An X., Zhang W., Li Y., Zhang L., Zhang Y., Wei W., Chu C. - Adv. Eng. Mater. - 2023 - 10.1002GT549adem.202201601

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RESEARCH ARTICLE
www.aem-journal.com
Microstructure and Solidification Behavior of

Co30Ni30Fe30Zr10 Eutectic Multi-Principal Element Alloy
Xulong An,* Wei Zhang, Yanhao Li, Lantian Zhang, Yong Zhang, Wei Wei,
and Chenglin Chu
and ultimate tensile strength. The alloy

Herein, the Co30Ni30Fe30Zr10 eutectic multi-principal element alloy is prepared by designing concept of a mixture of soft
vacuum arc melting. The phase composition and microstructure of eutectic alloy and hard phases is used, making
are analyzed by X-ray diffraction (XRD) and scanning electron microscope (SEM). AlCoCrFeNi2.1 EMPEA owning great
potential for engineering applications.[11]
It is showed in the results that the eutectic multi-component alloy is composed of In addition, the microstructure and proper-
primary phase and eutectic structure, in which the primary phase is Fe-rich ties of AlCoCrFeNi2.1 EMPEA are tuned
phase, and the eutectic structure is mainly composed of face-centered cubic by thermal–mechanical processing.[12–14]
(FCC) and body-centered cubic (BCC) phases. Co30Ni30Fe30Zr10 eutectic multi- The design methods of EMPEA are con-
component alloy possesses good room-temperature mechanical properties. Its stantly emerging, such as CALPHAD
(Calculation of Phase Diagrams) method,
yield strength, compressive strength, and compression ratio are 700, 1000 MPa,
pseudo binary method, parameter predic-
and 22%, respectively. tion method, and machine learning
method.[5,15,16] The aim of designing new
EMPEA is to overcome this strength–
ductility tradeoff. Among different types
1. Introduction of the EMPEA, the one with FCC/B2 structure has received
the highest attention due to its excellent mechanical properties
Multi-principal element alloys (MPEAs), also called high-entropy in both the as-cast and rolled states. Its excellent properties
alloy, extend the space of next-generation structural materials, mainly come from the composite structure of one ductile/soft
which have received increasing attention.[1–3] Eutectic multi- and one hard/strong phase. At the same time, the coherent phase
principal element alloys (EMPEAs) combining the advantages of interface of two-phase semi generates high back stress, which
MPEAs and eutectic alloys exhibit controllable near-equilibrium significantly improves the strain-hardening rate. However, there
microstructure, good castability, and excellent mechanical prop- are few studies on the formation of eutectic microstructure with
erties. Therefore, EMPEAs is one of the most promising MPEAs nano-lamellar soft and hard phase.
for industrial application, which is a research hot spot in the field In this article, a novel type of Co30Ni30Fe30Zr10 EMPEA
of structural materials.[4–6] In 2014, Lu et al.[7] have proposed and (ΔHmix = 1.31R) consisting of face-centered cubic (FCC) and
obtained the eutectic high-entropy alloys borrowing the eutectic body-centered cubic (BCC) phases was designed, and its
conception for the first time. structure and properties were investigated. The formation and
Recently, massive EMPEAs have been prepared. Most of them characterization of eutectic microstructure have been analyzed
mainly consist of face-centered cubic (FCC) and B2 phases or in detail during solidification. This work provides a theoretical
FCC and Laves phases.[8,9] Among these phases, FCC phase is reference for the design of a new type of eutectic multicompo-
a soft phase with good ductile and low strength, and B2 and nent alloy and expands the MPEA system.
Laves are hard phases having high-room-temperature
strength.[10] Therein, the AlCoCrFeNi2.1 EMPEAs consisting of
nano-lamellar L12 and B2 phases exhibit high yield strength 2. Results
The XRD the Co30Ni30Fe30Zr10 EMPEA is shown in Figure 1.
X. An, W. Zhang, W. Wei It can be seen that the alloy is mainly composed of FCC and
Department of Materials Science and Engineering
Changzhou University BCC phases, and the diffraction peak intensity of the crystal
Changzhou 213164, China plane (111) of the BCC phase is significantly higher than that
E-mail: axl@cczu.edu.cn of other crystal planes. It implies the grains growing mainly
Y. Li, L. Zhang, Y. Zhang, C. Chu along the crystal plane (111).
Department of Materials Science and Engineering The microstructure of Co30Ni30Fe30Zr10 EMPEA is given in
Southeast University Figure 2, where the obvious solidification structure can be seen.
Nanjing 211189, China
According to the different contrasts in the optical microscope
The ORCID identification number(s) for the author(s) of this article (OM) images, two structures can be easily discriminated, the
can be found under https://doi.org/10.1002/adem.202201601. bright areas represent the primary phase, and the dark ones
DOI: 10.1002/adem.202201601 exhibit lamellar eutectic structure. At the initial solidification
Adv. Eng. Mater. 2023, 2201601 2201601 (1 of 5) © 2023 Wiley-VCH GmbH

