Experimental and Thermodynamic Investigation of the

Ni-Al-Mo System
XIAOGANG LU, YUWEN CUI, and ZHANPENG JIN

The diffusion triple and electron probe microanalysis (EPMA) techniques have been adopted to study
the isothermal section of the Ni-Al-Mo system at 1373 K. Experimental data from present work and
literature have been assessed to evaluate the thermodynamic parameters of the ternary system by
means of the calculation of phase diagram (CALPHAD) method. A substitutional-solution model is
used to describe liquid, fcc, and bcc phases, while a sublattice model is used to describe intermetallic
phases. Two sets of thermodynamic descriptions have been obtained, and comparison has been made
between them. Also, calculations of equilibrium-phase diagrams compared to the experimental data
have been presented. There is good agreement between the calculations and the experimental data.

I. INTRODUCTION effective and powerful approach to determining phase dia-

grams, plays a dominant role in the study of complex metallic
A NEW generation of turbine-blade materials, necessary systems. Accordingly, this method is utilized in this study.
for advanced high-performance engines, has been under
development for decades. The Ni-Al-Mo system was chosen
as a base, since great attention has been focused on direc- A. Experimental Procedures
tional solidification of fcc(Ni)/L12 (Ni3Al) 1 bcc(Mo) eutec-
Starting materials were high-purity aluminum (99.99 wt
tic superalloys, which show excellentproperties both at room
pct), electrolytic nickel (99.97 wt pct), and a molybdenum
and at elevated temperatures. Much work has been done to
bar (99.97 wt pct).
investigate phase stabilities and to establish phase relations,
Alloys 1 and 2 were prepared by argon are melting on
such as that by Henry,[1] Yoshizawa et al.,[2,3] Wakashima
a cooled copper hearth, using a nonconsumable tungsten
et. al.,[4] Nash et al.,[5] Miracle et al.,[6] and Maslenkov et
electrode. Each alloy button was turned over three times
al.[7,8] However, they are not always consistent with each
and remelted to make it more homogeneous. No significant
other and even result in contradictions. To fully understand
loss in weight occurred, so the alloys were believed to have
the microstructural evolution of Ni-Al-Mo superalloys dur-
the desired compositions. The nominal compositions of the
ing processing and long-term exposure to various working
alloys are listed in Table I.
conditions, all related information should be assessed and a
Polished bulk Mo and Ni were first bound with thin Mo
complete thermodynamic description should also be
cords and put into vacuumed (1021 Pa) quartz tubes. After
obtained for the purpose of further theoretical prediction and
heating in a GK-2B–type diffusion furnace at 1373 K for
simulation. Early work by Kaufman and Nesor[9] has been
96 hours, a layer of compound appeared, binding the bulk
done to calculate some isothermal sections of the Ni-Al-Mo
Mo and Ni together to form the so-called diffusion couple.
system. However, due to the lack of experimental data at
Then, the couples and alloys were polished and assembled
that time, that work needs to be improved. Recent work by
to form well-contacted metal-alloy diffusion triples, as illus-
Huang and Chang,[10] Ansara et al.,[11] Saunders,[12] and Cui
trated in Figure 1. Triples 1 and 2 were again sealed in
and Jin,[13] which focused on sub-binary systems of the Ni-
evacuated (1021 Pa) quartz tubes, and triple 3 was argon
Al-Mo system, have formed the basis of the present work.
protected. All the triples were heated in the same type of
The objective of the present work is mainly centered on the
furnace, at 1373 K, for different times. The heat-treatment
assessment of thermodynamic parameters of each phase as
conditions are shown in Table II. The temperature was con-
well as experimental study.
trolled to within 65 K. After annealing, the triples were air-
quenched, during which the cooling rate is fast enough to
keep the microstructure at room temperature. The triples
II. EXPERIMENTAL INVESTIGATION were then polished parallel to the diffusion direction. Finally,
Almost all experiments conducted on the Ni-Al-Mo sys- the local compositions were analyzed by electron probe
tem to establish phase relations are based on the method of microanalysis (EPMA) performed on a CAMECA SX-50
analyzing the microstructure of alloys (Wakashima et al.,[4] electron probe. The measurement was operated at 15 kV
Nash et al.,[5] Miracle et al.,[6] and Maslenkov et al.[7,8]). using pure Ni, Al, and Mo as standards. The microprobe
The diffusion triple technique, on the other hand, as an intensity data were corrected using the ZAF computer soft-
ware program. The relative error of the compositional analy-
sis is estimated to be less than 1 pct of the individual element.

