Materialia 26 (2022) 101618

Contents lists available at ScienceDirect

Materialia
journal homepage: www.elsevier.com/locate/mtla

Effect of annealing treatment on microstructural and mechanical properties

of a hot-forged FeCrCuMn2 Ni2 high-entropy alloy
Seyyed Ali Sajadi a, Mohammad Reza Toroghinejad a,∗, Ahmad Rezaeian a, Zhenggang Wu b
a
Department of Materials Engineering, Isfahan University of Technology, Isfahan 8415683111, Iran
b
College of Materials Science and Engineering, Hunan University, Changsha, Hunan 410082, China

a r t i c l e i n f o a b s t r a c t

Keywords: The present study prepared an as-cast ingot of a FeCrCuMn2 Ni2 high-entropy alloy using vacuum induction
FeCrCuMn2 Ni2 high-entropy alloy melting process, followed by hot forging at 650–750 °C. The samples were then annealed at temperatures be-
Hot forging tween 600 and 1100 °C for 2 h, and were characterized in terms of their microstructural features and mechanical
Annealing
properties. No phase transformation was observed for the hot-forged and annealed samples. Compared to the as-
Microstructure
cast state, the hot-forged sample exhibited higher compressive yield strength and hardness, but lower compressive
Mechanical properties
Hardening capacity strain. This behavior can be due to the precipitation of hard 𝜎-phase with an average size of 0.55 μm during hot
Strain hardening behavior forging. It was further observed that the precipitates dissolved, when the temperature exceeded 1000 °C, resulting
in discontinuous static recrystallization with an average grain size of 15.9 μm. Annealing between 600 and 800
°C decreased the compressive yield strength and compressive strain, which could be attributed to 𝜎-precipitates
morphological change and their growth up to an average size of 1.34 μm. On the other hand, when the annealing
temperature increased above 800 °C, the compressive yield strength decreased and compressive strain increased.
This behavior was attributed to the dissolution of a large amount of 𝜎-precipitates, growth of the residual 𝜎-
precipitates, and softening of the alloy. Findings further revealed a decrease in the hardening capacity value of
annealed samples in the range of 600–800 °C, resulting from the formation of 𝜎-precipitates. In contrast, the
hardening capacity value of the alloy increased with the annealing temperature, due to the grains size increase
at higher temperatures.

1. Introduction solution structure exhibited exceptional ductility and fracture toughness

High entropy alloys (HEAs) were proposed by Yeh et al. in 2004,
consist of at least five principal elements with equiatomic or near-
equiatomic ratios [1]. Since then, various research works have widely
developed these alloys as a promising candidate utilized as high-
performance materials [1–3]. HEAs possess unique properties thanks to
multi-principal element composition, including high entropy, lattice dis-
tortion, sluggish diffusion, and cocktail effect, affecting final microstruc-
tural and mechanical properties [4,5]. The above-mentioned character-
istics of the alloy have been shown to enhance tendency for forma-
tion and stability of the resultant solid solution phases, which in turn
can ultimately inhibit dislocations motion and improve the mechanical
strength, especially at high temperature applications.
Despite the progress made, recent studies have indicated that HEAs,
especially those with a single FCC phase, are not strong enough for prac-
tical applications [6–9,36]. In this regard, few studies have focused on
improving the mechanical properties of HEAs [10–12]. For example, it
was reported that although the FeCoNiCrMn HEA with simple FCC solid
even at liquid-nitrogen temperature, its yield strength in as-cast condi-
tion was relatively as low as 200 MPa [6]. As a solution, Otto et al.
[7] found out that the room temperature yield strength of FeCoNiCrMn
HEA significantly increased from 200 to 350 MPa with decreasing grain
size from 144 to 4.4 μm. In this regard, many efforts have been made in
order to achieve a superior combination of strength-ductility in HAEs.
It has been proved that the annealing treatment plays a vital role in
improving the microstructure and properties of HEAs [2].
Most of the studies have currently focused on investigating the mi-
crostructure and properties of HEAs in as-cast condition. Also, there are
many studies attempted to evaluate the effects of annealing treatment on
HEAs behavior [2,13–15]. For instance, Zhang et al. [13] and Wen et al.
[14] have reported that the annealing resulted in a phase transforma-
tion from BCC to FCC, leading to decreased compressive strength and
increased plasticity in CoCrFeNiCuAl HEA. In another study, Zhuang
et al. [2] have reported that compressive strength of FeCoNiCuAl
HEA decreased with increasing annealing temperature. On the other
hand, various studies showed that the precipitation hardening, as a

∗
Corresponding author.
E-mail address: toroghi@iut.ac.ir (M.R. Toroghinejad).

