Abstract
In this work, the phase stability of non-equiatomic Fe50Mn30Co10Cr10 and Fe50Mn30Co10Ni10 high entropy alloys (HEAs) under strong constraining conditions as well as its effect on the mechanical properties were comparatively studied in the magnetron sputtered Cu/Fe50Mn30Co10Cr10 and Cu/Fe50Mn30Co10Ni10 nanolaminates with the layer thickness h ranging from 5 to 150 nm. During the deposition process, the size-driven hexagonal close packed (HCP) to face-centered cubic (FCC) phase transformation occurs in the Fe50Mn30Co10Cr10 layers as h < 25 nm due to the nanolayer constraining and template effects. Meanwhile, the stress-driven HCP-to-FCC phase transformation also occurs in the Cu/Fe50Mn30Co10Cr10 nanolaminates during the indentation deformation, which is attributed to the nucleation of stacking faults that could serve as the nuclei for phase transformation. However, the Fe50Mn30Co10Ni10 layers maintain stable microstructure without size-driven nor stress-driven phase transformation. With reducing h, both the Cu/HEA nanolaminates exhibit a transition from h-independent to h-dependent ultrahigh hardness, as elucidated by the partial dislocation-mediated mechanisms. In particular, the normalized hardness of Cu/Fe50Mn30Co10Cr10 nanolaminates represented by the ratio of measured hardness to predicted hardness from the rule-of-mixture is more superior to conventional Cu-based bimetal nanolaminates. These findings provide a new perspective to tailor the phase transformation of HEAs and thereby enhance their strength and plasticity.
摘要
本文通过磁控溅射制备了具有相同组元层厚度(h = 5–150 nm)的Cu/Fe50Mn30Co10Cr10和Cu/Fe50Mn30Co10Ni10金属/高熵合金纳米多层膜, 对比研究了强约束条件下非等原子比Fe50Mn30Co10Cr10和Fe50Mn30Co10Ni10高熵合金的相稳定性及其对力学性能的影响. 沉积过程中由于组元Cu层的约束与模板效应, 组元Fe50Mn30Co10Cr10层在层厚小于25 nm时发生了尺寸驱动的HCP到FCC相变. 与此同时, 由于堆垛层错可以作为相变的形核质点, Cu/Fe50Mn30Co10Cr10多层膜在压入变形过程中也发生了应力驱动的HCP到FCC相变. 相比之下, Cu/Fe50Mn30Co10Ni10多层膜组织稳定, 没有发生尺寸/应力驱动的相变行为. 随层厚减小, 两种Cu/高熵合金纳米多层膜均表现出了从层厚无关转变为层厚相关的超高硬度, 这源于偏位错形核主导的强化机制. 尤为特别的是, Cu/Fe50Mn30Co10Cr10多层膜的归一化硬度(实测硬度与混合法则预测硬度的比值)远高于传统的Cu基双金属多层膜. 本文研究结果从调控高熵合金相变行为的角度为提高复合材料的强度和塑性提供了新思路.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Ritchie RO. The conflicts between strength and toughness. Nat Mater, 2011, 10: 817–822
Wang X, De Vecchis RR, Li C, et al. Design metastability in high-entropy alloys by tailoring unstable fault energies. Sci Adv, 2022, 8: eabo7333
Zhang Y, Zuo TT, Tang Z, et al. Microstructures and properties of high-entropy alloys. Prog Mater Sci, 2014, 61: 1–93
Guo L, Gu J, Gong X, et al. CALPHAD aided design of high entropy alloy to achieve high strength via precipitate strengthening. Sci China Mater, 2020, 63: 288–299
Li Z, Zhao S, Ritchie RO, et al. Mechanical properties of high-entropy alloys with emphasis on face-centered cubic alloys. Prog Mater Sci, 2019, 102: 296–345
Yang C, Ren C, Jia Y, et al. A machine learning-based alloy design system to facilitate the rational design of high entropy alloys with enhanced hardness. Acta Mater, 2022, 222: 117431
Liu J, Guo X, Lin Q, et al. Excellent ductility and serration feature of metastable CoCrFeNi high-entropy alloy at extremely low temperatures. Sci China Mater, 2019, 62: 853–863
Lu W, Guo W, Wang Z, et al. Advancing strength and counteracting embrittlement by displacive transformation in heterogeneous highentropy alloys containing sigma phase. Acta Mater, 2023, 246: 118717
