The Fe-Ni system: thermodynamic modelling assisted by atomistic calculations

G. Cacciamani a, A. Dinsdale b, M. Palumbo c, A. Pasturel d

a
Dipartimento di Chimica e Chimica Industriale, Università di Genova, Italy
b
Materials Centre, National Physical Laboratory, Teddington, UK
c
Computational Materials Science Center, National Institute for Materials Science, Tsukuba,
Japan, now at ICAMS, STKS, Ruhr University Bochum, Germany
d
Laboratoire de Physique et Modélisation des Milieux Condensés (UMR 5493), CNRS, Grenoble,
France

Abstract

The Fe-Ni system is a key subsystem for several alloys with important applications. It has been
thermodynamically assessed according to the CALPHAD methodology and using 0 K enthalpies of
formation of the ordered phases resulting from ab-initio atomistic calculations. This allowed us to
model both stable and metastable fcc-based ordered phases (L1 2 Fe3Ni, L10 FeNi and L12 FeNi3) in
the framework of the compound energy formalism (CEF) by using a 4-sublattice model. The
combined ab-initio and CALPHAD approach enabled us to predict low temperature stable equilibria
which are experimentally not accessible due to an extremely sluggish kinetics.
A similar 4-sublattice model has also been used for the bcc-based ordered phases (D0 3 Fe3Ni, B2
and B32 FeNi, D03 FeNi3), which are metastable in the Fe-Ni system, but need to be reliably
modelled in order to enable extrapolations to higher order systems such as Al-Fe-Ni.
Magnetic ordering, which is particularly important in this system, has also been thermodynamically
described and the influence of magnetism on phase equilibria evidenced.

Keywords
Calphad, Fe-Ni, Phase diagram, First-principles calculations, order/disorder transformations

Corresponding Author

Gabriele Cacciamani
Dip. di Chimica e Chimica Industriale
Università di Genova
via Dodecaneso, 31
I-16146 Genova
Italy
Phone: +39 010 353 6130
Fax: +39 010 362 5051
E-mail: cacciamani@chimica.unige.it

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1. - Introduction

Fe-Ni is a key system for the development of various alloys of technological interest. The most
important Fe-Ni based alloys are Invar alloys (typically Fe-35%Ni with possible additions of Cr,
Cu, Mo). Thanks to their very low coefficient of thermal expansion they are used for thermostatic
bimetals, glass sealing, integrated circuit packaging, cathode ray tube shadow masks, composite
molds/tooling, and membranes for liquid natural gas tankers.
Fe-Ni alloys richer in Ni (typically Fe-48-50%Ni with possible additions of Co, Cr), because of
their soft magnetic properties with very high saturation flux density, are used for read-write heads
for magnetic storage, magnetic actuators, magnetic shielding and high performance transformer
cores.
Moreover Fe and Ni are important addition elements in many materials of technological interest
such as maraging steels, shape memory alloys, bulk metallic glasses, alloyed aluminides, etc.

The Fe-Ni system itself is interesting not only for these various applications but also from a
fundamental point of view. Despite the large number of investigations, started at the end of the XIX
century, some uncertainty still affects low temperature phase relations mainly because of the
difficulty in reaching stable equilibrium at temperatures lower than about 300°C. Moreover Fe-Ni is
a paradigmatic example of how structural and magnetic orderings interact and affect phase
equilibria. From this point of view it may be considered one of the best test systems to check the
effectiveness and efficiency of the models adopted to describe thermodynamic properties of the
different phases and to calculate phase equilibria.

To summarise, the aim of the present paper is many-fold:

1) To produce an accurate thermodynamic modelling of the system in the framework of the Calphad
methodology [1, 2] and the Compound Energy Formalism (CEF) [3] in order to clarify phase
equilibria at low temperature, which are still uncertain. This may be obtained on the basis of the
available experimental data, but also using phase stability data from atomistic calculations. These
are needed especially to get a reliable thermodynamic description of the Fe-Ni phases at low
temperature, where an extremely sluggish kinetics makes experimental investigations impossible or
very difficult.
2) To verify effectiveness and efficiency of the 4-sublattice models [4] recently adopted by the
Calphad community to describe thermodynamic relations within families of phases related by
structural ordering relations. In particular we will focus on the fcc (A1/L1 2/L10) and bcc

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(A2/B2/B32/D03) ordering, with special attention not only to the stable phase equilibria, but also to
the metastable ones, because both stable and metastable equilibria need to be thermodynamically
well described in order to be able to use the Fe-Ni description to calculate reliable phase relations in
higher order systems. In this case too atomistic calculations combined with Calphad modelling are
especially useful.
3) To highlight the role of magnetism in determining phase equilibria. This is made particularly easy
by the CEF modelling, where the magnetic contribution to the Gibbs energy of a phase may be
separated from the other contributions.

2. Literature overview
The Fe-Ni phase diagram has been studied for more than a century, the first investigations being
carried out by Osmond [5], Guertler and Tamman [6], Hegg [7] and Ruer and Schuz [8]. Critically
assessed Fe-Ni phase diagrams were elaborated by March [9], Kubaschewski [10], Swartzendruber
et al. [11], Yang et al. [12], and Kuznetsov [13]. A short discussion of the recent literature on the Fe-
Ni system and an updated phase diagram, here reproduced in Fig. 1a, was reported by [14], who
took in particular consideration low temperature phase equilibria proposed by [12], here reported in
Fig. 1b. Owing to the high number of investigations, some uncertainty still affects low temperature
phase relations mainly because of the difficulty in reaching stable equilibria at temperatures lower
than about 300°C.
The main features of the Fe-Ni phase diagram are: the -(Fe,Ni) solid solution, with an fcc (A1)
structure, extending over the complete composition range at high temperature and forming a very
narrow two-phase field with liquid; the high temperature -Fe and low temperature -Fe solid
solutions, with the bcc (A2) structure, which are restricted to a relatively narrow composition range
close to pure Fe; the FeNi3 solid solution, with an ordered fcc (L1 2) superstructure (AuCu3 type),
which forms congruently from A1 -(Fe,Ni) just over 500°C and shows an appreciable solubility
range.
Both -(Fe,Ni) and -Fe undergo para- to ferro-magnetic transitions with decreasing temperature
and ferromagnetic -(Fe,Ni)FM forms an eutectoid equilibrium with -Fe and FeNi3: -(Fe,Ni)FM  -
Fe + FeNi3 .
More detailed discussion of the available literature data is reported in the following description of
the Fe-Ni thermodynamic assessment. To this end the critical assessment by Swartzendruber [11]
will be taken as a starting point.