https://doi.org/10.1016/j.mtla.2022.101618
Received 12 August 2022; Accepted 29 October 2022
Available online 30 October 2022
2589-1529/© 2022 Acta Materialia Inc. Published by Elsevier B.V. All rights reserved.
S.A. Sajadi, M.R. Toroghinejad, A. Rezaeian et al.
strengthening mechanism, usually accrued in many HEAs systems dur-
ing annealing [11,15,16].
In this regard, it is reported that thermal mechanical methods such
as hot rolling and hot forging can decrease the casting defects and refine
the microstructure; as a result, stimulate precipitation in high entropy
alloys [11]. Indeed, the refinement during hot deformation along with
the crystalline defects forming during the deformation processes leading
to earlier nucleation of precipitates [10]. But up to now, there is very few
researches focusing on hot-deformed HEAs and its effects on mechanical
properties of HEAs. Shaysultanov et al. [17] have presented a transfor-
mation from a coarse dendritic structure to a fine equiaxed structure
in AlCoCrCuFeNi alloy through hot forging. They have reported a sig-
nificant improvement both in strength and ductility was obtained after
extensive forging at 950 °C. In another study, Cao et al. [12] have inves-
tigated the precipitation behavior and strengthening mechanism of the
hot deformed TiNbTa0.5 ZrAl0.5 HEA. The authors have indicated that
the aforementioned alloy decomposes into two phases, the BCC matrix
and the HCP (Zr, Al)-rich precipitates during hot forging, which can be
had significant strengthening effect.
Recently, a FeCrCuNiMn HEA as a dual-phase alloy composed of FCC
and BCC phases has been developed [4,18]. In this regard, Shabani et al.
[19] have evaluated the mechanical behavior of annealed FeCrCuNiMn
HEA. They have demonstrated that the tensile strength of the alloy was
decreased with increasing annealing temperature due to the dissolu-
tion of the BCC phase, grain growth, and stress relief. Our studies, sup-
ported by literature data, demonstrated that the effects of annealing on
HEAs behavior need accurate attention and deep investigation. There-
fore, many behavioral aspects of HEAs during annealing still remain un-
known. In addition, there was no information about the microstructure
and mechanical behavior of FeCrCuMn2 Ni2 HEA in our literature sur-
vey. Accordingly, the present study investigated the microstructural and
compressive properties of hot-forged FeCrCuMn2 Ni2 HEA, annealed at
different temperatures, in detail. To do so, as-cast FeCrCuMn2 Ni2 HEA
was hot-forged and then annealed in the temperature range of 600–
1100 °C for 2 h. Microstructural characterizations were carried out on
the samples, and also their mechanical properties were evaluated by
employing macrohardness and room temperature compression tests.
2. Experimental procedure
FeCrCuMn2 Ni2 as-cast ingot, with a dimension of 120 × 60 ×
35 mm3 , was prepared by vacuum induction melting (VIM) into a
graphite mold under a vacuum 10−3 mbar. To homogenize the chemical
composition of the alloy, the ingot was remelted 3 times. Then, the in-
got cut into a rectangular block with a dimension of 70 × 60 × 35 mm3
was hot-forged at 650–750 °C. The reduction in the height of the in-
got after hot forging was 50% of its initial height. Samples with a di-
mension of 140 × 60 × 17.5 mm3 were machined from the hot-forged
ingot, and then they were annealed in a temperature range of 600–
1100 °C for 2 h, followed by immediately quenching in water. X-ray
diffraction (XRD) was used for the phase analysis of all samples using
Philips X’PERT diffractometer (Cu K𝛼 radiation: 𝜆 = 1.54 Å at 20 kV
and 30 mA). The lattice parameter of the samples was calculated by
analyzing the XRD patterns via the Rietveld software Materials Analysis
Using Diffraction (MAUD) [20,21]. The microstructural investigations of
samples were performed by light optical microscopy (OM) and Philips
XI30 scanning electron microscopy (SEM) equipped with a backscat-
tered electron (BSE) detector. The pictures were processed through the
ImageJ software to measure the grains size. The grains size was calcu-
lated at least 6 different regions of the sample surface under different
conditions. Energy-dispersive X-ray spectrometry (EDAX) was used for
the chemical composition analysis. For OM and SEM analysis, cross-
sectional samples were cut along the hot forging direction, polished,
and etched by 15% CH3 COOH + 10% HNO3 + 10% HCL solution. In
this study, a wet chemistry method was used for a more accurate anal-
ysis of the precipitations. For this purpose, the hot-forged sample was
2
Materialia 26 (2022) 101618
dissolved in concentrated hydrochloric acid and passed through a filter.
Then the precipitations remaining on the filter were subjected to EDS
analysis.
Compression tests were carried out to determine the deformation
behavior of the alloy, using a hydraulic compression testing machine
model Instron 8802 at a ram rate of 0.001 s−1 . Cylindrical samples for
compression tests with a dimension of 6 mm in diameter and 9 mm
in height were cut from annealed samples and the hot-forged ingot in a
direction parallel to the direction of hot forging. The hardness of samples
was measured with a Vickers hardness tester at a load of 15 kg for 15 s.
Each sample was tested at least 3 times.
3. Results and discussion
3.1. X-ray diffraction analysis
Fig. 1 shows XRD patterns of the alloy after different processing
stages, i.e., as-cast, hot-forged, and annealed. According to Fig. 1, it
can be observed that the diffraction peaks that appeared in the XRD
pattern of as-cast alloy can be assigned to a dual-phase FCC structure
(named FCC1 and FCC2). The lattice parameter of the two FCC phases
