Journal of Alloys and Compounds 587 (2014) 533–543

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Journal of Alloys and Compounds

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

Thermodynamic assessment of the Cu–Fe–Ni system

Liya A. Dreval ⇑, Mikhail A. Turchanin, Pavel G. Agraval
Metallurgical Department, Donbass State Engineering Academy, Shkadinova Street 72, UA-84313 Kramatorsk, Ukraine

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

Article history: The thermodynamic description of the Cu–Fe–Ni system has been updated considering the newly avail-
Received 17 September 2013 able experimental data, as well as compatibility of the present modeling with those used for the Cu and
Received in revised form 27 October 2013 Fe systems. All of the experimental data available in the literature have been critically reviewed, and the
Accepted 29 October 2013
inconsistent information has been excluded. The thermodynamic parameters have been evaluated in
Available online 9 November 2013
order to properly describe the thermodynamic properties of the liquid phase and miscibility gap in the
solid state. A significant improvement in comparison with the previous thermodynamic descriptions
Keywords:
has been achieved. Additionally, for the ordered L12 phase the four-sublattice model has been adopted
Thermodynamic modeling
Phase diagram
to predict the ternary phase equilibria involving this phase. A set of thermodynamic parameters for
Thermodynamic properties the phases is given.
Compound energy formalism Ó 2013 Elsevier B.V. All rights reserved.

1. Introduction
The alloys of the Cu–Fe–Ni system are the basis of a wide range
of technologically important materials, e.g. structural steels, alloys
with special electrical and magnetic properties, and materials with
high corrosion-resistance. Recently, the copper–iron–nickel alloys
have been recognized as a potential anode material for aluminum
production [1]. Moreover, the system is one of the constituent ter-
naries used for the development of high-entropy alloys [2,3]. Be-
sides, the knowledge of the interaction between copper, iron, and
nickel in the liquid and solid state is essential as this information
provides the possibility to control and conduct different metallur-
gical processes, for example, electrical arc furnace steelmaking [4],
and pyrometallurgy of copper and nickel [5]. In addition, the Cu–
Fe–Ni system is regarded as a model system for the study of
decomposition process in solid multicomponent alloys [6,7]. The
optimization of the alloy composition and process conditions as
well as modeling of the physical effects require quantitative infor-
mation on the phase equilibria, driving forces for phase transfor-
mations, and the thermodynamic factors used in diffusion
simulation. The reliable thermodynamic description of the system
which should be based on correct thermodynamic models of the
phase is quite useful for these purposes.
A number of authors [6,8–11] have published isothermal sec-
tions of the ternary Cu–Fe–Ni phase diagram based on the thermo-
dynamic modeling. Thermodynamic calculations have been also
used to describe the measured mixing enthalpy of solid alloys
⇑ Corresponding author. Tel.: +38 (0) 626416701; fax: +38 (0) 626416315.
E-mail address: phch@dgma.donetsk.ua (L.A. Dreval).
[8]. The main drawback of the mentioned above works is that
the lattice stability parameters used in them have been updated
in a subsequent database [12]. The first Caphad-type assessment
has been provided by [13]. Later, [7] has revised this thermody-
namic model of the system by optimizing only the ternary param-
eters of the f.c.c._A1 phase in order to obtain the better fit to their
own experimental data. At last, for the description of the ordered
L12 phase in binary Fe–Ni system and derived ternary ordered
phase [14] have proposed the four-sublattice model instead of
those given by [13]. Thermodynamic optimization of the ternary
system has been also conducted by [15]. The main problem of all
these calculations, except for the [7], is the systematic overestima-
tion of the composition range of the f.c.c._A1 phase miscibility gap.
Well agreement between the experimental and calculated bound-
aries of this region is observed only in [7]. However, no attempts
have been made to prove the consistency of the obtained set of
thermodynamic parameters with respect to liquid–solid phase
equilibria. Moreover, new experimental data on mixing enthalpies
of liquid phase [16] and phase equilibria [1,5] have showed that
the thermodynamic model of the liquid phase is not quite satisfac-
tory. Recently, the present group of authors has published the pre-
liminary thermodynamic assessment of the system [17]. We used
the new data [1,16] to improve the description of the miscibility
gap and phase equilibria involving liquid phase. But the order/dis-
order phase transformations have not been considered.
The main objective of the present study is to update the
description of the ternary system. The thermodynamic model of
the binary Fe–Ni system is substituted for that compatible with
existing assessments of the ternary systems, e.g. the Cr–Fe–Ni
system, in order to create a database for Cu–Fe-based alloys. The

0925-8388/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jallcom.2013.10.223
534 L.A. Dreval et al. / Journal of Alloys and Compounds 587 (2014) 533–543

newly available experimental data are used to refine thermody- 2100

namic model of the system. The phase equilibria including ordered (δFe)
T, K 1760
L12 phase is predicted. L
1800 1811

2. Literature review (γFe) 1667

1500
2.1. Binary systems 1368
1358
1200 (Cu) 1185
A short review of the binary phase diagrams and their thermo- 1120
dynamic modeling is given in present subsection. The symbols to 1033 1043
denote the binary phases are given in Table 1 in order to facilitate bcc_A2
900 Tc (αFe)
reading.

2.1.1. Cu–Fe system 600

The phase diagram is characterized by the formation of terminal

solid solutions. The following crystalline phases are stable: (dFe), 300
Cu 0.2 0.4 0.6 0.8 Fe
(aFe), (cFe), and (Cu). xFe
For this binary system several assessments are available
[13,18–20]. The description of [13] as well as subsequent one by Fig. 1. The calculated Cu–Fe phase diagram by Turchanin et al. [20]. In this figure
the same group of authors [18] fail to reproduce experimental data and later on the dotted line denotes magnetic transformation.