XIAOGANG LU and YUWEN CUI, Postdoctoral Students, and ZHAN-

PENG JIN, Professor, are with the Department of Materials Science and B. Results and Discussion
Engineering, Central South University of Technology, Hunan 410083, Peo-
ple’s Republic of China. Figure 2(a) is the back-scattered electron (BSE) image of
Manuscript submitted August 24, 1998. triple 2 in the contacted region, which contains a two-phase

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 30A, JULY 1999—1785

 Table I. Nominal Compositions of Binary Alloys
Alloy Number Al(At. Pct) Second Element(At. Pct)
1 51.00 49.00 (Ni)
2 73.38 26.62 (Mo)

(a)

Fig. 1—Assembly of diffusion triple.

Table II. Heat Treatment Conditions of Diffusion Triples

Diffusion
Triple Time
Number Assembly Parts Atmosphere (Hour)
1 Mo-Ni 1 alloy 1 vacuum (10 Pa)
21
2 Mo-Ni 1 alloy 1 vacuum (1021 Pa)
3 Mo-Ni 1 alloy 2 argon protected
area. The BSE images of triple 3 are shown in Figures 3(a)
through (c), which correspond to areas A, B, and C in Figure
3(d), respectively. Figure 3(a) shows the contacted region
between the bulk Mo, Ni, and alloy 2. In Figure 3(b), three
two-phase layers can be seen. In Figure 3(c), two single-
phase layers are located between the bulk Ni and the afore-
mentioned two-phase layers. The dark black areas found in
Figures 3(a) through (c) are caused by small pores, which
are difficult to avoid when polished. Area D in Figure 3(d)
is also full of pores, and measurement cannot be performed
in this area.
The phase relations determined from the three triples agree
well with previous experiments (Nash et al.,[5] Miracle et
al.,[6] and Maslenkov et al.[8]). As seen in Figure 4, measure-
ments of triples 1 and 2 produce almost the same results,
which are listed in Table III and have been used in the
present thermodynamic assessment. All the determined equi-
librium tie-lines in Table III have been obtained by extrapo-
lating the concentration profile across the interface, between
pairs of phases. The equilibrium triangle, on the other hand,
has been measured in the area very close to the contacting
point of the three equilibrium phases by EPMA, and it is an
(b)
Fig. 2—(a) BSE image of triple 2 in the contacted region between Mo,Ni
and alloy. (b) Schematic diagram of phase distribution.
840
696
840 average value of several groups of individual measurements.
The measurements of triple 3, however, give imprecise com-
positions due to its fine particles and porous structure. So,
the tie-lines coming from triple 3, plotted in Figure 4, should
serve only as the indicative phase relations.
No ternary phase was found in the present experiment.
Guard and Smith[14] detected a ternary compound in the
vicinity of 58 at. pct Ni-34.5 at. pct Al-7.5 at. pct Mo, but did
not determine the crystal structure. Since their homogenizing
time was only 72 hours at 1448 K, this phase may not be
the stable one. Markiv[16] and Virkar and Raman[15] found
three ternary phases in the Al-rich corner at 1073 and 1223
K, respectively. However, no experiment confirms their
observations. Further work is needed to study the ternary
phase.
III. THERMODYNAMIC ASSESSMENT
A. Binary System
Thermodynamic descriptions of the binary subsystem of
the Ni-Al-Mo system must be done prior to the present
assessment.
1. Ni-Al System
Huang and Chang[10] and Ansara et al.[11] have calculated
Ni-Al, and their calculations agree with experimental data

1786—VOLUME 30A, JULY 1999 METALLURGICAL AND MATERIALS TRANSACTIONS A

 (a)

(d )
(b)

(c)
Fig. 3—BSE images of triple 3. (a) Contacted region between Mo,Ni and alloy, 1: L12(dark) 1 NiMo(gray), 2: L12(dark) 1 bcc(gray), and 3: B2(dark)
1 bcc(gray); (b) two-phase layers, 1: B2(dark) 1 bcc(bright), 2: B2(dark) 1 AlMo3(bright), and 3: AlMo3(bright) 1 Al8Mo3 (gray); (c) single-phase layers;
and (d ) schematic diagram of phase distribution, areas 1, 2, and 3 corresponding to (a), (b), and (c), respectively.

fairly well. Concerning the fcc and L12 phases, they used
the same method proposed by Ansara et al., which will be
reviewed briefly in Section III–B–3. But Huang and Chang
simplified the modeling by using a virtual disordered phase
other than fcc as the disordered contribution to the L12 phase,
which gave lesser parameters to describe this system. Table
IV lists some of the key parameters which show such differ-
ence. Figure 5 shows the calculated phase diagram by Huang
and Chang.
In this work, both sets of parameters are used to optimize
the ternary system, in order to determine which one is better.
2. Al-Mo system
This system has been evaluated by Saunders,[12] and the
calculated phase diagram is presented in Figure 6. Most
intermetallic phases in the Al-Mo system are treated as stoi-
chiometric phases, except for the AlMo phase.
3. Mo-Ni system
In Mo-Ni system, the solubility of Mo in the fcc phase,
determined by Casselton and Hume-Rothery,[17] is higher
than that of Heijwegen and Riech,[18] which was selected
for assessment by Frisk.[19] Also, Ni4Mo decomposes to
Ni3Mo and NiMo phases at very low temperatures, which
is not confirmed by the experiment. So, the thermodynamic
descriptions have been modified by Cui and Jin,[13] based
on the work of Frisk, to get a better agreement between
the experiments and calculations. In the present work, it is
important to note that such modification makes the ternary
assessment more easy and reasonable, which will be dis-
cussed in Section III–D. Figure 7 is the modified Ni portion
of the Mo-Ni phase diagram[13] compared to the experimental
data and that calculated by Frisk. The whole system is shown
in Figure 8.

