ISSN 0031-918X, The Physics of Metals and Metallography, 2016, Vol. 117, No. 12, pp. 1226–1236.

© Pleiades Publishing, Ltd., 2016.

Original Russian Text © I.I. Gorbachev, V.V. Popov, A.Yu. Pasynkov, 2016, published in Fizika Metallov i Metallovedenie, 2016, Vol. 117, No. 12, pp. 1277–1287.

STRUCTURE, PHASE TRANSFORMATIONS,

AND DIFFUSION

Calculations of the Influence of Alloying Elements (Al, Cr, Mn, Ni, Si)
on the Solubility of Carbonitrides in Low-Carbon Low-Alloy Steels
I. I. Gorbachev*, V. V. Popov, and A. Yu. Pasynkov
Institute of Metal Physics, Ural Branch, Russian Academy of Sciences, ul. S. Kovalevskoi 18, Ekaterinburg, 620990 Russia
*e-mail: gorbachev@imp.uran.ru
Received April 12, 2016; in final form, June 10, 2016

Abstract—Based on the CALPHAD method, a thermodynamic description of the Fe–M–V–NB–Ti–C–N

system (where M is Al, Cr, Mn, Ni, or Si) has been constructed and, using this description, the solubilities of
carbonitrides in austenite for low-alloy low-carbon steels with V, Nb, and Ti have been calculated using
10G2FB steel as an example. The influence of the alloy composition and temperature on the composition
and amount of carbonitride phases and on the concentration of these elements in the solid solution has been
analyzed.

Keywords: thermodynamics, steels, solubility, complex carbonitrides, CALPHAD method, phase equilibrium
DOI: 10.1134/S0031918X16120061

INTRODUCTION The amounts of the above elements in steels can

In microalloyed low-carbon steels, the key role in
the formation of the service properties belongs to addi-
tions of the carbonitride-forming elements, such as
titanium, niobium, and vanadium. Therefore, it is
important to know the influence of these elements on
the phase composition of the steel and to evaluate the
solubility of carbonitride phases in austenite. In order
to facilitate the solution of this problem to researchers
and specialists in the field of thermodynamic simula-
tion, based on the algorithm [1], we developed a spe-
cial program IMP Equilibrium [2] for calculations of
phase equilibria in steels. Using this program, we have
investigated the solubility of carbonitride phases in
austenite in a number of steels alloyed with carboni-
tride-forming elements [3–9]. In these works, the
steels were simulated by systems that contained three
to six components, which, in addition to Fe, C, and N,
included one to three carbonitride-forming elements,
namely, V, Nb, and/or Ti. However, since the modern
steels with a carbonitride strengthening can contain
more than ten elements, there is a need in the con-
struction of more complex thermodynamic descrip-
tions, which include these elements. In this work, we
propose a thermodynamic description of Fe–M–V–
Nb–Ti–C–N systems (where M is Al, Cr, Mn, Ni, or
Si) and, based on this description, investigate the
influence of these elements on the solubility of carbo-
nitride phases. The selection of these elements is by no
means accidental, since they are present in almost all
steels in some amount. They can remain in steel as
technological impurities or can be added on purpose.
vary in fairly wide limits. At the same time, our pre-
liminary computations showed that in the amounts in
which they usually are present in the low-alloy steels,
the character of the influence of these elements on the
solubility of carbonitride phases does not change qual-
itatively. Therefore, for definiteness, we oriented
toward the compositions of real industrial low-carbon
steels, such as 10G2FB or 10G2FBYu produced in
Russia at a number of metallurgical enterprises.
CONSTRUCTING
THE THERMODYNAMIC DESCRIPTION
To construct a thermodynamic description of the
Fe–M–V–Nb–Ti–C–N systems in this work, we
selected, as the base, the Fe–V–Nb–Ti–C–N system
used in [9] to investigate the formation of carboni-
trides in the low-carbon low-alloy steels with V, Nb,
and Ti. We have already used this description when
conducting kinetic calculations [10, 11], where it
showed good reliability. For the compatibility of the
thermodynamic models, we constructed the descrip-
tion of the Fe–M–V–Nb–Ti–C–N systems on the
basis of the CALPHAD method [12]. When conduct-
ing calculations, we have only taken into account con-
densed phases; for their description we used the Hil-
lert–Staffonsson sublattice model [13] generalized by
Agren and Sundman for the case of several sublattices
[14]. According to [14], the expression for the Gibbs
energy of a phase is written as follows as a function of