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2.1 High temperature equilibria (T>1000°C)
No recent experimental investigations are available on high temperature Fe-Ni phase equilibria.
Solid-liquid equilibria were investigated by several authors [6, 15, 16, 17, 18, 19, 20, 21], mainly in
the first half of the twentieth century. The -(Fe,Ni) + liquid two-phase field is very narrow with a
minimum which is most probably located at approximately 1440°C and 66 at% Ni, according to the
critical assessment by [11].
Phase boundaries between -Fe and -(Fe,Ni) were investigated by [22, 15, 16, 21]. A narrow
peritectic equilibrium -Fe + liquid  -(Fe,Ni) occurs at about 1514°C with phase compositions of
3.5, 4.9 and 4.2 at% Ni, respectively [11].

2.2 -Fe + -(Fe,Ni) equilibria

The -Fe + -(Fe,Ni) two-phase field starts at 912°C, the  to  transformation temperature of pure
Fe.
The investigation of the -Fe + -(Fe,Ni) phase equilibria is made difficult by the sluggishness of
the  to  transformation at temperatures lower than about 800°C. Several experimental techniques
were used: XRD [23, 24, 25, 26], EPMA [27], STEM [28]. All researchers agree in finding a
retrograde solubility of Ni in -Fe with a maximum of about 5-6 at% Ni at about 500°C.
Correspondingly, the Ni-rich boundary of the -Fe + -(Fe,Ni) two-phase field became flatter as the
temperature is decreased, indicating the presence of a low-temperature metastable miscibility gap in
the -(Fe,Ni) phase.
The -Fe + -(Fe,Ni) two-phase field ends at a monotectoid equilibrium -(Fe,Ni)PM  -Fe + -
(Fe,Ni)FM (where PM refers to a paramagnetic state and FM a ferromagnetic state) first proposed by
Nishizawa [29] and subsequently calculated by Chuang et al. [30, 31], but not observed
experimentally.

2.3 -(Fe,Ni)PM + -(Fe,Ni)FM equilibria

The second order paramagnetic to ferromagnetic transformation in pure Ni occurs at 354.3°C [32,
33]. With increasing Fe concentration the Curie temperature (TC) increases up to a maximum of
about 610°C at about 66 at% Ni and then decreases [34, 35, 36, 37, 38]. In 1986 Chuang et al. [30,
31] calculated the Fe-Ni phase diagram by taking into account the magnetic contribution to the
Gibbs energy of the -(Fe,Ni) phase. Due to the appreciable slope of the T C curve, they obtained a
tricritical point at about 462°C and 48 at% Ni, followed by a monotectoid equilibrium -(Fe,Ni)PM 
-Fe + -(Fe,Ni)FM at 389°C with phase compositions of 40, 6 and 46 at% Ni respectively. The

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monotectoid equilibrium was not reported by [11], who however set to 400°C the T C of -(Fe,Ni) in
equilibrium with -Fe. No direct experimental information is available on the -(Fe,Ni)PM + -
(Fe,Ni)FM two-phase field nor on the monotectoid equilibrium. Ref. [14] accepted the monotectoid
temperature of 415°C proposed by [13].

2.4 -Fe + -(Fe,Ni)FM equilibria

As a consequence of the monotectoid equilibrium an -Fe + -(Fe,Ni)FM two-phase field should be
stable below the invariant equilibrium. Zhang et al. [39] investigated martensitic Fe-Ni alloys aged
in the 300 to 450°C temperature range and measured -Fe and -(Fe,Ni)FM phase compositions in
this range. They did not find experimental evidence of the monotectoid equilibrium at temperature
lower than 400°C. Combining the results of previous investigations [28, 30, 31, 39] with new
measurements on meteoric samples Yang, Williams and Goldstein [12] concluded that the
monotectoid equilibrium should occur at about 400°C with phase compositions of about 6 [28], 40
and 46 at% Ni [39] for -Fe, -(Fe,Ni)PM and -(Fe,Ni)FM, respectively.
As for equilibrium phase compositions in the -Fe + -(Fe,Ni)FM two-phase field Yang et al. [12]
considered the -Fe compositions determined by [28] and -(Fe,Ni)FM compositions determined by
[39] as most reliable.

2.5 FeNi3 and related equilibria

With decreasing temperature -(Fe,Ni) at compositions around FeNi3 assumes the ordered L12
(AuCu3 type) structure. This ordering transformation has been investigated by several authors. It
was first studied by [40, 41, 42, 43, 44, 45] using XRD. [40, 41, 42] also measured magnetic
properties, electrical resistance and hardness of heat treated alloys. More detailed studies were
concentrated in the 65 to 80 at% Ni composition range by [46, 47] using Moessbauer spectroscopy,
by [48] using neutron diffuse scattering on single crystals quenched from different temperatures, by
[49, 50] using calorimetry, by [51, 52] using dilatometry, by [53] using carbonyl vapour pressure,
and by [45, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72].
On the basis of the literature data it can be concluded that ordering occurs through a first order
transformation with a maximum at about 517°C and 72-73 at% Ni, i.e. a slightly off-stoichiometric
composition. According to [46, 47] there is a 15°C hysteresis in the ordering temperature, which
may be explained by magnetic effects.
The Ni-rich side of the -(Fe,Ni) + FeNi3 region is not well defined. According to [53] it extends
between 874 and 924 at% Ni at about 300°C. On the other side, the existence of the eutectoid

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equilibrium -(Fe,Ni)  -Fe + FeNi3 at 345°C with -(Fe,Ni) at 52 at% Ni was proposed by the
same author, based on XRD and SEM observations and on the results by [73]. According to the
critical assessment of [11] the eutectoid temperature is 347°C and the corresponding phase
compositions are 49, 4.7 and 63 at% Ni, respectively. Slightly different values have been selected
by [13]: 345°C and 53, 3.2 and 63.6 at% Ni, respectively.

2.6 Low temperature equilibria (T<400°C)

Due to the very slow interdiffusion between Fe and Ni, equilibrium can hardly be reached at low
temperature (below about 400°C). Phase equilibria in this region have been studied in two ways: by
investigating irradiated samples (in which irradiation-induced crystal defects may increase inter-
diffusion) or by investigating meteoric samples which had cooled down very slowly in asteroid
bodies over time periods of between 1 and 1000 million of years. It has been estimated [12] that, at
temperatures lower than about 200°C, equilibrium cannot be reached even at geological time scale.
For this reason [12] considered his observations of meteoric samples to reflect phase equilibria at
20050°C.
A detailed discussion of the stable and metastable Fe-Ni equilibria at low temperature is reported in
the [12] assessment. It is mainly based on experimental results obtained by [28, 39, 74, 75] and by
[12] himself, together with thermodynamic calculations by [30, 31]. Conclusions by [12] can be
summarised as follows:
- the tricritical point and the miscibility gap between -(Fe,Ni)PM and -(Fe,Ni)FM, proposed by [30,
31] are confirmed and the consequent monotectoid equilibrium occurs at about 400°C. Below
this temperature, the miscibility gap and the related spinodal region are metastable. At about
200°C the metastable miscibility gap extends between about 8.5 and 50 at% Ni and the spinodal
region between about 27 and 45 at% Ni.
- The stability of the ordered L1 0, (AuCu type) FeNi phase previously proposed by [74, 75] is not
confirmed. However, the eutectoid reaction -(Fe,Ni)FM  -Fe + FeNi3 at about 345°C is
confirmed. At about 200°C -Fe containing 3.5 at% Ni is in equilibrium with FeNi3 at about 64
at% Ni.
- L10 FeNi can be obtained as a metastable phase at 50 at% Ni. It has a critical ordering temperature
of about 320°C, as determined by [76].
- The existence of a low spin paramagnetic phase at about 25-30 at% Ni proposed as an equilibrium
phase by [77] is not confirmed, but cannot be definitely excluded.

