Materials Science & Engineering A 734 (2018) 341–352

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Materials Science & Engineering A

journal homepage: www.elsevier.com/locate/msea

Properties of a high-strength ultrafine-grained CoCrFeNiMn high-entropy T

alloy prepared by short-term mechanical alloying and spark plasma
sintering
⁎
Filip Průšaa, , Alexandra Šenkováa, Vojtěch Kučeraa, Jaroslav Čapekb, Dalibor Vojtěcha
a
Department of Metals and Corrosion Engineering, University of Chemistry and Technology in Prague, Technická 5, 166 28 Prague 6, Czech Republic
b
Institute of Physics of the Czech Academy of Sciences, Na Slovance 1999/2, 182 21 Prague 8, Czech Republic

A R T I C LE I N FO A B S T R A C T

Keywords: An equiatomic CoCrFeNiMn high-entropy alloy was prepared by induction melting and a progressive combi-
High-entropy alloys nation of mechanical alloying and compaction via spark plasma sintering done at temperatures of 800 °C and
Mechanical properties 1000 °C. The chosen methods of preparation had a significant impact on the microstructure and mechanical
Hardness properties of the alloy. In comparison, the as-cast alloy had a much coarser microstructure while simultaneously
Compressive tests
obtaining inferior mechanical properties compared to those of the 8-h mechanically alloyed and spark plasma
Long-term annealing
sintered alloy compacted at 1000 °C, which achieved a hardness of 424 ± 7 HV, and the alloy compacted at
800 °C showed a lower but still highly comparable hardness of 352 ± 12 HV. Both alloys showed good thermal
stability, as expressed by almost negligible hardness changes during 100 h of annealing at temperatures of 400 °C
and 600 °C. The investigated alloys also showed their superiority during compressive stress-strain tests at am-
bient and elevated temperatures of 400 °C and 600 °C. At ambient temperature, the highest compressive yield
strength of 1534 MPa was observed for the sample compacted at 800 °C. As the temperature of the compressive
test increased, the investigated alloys reduced their compressive yield strengths.

1. Introduction several reports of materials composed of HCP solid solutions [12].

High-entropy alloys (HEAs) belong to a relatively new group of
materials that have been researched since 2004 [1]. Since then, these
materials have attracted increasing scientific interest due to their re-
markable properties, including high strength, as well as good plasticity
[2], good wear and corrosion resistance [3], magnetic properties [4],
and outstanding plastic deformation at cryogenic temperatures [5].
Generally, to be considered a high-entropy alloy, a material must in-
clude a mixture of at least five elements with almost equiatomic che-
mical compositions [6–8]. However, as demonstrated in previous re-
search, these conditions are rather flexible boundaries for the design of
high-entropy alloys. In the past few years, ongoing scientific research
has reported high-entropy alloys that may be composed of only four
elements whose chemical concentrations vary from 5 to 35 at%.
Therefore, such a loose definition can be substituted by a rather more
explicit characterization of the phase composition. According to the
initial definition, a high-entropy alloy forms because of the relatively
high entropy of mixing (ΔSmix), resulting in only a solid solution [9,10]
containing mostly FCC and BCC structures [11], and there are also
However, this definition has been corrected, given that some alloys are
solid solutions composed of Laves phases [3,11,13–15]. The presence of
Laves phases is beneficial since they are responsible for significant
strengthening of HEAs, simultaneously increasing elevated-temperature
mechanical properties and oxidation resistance [15]. Thus, since HEA
research is still developing, the boundaries defined above may be
broadened or even rejected completely. This may be demonstrated by a
newly developed thermodynamic criterion capable of predicting whe-
ther a system will form solid solutions or will be composed of inter-
mediary phases [16]. Among these thermodynamic parameters, the
mixing enthalpy (ΔHmix) [10,17–19], the omega parameter (Ω) [20],
the delta parameter (δ) [10,18,19] or the valence electron concentra-
tion (VEC) [17] theory may be used to design possible HEAs, although
the theoretical presumptions may differ from expectations [8]. For this
thermodynamic approach, the paired sigma-forming element (PSFE)
content and the average value of the d orbital energy level (Md̅ ) were
introduced to predict the behaviour of multi-component alloys [21–23].
In fact, many newly developed parametric models, mostly formed by a
combination of two or more parameters, have been used to predict/

⁎
Corresponding author.
E-mail address: Filip.Prusa@vscht.cz (F. Průša).