1226
 CALCULATIONS OF THE INFLUENCE OF ALLOYING ELEMENTS (Al, Cr, Mn, Ni, Si)
the mole fractions of each ith element in the sth sub-
lattice Yi s :
Gf = ∑∏ (Y )0G Ihf0 + RT
I0 I0
N A = 518 +
× ∑ (Y i
s
ln Yi s + Y Vas ln Y Vas
i =1
+ mag
Gf + ∑ ∑∏ (Y )L
Z > 0 IZ IZ
Here, R is the universal gas constant, T is the tempera-
ture, Va stands for a vacancy, as is the number of moles
of sites in the sth sublattice per one mole of formula
units of the phase, and Yi s is the mole fraction of the
ith component in the sth sublattice of the phase f. The
parameter 0G If0 means the Gibbs energy of 1 mole of
the formula units of a compound with the same crystal
structure as that of the phase f, which corresponds to
the element of the array I0, which determines a single
element for each sublattice;
I0 ∏
(Y )0G Ihf0 is the prod-
uct of the corresponding elements of the matrix Y .
I1 means an array that determines these variants of the
distribution of atoms in the sublattices for which one
sublattice contains atoms of two elements, whereas the
other sublattices contain atoms of only one element;
and ∏ I1
(Y ) stands for the product of the correspond-
ing elements of the matrix Y . Unlike the zero-order
array, I1 is called the first-order array. The arrays of
higher orders (IZ) correspond to various combinations
of a larger number of elements from different sublat-
tices. The parameters LIZ characterize the energy of
interaction of the components of the corresponding
element of the array IZ.
According to [15], the contribution of a magnetic
ordering to the Gibbs energy of a phase is described
based on the Inden model proposed in [16]. According
to [15], the contribution to the Gibbs energy caused by
magnetic ordering is given by the following expression:
mag
G mf = RT ln (β + 1) g(τ),
where τ = T/TC, TC is the critical temperature of the
destruction of the magnetic order (the Curie tempera-
ture for the ferromagnetic materials or the Néel tem-
perature for the antiferromagnetic materials), and β is
the average magnetic moment per atom in Bohr mag-
netons.
The function g(τ) is represented by the polynomials
⎡ −1 ⎛ ⎞
g(τ) = 1 − 1 ⎢79τ + 474 ⎜ 1 − 1⎟
A ⎣140 p 497 ⎝ p ⎠
⎛ ⎞⎤
× ⎜ τ + τ + τ ⎟⎥ for τ ≤ 1
3 9 15
⎝ 6 135 600 ⎠⎦
THE PHYSICS OF METALS AND METALLOGRAPHY
1227
and
⎡ −5 − 15 − 25
⎤
g ( τ) = − 1 ⎢τ + τ + τ ⎥ for τ > 1, (4)
l A ⎣ 10 315 1500⎦
∑a s
where
s =1 11692 ⎛ 1 ⎞
⎜ − 1⎟ . (5)
) (1)
1125 15975 ⎝ p ⎠
The magnitude of p depends on the structure. For
the bcc structure, p = 0.4; for the fcc, hcp, and β-Mn
IZ . structures, p = 0.28.
For the phases that do not experience ferromag-
netic or antiferromagnetic ordering at a certain tem-
perature, the value of magG f is taken to be zero.
The solid solutions and cubic and hexagonal car-
bides, nitrides, and carbonitrides were considered to
be compounds with two sublattices, the first of which
was filled with metallic atoms, and the second, by
interstitial atoms and vacancies. For the seven-com-
ponent system Fe–M–V–Nb–Ti–C–N, these phases
are described by the formula (Fe, M, V, Nb, Ti) a1 (Va,
C, N) a2 ; the bcc α solid solution (ferrite) has the sub-
lattice formula (Fe, M, V, Nb, Ti)1(Va, C, N)3; i.e.,
a1 = 1, a2 = 3; for the phases in which the metallic
atoms form an fcc lattice (austenite, cubic carbides,
nitrides, and carbonitrides), a1 = 1, a2 = 1; for the
compounds with an hcp lattice of metallic atoms (hex-
agonal solid solution, carbides, nitrides, and carboni-
trides), a1 = 1 and a2 = 0.5.
Since in this work we investigate the solubility of
cubic carbonitrides in austenite, below, we give the
parameters only for the fcc structures, as well as for the
phases that can appear in the equilibrium with austen-
ite in the low-alloy steels.
Fe–Al–V–Nb–Ti–C–N
The processing of the Al–C–Fe system using the
CALPHAD method was carried out in [17], where a
number of the thermodynamic parameters of this sys-
tem were evaluated via first-principles calculations.
However, in a later work on Al–C–Fe [18], it is noted
that the set of the parameters proposed in [17] badly
describes the expansion of the austenite field upon the
(2) addition of carbon to the Al–Fe system. Furthermore,
it is indicated in [18] that the extrapolations based on
the available evaluations of binary systems give an
underestimated solubility of Al in austenite and this
drawback cannot be corrected using any parameters of
the third order. Therefore, the authors of [18] per-
formed a reestimation of the parameters for the fcc
phases in the Al–Fe and Al–C systems based on first-
principles calculations. As a result, the following val-
ues were obtained for the Al–C system (hereinafter,
only those parameters are indicated, which have not
been given in our previous works [3–9]):
(3) FCC
G Al:C = 81000 + G Al
FCC
+ G CGrafit ; (6)
LFCC
Al:C,Va = − 80000 + 8T . (7)
Vol. 117 No. 12 2016
1228
0.10
0.08
N, wt %
0.06
0.04
0.02 1200°C
1050°C
0 0.05 0.10
Al, wt %
Fig. 1. Solubility of AlN in γ-Fe: (d) experimental data
[22]; dotted line represent calculations based on the data
on the solubility product [23]; dashed lines represent cal-
culations using expression (9); solid lines represent calcu-
lations using (12).
Hereinafter, the coefficients of the polynomials
have such a dimensionality that the parameters G and
L be expressed in joules.
In [18], the parameter LFCCAl,Fe:Va was also calculated,
but later the authors of [19] reestimated this parameter
(with taking into account the description proposed in
[18] as well) to obtain
Al,Fe:Va = − 104700 + 30.65T
LFCC
+ (30000 − 7T )(Y Al − YFe )
+ (32200 − 17T )(Y Al − YFe ) .
The parameters (6)–(8) are compatible with the
description of the Fe–V–Nb–Ti–C–N system we
constructed in [9], and they were used for the calcula-
tions performed in this work.
The optimization of the Al–Fe–N system was per-
formed in [20], where the parameters for the Fe–N
system were taken from [21] (just as in our work [9])
and, for Fe–Al system, from the personal communi-
cations due to M. Seiersten and J. Tibballs. The only
FCC
parameter that should be estimated was G Al:N . It was
noted in [20] that, since the content of Al and N in
γ-Fe is never very large simultaneously, its value can
be selected rather arbitrarily. Therefore, it was selected
from the general considerations so as to exceed the free
energy of the formation of the AlN phase as follows:
FCC
G Al:N = 20000 + G AlN
HCP
; (9)
G AlN = − 345837 + 359.862 T
HCP
− 54.3087 T ln( T ) + 8.56 × 10 −4T 2
−1
+ 2.326 × 10 T − 1.26 × 10 T .
6 8
However, the results of the calculations (Fig. 1)
performed using this value differs noticeably both from
the experimental results [22] (which were also taken
into account in [20]) and from the line of solubility con-
THE PHYSICS OF METALS AND METALLOGRAPHY
GORBACHEV et al.
structed according to the value of the product of the sol-
ubilities of Al and N in γ-Fe suggested in [23]
log([%Al][%N]) = 1.95 − 7400 T . (11)
For this reason, we have attempted to reestimate
1350°C FCC
the parameter G Al:N . It is noted in [22] that, in the case
of a small content of Al in the alloy, the solubility of N
in γ-Fe is almost independent of the amount of Al.
Therefore, upon the optimization of the value of
0.15
FCC
G Al:N , the significance of the experimental point that
corresponds to the temperature of 1050°C was taken
into account to a lesser degree. Furthermore, it turned
out that, without allowance for the temperature
dependence of this parameter, it is not possible to
reach satisfactory agreement with the data of [22, 23].
As a result of the optimization, we have obtained the
following expression:
G Al:N = − 2.555 × 10 + 16667T + G AlN .
FCC 7 HCP
(12)
The results of calculations of the solubility of AlN
in γ-Fe using (12) (they are represented in Fig. 1 by a
solid line) show much better agreement with the
experimental data of [22] and the value of the solubil-
ity product [23] than the calculations using (9). How-
ever, the attempt to use this parameter in the case of a
(8) system with a larger number of elements leads to anom-
alously high concentrations of Al in cubic nitrides. We
2
assume that this is caused by a lack of experimental data
and/or by high errors in the results based on which we
FCC
attempted to estimate the parameter G Al:N . Therefore,
the value we obtained should be rejected.
The thermodynamic description of the Al–C–Ti
system based on the CALPHAD method was pro-
posed in the recent work [24]. The data on the systems
Al–C, Al–Ti, and C–Ti in it were taken from [18],
[25], and [26], respectively. Thus, the description con-
structed in [24] is compatible with the one we used in
[9] for the subsystem Ti–C–N, as well as with the
parameters for the Al–C system we accepted above.
At the moment of the publication of the work due
to Witusiewicz et al. [25], there were several alternative
descriptions of the Al–Ti system. These were taken
into account in [25]; however, it was noted in this work
that none of the descriptions reflect the contemporary
experimental data. Therefore, in this work, а reestima-
tion of the parameters of the Al–Ti system was per-
(10) formed. In particular, for the fcc structure, the follow-
−2
ing expression was obtained:
Al,Ti:Va = − 119185 + 40.723T .
LFCC (13)
The expression (13), as well as the parameters for the
fcc phase in the Al–C–Ti subsystem proposed in [24],
Vol. 117 No. 12 2016
 CALCULATIONS OF THE INFLUENCE OF ALLOYING ELEMENTS (Al, Cr, Mn, Ni, Si) 1229

