J Mater Sci (2010) 45:5158–5163

DOI 10.1007/s10853-010-4246-5

Hot consolidation and mechanical properties of nanocrystalline

equiatomic AlFeTiCrZnCu high entropy alloy after mechanical
alloying
S. Varalakshmi • G. Appa Rao • M. Kamaraj •

B. S. Murty

Received: 27 September 2009 / Accepted: 18 January 2010 / Published online: 24 June 2010
Ó Springer Science+Business Media, LLC 2010

Abstract The present study is aimed to investigate the system with equiatomic and/or near equiatomic composi-
consolidation behaviour and mechanical properties of tions and form a simple crystal structures due to high
nanocrystalline equiatomic AlFeTiCrZnCu high entropy mixing entropy [1–3]. According to Boltzmann’s hypoth-
alloy after mechanical alloying. The consolidation was esis, the entropy of mixing is maximum at equiatomic
achieved by cold pressing with conventional sintering, compositions. The size factor is an important factor that
vacuum hot pressing and hot isostatic pressing techniques. decides whether the HEAs turn to be crystalline or amor-
The microstructure and mechanical properties were eval- phous [4]. Due to the large solid solution strengthening
uated. The hardness and compressive strength of nano- effect, the HEAs with high hardness offer potential
crystalline equiatomic AlFeTiCrZnCu high entropy alloy industrial applications, such as tools, molds, dies and high-
after vacuum hot pressing are 9.50 and 2.19 GPa and those temperature parts where high strength, good wear and
after hot isostatic pressing are 10.04 and 2.83 GPa, oxidation resistance are required [5–14].
respectively. The wear resistance is found to be higher than Mechanical alloying is an important non-equilibrium
the commercially used materials such as Ni-hard faced process and also one of the promising methods to produce
alloy. nanocrystalline materials [15, 16]. The present work is
the first attempt to consolidate the nanocrystalline equi-
atomic HEAs. In this work, the nanocrystalline equiatomic
Introduction AlFeTiCrZnCu HEA have been synthesised by mechanical
alloying and an attempt made to study the consolidation
According to thermodynamical concepts, solid solutions behaviour of the same with various routes. The elements of
with simple crystal structures form at the solvent-rich the HEA are carefully selected such that the size factor is
compositions and the ordered intermediate phases form at low so that they easily form a solid solution with crystalline
the centre of the phase diagram. The main problem with structure [4]. The microstructure and mechanical properties
multicomponent systems and equiatomic compositions is like hardness, compressive strength and wear resistance of
the anticipated formation of a variety of intermetallics with the HEA were also studied. For wear studies nickel hard
complex crystal structures, which causes difficulty in pro- faced alloy is used as disc and AlFeTiCrZnCu HEA is used
cessing of these alloys. High entropy alloys (HEAs) are as a pin. The nickel-based hard facing alloys have become
new generation alloys that are based on multicomponent increasingly popular in recent years owing to their excel-
lent performance under conditions of abrasion, corrosion
and elevated temperature [17].
S. Varalakshmi
M. Kamaraj
B. S. Murty (&)
Department of Metallurgical and Materials Engineering,
Indian Institute of Technology Madras, Chennai 600036, India
e-mail: murty@iitm.ac.in Experimental details
G. Appa Rao
Defence Metallurgical Research Laboratory (DMRL), The nanocrystalline equiatomic AlFeTiCrZnCu HEA
Hyderabad 500058, India powders were prepared by high-energy ball milling by