https://doi.org/10.1016/j.msea.2018.08.014
Received 7 May 2018; Received in revised form 2 August 2018; Accepted 3 August 2018
Available online 07 August 2018
0921-5093/ © 2018 Elsevier B.V. All rights reserved.
F. Průša et al.
describe the potential for the formation of HEAs [10,16,18–20,24–26].
Among the common HEAs, CoCrFeMnNi alloy, also denoted as
Cantor alloy [1], has been the most extensively studied system so far
[11,27–31] and is capable of achieving high hardness, strength [27]
and even superplasticity reaching up to > 600% [30]. More im-
portantly, the mechanical properties increase when tested at cryogenic
temperatures, further demonstrating the unique behaviour of this alloy
[32]. Although the alloy is composed of Co (HCP), Cr (BCC), Fe (FCC),
Mn (BCC) and Ni (FCC) with different crystallographic lattices, it forms
only a simple FCC solid solution, and it may precipitate some nano-
intermetallic phases when alloyed by other elements such as Ti and/or
Al [33] or when exposed to long-term annealing [34,35]. The pre-
cipitation of nano-intermetallic phases dramatically increases the yield
strength of as-cast HEAs up to 645 MPa while maintaining a ductility of
39%. Therefore, CoCrFeNiMn HEAs may be utilized in various highly
demanding applications by using proper processing steps to achieve a
suitable range of properties. In addition, recent ongoing research has
reported a quaternary CoCrFeNi HEA [36], which can be used as a
protective coating, improving both the tribological behaviour and the
corrosion resistance.
In general, the properties of all alloys are closely connected with
their chemical composition, which is restricted in HEAs by their ability
to form solid solutions, and with further processing steps responsible for
improvements in properties. Among these steps, induction melting
[28,29,37–39], arc melting [12,15,40–45] or magnetic levitation
melting [27] are usually used for the production of HEAs, while more
advanced post-processing technologies are used to increase the prop-
erties of the produced alloy. The methods actually used either for HEA
production or for subsequent processing strongly influence the resulting
properties since the methods may result in homogenization and re-
finement of the microstructure, significantly improving the properties
of the prepared HEAs, e.g., by rapid cooling [38,42,46], or due to se-
vere plastic deformation imposed via methods such as cold rolling
[28,33,46], hot forging [27], hot extrusion [38,46], ECAP and HPT
[30,47], which are currently used for processing of high-performance
HEAs. Among these techniques, powder metallurgy techniques, in-
cluding mechanical alloying (MA) and consequent compaction via
spark plasma sintering, are highly feasible options for the production of
ultrafine-grained HEAs that exhibit promising properties in just one
processing step [14,48].
Since HEAs are currently fabricated via MA, the total processing
time is still typically several tens of hours [4,49]. Only a few studies
have reported the successful fabrication of HEAs via ultrashort-term
MA. Among them, Raza et al. [14] reported the shortest duration to
date for CrFeMoVMnx (x = 0, 0.5, 1 atomic ratio) HEA alloys of only 6 h
while maintaining a relatively low 200 rpm. Considering the reduction
of undesirable contamination by the elements of the milling vessel, this
approach seems to be a crucial step towards the future direction of alloy
preparation via MA in coming years.
The present manuscript describes the preparation of a CoCrFeMnNi
HEA alloy by a combination of ultrashort-term mechanical alloying and
compaction via spark plasma sintering. The combination of these
techniques resulted in a refined ultrafine-grained microstructure and
excellent mechanical properties that exhibit an excellent balance of
strength and ductility even when tested at temperatures reaching up to
600 °C.
2. Experiment
The investigated equiatomic high-entropy CoCrFeMnNi alloy was
prepared by mixing pure powders of Co, Cr, Ni, Fe and Mn (see Fig. 1)
together in appropriate amounts to create a powder mixture (10 g). The
powder mixture was then blended and placed into a stainless-steel
mould with milling balls made from AISI 420 stainless steel. Ad-
ditionally, 5 wt% of n-heptane was added as a process control agent
(PCA), and the mould was sealed and flushed with argon (purity of
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Materials Science & Engineering A 734 (2018) 341–352
99.996%, 3 min flushing with flow of 2 l. min−1) to prevent undesirable
oxidation during MA. The weight ratio of the balls and the powder was
15:1. The MA treatment (Retsch PM-100, Haan, Germany) was per-
formed at 400 rpm for 30 min followed by a 10-min cool-down period
and further re-spinning in opposite direction. The process was then
repeated until reaching a total time of 8 h.
The prepared powders were then compacted via a spark plasma
sintering device (FCT Systeme HP D 10, Frankenblicke, Germany). For
this purpose, 10 g of the MA powder was heated to the compaction
temperature of 800 or 1000 °C with a heating speed of 200 °C min−1.
Afterward, the sample was compressed with a pressure of 48 MPa; the
sample remained at the compaction temperature for a duration of only
10 min, which minimized deleterious microstructure coarsening during
the compaction. The compaction temperature was established as the
maximum temperature the sample could withstand without melting
based on results obtained by differential thermal analysis (DTA, Setys
Evolution, Setaram, France).
For the DTA analysis, the powder product was placed into an Al2O3
crucible and heated at a rate of 10 °C min−1 under an argon atmosphere
up to at least 1400 °C. The CoCrFeNiMn alloy prepared via 8 h of MA
had a sharp endothermic peak that started at approximately 1250 °C
and corresponded to the melting of the powder material (see Fig. 2). On
the other hand, at lower temperatures up to 450 °C, rather exothermic
behaviour corresponding to lattice stress-strain relaxation was ob-
served. Therefore, the compaction temperatures were set at 800 and
1000 °C, which should provide compact samples with good particle-to-
particle contacts. Considering the results obtained by DTA analysis, a
temperature of 1200 °C was also tested for compaction via SPS. How-
ever, the process resulted in partial melting of the powder sample.
To demonstrate the beneficial effect of MA, an as-cast alloy with
identical chemical composition was prepared by induction melting in
an argon protective atmosphere at a temperature of approximately
1800 °C. The melt was then homogenized for several minutes by means
of eddy currents and poured into a steel crucible, forming an ingot
14 mm in diameter with a total length of 150 mm. The chemical com-
positions of both investigated alloys, including the as-cast and 8-h
MA+SPS alloy, are shown in Table 1.
The prepared as-cast and MA+SPS compact samples were cut
(LECO VARICUT VC-50) into metallographic samples that were etched
with a mixture of HNO3 and HCl (ratio of 1:3) and observed by light
microscopy (LM, Olympus PME-3) and electron scanning microscopy
(SEM, Tescan VEGA 3-LMU, 20 kV, SE+BSE detectors) equipped with
an energy dispersion spectrometer (EDS, Oxford Instruments, 20 mm2).
More detailed microstructural investigation was done by electron
transmission microscopy (TEM, JEOL JEM 2200 FS, 200 kV, TEM/
STEM mode) with EDS (Oxford Instruments, 80 mm2). The chemical
and phase composition of prepared materials was determined by X-ray
fluorescence spectroscopy (XRF, PANanalytical, Holland) and by X-ray
diffraction spectrometry (XRD, PANanalytical X′Pert PRO, Holland, Cu
Κα1 = 1.54059 ×10−10 m). The results of the XRF analysis are shown
in Table 1, confirming almost comparable equiatomic compositions of
the as-cast alloy and the alloy prepared via 8 h of MA. The porosity of
the prepared as-cast and MA+SPS samples was evaluated by ImageJ
software using the threshold method. For this purpose, at least 5 pic-
tures of the sample at a 50x magnification were used.
Prepared materials were tested for mechanical properties including
Vickers hardness and compressive/tensile stress-strain tests. The
Vickers hardness was measured according to ČSN EN ISO 6507-1 with a
30 kg load, a 10 s dwell time and an ambient temperature of 25 °C. For
the compressive stress-strain test, cubical samples with a side length of
4 mm and a height of 6 mm were used. The compressive tests were
performed at ambient temperature and at elevated temperatures of 400
and 600 °C. The tensile tests were performed according to ČSN EN ISO
6892-1. Samples used for the tensile test were prepared by an electro-
erosion cutting device. Both the as-cast and the MA+SPS materials
were cut to obtain a dog bone-shaped specimen with a body length of
F. Průša et al. Materials Science & Engineering A 734 (2018) 341–352

