Materials Science & Engineering A 796 (2020) 140065

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Materials Science & Engineering A

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

Investigating the micro and nanomechanical properties of CoCrFeNi-Cx

high-entropy alloys containing eutectic carbides
L.J. Zhang a, P.F. Yu b, J.T. Fan c, M.D. Zhang b, C.Z. Zhang a, H.Z. Cui a, *, G. Li b
a
School of Materials Science and Engineering, Shandong University of Science and Technology, Qingdao, 266590, Shandong, PR China
b
State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao, 066004, PR China
c
School of Materials Science and Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, 200240, PR China

A R T I C L E I N F O A B S T R A C T

Keywords: In this study, we systematically investigated the effect of the carbon content on the phase structure evolution and
Carbon content macro and nanomechanical properties of the equiatomic CoCrFeNi alloy. A series of CoCrFeNi-based high-en­
High-entropy alloy tropy alloys with 0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.7, and 0.9 wt% carbon were fabricated by vacuum arc melting. The
Microstructural evolution
results showed that the alloys retained their single face-center-cubic (FCC) structure with large grains at the
Nanoindentation
Tensile properties
carbon contents up to 0.2 wt%. However, in the case of the alloys with carbon contents higher than 0.3 wt%, the
single phase structure transformed into the dendrite structure. The inter-dendrite regions of these alloys were
eutectic carbides containing lath M7C3 carbides and the FCC phase. The tensile yield strength of the CoCrFeNi
alloy increased from 295 to 512 MPa with the addition of 0.9 wt% carbon. The strengthening mechanisms of the
alloys were investigated, including the solid solution strengthening due to the interstitial carbon atoms and the
precipitation strengthening due to the M7C3 carbides. In addition, the nanoindentation results revealed that the
M7C3 carbides showed a high nanohardness of ~17.7 GPa, which is almost four times of that of the FCC phase.
We also investigated the elasto-plastic relationships, plastic properties and wear resistance of the FCC phase,
while elucidating the eutectic carbide regions and M7C3 carbides. The eutectic carbide regions exhibited brittle
fracture, whereas the FCC phase showed plastic fracture.

1. Introduction
Traditional alloys consist of no more than two main components with
minor alloying elements. This alloy design strategy has limited the
development of novel alloys to some extent. Recently, high-entropy al­
loys (HEAs) [1] have gained significant attention in the field of materials
science. These alloys contain multiple principal elements (≥4) in
equiatomic or near-equiatomic ratios. The presence of multiple com­
ponents increases the configurational entropy of these alloys, which in
turn can stabilize their crystal structures [1–3]. HEAs or
multi-component alloys often show the simple face-center-cubic (FCC),
body-center-cubic (BCC), or hexagonal-close-packed (HCP) structures
[3,4]. Single-phase HEAs are often treated as base alloys and are alloyed
with other metals, such as Al [5,6], Ti [7,8], Mo [9], V [10,11], Nb [12,
13], Zr [14], and Y [15] to obtain multi-phase HEAs. The use of these
alloying elements can widen the application range of HEAs. Another
effective method to tune the phase structure and mechanical behavior of
the HEAs is to alloy them with interstitial elements such as N [16], O
[16], B [17,18], and C [19–22]. For example, Lei et al. [16] reported that
the tensile yield strength (YS) and ductility of TiZrHfNb alloy increase
by 48.5% and 95.2%, respectively, upon doping with 2 at.% oxygen. In
contrast, when 2 at.% nitrogen is alloyed, the YS of these alloys increases
by 73.3%, while the ductility decreases by 36.6%. This is because oxy­
gen doping leads to the formation of nano-sized ordered interstitial
complexes. The formation of a large number of nano-sized complexes
can hinder the formation of planar slip and promotes the formation of
wavy slip, which can lead to a high strain-hardening capacity of the
alloy. However, the addition of nitrogen atoms endows the alloys with
traditional interstitial solid-solution strengthening characteristics [16].
Seol et al. [17] revealed that by alloying 30 ppm of boron, the yield
strength of the FeMnCrCoNi HEA with the FCC structure increase by
~100% without sacrificing the ductility, because of the reduction of the
grain size and the strengthening of the interface by the segregation of
boron at the grain boundaries.
It’s well-known that carbon as an alloying element significantly af­
fects the phase constitution and mechanical performance of steels [23,

* Corresponding author.
E-mail address: cuihongzhi1965@163.com (H.Z. Cui).

