Journal of Alloys and Compounds 769 (2018) 27e36

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Journal of Alloys and Compounds

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

Effect of solid carburization on the surface microstructure and

mechanical properties of the equiatomic CoCrFeNi high-entropy alloy
L.J. Zhang a, Z.K. Jiang b, M.D. Zhang a, J.T. Fan a, D.J. Liu a, P.F. Yu a, G. Li a, *, R.P. Liu a
a
State Key Laboratory of Metastable Materials Science and Technology, Yanshan University, Qinhuangdao 066004, China
b
China Railway Shanhaiguan Bridge Group Co., Ltd. Shanhaiguan 066205, China

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

Article history: The surface modification of the equiatomic CoCrFeNi high-entropy alloy has been studied via solid
Received 14 May 2018 carburization at 920
C for 10 h. Microstructure, hardness and wear resistance were investigated by X-ray
Received in revised form diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM),
25 July 2018
microhardness and nanoindentation tester. Microstructure and phase analysis indicated that two types
Accepted 29 July 2018
Available online 31 July 2018
of nano-size carbide precipitates (M7C3 and M23C6) formed in the surface. The orientation relationship
between the M7C3 precipitate and FCC matrix were (1ð Þ100)C1//(11ð Þ1)M and [0001]C1//[1ð Þ12]M. The
M23C6 precipitate possessed a cube-cube orientation relationship with the FCC matrix. Vickers hardness
Keywords:
High-entropy alloy
and nanoindentation testing results indicated that the carburized surface performed significant
Solid carburization improvement of about 100% in hardness compared with the matrix. The strengthening mechanisms
Microstructure including solid-solution strengthening and precipitate strengthening were studied. Moreover, nano-
Hardness scratch experiments have been conducted on the cross section of the carburized sample under a con-
Wear resistance stant load mode to investigate the friction and wear behavior. The surface profile and depth of scratched
tracks were examined using scanning probe microscopy (SPM) technology. The wear and deformation
mechanisms at different distances from the surface have been discussed. The calculated values of the
wear volume, wear rate, and wear resistance coefficient reveal that the carbide precipitates can improve
the wear resistance of the carburized surface.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction Despite extensive research on the surface modification of the HEAs,

Based on a new alloy design concept with multi-principal ele-
ments, the high entropy alloys (HEAs) were successfully designed
and synthesized in recent years. Researchers have defined the HEAs
as the multi-component equimolar or near-equimolar alloys with
the simple solid solution phase structures [1e3]. The HEAs, as a
promising structural material, have gained much attention for their
remarkable performance, such as excellent mechanical properties
[4], superb specific strength [2], good oxidation and corrosion
resistance [5,6], outstanding wear resistance [7], and radiation
tolerance [8]. Recently, various surface modification methods have
been proposed to improve the surface mechanical properties and
corrosion resistance, such as direct current magnetron sputtering
[9], atmospheric plasma spraying [10], laser cladding [11] and
remelting [12], plasma cladding [13], electrospark process [14], etc.
* Corresponding author.
E-mail address: gongli@ysu.edu.cn (G. Li).
the industrial application of these methods is still in an early stage
due to their high costs and the technical limitations for preparing
the large size samples. However, solid carburization, as an effective
surface modification approach for the large-scale industrial appli-
cation, has not been given much attention. Solid carburization is a
diffusion-based process by the diffusion of carbon atoms into the
metal matrix to form a carbide layer [15]. What's more, as four or
more chemical elements in the multi-component alloys taking part
into the diffusion process, the formation of the carbide phases will
become more complex. Therefore, it is very meaningful and
necessary to explore the carburization process for the HEAs.
In this research, we select the typical equiatomic CoCrFeNi HEA
to investigate the microstructure and mechanical properties of the
carbide layer after solid carburization. X-ray diffraction (XRD),
scanning electron microscope (SEM), and transmission electron
microscope (TEM) were used to estimate the microstructure and
phase structure of the carbide coating. For the quantitative analysis
of the mechanical responses, we employ Vickers hardness, nano-
indentation, and nano-scratch technique to evaluate the variation

