Energy landscape in NiCoCr-based middle-entropy alloys

Nikolai A. Zarkevich,1 Timothy M. Smith,2 John W. Lawson1

1
Intelligent Systems Division, NASA Ames Research Center, Moffett Field, CA 94035, USA
2
NASA Glenn Research Center, 21000 Brook Park Rd., Cleveland, OH 44135, USA

Abstract:
NiCoCr middle-entropy alloy is known for its exceptional strength at both low and elevated
operating temperatures. Mechanical properties of NiCoCr-based alloys are affected by certain
features of the energy landscape, such as the energy difference between the hcp and fcc phases
(which is known to correlate with the stacking fault energy in the fcc phase) and curvature of the
energy surface. We compute formation energies in the Ni-Co-Cr ternary and related quaternary
systems and investigate dependences of the relative energies on composition. Such computed
composition-structure-property relations can be useful for tuning composition and designing next-
generation alloys with improved strength.

Keywords: NiCoCr, middle-entropy alloy, relative energies, composition-property relations.

1. Introduction:
Among multi-principal element alloys (MPEAs),1 the NiCoCr middle-entropy alloy
(MEA) has remarkable strength2 and ductility,3 especially at low and high operating temperatures
T.4 Due to their competitive mechanical properties and corrosion resistance,5 MPEAs find
applications in engines and heat exchangers in aerospace,6,7 automotive,8 nuclear,9,10 and energy11
industries. Such alloys are also suitable for additive manufacturing.12-15 There are attempts to
further improve strength16 by adjusting the composition and adding precipitates, such as oxides.17
Properties depend on microstructure, which is affected by composition and heat treatment.18
Although novel alloys with improved creep and strength are synthesized and investigated,19
theoretical understanding of the dependence of their properties on composition is still lacking.
Here we provide results of density functional theory (DFT) combined with multiple scattering
theory (MST) and predict the dependence of formation and relative energies on composition.
The enhanced strength-ductility balance in NiCoCr and related MPEAs is believed to result
from peculiarities in the microstructure,19 such as locally variable stacking fault energies,20 which
correlate with the energy difference between the face centered cubic (fcc) and hexagonal close-
packed (hcp) structures. Locally, the hcp phase looks like an intrinsic stacking fault in the fcc
structure, while a double hexagonal close-packed (dhcp) structure represents an extrinsic stacking
fault. Similarly, D019 and D024 structures locally look like intrinsic and extrinsic stacking faults in
the L12 phase,21 relevant for precipitation in Ni superalloys.22 Interestingly, there is no ordering
phase transition in Ni3(Ti0.9168Al0.0832)1 alloy, which has a frustrated ground state and an inherent
atomic disorder on the Ti/Al sublattice.21 Although not every disordered alloy is a compositional
glass,21 atomic disorder can be frozen at low temperatures. Diffusion depends on composition and
temperature T and typically becomes negligible at low T. In a doped alloy, defects interact with
the solute and can either attract or repel each chemical species. Hence, the local chemical
composition at and near defects can differ from that in the bulk. The energy surface near a defect
can be dimpled.23 Defects can be point (0-dimensional), linear (1D), planar (2D), or bulk (3D).
Examples of defects include vacancies (0D), dislocations20 (1D), surfaces, grain boundaries, twins,
stacking faults (2D), and precipitates (3D). The mobility of defects affects the mechanical
properties of an alloy.24 The behavior of defects, and atomic diffusion near defects, are governed
by relative energies and temperature. Computation of the energy-composition dependencies in
disordered alloys from the first principles is challenging.25 Here we address this challenge.
We combine several theoretical and computational methods for dealing with disordered
alloys.26 We apply them to homogeneous solid solutions and construct the composition-structure-
property relations, which can be useful for materials design.27
This article is organized as follows. Methods are described in section 2. Results and
discussion are in section 3. Summary (section 4) is followed by the Appendix.

2. Methods:
Density functional theory (DFT) is used to compute the electronic structure and energies
of ordered and homogeneously disordered structures.26 The ground state (GS) structure of Ni is
face-centered cubic (fcc); the GS of Cr is body-centered cubic (bcc); and the GS of Co is hexagonal
close-packed (hcp), see Fig. 1. We consider 3 phases: fcc (A1), bcc (A2), and hcp (A3). Both fcc
and hcp phases are close-packed and differ by the periodic stacking of atomic layers, which is
[ABC] along the cubic [111] direction in fcc and [AB] along the hexagonal [0001] direction in
hcp.
DFT is combined with multiple scattering theory (MST) 28 to address atomic disorder.26
Homogeneous atomic disorder is considered within the coherent potential approximation (CPA),29
combined with the Korringa-Kohn-Rostocker (KKR) method.30,31 Electronic-structure
calculations are performed in primitive unit cells using the all-electron KKR-CPA code32 with the
periodic boundary corrections. The hcp structure is considered with the ideal (c/a)=(8/3)1/2 within
the KKR method. We checked that the computed ground state structures of elemental Ni, Cr, and
Co are fcc, bcc, and hcp, respectively, see Fig. 1.
(d)
dhcp
(a)
(A3’)
fcc (A1) (c)
(b) hcp (A3)
bcc (A2)

Figure 1. The fcc (A1, cF4, Cu, 225), bcc (A2, cI2, W, 229), hcp (A3, hP2, Mg, 194), and dhcp (A3’, hP4,
a-La, 194) structures (with Strukturbericht designation, Pearson symbol, prototype, and space group
number). The fcc, hcp, and dhcp structures are close-packed and differ by a periodic stacking of atomic
layers: [ABC] along the cubic [111] direction in fcc and [AB] or [ABAC] along the hexagonal [0001]
direction in hcp or dhcp structures, respectively.