in the high temperature range, especially those associated with the

(cFe) solvus. The better agreement between calculated and exper-
imental values has been achieved by Cheng et al. [19] and Turcha-
nin et al. [20]. With respect to the assessment [19], Turchanin and
co-authors further improve the description of the equilibria involv-
ing (dFe)-phase by introducing new experimental data and a prop-
er thermodynamic model for the liquid phase. Consequently, the
parameters from [20] have been adopted for the Cu–Fe system in
the present work. The calculated phase diagram is shown in
Fig. 1. It is noteworthy that in Figures and Tables the concentra-
tions of elements are given in mole fractions.
2.1.2. Cu–Ni system
The Cu–Ni phase diagram is of the continuous solution type
with no intermediate phases. At low temperatures (Cu, Ni) phase
decomposes into the (Cu) and (Ni) one.
The phase equilibria and thermochemical data of the copper–
nickel system were thermodynamically assessed earlier in
[13,21,22]. The phase diagram and thermodynamic properties of
the phases calculated according to these works are shown in
Figs. 2–4. The relevant experimental points [10,23–44] are also
shown in the figures. Table 2 compares the calculated enthalpy
of formation of solid alloys at 298 K with literature data. Note that
the experimental results of [44] on the liquidus and solidus tem-
peratures, of [42,43] on the activity of copper in solid alloys, and
of [47] on the enthalpy of the solid alloys formation have not been
incorporated in the assessments [13,21,22]. As follows from the
figures, all authors reached fundamental agreement between the
calculated and experimental values. But the description of
Turchanin et al. [22] used in the present work yield a better overall
fit to the experimental data, especially those on the thermody-
namic properties of the phases, compared to the works by [13,21].
2.1.3. Fe–Ni system
The stable crystalline phases are (dFe), (aFe), (cFe, Ni), and or-
dered FeNi3. In this system (cFe, Ni) phase is an extended solid
solution, while the solubility of Ni in (dFe) and (aFe) is limited.
The ordered phase has a homogeneity range. Furthermore there
are paramagnetic (cFe, Ni)par and ferromagnetic (cFe, Ni)fer
f.c.c._A1 phases below the critical point at 890 K in the system.
Xing et al. [48] were the first who published the Calphad-type
assessment of the system. The parameters presented by them have
been rounded off and used in the work [49]. Thereafter the thermo-
dynamic description [49] was modified by Lee [50] in order to bet-
ter fit to the liquidus/solidus phase equilibria in the Fe-rich region
of the phase diagram and, recently, by Servant [14] to describe the
Gibbs energy of the ordered binary and derived ternary phases. In
our preliminary assessment of the ternary system [17] the binary
Fe–Ni has been taken from [49]. In present work we decide to com-
pile the parameters from works [14,49,50] to be able to use the ob-
tained thermodynamic model with the higher-order systems
[50,51] and to predict phase equilibria with ordered FeNi3 phase.
It should be noted that the model of the binary ordered phase pro-
posed by [14] is revised by some minor adjustment (for details see
Section 3.3). The calculated phase diagram is given in Fig. 5.

Table 1
The list of the binary phases and their description.

Symbol Phase description Temperature range, K Designation used in the thermodynamic database
L Liquid LIQUID
(dFe) High-temperature iron-based solution with b.c.c._A2 structure 1667–1811 BCC_A2
(aFe) Low-temperature iron-based solution with b.c.c._A2 structure <1185
(Cu) Copper-based solution with f.c.c._A1 structure <1358 FCC_A1
(cFe) Iron-based solution with f.c.c._A1 structure 1185–1667
(Ni) Nickel-based solution with f.c.c._A1 structure <606
(Cu, Ni) Copper- and nickel-based solution with f.c.c._A1 structure <1728
(cFe, Ni) Iron- and nickel-based solution with f.c.c._A1 structure <1790
(cFe, Ni)par Paramagnetic iron- and nickel-based solution with f.c.c._A1 structure <890
(cFe, Ni)fer Ferromagnetic iron- and nickel-based solution with f.c.c._A1 structure <890
FeNi3 Ordered L12 phase <790 L12_FCC
 L.A. Dreval et al. / Journal of Alloys and Compounds 587 (2014) 533–543 535

1800 1200
T, K T, K two phases, [27]
L 1728
one phase, [38]
[13]
900 [21]
(Cu,Ni)
[22]
[28] 723
1500 [29] 0.67
[30] 642
0.61 (Ni) 633
[32]
600 606
[44] (Cu) 0.6
1358
(Cu,Ni) [13]
[21]
[22] fcc_A1
Tc
1200 300
Cu 0.2 0.4 0.6 0.8 Ni Cu 0.2 0.4 0.6 0.8 Ni
xNi xNi
(a) (b)
Fig. 2. The calculated Cu–Ni phase diagram (lines) with experimental data (symbols): (a) the part of the phase diagram showing the liquid + (Cu, Ni) two-phase field, (b) the
part of the phase diagram showing the miscibility gap.

5.0 [29], 1753 K 1.0 [34], 1673 K

[31], 1733-1763 K [41], 1623 K
[35], 1748 K
0.8
ΔH, kJ/mol

0.6
2.5 aNi

0.4 aCu
[39], 1739 K
[40], 1753 K
[13], 1753 K 0.2 [13], 1753 K
[21], 1753 K [21], 1753 K
[22],1753 K [22],1753 K
0 0
Cu 0.2 0.4 0.6 0.8 Ni Cu 0.2 0.4 0.6 0.8 Ni
(L) xNi (L) (L) xNi (L)

(a) (b)
Fig. 3. The calculated mixing enthalpy (a) and activities of components (b) of the liquid phase in the Cu–Ni system (lines) and experimental values (symbols). The standard
element reference states are given below the chemical elements.

2.2. Ternary Cu–Fe–Ni system
There are seven stable crystalline phases, i.e. (dFe), (aFe),
(cFe, Ni), (cFe, Ni)fer, (cFe, Ni)par, (Cu, Ni), and ordered FeNi3, in
the ternary system. Authors of [52] have also shown an evidence
of a new (Cu, Ni)3Fe phase in this system.
As the most of the experimental data were thoroughly reviewed
in [17] a brief discussion of the experimental works is presented
here.
The liquidus and solidus temperatures have been determined
by [1,5,53,54]. These data indicate the flatness of the liquidus
surface. According to the investigations of [53,54], the three-phase
triangle L + (cFe, Ni) + (Cu, Ni) degenerates to a line L M ((cFe, Ni),
(Cu, Ni)). This critical tie-line has been found to occur at 1473 K
and 27 wt.% Ni in solid phases [54]. The most important result of
Gallino et al. [1] is the finding of a narrow temperature window
between solvus and solidus surfaces, in which the
Cux(Fe50Ni50)100x (x = 10, 20, 30, 40, 50, 60, 70 wt.%) alloys can
be successfully homogenized into a single f.c.c._A1 phase. At the
same time the authors reported that Cu60Fe20Ni20 and Cu70Fe15Ni15
alloys undergo peritectic reaction. The compositions of liquid and
(cFe, Ni) phases in equilibrium have been measured by Hasebe
et al. [9] at 1423, 1523 K and Ohtani et al. [55] at 1473, 1573 K.
The data on the miscibility gap in the f.c.c._A1 phase are numer-
ous from the several groups of authors [1,7,9,54,56–58]. Most stud-
ies show that the miscibility gap is almost symmetrical with
respect to the section (Cu50Fe50)1x–Nix and becomes wider while
the temperature decreasing. The data from [56] at el., which
indicate a peculiar increase in iron solubility in the (Cu, Ni) phase
when nickel is added, contradict the other experimental results
and have not been used in the present assessment. The experimen-
tal values at 873, 1023 and 1073 K [1,58] have been also excluded
536 L.A. Dreval et al. / Journal of Alloys and Compounds 587 (2014) 533–543

5.0 1.0 [10], 1273 K

[23], 995 K
[24], 913 K [25], 1273 K
[26], 773 K [33], 1273 K
0.8
[13], 1753 K
ΔH, kJ/mol

2.5 0.6

aNi
0.4 [36], 1273 K aCu
[37], 1300 K
[42], 1273 K
0.2 [43], 1173 K
0 [21], 1753 K [13], 1753 K
[22], 1753 K [21], 1753 K
[22],1753 K
0
Cu 0.2 0.4 0.6 0.8 Ni Cu 0.2 0.4 0.6 0.8 Ni
(FCC_A1) xNi (FCC_A1) (FCC_A1) xNi (FCC_A1)

(a) (b)
Fig. 4. The calculated mixing enthalpy (a) and activities of components (b) of the (Cu, Ni)-phase in the Cu–Ni system (lines) and experimental values (symbols). The standard
element reference states are given below the chemical elements.

