CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 46 (2014) 124–133

Contents lists available at ScienceDirect

CALPHAD: Computer Coupling of Phase Diagrams and

Thermochemistry
journal homepage: www.elsevier.com/locate/calphad

Solution-based thermodynamic modeling of the Ni–Al–Mo system

using first-principles calculations
S.H. Zhou a,b,n, Y. Wang a, L.-Q. Chen a, Z.-K. Liu a, R.E. Napolitano b,c
a
Department of Materials Science and Engineering, The Pennsylvania State University, University Park, PA 16802, USA
b
Materials & Engineering Physics Program, Ames Laboratory, USDOE, USA
c
Department of Materials Science and Engineering, Iowa State University, Ames, IA 50011, USA

art ic l e i nf o a b s t r a c t

Article history: A solution-based thermodynamic description of the ternary Ni–Al–Mo system is developed here,
Received 31 October 2013 incorporating first-principles calculations and reported modeling of the binary Ni–Al, Ni–Mo and
Received in revised form Al–Mo systems. To search for the configurations with the lowest energies of the N phase, the Alloy Theoretic
9 January 2014
Automated Toolkit (ATAT) was employed and combined with VASP. The liquid, bcc and γ-fcc phases are
Accepted 6 March 2014
modeled as random atomic solutions, and the γʹ-Ni3Al phase is modeled by describing the ordering
Available online 22 March 2014
within the fcc structure using two sublattices, summarized as (Al,Mo,Ni)0.75(Al,Mo,Ni)0.25. Thus, γ-fcc
Keywords: and γʹ-Ni3Al are modeled with a single Gibbs free energy function with appropriate treatment of the
CALPHAD chemical ordering contribution. In addition, notable improvements are the following: first, the ternary
First-principles calculation
effects of Mo and Al in the B2-NiAl and D0a-Ni3Mo phases, respectively, are considered; second, the
Ni–Al–Mo phase diagram
N-NiAl8Mo3 phase is described as a solid solution using a three-sublattice model; third, the X-Ni14Al75Mo11
ATAT
phase is treated as a stoichiometric compound. Model parameters are evaluated using first-principles
calculations of zero-Kelvin formation enthalpies and reported experimental data. In comparison with the
enthalpies of formation for the compounds ψ-AlMo, θ-Al8Mo3 and B2-NiAl, the first-principles results
indicate that the N-NiAl8Mo3 phase, which is stable at high temperatures, decomposes into other phases
at low temperature. Resulting phase equilibria are summarized in the form of isothermal sections and
liquidus projections. To clearly identify the relationship between the γ-fcc and γʹ-Ni3Al phases in the
ternary Ni–Al–Mo system, the specific γ-fcc and γʹ-Ni3Al phase fields are plotted in x(Al)–x(Mo)–T space
for a temperature range 1200–1800 K.
& 2014 Elsevier Ltd. All rights reserved.

1. Introduction which represented a great improvement over the modeling by

The high temperature performance of superalloys based on the
Ni–Al binary system is a critical factor in current and future power
generation and transportation technologies. Moreover, the refrac-
tory metal Mo is well established as a key contributor to the high
temperature stability of many multicomponent Ni-base super-
alloys [1–6]. Despite its widespread use, quantitative guidelines
for future alloy development and processing design call for more
complete descriptions of the effects of Mo additions on the phase
stability and phase transformation in the Ni–Al–Mo system. This is
the focus of the present work.
Thermodynamic modeling for the ternary Ni–Al–Mo system
was first performed by Kaufman and Nesor [7], in which all
compounds were described as stoichiometric compounds. Subse-
quent to treatments of the Ni–Al [8], Al–Mo [9], and Ni–Mo [10]
systems, Lu et al. [11] reassessed the ternary Ni–Al–Mo system
n
Corresponding author.
Kaufman and Nesor [7], and, despite several limitations, has been
used with reasonable success for quite some time. As increased
demands for high temperature materials drive the exploration of
new multicomponent alloy regimes, however, these limitations
become problematic. First, the binary Ni–Mo phase diagram
resulting from the model by Lu et al. [11] is different from those
by Frisk [10] in Fig. 1(a) although Lu et al. [11] use the database
developed by Frisk [10]. Lu’s model (dashed curves) indicates that
(i) the B2 phase becomes stable around 1900 K indicating the B2
phase can be a primary phase in a ternary Ni–Al–Mo system and
(ii) the γʹ phase becomes stable at low temperature, which does
not agree with Frisk’s model [10] and the reported experiments
[12–14]. In addition, Lu’s model was found to be inconsistent with
experimental phase equilibrium data [15–18], limiting its utility in
phase-field modeling [19]. These problems arise from inappropri-
ate descriptions of the thermodynamic effects of Mo in the ternary
system [11], and several important improvements are called here
for. First, recent advances in modeling the Ni–Al [20] and Ni–Mo
[21] binary systems should be incorporated into the ternary

http://dx.doi.org/10.1016/j.calphad.2014.03.002
0364-5916/& 2014 Elsevier Ltd. All rights reserved.
 S.H. Zhou et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 46 (2014) 124–133 125

Fig. 1. The binary phase diagrams of the (a) Ni–Mo system calculated using the parameters by Frist [10] in solid-line and Lu et al. [11] in dash-line; (b) Ni–Mo system
calculated using the parameters by Zhou et al. [21] in solid-line and Lu et al. [11] in dash-line; (c) Al–Mo system [9] and (d) Al–Ni system [8,20].

Table 1 description. Second, the ternary N and X phases listed in Table 1,

A listing of phases modeled in the current treatment. which were not described in previous reports [7,11], should be
considered.
Formula unit Sym. Lattice Struk. des. Prototype
In the present work, the thermodynamic descriptions of the binary
Phases extending from the pure component states: Ni–Al [8,20], Al–Mo [9], and Ni–Mo [21] systems with the associated
Ni, Ta, Mo – – – Liquid phase diagrams shown in Fig. 1(b–d) are employed within a general
Ni γ Cub A1 fcc solution-based approach, using first-principles calculations and experi-
Al γ Cub A1 fcc mental data [11,15–18,22–39], which are appropriate to determine the
Mo – Cub A2 bcc
Phases extending from the Ni–Al binary system:
ternary model parameters. The ternary N and X phases are included
Al3Ni – Ort D011 Fe3C and the full Ni–Al–Mo phase diagram is computed. The equilibrium
Al3Ni2 – Tri D513 Al3Ni2 phase diagram is presented with a series of isothermal sections and a
AlNi – Cub B2 ClCs 3D plot for the γ and γʹ phase fields. The resulting phase diagrams of
Al3Ni5 ε Ort – Ga5Pt3
the ternary Ni–Al–Mo system are compared with the experimental
AlNi3 γ’ Cub L12 AuCu3
Phases extending from the Ni–Mo binary system: data [11,15–18,22–39] and the prior report by Lu [11].
NiMo δ Orth – NiMo
Ni2Mo ρ Tet – Pt2Mo
Ni3Mo – Tet D0a Cu3Ti 2. First-principles calculations
Ni4Mo – Tet D1a Ni4Mo
Ni8Mo ζ Tet – Ni8Nb
Phases extending from the Al–Mo binary system: To determinate the Gibbs free energy of formation for the inter-
Al12Mo ϕ Cub – Al12W mediate phases, the zero-Kelvin energies of the N phases and the
Al5Mo η Hex – Al5W unstable end-members (described in Section 3) for the B2 and D0a-
Al4Mo φ Mon – Al4W
Ni3Mo phases as well as fcc-Al, fcc-Ni, bcc-Mo were calculated by
Al8Mo3 s Mon – Al8W3
Al63Mo37 τ – – – means of VASP [40] employing Vanderbilt ultrasoft pseudopotential
AlMo ψ Cub A2 W [41] and the generalized gradient approximation (GGA) [42] with the
AlMo3 – Cub A15 Cr3Si high precision choice. Monkhost 15
15
15 k points were used for
Ternary compounds the pure elements Ni, Al and Mo, 11
11
11 k points for the
NiAl8Mo3 N Tet D022 Al3Ti
Ni14Al75Mo11 X – – –
compounds B2 and D0a-Ni3Mo, and 6
6
6 k points for the com-
pound N. For the stable structures, we fully relaxed the volume, the
126 S.H. Zhou et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 46 (2014) 124–133