https://doi.org/10.1016/j.msea.2020.140065
Received 20 May 2020; Received in revised form 2 August 2020; Accepted 5 August 2020
Available online 7 August 2020
0921-5093/© 2020 Elsevier B.V. All rights reserved.
L.J. Zhang et al.
24]. At present, some HEAs containing carbon have been investigated. Li
et al. [19] investigated the effect of the carbon contents on the phase
structure and mechanical properties of CrMnFeCoNi alloys [19]. They
found that the yield strength of the CrMnFeCoNi HEAs increased from
371 to 792 MPa and the fracture strain reduced from 54 to 11% with an
increase in the carbon content from 0 to 3.0 at.%. The main strength­
ening mechanisms causing the yield strength increment in such HEAs
are precipitation strengthening by M23C6 nano carbides and dislocation
strengthening [19]. Chen et al. [20] reported that the addition of 3.3 at.
% carbon to the Fe40Mn40Co10Cr10 HEA promotes deformation-induced
twinning, which simultaneously improves both the yield strength and
plasticity of the HEA. In our previous study [21], a hard carbide coating
containing nano-sized M7C3 and M23C6 carbide precipitates was fabri­
cated on the surface of a CoCrFeNi HEA using the solid carburization
method. Nonetheless, the effect of the carbon content on the formation
of carbides and mechanical properties and strengthening mechanisms of
bulk CoCrFeNi HEAs should be investigated further.
In this study, we systematically investigated the effect of the carbon
content on the phase structure evolution and mechanical performance of
an equiatomic CoCrFeNi alloy. High carbon contents were observed to
change the microstructure of the alloy, resulting in the formation of a
new carbide phase, which was characterized using various analytical
techniques. Nanoindentation tests were carried out to investigate the
nanomechanical behaviors of the different phases of the alloys in the
micrometer region. The room-temperature tensile properties and
strengthening mechanisms of the alloys were also investigated. This
work aims to prepare high strength HEAs by addition different carbon
content, and explore the deformation mechanisms through character­
ization of mechanical properties at different scales. Investigation of the
eutectic carbides formation, macro and nanomechanical properties, and
deformation behaviors of these carbon-containing HEAs could benefit
future structural material design.
2. Experimental
CoCrFeNi HEAs doped with different carbon contents (wt.%) were
prepared using the arc-melting method in a vacuum arc melting furnace
equipped with a water-cooled copper crucible. The HEAs prepared using
0, 0.1, 0.2, 0.3, 0.4, 0.5, 0.7, and 0.9 wt% carbon were labeled as C0,
C0.1, C0.2, C0.3, C0.4, C0.5, C0.7, and C0.9, respectively. During the
melting process, these HEA ingots were remelted six times.
X-ray diffraction (XRD) measurements were carried out using a D/
MAX-2500/PC diffractometer with the Cu Ka radiation (λ = 1.54Å).
The samples for the scanning electron microscopy (SEM) observations
were cut from the as-cast alloys using wire electrode discharge
machining. The surfaces of these samples were ground using a 4000-
grade sand-paper, which was followed by polishing using a 1.5-μm
diamond paste. The polished samples were etched using an aqua-regia
solution and were then observed using a Hitachi S-3400 microscope.
For preparing the transmission electron microscopy (TEM) specimens,
the alloy samples were mechanically ground to 30 μm, which was fol­
lowed by ion thinning until the appearance of holes. An FEI TalosF200X
apparatus was used for carrying out the TEM investigations at an
accelerating voltage of 200 kV. The elemental analysis of the samples
was carried out using energy-dispersive X-ray spectroscopy (EDX).
Image-Pro Plus software was used to measure the volume fraction and
average lamellar thickness of the carbide phase in the HEAs [25].
The macromechanical properties of the HEAs were evaluated by
performing tensile measurements at room temperature on an INSTRON-
5982 machine. Flat Dog-bone tensile specimens were cut from the as-
cast ingots with the gauge size of 8 mm × 2 mm × 1 mm. During the
tensile tests, the tensile strain rate was 1 × 10− 3 s− 1. After the tensile
testing, the fracture morphologies of the tensile specimens were exam­
ined using SEM. The nanomechanical properties of the different phases
of the HEAs were investigated using a Hysitron TI-900 Triboindenter at