is close to each other (aFCC1 = 3.59 Ȧ and aFCC2 = 3.62 Ȧ ). Also, it can
be observed from Fig. 1 that after hot forging and annealing processes,
FCC phases remain unchanged, while the FCC1 and FCC2 phases’ peak
intensity was decreased and increased, respectively. It can also be seen
that by increasing annealing temperature in the range of 600–1000 °C,
FCC1 phase (dendritic regions (DR)) was dissolved into the alloy ma-
trix (FCC2 phase (interdendritic (ID) regions)); as a result, the volume
fraction of FCC2 phase (ID regions) was increased. Moreover, according
to Fig. 1, 𝜎-phase precipitates were formed during hot forging and an-
nealing in the range of 600–800 °C and it dissolved at higher annealing
temperature above 1000 °C, similar to what was seen before in other
works [15,19]. As shown in Fig. 1, by increasing annealing tempera-
ture to 1100 °C, dendritic regions were completely dissolved into the
alloy matrix, and the alloy was composed of a single FCC phase. Results
revealed that the crystal structure of the alloy has not changed during
annealing at different temperatures, indicating the thermal stability of
the alloy at high temperatures. In this regard, Ren et al. [15] have re-
ported that the crystal structure of CuCr2 Fe2 NiMn HEA also possesses a
suitable resistance during the age-hardening process.
Several experimental parameters such as Ω (thermodynamic param-
eter), 𝛿 (atomic size difference), and VEC (valence electron concentra-
tion) have been suggested to predict the structural stability and phase
formation of HEAs effectively. Indeed, Ω and 𝛿 parameters have been
proposed to predict the formation of stable solid solution phase and
characterize the lattice distortion in HEAs, respectively [22]. These pa-
rameters can be calculated using the following equations:
𝑇𝑚 Δ𝑆𝑚𝑖𝑥
Ω= (1)
|Δ𝐻 |
| 𝑚𝑖𝑥 |
√
√
√𝑁 𝑁 2
√∑ ∑
δ = √ 𝐶𝑖 (1 − 𝑟𝑖 ∕( 𝐶𝑖 𝑟𝑖 )) (2)
𝑖=1 𝑖=1
where Ci and ri represent the atomic fraction and atomic size of the ele-
ment i, respectively. ΔHmix , ΔSmix , and Tm are mixing enthalpy between
ith and jth elements, mixing entropy, and the melting point of the alloy,
respectively. These parameters are defined as follows:
𝑁
∑
𝑚𝑖𝑥
Δ𝐻𝑚𝑖𝑥 = 4 Δ𝐻𝐴𝐵 𝐶𝑖 𝐶𝑗 (3)
𝑖=1,𝑗≠𝑖
𝑛
∑
Δ𝑆𝑚𝑖𝑥 = −𝑅 𝐶𝑖 𝑙𝑛𝐶𝑖 (4)
𝑖=1
𝑁
∑
( )
𝑇𝑚 = 𝐶𝑖 𝑇𝑚 𝑖 (5)
𝑖=1
S.A. Sajadi, M.R. Toroghinejad, A. Rezaeian et al.
Fig. 2. The mixing enthalpy between the two constituent elements of the alloy.
Table 1
The calculated values of Tm , ΔHmix , ΔSmix , 𝛿, Ω, and VEC for the alloy.
Alloy Tm (K) ∆Hmix (kJ/mol) ∆Smix (kJ/mol) Ω 𝛿
FeCrCuMn2 Ni2 1692 −0.49 12.86 45.42 0.99
where R (= 8.314 J.mol−1 K−1 ) is the gas constant. The mixing enthalpy
between the related alloying elements in order to calculate the mixing
enthalpy of the studied alloy (Eq. (3)) is given in Fig. 2.
The calculated values of Tm , ΔHmix , ΔSmix , 𝛿, and Ω for the studied
HEA are given in Table 1. Values of Ω ˃ 1.1 and 𝛿 < 6.6% were pro-
posed as criteria for the formation of single-phase solid solution [22]. It
can be concluded from Table 1 that the studied HEA can form a single-
phase solid solution. It was reported that high mixing entropy decreased
the possibility of the formation of intermetallic and phase separation
during conventional preparation methods such as the casting of HEAs,
Materialia 26 (2022) 101618
Fig. 1. XRD patterns of the alloy after dif-
ferent processing conditions (as-cast, hot-
forged, and annealed for 2 h at 600, 800,
1000, and 1100 °C).
especially at high temperatures [22]. It can be noted that the introduced
Ω and 𝛿 criteria can only predict the possibility of the solid solution for-
mation in HEAs systems and cannot determine the type of phase struc-
ture. In this regard, Guo et al. [23] have shown that the VEC parameter,
expressed in Eq. (6), can be used to evaluate the stability of phase struc-
ture in HEAs.
∑𝑛
𝑉 𝐸𝐶 = 𝐶𝑖 (𝑉 𝐸𝐶 )𝑖 (6)
𝑖=1
where VEC is the valence electron concentration of the ith component
element. Studies have indicated that a single FCC solid solution phase
is stable when VEC ≥ 8, and a single BCC solid solution phase is formed
when VEC ≤ 6.87. A BCC and FCC phase mixture can also be obtained
when VEC is between 6.87 and 8 [23]. Based on Eq. (6), the VEC value
of the studied HEA was calculated to be 8.43, indicating that a single
FCC solid solution phase should be formed in this alloy. According to
Table 1, it can be observed that the phase prediction was in agreement
with the experimental results (as shown in Fig. 1). It is worth noticing
that the above prediction is strictly valid only to the phase equilibrium
at high temperatures near the melting point, where the mixing entropy
effect can be used to the formation of solid solutions [24].
3.2. Elemental distribution in the studied alloy
Fig. 3 shows the elemental segregation ratio (SR ) of DR and ID re-
VEC gions. SR represents the ratio of elemental concentration in DR region
8.43 to ID region and can be defined as follows:
𝐶𝐷𝑅
𝑆𝑅 = −1 (7)
𝐶𝐼𝐷
CDR and CID are the elemental concentrations in DR and ID regions,
respectively. It was reported that the SR value of an element larger than
1 means the element is rich in the DR region; hence, the higher the cal-
culated SR value, the higher the segregation degree in the DR region.
On the other hand, if the SR value of any element is smaller than 1, the
element will be rich in the ID region; that is, the smaller the calculated
SR value, the higher the elemental segregation degree in the ID region.
According to Fig. 3, for the as-cast FeCrCuMn2 Ni2 HEA, the segregation
degree of Cr and Fe elements is larger than 1; therefore, it can be con-
cluded that these elements were primarily distributed in DR regions. On
3
S.A. Sajadi, M.R. Toroghinejad, A. Rezaeian et al. Materialia 26 (2022) 101618