cell shape, and the internal atomic coordinates while for the unstable Table 2b
structures of the end-members we only relaxed the cell volume to The crystal structure of the lowest energy structure at composition NiAl8Mo3.
maintain the unit cell structures to their stable phases.
Position type Atomic position
The enthalpy of formation, ΔH Φ
f , for a given compound Φ is
calculated as the difference between the energy EΦ
TOT of the
Al1 0 0.9938 0.3284
Al1 0.5 0.4938 0.1716
compound and the linear combination of the pure element Al2 0 0.0194 0
reference state energies, EfAlcc , EfNicc and Ebcc
Mo
Mo 0.5 0.7525 0
Ni1 0 0.4821 0.3399

ΔH Φ Φ Φ f cc Φ f cc Φ bcc Ni1 0.5 0.9821 0.1601

f ¼ ETOT  xNi ENi xAl EAl  xMo E Mo ð1Þ Ni2 0 0.2486 0.1704
Ni2 0.5 0.7486 0.3296
where xΦ i is the mole fraction of component i in Φ. The calculated
Ni3 0 0.7503 0.1518
Ni3 0.5 0.2503 0.3482
enthalpies of formation of the compounds are listed in Table 2a.
Ni4 0 0.5210 0
The compositions of the N phase were reported as Ni5 0.5 0.2575 0
Ni12.5Al62.5Mo25 by Raman and Schubert [23,24] and as
Ni3Al72Mo25 by Markiv et al. [22] as the dashed-lines in Fig. 2,
respectively. To search for the configurations with the lowest c¼8.5710 Å. The primitive unit cell of this ternary compound
energies, ATAT developed by van de Walle [43] was employed contains 12 atoms which are arranged in the symmetry. The
and combined with VASP. The starting geometry was limited to atomic positions of this ternary compound are listed in Table 2b.
the D022 structure with the fixed composition (25 at% Mo) and Mo In this work, we designated this ternary compound as N-NiAl8Mo3
atom positions. Gamma centered k points were used and more and describe it as a solution phase with small homogeneous
than 65 configurations were studied. The calculated enthalpies of composition by considering the experimental observations by
formation for some of the structures found by ATAT are plotted in Raman and Schubert [23,24] and Markiv et al. [22].
Fig. 2 indicating that the structure at the lowest point along the As listed in Table 2a, the first-principles calculated enthalpy of
concave curve is at composition NiAl8Mo3 and gives a formation formation for the N-NiAl8Mo3 phase is  38.17 kJ/mol, which is
energy of  38.17 kJ/mol, which is lower than the those values at less negative than the enthalpy of mixing, i.e.  40.19 kJ/mol, for
both Ni12.5Al62.5Mo25 and Ni3Al72Mo25 by Raman and Schubert the ψ-AlMo, θ- and B2-NiAl phases from the binary systems,
[23,24] and Markiv et al. [22], respectively. This ternary compound indicating that the N phase decomposes into other phases at low
is a tripled superstructure of that of DO22 along b direction, temperature. Due to the lack of structural information, the first-
resulting in a body centered orthorhombic structure with the principles calculation was not performed for the compound X.
lattice parameters being a ¼3.6904 Å, b¼11.1050 Å, and

Table 2a
3. Thermodynamic models
A summary of results from the first-principles calculations.

Phase Symbol Prototype Formula ΔH, kJ/mol of atoms The thermodynamic properties of pure Al, Mo, and Ni in
various structures were computed using the parameters from
Ni fcc Ni 0 the SGTE database [44] as listed in Table 3. In addition to the
γ
Al fcc Al 0
compounds in the Ni–Al [8,20], Al–Mo [9] and Ni–Mo [21]
Mo A2 bcc Mo 0
NiMo 27.84
systems, the liquid, bcc, γ-fcc, B2-NiAl, γʹ-Ni3Al, D0a-Ni3Mo, and
NiAl B2 CsCl N were modeled as ternary solution phases and X phase as a
AlMo 5.88
Ni3Mo D0a Cu3Ti Ni3Al  38.12 stoichiometric compound. The associated Gibbs free energy func-
Ni3Mo  6.15 tions are defined in Table 4, where the total Gibbs free energy for
 28.01
the phase, Φ, is generally given by the sum of three contributions:
Al2NiMo
NiAl8Mo3 N Al3Ti
Al8NiMo3  38.17
 27.19
GΦ ref Φ
Gm þ id GΦ xs Φ
Al3Mo
m ¼ m þ Gm ; ð2Þ

Fig. 2. Enthalpy of formation for the N phase calculated using ATAT and VASP with
the fixed Mo atomic positions xMo ¼ 0.25 and current thermodynamic parameters in
Tables 6 and 7. Reference states: fcc-Ni, fcc-Al and bcc-Mo.
where the subscript m denotes that all terms are molar quantities.
The first term in Eq. (2) is the sum of occupancy-weighted
sublattice end-member contributions. The second and third terms
are the ideal and excess parts of the Gibbs free energy of mixing,
respectively. The excess Gibbs free energy in all Gibbs free energy
equations is expressed in terms of the Redlich–Kister polynomial
[45]. The specific treatment of each phase is discussed briefly here.
The liquid, bcc and γ-fcc are described using the model given in
Table 4, where 1GΦ i is the molar Gibbs free energy of the pure
element i with the structure Φ (Φ ¼ liquid, bcc or γ-fcc) as listed in
Table 3 and xi is the mole fraction of the indicated component
i. j LΦ Φ
i;k is the binary interaction parameter, and LAl;Mo;Ni is a composi-
tion dependent ternary interaction parameter evaluated with the
experimental data. Magnetic property of the Ni is considered for
its fcc structure. mg GΦ m is the magnetic contribution [46] to Gibbs
free energy in solution phases, and expressed as the following:
Φ
mg
GΦ Φ
m ¼ RT lnðβ þ1Þf ðτ Þ; ð3Þ
Φ
where β is the quantity related to the total magnetic entropy and
is set equal to the Bohr magnetic moment per mole of atom. τΦ is
 S.H. Zhou et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 46 (2014) 124–133 127

Table 3
Thermodynamic parameters for pure elements [44].

