Materials Science and Technology

ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/ymst20

Microstructure and solidification behaviour of

CuNiSiAl eutectic multi-principal element alloy

Xulong An, Xiaotong Zhang, Yudong Sui, Jing Hu, Zhengxiang Xu, Wei Wei,
Chenglin Chu & Wenwen Sun

To cite this article: Xulong An, Xiaotong Zhang, Yudong Sui, Jing Hu, Zhengxiang Xu, Wei
Wei, Chenglin Chu & Wenwen Sun (2023): Microstructure and solidification behaviour of
CuNiSiAl eutectic multi-principal element alloy, Materials Science and Technology, DOI:
10.1080/02670836.2023.2210917

To link to this article: https://doi.org/10.1080/02670836.2023.2210917

Published online: 14 May 2023.

Submit your article to this journal

Article views: 38

View related articles

View Crossmark data

Full Terms & Conditions of access and use can be found at

https://www.tandfonline.com/action/journalInformation?journalCode=ymst20
MATERIALS SCIENCE AND TECHNOLOGY
https://doi.org/10.1080/02670836.2023.2210917

Microstructure and solidification behaviour of CuNiSiAl eutectic multi-principal

element alloy
Xulong Ana , Xiaotong Zhangb , Yudong Suic , Jing Hua , Zhengxiang Xud , Wei Weia , Chenglin Chub and
Wenwen Sun b
a School of Materials Science and Engineering, Changzhou University, Changzhou, People’s Republic of China; b Department of Materials
Science and Engineering, Southeast University, Nanjing, People’s Republic of China; c School of Materials Science and Engineering,
Kunming University of Science and Technology, Kunming, People’s Republic of China; d Jiangsu Key Laboratory for Light Metal Alloys
(Nanjing Yunhai Special Metals Co., LTD), Nanjing, People’s Republic of China

ABSTRACT ARTICLE HISTORY

Eutectic multi-principal element alloys show great promise due to their exceptional castabil- Received 17 December 2022
ity, unique near-equilibrium microstructure, and controllability. In this study, a novel copper- Revised 5 April 2023
containing Cu42.3 Ni30 Si15 Al12.7 eutectic multi-principal element alloy was designed and inves- Accepted 30 April 2023
tigated. The microstructure of the alloy is composed of primary phase Ni2 Si and eutectic phase KEYWORDS
(FCC(Cu) + BCC(NiAl)). The eutectic reaction temperature is 1004°C. Understanding the solidifi- Metals and alloys; copper
cation process is crucial for optimising solidification parameters and subsequent annealing. The alloys; eutectic medium
as-cast Cu42.3 Ni30 Si15 Al12.7 alloy exhibits high micro-hardness (400 ± 2.4 HV) and compressive entropy alloys; phase
fracture strength (1511 MPa) transformation

Introduction
Multi-principal element alloys (MPEAs) that exhibit an
excellent combination of high strength and good duc-
tility have garnered significant attention [1]. Among
them, Eutectic multi-principal element alloys
(EMPEAs) are considered to be a promising materi-
als owe to exhibit excellent castability, controllable and
unique near-equilibrium microstructure [2–5]. Several
design methods have been proposed to expand the
variety of EMPEAs [6, 7]. Currently, EMPEAs are pre-
dominantly fabricated using conventional casting and
directional solidification techniques [8–10]. Various
microstructures can be formed depending on the eutec-
tic composition and temperature point. For instance, a
sunflower-like eutectic colony structure was observed
in a near-eutectic Al2 CrCuFeNi2 HEA, where the B2
phase formed as the primary phase with a spheri-
cal or ellipsoidal morphology, and the B2/A2 eutectics
grew on the primary phase in a radial manner [11].
Shi et al. [12] fabricated Al19 Fe20 Co20 Ni41 EMPEA
through directional solidification. The alloy has a hier-
archically organised herringbone structure that enables
bio-inspired hierarchical crack buffering. The uniform
and ultrafine L21 and BCC lamellar structures were
observed in an AlCr1.3 TiNi2 EHEA prepared by direct
solidification [13]. The CoCrFeNiNb0.65 eutectic alloy
is composed of a face centred cubic phase and laves
phase with fine laminar structures [14].
Copper-rich alloys are crucial and highly conductive
metals. Furthermore, copper is a commonly chosen ele-
ment in the design of MPEAs, often added by default
as a major principle alloying element in many systems
[15–17]. The role of Cu in MPEA systems is twofold,
with some research indicating it can enhance mechan-
ical properties, while other studies show it may not be
beneficial [18–20]. The high mixing enthalpy between
Cu and principle elements of MPEAs can result in
significant Cu segregation in the grain boundaries or
inter-dendrites when small amounts of Cu are added to
the alloy [21]. Currently, copper content in MPEAs is
strictly limited, even when it is a major element, with
a maximum content of 25%. There are no reports of
MPEAs containing high amounts of copper in the liter-
ature. However, a new MPEA that includes copper has
been developed, providing a new option for expanding
the range of copper alloys, including those used in the
outer cylinder of drilling tools.
This study designed a new containing-Cu Cu 42.3 Ni30
Si15 Al12.7 MPEA has an entropy of mixing Smix =
1.1R. The microstructure and solidification behaviour
of the alloy were analysed using transmission elec-
tron microscopy (TEM) and X-ray diffractometry
(XRD), with differential scanning calorimetry (DSC)
used to investigate phase transitions during solidifi-
cation. Understanding the microstructure and phase
changes in MPEAs during solidification is crucial for