At each composition, 5 points with 1.5% step in the lattice constant were used to fit the
Birch-Murnaghan33,34 equation of state (EoS), from which the equilibrium volume V0 and energy
E0 were determined and plotted versus composition x. The E0(x) data was interpolated using either
polynomials or cubic splines. Triangulation and cartesian interpolation were used to create ternary
contours.
The VASP full-potential code35,36 with the projector augmented-wave method37 was used
to compute energies of elemental solids. Assuming that the systematic error is linear versus
composition in each phase within the KKR method, the full-potential corrections were applied to
the KKR results. The PBEsol38 exchange-correlation functional was used in both VASP and KKR
codes.

3. Results and Discussion:

The equiatomic NiCoCr alloy is known to have the fcc structure at room temperature (RT)
in experiment. We find that its ground state is hcp, while the hcp and fcc homogeneously
disordered NiCoCr solid solutions have similar energies at 0K.
The computed total and projected on atomic spheres electronic density of states (DOS) in
fcc (A1) NiCoCr is shown in Fig. 2. At the Fermi energy EF, the total DOS and the atom-projected
electronic DOS of Ni and Co decreases with energy E, while that of Cr increases with E at EF in
all 3 phases. The total spin-projected DOS is similar in fcc (A1) and hcp (A3) phases, and these
phases have similar energies, while bcc (A2) phase is higher in energy at this composition, see
Fig. 3.

Total (A1) A1
Cr 1 A2
Spin DOS (eV atom )

Spin DOS (eV atom )

1
-1

Co -1 A3
Ni
-1

-1

0 0

-1
-1

-9 -8 -7 -6 -5 -4 -3 -2 -1 0 1 2 3 -9 -8 -7 -6 -5 -4 -3 -2 -1 0 1 2 3
E − EF (eV) E − EF (eV)
Figure 2. Electronic density of states in equiatomic NiCoCr: total and projected on the atomic spheres in
fcc phase (a), and total in fcc (A1), bcc (A2), and hcp (A3) phases (b).

The computed formation energy of NiCoCr is positive, see Fig. 4. Thus, development of
microstructure and atomic short-range order39 must be energetically favorable in experimental
samples.40 Relative energies are shown in Fig. 5, while formation energies and equilibrium
volumes (per atom) along selected cross sections of the compositional space are plotted in Figures
6 and 7 for the Ni-Co-Cr ternary system and Figures 8 and 9 for the quaternary (CrCoNi)1-xXx
alloys with X=(Ti, Zr, Hf; V, Nb, Ta; Mo, W; Re; Al, Cu, Fe).
Interestingly, at T=0 K the computed energy of the hcp NiCoCr homogeneously disordered
solid solution is slightly lower than that of fcc, while a small fcc-hcp energy difference of
2.67 meV/atom is comparable to the DFT error (of the order of ~1 meV/atom). The higher-
symmetry cubic fcc phase has a higher lattice entropy than the hexagonal hcp phase. Entropy is
expected to play a role in stabilizing the fcc phase at and above the room T. The computed
formation energy E0(fcc)=+143.6 meV/atom is positive for NiCoCr. For a homogeneously
disordered ternary equiatomic alloy, the mixing entropy is Smix/kB = ln(3) = 1.0986 per atom, where
kB=0.08617333 meV/K is the Boltzmann constant. At room T»25°C (298 K), TSmix=28 meV,
small compared to E0=+143.6 meV/atom for the fcc NiCoCr. Thus, the free energy (E0 –
TSmix)»+116 meV/atom is positive at RT, and NiCoCr is expected to be chemically
inhomogeneous, with energetically favorable deviations from homogeneity. Both energy and
mixing entropy are lowered by an atomic ordering, such as a short-range order (SRO) or a long-
range order (LRO).

700
280 NiCoCr Cr
600
260
500
E (meV/atom)

E (meV/atom)
240 A1
400 A2
220 A3
300
200

180 200
A1
A2
160 A3 100

140 0
10 11 12 10 11 12 13
3 3
V (Å /atom) V (Å /atom)

150
Ni 250 Co
E (meV/atom)

E (meV/atom)

200
100
150

100
50
A1 A1
A2 50 A2
A3 A3

0 0
10 11 12 9 10 11 12 13
3 3
V (Å /atom) V (Å /atom)
Figure 3. Computed formation energy versus volume in fcc (A1), bcc (A2), and hcp (A3) phases for the
equiatomic NiCoCr and the elemental Ni, Co, and Cr. DFT points are fitted by the Birch-Murnaghan EoS
(lines).

