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Nanoscience and Nanotechnology
All rights reserved Vol. 14, 8106–8109, 2014
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Effect of Molybdenum and Niobium on the Phase

Formation and Hardness of Nanocrystalline
CoCrFeNi High Entropy Alloys
S. Praveen, B. S. Murty∗ , and Ravi. S. Kottada
Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras,
Chennai 600036, India

In the present study, influence of molybdenum and niobium additions on phase formation during
mechanical alloying and spark plasma sintering of CoCrFeNi high entropy alloy was studied. Major
FCC and minor BCC phase were observed after mechanical alloying of CoCrFeNi. However, major
FCC and sigma phase were observed after spark plasma sintering. A maximum relative density of
95% was obtained with the hardness of 570 HV in CoCrFeNi HEA. The phase formation behavior
was not significantly affected by the addition of molybdenum or niobium. However, addition of Mo
to CoCrFeNi increased the hardness from 570 HV to 620 HV, and the hardness increased to
710 HV with combined addition of molybdenum and niobium. After sintering, major FCC phase with
crystallite size of 60–70
Delivered bynm was observed
Publishing in all theto:
Technology compositions. Further, the Library
Adelaide Theological microstructure and
hardness retention wasIP: observed in CoCrFeNiMo
205.217.244.67 On: Tue, 0
2 with annealing
01 Mar temperature up to 800  C.
2016 06:41:47
Copyright: American Scientific Publishers
Keywords: Phase Formation, Mechanical Alloying, Spark Plasma Sintering, Hardness
Retention.

1. INTRODUCTION Most of the HEA studied in literature are prepared

Conventional metallic alloys (steels, super alloys etc.) are
processed based on one principle element with minor
addition of alloying elements to meet the desired prop-
erties. In contrast, in high entropy alloys (HEA), there
is no principle element and all the elements are taken in
equi-atomic proportion, thus all the elements in HEAs are
considered as solute.1–3 Although one may anticipate the
formation of complex compounds and more number of
phases in a multi-component system, current research on
multi-component HEA has shown the formation of solid
solutions with simple crystal structure having enhanced
mechanical properties. Some of these exceptional proper-
ties include high strength and its retention at high tem-
perature, thermal stability, and good oxidation and wear
resistance.3–9
Further, a characteristic features such as extensive
solid solution strengthening effect, sluggish diffusion,
and resistance to anneal softening makes these HEAs
as a promising candidate materials for high temperature
applications.5
6
10–12
∗
Author to whom correspondence should be addressed.
by casting route with typical dendritic structure,2–9 and
very few studies are available on HEA synthesized by
mechanical alloying (MA) route.13–17 Since mechanical
alloying (MA) route is a well known method to produce
nanocrystalline material with good homogeneity of ele-
mental distribution, in the present study, CoCrFeNi HEA
are synthesized by MA followed by spark plasma sintering
(SPS). Since addition of high melting point elements are
expected to aid in retention of strength at high tempera-
ture, in the present study, molybdenum (Mo) and niobium
(Nb) are chosen as minor alloying additions to CoCrFeNi.
Their effects on phase formation during MA and SPS and
on hardness were studied.
2. EXPERIMENTAL DETAILS
Pure elemental powders of Ni, Co, Cr, Nb, Fe and Mo
were utilized for synthesizing HEA powders of CoCrFeNi,
CoCrFeNiMo004 , CoCrFeNiMo02 , CoCrFeNiNb008 and
CoCrFeNiMo014 Nb014 . Fritsch P5 high energy ball mill
with a ball to powder weight ratio of 10:1, toluene
as process controlling agent and hard chrome steel as

8106 J. Nanosci. Nanotechnol. 2014, Vol. 14, No. 10 1533-4880/2014/14/8106/004 doi:10.1166/jnn.2014.9441

Praveen et al. Effect of Molybdenum and Niobium on the Phase Formation and Hardness

the milling medium was utilized for synthesizing HEAs.

Subsequently, MA powders were consolidated using SPS
equipment in the temperature range of 900–1000  C by
applying a load of 30–50 MPa for 5 min. Panalyti-
cal Xpert Pro XRD equipment is utilized to study the
phase evolution during milling and after sintering. Theo-
retical density of HEA was calculated using molar average
density formula and experimental density was calculated
using Archimedes principle. Crystallite size was calculated
from Lorentzian contribution of integral breadth using sin-
gle peak analysis method in Xpert High Score Plus soft-
ware. Hardness was measured on the sintered sample by
applying a load of 1 kgf with dwell time of 10 s in
Wilson Wilpert Vickers hardness instrument. Hardness val-
ues were reported by taking an average of 20 readings
(10 on each side of the sintered pellet).

