Order-disorder phase transition in silicon-containing high-entropy materials

LU Xinyi; ZHANG Yong

doi:10.7498/aps.74.20250307

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:

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).

FullText HTML

References

[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
[20]	Wu G, Liu C, Yan Y Q, Liu S D, Ma X Y, Yue S Y, Shan Z W 2024 Nat. Commun. 15 1223 Google Scholar
[21]	Wu G, Liu S D, Wang Q, Rao J, Xia W Z, Yan Y Q, Eckert J, Liu C, Ma E, Shan Z W 2023 Nat. Commun. 14 3670 Google Scholar
[22]	Miracle D B, Senkov O N 2017 Acta Mater. 122 448 Google Scholar
[23]	Lei Z F, Liu X J, Wu Y, Wang H, Jiang S H, Wang S D, Hui X D, Wu Y D, Gault B, Kontis P, Raabe D, Gu L, Zhang Q H, Chen H W, Wang H T, Liu J B, An K, Zeng Q S, Nieh T G, Lu Z P 2018 Nature 563 546 Google Scholar
[24]	Soni V, Gwalani B, Senkov O N, Viswanathan B, Alam T, Miracle D B, Banerjee R 2018 J. Mater. Res. 33 3235 Google Scholar
[25]	Soni V, Senkov O N, Gwalani B, Miracle D B, Banerjee R 2018 Sci. Rep. 8 8816 Google Scholar
[26]	Soni V, Gwalani B, Alam T, Dasari S, Zheng Y, Senkov O N, Miracle D, Banerjee R 2020 Acta Mater. 185 89 Google Scholar
[27]	Huang X J, Miao J S, Luo A A 2018 J. Mater. Sci. 54 2271 Google Scholar
[28]	Huang X J, Miao J S, Luo A A 2022 Scr. Mater. 210 114462 Google Scholar
[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
[47]	Ma Y M, Fan J T, Zhang L J, Zhang M D, Cui P, Dong W Q, Yu P F, Li Y C, Liaw P K, Li G 2018 Intermetallics 103 63 Google Scholar
[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

Cited By

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]

Figure 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].

DownLoad: Full-Size Img PowerPoint

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

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

DownLoad: Full-Size Img PowerPoint

图 3 多元合金中参数Ω和δ之间的关系^[18]

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

DownLoad: Full-Size Img PowerPoint

图 4 无序(A2)和有序(B2) BCC晶体结构的图示^[28]

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

DownLoad: Full-Size Img PowerPoint

图 5 激光熔覆示意图^[38]

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

DownLoad: Full-Size Img PowerPoint

图 6 PPA-AM制备高熵合金示意图^[43]

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

DownLoad: Full-Size Img PowerPoint

图 7 (a)室温拉伸曲线; (b) BCC阶段强化^[32]

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

DownLoad: Full-Size Img PowerPoint

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]

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

DownLoad: Full-Size Img PowerPoint

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]

Figure 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].

DownLoad: Full-Size Img PowerPoint

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
[20]	Wu G, Liu C, Yan Y Q, Liu S D, Ma X Y, Yue S Y, Shan Z W 2024 Nat. Commun. 15 1223 Google Scholar
[21]	Wu G, Liu S D, Wang Q, Rao J, Xia W Z, Yan Y Q, Eckert J, Liu C, Ma E, Shan Z W 2023 Nat. Commun. 14 3670 Google Scholar
[22]	Miracle D B, Senkov O N 2017 Acta Mater. 122 448 Google Scholar
[23]	Lei Z F, Liu X J, Wu Y, Wang H, Jiang S H, Wang S D, Hui X D, Wu Y D, Gault B, Kontis P, Raabe D, Gu L, Zhang Q H, Chen H W, Wang H T, Liu J B, An K, Zeng Q S, Nieh T G, Lu Z P 2018 Nature 563 546 Google Scholar
[24]	Soni V, Gwalani B, Senkov O N, Viswanathan B, Alam T, Miracle D B, Banerjee R 2018 J. Mater. Res. 33 3235 Google Scholar
[25]	Soni V, Senkov O N, Gwalani B, Miracle D B, Banerjee R 2018 Sci. Rep. 8 8816 Google Scholar
[26]	Soni V, Gwalani B, Alam T, Dasari S, Zheng Y, Senkov O N, Miracle D, Banerjee R 2020 Acta Mater. 185 89 Google Scholar
[27]	Huang X J, Miao J S, Luo A A 2018 J. Mater. Sci. 54 2271 Google Scholar
[28]	Huang X J, Miao J S, Luo A A 2022 Scr. Mater. 210 114462 Google Scholar
[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
[47]	Ma Y M, Fan J T, Zhang L J, Zhang M D, Cui P, Dong W Q, Yu P F, Li Y C, Liaw P K, Li G 2018 Intermetallics 103 63 Google Scholar
[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

Catalog

Vol. 74, Issue 16 - 2025-08-20

Metrics

Abstract views: 4717
PDF Downloads: 126
Cited By: 0

姓名
邮箱
手机号码
标题
留言内容
验证码

Search

Article

留言板