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The Thermodynamics of Tetrataenite and Awaruite: A Review

of the Fe-Ni Phase Diagram
REED A. HOWALD

There are two well-known ordered ferromagnetic intermetallic compounds in the iron-nickel system:
tetrataenite, FeNi, and awaruite, FeNi3. Their thermodynamic properties are established from the various
stable and metastable equilibria in which they are involved, and a review to make this data accessible is
appropriate. The Fe-Ni phase diagram shows a paramagnetic face-centered cubic phase (gamma) with
well-measured properties over the entire composition range from 1184 to 1662 K. Its properties can be
extrapolated to lower temperatures, and known stable and metastable equilibria are used to establish
models for the thermodynamic properties of the ferromagnetic alpha phase, a high-temperature paramagnetic
alpha phase, a paramagnetic gamma-ordered Fe3Ni phase, the ferromagnetic disordered gamma phase,
and both ordered ferromagnetic gamma phases, tetrataenite, FeNi, and awaruite, FeNi3. The overestimate
of Chuang et al. for the entropy of ordering in awaruite is corrected. The standard enthalpies at 298.15 K
of tetrataenite (0.5 FeNi) and awaruite (0.25 FeNi3) are 1170 and 3560 1000 J mol1. The
corresponding standard entropy values are 35.7 and 33.3 3 J mol1 K1. All the second-order transitions
are accurately modeled and the full phase diagram is calculated. The spinodal regions and metastable
equilibria responsible for the complex behavior on cooling of alloys with mole fractions of nickel between
0.26 and 0.40 are described in detail.

I. INTRODUCTION
EQUILIBRIA in the Fe-Ni metallic phase are extremely
important in understanding the structure of iron and stony
iron meteorites.[1,2,3] Thus, some of the best data on the low-
temperature region of the Fe-Ni phase diagram was devel-
oped[1,2] in connection with accurate microprobe analysis
of meteorite sections, supplementing a calculated phase dia-
gram.[4] Iron and nickel are similar metals, and the high-
temperature Fe-Ni liquid and face-centered cubic (gamma)
crystalline phases are well described as subregular[4–7] solu-
tions. There is an astounding amount of data available[3,4,8,9]
There are similar equations for Se, Ge, and indeed for any
extensive thermodynamic quantity.
Table I gives the Redlich–Kister[10] coefficients for excess
enthalpy, He, and excess excess entropy, See, in consistent
units from that work,[5,6] Chuang et al. calculated phase dia-
gram,[4,11] and the current work. Power series cannot fit the
ideal entropy of mixing, so the Redlich–Kister equations for
entropy and Gibbs energy take the form
Se  See  n1*R*ln (X1)  n2*R*ln (X2) [2]
S  X1*X2*(A  B*(1 2*X1)
ee

on these phases (refer also to the references cited in
References 3, 4, 8, and 9.)
Below 1184 K, a body-centered cubic form is stable at
high iron concentrations, and at lower temperatures, order-
ing can occur within the face-centered cubic form. There
are four classes of sites in the face-centered cubic lattice
and, thus, three possible ordered A-B alloys. For the Fe-Ni
system, the three possibilities are Fe3Ni, FeNi, and FeNi3.
The last two are observed[3] in meteorites and are given the
names tetrataenite and awaruite, respectively. Reuter et al.[1]
proposed that tetrataenite is thermodynamically stable even
at room temperature, and these calculations show that it
has a region of stability in the phase diagram and just
narrowly misses stability at 298.15 K.
This system was selected as one edge of the first ternary
system I, which we attempted to model.[5,6] The excess
enthalpy of a solution, He, is defined as
He  (H  n1*H1o  n2*H20)/(n1  n2) [1]
REED A. HOWALD, formerly Professor, Department of Chemistry and
Biochemistry, Montana State University, Bozeman, MT, is retired. Contact
e-mail: howald@montana.edu
Manuscript submitted May 10, 2002.
 C*(1 2*X1)2  D*(1 2*X1)3) [3]
Gee  He  T*See  He  T*Se
 n1*R*T*ln (X1)  n2*R*T*ln (X2) [4]
Equations are available[12] for partial molal quantities using
the same Redlich–Kister coefficients. Calculations using the
coefficients are discussed further in Appendix A.
The best experimental data on both enthalpy and free
energy for the Fe-Ni system are for the liquid phase.
The values we are using for enthalpy for the liquid phase
are A  16,799.15 and B  10,820.27 J mol1, very
close to the values picked by Chuang et al.[4] Chuang’s[4]
choice for See does not fit the measured[13] activities at 1873
K accurately, so we did a least-squares fit of Gee at this
temperature, obtaining the entropy values A  2.439375
and B  2.531506 J mol1 K1. Then, for the gamma
phase, we picked Redlich–Kister values for enthalpy to fit
the selected values of Hultgren et al.,[8] and adjusted the
entropy values to get the minimum congruent melting point
at 1710 K. The resulting values shown in the bottom row
of Table I can be used to get the activities of iron and
nickel in the paramagnetic gamma phase at all tempera-
tures, even down to 400 K. Then, we can obtain data for
every other stable or metastable phase that can occur in

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equilibrium with the paramagnetic gamma phase at any
temperature and composition. The three studies cited in
Table I are in excellent agreement since a discrepancy of
1 J mol1 K1 in A or B corresponds to a discrepancy in
activity of 13 pct or less.
II. VALUES FOR PURE IRON AND NICKEL
Over the wide temperature range from 298.15 to 1873 K,
one cannot ignore the difference in heat capacity between
reactants and products. This is particularly true for iron,
where H for the transformation from body-centered to
face-centered cubic changes sign between the two equi-
librium points, 1184 and 1662 K. Thermodynamic data for
most of the pure iron phases were taken from an earlier
article,[14] but it was necessary to select values for ferro-
magnetic gamma iron and all the nickel phases at the start
of this work. These values are summarized in Table II
for iron and Table III for nickel. Polynomial power series
for heat capacity as used in these tables do not, and can-
not, accurately represent the large heat capacity values
found and projected as the lambda point is approached in
second-order magnetic and order-disorder transitions. Thus,
all calculated thermodynamic values within 50 K below
and 30 K above lambda points must be corrected using
the functions A( ) through E( ) given in the earlier arti-
cle.[14] Also, the points where G is calculated to be zero
lie 3.73 K below the corresponding lambda points. For
instance, both ferromagnetic and paramagnetic Ni are cal-
culated from Table III to have Gibbs energies of 22,633
J mol1 at 627.27 K, 3.73 K below the Curie temperature
of pure Ni, 631 K.