Fig. 1. Morphology of the Co, Cr, Ni, Fe and Mn powders used for MA (the average size of the powder particles was 2, 42, 5, 24 and 12 µm, respectively).

Table 2
The porosity of the prepared CoCrFeNiMn alloy under different
preparation conditions.
CoCrNiFeMn (preparation) Porosity [%]

As-cast 0.64 ± 0.13

8 h MA+SPS at 800 °C 7.61 ± 0.88
8 h MA+SPS at 1000 °C 0.12 ± 0.05

shown in Fig. 3. The images show an evident influence of the com-

paction temperature on the resulting porosity, which undergoes a sig-
nificant change in value as the SPS compaction temperature changes
from 800 °C to 1000 °C. The 8-h MA+SPS sample compacted at 800 °C
showed high residual porosity reaching up to 7.61% (Table 2), sug-
gesting that the compaction temperature was too low to deliver aa
Fig. 2. DTA results of the CoCrFeNiMn alloy prepared by 8 h of MA.
good-quality compact sample. The pores were irregular in shape, which
corresponded to the free spaces between loose powder particles that
Table 1 were not sealed during SPS compaction. On the other hand, a higher
XRF chemical compositions (at%) of the CoCrFeNiMn alloy at different states of temperature of compaction via SPS resulted in a tremendous decrease
preparation including as-cast material and material prepared via 8 h MA and in porosity, which was reduced from its initial high value of
compacted by SPS.
7.61–0.12%. The pores were uniformly distributed with a mostly cir-
Alloy Element content [at%] cular geometry and sub-micrometre dimensions. Simultaneously, mi-
crostructural coarsening was observed as the compaction temperature
Co Cr Fe Ni Mn
increased. In comparison, the as-cast alloy exhibited a rather average
As-cast 20.3 20.1 20.8 20.7 18.1 porosity of 0.64% when compared to that of the 8-h MA+SPS sample
8 h MA+SPS 16.9 19.9 24.0 20.7 18.5 compacted at 1000 °C. Although one of the 8-h MA+SPS samples
showed a porosity that was one order of magnitude bigger, both showed
a significantly more refined microstructure compared to that of the as-
5 mm for testing. The strain speed for both tests was set to 1.0 × 10−3 cast alloy, which was composed of dendritic-like structures.
s−1. The phase compositions of the 8-h MA and compact 8-h MA+SPS
samples were identified by XRD analysis (Fig. 4) as solid solutions with
an FCC crystallographic lattice. The solid solution with a FCC crystal-
3. Results lographic lattice corresponded to the spectra of the Fe0.58Ni0.42 phase
(JCPD database card no. 04–002-3696, space group Fm 3m ) and re-
3.1. Microstructure mained within the alloy even after compaction via SPS at 800 °C and
1000 °C. The as-cast alloy was also composed of a solid solution with an
LM micrographs of the prepared as-cast alloy and the 8-h MA+SPS FCC crystallographic lattice structure corresponding to the previously
samples at different compaction temperatures of 800 and 1000 °C are

Fig. 3. LM micrographs of the CoCrFeNiMn alloy prepared by a) induction melting, b) 8 h MA+SPS at 800 °C, and c) 8 h MA+SPS at 1000 °C (without etching).