room temperature. The samples were carefully polished to a mirror-like
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Materials Science & Engineering A 796 (2020) 140065
surface using a 0.5-μm diamond paste. During the nanoindentation tests,
both the loading and unloading rates were 1000 μN/s and the maximum
load was set at 3000 or 8000 μN. Thus, the loading, holding, and
unloading times were set at 3, 0, and 3 s (or 8, 0, and 8 s), respectively.
The values of the elastic modulus and nanohardness were calculated
using the Oliver-Pharr method [26]. In-situ scanning probe microscopy
(SPM) was used to examine the indentation morphology of the different
phases of the alloys. Each sample was subjected to at least six tensile and
nanoindentation tests to ensure the accuracy and reliability of the
results.
3. Results
3.1. Phase identification and microstructural evolution
The XRD patterns of the CoCrFeNi alloys with different carbon
contents are shown in Fig. 1(a). The results suggest that the FCC phase
was the main phase in the HEAs. An increase in the carbon content
resulted in the appearance of a minor reflection peak that indicated the
formation of M7C3-type carbides. The inset shows the enlarged image of
the (111) peak of the FCC phase. As can be observed, the (111) peak
shifted towards lower 2θ angles with an increase in the carbon content
from 0 to 0.4 wt%. However, a further increase in the carbon content
caused the (111) peak to shift toward higher 2θ angle. The lattice con­
stants of the FCC phase in the HEAs were estimated from their (111)
peaks, as shown in Fig. 1(b). The lattice constants increased with an
increase in the carbon content up to 0.4 wt%, indicating that the carbon
atoms dissolved in the interstitial sites of the FCC phase. The linear
fitting of the results indicated that the increase in the lattice constant
(Δa) per wt.% carbon (Δc), Δa/Δc, was 3.2 p.m./wt.%. However, the
lattice constant of the FCC phase decreased with an increase in the
carbon content beyond 0.4 wt%, indicating that the formation of the
carbides reduced the solid-solution limit of the C content in the FCC
phase. The lattice strain of the FCC phase can be expressed as ε = (|a-
a0|)/a0, where a0 is the lattice constant of the C0 alloy. As shown in
Fig. 1(b), the trend shown by the lattice strain was similar to that shown
by the lattice constant of the FCC phase.
The SEM results showed that the carbon content significantly
affected the microstructural evolution of the CoCrFeNi HEAs. The C0,
C0.1, and C0.2 HEAs were single-phase alloys with large grain sizes
(~400 μm), as shown in Fig. S1(a)-S1(c) (see the Supplementary Ma­
terial). As can be observed from Fig. 2(a), the C0.3 HEA consisted of a
small amount of carbides. With a further increase in the carbon content,
the dendrite (DR) and inter-dendrite (ID) structures became predomi­
nant (Fig. 2(b)-2(e)). The DR regions were the FCC phase. The grain size
of the FCC phase decreased from ~400 μm (C0.3 alloy) to ~30 μm (C0.9
alloy), while the size of the rod-shaped carbides increased from ~0.15
μm (C0.3 alloy) to ~0.75 μm (C0.9 alloy) with increasing the carbon
content. The ID region showed the formation of eutectic carbides. Fig. 3
shows the effect of the carbon content on the volume fraction of the ID
regions (fID) and the average lamellar thickness (λ) of the eutectic car­
bides. With an increase in the carbon content from 0.2 to 0.9 wt%, the fID
of the HEAs increased from ~2.2 to ~30.7%, while the λ increased from
~0.17 to ~0.82 μm, respectively.
To further investigate the phase composition of the HEAs, the TEM
images of the C0.7 HEA were obtained. Fig. 4 shows the bright-field
image of the C0.7 alloy and the selected area electron diffraction
(SAED) patterns for the FCC phase and M7C3 carbides. The dark region
in the image corresponded to the M7C3 carbides. The SAED pattern along
the [001] zone axis indicated that the alloy matrix showed an FCC phase
crystal structure. The SAED pattern along the [2110] zone axis sug­
gested that the M7C3 carbides had a hexagonal structure with the P31c
space group [21,27,28]. The lattice parameters a and c were estimated
to be approximately 1.3992 and 0.4533 nm, respectively. The
bright-field image clearly showed the presence of some stacking faults in
L.J. Zhang et al. Materials Science & Engineering A 796 (2020) 140065