Al phases

0
Gliq
Al
0
GfAlcc 0
Gbcc
Al

Tmin, K 298 933 298 700 933 298

Tmax, K 933 6000 700 933 6000 3200
0
GREF 0 f cc
GAl 0 f cc
GAl – – – 0 f cc
GAl
A 11,005.029 10,482.282  7976.15  11,276.24  11,278.378 10,083
B  11.841867  11.253974 137.093038 223.048446 188.684153  4.813
C – – 24.3671976  38.5844296  31.748192 –
D – –  1.884662
10  3 0.018531982 –
E – – 74,092 74,092 –
F – –  8.77664
10  7  5.764227
10  6 –
G 7.934
10  20 – – – –
H – 1.231
1028 – –  1.234
1028 –

Mo phases

0
Gliq
Mo
0
GfMo
cc 0
Gbcc
Mo

Tmin 298 2896 298 298 2896

Tmax 2896 6000 6000 2896 3000
0 0
GREF Gbcc
Mo
0
Gbcc
Mo
0 bcc
GMo 0 0
A 41,831.347 34,095.373 15,200  7746.302  30,556.41
B  14.694912  11.890046 0.63 131.9197 283.559746
C – – –  23.56414  42.63829
D – – –  3.443396
10  3 –
E – – – 65,812 –
F – – – 5.66283
10  7 –
G 4.24519
10  22 4.849315
1033 – – –
H – – – –  4.849315
1033
I – – – 1.30927
10  10 –

Ni phases

0
Gliq
Ni
0
Gbcc
Ni
0
GfNicc

Tmin 298 1728 298 298 1728

Tmax 1728 6000 6000 1728 3000
0 0 f cc 0 f cc 0 f cc 0 0
GREF GNi GNi GNi
A 16,414.686 18,290.88 8715.084  5179.159  27,840.655
B  9.397  10.537  3.556 117.854 279.135
C – – –  22.096  43.1
D – – –  4.8407
10  3 –
E – – – – –
F – – – – –
G  3.82318
10  21 – – – –
H –  1.12754
1031 – – 1.12754
1031
Tc – – 575 633 –
β – – 0.85 0.52 –

Note: O Gθi ¼ O GRef þ a þ bT þ cT ln T þ dT 2 þ eT  1 þ f T 3 þ gT 7 þ hT  9 þ iT 4 (J/mol) and Tc (K) is the Curie temperature and β is the average magnetic monent per atom (Bohr
magnetons).

defined as T=T Φ Φ
c and T c is the Curie temperature. For the solution
et al. [20] in the thermodynamic evaluation of the Ni–Al, and Ni–Al–Cr
Φ Φ systems with a special emphasis on the relationship among the
phase, T c and β are described as the following:
parameters for the ordered γʹ phase. The γʹ phase in the binary
n Ni–Al system was modeled with the two-sublattice model (Al,Ni)0.75
TΦ 0 Φ 0 Φ j Φ
c ¼ xA T cA þ xB T cB þ xA xB ∑ LTðA;BÞ ðxA  xB Þ
j
ð4Þ
j¼0
(Al,Ni)0.25 [8]. Considering the thermodynamic effect of the component
Mo, the two-sublattice model for γʹ was modified as (Al,Mo,Ni)0.75
(Al,Mo,Ni)0.25. Adopting the descriptions by Ansara et al. [8,47] and
n '
βΦ ¼ xA 0 βΦ 0 Φ j Φ
A þ xB β B þ xA xB ∑ Lβ ðA;BÞ ðxA  xB Þ
j
ð5Þ Dupin et al. [20], the Gibbs free energy, Gγm , for γʹ is expressed as the
j¼0
following:
0 Φ Φ
where β
T ci and 0 i are from the pure element i as listed in ðaÞ Gγm' ¼ Gγm ðxi Þ þ ΔGord
m ði : jÞ;
j Φ j Φ ð6Þ
Table 3. LTðA;BÞ and LβðA;BÞ are the magnetic interaction parameters ðbÞ ΔGord ord ord
m ði : jÞ ¼ Gm ði : jÞyIi ;yIIi  Gm ði : jÞxi ¼ yIi ¼ yIIi ;
between the elements A and B. In this work, the magnetic
parameters from the binary Al–Ni system [8] are employed as
where Gγm ðxi Þ is the Gibbs free energy of the disordered γ-fcc phase as
listed in Table 7.
The thermodynamic modeling of the ordered γʹ-Ni3Al and dis- described in Table 4. ΔGord
m ði; jÞ in Eq. (6) corresponds to the ordering
ordered γ-fcc phases was discussed by Ansara et al. [8,47] and Dupin energy, being described with Eq. (6b) [20,48]. Gord
m ði : jÞ in Eq. (6b) is
128 S.H. Zhou et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 46 (2014) 124–133

Table 4
Summary of the thermodynamic models used for the Al–Mo-Ni ternary system with the total Gibbs free energy GΦ
m ¼
ref Φ
Gm þ id GΦ xs Φ 0 ref
m þ Gm ( Gi ¼ 0 GfAlcc , 0 Gbcc 0 f cc
Mo or GNi ).

Phase Formulation Model

Liquid (Al,Mo,Ni)1 ref

GΦ
m ¼ ∑ xi 1GΦ
i
γ-fcc i ¼ Al;Mo;Ni

Bcc
id
GΦ
m ¼ RT ∑ xi ln xi
i ¼ Al;Mo;Ni
n n
xs
GΦ j Φ j j Φ
m ¼ xAl xMo ∑ LAl;Mo ðxAl  xMo Þ þ xAl xNi ∑ LAl;Ni ðxAl  xNi Þ
j
j¼0 j¼0
n
þ xMo xNi ∑ j LΦ j Φ
Mo;Ni ðxMo  xNi Þ þ xAl xMo xNi LAl;Mo;Ni ;
j¼0

LΦ 0 Φ 1 Φ 2 Φ
Al;Mo;Ni ¼ xAl LAl;Mo;Ni þ xMo LAl;Mo;Ni þ xNi LAl;Mo;Ni

ψ-AlMo (Al,Mo)1(Al,Mo)1 ref

GΦ yIIj 1GΦ
m ¼ ∑ yIi ∑ i:j
B2-NiAl (Al,Mo,Ni)1(Al,Mo,Ni,Va)1 i ¼ Al;Mo;Ni j ¼ Al;Mo;Ni
Φ
D0a-Ni3Mo (Al,Mo,Ni)0.75(Al,Mo,Ni)0.25 1GΦ
i:j ¼ p1G ref
i þ q1G ref
j þ ΔG Φ
i:j ¼ p1Gref
i þ q1Gref Φ
j þ ai:j þ bi:j T
GD0 D0a D0a
Al:Al ¼ GAl:Mo ¼ GAl:Ni ¼ 0
a id
GΦ ¼ RT ∑ ðpyIi ln yIi þ qyIIi ln yIIi Þ
m
i ¼ Al;Mo;Ni
xs
GΦ
m ¼ ∑ ∑ yIi yIl ∑ ∑ k LΦ I I k
i;l:j ðyi  yl Þ
i l4i j k¼0

þ ∑ ∑ ∑ yIIi yIIl ∑ k LΦ II II k
j:i;l ðyi  yl Þ
j i l4i k¼0

(p and q are the subscript numbers of sublattices, respectively)