The computed equations of state (EoS) in fcc (A1), bcc (A2), and hcp (A3) phases for the
equiatomic NiCoCr middle-entropy alloy are compared with those for the elemental solids in
Figure 3. One can see that the ground states of Ni, Cr, and Co are A1, A2, and A3, respectively,
while A1 and A3 close-packed structures have very similar energies in NiCoCr at T=0K. Because
A3 (hcp) structure locally looks like a stacking fault in A1 (fcc), the energy difference between
hcp and fcc phases correlates with the stacking fault energy, which is low in NiCoCr; this result
agrees with previous computations41 and experimental measurements.42,43
For the equiatomic NiCoCr, the computed at T = 0 K equilibrium fcc lattice constant is a0=
3.497 Å; it is 2% smaller than the experimental44 a = 3.564 Å, measured by the XRD at room T,
see Table A1. The computed at T = 0 K NiCoCr bulk modulus is B0=232 GPa, see Table A2. The
computed bulk moduli of the elemental Ni, Co, and Cr are 218, 227, and 260 GPa, while the
measured B values are 220 (Ni), 206 (Co), and 280 GPa (Cr), respectively. Interestingly,
B(NiCoCr) » [B(Ni)+B(Co)+B(Cr)]/3 = 235 GPa. However, the computed at 0K value of
B0=232 GPa for the homogeneously disordered NiCoCr solid solution differs from the
experimentally assessed value for a sample with microstructure and atomic ordering. In
 experiment,24 a sample was obtained by arc-melting, re-melted five times, drop-casting the melt
into a copper mold, and growing single crystals from the polycrystalline as-cast ingots using a
floating-zone directional solidification method. For the single-crystal NiCoCr sample,24 the
experimental values of the elastic constants are c11=249 GPa, c12=156 GPa, c44=142 GPa, the bulk
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modulus is B=(c11+2c12)/3=187 GPa, and the Young's modulus is E=234 GPa at room temperature.
24
A3 The experimental assessment
A1 A3 of Debye temperature was 490A2 KA2in NiCoCr.
A3

Cr Cr Cr
(a) CrCr (b) CrCr (c) CrCr

Formation Energy (meV/atom)

200
200
400
400 400
400
A1 fcc A3 hcp A2 bcc
0.80.8 0.2
0.2 0.80.8 0.2
0.2 0.8
0.8 0.2
0.2

150
150
300
300 300
0.60.6 0.4
0.4 0.60.6 0.4
0.4 0.6
0.6 0.4
0.4

100
100
200
200 200
0.40.4 0.6
0.6 0.40.4 0.6
0.6 0.40.4 0.6
0.6

0.8 50
0.8 100 0.8 100 0.2 50
0.20.2 0.8 100 0.20.2 0.8 100 0.2 0.8

9/29/22, 3:09 PM 0 9/29/22, 4:260PM

127.0.0.1:63433 127.0.0.1:637440
0.8 0.6 0.4 0.2 0 0.8 0.6 0.4 0.2 0 0.8 0.6 0.4 0.2 0
Ni 0.8 0.6 0.4 0.2 Co 3:09 PM
9/29/22,
Co Ni
Ni 0.8 0.6 0.4 0.2 127.0.0.1:63433Co 4:26 PM Ni
Co 9/29/22, Ni 0.8 0.6 0.4 0.2 Co Co
127.0.0.1:63744
Ni Co Ni Co Ni Co
Figure 4. Computed formation energy [meV/atom] at equilibrium volume versus composition (atomic
E(A1-A2)
fraction) in Ni-Co-Cr ternaryE(A3-A1)
alloys
E(A3-A1)in fcc, hcp (same scale), and bccE(A1-A2)
(different energy scale) phases.
Cr Cr
Cr Cr
Co

(a) Cr (b) Cr (c) Cr

Ni

Relative Energy (meV/atom)

50
50
400
400
0.8
0.8 0.2
0.2 40
40 0.8
0.8 0.2
0.2
)

)
5
5
0.7

cc

cc
0.7 .25
0.2

0
5

p-f

c-b
30 300
300
p

30
fcc
hc

bcc
(hc

(fc
0.6
0.6 0.4
0.4 0.6
0.6 0.4
0.4

ΔE
ΔE

20
20
0.5
0.5
0.5

0.5 200
200

0.6 10
10
0.4
0.4 0.6 0.4
0.4 0.6
0.6

5 00 100
100
5
0.2

0.2 5
0.7
0.7
5

0.2 0.8 0.2 0.8

0.2 0.8 0.2 0.8
hc

fcc

−10
c

bc

−10
bc

fcc hcp 0
p

0
c

−20
Co

−20
Ni
Cr

Cr

0.8 0.6 0.4 0.2 0.8 0.6 0.4 0.2

Ni 0.75 0.5 0.25 Co Ni
Ni 0.8 0.6 0.4 0.2 CoCo NiNi 0.8 0.6 0.4 0.2 CoCo
0.25
0.75

0.5

Ni Co Ni Co
Figure 5. Computed lowest-energy phase and relative energies in Ni-Co-Cr ternary alloys.

127.0.0.1:52975
On a ternary compositional grid, EoS was computed at each point and the values of 127.0.0.1:52975 1/1 127.0.0.1:52998 1/1

127.0.0.1:52963
equilibrium energy E0 were interpolated using triangulation in Fig. 4. Negative formation energies
127.0.0.1:52975 1/1 127.0.0.1:52998 1/1

are present along the Ni-Co binary solid solutions in A1 and A3 phases, see Fig. 6(a). However,
at most compositions, including the equiatomic NiCoCr, formation energies are positive; they
increase with increasing chromium fraction x(Cr) in fcc and hcp phases, see Fig. 4. If formation
energies are positive, then the lowest-energy phase is not the ground state, while the ground state
is phase segregated.
Energy differences are visualized in Fig. 5. The line depicting zero energy difference in
Fig. 5(a) is computed with a higher accuracy compared to the lines in Fig. 5(b,c), obtained from a
triangulation and cartesian extrapolation on a sparser grid. A2 (bcc) phase is lower in energy above
the red line in Fig. 5(a). The dashed black line shows E(A1)=E(A3)>E(A2); the solid black line
shows E(A1)=E(A3)<E(A2); two segments of the red line show E(A2)=E(A1)<E(A3) and
E(A2)=E(A3)<E(A1). Red and black lines intersect at the point where all 3 phases have equal
127.0.0.1:63433 127.0.0.1:63744 1/1

positive formation energies, E(A1)=E(A2)=E(A3), see Fig. 5(a). 127.0.0.1:63433 127.0.0.1:63744 1/1

