Materials and Design 139 (2018) 498–511

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Materials and Design

journal homepage: www.elsevier.com/locate/matdes

Compositional variation effects on the microstructure and properties of a

refractory high-entropy superalloy AlMo0.5NbTa0.5TiZr
O.N. Senkov a,⁎, J.K. Jensen b, A.L. Pilchak a, D.B. Miracle a, H.L. Fraser b
a
Air Force Research Laboratory, Materials and Manufacturing Directorate, Wright-Patterson AFB, OH 45433, United States
b
Center for the Accelerated Maturation of Materials, Department of Materials Science and Engineering, The Ohio State University, 1305 Kinnear Rd., Columbus, OH 43212, United States

H I G H L I G H T S G R A P H I C A L A B S T R A C T

• A BCC-based analog to superalloy

microstructures is sought with a ductile
BCC matrix and coherent ordered B2
nano-precipitates.
• AlMo0.5NbTa0.5TiZr has a brittle B2 ma-
trix, coherent BCC nano-precipitates and
coarse HCP particles at grain boundaries.
• Sequential composition changes removed
BCC and HCP phases in some alloys but
the B2 phase remained continuous.
• Deformation inverted the microstructure
into a continuous BCC matrix and discrete
B2 precipitates.

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

Article history: An AlMo0.5NbTa0.5TiZr baseline alloy was shown earlier to have good high temperature strength but poor ductility
Received 14 September 2017 below 600 °C due to coarse intermetallic grain boundary particles and a continuous ordered B2 matrix phase.
Received in revised form 19 October 2017 Systematic composition changes intended to remove the deleterious microstructural features and to improve
Accepted 17 November 2017
mechanical properties were explored in the present work. The baseline alloy and the new alloys studied here,
Available online 21 November 2017
AlMo0.5NbTa0.5TiZr0.5, AlNbTa0.5TiZr0.5, Al0.5Mo0.5NbTa0.5TiZr and Al0.25NbTaTiZr, all had an ordered B2 matrix
Keywords:
crystal structure. Additionally, coherent BCC nanoscale precipitates were present at a high volume fraction inside
High entropy alloy the B2 matrix grains in AlMo0.5NbTa0.5TiZr, Al0.5Mo0.5NbTa0.5TiZr and Al0.25NbTaTiZr, and/or coarse, grain-
Superalloy boundary particles existed in AlMo0.5NbTa0.5TiZr and AlMo0.5NbTa0.5TiZr0.5. The mechanical properties were
Microstructure assessed with microhardness and compression testing at 25 °C and 1000 °C. Al0.5Mo0.5NbTa0.5TiZr showed the
Mechanical properties highest hardness (Hv = 6.4 GPa) and strength (σ0.2 = 2350 MPa) at 25 °C and modest strength (σ0.2 =
579 MPa) at 1000 °C. AlMo0.5NbTa0.5TiZr0.5 had the highest strength (σ0.2 = 935 MPa) at 1000 °C, but was brittle
at 25 °C. High-temperature deformation produced a desirable microstructure in Al0.5Mo0.5NbTa0.5TiZr and
Al0.25NbTaTiZr alloys consisting of a continuous BCC phase and discontinuous B2 nano-precipitates. The
relationships between the composition, microstructure, and properties were identified and discussed.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction

High entropy alloys (HEAs) are one of the most recent developments
⁎ Corresponding author. in material science, which open a vast, unexplored area of alloy compo-
E-mail address: oleg.senkov.ctr@us.af.mil (O.N. Senkov). sitions and the potential to influence solid solution phase stability

https://doi.org/10.1016/j.matdes.2017.11.033
0264-1275/© 2017 Elsevier Ltd. All rights reserved.
 O.N. Senkov et al. / Materials and Design 139 (2018) 498–511
through control of configurational entropy [1–3]. Using the HEA con-
cept, several refractory high entropy alloys (RHEAs) have recently
been reported as promising alternatives to Ni-based superalloys
[4–11]. RHEAs with a low density and high strength are among the
most promising recent achievements in this field [10–17]. The reported
densities of these new RHEAs are in the range of 5.9 to 8.4 g/cm3 and
their specific strengths are often superior to Ni-based superalloys
[11–14]. Some of these alloys consist of very fine, nano-scale mixtures
of disordered BCC and ordered B2 phases with similar lattice parameters
[11,18,19], which may be responsible for their high strengths. Among
these RHEAs, AlMo0.5NbTa0.5TiZr has impressive yield strength of
745 MPa and good compressive ductility (N50% height reduction) at
1000 °C. Detailed analysis of the microstructure and crystal structure
of this alloy using advanced transmission electron microscopy (TEM)
and atom probe tomography (APT) techniques revealed a nano-scale,
modulated mixture of an ordered B2 matrix and coherent, cuboidal pre-
cipitates of a disordered BCC phase [18,19]. Based on these microstruc-
tural features, which are typical to superalloys, complex composition
and the high strength at temperatures from 25 °C to 1200 °C, this
two-phase alloy was named a “refractory high entropy superalloy” [19].
Despite showing exceptionally good high-temperature properties,
the AlMo0.5NbTa0.5TiZr superalloy has very limited ductility at temper-
atures ≤ 600 °C, which has been explained by the presence of brittle,
coarse intermetallic precipitates at grain boundaries [19,20]. It was
found that these grain-boundary (GB) precipitates have a hexagonal
(P63/mcm) crystal structure and are predominantly composed of Al
and Zr with an overall composition (in at.%) of ~Al37Mo2Nb8Ta2Ti9Zr42
[20]. Based on model γ/γ′ superalloys, an ‘ideal’ microstructure of re-
fractory superalloys would consist of two nanometer-scale, ordered/
disordered coherent phases, one of which is a disordered BCC matrix
and another is ordered B2 precipitates, while the deleterious hexagonal
intermetallic grain-boundary phase is completely removed. In some
cases, heat treatment and/or hot working processing are used to remove
intermetallic particles from grain boundaries, but annealing at
1000–1400 °C and water quenching of AlMo0.5NbTa0.5TiZr revealed
this phase to be stable over a large range of temperatures [20].
In this work, an attempt has been made to remove the coarse, GB in-
termetallic phase, while maintaining the equiaxed grain microstructure
(a)
AlMo0.5NbTa0.5TiZr0.5
Intesity (a.u.)
BCC, a = 326.9 pm
20 40 60 80 100
(c)
Al0.5Mo0.5NbTa0.5TiZr
Intesity (a.u.)
BCC, a = 328.3 pm
20 40 60 80 100
Fig. 1. X-ray diffraction patterns of (a) AlMo0.5NbTa0.5TiZr0.5, (b) AlNbTa0.5TiZr0.5, (c) Al0.5Mo0.5NbTa0.5TiZr, and (d) Al0.25NbTaTiZr.
499
comprised of the nano-scale interpenetrating phases, by adjusting the
composition of the base AlMo0.5NbTa0.5TiZr superalloy. Based on the
large number of intermetallic phases that form in the Al-Zr binary sys-
tem and the large electronegativity difference compared to other con-
stituent elements in the HEA composition, the effects of reducing Al
and Zr on the HEA microstructure were first investigated and character-
ized. In addition, the effect of removing Mo on the alloy phase composi-
tion, strength and ductility was also explored.
2. Experimental procedures
HEA ingots with the compositions AlMo0.5NbTa0.5TiZr (base compo-
sition, alloy #1), AlMo0.5NbTa0.5TiZr0.5 (reduction of Zr by ½ molar ratio,
alloy #2), AlNbTa0.5TiZr0.5 (reduction of Zr by ½ molar ratio and removal
of Mo, alloy #3), Al0.5Mo0.5NbTa0.5TiZr (reduction of Al by ½ molar ratio,
alloy #4), and Al0.25NbTaTiZr (reduction of Al by ¾ molar ratio and re-
placement of Mo with Ta, alloy #5) were prepared by vacuum arc melt-
ing in an inert gas atmosphere. The samples were then hot isostatic
pressed (HIP'd) for 2 h at 1400 °C and 207 MPa to remove any porosity
and annealed in a flowing argon furnace at 1400 °C for 6 h followed by a
furnace cool to room temperature with the initial cooling rate of 20 °C/
min.
A Bruker D2 Phaser X-ray diffractometer, at Cu Kα radiation, was
used to identify the crystal structure of main phases in the alloys. The
microstructure was characterized using scanning electron microscopy
(SEM) and transmission electron microscopy (TEM) techniques. SEM
was equipped with backscattered electron (BSE) and electron backscat-
ter diffraction (EBSD) detectors. BSE and EBSD image processing and
analysis was performed using the Materials Image Processing and Auto-
mated Reconstruction (MIPAR) software package [21].
Samples for TEM analysis were extracted at site specific locations
from the bulk sample using an FEI Helios NanoLab 600 Dual-Beam fo-
cused ion beam (DB-FIB) instrument. The FIB lift-out and thinning pro-
cedures are described elsewhere [18]. The thinned FIB lamellae were
characterized using conventional bright-field (BF) and dark-field (DF)
TEM imaging in an FEI CM200. Scanning transmission electron micros-
copy (STEM) high-angle annular dark-field (HAADF) micrographs
were taken with an FEI Probe-Corrected Titan 80-300 STEM operating
(b)
AlNbTa0.5TiZr0.5
Intesity (a.u.)
BCC, a = 330.6 pm
120 20 40 60 80 100 120
(Degrees)
(d)
Al0.25NbTaTiZr
Intesity (a.u.)
BCC, a = 330.0 pm
120 20 40 60 80 100 120
500 O.N. Senkov et al. / Materials and Design 139 (2018) 498–511