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following the same procedure as described in our earlier after wear test were measured in order to estimate the wear
study [4]. After the successful synthesis of nanocrystalline loss. The wear debris and worn surfaces were characterized
equiatomic AlFeTiCrZnCu HEA, the powders were con- using SEM after the wear test.
solidated by cold pressing and sintering, vacuum hot
pressing (VHP) and hot isostatic pressing (HIP) in order to
confirm the stability of structure and identify the suitable Results and discussion
consolidation technique. The nanocrystalline equiatomic
AlFeTiCrZnCu HEA was compacted with 2 GPa normal XRD and DSC analysis as nanocrystalline
load at room temperature using a uniaxial press of 1000 ton AlFeTiCrZnCu HEA
capacity and heat treated at 800 °C for 1 h in argon
atmosphere. The VHP was carried out with a semi-auto- The XRD patterns of nanocrystalline equiatomic
matic, computer-controlled 250 ton load capacity press AlFeTiCrZnCu HEA are shown in Fig. 1, which evidences
using graphite die with 65 mm diameter. The VHP was the phases formed in as milled and consolidated conditions,
carried out at 800 °C with 30 MPa for half an hour. To i.e. after 20 h of milling, cold press and heat treatment,
avoid graphite diffusion, the wall of the die was coated VHP and HIP conditions. The XRD pattern shows the
with boron nitride and 1 mm of metal was removed from single BCC phase and small traces of WC impurity in the
both surfaces of the VHP sample before its characteriza- 20 h milled sample. This WC is a contamination from
tion. In the case of HIP, stainless steel cans with dimen- the milling media. The consolidated samples show the two
sions of 50 9 40 mm were prepared by welding the BCC phases and a small volume fraction of FCC phase.
stainless steel sheets. The HIP was performed at 800 °C The d-spacing calculations from the 2h positions of the
with 1 GPa pressure for half an hour. An EDM wire cutting peaks present in the XRD pattern confirm these structures
was used for machining and cutting the VHP and HIP (Table 1). The DSC results shown in Fig. 2 clearly reveal
samples to the appropriate specifications to carry out the that there is no predominant endothermic or exothermic
necessary characterization and mechanical property peak up to 800 °C, which indicates that there is no phase
evaluation. change in the nanocrystalline equiatomic AlFeTiCrZnCu
The sectioned samples were characterized by the X-ray HEA up to 800 °C for 1 h. This suggests that the second
diffraction technique (XRD) using a Brucker D8 X-ray BCC phase and the small fraction of FCC phase observed in
diffractometer with Cu Ka radiation. The Netzsch STA409 the consolidated samples possibly existed in the as-milled
PC DSC/TGA apparatus has been used to study the sta- condition itself. However, the small volume fraction of FCC
bility of the alloy at a constant heating rate of 20 K/min. phase is not visible in the as-milled condition due to the
The energy dispersive X-ray (EDX) microanalysis equip- peak broadening caused by nanocrystalline nature of the
ped with FEI-Quanta 200 scanning electron microscope FCC phase. Moreover, the very close lattice parameters of
(SEM) was used for compositional analysis and micro-
structure analysis. The sectioned and polished samples
were used to measure the bulk hardness by Vickers hard-
ness tester with 3 kg load and the compressive strength by
1000 kN press. The wear behaviour of the HIP sample was
estimated using a pin-on-disc wear tester. For wear studies
the nickel hard faced alloy was used as a disc and the
AlFeTiCrZnCu HEA was used as a pin. In the present
study 2-mm-thick austenitic stainless steel of type 316 LN
was surfaced with a nickel-base hard facing alloy corre-
sponding to AWS NiCr-B and was taken as a disc material.
The deposition was made using plasma transferred arc
(PTA) surfacing and the deposit consists of the precipitates
like (Ni,Fe)3B, Ni3Si, Cr7C3, Cr5B3 and Cr7B3. The micro-
hardness values are about 2000 VHN for the floret-like
precipitates and about 1300 VHN for the needle-shaped
particles in the hard face alloy. The average hardness of the
deposit is around 550 VHN, which is maintained down to a
Fig. 1 XRD patterns of nanocrystalline equiatomic AlFeTiCrZnCu
distance of 0.5 mm from the interface. This available
HEA with various consolidation routes (20 h: 20 h ball milled, CP
material is thought to be potential alloy to be used as a disc cold pressed and sintered, VHP vacuum hot pressed, HIP hot isostatic
in the wear test [17]. The weight loss of the pin and disk pressed)