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F. Průša et al.
Fig. 4. XRD patterns of the CoCrFeNiMn alloy at different stages of preparation including as-mixed powders, powders prepared via 8 h of MA, compact MA+SPS
samples and the as-cast state.
mentioned Fe0.58Ni0.42 phase.
During compaction via SPS, which was done at temperatures of
800 °C and 1000 °C, a peak narrowed, suggesting microstructural
coarsening and partial recovery of the FCC phase. This effect was sig-
nificantly more pronounced as the temperature of the SPS increased
from 800 °C to 1000 °C (Fig. 4).
SEM micrographs of the as-cast and MA+SPS alloys are shown in
Fig. 5. The micrographs show the presence of pores whose dimensions
were further increased during etching. The as-cast alloy (Fig. 5a) con-
tained, as shown in Fig. 3a, dendritic-like structures (the hardly dis-
tinguishable dark-grey and light-grey areas) with a slightly varying
chemical composition, and the XRD analysis did not identify any other
phase except the previously mentioned Fe0.58Ni0.42. In comparison, the
MA+SPS alloys (Fig. 5b, c) showed a significantly refined micro-
structure with sub-micron or even nanocrystalline dimensions. The
porosity of the MA+SPS alloy compacted via SPS at 800 °C was several
times larger than that of the alloy compacted at 1000 °C (see Fig. 3b, c).
The higher compaction temperature of 1000 °C also resulted in some
microstructural coarsening, as shown in Fig. 5c.
The SEM+EDS element maps of the as-cast alloy and the alloys
prepared by a combination of MA and compaction via SPS at two dif-
ferent temperatures of 800 °C and 1000 °C are shown in Fig. 6. The as-
cast alloy showed the presence of areas that were enriched in certain
elements while the content of the rest was lowered and vice versa (see
Fig. 6a). On the other hand, the MA alloy that was compacted via SPS at
800 °C showed a homogeneous, well-refined microstructure without
any traces of chemical segregation, which was also partially caused by
the limits of the EDS detector with respect to the fine nature of the
examined grains (Fig. 6b).
Fig. 5. SEM micrographs of the CoCrFeNiMn alloy prepared via a) induction, b) 8 h MA+SPS at 800 °C, and c) 8 h MA+SPS at 1000 °C.
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Materials Science & Engineering A 734 (2018) 341–352
In comparison, compaction via SPS at 1000 °C resulted in some
microstructural coarsening that is evident in Fig. 6c and, more im-
portantly, in the formation of regions that were supersaturated by Cr
(see also results given in Table 3).
The chemical composition of various regions in the investigated
alloys was confirmed by SEM+EDS point analysis as shown in Fig. 7
and summarized in Table 3. The as-cast alloy contained a dendritic-like
structure that was enriched in Mn and Ni, reaching up to 28 at% (point
1 in Fig. 7a), while the interdendritic area was depleted of these ele-
ments.
On the other hand, the MA+SPS alloy compacted at 800 °C showed
uniformly distributed elements in the FCC solid solution without any
traces of segregation, which is also confirmed by the results presented
in Table 3.
In comparison, the same sample compacted via SPS at the higher
temperature of 1000 °C contained coarser grains (dark grey particles in
Fig. 8) that were enriched by Cr, reaching up to 51 at% (see also Figs. 6c
and 7c).
The microstructure of the as-cast and MA+SPS alloys was observed
by TEM; the resulting micrographs are shown in Fig. 8. The as-cast
alloy, although composed of large dendritic-like structures, contained
nano-scale regions with a mostly circular geometry and an average size
of approximately 10 nm (Fig. 8a). In comparison, the MA+SPS alloy
compacted at 800 °C contained grains mostly with a polyhedral geo-
metry and an average size of approximately 150 nm (Fig. 8b). On the
other hand, the alloy compacted via SPS at 1000 °C had polyhedral
grains with a slightly larger average size of approximately 250 nm
(Fig. 8c). Both MA+SPS alloys contained lattice defects in grains, and
the presence of equiaxed grains with an average diameter below
F. Průša et al.
Fig. 6. SEM+EDS maps of the CoCrFeNiMn alloy: a) as-cast; b) 8 h MA+SPS at 800 °C; and c) 8 h MA+SPS at 1000 °C.
100 nm suggests partial recrystallization during the compaction (see
Fig. 8b, c). Larger polyhedral grains and equiaxed grains formed a bi-
modal microstructure within both MA+SPS alloys.
The TEM+EDS maps of both the 8 h MA+SPS alloys are shown in
Fig. 9. The SPS compaction done at 800 °C suppressed the micro-
structural coarsening although the microstructure showed presence of
areas supersaturated by Cr (Fig. 9a). In comparison, higher compaction
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Materials Science & Engineering A 734 (2018) 341–352
temperature of 1000 °C during SPS resulted in coarser bimodal micro-
structure showing also a presence of large grains enriched in Cr (see
Fig. 9b). Nevertheless, these grains were approximately 500 nm in
diameter that almost corresponded to those observed by SEM+EDS
(see Fig. 7c). It should be noted, that the grains enriched in Cr were in
both the MA+SPS alloys distributed very randomly and their amount
was overall lower that displayed in Fig. 9a,b. Among that, the TEM
F. Průša et al. Materials Science & Engineering A 734 (2018) 341–352

Fig. 6. (continued)

