May 2000

Materials Letters 43 2000. 225229

www.elsevier.comrlocatermatlet

An effect of high magnetic field on phase transformation

in FeC system
H.D. Joo ) , S.U. Kim, N.S. Shin, Y.M. Koo
Center for Aerospace Materials, Pohang Uniersity of Science and Technology, Pohang 790-784, South Korea
Received 11 June 1999; accepted 5 October 1999

Abstract
The effect of a magnetic field on the Gibbs free energy of a material depends on its magnetization behaviors. To
investigate the change in the FeFe 3 C phase diagram caused by a high external magnetic field, the magnetic Gibbs free
energies of the phases austenite, ferrite, and cementite are calculated on the basis of the molecular field theory. Using the
calculated Gibbs free energy as a function of weight percentage carbon and temperature at a particular magnetic field, a
phase diagram of the FeFe 3 C system is drawn. The phase diagram is shifted upwards so that the Ac 1 and Ac 3 temperatures
increase as the magnetic field is applied, but the Ac m temperature change is almost independent of applied magnetic field
value. The increase of eutectoid temperature and composition and its application to microstructural control are discussed.
q 2000 Elsevier Science B.V. All rights reserved.
PACS: 75.20.H; 75.50B; 81.30B
Keywords: Molecular field theory; FeC system; Phase diagram; High magnetic field

1. Introduction
Magnetic field is one of the important external
physical quantities that affect properties of materials.
In recent years, development of instruments producing magnetic fields as high as 100 kOe in considerable volume enables one to research various properties in materials. Many studies have been carried out
on the effect of magnetic field on phase transformation in various ferrous alloys w1,2x. However, these
studies are not about the gra transformation, but the
martensitic transformation. Since discontinuity of
magnetic susceptibility between the g and a phases
)

Corresponding author.

exists at the transformation temperature, an external

magnetic field causes a difference in their Gibbs free
energies, namely, it causes the phase diagram to
change. In addition, it is supposed that high magnetic
field may affect grain refinement, and studies are in
progress. The calculations associated with the change
of phase diagram are very important because they
can be applied to control microstructure and mechanical properties from the viewpoint of kinetics as well
as thermodynamics.
In the present study, the Gibbs free energy change
of each phase in steel is determined on the basis of
molecular field theory when high magnetic field is
applied. The change of the FeFe 3 C phase diagram
by applied magnetic field is determined.

00167-577Xr00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 1 6 7 - 5 7 7 X 9 9 . 0 0 2 6 3 - 3

226

H.D. Joo et al.r Materials Letters 43 (2000) 225229

2. Theory
2.1. Magnetic moments of phases in FeC system
There are at least two divergent viewpoints in the
ferromagnetic model w3,4x. One is the Weiss model,
which is applicable to electrons that are localized
within the positive ions forming the lattice. The other
is the collective electron model, which deals with
almost free itinerant electrons. Although both theories have merits and demerits for describing the
magnetic properties of ferromagnetic materials, the
current consensus is that the collective electron model
is intrinsically closer to reality in most cases, but it
does not provide any simple model from which first
principle calculations can be made. Because of this
drawback, interpretations of magnetic properties are
still more often made on the basis of the Weiss
model w4x. Therefore, the theory of ferromagnetism
in steel is developed on basis of the Weiss model.
In order to calculate the Gibbs free energy change
induced by the applied magnetic field, determination
of the magnetization vs. temperature diagram is the
first consideration. For the calculation of the magnetic moment in ferrite, we use the molecular field
theory w3x. Although disagreement of the magnetic
moment per atom, m H , between paramagnetic and
ferromagnetic regions exists, it is assumed that the
magnetic moment per atom in the ferromagnetic
region, m H s 2.219m B , is valid in the whole temper-

Fig. 1. The relative magnetization of pure iron calculated from

molecular field theory as a function of temperature and applied
magnetic field.