CONTACT Wenwen Sun swwcsu@live.cn Department of Materials Science and Engineering, Southeast University, Nanjing 21118,
People’s Republic of China

© 2023 Institute of Materials, Minerals and Mining.

2 X. AN ET AL.
optimising solidification parameters to improve the
alloy’s mechanical properties.
Methods
As per the nominal composition, bulk non-equiatomic
Cu42.3 Ni30 Si15 Al12.7 (atomic percent, at.%) ingots with
diameter of 50 mm were cast using high purity
( > 99.9%) elements and a vacuum induction melting
equipment at a pressure of 5 × 10−4 Pa. The molten
metal was poured into a graphite crucible and air-
cooled to form the ingots. A schematic diagram of the
processing steps is provided in Figure 1.
X-ray diffraction (XRD) was used to determine
phase identities, with data collected on a Bruker D8-
discover diffractometer using Cu Kα radiation, scan-
ning between 40° and 110° (2θ) at a scanning rate
of 2.5°/min with step size 0.02°/step. Samples were
finished with colloidal silica suspension polishing.
Microstructure was characterised using optical micro-
scope, scanning electron microscopy (SEM), trans-
mission electron microscopy (TEM), and scanning
transmission electron microscopy (STEM) equipped
with energy-dispersive spectroscopy (EDS). Samples
for SEM were finished with 1μm diamond suspension
polishing and etched by a solution containing H2 O,
concentrated hydrochloric acid, saturated ferric chlo-
ride, and saturated copper sulfate. TEM specimens were
thinned by a Fischione Precision Ion Polishing system
after being ground to about 60 μm in thickness. The
temperature of phase transition was determined using
DSC, with heating and cooling rates of 20 K/min in a
flowing argon atmosphere and sintered Al2 O3 as the
reference substance.
Cylinder compression samples with a diameter of
6 mm and length of 12 mm were cut using electrical dis-
charge machining. Compression tests were performed
at room temperature using an Instron 5982 machine
with a crosshead speed of 1 mm/min, and three com-
pression specimens were tested for each condition to
confirm reproducibility.
Figure 1. The schematic diagram of the processing technique and steps.
Results
The as-cast microstructures of Cu42.3 Ni30 Si15 Al12.7
MPEA show significant variation between the centre,
edge, and middle positions of the ingot due to differ-
ences in cooling rate (Figure 2). The primary phase
appears as white maple leaf-like structures, while the
dark structures represent a lamellar eutectic structure.
The size of the primary phase decreases from the cen-
tre to the edge of the ingot, with diameters of ∼ 100,
∼ 50, and ∼ 25 μm in the inner, middle, and outer
regions, respectively. This size difference is attributed to
faster cooling rates resulting in smaller primary phases,
while slower cooling allows the primary phase to grow
larger. These observations were made using optical
microscopy.
Figure 3 displays the microstructure, elemental dis-
tributions, and phase identities of a sample cutting
taken from the edge part of a cylindrical ingot. X-
ray diffraction (XRD) analysis was used to identify the
phases present in the sample, as shown in Figure 3(m),
which confirms the presence of FCC-Cu, Ni2 Si, and
BCC-NiAl phases.
To obtain a detailed understanding of the microstruc-
ture of the sample, scanning electron microscopy
(SEM) was employed. Figure 3(f) shows a secondary
electron (SE) SEM image at a low magnification, which
reveals a significant amount of the primary phase in the
sample. Overall, the information provided in Figure 3
and the accompanying descriptions can be used to gain
insight into the composition and microstructure of the
sample.
Figure 3(a–e) shows an enlarged SE image and the
corresponding EDS mapping. The EDS mapping indi-
cates that the large primary phase is enriched in Si
and Ni, while the rest area is rich in Cu, and the
distribution of Al is more homogeneous with parti-
tioning only in a few areas. The fine eutectic struc-
ture is further investigated by TEM and STEM/EDS.
The Cu-rich lamellae are several hundred nanometres
to 1 um thick, while the rest of the eutectic region is
occupied with two distinct features possessing different
 MATERIALS SCIENCE AND TECHNOLOGY 3