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 30A, JULY 1999—1787

 Table IV. The Thermodynamic Data of Ni-Al System from
Huang and Chang [10] and Ansara et al.[11]

Data from Huang

Parameters and Chang[10] Data from Ansara et al.[11]
Liquid:
0L
Al,Ni 2194,177 1 28.663T 2207,109.28 1 41.31501T
1L
Al,Ni 4829 210,185.79 1 5.87140T
2L
Al,Ni 53,042 2 9.121T 81,204.81 2 31.95713T
3
LAl,Ni — 4365.35 2 2.51632T
4L
Al,Ni — 222,101.64 1 13.16341T
Fcc:
0L
Al,Ni 2168,292 1 16T 2162,407.750 1 16.212965T
1
LAl,Ni 32,712 73,417.798 2 34.914T
2L
Al,Ni 27998 1 35T 33,471.014 2 9.837T
3
LAl,Ni — 230,758.01 1 10.253T
L12:
u1AlNi 243,686 1 8.6418T 240,246.545 1 6.2457741T
u4AlNi — 7088.736 2 3.6868954T
0
LAl,Ni:* 2u1AlNi 2u1AlNi
1L
Al,Ni:* — 3u4AlNi
1
L*:Al,Ni — u4AlNi
Disordered contribution to L12:
Fig. 4—Present measured equilibrium data (thick lines and marks) at 0L
218,928 1 12u1AlNi (the same as fcc)
Al,Ni
1373 K. 1L
Al,Ni 27813 1 34.404T
2
LAl,Ni 67,054

Table III. The Equilibrium Data Determined by EPMA at

1373 K (Atomic Percent)

fcc L12 (Ni3Al) B2 (NiA1) L12 (Ni3Al)

Ni Mo Ni Mo Ni Mo Ni Mo
83.7 2.9 78.5 2.9 63.3 0.3 71.4 1.3
78.6 11.5 75.5 5.0 63.1 0.1 72.9 1.7
83.0 0.0 76.0 0.0 62.4 0.3 72.3 2.0
Ll2(Ni3Al) NiMo 63.7 0.0 71.8 0.2
Ni Mo Ni Mo fcc NiMo
74.9 4.0 46.7 51.2 Ni Mo Ni Mo
fcc Ll2(Ni3Al) NiMo 76.5 23.1 50.0 49.8
Ni Mo Ni Mo Ni Mo
76.3 14.9 75.9 5.0 48.9 49.4

B. Thermodynamic Modeling of the Ternary System

All the phases considered in the present work are listed
in Table V with their formulae. No ternary phase is consid-
ered in the present work, since there is no confirmed experi- Fig. 5—Calculated Ni-Al system by Huang and Chang.[10]
mental information.
1. Substitutional solutions 2 3
Liquid, fcc, and bcc phases are treated as substitutional
solutions. The molar Gibbs energy is expressed as
ex
Gm 5 o o
i51 j5i11
[xi xj /(Vi,jVj,i)]?exGi,j

Gm 5 xAl8GAl 1 xNi8GNi 1 xMo8GMo 1 xAl xMo xNi(xAl8LAl,Mo,Ni 1 xMo1LAl,Mo,Ni [2]

2
1 RT (xAl ln xAl 1 xMo ln xMo 1 xNi ln xNi) [1] 1 xNi LAl,Mo,Ni)
1 ex Gm 1 mag
Gm where *LAl,Mo,Ni denotes ternary interaction parameters
which will be evaluated in the present work, and exGi,j
where R 5 8.31451 J mol21 K21, xi is the mole fraction of denotes the binary excess Gibbs energy. The terms Vi,j and
element i, and 8Gi is the molar Gibbs energy of the element Vj,i are represented by
i in a hypothetical nonmagnetic state, which can be taken
from the database of Dinsdale.[20] The excess Gibbs energy 1 1 Xi 2 Xj 1 1 Xj 2 Xi
Vi,j 5 , Vj,i 5 [3]
(ex Gm) is represented by 2 2

1788—VOLUME 30A, JULY 1999 METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 6—Calculated Al-Mo system by Saunders.[12]
Fig. 8—The modified Mo-Ni system by Cui and Jin.[13]

