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Abstract
The phase diagram of the ternary FeNiCr alloys has been reassessed for temperatures higher than 1070 K using substantially more
thermodynamic data from experimental investigations than previous attempts. The new thermodynamic description reduces the magnetic
contribution terms to the expressions of the pure species only. The calculated phase equilibria yield a distinct improved overall-agreement
with the experimental data than the results of previous assessments. The present thermodynamic description reproduces the distribution
coefficients better than previous data. Complete lists of the data sets of all binary and ternary parameters, several isothermal and vertical
sections as well as various projections are presented.
2004 Elsevier B.V. All rights reserved.
Keywords: Phase diagrams; FeNiCr system; Thermodynamics; Metals; Ternary alloys
1. Introduction
The phase relations of ternary FeNiCr alloys have
been investigated by many authors because these alloys are
of considerable technical and great practical importance:
Many corrosion-resistant alloys, e.g. austenitic stainless
steels have the Fe-rich corner of the FeNiCr system as
their compositional base. Critical assessments of the experimental literature on phase equilibria of FeNiCr alloys up
to the middle of the 1980s has been compiled thoroughly by
Rivlin [1] and Raynor and Rivlin [2]. Newer measurements
on the tie lines and the liquidus surfaces of the liquidbcc
solid and liquidfcc solid equilibria in the iron-rich corner
of the Gibbs triangle are reported by Kundrat and Elliott
[3]. Sopousek and Kruml [4] determined some points of the
sigma()-fcc solid equilibrium.
Computer synthesis of ternary phase equilibria curves
have been performed by several authors until now [3,59].
However, these assessments are based upon poor experimental data of the thermodynamic mixing behavior, only. The
cited authors employed mainly sets of Gibbs energy data
which have been obtained by means of trial and error
techniques. It is not surprising that Hillert and Qiu [8] re
1.2
1.1
1.0
0.9
1620
1660
(a)
1700
Temperature, K
1740
1780
1.2
1.1
1.0
0.9
1620
Gk (T, Fe
, Ni
, Cr
) = Gk (T, Fe , Ni , Cr ) =
(b)
177
1660
1700
1740
1780
Temperature, K
/l
(1)
LIQ
1600
1667 K
FCC
1400
1185 K
1200
BCC
1073 K
1000
Fe
0.2
0.4
0.6
0.8
Ni
xNi
(a)
2200
2180 K
LIQ
2000
1873 K
1800
1728 K
1618 K
1600
FCC
BCC
1400
1200
1073 K
1000
Ni
0.2
0.4
(b)
0.6
0.8
Cr
xCr
2200
2180 K
Gid
LIQ
2000
1811 K
1873 K
Temperature, K
and
denote the contributions of the pure
where
species, and of the ideal alloy, respectively. In Eq. (2)
the terms GE and Gg are assumed commonly to be due to
the intermolecular and magnetic forces, respectively. These
authors assessed the ternary parameters for the liquid, bcc,
and fcc phases, and obtained satisfactory agreement with the
experimental phase boundary data. Their assessment reproduced the distribution coefficients better than previous phase
synthesis, but still unsatisfying as can be seen from Fig. 1.
Lees assessment of the thermodynamic data sets for the
FeCr and FeNi liquid phase yields a better agreement
with experimental data on the bcc/liquid and fcc/liquid
tie-lines and liquidus temperatures in the Fe-rich region of
the FeNiCr ternary system than the previous assessments.
But, as can be noticed from Fig. 1, the distribution coefficients due to Lees assessment show partly distinct less
agreement with the experimentally determined ones than
those as reported by Hillert and Qiu [8].
The experimental data as employed in previous assessments consisted mainly of the results of phase equilibria
investigations, and only poor measurements on the molar
Gibbs energy have been incorporated. Partly the reason
may be seen on a lack of thermodynamic measurements,
1728 K
BCC
1873 K
1811 K
1800
Temperature, K
Their experimental data were then analyzed thermodynamically using an extended regular solution model and
the thermodynamic data on the binary systems concerned.
Linear programming yielded finally the thermodynamic parameters required by the authors for synthesis of the phase
diagram over a wide range of temperature.
Chart et al. [7] also used for their assessment the concept of lattice stability functions. These authors generated
for their computations of the phase relations in the temperature range 6501000 K a thermodynamic data set distinctly
different to that of Hasebe and Nishizawa [6]. The latest assessment employing Kaufmans lattice stability concept has
been performed by Kundrat and Elliott [3]. They reinvestigated the iron rich corner of the FeNiCr system both
by measurements as well as by modeling of tie-lines and
the liquidus surfaces of the liquidbcc () and liquidfcc
() equilibria and the peritectic surface involving all three
phases in the iron-rich corner of the Gibbs triangle. The
thermodynamic parameters as used in [3,5,7] for the phase
diagram calculations based upon lattice stability functions
are called in the literature as Gibbs energy, although they
are basically different to the physical notion of the molar
Gibbs energy. Therefore Gibbs energy should not be used
in context with lattice stability functions any longer. May
be a notion like phase equilibria function should be introduced instead to characterize apparently that these functions
are only employable for phase diagram computationsand
not for any other application in alloy thermodynamics.