Table I. Redlich–Kister Coefficients for the Liquid and for

the Face-Centered Cubic Solid in the Fe – Ni System III. THE PARAMAGNETIC BODY-CENTERED
CUBIC PHASE
Enthalpy, Entropy,
J mol1 J mol1 Paramagnetic body-centered solids rich in iron are in
Reference A B A B
equilibrium with the paramagnetic face-centered gamma
alloys in two temperature regions, 1024 to 1184 K, and
Liquid again between 1662 and 1785 K. At 1785 K, the line tangent
Eliezer [5,6] 19,016 10,384 4.5516 2.4447 to the free energies vs mole fraction curves for the gamma
Chuang [11] 16,692 10,751 2.3998 3.5924 and liquid phases has intercepts near 157,770 and
This work 16,799 10,820 2.4394 2.5315 106,390 J mol1 K1, corresponding to activities for body-
centered cubic Ni and Fe of 0.0237 and 0.9624, respectively,
Gamma, fcc, paramagnetic, disordered
for a total near 1.0. Thus, the body-centered cubic phase
Eliezer [5,6] 16,334 10,598 3.9539 2.4137 has only small negative deviations from ideality, and
Chuang [11] 14,651 10,571 3.3266 2.3977 can be represented as a subregular solution with smaller
This work 15,663.1 11,893.8 2.707 3.12
Redlich–Kister parameters than are used for the gamma

Table II. Thermodynamic Properties of the Pure Iron Phases in SI Units

Element Fe Fe Fe Fe Fe Fe
Crystal form fcc fcc bcc bcc bcc liquid
Magnetism paramagnetic ferromagnetic paramagnetic paramagnetic ferromagnetic paramagnetic
T range, K 200 to 2000 200 to 2000 1040 to 2000 200 to 1040 200 to 2000 1000 to 2000
Property
S298* 35.487996 34.57 175.0488 33.0642215 27.280 30.737078
H298** 7778.385 7851.185 0.000 5049.063 0.000 10144.85
Cp, 298* 26.9945 26.45589 548.73977† 26.45589 24.9945 41.418524†
V‡ 6.83531 6.83531 7.18933 7.18933 7.09087 6.8511
V§ 0.52168 0.52168 0.060423 0.061423 0.30626 4.0642
V/B¶ 37.15 37.15 47.72 47.72 43.73 40.64
H**,† 0.0 0.0 129610.2‡ 0.0 0.0 2166.4‡
C# 8.4014 8.4014 1592.268‡ 8.4014 20.083058 1.6736‡
D 0.017411 0.01711 1842.0849 0.017411 42.611781 0.0
E 0.0 0.0 9.385334 0.0 1.690766 0.0
F 0.0 0.0 1.787555 0.0 2.1357377 0.0
Reference 14 this work 14 this work 14 14

*Units of J mol1 K1.

**Units of J mol1.
†Some of the heat capacity equations are not valid at 298.15 K, and can only be used in the appropriate temperature range specified.
In these cases, an additional parameter H is required, the difference between the enthalpy at 298.15 and the constant term for a
polynomial for H as a function of   T  298.15.
‡Units of cm3 mol1.
§Units of cm3 mol1 kK1.
¶Units of m3 mol1 GPa1.
#The power series in   T  298.15 for heat capacity is Cp  Cp,298.15  C*103  D*106 2  E*107 3  F*1010 4.

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Table III. Thermodynamic Properties of the Pure Nickel Phases in SI Units

Element Ni Ni Ni Ni Ni Ni
Crystal form fcc fcc fcc bcc bcc liquid
Magnetism ferromagnetic ferromagnetic paramagnetic paramagnetic ferromagnetic paramagnetic
Trange, K 200 to 631 631 to 2000 500 to 1200* 200 to 2000 200 to 2000 1000 to 2000
Property
S298** 29.874 28.617802 30.7495727 33.4192443 31.4 20.4803861
H298† 0.000 0.000 0.000 6992.526 7800.0 3471.869
Cp,298* 26.06189 25.918124 30.19135 26.067 26.067 43.095
H†‡ 0.0 917.816‡  672.330‡ 0.0 0.0 0.0
C§ 23.43574 8.11569 5.0 8.5 8.5 0.0
D 1.734106 0.0 0.0 0.0 0.0 0.0
*The heat capacity equation shown here for fcc paramagnetic nickel is valid only in the temperature range 500 to 1200 K. The
equation Cp  26.067  8.5*103  is used below 500 K, and Cp  30.19135  5*103  is used above 1200 K for this material.
**Units of J mol1K1.
†Units of J mol1.
‡Some of the heat capacity equations are not valid at 298.15 K, and can only be used in the appropriate temperature range specified.
In these cases, an additional parameter H may be required. The term H is the difference between the enthalpy at 298.15 and the
constant term for a polynomial for H as a function of   T  298.15.
§The power series in   T  298.15 for heat capacity is Cp  Cp,298.15  C*103  D*106 2

Table IV. Redlich–Kister Coefficients for the Paramagnetic Table V. Redlich–Kister Coefficients for the Ferromagnetic
Body-Centered Cubic Phase in the Iron-Nickel System Disordered Body-Centered Cubic Phase in the Iron-Nickel
(Nickel is Component 1) System (Nickel is Component 1)*

