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Procedia Materials Science 6 (2014) 641 647

3rd International Conference on Materials Processing and Characterization (ICMPC 2014)

Thermal Analysis and Nanoindentaion Studies on Nanocrystalline

AlCrNiFeZn High Entropy Alloy
C.Sajith babua, N.T.B.N. Koundinyab, K. Sivaprasadc, Jerzy.A.Szpunard
a,c

Advanced Materials Processing Laboratory, Department of Metallurgical and Materials Engineering, National Institute of Technology,
Tiruchirappalli -620015,India
b
Department of Metallurgical and Materials Engineering, Indian Institute of Technology Madras, Chennai 600036, India
c
Department of Mechanical Engineering, University of Saskatchewan, 57 Campus Drive, Saskatoon, SK, Canada S7N 5A9

Abstract
The nanocrystalline AlNiFeCrZn pentanary high entropy alloy was synthesised by mechanical alloying (MA) and
characterised by XRD, SEM and TGA. The AlNiFeCrZn high entropy alloy is mainly BCC structure with a crystallite size less
than 10nm in as milled condition. It retained its nanosrtructure at elevated temperature of 850 0C and it is found to be thermally
stable without phase transformation. The 30 hr milled AlNiFeCrZn alloy powder was consolidated using hot compaction unit at
850 0C for 2hr. From Nanoindendation measurements on consolidated samples, hardness and Youngs modulus values are found
to be 7.427 and 153.03 GPa respectively.

Ltd. This
is an open
article
under the CC BY-NC-ND license
2014
2014Elsevier
The Authors.
Published
byaccess
Elsevier
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(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Selection and peer-review under responsibility of the Gokaraju Rangaraju Institute of Engineering and Technology (GRIET).
Selection and peer review under responsibility of the Gokaraju Rangaraju Institute of Engineering and Technology (GRIET)
Keywords: Nanocrystalline materials, High entropy alloys, Mechanical alloying, Nanoindentation

1. Introduction
High entropy alloys are a new concept in alloy design and are quite different from traditional alloys, in which
one or two elements as principal elements for primary properties and other minor elements incorporated to get
improved properties and new microstructure (Ranganathan, 2003; Suryanarayana, 1999). The high entropy alloys
(HEA) are developed by Yea et al. (Hung et al., 2004; Wang et al., 2007; Zhang et al.,2009), and defined as alloys
that contain at least five principal elements with each elemental concentration between 5 and 35 at. %. Utilization of
high configurational entropy in the liquid state or regular solid state is the core principle behind the high entropy
alloys, which leads to the formation of simple FCC or BCC solid solutions, nanosized precipitates and even
amorphous phases (Cantor et al., 2004; Shun et al., 2005; Wang et al.,2008; Zhang et al.,2009; Zhou et al., 2007).
* Corresponding author. Tel.: +0-000-000-0000 ; fax: +0-000-000-0000 .
E-mail address: babusajith@gmail.com

2211-8128 2014 Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Selection and peer review under responsibility of the Gokaraju Rangaraju Institute of Engineering and Technology (GRIET)
doi:10.1016/j.mspro.2014.07.079

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C. Sajith Babu et al. / Procedia Materials Science 6 (2014) 641 647

