<strong>AlCrFeCoNi</strong>低膨胀合金的成分设计及组织和性能优化

doi:10.11900/0412.1961.2025.00348

金属学报

2026, Vol. 62

Issue (6): 1021-1031 DOI: 10.11900/0412.1961.2025.00348

研究论文

本期目录 | 过刊浏览

AlCrFeCoNi低膨胀合金的成分设计及组织和性能优化

许鼎锋¹^,², 韩飞扬¹^,², 姜琦成¹^,², 王欢¹^,², 尚利媛¹^,², 卢一平¹^,²(

)

1 大连理工大学材料科学与工程学院辽宁省凝固控制与数字化制备技术重点实验室大连 116024
2 大连理工大学材料科学与工程学院辽宁省高熵合金材料工程研究中心大连 116024

Composition Design and Optimization of Microstructure and Properties for an AlCrFeCoNi Low-Expansion Alloy

XU Dingfeng¹^,², HAN Feiyang¹^,², JIANG Qicheng¹^,², WANG Huan¹^,², SHANG Liyuan¹^,², LU Yiping¹^,²(

)

1 Key Laboratory of Solidification Control and Digital Preparation Technology (Liaoning Province), School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China
2 Engineering Research Center of High-Entropy Alloy Materials (Liaoning Province), School of Materials Science and Engineering, Dalian University of Technology, Dalian 116024, China

引用本文:

许鼎锋, 韩飞扬, 姜琦成, 王欢, 尚利媛, 卢一平. AlCrFeCoNi低膨胀合金的成分设计及组织和性能优化[J]. 金属学报, 2026, 62(6): 1021-1031.
Dingfeng XU, Feiyang HAN, Qicheng JIANG, Huan WANG, Liyuan SHANG, Yiping LU. Composition Design and Optimization of Microstructure and Properties for an AlCrFeCoNi Low-Expansion Alloy[J]. Acta Metall Sin, 2026, 62(6): 1021-1031.

全文: PDF(2705 KB) HTML

摘要:

针对传统因瓦(Invar)合金因室温屈服强度不足而难以应用于承重件的问题，本工作通过在FeCoNi合金体系中引入Al、Cr元素并结合热机械处理，旨在开发兼具低膨胀与高强度的新型Al₁Cr₁(Fe₆₅Co₄Ni₃₁)₉₈合金。结果表明，该合金经热机械处理后晶粒显著细化，马氏体体积分数升高至8.91%，并伴随孪晶和高密度缺陷的生成。在-60~100 ℃范围内，合金热膨胀系数降低至1.10 × 10^-6~2.04 × 10^-6 ℃^-1。除了Invar效应外，这种低膨胀行为还源于升温过程中马氏体相减少引起的体积收缩部分抵消了晶格热振动，以及界面和缺陷抑制了非谐性晶格振动，同时该微观组织特征使合金的屈服强度和抗拉强度分别达到324和452 MPa，断后伸长率保持在20%以上。与典型的Fe-Ni系Invar合金相比，本工作设计的合金在具有高比强度的同时保持了较低的热膨胀系数，表明合金成分设计与热机械处理的协同优化能够在低膨胀与力学性能之间实现优异平衡，为形变敏感构件的材料设计提供了新思路。