Cantor B. Multicomponent high-entropy Cantor alloys. Prog Mater Sci, 2021, 120: 100754
Mao W, Gao S, Gong W, et al. Quantitatively evaluating respective contribution of austenite and deformation-induced martensite to flow stress, plastic strain, and strain hardening rate in tensile deformed TRIP steel. Acta Mater, 2023, 256: 119139
Li Z, Pradeep KG, Deng Y, et al. Metastable high-entropy dual-phase alloys overcome the strength-ductility trade-off. Nature, 2016, 534: 227–230
Huang H, Wu Y, He J, et al. Phase-transformation ductilization of brittle high-entropy alloys via metastability engineering. Adv Mater, 2017, 29: 1701678
Ma Y, Yang M, Yuan F, et al. Deformation induced hcp nano-lamella and its size effect on the strengthening in a CoCrNi medium-entropy alloy. J Mater Sci Tech, 2021, 82: 122–134
Lin Q, Liu J, An X, et al. Cryogenic-deformation-induced phase transformation in an FeCoCrNi high-entropy alloy. Mater Res Lett, 2018, 6: 236–243
Vakili SM, Zarei-Hanzaki A, Anoushe AS, et al. Reversible dislocation movement, martensitic transformation and nano-twinning during elastic cyclic loading of a metastable high entropy alloy. Acta Mater, 2020, 185: 474–492
Lu W, Liebscher CH, Dehm G, et al. Bidirectional transformation enables hierarchical nanolaminate dual-phase high-entropy alloys. Adv Mater, 2018, 30: 1804727
Li Z, Tasan CC, Pradeep KG, et al. A TRIP-assisted dual-phase highentropy alloy: Grain size and phase fraction effects on deformation behavior. Acta Mater, 2017, 131: 323–335
Vorobiov S, Pylypenko O, Bereznyak Y, et al. Magnetic properties, magnetoresistive, and magnetocaloric effects of AlCrFeCoNiCu thin-film high-entropy alloys prepared by the co-evaporation technique. Appl Phys A, 2021, 127: 179
Cao ZH, Cai YP, Sun C, et al. Tailoring strength and plasticity of Ag/Nb nanolaminates via intrinsic microstructure and extrinsic dimension. Int J Plast, 2019, 113: 145–157
Ovid’Ko IA. Review on the fracture processes in nanocrystalline materials. J Mater Sci, 2007, 42: 1694–1708
Meyers MA, Mishra A, Benson DJ. Mechanical properties of nanocrystalline materials. Prog Mater Sci, 2006, 51: 427–556
Fu Z, Chen W, Wen H, et al. Microstructure and strengthening mechanisms in an FCC structured single-phase nanocrystalline Co25Ni25-Fe25Al7.5Cu17.5 high-entropy alloy. Acta Mater, 2016, 107: 59–71
Wu G, Chan KC, Zhu L, et al. Dual-phase nanostructuring as a route to high-strength magnesium alloys. Nature, 2017, 545: 80–83
Yang Z, Fu B, Ning Z, et al. Amorphization activated by semicoherent interfaces of FCC/BCC HEA multilayers during deformation. Mater Des, 2023, 225: 111469
Beyerlein IJ, Demkowicz MJ, Misra A, et al. Defect-interface interactions. Prog Mater Sci, 2015, 74: 125–210
Fan Z, Xue S, Wang J, et al. Unusual size dependent strengthening mechanisms of Cu/amorphous CuNb multilayers. Acta Mater, 2016, 120: 327–336
Jain M, Yaddanapudi K, Kidigannappa AT, et al. Simultaneous high strength and mechanical stability of bcc Nb/Mg nanolaminates. Acta Mater, 2023, 242: 118487
Wan Q, Liu Y, Yang B, et al. Enhancing irradiation tolerance via building 3D diffusion paths for He+ in multilayers by epitaxial growth. Mater Des, 2022, 221: 111020