Quantity A B
He
J mol 1
2342.00 0.0
See J mol1 K1 5.29 0.0
G1785ee J mol1 7100.65 0.0
phase. The composition range observed is very narrow, and
we cannot fit two Redlich–Kister coefficients accurately.
Therefore, we are arbitrarily assigning B  0 at all
temperatures. A(Gee) for excess free energy at 1785 K is
7100 J mol1.
Similarly fitting the observed equilibria near 1020 K gives
an A(Gee) near 4000 J mol1. This allows us to fit both
enthalpy and entropy portions of the deviations from ideal-
ity, with A(H) near zero and A(See) near 4 J mol1 K1. This
is not the end of the story, however. To get the curie tem-
perature correct,[4,15] it was necessary to continue adjusting
the Redlich–Kister coefficients for both paramagnetic and
ferromagnetic body-centered cubic phases, eventually reach-
ing the values shown in Tables IV and V. The calculated
mole fractions of nickel for the three-phase equilibrium at
1785 K are 0.037, 0.044, and 0.050. The mole fractions for
equilibrium at 1020 K are near 0.026 and 0.060. These cal-
culations required great care not only in fitting the
Redlich–Kister coefficients, but in getting good values for
the reference phase of paramagnetic body-centered cubic
iron at temperatures below 1043 K.
The paramagnetic body-centered cubic phase for pure iron
is stable and has been well studied in two temperature
regions, 1043 to 1184 K and 1665 to 1809 K. Thus, it is
possible to get an accurate heat capacity equation that fits
the observed heat capacity in both regions and gives the
correct change in delta H between the observed transitions
at 1104 and 1665 K. However, if one tries to extrapolate
this heat capacity equation for temperatures below 1043 K,
one soon obtains nonsense, with a low-temperature region
of stability for the paramagnetic phase below the curie point.
Quantity A B C D
He J mol1 3793.0 8500.0 4500.0 0.0
See J mol1 K1 0.812 6.536 3.4 0.0
*This is the alpha iron phase. This phase is called kamacite
when small amounts of nickel are present and martensite when
it is supersaturated with nickel and formed from the face-
centered cubic phase on cooling.
However, to use Redlich–Kister coefficients for the para-
magnetic body-centered cubic phase, which is stable at
1024 K and 0.027 mole fraction of nickel, we need thermo-
dynamic values for both pure materials at this temperature.
One cannot do much better than guesswork for pure body-
centered cubic nickel at any temperature, and the guesses
for Table III are reasonable. For iron, it is necessary to
assume a reasonable heat capacity equation, estimated from
that for gamma iron, and adjust the enthalpy and entropy
terms so that the calculated values agree at 1040 K, the
arbitrary point selected for switching between polynomial
equations for the heat capacity in Table II.
With the choices for the references states in Tables II and
III, and the Redlich–Kister coefficients in Tables IV and
V, the paramagnetic and ferromagnetic body-centered cubic
phases at 1020 K have equal calculated free energies at a
mole fraction for nickel of 0.049. Thus, the alloy with this
composition is calculated to have a curie temperature of
1020  3.73  1023.73 K.
IV. THE FERROMAGNETIC BODY-CENTERED
CUBIC PHASE, ALPHA
Kaufman and Cohen[16] report the temperatures at which
the paramagnetic face-centered cubic phase, , and the
ferromagnetic body-centered cubic phase, , have equal
Gibbs energies for all compositions from X Ni between
0.095 and 0.33, temperatures from 876 to 312 K. Simply

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assuming that the values for the phase in Table I still
work at these lower temperatures gives us the Gibbs energy
for the  phase at 12 compositions and temperatures. From
this, we get good starting Redlich–Kister coefficients for
the  phase. While the deviations from ideality are not
large, it was still necessary to use three Redlich–Kister
coefficients to get an accurate fit over the entire compo-
sition range. And some further adjustments were neces-
sary to get the curie temperatures for the body-centered
cubic alloys calculated correctly, as shown previously. The
final values for the alpha iron phase (bcc, ferromagnetic,
disordered) are shown in Table V. Calculated points for
equal Gibbs energy for the  and phases are plotted in
Figure 1 along with Kaufman and Cohen[16] data points
for comparison.
At 1020 K, the gamma Fe-Ni alloy with XNi  0.062 is
in equilibrium with ferromagnetic body-centered iron with
XNi of about 0.026. At 1030 K, the equilibrium is with para-
magnetic body-centered cubic iron, and the mole fractions
are about 0.054 and 0.024. There may or may not be a pos-
sible three-phase equilibrium between these temperatures,
but it has not been observed experimentally and the point
is a minor one. It is much more interesting to examine the
magnetic transition in the gamma phase that occurs at lower
temperatures.
Fig. 1—Temperature at which the alpha and gamma phases have equal
Gibbs energy as a function of composition. The points cited in Kaufman
and Cohen[16] are plotted along with calculated temperatures for equal Gibbs
energy for the paramagnetic face-centered cubic disordered phase and the
ferromagnetic body-centered cubic phase, using Redlich–Kister coefficients
from Tables I and V.
V. THE FERROMAGNETIC DISORDERED
FACE-CENTERED CUBIC PHASE
Pure nickel has a curie temperature of 631 K, and the curie
temperature rises as iron is added up to a maximum of 885 K
at XNi  0.65. As the mole fraction of nickel is reduced fur-
ther, the curie point drops in temperature, and values below
400 K have been observed for alloys near XNi  0.31.[4,16] It
is fairly easy to find Redlich–Kister coefficients to make the
free energy curve for the ferromagnetic gamma phase tangent
to that for the paramagnetic gamma phase at XNi  0.65 and
881.27 K, 3.73 K below the curie point, but fitting the entire
graph of curie point vs composition was quite difficult. It is
true that H for the magnetic transition changes sign at high
iron content, since pure gamma iron is antiferromagnetic rather
than ferromagnetic. It was necessary to add two additional
Redlich–Kister coefficients to avoid a minimum negative
H near XNi  0.15. Trial and error adjusting of four
Redlich–Kister coefficients for enthalpy to match the Crangle
values[4,17] for the curie temperature was slow and difficult.
The final selected values are shown in Table VI.
Figure 2 shows a graph of the curie temperature vs the
mole fraction of nickel. The crosses represent the experi-
mental values,[17] the dashed parabola is the fit used by
Chuang et al.,[4] and the solid line shows our values calcu-
lated at 25 or 50 K intervals.
Figure 3 shows calculated H, TS, and G values
calculated in this work at 881.27 K. The value for H at
XNi  0.75 is  291 J mol1. The values do a very good
job of fitting the observed curie temperature, and of repre-
senting G  0 with zero slope at XNi  0.65. Beyond this,
the details of the free energy vs composition curve in Figure
3 are not significant. Similarly breaking G into H and TS
is only approximate. In fact, for a true second-order process,
H  0 at the lambda point. Delta H should be small, as it
simply represents the failure of polynomial heat capacity
expressions near the lambda point, and a value near
300 J mol1 is required to give the observed curvature for a
plot of Tcurie vs XNi in this region. It is very easy to make large
errors in estimating the enthalpy or entropy difference between
the paramagnetic and ferromagnetic states, and it is best to
compare enthalpies about 100 K apart. Thus, for the awaruite
composition, Fe.25 Ni.75, we have H900  H800  3364 J mol1,
of which most, about 3000 J mol1, is due to normal heat

Table VI. Redlich–Kister Coefficients for the Various Ordered Face-Centered Cubic Phases, Gamma, in the Iron-Nickel
System (Nickel is Component 1 in All Cases)

A B C D
Gamma prime, ferromagnetic disordered
He J mol1 15,935.0 10,000.0 1000.0 2584.0
See J mol1 K1 0.845 1.211 0.0 1.23
Awaruite, ferromagnetic ordered as FeNi3
He J mol1 12,875.6 41,568.0 8811.6 15,916.0
See J mol1 K1 2.373 18.533 12.562 16.957
Tetrataenite, ferromagnetic ordered as FeNi
He J mol1 20,380.6 6268.0 33,811.605 3084.0
See
J mol1 K1 9.264 5.259 24.113 1.23
Paramagnetic, ordered as Fe3Ni
He J mol1 5460.0 40,000.0 20,000.0 25,000.0
See J mol1 K1 12.406 3.892 17.338 12.208