Fig. 3. The elemental segregation degree in DR and ID regions

of the alloy.

Table 2 According to Table 2 and elemental distribution maps of the as-cast mi-
The chemical composition of the alloy after different processing conditions (de- crostructure (Fig. 4 (b–f)), it can be realized that Cr and Fe were dis-
termined by EDS). tributed in DR regions, while Cu and Mn were distributed in ID regions.
State Phase Location Fe (at%) Cr (at%) Cu (at%) Mn (at%) Ni (at%) Due to the formation of 𝜎-precipitates, the elemental segregation de-
gree in DR and ID regions of the samples, which were hot-forged and
Nominal FCC 12.7 13.3 11.4 31.5 31.2
As- FCC1 DR 23.8 23.2 4.2 21.1 27.7
annealed in the range of 600–800 °C, increased compared to the as-cast
cast FCC2 ID 2.9 3.7 26.7 38.8 28.0 sample. Afterward, the elemental segregation degree decreased with fur-
Hot- 𝜎 12.1 67.4 2.8 13.3 4.7 ther increasing annealing temperature, and the homogeneous composi-
forged FCC1 DR 25.3 18.4 4.8 23.9 27.7 tion was eventually achieved in the alloy after annealing at 1100 °C. BSE
FCC2 ID 6.9 5.9 21.7 34.0 31.5
image and elemental distribution maps of the sample annealed at 1100
°C for 2 h, as shown in Fig. 5, indicate the homogeneous distribution for
all elements in a single-phase matrix.
In current study, the precipitates were separated from the matrix
the contrary, the segregation degree of Cu and Mn elements are smaller
of the hot-forged sample using a wet chemistry method and then were
than 1; consequently, they were rich in ID regions. Additionally, the Ni
analyzed using the EDS method. The chemical compositions of the pre-
element was relatively homogeneously distributed in both regions. Ren
cipitates after different processing conditions are given in Table 2. It
et al. [4] have shown that the elemental distribution between the DR
can be seen that distribution of the three elements Fe, Cr and Mn over
and ID regions can be affected by elemental interaction and the mixing
the precipitates. Precipitates formed in the studied alloy are the 𝜎-phase
enthalpy between the principal elements. According to Fig. 2, the mix-
rich in Cr, Fe and Mn elements, similar to what was seen before in other
ing enthalpy of Cu with Cr, Fe, Ni, and Mn is 12, 13, 4, and 4 kJ/mol,
works [15,19].
respectively. Therefore, Cr and Fe elements are repelled from the Cu-
rich regions, mainly due to the relatively higher mixing enthalpies of
Cu-Cr and Cu-Fe compared to other element pairs. On the other hand, 3.3. Microstructural evaluations
the relatively low mixing enthalpies of Cu-Ni and Cu-Mn lead to the fur-
ther dissolution of Ni and Mn elements into the Cu-rich regions. More- Fig. 6 shows the optical microstructure of the studied HEA after dif-
over, since the mixing enthalpy of Ni with Cr, Fe and Mn are −7, −2, ferent processing conditions, i.e. as-cast, hot-forged, and annealed. Ac-
and −8 kJ/mol, respectively, Ni is homogeneously distributed in the cording to Fig. 6(a), the as-cast sample exhibited typical DR (FCC1) and
FeCrCuMn2 Ni2 system. ID (FCC2) regions.
The chemical compositions of the alloy after different processing The microstructure of the hot-forged alloy was shown in Fig. 6 (b).
conditions are given in Table 2. According to nominal composition, all It can be seen that Cr and Fe-rich DR regions (as shown in Table 2) were
constituent elements must present an equal ratio in the studied HEA. partially dissolved into the matrix during hot forging, resulting in the
The as-cast sample’s chemical composition of DR and ID regions was formation of a large amount of precipitates in the matrix [11,19]. These
different, mainly attributed to the elemental segregation during the so- precipitates are the 𝜎 phase rich in Cr, Fe and Mn elements according to
lidification. the EDS (as listed in Table 2) and XRD results. According to XRD results
Backscattered electron (BSE) image and elemental distribution maps (Fig. 1) and microstructural analysis (Fig. 6 (c and d)), 𝜎-precipitates
of the as-cast microstructure of the studied HEA, as shown in Fig. 4. As also formed during annealing in the range of 600–800 °C as also re-
can be seen, the microstructure consists of a dendritic phase with FCC1 ported in other works [15,19]. The formation of these 𝜎-precipitates can
structure and an interdendritic phase with FCC2 structure (Fig. 4(a)). inhibit both the discontinuous dynamic recrystallization (dDRX) during

4
S.A. Sajadi, M.R. Toroghinejad, A. Rezaeian et al. Materialia 26 (2022) 101618

Fig. 4. (a) BSE image and elemental distribution maps of the as-cast microstructure of the alloy (b) Cr, (c) Mn, (d) Fe, (e) Ni, and (f) Cu.

Fig. 5. (a) BSE image and elemental distribution maps of the alloy annealed at 1100 °C for 2 h (b) Cr, (c) Mn, (d) Fe, (e) Ni, and (f) Cu.

hot forging and the discontinuous static recrystallization (dSRX) dur-
ing annealing in the temperature range of 600–800 °C. The inhibition
of dDRX via precipitate has been reported by Zhang et al. [25]. It was
also reported that thermomechanical processing (TMP) promotes the
possibility of precipitation of secondary phases in HEAs [26]. Zhang
et al. [27] have also observed phase transformation and precipitation in
CrMnFeCoNi HEA while employing the high-pressure synchrotron radi-
ation x-ray diffraction. Indeed, the refinement during hot deformation
along with the structural defects forming during the deformation pro-
cesses, such as vacancy, dislocations and stacking faults, accelerate the
diffusion process, leading to earlier nucleation of precipitates [10]. On
the other hand, TMP methods such as hot rolling and hot forging can
decrease the structural defects and refine the microstructure. This im-
provement can promote the strength and ductility of HEAs and enhance
the diffusion rate, thus facilitating the precipitates nucleation in HEAs.
After annealing at 1000 °C (Fig. 6 (e)), the microstructure of the
studied HEA has begun to change in such a way that DR regions and
precipitates dissolved into the alloy matrix (FCC2). Accordingly, the DR
structure gradually disappeared, ID regions enlarged. In addition, it can
been that fine recrystallized grains with an average size of 15.9 μm were
formed, indicating the occurrence of dSRX during annealing at 1000 °C,
as shown in Fig. 6 (e). It was also found that with increasing annealing