15272648, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adem.202201601 by Indian Institute of Technology, Indore, Wiley Online Library on [11/02/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
www.advancedsciencenews.com www.aem-journal.com
structure, and the eutectic structure is composed of soft FCC

600 (111) phase and hard BCC phase.
fcc-
The SEM microstructure of the as-cast alloy is shown in
500 bcc- Figure 3. Figure 3a clearly reveals the solidification structure con-
tain ellipsoid primary phase and lamellar eutectic structure.
400 The eutectic structure is regular and interphase arrangement
Intensity/a.u
(110)
in the same group, but the orientation of eutectic structure group
300 is different.
The corresponding EDS mapping of Co30Ni30Fe30Zr10
200 EMPEA is shown in Figure 4. It indicates that the large primary
(200)
phase is enriched with Fe, the eutectic phases are enriched with
(311)
100 (220)
Zr, and the distribution of Co and Ni is relatively homogeneous.
(222)
(200) (211) Eutectic transformation is also a process of nucleation and
0
growth. During nucleation, one of the phases is preferentially
nucleated as the primary phase. At the same time, due to the dif-
40 50 60 70 80 90 100 fusion and enrichment of elements, the nucleation of the other
2θ/° phase is induced. Then, the two phases grow alternately, forming
a eutectic group. In Co30Ni30Fe30Zr10 EMPEA, the primary phase
Figure 1. X-ray diffraction pattern of Co30Ni30Fe30Zr10 eutectic multi-
is an Fe-rich phase. At the beginning of solidification, this phase
principal element alloy (EMPEA).
is not a lamellar structure but irregular shaped. With the progress
of solidification, the irregular shape gradually changed into lamel-
lar structure, finally the eutectic structure of two-phase coexis-
stage, some fine grains nucleate from liquid phase at a lower tence was formed. In addition, the characters of various
undercooling. Those grains are growing gradually forming the phases in Co30Ni30Fe30Zr10 EMPEA are summarized in Table 1.
primary phase. When temperature is decreasing, the primary To further investigate the phase structure information, the
phase becomes the new nucleation core. Along the grain bound- eutectic structure in the as-cast Co30Ni30Fe30Zr10 EMPEA is ana-
ary of the primary phase, lamellar eutectic structure appears. The lyzed by TEM. The bright-field images in Figure 5a,b show that
two phases of eutectic structure grow continuously in a “bridg- eutectic morphology consists of thicker FCC (white regions
ing” way, resulting in the formation of regular and fine lamellar having average thickness 60 nm) and BCC (gray regions having
structure. In combination with XRD diffraction analysis average thickness 50 nm) lamellae. The selected area diffrac-
(Figure 1), it can be seen that the primary phase has BCC tion patterns (SADPs) obtained from the matrix FCC phase
Figure 2. OM images of Co30Ni30Fe30Zr10 EMPEA with different magnification. a) 10, b) 20, c) 50, and d) 100.