Fig. 1. (a) XRD patterns of the CoCrFeNi HEAs with different carbon content. The insert shows the high magnification images of the (111) peak of the FCC phase. (b)
The lattice constants and lattice strain of the FCC phase versus carbon content of the present HEAs.

Fig. 2. SEM images of the C0.3 (a), C0.4 (b), C0.5 (c), C0.7 (d), and C0.9 (e) HEAs.

Fig. 3. The volume fraction of the ID regions (fID) and the average lamellar Fig. 4. TEM observations of the C0.7 alloy display the bright-field image and
thickness (λ) of the M7C3 carbides versus different carbon content in the pre­ the corresponding SAED patterns of the FCC phase and M7C3 carbides.
sent HEAs.

3
L.J. Zhang et al.
the M7C3 carbides. The faulting streaks were parallel to the {0110}
growth planes of the M7C3 carbide. Ma observed similar stacking faults
in (Cr, Fe)7C3 carbides [28]. Fig. S2 shows the scanning transmission
electron microscopy image of the C0.7 HEA and its Co, Cr, Fe, Ni, and C
EDX elemental maps. A segregation in the concentration of Cr and C
elements was evident in the carbide precipitates. The EDX point analysis
results revealed that the carbides consisted of 61.59 at.% Cr, 6.00 at.%
Fe, 3.20 at.% Co, 1.23 at.% Ni, and 27.98 at.% C. This elemental
composition is consistent with that of M7C3-type carbide precipitates (M
= sum of all metal elements). Table 1 shows the mixing enthalpy of
different atom pairs in the present alloys obtained by Miedema’s
approach [29]. The M7C3 carbides consisted of large amounts of Cr and
C. This is because the negative mixing enthalpy between Cr and C atoms
(see Table 1) resulted in a stronger atomic affinity than those of the other
metal elements [29].
3.2. Macromechanical properties
The typical engineering tensile stress-strain curves of the CoCrFeNi
HEAs with different carbon contents are shown in Fig. 5(a). Fig. 5(b)
shows the YS, ultimate tensile strength (UTS), and total elongation (TE)
of the HEAs with different C contents. Table 2 lists the YS, UTS, and TE of
the HEAs. Both the YS and UTS of the HEAs increased with an increase in
the carbon content. For example, the C0.9 HEA showed higher YS (512
MPa) and UTS (693 MPa) than those of the C0 alloy. The alloys showed
an increase in the YS per wt.% carbon of approximately 369 MPa/wt.%
(Fig. 5(b)). However, the plastic deformation ability of the HEAs
decreased with an increase in the C content. The total elongation of the
HEAs decreased from 80.6 to 22.1% with an increase in the carbon
content from 0 to 0.9 wt%, respectively. This can be attributed to the
formation of carbide precipitates in the HEAs with the addition of
carbon.
The true stress-logarithmic strain curves of the HEAs are shown in
Fig. 5(c), and the corresponding work hardening rate vs. logarithmic
strain curves are shown in Fig. 5(d). The true stress of the HEAs was
differentiated over the logarithmic strain to obtain their work hardening
rate curves (dσ/dε). The work hardening rate of the HEAs increased with
an increase in the carbon content. The work hardening rate curves of the
C0, C0.1, C0.2, C0.3, and C0.4 HEAs showed a similar trend. These
curves could be divided into three regions: a rapid drop in the strain
hardening rate (Region I), a continuous increase in the strain hardening
rate (Region II), and a decrease in the strain hardening rate (Region III).
However, at the carbon contents higher than 0.5 wt%, the strain hard­
ening rate curves exhibited two regions (Region I and III). According to
Liu [30], the continuous increase in the strain hardening rate of CoCr­
FeNi HEAs is caused by their twinning-induced plasticity behavior.
The microstructural changes of the HEAs after the tensile deforma­
tion were examined using TEM. The bright-field TEM image at 3%
tensile strain of the C0.1 HEA shows the planar slip feature with dislo­
cations and the dislocation arrays along the primary slip system, as
shown in Fig. 6(a). The dark-field TEM image at 20% tensile strain
shows pronounced deformation twins in Fig. 6(b). Fig. 6(c) shows the
deformed microstructure of the C0.7 alloy after the application of 14%
tensile strain with a large amount of dislocation pileups in the FCC re­
gion. The addition of carbon significantly affected the deformation
Table 1
Summary of the mixing enthalpy of different atom pairs in the present alloys
obtained by Miedema’s approach [29].
Elements C Co Cr Fe Ni
C – 42 − 61 50 39
Co – – − 4 − 1 0
Cr – – – − 1 − 7
Fe – – – – − 2
Ni – – – – –
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Materials Science & Engineering A 796 (2020) 140065
behavior and tensile properties of the HEAs.
3.3. Nanomechanical properties
The nanoindentation technology is an efficient method to investigate
the mechanical performance of a micro/nano-sized area such as those of
small-sized phases [31] and thin films [32]. The nanoindentation
load-displacement curves of the FCC phase and eutectic carbides in the
C0.5, C0.7, and C0.9 alloys are shown in Fig. 7(a). The displacement at
peak load of the FCC phase shows larger than that of the eutectic car­
bides, indicating a higher hardness in eutectic carbides. The nanohard­
ness (H) and elastic moduli (E) of the FCC phase and eutectic carbide
regions of the HEAs are shown in Fig. 7(b). The nanohardness of the FCC
phase increased slightly from 3.5 to 4.6 GPa with an increase in the
carbon content from 0 to 0.9 wt%, respectively. This trend is similar to
that shown by the elastic moduli. The nanohardness and the elastic
moduli of the eutectic carbides were approximately 7.5 and 220 GPa,
respectively.
Fig. 8(a) shows the typical load-displacement curves of the FCC
phase and M7C3 carbide precipitates of the C0.7 alloy. The sample was
loaded to 3000 μN and then unloaded to zero load at a constant rate of
1000 μN/s. The residual indentation depths (hf) for the FCC phase and
M7C3 carbides were 15 and 90 nm, respectively, while the corresponding
maximum depths (hmax) were 58 and 114 nm. The hf and hmax values of
the FCC phase were higher than those of the M7C3 phase, indicating that
the M7C3 carbides showed higher resistance to plastic deformation than
that offered by the FCC phase. Fig. 8(b) shows the in-situ SPM images of
the indentations on the two phases. The M7C3 phase showed a smaller
indent size than that of the FCC phase. Fig. 8(c) shows the nanohardness
(H) and elastic modulus (E) of the FCC phase and M7C3 carbides of the
C0.7 alloy calculated using the Oliver-Pharr method [26]. The M7C3
carbides showed a high nanohardness of approximately 17.7 GPa, which
is almost four times of that of the FCC phase (~4.5 GPa). These results
are consistent with those obtained by Casellas et al. [33]. They reported
that the microhardness of the chromium primary M7C3 carbides present
in tool steels is approximately 18 GPa. However, the elastic moduli of
the M7C3 carbides and FCC phase were ~235 and ~204 GPa,
respectively.
Because of the geometric size limitation of the local phase area, it is
challenging to carry out uniaxial tensile or compression measurements.
Dao [34] and Gouldstone [35] reported that the compressive
stress-strain curves of different phases can be obtained using the reverse
analysis algorithm. The stress-strain curves of the FCC phase, eutectic
carbide regions, and M7C3 carbides of the C0.7 HEA (obtained from the
load-displacement curves) are shown in Fig. 9.
3.4. Fracture morphology
The SEM images of the fracture surfaces of the tensile specimens
were obtained to examine their fracture morphologies (see Fig. S3). The
HEAs showed two fracture modes: ductile and brittle fracture. The C0
HEA showed large dimples, as shown in Fig. 10 (a). However, the C0.7
HEA underwent a brittle-like fracture, which was similar to the dendrite
structure. (see Fig. 10 (b)). The percentage reduction in the area (RA) of
an alloy after the fracture is a measure of its plastic deformation ability.
Table 2 lists the RA values of the HEAs. As can be observed from the
table, the RA value of the HEAs decreased with an increase in the carbon
content. This trend is similar to that shown by the TE values. The for­
mation of the eutectic carbides changed the fracture mode of the HEAs
from plastic to brittle-like fracture. The detailed fracture mechanisms
are discussed in the following section.
L.J. Zhang et al. Materials Science & Engineering A 796 (2020) 140065

