCC+L12 W0.5Ni2Co2VMo0.5[40] As-cast W0.5Ni2Co2VCr0.5[40] As-cast W0.5Ni2Co2CrMo0.5[40] As-cast 
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