γ’-Ni3Al (Al,Mo,Ni)0.75(Al,Mo,Ni)0.25 0
Gord 0 ord
i:j ¼ Gj:i ¼ 3uij
1

0 ord
Li;j:i ¼ 0 Lord 1
i;j:j ¼ 6uij
1 ord
Li;j:i ¼ 1 Lord 4
i;j:j ¼ 3uij
1 ord
Li:i;j ¼ 1 Lord 4
j:i;j ¼ uij
0 ord
Li;j:k ¼ 6u1ij þ ðuiijk þ ujijk Þ3=2
1 ord
Li;j:k ¼ 3u4ij þ ðuiijk  ujijk Þ=2
0 ord
Li;j;k:i ¼ 6uiijk  3ujijk =2  3ukijk =2

N (Al,Ni)2(Al,Ni)1(Mo)1 ref
GΦ I II III N
m ¼ ∑ yi ∑ yj ∑ yk 1Gi:j:k
GN
Ni:Al:Mo ¼ 0
i j k

D513-Al3Ni2 (Al)3(Al,Ni)2(Ni,Va)1 1GΦ ref ref ref N

i:j:k ¼ p1Gi þ q1Gj þ r1Gk þ ΔGi:j:k

δ-NiMo (Ni)24(Mo,Ni)20(Mo)12 id
GΦ I I II II III III
m ¼ RT∑ðpyi ln yi þ qyi ln yi þ ryi ln yi Þ
i
xs
GΦ I I n Φ I I n II II n Φ II II n
m ¼ ∑ ∑ yi yl ∑ ∑ Li;l:j:k ðyi  yl Þ þ ∑ ∑ ∑ yi yl ∑ Lj:i;l:k ðyi  yl Þ
i l4i j n¼0 j i l4i n¼0
n Φ III n
þ ∑ ∑ ∑ yIII III III
i yl ∑ Lk:j:i;l ðyi  yl Þ
j i l4i n¼0

ϕ-Al12Mo (Al)12(Mo)1 GΦ Φ ref ref

m ¼ ΔGi:j þ p1Gi þ q1Gj
φ-Al4Mo (Al)4(Mo)1 Φ
¼ aΦ þ b T þ p1Gref ref
i þ q1Gj
η-Al5Mo (Al)5(Mo)1
τ-Al63Mo37 (Al)63(Mo)37 (p and q represent subscript values in formulation, respectively.)
θ-Al8Mo3 (Al)8(Mo)3
A15–AlMo3 (Al)0.75(Mo)0.25
D011-Al3Ni (Al)0.75(Ni)0.25
ε-Al3Ni5 (Al)0.375(Ni)0.625
D1a-Ni4Mo (Ni)0.8(Mo)0.2
ρ-Ni2Mo (Ni)0.67(Mo)0.33
ζ-Ni8Mo (Ni)0.89(Mo)0.11

X (Al)0.75(Mo)0.11(Ni)0.14 GXm ¼ 0:750 GfAlcc þ 0:110 Gbcc 0 f cc X

Mo þ 0:14 GNi þ a þ b T
X

the Gibbs free energy contribution due to ordering with temperature and composition ranges, Gγm' should always have an
xi ¼ 3yIi =4 þ yIIi =4 as described by the two-sublattice model in extremum when yIi ¼ yIIi ¼ xi . When the disordered phase is stable,
Table 4 where yIi and yIIi are sit-fraction in first and second sublattices, this extremum is a minimum. Hence, the following equation [8,47]
respectively. It has three terms as shown in Eq. (2) and in Table 4 and has to be fulfilled:
contains implicitly a contribution to the disordered state also. When !
γ' ∂Gγm'
yIi ¼ yIIi ¼ xi , Gord
m ði : jÞ represents the extraneous excess energy con-
ðdGm Þxi ¼ ∑ ∑ dyðsÞ
i ¼0 ð7Þ
i s yðsÞ
i
tribution to the disorder state. Thus ΔGord
x
m ði; jÞ is described as the
i

difference between Gord

m ði : jÞyI ;yII and Gord
m ði : jÞxi ¼ yI ¼ yII in Eq. (6b) and From this equation, the parameters 0 Gord k ord k ord
i:j , Li;j:l , and Li:j;l can be
i i i i

must be zero when the phase is disordered. 0 Gord k ord k ord

i:j , Li;j:l , and Li:j;l
listed in Table 4 are the parameters for Gord
m ði : jÞ.
As described in reports [8,20,47,49], in order to favor the
stability of the ordered phase to disorder transit in certain
expressed with the parameters u1ij , u4ij , uiijk , ujijk , and ukijk (i, j, or
k¼ Al, Mo, or Ni) as shown in Table 4. The detail descriptions of the
parameter derivation for the ordered γʹ-Ni3Al phase can be found
in Refs. [20,49].
 S.H. Zhou et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 46 (2014) 124–133 129

Table 5
Symbols and related references used in Figs. 2–4.

Figure Boundary Single phase Two-phase Three-phase

Symbol Ref. Symbol Ref. Symbol Ref. Symbol Ref.

Figs. 3 and 5(b) ▽γ [26] ◆ γ þγʹ [27] ▼γ þδ þ bcc [26]

●bcc □γ þγʹ þbcc
△ γʹ ▲γ þγʹ þbcc [25]
◇δ
þγ [27]
*
γʹ

Fig. 4 ▲ bcc þliq [25] △fccþ bcc þliq [37]

○ bcc þliq [34]
■ fcc þ liq
◆ bccþ liq [38]
◇ fccþ liq
▼ Nþ liq [22]

Fig. 5(a) and (c) ▽γ [15] ✖N [22] ■ γ þγʹ [15]  γ þγʹ þbcc [15]
△ γʹ ●γ [15] δ þγ ◆ bcc þ B2 þγʹ
□ B2 N [23,24] ▼ bcc þγʹ ▲ γ þ bcc þδ
*

δ bcc þ B2 [29] B2þ bcc þ l12 [29]
þ bcc fccþ l12 þbcc
γ [22]
✧γʹ
◯γ [35]
◇γʹ
B2 [15]

Fig. 5(d) and (f) ▽γ ■ γ þγʹ [15] ✖ γ þγʹþ δ [15]

△ γʹ ▲ γʹþ δ * bcc þ δ þγʹ
□ B2 δþ γ ◆ bcc þ B2 þ γʹ

δ ▼ bcc þγʹ D0a þ γʹ þδ
γ [11] ✰γʹþ D0a γ þ γʹþ D0a [24]
✧γʹ ∅δ þD0a ✡ B2 þAlMo3 þN
 B2 ⊖γ þ D0a
δ
○γ [35]
◇γʹ
B2

Fig. 5(e) and (g) ▽γ [22] ● γʹ [28] ◇ δþ γ [31] ⊖ γ þ γʹþ δ [31]

*
△ γʹ N [22] ✰δ þ γʹ bcc þ δþ γʹ
○D0a ■X ∅ bcc þ γʹ ✶liqþ Al3Moþ N [36]
□ B2 ▲Al3Niþ X [36] liq þ Al3Ni2 þX
@
γ [32] ▼ γ þ γʹ [18] N þAl3Ni2 þ X
✧γʹ ◆γ þγʹ þ D0a [32]

δ ✖ γ þγʹþ δ
 D0a
Y γʹ [35]
✚γ

@γ þ γʹ two-phase field at 1048 K.

