Trans Indian Inst Met (August 2013) 66(4):369373

DOI 10.1007/s12666-013-0268-4

TECHNICAL PAPER

TP 2687

Characterization of Oxide Dispersed AlCoCrFe High Entropy

Alloy Synthesized by Mechanical Alloying and Spark Plasma
Sintering
S. Praveen Ameey Anupam Teja Sirasani
B. S. Murty Ravi S. Kottada

Received: 30 November 2012 / Accepted: 7 March 2013 / Published online: 22 May 2013
Indian Institute of Metals 2013

Abstract The present study deals with phase evolution of

oxide dispersed AlCoCrFe high entropy alloy during
mechanical alloying and spark plasma sintering. Mechanical alloying of AlCoCrFe resulted in a single BCC phase.
However, ordering of BCC phase with evolution of chromium carbide and sigma phase were observed after spark
plasma sintering. High hardness of 1,050 20 HV1 and
1,070 20 HV1 was observed for AlCoCrFe high entropy
alloy without and with oxide dispersion, respectively.
Significant contribution from solid solution strengthening
effect in high entropy alloys appears to have overwhelmed
the effect of oxide dispersion on hardness.
Keywords Phase evolution
Mechanical alloying

Oxide dispersion
Solid solution strengthening effect

1 Introduction
Designing new alloys to enhance the certain desired
properties for any specific application always kindle the
research community to try innovative and novel ideas to
come up with new synthesize routes or inventive alloy
design. In this connection, discovery of high entropy alloys
(HEAs) by Yeh et al. [1] is a notable concept that has made
a considerable impact in alloy designing because of their
simple microstructures with enhanced properties [16].
S. Praveen (&)
T. Sirasani
B. S. Murty
R. S. Kottada
Department of Metallurgical and Materials Engineering, Indian
Institute of Technology Madras, Chennai, India
e-mail: spravin88@gmail.com
A. Anupam
Department of Metallurgical and Materials Engineering,
National Institute of Technology, Jamshedpur, India

Most widely used conventional alloys like steels for

structural applications, superalloys for high temperature
applications are based on one principal element to which
minor portion of solutes are added. Contrast to that, synthesis of HEAs involves mixing of more number of elements in equi-atomic proportion. The idea of mixing more
number of elements at equi-atomic proportion is to increase
the configurational entropy, which consequently decreases
the free energy of the system. Thus, alloy system tends to
form a simple solution instead of complex structure and
complex phases. These HEAs are reported to have good
thermal stability, wear resistance and high strength and its
retention at high temperature [18].
Among the strengthening mechanisms, strengthening
from oxide dispersion is effective even at higher temperatures and it has been widely implemented in conventional
alloys to enhance the high temperature creep resistance
[912]. The selection of oxide particle is based mainly on
the stability of the oxide together with matrix at high
temperatures, and accordingly Y2O3 is the mostly widely
used oxide in ODS steels [1315]. It is established from
atom probe tomography (APT) together with TEM studies
that Y2O3 oxide particles tend to form nano clusters of
complex oxide (Y2Ti2O7, Y2TiO5) in the presence of Ti
[1619]. These nano clustered complex oxides are
observed to be stable at high temperatures and enhance the
hardness and creep properties than that achieved by the
dispersion of Y2O3 alone [1921]. Further, it has been
anticipated that Y2O3 together with Ti in any alloy would
form these beneficial nano clusters.
Thus, the present study was motivated with an ambition
of maximizing the benefit of oxide dispersion strengthening together with high strength HEAs. The present work
involves characterizing the effect of oxide dispersion
(YTiO) on AlCoCrFe HEA in terms of phase evolution,

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Trans Indian Inst Met (August 2013) 66(4):369373

densification and hardness. To the best of our knowledge,

this is the first report in the literature aimed at understanding the influence of oxide dispersion on HEAs.

