含硅高熵材料中的有序-无序相变

路辛夷; 张勇

doi:10.7498/aps.74.20250307

摘要

高熵合金(HEAs)作为多主元合金的重要分支, 因其优异的力学性能与功能特性受到广泛关注. 本文聚焦含硅高熵合金中的有序-无序相变机制, 系统综述其热力学与动力学调控规律及其对材料性能的影响. 研究表明, 硅的引入通过优化原子尺寸匹配与混合焓, 实现高熵合金中有序相和无序相的匹配, 显著提升合金的机械以及物理化学性能. 同时, 制备工艺与温度/压力调控可通过影响相形成实现多相结构的协同强化. 通过成分设计与工艺优化, 含硅高熵材料在航空航天、能源及电子器件等领域展现出广阔应用潜力. 未来研究需进一步结合多尺度表征与理论模型, 揭示相变动态机制, 推动其工程化应用.

关键词:

Abstract

High-entropy alloys (HEAs), representing a significant category of multi-component alloys, have attracted significant attention due to their outstanding mechanical and functional properties. This review focuses on the order-disorder phase transition mechanisms in silicon-based HEAs, systematically addressing the thermodynamic and kinetic regulation principles and their effects on material performance. The research has shown that adding silicon improves atomic size matching and mixing enthalpy, allowing high-entropy alloys to have both ordered and disordered phases, thereby significantly enhancing their mechanical and physicochemical properties.The evolution of ordered and disordered phases is strictly controlled by fabrication processes. Advanced fabrication techniques, such as laser cladding and powder metallurgy, as well as temperature/pressure modulation, can precisely control phase formation and layered structure, achieving synergistic strengthening through multiphase structures. Rapid cooling techniques such as laser cladding suppress the nucleation and growth of brittle intermetallic compounds, which is beneficial for single-phase FCC structures. On the contrary, controlled annealing treatments can induce phase transitions towards ordered BCC/B2 structures, enhancing high-temperature stability. Advanced techniques such as powder plasma arc additive manufacturing (PPA-AM) utilize rapid solidification to refine grain size and effectively disperse second phases. Thermodynamic drivers, particularly the competition between entropy and enthalpy quantified by the parameter Ω, as well as external stimuli such as pressure, provide precise control over the phase transition pathways and final microstructures. Furthermore, the incorporation of sillicon enhances functional performance, including increasing electrical resistivity, customizing magnetic responses, and improved high-temperature oxidation resistance through the formation of Al₂O₃/SiO₂ layers. Despite these advancements, there are still challenges in understanding atomic-scale dynamics of phase transitions and expanding cost-effective manufacturing processes. Future efforts should integrate multiscale characterization, computational modeling, and performance validation under extreme conditions to accelerate the engineering applications of silicon-based HEAs in aerospace, energy storage, and electronic devices.

Keywords:

作者及机构信息

路辛夷¹,
张勇^1,2

1.
北京科技大学, 新金属材料全国重点实验室, 北京　100083

2.
福耀科技大学新材料与新能源学院, 硅基材料教育部重点实验室, 福州　350109

通信作者: 张勇, drzhangy@ustb.edu.cn

基金项目: 国家自然科学基金(批准号: 52273280)资助的课题.

Authors and contacts

LU Xinyi¹,
ZHANG Yong^1,2

1.
State Key Laboratory for Advanced Metals and Materials, University of Science and Technology Beijing, Beijing 100083, China

2.
Key Laboratory of Silicon-based Materials for the Ministry of Education, School of Materials Science and Engineering, Fuyao University of Science and Technology, Fuzhou 350109, China

Corresponding author: ZHANG Yong, drzhangy@ustb.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant No. 52273280).

文章全文

参考文献

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施引文献

图 1 (a)各种合金和HEAs的强度-塑性图以及含Si HEAs的数据; (b)不同的合金元素对HEAs延展性和拉伸强度的影响^[6]

Fig. 1. (a) Strength-ductility diagram of various alloys and HEAs with the addition of the data of the Si-containing HEAs; (b) changes in the ductility and tensile strength with the addition of the different alloying elements in HEAs^[6].

下载: 全尺寸图片幻灯片

图 2 基于混合焓$\Delta H_{\text{mix}}$和原子尺寸差δ的相形成图^[17]

Fig. 2. Phase formation map based on the enthalpy of mixing $\Delta H_{\text{mix}}$ and the atomic size difference δ^[17].

下载: 全尺寸图片幻灯片

图 3 多元合金中参数Ω和δ之间的关系^[18]

Fig. 3. Relationship between parameters Ω and δ for multi-component alloys^[18].

下载: 全尺寸图片幻灯片

图 4 无序(A2)和有序(B2) BCC晶体结构的图示^[28]

Fig. 4. Illustration of disordered (A2) and ordered (B2) BCC crystal structure^[28].