Table 1
Lattice parameters of the BCC phase, a, alloy density, ρ (measured vs. calculated), Vickers micro-hardness, Hv, and room temperature compression properties (Young's modulus, E, yield
stress, σ0.2, fracture stress, σf, and fracture strain, εf) of the studied RHEAs.

Alloy no. Alloy ID a ρ Hv E σ0.2 σf εf

pm g/cm3 GPa GPa MPa MPa %

1 AlMo0.5NbTa0.5TiZr 326.9/330.4 7.4/7.31 5.8 ± 0.1 122 2197 2370 4.1

2 AlMo0.5NbTa0.5TiZr0.5 326.9 7.4/7.32 6.2 ± 0.1 133 – 1320 1.0
3 AlNbTa0.5TiZr0.5 330.6 7.1/7.02 5.0 ± 0.1 124 1352 1357 1.3
4 Al0.5Mo0.5NbTa0.5TiZr 328.3 8.1/7.96 6.4 ± 0.1 132 2350 2460 3.2
5 Al0.25NbTaTiZr 330.0 9.4/9.27 4.9 ± 0.1 118 1745 1830 3.8

at 300 kV and a camera length of 115 mm. The convergence semiangle
of the electron beam was 11.4 mrad and the inner and outer collection
angles of the HAADF detector were 34.8 and 230.0 mrad, respectively.
X-ray energy dispersive spectroscopy (XEDS) was performed using an
FEI Image-Corrected Titan 60-300 STEM equipped with a Super-X™
XEDS detector system. The TEM was operated with an accelerating
voltage of 300 kV and an electron beam convergence semiangle of
25 mrad. Cliff-Lorimer quantification and analysis of Super-X™ XEDS
data was performed using standardless native k-factors in the Bruker
Esprit software.
A Vickers microhardness unit was used to measure room tempera-
ture microhardness. Ten measurements were collected and averaged
for each sample using a 1000 g load applied for 15 s. Room temperature
compression tests were conducted using a servo-hydraulic MTS
machine operating at a constant ram speed of 0.008 mm/s and silicon
carbide dies. A thin (~50 μm) teflon foil was used as a lubricating mate-
rial between the die and sample contacting surfaces. The initial sample
dimensions were 5 mm × 5 mm × 8 mm, giving an initial strain rate of
0.001 s−1. Sample deformation was monitored and synced with the
load output from the test frame using a Video Displacement and
Image Correlation System (Correlated Solutions Inc.), which also pro-
vided a visual record of individual specimen deformation response.
Compression tests at 1000 °C were conducted in a computer-
controlled Instron mechanical testing machine outfitted with a Brew vac-
uum furnace and silicon carbide dies covered by boron-nitride powder to
reduce friction. The specimen dimensions were 5 mm × 5 mm × 8 mm.
Prior to each test, the furnace chamber was evacuated to 10−6 Torr. The
sample was then heated to the test temperature over a period of
~45 min and soaked at 1000 °C for 15 min under 22 N load control, and
then compressed to fracture or to a 55% height reduction, whichever
occurred first, at a constant ram speed of 0.008 mm/s that provided
an initial strain rate of 0.001 s− 1. Load versus frame displacement re-
sponses were registered without specimens and these displacement
values were subtracted from the frame displacements measured
during the specimen compression at every registered load value.
This procedure allowed measurements of deformation of the speci-
mens only and excluded the elastic responses of the dies, machine
frame and load cell.
3. Results and discussion
alloy) retained a single-phase BCC structure, but with an increased lat-
tice parameter a = 330.6 pm (Fig. 1b). According to the X-ray diffrac-
tion analysis, the reduced Al content alloy (Al0.5Mo0.5NbTa0.5TiZr) also
contained a single BCC phase with a lattice parameter a = 323.3 pm
(Fig. 1c), which is the average value of the lattice parameters of the
BCC and B2 phases in the base AlMo0.5NbTa0.5TiZr alloy. Finally, the
alloy with a reduced Al and Mo content replaced with Ta
(Al0.25NbTaTiZr) has a BCC crystal structure with a = 330.0 pm, similar
to the Al, Zr-rich phase in the base alloy.
The alloy density was measured using a helium pycnometer and the
results are given in Table 1. The density values calculated using the rule
of mixtures of pure elements, Eq. (1), are also given in Table 1 for com-
parison.
X X
ρcalc ¼ ci M i = ci V i ð1Þ
In Eq. (1), ci, Mi and Vi are the atomic fraction (taken from Table 2),
atomic mass, and atomic volume of element i, respectively. The mea-
sured density is always higher than the calculated density, which is an
indication that the average atomic volume of the elements in each of
the alloys is smaller than the average atomic volume of the pure ele-
ments, i.e. the elements experience some constraints (shrinkage) in
the studied alloys. The atomic volume reduction is ~1% in these alloys.
The atomic volume reduction is an indication of formation of some
degree of covalency in the bonds between the elements and may also
indicate ordering.
3.2. Microstructure of the annealed alloys
3.2.1. AlMo0.5NbTa0.5TiZr
The microstructure of the base AlMo0.5NbTa0.5TiZr alloy was report-
ed in detail elsewhere [11,12,18,19]. SEM-BSE images show the micro-
structure consisted of equiaxed grains, with low-angle subgrain
boundaries inside the grains and coarse intermetallic particles at grain
Table 2
Chemical composition (in at.%) of the studied alloys and phases in these alloys determined
using SEM/EDS analysis.
Alloy constituent Al Mo Nb Ta Ti Zr