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Fig. 2—A plot of the curie temperature of the face-centered cubic solid
phase vs mole fraction of Ni in the Fe-Ni system. The experimental points[17]
are shown along with the smooth calculated curve from this work. The
quadratic fit of Chuang et al.4 is shown as a dashed line.
Fig. 3—Calculated values for the enthalphy of magnetization, H 
Hferromagnetic Hparamagnetic, in J mol1, vs composition for the ferromag-
netic disordered face-centered cubic solid phase at 881.27 K. Values
for free energy, G, and  T*S are plotted as well as dashed lines.
These curves come directly from the Redlich–Kister coefficients and the
properties of the pure metals in Tables I, II, III, and VI.
capacity over 100 K, and only about 10 pct is due to the mag-
netic transition. Similarly, S900  S800  3.96 J mol1 K1.
A similar calculation with Chuang’s4 parameters gives
H900  H800  4138 J mol1 and S900  S800  4.93 J mol1
K1 for one mole of alloy at the awaruite composition. These
values are larger but still reasonable. Both treatments of the
magnetic transition appear satisfactory.
Another test of the Redlich–Kister coefficients in Table VI
is the calculation of the thermodynamic properties for the
awaruite composition, XNi  0.75, at 298.15 K. This gives the
values H°  1976 J mol1 and S298.15  35.4228 J mol1 K1
for the disordered but ferromagnetic phase. Awaruite itself has
slightly lower values for both of these quantities due to order-
ing of the iron atoms, and these values compare favorably
with our selected values for awaruite, H°  3560 J mol1
and S298.15  33.3 J. mol1 K1. The values for the disordered
and paramagnetic fcc alloy from the parameters in Table I
are H°  1664 J mol1 and S298.15  36.0 J mol1 K1. The
standard entropy for the disordered and ferromagnetic form
at XNi  0.75 must lie between these values, and the sequence
33.3, to 35.4, to 36.0 J mol1 K1 with increasing disorder is
entirely reasonable. All three of these entropy values have
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 4—Corrected Gibbs energy, G  26394.11*XFe  37,641.01*XNi, in
J mol1, vs mole fraction of Ni at 700 K for both paramagnetic (solid) and
ferromagnetic (dashed) alloys near XNi  0.46.
an uncertainty of about  3 J mol1 K1 due primarily to
the neglect of excess heat capacity of mixing terms in this
work. This could give changes in H and S of mixing in
the gamma phase with temperature, but the total change in
S is probably less than 3 J mol1 K1 even over the range
from 298 to 1700 K.
At 700 K, there are two composition regions (near 0.46
and 0.96 mole fractions of Ni) where the second-order
magnetic transition occurs. Figure 4 shows corrected
calculated Gibbs energies of both the paramagnetic and
ferromagnetic forms as functions of composition near
XNi  0.46. A correction to the Gibbs energy values is
necessary to keep the values on scale, and the Y coordi-
nate in Figure 3 is G  26,394.11*XFe  37,641.01*XNi.
The paramagnetic curve should be valid for all composi-
tions for which the curie point is below 670 K, i.e., XNi
0.443. Similarly, the ferromagnetic curve (dashed) is
valid for XNi 0.483. There must be a smooth transition
from one curve to the other at intermediate mole fractions.
Mathematical forms for expressing this transition have
been worked out,[14] and can be represented by the four
equations (from the earlier article[14]) with two mathe-
matical errors corrected:
 T  Tc [5]
(correction for G)  C*s E(u)  E (u) S/6.672607
*
[6]
E(u)  29.4628  5.30330087 u  0.10606617 u
* * 2
 0.0002357022*u3  1.333333333* (u)1.5 [7]
For 50 u 0
E(u)  4.56436  1.369306421*u  0.045643546*u2
 0.000169050172*u3  0.444444444* (u)1.5 [8]
For 0 u 30
Calculating the correction for G in this way, with the add-
itional approximation of evaluating S at 700 K instead
of at the calculated curie temperature, Tc, for each com-
position, gives the smooth curve in Figure 5. The resulting
single smooth curve for free energy vs mole fraction can
have two minima, as in this case. Here, the corrections to
G were chosen to place both minima near 0 J mol 1 ,
at mole fractions of 0.4531 and 0.4646. So for true
thermodynamic equilibrium at 700 K, one should have a
VOLUME 34A, SEPTEMBER 2003—1763
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ferromagnetic phase with XNi  0.4646 in equilibrium with
a paramagnetic phase slightly richer in iron, XNi  0.4531.
In between these compositions, there is a tiny spinodal
region, a region where G vs X has negative curvature and
in which separation into two phases with slightly differ-
ent compositions can be spontaneous. The effects of a spin-
odal region at 700 K may not be noticeable, but they can
and do become more important at lower temperatures and
lower mole fractions of Ni.
Chuang et al.[4] calculated a three-phase equilibrium for
the body-centered cubic alloy, paramagnetic face-centered
cubic, and ferromagnetic face-centered cubic at 662 K and
mole fractions of 0.065, 0.40, and 0.46. Our fit of the curie
temperature data is quite different from theirs near
XNi  0.43, so our calculations place this equilibrium at
a lower temperature, 633 K, and mole fractions of 0.081,
0.42, and 0.44. Hultgren et al.[8] shows this portion of
the phase diagram with dashed lines, so there are no solid
experimental data to favor either calculation. This could
very well be the eutectoid reported by Heumann and
Karsten [18] at 618 K. Wholly unrealistic thermody-
namic values are required for awaruite to place the body-
centered cubic, disordered ferromagnetic face-centered
cubic, awaruite equilibrium at 618 K as in Chuang et al.’s[4]
calculations.
VI. COMPARISON OF CALCULATIONS FOR
THE DISORDERED FERROMAGNETIC ALLOY
AT XNi  0.75 and 800 K
A good comparison of different treatments of the Fe-Ni
system is possible for the awaruite composition at 800 K. The
values for the enthalpy and entropy of 0.25 FeNi3 at 800 K
in this work are 12817 J mol1 and 64.2 J mol1 K1.
Larraine[9] gives data graphically, which convert to
12,100 J mol1 and 64.4 J mol1 K1, in excellent agreement.
Calculating with the mixing parameters of Chuang et al.[4] at
800 K and adding in their4 magnetic correction at this
temperature gives similar values 13,275 J mol1 and
64.3 J mol1 K1, well within reasonable error estimates. In
contrast, the equation for awaruite in the Chuang et al. art-
icle[4] gives  1150 J mol1 and 47.4 J mol1 K1, neither of
which is anywhere close to the values from the other studies.
Apparently, the Chuang et al.article[4] greatly overestimates
the entropy change on ordering in awaruite.
Fig. 5—The smooth double minimum calculated curve for corrected Gibbs
energy, G  26394.11*XFe  37,641.01*XNi, in J mol1, vs mole fraction
of Ni at 700 K for Fe-Ni alloys when the corrections for the second order.
1764—VOLUME 34A, SEPTEMBER 2003
VII. AWARUITE, THE ORDERED
FERROMAGNETIC FCC PHASE
When the XNi  0.75 phase is cooled to about 860 K,
it will transform to the ferromagnetic form with or with-
out a slight phase separation. On further cooling, a second-
order transformation occurs near 786 K as the ordered
FeNi3 awaruite phase is formed. Here, very careful near-
equilibrium studies are available[19] and measurable phase
separation occurs. Again, the awaruite phase must be mod-
eled over a range of compositions using Redlich–Kister
coefficients. The maximum equilibrium temperature for
the ordered phase occurs near 789 K and X Ni  0.73.
The Redlich–Kister coefficients in Table VI for awaruite
are selected to give a Gcorr vs X curve tangent to that for
the disordered ferromagnetic phase at X Ni  0.73 and
785.27 K (789  3.73). This required four Redlich–Kister
coefficients for both enthalpy and excess entropy, and both
entropy estimates and trial and error on enthalpy were
used in the fitting process. Once these fitting values are
obtained, one can calculate the thermodynamic proper-
ties of the ordered ferromagnetic face-centered cubic phase
(awaruite) at any temperature. Figure 6 shows the agree-
ment between the experimental[19] and calculated phase
diagram in the region of this order-disorder transition.
Figure 7 shows the calculated corrected Gibbs energies
at 298.15. The corrections (15,835.4 and 8257.4 J mol1)
were chosen to give tangents at Gcorr  0 for the thermo-
dynamically stable phases at room temperature, ferro-
magnetic body-centered cubic iron with XNi  0.043, and
awaruite (ferromagnetic ordered face-centered cubic) with
X Ni  0.67. Figure 7 also includes the curves for
paramagnetic disordered and ferromagnetic disordered
alloys from Table I and VI with minima at 718.3 and
576.6 J mol1, respectively. The other two curves in Fig-
ure 7 are estimates for the other two possible ordered
phases, FeNi and Fe3Ni.
Table VII summarizes the choices used for enthalpy,
entropy, and free energy at 298.15 K for the pure Fe and
Ni end points for curves such as those in Figure 7. Note
that this article uses a nonstandard convention for
free energy for which G is always H-TS, and the value for
pure alpha iron is 298.15*27.28 8133.54 J mol 1 .
Thus, the value for the corrected free energy of alpha iron
Fig. 6—Comparison between the calculated phase diagram near XNi  0.73
and 780 K and the experimental points of Van Deen and Van der Woude.[19]
A better fit of the experimental points requires a shift of the maximum
from XNi  0.73 and 789 K to near XNi  0.725 and 790 K. The change in
the thermodynamic properties for awaruite for this shift is negligible.
METALLURGICAL AND MATERIALS TRANSACTIONS A
02-247A-1.qxd 31/7/03 8:36 PM Page 1765