2 Experimental Details
Pure elemental powders of Al, Co, Cr, Fe, Ti and Y2O3
were utilized for synthesizing oxide dispersed AlCoCrFe
HEA. AlCoCrFe HEA and oxide dispersoids were synthesized separately and milled together to produce oxide
dispersed HEA, which are designated as OD-AlCoCrFe in
this study. To synthesize oxide dispersoids, Y2O3 (33 wt%)
and Ti (67 wt%) were milled together with ball to powder
weight ratio of 20:1; whereas to synthesize AlCoCrFe
HEA, elements are taken in equi-atomic percentage and
milled with ball to powder weight ratio of 10:1. Mechanical alloying (MA) to synthesize OD-HEA (OD-0.8 wt%,
HEA-99.2 wt%) was carried out in Fritsch P5 high energy
ball mill using hard chrome steel balls as milling medium
and toluene as process controlling agent. At regular intervals of ball milling, powder samples were taken for XRD
analysis. Subsequently, MA powders were consolidated in
spark plasma sintering (SPS) machine (Dr Sinter SPS2500, Sumitomo Metals, Japan) at 900 and 1,000 C for
5 min with a heating rate of 100 K/min and by applying a
pressure of 50 MPa. Panalytical Xpert Pro XRD equipment with Cu target was utilized to study the phase evolution during milling and after sintering. Experimental
density of consolidated pellet was calculated using Archimedes principle. Crystallite size was calculated from
Lorentzian contribution of integral breadth using single
peak analysis method in Xpert High Score Plus software.
Hardness was measured on the sintered sample by applying
a load of 1 kgf with a dwell time of 10 s in Wilson Wilpert
Vickers hardness instrument. Hardness values reported are
from an average of 20 readings (10 on each side of the
sintered pellet).

3 Results and Discussion

3.1 Phase Evolution
XRD patterns in Fig. 1 illustrate the phase formation
behaviour of AlCoCrFe alloy during mechanical alloying.
Individual elemental diffraction peaks that appeared at the
initial milling time (after 15 min of milling) evolve into
diffraction peaks corresponding to single BCC phase after
10 h of milling. The evolution of BCC phase can be
attributed to the presence of strong BCC forming elements
such as Cr, Fe and Al in AlCoCrFe HEA. Decrease in the
peak intensity of Al and Co after 5 h of milling is a clear

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Fig. 1 Phase evolution of AlCoCrFe HEA with milling time

Fig. 2 Evolution of oxide dispersoids with milling time

indication that Al and Co dissolve first into a BCC lattice of

Fe/Cr. The peak positions of Fe and Cr have same 2h
values, thus it is difficult to comment on which one of these
two will act as BCC lattice. However, Cr being the highest
melting point element followed by Fe, Co and Al, the
diffusivity of Cr will be lower than other elements. From
the relative diffusivity and peaks intensity, it may be
inferred that BCC phase evolves by dissolution of Al followed by Co and Fe into Cr lattice. An observation of same
2h values for the final BCC peaks and the original Fe/Cr
peaks implies that there may not be a significant change in
the lattice parameter due to mechanical alloying. Lattice
parameter calculated from 112 peak of Fe, Cr and BCC
, 2.880 A
and 2.878 A

phase of AlCoCrFe are 2.870 A

respectively. Such an observation may also be attributed to
open packed nature of BCC unit cell which can accommodate elements without much expansion of lattice. The
XRD pattern of oxide dispersion and its synthesis by
milling Y2O3 and Ti are shown in Fig. 2. This XRD pattern

Trans Indian Inst Met (August 2013) 66(4):369373

371

Fig. 3 a Phase evolution and

b crystallite size variation of
oxide dispersed AlCoCrFe HEA
with annealing temperature

Fig. 4 Phase evolution of oxide dispersed AlCoCrFe HEA after

sintering

after 10 h shows a considerable dissolution of Ti, and

formation of new phase, which could be complex oxide of
yttrium and titanium. Subsequently, these oxide particles
were milled together with AlCoCrFe HEA for 5 h to disperse them uniformly in AlCoCrFe matrix.
3.2 Phase Stability
In order to confirm the stability of the phase formed after
MA, XRD was carried out on OD-AlCoCrFe powders that
were annealed at 500, 600, 700 and 800 C for 15 min in
Argon atmosphere. Figure 3 shows the phase evolution and
crystallite size variation of OD-AlCoCrFe due to annealing
at high temperatures of 500800 C. It is clear from Fig. 3a
that chromium carbide and ordered B2 phase have formed
during annealing. It is also interesting to note that there is
not much increase in the crystallite size due to annealing
(Fig. 3b) -illustrating excellent thermal stability of this
alloy powders at high temperatures. Figure 4 illustrates the
phase evolution of OD-AlCoCrFe after SPS. It is important
to note that phases similar to annealed powders were

