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Josef Tomiska

Institute of Physical Chemistry, University of Vienna, Waehringerstrasse 42, A-1090 Vienna, Austria

Received 15 January 2004; received in revised form 17 February 2004; accepted 17 February 2004

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

E-mail address: josef.tomiska@univie.ac.at (J. Tomiska).

URL: http://www.univie.ac.at/tomiska.

0925-8388/$ see front matter 2004 Elsevier B.V. All rights reserved.

doi:10.1016/j.jallcom.2004.02.027

suffered from the same difficulties, especially concerning the

distribution coefficients (the isothermal ratio of equilibrium

species-concentration in two coexisting phases) of Ni and

/l

Cr, Kk (l = liquid; k = Ni, = fcc; k = Cr, = bcc).

These authors concluded that it is not possible to get good

agreement between the computed distribution coefficients

and the experimental tie lines within the framework of the

thermodynamic models and binary descriptions adopted in

their work (compare Fig. 1).

Lee [9] reported later, a revision of the thermodynamic

data as assessed by Hillert and Qiu [8] especially with respect to the descriptions of the binary FeNi and CrFe alloys that yields a better agreement with the experimental data

in the Fe-rich region of the FeNiCr ternary system than

previous assessments. This is in full agreement with mass

spectrometric measurements on FeNi and CrFe alloys as

published earlier [1012]. Nevertheless, the full experimental FeNi data available at that time was not considered, not

even in the revision by Lee [9].

In the last years mass spectrometric investigations have

yielded the thermodynamic mixing behavior of binary bcc

solid NiCr [13] alloys, as well as ternary liquid [14] and

fcc solid [15] FeNiCr alloys. Furthermore, it has been

shown in [16] that the liquidus/solidus and bcc/fcc phase

equilibria in the FeNi system can be computed in full

agreement with the experimental data without any binary

and Lee [9]. As an illustration in Fig. 2 the liquidusfcc

phase boundary as obtained in [16] is compared with the

corresponding phase boundaries as reported by Hasebe and

Nishizawa [6], Hillert and Qiu [8], and Lee [9]. Therefore

a re-calculation of the FeNiCr phase diagram in the temperature range 10731873 K without employing binary or

ternary magnetic corrections seemed to be of interest.

1.2

1.1

1.0

0.9

1620

1660

(a)

1700

Temperature, K

1740

1780

diagram

The computations of phase boundaries are using the thermodynamic equilibrium conditions that at constant temperature T the partial Gibbs energy Gk (T, xk ) (also: molar

chemical potential k (T, xk )) for each component k (this

work: k = Fe, Ni, Cr; xk are the mole fractions) must be

equal in each of the coexisting phases , , . . . (, , . . . =

l, f, b, s, . . . ; l = liquid, f = fcc, b = bcc, s = sigma())

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

(experimental points from [37] (); this work (); Hillert and Qiu [8]

fcc/l

bcc/l

( ); after Lees assessment [9] ( )). (a) KNi of Ni; (b) KCr of Cr.

points (for references see [16]): liquid (); fcc solid (); Hasebe and

Nishizawa [6] and [16] (); Hillert and Qiu [8]; Lee [9] ( ); bcc/fcc

solid equilibria ( ).

(1)

, , . . . . Additional advantage of this method is the possibility to synthesize the phase diagrams of real alloys over

a wide range of composition and temperature by computation combined with thermodynamic analysis of experimental molar functions Z (Z = Gibbs energy G, heat of mixing

H, entropy S).

However, the computational techniques require the explicit values of the molar Gibbs energy G in all coexisting

phases over the whole employed temperature rangeseven

at temperatures at which the various phases are not stable any more. Consequently, no phase equilibrium can be

computed by means of experimentally determined thermodynamic data only. Data required additionally have to be

estimated and/or derived by means of more or less suitable

extrapolation techniques. It is obvious from Eq. (1), computational synthesis of phase equilibria curves require only

the differences of the molar Gibbs energy G, and not their

absolute values. This makes possible not only basically different strategies of assessment, but also the use of many different sets of thermodynamic parameters to describe more

or less satisfactorily the FeNiCr phase diagram. Concerning details of the various techniques the book of Saunders

and Miodownik [17] should be consulted.