Table 2
The enthalpy of formation of the solid Cu–Ni alloys calculated at room temperature,
2100
DfH298, in comparison with experimental data. T, K 1811 L
xNi
1790
Df H273
exp Df H300
exp Df H298
exp Df H298
calc Df H298
calc Df H298
calc 1800
[13] [21] [22]
1728
[45] [46] [47]
1667 (δFe)
0.05 0.5 ± 1.8 0.3 0.4 0.3
0.12 2.678 ± 0.6 0.8 0.9 0.8 1500
0.17 1.9 ± 1.4 1.1 1.3 1.1 (γFe,Ni)
0.2 3.096 ± 1.2 1.3 1.5 1.2 1185
0.21 2.1 ± 1.4 1.4 1.5 1.3 1200
bcc_A2
0.298 0.7 ± 1.7 1.9 2.1 1.8 Tc
0.32 3.745 ± 2.0 2.1 2.2 1.9
1043 (αFe) fer
par (γFe,Ni) 890 T fcc_A1
0.4 3.933 ± 1.7 2.5 2.6 2.3 900 (γFe,Ni) c
0.414 2.5 ± 1.2 2.6 2.6 2.3 790
730
0.5 3.2 ± 1.8 3.0 2.9 2.6 680 0.74
0.52 5.0 ± 1.6 3.1 3.0 3.1 FeNi3 633
600
0.6 2.9 ± 2.1 3.3 3.1 2.9 642
0.689 3.6 ± 1.4 3.3 3.1 2.8
0.83 3.4 ± 2.0 2.2 2.0 1.9
0.85 2.2 ± 1.8 2.0 1.8 1.7 300
Fe 0.2 0.4 0.6 0.8 Ni
xNi
Fig. 5. The calculated Fe–Ni phase diagram according to the thermodynamic
from the modeling since the tie-line between (cFe, Ni) and (Cu, Ni) descriptions of [14,49,50].
phases along the binary Cu–Fe side shows a noticeable discrepancy
from the phase equilibria in the binary system [20]. For the same
reason the data on the tie-line between (cFe, Ni) and (aFe) at
873 and 1073 K by Qin et al. [58] along the binary Fe–Ni side have 3. Thermodynamic modeling
been neglected in the optimization.
The phase transformations associated with the formation of or- 3.1. Pure elements
dered FeNi3 cubic phase in the system are less studied. Servant
et al. [52] reported that the new phase with an atomic composition The molar Gibbs energy for the element i (i = Cu, Fe, Ni) in the u
Cu5.6Fe22.2Ni72.2 seems to derive from the binary ordered phase. phase relative to the standard element reference (SER) state is de-
However, the thermal treatment used in this investigation is scribed by
doubtful since the sample was aged only for 2 h at 773 K after
2 3
one week at 1423 K. Further experimental results are needed to 
Gi ðTÞ  HSER
i ¼ a þ bT þ cT ln T þ dT þ eT 1 þ fT þ gT 9
determine exactly the composition range of this phase. 7
þ hT þ Gmagn ðTÞ ð1Þ
The thermodynamic properties of the phases of the Cu–Fe–Ni
system were studied by several groups of authors. Dreval’ et al. where HSER
is the molar enthalpy of the element in its reference
i
[16] and Counsell et al. [8] have measured the mixing enthalpy state at 298.15 K, a through h are coefficients, T is the temperature,
of the copper–iron–nickel alloys at 1873 and 1323 K. Activity data and Gmagn ðTÞ is the magnetic contribution to the Gibbs energy due
for liquid alloys have been obtained at 1623 K by [41], at 1673 K by to the magnetic ordering. The last one term is only needed for
[59], and at 1793 K by [60]. The thermochemical activities of com- f.c.c._A1 and b.c.c._A2 phases.
ponents in solid alloys have been investigated at 1023, 1273 K by The magnetic contribution is expressed according to Inden [62]
[36] and 1520 K by [61]. and Hillert and Jarl [63]
 L.A. Dreval et al. / Journal of Alloys and Compounds 587 (2014) 533–543 537

Gmagn ðTÞ ¼ RT lnðb þ 1Þf ðsÞ ð2Þ u u

X
n
u
bu ðxCu ; xFe ; xNi Þ ¼ xFe  bFe þ xNi  bNi þ xCu xFe bi;CuFe ðxCu  xFe Þi
where R is the gas constant, s is equal to T=T cr ; T cr is the critical i¼0
temperature for magnetic ordering (i.e. Curie or Neel tempera- X
n

ture); b is the average magnetic moment per atom in Bohr þ xCu xNi bu
i;CuNi ðxCu  xNi Þ
i

i¼0
magnetons.
The coefficients a, b . . . h, Tcr, and b for pure elements are taken X
n
þ xFe xNi bu
i;FeNi ðxFe  xNi Þ
i
from the SGTE compilation of Dinsdale [12]. Obviously, since no i¼0
magnetic transition occurs in pure Cu, the relative values are nil.
þ xCu xFe xNi bu
i;CuFeNi ð6Þ
3.2. Solution phases here  T u  u  u  u
crFe , T crNi , bFe , bNi are the critical temperatures and the
average magnetic moments of pure elements; T u u
i;crCuFe , T i;crCuNi ,
For the solution u phase (u = liquid, f.c.c._A1, and b.c.c._A2) the
molar Gibbs energy is expressed by Tu u u /
i;crFeNi , bi;CuFe , bi;CuNi , bi;FeNi are the binary interaction parameters;
u
X Tu
crCuFeNi , bCuFeNi are the ternary interaction terms. For the binary
u u
G ðxCu ; xFe ; xNi ; TÞ ¼ 
xi ð Gi ðTÞ  HSER
i Þ systems the parameters has been accepted according to the thermo-
X
i¼Cu;Fe;Ni dynamic assessments [20,22,49], and the T u u
i;crCuFeNi , bi;CuFeNi param-
þ RT xi lnðxi Þ þ DGex;u ðxCu ; xFe ; xNi ; TÞ eters from [13] have been adopted in the present description.
i¼Cu;Fe;Ni