Zhang YF, Su R, Niu TJ, et al. Thermal stability and deformability of annealed nanotwinned Al/Ti multilayers. Scripta Mater, 2020, 186: 219–224
Li JC, Liu W, Jiang Q. Bi-phase transition diagrams of metallic thin multilayers. Acta Mater, 2005, 53: 1067–1071
Wan L, Yu X, Thompson GB. Phase stability and in situ growth stresses in Ti/Nb thin films. Acta Mater, 2014, 80: 490–497
Misra A, Hirth JP, Hoagland RG. Length-scale-dependent deformation mechanisms in incoherent metallic multilayered composites. Acta Mater, 2005, 53: 4817–4824
Liu Y, Bufford D, Wang H, et al. Mechanical properties of highly textured Cu/Ni multilayers. Acta Mater, 2011, 59: 1924–1933
Zhao YF, Zhang JY, Wang YQ, et al. Unusual plastic deformation behavior of nanotwinned Cu/high entropy alloy FeCoCrNi nanolaminates. Nanoscale, 2019, 11: 11340–11350
Zhao YF, Feng XB, Zhang JY, et al. Tailoring phase transformation strengthening and plasticity of nanostructured high entropy alloys. Nanoscale, 2020, 12: 14135–14149
Wang Y, Liu B, Yan K, et al. Probing deformation mechanisms of a FeCoCrNi high-entropy alloy at 293 and 77 K using in situ neutron diffraction. Acta Mater, 2018, 154: 79–89
Zhao S, Stocks GM, Zhang Y. Stacking fault energies of face-centered cubic concentrated solid solution alloys. Acta Mater, 2017, 134: 334–345
Yang H, Zhu L, Zhang R, et al. Influence of high stacking-fault energy on the dissociation mechanisms of misfit dislocations at semi-coherent interfaces. Int J Plast, 2020, 126: 102610
Zhang YH, Zhuang Y, Hu A, et al. The origin of negative stacking fault energies and nano-twin formation in face-centered cubic high entropy alloys. Scripta Mater, 2017, 130: 96–99
Deng Y, Tasan CC, Pradeep KG, et al. Design of a twinning-induced plasticity high entropy alloy. Acta Mater, 2015, 94: 124–133
Gao Q, Gong M, Wang Y, et al. Phase transformation and properties of Fe-Cr-Co alloys with low cobalt content. Mater Trans, 2015, 56: 1491–1495
Oliver WC, Pharr GM. An improved technique for determining hardness and elastic modulus using load and displacement sensing indentation experiments. J Mater Res, 1992, 7: 1564–1583
Xue S, Fan Z, Lawal OB, et al. High-velocity projectile impact induced 9R phase in ultrafine-grained aluminium. Nat Commun, 2017, 8: 1653
Zhang X, Misra A, Wang H, et al. Enhanced hardening in Cu/330 stainless steel multilayers by nanoscale twinning. Acta Mater, 2004, 52: 995–1002
Liu Y, Chen Y, Yu KY, et al. Stacking fault and partial dislocation dominated strengthening mechanisms in highly textured Cu/Co multilayers. Int J Plast, 2013, 49: 152–163
Chen Y, Liu Y, Sun C, et al. Microstructure and strengthening mechanisms in Cu/Fe multilayers. Acta Mater, 2012, 60: 6312–6321
Thompson GB, Banerjee R, Dregia SA, et al. Phase stability of bcc Zr in Nb/Zr thin film multilayers. Acta Mater, 2003, 51: 5285.5294
Banerjee R, Dregia SA, Fraser HL. Stability of f.c.c. titanium in titanium/aluminum multilayers. Acta Mater, 1999, 47: 4225.4231
Bufford D, Liu Y, Zhu Y, et al. Formation mechanisms of high-density growth twins in aluminum with high stacking-fault energy. Mater Res Lett, 2013, 1: 51–60
Chen N, Kou H, Wu Z, et al. Design of metastable g-Ti alloys with enhanced mechanical properties by coupling αS precipitation strengthening and TRIP effect. Mater Sci Eng-A, 2022, 835: 142696