The N-NiAl8Mo3 phase has the D022 structure with the space The X phase was treated as stochiometric compounds with the
X
group I4/mmm [22,24]. Their atoms distribute in three-sublattices. Gibbs free energy functions as shown in Table 4, where aX and b
According to the first-principles data in Table 2a and experimental are the model parameters to be evaluated.
data [22,24] discussed in Section 2, the N-NiAl8Mo3 phase is
described with the three-sublattice model, (Al,Ni)2(Al,Ni)1(Mo)1, with
the Gibbs free energy given in Table 4, where yI and yII are the site 4. Determination of the thermodynamic model parameters
fractions in the first and second sublattices, respectively. The Gibbs
free energy of formation ΔGN i:j:Mo of the end-member i:j:Mo is The parameters described in the preceding section for the
ternary Ni–Al–Mo system were determined in the order of γ-fcc
N xs N
expressed as aN i:j:Mo þ bi:j:Mo T. G m is the excess Gibbs free energy
with the interaction parameters 0 LN 1 N
Al:Al;Ni:Mo and LAli:Al;Ni:Mo being and γʹ-Ni3Al phases, B2-NiAl, D0a-Ni3Mo, liquid, N and X phases
N
assumed as a constant. Both of them as well as aN i:j:Mo and bi:j:Mo are using the available experimental data in Table 5 and first-principles
evaluated with the experimental and first-principles data. data in Table 2a. The evaluated parameters as well as those of the
The thermodynamic models of B2-NiAl and D0a-Ni3Mo phases binary Ni–Al [8,20], Al–Mo [9] and Ni–Mo [21] systems are listed in
were described in detail in Refs. [8,21], respectively. The experi- Tables 6 and 7. In the present section, the methodology used for
mental data [11,15,35] revealed a small solubility of Mo in B2-NiAl the determination of the parameters is discussed.
and Al in D0a-Ni3Mo. The non-stoichiometric B2-NiAl and D0a- In both binary Ni–Al and Ni–Mo systems, Al and Mo dissolve in
Ni3Mo phases were modified here with the model shown in γ-fcc(Ni). The isothermal section at 1533 K is calculated only using
Table 4. Here we only consider the unstable end-members with the parameters of the three binary systems in Tables 6 and 7 and
the Gibbs free energy of formationsΔGB2 Al:Mo and ΔGMo:Ni for B2-
B2
shown in Fig. 3, where the calculated γ and γʹ two-phase region
NiAl and ΔGNi:Al for D0a-Ni3Mo.
D0a
deviates far from the experimental data [25–27] indicating that the
130 S.H. Zhou et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 46 (2014) 124–133

Table 6
Gibbs free energy of formation for end-member reference states (per mole of formula unit).

Phase Parameters Value, J/mol of atoms Ref.

D011-Al3Ni ΔGD0 11  48,483.73þ 12.299T

Al:Ni

D513-Al3Ni2a ΔGD5 13  39,465.978þ 7.895T

Al:Al:Ni
ΔGD5 13  427,191.9þ 79.217T
Al:Ni:Ni
ΔGD5 13 30,000  3T
Al:Al:Va
ΔGD5 13  357,725.92 þ 68.322T
Al:Ni:Va

ε-Al3Ni5 ΔGεAl:Ni  55,507.7594 þ7.265T [8]

B2-NiAl ΔGB2 a 0
Al:Al
ΔGB2 B2 a  152,397.3 þ 26.406T
Al:Ni , ΔGNi:Al
ΔGB2 a 1000  T
Al:Va
ΔGB2 a 0
Ni:Ni
ΔGB2 a 162,397.3  27.406T
Ni:Va
ΔGB2 150,000 [9]
Mo:Va
ΔGB2 150,000
Mo:Mo
ΔGB2 B2 5876 This work
Al:Mo , ΔGMo:Al
ΔGB2 B2 27,844
Mo:Ni , ΔGNi:Mo

γʹ-Ni3Al u1AlNi  13,415.515 þ 2.082T [8]

u4AlNi 7088.7363  3.687T
u1MoNi  341  3.515T This work
u4MoNi  3621.1 þ3.411T
u1AlMo 0
u4AlMo 0
uNi
AlMoNi
20,375 12.033T

ϕ-Al12Mo ΔGφAl:Mo  139,100 þ 26.975T [9]

φ-Al4Mo ΔGϕAl:Mo  137,570 þ29.69T
η-Al5Mo ΔGηAl:Mo  139,104þ 30.156T
τ-Al63Mo37 ΔGτAl:Mo  2,268,100 þ167.2T
θ-Al8Mo3 ΔGθAl:Mo  412,500 þ105.05T
ψ-AlMo ΔGψAl:Al 20,166.8  9.626aT
ΔGψMo:Al  36,850þ 1.0T
ΔGψMo:Mo 0
A15–AlMo3 ΔGA15  89,000 þ20T  0.003T2
Al:Mo
δ-NiMo ΔGδNi:Mo:Mo  169,981 þ1154.981T  155.484T ln (T) [21]
ΔGδNi:Ni:Mo  154,106þ 2855.001T  94.923T ln (T)
ρ-Ni2Mo ΔGρNi:Mo  9421 þ 49.551T  6.231T ln (T)

D0a-Ni3Mo ΔGD0 a 42,650 [21]

Mo:Mo
ΔGD0 a  10,131.9þ 58.132T  7.366T ln (T)
Ni:Mo
ΔGD0 a
Mo:Ni
17,060
ΔGD0 a 2840
Ni:Ni
ΔGD0 a  37,910 þ5.651T This work
Ni:Al
D1a-Ni4Mo ΔGD1 a  9021 þ 55.004T  7.080T ln (T) [21]
Ni:Mo
ζ-Ni8Mo ΔGςNi:Mo  6115 þ33.258T  4.085T ln (T)
N ΔGN  29,600þ 32.028T This work
Ni:Ni:Mo
ΔGN  119,040
Al:Ni:Mo
ΔGN  108,760 þ22.128T
Al:Al:Mo
X ΔGXAl:Mo:Ni  39,464.2 þ6.521T

0 0 0
a
Reference state is Al-bcc and Ni-bcc, i.e. Gref
i
¼ Gbcc bcc
Al or GNi .

binary interaction parameters for γ-fcc from both Ni–Al [8,20] and experimental data [11,15,22,26,35] indicate little solubility of Mo
Ni–Mo [21] systems predict a ternary γ-fcc-field that is too expan- in B2-NiAl. The model parameters ΔGB2 Mo:i (i ¼ Al,Ni), which are
sive; hence positive ternary interaction parameters here had to be considered as a constant in Table 4, were fixed with the first-
considered to reduce it. Similar behavior was also found in the principles data as listed in Tables 6 and 7.
ternary Ni–Al–Cr system modeled by Dupin et al. [20], in which the Based on the thermodynamic description in Section 3, the
positive ternary interaction parameter for γ-fcc(Ni) was employed. model parameters aD0 a D0a
and bNi:Al in Table 4 are used for the
Ni:Al
In addition to the parameters in the Al–Ni [8,20] and Ni–Mo
compound D0a-Ni3Mo. The parameter aD0 a
was determined with
[21], the thermodynamic properties of the γ and γʹ phases in the
Ni:Al
D0
the first-principles data, while bNi:Al
a
was evaluated with the phase
ternary Ni–Al–Mo system are described with the ternary interac-
tion parameters 0 γ γ γ
LAl;Mo;Ni , 1 LAl;Mo;Ni , 2 LAl;Mo;Ni , u1Mo;Ni , u4Mo;Ni and equilibrium data [15], i.e. the four-phase δ þ γ-γʹ þD0a reaction at
11637 5 K. The evaluated parameters are listed in Table 6.
uNi
AlMoNi .
These parameters are evaluated with the experimental According to the experimental phase equilibrium data [22–24]
data [11,15–18,22,26–35] and listed in Tables 6 and 7. The and first-principles data in Fig. 2, the composition range of the
 S.H. Zhou et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 46 (2014) 124–133 131

Table 7
Excess Gibbs free energy interaction parameters.