Fig. 5. (a) Typical engineering stress-strain curves of CoCrFeNi HEAs with various carbon contents. (b) Yield strength (YS), ultimate tensile strength (UTS), and total
elongation (TE) as a function of carbon content. True stress-logarithmic strain curves (c), and the corresponding work hardening rate-logarithmic strain curves (d) of
the current HEAs.

4. Discussion
Table 2
Summary of the yield strength (YS), ultimate tensile strength (UTS), total
4.1. Analysis of deformation and strengthening mechanisms
elongation (TE) and reduction in area (RA) of the current HEAs.
Alloys YS (MPa) UTS (MPa) TE (%) RA (%) With increasing the carbon content, the yield strength of the present
C0 180 ± 9 423 ± 15 74.8 ± 2.3 80.6 ± 2.1 HEAs showed an increasing trend (Fig. 5(b)). For the single FCC HEAs
C0.1 194 ± 10 445 ± 17 68.6 ± 2.4 71.7 ± 1.5 (<0.3 wt%), the evolution tendencies of the yield strength and nano­
C0.2 235 12 454 ± 16 52.2 ± 2.6 63.2 ± 1.8
±
hardness (Fig. 7(b)) of these alloys are in complete agreement, due to the
C0.3 295 ± 14 560 ± 18 49.1 ± 2.5 53.5 ± 1.6
C0.4 340 ± 17 581 ± 20 48.3 ± 2.4 53.1 ± 2.3 solid solution strengthening of carbon atoms. When the carbon content
C0.5 383 ± 18 590 ± 19 31.2 ± 2.0 39.7 ± 1.9 exceeds 0.3 wt%, the increase of the yield strength is attributed to the
C0.7 431 ± 21 603 ± 21 16.3 ± 1.8 28.7 ± 1.6 formation of M7C3 carbides with high hardness and the high volume
C0.9 512 ± 25 693 ± 23 15.8 ± 2.0 22.1 ± 1.5 fraction. The work-hardening behavior and tensile deformation process
of the HEAs were also significantly affected by their carbon contents
(Fig. 5(d)). To investigate the deformation behaviors of these alloys,

Fig. 6. (a) Bright field TEM images and the corresponding SAED patterns after 3% tensile strain of the C0.1 HEA. (b) Dark field TEM images and the corresponding
SAED patterns after 20% tensile strain of the C0.1 HEA. (c) Bright field TEM images of the C0.7 HEA after 14% tensile strain.