https://doi.org/10.1016/j.jallcom.2018.07.329
0925-8388/© 2018 Elsevier Ltd. All rights reserved.
28 L.J. Zhang et al. / Journal of Alloys and Compounds 769 (2018) 27e36
of the hardness and wear properties. The mechanisms of the
reinforcement phenomena by carbide precipitates and enhance-
ment of wear resistance of the surface after solid carburization
were discussed. The results of this study can provide a guide for the
surface modification of the multi-component alloys.
2. Experimental procedure
2.1. Sample preparation
The equiatomic CoCrFeNi HEA was prepared by arc-melting a
mixture of pure metals (purity > 99.9 wt%) in a vacuum arc melting
furnace with a water-cooled Cu crucible under a high-purity argon
atmosphere. The ingot was remelted six times to ensure a good
chemical homogeneity. The rectangular sample
(40 mm  40 mm  8 mm) cut from the as-cast button was subse-
quently cold rolled to ~ 60% reduction in thickness, using a rolling
machine with the roll diameter of 140 mm. The cold-rolled sample
was homogenized in the vacuum tube furnace at 1200
C for 4 h
and followed by water quenching. Prior to the solid carburization
process, the surface oxide layers were removed by fine grinding
with the emery papers to grade 4000. Following this, alcohol and
acetone were used to remove the grease and other contaminants by
ultrasonic cleaning. Then, the sample was wrapped in the graphite
powder and placed in the muffle furnace, followed by solid
carburization at a temperature of 920
C for 10 h. In order to better
characterize the structure and properties of the carburized layer,
the coating cross section was mounted using epoxy and ground up
to 4000 grit size emery paper followed by mechanical polishing
with diamond paste up to 0.5 mm.
2.2. Macro- and nano-hardness tests
The Vickers hardness of the sample was measured using a HVS-
1000 hardness tester under a load of 25 g for 10 s. The macro-
hardness measurement was performed from the surface to inte-
rior to check variation of hardness in the carburized layer. The
nanoindentation experiments were conducted using a Hysitron TI-
900 Triboindenter with a diamond Berkovich indenter in load-
control mode at room temperature. The sample was loaded to a
maximum load of 8 mN under the constant loading rate of
1 mN s1, followed by unloading to zero at the same loading rate.
The indentation spacing was 10 mm. The reduced elastic modulus
Fig. 1. Determination of background noise. (a) Lateral force fluctuation during the air-scratch process. (b) The enlarged curve corresponding to the region covered by dashed line in
(a).
and nano-hardness were determined by Oliver-Pharr method [16].
At least five measurements were carried out at each location to
ensure the accuracy of the result.
2.3. Nano-scratch tests
Nano-scratch experiments were conducted using also a Hysi-
tron TI-900 Triboindenter equipped with a 2D transducer. A cube
corner diamond tip was used for scratching. Nano-scratch tests
were conducted in constant load mode at room temperature.
Before the experiments, air-scratch was carried out to determine
the background noise from the machine vibration. The lateral force
as a function of the lateral displacement was shown in Fig. 1. The
enlarged curve [Fig. 1 (b)] shows that the amplitudes of the lateral
force fluctuation are approximately 6.34 mN, which is related with
the background noise [17]. Therefore, in the following analysis, the
lateral force fluctuations within 6.34 mN are excluded to eliminate
the effect of the background noise.
The nano-scratch measurements were performed on the cross
section of the carburized sample at different distances (20 mm,
60 mm, 120 mm, 200 mm, and 500 mm) from the surface. To clearly
describe the nano-scratch process, we representatively plot the
lateral displacement [see Fig. 2(a)] and the normal force [see
Fig. 2(b)] as a function of time. According to the curves, five stages
are distinguished. The first stage is from 0 to 5 s, in which the
indenter moves from 0 to 5 mm on the surface of the sample, and
the normal force is zero. In the second stage (from 5 to 8 s), the
indenter penetrates into the sample at the normal force increasing
from 0 to 3 mN with no lateral displacement. From 8 to 38 s, the
third stage, the indenter scratch on the sample surface at a speed of
0.333 mm/s over a scratch distance of 10 mm under a constant
normal force of 3 mN. In this stage, the nano-scratch process has
really started. The fourth stage is from 38 to 41 s. The normal force
decreases from 3 to 0 mN at the lateral displacement of 5 mm. Then,
the indenter moves from 5 to 0 mm (the fifth stage) and the
scratching process is finished. The surface profile and depth of
scratched tracks of the scratched specimens are examined using
scanning probe microscopy (SPM) integrated in the Hysitron
Triboindenter.
2.4. Structure characterization
The microstructure after the solid carburization was
 L.J. Zhang et al. / Journal of Alloys and Compounds 769 (2018) 27e36
Fig. 2. Representative profile of nano-scratch process. The lateral displacement as a
function of time (a) under the normal force at different stages shown in (b).
characterized by XRD, SEM, and TEM. XRD measurements were
performed to determine the phase composition of the carburized
layer using a D/MAX-2500/PC diffractometer with Cu Ka radiation
(l ¼ 1.54 Å). The XRD analyses were carried out along the cross-
sectional direction. The samples were carefully prepared by me-
chanical polishing from the surface to reach the desired depths. The
Fig. 3. (a) Cross-section SEM image of the carburized sample. The local magnification images were shown in A, B, C, and D, respectively. (b) XRD patterns of the carburized CoCrFeNi
HEA. (c) EDS line-scanning profiles along the orange arrow in (a). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this
article.)
29
cross section of the sample was etched for SEM investigation, using
a Hitachi S-3400 microscope equipped with an energy-dispersive
X-ray spectrometer (EDS). The EDS point analysis and line anal-
ysis were performed to check the chemical compositions of
different phases. The volume fraction and the precipitate size of the
carbide precipitates were evaluated using the Image-Pro Plus
software. Samples for TEM investigation were also prepared by
mechanical grinding to a thickness of less than 20 mm and further
thinning was done using a Precision Ion Polisher (Gatan 695.B).
TEM measurements were performed using a JEM-2010 apparatus at
an accelerating voltage of 200 kV. The scratching morphology at
different area was observed by SEM.
3. Results and discussion
3.1. Microstructure
Fig. 3(a) shows the cross-section SEM image of the carburized
CoCrFeNi HEA. It's obvious that a large amount of precipitates form
along the surface after solid carburization. According to the
morphology and distribution of these precipitates, the carburizing
area can be divided into three regions, marked as I-III. There is a
clear border between the region I and region II. In region I, the short
rod-shaped precipitates with a thickness of about 1 mm are shown
in the higher-magnification image. The thickness of the region I was
about 45 mm. In region II, a large number of small precipitates
dispersedly distributed in the matrix. The size of the precipitates
increased with increasing the distance from the surface, while the
distribution density (or volume fraction) decreased (see Fig. 4). The
thickness of this region was about 140 mm. The region III was
treated as the metallic matrix containing no precipitates. The SEM
results indicated that the carburized layer with the thickness of
~185 mm formed on the surface of the carburized CoCrFeNi HEA.
The XRD patterns at different regions are shown in Fig. 3(b). In
addition to the face-centered cubic (FCC) peaks of the matrix alloy,
the peaks of M7C3 phase and M23C6 phase (where M represents
30 L.J. Zhang et al. / Journal of Alloys and Compounds 769 (2018) 27e36