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2.7 Martensitic transformations
Martensitic transformations were reported in the Fe-Ni system from an austenitic  parent phase to a
ferritic  product phase [78, 79, 80]. A review of experimental data on the martensitic reaction in
several Fe-X systems, including X=Ni, is reported in [81], while a review on the thermodynamic
modelling of the martensitic transformation is reported in [82]. Measurements of the transformation
temperature under different conditions evidenced that at least two different martensitic
transformations take place in the Fe-Ni system [78, 81, 83]. A lath martensite and a plate martensite
can be distinguished in an optical microscope. On a transmission electron microscope the lath
martensite appears to be rich in dislocations, while the plate martensite is heavily twinned,
suggesting a different formation mechanism. In [83] a third type of martensitic transformation was
reported for low Ni content, but its nature is still unclear and controversial. Martensitic
transformations are not considered any more in this paper.

2.8 Crystal structures and lattice parameters

Crystal structures and lattice parameters of stable Fe-Ni phases are reported in Table 1 together with
crystal structure data about metastable phases considered in this work. Room temperature lattice
parameters of the -(Fe,Ni) and -(Fe,Ni) solid solutions according to [11] are reported in Fig. 2 as
a function of the phase composition. It can be noticed, in particular, that the lattice parameter of -
(Fe,Ni) shows a maximum at about 38-40 at% Ni which corresponds to the composition range
where the magnetic moment reaches its maximum value.

2.9 Magnetic properties

The Curie temperature has been determined in the 0-30 at% Ni range for A2 -Fe by [34, 35, 36]
and for A1 -(Fe,Ni) in the 30-100 at% Ni by [34, 35, 36, 37, 38, 84]. In addition [37] showed that
the TC, for the ordered FeNi3 structure was appreciably higher than those for the disordered -
(Fe,Ni) phase.
Magnetic moments have been determined, in the above mentioned composition ranges, by [34, 38]
for A2 -Fe and by [34, 38, 85, 86, 87] for A1 -(Fe,Ni), respectively.

2.10 Thermodynamics
Thermodynamic measurements in the Fe-Ni system up to 1989 have been discussed by [11] and
more recent investigations have been described in [14]. Two phases have been mainly investigated:
liquid and -(Fe,Ni) at temperatures generally higher than 1000°C. For both phases several authors

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have measured the integral enthalpy of mixing and activity, or activity coefficient of the component
elements. A selection of thermodynamic measurements reported in literature is summarised in
Tables 2a and 2b.

2.11 Atomistic calculations

The theoretical investigation of magnetic and thermodynamic properties in pure Fe and in binary
Fe-Ni alloys has attracted great interest in the ab initio community both because of the importance
of Fe alloys and to the complexity of phenomena involved with magnetic and chemical ordering
and the Invar effect. In all calculations magnetism has been found to play a crucial effect and
neglecting magnetism in first principles calculations of these alloys can lead to misleading results.
Mohri and co-workers [113, 114, 115] have systematically investigated the behaviour of L10 and
L12 fcc order-disorder transformations in the Fe-Ni, Fe-Pd and Fe-Pt systems by means of first
principles calculations, using the full potential linearised augmented plane wave (LAPW) method
[116], Cluster Expansion Method (CEM) [117] and Cluster Variation Method (CVM) [118]. In the
Fe-Ni system, they found that, besides the L12 FeNi3 ordered phase, the L10 is also stable at low
temperature with a transition temperature around 250°C. The inclusion of vibrational effects has
confirmed this result in the most recent work [115], where the calculated transition temperature has
been reduced by about 40 K. According to these papers, the L1 0 ordered phase is thus stable in the
Fe-Ni system, even if a full equilibrium state is never achieved due to sluggish kinetics.
Interestingly, a systematic variation in the appearance/disappearance of the L10 and L12 ordered
compounds is observed in the Fe-X (X=Ni, Pd, Pt) systems, with the L1 0 FePd phase appearing to
be stable in the Fe-Pd phase diagram as well as the L1 2 FePd3 phase, while in the Fe-Pt system all
L12 Fe3Pt, L10 FePt, and L12 FePt3 ordered phases appear to be stable.
Several atomistic computer simulations [119, 120, 121] have been performed in the Fe-Ni system
by applying semi-empirical potentials of the embedded-atom method (EAM) [122]. More recently,
Mishin et al. [123] have developed a modified EAM method, with angular dependent potentials, for
Fe-Ni alloys based on first principles calculations of some ordered Fe-Ni compounds using full
potential linearised augmented plane wave (LAPW) method within the PW-91 GGA approximation
[124]. They have calculated several competing ordered structures with different magnetic ordering,
mostly ferromagnetic, at 0 K. According to their results, both the L1 2 FeNi3 and L10 FeNi ordered
phases appear to be stable at 0 K. In this work, the authors also suggest the possible existence of
two more ordered phases with compositions Fe2Ni and FeNi2 and structure C11f (the fcc-based
analogue of the bcc-based MoSi2 type structure) obtained by stacking Fe and Ni (002) layers
according to the sequences NiFeFeNiFeFe and FeNiNiFeNiNi, respectively. Their conventional unit

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cell is a triple size fcc super-cell (a x a x 3a) along the [001] direction. According to the angular
EAM potentials developed by Mishin et al., these phases are stable at 0 K.
The stability of the L10 FeNi phase in addition to the L12 FeNi3 ordered structure is also confirmed
by atomistic calculations carried out by Lechermann et al. [125], who performed DFT calculations
in the GGA-PBE approximation using their own ab initio mixed-basis pseudopotential (MBPP)
code. They have also applied the Cluster Expansion Method to the fcc and bcc lattice in the ternary
Fe-Ni-Al and all binary subsystems and they have calculated the finite temperature ternary phase
diagram by means of the Cluster Variation Method. The Cluster Expansion of the fcc lattice
confirms the stability of L10 FeNi ordered compound at 0 K in relation to the bcc and other ordered
fcc phases.
A significant number of works in the literature deals with magnetic structures in Fe-Ni alloys [126,
127, 128, 129, 130 and references therein]. For example, it has been pointed out that at 0 K there is
a continuous transition from the high-spin ferromagnetic configuration at large unit cell volumes to
a disordered non-collinear configuration at smaller volumes in the fcc Fe-Ni phase [126, 127]. In
[128], several possible magnetic configurations (ferromagnetic, antiferromagnetic, ferromagnetic
and spin spirals) have been considered in fcc Fe-Ni alloys. It has been shown that the difference in
energy between different competing magnetic configurations is rather small and the determination
of the exact ground state magnetic structure could be beyond present day capability of first
principles calculations based on local exchange-correlation functionals. In fact, different results
have been obtained not only between LDA and GGA approximations, but also between GGA-PW91
and GGA-PBE potentials for the ground state stability of magnetic structures. Nonetheless, first
principles results have proved to be useful in showing the potential complexity of magnetic
structures in Fe-Ni alloys and identifying some possible trends in magnetic structures transitions.