5
L.J. Zhang et al.
Fig. 7. (a) Typical nanoindentation load-displacement curves of FCC phase and eutectic carbides in C0.5, C0.7, and C0.9 HEAs. (b) The nanohardness and elastic
moduli values of the FCC phase and eutectic carbides for the current HEAs.
Fig. 8. (a) Typical nanoindentation load-displacement curves on the FCC and M7C3 phases of the C0.7 alloy. (b) The in-situ SPM images of the indents on different
phases. (c) The average values of nanohardness and elastic moduli of the FCC and M7C3 phases.
Fig. 9. The compressive true stress-strain curves of the FCC phase, eutectic
carbides, and M7C3 phase of C0.7 alloy, obtained by reverse anal­
ysis algorithms.
TEM was carried out to examine their dislocation substructures at
different tensile strain levels. The TEM image of the C0.1 HEA at the
strain of 3% (see Fig. 6(a)) showed some slip traces and dislocation
configurations. This indicates that the planar slips dominated the
deformation process at low strain levels. However, when the strain
increased to 20%, a large number of deformation twins appeared along
the [110] zone axis, as revealed by the dark-field TEM image shown in
Fig. 6(b). Although there are pronounced twinning activities in this
alloy, increasing carbon content can increase critical stress and retard
the formation of deformation twins [36]. The formation of the
deformation-twin boundaries will lead to a microstructure refinement,
6
Materials Science & Engineering A 796 (2020) 140065
which is often referred to as a “dynamic Hall-Petch effect”. Twin
boundaries hinder the movement of dislocations and create more
localized sites for dislocation nucleation and accommodating the dis­
locations, thereby improving the work hardening ability of the alloy
(corresponding to Region II in Fig. 5(d)). The C0.7 alloy subjected to
14% tensile strain showed dislocation cells with high-density dislocation
tangles in the FCC phase region (see Fig. 6(c)). For these alloys con­
taining carbides, the dislocation substructures and strain concentration
could easily be caused by the high volume fraction of the hard carbides,
which increased the work hardening ability. Because of the high hard­
ness of the M7C3 carbides, it is difficult for the dislocations to cross the
phase boundaries between the FCC phase and M7C3 carbides. The dif­
ferences of hardness and elastic moduli between the two phases (see
Figs. 7(b) and 8(c)) can result in different deformation behavior. A large
number of dislocations accumulate at the phase boundaries, leading to
stress concentration and crack initiation. Thus, the high volume fraction
of the carbides can increase the tendency of forming crack during
deformation and then decrease the plasticity. Therefore, the plasticity of
the HEAs decreased with an increase in their carbon content.
In the case of the C0.1 and C0.2 HEAs with the single FCC structure,
the increase in the YS can be attributed to the solid solution strength­
ening caused by the interstitial carbon atoms impeding the dislocation
movement. The Labusch model is applied to evaluate the effect of carbon
on the interstitial strengthening of CoCrNi alloys [36]. The solid solution
strengthening of these alloys causing an increase in the YS can be
2/3
described as [36,37]: Δσss = fG[cξ2 (a0 − a)2 /(1 − c)2 a20 ] , where f is a
dimensionless parameter, G is the shear modulus (84 GPa for the
CoCrFeNi HEA [38]), c is the mole fraction of carbon atoms, a0 is the
lattice constant of the C0 HEA, ξ (= 16) is a constant corresponding to
the dislocation type, and a is the lattice constant of the HEAs with
different carbon contents. The YS increments of the C0.1 and C0.2 HEAs
caused by solid solution strengthening were approximately 14 and 55
MPa, respectively. The solid solution strengthening caused by the
interstitial carbon atoms showed little effect on the strength of the
L.J. Zhang et al.
Fig. 10. SEM images of the fracture surfaces of C0 (a1)-(a2) and C0.7 (b1)-(b2) HEAs at low and high magnification. The contour of fracture surfaces indicated by the
red dotted line and the values of the reduction in area (RA) for the alloy are shown in (a1) and (b1). (For interpretation of the references to colour in this figure legend,
the reader is referred to the Web version of this article.)
alloys. However, at the carbon contents >0.3 wt%, the strength of the
HEAs increased dramatically because of hard carbide precipitate
strengthening. With an increase in the carbon content, the YS of the
HEAs improved along with an increase in the volume fraction of the
eutectic carbides (fID). The SEM images revealed that the DR regions of
these alloys were soft FCC phases. Based on the simple rule-of-mixture,
the relationship between the YS and the DR/ID volume fraction of the
