Scripta Materialia 161 (2019) 28–31

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Scripta Materialia

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Regular article

High temperature wear in CoCrFeNiCux high entropy alloys: The role

of Cu
A. Verma a,b, P. Tarate a, A.C. Abhyankar a, M.R. Mohape c, D.S. Gowtam c,
V.P. Deshmukh c, T. Shanmugasundaram a,⁎
a
Department of Metallurgical and Materials Engg., Defence Institute of Advanced Technology, Pune, India
b
L&T Defence, Pune, India
c
Naval Materials Research Laboratory, Ambernath, India

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

Article history: A series of CoCrFeNiCux (x = 0, 0.2, 0.4, 0.6, 0.8, 1.0) high entropy alloys (HEA) were prepared using arc melting
Received 17 September 2018 technique and the effect of Cu on microstructure evolution and wear was studied both at room and high temper-
Accepted 8 October 2018 ature. Microstructure reveals two phases, namely, CoCrFeNi and pure Cu. Wear rate at room temperature (RT) as
Available online 15 October 2018
well as at elevated temperatures (ET) decreases with increase in Cu content. However, wear resistance is found to
be more at ET than RT. This is attributed to the self-lubricating behaviour of Cu at elevated temperature.
Keywords:
High entropy alloys
© 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
CoCrCuFeNi
High temperature wear
Phase formation
Self-lubricating behaviour

High entropy alloys [HEAs] were reported recently in the early 21st
century [1]. Since then HEAs have received considerable attention due
to their extraordinary properties caused by following four core effects:
high entropy effect, lattice distortion effect, sluggish diffusion effect
and cocktail effect [1–4]. Among the HEA systems, CoCrCuFeNi is a
well-known system and extensive work has been done to understand
its microstructure and mechanical properties [5–10]. S. Thangaraju
et al. observed a single phase FCC structure in a mechanically alloyed
CoCrCuFeNi alloy [8]; whereas, in other studies on the same system,
two FCC phases were reported [6,10]. The latter was processed by arc
melting. A small amount of other alloying elements such as Ti, Al, Mn,
Mo and Nb are usually added to improve strength, hardness, high tem-
perature wear, fatigue resistance, corrosion resistance etc. [11–14]. An-
nealing of CoCrCuFeNi based alloys results in segregation and
accumulation of Cu rich phase which leads to a decrease in hardness [6].
Ti, Zr and Al are specially added to improve the wear resistance of
the CoCrCuFeNi HEA [15–17]. Recently, Y. Cai et al. found that addition
of Cu also improves the hardness, wear and oxidation resistance of the
alloy [7]. In contrast, Shang et al. reported that adding Cu in CoCrFeNi
system decreases hardness and wear resistance in CoCrCuFeNi coated
Q235 alloy [18]. However, formation of oxides such as Al-oxide, Cu-
oxide and Fe-oxide reduces the coefficient of friction and thus enhances
tribological properties at elevated temperature [19]. In contrast, wear
property of the HEA alloys is improved by adding a self-lubricating
⁎ Corresponding author.
E-mail address: thangaraju@diat.ac.in (T. Shanmugasundaram).
elements which reduces the coefficient of friction and wear rate [20].
Usually, to enhance the wear resistance at elevated temperature, solid
lubricants such as Ag-BaF2/CaF2, graphite and MoS2 coated with Ni
were added in CoCrFeNi alloy which formed a glaze layer predominately
made up of oxides of these metal [20,21]. However, contradicting re-
sults are found in the above literature, in few studies, Cu was shown
to be beneficial in improving wear and other properties, but in some
studies it was found to be not beneficial [7,18,19]. Similarly, in
CoCrCuFeNi system, a single phase structure was reported in one
study [8] and two phases were found in other studies [6,10]. Even
now, the role of Cu in HEA systems is ambiguous. Nevertheless, Cu is
added by default as one of the major principle alloying element in
many systems, Al2CoCrCuFeNiTix, GdxCoCrCuFeNi, Al1.25CoCrCuFeNi,
TiCuFeCoNi, AlCuCrFeMnW, CuZrAlTiNi, TiZrHfCuNi [16,22–27]. There-
fore, for the first time, in this study we shed light on this confusing
issue to reveal the effect of Cu on microstructure evolution and espe-
cially wear property at elevated temperature. For this, CoCrFeNi HEA
alloy is prepared with different Cu (X = 0, 0.2, 0.4, 0.6, 0.8, 1.0 in atomic
percent) concentrations through arc melting and detail microstructural
and wear at RT and ET are studied.
The melting was performed using arc-melting process in argon at-
mosphere using 99.5% purity of all the elements (Co, Cr, Fe, Ni and
Cu). Homogenous distribution was achieved by re-melting the ingots
5 times. As-cast samples crystal structure and phase formation were
studied using Bruker D8 Advanced diffractometer using Cu Kα (λ =
1.5418 Å) radiation scanning between 20° to 100° with the scanning
rate of 1°/s. Samples were wire cut and mechanically polished before

https://doi.org/10.1016/j.scriptamat.2018.10.007
1359-6462/© 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
 A. Verma et al. / Scripta Materialia 161 (2019) 28–31 29