Phase Parameters Value, J/mol Ref.

Liquid 0 Liq
LAl;Ni  207,109þ 41.315T [8]
1 Liq
LA;Ni  10,186þ 5.871T
2 Liq
LA;Ni 81,205  31.957T
3 Liq
LA;Ni 4365  2.516T
4 Liq
LA;Ni  22,101.64 þ 13.163T
0 liq
LAl;Mo  100,000 þ 35T [9]
1 liq
LAl;Mo  15,000 þ 6.3T
0 liq
LMo;Ni  39,597þ15.935T [21]
1 liq
LMo;Ni  7373þ 4.102T
2 liq
LMo;Ni  12,123þ 5.551T
0 liq
LAl;Mo;Ni 50,748 This work
1 liq 70,748 Fig. 3. Isothermal section of the Ni–Al–Mo phase diagram calculated at 1533 K
LAl;Mo;Ni
using the parameters of the three binary systems in Tables 6 and 7 in comparison
2 liq
LAl;Mo;Ni 115,748 with experimental data with the symbols listed in Table 5.
bcc 0 bcc
LMo;Ni 27,691 [21]
1 bcc
LMo;Ni 18,792
0 bcc
LAl;Mo  75,000þ 25T [9]
γ-Fcc 0 γ
LAl;Mo  92,220 þ 20T
0 γ
LAl;Ni  162,407.75 þ16.213T [20]
1 γ
LAl;Ni 73,417.798  34.914T
2 γ
LAl;Ni 33,471.014  9.837T
3 γ
LAl;Ni  30,758.01 þ10.253T
0 γ
LTðAl;NiÞ  1112 [8]
1 γ 1745
LTðAl;NiÞ
0 γ
LMo;Ni  8916 þ3.591T [21]
1 γ
LMo;Ni 5469  0.249T
2 γ
LMo;Ni  1549  2.741T
0 γ
LAl;Mo;Ni 41,546  50.349T This work
1 γ 91,047
LAl;Mo;Ni
2 γ 193,074 12.948T
LAl;Mo;Ni
D513-Al3Ni2 0 D513
LAl:Al;Ni:Ni  193,484.18 þ 131.79T [8] Fig. 4. Liquidus projection of the Ni–Al–Mo system calculated in the composition
triangle using the parameters in Tables 6 and 7 indicating the primary phases and com-
0 D513
LAl:Al:Ni;V a  22,001.7þ 7.033T
paring with experimental data as the symbols in Table 5 and dash-line by Lu et al. [11].
0 D513
LAl:Ni:Ni;Va  22,001.7þ 7.033T
0 D513
LAl:Al;Ni:V a  193,484.18 þ 131.79T
B2-NiAl 0 B2  52,440.88 þ 11.3012T
LAl;Ni:Ni function of the N phase in which ΔGN Al:Ni:Mo ,
0 N
LAl:Al;Ni:Mo and
0 B2
LAl:Ni;Va  64,024.38þ 26.4949T 1 N
LAl:Al;Ni:Mo were assumed to be constant. The parameters,
0 B2  64,024.38þ 26.494T
aN Al:Al:Mo , were fixed by the first-principles
N
LNi:Ni;Va
Ni:Ni:Mo , aAl:Ni:Mo and aN
0 B2
LAl;Ni:Va  52,440.88 þ 11.301T N N
data. The parameters, bNi:Ni:Mo and bAl:Al:Mo , were evaluated with
ψ-AlMo 0 ψ
LAl;Mo:Al  5000 [9] the phase equilibrium data [22,24]. The interaction parameters,
0 N
0 ψ
LAl:Al;Mo  5000 LAl:Al;Ni:Mo and 1 LN
Al:Al;Ni:Mo , were evaluated with the first-principles
0 ψ 25,000 data in Fig. 2. For the X phase, due to the lack of experimental data,
LMo:Al;Mo
1 ψ
LMo:Al;Mo  10,000 the parameter aX in Table 4 had to be assumed by calculating the
0 ψ
LAl;Mo:Mo 25,000 enthalpy of mixing of the compounds N, D011-Al3Ni and D513-
X
1 ψ
LAl;Mo:Mo  10,000 Al3Ni2. The parameter b was evaluated with the phase equili-
δ-NiMo 0 δ  829,211þ 825.923T [21]
brium data [36].
LNi:Mo;Ni:Mo
1 δ  417,368 þ 326.504T
The liquid phase was described with the parameters of the
LNi:Mo;Ni:Mo
D0a-Ni3Mo 0 D0a
LMo;Ni:Mo  6710 three binary systems and ternary parameters, 0 Lliq
Al;Mo;Ni
, 1 Lliq
Al;Mo;Ni
0 D0a
LNi:Mo;Ni 1198–0.401T and 2 Lliq
Al;Mo;Ni
. Henry [25] studied the two alloys of Ni65.7Al17.6Mo16.7
N 0 N
LAl:Al;Ni:Mo  140,870 This work and Ni65.6Al14.4Mo20 using the optical microscopy and observed
1 N
LAl:Al;Ni:Mo  60,570 that the primary phase of the two alloys is the Mo-bcc phase
during the solidification. Svetlov et al. [34] studied the
liquid þsolids (solid¼ fcc or bcc) two-phase field at the Ni-rich
stable N phase is estimated between Ni12.5Al62.5Mo25 and corner using DTA and optical microscopy. Yoshizawa et al. [37]
Ni3Al72Mo25 at high temperatures. Fig. 2 shows the composition studied the eutectic reaction (liquid-bcc þ γ) using SEM and TEM.
with the minimum enthalpy of formation for the N phase being at The parameters, 0 Lliq , 1 Lliq and 2 Lliq , were evaluated
Al;Mo;Ni Al;Mo;Ni Al;Mo;Ni
NiAl8Mo3. Therefore, the interaction parameters, 0 LN Al:Al;Ni:Mo and with the primary solidification phase data [25,34,37]. The para-
LAl:Al;Ni:Mo , and the Gibbs free energies of formation, ΔGN
1 N
Ni:Ni:Mo ,
meters 0 Lbcc 1 bcc 2 bcc
Al;Mo;Ni , LAl;Mo;Ni and LAl;Mo;Ni were considered to be zero.
ΔGNAl:Ni:Mo and ΔGNAl:Al:Mo were considered for the Gibbs free energy
132 S.H. Zhou et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 46 (2014) 124–133
5. Phase equilibrium results
The Ni–Al–Mo phase diagrams computed from the Gibbs free energy functions
of individual phases described above are shown in Figs. 4 and 5. Relevant
Fig. 5. The isothermal section calculated at different temperatures in comparison
with experimental data as the symbols in Table 5 and the calculated results in
dash-line by Lu et al. [11]. (a) At 1573K, (b) at 1533K, (c1) overall composition at
1473K, (c2) Ni–rich corner at 1473K, (d1) overall composition at 1373K, (d2) Ni–
corner at 1373K and at 1273K, (e) at 1273K, (f) at 1153K and (g) at 1073K.
experimental data in Table 5 as well as the phase diagram calculated using the
parameters by Lu et al. [11] are also shown in Fig. 1(a), Figs. 4 and 5 for comparison.
The phase diagrams we propose here include several dramatic differences from
previously suggested phase diagrams as described briefly here.
Our model describes the ternary compound N and X phases using a three-
sublattice model and as a stoichiometric compound, respectively, which were
ignored by Lu et al. [11]. The first-principles calculated enthalpies of formation of
the N phase in Fig. 2 were used to evaluate the thermodynamic parameters of the N
phase. In addition, our first-principles data were used to determine the Gibbs