3.1. X-ray diffraction analysis and alloy density AlMo0.5NbTa0.5TiZr

Alloy 17.6 10.1 21.1 10.6 20.9 19.7
Grains 16.7 11.1 21.7 11.0 22.9 16.6
X-ray diffraction (XRD) patterns of the four modified alloys after HIP GB particles 36.6 2.5 8.1 2.5 8.6 41.7
and annealing at 1400 °C are given in Fig. 1. The diffraction peaks in
AlMo0.5NbTa0.5TiZr0.5
these alloys correspond to a single-phase BCC crystal structure, with Alloy 20.7 12.7 22.3 13.6 20.2 10.4
the lattice parameter changing with composition (Table 1). XRD of the Grains 20.6 12.3 22.9 13.3 22.5 8.4
base AlMo0.5NbTa0.5TiZr alloy conducted in previous work clearly GB particles 37.7 1.2 12.2 3.6 9.9 35.3
showed the presence of two BCC phases [11,19]. Detailed TEM and AlNbTa0.5TiZr0.5
APT phase analysis in AlMo0.5NbTa0.5TiZr revealed that one is a disor- Alloy 25.8 0 24.8 13.5 24.1 11.8
dered BCC (A2) phase enriched with Nb and Ta with the lattice param-
Al0.5Mo0.5NbTa0.5TiZr
eter a = 326.9 pm, and another is an ordered B2 phase enriched with Al Alloy 9.8 11.2 24.5 13.6 21.4 19.5
and Zr with a = 330.4 pm [18,19]. Reducing the amount of Zr in the
AlMo0.5NbTa0.5TiZr0.5 alloy resulted in a single BCC crystal structure Al0.25NbTaTiZr
Alloy 5.0 0 26.0 28.9 21.1 19.0
with a = 326.9 pm (Fig. 1a). Additional removal of Mo (AlNbTa0.5TiZr0.5
 O.N. Senkov et al. / Materials and Design 139 (2018) 498–511 501

Fig. 2. AlMo0.5NbTa0.5TiZr: (a) Low-magnification SEM BSE micrograph showing grains, a subgrain structure inside the grains and dark intermetallic particles at grain boundaries. (b) High
magnification BSE image revealing a two-phase, basket-weave nano-lamellar structure inside the grains.

boundaries (GBs) (Fig. 2a). The chemical composition of the alloy, ma-
trix grains and GB particles is given in Table 2. The GB particles are
rich in Al and Zr while the matrix grains are slightly depleted with
these elements, relative to the alloy composition. The volume fraction
of the GB particles was estimated to be ~6–12%, depending on the loca-
tion in the alloy. A detailed analysis using converged beam electron dif-
fraction (CBED) revealed that the GB intermetallic particles have an
ordered hexagonal crystal structure (space group P63/mcm) [20]. A
very fine, basket-weave nano-lamellar structure was identified at high
magnifications inside the grains (Fig. 2b). It consists of continuous chan-
nels of an ordered B2 phase and cuboidal and/or plate-like disordered
A2 (BCC) phase between the channels (Fig. 3). These phases are coher-
ent with each other and exhibit continuous lattice registry with a cube-
on-cube orientation relationship described by 〈100〉BCC//〈100〉B2,
{001}BCC//{001}B2 [18]. The precipitate dimensions in two orthogonal
directions parallel to the precipitate edges vary from ~ 10 to ~ 55 nm
and from ~25 to ~55 nm, respectively. The width of the B2 channels is
~ 7.0 ± 1.0 nm. The volume fraction of the disordered BCC phase was
estimated to be 62 ± 2% [19].
3.2.2. AlMo0.5NbTa0.5TiZr0.5
SEM-BSE micrographs of the annealed AlMo0.5NbTa0.5TiZr0.5 alloy
are shown in Fig. 4. The low magnification microstructure looks similar
to that from the base alloy, AlMo0.5NbTa0.5TiZr. It consists of equiaxed
grains and dark-contrast second-phase GB particles (Fig. 4a). However,
unlike AlMo0.5NbTa0.5TiZ, the higher magnification BSE images do not
show contrast modulations inside the grains (Fig. 4b), suggesting that
the matrix grains are likely single-phase. XEDS analysis reveals that
the GB particles have high concentrations of Al and Zr and their compo-
sition is similar to the GB particles in the base alloy (Table 2). The com-
position of the grains is only slightly different from the composition of
the alloy.
A STEM-HAADF micrograph taken from the interface between a
darker contrast GB precipitate phase and a lighter contrast intragranular
(matrix) phase is shown in Fig. 5. The intragranular region is a single
phase. A selected area diffraction analysis revealed that this phase has
an ordered B2 crystal structure. For example, the (100) super-lattice re-
flections indicating ordering are clearly seen in the [001] zone axis of the
B2 (intragranular) phase (inset in Fig. 5). A low-angle boundary
consisting of an array of dislocation can also be seen inside the matrix
grain in Fig. 5.
Super-X™ XEDS composition maps were acquired from the region of
the AlMo0.5NbTa0.5TiZr0.5 thinned foil indicated by the HAADF micro-
graph in Fig. 5. The XEDS spectra were only used to describe general
trends in composition. As shown in the elemental maps, Fig. 6, the GB
particle has a higher concentration of Al and Zr and reduced