was accepted in this work to carry out calculations in the
Fe–Al–Ti–Nb–V–C–N system as follows:
LAl,Ti:C = − 110000 − 75000 (Y Al − Y Ti )
FCC
(14)
− 110000 (Y Al − Y Ti ) .
2
An evaluation of the Al–N–Ti system was per-
formed in [27, 28]. Although in those works the
authors used different descriptions of the Al–Ti sys-
tem (moreover, neither was based on [25]), they are
potentially compatible with our description: both use
the same description of the Ti–N system [29] as in [9],
and of the Al–N system [20]. However, in both [27]
and [28] the description of the δ phase (TiN1–x) was
based only on the parameters for the binary subsys-
tems, i.e., the parameters LFCC FCC
Al,Ti:N and LAl,Ti:Va,N were
not evaluated, but were accepted to be equal to zero.
At the same time, the authors of [27] proposed
FCC
their own value of the parameter G Al:N in the follow-
ing form:
[35], but both in [33] and in [34] a number of the
parameters for the Fe–Cr–C system were re-esti-
mated with taking into account new data on the solu-
bility of chromium carbides. However, other research-
ers subsequently considered the description by Lee
[34] to be more suitable, and this description was used
as the basis for constructing descriptions of other sys-
tems as, e.g., in work [36] on the C–Cr–Fe–Ni–O
system. Based on Lee’s description [34], the authors
of [37, 38] have re-estimated some parameters for the
Fe–Cr–C system with taking into account new exper-
imental data. Unfortunately, the values of the param-
eters obtained were not given in [37]; therefore, in this
work, we used the refined description of the Fe–Cr–
C system proposed in [38] as shown below:
FCC
G Cr:C = 1200 − 1.94T + G Cr
BCC
+ G CGrafit; (18)
Cr:C,Va = − 11977 + 6.8194T ;
LFCC (19)
Cr,Fe:Va = 10833 − 7.477T + 1410 (YCr − Y Fe ) ; (20)
LFCC

= 70000 + 10T + G AlN Cr,Fe:C = − 69534 + 3.2353T .

LFCC (21)
FCC HCP
G Al:N . (15)
In contrast to [20], where the value of this parameter
was taken to be fairly arbitrary, in [27], this value was Cementite
evaluated based on the data of [30] for the Gibbs energy The sublattice formula is as follows: (Fe, Cr)3(C)1;
of the transition from the field of the metastable
δ-(Ti,Al) into the stable two-phase field of δ-TiN + G Fe:C = − 10195.860754 + 690.949887637T
Cem

AlN. However, the estimation was carried out under (22)

− 118.47637T ln T − 0.00007T + 590527 T .
2
the assumption of the ideal mixing of Al and Ti in the
first sublattice of the fcc phase, whereas, judging from
the value of the parameter LFCC Al,Ti:Va (13), these ele- M23C6
ments are by no means ideally mixed up. This circum- The sublattice formula is as follows:
stance indicates the existence of a systematic error in (Fe, Cr)20(Fe,Cr)3(C)6;
parameter (15). Nevertheless, since no better estimate
has been proposed to date, we use precisely this value M 23C 6
G Fe:Fe:C = 15000 + (23 3)G Fe:C
Cem
− (5 3)G CGrafit; (23)
when constructing the description of the Fe–Al–V–
Nb–Ti–C–N system and conducting calculations. M 23C 6
G Cr:Cr:C = − 521983 + 3622.24T
Analogously to the Al–Ti system, the authors of (24)
[25] have analyzed the available information for the − 620.965T ln T − 0.126431T 2;
Al–Nb system [31] and made a reestimate of the M 23C 6
G Fe:Cr:C = (20 23)G Fe:Fe:C
M 23C 6
+ (3 23)G Cr:Cr:C
M 23C 6
; (25)
parameter LFCC Al,Nb:Va . In our work, we used just this
value: M 23C 6
G Cr:Fe:C = (3 23)G Fe:Fe:C
M 23C 6
+ (20 23)G Cr:Cr:C
M 23C 6
; (26)

Al,Nb:Va = − 69684 − 40679 (Y Al − Y Nb ) .

LFCC = LCr,Fe:Fe:C
M C M C
(16) 23 6
LCr,Fe:Cr:C 23 6

(27)
The value of the parameter LFCC = 6609 − 43600 (YCr − YFe ) ;
Al,V:Va was taken

Cr:Cr,Fe:C = LFe:Cr,Fe:C = 991 − 6540 (YCr − Y Fe ) . (28)

from [32] LM 23C 6 M 23C 6

Al,V:Va = − 69800 + 15T − 8000 (Y Al − Y V ) .