5
S.A. Sajadi, M.R. Toroghinejad, A. Rezaeian et al.
Fig. 6. The optical microstructure of the alloy processed after different processing conditions: (a) as-cast, (b) hot-forged, and hot-forged and annealed for 2 h at
temperature of (c) 600 °C, (d) 800 °C, (e) 1000 °C, and (f) 1100 °C.
temperature above 1000 °C, the recrystallized grains grew up and their
average grain size increased to about 30.5 μm in temperature of 1100 °C.
Moreover, at the temperature of 1100 °C the remaining precipitates can
be observed along the grain boundaries and inside the grains (Fig. 6 (F)).
Cao et al. [11] also observed similar behavior for the TiNbTa0.5 ZrAl0.5
HEA after annealing above 1000 °C, resulting in embrittlement of the
alloy. This can be related to the reversible wetting of grain boundaries
by the second solid phase, previously observed by Straumal et al. in a
Cu-In system [28].
The homogenization treatment of the studied HEA showed that the
alloy was homogenized at 1100 °C after 10 h, having a grain size of
73.2 ± 3 μm. In return, the results indicated that hot forging at 650–750
°C and then annealing at 1100 °C for 2 h led to the homogeneous com-
6
Materialia 26 (2022) 101618
position with a grain size of 30.5 ± 3 μm, as shown in Fig. 6 (F), which
was more than 2 times smaller than that of the one for the homogenized
sample. Indeed, it can be suggested that hot forging can effectively result
in grain refining of alloy via dDRX. It has been well-known that dDRX
results in much smaller grain size than the one from dSRX [29,30,36].
Grain refining plays a vital role in promoting diffusion rate, resulting in
enhancing the homogenizing process of the alloy.
SEM images with different magnifications of the microstructure of
the alloy after hot forging and annealing at different temperatures are
shown in Fig. 7. Microstructural evaluations indicated that the alloy con-
sists of DR and ID regions. Based on EDS results given in Table 2, it can
be seen that the particles (marked in Fig. 7) were 𝜎-phase precipitates
enriched with Cr and Mn. This finding is in line with the previous works
S.A. Sajadi, M.R. Toroghinejad, A. Rezaeian et al.
Fig. 7. The SEM images of the alloy: (a) hot-forged, hot-forged, and annealed for 2 h at temperatures of (b) 800 °C, (c) 1000 °C, and (d) 1100 °C.
on HEAs with similar composition as of the current study [15,19]. More-
over, a large number of these precipitates were formed in a spherical
shape with an average size of 0.55 and 1.34 μm during hot forging and
annealing at 800 °C, respectively, marked by “1” as shown in Fig. 7 (a
and b). With increasing annealing temperature more than 1000 °C, the
average size of precipitates slightly increased from 1.88 μm in tempera-
ture of 1000 °C to about 2.76 μm in temperature of 1100 °C. In addition,
their morphology gradually changed from spherical shape to fine rod-
like or blade-like form, as marked by “2” in Fig. 7 (c). Due to the increase
in precipitates size and change in their morphology, the hardness and
strength of the hot-forged sample decreased during annealing at higher
temperatures, which will be fully explained in the next section.
It was reported that the phase transformation and precipitation had
been observed in many HEAs which were annealed at intermediate tem-
peratures or under hot deformation [12,24,31]. As described above, pre-
cipitation was observed in the alloy during hot forging and annealing.
The crystal structure of constituent elements and binary phase diagrams
of elemental pairs of the alloy being studied were evaluated in detail to
investigate the precipitation. In this regard, it was found that Cu and Ni
elements tend to form a solid solution at all concentrations and also lead
to stabilizing of the FCC structure at high and low temperatures [24]. In
addition, according to Fe-Ni and Fe-Cu phase diagrams, it is clear that
a solid solution forms at temperatures higher than 600 °C for all com-
positions [24]. On the other hand, Cr and Mn elements tend to form
7
Materialia 26 (2022) 101618
intermetallic compounds in the temperature range of 600–800 °C [24].
Based on the mixing enthalpy between elemental pairs in the Fe-Cr-Cu-
Ni-Mn system, it can be realized that the Mn element plays a vital role
in the formation of the intermetallic phases. It is necessary to note that
annealing at intermediate temperatures and TMP facilitate the precipi-
tation of secondary phases in HEAs. Consequently, the formation of Cr
and Mn-rich 𝜎-precipitates in the studied HEA in the temperature range
of 600–800 °C can be attributed to hot forging and annealing operations.
3.4. Mechanical behavior
Fig. 8(a) represents compressive stress-strain curves of the alloy af-
ter different processing conditions, i.e., as-cast, hot-forged, and annealed
at different temperatures for 2 h. In addition, the variations of the yield
strength (𝜎 YS ), maximum compressive strength (𝜎 MCS ), and compressive
strain as a function of annealing temperature are shown in Fig. 8 (b).
It can be seen that compared to the as-cast condition, the hot-forged
sample exhibited higher compressive yield strength while lower com-
pressive strain. This could be due to the formation of 𝜎-precipitates
during hot forging. Indeed, since the size of 𝜎-precipitates formed dur-
ing hot forging was small (about 0.55 μm) (Fig. 7(a)), they can restrict
the dislocations movement by pinning them, ultimately increasing the
strength and decreasing the compressive strain of the alloy. Moreover,
as shown in Fig. 3, the elemental segregation degree in DR and ID re-
S.A. Sajadi, M.R. Toroghinejad, A. Rezaeian et al.
gions of the hot-forged sample was increased which could have also
increased the compressive yield strength of the alloy compared to the