Figure 2. Optical micrographs of as-cast Cu42.3 Ni30 Si15 Al12.7 MPEA in different section of cast ingot. (a, d) Centre region, (b, e) middle
region between centre and edge parts, and (c, f) edge region.

Figure 3. Characterization and phase identifications in as-cast Cu42.3 Ni30 Si15 Al12.7 MPEA cutting from the edge region of the cylin-
drical ingot. (a–f) SEM SE images and EDS mapping, (g–l) STEM/EDS mapping of eutectic structure, (m) XRD spectrum, (n) a TEM BF
image, (o–q) SAD patterns of regions A, B and C in (l) and (n).

elemental partitioning, labelled as regions B and C
in Figure 3(g–l). The phases are further confirmed
by selected area electron diffraction (SAED) patterns,
with the Cu-rich lamellar having FCC structure, Ni-
Si rich region having Orthorhombic Ni2 Si structure,
and Ni-Al rich region having BCC NiAl B2 structure
(Figure 3(o–q)).
DSC measurement was utilised to discern the
phase transformation processes during solidification, as
shown in Figure 4. In the case of Cu42.3 Ni30 Si15 Al12.7
MPEA, four distinct exothermic peaks were observed
during cooling, occurring at temperatures of 1055°C,
1004°C, 946°C, and 877°C, respectively. The first peak
at 1055°C corresponds to the liquid phase transforming
4 X. AN ET AL.
Figure 4. DSC heating and cooling curves of Cu42.3 Ni30 Si15
Al12.7 MPEA.
into a solid phase. The second peak at 1004°C indicates
the nucleation of primary Ni2 Si, followed by the for-
mation of FCC phase nucleating on it. Subsequently,
the residual liquid undergoes a eutectic transformation,
simultaneously forming FCC and BCC phases, result-
ing in the formation of an FCC + BCC-NiAl eutec-
tic microstructure. This phase transformation process
is further illustrated in the provided schematic dia-
gram (Figure 4). Overall, DSC measurement provides
valuable insights into the solidification behaviour of
Cu42.3 Ni30 Si15 Al12.7 MPEA.
Figure 5. Schematic drawing of the solidification process of Cu42.3 Ni30 Si15 Al12.7 MPEA. (a) The liquid phase, (b) Nucleation and
growth of the primary phase, (c) The eutectic reaction surrounding the primary phase, (d) the primary islands like maple leaves,
and (e) the enlarged red box in (c).
Based on the above analysis of XRD, TEM SAD pat-
terns and DSC, it can be concluded that the as-cast
Cu42.3 Ni30 Si15 Al12.7 MPEA is consist of Ni2 Si phase,
Cu-rich FCC phase and NiAl-rich BCC phase. The
overall solidification process of the alloy is schemati-
cally shown in Figure 5. When the alloy begins to solid-
ify, the Ni2 Si phase nucleates preferentially from the
liquid as the primary phase, then grows (Figure 5(b)).
The formation of primary phase islands causes a slight
depletion of Ni and Si in the residual liquid phase, and
its composition changes and approaches the eutectic
composition. When the temperature drops to the eutec-
tic point, FCC starts to emerge, evidently on the Ni2Si
interface, quickly followed by an FCC + BCC-NiAl
eutectic. The eutectic reaction L → FCC-Cu + BCC-
NiAl initiates in the remaining liquid (Figure 5(c)),
and similar results have been reported in CuNiSi alloys
[22]. Interesting observation, the primary phase islands
have a maple leaf-like appearance, as shown in Figure
5(d). Furthermore, the eutectic microstructure is dif-
ferent from the traditional one, as FCC first nucleates
on the Ni2 Si before being infilled with FCC and BCC
lamellae.
The mechanical properties of the as-cast Cu42.3 Ni30
Si15 Al12.7 MPEA were evaluated in terms of hard-
ness and compression strength, as shown in Figure 6.
The average microhardness is 400 ± 2.4HV, and the
alloy has an excellent compression strength of about
1511 MPa. The primary phase Ni2 Si, which forms a