LFCC (17)
Fe–Cr–V–Nb–Ti–C–N
The thermodynamic description of the Fe–Cr–C
system was suggested in the works on the Fe–Cr–Ni–
C system by Hillert and Qiu [33] and by Lee [34]. Both
works are based on the estimation of the parameters
for the Fe–Cr–C system carried out by Anderson
The best-known evaluation of the Fe–Cr–N sys-
tem in the CALPHAD method was carried out by
Frisk [39]. This treatment is based on the description
of the Cr–Fe system proposed in [35]; in our previous
description of the Fe–V–Nb–Ti–C–N system [9],
the parameters for the Fe–N subsystem were taken
from [39]. Thus, the description proposed by Frisk
satisfies the requirements of compatibility. Further-
more, the thermodynamic parameters obtained in this

THE PHYSICS OF METALS AND METALLOGRAPHY Vol. 117 No. 12 2016

1230 GORBACHEV et al.

work were later approved in a number of higher-order better correspondence to experimental data on the sol-
systems and today are considered to be fairly reliable. ubility of NbN in austenite. Upon the reestimation of
For these reasons, in this work, to describe the LFCC
Fe,Nb:va , the values of other parameters in the Fe–
Fe‒Cr–N subsystem, we used the parameters sug-
gested by Frisk shown below: Nb–C system were taken from the work devoted to the
Fe–Nb–Ti–C–N system [51] and were fixed. The
G Cr:N = − 124 460 + 142.16T latter is especially important, since this ensures the
FCC
(29) compatibility of the description presented in [45] with
− 8.5T ln T + G Cr + 1 2 G N2 ;
BCC Gas
the description of the Fe–V–Nb–Ti–C–N system we
constructed in [9].
Cr:N,Va = 20 000;
LFCC (30) In this work, the following parameters were used
for the Fe–Mn–Nb–C subsystem:
Cr,Fe:N = − 128930
LFCC
(31)
+ 86.49T + 24330 (YCr − YFe ) ; = 13.659T + G Mn + G CGrafit;
FCC BCC _ A12
G Mn:C (37)

Cr,Fe:N,Va = − 162516.
LFCC (32) Fe,Mn:va = − 7762 + 3.865T − 259 (Y Fe − Y Mn ) ; (38)
LFCC

The parameter LFCC

Cr,Ti:va was taken from [40] as Fe,Mn:C = 20 082 − 11.6312T ;
LFCC (39)
follows:
Mn:C,va = − 41333;
LFCC (40)
LFCC
Cr,Ti:va = 66300 − 27.7T , (33)
Mn,Nb:va = 6305.5;
LFCC (41)
and the parameters for the fcc phases in the Fe–
Fe,Nb:va = − 6176 − 2.04T ;
Cr–V–C subsystem were taken from [41], refined in LFCC (42)
[38] as shown below except for the parameter LFCC
Cr,Fe:C :
Mn:va = − 1620;
Tc FCC (43)
Cr,V:C = 35698 − 50.0981T ;
LFCC (34)
Fe,Mn:va = − 2282 − 2068 (Y Fe − Y Mn ) ;
Tc FCC (44)
LFCC = − 9874 − 2.6964T
Cr,V:Va
β Mn:va = 1.86.
(35) FCC
(45)
− (1720 + 2.5237T )(YCr − Y V ) .
The authors of the recent work [50] constructed a
The only optimization of the parameters for the
description of the Fe–Mn–Nb–N system as in [45]
Cr–Nb–C system was carried out in [42]. Therefore,
based mainly on the data for binary subsystems. The
we have taken the parameter LFCC
Cr,Nb:C from that work as parameters for Mn–N were taken from the work of
shown below: Qiu and Guillermet [52]. However, Qiu also proposed
the description of the three-component system
Cr,Nb:C = − 23000.
LFCC (36) Fe‒Mn–N [53]. Similar to our work [9], the parame-
ters for the Fe–N system were taken in it from [21]
and, for the Fe–Mn system, from [46] (just as in [45]),
Fe–Mn–V–Nb–Ti–C–N which makes it possible to use the description of the
When selecting the thermodynamic descriptions of Fe–Mn–N system suggested in [53] in the present
the subsystems that include Mn and C, both relatively work as follows:
old estimations, e.g., those carried out in [43] (for the
Fe–Cr–Mn–C system) and in [44] (for the Fe–Mn–
FCC
G Mn:N = − 75940 + 292.226T
(46)
V–C system) and new ones [45] (for Fe–Mn–Nb–C), − 50.294T ln T + 265051 T ;
can be used. Other conditions being equal, it is better
to use newer descriptions, since, as a rule, they con- Mn:N,va = − 69698 + 11.5845T ;
LFCC (47)
sider all of the recent experimental data. Therefore, in
this work, we used the description constructed in [45]. Fe,Mn:N = 53968 − 38.102T
LFCC
(48)
It is based on the same description of the Fe–Mn sys- − 28787 (YFe − YMn ) .
tem [46] as in the work due to Huang [44] and on rees-
timations of the Mn–C and Fe–Mn–C systems per- The parameter
formed in [47, 48], respectively. For the Fe–Mn–Nb
subsystem, the authors of [45] used the set of parame- Mn,V:va = − 11 820
LFCC (49)
ters proposed in [49], except for the parameter was taken from [44].
LFCC
Fe,Nb:va ,, which was re-estimated in [45]. However, We could not find any estimates of the parameters
the authors of [45] in the work [50] devoted to the esti- of interaction with Mn and Ti for phases with the fcc
mation of the Fe–Mn–Nb–N system again reexam- structure in the literature; therefore, these parameters
ined the value of this parameter in order to obtain a were taken to be equal to zero.