HEAs could be described as [5]: σYS = σFCC VDR + σ EC VID , where σ FCC and
σ EC are the tensile YS values of the FCC phase and eutectic carbides,
respectively and VDR and VID are the volume fractions of the DR and ID
regions, respectively. These HEAs containing the carbides obeyed the
relationship: VDR + VID = 1. Thus, the YS of the HEAs could be expressed
as: σYS = σ FCC + (σ EC − σ FCC )VID . Fig. S4 shows the linear relationship
between the YS and VID of the HEAs. Thus, the traditional composite
model was used to explain the increase in the YS of the HEAs.
4.2. Nanomechanical properties of different phases
The compressive true stress-strain curves for the different local re­
gions of the HEAs could be obtained from their load-displacement curves
using the reverse analysis algorithm. A simple elasto-plastic relationship
is assumed by defining the elastic stage that follows the Hooke’s law and
by defining the plastic stage that follows the power-law [34,35,39]:
⎧
⎨ Eε
⎪ σ ≤ σy
( )n
σ= E (1)
⎪
⎩ σ y 1 + εp σ > σy
σy
where E is the elastic modulus, σy (= Eεy) is the initial yield stress, εp is
the plastic strain, the total strain can be expressed as ε = εy +εp, and n
represents the strain hardening exponent. The constitutive equations of
the stress-strain relationship of the present HEAs were obtained through
the dimensional analysis [39]. Depending on this method, the load (P) of
the loading segment in the load-displacement curves can be given as [34,
35,39]: P = σ Γ h2 Π 1 (E* /σΓ ,n), where σ Γ is the stress at the strain of εΓ for
7
Materials Science & Engineering A 796 (2020) 140065
the loading curve, h is the displacement, E* is reduced modulus. And Π1
is a dimensionless function, which is independent of n when εΓ = 0.033,
and can be expressed as: Π 1 = C/σ0.033 [39]. Similarly, the unloading
segment of the curves can be calculated [34,35,39]: S = dP dh |h = hmax =
U
(
*
)
E* hmax Π 2 σEΓ , n , where S is contact stiffness, and the dimensionless
function Π2 can be given by Refs. [39]: Π 2 = S/E* hmax . Combining Eq.
(1), dimensionless function Π1 and Π2, initial yield stress σ y and strain
hardening exponent n can be obtained. Thus, depending on the
load-displacement curves in Fig. 7 (a), the constitutive stress-strain
equation of the FCC phase in the C0.7 HEA can be calculated:
{
204.22ε σ ≤ 0.52 GPa
σ= (2)
0.52(1 + 392.73ε)0.34 σ > 0.52 GPa
Similarly, based on the load-displacement curve (see Fig. 7 (a)) and
dimensional analysis, the constitutive stress-strain equation of the
eutectic carbides in the C0.7 HEA was obtained:
{
σ=
220.32ε σ ≤ 1.18 GPa
(3)
1.18(1 + 186.71ε)0.33 σ > 1.18 GPa
The σy and n values of the M7C3 carbides could not be determined
using the reversible analysis algorithm, indicating that the M7C3 phase
was the brittle phase with only the elastic stage. The corresponding
stress-strain equation can be expressed as:
σ = 237.51ε (4)
The true stress-strain curves (Eqs. (2)–(4)) of the FCC phase, eutectic
carbide region, and M7C3 phase are shown in Fig. 9. The M7C3 phase
showed the highest strength, and the eutectic carbide region showed
higher strength than that of the FCC phase. In addition, the strain
hardening exponent of the eutectic carbide region was comparable to
that of the FCC phase, indicating that the eutectic carbides showed a
high work hardening ability. As reported previously [12,14,40], eutectic
alloys generally show high strength and plasticity.
L.J. Zhang et al.
The plastic properties of the FCC phase and M7C3 carbides of the
HEAs could also be analyzed from their load-displacement curves shown
in Fig. 8(a). The loading stage is a process of energy dissipation. The
dissipated total energy (Wt) of the HEAs was calculated using the area
integration of the loading stage (from 0 to hmax) in the load-
displacement curves. The area under the unloading stage represents
the elastic energy (We), which was recovered completely during the
unloading to zero load. The remaining part of Wt is the plastic energy
(Wp), which was unrecovered during an indentation loading-unloading
cycle, with Wt = We + Wp. The plastic energy dissipation ratio can be
expressed as Wp/Wt, which is related to the crystal structures and me­
chanical behaviors of the different phases present in the alloys. Thus, the
calculated Wp/Wt values of the FCC phase and M7C3 carbides were
72.5% and 27.2%, respectively. The higher Wp/Wt value of the FCC
phase indicates that the FCC phase showed a larger plastic deformation
than that of M7C3 carbides. In addition, the H/E and H3 /E2 parameters
can be used to qualitatively evaluate the wear resistance of a materials
[41]. In this study, the M7C3 carbides showed higher H/E and
H3 /E2 (~0.077 and ~0.1039 GPa) values than those of the FCC phase
(~0.021 and ~0.0019 GPa). This indicates that the M7C3 carbides show