After an early modeling by Kaufman and Nesor [5] especially Hasebe and Nishizawa [6] succeeded in employing

Kaufmans so-called lattice stability functions for computational establishing of phase equilibria in the ternary

FeNiCr system which are in reasonable agreement with

experimental data. In a first step the phase equilibria in the

FeNiCr system were examined by microprobe analysis

of ternary diffusion couples consisting of their components.

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

G0

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

the FeNiCr ternary system including the three binary

boundary systems the thermodynamic investigations for the

determination of reliable molar Gibbs energy data are very

time-wasting, and usually beset with considerable experimental difficulties. Therefore it may be understandable that

authors are ignoring the lack of experimental investigations,

and produce their own sets of assessed data. But sometimes

the lack of incorporated experimental results cannot be

explained by this reasoning: e.g., Hillert and Qiu [8] have

taken for their assessment of the FeNiCr phase diagram

the thermodynamic assessment of the binary boundary system FeNi as reported by Xing et al. [18] and not of the

results of mass spectrometric measurements as reported in

the same year for the liquid phase in [10], and for the fcc

solid alloys in [11]. Fig. 2 shows that the synthesis of phase

equilibria curves based upon these mass spectrometrically

determined molar excess Gibbs energies GE as reported

in [16] will agree even better with experimental data than

Lees improved assessment of the data as assessed by

Xing et al. [18].

The introduction of a magnetic term Gg as expressed in

Eq. (2) is a bit problematical, because experimental investigations will only yield the total excess sum (GE + Gg ).

However, especially the databases offered by the ThermoCalc group are based upon the use of magnetic terms Gg

as expressed by Sundman and Agren [19], which from a

physico-chemical point of view their description of assumed

magnetic influence, Gg , looks a bit strange, e.g., polynomials in temperature up to the power 25 (!) are employed (see

[19]). Nevertheless, with respect to support the efforts of establishing a general data base for the reference states of the

elements it is meaningful to employ elementary magnetic

contributions.

By means of newer mass spectrometric investigations on

bcc solid CrFe alloys by [12] molar excess Gibbs energies

GE have been determined which are distinctly different to

the values of the assessments by Anderson and Sundman

[20] and Lee [9]. But, as can be seen from Fig. 3c, a better

agreement with the experimental phase equilibria data have

been obtained by means of computations based upon these

experimentally determined data but without any binary magnetic correction, than the in the assessments by Anderson

and Sundman [20] and Lee [9] which have used the binary

magnetic contributions. The same situation we are faced in

the binary CoCr system as reported in [21]. Therefore the

suspicion raises, that especially at temperatures above the

Nel or Curie temperatures the use of a binary magnetic

correction will only improve the quality of binary phase diagrams in cases of employing a bit doubtful excess data.

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

on all three mole fractions xk ) of an alloy system with K

0,g

the pure species, Gk (T, xk ) as presented by Sundman and

Z(T, x) =

K

xk Zk (T, xk ).

(3)

k=1

partial pressures of all constituents can be assumed to be

inverse proportional to T, both the enthalpy of mixing as

well as the excess entropy result as temperature independent.

The temperature dependence of the molar Gibbs energy G

is then given by the well-known relation

G(T, x) = H(x) TS(x),

(4)

excess heat capacity (Cp = 0), expressed by the rule of

Neumann and Kopp, according to which the difference between the heat capacity of an alloy and the heat capacities of

the corresponding amounts of the pure species at the same

temperature is zero.

With respect to support the efforts of establishing a general data base for the reference states of the elements the

magnetic correction term of Eq. (2) have not been omitted entirely but they are reduced to their elementary mag0,g

netic contributions Gk (T, xk ). In this work the partial molar Gibbs energy Gk (T, xk ) are composed therefore by

0,g

E

+ Gid

k (T, xk ) + Gk (T, xk )

(5)

Gid

k (T, xk ) = RT ln(xk ).