2.12 CALPHAD Thermodynamic assessments

Previous CALPHAD-type thermodynamic assessments of the Fe-Ni system have been obtained by
Kaufman and Nesor [131], Chart et al. [132, 133], Chuang et al. [30, 31]. These have been
improved by Lee and Lee [134], who used a single two-sublattice model to described both the
ordered FeNi3 phase and the disordered fcc phase as one phase. He also reoptimised the liquid
parameters. Subsequently Ohnuma et al. [135, 136], re-modelled the magnetic contribution to the
Gibbs energy of the ordered FeNi3 phase. The L10 FeNi phase, which appeared to be stable in the
first paper [135], was calculated to be metastable in the latter publication [136]. In an independent
thermodynamic calculation of the Fe-Ni phase equilibria recently published by Howald [137] the
L10 FeNi phase is stable in the 100 to 250°C temperature range. It has to be mentioned, however,

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that this cannot be considered as a completely reliable assessment because most of the recent Fe-Ni
literature was not considered by the author.

3. Methodology
3.1 Atomistic calculations
First principles calculations have been carried out in order to determine the thermodynamic and
magnetic properties of several ordered structures in the Fe-Ni system. A complete list of these
structures is given in Table 1.
A full structure minimization at the ground state (0 K) has been carried out using density functional
theory (DFT) as implemented in the Vienna Ab initio Simulation Package (VASP) with plane wave
basis sets [138, 139, 140]. The calculations employed the generalized gradient approximation
(GGA) of Perdew and Wang [124] and valence electrons were explicitly represented with projector
augmented wave (PAW) pseudopotentials. The plane wave cut-off energy was set to 450 eV for all
structures. k-points meshes were created by a Monkhorst-Pack scheme [141] and convergence on
the number of k-points in the irreducible wedge of the first Brillouin zone has been carefully
checked for each structure. The ground state (0 K) relaxed structure was determined by minimizing
the Hellmann-Feynman forces with a conjugate gradient algorithm, until all ionic forces were less
than 0.01 eV/A. For magnetism, collinear magnetic configurations have been considered, although
spin flips were allowed. As pointed out in Section 2.11, differences in energy between possible
magnetic structures are small and non-collinear effects are negligible for the purpose of the present
work. Harmonic and anharmonic contributions at higher temperature have been neglected in the
present calculations.

3.2 Thermodynamic modelling

Thermodynamic modelling of the Fe-Ni phases based on the Compound Energy Formalism (CEF)
[3l] has been carried out using the CALPHAD method [1, 2]. The molar Gibbs energy of a generic
phase is described as the sum of four terms:
G ϕ = ref G ϕ  id G ϕ  ex G ϕ  mag G ϕ (1)
ref ϕ id ϕ ex ϕ
where G is the reference Gibbs energy, G is the ideal mixing contribution, G is the
mag
excess Gibbs energy and G ϕ is the magnetic contribution.

For the liquid phase and the disordered solid solutions -Fe (A2) and -(Fe,Ni) (A1) the different
terms are discussed in the following.

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The reference Gibbs energy can be written as:
ref ϕ ϕ
G = ∑ x i⋅G i  T  (2)
i

ϕ
where x i is the mole fraction of component i and G i  T  the Gibbs energy of the pure component

i in the structure of the phase , referred to the standard element reference (SER) state. Its
temperature dependence is expressed as:
G ϕ  T  − H SER =A ϕ +B ϕ T+C ϕ T ln  T  +D ϕ T 2  . .. (3)
with A, B, C, D,… empirical parameters evaluated on the basis of the experimental information.
ϕ
Several temperature ranges with different expression of this type can actually be needed. G i  T 
functions for the pure elements in different stable and metastable phases are available from the
Unary database by SGTE [142].
The ideal mixing contribution is:
id
G ϕ =RT ∑ x i ln  x i  (4)
i

where R is the gas constant and T the absolute temperature.

The excess Gibbs energy is expressed by a Redlich–Kister series and, for a generic binary A-B
system, it is:
ex i
G ϕ =x A x B ∑ i
L ϕ  T ⋅ x A − x B  (5)
i= 0 .. n

i ϕ ϕ
where the L  T  functions, which may have the same temperature dependence of G i  T  reported
in eq. (3), include empirical parameters to be evaluated during the optimisation process.
Finally, the magnetic contribution is expressed, for the pure components, according to the model
introduced by Inden [143, 144] and subsequently adapted by Hillert and Jarl [145]:
mag
G φ =RT⋅f  τ ⋅ln  β+ 1  (6)
where  is the average magnetic moment per mole of atoms in Bohr magnetons,  is the ratio T/TC
(TC= critical temperature for magnetic ordering), and f() is a polynomial expression obtained by
expanding Inden's description of the magnetic heat capacity into a power series of . For a binary
phase the composition dependence of TC and  is given by a Redlich–Kister series expansion:
i
T φC  x  =x A T Cφ  A  +x B T φC  B  +x A x B ∑ i
T φC⋅ x A − x B  (7)
i=0 .. n

i
β φ  x  =x A β φ  A  +x B β φ  B  +x A x B ∑ i
β φ⋅ x A − x B  (8)
i=0 . . n

i φ i
where T C and β φ are expansion parameters to be evaluated on the basis of the experimental
information available.