The nanocrystalline structure and the microstructural stability even at higher temperature offer many potential
applications for HEA, such as tools, moulds and mechanical parts, etc. (Lee et al., 2008; Yeh et al., 2004; Zhang et
al., 2008). Solid solutions of multi component alloys generally found to be more stable than intermetallic
compounds at higher temperatures due to their large entropies of mixing, which lead to the sluggish diffusion of
atoms (Hung et al., 2004; Hsu et al., 2004; Tong et al.,2005; Varalakshmi et al., 2008; Wang et al.,2004 ). Most of
the common metals are having their entropy of fusion less compared to the configurational entropy at equiatomic
compositions for binary, ternary, quaternary, pentanary alloys is 5.8, 9.2, 11.6, 13.5 respectively. The amorphous
phase formation can be avoided by choosing elements with small size factors carefully, which can be another phase
to arise in these multicomponent alloys (Varalakshmi et al., 2008). Comparing to the other non - equilibrium
processing of materials such as vacuum arc melting, rapid solidification, etc., mechanical alloying is a versatile
method for synthesising nanocrystalline material (Chen et al., 2009; Suryanarayana, 1999; Zhang et al., 2009).In our
previous work AlCrCuNiFeZn HEA system had been investigated and results showed that the equiatomic
nanocrystalline AlCrCuNiFeZn HEA possessed excellent integrated mechanical properties (Koundinya et al., 2013).
In this paper, AlCrNiFeZn HEA powder was synthesised by mechanical alloying and consolidated through hot
compaction at 850 0C for 2h. Thermal stabilities of these nanocrystalline powder and nanoindentation studies of the
consolidated powder were also studied.
2. Experimental Procedure
Al, Cr, Fe, Ni, Zn elemental powders with a mesh size -325 and a higher purity of 99.5% were prepared through
MA in equi - atomic ratio. The milling was carried out in a high energy planetary ball mill (Insmart Systems, India)
with hardened steel medium and toluene as a process control agent (PCA) for 30 h at 300 rpm. High hardened steel
vials and balls of 10 mm diameter with a ball to powder weight ratio (BPR) of 10:1were used for milling. The
structure of the ball milled powders and sintered samples were characterized by Rigaku Ultima-III X-ray
diffractometer with Cu Ka radiation (1.5406 A) at a scan step of 0.02. Xpert high score plus was used to measure
crystallite size and lattice strain of milled powders. The microstructure of the alloy powders was observed using
scanning electron microscopy (SEM, JEOL JSM 6010). Thermo gravimetric (TG) analysis / Differential Thermal
Analysis (DTA) was carried out on 30 h milled HEA powder in Exstar 6200 TG/DTA with heating rate 20 C/min.
Hot pressing was used for consolidation of HEA powder at 850 C for 2 h with a pressure of 200 MPa.
Nanoindentation measurements were performed on consolidated samples using NH-type Nanohead UMT/UMNT
Universal Materials Tester with a load of 40mN and a holding time of 10 s. The reported hardness value is the
average of twenty five readings.
3. Results and discussion
3.1. Phase Evaluations of AlCrFeNiZn HEA
The XRD patterns of the milled equiatomic AlCrFeNiZn HEA powders for different time periods are shown in
Fig. 1(Sajith babu et al., 2014). XRD results shows that the intensity of the peaks corresponding to individual
elements present in the system dramatically decrease after 5 hr of milling and with further milling time, peaks
corresponding to individual elements have disappeared. The reduction in intensity of the peaks with milling time
and the peak broadening is due to refined crystal size and high lattice strain due to mechanical alloying and the
formation of solid solution (Yeh et al., 2007; Zhang et al., 2009). It is observed that a BCC solid solution with a
lattice parameter of 0.290nm has been formed after 30 h of milling. The favourable factors for the formation of solid
solution among the elements chosen are: (i) elements chosen for HEA are of simple crystal structures, (ii)
electronegativity difference between the elements chose is less as indicated in Table 1 (Lee et al., 2008; Zhang et al.,
2008; Zhou et al., 2007), that favours the formation of metallic bond and inhibits the nonmetallic bond formation,
and (iii) the relative atomic size difference is less than 15%, which is also a favourable factor for the formation of
solid solution. Most of the atomic pairs exhibit high negative entropy, which attributed for the high solid solubility
(Takeuchi et al., 2001).
The crystallite size and lattice strain with various milling time have been calculated from XRD using Xpert high
score plus software. The crystallite size and lattice strain as a function of milling time are presented in Table 2. As