Fig. 2. Magnetization and inverse susceptibility curves below and

above the Curie temperature of ferrite: a. is the relative magnetization when applied magnetic field is zero, b., c., d. and e. are
susceptibility data; b. is from the CurieWeiss equation fitted
from other data w6x, c., d. and e. are experimental data w5,7x.

ature range and all data for pure iron can be applied
to the FeC system. Because the paramagnetic susceptibility of ferrite satisfies the CurieWeiss law
only above 1150 K, the paramagnetic m H s 1.82 m B
derived from the Curie constant cannot be used for
ferrite in most temperature ranges and it may be
more reasonable to use the ferromagnetic m H w5x. A
mapping of the MHT surface is calculated and it
is shown in Fig 1. This curve corresponds to the
shape of an experimental curve, such as reported by
Gorodestsky et al. w6x, for the weak ferromagnet
YFeO 3 .
The Gibbs free energy of the paramagnetic region
can be determined by the susceptibility x , which is
the ratio of the induced magnetization to the inducing field and roughly follows the CurieWeiss law.
The paramagnetic susceptibilities of g and a phases
have been measured by Arajs and Miller w7x. Their
susceptibility data also satisfy the CurieWeiss law
and the susceptibility can be determined by fitting
the susceptibility data to the CurieWeiss equation.
1.23
w emu moly1 Oey1 x
xa s
1.
T y 1093
7.31
w emu moly1 Oey1 x
xg s
2.
T q 3370
where xa and xg are the magnetic susceptibilities
for a-Fe and g-Fe, respectively. It is known that the

H.D. Joo et al.r Materials Letters 43 (2000) 225229

Neel temperature of g-Fe is 44 K w8x, but Eq. 2. is

appropriate for describing the paramagnetic susceptibility of g-Fe in this temperature region. Fig. 2
shows the magnetization and inverse susceptibility
curve below and above the Curie temperature drawn
from the experimental data of Refs. w5,7,8x.
Next, the susceptibility of cementite, Fe 3 C, must
be determined. Cementite is ferromagnetic like a-Fe.
Cementite satisfies the CurieWeiss relation, which
is given by Eq. 3. w9x.
1.95
w emu moly1 Oey1 x
x Fe 3 C s
3.
T y 506
where x Fe 3 C is the magnetic susceptibility for Fe 3 C.
This has been measured below 575 K, but we assume that the equation holds at high temperatures up
to 1400 K.
2.2. Gibbs free energy change by magnetic field
When magnetic field is applied, the resulting free
energy changes are classified into two terms; the
thermal Gibbs free energy, G T T, X ., and the magnetic Gibbs free energy, DG M T, H ..
Gtotal T , X . s G T T , X . q DG M T , H .

4.

The thermal Gibbs free energies of austenite and

ferrite are derived on the basis of the KRC model by
Shiflet et al. w10x.

qX

DHcg y TDS X S ,g

q 1 y X . RT

=ln

y0.00173T 2
DG aM T ,12T . s 5.18

X
1 y X 14 y 12exp yWgrRT

figurational entropy of solution in austenite, respectively. We take Wg s 5880 J moly1 , DHcg s 444 000
J moly1 and DS X S ,g s 17.2 J moly1 Ky1 from
Shiflet et al. w10x. G aFe T . can be obtained from
SGTE DATA w11x.
The magnetic Gibbs free energy, DG M T, H ., can
be written in terms of an extensive variable, M, and
an intensive variable, H.
dG M T , H . s Hd M
7.
Generally, the paramagnetic Gibbs free energy
change by a magnetic field is given by
1
para
DG M
T ,H . sy x H 2.
8.
2
Since the magnetic moment of ferrite is not linear
and the magnetic susceptibilities from the Curie
Weiss equation disagree with experimental data at
near the Curie point in Figs. 1 and 2, it is more
reasonable to use the magnetization determined by
the Weiss theory rather than the susceptibility to
calculate the Gibbs free energy of ferrite. Integration
of Eq. 7. from the previous MH curves in Fig. 1 is
carried out at each temperature to yield the magnetic
Gibbs free energy of ferrite as a function of applied
magnetic field. These are fitted as functions of temperature at the magnetic fields of 120, 200 and 500
kOe, and are described by Eqs. 9. 11., respectively.
DG aM T ,12T . sy1200q3.00T

G gT T , X . s 1 y X . G gFe T .
qRTX ln

227

at T -1043 K
T y1045

q36.1exp y
67.3

at T )1043 K

9.
1

DG aM T ,20T . sy1200q3.28T

13 y 12exp yWgrRT

1 y X 14 y 12exp yWgrRT

1yX
G aT T , X . s 1 y X . G aFe T .

y0.00197T 2

5.

T y1045
q69.3exp y
88.7

at T )1043 K

10 .

q X 112 000 y 51.4T . RT X ln X

q 1 y X . ln 1 y X .

at T -1043 K

DG aM T ,20T . s11.5

DG aM T ,50T . sy890q3.64T

6.

where X is the mole fraction of carbon, G aFe T . and

G gFe T . are the Gibbs free energies of pure a-Fe and
g-Fe at temperature T, and DHcg, DS X S ,g are the
partial molar enthalpy and the partial molar noncon-

y0.00243T 2

at T -1043 K

DG aM T ,50T . s 39.1

.
T y1045

q227exp y
162

at T )1043 K

11 .