Table 2
The mixing enthalpy, DHmix (kJ/mol), of the atomic pairs among different elements
(Co, Cr, Fe, Ni, and C) calculated by Miedema's approach [18].

Elements Atomic radius (Å) Cr Fe Ni C

Co 1.25 4 1 0 42
Cr 1.28 e 1 7 61
Fe 1.26 e e 2 50
Ni 1.24 e e e 39
C 0.77 e e e e

Fig. 4. Variations of the volume fraction (f) and the particle diameter (d) with different
distances from the surface.

transition metal atoms) appear in the region I and II, respectively.

The chemical compositions of the different phases in the region I
and II were identified by EDS point analysis and the results were
summarized in Table 1. The precipitate phase in the region I con-
tains 67.2 at.% of Co, Cr, Fe, Ni in total, and 32.8 at.% of C, which
agrees with the 7:3 stoichiometry of the M7C3 type structure. The
M23C6 precipitate (region II) can also be identified as (Co, Cr, Fe,
Ni)23C6 phase. One can note that the concentration of Cr in the M7C3
and M23C6 phases is higher than other transition metal elements.
The results of the EDS line-scanning [Fig. 3(c)] conducted along the
orange arrow reveal that the region I contains a higher content of Cr
and C compared to region II and III. These behaviors may be
explained from two aspects. Firstly, the negative mixing enthalpy of
Cr-C (- 61 kJ/mol) suggest that Cr has a stronger atomic affinity with
the C atom than other metal elements (Co-C: 42 kJ/mol; Fe-C: 50 kJ/
Fig. 5. (a) The bright-field TEM micrograph in the region I and the SAED patterns (b)
mol; Ni-C: 39 kJ/mol) [18], as shown in Table 2. Secondly, in the taken at the area covering the M7C3 phase and the metallic matrix. (c) The bright-field
CoCrFeNi HEA, the migration activation energy of Cr (0.84 eV) is the TEM micrograph in the region II and the SAED patterns (d) taken at the area covering
lowest followed by Co (1.07 eV), Fe (1.32 eV) then Ni (1.36 eV). The the M23C6 phase and the metallic matrix.
negative vacancy formation energy for Cr (- 0.55 eV) and the pos-
itive values for Fe (1.95 eV), Ni (1.78 eV) and Co (1.70 eV) will lead to
the Cr precipitate out of the CrCoFeNi alloy [19]. the analyses of the XRD and the SAED patterns Fig. 5(d), it is
Fig. 5 shows the TEM micrographs in the region I and II to give a confirmed that the M23C6 precipitate has a complex FCC structure
further investigation of the carbide precipitates structure. Fig. 5(a) with the space group of Fm3m and the lattice parameter of M23C6
is the bright-field TEM micrograph in the region I. Fig. 5(b) is the precipitate (a ¼ 10.942 ± 0.005 Å) is approximately three times
selected area electron diffraction (SAED) patterns obtained from larger than that of the matrix (a ¼ 3.672 ± 0.006 Å). The orientation
the area containing M7C3 phase and the FCC matrix. Combining the relationship between the two phases can be determined to be
XRD results, the M7C3 phase has a complex hexagonal structure (110)C2//(110)M and [1ð Þ11]C2//[1ð Þ11]M (where C2 represents
(space group P31c) with the lattice parameters M23C6 carbide), which is consist with the well known cube-cube
a ¼ b ¼ 13.997 ± 0.005 Å and c ¼ 4.536 ± 0.006 Å, which shows orientation relationship [21,22].
good agreement with the (Fe, Cr)7C3 carbide [20]. The orientation
relationship between the M7C3 phase and the FCC matrix is 3.2. Mechanical properties
(1ð Þ100)C1//(11ð Þ1)M and [0001]C1//[1ð Þ12]M, where C1 repre-
sents M7C3 carbide and M represents the FCC matrix. The nano-size From the nanoindentation load-depth curves [Fig. 6(a)], it is
M23C6 precipitates at region II can be observed in Fig. 5(c). Based on seen that the maximum penetration depth increases with

Table 1
Chemical compositions of different phases determined by EDS (at.%) in the CoCrFeNi HEA after carburizing at 920
C for 10 h.

Regions Alloy phase Chemical compositions (at.%)