Energies of binary systems in Fig. 6 and cross sections of the Ni-Co-Cr ternary
compositional space in Fig. 7 further elucidate details of the energy-composition dependencies.
Equilibrium volumes V0 and formation energies E0 are computed along the selected cross sections
of the compositional space on a finer grid in Figs. 6 and 7. Cr stabilizes the bcc (A2) phase, while
weakly affecting the hcp-fcc energy difference. This allows for alterations of Cr fraction in the
NiCoCr-based middle-entropy alloys. Ni stabilizes the fcc (A1) phase, while Co stabilizes the hcp
(A3) phase. Among these 3 elements, Cr atom is the largest, while Ni and Co have comparable
sizes.
Impact of the additional chemical elements on the energy landscape is considered in Figs. 8
and 9. Additions of group 4, 5, and 6 metals stabilizes the bcc (A2) phase, see Fig. 8; one can
compare their effects with adding more Cr at x(Cr)>1/3 in Fig. 7(a). Additions of Al or Fe also
stabilizes the bcc phase, see Fig. 9; this effect is expected for the bcc Fe, but is surprising for the
fcc Al. (NiCoCr)92Al6Ta2 medium-entropy alloy was claimed to have improved yield strength,
ultimate strength, and tensile ductility at cryogenic temperatures.45 Addition of both Al and Ti in
(NiCoCr)94Al3Ti3 alloy resulted in formation of L12 precipitates.46 At small Al concentrations, Al
weakly affect the hcp-fcc energy difference, see Fig. 9(a). In contrast, Cu reduces energy of the
fcc phase relative to the hcp even at small concentrations x(Cu), see Fig. 9(b). Cu increases
formation energy of each phase at small x(Cu); E(x) dependence is concave at any x for each phase.
From experiment, Cu is known to deteriorate the corrosion resistance and reduce the high-
temperature oxidation resistance in FeCoCrNiCux alloy.47
Iron is magnetic. Fe atoms retain a large magnetic moment M(Fe)³2.2 Bohr magnetons
(µB) in the bcc phase at all concentrations x(Fe). In contrast, in the close-packed fcc and hcp phases
Fe atoms have a magnetic moment at small x but become non-magnetic (with zero atomic magnetic
moment) and larger x(Fe). A magnetic phase has a larger equilibrium volume V0 and a lower
density. Due to this change of the magnetic state, the V(x) curves are not smooth in the close-
packed fcc and hcp phases in Fig. 9(c). In a Fe-doped NiCoCr with Fe solute, Fe atoms are
magnetic impurities. Magnetic point defects are chemically active; they reduce corrosion
resistance of an alloy but can be beneficial for designing catalysts. CrFeCoNi medium-entropy
alloy was considered for additive manufacturing.48
Chemical homogeneity of an alloy depends on the curvature of energy versus composition
dependence E(x).49 Stabilization of defects by chemistry reduces mobility of those defects and
improves creep. Defects can be point (e.g., vacancies), linear (dislocations), planar (stacking faults,
twins, grain boundaries, etc.), or bulk (precipitates). Segregation tendency is manifested by the
concave E(x) dependence, which makes it energetically favorable to form chemical
inhomogeneities. Segregation from bulk results in accumulation of solute near defects that attract
solute atoms, acting as a sink. A similar phenomenon was observed in L12-type precipitates in Ni
superalloys.22
A concave E(x) dependence is predicted for Zr, Hf, Nb, Ta, Mo, W, and Re, see Fig. 8. In
modest amounts, these elements are expected to be beneficial for improving creep in NiCoCr-
based alloys.
There are attempts to add simultaneously several elements to NiCoCr. For example,
Ni24.27Co35.37Cr20.51Fe9.19Mo4.80Ti4.03Al0.76Nb1.07 MP159 alloy was found to have a single-phase fcc
structure with a relatively low stacking fault energy; its strength and plasticity were increasing
during temperature lowering from 298 K to 77 K.50
Addition of large atoms (e.g., La, Ce, and rare earth) can improve strength of alloys, if
atomic size mismatch reduces mobility of certain defects. Diffusion of these large and heavy
atoms is low, and they can pin the moving defects. Minor inclusion of lanthanum into the high-
entropy CrMnFeNi alloy affected corrosion resistance.51
 10.8 11.6 11.6
(a) (b) 11.4 (c)

V (Å /atom)
V (Å /atom)
V (Å /atom)
11.4
11.2 11.2

3
3
3

11
10.7 11
10.8
10.8
10.6
500 500
70 A1 A1
A2 A2
60 400 A3 400 A3

E (meV/atom)

E (meV/atom)
E (meV/atom)

50 A1
A2 300 300
40 A3
30
200 200
20

10 100 100
0
0 0
0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1
x(Ni) in Co1-xNix x(Ni) in Cr1-xNix x(Co) in Cr1-xCox

Figure 6. Computed equilibrium volume [Å3/atom] and formation energy [meV/atom] in 3 binary alloys.
Formation energies of fcc (A1) Ni0.75Co0.25 and hcp (A3) Ni0.25Co0.75 are negative. In bcc (A2) phase,
formation energy of elemental Cr is zero, all others are positive.