Fig. 3. STEM-HAADF images of the nano-phase structure present inside the grains of AlMo0.5NbTa0.5TiZr. (a) Cuboidal and plate-like precipitates of a disordered BCC phase are separated by
continuous channels of an ordered B2 phase. (b) The fast Fourier transforms (shown inside the red squares) reveal an ordered B2 structure for the dark channels and a disordered A2 (BCC)
structure for the cuboidal precipitates.
502 O.N. Senkov et al. / Materials and Design 139 (2018) 498–511
Fig. 4. AlMo0.5NbTa0.5TiZr0.5: (a) Low-magnification BSE micrograph showing grains and dark intermetallic particles at grain boundaries. (b) High magnification BSE image revealing a
single-phase structure inside the grains.
concentrations of other elements relative to the matrix (B2) phase,
which is in agreement with SEM/EDS (Table 2). The regions on both
sides of a subgrain boundary inside the matrix show the same composi-
tion as the matrix phase, further indicating a single B2 phase matrix
microstructure.
3.2.3. AlNbTa0.5TiZr0.5
SEM BSE images of annealed AlNbTa0.5TiZr0.5 are shown in Fig. 7. Low
magnification micrographs of this Mo-free alloy reveal a coarse-grained
(mm size scale), equiaxed single-phase microstructure and complete
absence of coarse GB precipitates typical in AlMo0.5NbTa0.5TiZr and
AlMo0.5NbTa0.5TiZr0.5 RHEAs (Fig. 7a). Higher magnification micro-
graphs show no evidence of the modulated two-phase structure inside
the equiaxed grains. Fig. 7b shows a triple point and grain boundaries be-
tween three large grains. A dark contrast phase with a thin, serrated
morphology is present uniformly along the grain boundaries. The dark
contrast and jaggedness of the grain boundary look similar to inter-
granular cracks. However, a TEM FIB sample extracted and thinned
along a similar grain boundary verified that the contrast was caused by
Fig. 5. AlMo0.5NbTa0.5TiZr0.5: STEM-HAADF image acquired along the [001] zone axis of
the intragranular B2 phase bordering an ordered intermetallic GB particle. The selected
area diffraction pattern (SADP) shown in the insert was taken from the area indicated
by the arrow.
a second phase with a lower average atomic number, and no voids or
inter-granular cracks were detected along GBs.
A STEM-HAADF micrograph of a GB region showing two adjacent
matrix grains and a darker contrast, second phase along the GB in
shown in Fig. 8. The matrix grains are single phase with an ordered B2
crystal structure, based on the inset selected area diffraction pattern of
a [001] zone axis of the B2 phase. Element ordering is revealed by the
presence of faint (100) super-lattice reflections. XEDS composition
maps from the same region are also shown in Fig. 8. Qualitatively, the
darker contrast GB phase was rich in Al and Zr compared with the B2
intra-granular phase. The overall composition of the GB phase in this
modified alloy is similar to the composition of the ordered hexagonal
phase in the base alloy. This Al-Zr intermetallic is surrounded by a re-
gion deficient in Al and Zr and higher in Ta, which appears as a bright-
contrast layer in the HAADF images. Despite the reduction in Zr and
Mo concentration, the microstructure still contains a thin layer of the
secondary intermetallic Al-Zr phase along high-angle grain boundaries.
3.2.4. Al0.5Mo0.5NbTa0.5TiZr
The effect on the microstructure by reducing Al was very different
from reducing Zr. SEM BSE micrographs of Al0.5Mo0.5NbTa0.5TiZr (Al
was decreased by half relative to the base alloy) are shown in Fig. 9.
The low magnification BSE image shows an equiaxed grain microstruc-
ture with needle-like features inside the grains (Fig. 9a). A lamellar
eutectic-like two-phase microstructure is present along high- and
low-angle GBs (Fig. 9b). High magnification images of the grain interior
revealed an orthogonally aligned nanoscale microstructure of two dis-
tinct phases (Fig. 9c), nearly identical to the base alloy nanoscale micro-
structure. Subgrain boundaries within the equiaxed grains are also
present and look similar to those in the AlMo0.5NbTa0.5TiZr base alloy.
The needle-like features inside grains consist of three phases with dis-
tinct Z contrasts (Fig. 9d). The core of the needles consists of a bristle
of a dark phase surrounded by a bright phase. This core is surrounded
by another dark phase, which also contains fine spherical bright parti-
cles at the boundary with the matrix (Fig. 9d). XEDS chemical analysis
of the bright- and dark- contrast phases inside the needle-like features
and at grain/subgrain boundaries (i.e. in the locations containing coarse
particles of these phases) shows that the bright phase is enriched in Mo,
Nb and Ta, while the dark phase is rich in Al and Zr. The dark core bristle
is heavily rich in Zr.
STEM-HAADF micrographs of Al0.5Mo0.5NbTa0.5TiZr are shown in
Fig. 10. An edge of a needle-like precipitate surrounded by the two-
phase nanoscale microstructure is seen at the top of Fig. 10a. The nano-
scale microstructure consists of a higher average atomic number phase
of rounded cuboidal precipitates aligned along 〈100〉 orientations in a
lower average atomic number continuous matrix (Fig. 10b). The inset
SADP shows (100) superlattice reflections indicating sublattice ordering
in at least one of the nanoscale phases. The nanoscale precipitate phase
 O.N. Senkov et al. / Materials and Design 139 (2018) 498–511 503

Fig. 6. Super-X™ XEDS compositional maps acquired at the boundary between the intermetallic precipitate and the intragranular phase in annealed AlMo0.5NbTa0.5TiZr0.5.

was of the same size scale of the disordered BCC cuboidal precipitates in
the base alloy microstructure but was not as periodic, and only a single
precipitate morphology was present.
XEDS elemental maps acquired near the needle-like precipitate are
shown in Fig. 11. The lighter contrast phase (Fig. 10) has a composition
higher in Mo, Nb, and Ta compared to the darker contrast matrix phase
rich in Al and Zr. The partitioning of elements in the nanoscale phases is
similar to the as-received base alloy microstructure in which BCC pre-
cipitates (rich in Mo, Nb, and Ta) are present in a continuous B2 matrix
(rich in Al and Zr). Bright-field and dark-field micrographs of the nano-
scale microstructure revealed that, in similar fashion to the base RHEA,
the precipitate phase is a disordered solid solution A2 (BCC) phase
while the continuous matrix is an ordered B2 phase. The phases in the
needle-like precipitate (at the top and in the center of the XEDS scan)
have the same composition as the nano-scale intra-granular phases,
with the exception of the acicular feature in the center, which has a
high concentration of Zr (Fig. 11). It is possible that bristles of almost
pure Zr precipitated inside grains in the annealed alloy, which are nuclei
for the formation of the needle-like two-phase precipitates.
3.2.5. Al0.25NbTaTiZr
The Al0.25NbTaTiZr RHEA has even less Al than the previous alloy and
all Mo is replaced with Ta. SEM/BSE micrographs of this alloy are shown
in Fig. 12. The lower magnification BSE images reveal a microstructure
consisting of equiaxed grains and a well-developed subgrain structure
inside the grains (Fig. 12a). No coarse GB particles are present. Higher
magnification micrographs show a two-phase nanoscale interpen-
etrating microstructure, with the two phases coarsened at grain/
subgrain boundaries (Fig. 12b), similar to the base alloy.
A STEM-HAADF micrograph of a thin foil, which was extracted from
a grain interior by FIB, is shown in Fig. 13. The nanoscale microstructure
consists of brighter contrast cuboidal and plate-like precipitates in a
darker contrast continuous matrix. The lighter contrast precipitates co-
alesce together to form larger structures but remain aligned along cube
face directions. Complimentary BF and DF micrographs were acquired
with the electron beam parallel to the [001] zone axis of the nanoscale
microstructure and are shown in Fig. 14. The inset [001] SADP taken
with a large selected area aperture over both phases is consistent with
a BCC crystal structure. The contrast observed in the dark-field micro-
graph indicates that the continuous channels of the matrix phase are
an ordered B2 structure while the cuboidal precipitates are a disordered
BCC solid solution phase. While the morphology of the BCC precipitates
is slightly different from the periodic plate and cube structure in the
base RHEA composition, the phases present in the nanoscale micro-
structure are the same. A region of the nanoscale microstructure and
grain boundary was compositionally mapped using Super-X™ TEM

Fig. 7. SEM BSE micrographs of AlNbTa0.5TiZr0.5 showing (a) equiaxed grain structure and (b) a secondary phase present at grain boundaries.
504 O.N. Senkov et al. / Materials and Design 139 (2018) 498–511

Fig. 8. STEM-HAADF micrograph of grain boundary precipitates between two B2 phase regions with associated SADP taken from the area indicated by the arrow (HAADF) and super-X™
XEDS compositional maps acquired across a high angle grain boundary in annealed AlNbTa0.5TiZr0.5.