Table V. All the Phases and their Formulae Included in

Ternary System

Phase Formula
Liquid, bcc, and fcc (Al,Mo,Ni)
Al3Ni (Al)0.75(Ni)0.25
Al3Ni2 (Al)3(Al,Mo,Ni)2(Mo,Ni,Va)1
Al3Ni5 (Al)0.375(Ni)0.625
B2(NiAl) (Al,Mo,Ni)1(Mo,Ni,Va)1
L12(Ni3Al) (Al,Mo,Ni)0.75(Al,Mo,Ni)0.25
Disordered contribution (Al,Mo,Ni)
Al12Mo (Al)0.923(Mo)0.077
Al4Mo (Al)0.8(Mo)0.2
Al5Mo (Al)0.833(Mo)0.167
Al63Mo37 (Al)0.63(Mo)0.37
Al8Mo3 (Al)0.727(Mo)0.273
AlMo (Al,Mo,Ni)1(Al,Mo,Ni)1
Cub A15(AlMo3) (Mo)0.75(Al)0.25
NiMo (Ni)24(Al,Mo,Ni)20(Mo)12
Ni4Mo (Mo)4(Ni)1
Ni3Mo (Al,Mo,Ni)3(Al,Mo,Ni)1
Fig. 7—The modified Ni-rich portion of the Mo-Ni system together with
the experimental data. Dashed lines are the calculated results by Frisk.[19]

characterize the L12 phase. The molar Gibbs free energy of

where both i and j represent the elements Al, Mo, and Ni the phase is expressed by
(i Þ j). The first group of terms in Eq. [2] represents the
binary contribution to the excess Gibbs energy, according Gm 5 y1Ni y2Ni 8GNi:Ni 1 y1Ni y2Al 8GNi:Al 1 y1Ni y2Mo 8GNi:Mo
to the extrapolation scheme suggested by Muggianu et al.[21] 1 y1Al y2Ni 8GAl:Ni 1 y1Al y2Al 8GAl:Al 1 y1Al y2Mo 8GAl:Mo
The last term is the ternary contribution. All the interaction
parameters may contain a temperature coefficient. The term 1 y1Mo y2Ni 8GMo:Ni 1 y1Mo y2Al 8GMo:Al 1 y1Mo y2Mo 8GMo:Mo
mag
Gm is the magnetic contribution described by Hillert and
Jarl.[22] This term is assumed to be zero for the liquid phase. 1 RT [0.75 ( y1Ni ln y1Ni 1 y1Al ln y1Al 1 y1Mo ln y1Mo)

2. Intermetallic phases 1 0.25 ( y2Ni ln y2Ni 1 y2Al ln y2Al 1 y2Mo ln y2Mo)] 1 ex Gm [4]
Six phases (Al3Ni2, B2, L12, AlMo, Ni3Mo, and NiMo) The site fraction of element i in sublattice s is denoted as
are treated as phases with solubilities in the ternary system. y si . The parameter 8GNi:Al is the Gibbs energy of phase L12,
They are described using the sublattice model developed by with Ni in the first sublattice and Al in the second. Its value
Hillert and Staffanson.[23] Here, an expression of molar is given by the following expression:
Gibbs energy is provided as an example.
The formula (Al, Ni, Mo)0.75(Al, Ni, Mo)0.25 is used to 8GNi:Al 5 0.75 8Gfcc fcc
Ni 1 0.25 8GAl 1 DG [5]