better wear resistance than that of the FCC phase. The high plasticity and
low wear resistance of the FCC phase can be attributed to the multipli­
cation and interaction of the dislocations underneath the indenter. The
hard and brittle M7C3 carbides showed high hardness and good wear
resistance because of the activation of only few slip systems during the
deformation process.
4.3. Analysis of the fracture mechanisms
The fracture mechanisms of the HEAs were investigated by exam­
ining their fracture morphologies (see Figs. 10 and S3). The C0, C0.1,
C0.2, and C0.3 HEAs showed a large number of ductile pimples on their
fracture surfaces. This indicates that these alloys showed a ductile
fracture with excellent plasticity. The fracture surfaces of the C0.4, C0.5,
C0.7, and C0.9 HEAs showed distinct ID and DR structures. This is
consistent with the SEM results shown in Fig. 2. The nanoindentation
results showed that the nanohardness of the M7C3 carbide was four times
higher than that of the FCC phase, indicating that the M7C3 carbides
showed a higher YS than that of the FCC phase. During the tensile
process, the FCC phase yielded first. The hard and brittle M7C3 carbides
hindered the dislocation movement and expansion in the FCC phase,
resulting in stress concentration at the phase interface. Thus, the
nucleation of cracks occurred at the M7C3 carbides and FCC phase
boundaries. These cracks propagated along the phase boundaries. In the
case of the C0.4 HEA with a low volume fraction of the eutectic carbides
(FCC + M7C3), the formation of cracks could be clearly observed in the
ID region (Fig. S3(e2)). With a further increase in the carbon content,
clear step-like fracture features were observed (as in the case of the C0.7
alloy; Fig. 10(b2)). These features were produced by the shedding of the
lath M7C3 carbides along the phase boundaries. In addition, the FCC
phases necked into bright sharp lines [bright lines in Fig. S3(e2)-S3 (h2)]
without any dimples. This is consistent with the results reported by Gao
[42]. The FCC phases exhibited excellent plastic deformation before
fracture. Therefore, an increase in the carbon content resulted in the
formation of M7C3 carbides, which changed the fracture mode of the
HEAs from ductile to brittle-like.
5. Conclusions
In this study, we fabricated a series of CoCrFeNi-based HEAs with 0,
0.1, 0.2, 0.3, 0.4, 0.5, 0.7 and 0.9 wt% carbon through vacuum arc
melting. The microstructural evolution, tensile properties, local nano­
mechanical properties, strengthening mechanism, and fracture mecha­
nism of these alloys were investigated systematically. At the carbon
contents higher than 0.3 wt%, the microstructure of the HEAs changed
8
Materials Science & Engineering A 796 (2020) 140065
from the single FCC phase to a dendritic structure with the formation of
eutectic carbides (FCC + M7C3) in the ID regions. The YS of the CoCr­
FeNi HEA increased with the addition of carbon because of solid solution
and secondary phase strengthening. The M7C3 carbides, with a high
nanohardness of approximately 17.7 GPa, showed good wear resistance.
The stress concentration at the phase interface caused brittle-like frac­
ture in the HEAs containing the eutectic carbides. The results suggested
that the macro and nanomechanical properties of the CoCrFeNi HEA
could be efficiently tailored by adding a small amount of carbon. Thus,
the addition of carbon to CoCrFeNi and the optimization of the defor­
mation and heat treatment processes can lead to the formation of
eutectic carbides and high-strength HEAs with different carbide types,
sizes, shapes, and distribution.
CRediT authorship contribution statement
L.J. Zhang: Investigation, Writing - original draft, Conceptualiza­
tion, Methodology, Formal analysis. P.F. Yu: Resources, Data curation,
Methodology. J.T. Fan: Data curation, Formal analysis. M.D. Zhang:
Data curation. C.Z. Zhang: Conceptualization, Project administration.
H.Z. Cui: Funding acquisition, Writing - review & editing. G. Li:
Conceptualization, Supervision.
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.
Acknowledgments
The authors gratefully acknowledge support from the Taishan
Scholarship of Climbing Plan (No. tspd20161006), and the National
Natural Science Foundation of China (No. 51772176, No.51971121, No.
51801114). L.J. Zhang would like to acknowledge the open subject of
State Key Laboratory of Metastable Materials Science and Technology
(No. 202012).
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.msea.2020.140065.
The authors declare that they have no known competing financia­
linterestsor personal relationships that could have appeared to influence
the work reported in this paper.
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