(6)

The G0k (T) term in Eq. (5) acts as reference level for

the partial Gibbs energy only, and has been expressed as

polynomials in T for a long time in literature. With respect

to establish a general data base for these reference states of

the elements, it is meaningful to employ the reference data

as developed by SGTE [22] for this purpose

G0k (T) = k C1 + k C2 T + k C3 T ln T + k C4 T 2

+ k C5 T 3 +

kC

+ k C7 T 7 +

kC

T9

(7)

element. Table 1 gives the numerical values of the coefficients k Cn after [22] as employed in this work.

0,g

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

T

0,g

Gk (T) = RT ln(k B0 + 1)g k

,

(8)

Tc

for > 1 :

5 /10 + 15 /315 + 25 /1500

g() =

,

B1

magnetic ordering temperature (Nel or Curie temperature).

The numerical values employed in this work are summarized

in Table 2. These authors assumed the function g(T/k Tc ) to

be ( := T /k Tc ):

for 1 :

(9a)

and

g() = 1 +

B2 + B3 ( 3 /6 + 9 /135 + 15 /600)

,

B1

(9b)

Table 3.

Table 2

The atomic magnetic moments k B0 , and critical magnetic ordering temperature (Neel or Curie temperature) k Tc of Eq. (8) of Fe, Ni, and Cr

from Sundman and Agren [19]

k = Fe

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

The binary excess functions j,k ZE (j, k components) are

represented by (N is the number of adjustable parameters

j,k C ) [23]:

n

j,k

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)

the complexity of their excess properties may be performed

with more clarity: The TAP parameter j,k C1 and j,k C2 characterize the regular and sub-regular solution contributions as

pointed out in [23]. Interchange of the components, as well

as conversion of the various literature proposals for polynomial representing of j,k ZE (x), especially of the frequently

used, but distinctly more complicated RedlichKister

polynomial into the TAP-series and vice versa can be

performed easily by means of the algorithm developed,

e.g. in [23].

The ternary excess properties ZE are represented by

adding a ternary interaction term Fe,Ni,Cr ZE to the simple

sum of the three binary boundary systems, j,k ZE [23]. The

ternary interaction term Fe,Ni,Cr ZE is preferably a simple

polynomial in all three mole fractions. Concerning the

FeNiCr system a polynomial of third order in x was sufficient in all three (bcc, fcc and liquid) phases. The molar

excess quantities of FeNiCr alloys are represented therefore by Eq. (11) (1 = Fe, 2 = Ni, 3 = Cr; 1,2,3 CE is the

ternary adjustable parameter):

ZE = 1,2,3 CE x1 x2 x3 + x1

+ x2

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)

considerably the computational effort. Conversion of the

TAP series into other polynomial representations (e.g.

RedlichKister expansions as employed in [8,9]), and vice

versa, can be performed easily by means of the algorithm

presented in [23].

3.4. Modeling of the -phase

Considering the -phase of the investigated temperature

range in literature no experimental thermodynamic data are

available. Therefore the adjustment to phase equilibrium

data has been performed using the sublattice model of solid

phases according to Anderson and Sundman [20]. The atoms

in different sublattices are compared with the atoms in the

bcc or fcc structures. Formally, three sublattices are considered [20]: The first occupied by 8 atoms is compared with

fcc lattice and the other two occupied by 4 and 18 atoms, respectively, with the bcc lattice. In third sublattice both iron

and chromium atoms can be present. Standard Gibbs energy

is equal to

,o

hbcc,o

GFe:Cr:Cr

= 8Gfcc,o

+ 18Ghbcc,o

Fe + 4GCr

Cr

+ [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)

be present in the first sublattice with iron and in the third

sublattice with iron and chromium:

,o

hbcc,o

GFe:Cr:Ni

= 8Gfcc,o

+ 18Ghbcc,o

,

Fe + 4GCr

Ni

(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

fitted in this work are presented in Table 4.

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

are not precise enough for this purpose. However, assessments within the accuracy limits of 520% of the parameter

values of trusted experimental investigations should yield

reasonable results, and unrealistic behavior of the thermodynamic activities avoided. The phase relations as presented in

this work have been obtained by means of minor optimizations of about 5% of the original mass spectrometric data.