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 30A, JULY 1999—1789

where DG is obtained from optimization.Other 8G*:* parame-
ters have similar meanings.
All other intermetallic phases have negligible solubility
ranges in binary systems. They are assumed to be stoichio-
metric phases in the ternary system and are not remodeled
in the present work.
3. Fcc and L12 phases
There is an order-disorder transformation between the fcc
and L12 phases, which are based on the same fcc structure
despite of a different occupancy of atoms on each sublattice.
So, it is reasonable to describe both phases with a united
model. To study such transformation in the Ni-Al system,
Ansara et al.[11] used a two-sublattice model to describe
them after the formula (Ni, Al)0.75(Ni, Al)0.25. The molar
Gibbs free energy of the phases is expressed by
Gm 5 y1Ni y2Ni 8GNi:Ni 1 y1Ni y2Al 8GNi:Al 1 y1Al y2Ni 8GAl:Ni
1 y1Al y2Al 8GAl:Al 1 RT [0.75 ( y1Ni ln y1Ni 1 y1Al ln y1Al)
1 0.25 ( y2Ni ln y2Ni 1 y2Al ln y2Al)]
1 y1Ni y1Al ( y2Ni 8LNi,Al:Ni 1 y2Al 8LNi,Al:Al)
1 y2Ni y2Al ( y1Ni 8LNi:Ni,Al 1 y1Al 8LAl:Ni,Al)
The meaning of the symbols in Eq. [6] is the same as
those in Eq. [4]. When y1i 5 y2i 5 xi, where xi is the mole
fraction of element i of the phase, this is the case of a
disordered state, i.e., the fcc phase; thus, Eq. [6] is equivalent
to the molar Gibbs energy of the substitutional model. When
y1i Þ y2i, there is ordering on each sublattice, i.e., the phase
exists with the structure of the L12 phase. In order to ensure
that the disordered state is always possible, there are con-
straints for the parameters in Eq. [6]:[11]
8GNi:Al 5 u1
8GAl:Ni 5 u2
8LNi,Al:Ni 5 3u1 1 u2/2 1 3u3
8LNi,Al:Al 5 3u2 1 u1/2 1 3u3
8LNi:Ni,Al 5 u2/2 1 u3
8LAl:Ni,Al 5 u1/2 1 u3
8LNi,Al:Ni,Al 5 4u4 2 4u5
1 1
LNi,Al:Ni 5 3u4 LNi,Al:Al 5 3u5
1
LNi:Ni,Al 5 u4 1
LAl:Ni,Al 5 u5
where u1 through u5 are variables which need to be opti-
mized. In practice, the number of parameters can be reduced
by assuming that u1 5 u2, u4 5 u5, and u3 5 0.
In the ternary system, a similar formula, (Al, Ni,
Mo)0.75(Al, Ni, Mo)0.25, is used,[24] and there are also con-
straints for parameters.
8Gi:j 5 8Gj:i 5 u1ij
8Li,j:A 5 8Li,j:B 5 8Li,j:C 5 2u1ij 1 3u3ij
8LA:i,j 5 8LB:i,j 5 8LC:i,j 5 u3ij
1
Li,j:A 5 1Li,j:B 5 1Li,j:C 5 3u4ij
1 Mo-Ni system has been made,[13] as mentioned previously,
LA:i,j 5 1LB:i,j 5 1LC:i,j 5 u4ij
where i, j, A, B, and C represent the elements Ni, Al, and Mo.
1790—VOLUME 30A, JULY 1999
This model has been implemented in the ThermoCalc
calculation package developed by Sundman et al.,[25] where
the Gibbs energy of L12 is separated into disordered and
ordered contributions. So, the thermodynamic properties of
the disordered phase (fcc phase, in this case) can be evaluated
independently. This could be represented by the following
equation:
Gm 5 Gdis ord 1 2 ord
m (xi) 1 Gm ( y i , yi ) 2 Gm (xi) [9]
where Gdis
m (xi) is the Gibbs energy of the disordered state.
The term Gord 1 2
m ( yi , yi ) is the Gibbs energy as described by
the model (Eq. [4] or [6]) and contains, implicitly, a contribu-
tion of the disordered state. The term Gordm (xi) represents the
energy contribution of the disordered state to the ordered
phase. The last two terms cancel each other when y1i 5 y2i,
thus corresponding to the disordered state.
C. Selection of Experimental Information
Miracle et al.[6] analyzed alloys of desired compositions
after long-term heat treatment (up to 2500 hours) by EPMA
and X-ray diffraction and constructed an experimentally vali-
[6] dated ternary equilibrium-phasediagram at 1200, 1311, l366,
1444, and 1533 K. Systematic experimental studies by
Wakashima et al.,[4] by means of transmission electron
microscopy and selected-area diffraction along with differ-
ential thermal analysis (DTA) have been carried out on a
series of alloys containing about 65 at. pct Ni. Based on the
experimental observations, the phase diagram is recon-
structed with emphasis on the isothermal section at 1273 K.
They also presented a flow chart of invariant reactions in
the Ni-rich part. Hong et al.[26] measured the fcc solvus at
four temperatures, employing DTA and scanning electron
microscopy–energy-dispersive X-ray. These experiments
and the present experimental work are believed to be well
conducted, and the present optimization sets high weight on
these data. Other experimental data are compared to
calculations.
D. Results and Discussion
The optimization and calculations were conducted using
the ThermoCalc package. The optimization was performed
with the selected experimental data, and each piece of infor-
mation was given a certain weight, reflecting the experimen-
[7] tal uncertainty.
Much attention has been paid to the fcc solvus at the
Ni-rich corner. There appears to be a trend that, with the
temperature decreasing, the experimental Mo contents of
the fcc phase in fcc 1 L12 1 NiMo (or fcc 1 L12 1
bcc) three-phase equilibria are somewhat higher than the
calculated ones and also that the experimental fcc solvus is
more Ni-rich (Figures 9 through 15(a) and (b)). Such devia-
tions can be eliminated with unusual large temperature coef-
ficients of the ternary interaction parameters of the fcc phase