XEDS. Similar to the nanoscale microstructure of the base alloy, the or-
dered continuous matrix is rich in Al and Zr while the disordered precip-
itate phase has a higher concentration of Nb and Ta (no Mo in this
modified composition). The coarser precipitates at subgrain/grain
boundaries, similar to those shown in Fig. 12b, have the same composi-
tion and the BCC and B2 crystal structures as in the respective intra-
granular nanoscale phases.
3.3. Mechanical properties
3.3.1. Hardness and compression properties at room temperature
Room temperature Vickers hardness and compression properties of
the alloys are given in Table 1 and typical stress-strain curves are
shown in Fig. 15a. The base AlMo0.5NbTa0.5TiZr alloy has rather high
hardness (Hv = 5.8 GPa), yield (σ0.2 = 2197 MPa) and fracture stress

Fig. 9. BSE images of Al0.5Mo0.5NbTa0.5TiZr showing (a) equiaxed grains with needle-like precipitates inside the grains, (b) eutectic-like microstructure at grain/subgrain boundaries,
(c) nanoscale interpenetrating two phase microstructure and a low-angle boundary, and (d) a needle-like particle.
 O.N. Senkov et al. / Materials and Design 139 (2018) 498–511 505

Fig. 10. STEM-HAADF micrographs of the Al0.5Mo0.5NbTa0.5TiZr alloy showing the two phase nanoscale microstructure along with (a) a coalesced precipitate and (b) an inset SADP
acquired from the two phase region.

(σf = 2370 MPa), but relatively low fracture strain (εf = 4.1%). A de-
crease in the amount of Zr (AlMo0.5NbTa0.5TiZr0.5) increases Hv to
6.2 GPa but makes the alloy brittle and fracture occurs during elastic
loading at a relatively low fracture stress (σf = 1320 MPa, Table 1). An
additional removal of Mo (AlNbTa0.5TiZr0.5) slightly improves compres-
sion ductility, but this alloy has low σ0.2 = 1352, σf = 1357 MPa and
Hv = 5.0 GPa. A decrease in the amount of Al in Al0.5Mo0.5NbTa0.5TiZr
RHEA slightly decreases the compression ductility (εf = 3.2%) but no-
ticeably increases σ0.2 (= 2350 MPa), σf (= 2460 MPa) and Hv
(=6.4 GPa) relative to the base alloy. Finally, Al0.25NbTaTiZr, which has
even lower Al and completely replaced Mo with Ta, drops σ0.2 to
1745 MPa, σf to 1830 MPa and Hv to 4.9 GPa, while having εf = 3.8%.
The Young's modulus E is highest (≈132–133 GPa) for
AlMo0.5NbTa0.5TiZr0.5 and Al0.5Mo0.5NbTa0.5TiZr RHEAs. These are about
10 GPa higher than the Young's modulus of the base, AlMo0.5NbTa0.5TiZr,
alloy. Alloys without Mo (AlNbTa0.5TiZr0.5 and Al0.25NbTaTiZr) have re-
duced Young's moduli of 124 GPa and 118 GPa, respectively (Table 1).
These results indicate that Al and Zr reductions strengthen the alloys
while Mo reductions soften the alloys considerably. Therefore, the room
temperature strength of the base alloy can be improved by increasing
the amount of Mo and/or by decreasing the amount of Al. The results
also show that a decrease in Zr makes the alloy more brittle. This simple
analysis does not address the influence of compositional changes on mi-
crostructure, which will be considered in the Discussion.
3.3.2. Compression properties at 1000 °C
During compression deformation at 1000 °C all five RHEAs had good
ductility and showed no evidence of fracture when deformation
stopped upon reaching a compression strain of 55%. Typical engineering
stress vs. engineering strain curves for these alloys are shown in Fig. 15b
and the characteristic properties are given in Table 3. After plastic yield-
ing, all the alloys show a rapid stress increase to a peak value (σp)
followed by a flow softening stage. This flow softening stage switched
to a steady-state stage with a nearly constant flow stress in the