is 8133.54  8257.4  123.86. The two values for pure
face-centered cubic nickel are 8906.94 15835.4
 6926.46 and 8663.24  15835.4  7172.16 J mol1.
On this scale, the value plotted for stoichiometric awaruite
(435.37 J mol1 at XNi  0.75) corresponds to a free energy
of 13,540.7 J mol1, and the corresponding enthalpy and
entropy values for pure 0.25 FeNi 3 from Table VI are
3597.5 J mol1 and 33.3497 J mol1 K1. These val-
ues are also given in Table VII, rounded off, and similar
values are reported in Table VII for X Ni  0.25 and
0.50. Similar values can be calculated with earlier sets
of Redlich–Kister coefficients in the trial and error fit-
ting process, but they all fall within uncertainties of
1000 J mol 1 and 3 J mol 1 K 1 for enthalpy and
entropy, respectively, except that lower enthalpies by as
much as 3000 J mol1 were required for awaruite to get
it present in equilibrium with the alpha phase and the
ferromagnetic disordered phase at 618 K.
Chuang[4] reports 18,241.5  13.1714*T for the free
energy of formation of awaruite from gamma Fe and Ni.
Converting this to the alpha iron standard state as used here
gives G  21,695.2 J mol1, H  16,296.9 J mol1, and
S  18.1061 J mol1 K1 at 298.15 K, none of which is even
close to the values here. The free energy values are rea-
sonably close at high temperatures, but the division into
enthalpy and entropy values used by Chuang et al.[4] appears
to be unreasonable, as discussed previously. The entropy
of awarite cannot be significantly lower than the values for
face-centered cubic iron and nickel at 298.15 K, 35.488, and
29.874 J mol1 K1, respectively.

VIII. TETRATAENITE, THE ORDERED

Fig. 7—Corrected Gibbs energy (G  15,835.4*XFe  8257.4*XNi) at 298.15 K
in J mol1, vs mole fraction of Ni for six different solid forms. The corrections
are chosen to give tangents at 0 J mol1 for the body-centered ferromagnetic
alloys (at XNi  0.043) and awaruite ( at XNi  0.67). These are shown as
solid lines. The tetrataenite curve (long dashes) has a minimum of 204 J mol1.
The other three curves are for face-centered cubic phases. They are identi-
fied by their values at their minima, ferromagnetic disordered (solid) at
577 J mol1, paramagnetic disordered (dashed) at 718 J mol1, and para-
magnetic ordered as Fe3Ni (dashed) at 2025 J mol1.
FERROMAGNETIC FENI PHASE
It is possible that tetrataenite is thermodynamically stable
at 298.15 K, as suggested by Reuter et al.[1] Figure 7 shows
that this would require only a further lowering of the cor-
rected free energy of tetrataenite by 300 J mol1. However,
tetrataenite is observed only within the taenite phase,
particularly in the cloudy zone with average Ni content
between 0.25 and 0.41 mole fraction of Ni, and not at the
outer taenite rim in contact with kamacite, the stable
body-centered cubic phase. This indicates that the true
thermodynamic equilibrium at room temperature involves
the alpha and awaruite phases only as indicated in Figure 7,
and tetrataenite is merely metastable. This fixes the ther-
modynamic properties of tetrataenite quite closely, since
the tetrataenite curve in Figure 7 must cross 0.50 mole
fraction of Ni at a value between 50 and 750 J mol 1 .
The tetrataenite curve in Figure 7 is calculated with the