11
11.5
(a) (b) 10.9 (c)
V (Å /atom)

V (Å /atom)

V (Å /atom)
10.9

10.8
10.8
3

3
11
10.7 10.7

500
200
A1
A2
400 A3 150
150
E (meV/atom)

E (meV/atom)

E (meV/atom)
300
100
100
200

50 A1 50 A1
100 A2 A2
A3 A3
0 0 0
0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1
x(Cr) in Crx(Co0.5Ni0.5)1-x x(Co) in Cox(Cr0.5Ni0.5)1-x x(Ni) in Nix(Co0.5Cr0.5)1-x

10.9 11

(d)
V (Å /atom)

V (Å /atom)
V (Å /atom)

10.8
10.8
10.9
3

3
3

10.7
10.7
10.6
(e) 10.8 (f)
160
150 A1 200 A1 A1
140 A2 A2 A2
A3 A3 200 A3
130
E (meV/atom)
E (meV/atom)
E (meV/atom)

120
110
100 190
90 150
80
70 180
60
50
0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1
x(Ni) in Cr0.1336(Co1-xNix)0.8664 x(Ni) in Cr1/3(Co1-xNix)2/3 x(Ni) in Cr0.5(Co1-xNix)0.5

Figure 7. Computed equilibrium volume [Å3/atom] and formation energy [meV/atom] along the median
compositions of ternary Ni-Co-Cr alloy (upper) and 3 cross-sections at constant Cr fractions: 0.1336, 1/3,
and 1/2 (lower). Energy dependence E(x) in bcc (A2) phase is concave. Energies of the fcc (A1) and hcp
(A3) phases intersect.

Interstitial dopants (e.g., boron or carbon) are mobile and interact with defects. Such
interactions are beneficial in carbon steels.52 Boron was claimed to enhance resistance to hydrogen
embrittlement in a CrCoNi-based medium-entropy alloy.53 Addition of carbon into NiCoCr
resulted in simultaneous increase of strength and ductility, and also increased the stacking fault
energy.54
15
16 A1 13 A1 A1
14

V (Å /atom)
V (Å /atom)

V (Å /atom)
A2 A2 A2
A3 A3 A3
14 13
12

3
3

3
12
12
11
11

150 300
200

E (meV/atom)
E (meV/atom)

E (meV/atom)
100
200
100

50
100
0
0
(a) 0 (d) (g)
-100
0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1
x(Ti) in (CrCoNi)(1-x)/3Tix x(V) in (CrCoNi)(1-x)/3Vx x(Re) in (CrCoNi)(1-x)/3Rex

22 18
20 A1 17 A1 15 A1
V (Å /atom)

V (Å /atom)

V (Å /atom)
A2 16 A2 A2
18 A3 A3 14 A3
15
16 14 13
3

3
14 13
12
12
12 11
11

500
400
400
400
E (meV/atom)

E (meV/atom)

E (meV/atom)
300
300
300
200
200
200

100 100
100
(b) (e) (h)
0 0 0
0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1
x(Zr) in (CrCoNi)(1-x)/3Zrx x(Nb) in (CrCoNi)(1-x)/3Nbx x(Mo) in (CrCoNi)(1-x)/3Mox

18 16
20 A1 A1 A1
15
V (Å /atom)
V (Å /atom)
V (Å /atom)

A2 16 A2 A2
18 A3 A3 A3
14
16
3
3
3

14 13
14
12
12
12 11
500
600
400
400 500
E (meV/atom)
E (meV/atom)
E (meV/atom)

300 400
300

200 300
200
200
100
100 100
(c) (f) (i)
0
0
0
0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1
x(Hf) in (CrCoNi)(1-x)/3Hfx x(Ta) in (CrCoNi)(1-x)/3Tax x(W) in (CrCoNi)(1-x)/3Wx

Figure 8. Computed equilibrium volume [Å3/atom] and formation energy [meV/atom] for the selected
quaternary alloys (CrCoNi)1-xXx with X=(Ti, Zr, Hf, V, Nb, Ta, Mo, W, Re).

The low stacking fault energy of 18±4 mJ/m2 was measured in NiCoCr sample,42 which
was homogenized at 1473 K for 10 hours, water quenched, cold-rolled, and annealed at 1073 K
(800°C) for 1 hour. A similar value of 22±4 mJ/m2 was reported43 for the NiCoCr sample with the
measured composition (at.%) Ni32.85Co33.30Cr32.53Fe0.95Mn0.09O0.226C0.019S0.004, produced by
vacuum induction melting and casting followed by swaging at room temperature and
recrystallization at 1173 K for 1 hour.
Fracture toughness of NiCoCr at the cryogenic temperature of 20K was measured to be
459 MPa×m1/2 for crack initiation and 540 MPa×m1/2 for crack growth after 2.25 millimeters of
stable cracking.55 These exceptionally high values were attributed to a synergy of deformation
mechanisms, that included dislocation glide, stacking-fault formation, nano-twinning, and phase
transformation. The observed55 fcc→hcp transformation at cryogenic T is consistent with our
calculations, according to which the hcp phase has a slightly lower energy than fcc at 0K in
NiCoCr, see Fig. 2 and Table A2. A similar fcc→hcp phase change was reported in several
experiments.4,18 Our results in Figs. 4 and 5 allow to adjust the hcp-fcc energy difference (which
is correlated with the stacking fault energy) in a ternary Ni-Co-Cr system, while our data in Figs. 8
and 9 should be useful for considering other chemical elements as dopants.56
11.6 76
16 A1 A1
11.4
V (Å /atom)