þ DGmagn;u ðxCu ; xFe ; xNi ; TÞ ð3Þ 3.3. Ordered FeNi3 phase

where xi is the mole fraction of the element i, the first term is the
The sublattice model developed by Hillert and Staffansson
contribution of the pure components of the u phase to the Gibbs
[65], and Sundman and Ågren [66] used widely to describe
energy; the second is the ideal mixing contribution, the third is
compound and ordered phases. This approach was extended by
the contribution due to non-ideal interactions between the compo-
Dupin [67] who used a more complex formulation for the
nents, and the last one is the magnetic contribution to the Gibbs en-
ordering phase.
ergy of the phase.
The ordered binary FeNi3 phase and derived ternary
The excess Gibbs energy has been described using the conven-
(Cu, Ni)3Fe compound has been modeled by Servant et al. [14]
tional equation developed by Muggianu et al. [64]
according to [67] using five sublattices as (Cu, Fe, Ni)0.25(Cu,
X
n Fe, Ni)0.25(Cu, Fe, Ni)0.25(Cu, Fe, Ni)0.25(Va)1, where Va are
i u
DGex;u ðxCu ; xFe ; xNi ; TÞ ¼ xCu xFe LCuFe ðxCu  xFe Þi vacancies. The Gibbs energy per mole of atoms is described by
i¼0 the following expression
X
n
i u
þ xCu xNi LCuNi ðxCu  xNi Þi GL12 FCC
ðfxi g; fysi g; TÞ ¼ GFCC A1
ðfxi g; TÞ
i¼0 X
4 X
4 X
4 X
4 XX X X
L12 FCC
þ ysi yrj ytk yul y5Va  Gi:j:k:l:Va
X
n
i u s¼1 r¼1 t¼1 u¼1 i¼Ni j¼Fe k¼Fe l¼Fe
þ xFe xNi LFeNi ðxFe  xNi Þi
X
4 X
4 X
4 X
4 XX X X
L12 FCC
i¼0 þ ysi yrj ytk yul y5Va  Gi:j:k:l:Va
þ xCu xFe xNi ðxCu 0 Lu 1 u s¼1 r¼1 t¼1 u¼1 i¼Fe j¼Ni k¼Ni l¼Ni
CuFeNi þ xFe LCuFeNi X
4 X
4
!
ysi lnðysi Þ þ y5Va lnðy5Va Þ
þ xNi 2 Lu
CuFeNi Þ ð4Þ þ RT 0:25
s¼1 i¼Cu;Fe;Ni

u u u X
4 X
4 X
4 X
4 XX X X X
where i LCuFe ; i LCuNi , and i LFeNi are the interaction parameters þ L12 FCC
ysi ysj yrk ytl yum y5Va Li;j:k:l:m:Va
between the elements in the corresponding binary systems, n is s¼1 r¼1 t¼1 u¼1 i¼Fe j¼Ni k¼Cu;Fe;Nil¼Cu;Fe;Nim¼Cu;Fe;Ni
u u X
4 X
4 X
4 X
4 XX X X X
the power of the Redlich–Kister polynomial; 0 LCuFeNi , 1 LCuFeNi , þ L12 FCC
ysi ysj yrk ytl yum y5Va Li;j:k:l:m:Va
and 2 Lu
CuFeNi are the ternary interaction parameters. The parame- s¼1 r¼1 t¼1 u¼1 i¼Cu j¼Fe k¼Cu;Fe;Nil¼Cu;Fe;Nim¼Cu;Fe;Ni

ters for the binary systems have been taken from the assessments ð7Þ
stated in the Section 2.1. The value of the binary interaction
ysi
where are the site fractions of species i in their respective sublat-
parameter for a hypothetical b.c.c._A2 phase in the Cu–Ni system
tices, s, r, t, u are the sublattices (s, r, t, u are not equal for the param-
has been assessed in the present work.
eters), GFCC A1 ðfxi g; TÞ is the Gibbs energy of the disordered f.c.c._A1
The magnetic contribution to the Gibbs energy of the u
solution, which is described by Eq. (3), the next two terms denote
phase (u = (Cu, Ni), (Ni), (cFe, Ni)fer, (aFe)) is expressed by
the Gibbs energies of formation of the stoichiometric compounds
equation similar to that used for the pure metals, but both
FeNi3 and Fe3Ni, the fourth line is the ideal entropy term, the last
parameters T cr and b are the functions of alloy composition as L12 FCC
two terms correspond to the excess term. The parameters  Gi:j:k:l:Va
follows
relative to the same stoichiometry are identical, whatever the occu-
pation of the sublattices. Furthermore, the interactions between
Tu  u  u
cr ðxCu ; xFe ; xNi Þ ¼ xFe T crFe þ xNi T crNi
species in a given sublattice are assumed to be independent of
X
n
u the site occupations in the others, and identical in whatever sublat-
þ xCu xFe T i;crCuFe ðxCu  xFe Þi
i¼0
tice the interaction takes place.
X
n
u
þ xCu xNi T i;crCuNi ðxCu  xNi Þi 3.4. Optimization
i¼0
X
n
All calculations have been performed using the software pack-
þ xFe xNi Tu
i;crFeNi ðxFe  xNi Þ
i
age Thermo-Calc and the PARROT module for optimization [68].
i¼0
The following assumptions were made prior to optimization. No
þ xCu xFe xNi T u
i;crCuFeNi ð5Þ ternary interaction parameters were introduced for the b.c.c._A2
538 L.A. Dreval et al. / Journal of Alloys and Compounds 587 (2014) 533–543

solution due to the lack of the accurate experimental information. could not reach the equilibrium state during the specimen
For the ordered FeNi3 phase the model and parameters by Servant preparation at mentioned above temperatures. Moreover, the
et al. [14] were adopted in present assessment except for the ex- results of [54] obtained for the vertical sections of the ternary
cess parameters LL12 FCC L12 FCC
Cu;Fe::::Va ; L:Cu;Fe:::Va ; . . . (the last line in Eq. (7)) phase diagram testify that the (cFe, Ni) + (Cu, Ni) region should
since no reliable data on the solubility of copper in this phase avail- be wider than that proposed by Qin et al. [58] and Gallino et al.
able in the literature. The optimization was conducted in the three [1]. As for the dataset of [58] on the (aFe) + (cFe, Ni) and
stages. At first, all reliable experimental values associated with the
liquid phase were employed for evaluation. Considering a large
number of experimental points, the three ternary interaction
parameters, which are temperature dependent, could be intro-
Table 3
duced to obtain a good fit to those experimental data. At the sec- Thermodynamic parameters for the phases of the Cu–Fe–Ni system. All values are
ond stage, the parameters of the liquid phase were temporarily given in SI units (J, mol, K).
fixed, and the parameters of the f.c.c._A1 phase were optimized
Model/parameters of the phase References
by adding the experimental data relative to the miscibility gap.
LIQUID: model (Cu, Fe, Ni)1
Again, it was found that for the f.c.c._A1 phase three ternary inter-
0 LIQUID [20]
LCuFe ¼ 73316:72  142:79T þ 15:82T ln T
action parameters, which are function of the temperature, were
1 LIQUID [20]
LCuFe ¼ 9100:15  5:94T
necessary to fit the experimental results over a large temperature
2 LIQUID [20]
LCuFe ¼ 2428:96
range. At last, the ternary thermodynamic parameters of liquid
3 LIQUID
LCuFe ¼ 233:62 [20]
and f.c.c._A1 phases were optimized simultaneously based on all
0 LIQUID
LCuNi ¼ 14259 þ 0:45T [22]
reliable experimental data.
0 LIQUID
LFeNi ¼ 16911 þ 5:1622T [50]
The set of the thermodynamic parameters obtained in this work
1 LIQUID
LFeNi ¼ 10180  4:146656T [50]
is listed in Table 3.
0 LIQUID
LCuFeNi ¼ 52087 þ 12:642T This work
1 LIQUID
LCuFeNi ¼ 37431 þ 28:286T This work
2 LIQUID
LCuFeNi ¼ 151450  107:050T This work
4. Results and discussion
FCC_A1: model (Cu, Fe, Ni)1Va1
Figs. 6 and 7 show the calculated values of the thermodynamic 0 FCC A1
LCuFe ¼ 48885:74  11:51T [20]
properties of the liquid and f.c.c._A1 phases together with relevant 1 FCC A1
LCuFe ¼ 12687:16  8:01T [20]
experimental points. As can be seen from the figures most of the 2 FCC A1
LCuFe ¼ 4054:11 [20]