Raabe D, Sandlöbes S, Millán J, et al. Segregation engineering enables nanoscale martensite to austenite phase transformation at grain boundaries: A pathway to ductile martensite. Acta Mater, 2013, 61: 6132–6152
Fang Q, Chen Y, Li J, et al. Probing the phase transformation and dislocation evolution in dual-phase high-entropy alloys. Int J Plast, 2019, 114: 161–173
Chen W, Zhang J, Cao S, et al. Strong deformation anisotropies of ω-precipitates and strengthening mechanisms in Ti-10V-2Fe-3Al alloy micropillars: Precipitates shearing vs precipitates disordering. Acta Mater, 2016, 117: 68–80
Zhu YT, Liao XZ, Wu XL. Deformation twinning in nanocrystalline materials. Prog Mater Sci, 2012, 57: 1–62
Lu S, Sun X, Tian Y, et al. Theory of transformation-mediated twinning. PNAS Nexus, 2023, 2: pgac282
Chen Y, An X, Zhou Z, et al. Size-dependent deformation behavior of dual-phase, nanostructured CrCoNi medium-entropy alloy. Sci China Mater, 2021, 64: 209–222
Chen Y, Chen D, An X, et al. Unraveling dual phase transformations in a CrCoNi medium-entropy alloy. Acta Mater, 2021, 215: 117112
An XH, Zhu SM, Cao Y, et al. Atomic-scale investigation of interface-facilitated deformation twinning in severely deformed Ag-Cu nanolamellar composites. Appl Phys Lett, 2015, 107: 011901
Lu L, Chen X, Huang X, et al. Revealing the maximum strength in nanotwinned copper. Science, 2009, 323: 607–610
Li X, Wei Y, Lu L, et al. Dislocation nucleation governed softening and maximum strength in nano-twinned metals. Nature, 2010, 464: 877–880
Chen XH, Lu L, Lu K. Grain size dependence of tensile properties in ultrafine-grained Cu with nanoscale twins. Scripta Mater, 2011, 64: 311–314
Zhu T, Li J, Samanta A, et al. Temperature and strain-rate dependence of surface dislocation nucleation. Phys Rev Lett, 2008, 100: 025502
Asaro RJ, Suresh S. Mechanistic models for the activation volume and rate sensitivity in metals with nanocrystalline grains and nano-scale twins. Acta Mater, 2005, 53: 3369–3382
Liu SF, Wu Y, Wang HT, et al. Stacking fault energy of face-centeredcubic high entropy alloys. Intermetallics, 2018, 93: 269–273
Wu Z, Bei H, Pharr GM, et al. Temperature dependence of the mechanical properties of equiatomic solid solution alloys with face-centered cubic crystal structures. Acta Mater, 2014, 81: 428–441
Colla MS, Wang B, Idrissi H, et al. High strength-ductility of thin nanocrystalline palladium films with nanoscale twins: On-chip testing and grain aggregate model. Acta Mater, 2012, 60: 1795–1806
Varvenne C, Luque A, Curtin WA. Theory of strengthening in fcc high entropy alloys. Acta Mater, 2016, 118: 164–176
Yin B, Maresca F, Curtin WA. Vanadium is an optimal element for strengthening in both fcc and bcc high-entropy alloys. Acta Mater, 2020, 188: 486–491
Li XG, Cao LF, Zhang JY, et al. Tuning the microstructure and mechanical properties of magnetron sputtered Cu-Cr thin films: The optimal Cr addition. Acta Mater, 2018, 151: 87–99
Fan Z, Liu Y, Xue S, et al. Layer thickness dependent strain rate sensitivity of Cu/amorphous CuNb multilayer. Appl Phys Lett, 2017, 110: 161905
Van Swygenhoven H. Grain boundaries and dislocations. Science, 2002, 296: 66–67
Yip S. The strongest size. Nature, 1998, 391: 532–533