Figure 2. Effect of Mo and Nb on phase formation after mechanical

3. RESULTS AND DISCUSSION
3.1. Alloying Behavior During Milling
It is clear from the XRD pattern (Fig. 1) that diffrac-
tion peaks of individual elements of CoCrFeNi observed
at 10 min disappear with the milling time and form major
FCC phase (F) with minor BCC phase (B) after 15 h
of milling. FCC phase was observed to form after 5 h of
milling, and with increase in milling time, the fraction of
FCC phase increased together with decrease in the fraction
Delivered
of BCC phase. To a certain extent,byformation
Publishing Technology
of FCC and
IP: 205.217.244.67 On: Tue,CoCrFeNi
BCC phase can be explained based on the binary phase Scientific Publishers
Copyright: American
diagram of elemental pairs. From the binary phase dia-
gram, it is expected that Co–Ni, Fe–Ni will form a FCC
structure; Cr–Ni will form a mixture of BCC and FCC
phase; and Co–Fe, Cr–Fe will form a BCC structure. So
the element responsible for the formation of FCC and BCC
phase during mechanical alloying in CoCrFeNi could be
Ni and Cr, respectively, with other elements distributed in
both Ni and Cr.15
16 Addition of either Mo or Nb, or both
Figure 1. Phase evolution of CoCrFeNi HEA with milling time.
alloying.
to CoCrFeNi did not affect the phase formation behavior
during mechanical alloying (Fig. 2).
However, Mo did not dissolve completely even after
milling for 20 h and 30 h in CoCrFeNiMo02 and
CoCrFeNiMo014 Nb014 , respectively. Interestingly, Nb dis-
solved completely during milling in both CoCrFeNiNb008
and CoCrFeNiMo 014 Nb014 .Library
Partial dissolution of Mo in
to: Adelaide Theological
01 Mar 2016
can be06:41:47
attributed to sluggish diffusivity because
of its high melting point (2617  C). Although Nb has high
melting point (2468  C) but relatively lower than that of
Mo (2617  C), a complete dissolution of Nb in CoCrFeNi
could be because of its high frequency factor (Do/Nb =
1240 mm2 /s and Do/Mo = 180 mm2 /s) and lower activa-
tion energy than that of Mo (QSD/Nb = 440 kJ/mol and
QSD/Mo = 460 kJ/mol).18
3.2. Phase Evolution After SPS
From the XRD pattern of CoCrFeNiMox after SPS
(Fig. 3), FCC phase was observed as a major phase with
evolution of sigma phase () and absence of BCC phase.
This sigma phase was observed in previous studies and
was mainly attributed to Co–Cr/Fe–Cr related tetragonal
phase.15 Apart from major FCC phase and sigma phase,
a new phase (19  was observed in CoCrFeNiMo02 . This
new phase  could be attributed to the presence of Mo as
it was not observed in CoCrFeNi alloy. This phase could
be (Mo, Cr) rich phase, as reported in the previous study
on as cast CoCrFeNiMo08 .19
To study the phase evolution of mechanically alloyed
powder with temperature, MA-CoCrFeNiMo02 HEA pow-
der was annealed in air for 1 h at different temperatures
from 400  C to 900  C, and XRD was carried out on
the annealed powder. Following significant changes were
observed from the XRD pattern with annealing tempera-
ture (Fig. 4): complete dissolution of Mo, dissolution of

J. Nanosci. Nanotechnol. 14, 8106–8109, 2014 8107

Effect of Molybdenum and Niobium on the Phase Formation and Hardness Praveen et al.

Figure 5. BSE image of sintered CoCrFeNi HEA.