Hillert and Qiu [8] as well as Lee [9] based their assessments upon modeling the molar Gibbs energy G (T, x ) in
a phase as following (phase index omitted)
Temperature, K
178
1800
1667 K
1600
1400
BCC
1200
FCC
SIGMA
1073 K
1185 K
1000
Cr
(c)
0.2
0.4
0.6
0.8
Fe
xFe
Fig. 3. The equilibrium phase diagrams of the three binary boundary systems (temperature range of ternary phase equilibria computations marked
by ( )). (a) FeNi (this work ()). (b) NiCr (experimental points (for
references see [13]) (); [13] ()). (c) CrFe (experimental points (for
references see [12]) (); this work (); Hillert and Qiu [8]; Lee [9]
( )).
179
components k (this work: K = 3) in the phase are characterized commonly by means of the contributions made by
the alloy constituents k, the so-called partial molar properties Zk (T, xk ) (phase index omitted):
3. Thermodynamic models
Z(T, x) =
K
xk Zk (T, xk ).
(3)
k=1
(4)
(5)
(6)
kC
+ k C7 T 7 +
kC
T9
(7)
180
Table 1
The coefficients k Cn of the G0k (T) reference terms, Eq. (7), of the liquid, bcc solid, and fcc solid phases from SGTE [22]
n
Liquid
bcc
fcc
2981811 K
18116000 K
2981811 K
18116000 K
2981811 K
18116000 K
k = Fe
1
2
3
4
5
6
7
8
13265.9
117.576
23.5143
4.39752 103
5.89269 108
77358.5
3.67516 1021
0
10838.8
291.302
46.0
0
0
0
0
0
1225.7
124.134
23.5143
4.39752 103
5.89269 108
77358.5
0
0
25383.6
299.313
46.0
0
0
0
0
2.29603 1031
236.7
132.416
24.6643
3.75752 103
5.89269 108
77358.5
0
0
27097.4
300.253
46.0
0
0
0
0
2.78854 1031
Liquid
k = Ni
1
2
3
4
5
6
7
8
n
k = Cr
1
2
3
4
5
6
7
8
bcc
fcc
2981728 K
17286000 K
2981728 K
17286000 K
2981728 K
17286000 K
11235.6
108.457
22.096
4.8407 103
0
0
3.82318 1021
0
9549.78
268.598
43.10
0
0
0
0
0
3535.93
114.298
22.096
4.8407 103
0
0
0
0
19125.6
275.579
43.10
0
0
0
0
1.12754 1031
5179.16
117.854
22.096
4.8407 103
0
0
0
0
27840.7
279.135
43.10
0
0
0
0
1.12754 1031
Liquid
2982180 K
bcc
2982180 K
fcc
2982180 K
15483.0
146.060
26.908
1.89435 103
1.47721 103
139250
2.37615/1021
0
8856.94
157.48
26.908
1.89435 103
1.47721 103
139250
0
0
1572.94
157.643
26.908
1.89435 103
1.47721 103
139250
0
0
for > 1 :
5 /10 + 15 /315 + 25 /1500
g() =
,
B1
for 1 :
(9a)
and
g() = 1 +
B2 + B3 ( 3 /6 + 9 /135 + 15 /600)
,
B1
(9b)
kT
kB
(K)
k = Ni
Table 3
The constants B1 to B3 of the function g(T/k Tc ), Eq. (9), from Sundman
and Agren [19]
k = Cr
bcc
fcc
bcc
fcc
bcc
fcc
1043
2.22
67
0.7
575
0.85
633
0.52
311.5
0.008
367
0.82
B1
B2
B3
bcc A2
1.410714
1.430584
1.558285
2.015306
2.452429
2.342457
Z (xk ) = xj
E
N
Cn xkn ,
(10a)
xj j,k ZE
,
xk
(10b)
xk j,k ZE
,
xk
(10c)
n=1
j,k
j,k
ZjE = j,k ZE +
ZkE = j,k ZE
j,k ZE
xk
N
j,k
n=1
j,k
(10d)
N2
n=1
Z1E
N1
1,2
n=1
N3
CnZ x3n + x3
n=1
3,1
CnZ x3n ,
x2 ZE
x3 ZE
=Z +
,
x2
x3
(1 x2 )ZE
x3 ZE
,
x2
x3
x2 ZE
(1 x3 )ZE
=Z
+
,
x2
x3
E
ZE 1,2,3 E
1,2
=
C x2 (x1 x3 ) +
Cn x2n
x3
2,3
3,1
+ x2
Cn nxn1
Cn x1n1 (nx3 x1 ).