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the milling prolongs crystal size decreases, the 30 h mechanically alloyed powder exhibits a crystal size of 7.5 nm.
The lattice strain of HEA powders increases with increasing milling time and the 30 h mechanically alloyed powder
exhibits a lattice strain of 1.39%. The increment in lattice strain is due to: (1) the effect of relative size difference
size between the elements chosen, (2) increasing grain boundary fraction and (3) mechanical deformation due to
milling (Sui et al., 1993). As the milling time increases, the grain boundary fraction and mechanical deformation are
increased continuously due to the grain size decrement. The increased lattice strain is the result of the increased
dislocation density produced by severe plastic deformation during milling (Yavari et al., 1992).
Fig 2 shows the XRD pattern of the consolidated sample, which evidences three distinct solid solution phases
with two FCC and one BCC structure. The density of consolidated sample is measured by Archimedes principle and
found to be 6.18 gm/cc. And the crystallite size of the consolidated sample is 62 nm calculated using Xpert high
score plus software system. From XRD pattern (Fig 2) it is observed that, consolidated samples shows additional
diffraction peaks corresponding to new phases that are evolved during sintering compared to 30 h milled powder.
Qualitatively it can be seen that BCC phase is small in quantity. The relative volume fractions of the phases are
calculated from the XRD profiles, BCC phase shows 10.56% compared to FCC1 49.56% and FCC2 39.87%.

Figure 1: XRD pattern of milled powders with different milling time

Figure 2: XRD pattern of consolidated AlCrFeNiZn HEA

Table 1: Thermo physical properties of the elements chosen for AlCrFeNiZn HEA (Lee et al., 2008; Zhang et al., 2008)

Melting
point
(oC)*

Density
(g/cm3)*

Al

0.143

660.5

2.70

FCC

1.61

10-23

Cr

0.128

1860

7.19

BCC

1.66

10-53

Fe

0.127

1538

7.87

BCC

1.83

10-40

Ni

0.125

1455

8.91

FCC

1.91

10-47

Zn

0.139

419.7

7.13

HCP

1.65

10-16

Element

Self-Diffusion
Coefficient
(mm2s-1) at
(27C) #

Atomic
Radius
(nm) *

(Lee et al., 2008); #(Zhang et al., 2008).

Crystal
structure*

Electro
negativity*

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Table 2: Variation of crystallite size and lattice strain of AlCrFeNiZn pentanary HEA with milling time.

Milling
Time (h)

Crystallite
Size (nm)

Lattice
Strain (%)

103

0.09

10

44

0.23

15

17

0.61

20

11

0.95

25

1.35

30

7.5

1.39

3.2 Microstructure study on consolidated samples

Figure 3 depicts the SEM images of the AlCrFeNiZn HEA consolidated samples, which reveals the presence of
multi phases. It is very difficult to detect the third phase by SEM because of very small amount comparing to other
two phases. The homogeneity of the chemical composition of the AlCrFeNiZn pentanary high entropy alloys has
been confirmed by EDX microanalysis. Fig. 4 shows the EDX spectrum obtained for AlCrFeNiZn high entropy
alloy consolidated at a temperature of 850 C for 2 hr. The nominal composition of each element in this alloy is 20
at.%, and the quantitative elemental analysis results from the EDX spectrum in Fig. 4 clearly indicate that the
homogeneity and the equiatomic composition is maintained in each particle of the alloy even after sintering also.