THE PHYSICS OF METALS AND METALLOGRAPHY Vol. 117 No. 12 2016

 CALCULATIONS OF THE INFLUENCE OF ALLOYING ELEMENTS (Al, Cr, Mn, Ni, Si)
Fe–Ni–V–Nb–Ti–C–N
Unlike the systems with Al, Cr, and Mn, the ther-
modynamic information concerning the system with Ni
is much more scarce. In particular, this concerns esti-
mates of the parameters of interactions with C and N.
The optimization of the parameters for the
Fe‒Ni–C system was executed in a work that is
already fairly old work [54], but other estimates of this
system were not carried out from those times. Never-
theless, the description proposed in [54] can be used in
the present work, since, first, the authors of [54] have
used the same parameters for the Fe–C system as in
[9] and, second, is based on the same values of the
energies of the pure elements as those given in the
now-standard database SGTE [55]. Finally, the
description presented in [54] has been approved upon
estimating other systems and has been used until now
(albeit with some modifications due to Lee that con-
cern the liquid phase [56]). From [54], we used the
following parameters:
FCC
G Ni:C = 45000 + 1.88T + G Ni
FCC
+ G CGrafit;
= − 12 054.335 + 3.27413T
FCC
LFe,Ni:va
+ (11082.1315 − 4.45077 ) (YFe − Y Ni )
− 725.805174 (YFe − Y Ni ) ;
2
Fe,Ni:C = 49 074 − 7.32T − 25800 (Y Fe − Y Ni ) ; (52)
LFCC
= 633;
FCC
Tc Ni:va
= 2133 − 682 (YFe − YYNi ) ;
FCC
Tc Fe,Ni:va
β Ni:va = 0.52;
FCC
β Fe,Ni:va = 9.55 + 7.23 (YFe − Y Ni )
FCC
(56)
+ 5.93 (YFe − Y Ni ) + 6.18 (YFe − Y Ni ) .
2 3
Works devoted to evaluating the parameters of the
interactions of Ni with N in fcc Ni are currently
absent; therefore, the appropriate parameters were
taken to be equal to zero.
The evaluation of the Fe–Nb–N system was
undertaken in [57] based on the same description of
the Fe–Ni system as in [54]; this estimation is com-
patible with our description of the subsystem Fe–N
subsystem in the Fe–V–Nb–Ti–C–N system [9]. For
these reasons, we used the parameters calculated in
[57] for the simulation of the Fe–Ni–V–Nb–Ti–C–N
system:
LNb,Ni:va = − 70 007.4 − 7.39665T
FCC
+ (96115 − 23.07497 ) (Y Nb − Y Ni ) ;
Nb,Ni:va = − 1200 + 760 (Y Nb − YYNi ) ;
Tc FCC
β Nb,Ni:va
= 0.
FCC
(59)
The Nb–Ni–Ti system was considered in [58], but
the authors used in it the description of the Nb–Ni
system proposed in [59] and of the Nb–Ti system pro-
THE PHYSICS OF METALS AND METALLOGRAPHY
1231
posed in [60], which makes it incompatible with our
description of the Fe–V–Nb–Ti–C–N system. For
these reasons, we cannot use the parameter
LFCC
Nb,Ni,Ti:va , which was calculated in [58], but can use
the parameters for the Ni–Ti system. Some different
values of the parameters for this system were also
obtained in other studies, but in the context of our
work, they do not possess any special advantages;
therefore, we decided to use the newest description of
the Ni–Ti system obtained in [58] as follows:
Ni,Ti:va = − 121925
LFCC
(60)
+ 16.994T − 32 260 (Y Nb − Y Ni ) ;
= − 4670;
FCC
Tc Ni,Ti:va (61)
β Ni,Ti:va = 0.
FCC
(62)
The parameters of interactions of Ni and V in the
fcc phase were taken from [61] as follows:
(50)
LNi,V:va = − 36365.6 + 3.75677T
FCC
(51) + (11860.7 − 9.0302T ) (Y Ni − Y V ) (63)
+ ( − 10647.5 + 7.00954T ) (Y Ni − Y V ) .
2
We do not know other works in which these esti-
mates were made.
(53)
Fe–Si–V–Nb–Ti–C–N
(54)
The thermodynamic description of the Fe–Si–C
(55) system was presented in [62]; in [63], reestimations
were made for a number of the parameters of the fcc,
bcc, and liquid phases. The description presented in
[63] satisfies the requirements of the compatibility
with what was constructed in the present work; it is
based on the Gibbs energies of pure elements given in
the SGTE [55] and uses the same parameters for the
Fe–C system as in [9]. Therefore, we used the param-
eter of interaction of Fe, Si, and C in the phases with
the fcc lattice estimated in [63]
Fe,Si:C = 226100 − 34.25T − 202 400 (Y Fe − YSi ) .(64)
LFCC
Unfortunately, this is the only parameter we suc-
ceeded at integrating into our description, since in the
potentially interesting works, where the thermody-
namic estimate of systems with silicon is conducted,
e.g., for the Ti–Si–N [64] or Nb–Si–Ti [65] systems,
(57)
there are no parameters that describe the interaction
of the elements in the fcc phase. This is due to the fact
(58) that, in these systems, a phase with an fcc structure is
not equilibrium. In these cases, the corresponding
parameters are evaluated based on studies of systems
with chemical elements that can form phases with the
fcc lattice; however, we could not find such works to
date, except for [63].
Vol. 117 No. 12 2016
1232 GORBACHEV et al.

(V, Ti)N culations were carried out for the range of the compo-
0.03 sitions that correspond to the low-carbon low-alloy
steels in the range of temperatures that involves the aus-
tenite field and can represent a practical interest. As the
0.02 base, we selected the tube steel of grade 10G2FBYu
F, wt %

produced at a number of enterprises in Russia accord-

ing to the State Specifications TU 14-3-1573-96 and
0.01 0.02% Al TU 14-158-146-2004. The composition of the steel is
0.035% Al given in the table.
0.05% Al The following concentrations of the elements were
0 assigned for the calculations: 0.1 wt % C; 0.01 wt % N,
900 950 1000 1050 1100 0.035 wt % Nb, 0.1 wt % V, and 0.01 wt % Ti.
T, °C
It can be assumed a priori that Al will compete with
Nb(C, N) Ti in their tendency to become bound with nitrogen;
the first will attempt to bind it into AlN and the second
will attempt to bind it into cubic nitride or carboni-
0.03 tride. Note that the affinity of N to Ti is higher than to
Al. To better demonstrate the cases in which alloying
with Al can affect the carbonitride formation, the
F, wt %

0.02 amount of Ti was selected at the lower boundary spec-

0.02% Al ified by the above TU.
0.01 0.035% Al In the investigated range of compositions and tem-
0.05% Al peratures, two carbonitride phases coexist in equilib-
0
rium with austenite; one of them is closer in composi-
900 950 1000 1050 1100 tion to Nb(C,N) and the other is closer to (V, Ti)N.
T, °C These are the designations used for these phases in
Fig. 2, which displays the results of the calculations of
AlN the dependence of the equilibrium phase composition
0.03 of steel 10G2FBYu on the temperature and on the
amount of Al in the steel.
0.02% Al
0.035% Al The results of the calculations given in Fig. 2 show
0.02 0.05% Al that Al can noticeably influence the formation of car-
F, wt %

bonitrides, even in the case of the small amount in

0.01
0 mation of the AlN phase. The formation of AlN affects
900 950 1000 1050 1100
T, °C
Fig. 2. Dependence of the weight fraction of the second
phases on the temperature and amount of Al in 10G2FBYu
steel.
RESULTS
OF THERMODYNAMIC CALCULATIONS
Based on the previously developed algorithm [1]
and the above-considered thermodynamic descrip-
tions, we performed a number of the calculations of
the phase equilibrium, in which we investigated the
influence of Al, Cr, Mn, Ni, and Si on the solubility of
carbonitrides in low-carbon low-alloy steels. The
steels were simulated by the system Fe–M–V–Nb–
Ti–C–N, where M = Al, Cr, Mn, Ni, or Si. The cal-
which it is present in this alloy. The presence of Al in
the solid solution in γ-Fe changes the solubility of car-
bonitrides of the V, Nb, and Ti (see the parameters (6),
(7) and (13)–(17)), but mainly its effect lies in the for-
the amount of (V,Ti)N especially strongly; the greater
the amount of Al in the alloy and, correspondingly,
the greater amount of nitrogen is bound to AlN, the
smaller the fraction of (V,Ti)N in it. It is also interest-
ing to note that, in the presence of AlN, the amount of
(V,Ti)N in the alloy grows, rather than decreases. This
dependence is apparently caused by binding into
(V,Ti)N of nitrogen supplied from dissolving AlN.
The calculations carried out also show that the
fraction of (V,Ti)N is in fact independent of the
amount of Al in the system at temperatures at which
AlN becomes completely dissolved. It can also be seen
from Fig. 2 that the amount of Al in the system has a
very insignificant effect on the solubility of the nio-
bium carbonitride in the entire temperature range
investigated.
The other alloying additives, e.g., Cr, Mn, Ni, and
Si, can be present in the steel in a larger amount (the