关键词 ：因瓦合金, 低膨胀, 热机械处理, 马氏体, 力学性能

Abstract：

Low-expansion alloys are essential structural-functional materials for advanced technologies requiring stringent dimensional stability. They are key components in precision metrology, electronic and microwave devices, cryogenic systems, and ultraprecision manufacturing equipments, where thermal deformation must be strictly controlled. However, conventional Fe-Ni Invar alloys possess insufficient mechanical strength despite their exceptionally low coefficient of thermal expansion, which limits their applicability in load-bearing environments. Design concept of high-entropy alloys offer a promising pathway to overcome this limitation through multiprinciple element alloy design and the associated synergistic effects. In this work, a novel low-expansion alloy, Al₁Cr₁(Fe₆₅Co₄Ni₃₁)₉₈, was developed by introducing Al and Cr into the multicomponent system and applying thermomechanical processing to tailor and refine its microstructure. This design strategy aims to achieve the synergistic optimization of thermal expansion behavior and mechanical performance. Additionally, in situ XRD during heating was employed to elucidate the underlying mechanism and monitor phase evolution. After thermomechanical processing, the alloy exhibited pronounced grain refinement and an increased martensite volume fraction of 8.91%. The microstructure further contained abundant deformation twins and a high density of lattice defects, which collectively enhanced the mechanical strength and thermal stability. Within the temperature range of -60 ^oC to 100 ^oC, the coefficient of thermal expansion decreased to 1.10 $×$ 10^-6-2.04 $×$ 10^-6^oC^-1. In addition to the Invar effect, this ultralow expansion behavior is attributed to the partial compensation of lattice thermal vibrations by the volume contraction associated with martensite reduction during heating, together with the suppression of anharmonic lattice vibrations induced by interfaces and defects. Meanwhile, the refined microstructure delivered an excellent combination of strength and ductility, achieving a yield strength of 324 MPa, an ultimate tensile strength of 452 MPa, and a fracture elongation greater than 20%. Compared with conventional Invar alloys, the designed alloy exhibited a higher specific strength while maintaining a low coefficient of thermal expansion. These results demonstrate that the synergistic optimization of compositional design and thermomechanical processing enables the exceptional integration of low thermal expansion with robust mechanical properties, offering valuable guidance for developing dimensionally stable structural alloys.

Key words： Invar alloy low expansion thermomechanical processing martensite mechanical property

收稿日期: 2025-10-29

ZTFLH:

TG132.1

基金资助:国家自然科学基金项目(U2341261);辽宁省科技计划联合计划项目(2024JH2/102600019);大连市高层次人才创新支持计划项目(2023RG006)

通讯作者: 卢一平，luyiping@dlut.edu.cn，主要从事先进合金的设计与制备研究

Corresponding author: LU Yiping, professor, Tel: (0411)84709400, E-mail: luyiping@dlut.edu.cn

作者简介: 许鼎锋，男，1996年生，博士生
第一联系人：韩飞扬(共同第一作者)，男，2002年生，硕士生

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https://www.ams.org.cn/CN/10.11900/0412.1961.2025.00348 或 https://www.ams.org.cn/CN/Y2026/V62/I6/1021

表1 低膨胀合金的名义成分 (atomic fraction / %)

图1 均匀化热处理后低膨胀合金的热膨胀系数和拉伸力学性能

表2 均匀化热处理后低膨胀合金的拉伸强度和塑性

图2 均匀化热处理后低膨胀合金微观组织的电子探针表征

图3 Al1Cr1合金的物相分析

表3 图3b中衍射峰强度的理论值和不同温度下的测量值

图4 热机械处理后Al1Cr1合金的热膨胀系数和拉伸力学性能

图5 热机械处理后Al1Cr1合金的微观组织表征

图6 热机械处理后Al1Cr1合金的原位升温XRD谱

表4 热机械处理后Al1Cr1合金不同温度下各相的晶格常数和体积分数

图7 Al1Cr1合金的差示扫描量热曲线

图8 比强度与热膨胀系数的Ashby图[10,11,36~49]