experimental data are well reproduced. Good correspondence 0 FCC A1

LCuNi ¼ 6877:12 þ 4:6T [22]

between calculated and experimental values has also been 1 FCC A1

LCuNi ¼ 2450:1 þ 1:87T [22]
T FCC A1 [22]
achieved for aFe at 5 at.% Fe and 1673 K [59], and 1520 K [61]. For 0;cr CuNi ¼ 935:5

the activities of the components in liquid alloys by [59,60] the T FCC A1 [22]
1;cr CuNi ¼ 594:9

qualitative agreement is obtained. The data on the copper and bFCC A1

0;CuNi ¼ 0:732
[22]
nickel activities in f.c.c._A1 phase of Velisek et al. [61] cannot be bFCC A1
1;CuNi ¼ 0:317
[22]
described by the calculations. It was proved that better fitting to 0 FCC A1
LFeNi ¼ 12054 þ 3:27T [49]
these data resulted in the worse description of the two-phase 1 FCC A1
LFeNi ¼ 11082  4:45T [49]
(cFe, Ni) + (Cu, Ni) region and phase equilibria involving the liquid 2 FCC A1
LFeNi ¼ 725:8 [49]
and (cFe, Ni) phases. T FCC A1
0;cr FeNi ¼ 2133
[49]
The isothermal sections of the ternary phase diagram calcu- T FCC A1
1;cr FeNi ¼ 682
[49]
lated for different temperatures are shown in Figs. 8 and 9. Results FCC A1
b0;FeNi ¼ 9:55 [49]
according to assessment by Jansson [13] and corresponding bFCC A1 [49]
1;FeNi ¼ 7:23
experimental data are also given for comparison. As follows from FCC A1
b2;FeNi ¼ 5:93 [49]
the Figures, the present calculations yield a better overall fit to the bFCC A1 [49]
3;FeNi ¼ 6:18
experimental data, compared to those of [13]. For example, we 0 FCC A1 This paper
LCuFeNi ¼ 130430 þ 70:251T
improved significantly the description of the (cFe, Ni) + (Cu, Ni) 1 FCC A1 This paper
LCuFeNi ¼ 78396  65:505T
two-phase field in the temperature range 1123–1323 K (Fig. 9a– 2 FCC A1
LCuFeNi ¼ 57712 þ 48:594T This paper
d) with respect to previous calculation. For lower temperatures, T FCC A1 [13]
cr CuFeNi ¼ 7000
our description, as well as that by Jansson [13], fails to reproduce FCC A1 [13]
bCuFeNi ¼ 20
the data on the f.c.c._A1 miscibility gap of [1,58]. As already
BCC_A2: model (Cu, Fe, Ni)1Va3
pointed out, the discrepancies between calculation and experi- 0 BCC A2
LCuFe ¼ 40146:22  4:91T [20]
mental values result from contradiction between the ternary
T BCC A2
¼ 41:4 [20]
0;cr CuFe
phase equilibria observed by [1,58] and accepted binary Cu–Fe 0 BCC A2
LCuNi ¼ 10000 This paper
phase diagram [20]. In present work an explanation of this contra- 0 BCC A2
LFeNi ¼ 956:63  1:29T [49]
f:c:c: A1
diction is proposed based on the position of the spinodal xspin of 1 BCC A2
LFeNi ¼ 1789:03  1:93T [49]
f:c:c: A1
the f.c.c._A1 phase. The spinodal xspin is calculated according to
the procedure by Chuang et al. [6] and shown by dash-dot-dot L12_FCC: model (Cu, Fe, Ni)0.25(Cu, Fe, Ni)0.25
(Cu, Fe, Ni)0.25(Cu, Fe, Ni)0.25Va1
line in Fig. 9. As temperature decreases from 1123 to 873 K, the L12 FCC L12 FCC

GNi:Fe:Fe:Fe:Va ¼ GFe:Ni:Fe:Fe:Va ¼  GL12 FCC
Fe:Fe:Ni:Fe:Va ¼
[14]
ends of the tie-lines [1,58] gradually shift from the binodal to  L12 FCC
GFe:Fe:Fe:Ni:Va ¼ 9171
spinodal line. They occupy intermediate position between these  L12 FCC L12 FCC L12 FCC [14]
GFe:Ni:Ni:Ni:Va ¼  GNi:Fe:Ni:Ni:Va ¼  GNi:Ni:Fe:Ni:Va ¼
lines at 1073 K (Fig. 9e), and almost coincide with the spinodal  L12 FCC
GNi:Ni:Ni:Fe:Va ¼ 14400 þ 12:55471T
at 873 K (Fig. 9f). This behavior could be attributed to the non- 0 L12 FCC
LFe;Ni::::Va ¼ 0 LL12 FCC
:Fe;Ni:::Va
L12 FCC
¼ 0 L::Fe;Ni::Va ¼ [14]
equilibrium state of investigated alloys. It was also noted by Gal- 0 L12 FCC
L:::Fe;Ni:Va ¼ 345:08a
lino et al. [1] that spinodal decomposition and gradual structure
a
coarsening occurred during the quenching and equilibrating of An asterisk, ‘‘’’, denotes that the parameter is independent of the constituents
the specimens at 1023 and 1073 K. This indicates that the authors of a specific sublattice.
 L.A. Dreval et al. / Journal of Alloys and Compounds 587 (2014) 533–543 539

20
xCu/xFe=3
0

−20
ΔH Ni , kJ/mol

xCu/xFe=1
0
1873

[16]
−20
xCu/xFe=1/3
0

−30
CuxFe1-x 0.2 0.4 0.6 0.8 Ni
xNi
(L) (L)
(a)

10 xCu/xFe=3

20
, kJ/mol

10 xCu/xFe=1
1873

0
ΔH

[16]
10
xCu/xFe=1/3
0

−10
CuxFe1-x 0.2 0.4 0.6 0.8 Ni
(L) xNi (L)
(b)
1.0 xCu/xNi=9
xCu/xNi=3 xCu/xNi=3/2

0.8 1623
aCu

xCu/xNi=1
0.6

0.4

1623
0.2 a Fe
[41]

CuxNi1-x 0.2 0.4 0.6 0.8 Fe

(L) xFe
(c)
Fig. 6. The calculated partial mixing enthalpy of nickel (a), integral mixing enthalpy
(b), activities of copper and iron (c) of the liquid alloys in the Cu–Fe–Ni system
(continuous lines) and experimental values (symbols). The standard element
reference states are given below the chemical elements.
(L)
Fig. 7. The calculated mixing enthalpy (a) and activity of iron (b and c) of the
f.c.c._A1 phase in the Cu–Fe–Ni system (continuous lines) and experimental values
(symbols). The standard element reference states are given below the chemical
elements.
540 L.A. Dreval et al. / Journal of Alloys and Compounds 587 (2014) 533–543

Ni [55] Ni [9]
1573 K [13] 1523 K [13]
This work This work
0.2 0.8 0.2 0.8

0.4 0.6 0.4 0.6

u
x Ni

x Ni
xC

xC
(γFe,Ni)
0.6 (γFe,Ni) 0.4 0.6 0.4

0.8 L 0.2 0.8 0.2

L

Cu 0.2 0.4 0.6 0.8 Fe Cu 0.2 0.4 0.6 0.8 Fe

xFe xFe

(a) (b)

Ni [55] Ni [9]
1473 K [13] 1423 K [13]
This work This work
0.2 0.8 0.2 0.8

0.4 0.6 0.4 0.6

u

u
x Ni

x Ni
xC

xC
(γFe,Ni) (γFe,Ni)
0.6 0.4 0.6 0.4

0.8 0.2 0.8 0.2

L
L
Cu 0.2 0.4 0.6 0.8 Fe Cu 0.2 0.4 0.6 0.8 Fe
xFe xFe

(c) (d)
Fig. 8. Isothermal sections of the ternary Cu–Fe–Ni system: (a) T = 1573 K; (b) T = 1523 K; (c) T = 1473 K; and (d) T = 1423 K. Calculated phase boundaries – solid and dashed
lines; experimental values – symbols.