Table 3 65 at% during compaction at 1000 °C (Table 5). On the other hand, the
The results of SEM+EDS analysis of points marked in Fig. 7. large polyhedral grains were almost identical in theirs chemical com-
CoCrNiFeMn (preparation) Point Chemical compositon [at%]
position for both the MA+SPS alloys regardless of the selected com-
paction temperature. Both the alloys showed presence of small
Co Cr Fe Ni Mn equiaxed grains that were enriched in Mn which content varied in a
range of 40–65 at%.
As-cast 1 16.7 16.8 15.3 23.6 27.6
2 21.0 21.4 21.6 18.2 17.8
8 h MA+SPS at 800 °C 3 18.3 20.9 24.1 17.9 18.8
3.2. Mechanical properties
4 18.6 20.4 24.0 18.2 18.8
8 h MA+SPS at 1000 °C 5 10.0 50.5 16.1 8.7 14.7
6 19.3 17.3 25.3 19.3 18.8 The thermal stability of the tested alloys was evaluated as the
hardness change during long-term annealing tests performed at 400 °C
and 600 °C and is shown in Fig. 10 and clearly summarized in Table 6.
+EDS maps showed slightly higher content of Mn in equiaxed grains Both MA+SPS alloys exhibited significantly higher hardness than the
(see Fig. 9a,b). as-cast alloy. The highest initial hardness of 424 ± 7 HV was achieved
The TEM+EDS results of point analysis of the sample compacted at by the alloy compacted via SPS at 1000 °C, while the alloy compacted at
800 °C (Table 4) showed that the Cr-rich grains contained approxi- 800 °C showed a slightly lower hardness of 352 ± 12 HV. In compar-
mately 50.5 at% of Cr. Simultaneously, the content of Cr increased up to ison, the as-cast alloy exhibited a lower hardness of only 120 ± 3 HV.

Fig. 7. SEM+EDS point analysis of the CoCrFeNiMn alloy prepared: a) as-cast; b) 8 h MA+SPS at 800 °C; and c) 8 h MA+SPS at 1000 °C.