[1]	Zhao Z Y. Research on low expansion alloys, preparation technology of core components and key theoretical issues of the spectrometer[D]. Ji'nan: Shandong University, 2017
[1]	赵珍阳. 光谱仪用低膨胀合金和核心部件的制备技术及关键理论问题研究[D]. 济南: 山东大学, 2017
[2]	Deng S P, Tang G M, Zhao Y. Study of super-Invar alloy Fe-33Ni-4Co-1.2Nb[J]. J. Funct. Mater., 2010, 41: 677
[2]	邓世平, 唐光明, 赵彦. Fe-33Ni-4Co-1.2Nb超低膨胀合金研究[J]. 功能材料, 2010, 41: 677
[3]	Zhang H, Lin F X, Liu Y, et al. Research progress on Ti-Mn based hydrogen storage alloys[J]. J. Chin. Ceram. Soc., 2024, 52: 1873
[3]	张贺, 林繁鑫, 刘勇等. Ti-Mn系储氢合金的研究进展[J]. 硅酸盐学报, 2024, 52: 1873
[4]	Huang G L, He G M, Liu Y, et al. Anisotropy of microstructure, mechanical properties and thermal expansion in Invar 36 alloy fabricated via laser powder bed fusion[J]. Addit. Manuf., 2024, 82: 104025
[5]	Lohaus S H, Heine M, Guzman P, et al. A thermodynamic explanation of the Invar effect[J]. Nat. Phys., 2023, 19: 1642 doi: 10.1038/s41567-023-02142-z
[6]	Lin F, Wan J, Yang D Y, et al. Achieving high strength and low thermal expansion coefficient in additively manufactured Invar alloys by leveraging the effect of alloying elements[J]. J. Mater. Sci. Technol., 2026, 254: 81 doi: 10.1016/j.jmst.2025.08.006
[7]	van Schilfgaarde M, Abrikosov I A, Johansson B. Origin of the Invar effect in iron-nickel alloys[J]. Nature, 1999, 400: 46 doi: 10.1038/21848
[8]	Li W J, Lin K, Yan Y, et al. A seawater-corrosion-resistant and isotropic zero thermal expansion (Zr,Ta)(Fe,Co)₂ alloy[J]. Adv. Mater., 2022, 34: 2109592 doi: 10.1002/adma.v34.34
[9]	Barron T H K, Collins J G, White G K. Thermal expansion of solids at low temperatures[J]. Adv. Phys., 1980, 29: 609 doi: 10.1080/00018738000101426
[10]	Wang Q, Dong Y W, Jiang Z H, et al. Enhancing low thermal expansion behavior and strength via induced Zr-rich intermetallic phase in Fe-36Ni Invar Alloy[J]. Mater. Des., 2023, 226: 111644 doi: 10.1016/j.matdes.2023.111644
[11]	Sui Q S, He J, Zhang X, et al. Strengthening of the Fe-Ni Invar alloy through chromium[J]. Materials, 2019, 12: 1297 doi: 10.3390/ma12081297
[12]	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]. Adv. Eng. Mater., 2004, 6: 299 doi: 10.1002/adem.v6:5
[13]	Xiong W, Guo A X Y, Zhan S, et al. Refractory high-entropy alloys: A focused review of preparation methods and properties[J]. J. Mater. Sci. Technol., 2023, 142: 196 doi: 10.1016/j.jmst.2022.08.046
[14]	Yeh J W. Recent progress in high entropy alloys[J]. Ann. Chim. Sci. Mat., 2006, 31: 633 doi: 10.3166/acsm.31.633-648
[15]	Deng C, Wang T, Wu P W, et al. High entropy materials for catalysis: A critical review of fundamental concepts and applications[J]. Nano Energy, 2024, 120: 109153 doi: 10.1016/j.nanoen.2023.109153
[16]	Rao Z Y, Tung P Y, Xie R W, et al. Machine learning-enabled high-entropy alloy discovery[J]. Science, 2022, 378: 78 doi: 10.1126/science.abo4940 pmid: 36201584
[17]	Takeuchi A, Inoue A. Classification of bulk metallic glasses by atomic size difference, heat of mixing and period of constituent elements and its application to characterization of the main alloying element[J]. Mater. Trans., 2005, 46: 2817 doi: 10.2320/matertrans.46.2817