(aFe) + (Cu, Ni) + (cFe, Ni) phase regions, it can hardly be repro-
duced within any equilibrium thermodynamic calculations be-
cause of its contradiction with stable phase diagram of the Cu–
Fe and Fe–Ni systems.
Some calculated vertical sections of the ternary phase diagram
are compared with experimental data from [1,5,53,54] in Fig. 10.
The agreement between results of calculation and experiments is
generally good. For the section Cux–(Fe50Ni50)1x temperature win-
dow between the solvus and solidus of the f.c.c._A1 phase and the
ternary peritectic reaction reported by Gallino et al. [1] are repro-
duced by our calculation. However, calculated L + (cFe, Ni) + (Cu,
Ni) three-phase region is very narrow, whereas according to the
experiment peritectic melting was observed for alloys with 16
and 21 at.% Fe. Attempts to obtain a closer fit to such details led
to a simultaneous worsening in the description of the f.c.c._A1 mis-
cibility gap and disappearance of the narrow window of
temperatures.
The model predicts two invariant reactions in the ternary
system at low temperatures. The first one is the monotectoid
four-phase transition reaction (cFe, Ni)par + (Cu, Ni) M (cFe,
Ni)fer + (aFe) at 686 K. The compositions of the phases in atomic
percent are follows: Cu0.63Fe55.63Ni43.74 for the (cFe, Ni)par,
Cu96.87Fe0.02Ni3.11 for the (Cu, Ni), Cu0.83Fe51.77Ni47.40 for the (cFe,
Ni)fer, Cu0.03Fe95.79Ni4.18 for the (aFe). This monotectoid reaction
associated with the miscibility gap in the Fe–Ni system is of
magnetic origin. The second one is the four-phase eutectoid reac-
tion (cFe, Ni)fer M FeNi3 + (Cu, Ni) + (aFe) at 640 K. The calculated
compositions of the coexisting phase in atomic percent are Cu0.79-
Fe47.38Ni51.83 for the (cFe, Ni)fer, Cu0.67Fe36.51Ni62.82 for the FeNi3,
Cu97.26Fe0.01Ni2.73 for the (Cu, Ni), Cu0.02Fe96.50Ni3.48 for the (aFe).
It should be noted that even though the excess parameters
corresponding to the last line in the Eq. (7) have been excluded
from the model of the ordered phase, the thermodynamic calcula-
tion still predicts the small Cu solubility in the phase. Further
experimental data are needed to verify these low temperature
equilibria.
Fig. 11 shows the projections of liquidus and solidus surfaces
calculated according to the present description. The assessed
coordinates of the critical tie-line L M ((cFe, Ni), (Cu, Ni))
(Fig. 11a) in atomic percent are follows: Cu65.0Fe18.8Ni16.2 for the
((cFe, Ni), (Cu, Ni)) phases and Cu89.8Fe4.4Ni5.8 for the liquid phase
at 1420 K. As a consequence, the L + (cFe, Ni) + (Cu, Ni))
three-phase region turn out to be not so extended in the ternary
system as reported in [53,54]. The calculated liquidus isolines are
in satisfactory agreement with experimental results by Sinyova
et al. [5] based on thermal analysis of 36 alloys. According to our
modeling results, the solidus of the (cFe, Ni)-phase (Fig. 11b) is ret-
rograde in wide temperature range.
 L.A. Dreval et al. / Journal of Alloys and Compounds 587 (2014) 533–543 541

Ni [9] Ni one phase [7]

1323 K 1273 K [7]
[58]
[9]
0.2 0.8 [13] 0.2 0.8 [58]
This work [13]
This work
u 0.4 0.6 0.4 0.6

x Ni
xC

x Ni
u
xC
0.6 0.4 0.6 0.4
(Cu,Ni) (γFe,Ni) (Cu,Ni) fcc_A1
(γFe,Ni)
x spin
fcc_A1
x spin
0.8 0.2 0.8 0.2

Cu 0.2 0.4 0.6 0.8 Fe Cu 0.2 0.4 0.6 0.8 Fe

xFe xFe
(a) (b)
Ni [9] Ni [9]
1173 K 1123 K [13]
[57]
This work
0.2 0.8 [13] 0.2 0.8
This work

0.4 0.6 0.4 0.6

u

u
x Ni

x Ni
xC

xC

fcc_A1
0.6 x spin 0.4 0.6 0.4
(Cu,Ni) (γFe,Ni) (Cu,Ni) (γFe,Ni)

0.8 0.2 0.8 fcc_A1

x spin 0.2
(αFe)

Cu 0.2 0.4 0.6 0.8 Fe Cu 0.2 0.4 0.6 0.8 Fe

xFe xFe

(c) (d)
Ni Ni
[1] [54]
1073 K 873 K
[58] [58]
0.2 0.8 [13] 0.2 0.8 [13]
This work 847Κ 862Κ This work
(Cu,Ni) (γFe,Ni)
886Κ
0.4 0.6 0.4 884Κ 0.6
u
u

x Ni

x Ni
xC
xC

(Cu,Ni) (Cu,Ni)+(γFe,Ni)+(αFe) (Cu,Ni)+(γFe,Ni)+(αFe)

0.6 0.4 0.6 0.4
fcc_A1
(γFe,Ni) x spin

0.8 fcc_A1 0.2 0.8 0.2

x spin
(αFe) (αFe)

Cu 0.2 0.4 0.6 0.8 Fe Cu 0.2 0.4 0.6 0.8 Fe

xFe xFe

(e) (f)
Fig. 9. Isothermal sections of the ternary Cu–Fe–Ni system: (a) T = 1323 K; (b) T = 1273 K; (c) T = 1173 K; (d) T = 1123 K; (e) T = 1073 K; and (f) T = 873 K. Calculated phase
boundaries – solid and dashed lines; experimental values – symbols.
542 L.A. Dreval et al. / Journal of Alloys and Compounds 587 (2014) 533–543