Figure 3. Scanning electron microscope (SEM) images of Co30Ni30Fe30Zr10 EMPEA with different magnification. a) 12500, b) 40000, and c) 50000.
Figure 4. Energy-dispersive spectroscopy (EDS) compositional maps acquired at primary phase and eutectic phases of Co30Ni30Fe30Zr10 EMPEA. a) Fe
element, b) Co element, c) Ni element, and d) Zr element.
Table 1. The structure, compositions, and size of the various phases in structure of Co30Ni30Fe30Zr10 EMPEA with a simple model by
Co30Ni30Fe30Zr10 EMPEA. studying the solidification structure of the MPEA. Figure 6 shows
the formation of eutectic structure in Co30Ni30Fe30Zr10 EMPEA.
Phase Crystal structure Compositions Size In the solidification process of the alloy, when the temperature
Fe Co Ni Zr reaches the eutectic transition point, eutectic reaction will
Primary phase FCC 41 34 25 0 2 20 3 μm occur. However, the primary phases will form first in the liquid
Eutectic phases FCC þ BCC 28 31 33 8 50 5 nm
phase, which was seldom remelted and retained to room
temperature.[17] So the primary phase will soon become the
nucleation point of the new phase. The primary phase is rich
and BCC phase are shown in Figure 5c. The lattice constant of in Fe and poor in Zr, indicating that some atoms will be excluded
FCC phase is about 3.59 Å. The lattice constant of BCC phase is during the formation of the primary phase, making the liquid
about 2.84 Å, which is consistent with the test results of XRD. In phase near the interface rich in Zr, which leads to the crystalli-
addition, the two phases of lamellar eutectic have the following ori- zation of another phase. Therefore, the eutectic phases nucleate
entation relationship: {111}FCC∥{110}BCC,<121>FCC∥<110>BCC. and grow attached to grain boundary of the primary phases. At
The eutectic microstructure formation process of MPEA is the same time, due to the diffusion of Zr element in the matrix,
complex, and there is still no reasonable model to describe lamellar eutectic clusters are formed by bridging connection. It
the formation process of multicomponent eutectic structure. can be seen that the lamellar eutectic structure is mainly com-
This paper attempts to analyze the formation process of eutectic posed of FCC phase and BCC phase, in which BCC is Zr-rich

Figure 5. Transmission electron microscope (TEM) images of Co30Ni30Fe30Zr10 EMPEA: a,b) bright-field images, showing the lamellar eutectic structure;
c) diffraction pattern confirming the lamellar eutectic structure including face-centered cubic (FCC) and body-centered cubic (BCC) phases.
Figure 6. Schematic diagram showing the formation processing of primary phase and lamellar eutectic phase in Co30Ni30Fe30Zr10 EMPEA.
phase, and the lamellar layer has the same FCC phase structure as curve, it can be seen that the yield strength, compressive strength,
the matrix and primary phase. In addition, in the eutectic reac- and compression ratio of alloy are 700, 1000 MPa, and 24%,
tion, the two phases of the eutectic often have a certain orientation respectively. Some researches show that the eutectic interface
relationship, which can reduce the specific interface energy of the of BCC/FCC is semi-coherent, which belongs to the strong inter-
lamellar interface and make the lamellar eutectic structure stable. facial combination with a high interfacial bonding strength.[18,19]
Figure 7 shows compression engineering stress–strain curve
of Co30Ni30Fe30Zr10 EMPEA at room temperature. From the
3. Conclusions
1100
In summary, Co30Ni30Fe30Zr10 EMPEA cast by vacuum arc meta-
1000
ling and suction melting has been successfully designed and
investigated. The microstructure and solidification behavior of
900 the alloy have been systemically studied by means of OM,
Engineering stress/MPa
SEM, XRD, and TEM techniques. The results show that the alloy
800 is mainly composed of FCC and BCC phases. The XRD analysis
implies the grains of BCC growing mainly along the crystal plane
700 (110). The primary phase is rich in Fe and poor in Zr. The alloy
has good room-temperature properties, and its yield strength,
600 compressive strength, and compression ratio are 700, 1000,
and 22%, respectively.
500
400 4. Experimental Section