[18]	Li Z, Jiang H, Wang T, et al. Microstructure evolution of GH2909 low expansion superalloy during heat treatment[J]. Acta Metall. Sin., 2022, 58: 1179 doi: 10.11900/0412.1961.2021.00078
[18]	李钊, 江河, 王涛等. GH2909低膨胀高温合金热处理中的组织演变行为[J]. 金属学报, 2022, 58: 1179
[19]	Yang Z, Liu X P, Fu J, et al. Thermal expansion properties of Fe-Ni-Co super-Invar alloy with Mn[J]. Chin. J. Rare Met., 2013, 37: 501
[19]	杨正, 刘晓鹏, 符佳等. Mn元素对Fe-Ni-Co合金热膨胀性能影响[J]. 稀有金属, 2013, 37: 501
[20]	Hart E W. Theory of the tensile test[J]. Acta Metall., 1967, 15: 351 doi: 10.1016/0001-6160(67)90211-8
[21]	Zaefferer S, Elhami N N. Theory and application of electron channelling contrast imaging under controlled diffraction conditions[J]. Acta Mater., 2014, 75: 20 doi: 10.1016/j.actamat.2014.04.018
[22]	Mao W Q, Gao S, Gong W, et al. Martensitic transformation-governed Lüders deformation enables large ductility and late-stage strain hardening in ultrafine-grained austenitic stainless steel at low temperatures[J]. Acta Mater., 2024, 278: 120233 doi: 10.1016/j.actamat.2024.120233
[23]	Gou J M, Pan Y, Liu X L, et al. Ultrastrong negative thermal expansion compositionally complex alloy[J]. Adv. Mater., 2025, 37: e07767 doi: 10.1002/adma.v37.40
[24]	Zhai Y, Su W L, Guo F J, et al. Experimental and numerical investigation of the yield point phenomenon and strain partitioning behavior in a dual-phase steel with lamellar structure[J]. Mater. Sci. Eng., 2024, A897: 146356
[25]	Xi X H, Dong G Q, Wang L Y, et al. Formation mechanism of faulted bands and its effect on α′-martensitic transformation[J]. Mater. Des., 2022, 224: 111321 doi: 10.1016/j.matdes.2022.111321
[26]	Zhang Z J, Sheng H W, Wang Z J, et al. Dislocation mechanisms and 3D twin architectures generate exceptional strength-ductility-toughness combination in CrCoNi medium-entropy alloy[J]. Nat. Commun., 2017, 8: 14390 doi: 10.1038/ncomms14390 pmid: 28218267
[27]	Shi S, Liu C, Wan J F, et al. Thermodynamics of fcc-fct martensitic transformation in Mn-X (X = Cu, Fe) alloys[J]. Mater. Des., 2016, 92: 960 doi: 10.1016/j.matdes.2015.12.093
[28]	Yang S J, Yang Y, Wang H M. The characteristic and thermodynamics/kinetics of martensitic transformation in Fe₅₀Mn₃₀Co₁₀Cr₁₀ high-entropy alloy during deformation/heat treatment[J]. Adv. Eng. Mater., 2020, 22: 1900868 doi: 10.1002/adem.v22.3
[29]	Liu Q, Ghodrat S, Huisman G, et al. Shape memory alloy actuators for haptic wearables: A review[J]. Mater. Des., 2023, 233: 112264 doi: 10.1016/j.matdes.2023.112264
[30]	Song Y Z, Shi N K, Deng S Q, et al. Negative thermal expansion in magnetic materials[J]. Prog. Mater. Sci., 2021, 121: 100835 doi: 10.1016/j.pmatsci.2021.100835
[31]	Nadutov V M, Vashchuk D L, Svystunov Y O, et al. Magnetic and Invar properties of Fe-35%Ni alloy after grinding of structure by hydroextrusion[J]. Funct. Mater., 2012, 19: 334
[32]	Drebushchak V A. Thermal expansion of solids: Review on theories[J]. J. Therm. Anal. Calorim., 2020, 142: 1097 doi: 10.1007/s10973-020-09370-y
[33]	Ishida K. Effect of grain size on grain boundary segregation[J]. J. Alloys Compd., 1996, 235: 244 doi: 10.1016/0925-8388(95)02094-2
[34]	Rogl G, Rogl P F. How severe plastic deformation changes the mechanical properties of thermoelectric skutterudites and half Heusler alloys[J]. Front. Mater., 2020, 7: 600261 doi: 10.3389/fmats.2020.600261