Figure 3. Illustration of phase evolution and effect of alloying addition phase contrast can be correlated to FCC and sigma phase
due to spark plasma sintering. observed in XRD pattern of sintered CoCrFeNi HEA.
Crystallite size of 60–70 nm was observed in all sin-
BCC phase, formation of carbide (Ni3 Mo3 C) (ICSD ref- tered HEA.
erence number-98-005-1497) above 500  C and its dis-
solution below 900  C, formation of sigma phase and  3.3. Effect of Alloying Elements on Hardness
phase. Phases formed after annealing of MA powder of Relative density and hardness achieved for CoCrFeNi were
CoCrFeNiMo02 at 900  C and SPS compact are similar. 95% and 570 HV1 respectively. Addition of Nb or Mo
In the case of CoCrFeNiNb008 and CoCrFeNiMo014 Nb014 or both did not affect the final densification of CoCrFeNi
Delivered by Publishing Technology (Table
(Fig. 3), niobium carbide was observed apart from sigma I). However,
to: Adelaide minorLibrary
Theological addition of 0.2 mole of Mo
phase and FCC phase. IP: 205.217.244.67 On: Tue,increased
01 Mar 2016hardness by 10%. Further, addition of Nb and
06:41:47
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Source of carbon to form carbide could American
be attributed to Scientific Publishers
Mo together enhanced the hardness by 20%, whereas addi-
the contamination coming from the milling media. In this tion of Nb did not enhance the hardness. As the relative
connection, it is also important to note that these carbides density and crystallite size are nearly same for all the
are observed only when Mo or Nb was added. sintered HEA, meagre increase in hardness could be due
Two phase contrast was observed in the back scat- to smaller amount of alloying addition and thus insignif-
tered electron (BSE) image of CoCrFeNi with porosity icant solid solution strengthening. Hardness observed for
distributed along one of the phases (Fig. 5). This two CoCrFeNiMo02 was 20% higher than that of as cast
CoCrFeNiMo19 08 HEA, and hardness of all HEAs studied
in this work are greater than HEA made from refractory
elemental composition WNbMoTaV.20 Overall, very high
hardness of these HEAs could be attributed to the solid
solution strengthening effect and nanocrystallinity.
Stability of the phases formed and hardness of sintered
CoCrFeNiMo02 HEA were studied by annealing the sin-
tered compact at different temperatures for one day, and
subsequent XRD and hardness measurement were taken at
room temperature. No structural change was observed in

Table I. Relative density and hardness of HEAs obtained after spark

plasma sintering.

Sintering Relative Hardness

HEA system condition density (%) (HV1 

CoCrFeNi 900  C, 5 min 95 570 ± 10

CoCrFeNiMo004 900  C, 5 min 94 580 ± 10
CoCrFeNiMo02 900  C, 5 min 94 620 ± 10
CoCrFeNiNb008 1000  C, 5 min 95 530 ± 25
Figure 4. Phase evolution of CoCrFeNiMo02 HEA with annealing
CoCrFeNi Mo014 Nb014 1000  C, 5 min 94 710 ± 25
temperature.

8108 J. Nanosci. Nanotechnol. 14, 8106–8109, 2014

Praveen et al.
Figure 6. Thermal stability of sintered CoCrFeNiMo02 with annealing
temperature.
Delivered by Publishing Technology to: Lin, Adelaide
IP: 205.217.244.67 On: Tue,7.01X.Mar
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Figure 7. Hardness variation with annealing temperature.
XRD pattern with annealing temperature (Fig. 6), which
was reflected in the hardness value, as the decrease in
hardness is less than 15% (Fig. 7).
4. CONCLUSIONS
Nanocrystalline CoCrFeNi HEA was synthesized success-
fully by mechanical alloying and spark plasma sintering
with high hardness of 570 HV1 . Partial dissolution of Mo
during mechanical alloying, and complete dissolution of
Mo was observed during annealing treatment and after
spark plasma sintering. Unlike Mo, Nb completely dis-
solves during mechanical alloying. Addition of Mo and
J. Nanosci. Nanotechnol. 14, 8106–8109, 2014
Effect of Molybdenum and Niobium on the Phase Formation and Hardness
Nb did not change the microstructure of CoCrFeNi HEA
except for the formation of carbide after spark plasma sin-
tering. FCC phase was observed as the major phase in all
HEA studied in the present paper. These alloys have also
shown nanocrystallinity even after sintering at 1000  C. An
FCC phase, high hardness and its retention with annealing
temperature in CoCrFeNiMo02 is an indication that HEAs
with proper alloy designing can be considered as potential
candidates for high temperature applications.
Acknowledgment: Authors would like to thank Naval
Research Board (NRB), Directorate of Naval R&D, New
Delhi, India for the financial support through the project #
DNRD/05/4003/NRB/190.
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