Co Cr Fe Ni C

Ⅰ M7C3 7.8 ± 0.3 35.5 ± 0.2 15.8 ± 1.1 8.1 ± 0.9 32.8 ± 1.3
FCC 20.9 ± 1.5 28.7 ± 1.5 21.6 ± 0.7 20.8 ± 1.3 5.5 ± 2.5
Ⅱ M23C6 12.1 ± 0.4 31.7 ± 0.6 22.8 ± 0.9 13.4 ± 0.7 19.8 ± 1.2
FCC 23.9 ± 0.5 25.4 ± 0.7 27.9 ± 0.6 23.6 ± 0.8 2.5 ± 1.3
 L.J. Zhang et al. / Journal of Alloys and Compounds 769 (2018) 27e36
Fig. 6. (a) The nanoindentation load-depth curves at different distances from the surface of the carburized sample. (b) Distributions of the Vickers hardness (Hv), nano-hardness
(Hn), and reduced elastic modulus (Er) from the surface to the matrix. (c) The hardness contributions from different hardening mechanisms in the region I and II. (d) Variations of the
Hn/Er and H3n/E2r with different distances.
increasing the distance from the surface of the carburized sample.
Both the nano-hardness (Hn) and reduced elastic modulus (Er) can
be obtained according to the Oliver-Pharr method [16], as shown in
Fig. 6(b). From Fig. 6(b), the values of Hn decrease gradually from
5.2 GPa to a stable value of about 3.0 GPa at the depth of 400 mm,
while Er remains almost constant (~225 GPa). The same trend can
be observed for the variation of the Vickers hardness (Hv) from 400
HV to 180 HV [Fig. 6(b)]. Based on the results of Hn and Hv, we can
find that the maximum hardness obtained on the carburized sur-
face shows an improvement of about 100% compared with the in-
ternal hardness. The increasing of the hardness is closely related
not only to the carbon diffusion but also to the carbide precipitate
type, properties, size, and distribution.
Both the region I and region II are full of fine carbide precipitates
(M7C3 and M23C6), as shown in Fig. 3(a). These precipitates are
expected to produce hardening by Orowan-type dislocation by-
passing or dislocation shearing mechanisms. Generally, the dislo-
cation shearing mechanism occurs when the particle diameter does
not exceed a critical value (~20 nm) [23]. While for the current
study, the M7C3 and M23C6 carbide precipitates have the large
diameter (>100 nm) and high hardness [24], which can be treated
as the impenetrable particles. Therefore, the Orowan by-passing
mechanism is considered for the carburized layer. The increment
of the yield strength caused by the carbide precipitates can be
approximated by employing the following Ashby-Orowan equation
[25]:
31