V (Å /atom)

V (Å /atom)
A2 A2 74
A3 A1
14 11.2
72
3

3
3

11 A1
70 A2
12
10.8 A3
68

200
150 150
E (meV/atom)

E (meV/atom)
E (meV/atom)

100 150
100
50
100

0 50
50
-50 (a) (b) (c)
0 0
0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1 0 0.25 0.5 0.75 1
x(Al) in (CrCoNi)(1-x)/3Alx x(Cu) in (CrCoNi)(1-x)/3Cux x(Fe) in (CrCoNi)(1-x)/3Fex

Figure 9. Computed equilibrium volume [Å3/atom] and formation energy [meV/atom] for the quaternary
alloys composed by Ni, Co, and Cr with added Al, Cu, or Fe. Convex E(x) points at a mixing tendency for
Al (a). Concave E(x) points at a segregation tendency for Cu (b). V(x) dependency is not smooth due to a
magnetic phase change in Fe-rich fcc and hcp phases (c).

4. Summary:
We combined density functional theory with multiple scattering theory, computed energy-
composition dependencies, and investigated the energy landscape in NiCoCr-based middle-
entropy alloys. Our results will be useful as a guidance for adjusting composition and designing
next-generation alloys with improved strength, creep, ductility, radiation tolerance and corrosion
resistance.

Acknowledgements:
We acknowledge funding by NASA’s Aeronautics Research Mission Directorate (ARMD) via
Transformational Tools and Technologies (TTT) Project. We thank Shreyas J. Honrao, Mikhail
Mendelev, Valery V. Borovikov, Zhigang Wu, and Anupa R. Bajwa for discussion.

Appendix:
The computed lattice constants are compared with experimental ones in Table A1. DFT
computations were performed at T=0K, while measurements were done at room temperature (RT).
Considering thermal expansion, the agreement is reasonable, as expected for the PBEsol exchange
correlation functional. The computed EoS parameters of NiCoCr in 3 phases are compared with
those of elemental solids in Table A2. The homogeneously disordered NiCoCr alloy has a positive
formation energy (e.g., E(hcp) = +141 meV/atom), and the energies of its fcc and hcp phases are
very similar: E(fcc) – E(hcp) < 3 meV/atom.

Table A1. Computed at T=0K and experimental44 (at RT) lattice constants.
a (Å) DFT (0K) Expt. (RT)
NiCoCr fcc 3.497 3.564
Ni fcc 3.49 3.52
Co hcp 2.47 2.51
Cr bcc 2.83 2.88

Table A2. The computed equation of state (EoS) parameters for the equiatomic NiCoCr in fcc
(A1), hcp (A3), and bcc (A2) phases: equilibrium formation energy E0 (eV/atom), atomic volume
V0 (Å3/atom), bulk modulus B0 (eV/Å3), and pressure derivative 𝐵!" (dimensionless), compared
to the computed EoS parameters of the elemental solids (Ni, Co, Cr) in their ground states.
NiCoCr A1 (fcc) A3 (hcp) A2 (bcc)
E0 (meV/atom) 143.6 141.0 188.1
V0 (Å3/atom) 10.69 10.70 10.84
B0 (GPa) 232 231 228
𝐵!" 5.2 4.8 4.4