Figure 6. Compression engineering stress-strain curve with
microhardness value inserted of the as-cast Cu42.3 Ni30 Si15 Al12.7
MPEA.
stable intermetallic compound and has a large mis-
fit strain with the CuNi matrix, is responsible for
the high strength of the MPEA [23, 24]. Addition-
ally, studies have shown that a fine and/or lamellar
FCC/BCC structure leads to superior mechanical prop-
erties. The eutectic phase interface of FCC/BCC is
semi-coherent, which has a strong interfacial com-
bination and high interfacial bonding strength. The
large number of eutectic phase interfaces and high
density of interfacial dislocations can hinder dis-
location motion, as reported in previous studies
[10, 13, 25, 26].
Conclusions
(1) The microstructure and solidification behaviour
of the alloy have been systemically studied using
Optical microscope, Scanning Electron Micro-
scope, X-Ray Diffraction, Transmission Electron
Microscope /Scanning Transmission Electron
Microscope and Differential Scanning Calorime-
try techniques. The results show that primary
Ni2 Si phase is inclined to nucleate and grow dur-
ing the initial stage of solidification, forming maple
leaves-like islands.
(2) The size of the primary Ni2 Si decreases from
centre to edge part of cylindrical ingot, due to
the increasing cooling rate. When temperature
drops to 1004°C, the eutectic reaction L → FCC
(Cu) + BCC (NiAl) initiates in the remaining liq-
uid.
(3) The microstructure of the final as-cast alloy is com-
posed of primary Ni2 Si and eutectic phase FCC-
Cu + BCC-NiAl.
Disclosure statement
No potential conflict of interest was reported by the author(s).
MATERIALS SCIENCE AND TECHNOLOGY 5
Funding
This work was supported by Natural Science Founda-
tion for Young Scholars of Jiangsu Province [Grant No.
BK20220628], Scientific Research Foundation of Jiangsu
Provincial Education Department [Grant No. 21KJB430012],
Changzhou Sci&Tech programme Sci&Tech programme
[Grant No. GJ20220153], National Natural Science Foun-
dation for Young Scholars of China [Grant No. 52001063],
Natural Science Foundation for Young Scholars of Jiangsu
Province [Grant No. BK20200387], and Jiangsu Key Labora-
tory for Light Metal Alloys [Grant No. LMA202201] and State
Key Programme of National Natural Science Foundation of
China [Grant No. 52231005].
ORCID
Wenwen Sun http://orcid.org/0000-0002-2800-384X
References
[1] Jin X, Bi J, Zhang L, et al. A new CrFeNi2 Al eutec-
tic high entropy alloy system with excellent mechanical
properties. J Alloys Compd. 2019;770:655–661.
[2] Mukarram M, Mujahid M, Yaqoob K. Design and devel-
opment of CoCrFeNiTa eutectic high entropy alloys. J
Mater Res Technol. 2020;10:1243–1249.
[3] Guo S, Chun N, Liu CT. Sunflower-like solidification
microstructure in a near-eutectic high-entropy alloy.
Mater Res Lett. 2013;1(4):228–232.
[4] Ding ZY, He QF, Wang Q, et al. Superb strength and high
plasticity in laves phase rich eutectic medium-entropy-
alloy nanocomposites. Int J Plast. 2018;106:57–72.
[5] Jiang ZF, Chen WP, Xia ZB, et al. Influence of synthe-
sis method on microstructure and mechanical behav-
ior of Co-free AlCrFeNi medium-entropy alloy. Inter-
metallics. 2019;108:45–54.
[6] Sheikh S, Shafeie S, Hu Q, et al. Alloy design for intrinsi-
cally ductile refractory high-entropy alloys. J Appl Phys.
2016;120(16):164902.