as-cast one (Fig. 8 (b)). This behavior also reported by Salishchev et al.
in other work [32]. They have shown that the dendritic segregations
in HEAs could have also increased the yield strength and also reduced
ductility of the alloy. In this case, more study was needed to better un-
derstand the role of dendrite segregations in these phenomena. In addi-
tion, according to Fig. 8 (b), the annealing of the hot-forged samples at
800 °C led to a dramatic decrease in both 𝜎 YS , 𝜎 MCS , and compressive
strain compared to the as-cast sample. Such a reduction in the strength
of hot-forged sample after annealing at 800 °C can be attributed to the
8
Materialia 26 (2022) 101618
Fig. 8. (a). Compressive stress-strain curves and (b) variations
of the yield strength (𝜎 YS ), maximum compressive strength
(𝜎 MCS ), and compressive strain after different processing con-
ditions.
formation of 𝜎-precipitates and growth of residual 𝜎-precipitates with
an average size of 1.34 μm (as shown in Fig. 7 (b)), resulting in loss of
coherency with the matrix. With further increasing annealing temper-
ature, the compressive strain of the studied HEA increased; however,
the strength was raised and then reduced. According to Fig. 6 (e and
f) and also Fig. 7 (c and d), it can be concluded that the increasing of
compressive strain after annealing above 800 °C can be due to the par-
tial dissolution of the 𝜎-precipitates, growth of residual 𝜎-precipitates,
decrease of internal defects, and softening of the alloy resulted from the
grains growth and stress relieving [29] during annealing. It is worth
mentioning that the last two these phenomena led to a decrease in the
S.A. Sajadi, M.R. Toroghinejad, A. Rezaeian et al.
strength. Moreover, the increase of maximum compressive strength of
the 1000 °C annealed alloy may due to the increase of plasticity and
greater compression deformation.
The changes in the average hardness of the studied HEA after differ-
ent processing conditions are given in Fig. 9. As can be seen, the average
hardness of the alloy was increased from 222 ± 5.6 HV in as-cast condi-
tion to 333 ± 4.5 HV in hot-forged condition, which can be attributed
to the same reason that strength was increased, i.e., formation of 𝜎-
precipitates (Fig. 7(a)) during hot forging. Furthermore, as can be seen
in Fig. 9, when the annealing in the range of 600–800 °C, a plateau in
the value of hardness was observed, which can be due to the presence of
hard 𝜎-precipitates without change in them morphology within the an-
nealing temperature range. On the other hand, the hardness decreased
with further increasing of annealing temperature above 800 °C, which
can be related to the dissolution of the 𝜎-precipitates and softening of
the alloy.
A comparison of Figs. 8 (b) and 9 reveals that the hardness of the
studied HEA with correlated yield strength exhibits similar behavior at
all processing conditions, except annealing at 1000 °C for 2 h. It seems
that the 𝜎-precipitates dissolution played a more influential role in de-
termining the mechanical properties of the alloy at the mentioned an-
nealing temperature, eventually leading to a decrease in the hardness
9
Materialia 26 (2022) 101618
Fig. 9. Variations in average hardness after different process-
ing conditions.
Fig. 10. The hardening capacity as a function of heat treatment
temperature.
and increase in the strength of the alloy. In general, it can be concluded
that the 𝜎-precipitates characteristics had the most significant effect on
the mechanical behavior of the studied HEA. TEM investigation is re-
quired to address such a significant effect.
The hardening capacity (Hc ) was calculated using the following
equation [19,33]:
𝜎𝑀𝐶𝑆 − 𝜎𝑌 𝑆
𝐻𝐶 = (8)
𝜎𝑌 𝑆
where 𝜎 MCS and 𝜎 YS are maximum strength and yield strength of the
samples in compression conditions, respectively. It is noteworthy that
HC the capacity of the material indicates that matter can be strain hard-
ened [33]. Fig. 10 shows the hardening capacity of the alloy as a func-
tion of annealing temperature. The lower hardening capacity value of
the hot-forged sample annealed in the range of 600–800 °C can be due to
the formation of hard 𝜎-precipitates. Indeed, the mentioned precipitates
can inhibit the dislocation sliding, leading to a decrease in hardening ca-
pacity value. With increasing annealing temperature, as expected, the
grains size increased (Fig. 6 (e and f)); as a result, the yield strength
was decreased, and the hardening capacity value was increased, as also
reported by other researchers [29,33].
S.A. Sajadi, M.R. Toroghinejad, A. Rezaeian et al.
Fig. 11. The ln(𝜎)-ln(𝜀) plots; (a) as-cast sample, (b) hot-forged sample, and (c) hot-forged and annealed sample at different temperatures for 2 h.
Different equations are proposed to investigate the strain hardening
behavior of materials [34]. In the present study, Hollomon equation
[34] is used to describe the strain hardening behavior as follows:
𝜎 = 𝐾𝜀𝑛
where 𝜎 and 𝜀 are the true stress and total true strain, respectively. K is
the strength coefficient, and n represents the strain hardening exponent.
The n parameter is calculated using the following equation:
𝑑 (𝑙𝑛𝜎)
𝑛=
𝑑 (𝑙𝑛𝜀)
Fig. 11 illustrates the ln(𝜎)-ln(𝜀) plots obtained from strain-stress
curves at different processing conditions. According to Fig. 11(a), the
strain hardening behavior of the as-cast sample consisted of two stages.
In the first stage, the softer phase (FCC2) (interdendritic regions) de-
formed plastically. In contrast, other phase (FCC1) (dendritic regions),
i.e., the harder phase, was in the elastic-plastic regime as also re-
ported in other works [19,35], consequently resulting in a low strain
Materialia 26 (2022) 101618
hardening rate. In this stage, the FCC2 phase, accommodated most