2100 L+(Cu,Ni)+(γFe,Ni) [5] 2100 [5]

T, K T, K (δFe)
L [53] [53] L L+(γFe,Ni)+(δFe)
1800 [54] 1800
(αFe)+(γFe,Ni)+(Cu,Ni) L+(Cu,Ni)+(γFe,Ni)
(γFe,Ni)
1500 fer
(γFe,Ni) +(γFe,Ni)
par
+(Cu,Ni) 1500
(αFe)
fer
(γFe,Ni) +(αFe)+(Cu,Ni) (Cu,Ni) (αFe)+(γFe,Ni)+(Cu,Ni)
1200 (γFe,Ni)fer+FeNi3+(Cu,Ni) 1200 fer
(γFe,Ni) +FeNi3+(Cu,Ni)
(γFe,Ni)fer+(γFe,Ni)par+(Cu,Ni)
(γFe,Ni)
900 900
686 T cfcc_A1 686
600 640 600 640
(γFe,Ni)fer+(αFe)+(Cu,Ni)
(αFe)+FeNi3+(Cu,Ni) T cfcc_A1 (αFe)+FeNi3+(Cu,Ni)
300 300
Cu0.5Fe0.5 0.2 0.4 0.6 0.8 Ni Cu0.75Ni0.25 0.2 0.4 0.6 0.8 Fe
xNi xFe
(a) (b)
2100 2100
[5] [1] [53]
T, K L T, K [5] L [54]
[53] (δFe)
1800 1800
L+(Cu,Ni)+(γFe,Ni)

1500 (γFe,Ni) 1500

(Cu,Ni) (γFe,Ni)
L+(Cu,Ni)+(γFe,Ni)
1200 1200 (Cu,Ni)
(αFe)+(γFe,Ni)+(Cu,Ni)
(γFe,Ni)fer+(γFe,Ni)par+(Cu,Ni)
900 900 fer
(γFe,Ni) +(αFe)+(Cu,Ni)
(αFe)+(γFe,Ni)+(Cu,Ni) 686 686
600 640 600 640
(γFe,Ni)fer+(αFe)+(Cu,Ni)
(αFe)+FeNi3+(Cu,Ni) fcc_A1 (αFe)+FeNi3+(Cu,Ni)
Tc
300 300
Cu 0.2 0.4 0.6 Fe0.75Ni0.25 Cu 0.2 0.4 Fe0.50Ni0.50
xFe xFe
(c) (d)
2100 2100
T, K [5] T, K [5]
[54] L [54] L
1800 1800

1500 1500 fer

(γFe,Ni) +FeNi3+(αFe)
fer par (αFe)+FeNi3+(Cu,Ni)
(γFe,Ni) +(γFe,Ni) +(Cu,Ni)
1200 (γFe,Ni) 1200 fer
(γFe,Ni) +FeNi3+(Cu,Ni)
(Cu,Ni)
fer
(γFe,Ni) +FeNi3+(Cu,Ni) (γFe,Ni)
900 900 (Cu,Ni)
T cfcc_A1
686
640
600 640 fer 600
(γFe,Ni) +(αFe)+(Cu,Ni)
(αFe)+FeNi3+(Cu,Ni)
300 300
Cu0.60Ni0.40 0.2 0.4 Fe0.60Ni0.40 Cu0.40Ni0.60 0.2 Fe0.40Ni0.60
xFe xFe

(e) (f)
Fig. 10. Calculated vertical sections of the ternary Cu–Fe–Ni system: (a) (Cu50Fe50)1x–Nix; (b) (Cu75Ni25)1x–Fex; (c) Cux–(Fe75Ni25)1x; (d) Cux–(Fe50Ni50)1x; (e) 40 at.% Ni;
and (f) 60 at.% Ni. Calculated phase boundaries – lines; experimental values – symbols.

5. Conclusions model of the system, and predict phase equilibria including

The description of the CuFeNi phase diagram has been up-
dated using the new experimental data and models compatible
with existing assessments of the ternary Fe-based systems in order
to create a database for Cu, Fe-based alloys, refine thermodynamic
ordered L12 phase.
Calculated values of the thermodynamic functions, vertical and
isothermal sections compared to experimental data from various
sources. The liquidus and solidus projections are also presented.
A good agreement has been achieved between our thermodynamic
 L.A. Dreval et al. / Journal of Alloys and Compounds 587 (2014) 533–543 543

Ni of Phase Diagrams in Metallurgy and Ceramics, vol. 496, NBS Special

T, K 1723 Publication, 1977, pp. 911–954.
[10] Z. Moser, W. Zakulski, P. Spencer, K. Hack, CALPHAD 9 (3) (1985) 257–269.
[11] P. Spencer, K. Hack, Z. Moser, W. Zakulski, CALPHAD 9 (2) (1985) 191–198.
1673 [12] A.T. Dinsdale, CALPHAD 15 (4) (1991) 317–425.
0.2 0.8
[13] A. Jansson, A thermodynamic evaluation of the Cu–Fe–Ni system, Materials
1648
Research Center, The Royal Institute of Technology, Stockholm, 1987. pp. 1-10,
1623 Report No. TRITA-MAC-0340.
[14] C. Servant, B. Sundman, O. Lyon, CALPHAD 25 (1) (2001) 79–95.
0.4 1598 0.6
[15] C.P. Wang, Ph.D. Thesis, Tohoku University, Japan, 2001.
u

x Ni
xC

[16] L.A. Dreval’, A.R. Abdulov, P.G. Agraval, M.A. Turchanin, Russian Metall.
1573 (Metally) 2010 (1) (2010) 6–12.
[17] M.A. Turchanin, T.Ya. Velikanova, L.A. Dreval’, A.R. Abdulov, P.G. Agraval,
0.6 1548 0.4
1698 Powder Metall. Met. Ceram. 48 (11–12) (2009) 672–692.
1523 [18] I. Ansara, A. Jansson, Assessment of the copper–iron system, Materials
Research Center, The Royal Institute of Technology, Stockholm, 1993. pp. 1–
1473 1498 1723
4, Report No. TRITA-MAC-0533.
0.8 1748 0.2
pc 1423 [19] Q. Chen, Z. Jin, Metall. Mater. Trans. A 26A (2) (1995) 417–426.
c (δFe)
1420 1773 [20] M.A. Turchanin, P.G. Agraval, I.V. Nikolaenko, J. Phase Equilib. 24 (3) (2003)
p1 307–319.
1373 p2 1790
p3 (γFe,Ni) [21] S.A. Mey, CALPHAD 16 (3) (1992) 255–260.
1760 1798
1368 [22] M.A. Turchanin, P.G. Agraval, A.R. Abdulov, Powder Metall. Met. Ceram. 46 (9–
Cu 0.2 0.4 0.6 0.8 Fe 10) (2007) 467–477.
xFe [23] O. Kubaschewski, W.A. Dench, V.A. Genta, A high temperature calorimeter for
slow reactions, in: Proc. N. P. L. Sympos. No. 9, Phys. Chem. Met. Solns. and
(a) Intermet. Compounds, HMSO 1, 1958, pp. 1–8.
[24] R.J. Oriani, U.K. Murphy, Acta Met. 8 (1960) 23–25.
[25] R.A. Rapp, F. Maak, Acta Metall. 10 (1) (1962) 63–69.
Ni [26] L. Elford, F. Muller, O. Kubaschewski, Ber. Bunsengesellschaft 73 (1968) 601–
1723 605.
T, K
[27] M.F. Ebel, Phys. Status Solidi A 5 (1) (1971) 91–94.
1673 [28] E.A. Feest, R.D. Doherty, J. Inst. Metals 99 (1971) 102–103.
[29] B. Predel, R. Mohs, Arch. Eisenhütten. 42 (8) (1971) 575–579.
0.2 0.8 [30] E. Schurmann, E. Schultz, Z. Metallkd. 62 (10) (1971) 758–762.
1623
[31] Y. Tozaki, Y. Iguchi, S. Ban-ya, T. Fuwa, Heat of mixing of iron alloys, in: Proc.
Intern. Symp. On Chem. Metallurgy of Iron and Steel, 1971, pp. 130–132.
1573 [32] B.D. Bastow, D.H. Kirkwood, J. Inst. Metals 100 (1971) 277–283.
0.4 0.6 [33] I. Katayama, H. Shimatani, Z. Kozuka, J. Jpn. Inst. Met. 37 (5) (1973) 509–515.
u