[7] Zhang F, Zhang C, Chen SL, et al. An understanding
of high entropy alloys from phase diagram calculations.
Calphad Comput Coupling Ph Diagr Thermochem.
2014;45:1–10.
[8] Wang M, Lu Y, Wang T, et al. A novel bulk eutec-
tic high-entropy alloy with outstanding as-cast spe-
cific yield strengths at elevated temperatures. Scr Mater.
2021;204:114132.
[9] Lu Y, Dong Y, Guo S, et al. A promising new class of
high-temperature alloys: eutectic high-entropy alloys.
Sci Rep. 2014;4:6200.
[10] Jin X, Zhou Y, Zhang L, et al. A novel Fe20 Co20 Ni41 Al19
eutectic high entropy alloy with excellent tensile prop-
erties. Mater Lett. 2018;216:144–146.
[11] Sheng G, Ng C, Liu CT. Sunflower-like solidification
microstructure in a near-eutectic high-entropy alloy.
Mater Res Lett. 2013;1:228–232.
[12] Shi P, Li R, Li Y, et al. Hierarchical crack buffering triples
ductility in eutectic herringbone high-entropy alloys.
Science. 2021;373(6557):912–918.
[13] Wang M, Lu Y, Wang T, et al. A novel bulk eutec-
tic high-entropy alloy with outstanding as-cast spe-
cific yield strengths at elevated temperatures. Scr Mater.
2021;204:114132.
[14] Feng H, Wang Z, Peng C, et al. Designing eutectic
high entropy alloys of CoCrFeNiNbx. J Alloys Compd.
2016;656:284–289.
6 X. AN ET AL.
[15] Munitz A, Kaufman MJ, Nahmany M, et al. Microstruc-
ture and mechanical properties of heat treated Al1.25Co
CrCuFeNi high entropy alloys. Mater Sci Eng A.
2018;714:146–159.
[16] Zhang LJ, Yu PF, Zhang M, et al. Microstructure
and mechanical behaviors of GdxCoCrCuFeNi high-
entropy alloys. Mater Sci Eng A. 2017;707:708–716.
[17] Han Z, Wang D, Chen X, et al. Characterization and
properties of CuZrAlTiNiSi high entropy alloy coat-
ing obtained by mechanical alloying and vacuum Hot-
pressing sintering. JOM. 2020;72(3):1254–1263.
[18] Verma A, Tarate P, Abhyankar AC, et al. High tempera-
ture wear in CoCrFeNiCux high entropy alloys: the role
of Cu. Scr Mater. 2019;161:28–31.
[19] Shang C, Axinte E, Ge W, et al. High-entropy alloy
coatings with excellent mechanical, corrosion resis-
tance and magnetic properties prepared by mechani-
cal alloying and hot pressing sintering. Surf Interfaces.
2017;9:36–43.
[20] Cai Y, Chen Y, Luo Z, et al. Manufacturing of FeCoCr-
NiCu x medium-entropy alloy coating using laser
cladding technology. Mater Des. 2017;133:91–108.
[21] Yu Y, Xu N, Zhu S, et al. A novel Cu-doped high entropy
alloy with excellent comprehensive performances for
marine application. J Mater Sci Technol. 2021;69:48–59.
[22] Liu X, Xiang S, Yang S, et al. Experimental investiga-
tion of phase equilibria in the Cu-Ni-Si ternary system.
J Alloys Compd. 2013;578:439–447.
[23] Fukamachi K, Kimura M. Age-hardening structure
and mechanism of Cu–3at%Ni–1.5 at%Si corson alloy.
Mater Sci Eng A. 2022;831:142220.
[24] Cao YC, Han SZ, Choi EA, et al. Effect of inclu-
sion on strength and conductivity of Cu-Ni-Si alloys
with discontinuous precipitation. J Alloys Compds.
2020;843:156006.
[25] Jin X, Zhou Y, Zhang L, et al. A new pseudo binary strat-
egy to design eutectic high entropy alloys using mix-
ing enthalpy and valence electron concentration. Mater
Des. 2018;143:49–55.
[26] Shang Z, Shen J, Wang L, et al. Effect of microstruc-
ture morphology on the high temperature tensile
properties and deformation in directionally solidified
NiAl-Cr(Mo) eutectic alloy. Mater Charact. 2015;109:
152–159.