of the deformation and transferred load to other phase. In the sec-
ond stage, both phases, FCC1 and FCC2, were seemed to be deformed
plastically.
(9)
As shown in Fig. 11 (b), similar to the as-cast sample, the strain
hardening behavior of the hot-forged sample can be divided into two
distinct hardening stages. In the first stage, the softer phase (FCC2) de-
formed plastically, whereas the harder phases (FCC1 and 𝜎) were in
the elastic-plastic regime. For this reason, the strain-hardening rate was
(10) low in this stage. In the second stage, both FCC phases were plastically
deformed simultaneously, whereas the 𝜎-precipitates deformed elasti-
cally, thus leading to the non-homogeneous deformation. In these cir-
cumstances, a higher density of geometrically necessary dislocations
could be generated in the microstructure; as a result, the strain hard-
ening rate was higher than that of in the first stage, as also reported in
refs [19,35].
It can be realized from Fig. 11 (c) that the strain hardening behavior
of annealed samples at different temperatures was almost similar and
10
S.A. Sajadi, M.R. Toroghinejad, A. Rezaeian et al.
consisted of two distinct stages; however, the hardening rate was af-
fected by annealing temperature. As can be seen from Fig. 11 (c), the
hardening rate decreased in both stages with increasing annealing tem-
perature. As discussed earlier, such a trend can be attributed to the in-
crease of the volume fraction of softer phase, grains growth, and stress
relieving. Moreover, from Fig. 8 (b), it can be suggested that the forma-
tion of 𝜎-precipitates resulted in the embrittlement of annealed samples
in the range of 600–800 °C and played a major role in decreasing plastic
deformation and hardening of the alloy.
4. Conclusions
The present study aimed to investigate the effects of annealing
treatment on microstructural and mechanical properties of hot-forged
FeCrCuMn2 Ni2 high-entropy alloy. For this purpose, the as-cast alloy
was hot-forged at 650–750 °C and then annealed at temperatures rang-
ing from 600 to 1100 °C for 2 h. As such, the following main conclusions
were made:
1 The microstructure of hot-forged alloy consisted of dendritic struc-
ture, gradually dissolving with increasing annealing temperature,
and refined recrystallized grains were formed within the interden-
dritic regions.
2 The microstructural observations indicated that the 𝜎-precipitates
were formed during hot forging and annealing of hot-forged sam-
ples in the range of 600–800 °C, and dissolved at higher annealing
temperature than 1000 °C.
3 The results confirm that the occurrence of dSRX during annealing in
the annealing temperature above 1000 °C.
4 Findings revealed that the hot forging followed by annealing process
effectively resulted in grain refinement of the alloy than the homog-
enization treatment.
5 Hot forging of the as-cast sample led to the increased compressive
yield strength, hardness, and decreased compressive strain.
6 When annealing in the range of 600–800 °C, the alloy’s compressive
yield strength and compressive strain were significantly decreased.
Moreover, with increasing annealing temperature to 1100 °C, the
alloy’s compressive strain and hardening capacity were enhanced.
7 Results indicated that two separate regimes of strain hardening were
found for the studied HEA before/after annealing, which was differ-
entiable based on the plastic strain distribution in each phase.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
References
[1] J.W. Yeh, S.K. Chen, S.J. Lin, J.Y. Gan, T.S. Chin, T.T. Shun, C.H. Tsau,
S.Y. Chang, Nanostructured high-entropy alloys with multiple principal elements:
novel alloy design concepts and outcomes, Adv. Eng. Mater. 6 (2004) 299–303,
doi:10.1002/adem.200300567.
[2] Y.X. Zhuang, H.D. Xue, Z.Y. Chen, Z.Y. Hu, J.C. He, Effect of annealing treatment
on microstructures and mechanical properties of FeCoNiCuAl high entropy alloys,
Mater. Sci. Eng. A 572 (2013) 30–35, doi:10.1016/j.msea.2013.01.081.
[3] Z. Savaedi, R. Motallebi, H. Mirzadeh, A review of hot deformation behavior and
constitutive models to predict flow stress of high-entropy alloys, J. Alloy. Compd.
903 (2022) 163964, doi:10.1016/j.jallcom.2022.163964.
[4] B. Ren, Z. Liu, D. Li, L. Shi, B. Cai, M. Wang, Effect of elemental interaction on mi-
crostructure of CuCrFeNiMn high entropy alloy system, J. Alloy. Compd. 493 (2010)
148–153 J Alloy. Compd., doi:10.1016/j.jallcom.2009.12.183.
[5] W. Li, D. Xie, D. Li, Y. Zhang, Y. Gao, P.K. Liaw, Mechanical behavior of high-entropy
alloys, Prog. Mater. Sci. 118 (2021) 100777, doi:10.1016/j.pmatsci.2021.100777.
[6] B. Gludovatz, A. Hohenwarter, D. Catoor, E. Chang, E. George, R. Ritchie, A fracture-
resistant high-entropy alloy for cryogenic applications, Science 345 (2014) 1153–
1158 (80-.), doi:10.1126/science.1254581.
[7] F. Otto, A. Dlouhý, C. Somsen, H. Bei, G. Eggeler, E.P. George, The influences of tem-
perature and microstructure on the tensile properties of a CoCrFeMnNi high-entropy
alloy, Acta Mater. 61 (2013) 5743–5755, doi:10.1016/j.actamat.2013.06.018.
11
Materialia 26 (2022) 101618
[8] Y. Wu, W.H. Liu, X.L. Wang, D. Ma, A.D. Stoica, T.G. Nieh, Z.B. He, Z.P. Lu, In-
situ neutron diffraction study of deformation behavior of a multi-component high-
entropy alloy, Appl. Phys. Lett. 104 (2014) 51910, doi:10.1063/1.4863748.
[9] S.A. Sajadi, M.R. Toroghinejad, A. Rezaeian, G.R. Ebrahimi, Dynamic recrystalliza-
tion behavior of the equiatomic FeCoCrNi high-entropy alloy during high tempera-
ture deformation, J. Mater. Res. Technol. (2022), doi:10.1016/j.jmrt.2022.07.055.
[10] Y. Cao, Y. Liu, B. Liu, W. Zhang, Precipitation behavior during hot deformation of
powder metallurgy Ti-Nb-Ta-Zr-Al high entropy alloys, Intermetallics 100 (2018)