THE PHYSICS OF METALS AND METALLOGRAPHY Vol. 117 No. 12 2016

 CALCULATIONS OF THE INFLUENCE OF ALLOYING ELEMENTS (Al, Cr, Mn, Ni, Si) 1233

900°C (V, Ti)N 1000°C (V, Ti)N

0.05 0.05

0.04 0.04

0.03 0.03
F, wt %

F, wt %
0.02 Cr 0.02 Cr
Ni Ni
0.01 Mn 0.01 Mn
Si Si

0 0.5 1.0 1.5 2.0 0 0.5 1.0 1.5 2.0

Amount of element, wt % Amount of element, wt %

900°C Nb(C, N) 1000°C Nb(C, N)

0.05 0.05

0.04 0.04

0.03
F, wt %

0.03

F, wt %
0.02 Cr 0.02
Ni Cr
0.01 Mn Ni
0.01 Mn
Si
Si
0 0.5 1.0 1.5 2.0 0 0.5 1.0 1.5 2.0
Amount of element, wt % Amount of element, wt %

Fig. 3. Dependence of the weight concentrations of the Fig. 4. Dependence of the concentrations of the second
second phases on the amount of alloying elements in phases on the amount of alloying elements in 10G2FBYu
10G2FBYu steel at 900°C. steel at 1000°C.

content of Mn can reach almost 2 wt %). In order to
compare the degree of their influence, we plotted the
dependences of the equilibrium phase composition of
steel 10G2FBYu on the amount of these elements
(up to 2%). Just as for Al, the steel was simulated by
the Fe–M–V–Nb–Ti–C–N system, where M = Cr,
Mn, Ni, or Si. The composition of the system was
taken to be the same as for Al. The results of calcula-
tions are given in Figs. 3–5.
In contrast to the system with Al, the other ele-
ments, i.e., Cr, Mn, Ni, and Si, do not form new
phases in the investigated range of compositions and
temperatures, although the appearance of M23C6 car-
bides could be expected. Thus, only two cubic carbo-
nitrides are in equilibrium with austenite. As can be
seen from the results of calculations, the following can
be noted: first, in the entire investigated range of com-
positions, the fraction of carbonitride phases linearly
depends on the amounts of Cr, Mn, Ni, and Si; and,
second, all these elements have an insignificant effect
on the formation of carbonitrides in this steel. The
strongest effect is caused by silicon. However, in the
limits of the chemical composition of steel 10G2FBYu

Composition of the steel 10G2FBYu (wt %) according to the specifications TU 14-3-1573-96

Al C Cr Mn N Nb Ni Si Ti V

0.02–0.05 0.09–0.12 ≤0.3 1.55–1.75 ≤0.012 0.02–0.05 ≤0.3 0.15–0.5 0.01–0.035 0.08–0.12

THE PHYSICS OF METALS AND METALLOGRAPHY Vol. 117 No. 12 2016

1234 GORBACHEV et al.

1100°C (V, Ti)N ACKNOWLEDGMENTS

0.05 This work was carried out under the State Task of
FASO of Russian Federation according to the theme
0.04 “Spin” (no. 01201463330) and was supported in part
by the program of Basic Research of the Ural Branch,
F, wt %

0.03 Russian Academy of Sciences (project no. 15-9-2-44)

and by the Russian Foundation for Basic Research
0.02 (project no. 16-38-00164 mol_a).
Cr
Ni
0.01 Mn
Si REFERENCES
1. V. V. Popov and I. I. Gorbachev, “Analysis of solubility
0 0.5 1.0 1.5 2.0 of carbides, nitrides, and carbonitrides in steels using
Amount of element, wt % methods of computer thermodynamics: I. Description
of thermodynamic properties. Computation proce-
1100°C Nb(C, N) dure,” Phys. Met. Metallogr. 98, 344–354 (2004).
0.05 2. Certificate of State Registration of Computer Program
Cr 2011618874 (IMP Equilibrium, November 15, 2011).
0.04 Ni 3. V. V. Popov and I. I. Gorbachev, “Analysis of solubility
Mn of carbides, nitrides, and carbonitrides in steels using
F, wt %