Fig. 11. XEDS compositional maps acquired at a lamellar precipitate surrounded by a two phase nanoscale microstructure in Al0.5Mo0.5NbTa0.5TiZr.
506 O.N. Senkov et al. / Materials and Design 139 (2018) 498–511
Fig. 12. BSE images of Al0.25NbTaTiZr showing (a) equiaxed grains and low-angle grain boundaries inside the grains and (b) a two phase interpenetrating nanoscale microstructure inside
the grains and coarser particles at a subgrain boundary.
AlMo0.5NbTa0.5TiZr and AlMo0.5NbTa0.5TiZr0.5 alloys, or replaced by a
hardening stage in the AlNbTa0.5TiZr0.5 alloy, or continued up to about
30% compression strain in the Al0.5Mo0.5NbTa0.5TiZr and Al0.25NbTaTiZr
alloys (Fig. 15b). A stress increase after ~ 30% compression strain, ob-
served in all samples, was due to friction between the contact surfaces
of the specimens and the dies.
The AlMo0.5NbTa0.5TiZr0.5 RHEA (with a reduced amount of Zr) was
the strongest one at 1000 °C, having σ0.2 = 935 MPa and σp =
1019 MPa. This alloy also showed a steady-state flow, with the steady-
state flow stress of ~910 MPa. These stress values are noticeably higher
than those shown by the base alloy. Additional removal of Mo resulted
in a significant decrease in σ0.2 to 535 MPa and σp to 542 MPa in the
AlNbTa0.5TiZr0.5 RHEA. The Al0.5Mo0.5NbTa0.5TiZr alloy (with a reduced
amount of Al) has σ0.2 = 579 MPa and σp = 646 MPa. The
Al0.25NbTaTiZr RHEA, which has even less Al and no Mo, shows the
smallest strength at 1000 °C: σ0.2 = 366 MPa, σp = 408 MPa. After
reaching the peak stress at εp ≈ 1.6–2.0% these two alloys started losing
strength continuously, and after 20% compression strain they had a flow
stress σ20 = 312 MPa and 162 MPa, respectively. It can be clearly seen
that Mo has a strong strengthening effect in these RCCAs. The presence
of Al is likely also beneficial for the high-temperature strength, while Zr
has an opposite effect.
Fig. 13. STEM-HAADF micrograph of Al0.25NbTaTiZr showing a nanoscale two phase
microstructure.
3.3.3. Microstructure after compression deformation at 1000 °C
After 55% compression deformation at 1000 °C, grains retained near-
equiaxed shapes and their average size was almost the same as before
deformation (Figs. 16–19). Characteristic electron channeling contrast
features in the form of bands, spots and/or protrusions were found on
the BSE images of many deformed grains (e.g. Figs. 16a–b, 17a, 18a,
19a). These channeling contrast features reveal the presence of internal
stresses and local rotations of the crystal lattice inside the deformed
grains [22]. The matrix grains in alloys with reduced Zr retain their
single-phase B2 structure (Fig. 16b). A few former GB precipitates in
the AlMo0.5NbTa0.5TiZr0.5 alloy are located inside the grains (Fig. 16a),
which could indicate a high mobility of grain boundaries and their
unpinning from GB particles during deformation at 1000 °C.
Submicron-sized, dynamically recrystallized grains are present at the
boundaries of deformed grains in the AlNbTa0.5TiZr0.5 alloy (Fig. 17b).
Dynamic recrystallization broke up a continuous layer of the Al-Zr rich
phase observed at grain boundaries before deformation (Fig. 7b). After
deformation, this secondary phase is present in the form of fine, individ-
ual particles mixed with the recrystallized grains (Fig. 17b).
The alloys with reduced Al (Al0.5Mo0.5NbTa0.5TiZr and
Al0.25NbTaTiZr) retained their two-phase nano-structure inside grains
(Figs. 18 and 19). However, in both the alloys the nano-scale precipi-
tates coarsened during deformation and the BCC phase (bright in the
BSE images) became continuous, while formerly continuous B2
channels broke into separate elongated particles (Figs. 18d and 19c).
No noticeable coarsening of the needle-like features common to the
annealed Al0.5Mo0.5NbTa0.5TiZr alloy (see Fig. 9) occurred during defor-
mation at 1000 °C, they became hardly visible on the low-magnification
images (Fig. 18a) but could be identified at high magnifications as long
chains of elongated B2 particles covered by a layer of the BCC phase
(Fig. 18c).
3.4. Discussion
3.4.1. Alloys with a reduced amount of Zr
The results of this work show that a ½ decrease in the molar ratio of
Zr relative to the base alloy does not remove the hexagonal GB phase
from the RHEA microstructure. Moreover, the average particle size
and the volume fraction of this phase are not affected. However, the
nano-scale disordered BCC precipitates disappear and the matrix grains
have an ordered single-phase B2 crystal structure. The B2 phase has a
composition close to the overall composition of the modified alloy
(AlMo0.5NbTa0.5TiZr0.5). The fully ordered state explains the lack of
ductility of this alloy at room temperature and the highest plastic flow
stress among the studied alloys at 1000 °C (see Fig. 15).
When Mo is additionally removed (AlNbTa0.5TiZr0.5), the coarse GB
particles disappear and are replaced by a thin, continuous GB layer of
 O.N. Senkov et al. / Materials and Design 139 (2018) 498–511
Fig. 14. TEM (a) BF and (b) DF images of a nano-phase structure of Al0.25NbTaTiZr acquired with the transmitted and (100) superlattice reflection, respectively, as indicated by the circles in
the SADP insets.
the ordered hexagonal phase. This Mo-free alloy is essentially a single-
phase ordered B2 crystal structure. Mo is present in the hexagonal GB
phase in a very small amount and removing this element from the
alloy was not expected to affect the nature of the GB phase. Mo may fa-
cilitate formation of the GB particles by restricting solubility of Al in the
matrix phase. When Mo is removed, the solubility of Al in the B2 phase
may increase, leaving no extra Al to form the coarse (Al, Zr)-rich GB par-
ticles. However, the amount of Al in AlNbTa0.5TiZr0.5 alloy probably still
exceeds the maximum solubility, which results in the formation of a
thin, Al-Zr-rich layer at grain boundaries. The removal of Mo slightly im-
proves ductility of this alloy (relative to the completely brittle
AlMo0.5NbTa0.5TiZr0.5) at room temperature, which may indicate that
the coarse GB particles do deteriorate RT ductility. The removal of Mo
also considerably decreases the plastic flow stress at 1000 °C, indicating
that Mo is a strong solid solution strengthening element in this alloy
system.
3.4.2. Alloys with a reduced amount of Al
Reducing the amount of Al in Al0.5Mo0.5NbTa0.5TiZr and
Al0.25NbTaTiZr RHEAs is much more effective for removing the ordered
hexagonal GB phase. This phase is absent in both of the Al-lean alloys,
supporting our earlier suggestion that excessive Al is likely responsible
for the formation of this GB phase. Similar to the base alloy, those
with the reduced Al consist of two coherent phases: an ordered (Al
and Zr rich) B2 matrix and a disordered (Nb, and Ta rich) BCC phase
with spherical (in Al0.5Mo0.5NbTa0.5TiZr) or cuboidal (in Al0.25NbTaTiZr)
(a)
2500
#4
Engineering Stress (MPa)
#1
2000
1500 #2 #5
#3
1000
500
T = 25 oC
0 0
0 1 2 3 4 5
Engineering Strain (%)
Fig. 15. Engineering stress vs. engineering strain curves obtained during (a) room temperature (T = 25 °C) and (b) elevated temperature (T = 1000 °C) compression testing of
AlMo0.5NbTa0.5TiZr (alloy #1), AlMo0.5NbTa0.5TiZr0.5 (#2), AlNbTa0.5TiZr0.5 (#3), Al0.5Mo0.5NbTa0.5TiZr (#4) and Al0.25NbTaTiZr (#5).
507
nano-scale morphologies. Additionally, Al0.5Mo0.5NbTa0.5TiZr RHEA
contains needle-like features that are evenly distributed in the alloy.
These features consist of coarser BCC lamellae nucleated on Zr-rich bris-
tles. This indicates that reducing Al in Al0.5Mo0.5NbTa0.5TiZr produces Zr
supersaturation and forms Zr-rich bristles in a BCC solid solution phase
present at high temperatures. These bristles become nucleation sites for