Fig. 1. (a) XRD pattern of high entropy alloys of as cast sample; (b) Deconvoluted pattern of CoCrFeNiCu.

applying aqua regia (HCl:HNO3 = 3:1) for 15 s. Field Emission Scanning
Microscopy (FESEM, SIGMA, Carl Zeiss) equipped with energy disper-
sive X-ray spectrometry (EDS, Oxford instrument) was used for micro-
structure and compositional studies. Microhardness test was
performed with the load of 300 kgf and 15 s dwell time; and 10 reading
were taken for each specimen. Dry friction wear tests at room tempera-
ture (RT) and elevated temperature (600 °C) were performed using a
pin on disk tribometer (Ducom TR-20L) with pin size ø 8 mm. Wear
tests were performed in air at a load of 100 N for 1000 s at 95 rpm;
and for repeatability three samples were tested.
XRD patterns of as cast samples are shown in Fig. 1a. The crystal
structure of all the samples is FCC which is identified by the peak posi-
tion of the samples. As the experimental ratios of dhkl/d111 match with
the theoretical ratios of FCC pattern which clearly shows that the struc-
ture is FCC. Lattice parameter calculated from the major peak for
CoCrFeNiCuX (X = 0, 0.2, 0.4, 0.6, 0.8 & 1.0) alloys are 0.3578, 0.3578,
0.3582, 0.3583, 0.3577 and 0.3582 nm, respectively. These values
match with previously reported results [9,13,14]. A small peak is also
identified before (311) major peak for the alloy systems having higher
Cu content (x = 0.8 and 1.0). Lattice parameter of the phase (estimated
from the small peak) is found to be close to that of pure Cu (0.3606 nm).
The small Cu peak is difficult to resolve by XRD in the systems having
lower Cu content. Reports have claimed that equiatomic composition
consists of 2 FCC phases; one is Cu rich while other is Cu depleted
[5,8,9]. Nevertheless, in this study, XRD results reveal one major FCC
HEA phase (~0.3582 nm) which does not contain Cu and other minor
FCC phase (0.3606 nm) has only Cu and these are confirmed by EDS
analysis as well. As per thermodynamic calculations [8], Cu has a posi-
tive enthalpy of mixing with all other elements. Therefore, it will not
mix with other elements and may remain as Cu in the system.
Deconvolution of XRD data of CoCrFeNiCu sample was performed and
shown in Fig. 1b. After deconvolution, the weight fraction of the phase
was calculated. It is found from the calculation that 23.19 wt% of Cu is
being present in the equiatomic sample which is in agreement with
the amount initially taken for melting.
Fig. 2 shows microstructures of CoCrFeNiCuX (X = 0, 0.2, 0.4, 0.6, 0.8
& 1.0) alloys. The grain size of CoCrFeNi alloy (Fig. 2a) is found to be
larger than the systems which contain Cu. Further, it is observed that
with increase in Cu percentage there is an increases in second phase
(Cu precipitates) at grain boundary region. In the alloys having Cu con-
tent up to 2 at.%, there isn't significant grain size reduction observed and
all Cu is precipitated at grain boundaries. In the alloys having Cu content
above 2 at.%, grain size decreases with increasing Cu and the second
phase (Cu) is found to be segregated as dendrites and inter-dendrites.

Fig. 2. FESEM micrographs in BSE mode at 1000X for (a) CoCrFeNi (b) CoCrFeNiCu0.2 (c) CoCrFeNiCu0.4 (d) CoCrFeNiCu0.6 (e) CoCrFeNiCu0.8 (f) CoCrFeNiCu.
30 A. Verma et al. / Scripta Materialia 161 (2019) 28–31

Fig. 3. EDS Images CoCrFeNiCu (a) CoCrFeNiCu in SE mode (b) Cr mapping (c) Fe mapping (d) Co mapping (e) Ni mapping (f) Cu mapping.