energy of the end-members of the B2-NiAl and D0a-Ni3Mo phases. This differs
greatly from the modeling by Lu et al. [11]. The other major contributor of this work
is that the recent descriptions of the binary Ni–Al [20] and Ni–Mo [21] in Fig. 1
were adopted for better description of γ and γʹ in the Ni–Al–Mo system.
The current model liquidus projection of the Ni–Al–Mo system is plotted in
Fig. 4, showing a good agreement with experimental data [22,25,34,37,38]. In
comparison with our results, the liquidus projection calculated using parameters by
Lu et al. [11] shows two significant differences in Fig. 4. In our calculation, the N
phase is a primary phase on Al rich side while the calculated primary phase by Lu
et al. [11] is the θ-Al8Mo3 phase as marked with “Al8Mo3” in gray in Fig. 4. Second, a
curve as marked “A-line” in Fig. 4 is calculated using the parameters by Lu et al.
[11]. This curve starts from the binary Ni–Mo system as shown in Fig. 1
(a) indicating that the B2 phase can be the primary phases in the liquidus
projection.
Fig. 6. γ-fcc and γʹ-Ni3Al single-phase domains plotted in 3D as computed using the
present model where symbol ϑ (ϑ ¼ liq, bcc, B2, and δ) indicates the phase
equilibrium with γ-fcc or γʹ-Ni3Al.
 S.H. Zhou et al. / CALPHAD: Computer Coupling of Phase Diagrams and Thermochemistry 46 (2014) 124–133
The calculated isothermal sections at 1573, 1533 and 1473 K along with the
experimental data in Table 5 are shown in Fig. 5(a–c), in which the calcu-
lated equilibrium phases are in good agreement with the experimental data
[15,22–27,29,35]. The calculated isothermal sections at 1473 and 1373 K plotted
in Fig. 5 (c and d) show the invariant reaction γ þbcc-γʹ þ δ, which occurs at
1400 K. According the experimental data, the invariant reaction γ þbcc-γʹþ δ
temperature is between 1356 and 1420 K by Miracle et al. [26], between 1300 and
1400 K by Hong et al. [30] and at 1403 K by Wakashima et al. [31]. This means that
our calculated invariant reaction γ þ bcc-γʹþ δ is in good agreement with the
experimental data [26,30,31]. Furthermore, our calculated results show an agree-
ment with the experimental data [15] of the γ þ γʹ two-phase region in Fig. 5(c),
while the calculated results by Lu et al. [11] are in the single fcc phase region.
Fig. 5(d) and (e) shows the isothermal section calculated at 1373 and 1273 K
with experimental data [11,15,18,22,24,28,31,32,35,36]. There are two significant
differences between Fig. 5(d) and (e). First, the X phase appears in Fig. 5(e). Our
calculated results indicate that the X phase forms at 1282 K, which is in reasonable
agreement with the experimental data 1288 K measured by Grushko et al. [36].
Second, the invariant reaction, liqþ θ-Nþ φ, occurs at 1355 K. It should be noted
that the data by Grushko et al. [36] plotted in Fig. 5(e) indicate the liqþ Al3Mo þN
three phases in equilibrium at 1273 K. This is inconsistent with our calculated
liq þ φ-Al4Mo þN three-phase equilibrium. According to the thermodynamic
description for the binary Al–Mo system [9] adopted in this work with the
associated phase diagram in Fig. 1(d), the liquid, Al4Mo, Al8Mo3, AlMo3 and bcc
phases are stable at 1273 K, while the Al3Mo phase is not considered as a stable
phase. The stability of the Al3Mo phase needs to be confirmed in future work.
Fahrmann et al. [16,17] investigated the Ni79.2Al6.4Mo14.4 and Ni77.97Al12.9Mo9.13
alloys. In the Ni79.2Al6.4Mo14.4 alloy aged at 1258 K, minor amounts of the δ-NiMo
phase was observed [16,17] which is consistent with our calculated result i.e. the
mole fraction of the δ-NiMo phase in Ni79.2Al6.4Mo14.4 alloy is 0.0057 which is very
little. The volume fraction of the γʹ phase for the Ni77.97Al12.9Mo9.13 alloy calculated
at 1258 K in this work is 0.61, which is in good agreement with the experimental
data 0.60 7 0.06 [16,17], while that calculated using parameters by Lu et al. [11] is
0.54. It is clear that our model yields better agreement with experimental data
[16,17].
Fig. 5(f) and (g) shows the isothermal sections calculated at 1153 and 1073 K,
respectively, with the experimental data [15,22,24,32,35,36]. Comparing with Fig. 5
(e), the calculated four phase δ þ γ-γʹþ D0a reaction occurs at 1167 K, which is in a
good agreement with the experimental phase transformation data 1163 75 K [15].
In Fig. 5(f), the experimental data [15], which indicated the γ þ γʹ two-phase region,
are in agreement with our calculated results, but outside the calculated γ þ γʹ two-
phase region using the parameters by Lu et al. [11]. A similar problem is also shown
in Fig. 5(g), where our calculated results shown better agreement with the
experimental γ þ γʹ two-phase field data [18] than those by Lu et al. [11]. To
understand the stabilities of the γ and γʹ phases, we plotted the stable γ and γʹ
phase field in the related composition triangle over the temperature range 1200–
1800 K in Fig. 6, which is useful for Ni-based superalloy design by showing the
stable γ, γʹ and γ þ γʹ phase domains with related composition and temperature
dimensions.
6. Summary
By combining CALPHAD approach with the first-principles
calculations, a thermodynamic model was developed for the
ternary Ni–Al–Mo system. The present work exhibits several key