in Eq. [2], but this is not favorable. In order to fit the
experimental data, it seems that it is not adequate to adjust
the ternary interaction parameters only; the binary systems
have to be reexamined as well. So, modification of the binary
[8]
and it actually improves the situation. Also, two sets of
parameters about the Ni-Al system are used to optimize
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 9—Calculated isothermal section (thin lines) compared with experi-
mental data at 1373 K. I: L12 1 NiMo 1 bcc; and II: L12 1 B2 1 bcc.
Fig. 10—Calculated isothermal section (thin lines) compared with experi-
mental data at 1200 K. I: L12 1 NiMo 1 bcc; and II: L12 1 B2 1 bcc.
the ternary system, as discussed in Section III–A–1. Here,
optimization using data from Huang and Chang[10] and
Ansara et al.[11] are denoted as assessments 1 and 2, respec-
tively. The optimized thermodynamic parameters are listed
in Table VI. Both assessments give almost the same results,
except for the fcc solvus at the Ni-rich corner, as seen in
Figure 15(a). Assessment 1 results in smaller deviations to
the fcc solvus than assessment 2, as shown in Figures 15(a)
and (b). In assessment 1, due to the limited experimental
data concerning the L12 phase, the excess Gibbs energy in
Eq. [4] is neglected. So, assessment 1 gives lesser parameters
than assessment 2; i.e., the thermodynamic modeling in
assessment 1 is simpler than that in assessment 2. As the
experimental data, especially the thermodynamic ones, are
relatively few, the simple model may be preferred, even
though the model proposed by Ansara et al. is more realistic
and more reasonable. For these reasons, assessment 1 is
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 11—Calculated isothermal section (thin lines) compared with experi-
mental data at 1311 K. I: L12 1 NiMo 1 bcc; and II: L12 1 B2 1 bcc.
Fig. 12—Calculated isothermal section (thin lines) compared with experi-
mental data at 1366 K. I: L12 1 NiMo 1 bcc; and II: L12 1 B2 1 bcc.
thought to be better than assessment 2, and all the following
phase diagrams are calculated using data from assessment 1.
Figures 4 and 9 show the calculated isothermal sections
compared to the present experimental work. Figures 10
through 14 illustrate the isothermal sections at 1200, 1311,
1366, 1444, and 1533 K, respectively. There is good agree-
ment between the experiments and calculations. At 1366 K
(Figure 12), the solubility of Mo in the B2 phase, as reported
by Miracle et al.,[6] was too large compared to that reported
by Nash et al.,[5] Maslenkov et al.,[8] and to the present
measurement. As mentioned by Miracle et al.,[6] the volume
fraction of B2 was very low and the particles were very
small; thus, the measured composition may be unbelievable.
So, his measurement of B2 has not been considered in the
present optimization.
Comparison is made between the fcc solvis measured by
VOLUME 30A, JULY 1999—1791
Fig. 13—Calculated isothermal section (thin lines) compared with experi-
mental data at 1444 K. I: fcc 1 NiMo 1 bcc; II: fcc 1 L12 1 bcc; and
III: L12 1 B2 1 bcc.
Fig. 14—Calculated isothermal section (thin lines) compared with experi-
mental data at 1533 K. I: fcc 1 NiMo 1 bcc; II: fcc 1 L12 1 bcc; and
III: L12 1 B2 1 bcc.
Hong et al.[26] and the calculated results, except at 1100 K
(Figure 15(b)). Since they have not detected Ni3Mo and
Ni4Mo phases at this temperature, the fcc solvus at 1100 K
may not be true and is not included in Figure 15(b).
As seen in Figures 16 and 17, the calculated phase dia-
grams fit the experimental points well enough. At 1553 K,
as discussed by Wakashima et al.,[4] the alloy with fcc 1
bcc phases and the alloys with fcc 1 bcc 1 L12 phases
(except the alloy with “1” marked in Figure 17) are actually
in the same phase region, but the latter ones have extra
L12 phase due to ineffective quenching. This can be well
reproduced, as in Figure 17. The calculated temperatures of
Ni-corner invariant reactions, compared to those summa-
rized by Wakashima et al., are listed in Table VII. It can be
1792—VOLUME 30A, JULY 1999
(a)
(b)
Fig. 15—Calculated fcc solvus at 1200, 1300, and 1400 K in assessment
1 (solid lines) compared with (a) that in assessment 2 (dashed lines) and
(b) experimental data.
seen that it is acceptable, except that the peritectic-eutectic
reaction concerning the liquid, NiMo, fcc, and bcc phases
is a ternary eutectic reaction, L Ö NiMo 1 fcc 1 bcc,
instead. As there is no experimental information to verify
the type of reaction, it is also acceptable.
Figure 18 shows the calculated isothermal section, with
experimental information by Nash et al.[5] and Maslenkov
et al.,[8] at 1473 K. There is good agreement between the
calculations and the measurements of Nash et al., whereas
the fcc compositions in equilibria with NiMo, detected by
Maslenkov et al., are more Mo depleted than the calculated
ones. At 1373 K, experimental data by Maslenkov et al.
also show such deviation, as seen in Figure 9.
There are few equilibrium experimental data regarding
METALLURGICAL AND MATERIALS TRANSACTIONS A
 Table VI. Assessed Thermodynamic Parameters in the
Present Work (J/Mol)