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Table 1 Calculated and

S. no. Angle d-spacing d-spacing Planes–crystal
experimental d-spacing values
(2h) (°) (experimental) (nm) (calculated) (nm) structure
of the phases present in
nanocrystalline equiatomic 1. 36.14 0.248 0.248 (111)–FCC
AlFeTiCrZnCu HEA in heat
treated condition 2. 42.30 0.214 0.215 (200)–FCC
3. 43.29 0.209 0.209 (110)–BCC1
4. 44.14 0.205 0.205 (110)–BCC2
5. 60.91 0.152 0.152 (220)–FCC
6. 62.83 0.148 0.148 (200)–BCC1
7. 64.31 0.145 0.145 (200)–BCC2
8. 72.96 0.130 0.130 (311)–FCC
9. 77.03 0.124 0.124 (222)–FCC
10. 79.41 0.121 0.121 (211)–BCC1
11. 81.28 0.118 0.118 (211)–BCC2
12. 89.92 0.109 0.108 (400)–FCC
13. 94.68 0.105 0.104 (220)–BCC1
14. 97.57 0.102 0.103 (220)–BCC2

order to reduce the porosity and also retain the nanocrys-

talline nature with better mechanical properties, they have
been consolidated using VHP and HIP.
The SEM-BSE micrograph shown in Fig. 3b proved that
the nanocrystalline HEA can be processed using VHP with
very little porosity. The SEM-BSE-EDX results are given
in Table 2, which gives the compositions of the each phase
present in the alloy. Phase 1, (light grey in Fig. 3b),
labelled as grey-1, has all the six elements and is rich in
Cu, Zn and Ti. Phase 2 (dark grey in Fig. 3b) labelled as
grey-2 is rich in Al, Fe and Cr and depleted in Cu, Zn and
Ti. Phase 3 (white in Fig. 3b) labelled as white is rich in Cu
and Zn. From the volume fractions of the phases, it appears
that the two grey (light and dark) coloured phases are the
BCC phases and the white one is the FCC phase. The three-
phase microstructure has also been confirmed in the HIPed
sample by SEM–BSE image as shown in Fig. 3c. Table 2
Fig. 2 DSC trace of 20 h milled nanocrystalline equiatomic gives the composition of each phase present in the alloy,
AlFeTiCrZnCu HEA heated to 800 °C which indicates the composition of the three phases in the
HIPed alloy is similar to that of the three phases observed
the two BCC phases and peak broadening caused by in VHP alloy. The XRD results are also similar in both the
nanocrystalline nature of the phases is the reason for the VHP and HIP samples. However, the microstructure and
overlapping of the peaks in the as-milled condition. the distribution of the phases are different in HIPed sample
in comparison to VHP sample. In the microstructure of the
Microstructure analysis of nanocrystalline HIPed sample, the phases are spherical in shape and small
AlFeTiCrZnCu HEA in size, which is attributed to the isostatic pressure during
the HIP process. According to the Gibb’s phase rule
The SEM analysis of the cold pressed and sintered sample (F = C - P ? 1; F is the degree of freedom; C the
(Fig. 3a) evidenced the more number of porosity, which is number of components; P the number of phases), the
expected. As MA powders are prone to minimum plastic maximum number of equilibrium phases in a C component
deformation during cold consolidation as they are already system at constant pressure is P = C ? 1. The value of P
deformed extensively during the milling process. This may even be greater under non-equilibrium conditions. The
study suggests that the simultaneous application of pressure study of conventional alloys also indicates that a large
and temperature might give better density in this alloy. In number of intermetallic compounds or other complex

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Fig. 3 SEM–BSE images of

nanocrystalline equiatomic
AlFeTiCrZnCu HEA: a cold
pressed and sintered, b VHP and
c HIP

Table 2 SEM-EDX results of nanostructured equiatomic AlFeTiCrZnCu HEA

Condition Phase Al (at.%) Fe (at.%) Ti (at.%) Cr (at.%) Zn (at.%) Cu (at.%)