The results of EDS elemental mapping of CoCrFeNiCu alloy also reflects
(shown in Fig. 3) that dendrites and inter-dendrites are rich in Cu
(marked in yellow colour). Table 1 depicts the chemical composition
of the matrix and the grain boundary region of CoCrFeNiCuX (X = 0,
0.2, 0.4, 0.6, 0.8 & 1.0) alloy systems. Light contrast area (Fig. 3a) is def-
icit in Cu and the black contrast region, either grain boundary area or
dendrites/inter-dendrites area, is found to be rich in Cu. The weight frac-
tion of the dark phases (Cu) from several FESEM images was calculated
using Image J software [28]. It is found that the calculated weight frac-
tion of Cu is matching with the original Cu content used for melting.
The XRD and EDS results clearly show that the observed second FCC
peak in CoCrFeNiCu systems is nothing but pure Cu phase (Fig. 1b)
and it is in agreement with the thermodynamic calculations [8]. How-
ever, the composition of the Cu (EDS - Table 1) at the grain boundaries
is not 100%. This could be mainly due to the chemical composition (XRD
signal) in EDS is determined from 1 μm surroundings, as a result there is
a possibility of having both grain boundary and matrix at the point of
measurement. Nevertheless the accurate composition of Cu can be de-
termined using electron probe microscopy analysis (EPMA) or trans-
mission electron microscopy (TEM).
Micro-hardness values of all alloy systems are shown in Fig. 4a.
Hardness varies from 136 HV to 169 HV and there is a slight increase
in hardness with increasing Cu content. When the hardness is converted
into strength using generalized relationship [29], it is found that nearly
100 MPa increase in strength in the system that contains Cu (Cu =
1.0 at.%) as compared to CoCrFeNi alloy. The reason for the increase in
strength is mainly attributed due to the reduction in grain size and seg-
regation of Cu. Since, Cu is a ductile element and has lower strength as
compared to other elements; the direct effect of Cu on strength is ex-
pected to be less. However, it is found that Cu imparts indirect grain
boundary strengthening by reducing the grain size of the alloy. Similar
finding was observed in CoCrCuFeMnNi alloy where (Cu, Mn)-rich
phase precipitated out in the matrix due to positive enthalpy and it
causes interlooping of dislocation thereby increasing dislocation density
and mechanical properties [10].
The microstructure of the CoCrFeNiCu alloy after wear test at 600 °C
is shown in Fig. 4a. Smooth surface and elongated wear marks are
clearly seen in the microstructure (Fig. 4a). EDS of smooth surface is
confirmed the presence of oxide layer which helps in improving wear
properties. Room and elevated temperature wear results of
CoCrFeNiCuX (X = 0, 0.2, 0.4, 0.6, 0.8 & 1.0) alloys are also shown in
(Fig. 4b). Wear rate at room temperatures decreases with increase in
Cu content which is in agreement with Archard's law which states
that wear resistance is proportional to material hardness [18]. Wear
rate at 600 °C, also decreases with increase in Cu content. Nevertheless,
in the alloy which does not contain Cu (CoCrFeNi), there is a significant
increase in wear rate (2.3 × 10−5 to 2.5 × 10−5 mm3/N.m.) is observed
at 600 °C as compared to RT. Whereas, in CoCrFeNiCu system, there is a

Table 1
Showing starting composition, grain boundary composition and matrix composition for all the CoCrFeNiCu alloys composition.

Alloy composition Ingot (at.%) Grain boundary (at.%) Matrix (at.%)

Co/Cr/Fe/Ni (each element) Cu Co Cr Fe Ni Cu Co Cr Fe Ni Cu

CoCrFeNi 25 – 25.04 24.95 25.57 24.44 – 24.76 25.25 25.51 24.48 –

CoCrFeNiCu0.2 23.81 4.76 22.04 26.51 22.89 23.30 5.35 22.92 24.95 23.48 23.48 5.17
CoCrFeNiCu0.4 22.73 9.09 5.30 5.59 5.74 10.85 72.52 23.36 23.60 23.56 22.17 7.31
CoCrFeNiCu0.6 21.74 13.04 6.17 6.86 6.47 9.52 70.98 23.57 23.17 23.28 21.57 8.41
CoCrFeNiCu0.8 20.83 16.67 8.47 7.62 7.03 8.46 68.42 23.61 23.25 23.17 20.64 9.33
CoCrFeNiCu 20.00 20.00 7.33 5.62 6.28 9.77 71.00 23.47 23.36 23.10 20.01 10.06
 A. Verma et al. / Scripta Materialia 161 (2019) 28–31 31

Fig. 4. (a) Microstructure of CoCrFeNiCu alloy after wear test at 600 °C (b) Microhardness and wear rate as a function of Cu content.

drastic decrease in wear rate (1.7 × 10−5 to 1.3 × 10−5 mm3/N.m.) is ob- Acknowledgement
served at 600 °C as compared to RT. For the first time, such a unique self-
lubricating property of Cu is observed and reported in HEAs. Usually, at We thank the Director, Naval material research laboratory,
elevated temperature material start losing its hardness and becomes Ambernath for providing us vacuum arc melting and XRD facility. This
softer and ductile which causes severe wear. These characteristics sig- work is supported by Science & Engineering Research Board, Depart-
nify plastic deformation and abrasive wear. Nevertheless, in the Cu con- ment of Science & Technology (DST), India (No: EEQ/2017/000724).
taining HEAs systems, a smooth and continuous oxide glaze layer is
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