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In the Fe-Ni system only one intermetallic phase, L1 2 FeNi3 (AuCu3 type), seems to be stable at
room and higher temperatures. Its structure is an ordered form of A1 -(Fe,Ni). It could be described
in the CEF by a 2-sublattice model (Fe,Ni)(Fe, Ni)3 where both elements are present in each
sublattice in order to describe the homogeneity range of the phase, mainly due to the mutual
substitution between Fe and Ni.
However, other fcc ordered forms of A1 -(Fe,Ni), namely L12 Fe3Ni (anti-AuCu3 type), and L10
FeNi (AuCu type), compete for equilibrium in this system and must be thermodynamically
modelled. Data for these are also necessary when modelling higher order systems (e.g. Al-Fe-Ni-Ti)
where such phases become stable. This can be achieved by using a 4-sublattice model, as already
introduced by Sundman et al. [146] and adopted by De Keyzer et al. [147] while modelling the Fe-
Ni-Ti ternary system.
In the case of multi-sublattice models the Gibbs energy of a phase is expressed as a function of the
 s
site fractions y i , the mole fractions of each component i in the sublattice (s). Site fractions obey
the conditions:

∑ y is =1
i

∑ n s  y is 
s
=xi

∑ n s  1− y Vas  
s

where n ( s ) are the stoichiometric coefficients relating the sublattices and s itself indicates the s-th
sublattice. Va identifies vacancies.
For a 4-sublattice model (A1, … ,Ai)1/4 (A1, … ,Ai)1/4 (A1, … ,Ai)1/4 (A1, … ,Ai)1/4 where i different
constituents may occupy the four sublattices the different contributions to the Gibbs energy are
given by:
ref
G ϕ =∑ ∑ ∑ ∑ y i1  y  j2  y k3  y l4  G ϕi: j :k : l (9)
i j k l

id 1
Gϕ= RT ∑ ∑ y is  ln y is  (10)
4 s i

ex
G ϕ = ∑ ∑ y j1  y i1  ∑ ∑ ∑ y k2  y l3  y m4  Lϕi,j : k :l : m  T 
i j>i k l m
 2 2  1  (11)
∑ ∑ y j y i ∑ ∑ ∑ yk y l3  y m4  Lkϕ : i,j : l: m  T  .. .
i j>i k l m

ϕ ref
where Gi: j:. . .: k in Gϕ are the Gibbs energies of all the so-called end members, i.e. the
stoichiometric compounds (either stable, metastable or unstable) formed when only one constituent

28/09/09 376887662.doc 12
 ϕ ex ϕ
is present on each sublattice. L i,j : k : l: m  T  in G is the interaction parameter, described by a
Redlich-Kister series expansion, corresponding to the mixing of components i and j on the first
sublattice while the other sublattices are singly occupied. It has the same T dependence as the
i ϕ
L  T  parameters of eq. (5). The terms not shown correspond to all possible permutations
ex
between the four sublattices. Moreover, additional terms may be added to G
ϕ
, corresponding to
simultaneous mixing on two sublattices while the remaining sublattices are singly occupied.
The composition dependence of mag
G
ϕ
derives by the composition dependence of TC and , which
are given by expressions similar to eq. (11). This may account for the TC and  variations related to
the structural ordering.
In the present case L12 FeNi3 results when three of the sublattices have identical occupancy with Ni
being the main constituent, while Fe is the main constituent on the fourth sublattice. The opposite
occupation corresponds to the L12 Fe3Ni. L10 FeNi results when site occupancy splits into two
groups of two sublattices, the first group having identical site occupancy with Ni the main element
and the second group similarly with Fe as the main element. When each element occupies all
sublattices with the same site fraction the disordered state (A1 structure) is attained and the
equations (9, 10, 11) become equivalent to equations (2, 4, 5), respectively.
As a result of their crystallographic equivalence the four sublattices are also thermodynamically
equivalent, which means that groups of selected G functions must be equal to each other. A number
of constraints arise:
Gfcc fcc fcc fcc
Fe:Ni:Ni:Ni= G Ni:Fe:Ni:Ni= G Ni:Ni:Fe:Ni= G Ni:Ni:Ni:Fe= G Fe1Ni3
Gfcc fcc fcc fcc fcc fcc
Fe:Fe:Ni:Ni= G Fe:Ni:Fe:Ni= G Fe:Ni:Ni:Fe= G Ni:Fe:Fe:Ni= G Ni:Fe:Ni:Fe= G Ni:Ni:Fe:Fe= GFe2Ni2 (12)
Gfcc fcc fcc fcc
Fe:Fe:Fe:Ni= G Fe:Fe:Ni:Fe= G Fe:Ni:Fe:Fe= G Ni:Fe:Fe:Fe= GFe3Ni1

Moreover the three quantities GFe1Ni3, GFe2Ni2 and GFe3Ni1 may be related to each-other if a number of
approximations is assumed. In particular, if we assume that the same relations which hold between
bond energies can also be applied to Gibbs energies, and that bond energies are the result of the sum
of all nearest neighbour interactions, the following relations arise:
G Fe1Ni3= 3 U FeNi + U' FeNi
G Fe2Ni2= 4 U FeNi (13)
G Fe3Ni1= 3 U FeNi - U' FeNi

where UFeNi is related to the Fe-Ni bond energy while U'FeNi accounts for its dependence on
composition.
Even if the above-mentioned approximations are not completely fulfilled it could be expected that
GFe1Ni3, GFe2Ni2 and GFe3Ni1 would not not deviate too much from these relationships.

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Similar considerations also lead to similar constraints on the interaction parameters:
Lfcc fcc fcc fcc
Fe,Ni:Ni:Ni:Ni= L Ni:Fe,Ni:Ni:Ni= LNi:Ni:Fe,Ni:Ni= LNi:Ni:Ni:Fe,Ni = . ..
Lfcc fcc fcc fcc
Fe:Fe,Ni:Ni:Ni= L Fe:Fe,Ni:Ni:Ni= L Fe:Ni:Fe,Ni:Ni= L Fe:Ni:Ni:Fe,Ni= .. .
(14)
. ..
These constraints considerably reduce the number of independent empirical parameters to be
evaluated during optimization. See for instance the work of Kussofsky et al. [4] for a detailed
discussion of the relations and constraints between parameters in the four-sublattice modelling of
the fcc ordered phases.
The relation between the disordered (A1) and ordered (L1 2, L10) phases is realised by using a
unique Gibbs energy expression for all of them [148, 4]:

  s 
G m =Gmdis  x i  +ΔGord
m yi (15)
dis
where G m  x i   is the Gibbs energy of the disordered state and is given by equations (2, 4, 5) while
the ordering contribution is given by:
ΔG ord  
 s  s
m =G m y i −G m y i =xi  (16)

the difference between two terms expressed according to equations (9, 10, 11): the first term
calculated by using the actual site fractions and the second one by replacing the site fractions by the
global mole fractions in order to get the disordered state.

The bcc (A2) -Fe phase, which is only stable as a narrow terminal solid solution in the Fe-rich
side, is also described by a 4-sublattice model, to enable consideration of its ordered forms B2
(CsCl type), B32 (NaTl type) and D03 (BiF3 type). This would not be strictly necessary for the
calculation of the stable Fe-Ni phase equilibria, but it is necessary when Fe-Ni based higher order
systems (e.g. Al-Fe-Ni) are modelled. Detailed modelling of the bcc ordered forms is similar to that
already expressed for the 4-sublattice modelling of the fcc phases. They have recently been
illustrated by Sundman et al. [149].

4 Results and discussion

4.1 Atomistic calculations
The results of the present first principles calculations for several ordered structures are shown in
Table 3. The composition of the selected compounds were chosen in order to provide input
parameters for thermodynamic modelling and to cover a wide enough composition range in the
binary system.