[35]	Kul M, Akgul B, Karabay Y Z. The relationship of hot and cold rolling processes with the structure and properties of Invar 36[J]. Mater. Chem. Phys., 2023, 295: 127215 doi: 10.1016/j.matchemphys.2022.127215
[36]	Zhang L J, Zhou G Z, Zhao F J. Process of producing expansion alloy Ni29Co18[J]. Chin. J. Nonferrous Met., 1998, 8(suppl.2) : 54
[36]	张丽君, 周广智, 赵福佳. 定膨胀合金Ni29Co18的工艺[J]. 中国有色金属学报, 1998, 8(增刊2): 54
[37]	Huang H T, Wang F J, Meng G, et al. Research progress on microstructure and properties of Invar alloy[J]. J. Funct. Mater., 2024, 55: 12084 doi: 10.3969/j.issn.1001-9731.2024.12.010
[37]	黄海堂, 王方军, 孟刚等. 因瓦合金组织性能的研究进展[J]. 功能材料, 2024, 55: 12084 doi: 10.3969/j.issn.1001-9731.2024.12.010
[38]	Zhang W C. Studies of microstructures and Invar effect of the Fe-Ni-Co alloys[D]. Nanning: Guangxi University, 2013
[38]	张文春. Fe-Ni-Co合金的微结构及其因瓦效应研究[D]. 南宁: 广西大学, 2013
[39]	Li P P, Wang A D, Liu C T. A ductile high entropy alloy with attractive magnetic properties[J]. J. Alloys Compd., 2017, 694: 55 doi: 10.1016/j.jallcom.2016.09.186
[40]	Song Y Z, Sun Q, Yokoyama T, et al. Transforming thermal expansion from positive to negative: The case of cubic magnetic compounds of (Zr, Nb)Fe₂[J]. J. Phys. Chem. Lett., 2020, 11: 1954 doi: 10.1021/acs.jpclett.9b03880
[41]	Sun Y M, Cao Y L, Hu S X, et al. Interplanar ferromagnetism enhanced ultrawide zero thermal expansion in Kagome cubic intermetallic (Zr, Nb)Fe₂[J]. J. Am. Chem. Soc., 2023, 145: 17096 doi: 10.1021/jacs.3c03160
[42]	Cao Y L, Xu Y, Khmelevskyi S, et al. Interplanar magnetic orders and symmetry-tuned zero thermal expansion in Kagomé metal (Zr,Ta)Fe₂[J]. Chem. Mater., 2023, 35: 9167 doi: 10.1021/acs.chemmater.3c01894
[43]	Song Y Z, Sun Q, Xu M, et al. Negative thermal expansion in (Sc,Ti)Fe₂ induced by an unconventional magnetovolume effect[J]. Mater. Horiz., 2020, 7: 275 doi: 10.1039/C9MH01025D
[44]	Jing-Ting Z, Yibole H, Narsu B, et al. Structural and magnetic properties of Sc_1-_xNb_xFe₂ intermetallics showing anomalous zero thermal expansion[J]. Intermetallics, 2021, 136: 107252 doi: 10.1016/j.intermet.2021.107252
[45]	Xu M, Song Y Z, Xu Y J, et al. High-temperature zero thermal expansion in HfFe₂₊_δ from added ferromagnetic paths[J]. Chem. Mater., 2022, 34: 9437 doi: 10.1021/acs.chemmater.2c01732
[46]	Hao J Z, Shen F R, Hu F X, et al. Realization of ultra-low thermal expansion over a broad temperature interval in Gd_x (Dy_0.5Ho_0.5)_1-_xCo₂ compounds[J]. Scr. Mater., 2020, 185: 181 doi: 10.1016/j.scriptamat.2020.04.043
[47]	Li W J, Lin K, Cao Y L, et al. Strong coupling of magnetism and lattice induces near-zero thermal expansion over broad temperature windows in ErFe₁₀V_2-_xMo_x compounds[J]. CCS Chem., 2021, 3: 1009 doi: 10.31635/ccschem.020.202000279
[48]	Yu C Y, Lin K, Zhang Q H, et al. An isotropic zero thermal expansion alloy with super-high toughness[J]. Nat. Commun., 2024, 15: 2252 doi: 10.1038/s41467-024-46613-0 pmid: 38480744
[49]	Cui J, Sun Y, Shi K W, et al. Invar effect in the wide and higher temperature range by coherent coupling in Fe-based alloy[J]. Adv. Funct. Mater., 2024, 34: 2309431 doi: 10.1002/adfm.v34.1

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