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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.
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
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-
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
4.
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 .
at T -1043 K
DG aM T ,20T . s11.5
DG aM T ,50T . sy890q3.64T
6.
y0.00243T 2
at T -1043 K
DG aM T ,50T . s 39.1
.
T y1045
q227exp y
162
at T )1043 K
11 .
228
12 .
s DG gT a T , H . y G aM T , H . y
1
2
xg H 2
/
13 .
Fig. 4. FeC phase diagram associated with the gra and grFe 3 C
transformation for various applied magnetic fields.
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
Acknowledgements
This work was supported by Pohang Steel and the
Ministry of Commerce, Industry and Energy of the
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