28/09/09 376887662.doc 14
For pure Fe the present results are in agreement with previous works [123, 128]. In particular, the
energy of the fcc ferromagnetic pure Fe presents a double minima as a function of lattice parameter,
as pointed out in [128]. A ferromagnetic fcc Fe has been found at higher volumes, while a nearly
non magnetic state is stable at lower volumes.
The present ab-initio results for ordered compounds are also in agreement with previous
calculations using different methods [123, 125]. In both pure components and ordered compounds,
magnetism significantly decreases the energy at 0 K and cannot be neglected. However, as pointed
out in [128], the competition between different magnetic structures in fcc pure Fe and Fe-Ni alloys
is rather complex and the exact determination of the magnetic ground state structure could even be
not possible within present day local approximated potentials (both LDA and GGA). Fortunately,
the energy difference between competing structures is small and therefore this issue does not
significantly affect the following results for thermodynamic modelling. Thus, for simplicity, only
ferromagnetic structures have been calculated for binary compounds.
As shown in Table 3, nearly all Fe-Ni structures have been found to be unstable with respect to A2
Fe and A1 Ni. The most stable structure is the L1 2 FeNi3, which is consistent with previous
calculations [123, 125] and with the assessed phase diagram [11]. According to present results the
controversial L10 FeNi phase is stable at 0 K, in agreement with previous first principles
calculations [123, 125, 113]. This is also in agreement with recent findings about the possible
stability of the L10 FeNi phase found in meteorite samples [77, 12] and thus the difficulty in
achieving this phase in equilibrium is due to sluggish kinetics. However, the energy of the L1 0 FeNi
phase is very close to the convex hull line, the difference being only about 0.4 kJ/mol of atoms.
Approximately the same difference has been obtained using both normal and pv PAW
pseudopotentials in VASP.
Finally, the C11f phases with compositions Fe2Ni and FeNi2 suggested by Mishin and coworkers
[123] as possible stable phases have also been calculated in the present work. According to the
present results these structures are not stable at 0 K and their energy lie above the convex hull line.
Nonetheless, since the difference is only a few kJ/mol, it may be possible to obtain these phases in
metastable equilibrium under certain experimental conditions. However, to the best Authors’
knowledge, the existence of these phases has never been confirmed experimentally.
The present first principles results have been used in the thermodynamic modelling of the Fe-Ni
system as discussed in the next section.

4.2 Assessment procedure

The thermodynamic optimisation of the system has been achieved by successive refinements. A first

28/09/09 376887662.doc 15
set of parameters has been calculated for the liquid and the A1 phases on the basis of the available
thermodynamic data. Then the composition dependence of TC and  for the solid phases A1 and A2
has been modelled. Subsequently liquid, A1 and A2 parameters have been refined by using phase
equilibrium data. Finally the FCC4 and BCC4 phases have been added and their parameters
optimised using experimental phase equilibria and atomistic calculation results. The final
refinement of the optimisation parameters has been obtained by using all the available experimental
and calculation results with appropriate weight factors. The temperature range of validity of the
present assessed data is, at least, -100 to 2500°C.

4.3 Calculation results

The Fe-Ni thermodynamic database resulting from the present work is reported in the Appendix
and, in electronic format, as supplementary data attached to the present paper.

4.3.1 Thermodynamics
Thermodynamic functions calculated in this work are presented and compared with experimental
data in Fig. 3 for the liquid and in Fig. 4 for the A1 phase. The validity of the Kopp-Neumann rule
has been assumed on the basis of the literature data [150]. Good agreement between experimental
data and computed functions has been generally obtained. In particular it may be observed that the
enthalpy of mixing of the liquid (Fig. 3a) is now less exothermic and less asymmetric than would be
expected from the previous assessment done by Lee [134]. The enthalpy of formation of the liquid
and the A1 solid solution in the paramagnetic state are very similar to each other (Fig. 4c): this
suggests that the average bond energy between Fe and Ni atoms in disordered close packed phases
is weakly dependent on the aggregation state or structure. Other thermodynamic quantities, such as
element activities (Figs. 3b) or activity coefficients (Figs 3c and 4b) also show that calculated
functions are well within the range of experimental uncertainty.

At temperatures lower than about 1000 K ferromagnetic ordering occurs in both fcc and bcc phases.
The composition dependence of the Curie temperature and the average magnetic moment per atom
have been evaluated and experimental data reproduced as close as possible (Figs. 5). The
polynomial expansion used to approximate the composition dependence (eq. 8) did not allow us to
closely reproduce the sharp variation of the magnetic moment around 0.4 at% Ni. The adoption of
the order-disorder relation between the fcc phases however allowed us to well reproduce the TC
increment and its asymmetric trend around 0.75 at% Ni (Fig. 5a) related to the L12 ordering.

28/09/09 376887662.doc 16
The enthalpy of formation of the solid phases (both stable and metastable) is shown in Fig 6. It was
possible to model the enthalpy of formation of the solid phases, especially the metastable ones, only
as a result of the atomistic calculations. Considering the scatter of the literature data reported in the
figure, it could be concluded that L10 may be either weakly stable or weakly metastable with respect
to A2 Fe and L12 FeNi3. However, our calculations, in agreement with the most recent literature,
indicate that it is stable at 0 K. According to our thermodynamic assessment, which takes also into
account phase equilibria, we concluded that L10 should become stable at temperatures below room
temperature. Unfortunately this conclusion cannot be verified experimentally, due to the slow
diffusivity of Fe and Ni, which make it impossible to reach equilibrium at such a low temperature.
It is interesting to observe that assessed enthalpies of formation are in good agreement with ab-
initio results and this is as a result of applying relations (13) between the interaction parameters of
the fcc ordered phases. This supports the validity of the assumptions and approximations underlying
relations (13).

4.3.2 Stable phase equilibria

The stable Fe-Ni phase equilibria calculated in this work are shown and compared to literature data
in Fig. 7 and computed invariant equilibria are summarised and compared to literature data in Table
4. In general there is good agreement between experimental data and calculations.
In particular the tricritical point generating the -(Fe,Ni)PM + -(Fe,Ni)FM two-phase field, first
calculated by Chuang et al. [30], has been confirmed. According to the present assessment the
monotectoid equilibrium -(Fe,Ni)PM  -Fe + -(Fe,Ni)FM, never observed experimentally, occurs at
428°C.
The only appreciable discrepancy between experiments and calculations (in the order of about 8-10
at%) concerns the composition of the L12 FeNi3 phase in equilibrium with -Fe: at 300°C it is about
65 at% Ni according to [53] while it is about 58 at% Ni according to the present assessment. It was
not possible to obtain a better agreement with the experimental results by [53] without decreasing
the general good agreement of other equilibria. On the other hand, according to the critical
assessment by [12] the solubility limit of L1 2 FeNi3 at about 200°C is 64 at% Ni, 6-7 at% Ni lower
than the experimental observations by [53] and more consistent with our calculations.