Table VII. Thermodynamic Values at 298.15 K Selected in This Work

H S G  H  TS Cp
Material Form (kJ mol1) (J mol1 K1) (kJ mol1) (J mol 1 K1)
Fe (c, bcc) ferromagnetic 0.000 27.280 8.133 24.994
Fe (c, bcc) paramagnetic 5.049 33.064 4.809 26.466
Fe (c, fcc) paramagnetic 7.778 35.488 2.802 26.994
Fe (c, fcc) antiferromagnetic 7.706 34.570 2.601 26.456
Fe (c, fcc) ferromagnetic 7.851 34.570 2.456 26.456
Ni (c, fcc) ferromagnetic 0.000 29.874 8.907 26.062
Ni (c, fcc) paramagnetic 0.591 31.038 8.663 26.067
Ni (c, bcc) paramagnetic 6.993 33.419 2.971 26.067
Ni (c, bcc) ferromagnetic 7.800 31.400 1.562 26.067
Fe.75Ni.25(c, fcc) paramagnetic, ordered 2.731 35.261 7.782 26.762
Fe.75Ni.25(c, fcc) paramagnetic, disordered 4.159 38.836 7.419 26.762
Fe.75Ni.25(c, bcc) ferromagnetic, disordered* 0.653 32.684 9.092 25.261
Fe.50Ni.50(c, fcc) ferromagnetic, ordered** 1.170 35.669 11.804 26.259
Fe.50Ni.50(c, fcc) ferromagnetic, disordered 0.058 37.774 11.320 26.259
Fe.50Ni.50(c, fcc) paramagnetic, disordered 0.269 38.349 11.165 26.266
Fe.25Ni.75(c, fcc) ferromagnetic ordered† 3.562 33.350 13.506 26.160
Fe.25Ni.75(c, fcc) ferromagnetic disordered 1.976 35.423 12.538 26.160
Fe.25Ni.75(c, fcc) paramagnetic, disordered 1.664 36.026 12.404 26.299
*Martensite at XNi  0.25.
**Tetrataenite.
†Awaruite.