300 Bulk non-equiatomic Co30Ni30Fe30Zr10 ingots with diameter of 10 mm
0 5 10 15 20 25 30 were cast by employing a vacuum arc melting equipment at a pressure of
Engineering strain/% 1 103 Pa using high purity (>99.9%) elements. The molten liquid metal
was suctioned into a copper crucible followed by air cooling. Phase identi-
Figure 7. Compressive engineering stress–stain curve of Co30Ni30Fe30Zr10 ties were determined using X-ray diffraction (XRD) and the data were col-
EMPEA at room temperature. lected with Cu Kα radiation on a Bruker D8-discover diffractometer

operating at 40 kV and 150 mA between 40° and 110° (2θ) at a scanning Received: November 7, 2022
rate of 2.5° min1 with step size 0.02° step1. Samples for XRD measure- Revised: December 31, 2022
ments were finished with colloidal silica suspension polishing. The micro- Published online:
structure was characterized using OM, scanning electron microscopy
(SEM, Sirion FEG), and transmission electron microscopy (TEM, G20)
equipped with energy-dispersive spectroscopy (EDS) operating with an [1] Y. Zhang, X. Yang, P. K. Liaw, JOM 2012, 64, 830.
accelerating voltage of 200 kV. Samples for SEM were prepared through
[2] D. B. Miracle, Acta Mater. 2017, 122, 448.
an initial polishing down to a 2000 grit SiC paper and finished with 1 μm
[3] P. Shi, R. Li, Y. Li, Y. Wen, Y. Zhong, W. Ren, Z. Shen, T. Zheng,
diamond suspension polishing, and etched by a solution containing 80 mL
H2O þ 20 mL aqua regia. The TEM specimens were first ground to about J. Peng, X. Liang, P. Hu, N. Min, Y. Zhang, Y. Ren, P. K. Liaw,
60 μm in thickness and followed by electro-polishing (temperature: D. Raabe, Y.-D. Wang, Science 2021, 373, 912.
20 °C, voltage: 20 V, electrolyte: 10% perchlorate ethanol). The compres- [4] C. Ai, F. He, M. Guo, J. Zhou, Z. Wang, Z. Yuan, Y. Guo, Y. Liu, L. Liu,
sion test was carried out on the GMT5105 universal testing machine with a J. Alloys Compd. 2017, 735, 2653.
compression rate of 1 mm min1. To ensure the accuracy of data, at least [5] Y. Lu, H. Jiang, S. Guo, T. Wang, Z. Cao, T. Li, Intermetallics 2017,
three samples shall be selected for samples in the same state. 91, 124.
[6] S. Muskeri, V. Hasannaeimi, R. Salloom, M. Sadeghilaridjani,
S. Mukherjee, Sci. Rep. 2020, 10, 2669.
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J. Jie, Z. Cao, H. Ruan, T. Li, Sci. Rep. 2014, 4, 6200.
This research was supported by Natural Science Foundation for Young [8] X. Chen, J. Q. Qi, Y. W. Sui, Y. Z. He, F. X. Wei, Q. K. Meng, Z. Sun,
Scholars of Jiangsu Province (Grant no. BK20220628), Scientific Mater. Sci. Eng., A 2017, 681, 25.
Research Foundation of Jiangsu Provincial Education Department
[9] X. Jin, Y. Zhou, L. Zhang, X. Du, B. Li, Mater. Lett. 2018,
(Grant no. 21KJB430012), Changzhou Sci&Tech program (Grant no.
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15272648, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/adem.202201601 by Indian Institute of Technology, Indore, Wiley Online Library on [11/02/2023].

Microstructure and Solidiﬁcation Behavior of

and ultimate tensile strength. The alloy

Adv. Eng. Mater. 2023, 2201601 2201601 (1 of 5) © 2023 Wiley-VCH GmbH

structure, and the eutectic structure is composed of soft FCC

Adv. Eng. Mater. 2023, 2201601 2201601 (2 of 5) © 2023 Wiley-VCH GmbH

Adv. Eng. Mater. 2023, 2201601 2201601 (3 of 5) © 2023 Wiley-VCH GmbH

400 4. Experimental Section

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