346
F. Průša et al.
Fig. 8. TEM bright field micrographs of the CoCrFeNiMn alloy: a) as-cast; b) 8 h MA+SPS at 800 °C; and c) 8 h MA+SPS at 1000 °C.
During long-term annealing at 400 °C, both alloys exhibited good
thermal stability, which was confirmed by an almost negligible change
in hardness. After 100 h of annealing, both alloys showed an almost
identical hardness of 406 HV, outperforming the as-cast alloy by more
than three times. The superior thermal stability of the MA+SPS alloys
was confirmed at an even higher long-term annealing temperature
(600 °C). The MA+SPS alloys again showed good thermal stability,
expressed by an almost negligible change in hardness, and the highest
hardness of 416 ± 8 HV was achieved by the MA+SPS alloy com-
pacted at 1000 °C. The as-cast alloy exhibited a similar behaviour,
confirming the good thermal stability of these alloys even when their
hardness reached only one quarter of the MA+SPS alloys’ hardness.
The results of the compressive stress-strain test at ambient tem-
perature and at the elevated temperatures of 400 °C and 600 °C are
clearly summarized in Table 6. One can see that both MA+SPS alloys
had a higher compressive yield strength (CYS) than the as-cast alloy
when tested at ambient or at elevated temperatures. The tests per-
formed at ambient temperature revealed that the highest CYS, com-
pressive strength (CS) and plastic deformation of 1534 MPa, 1610 MPa
and 1.2%, respectively, were achieved for the MA+SPS alloy com-
pacted at 800 °C. On the other hand, these results were only slightly
higher than those for the sample compacted via SPS at 1000 °C, showing
a CYS of 1340 MPa. However, this alloy showed continuous plastic
deformation that reached several tens of percents, which did not result
in specimen rupture, and thus, the CS value could not be determined.
The results of the compressive stress-strain test performed at 400 °C
showed a reduction in the CYS of the investigated alloys. The highest
CYS of 1125 MPa was that of the MA+SPS alloy compacted at 800 °C,
followed by 890 MPa for the sample compacted at 1000 °C. In com-
parison, the values observed for the MA+SPS alloys were superior to
that of the as-cast alloy, which reduced its original CYS to only
160 MPa.
Additionally, the compressive tests were also performed at a tem-
perature of 600 °C. A relatively high testing temperature resulted in
further reduction of the CYS values of the as-cast and MA+SPS alloys.
However, the CYS values of the MA+SPS alloys were superior to that of
the as-cast alloy. The highest CYS value of 601 MPa was observed for
the MA+SPS alloy compacted at 1000 °C, which was more than four
times higher than that of the as-cast alloy.
Similar findings were observed during tensile tests performed at
ambient temperature, and the results are shown in Fig. 11 and are more
clearly summarized in Table 7. Both MA+SPS samples showed higher
ultimate tensile strength (UTS) and yield tensile strength (YTS) values
than the as-cast alloy, which, in contrast, had high ductility, with total
plastic deformation reaching 39%. The highest YTS and UTS values of
855 and 892 MPa, respectively, were achieved by the MA+SPS alloy
compacted at the higher temperature of 1000 °C.
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Materials Science & Engineering A 734 (2018) 341–352
Similarly, this alloy also exhibited ductile behaviour, with a total
plastic deformation value of 2%. A lower temperature of compaction
via SPS resulted in rather brittle behaviour of the alloy, which still had
a higher UTS of 685 MPa compared to the CS (443 MPa) of the as-cast
alloy.
Detailed micrographs of the fracture surface of MA+SPS alloy
compacted at 800 °C are shown in Fig. 12. There is evidence of the
possible fracture starting point (see the left bottom corner in Fig. 12a)
and an intercrystalline fracture morphology typical of brittle fractures,
with clearly distinguishable particles of MA powder. More detailed
views shown in Fig. 12b and in Fig. 12c reveal the presence of a small
volume fraction of fine microvoids (marked with an arrow) that cor-
respond to ductile fracture, and the alloy showed no traces of ductile
behaviour (see Fig. 11). These observations suggest that a compaction
temperature of 800 °C is insufficiently low.
On the other hand, the MA+SPS alloy compacted at a temperature
of 1000 °C showed a fracture morphology typical of ductile fractures,
with clearly distinguishable microvoids (see Fig. 13c). Thus, the higher
the temperature of SPS compaction, the better the inter-particle cohe-
sion, the lower the porosity and the better the mechanical properties
during tensile tests. Although some microstructural coarsening was
observed, the positive effect on overall mechanical properties was much
more beneficial, compensating for the potentially undesirable effects.
4. Discussion
4.1. Microstructure
The processing steps combining short-term mechanical alloying and
compaction via spark plasma sintering resulted in a significantly refined
microstructure of the investigated alloys (Fig. 3b, c), with average grain
sizes of approximately 150 nm and 250 nm corresponding to the alloys
compacted at 800 °C and 1000 °C (Fig. 8b, c), respectively. On the other
hand, the as-cast alloy had large dendritic-like structures (Fig. 3a) with
longitudinal dimensions reaching several hundred μm. All the alloys
were composed of a solid solution with a beneficial FCC crystal-
lographic lattice, although the TEM+EDS investigations of the
MA+SPS alloys showed also presence of phases enriched in Cr reaching
up to 65 at%. The formation of phases containing up to 55 at% of Cr
after long-term annealing at 700 °C for 500 days has been already re-
ported by Dlouhý et al. [35] who prepared equiatomic CoCrNiFeMn
alloy using arc melting. It should be noted, that the preparation route is
not comparable to the combination of MA+SPS which generate sig-
nificant lattice stress-strains due to imposed plastic deformation. The
MA alloys consisting of FCC solid solutions might decompose into
phases which are supersaturated of Cr even during short compaction via
SPS at slightly higher temperatures to those used in [35]. Considering
F. Průša et al.
Fig. 9. TEM+EDS maps with points of chemical analysis of the 8 h MA+SPS alloy: a) compacted at 800 °C, b) compacted at 1000 °C.
the different preparation conditions, the presence of areas super-
saturated by Cr, which content ranged from 50.5 up to 65 at%, is in
good agreement with the already published results. Among that, both
alloys showed also presence of smaller equiaxed phases that were en-
riched in Mn that has been, to our best knowledge, observed for the first
time.
The phases in MA+SPS alloys were thermodynamically stable,
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Materials Science & Engineering A 734 (2018) 341–352
which was confirmed by the results of XRD analysis, predicting good
mechanical properties even at higher temperatures, which will be dis-
cussed in greater detail in further text. During MA, a peak broadening
was observed that partially corresponded to the observed micro-
structural refinement and to lattice stress and strains induced by the
intensive plastic deformation characteristic of the chosen processing
technology. The compaction via SPS resulted in peak narrowing,
F. Průša et al. Materials Science & Engineering A 734 (2018) 341–352

Table 4 Table 6
The results of TEM+EDS analysis of points marked in Fig. 9a. Summary of mechanical properties of the prepared alloys. (CYS – compressive
yield strength in MPa; CS – compressive strength in MPa; D – total plastic de-
CoCrNiFeMn (preparation) Point Chemical compositon [at%]
formation in %; HV – Vickers hardness measured with 30 kg load) *The CS
Co Cr Fe Ni Mn value could not be determined since the sample exhibited continuous plastic
deformation.
8 h MA+SPS at 800 °C 1 19.8 14.7 25.2 19.9 20.4
CoCrNiFeMn Test CYS CS [MPa] D [%] HV
2 21.1 12.7 27.4 20.1 18.7
(preparation) temperature [MPa]
3 3.4 51.1 6.7 2.7 36.1
[°C]
4 4.7 49.8 10.1 5.7 29.7
5 15.6 10.1 19.9 15.2 39.2
As-cast 25 227 * > 24 120 ± 3
6 9.7 7.2 12.3 8.9 61.9
400 160 * > 25 –
600 140 * > 26 –
8 h MA+SPS at 25 1534 1610 1,2 352 ± 12
Table 5 800 °C
The results of TEM+EDS analysis of points marked in Fig. 9b. 400 1125 * > 10 –
600 350 * > 20 –
CoCrNiFeMn (preparation) Point Chemical compositon [at%] 8 h MA+SPS at 25 1340 * > 10 424 ± 7
1000 °C
Co Cr Fe Ni Mn 400 890 * > 15 –
600 601 * > 15 –
8 h MA+SPS at 1000 °C 1 20.5 13.0 28.7 19.5 18.3
2 20.6 12.5 27.7 20.7 18.5
3 2.4 69.9 7.5 0.5 19.7
4 1.9 60.5 6.8 1.1 29.7
5 7.0 11.5 9.6 7.2 64.7
6 9.8 13.4 11.8 6.8 58.2