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

Sully [27] (), Owen and Liu [28] ( ); corresponding points (); Lee

[9] ( ); [16] ().

and Liu [28] are plotted together with the phase boundary

curves as computed by Lee [9] and in [16]. As can be seen

from Fig. 4 the tie lines as reported in [16] show a distinct

better agreement with the experimental data than Lees

assessment using a magnetic fcc solid contribution instead

of employing the experimental molar excess Gibbs energies from [10,11]. For discussion of earlier experimental

investigations see [10,11].

Fig. 3b shows the equilibrium phase diagram of NiCr

after [13] as employed for the ternary assessment of this

work. Phase diagram calculations including and excluding

the magnetic terms yield corresponding tie lines, so no magnetic contribution affects the phase boundaries in the system

NiCr. As can be seen from Fig. 3b, and discussed in detail in [13] the phase equilibria curves computed by means

of the TAP parameters as presented in Table 6 show really

good agreement with the experimental phase diagram data.

Table 7

TAP parameters

n

Cr,Fe C Z

n

1

2

agrees also well with the assessed NiCr diagram reported

by Nash [29]. The fccbcc equilibrium calculated by Chuang

and Chang [30] coincides also with the results plotted in

Fig. 3b, whereas the computations of these authors yielded

fccliquid and liquidbcc equilibria which show less agreement with the experimental data than the phase equilibria

curves based upon the TAP parameters given in Table 6.

A detailed discussion of the experimental studies of binary CrFe alloys is given in [12]. Based upon their own

experimental data of the excess properties, in [12] the thermodynamic descriptions of the liquid, the fcc solid, and the

sigma phase have been re-optimized by means of computational phase equilibria synthesis. The assessment as reported in [12] yielded a description of the solidusliquidus

equilibrium of FeCr alloys showing better agreement

with the experimental phase equilibria data than the earlier

optimizations.

The synthesis in [12] still used magnetic correction terms,

and it seemed to these authors that the magnetic contribution

should be essentially for describing the phase regions of

solid FeCr alloys. However the computations in this work

showed that the binary magnetic correction can be omitted

by simple raising the assessed TAP parameter Cr,Fe C1H of the

heat of mixing of the fcc solid phase about 4%! This slight

correction makes it already unnecessary to employ a binary

magnetic correction. The corresponding TAP parameters are

summarized in Table 7. Consequently the thermodynamic

characterization of the -phase have been re-assessed in this

and Cn,2

;

n = 1, 2). The resultant phase equilibria curves are plotted

together with the experimental phase diagram data in Fig. 3c.

4.2. Ternary FeNiCr alloys

The ternary interaction TAP parameters Fe,Ni,Cr CZ of

the molar excess quantities properties ZE (Z = G, H, S) of

ternary FeNiCr alloys as used in this work are summarized in Table 8. The resultant phase equilibria curves are

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

and Cn,2

; n = 3, 4) are summarized in

Table 4.

Fig. 5 shows selected isothermal sections involving the

liquid phase from 1873 down to 1625 K. In Fig. 6 the temperature development is presented as obtained in this work

for the liquid/bcc/fcc solid three phases equilibria in the

FeNiCr system between 1770 and 1625 K. Fig. 7 illustrates the temperature development of only existing bcc/fcc

solid equilibria by four isothermal sections between 1573

and 1273 K. Finally Fig. 8 shows the isothermal sections at

1173 and 1073 K involving the -phase.