0.03 Si methods of computer thermodynamics: II. Solubility of

0.02
0.01
0 0.5 1.0 1.5 2.0
Amount of element, wt %
Fig. 5. Dependence of the weight concentrations of the
second phases on the amount of alloying elements in
10G2FBYu steel at 1100°C.
specified by the TU, the influence of this element is
also very insignificant.
CONCLUSIONS
A critical analysis of the available information con-
cerning the Fe–M–V–Nb–Ti–C–N system (M = Al,
Cr, Mn, Ni, or Si) has been carried out, and a compat-
ible thermodynamic description of this system and
constituent subsystems has been performed. Based on
the proposed description, calculations were per-
formed to investigate the influence of the alloying ele-
ments, i.e., Al, Cr, Mn, Ni, and Si, on the formation
of carbonitrides in the low-carbon low-alloy steels. It
has been shown that the greatest effects on the solubil-
ity of carbonitrides of these elements are caused by Si
and Al (the latter only if AlN is formed along with
cubic carbonitrides). The other elements exert only an
insignificant effect on the solubility of carbonitrides in
the range of compositions characteristic of the typical
degree of alloying with these elements.
carbides, nitrides, and carbonitrides in the Fe–V–C,
Fe–V–N, and Fe–V–C–N systems,” Phys. Met.
Metallogr. 99, 286–299 (2005).
4. I. I. Gorbachev and V. V. Popov, “Analysis of solubility
of carbides, nitrides, and carbonitrides in steels using
methods of computer thermodynamics: III. Solubility
of carbides, nitrides, and carbonitrides in the Fe–Ti–
C, Fe–Ti–N, and Fe–Ti–C–N systems,” Phys. Met.
Metallogr. 108, 484–495 (2009).
5. I. I. Gorbachev and V. V. Popov, “Analysis of solubility
of carbides, nitrides, and carbonitrides in steels using
methods of computer thermodynamics: IV. Solubility
of carbides, nitrides, and carbonitrides in the Fe–Nb–
C, Fe–Nb–N, and Fe–Nb–C–N systems,” Phys.
Met. Metallogr. 110, 52–61 (2010).
6. I. I. Gorbachev and V. V. Popov, “Thermodynamic
simulation of the Fe–V–Nb–C–N system using the
CALPHAD method,” Phys. Met. Metallogr. 111, 495–
502 (2011).
7. I. I. Gorbachev, V. V. Popov, and A. Yu. Pasynkov,
“Thermodynamic simulation of the formation of car-
bonitrides in steels with Nb and Ti,” Phys. Met. Metal-
logr. 113, 687–695 (2012).
8. I. I. Gorbachev, V. V. Popov, and A. Yu. Pasynkov,
“Thermodynamic simulation of the formation of car-
bonitrides in steels with V and Ti,” Phys. Met. Metal-
logr. 113, 974–981 (2012).
9. I. I. Gorbachev, V. V. Popov, and A. Yu. Pasynkov,
“Thermodynamic calculations of carbonitride forma-
tion in low–alloy low–carbon steels containing V, Nb,
and Ti,” Phys. Met. Metallogr. 115, 69–76 (2014).
10. I. I. Gorbachev, V. V. Popov, and A. Yu. Pasynkov,
”Simulation of precipitate ensemble evolution in steels
with V and Nb,” Phys. Met. Metallogr. 116, 356–366
(2015).
11. I. I. Gorbachev, A. Yu. Pasynkov, and V. V. Popov,
“Prediction of the austenite-grain size of microalloyed
steels based on the simulation of the evolution of carbo-
nitride precipitates,” Phys. Met. Metallogr. 116, 1127–
1192 (2015).