Fig. 5 a SEM-BSE image and b EDS analysis on sintered oxide

dispersed AlCoCrFe

observed for sample sintered at 900 C, whereas carbide

peaks disappeared and sigma phase was observed for
sample sintered at 1,000 C.
Since mechanical alloying is a non-equilibrium route,
where large number of defects is introduced during milling,
most of the alloys tend to form disordered phase as was
observed in the present case. It is important to note that Al
together with Co and Fe forms ordered B2 compound,
while the super lattice reflections of such a B2 phase were
not observed in the as milled condition. The (100) super

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Trans Indian Inst Met (August 2013) 66(4):369373

quantity of 0.8 wt%, peaks corresponding to dispersoids

are not visible in XRD pattern.
3.3 Densification and Hardness
Recent studies on SPS have shown that applying a maximum pressure at higher temperature helps in better bonding
between the powder particles and enhanced ductility [23,
24]. Thus, in the present study, a maximum pressure of
50 MPa was applied at Ts - 100 C (Tssintering temperature). Figure 6 illustrates the density and densification
rate variation with temperature obtained for sample sintered at 900 and 1,000 C. It is clear that maximum density
was observed for sample sintered at 1,000 C, and a
decrease in densification rate above 950 C implies that
increase in densification will not be significant above
1,000 C.
Table 1 lists the comparison of hardness of the HEAs
obtained in the present study (OD-AlCoCrFe) with previous studies from literature. Very high hardness of
950 110 HV1 and 1,070 20 HV1 were obtained for
the alloy OD-AlCoCrFe sintered at 900 and 1,000 C,
respectively. Crystallite size obtained for sample sintered
at 900 and 1,000 C are in the range of 5060 nm. Similar
density and hardness were achieved when AlCoCrFe HEA
was sintered at 1,000 C. Strengthening from solid solution
strengthening and inherent high strength nature of ordered
BCC structure could be more prominent than the effect of
dispersion, and hence the effect of oxide dispersions is not
apparently visible. Besides, the fraction of ODS is too
small to bring an impact in hardness. However, it is
important to assert that oxide dispersions may also aid in
thermal stability, and consequently helps in arresting the
grain growth.
The comparison of density, hardness and specific hardness of alloys of present work with literature suggest that
OD-AlCoCrFe is lighter and has got higher hardness, and
consequently higher specific hardness than most of the
HEAs synthesized by MA route [2527].

Fig. 6 Density and densification rate curve of sintered sample at 900

and 1,000 C

lattice reflection in the sample was only observed after

annealing the MA sample. This reordering of BCC phase
after sintering or annealing could be attributed to annihilation of this large number of defects [22]. This B2 ordered
phase could be based on AlCo B2 phase [6].
It is quite probable that carbon would have come from
milling medium as impurities and could be responsible for
formation of chromium carbide. Figure 5a shows the BSE
image of OD-AlCoCrFe pellet sintered at 1,000 C. Twophase contrast with distribution of black particles was
observed in BSE image. Besides, BSE image illustrates
lack of porosity, and was consistently observed in several
random locations on more than one SPS sample. Such lack
of porosity in BSE images is an indicative of excellent
densification during SPS. Figure 5b shows the EDS analysis of black particle and the rest of the region corresponding to Fig. 5a. The black particles in EDS analysis
show an increased atomic percentage of yttrium and titanium relative to the remaining region, which illustrates the
possible presence of complex YTiO compound in ODAlCoCrFe alloy. Since the dispersoids mixed are of a small

Table 1 Hardness comparison of HEAs in the present study with literature

Composition

Synthesizing route

AlCoCrFe?ODS

SPS

AlCoCrFe?ODS

Sintering Condition

Density of sintered
compact (g/cm3)

Hardness (HV)

Specific hardness
(HV/g/cm3)

Reference
Present study

900 C, 5 min, 50 MPa

6.13

950 110

155

1,000 C, 5 min, 50 MPa

6.55

1,070 20

163
160

6.57

1,050 20

AlFeTiCrZnCu

AlCoCrFe
HIP

800 C, 30 min, 1 GPa

1,000

24

AlCoCrCuFe

SPS

900 C, 15 min, 50 MPa

6.75

770

114

25

Co0.5FeNiCrTi0.5

SPS

1,000 C, 8 min, 30 MPa

7.59*

846

111

26

Calculated based on the reported relative density

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Trans Indian Inst Met (August 2013) 66(4):369373