indicating partial recovery that reduces lattice stresses and strains, as

well as microstructural coarsening, as shown in Figs. 6c and 8b,c. The
degree of this effect was greater as the temperature of compaction in-
creased from 800 °C to 1000 °C. More importantly, a higher compaction
temperature of 1000 °C resulted in the formation of larger areas su-
persaturated with Cr, reaching up to 65 at%. However, XRD analysis
did not confirm the presence of a newly formed phase, which may be
explained by the similar atomic radii of the used elements, allowing
elemental substitution in the positions of the crystallographic lattice in
the FCC solid solution. The detailed TEM micrographs revealed the
Fig. 11. Tensile stress-strain tests of the CoCrFeNiMn alloy performed at am-
presence of a bimodal microstructure composed of polyhedral grains
bient temperature.
with lattice defects and equiaxed grains, as well as a defect-free interior,
suggesting partial recrystallization during SPS compaction (Fig. 8b, c).
The rest of the material contained solid-solution grains with a high Table 7
content of lattice defects mainly composed of dislocations. The presence Summary of the results obtained from tensile tests performed at ambient tem-
perature. (YTS – yield tensile strength in MPa; UTS – ultimate tensile strength in
of partially recrystallized grains in the same HEA has been previously
MPa; D – total plastic deformation in %) *The TYS value of the alloy compacted
reported in an alloy compressed at temperatures above 600 °C, allowing
at 800 °C could not be determined.
discontinuous dynamic recrystallization [44]. On the other hand, the
formation of equiaxed grains enriched in Mn in both MA+SPS HEAs CoCrNiFeMn Test temperature YTS [MPa] UTS D [%]
(preparation) [°C] [MPa]
may be attributed to a theoretical presence of spark plasma discharge at
the edges of compacted powders; the presence of spark plasma dis- As-cast 25 220 443 39
charge, even though previously described in some scientific contribu- 8 h MA+SPS at 800 °C 25 * 685 –
tions [50], is still highly controversial. Thus, the results of XRD analysis 8 h MA+SPS at 25 855 892 2
1000 °C
and the size of the observed grains predicted the good thermal stability

Fig. 10. Thermal stability of the tested CoCrFeNiMn alloys during long-term annealing performed for up to 100 h at a) 400 °C and b) 600 °C.

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F. Průša et al. Materials Science & Engineering A 734 (2018) 341–352

Fig. 12. The morphology of the crack surface of the CoCrFeNiMn alloy compacted at 800 °C after tensile tests: a) complex overview and b, c) details of the crack
surface with white arrows pointing at microvoids.

Fig. 13. The morphology of the crack surface of the CoCrFeNiMn alloy compacted at 1000 °C after tensile tests: a) complex overview and b, c) details of the crack
surface with white arrows pointing at clearly distinguishable microvoids.