a lower-temperature, Mo-Nb-Ta-rich BCC phase leading to local coars-
ening relative to homogeneously nucleated nano-scale particles in
other regions. After substituting Mo with Ta and an additional Al de-
crease in the Al0.25NbTaTiZr RHEA, Zr-rich bristles do not form and the
needle-like features disappear. This RHEA has the most homogeneous
and refined microstructure among the five studied alloys. This suggests
that Mo reduces the solubility of not only Al but also Zr in the high-
temperature BCC phase. Both the Al0.5Mo0.5NbTa0.5TiZr and
Al0.25NbTaTiZr RHEAs have high strength and some ductility at room
temperature, although substitution of Mo with Ta decreases the RT
strength by ~ 600 MPa and the 1000 °C strength by ~ 150–200 MPa.
The most dramatic effect from decreasing the amount of Al (and Mo re-
moval) is observed during compression testing at 1000 °C. These alloys
soften continuously after reaching the peak stress at the beginning of
plastic deformation, and the flow stress drops by ~50% after 20% plastic
strain. The flow softening is likely due to coarsening and coalescence of
the BCC nano-scale particles (compare Fig. 18 with Fig. 9 and Fig. 19
with Fig. 12). As a result, these BCC nano-particles transform to a contin-
uous matrix phase, while the formerly continuous channels of the or-
dered B2 phase fragment and become embedded inside the BCC
(b)
1200
T = 1000oC
#2
Engineering Stress (MPa)
1000
800 #1
600 #3
#4
400
200
#5
0 10 20 30 40 50 60
Engineering Strain (%)
508 O.N. Senkov et al. / Materials and Design 139 (2018) 498–511
Table 3
Compression properties of the compositionally modified RHEAs at 1000 °C (Young's mod-
ulus, E, yield stress, σ0.2, peak stress, σp, peak strain at peak stress, εp, stress at 10% strain,
σ10, and stress at 20% strain, σ20).
Alloy no. Alloy ID E σ0.2 σp
GPa MPa MPa
1 AlMo0.5NbTa0.5TiZr [11] 70 745 792
2 AlMo0.5NbTa0.5TiZr0.5 76 935 1019
3 AlNbTa0.5TiZr0.5 53 535 542
4 Al0.5Mo0.5NbTa0.5TiZr 78 579 646
5 Al0.25NbTaTiZr 63 366 408
matrix (see Figs. 18d and 19c). Eventually, the microstructure contain-
ing the continuous disordered BCC matrix is softer and more ductile
than that with continuous ordered B2 matrix phase.
3.4.3. The mechanism of formation of nanometer-scaled B2/BCC
microstructure
The mechanism of formation of the coherent, two-phase nano-
scaled microstructure inside the matrix grains of this refractory alloy
system has not been well understood [12,18,19]. Results of the present
work suggest that Zr is somehow responsible for the formation of this
two-phase nano- structure. Decreasing the concentration of this ele-
ment suppresses the phase separation resulting in an ordered single-
phase B2 crystal structure. On the other hand, Al does not seem to
play important role in the phase separation, although its presence is
likely responsible for the formation of the ordered B2 phase [23,24].
The refractory elements Mo, Nb and Ta are completely miscible in
both liquid and solid states, and in the solid state they form continuous
BCC solid solutions [25]. Ti also forms continuous BCC solid solutions
with these three refractory elements at high temperatures, but a two-
phase range, BCC + HCP, can be present below 880 °C with the refracto-
ry elements suppressing the HCP solvus temperature. In the Ti-Zr sys-
tem, a continuous BCC solid solution region is present at high
temperatures and an HCP solid solution region is present at lower tem-
peratures. Zr forms continuous BCC solid solutions with Nb and Ta at
high temperatures. At lower temperatures, a two-phase, BCC + HCP re-
gion is present at the concentrations of Nb and Ta below 19% and. 6.5%,
respectively. At higher Nb and Ta concentrations, i.e. 19–92.2% Nb or
6.5–91% Ta, a miscibility gap is present in the temperature range of
620–977 °C in Nb-Zr or 800–1760 °C in Ta-Zr systems, where the
high-temperature BCC phase separates in two BCC phases, one of
which is rich with Nb or Ta and another with Zr [25]. Finally, both Nb-
Zr and Ta-Zr experience eutectoid reactions (at 620 °C or 800 °C, respec-
tively) during which the Zr-rich BCC phase transforms to Zr-rich HCP
and Nb- or Ta-rich BCC phases. In the Mo-Zr system, Zr has the maxi-
mum solubility of ~10% in BCC-Mo and Mo has a maximum solubility
of ~41% in BCC-Zr. Beyond these solubility limits, a Laves Mo2Zr phase
Fig. 16. Microstructure of AlMo0.5NbTa0.5TiZr0.5 after 55% compression at 1000 °C.
forms, while Zr-rich alloys also experience an eutectoid transformation
BCC → HCP + Laves at 738 °C [25].
Al forms numerous binary intermetallic compounds with all the ele-
ments in the studied alloy systems; however, none of these binary com-
εp σ10 σ20 pounds has an ordered B2 crystal structure. B2 ordering has, however,
% MPa MPa
been observed in ternary or higher order Al-Ti-X and Al-Zr-X systems,
1.9 735 727 where X is Mo, Nb, Ta or the combination of these elements [26–28].
2.0 907 912
Using this information on phase relationships, it is suggested that
1.4 433 483
2.0 461 312 Nb, Ta and Zr are responsible for the formation of the two-phase,
1.6 288 162 nano-scale microstructure inside the matrix grains. The matrix grains
represent a high-temperature BCC phase, which, during cooling, sepa-
rates into two BCC phases due to the presence of the miscibility gap.
One phase is rich in Nb and Ta and another phase is rich in Zr. Ti
seems to be neutral in this reaction and is distributed almost evenly be-
tween these two phases. Mo prefers the Nb and Ta rich phase due to its
complete solubility with these elements. On the other hand, Al prefers
the Zr-rich BCC phase due to a higher solubility and the highest negative
enthalpy of mixing between Al and Zr, relative to those with other
alloying elements [29]. The presence of Nb and Ta in the Al-Zr rich
BCC phase allows the disorder-order transformation (BCC → B2) during
cooling, without formation of other Al-containing phases. It is likely that
a decrease in the amount of Al in the Al0.5Mo0.5NbTa0.5TiZr and
Al0.25NbTaTiZr RHEAs decreases the disorder-order transformation
temperature below 1000 °C, which explains the reduced strength and
noticeable deformation softening in these Al lean alloys during defor-
mation at 1000 °C. A decrease in the amount of Zr moves the alloy com-
position outside the miscibility gap and the Zr-rich BCC phase does not
form. In this case, the interaction of Al with other elements in the high-
temperature BCC phase results in ordering and complete transforma-
tion of this phase in the ordered B2 phase upon cooling. It is likely that
ordering in this case occurs at temperatures above 1000 °C, because
these Zr-lean alloys show high strength, no softening and no evidence
of the phase transformations during deformation at 1000 °C.
3.4.4. Mechanical properties
Single-phase B2 RHEAs show the highest (AlMo0.5NbTa0.5TiZr0.5)
and next-to-lowest (AlNbTa0.5TiZr0.5) yield strengths at 1000C, suggest-
ing that this phase can be intrinsically strong at high temperatures, and
that solid solution hardening (Mo-induced in this case) plays a signifi-
cant role. However, these are the most brittle alloys and show essential-
ly no plastic deformation in room temperature compression. The B2
phase typically deforms either by ½ 〈111〉 or by 〈100〉 dislocations.
The former provides 5 independent strains needed for plasticity in poly-
crystalline materials and the latter do not. The present results suggest
that the B2 phase studied here may deform by 〈100〉 dislocations at
room temperature. However, some B2 compounds that deform by ½
〈111〉 slip can still be brittle [30], and so TEM studies are required
to determine which type of dislocations operate in these RHEAs.
 O.N. Senkov et al. / Materials and Design 139 (2018) 498–511 509