下载: 全尺寸图片幻灯片

图 5 激光熔覆示意图^[38]

Fig. 5. Schematic diagram of laser cladding^[38].

下载: 全尺寸图片幻灯片

图 6 PPA-AM制备高熵合金示意图^[43]

Fig. 6. Schematic diagram of high-entropy alloys fabricated by PPA-AM^[43].

下载: 全尺寸图片幻灯片

图 7 (a)室温拉伸曲线; (b) BCC阶段强化^[32]

Fig. 7. (a) Room-temperature tensile curves; (b) strengthening by the BCC phase^[32].

下载: 全尺寸图片幻灯片

图 8 (a) CoCrFeMnNiSi_x高熵合金涂层的动电位极化曲线; (b)电化学腐蚀参数^[51]

Fig. 8. (a) Potentiodynamic polarization curves of CoCrFeMnNiSi_x high-entropy-alloy coatings; (b) parameters of electrochemical corrosion^[51].

下载: 全尺寸图片幻灯片

图 9 AlCoCrFeNiSi_x HEAs在1100 ℃下200 h的氧化行为示意图　(a) Si₀; (b) Si_0.2; (c) Si_≥0.5^[11]

Fig. 9. Schematic diagram of oxidation behavior for AlCoCrFeNiSi_x HEAs at 1100 ℃ for 200 h: (a) Si₀; (b) Si_0.2; (c) Si_≥0.5^[11].