3
(11f)
In accordance with Eq. (4), the TAP parameters of the molar
excess Gibbs energy GE , of the molar heat of mixing HE ,
and of the molar excess entropy SE are connected by
j,k
CG = 1,2,3 CH T 1,2,3 CS ,
(11a)
(11b)
(11c)
(11d)
(12a)
(12b)
+ [C1,1
+ C1,2
T ],
CnZ x2n
Z2E = ZE +
Z3E
2,3
ZE 1,2,3 E
1,2
=
C x3 (x1 x2 ) +
Cn x2n1 (nx1 x2 )
x2
2,3
3,1
Cn x3n x3
Cn x1n1 ,
(11e)
+
1,2,3
Cn xkn1 (nxj xk ).
181
(13a)
,o
hbcc,o
GFe:Cr:Fe
= 8Gfcc,o
+ 18Ghbcc,o
Fe + 4GCr
Fe
+ [C2,1
+ C2,2
T ].
(13b)
(13c)
,o
hbcc,o
GNi:Cr:Cr
= 8Gfcc,o
+ 18Ghbcc,o
Cr
Ni + 4GCr
+ [C3,1
+ C3,2
T ],
(13d)
182
Table 4
and C parameters of Eq. (12) for the molar Gibbs energy of
The Cn,1
n,2
-phase as fitted in this work
n
(J/mol)
Cn,1
(J/mol K)
Cn,2
1
2
3
4
49000
72000
187000
305000
31
31
200
0
,o
hbcc,o
GNi:Cr:Fe
= 8Gfcc,o
+ 18Ghbcc,o
,
Fe
Ni + 4GCr
,o
GNi:Cr:Ni = 8Gfcc,o
Ni
+ 4Ghbcc,o
Cr
(13e)
+ 18Ghbcc,o
Ni
+ [C4,1
+ C4,2
T ].
(13f)
and
bcc-phase. The numerical values of the parameters Cn,1
4. Thermodynamics
Following the SGTE [22] the latest values for the
melting temperatures of Fe, Ni, and Cr are: Fe Tm =
1811 K (instead of 1808 or 1809 K), Ni Tm = 1728 K (instead of 17251726 K), and Cr Tm = 2180 K (instead of
21232151 K). These data have been used first by the assessments of Hillert and Qiu [8] and Lee [9]. The synthesis
of the phase relations of this work is also based upon these
melting points of the three constituents. In [12] the experimental phase diagram data of CrFe at temperatures higher
than the melting point of Fe have been raised proportional
to the old and new differences of the melting points of the
constituents, therefore. This causes some discrepancies to
the figures as presented in the original literature.
We cannot expect that experimental data of the thermodynamic mixing behavior yield directly satisfactory phase
Table 5
TAP parameters
n
Fe,Ni C Z
n
1
2
3
1
2
(J/mol)
Ni,Cr C Z
n
The TAP parameters j,k Cn of the molar excess properties ZE (Z = G, H, S) of the three binary boundary systems
FeNi, NiCr, and CrFe as used in this work are given in
Tables 57. The resultant phase equilibria curves are presented in Fig. 3. As carried out in [16] slight modifications
(up to 5%) of the results of mass spectrometric measurements both on the liquid [10] and on the fcc solid [11] phase
makes possible to determine FeNi phase equilibria curves
without involving any binary magnetic correction term. As
Fig. 3a makes evident, the liquidus/solidus phase equilibria
of FeNi based upon the simpler thermodynamic modeling
as suggested in [16] yield full agreement with both the experimental phase equilibria data as well as with the results of
the assessment of Hasebe and Nishizawa [6]. The peritectic
temperature (1786 K) is in accordance with the experimentally determined data of Hellawell and Hume-Rothery [25]
and Schrmann et al. [26] as well as with the critical experimental assessment of Rivlin [1], and with the computations
of Hasebe and Nishizawa [6]. Whereas Lees assessment
yielded a peritectic temperature of 1791 K.
The assessment of the thermodynamic excess behavior
of the bcc solid phase has been based in [16] on the mass
spectrometrically determined data of the liquid and the fcc
solid phases. As carried out in detail in [16], the resultant
bcc/liquid and bcc/fcc phase equilibria lines are in good
agreement with the experimental information. In Fig. 4
the experimental points of the low temperature bcc/fcc
bcc
10500
12000
6000
Table 6
TAP parameters
Liquid
CnH
CnS
(J/mol K)
1.85
2.35
5.05
CnH
fcc
(J/mol)
2400
16000
12000
CnS
(J/mol K)
1.90
7.10
4.00
CnH (J/mol)
CnS (J/mol K)
6300
12200
7500
0.80
1.20
6.80
Liquid
bcc
fcc
CnH (J/mol)
CnS (J/mol K)
CnH (J/mol)
CnS (J/mol K)
CnH (J/mol)
3975
5400
5.387
0
3900
44610
9.710
13.52
21550
59790
Liquid and fcc phase optimized in [24] (all data converted into TAP series concept); bcc phase from [13].