Fig. 17. Microstructure of AlNbTa0.5TiZr0.5 after 55% compression at 1000 °C: (a) heavily deformed grains and (b) dynamically recrystallized grains and second-phase particles (dark) at a
grain boundary.

The two-phase intragranular microstructure in the base
AlMo0.5NbTa0.5TiZr RHEA and in the Al-lean alloys Al0.5Mo0.5NbTa0.5TiZr
and Al0.25NbTaTiZr can be thought of as analogous to the γ/γ′ microstruc-
ture in superalloys. In those microstructures, a relatively soft and ductile
disordered FCC continuous phase (γ) surrounds nanometer-sized, coher-
ent precipitates of the ordered FCC Ni3Al intermetallic phase. It might
therefore be expected that the BCC/B2 (or β/β′) microstructures in
these three alloys may have potential to provide a balance of strength
and ductility. Supporting this view, these alloys have the highest com-
pressive strengths at room temperature and the base alloy is the second
strongest at 1000 °C. However, the present microstructures are reversed
from the γ/γ′ stereotype – the strong but brittle B2 phase is continuous
and the disordered BCC precipitates are discontinuous. This may explain
the poor room temperature ductility of these alloys. The BCC phase does
become continuous during deformation at 1000 °C. This transition is
accompanied by extensive compressive ductility and a continuous drop
in flow stress, which could result from the rather high volume fraction
of the BCC phase (see Fig. 18d). These results also indicate that the low
ductility B2/BCC structure can be transformed in a more ductile BCC/B2
structure by extensive hot working, such as forging and/or rolling. The
concept of designing a BCC/B2 analog to the γ/γ′ microstructure of
superalloys thus requires further study to provide a balance of room
temperature ductility and high temperature strength.
4. Summary and conclusions
Compositional adjustments of the base AlMo0.5NbTa0.5TiZr refractory
high entropy superalloy were made to improve mechanical properties

Fig. 18. Microstructure of Al0.5Mo0.5NbTa0.5TiZr after 55% compression at 1000 °C: (a) Equiaxed grain structure, (b) subgrain and nano-phase structures inside a grain, (c) needle-like
features consisting of a B2 core and a BCC shell and (d) a high magnification image illustrating that the BCC phase (bright) is a matrix phase and the B2 phase is discontinuous after
the compression deformation.
510 O.N. Senkov et al. / Materials and Design 139 (2018) 498–511
Fig. 19. Microstructure of Al0.25NbTaTiZr after 55% compression at 1000 °C: (a) Equiaxed grain structure, (b) a junction of three grains, (c) nano-phase structures inside a grain.
by modifying the phase content and microstructure. For this, four new
alloys were produced by reducing the amounts of Zr, Al and/or Mo.
These are AlMo0.5NbTa0.5TiZr0.5, AlNbTa0.5TiZr0.5, Al0.5Mo0.5NbTa0.5TiZr
and Al0.25NbTaTiZr. The microstructure, microhardness and compression
properties of the cast alloys were studied in a 1400 °C annealed
condition.
The microstructure of the base AlMo0.5NbTa0.5TiZr RHEA consists of
equiaxed grains of an ordered B2 matrix phase, coherent, nanometer-
sized precipitates of a disordered BCC phase (~60% by volume) inside
the grains and coarse particles (~10%) of an ordered hexagonal phase
at GBs. The alloy has Hv = 5.8 GPa, σ0.2 = 2197 MPa, εf = 4% at 25 °C
and σ0.2 = 735 MPa, εf N 55% at 1000 °C.
Reducing Zr eliminates the BCC phase in AlMo 0.5NbTa0.5TiZr0.5
and additional removal of Mo also eliminates the ordered hexago-
nal phase in AlNbTa0.5 TiZr 0.5 , making the latter RHEA a single-
phase B2 structure. Both alloys are brittle (εf b 1.5%) at 25 °C and
ductile (εf N 55%) at 1000 °C. AlMo0.5NbTa0.5TiZr0.5 has exception-
ally high strength (σ 0.2 = 935 MPa) at 1000 °C. Removing Mo
decreases the 1000 °C strength by 400 MPa (σ0.2 = 535 MPa) in
AlNbTa0.5TiZr0.5.
Decreasing Al produces a two-phase Al0.5Mo0.5NbTa0.5TiZr
consisting of the ordered B2 matrix and coherent nano-meter-sized
spherical BCC precipitates. A further decrease in Al and replacement of
Mo with Ta retained the two-phase structure in Al0.5NbTaTiZr, however,
with cuboidal-shaped coherent nano-meter-sized BCC precipitates.
Al0.5Mo0.5NbTa0.5TiZr has σ0.2 = 2350 MPa, εf = 3.2% at 25 °C and
σ0.2 = 579 MPa, εf N 55% at 1000 °C. The alloy strength decreases con-
siderably, by ~600 MPa at 25 °C and 210 MPa at 1000 °C, when Mo is re-
placed with Ta, so that Al0.25NbTaTiZr has σ0.2 = 1745 MPa, εf = 3.8% at
25 °C and σ0.2 = 366 MPa, εf N 55% at 1000 °C. Both these alloys soften
during deformation at 1000 °C due to microstructural transformations
resulting in the disordered BCC phase becoming a continuous matrix
and the ordered B2 phase to transform to discrete particles inside the
BCC matrix.
Analysis of available phase diagrams suggests that Nb, Ta and Zr are
likely responsible for the decomposition of a high-temperature BCC
phase in two BCC phases during cooling due to a miscibility gap in the
studied alloy system. When the amount of Zr is reduced, the alloy com-
position is moved outside the miscibility gap and no phase separation
occurs. Strong interaction of Al with Zr in the presence Nb and Ta is like-
ly responsible for the BCC → B2 ordering of a Zr-rich phase upon cooling.
The ordered intermetallic B2 phase is strong when Mo is present, but
is brittle at room temperature causing brittleness or low ductility of the
studied RHEAs. In the two-phase B2/BCC RHEAs the disordered BCC
phase becomes continuous during deformation at 1000 °C, and this
transformation is accompanied by extensive compressive ductility and
a progressive drop in flow stress. It is suggested that the transformed
microstructure consisting of the disordered BCC matrix and ordered
B2 nanometer-sized precipitates would have room temperature ductil-
ity sufficient for engineering applications. Additional work is suggested
to engineer two-phase BCC/B2 microstructures with a balance of room
temperature tensile ductility and high temperature strength.
Acknowledgements
Work by ONS was supported through the Air Force on-site contract
FA8650-15-D-5230 managed by UES, Inc., Dayton, Ohio and through
the Air Force Research Laboratory, Materials and Manufacturing Direc-
torate, Lab Director's funds. JKJ acknowledges the financial support of
the Dayton Area Graduate Studies Institute (DAGSI) program of the
State of Ohio and the Air Force Research Laboratory, grant number
RX0(1)-OSU-13-4.
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