Assessment 1 Assessment 2
Liquid:
8LAl,Mo,Ni 5 221,341 2
21.7926T 218,000 2 18.4362T
1L
Al,Mo,Ni 5 16,626 1 6.1815T 22,507.8 1 7.3334T
2L
Al,Mo,Ni 5 133,084 1 1.6964T 145,772 1 1.6244T
Fcc:
8LAl,Mo,Ni 5 243,250 2 94.38T 243,645 2 94.31T
1
LAl,Mo,Ni 5 264,492 1 98.74T 264,415 1 99.02T
2L
Al,Mo,Ni 5 271,000 2 75.075T 277,730 2 74.38T
Bcc:
8LAl,Mo,Ni 5 2160,000 2160,000
B2:(Al, Mo, Ni)1(Mo, Ni, Va)1:
8GMo:Ni 2 8Gbcc Mo 2 8GNi
bcc

5 213,176 1 31.4465T 213,176 1 31.4465T

8GNi:Mo 2 8Gbcc Mo 2 8GNi
bcc

5 213,176 1 31.4465T 213,176 1 31.4465T

8GMo:Va 2 8Gbcc Mo 5 150,000 150,000
8GAl:Mo 2 8Gbcc Mo 2 8GAl
bcc
Fig. 16—Calculated isothermal section (thin lines) compared with experi-
5 244,629 1 39.7878T 244,629 1 39.7878T mental data at 1273 K. I: L12 1 NiMo 1 bcc; and II: L12 1 bcc.
L12:(Al, Mo, Ni)0.75(Al, Mo, Ni)0.25:
8GMo:Ni 2 0.758Gfcc Mo 2 8GMo:Ni 2 0.758GfccMo 2
0.258Gfcc
Ni 5 213,849 1 0.258Gfcc
Ni 5 235,361 1
4.6243T 16.23T 5 u1NiMo
8GNi:Mo 2 0.758Gfcc Ni 2 8GNi:Mo 2 0.758GfccNi 2
0.258Gfcc
Mo 5 213,849 1 0.258Gfcc
Mo 5 235,361 1
4.6243T 16.23T 5 u1NiMo
8LMo,Ni:* 5 2u1NiMo
1
LMo,Ni:* 5 3u4NiMo
1L
*:Mo,Ni 5 780 2 0.9T 5
u4NiMo
NiMo:(Ni)24(Al, Mo, Ni)20(Mo)12:
8GNi:Al:Mo 2 128GbccMo 2
248Gfcc
Ni 2 208GAl
bcc

5 21,750,000 21,750,000
Ni3Mo:(Al, Mo, Ni)3(Al, Mo, Ni)1:
8GAl:Ni 2 8GbccAl 2 38GNi
fcc

5 2173,798 1 31.91T 2239,987 1 91.49T

AlMo:(Al, Mo, Ni)1(Al, Mo, Ni)1:
8GMo:Ni 2 8Gbcc fcc
Mo 2 8GNi 5
57,500 2 2.5T 57,500 2 2.5T
8GNi:Mo 2 8Gbcc fcc
Mo 2 8GNi 5
57,500 2 2.5T 57,500 2 2.5T
Al3Ni2:(Al)3(Al, Mo, Ni)2(Ni, Mo, Va)1:
8GAl:Mo:Ni 2 28GbccNi 2 38GAl 5
bcc
Fig. 17—Calculated isothermal section (thin lines) compared with experi-
230,000 230,000 mental data at 1553 K. I: fcc 1 NiMo 1 bcc; II: fcc 1 L12 1 bcc; and
8GAl:Ni:Mo 2 8GbccMo 2 28GNi 2
bcc
III: L12 1 B2 1 bcc.
38Gbcc
Al 5 230,000 230,000

Table VII. Invariant Reaction Temperatures (K)

the Ni3Mo phase. Figure 19 shows the work of Maslenkov
et al.[8] and a calculated one at 1153 K. Summarized by
Wakashima et Present
Henry[1] studied the precipitation of the L12 phase in fcc 1
Reaction al.[4] Calculations
bcc eutectics using the alloys AG34 (65.6 at. pct Ni, 14.4
at. pct Al, and 20.0 at. pct Mo) and AG8 (65.7 at. pct Ni, L Öfcc 1 L12 1 bcc 1573 1572
17.6 at. pct Al, and 16.7 at. pct Mo). The lower Al content Fcc 1 bcc ÖL12 1 NiMo 1403 1403
L ÖNiMo 1 bcc 1 fcc 1583 1577
alloy, AG34, yields a structure as-directionally solidified,
L 1 B2 ÖL12 1 bcc 1576 1577
consisting of primary Mo fibers surrounded by an L12 matrix
with fcc phase centered in the L12 phase, whereas, at 1260
8C, the L12 precipitate is dissolved and the matrix is almost
all back to the parent fcc phase. The calculated AG34 struc- from the fcc 1 bcc structure, and the fcc 1 L12 1 bcc
ture is fcc 1 L12 1 bcc at 1200 8C and fcc 1 bcc at 1260 structure could be kept at room temperature in an ordinary
8C. This can, approximately, be seen in Figure 20. As the furnace-cooling condition without undergoing the peritec-
temperature is lowered, the L12 phase precipitates readily toeutectoid reaction (fcc 1 bcc ÖL12 1 NiMo). The reason