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 34A, SEPTEMBER 2003—1765

02-247A-1.qxd 31/7/03 8:36 PM Page 1766
Table VIII. Calculated Stable Three-Phase Equilibria Involving Tetrataenite (Values Given are the Temperature, Three Mole
Fractions of Nickel, and Activities)
Face-Centered Cubic
T, K Phase Alpha Ferromagnetic
528 0.081 0.493*
517 — 0.542
392 0.0646 — 0.516
*This is probably not really a three-phase system, but there may be a single partially disordered tetrataenite in equilibrium with alpha
iron at 528 K.
Fig. 8—The Fe-Ni phase diagram as calculated in this work. The single-
phase regions are labeled, except for the small tetrataenite region, which
is marked with an asterisk (*).
Redlich–Kister coefficients in Table VI. Combining these
values with Table VII gives the properties of tetrataenite,
0.5 FeNi, as H  1169.6 J mol1, S  35.6692 J mol1 K1,
and G  11,804.3 J mol1. The entropy value is reasonable
in comparison with the values for awaruite, iron, and nickel
at 298.15 K, and the free energy is determined by a cor-
rected free energy curve that dips just a small amount below
the curves for the disordered face-centered cubic phases in
Figure 7, the two with minima at 576.7 and 718.3 J mol1 K1
at XNi  0.58.
The metastable equilibrium between the alpha phase and
tetrataenite at 298.15 K would involve mole fractions near
XNi  0.04 and 0.53, as indicated by a tangent to these two
curves in Figure 7. This equilibrium is apparently very dif-
ficult to achieve. The cloudy zone within the taenite region
of meteorites apparently[3] consists of an intimate mixture
of body-centered cubic crystals (martensite) with XNi  0.086
and tetrataenite at XNi  0.51. Martensite with XNi  0.086
is definitely supersaturated with nickel and not an equilib-
rium phase.
The order-disorder transition in stoichiometric tetrataenite
is reported[2,3,20] to occur at 593 K. The parameters in Table
VI place G  0 at 528 K for a lambda point at 528  3.73
 531.73 K, a much lower temperature. Using the higher
temperature makes tetrataenite too stable. Even with a lambda
point of 531.73 K, it is thermodynamically stable from 392 to
531 K. The calculated points for three-phase equilibria
involving tetrataenite are listed in Table VIII and illustrated
in the calculated equilibrium phase diagram (Figure 8). The
recognition that tetrataenite has a region of stability in the
equilibrium phase diagram is important, and was missed by
Chuang et al.[4] only because they assigned too much stability
to the awaruite phase.
1766—VOLUME 34A, SEPTEMBER 2003
Tetrataenite Awaruite aFe aNi
0.493* — 0.909 0.116
0.525 0.638 0.683 0.1513
0.650 0.9262 0.0944
Fig. 9—The calculated high Ni boundary of the alpha phase in the equi-
librium phase diagram compared to experimental data.[21–24]
IX. THE CALCULATED EQUILIBRIUM PHASE
DIAGRAM
It is important to check calculated phase diagrams by
a direct comparison to experimental data on phase equilibria
whenever possible. The only well-studied phase equilib-
rium in the iron-nickel system at intermediate temperatures
is that between  and , between the body-centered cubic
and face-centered cubic phases. There are a great many
reported values for the nickel content of the body-centered
cubic phase at different temperatures, and it is barely
possible and not very instructive to plot them all. Thus, we
have limited Figure 9 to four of the best experimental
studies[21–24] and the calculated values from this work.
There is excellent agreement between the calculated val-
ues and the 1965 and 1980 articles[21,22] above 850 K, and
it is not likely that the sharp maxima below 850 K in the
experimental articles represent true thermodynamic
equilibria.
Figure 10 shows a similar comparison for the composition
of the gamma phase in equilibrium with the body-centered
cubic phase. Here, good agreement with the recent experi-
mental[21,22] studies extends down to 700 K. This agreement
is very gratifying because the experimental data on these
compositions was not used in fitting the parameters for the
calculations.
The calculations at 517 K summarized in Table VIII show
awaruite XNi  0.638 in equilibrium with the ferromagnetic
disordered gamma phase with XNi  0.542. This is a some-
what surprisingly large concentration difference because all
of the other calculated pairs on both sides of the second-
order transitions in Figure 8 show much smaller concen-
tration differences, often too small to be seen in the figure.
This spread can be reduced, but only by making high iron
METALLURGICAL AND MATERIALS TRANSACTIONS A
02-247A-1.qxd 31/7/03 8:36 PM Page 1767
Fig. 10—The calculated composition of the gamma phase in equilibrium with
the alpha phase as a function of temperature compared to experimental data.[21–24]
awaruite more stable, and it is quite unlikely for awaruite
at XNi  0.55 to have nearly as much enthalpy of ordering
as at the stoichiometric composition, XNi  0.75. It appears
that this feature of the calculated phase diagram, a major
difference in composition between ordered and disordered
gamma phases on the iron-rich side of the awaruite bulge,
is probably present in the true equilibrium phase diagram
at these temperatures.
There are many possibilities for spinodal regions at
nickel mole fractions near 0.50 from the order-disorder
transition in tetrataenite, but phase separation is likely to
be slow at temperatures below 530 K; and, in fact, alloys
in this composition region are easily quenched to essen-
tially single-phase tetrataenite on cooling. It is the materials
with XNi between 0.25 and 0.40 that form the cloudy zone,
mixtures of martensite and tetrataenite, on cooling. Fig-
ure 2 shows that gamma phases in this composition range
will reach their curie point and possible spinodal phase
separation at temperatures between 300 and 570 K. This
is too wide a temperature range to expect similar behav-
ior on cooling if the phase separation is due only to the
magnetic transition, as suggested by Chuang.[4] It appears
that the order-disorder transitions in FeNi and Fe3Ni must
play a major role as well.
X. THE ORDER-DISORDER TRANSITION
IN Fe3Ni
Figure 11 shows corrected Gibbs energy at 385 K cal-
culated as a function of nickel content for body-centered
cubic alloys (which on this scale is a nearly vertical line
near XNi  0.31), and for four face-centered cubic alloys
identified in the caption of Figure 11. The line for
G corr  0 is tangent to two of the curves, indicating a
metastable equilibrium between tetrataenite at XNi  0.414
and paramagnetic ordered Fe3Ni at XNi  0.252. The para-
meters used in calculations for the paramagnetic ordered
phase are also given in Table VI.
Between the two compositions XNi  0.252 and 0.414, cal-
culations with these selected parameters show three small
spinodal regions in which phase separation could start
spontaneously. An alloy with XNi  0.31 will start to form
ferromagnetic regions on reaching 385 K and will try to reach
a metastable equilibrium at the tangent to the two upper
curves at XNi  0.27 and 0.33. However, XNi  0.27 lies in
another spinodal region and ordered Fe3Ni should form.
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 11—Corrected Gibbs energy (G  6797.85 XFe  24,215.27*XNi),
in J mol1, vs mole fraction of Ni at 385 K. The nearly vertical solid
line with XNi from 0.30 to 0.32 is for the body-centered cubic phase.
The two solid curves tangent to the x-axis are for paramagnetic ordered
fcc Fe3Ni and for tetrataenite. The dashed curve with a minimum of
50.8 J mol1 is for disordered paramagnetic fcc alloys, and the solid curve
with a minimum of 63.3 J mol1 is for disordered ferromagnetic fcc alloys.
A full calculation including all the second-order transitions would show
a smooth curve with spinodal regions connecting the lower portions of
the four fcc curves.
This will push the high Ni regions to still higher mole frac-
tions and into the third spinodal region, seeding tetrataenite.
If seed crystals are absent for both the body-centered cubic
phase and awaruite, one should be left with the same
metastable equilibrium at 385 K starting with any composi-
tion between XNi  0.252 and 0.414 in face-centered cubic
crystals. It is unlikely that this result could be reached from
the magnetic transition in these alloys alone; however, with
the additional order-disorder transitions centered at XNi values
of both 0.25 amd 0.50, it is quite reasonable.
On further cooling, the concentrations will shift but only
slightly, and the Fe3Ni ordered paramagnetic phase will
become less and less stable compared to a ferromagnetic
body-centered phase of the same composition, martensite.
Kaufman and Cohen [16] have studied the formation of
martensite by shear deformation of face-centered cubic
alloys over a wide range of temperatures and composi-
tions, and the crystals with XNi  0.252 are expected to
convert to martensite near 350 K. In this way, we can
understand the formation of the cloudy zone within the
taenite layers of meteorites over almost exactly this range
of nickel content.
XI. EXAMPLE: COOLING AN ALLOY
WITH XNI  0.38
At a temperature of 1200 K, the stable form of all iron-
nickel alloys is a paramagnetic face-centered cubic solid. The
XNi  0.38 alloy will stay in this single-phase region down
to 675 K. At all temperatures below 675 K, it is supersatu-
rated with respect to an iron-rich body-centered cubic phase;
however, if the new phase is not seeded, it will cool further
as a metastable single face-centered cubic phase. Figure 2
shows that the curie temperature for this composition is near
525 K, and it will pass through a spinodal region; there will
be some phase separation during the paramagnetic to ferro-
magnetic transition. However, by 515 K, the alloy should
be back to pure ferromagnetic face-centered cubic crystals
with a uniform composition of XNi  0.38. At 410 K, the
VOLUME 34A, SEPTEMBER 2003—1767
02-247A-1.qxd 31/7/03 8:36 PM Page 1768
ordered ferromagnetic form, tetrataenite, will start to form at
equilibrium, but by 400 K, it will have entered a spinodal
region for this transition, and phase separation will start
spontaneously. It should proceed almost to the metastable
equilibrium of disordered ferromagnetic crystals with
XNi  0.34 and tetrataenite with XNi  0.40. Figure 11 shows
that this metastable two-phase region will widen as the tem-
perature drops approaching XNi  0.31 and 0.41 at 385 K.
However, the XNi  0.31 ferromagnetic crystals are not sta-
ble with respect to magnetic disorder. At a little above 385 K,
the low nickel regions will hit a spinodal region and spon-
taneously form paramagnetic regions, which will transfer
nickel to the tetrataenite. However, this will push the low
nickel regions into a third spinodal region, and ordered para-
magnetic Fe3Ni will start to form. Thus, this composition
should reach a metastable equilibrium of Fe3Ni with XNi 
0.252 and tetrataenite with XNi  0.414 at 385 K. Then, on
further cooling, the Fe3Ni phase will undergo the martensitic
transition giving a body-centered cubic form supersaturated
with nickel at about 350 K. Presumably, the outermost lay-
ers of the bcc and tetrataenite crystals will come close to
the metastable equilibrium compositions, 0.06 and 0.53 at
350 K, but there are no substantial regions with these
compositions near each other in even the slowest cooled
meteorites.
XII. SUMMARY
The thermodynamic properties of gamma paramagnetic
iron nickel alloys are well known at high temperatures over
the entire composition range from pure iron to pure nickel.
Extrapolating these values to lower temperatures assuming
the H of mixing curve is independent of temperature allows
one to accurately assign thermodynamic values to the phases
with which it is known to be in equilibrium, the ferromag-
netic face-centered cubic phase, and body-centered cubic
phases, both paramagnetic and ferromagnetic. This, in turn,
allows one to obtain thermodynamic values for even the
lower temperature ordered phases awaruite and tetrataenite,
FeNi. Tetrataenite has a region of stability in the equilib-
rium phase diagram (Figure 8). Thermodynamic values for
tetra-taenite at 298.15 are reported here for the first time,
and substantially improved values are reported for awaruite,
FeNi3. The behavior of iron-nickel alloys on cooling is
discussed and related to observations on iron and stony iron
meteorites.
APPENDIX A
Spreadsheet calculations for binary systems
The enthalpy of the paramagnetic face-centered cubic
phase at a particular temperature is given by an equation
with four parameters:
H  XNi* H oNi  (1  XNi)*H oFe  A*XNi*(1  XNi)
 B*XNi*(1  XNi)*(1  2*XNi) [9]
The two standard enthalpies, H oNi and H oFe, are strongly tem-
perature dependent, but the Redlich–Kister coefficients A and
B can be used over a wide temperature range. However, for
other solid phases in the Fe-Ni system, a cubic in X is not
adequate to represent the concentration dependence of the
1768—VOLUME 34A, SEPTEMBER 2003
enthalpy. Thus, for tetrataenite, we have four Redlich–Kister
coefficients:
H  He  XNi*HNi 
 (1  XNi)*HFe 
[10]
He  XNi*(1  XNi)[A  B*(1  2*XNi)
 C*(1  2*XNi)2  D*(1  2*XNi)3 ] [11]
or
He/(XNi*XFe)  A  B*(XNi  XFe)
 C*(XNi  XFe)2  D*(XNi  XFe)3 [12]
The additional terms are necessary to express the increased
upward curvature, which must be present near the Gibbs
energy minimum of an ordered phase so that it is stable over
a smaller concentration range than the disordered phase at
each temperature. It is easy to make errors in calculating
and adding four terms, and the equation for He can be con-
fused with similar equations for the partial molal
enthalpies.[12] But one of the beauties of doing a calcula-
tion in a modern spreadsheet is that once it is correct for
one line for one value of XNi, it can be copied for any num-
ber of concentrations and the results are easily plotted. The
equations for entropy are similar, but with the addition of
an ideal entropy of mixing term:

S  Se  XNi*SNi 
 (1  XNi)*SFe [13]
S  S  R*[XNi*ln(XNi)
ee

 (1  XNi)*ln(1  XNi)]  XNi*SNi 
 (1  XNi)*SFe [14]
See  XNi*(1  XNi)[A  B*(1  2*XNi)
 C*(1  2*XNi)2  D*(1  2*XNi)3] [15]
Note that this requires the additional symbol, See, which can
be described as the excess excess entropy.
The Gibbs energy is given by equations of the form
G  H  T*S [16]
Ge  He  T*Se [17]
G  H  T*S
ee ee ee
[18]
Alternatively, Redlich–Kister coefficients for Gee can be
calculated from those for enthalpy and entropy. For the third
coefficient, C, this takes the form
CG  CH  T*CS [19]
Either way the Gibbs energy per mole at one temperature
can be calculated for each phase at 101 mole fractions and
the results plotted as in Figure 12. This shows the values
for four face-centered cubic phases at 500 K: paramagnetic
disordered, ferromagnetic disordered, tetrataenite, and
awaruite. Note that all three curves for ferromagnetic phases
have the same endpoints, GoFe and GoNi. There are five
different values for GoFe at 500 K, which can be calculated
from the values in Table II. The least negative one is
10,962 J mol1, for the least stable solid, ferromagnetic
face-centered cubic iron. This is the starting point for three
of the four curves in Figure 12, each of which uses four
Redlich–Kister coefficients (Table VI). Four are required
for the ferromagnetic disordered phase to get reasonable
behavior over the entire concentration range. The awaruite
and tetrataenite curves need to be accurate only over limited
concentration ranges centered on mole fractions of 0.75 and
0.50, respectively, but it still takes four coefficients to give
METALLURGICAL AND MATERIALS TRANSACTIONS A
02-247A-1.qxd 31/7/03 8:36 PM Page 1769
Fig. 12—Gibbs energy at 500 K in J mol1 for four face-centered cubic
phases in the Fe-Ni system. Curves are shown over the entire concentra-
tion range for the disordered paramagnetic phase, the disordered ferro-
magnetic phase, tetrataenite, and awaruite. The values at XNi  0.50 are
20,488.6, 20,423.2, 20,547.6, and 19,532.7 J mol1, respectively.
To further distinguish the lines, the curves for tetrataenite and for the dis-
ordered paramagnetic phase are shown dashed.
the correct values, slopes, and curvatures in these limited
concentration ranges.
A spreadsheet or other computer program is almost essen-
tial for keeping all the different parameters straight, but it
is easy to check the computer calculations by hand, espe-
cially at XNi  0.50. We start at G  0.50* GoFe  0.50*
GoNi  (10,962 16,496)/2  13,729 J mol1. Putting
in the ideal entropy of mixing lowers this by R*T*ln (0.50)
to 16,610 J mol 1 . At this composition, the quantity
(1 2* XNi) is 0, so only the A term has any contri-
bution, and that is given by 0.25*AG  0.25*(AH  T*AS),
or 3878, 2922, and 3937 J mol1, with the last and
most negative being for tetrataenite.
The temperature chosen for Figure 12, 500 K, is close to
the lambda temperature for the tetrataenite order-disorder
transition, and, in fact, the lambda temperature is 503.73 K
for the two points where the tetrataenite and disordered curves
intersect, at about XNi  0.439 and 0.547. Thus, for the highest
accuracy, additional corrections of E( )*S/6.672607 from
Eq. [2] should be applied to these two curves in this compo-
sition range. However, these corrections will be less than 10
J mol1, and not visible on the scale of Figure 12.
One can find equilibrium concentrations by finding lines
tangent simultaneously to two free energy curves like those
in Figure 12. Again, the scale in Figure 12 makes this
METALLURGICAL AND MATERIALS TRANSACTIONS A
inaccurate, but it is a simple matter to correct the calculated
values near the points of tangency with two adjustable constants,
and plot Gcorr  G  C1*XNi  C2*XFe vs mole fraction. This
was done to obtain accurate points of tangency for Figure 8.
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