2MGb d
sp ¼
 ln (1)
2b
1:18  4p pffiffiffiffiffiffiffi  d
1
NV d
where, M is the mean orientation factor, taken as 3.06 for the FCC
structure [26]; G is the shear modulus of the FCC matrix obtained
using the equation G ¼ E/2(1 þ n), E is the Young's modulus, the
relationship between the Young's modulus (E) and the reduced
1
elastic modulus (Er) is Er ¼ ½ð1  v2i Þ=Ei þ ð1  v2 Þ=E , where vi (¼
0.07) and Ei (¼ 1141 GPa) are the Poisson's ratio and Young's
modulus of the indenter, v (¼ 0.3) is the Poisson's ratio of the FCC
matrix [16], the shear modulus (Gz84 GPa) of the current FCC
matrix is estimated based on the values of Er in Fig. 6(b); the Bur-
pffiffiffi
gers vector of the FCC matrix is b ¼ 2a=2z0:2595nm; NV is the
count of dispersoid per unit volume; d is the particle diameter, as
shown in Fig. 4.
In the region III, the hardness gradually decreases to a stable
value as the distance increasing, as shown in Fig. 6(b). The solid
solution of carbon atoms in the FCC matrix is the main reason. On
the one hand, the interstitial strengthening from the solute carbon
leads to the increase of the lattice friction stress, sfr , which can
increase the yield strength [27]. The effect of the solid solution
hardening due to the carbon interstitial atom can be observed in
other HEAs, such as, Fe40.4Ni11.3Mn34.8Al7.5Cr6 [27] and CoCrFeNiMn
[28,29]. On the other hand, the stacking fault energy can be
decreased by the addition of C [29]. Twining will be more easily
activated with the lower stacking fault energy. During plastic
32 L.J. Zhang et al. / Journal of Alloys and Compounds 769 (2018) 27e36
deformation, the interactions between the dislocations and twins
will cause a large amount of accumulated dislocations, which are
potentially effective obstacles to dislocation motion and can pro-
vide additional strengthening. The increment of the yield strength
caused by the solid solution of carbon atoms can be expressed by so.
Tabor relation was used to estimate the hardness from the yield
strength [30]:
Hn z3s
The total hardness of the region III is estimated as: Hn ¼ Hm þ
Ho , where Hm (~3 GPa) is the hardness of CoCrFeNi matrix, which is
the intrinsic strength; Ho is the contribution from the solid solution
of carbon atoms, the value of Ho will gradually decrease from
0.8 GPa to zero with decreasing the C content. In the region I and
region II, the hardness is a simple summation of the three indi-
vidual contributions and can be expressed as: Hn ¼ Hm þ Hp þ Ho ,
where Hp is the strengthening contribution from carbide pre-
cipitates, the calculated value of Hp from the M7C3 precipitates in
region I is about 1.1 GPa (or ~ 110 HV), the values of Hp in region II
decrease from ~1 GPa to 97 MPa with increasing the distance from
the surface; the value of Ho is difficult to calculate quantitatively in
the region I and II, we use 0.8 GPa (the maximum value in region III)
to assess the contribution from the solid solution of carbon atoms.
Based on the above discussion, we summarize a column chart to
show the hardening contributions from different mechanisms in
the region I and II, as shown in Fig. 6(c). The estimated hardness
agreed well with the experimental data. In short, the enhancement
of the hardness can be attributed to the generation of high volume
fraction of M7C3 and M23C6 carbide precipitates (precipitation
hardening) and the increase of carbon content in the FCC matrix
(solid solution hardening and other).
3.3. Friction and wear behaviors
The values of Hn and Er can also be used to qualitatively evalu-
ated the wear resistance of the carburized sample. The ratio Hn/Er
(related to the ability to resist elastic strain to failure) is a suitable
parameter to describe the wear resistance [31,32]. Another
parameter, H3n/E2r , treated as yield pressure, represents the resis-
tance to plastic deformation, which can also be used to assess the
wear resistance [31,32]. In the current study, the nanohardness and
the reduced elastic modulus at the maximum load of 8 mN [see
Fig. 6(b)] are used to determine the Hn/Er and H3n/E2r ratios. The