H.D. Joo et al.r Materials Letters 43 (2000) 225229

228

particular magnetic field in pure iron. Since Ac 1 is

equal to Ac 3 in pure iron, the temperature at which
g a
DGtotal
T, H . s 0 is simply determined as the transformation temperature, which increases 10 K at 120
kOe.
3. Results and discussions

Fig. 3. The Gibbs free energy difference between g and a phase

of pure iron as a function of temperature for various magnetic
fields.

Eq. 8. may also be applied to the magnetic Gibbs

free energy change of austenite as the Neel temperature of austenite is very low.
In contrast to ferrite and austenite, the thermal
Gibbs free energy of cementite is difficult to calculate. Thus, the thermal Gibbs free energy is calculated reversely from the experimental phase diagram
of the FeC system. This method is quite simple
because the cementite austenite equilibrium temperature, Ac m , in the phase diagram is almost a straight
line and the composition of cementite is constant.
The thermal Gibbs free energy of cementite determined in this way is given as follows.
3C T
G Fe
. s 16 700 y 43.4T
T

The Gibbs free energy calculated in the previous

section is used to determine the change of the gra
phase diagram. Fig. 4 shows the phase diagram
associated with the gra and grFe 3 C transformations as a function of weight percentage carbon. Ac 3
increases as magnetic field is applied, but the Ac m
temperature hardly moves so that both the eutectic
temperature and composition increase. Eutectoid
temperature, eutectoid composition and the gra
transformation temperature are determined from Fig.
4, which is summarized in Table 1.
Considering kinetics, the change of phase transformation temperature can be affected by many factors such as heatingrcooling rates and strain energy
per unit volume. The Ac 3 temperatures have been
measured at various heating rates by Abiko and
Sadamori w12x. As the heating rate is increased from
1 to 20 to 50 Krs, the Ac 3 temperature increases
from 1180 to 1187 to 1198 K, respectively. The
increase in the Ac 3 temperature at a heating rate of
50 Krs is similar to the change of transformation
temperature at 120 kOe. Also, the strain energy due
to dislocation accumulation causes a metastable phase

12 .

Thus, the magnetic Gibbs free energy of cementite

can be evaluated from Eq. 8. because it is formed at
a much higher temperature than its Curie temperature.
The Gibbs free energy change of the gra transformation in pure iron is given as follows.
g a
DGtotal
T,H .

s DG gT a T , H . y G aM T , H . y

1
2

xg H 2

/
13 .

Fig. 3 shows the Gibbs free energy change of the

gra transformation vs. temperature diagram at a

Fig. 4. FeC phase diagram associated with the gra and grFe 3 C
transformation for various applied magnetic fields.

H.D. Joo et al.r Materials Letters 43 (2000) 225229

229

Table 1
Eutectoid temperature, eutectoid composition and the gra transformation temperature determined from the calculated phase diagram
Applied magnetic field
T.
Calculated data

0
12
20
50

Eutectoid composition
wt.%.

Eutectoid temperature
8K.

gra Transformation
temperature in pure iron
8K.

0.76
0.795
0.818
0.914

1000
1012
1019
1051

1184
1194
1209
1306

transformation w13x. These factors have been widely

used for controlling microstructure. For example,
accelerated cooling and recrystallization-controlled
rolling are applied to grain refinement. Similarly, the
change of transformation temperature by high magnetic field can be applied to microstructural control.
Dynamical applications such as imposing magnetic
cycles at a particular temperature gives additional
driving force for phase transformation; therefore, it
can be applied to microstructural control, too.
In addition, the possibility of improving mechanical properties may be realized from the eutectoid
composition shift. Increased carbon content is associated with strengthening and hardening, but hypereutectoid primary cementite decreases ductility. Since
external magnetic field enables us to increase carbon
content without hypereutectoid transformation, it may
improve mechanical properties. Tensile strength increases by 6% and Brinell hardness and yield strength
also increase without producing primary cementite
when a 120-kOe magnetic field is applied w14x.

Acknowledgements
This work was supported by Pohang Steel and the
Ministry of Commerce, Industry and Energy of the

Republic of Korea, and the authors wish to express

appreciation for the financial support.

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