4.3.3 Metastable phase equilibria

It is well known that the ability to calculate a stable binary phase diagram in good agreement with
the experimental data is not a sufficient condition to conclude that a sound thermodynamic

28/09/09 376887662.doc 17
assessment has been obtained which is suitable for reliable extrapolation to higher order systems.
This means that metastable phase equilibria are also important and these have to be calculated and
discussed. On the other hand, metastable phase equilibria are, in most cases, not experimentally
accessible and there is no way to check the soundness of the calculated values by comparison with
experiments. In most cases the only possibility is to check their compatibility with stable equilibria
in higher order systems, an indirect procedure which is time consuming and itself may not be free
from ambiguity. In our case, however, the very slow kinetics of the system makes observable
metastable states which may result when the formation of selected phases is kinetically inhibited.
Some information on metastable Fe-Ni equilibria is summarised in the critical assessment by Yang
et al. [12], where a semi-quantitative phase diagram including both stable and metastable equilibria,
reported here in Fig. 1b, is presented.
Moreover atomistic calculations may also be very useful because they allow us to calculate
thermodynamic functions (especially enthalpy of formation) of experimentally inaccessible
metastable states with uncertainties comparable to the experimental values. In our case the atomistic
calculations available in literature combined with those carried out in this work made possible to
evaluate thermodynamic functions at 0 K for several metastable ordered phases such as L1 2 Fe3Ni,
L10 FeNi, D03 Fe3Ni and FeNi3, B2 and B32 FeNi, etc. This, in turn, made it possible to simulate
metastable phase diagrams where only selected phases are allowed to form.
Fig. 8 shows the Fe-Ni phase diagram resulting when only fcc-based phases (A1, L1 2 and L10) are
considered. In this figure several phase equilibria are shown: 1) “stable” fcc phase equilibria by
continuous lines; 2) metastable continuation of the -(Fe,Ni)PM + -(Fe,Ni)FM miscibility gap and, at
low temperature in the Fe-rich part of the diagram, the metastable miscibility gap occurring in -
(Fe,Ni)PM, both indicated by dashed lines; 3) spinodal boundaries within the -(Fe,Ni)PM + -
(Fe,Ni)FM miscibility gap, marked by dotted lines and 4) the Curie temperature by a dash-dotted
line. Curves calculated in this work, may be compared to those proposed by Yang et al. [12] (Fig.
1b). Considering the difficulty of the experimental investigations and the consequent uncertainty of
the critically assessed equilibria, the agreement between our calculations and Yang et al. [12] is very
good. This means that data coming from very different sources, such as phase equilibria observed in
meteoric samples, results from 0 K atomistic calculations, thermodynamic measurements at
relatively high temperature, are fundamentally consistent with each other. This also means that
thermodynamic models adopted in this work and, in particular, constraints here assumed between
model parameters of the fcc ordered phases are significant, at least for this system.

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4.3.4 Role of magnetism
Finally, it may be interesting to discuss the role of magnetism in determining Fe-Ni thermodynamic
functions and phase equilibria. To this end it is useful to compare thermodynamic functions and
phase diagrams calculated with and without magnetic contribution.
Entropies of mixing of the A1 and A2 phases calculated at various temperatures with and without
magnetic contributions are shown in Fig. 9 (a and b). Similarly, enthalpies of mixing are reported in
Fig. 10. Notice that all the functions reported in figures 9 and 10 are referred to the pure elements at
the stated temperature in a paramagnetic state. From the figures it is evident that, especially at lower
temperatures, the contribution due to magnetic ordering exceeds, even largely, the contribution due
to element mixing, which has been considered as temperature independent. As a result, in the
“paramagnetic” phase diagram (Fig. 11), calculated by neglecting the Curie temperature and the
magnetic contribution to the Gibbs energy of the different phases, the A2 phase never appears, ever
for pure Fe. Moreover L12 FeNi3 is slightly destabilised and L10 FeNi slightly stabilised with
respect to the equilibrium phase diagram (Fig. 7a).

5 Conclusions
The Fe-Ni system has been thermodynamically assessed according to the CALPHAD methodology,
using the compound energy formalism to express the Gibbs energy of Fe-Ni stable and metastable
phases: liquid, A1 and related fcc-based ordered phases (L12 Fe3Ni, L10 FeNi and L12 FeNi3), A2
and related bcc-based ordered phases (D03 Fe3Ni, B2 and B32 FeNi, D03 FeNi3). To this end both
experimental data from literature and ab-initio enthalpies of formation have been used. As a result
thermodynamic functions and stable phase equilibria experimentally known have been reproduced
within the range of the experimental uncertainties. In particular low temperature (below about
300°C) equilibria, hardly accessible experimentally due to an extremely sluggish kinetics, have
been calculated and conclusions drawn by [12] on the basis of meteoric samples investigations have
been confirmed.
Atomistic simulations carried out in this work by means of the VASP software using GGA
approximation and PAW pseudopotentials lead to the calculation of 0 K enthalpies of formation,
lattice parameters and magnetic moment of several Fe-Ni phases. In particular the stability of the
L10 phase at 0 K was confirmed, while C11f phases resulted to be metastable.

Ab-initio results both from literature and from the present work enabled us to model both stable and
metastable ordered phases which need to be thermodynamically evaluated in order to make the Fe-
Ni assessment suitable for extrapolations to higher order systems (such as Al-Fe-Ni, where e.g. bcc-

28/09/09 376887662.doc 19
based ordered phases are stable). To this end all disordered and related ordered phases were
modelled by a single 4-sublattice model for both fcc-based (A1, L1 2 Fe3Ni, L10 FeNi and L12 FeNi3)
and bcc-based (A2, D03 Fe3Ni, B2 and B32 FeNi, D03 FeNi3) structures. The use of a single model
for a disordered phase and its ordered forms makes it possible to calculate both first and second
order transformations. In particular a metastable phase diagram including only fcc-based phases has
been calculated, which is in good agreement with metastable phase equilibria experimentally
observed in meteorites. That means that thermodynamic functions essentially based on ab-initio
data and high temperature phase equilibria are consistent with metastable phase equilibria deducted
from meteorite analyses.
Magnetic ordering was also taken into account. Unfortunately the Redlich-Kister expansion is
inadequate to well reproduce the sharp variation of the average magnetic moment versus
composition observed in Fe-Ni, especially for the A1 phase around 30-40 at% Ni. Fortunately this
do not appreciably affects stable phase equilibria. It may be interesting to emphasize that, in
particular, it has been possible to calculated the T C increase due to the combination of magnetic and
structural ordering: this was experimentally known for the FeNi 3 phase, but not for the other
ordered phases. Finally the general influence of magnetism on the Fe-Ni thermodynamics and phase
equilibria has been evidenced: when magnetism is switched off bcc-based phases are heavily
destabilised with respect to fcc and A2 completely disappears, even for pure Fe.

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Appendix
Interaction parameters evaluated in this work with a non-zero value are listed here below.
A complete database file (a text file in .TDB format) is supplied as supplementary data associated
with this article.