下载: 全尺寸图片幻灯片

map

[1]	Yeh J W, Chen S K, Lin S J, Gan J Y, Chin T S, Shun T T, Tsau C H, Chang S Y 2004 Adv. Eng. Mater. 6 299 Google Scholar
[2]	Cantor B, Chang I T H, Knight P, Vincent A J B 2004 Mater. Sci. Eng. A 375–377 213 Google Scholar
[3]	Huang E W, Lee W J, Singh S S, Kumar P, Lee C Y, Lam T N, Chin H H, Lin B H, Liaw P K 2022 Mater. Sci. Eng. : R: Rep. 147 100645 Google Scholar
[4]	Tsai M H, Yeh J W 2014 Mater. Res. Lett. 2 107 Google Scholar
[5]	Chandrakar R, Chandraker S, Kumar A, Jaiswal A 2024 Mater. Res. Express 11 116512 Google Scholar
[6]	Sohrabi M J, Kalhor A, Mirzadeh H, Rodak K, Kim H S 2024 Prog. Mater Sci. 144 101295 Google Scholar
[7]	Wu Y, Li Z, Feng H, He S 2022 Materials 15 3992 Google Scholar
[8]	Liu F F, Liaw P, Zhang Y 2022 Metals 12 501 Google Scholar
[9]	Luan H W, Shao Y, Li J F, Mao W L, Han Z D, Shao C, Yao K F 2020 Scr. Mater. 179 40 Google Scholar
[10]	叶喜葱, 徐张洋, 王童, 徐东, 张文, 方东 2020 特种铸造及有色合金 40 1323 Google Scholar Ye X C, Xu Z Y, Wang T, Xu D, Zhang W, Fang D 2020 Spec. Cast. Nonferrous Alloys 40 1323 Google Scholar
[11]	Li Y T, Zhang P, Zhang J Y, Chen Z, Shen B L 2021 Corros. Sci. 190 109633 Google Scholar
[12]	Kumar A, Chandrakar R, Chandraker S, Rao K R, Chopkar M 2021 J. Alloys Compd. 856 158193 Google Scholar
[13]	Zhang Y T, Zhang M, Li D, Zuo T, Zhou K, Gao M C, Sun B, Shen T 2019 Metals 9 382 Google Scholar
[14]	Lee H, Sharma A, Ahn B 2023 J. Alloys Compd. 947 169545 Google Scholar
[15]	Gearhart C A 1990 Am. J. Phys. 58 468 Google Scholar
[16]	Li Z Z, Zhao S T, Ritchie R O, Meyers M A 2019 Prog. Mater Sci. 102 296 Google Scholar
[17]	Zhang Y, Zhou Y J, Lin J P, Chen G L, Liaw P K 2008 Adv. Eng. Mater. 10 534 Google Scholar
[18]	Yang X H, Zhang Y 2012 Mater. Chem. Phys. 132 233 Google Scholar
[19]	Yan X H, Liaw P K, Zhang Y 2021 Metall. Mater. Trans. A 52 2111 Google Scholar
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[27]	Huang X J, Miao J S, Luo A A 2018 J. Mater. Sci. 54 2271 Google Scholar
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[29]	Sundman B, Chen Q, Du Y 2018 J. Phase Equilib. Diffus. 39 678 Google Scholar
[30]	Singh P, Johnson D D 2021 J. Mater. Res. 37 136 Google Scholar
[31]	Zhang Y, Zuo T T, Tang Z, Gao M C, Dahmen K A, Liaw P K, Lu Z P 2014 Prog. Mater Sci. 61 1 Google Scholar
[32]	Gu X Y, Zhuang Y X, Jia P 2022 Mater. Sci. Eng. A 840 142983 Google Scholar
[33]	Cheng P, Zhao Y H, Xu X T, Wang S, Sun Y Y, Hou H 2020 Mater. Sci. Eng. A 772 138681 Google Scholar
[34]	Zhu J M, Fu H M, Zhang H F, Wang A M, Li H, Hu Z Q 2010 Mater. Sci. Eng. A 527 7210 Google Scholar
[35]	林应征, 杨洪宇, 陈芳, 颜建辉 2023 材料热处理学报 44 69 Google Scholar Lin Y Z, Yang H Y, Chen F, Yan J H 2023 Trans. Mater. Heat Treat. 44 69 Google Scholar
[36]	Babilas R, Łoński W, Boryło P, Kądziołka Gaweł M, Gębara P, Radoń A 2020 J. Magn. Magn. Mater. 502 166492 Google Scholar
[37]	Zhang H, Pan Y, He Y Z 2011 J. Therm. Spray Technol. 20 1049 Google Scholar
[38]	Zhang S Y, Han B, Li M Y, Zhang Q, Hu C Y, Jia C X, Li Y, Wang Y 2021 Surf. Coat. Technol. 417 127218 Google Scholar
[39]	Santodonato L J, Liaw P K, Unocic R R, Bei H, Morris J R 2018 Nat. Commun. 9 4520 Google Scholar
[40]	Torralba J M, Alvaredo P, García Junceda A 2020 Powder Metall. 63 227 Google Scholar
[41]	Brif Y, Thomas M, Todd I 2015 Scr. Mater. 99 93 Google Scholar
[42]	Han C J, Fang Q H, Shi Y S, Tor S B, Chua C K, Zhou K 2020 Adv. Mater. 32 1903855 Google Scholar
[43]	Luo J, Wang J, Su C, Geng Y, Chen X 2024 J. Mater. Eng. Perform. 33 12413 Google Scholar
[44]	Shun T T, Hung C H, Lee C F 2010 J. Alloys Compd. 493 105 Google Scholar
[45]	Hazen R M, Navrotsky A 1996 Am. Mineral. 81 1021 Google Scholar
[46]	Starenchenko S V 2012 Russ. Phys. J. 54 965 Google Scholar
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[48]	Ma L L, Wang L, Nie Z H, Wang F C, Xue Y F, Zhou J L, Cao T Q, Wang Y D, Ren Y 2017 Acta Mater. 128 12 Google Scholar
[49]	Ji C W, Ma A, Jiang J H 2022 J. Alloys Compd. 900 163508 Google Scholar
[50]	Kumar A, Dhekne P, Swarnakar A K, Chopkar M 2018 Mater. Res. Express 6 026532 Google Scholar
[51]	Lin T X, Feng M Y, Lian G F, Lu H, Chen C R, Huang X 2024 Mater. Charact. 216 114246 Google Scholar
[52]	Li Z, Taheri M, Torkamany P, Heidarpour I, Torkamany M J 2024 Vacuum 219 112749 Google Scholar
[53]	Shang X L, Wang Z J, He F, Wang J C, Li J J, Yu J K 2017 Sci. China Technol. Sci. 61 189 Google Scholar
[54]	Wang S, Wu Y, Gesmundo F, Niu Y 2008 Oxid. Met. 69 299 Google Scholar
[55]	Jiang S M, Xu C Z, Li H Q, Liu S C, Gong J, Sun C 2010 Corros. Sci. 52 435 Google Scholar
[56]	Zuo T T, Li R B, Ren X J, Zhang Y 2014 J. Magn. Magn. Mater. 371 60 Google Scholar
[57]	Wen J J, Liu X, Li Z H, Li W W 2023 J. Alloys Compd. 934 167622 Google Scholar
[58]	Su Y, Lei X C, Chen W J, Su Y P, Liu H W, Ren S Y, Tong R Y, Lin Y T, Jiang W J, Liu X Z, Su D, Zhang Y G 2024 Chem. Eng. J. 500 157197 Google Scholar
[59]	Lei X C, Wang Y Y, Wang J Y, Su Y, Ji P X, Liu X Z, Guo S N, Wang X F, Hu Q M, Gu L, Zhang Y G, Yang R, Zhou G, Su D 2023 Small Methods 8 2300754 Google Scholar

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含硅高熵材料中的有序-无序相变