At 1873 K the isothermal section shows in Fig. 5a the

liquid/bcc solid equilibria existing only. Three-phase region

starts at the peritectic temperature in the FeNi system at

1786 K (compare Fig. 3a). Also plotted in Fig. 5a is the

isothermal section of the FeNiCr system at 1770 K. We

can notice from Fig. 5a that the liquid/fcc solid equilibrium

lines as computed in this work agree reasonably with the

experimental results of Schrmann et al. [26], and Kundrat

and Elliott [3]. As reported already in [16], the liquidus

lines of the assessments of the latter authors, and of Hillert

and Qiu [8] show distinctly less agreement with experimental points than the optimization based upon mass spectrometric data of the ternary FeNiCr alloys. In Fig. 5b

the phase equilibrium lines as computed in this work at

1723 K are compared with the results of the calculations

by Hasebe and Nishizawa [6]. The severe discrepancies

(a) This work at 1873 K ( ) and at 1770 K (); experimental points

of fccliquid equilibrium at 1770 K: Schrmann et al. [26] (); Kundrat

and Elliott [3] (). (b) This work at 1723 K (); Hasebe and Nishizawa

[6] ( ). (c) This work at 1675 K ( ) and at 1625 K ().

185

phases equilibria in the FeNiCr system. The gray fields gives the three

phases area at selected temperatures.

caused by the evaluated zero value of ternary interaction

parameters in [6]. Finally Fig. 5c shows the results of the

phase equilibria synthesis of this investigations at 1675

and 1625 K.

The resultant temperature development of the liquid/bcc/fcc three phases equilibria as presented in Fig. 6

in steps of 2025 K (gray fields) yields liquidus and fcc

solidus lines between 1775 K (binary FeNi) and 1618 K

(binary NiCr) showing even a better agreement with the

experimentally determined points than the results of the

previous assessments (see also [16]). Fig. 1 illustrates,

that the temperature dependence of the distribution coefficients of Ni and Cr as obtained in this work clearly

shows better agreement with experimental data than the

computed curves from Hillert and Qiu [8] and Lee [9].

However, the melting and solidification temperatures of

the binary FeNi alloys cover only a small temperature

interval of about 100 K over the whole range of compositions, and the two binary boundary systems FeNi and

CrFe show very narrow liquidsolid two-phase regions,

as obviously from Fig. 3. We cannot therefore expect

too precise determinations of the temperature dependencies of the corresponding binary and ternary equilibrium

compositions.

The optimization of this work yielded fccbcc phase equilibria which are in excellent agreement with the experimental phase diagram information. Fig. 7a illustrates this for

the isothermal sections at 1573 and 1473 K, comparing the

computed tie lines of this work with the experimental points

reported by Mundt and Hoffmeister [31] for these temperatures, and by Hasebe and Nishizawa [6] and Schultz and

Merrick [32] for 1473 K. In Fig. 7b the results of this assessment at 1373 and 1273 K are plotted together with the

( ) and at 1473 K (); Mundt and Hoffmeister [31] at 1573 K ( )

and at 1473 K (); Hasebe and Nishizawa [6] at 1473 K (); Schultz

and Merrick [32] at 1473 K (). (b) This work at 1373 K ( ) and at

1273 K (); Hasebe and Nishizawa [6] at 1373 K () and at 1273 K

(); Schultz and Merrick [32] at 1373 K (); Chiba [33] at 1373 K ( ).

[6] at these temperatures, as well as by Schultz and Merrick

[32] and Chiba [33] at 1373 K.

The isothermal sections involving the -phase at 1173

and 1073 K show also satisfactory agreement of the results

of this assessment with the corresponding experimental

information (Fig. 8). At 1173 K full agreement is achieved

with the measurements as reported by Sopousek and Kruml

[4] and Hasebe and Nishizawa [6] and Schrmann et al. [26]

(Fig. 8a). As can be seen from Fig. 8b, at 1073 K also satisfactory agreement is obtained with the experimental points

from Sopousek and Kruml [4] and Rees et al. [34]. The

agreement between experimental and calculated equilibrium

composition values is again better than in calculations using

186

raises the suspicion that especially at temperatures above

the Nel or Curie temperatures the use of binary magnetic

corrections will only improve the quality of binary phase

diagrams in cases of employing a bit doubtful excess data.

Complete thermodynamic parameter sets of all three binary boundary systems as well as the new ternary interaction

terms are presented. Several isothermal and vertical sections

as well as various projections of the FeNiCr phase diagram in the temperature range from 1073 to 1873 K illustrate reliability of the new description. The thermodynamic

parameters of this investigation yield better reproducing of

the distribution coefficients of Cr and Ni than data assessed

previously.