Figure 3: SEM Image of consolidated AlCrFeNiZn HEA

Figure 4: The EDX spectrum and quantitative analysis of

AlCrFeNiZn HEA after consolidation

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3.3 Thermal Analysis of 30 h AlCrFeNiZn HEA milled powder

Figure 5 shows the DTA curves of 30 h mechanically AlCrFeNiZn HEA powder with a heating rate of 20 C/min
and up to 1000 C. The exothermic curve was observed in a temperature range of about 150 to 400 C, is due to the
relieving of internal stresses, such as structural deformation, lattice strain etc. during high energy ball milling. The
exothermic peaks above 400C, approximately 415C, 480C may be associated with the energy release during
phase transformation process. After heating to 480C an endothermic curve was observed and it may be due to the
increase in crystallite size with the increasing temperature. Around 650 C, a small endothermic peak was observed,
it may be attributed to the new phase evolution with increasing temperature and this phase may be corresponds to
FCC phase seen in XRD profiles of consolidated samples. This is due to the formation a new phase and occurrence
of diffusion of atoms at a faster rate. The TG curve, Fig 6 shows the weight change of the 30 hr mechanically
alloyed powder. From TG analysis at a heating rate of 20 C/min it is observed that, first the gross weight decreases
at an amount of 0.4 wt. % and then it increases at an amount of 12.5 wt. % as the temperature increases. The weight
loss is the result of evaporation of process controlling agent used during milling and other phases with low melting
points and the weight gain can be attributed to the surface oxidation (Varalakshmi et al., 2008; Zhang et al., 2009).

Figure 5: DTA and TG curves of 30 hour AlCrFeNiZn HEA milled powder

3.4 Hardness and Youngs modulus values of AlCrFeNiZn HEA

Nanoindentation measurements performed on consolidated samples at temperature of 850 C for 2 hr. with a load
of 40mN and they exhibited very high hardness value. Figure (6a) shows a typical load displacement curves for
AlCrFeNiZn HEA during and after indentation. The hardness and Youngs modulus values as a function of contact
depth is also shown in figure (6b), and these values are almost constant at all points. The hardness and Youngs
modulus values obtained from the nanoindentation measurements for AlCrFeNiZn HEA are 7.427GPa and
153.03GPa respectively. From the XRD analysis (Fig. 2), the majority volume fraction of the phase was observed to
be FCC phases. Compared to other HEA like AlCrCuFeNiZn(Koundinya et al., 2013), Al0.3CoCrFeNi(Li et al.,
2009), FeNiCrCuCo, FeNiCrCuMo, FeNiCrCuAl(Shun et al., 2010), etc., the present AlCrFeNiZn HEA shows
higher hardness. This solid solution strengthening is due to the relative size difference between atoms present in
HEA. It is believed that Zn (hcp) has introduced large misfit strain while accommodating in its lattice position.
Further, high lattice distortion present in the system causing restricted of dislocation mobility in the present HEA.

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In addition to the above strengthening mechanisms the grain size in nano scale causes grain boundary strengthening.
All these properties like sluggish diffusion of atoms, nanocrystalline nature in microstructure with FCC phases,
proves AlCrFeNiZn HEA is a best alternative material for a wide range of high temperature application.

Figure 6: (a) Typical load displacement curve (b) the hardness and Youngs modulus versus contact depth

4. Conclusions
The nanocrystalline equiatomic AlCrFeNiZn HEA has been successfully synthesized by mechanical alloying and
the solid solution can be obtained when the powder milled more than 20 hr. The 30 hr. ball milled alloy powder
shows nano sized crystalline structure with a crystallite size of about 7.5 nm with high lattice strain of 1.39%. From
TGA, it is observed that a maximum weight gain of 15.3 wt. % at 800 qC due to oxidation. Initial weight loss of 0.4
wt. % due to PCA evaporation at around 90qC. The structure transforms to two FCC phases and one BCC phase
when it is annealed at 850 qC for 2 hr. The homogeneity of the chemical composition of the AlCrFeNiZn HEA has
been confirmed by EDX microanalysis. AlCrFeNiZn pentanary HEA exhibit highest hardness of 7.427 GPa, and the
Youngs modulus of 153.03 GPa.
Acknowledgment
The authors express their gratitude to the Canadian Govt. for the award of Canada Commonwealth GSEP
Scholarships - 2012-13.
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