values of Hn/Er and H3n/E2r at different distances from surface are
shown in Fig. 6(d). It is obvious that the surface has the higher
values (~0.023 and ~0.0027 GPa) than the matrix (~0.014 and
~0.0005 GPa), which means the surface has the better wear resis-
tance. The results indicate that the wear resistance can be enhanced
via solid carburization process for the CoCrFeNi HEA.
In order to quantitatively analyze the friction and wear behavior
of the carburized layer, nano-scratch experiments have been con-
ducted on the polished cross section of the carburizing sample at
different distances (20 mm, 60 mm, 120 mm, 200 mm, and 500 mm)
from the surface. SEM images of the nano-scratched surface under
the constant load mode are shown in Fig. 7. The scratched grooves
at different distances are very obvious. During the entire scratched
process, the indenter can shear the hard carbide precipitates (M7C3
or M23C6) and the width and depth of scratched grooves show a
slight change at the distances of 20 mm, 60 mm, and 120 mm, as
shown in Fig. 7(a)-(c). However, when the indenter scratched on
the single FCC phase at 200 mm and 500 mm [see Fig. 7(d) and (e)],
the width and depth remained essentially unchanged. The
morphology of the scratch traces can be detected by SPM tech-
nology. SPM images of the scratches at different distances were
(2)
Fig. 7. SEM images of scratched morphologies on the cross section of the carburizing
sample at different distances of 20 mm (a), 60 mm (b), 120 mm (c), 200 mm (d), and
500 mm (e), respectively.
shown in Fig. 8(a)-(e). The bright area on the sides of the scratch
was the pile-up of the displaced material by the indenter. One can
note that the pile-ups at the distances of 20 mm, 60 mm, and 120 mm
are obvious and inhomogeneous, as shown in Fig. 8(a)-(c). The true
scratch depth (htrue) of a scratch can be measured from the SPM
image. Fig. 8(f) shows the variation of the true depth as a function of
scratch distance along with the dashed line in the SPM images. It
can be seen that the values of htrue show a remarkable fluctuation
with the scratch distance for the scratches at 20 mm, 60 mm, and
120 mm, which is the so-called stick-slip behavior [33]. The
maximum undulation amplitudes of htrue at the distances of 20 mm,
60 mm, 120 mm, 200 mm, and 500 mm are 23.2 nm, 21.4 nm, 30.1 nm,
5.9 nm, and 7.6 nm, respectively.
The topography of scratch track after being tested at the dis-
tance of 60 mm from the surface is shown in Fig. 9(a). The dark area
is the scratched groove and the bright area is the pile-ups caused by
the scratch process. Patterns of the groove and pile-ups can be
better observed in the 3D view, as shown in Fig. 9(b). The units for
the x-axis, y-axis, and z-axis are in mm, mm, and nm, respectively.
The cross-section profiles of the grooves are presented in Fig. 9(c),
in which data measured from other distances are also included for
comparison. With increasing distance from the carburized surface,
the depth of the groove becomes shallow, indicating that the
carburized layer has the better wear resistance than the FCC matrix.
The coefficient of friction (COF) is another important aspect of
the wear behavior. Fig. 10(a) shows the variation of the COF values
with time (or lateral displacement) at different distances under a
constant normal force of 3 mN. It is observed that the COF values
display great fluctuations for the scratches at 20 mm, 60 mm, and
120 mm. The values of COF are calculated by the ratio of the lateral
force and normal force during scratching, which suggests that the
fluctuation of the lateral force corresponds to the change in COF. In
order to demonstrate the fluctuation mechanism of the lateral
force, a further exploration of the hidden information in the curves
of the lateral force as a function of time [Fig. 10(b)] is required. From
Fig. 10(b), it is observed that the average undulation amplitudes of
lateral force at the distances of 20 mm, 60 mm, 120 mm, 200 mm, and
 L.J. Zhang et al. / Journal of Alloys and Compounds 769 (2018) 27e36 33