95–103, doi:10.1016/j.intermet.2018.06.007.
[11] Y. Cao, Y. Liu, Y. Li, B. Liu, J. Wang, M. Du, R. Liu, Precipitation strengthening
in a hot-worked TiNbTa0.5ZrAl0.5 refractory high entropy alloy, Mater. Lett. 246
(2019), doi:10.1016/j.matlet.2019.03.075.
[12] Y. Cao, Y. Liu, Y. Li, B. Liu, A. Fu, Y. Nie, Precipitation behavior and mechanical
properties of a hot-worked TiNbTa0.5ZrAl0.5 refractory high entropy alloy, Int. J.
Refract. Met. Hard Mater. 86 (2020) 105132, doi:10.1016/j.ijrmhm.2019.105132.
[13] K. Zhang, Z. Fu, J. Zhang, W. Weimin, H. Wang, Y. Wang, Q. Zhang, Annealing on the
structure and properties evolution of the CoCrFeNiCuAl high-entropy alloy, J. Alloy.
Compd. 502 (2010) 295–299 J Alloy. Compd., doi:10.1016/j.jallcom.2009.11.104.
[14] L.H. Wen, H. Kou, J.S. Li, H. Chang, X. Xue, L. Zhou, Effect of aging temperature on
microstructure and properties of AlCoCrCuFeNi high-entropy alloy, Intermetallics
17 (2009) 266–269, doi:10.1016/j.intermet.2008.08.012.
[15] B. Ren, Z.X. Liu, B. Cai, M.X. Wang, L. Shi, Aging behavior of a CuCr2Fe2NiMn high-
entropy alloy, Mater. Des. 33 (2012) 121–126, doi:10.1016/j.matdes.2011.07.005.
[16] S.T. Chen, W.Y. Tang, Y.F. Kuo, S.Y. Chen, C.H. Tsau, T.T. Shun, J.W. Yeh, Mi-
crostructure and properties of age-hardenable AlxCrFe1.5MnNi0.5 alloys, Mater. Sci.
Eng. A 527 (2010) 5818–5825, doi:10.1016/j.msea.2010.05.052.
[17] D.G. Shaysultanov, N.D. Stepanov, A.V. Kuznetsov, G.A. Salishchev, O.N. Senkov,
Phase composition and superplastic behavior of a wrought AlCoCrCuFeNi high-
entropy alloy, JOM 65 (2013) 1815–1828, doi:10.1007/s11837-013-0754-5.
[18] C. Li, J.C. Li, M. Zhao, Q. Jiang, Effect of alloying elements on microstructure and
properties of multiprincipal elements high-entropy alloys, J. Alloy. Compd. 475
(2009) 752–757, doi:10.1016/j.jallcom.2008.07.124.
[19] A. Shabani, M.R. Toroghinejad, A. Shafyei, R. Logé, Evaluation of the mechanical
properties of the heat treated FeCrCuMnNi high entropy alloy, Mater. Chem. Phys.
221 (2018), doi:10.1016/j.matchemphys.2018.09.033.
[20] A. Shabani, M.R. Toroghinejad, A. Shafyei, P. Cavaliere, Effect of cold-rolling on
microstructure, texture and mechanical properties of an equiatomic FeCrCuMnNi
high entropy alloy, Materialia 1 (2018) 175–184, doi:10.1016/j.mtla.2018.06.004.
[21] H. Pal, A. Chanda, M. De, Characterisation of microstructure of isothermal marten-
site in Fe–23Ni–3.8Mn by Rietveld method, J. Alloy. Compd. 278 (1998) 209–215,
doi:10.1016/S0925-8388(98)00583-0.
[22] X. Yang, Y. Zhang, Prediction of high-entropy stabilized solid-solution
in multi-component alloys, Mater. Chem. Phys. 132 (2012) 233–238,
doi:10.1016/j.matchemphys.2011.11.021.
[23] S. Guo, C. Ng, J. Lu, C.T. Liu, Effect of valence electron concentration on stabil-
ity of fcc or bcc phase in high entropy alloys, J. Appl. Phys. 109 (2011) 103505,
doi:10.1063/1.3587228.
[24] S.Y. Chen, Y. Tong, K.K. Tseng, J.W. Yeh, J.D. Poplawsky, J.G. Wen, M.C. Gao,
G. Kim, W. Chen, Y. Ren, R. Feng, W.D. Li, P.K. Liaw, Phase transformations of
HfNbTaTiZr high-entropy alloy at intermediate temperatures, Scr. Mater. 158 (2019)
50–56, doi:10.1016/j.scriptamat.2018.08.032.
[25] Y. Zhang, X. Wang, J.G. Li, Y. Huang, Y. Lu, X. Sun, Deformation mechanism dur-
ing high-temperature tensile test in an eutectic high-entropy alloy AlCoCrFeNi 2.1,
Mater. Sci. Eng. A 724 (2018), doi:10.1016/j.msea.2018.03.078.
[26] W. Zhou, L.M. Fu, P. Liu, X.D. Xu, B. Chen, G.Z. Zhu, X.D. Wang,
A.D. Shan, M.W. Chen, Deformation stimulated precipitation of a single-
phase CoCrFeMnNi high entropy alloy, Intermetallics 85 (2017) 90–97,
doi:10.1016/j.intermet.2017.02.010.
[27] F. Zhang, Y. Wu, H. Lou, Z. Zeng, V.B. Prakapenka, E. Greenberg, Y. Ren, J. Yan,
J.S. Okasinski, X. Liu, Y. Liu, Q. Zeng, Z. Lu, Polymorphism in a high-entropy alloy,
Nat. Commun. 8 (2017) 15687, doi:10.1038/ncomms15687.
[28] B. Straumal, O. Kogtenkova, K. Kolesnikova, A. Straumal, M. Bulatov, A. Nekrasov,
Reversible “Wetting” of grain boundaries by the second solid phase in the Cu-In
system, JETP Lett. 100 (2015) 535–539, doi:10.1134/S0021364014200107.
[29] F.J. Humphreys, M. Hatherly, Recrystallization and Related Annealing Phenomena,
Elsevier, Oxford, 2004, doi:10.1016/B978-0-08-044164-1.X5000-2.
[30] K. Huang, R.E. Logé, A review of dynamic recrystallization phenomena in metallic
materials, Mater. Des. 111 (2016) 548–574, doi:10.1016/j.matdes.2016.09.012.
[31] Z.A. Mohammed, K. Chadha, R. Seelam, D. Shahriari, P. Bhattacharjee, M. Jahazi,
Influence of process parameters on microstructure evolution during hot deforma-
tion of a Eutectic High-Entropy Alloy (EHEA), Metall. Mater. Trans. A (2020),
doi:10.1007/s11661-020-05991-y.
[32] G.A. Salishchev, M.A. Tikhonovsky, D.G. Shaysultanov, N.D. Stepanov,
A.V. Kuznetsov, I.V. Kolodiy, A.S. Tortika, O.N. Senkov, Effect of Mn and V
on structure and mechanical properties of high-entropy alloys based on CoCrFeNi
system, J. Alloy. Compd. 591 (2014) 11–21, doi:10.1016/j.jallcom.2013.12.210.
[33] J. Luo, Z. Mei, W. Tian, Z. Wang, Diminishing of work hardening in electroformed
polycrystalline copper with nano-sized and uf-sized twins, Mater. Sci. Eng. A 441
(2006) 282–290, doi:10.1016/j.msea.2006.08.051.
[34] J.H. Hollomon, Tensile deformation, Transa. Metall. Soc. AIME 162 (1945) 268–290.
[35] N. Saeidi, M. Karimi, M.R. Toroghinejad, Development of a new dual phase steel
with laminated microstructural morphology, Mater. Chem. Phys. 192 (2017) 1–7,
doi:10.1016/j.matchemphys.2017.01.052.
[36] S.A. Sajadi, M.R. Toroghinejad, A. Rezaeian, G.R. Ebrahimi, A study of hot compres-
sion behavior of an as-cast FeCrCuNi2Mn2 high-entropy alloy, Journal of Alloys and
Compounds 896 (2022), doi:10.1016/j.jallcom.2021.162732.