Elements Ni fcc Co hcp Cr bcc

E0 (meV) 0 0 0
V0 (Å3) 10.64 10.66 11.29
B0 (GPa) 218 227 260
𝐵!" 4.7 4.5 3.7

References:
1 Senkov, O. N., Miller, J. D., Miracle, D. B. & Woodward, C. Accelerated exploration of
multi-principal element alloys with solid solution phases. Nature Communications 6,
6529, doi:10.1038/ncomms7529 (2015).
2 Gludovatz, B. et al. Exceptional damage-tolerance of a medium-entropy alloy CrCoNi at
cryogenic temperatures. Nature Communications 7, 10602, doi:10.1038/ncomms10602
(2016).
3 Slone, C. E., Miao, J., George, E. P. & Mills, M. J. Achieving ultra-high strength and
ductility in equiatomic CrCoNi with partially recrystallized microstructures. Acta
Materialia 165, 496-507, doi:10.1016/j.actamat.2018.12.015 (2019).
4 Miao, J. et al. The evolution of the deformation substructure in a Ni-Co-Cr equiatomic
solid solution alloy. Acta Materialia 132, 35-48, doi:10.1016/j.actamat.2017.04.033
(2017).
5 Miracle, D. B. & Senkov, O. N. A critical review of high entropy alloys and related
concepts. Acta Materialia 122, 448-511, doi:10.1016/j.actamat.2016.08.081 (2017).
6 Smith, T. M., Thompson, A. C., Gabb, T. P., Bowman, C. L. & Kantzos, C. A. Efficient
production of a high-performance dispersion strengthened, multi-principal element alloy.
Sci Rep-Uk 10, 9663, doi:10.1038/s41598-020-66436-5 (2020).
7 Modupeola, D., Patricia, P., Samson, A. & Ntombi, M. in Aerodynamics (eds Gorji-
Bandpy Mofid & Aly Aly-Mousaad) Ch. 7 (IntechOpen, 2019).
8 Maulik, O., Kumar, D., Kumar, S., Dewangan, S. K. & Kumar, V. Structure and
properties of lightweight high entropy alloys: a brief review. Mater Res Express 5,
052001, doi:10.1088/2053-1591/aabbca (2018).
9 Lu, C. et al. Irradiation effects of medium-entropy alloy NiCoCr with and without pre-
indentation. Journal of Nuclear Materials 524, 60-66, doi:10.1016/j.jnucmat.2019.06.020
(2019).
10 Lu, C. et al. High radiation tolerance of an ultrastrong nanostructured NiCoCr alloy with
stable dispersed nanooxides and fine grain structure. Journal of Nuclear Materials 557,
153316, doi:10.1016/j.jnucmat.2021.153316 (2021).
11 Zarkevich, N. A. Electricity without Fuel. Journal of Energy and Power Technology 2,
14, doi:10.21926/jept.2001001 (2020).
12 Brif, Y., Thomas, M. & Todd, I. The use of high-entropy alloys in additive
manufacturing. Scripta Mater 99, 93-96, doi:10.1016/j.scriptamat.2014.11.037 (2015).
13 Chen, S., Tong, Y. & Liaw, P. K. Additive Manufacturing of High-Entropy Alloys: A
Review. Entropy 20, 937 (2018).
14 Ostovari Moghaddam, A., Shaburova, N. A., Samodurova, M. N., Abdollahzadeh, A. &
Trofimov, E. A. Additive manufacturing of high entropy alloys: A practical review.
Journal of Materials Science & Technology 77, 131-162, doi:10.1016/j.jmst.2020.11.029
(2021).
15 Zhang, W., Chabok, A., Kooi, B. J. & Pei, Y. Additive manufactured high entropy alloys:
A review of the microstructure and properties. Mater Design 220, 110875,
doi:10.1016/j.matdes.2022.110875 (2022).
16 Argon, A. Strengthening Mechanisms in Crystal Plasticity. (Oxford University Press,
2007).
17 Li, M., Guo, Y., Li, W., Zhang, Y. & Chang, Y. Property enhancement of CoCrNi
medium-entropy alloy by introducing nano-scale features. Materials Science and
Engineering: A 817, 141368, doi:10.1016/j.msea.2021.141368 (2021).
18 Schuh, B. et al. Influence of Annealing on Microstructure and Mechanical Properties of a
Nanocrystalline CrCoNi Medium-Entropy Alloy. Materials 11, 662 (2018).
19 Smith, T. M. & et al. Microstructural and Mechanical Characterization of a Dispersion
Strengthened Medium Entropy Alloy Produced Using Selective Laser Melting. USA
patent (2019).
20 Smith, T. M. et al. Atomic-scale characterization and modeling of 60° dislocations in a
high-entropy alloy. Acta Materialia 110, 352-363, doi:10.1016/j.actamat.2016.03.045
(2016).
21 Zarkevich, N. A., Smith, T. M., Baum, E. N. & Lawson, J. W. Compositional Glass: A
State with Inherent Chemical Disorder, Exemplified by Ti-rich Ni3(Al,Ti)1 D024 Phase.
Crystals 12, 1049 (2022).
22 Smith, T. M. et al. Utilizing local phase transformation strengthening for nickel-base
superalloys. Communications Materials 2, 106, doi:10.1038/s43246-021-00210-6 (2021).
23 Zarkevich, N. A. & Johnson, D. D. Between Harmonic Crystal and Glass: Solids with
Dimpled Potential-Energy Surfaces Having Multiple Local Energy Minima. Crystals 12,
84 (2022).
24 Jin, K., Gao, Y. F. & Bei, H. Intrinsic properties and strengthening mechanism of
monocrystalline Ni-containing ternary concentrated solid solutions. Materials Science
and Engineering: A 695, 74-79, doi:10.1016/j.msea.2017.04.003 (2017).
25 Yin, B., Yoshida, S., Tsuji, N. & Curtin, W. A. Yield strength and misfit volumes of
NiCoCr and implications for short-range-order. Nature Communications 11, 2507,
doi:10.1038/s41467-020-16083-1 (2020).
26 Zarkevich, N. A. Theoretical and computational methods for accelerated materials
discovery. Modern Physics Letters B 35, 2130003, doi:10.1142/S0217984921300039
(2021).
27 Zarkevich, N. A. Structural database for reducing cost in materials design and complexity
of multiscale computations. Complexity 11, 36-42, doi:10.1002/cplx.20117 (2006).
28 Faulkner, J. S., Stocks, G. M. & Wang, Y. in Electronic structure of solids (IOP
Publishing, 2018).