4 Conclusions
Oxide dispersed nanocrystalline AlCoCrFe HEA was successfully synthesized by mechanical alloying and spark
plasma sintering. Ordered BCC phase was observed as a
major phase after sintering and annealing of mechanical
alloyed powder with small amount of carbide and sigma
phase. Very high hardness of 1,050 20 HV1 and
1,070 20 HV1 were observed for AlCoCrFe and ODAlCoCrFe HEA respectively. Effect of oxide dispersion on
hardness of HEA is not significant, possibly because of
overwhelming contribution of solid solution strengthening
effect from more number of elements in HEAs.

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Acknowledgments 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.

19.

References

21.

1. Yeh J W, Patent Publication Application, US 2002/0159914 A1

(2002).
2. Yeh J W, Chen S K, Lin S J, Gan J Y, Chin T S, Shun T, Tsau C
H, and Chang S Y, Adv Eng Mater 6 (2004) 299.
3. Tong C J, Chen M R, Chen S K, Yeh J W, Shun T, Lin S J, and
Chang S Y, Metall Mater Trans 36 (2005) 1263.
4. Varalakshmi S, Kamaraj M and Murty B S, J Alloys Compd 460
(2008) 253.
5. Zhang Y, Yang X, and Liaw P K, JOM 64 (2012) 830.
6. Sriharitha R, Murty B S and Kottada R S, Intermetallics 32
(2013) 119.

20.

22.
23.
24.

25.
26.
27.

Zhang Y and Zhou Y J, Mater Sci Forum 561 (2007) 1337.

Yang X and Zhang Y, Mater Chem Phys 132 (2012) 233.
Lin J and Sherby O D, Res Mech 2 (1981) 251.
Arzt E, Res Mech 31 (1991) 399.
Czyrska F A and Dubiel B, J Mater Process Tech 64 (1997) 53.
Nganbe M and Heilmaier M, Mater Sci Eng A 387 (2004) 609.
Ukai S, Harada M, Okada H, Inoue M, Nomura S, Shikakura S,
Asabe k, Nishida T and Fujiwara M, J Nucl Mater 204 (1993) 65.
Kang C, Fujiwara M, Bae D and Miyahara K, ISIJ Int 36 (1996)
1518.
Susila P, Sturm D, Heilmaier M, Murty B S, and Subramanya
Sarma V, Mater Sci Eng A 528 (2011) 4579.
Larson D J, Maziasz P J, Kim I S and Miyahara K, Scripta Mater
44 (2001) 359.
Miller M K, Hoelzer D T, Kenik E A and Russell K F, Intermetallics 13 (2005) 387.
Alinger M J, Odette G R, Hoelzer D T, Acta Mater 57 (2009)
392.
Schneibel J H, Liu C T, Miller M K, Mills M J, Sarosi P, Heilmaier M, and Sturm D, Scripta Mater 61 (2009) 793.
Sakasegawa H, Legendre F, Boulanger L, Brocq M, Chaffron L,
Cozzika T, Malaplate J, Henry J and Carlan Y, J Nucl Mater 417
(2011) 229.
Karthikeyan R, Subramanya S V, Kutty T R G and Murty B S,
Mater Sci Eng A 558 (2012) 492.
Murty B S and Ranganathan S, Int Mater Rev 43 (1998) 122.
Guillard F, Allemand A, Lulewicz J D and Galy J, J Eur Ceram
Soc 27 (2007) 2725.
Liu D, Xiong Y, Topping T D, Zhou Y, Haines C, Paras J, Martin
D, Kapoor D, Schoenung J M, and Lavernia E J, Metall Mater
Trans A 43 (2012) 340.
Varalakshmi S, Appa Rao G, Kamaraj M, Murty B S. J Mater Sci
45 (2010) 5158.
Praveen S, Murty B S, Kottada R S, Mater Sci Eng 534 (2012) 83.
Fu Z, Chen W, Xiao H, Zhou L, Zhu D and Yang S, Mater Des 44
(2013) 535.

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