Phase LIQUID  Model (FE,NI)
G(LIQUID,FE,NI;0) = ­18782+3.7011*T
G(LIQUID,FE,NI;1) = +12308­2.7599*T
G(LIQUID,FE,NI;2) = +4457.0­4.1536*T

Phase A1  Model (FE,NI)
G(A1,FE,NI;0) = ­15500+2.850*T
G(A1,FE,NI;1) = +14000­4.000*T
G(A1,FE,NI;2) = ­3000
TC(A1,FE,NI;0) = 2200
TC(A1,FE,NI;1) = ­700
TC(A1,FE,NI;2) = ­800
BMAGN(A1,FE,NI;0) = 10
BMAGN(A1,FE,NI;1) = 8
BMAGN(A1,FE,NI;2) = 4

Phase A2  Model (FE,NI,VA)
G(A2,FE,VA;0) = 80*T
G(A2,NI,VA;0) = 80*T
G(A2,FE,NI;0) = ­7500
G(A2,FE,NI;1) = +8500­5.0*T
TC(A2,FE,NI;0) = ­1000
TC(A2,FE,NI;1) = 1500
BMAGN(A2,FE,NI;0) = ­0.5
BMAGN(A2,FE,NI;1) = 3.5

Phase FCC4  Model (FE,NI)1/4(FE,NI)1/4(FE,NI)1/4(FE,NI)1/4
G(FCC4,NI:FE:FE:FE;0) = G(FCC4,FE:NI:FE:FE;0) = G(FCC4,FE:FE:NI:FE;0) = 
G(FCC4,FE:FE:FE:NI;0) = 3*UFENI­3000+.3*T
G(FCC4,NI:NI:FE:FE;0) = G(FCC4,NI:FE:NI:FE;0) = G(FCC4,FE:NI:NI:FE;0) = 
G(FCC4,NI:FE:FE:NI;0) = G(FCC4,FE:NI:FE:NI;0) = G(FCC4,FE:FE:NI:NI;0) = 4*UFENI
G(FCC4,NI:NI:NI:FE;0) = G(FCC4,NI:NI:FE:NI;0) = G(FCC4,NI:FE:NI:NI;0) = 
G(FCC4,FE:NI:NI:NI;0) = 3*UFENI+3000­.3*T
       with UFENI = ­2125+.625*T

28/09/09 376887662.doc 21
 TC(FCC4,NI:FE:FE:FE;0) = TC(FCC4,FE:NI:FE:FE;0) = TC(FCC4,FE:FE:NI:FE;0) = 
TC(FCC4,FE:FE:FE:NI;0) = 155
TC(FCC4,NI:NI:FE:FE;0) = TC(FCC4,NI:FE:NI:FE;0) = TC(FCC4,FE:NI:NI:FE;0) = 
TC(FCC4,NI:FE:FE:NI;0) = TC(FCC4,FE:NI:FE:NI;0) = TC(FCC4,FE:FE:NI:NI;0) = 200
TC(FCC4,NI:NI:NI:FE;0) = TC(FCC4,NI:NI:FE:NI;0) = TC(FCC4,NI:FE:NI:NI;0) = 
TC(FCC4,FE:NI:NI:NI;0) = 245
BM(FCC4,NI:FE:FE:FE;0) = BM(FCC4,FE:NI:FE:FE;0) = BM(FCC4,FE:FE:NI:FE;0) = 
BM(FCC4,FE:FE:FE:NI;0) = 0.115
BM(FCC4,NI:NI:FE:FE;0) = BM(FCC4,NI:FE:NI:FE;0) = BM(FCC4,FE:NI:NI:FE;0) = 
BM(FCC4,NI:FE:FE:NI;0) = BM(FCC4,FE:NI:FE:NI;0) = BM(FCC4,FE:FE:NI:NI;0) = 0.115
BM(FCC4,NI:NI:NI:FE;0) = BM(FCC4,NI:NI:FE:NI;0) = BM(FCC4,NI:FE:NI:NI;0) = 
BM(FCC4,FE:NI:NI:NI;0) = 0.115

Phase BCC4  Model (FE,NI,VA)1/4(FE,NI,VA)1/4(FE,NI,VA)1/4(FE,NI,VA)1/4
G(BCC4,NI:FE:FE:FE;0) = G(BCC4,FE:NI:FE:FE;0) = G(BCC4,FE:FE:NI:FE;0) = 
G(BCC4,FE:FE:FE:NI;0) = 3*UFENI­3000+.3*T
G(BCC4,NI:NI:FE:FE;0) = G(BCC4,NI:FE:NI:FE;0) = G(BCC4,FE:NI:NI:FE;0) = 
G(BCC4,NI:FE:FE:NI;0) = G(BCC4,FE:NI:FE:NI;0) = G(BCC4,FE:FE:NI:NI;0) = 4*UFENI
G(BCC4,NI:NI:NI:FE;0) = G(BCC4,NI:NI:FE:NI;0) = G(BCC4,NI:FE:NI:NI;0) = 
G(BCC4,FE:NI:NI:NI;0) = 3*UFENI+3000­.3*T
       with UFENI = ­2125+.625*T
TC(BCC4,NI:FE:FE:FE;0) = TC(BCC4,FE:NI:FE:FE;0) = TC(BCC4,FE:FE:NI:FE;0) = 
TC(BCC4,FE:FE:FE:NI;0) = 155
TC(BCC4,NI:NI:FE:FE;0) = TC(BCC4,NI:FE:NI:FE;0) = TC(BCC4,FE:NI:NI:FE;0) = 
TC(BCC4,NI:FE:FE:NI;0) = TC(BCC4,FE:NI:FE:NI;0) = TC(BCC4,FE:FE:NI:NI;0) = 200
TC(BCC4,NI:NI:NI:FE;0) = TC(BCC4,NI:NI:FE:NI;0) = TC(BCC4,NI:FE:NI:NI;0) = 
TC(BCC4,FE:NI:NI:NI;0) = 245
BM(BCC4,NI:FE:FE:FE;0) = BM(BCC4,FE:NI:FE:FE;0) = BM(BCC4,FE:FE:NI:FE;0) = 
BM(BCC4,FE:FE:FE:NI;0) = 0.115
BM(BCC4,NI:NI:FE:FE;0) = BM(BCC4,NI:FE:NI:FE;0) = BM(BCC4,FE:NI:NI:FE;0) = 
BM(BCC4,NI:FE:FE:NI;0) = BM(BCC4,FE:NI:FE:NI;0) = BM(BCC4,FE:FE:NI:NI;0) = 0.115
BM(BCC4,NI:NI:NI:FE;0) = BM(BCC4,NI:NI:FE:NI;0) = BM(BCC4,NI:FE:NI:NI;0) = 
BM(BCC4,FE:NI:NI:NI;0) = 0.115

28/09/09 376887662.doc 22
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