Gruber PA, Böhm J, Onuseit F, et al. Size effects on yield strength and strain hardening for ultra-thin Cu films with and without passivation: A study by synchrotron and bulge test techniques. Acta Mater, 2008, 56: 2318–2335
Chen M, Ma E, Hemker KJ, et al. Deformation twinning in nanocrystalline aluminum. Science, 2003, 300: 1275–1277
Zhang JY, Liu G, Wang RH, et al. Double-inverse grain size dependence of deformation twinning in nanocrystalline Cu. Phys Rev B, 2010, 81: 172104
Acknowledgements
This work was supported by the National Natural Science Foundation of China (U2067219, 92163201, and 52001247), the Initiative Postdocs Supporting Program (BX20190266), Shaanxi Province Youth Innovation Team Project (22JP042), and the Fundamental Research Funds for the Central Universities (xtr022019004 and xzy022019071). We would thank Dr. Shengwu Guo, Yanhuai Li and Jiao Li for their kind help with the microstructural characterization of materials.
Author information
Authors and Affiliations
Contributions
Author contributions Sun J and Liu G supervised the project. Wang Y and Zhang J initiated the research concept. Zhao Y and Wu K conducted the experiments. Wang Y and Zhang J interpreted the results and wrote the manuscript, with significant input from all other authors.
Corresponding authors
Ethics declarations
Conflict of interest The authors declare that they have no conflict of interest.
Additional information
Yufang Zhao received her BSc degree from Xi’an Jiaotong University in 2016 and earned her PhD degree in 2022, under the supervision of Prof. Jun Sun at the College of Materials Science and Engineering, Xi’an Jiaotong University. She joined the North University of China in 2022. Her current research interest is the mechanical behavior of nanolaminates.
Yaqiang Wang obtained his BSc degree (2012) and PhD degree (2019) in materials science and engineering from Xi’an Jiaotong University. He joined Prof. Gang Liu’s group after PhD graduation and was promoted to associate professor in 2021. His current research focuses on the deformation and fracture of nanostructured metal thin films/nanolaminates.
Jinyu Zhang earned his BSc degree (2005) from Lanzhou University of Technology and PhD degree (2011) in materials science and engineering from Xi’an Jiaotong University. He joined Prof. Gang Liu’s group in 2012 and was promoted to professor in 2017. His research focuses on the strengthening & toughening and deformation of nanostructured metals.
Jun Sun obtained his BSc degree from Jilin University (1982) and PhD degree (1989) in materials science and engineering from Xi’an Jiaotong University. In 2002, he joined the State Key Laboratory for Mechanical Behavior of Materials at Xi’an Jiaotong University, where he is currently a professor and group leader. His research focuses on the multiscale effect of materials’ deformation and transformation, and microstructure optimization and mechanical property enhancement of metals.
Rights and permissions
About this article
Cite this article
Zhao, Y., Wang, Y., Zhang, J. et al. Ultra-strong metal/high entropy alloy nanolaminates: Utilizing size constraining effects on phase transformation. Sci. China Mater. 66, 4207–4219 (2023). https://doi.org/10.1007/s40843-023-2623-x
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s40843-023-2623-x