[34] A.D. Kulkarni, R.E. Johnson, Metal. Trans. 4 (7) (1973) 1723–1727.
x Ni
xC

1523 [35] Y. Iguchi, Y. Tozaki, M. Kakizaki, S. Ban-ya, T. Fuwa, J. Iron Steel Inst. Jpn. 63
(1977) 953–961.
0.6 0.4 [36] A. Kontopoulos, Trans. Inst. Min. Metall. Sect. C 87C (1978) C1–C5.
1473 [37] M. Notin, G. Lefebvre, J. Hertz, J. Solid State Chem. 28 (1979) 109–120. in
French.
1723 [38] T. Tsakalakos, Scr. Metall. 15 (3) (1981) 255–258.
1373
0.8 0.2 [39] U.K. Stolz, I. Arpshofen, F. Sommer, B. Predel, J. Phase Equilib. 14 (4) (1993)
(Cu,Ni) 1423 1773
1420 1398 (γFe,Ni) 473–478.
1398 1790 [40] I.V. Nikolaenko, M.A. Turchanin, Metall. Mater. Trans. B 28B (6) (1997) 1119–
1373 1130.
(δFe) [41] Y. Fujita, R.U. Pagator, M. Hino, T. Azakami, J. Jpn. Inst. Met. 61 (7) (1997) 619–
Cu 0.2 1368 0.4 0.6 0.8 1760 Fe
624.
xFe [42] T. Oishi, S. Tagawa, S. Tanegashima, Mater. Trans. 44 (6) (2003) 1120–1123.
[43] T. Oishi, S. Tagawa, S. Tanegashima, J. Phys. Chem. Solids 66 (2005) 251–255.
(b) [44] K. Ananthasivan, S. Balakrishnan, I. Kaliappan, S. Anthonysamy, R. Pankajavalli,
P.R. Vasudeva, J. Alloys Comp. 468 (2009) 275–279.
Fig. 11. Calculated liquidus (a) and solidus (b) surfaces projections. [45] J.S.LI. Leach, M.B. Bever, Trans. Metall. Soc. AIME 215 (1959) 728–729.
[46] J. Rogez, R. Castanet, Mater. Chem. Phys. 9 (1983) 597–602 (in French).
[47] V.P. Glibin, B.V. Kuznetsov, T.N. Vorobyova, J. Alloys Comp. 386 (2005) 139–
description and experimental data. However, low temperature 143.
equilibria (T < 800 K) need to be confirmed by future experimental [48] Z.S. Xing, D.D. Gohil, A. Dinsdale, T. Chart, DMA (A) 103, National Physical
work. Laboratory, London, 1985.
[49] A. Dinsdale, T. Chart, MTDS NPL, Unpublished work, 1986.
[50] B.-J. Lee, CALPHAD 17 (3) (1993) 251–268.
Acknowledgment [51] B.-J. Lee, Unpublished revision of C–Cr–Fe–Ni, 1991.
[52] C. Servant, M. Guymont, O. Lyon, Scr. Mater. 45 (1) (2001) 103–108.
[53] R. Vogel, Z. Anorg. Chem. 67 (1910) 1–16.
This work was supported by the Ministry of Education and
[54] W. Köster, W. Dannöehl, Z. Metallkd. 27 (1935) 220–226.
Science of Ukraine under the grant 0109U002665. [55] H. Ohtani, H. Suda, K. Ishida, ISIJ Int. 37 (3) (1997) 207–216.
[56] A.J. Bradley, W.F. Cox, H.J. Goldschmidt, J. Inst. Met. 67 (1941) 189–201.
References [57] W. Gan, Z. Jin, Chin. J. Met. Sci. Technol. 8 (3) (1992) 181–184.
[58] G.W. Qin, G. Zhao, M. Jiang, H.X. Li, S.M. Hao, Z. Metallkd. 91 (5) (2000) 379–
382.
[1] I. Gallino, S. Curiotto, M. Baricco, M.E. Kassner, R. Busch, J. Phase Equilib. Diffus. [59] V.I. Volkov, N.N. Novikova, S.E. Vaisburd, Izvest. VUZ Tsvetn. Metall. 4 (1986)
29 (2) (2008) 131–135. 127–128 (in Russian).
[2] C.-M. Lin, H.-L. Tsai, J. Alloys Comp. 489 (2010) 30–35. [60] L.Sh. Tsemekhman, V.P. Mintsis, B.P. Burylev, V.D. Linev, V.I. Volkov, Izv. VUZ
[3] C.-M. Lin, H.-L. Tsai, H.-Y. Bor, Intermetallics 18 (2010) 1244–1250. Chern. Metall. 3 (1985) 1–4 (in Russian).
[4] L. Yin, S. Balaji, S. Sridhar, Metall. Mater. Trans. B 41B (2010) 598–611. [61] J. Velisek, J. Vrestal, A. Rek, Kovove Mater. 15 (1) (1977) 3–13.
[5] S.I. Sineva, R.V. Starykh, M.V. Frolenkova, S.B. Zakhryapin, Russian Metall. [62] G. Inden, Z. Metallkd. 68 (1977) 529–534.
(Metally) (3) (2009) 263–270. [63] M. Hillert, M. Jarl, CALPHAD 2 (3) (1978) 227–238.
[6] Y.Y. Chuang, R. Schmid, Y.A. Chang, Acta Metall. 33 (8) (1985) 1369–1380. [64] Y.M. Muggianu, M. Gambino, J.P. Bros, J. Chim. Phys. 72 (1) (1975) 83–88.
[7] K.J. Rönkä, A.A. Kodentsov, P.J.J. Van Loon, J.K. Kivilahti, F.J.J. Van Loo, Metall. [65] M. Hillert, L.-I. Staffanson, Acta Chem. Scand. 24 (1970) 3618–3626.
Mater. Trans. A 27A (8) (1996) 2229–2238. [66] B. Sundman, J. Ågren, J. Phys. Chem. Solids 42 (1981) 297–301.
[8] J.F. Counsell, E.B. Lees, P.J. Spencer, Metall. Chem. Proc. Symp. HMSO (1972) [67] N. Dupin, Ph.D. Thesis, Institute National Polytechnique, Grenoble, France
451–458. 1995.
[9] M. Hasebe, T. Nishizawa, Analysis and synthesis of phase diagrams of the [68] B. Sundman, B. Jansson, J.O. Andersson, CALPHAD 9 (2) (1985) 153–190.
Fe–Cr–Ni, Fe–Cu–Mn and Fe–Cu–Ni systems, in: G.C. Carter (Ed.), Applications