differences relative to previously reported models: (i) first-
principles calculations were used to determine some thermody-
namic parameters, (ii) both ternary compounds N and X, and the
first-principles calculations confirm that the N-compound is only
marginally stable; (iii) calculated phase diagrams exhibit improved
agreement with the experimental data.
Acknowledgment
This work was supported by the Pennsylvania State University
by the NSF Grants (DMR-9983532, DMR-0122638, and DMR-
0205232). First-principles calculations were carried out on the
LION clusters at the Pennsylvania State University supported in
part by the NSF Grants (DMR-9983532, DMR-0122638, and DMR-
0205232).
133
Appendix A. Supporting information
Supplementary data associated with this article can be found in
the online version at http://dx.doi.org/10.1016/j.calphad.2014.03.002.
References
[1] S. Miyazaki, Y. Murata, M. Morinaga, Tetsu To Hagane—J. Iron Steel Inst. Jpn. 80
(1994) 166.
[2] S. Miyazaki, Y. Kusunoki, Y. Murata, M. Morinaga, Tetsu To Hagane–J. Iron Steel
Inst. Jpn. 81 (1995) 1168.
[3] R. Hashizume, A. Yoshinari, T. Kiyono, Y. Murata, M. Morinaga, Development of
Ni-based single crystalsuperalloys for power-generation gas turbines, in:
K.A. Green, H. Harada, T.M. Pollock, T.E. Howson, R.C. Reed (Eds.), Superalloys
2004, Minerals, Metals & Materials Soc, Champion, PA, 2004, p. 53.
[4] R. Yamamoto, Y. Kadoya, H. Kawai, R. Magoshi, S. Ueta, T. Noda, S. Isobe, J. Iron
Steel Inst. Jpn. 90 (2004) 37.
[5] J.E. Gould, F.J. Ritzert, W.S. Loewenthal, Preliminary investigations of joining
technologies for attaching refractory metals to Ni-based superalloys, in:
M.S. ElGenk (Ed.), Space Technology and Applications International Forum
(STAIF 2006), Amer Inst Physics, Albuquerque, NM, 2006, p. 757.
[6] J. Lapin, J. Marecek, M. Kursa, Kov. Mater. Met. Mater. 44 (2006) 1.
[7] L. Kaufman, H. Nesor, Metall. Trans. 5 (1974) 1623.
[8] I. Ansara, N. Dupin, H.L. Lukas, B. Sundman, J. Alloy. Compd. 247 (1997) 20.
[9] N. Saunders, J. Phase Equilib. 18 (1997) 370.
[10] K. Frisk, CALPHAD 14 (1990) 311.
[11] X. Lu, Y. Cui, Z. Jin, Metall. Mater. Trans. A 30A (1999) 1785.
[12] R.E.W. Casselton, W. Hume-Rothery, J. Less-Common Met. 7 (1964) 212.
[13] G. Grube, H. Schlecht, Z. Elektrochem. 44 (1938) 413.
[14] C.P. Heijwegen, G.D. Rieck, Z. Metallkd. 64 (1973) 450.
[15] S.B. Maslenkov, N.N. Burova, V.A. Rodimkina, Russ. Metal (1988) 179.
[16] M. Fahrmann, W. Hermann, E. Fahrmann, A. Boegli, T.M. Pollock, H.G. Sockel,
Mater. Sci. Eng. A 260 (1999) 212.
[17] M. Fahrmann, E. Fahrmann, T.M. Pollock, W.C. Johnson, Metall. Mater. Trans.
A 28 (1997) 1943.
[18] M. Fahrmann, P. Fratzl, O. Paris, E. Fahrmann, W.C. Johnson, Acta Metall. Mater.
43 (1995) 1007.
[19] S.H. Zhou, Y. Wang, C. Jiang, J.Z. Zhu, R.A. MacKay, L.Q. Chen, Z.K. Liu, in: K.A.
Green, H. Harada, T.M. Pollock, T.E. Howson, R.C. Reed (Eds.), Superalloys 2004,
Champion, PA, TMS (The minerals, Metals & Materials Society 2004), 2004, p.
969.
[20] N. Dupin, I. Ansara, B. Sundman, CALPHAD 25 (2001) 279.
[21] S.H. Zhou, Y. Wang, C. Jiang, J.Z. Zhu, L.-Q. Chen, Z.-K. Liu, Mater. Sci. Eng. A 397
(2005) 288.
[22] V.Y. Markiv, V.V. Burnashova, L.I. Pryakhina, K.P. Myasnikova, Izv. Akad. Nauk
SSSR Metall 5 (1969) 180.
[23] K. Schubert, A. Raman, W. Rossteutscher, Naturwissenschaften 51 (1964) 506.
[24] A. Raman, K. Schubert, Z. Metallkd 56 (1965) 99.
[25] M.F. Henry, Scripta Metall 10 (1976) 955.
[26] D.B. Miracle, K.A. Lark, V. Srinivasan, H.A. Lipsitt, Metall. Trans. A 15A (1984)
481.
[27] S. Chakravorty, D.R.F. West, Met. Sci 18 (1984) 207.
[28] M.P. Arbuzov, I.A. Zelenkov, Fiz. Metal. Metalloved. 15 (1963) 725.
[29] P. Nash, S. Fielding, D.R.F. West, Met. Sci 17 (1983) 192.
[30] Y.M. Hong, Y. Mishima, T. Suzuki, Mater. Res. Soc. Symp. Proc 133 (1989) 429.
[31] K. Wakashima, K. Higuchi, T. Suzuki, S. Umekawa, Acta Metall. 31 (1983) 1937.
[32] S. Chakravorty, D.R.F. West, J. Mater. Sci. 19 (1984) 3574.
[33] S. Chakrovorty, D.R.F. West, Mater. Sci. Technol. 1 (1985) 61.
[34] I.L. Svetlov, A.L. Udovskii, E.V. Monastyrskaya, I.V. Oldakovskii, M.P. Nazarova,
Russ. Metal (1987) 186.
[35] C.C. Jia, K. Ishida, T. Nishizawa, Metall. Mater. Trans. A 25 (1994) 473.
[36] B. Grushko, S. Mi, J.G. Highfield, J. Alloy. Compd. 334 (2002) 187.
[37] H. Yoshizawa, K. Wakashima, S. Umekawa, T. Suzuki, Scr. Metall. 15 (1981)
1091.
[38] H. Sprenger, H. Richter, J.J. Nickl, J. Mater. Sci. 11 (1976) 2075.
[39] Y. Jin, M.C. Chaturvedi, Y.F. Han, Y.G. Zhang, Mater. Sci. Eng. A 225 (1997) 78.
[40] G. Kresse, T. Demuth and F. Mittendorfer. 〈http://cms.mpi.univie.ac.at/vasp/〉
vol. 2003, 2003 .
[41] D. Vanderbilt, Phys. Rev. B 41 (1990) 7892.
[42] J.P. Perdew, J.A. Chevary, S.H. Vosko, K.A. Jackson, M.R. Pederson, D.J. Singh,
C. Fiolhais, Phys. Rev. B 46 (1992) 6671.
[43] A. van de Walle, M. Asta, G. Ceder, CALPHAD 26 (2002) 539.
[44] A.T. Dinsdale, CALPHAD 15 (1991) 317.
[45] O. Redlich, A.T. Kister, Ind. Eng. Chem. 40 (1948) 345.
[46] M. Hillert, M. Jarl, CALPHAD 2 (1978) 227.
[47] I. Ansara, B. Sundman, P. Willemin, Acta Metall. 36 (1988) 977.
[48] B. Sundman, I. Ansara, M. Hillert, G. Inden, H.L. Lukas, K.C.H. Kumar, Z. Metallk.
92 (2001) 526.
[49] C.R. Li, J.C. Hu, F.M. Wang, Z.M. Du, W.J. Zhang, CALPHAD 30 (2006) 387.