VHP Bulk 18.0 16.1 16.4 16.8 16.2 16.5

Grey-1 11.4 7.2 25.0 7.2 24.7 24.4
Grey-2 27.6 31.6 4.1 30.1 3.0 3.5
White 13.9 11.3 2.4 11.8 30.6 30.1
HIP Bulk 18.9 16.2 15.7 15.9 17.2 16.1
Grey-1 14.3 11.4 18.7 11.5 23.0 21.1
Grey-2 24.9 28.7 5.3 28.4 6.2 6.5
White 9.3 4.4 1.6 4.2 40.3 40.1

ordered phases are expected to form in multicomponent crystal structure in this HEA. The formation of amorphous
alloy systems. However, the total number of phases phase at the equiatomic composition in the present system
observed in nanocrystalline equiatomic AlFeTiCrZnCu is not observed, possibly due to the smaller differences in
HEA is well below the number of phases allowed atomic sizes. The formation Cu–Zn, Al–Fe–Cr and Ti–Cu–
by Gibb’s phase rule. The phases present in the Zn based solid solutions in the VHP and HIP alloy, instead
AlFeTiCrZnCu HEA are found to be stable up to 800 °C of the formation of intermetallics, indicates the role of
for 1 h. configurational entropy even after the alloy is heated to
The entropy of fusion of all the individual elements in 800 °C.
the present system is less than that of configurational
entropy of the hexanary system (14.9 J/mol K), which Mechanical properties of AlFeTiCrZnCu HEA
means the randomness due to the number of elements
present in the system is higher than randomness caused by The Vickers’s bulk hardness of VHPed nanocrystalline
melting. This high configurational entropy (high random- equiatomic AlFeTiCrZnCu HEA is 9.50 GPa and the
ness in the system) and also the large quantity of defects compressive strength is 2.19 GPa against fracture. The
induced during MA may lead to the formation of simple high values of hardness and strength might be attributed to

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the presence of a larger volume fraction of nanocrystalline In general, nanocrystalline structure is expected to
BCC phases and minor FCC phase. The larger grain enhance the hardness and wear resistance of the material.
boundary area and the presence of three phase boundaries Therefore, the present study on mechanical properties has
may be another reason for the higher strength of this alloy. been extended to evaluate the wear resistance of the HIPed
The hardness and compressive strength of the HIPed AlFeTiCrZnCu HEA. A room temperature wear study was
nanocrystalline equiatomic AlFeTiCrZnCu HEA are 10.04 carried out using a pin-on-disc machine. A pin prepared
and 2.83 GPa, respectively, and are similar to those from the HIPed AlFeTiCrZnCu HEA was used against the
observed in the VHPed HEA. Ni-hard faced disc (hardness = 650 HV) at a constant load
of 3 kg by varying track distance as 450, 800, 1200, and
1600 m. The results of the wear test are presented in
Figs. 4 and 5. Figure 4 shows that the wear loss increases
with sliding distance. However, the wear loss of HEA is
significantly lower than the disc material. This clearly
indicates that the HEA has better wear resistance than the
Ni-hard faced alloy. The entropy of fusion of all the ele-
ments in the present system is less than that of the con-
figurational entropy of the hexanary system (14.9 J/mol K),
which means the randomness due to the number of ele-
ments present in the system is higher than the randomness
in the melting. This high configurational entropy (high
randomness in the system) and also the large quantity
of defects induced during MA may lead to the formation
of simple crystal structure in this HEA. The formation of
amorphous phase at the equiatomic composition in the
present system is not observed, possibly due to the smaller
Fig. 4 Variation of wear loss with sliding distance differences in the atomic sizes.

Fig. 5 SEM images of the wear

tested pin at a sliding distance
of a 450 and b 1600 m and
those of wear debris (c) at a
sliding distance of 450 and
d 1600 m

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This result was further supported by the SEM micro- is 9.50 and 2.19 GPa and those after HIP are 10.04 and
graphs taken on worn surfaces (Fig. 5). Morphology of 2.83 GPa, respectively.
wear tracks on pin at varying sliding distance is given in 3. The wear resistance is found to be higher than the
Fig. 5a and b and accumulated debris at different sliding commercially used materials such as Ni-hard faced
distance is shown in Fig. 5c and d. Figure 5a and b reveals alloy.
that the formation of wear tracks on pin (HEA) is observed
only at a sliding of 1600 m. No severe ploughing was
observed at a lower sliding distance below 1600 m except
some sort of macroscopic plastic deformation. These References
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