29 Johnson, D. D., Nicholson, D. M., Pinski, F. J., Gyorffy, B. L. & Stocks, G. M. Density-
Functional Theory for Random Alloys: Total Energy within the Coherent-Potential
Approximation. Physical Review Letters 56, 2088-2091,
doi:10.1103/PhysRevLett.56.2088 (1986).
30 Korringa, J. On the calculation of the energy of a Bloch wave in a metal. Physica 13,
392-400, doi:10.1016/0031-8914(47)90013-X (1947).
31 Kohn, W. & Rostoker, N. Solution of the Schr\"odinger Equation in Periodic Lattices
with an Application to Metallic Lithium. Physical Review 94, 1111-1120,
doi:10.1103/PhysRev.94.1111 (1954).
32 Johnson, D. D., Smirnov, A. V. & Khan, S. N. MECCA: Multiple-scattering electronic-
structure calculations for complex alloys. KKR-CPA program. (Iowa State University
and Ames Laboratory, Ames, Iowa, 2015).
33 Birch, F. Finite Elastic Strain of Cubic Crystals. Physical Review 71, 809-824,
doi:10.1103/PhysRev.71.809 (1947).
34 Murnaghan, F. D. The Compressibility of Media under Extreme Pressures. Proceedings
of the National Academy of Sciences 30, 244-247, doi:10.1073/pnas.30.9.244 (1944).
35 Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys Rev B 47,
558-561, doi:10.1103/PhysRevB.47.558 (1993).
36 Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal--
amorphous-semiconductor transition in germanium. Phys Rev B 49, 14251-14269,
doi:10.1103/PhysRevB.49.14251 (1994).
37 Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-
wave method. Phys Rev B 59, 1758-1775, doi:10.1103/PhysRevB.59.1758 (1999).
38 Perdew, J. P. et al. Restoring the Density-Gradient Expansion for Exchange in Solids and
Surfaces. Physical Review Letters 100, 136406, doi:10.1103/PhysRevLett.100.136406
(2008).
39 Pei, Z., Li, R., Gao, M. C. & Stocks, G. M. Statistics of the NiCoCr medium-entropy
alloy: Novel aspects of an old puzzle. npj Computational Materials 6, 122,
doi:10.1038/s41524-020-00389-1 (2020).
40 Zhang, F. X. et al. Local Structure and Short-Range Order in a NiCoCr Solid Solution
Alloy. Physical Review Letters 118, 205501, doi:10.1103/PhysRevLett.118.205501
(2017).
41 Zhao, S., Osetsky, Y., Stocks, G. M. & Zhang, Y. Local-environment dependence of
stacking fault energies in concentrated solid-solution alloys. npj Computational Materials
5, 13, doi:10.1038/s41524-019-0150-y (2019).
42 Liu, S. F. et al. Stacking fault energy of face-centered-cubic high entropy alloys.
Intermetallics 93, 269-273, doi:10.1016/j.intermet.2017.10.004 (2018).
43 Laplanche, G. et al. Reasons for the superior mechanical properties of medium-entropy
CrCoNi compared to high-entropy CrMnFeCoNi. Acta Materialia 128, 292-303,
doi:10.1016/j.actamat.2017.02.036 (2017).
44 Hermann, K. in Crystallography and Surface Structure 265-266 (Wiley, 2011).
45 Zhang, D. D., Zhang, J. Y., Kuang, J., Liu, G. & Sun, J. Superior strength-ductility
synergy and strain hardenability of Al/Ta co-doped NiCoCr twinned medium entropy
alloy for cryogenic applications. Acta Materialia 220, 117288,
doi:10.1016/j.actamat.2021.117288 (2021).
46 Peng, H. et al. Optimization of the microstructure and mechanical properties of electron
beam welded high-strength medium-entropy alloy (NiCoCr)94Al3Ti3. Intermetallics
141, 107439, doi:10.1016/j.intermet.2021.107439 (2022).
47 Cai, Y., Chen, Y., Luo, Z., Gao, F. & Li, L. Manufacturing of FeCoCrNiCux medium-
entropy alloy coating using laser cladding technology. Mater Design 133, 91-108,
doi:10.1016/j.matdes.2017.07.045 (2017).
48 Kuzminova, Y. et al. The effect of the parameters of the powder bed fusion process on
the microstructure and mechanical properties of CrFeCoNi medium-entropy alloys.
Intermetallics 116, 106651, doi:10.1016/j.intermet.2019.106651 (2020).
49 Yibole, H. et al. Manipulating the stability of crystallographic and magnetic sub-lattices:
A first-order magnetoelastic transformation in transition metal based Laves phase. Acta
Materialia 154, 365-374, doi:10.1016/j.actamat.2018.05.048 (2018).
50 Pei, B. et al. Excellent combination of strength and ductility in CoNiCr-based MP159
alloys at cryogenic temperature. Journal of Alloys and Compounds 907, 164144,
doi:10.1016/j.jallcom.2022.164144 (2022).
51 Sun, Y. P., Wang, Z., Yang, H. J., Lan, A. D. & Qiao, J. W. Effects of the element La on
the corrosion properties of CrMnFeNi high entropy alloys. Journal of Alloys and
Compounds 842, 155825, doi:10.1016/j.jallcom.2020.155825 (2020).
52 Dwivedi, D., Lepková, K. & Becker, T. Carbon steel corrosion: a review of key surface
properties and characterization methods. Rsc Adv 7, 4580-4610,
doi:10.1039/C6RA25094G (2017).
53 Chen, X. H. et al. Enhanced resistance to hydrogen embrittlement in a CrCoNi-based
medium-entropy alloy via grain-boundary decoration of boron. Materials Research
Letters 10, 278-286, doi:10.1080/21663831.2022.2033865 (2022).
54 Shang, Y. Y. et al. Solving the strength-ductility tradeoff in the medium-entropy NiCoCr
alloy via interstitial strengthening of carbon. Intermetallics 106, 77-87,
doi:10.1016/j.intermet.2018.12.009 (2019).
55 Liu, D. et al. Exceptional fracture toughness of CrCoNi-based medium- and high-entropy
alloys at 20 kelvin. Science 378, 978-983, doi:doi:10.1126/science.abp8070 (2022).
56 T.M. Smith et al. A 3D Printable Alloy Designed for Extreme Environments. Nature
(2023).