Oates et al. [35] required to put more physics into CALPHAD solution models. And even Hillert, the founder and

mentor of the ThermoCalc group, regretted some developments in the phase diagram engineering at the CALPHAD

XXVI Conference. He was concerned that CALPHAD had

reached a stage where its future scientific status might be in

danger [36]. Omitting the problematic splitting of the excess

contribution in favor of employing thermodynamic mixing

properties more experimentally proved, may be the right way

doing this.

Acknowledgements

The authors would like to thank Prof. RNDr. Jan Vrestal (Institute of Physical Chemistry, Masaryk University

Brno, Czech Republic) and Mrs. Susanna Tomiska-Szeles

for essential assistance. All ternary phase diagram calculations were performed using both PD-Package [38] and

Thermo-Calc program.

Fig. 8. Isothermal section of FeNiCr system involving -phase (this

work (); experimental points of -fcc solid equilibrium from Sopousek

and Kruml [4] ()). (a) At 1173 K. Experimental points of bcc/fcc solid

equilibrium: Schrmann et al. [26] (); Hasebe and Nishizawa [6] ().

(b) At 1073 K. Experimental points of bcc/fcc solid equilibrium from

Rees et al. [34] ().

be verified from the corresponding literature.

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]

Warrendale, PA, 1996, p. 309.

J. Tomiska, J. Vrestal, Thermochim. Acta 314 (1998) 155.

N. Saunders, A.P. Miodownik, CALPHAD: Calculation of Phase

Diagrams, Pergamon Press, Oxford, 1998.

Z.S. Xing, D.D. Gohil, A.T. Dinsdale, T. Chart, DMA(A) 103,

National Physical Laboratory, London, 1985.

B. Sundman, J. Agren, J. Phys. Chem. Solids 42 (1981) 297.

J.-O. Anderson, B. Sundman, CALPHAD 11 (1987) 83.

J. Havrankova, J. Vrestal, J. Tomiska, Ber. Bunsenges. Phys. Chem.

102 (1998) 1225.

A.T. Dinsdale, CALPHAD 15 (1991) 317.

J. Tomiska, CALPHAD 26 (2002) 143.

B.J. Lee, CALPHAD 16 (1992) 121.

A. Hellawell, W. Hume-Rothery, Phil. Trans. R. Soc. London Ser.

A 249 (1957) 417.

E. Schrmann, J. Brauckmann, Arch. Eisenhttenwesen 48 (1977) 3;

E. Schrmann, H.-J. Voss, Arch. Eisenhttenwesen 48 (1977) 129.

187

[28] E.A. Owen, Y.H. Liu, J. Iron Steel Inst. 163 (1949) 132.

[29] P. Nash, Bull. Alloy Phase Diagrams 7 (1986) 466;

P. Nash, in: T.B. Massalski (Ed.), Binary Alloy Phase Diagrams, 2nd

ed., American Society for Metals, Metals Park, OH, 1990.

[30] Y-Y. Chuang, Y.A. Chang, Z. Metallkd. 77 (1986) 460.

[31] R. Mundt, H. Hoffmeister, Arch. Eisenhttenwesen 54 (1983) 253.

[32] J.W. Schultz, H.F. Merrick, Met. Trans. 3 (1972) 2479.

[33] A. Chiba, Thesis, Tohoku University, Japan, 1971.

[34] W.P. Rees, B.D. Burns, A.J. Cook, J. Iron Steel Inst. 20 (1949)

325.

[35] W.A. Oates, H. Wenzl, T. Mohri, CALPHAD 20 (1996) 37.

[36] M. Hillert, in: Proceedings of the CALPHAD XXVI Conference,

Palm Coast, Florida, 1116 May 1997, p. 6e.

[37] C.H.M. Jenkins, E.H. Bucknall, C.R. Austin, G.A. Mellor, J. Iron

Steel Inst. 136 (1937) 187.

[38] J. Sopousek, A. Kroupa, R. Dojiva, J. Vrestal, CALPHAD 17 (1993)

229.

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