Fig. 8. Morphology of the scratch traces observed by SPM at the different distances of 20 mm (a), 60 mm (b), 120 mm (c), 200 mm (d), and 500 mm (e) from the surface. (f) shows the
variation of the true depth as a function of scratch distance during nano-scratch along with the dashed line in the SPM images.

500 mm are 154.1 mN, 67.9 mN, 145.3 mN, 31.7 mN, and 26.2 mN,
respectively. The carburized layer had the higher undulation am-
plitudes of lateral force than the single phase FCC region, which
indicated that the carbide precipitates had a great influence on the
scratch process. The enlarged curve of the lateral force versus time
at 60 mm is shown in the inset of Fig. 10(b). It can be seen that the
curve is composed of numerous serration events. Each serration
event includes a force-increasing stage and a force-decreasing
stage. During the force-increasing stage, the hard carbide pre-
cipitates are treated as the obstacle against dislocation movement,
which can lead to the structural strengthening and the gradual
accumulation of the plastic shear strain. Once the force approaches
the maximum value, the micro-crack or fracture of the piled-up
material will be activated, which can result in a sudden decrease
in the lateral force. The lateral force-increasing time (tl) and the
force-decreasing time (tR) are marked in the inset of Fig. 10(b). In
fact, similar serration characteristics have been observed in many
structural and functional materials in the stress-strain curves [17].
The plastic deformation mechanisms and the structural evolution
during deformation can be detected through these serration
behaviors.
Generally, the wear volume was often used to quantitatively
evaluate the wear resistance [33e35]. The volume of material
removed due to the scratching depends on the true depth of the
34 L.J. Zhang et al. / Journal of Alloys and Compounds 769 (2018) 27e36

Fig. 9. (a) A representative SPM image showing the topography of scratch track at the distance of 60 mm from the surface. The corresponding 3D view is shown in (b). (c) The cross-
section profiles as indicated with the dashed line in (a) as well as those of other scratches at different distances from the surface.

following equation [35]:

Zl=2
V¼ Ch2true ðxÞdx (3)
l=2

where, l is the lateral displacement and h2true ðxÞ is the true depth at
scratch distance of x, C is the area factor corresponding to the
indenter parameters. However, in the present work, it is difficult to
obtain the function of h2true ðxÞ because of the great fluctuations of
the true depth, especially for the scratches at the distances of
20 mm, 60 mm, and 120 mm. Here, we can obtain the wear volume by
directly measuring from the average true depth (htrue ) and cross-
sectional profile. The calculation of V is simply based on V ¼ S 
L, where L (¼ 10 mm) is the total scratch length, S is the cross-
section area of the scratched groove (see the insert of Fig. 11). The
values of V at different distances have been summarized in Table 3
and Fig. 11.
The wear rate (W), defined as the volume removed per unit
scratch distance, is written as:


V P
W¼ ¼K (4)
L Hn

Fig. 10. (a) The variation of the COF values with time (or lateral displacement) at
different distances from the carburized layer surface. (b) Lateral force as a function of
time at different distances. Inset shows the enlarged lateral force vs time curve at the
distance of 60 mm.

scratch and the parameters of the indenter, which can be measured

Fig. 11. Wear volume (V) and wear resistance coefficient (R) at different distances from
after the scratch test. The wear volume (V) can be calculated by the the surface. The insert shows depth variation along the cross section of a scratch.
 L.J. Zhang et al. / Journal of Alloys and Compounds 769 (2018) 27e36
Table 3
Values of the average true depth (htrue), wear volume (V), wear rate (W), and wear
resistance coefficient (R) calculated for scratches at different distances from the
surface.
Location (mm) htrue (nm) V (mm3) W (103 nm2) R (1011 Pa)
20 54.4 0.223 22.3 1.35
60 67.2 0.259 25.9 1.16
120 68.0 0.263 26.3 1.14
200 86.3 0.339 33.9 0.85
500 94.6 0.366 36.6 0.82
where, K is the wear coefficient, P is the normal force, and Hn is the
nano-hardness. The calculated values of W are tabulated in Table 3.
The wear resistance coefficient, R ¼ Hn =K [36,37], can be obtained
through the Function (4), as shown in Table 3 and Fig. 11. Depending
on the results in Table 3 and Fig. 11, we can note that the carburized
layer, with the lower wear volume (0.223 mm3), wear rate
(22.3  103 nm2), and a higher wear resistance coefficient
(1.35  1011 Pa), has a better wear resistance than the FCC matrix.
The hard carbide precipitates (M7C3 or M23C6) can effectively
hinder the dislocation movement, which can not only improve the
strength but also increase the wear resistance. Moreover, the wear
resistance at the distance of 200 mm shows a slightly higher than
that at 500 mm, which indicates that solid solution of carbon atoms
can also enhance the wear resistance.
4. Conclusions
The surface modification of the equiatomic CoCrFeNi HEA via
solid carburization was investigated. A hard carburized layer with
the thickness of ~185 mm was fabricated. The short rod-shaped
M7C3 precipitates formed in the region I. The orientation relation-
ship between the M7C3 phase and the FCC matrix is (1ð Þ100)C1//
(11ð Þ1)M and [0001]C1//[1ð Þ12]M. The nano-size M23C6 pre-
cipitates in the region II had a cube-cube orientation relationship
with the FCC matrix. The surface hardness of the carburized sample
was improved significantly by about 2 GPa (or 220 HV) compared
with the matrix. The wear resistance of the carburized layer was
evaluated through nano-scratch tests. The results indicate that the
carburized layer, with the lower wear volume (0.223 mm3), wear
rate (22.3  103 nm2), and a higher wear resistance coefficient
(1.35  1011 Pa), has a better wear resistance than the FCC matrix.
Acknowledgments
Gong Li would like to acknowledge the Basic Research Project in
the Hebei Province (Grant No. A2016203382), and the support from
the National Science Foundation of China (Grant No. 11674274).
Peng Fei Yu would like to acknowledge the National Natural Science
Funds of China (Grant No. 51601166), and the Research Program of
the College Science & Technology of the Hebei Province (Grant No.
QN2016167).
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