THE PHYSICS OF METALS AND METALLOGRAPHY Vol. 117 No. 12 2016

 CALCULATIONS OF THE INFLUENCE OF ALLOYING ELEMENTS (Al, Cr, Mn, Ni, Si)
12. H. L. Lukas, S. G. Fries, and B. Sundman, Computa-
tional Thermodynamics: The CALPHAD Method (Cam-
bridge Univ., Cambridge, 2007).
13. M. Hillert and L.-I. Staffonsson, “The regular solution
model for stoichiometric phases and ionic melts,” Acta
Chem. Scand. 24, 3618–3626 (1970).
14. B. Sundman and J. Agren, “A regular solution model
for phase with several components and sublattices, suit-
able for computer applications,” J. Phys. Chem. Solids
42, 297–301 (1981).
15. M. Hillert and M. Jarl, “Model for alloying effects in
ferromagnetic metals,” CALPHAD 2, 227–238 (1978).
16. G. Inden, “Determination of chemical and magnetic
interexchange energies in bcc alloys. III. Application to
ferromagnetic alloys,” Z. Metallkd. 68, 529–534
(1977).
17. H. Ohtani, M. Yamano, and M. Hasebe, “Thermody-
namic analysis of the Fe–Al–C ternary system by
incorporating ab initio energetic calculations into the
CALPHAD approach,” Iron Steel Inst. Jpn. Int. 44,
1738–1747 (2004).
18. D. Connetable, J. Lacazea, P. Maugisb, and B. Sund-
man, “A CALPHAD assessment of Al–C–Fe system
with the κ carbide modelled as an ordered form of the
fcc phase,” CALPHAD 32, 361–370 (2008).
19. B. Sundman, I. Ohnuma, N. Dupin, U. R. Kattner,
and S. G. Fries, “An assessment of the entire Al–Fe
system including D03 ordering,” Acta Mater. 57, 2896–
2908 (2009).
20. M. Hillert and S. Jonsson, “An assessment of the Al–
Fe–N system,” Metallur. Trans. A 23, 3141–3149
(1992).
21. K. Frisk, “A thermodynamic evaluation of the Cr–N,
Fe–N, Mo–N and Cr–Mo–N systems,” CALPHAD
15, 79–106 (1991).
22. L. S. Darken, R. P. Smith, and E. W. Filer, “Solubility
of gaseous nitrogen in gamma iron and the effect of
alloying constituents–aluminum nitride precipitation,”
Trans. AIME 191, 1174–1179 (1951).
23. J. Krueger, H. D. Kunze, and E. Schuermann, in Gases
and Carbon in Metals, Ed. by E. Fromm and E. Geb-
hardt, (Springer-Verlag, Berlin, 1976), pp. 578–613.
24. V. T. Witusiewicz, B. Hallstedt, A. A. Bondar,
U. Hecht, S. V. Sleptsov, and T. Ya. Velikanova, “Ther-
modynamic description of the Al–C–Ti system,”
J. Alloys Compd. 623, 480–496 (2015).
25. V. T. Witusiewicz, A. A. Bondar, U. Hecht, S. Rex, and
T. Ya. Velikanova, “The Al–B–Nb–Ti system.
III. Thermodynamic re-evaluation of the constituent
binary system Al–Ti,” J. Alloys Comp. 465, 64–77
(2008).
26. L. F. S. Dumitrescu, M. Hillert, and B. A. Sundman,
“Reassessment of Ti–C–N based on a critical-review
of available assessments of Ti–N and Ti–C,”
Z. Metallkd. 90, 534–541 (1999).
27. G. Chen and B. Sundman, “Thermodynamic analysis
of the Ti–Al–N system,” J. Phase Equil. 19, 146–160
(1998).
28. J. Gao, Ch. Li, N. Wang, and Zh. Du, “Thermody-
namic analysis of the Ti–Al–N system,” J. Beijing
Univ. Sci. Technol. 15, 420–424 (2008).
THE PHYSICS OF METALS AND METALLOGRAPHY
1235
29. S. Jonsson, “Assessment of the Ti–N system,”
Z. Metallkd. 87, 691–702 (1996).
30. P. J. Spencer, “The decisive role of calorimetric mea-
surements in equilibrium phase diagram calculations,”
J. Therm. Anal. 41, 1305–1318 (1994).
31. V. T. Witusiewicz, A. A. Bondar, U. Hecht, and
T. Ya. Velikanova, “The Al–B–Nb–Ti system.
IV. Experimental study and thermodynamic re-evalua-
tion of the binary Al–Nb and ternary Al–Nb–Ti sys-
tems,” J. Alloys Compd. 472, 133–161 (2009).
32. N. Saunders, “System Al–V, ” in COST-507 Project:
Thermochemical Database for Light Metal Alloys
(Vol. 2), Ed. by A. Ansara, T. Dinsdale, and
M. H. Rand (Office for Official Publications of the Euro-
pean Communities, Luxembourg, 1998), pp. 95–98.
33. M. Hillert and C. Qiu, “A thermodynamic assessment
of the Fe–Cr–Ni–C system,” Metall. Trans. A 22,
2187–2198 (1991).
34. B.-J. Lee, “On the stability of Cr carbides,” CALPHAD
16, 124–149 (1992).
35. J.-O. Andersson, “A thermodynamic evaluation of the
Fe–Cr–C system,” Metall. Trans. A 19, 627–636
(1988).
36. L. Kjellqvist and M. Selleby, “Adding C to the thermo-
dynamic description of the Cr–Fe–Ni–O system,”
CALPHAD 33, 393–397 (2009).
37. J. Bratberg and K. Frisk, “An experimental and theo-
retical analysis of the phase equilibria in the Fe–Cr–V–C
system,” Metall. Mater. Trans. A 35, 3649–3663
(2004).
38. A. Khvan, B. Hallstedt, and C. Broeckmann, “A ther-
modynamic evaluation of the Fe–Cr–C system,”
CALPHAD 46, 24–33 (2014).
39. K. Frisk, “A thermodynamic evaluation of the Cr–Fe–N
system,” Metall. Trans. A 21, 2477–2488 (1990).
40. N. Saunders, “System Cr–Ti, ” in COST-507 Project:
Thermochemical Database for Light Metal Alloys (Ver-
sion 2.1) (Vol. 2),” Ed. by A. Ansara, T. Dinsdale, and
M. H. Rand (Office for Official Publications of the
European Communities, Luxembourg, 1999/2003).
41. B.-J. Lee and D. N. Lee, “A thermodynamic evalua-
tion of the Fe–Cr–V–C system,” J. Phase Equil. 13,
349–364 (1992).
42. A. Khvan, B. Hallstedt, and K. Chang, “Thermody-
namic assessment of Cr–Nb–C and Mn–Nb–C sys-
tems,” CALPHAD 39, 54–61 (2012).
43. B.-J. Lee, A thermodynamic evaluation of the Fe–Cr–
Mn–C system,” CALPHAD 24, 1017–1025 (1993).
44. W. Huang, “Thermodynamic properties of the Fe–
Mn–V–C system,” Metall. Mater. Trans. A 22, 1911–
1920 (1991).
45. A. V. Khvan and B. Hallstedt, “Thermodynamic descrip-
tion of the Fe–Mn–Nb–C system,” CALPHAD 39, 62–
69 (2012).
46. W. Huang, “An assessment of the Fe–Mn system,”
CALPHAD 13, 243–252 (1989).
47. D. Djurovic, B. Hallstedt, J. von Appen, and R. Dron-
skowski, “Thermodynamic assessment of the Mn–C
system,” CALPHAD 34, 279–285 (2010).
Vol. 117 No. 12 2016
1236 GORBACHEV et al.
48. D. Djurovic, B. Hallstedt, J. von Appen, and R. Dron-
skowski, “Thermodynamic assessment of the Fe–Mn–
C system,” CALPHAD 35, 479–491 (2011).
49. S. Liu, B. Hallstedt, D. Music, and Y. Du, “Ab initio
calculations and thermodynamic modeling for the
Fe‒Mn–Nb system,” CALPHAD 38, 43–58 (2012).
50. A. V. Khvan and B. Hallstedt, “Thermodynamic
assessment of Fe–Mn–Nb–N and Nb–C–N sys-
tems,” CALPHAD 40, 10–15 (2013).
51. B.-J. Lee, “Thermodynamic assessment of the
Fe‒Nb–Ti–C–N system,” Metall. Mater. Trans. A 32,
2423–2439 (2001).
52. C. Qiu and A. F. Guillermet, “Predictive approach to
the entropy of manganese nitrides and calculation of
the Mn–N phase diagram,” Z. Metallkd. 84, 11–22
(1993).
53. C. Qiu, “A thermodynamic evaluation of the Fe–Mn–
N system,” Metall. Trans. A 24, 629–645 (1992).
54. A. Gabriel, P. Gustafson, and I. Ansara, “A thermody-
namic evaluation of the C–Fe–Ni system,” CALPHAD
11, 203–218 (1987).
55. A. T. Dinsdale, “SGTE data for pure elements,”
CALPHAD 15, 317–425 (1991).
56. B.-J. Lee, “Revision of thermodynamic descriptions of
the Fe–Cr and Fe–Ni liquid phases,” CALPHAD 17,
251–268 (1993).
57. M. Mathon, D. Connetable, B. Sundman, and
J. Lacaze, “CALPHAD-type assessment of the Fe–
Nb–Ni ternary system,” CALPHAD 33, 136–161
(2009).
THE PHYSICS OF METALS AND METALLOGRAPHY
58. K. Santhy and K. C. H. Kumar, “Thermodynamic
reassessment of Nb–Ni–Ti system with order–disorder
model,” J. Alloys Compd. 619, 733–747 (2015).
59. H. Chen and Y. Du, “Refinement of the thermody-
namic modeling of the Nb–Ni system,” CALPHAD
30, 308–315 (2006).
60. K. C. H. Kumar, P. Wollants, and L. Delaey, “Ther-
modynamic calculation of Nb–Ti–V phase diagram,”
CALPHAD 18, 71–79 (1994).
61. N. Saunders, “System Ni–V,” in COST-507 Project:
Thermochemical Database for Light Metal Alloys (Vol.
2), Ed. by A. Ansara, T. Dinsdale, and M. H. Rand
(Office for Official Publications of the European Com-
munities, Luxembourg, 1998), pp. 261–263.
62. J. Lacaze and B. Sundman, “An assessment of the Fe–
C–Si system,” Metall. Mater. Trans. A 22, 2211–2223
(1991).
63. J. Miettinen, “Reassessed thermodynamic solution
phase data for ternary Fe–Si–C system,” CALPHAD
22, 231–256 (1998).
64. X. Ma, Ch. Li, and W. Zhang, “The thermodynamic
assessment of the Ti–Si–N system and the interfacial
reaction analysis,” J. Alloys Compd. 394, 138–147
(2005).
65. H. Liang and Y. A. Chang, “Thermodynamic modeling
of the Nb–Si–Ti ternary system,” Intermetallics 7,
561–570 (1999).
Translated by S. Gorin
Vol. 117 No. 12 2016