CnS (J/mol K)
4.28
32.77
Temperature, K
1200
1185 K
1000
FCC
800
BCC
600
Fe
0.2
0.4
xNi
0.6
Cr,Fe C Z
n
1
2
Liquid
CnH
183
(J/mol)
4300
3500
bcc
CnS
(J/mol K)
3.00
3.80
CnH
fcc
(J/mol)
21290
4490
CnS
(J/mol K)
6.220
2.065
CnH (J/mol)
12700
4500
CnS (J/mol K)
6.60
3.50
fcc phase optimized in this work from phase diagram calculations; liquid and bcc phase from [12].
Table 8
Ternary interaction TAP parameters
n
Liquid
CnH
Fe,Ni,Cr C Z
(J/mol)
43700
bcc
CnS
(J/mol K)
20.18
CnH
fcc
(J/mol)
3100
CnS
(J/mol K)
5.2
bcc phase optimized in this work from phase diagram calculations; liquid phase from [14]; fcc phase from [15].
CnH (J/mol)
CnS (J/mol K)
39870
19.89
184
presented in Figs. 58. The mass spectrometric investigations from [14] yielded the first experimental data for the
thermodynamic mixing behavior of the liquid FeNiCr
alloys over the whole range of ternary compositions. The
molar excess properties of fcc solid FeNiCr alloys have
been determined mass spectrometrically by [15]. In both
cases using one adjustable ternary interaction term is sufficient, but really necessary, for a satisfying description
of experimental molar excess properties. Whereas the assessments by Hillert and Qiu [8] and Lee [9] employed
three ternary terms for this purpose in the fcc solid phase.
For discussion of the poor earlier experimental studies see
[14,15].
Concerning the bcc and the -phases no experimental
molar excess properties have been available, the thermodynamic description of these two phases have been
re-assessed in this work by means of the computational
phase equilibria synthesis using the molar mixing behavior
of the liquid and fcc solid phases from [14,15]. Again only
one temperature dependent ternary interaction term was
necessaryin contrast to the previous assessments of by
Hillert and Qiu [8] and Lee [9] which required two ternary
interaction terms. The resultant ternary TAP parameters
Fe,Ni,Cr C Z of the bcc phase are presented in Table 8. The
new values of the adjustable coefficients for the description
185
186
6. Conclusion
In this work the computational synthesis of the phase
equilibria curves of ternary FeNiCr alloys has been based
upon substantial more experimental data of the thermodynamic mixing behavior than previous attempts. This yields
a distinct improved overall-agreement with the experimental phase literature than the results of previous assessments.
The thermodynamic description used in this work is simpler
than that of previous assessments, and restricted the mag-
References
[1] V.G. Rivlin, Int. Met. Rev. 20 (1981) 269.
[2] G.V. Raynor, V.G. Rivlin, Phase Diagrams of Ternary Iron Alloys,
Part 4, The Institute of Metals, Sweden, 1988, p. 316.
[3] D.M. Kundrat, J.F. Elliot, Met. Trans. A 19A (1988) 899.
[4] J. Sopousek, T. Kruml, Scripta Materialia 35 (1996) 689.
[5] L. Kaufman, H. Nesor, Z. Metallkd. 64 (1973) 249.
[6] M. Hasebe, T. Nishizawa, in: Proceedings of the Workshop, SP 496,
National Bureau of Standards, Gaithersburg, MD, 1012 January
1977, p. 911.
[7] T. Chart, F. Putland, A.T. Dinsdale, CALPHAD 4 (1980) 27.
[8] M. Hillert, C. Qiu, Met. Trans. A 21A (1990) 1673.
[9] B.J. Lee, CALPHAD 17 (1993) 251.
[10] J. Tomiska, Z. Metallkd. 76 (1985) 532.
[11] J. Tomiska, A. Neckel, Ber. Bunsenges. Phys. Chem. 89 (1985) 1104.
[12] J. Vrestal, P. Broz, J. Tomiska, Ber. Bunsenges. Phys. Chem. 98
(1994) 1601.
[13] J. Tomiska, K. Kopecky, M.S. Belegratis, C. Myers, Met. Trans. A
26A (1995) 259.
[14] J. Vrestal, J. Theiner, P. Broz, J. Tomiska, Thermochim. Acta 319
(1998) 193.
[15] J. Tomiska, P. Broz, J. Vrestal, in: R.Y. Lin, Y.A. Chang, R.G.
Reddy, C.T. Liu (Eds.), Design Fundamentals of High Temperature
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
187