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 30A, JULY 1999—1793

Fig. 18—Calculated isothermal section (thin lines) compared with experi-
mental data at 1473 K. I: fcc 1 NiMo 1 bcc; II: fcc 1 L12 1 bcc; and
III: L12 1 B2 1 bcc.
Fig. 19—Calculated isothermal section (thin lines) compared with experi-
mental data at 1153 K. I: L12 1 NiMo 1 bcc; and II: L12 1 B2 1 bcc.
for this has been proposed by Wakashima et al.,[4] by recog-
nizing that, when surrounded by thick L12-phase walls, the
bcc phase would be prevented from reacting with the fcc
phase. Alloy AG8, on the other hand, consists of primary
Mo fibers in an essentially pure L12 matrix, and L12 progres-
sively dissolves into fcc phase as the annealing temperature
is raised from 1220 8C to 1280 8C. The present calculation
shows that AG8 has an L12 1 bcc two-phase structure at
1000 8C (or even lower) and an fcc 1 L12 1 bcc three-phase
structure at 1280 8C, as seen, approximately, in Figure 20.
Yoshizawa et al.[2,3] studied the phase stability of a direc-
tionally solidified eutectic alloy of composition 12.7 at. pct
Al, 21.6 at. pct Mo, and the balance Ni. They measured the
1794—VOLUME 30A, JULY 1999
Fig. 20—Calculated isopleth section at 65 at. pct Ni of Ni-Al-Mo system.
Fig. 21—Calculated liquidus projection compared with experimental data.
eutectic reaction (L Ö fcc 1 bcc) occurring at about 1310
8C and found the L12 solvus to be 1248 6 2 8C on heating
and 1234 6 2 8C on cooling, at a heating/cooling rate of
10 K per minute. Thus, they reported a bcc 1 fcc two-phase
structure at 1260 8C. The calculated results, on the other
hand, are that the L12 solvus is 1234 8C and that the alloy
with this composition is in bcc 1 fcc equilibrium at 1260
8C (Figures 14 and 20). Also, simple simulation of the solidi-
fication path is conducted using a Scheil model for example,
(Reference 27) and an equilibrium model with the present
thermodynamic parameters. They produce almost the same
eutectic temperature, 1305.6 8C. The Scheil model neglects
back-diffusion in solid and assumes perfect mixing in liquid;
METALLURGICAL AND MATERIALS TRANSACTIONS A
thus, it is often used to simulate solidification behavior with
extremely high cooling rates. The equilibrium model, on the
other hand, assumes that the equilibrium state is obtained
in the process of solidification, which corresponds to the
condition of extremely slow cooling rates. Since such models
describe two limiting cases, all other solidification paths
will go in between. So, the calculated eutectic temperature
agrees with the experimental one very well.
The liquidus projection is plotted in Figure 21 using the
experimental data by Svetlov et al.[28] The two alloys used
by them have different primary phases, and the eutectic
trough must go between them.
IV. SUMMARY
1. The isothermal section of the Ni-Al-Mo system at 1373
K has been studied by means of the diffusion triple tech-
nique. Equilibrium tie-lines have been measured and
phase relations have been established. There is good
agreement between the present work and other
experiments.
2. Thermodynamic parameters of the Ni-Al-Mo ternary sys-
tem have been evaluated from the present experimental
data and from those available in the literature. Two sets
of thermodynamic parameters have been optimized, and
assessment 1 is thought to be the better one. The compari-
sons between experimental data and the calculated equi-
librium phase diagrams were made, and experimental
facts have been explained. They show that, thermody-
namically, this ternary system has been satisfactorily
described.
ACKNOWLEDGMENTS
This work is financially supported by the General Electric
Company, under Research Contract No. 9622031. The
authors thank Dr. J.-C. Zhao, GE Company, for his invalu-
able help during the work. We are indebted to Mrs. Xiulin
Han (The Geology Institute, Chinese Academy of Science),
who performed the EPMA measurements reported in the
present work. We also thank Mr. Zhongyi Liu for valuable
comments on the manuscript.
METALLURGICAL AND MATERIALS TRANSACTIONS A
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