350
F. Průša et al.
and overall mechanical properties of the investigated materials.
4.2. Mechanical properties
Compared to the as-cast alloy, which exhibited rather average va-
lues in properties, the investigated alloys prepared by a combination of
MA+SPS showed superior properties at both ambient temperature and
elevated temperatures (see results shown in Figs. 10 and 11, Tables 6
and 7). The main reason the MA+SPS alloys outperformed the as-cast
alloy was their ultra-fine-grained microstructure, in which grain sizes in
both materials did not exceed 250 nm. In comparison, the as-cast alloy
microstructure consisted of dendritic-like structures with a large long-
itudinal dimension, which reduced the mechanical properties but in-
creased the ductility. The different character of the alloy microstructure
resulted in large differences in the measured mechanical properties.
The MA+SPS alloys showed ultra-high CYS during compressive tests at
ambient temperature, reaching 1534 MPa and 1340 MPa for the alloys
compacted via SPS at temperatures of 800 °C and 1000 °C, respectively;
these alloys had CYS values almost six time that of the as-cast alloy. The
results are in good agreement with the Hall-Petch equation established
by Sun et al. [27] and expressed by (Eq. (1)):
1 crease of MA+SPS alloys during compressive tests at elevated tem-
σYS = 194 + 490∙d− 2 (1)
where the unit of the calculated strength is in MPa, and the unit of grain
size is in µm. It should be noted that the Hall-Petch equation has been
used to describe the yield strength of a CoCrFeMnNi alloy with an
average grain size in the range of 503 nm < d < 88.9 µm. According to
this equation, the MA+SPS alloy compacted at 800 °C with a majority
of grain sizes of approximately 150 nm should exhibit a CYS of
1459 MPa. The calculated value is still in relatively good agreement
with the observed CYS value of 1534 MPa. On the other hand, the
calculated CYS value for the 1000 °C MA+SPS alloy using the pre-
viously mentioned equation should be 1174 MPa instead of the ob-
served 1340 MPa. The same alloy showed continuous work hardening
typical of FCC HEAs due to the combined effect of a variety of de-
formation mechanisms including slips, twinning, reorientation of grains
and others [5]. More importantly, the work hardening of the latter-
mentioned MA+SPS HEA continuously increased, suggesting the pre-
vailing influence of a continuous increase in dislocation density over
the speed of dynamic recovery. This behaviour is similar to the results
reported by Ji et al. [4], who prepared their CoCrFeNiMn HEA via 60 h
of MA, resulting in a bimodal FCC structure with a CS of 1987 MPa and
a plastic deformation below 8%. On the other hand, the investigated
MA+SPS alloy compacted at 1000 °C showed a plastic deformation of
at least 10% without any traces of sample fracture (total relative de-
formation was ≈ 30%). These results are also superior to those reported
by Hadraba et al. [31], who prepared an oxide-dispersion-strengthened
CoCrFeNiMn alloy (ODS HEA) via mechanical alloying with CYS values
of 1005 MPa and 1232 MPa for the HEA and the ODS HEA, respectively.
It should be noted that the superiority of our MA+SPS alloys, which
were free of oxide particles, may be further highlighted by the short
duration of MA, which took only 8 h instead of the 24 h reported in
[31]. Since mechanical properties are closely related to both the mi-
crostructure and the preparation technique, it is not surprising that the
thixoformed CoCrFeMnNi alloy prepared by Rogal et. al [29] exhibited
a significantly lower CYS below 500 MPa. The main reason why the
investigated MA+SPS alloys exhibited such high values of mechanical
properties is because ultrahigh-energy MA produces alloys with grain
sizes below 200 nm during the first 8 h of the process but is still highly
capable of inducing considerable stress-strains in the crystallographic
lattice of the material. More importantly, a similar quaternary alloy
composed of CoCrFeNi prepared by gas atomization exhibited a CYS of
only 387 MPa [51], confirming the importance of both the chosen
processing technique and the chemical composition of the investigated
alloy when maximizing the resulting properties of prepared alloys.
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Materials Science & Engineering A 734 (2018) 341–352
Compressive tests performed at elevated temperatures of 400 °C and
600 °C more clearly demonstrated the superior behaviour of the
MA+SPS alloys, achieving CYS values of 890 and 601 MPa, respec-
tively. Both the as-cast and MA+SPS alloys exhibited continuous
strengthening during the compressive tests at elevated temperatures, a
result that has also been reported by Stepanov et al. [44] at tempera-
tures below 1073 K. On the other hand, Stepanov et al. examined the
mechanical properties of arc-melted CoCrFeNiMn equiatomic HEA,
finding a CYS of only 125 MPa when compressively tested at 600 °C.
The main reason for this result can be found in the microstructural
refinement achieved by mechanical alloying due to the large imposed
intensive plastic deformation. The high energy of the balls used in MA
limits diffusion in the cold-welded powder particles; combined with
continuous deformation strengthening, which causes further fracturing
of the newly formed phases, these processes result in a well-refined
microstructure containing a high volume fraction of crystallographic
defects composed mainly of dislocations. Therefore, the behaviour of
the prepared alloys corresponded to the prediction that the main
strengthening mechanism found in this alloy can be mainly attributed
to the Hall-Petch relationship and to deformation strengthening due to
increased dislocation densities. The latter-mentioned high dislocation
density is responsible for the softening and simultaneous ductility in-
peratures due to the thermal activation of non-conservative movements
of dislocations, resulting in climbs. On the other hand, when subjected
to tensile testing, the MA+SPS alloy compacted at 800 °C exhibited
brittle behaviour, which can be attributed to a relatively high porosity
of 7.61%. The increase in compaction temperature from 800 °C to
1000 °C resulted in a significant decrease in porosity to 0.12%. There-
fore, since tensile tests are more susceptible to such structural defects
compared with compressive tests, the highest UTS of 892 MPa was
observed in the case of the sample containing the lower residual por-
osity of only 0.12% (sample compacted at 1000 °C). This material also
exhibited ductile behaviour, achieving a total plastic deformation of
approximately 2%. The MA+SPS sample compacted at the lower
temperature of 800 °C, with a higher porosity of 0.87%, showed only
brittle behaviour. The hardness of the prepared MA+SPS alloys
reached 424 ± 7 HV, which is higher than the 231 ± 23 HV of a
CoCrFeNi alloy [51] prepared by a combination of gas atomization and
consequent compaction via SPS. On the other hand, the results for
MA+SPS HEAs are comparable to those reported by Schuh et al. [52],
who prepared a CoCrFeNiMn alloy by HPT, increasing the initial
hardness of the as-cast alloy from 150 HV to approximately 500 HV as
the number of HPT rotations reached 5 revolutions. More importantly,
the same author reported a tremendous hardness increase during heat
treatment performed at 450 °C, increasing the hardness of the HEA to an
outstanding 900 HV due to the formation of new nano-scaled phases.
Thus, this approach may be applied to the investigated MA+SPS alloys,
which may further enhance their mechanical properties with proper
thermal treatment. The preparation technique mentioned by Schuh
et al. is completely different from our combination of MA powders
compacted via SPS. In direct comparison, MA seems to be a much easier
process that is suitable for producing HEAs on a large scale while re-
ducing the amount of energy that would be otherwise spent melting the
elements by induction or arc melting. Moreover, since the currently
available SPS devices may produce mostly circular or rectangular spe-
cimens with diameters of several tens of centimetres, the combination
of MA+SPS seems to be more readily applicable for industrial pro-
duction.
5. Conclusion
The present work demonstrates the positive influence of ultrashort-
term MA on the microstructural refinement and resulting mechanical
properties of CoCrFeNiMn alloys. The combination of MA and com-
paction via SPS resulted in a bimodal microstructure composed of
F. Průša et al. Materials Science & Engineering A 734 (2018) 341–352

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