Eect of High Magnetic Field on Phase Transformation Temperature

in Fe-C Alloys
*
Xin Jiang Hao and Hideyuki Ohtsuka
Tsukuba Magnet Laboratory, National Institute for Materials Science, Tsukuba 305-0003, Japan
Magnetic eld can aect the transformation temperature and microstructure if a transformed phase has dierent susceptibility with parent
phase. Fe-C alloy is an ideal system to show the magnetic eld eect since in this system, austenite (fcc structure) is a paramagnetic phase and
ferrite (bcc structure) is a ferromagnetic phase below 770

C. In this paper, phase transformation temperature in Fe-C alloys in a magnetic eld

was measured from cooling curve. It was found that the transformation temperature for pure Fe from austenite to ferrite has a linear relationship
with magnetic eld strength, increasing about 0.8

C per unit of magnetic eld of 1 T. For eutectoid transformation in Fe-0.8C alloy, similar
relationship exists, the transformation temperature increases about 1.5

C per unit of magnetic eld of 1 T. Experimental results do not agree well

with that calculated by molecular eld theory. An elongated and aligned microstructure by transformation in a high magnetic eld was found in
an Fe-0.4C alloy, but was not found in pure Fe and Fe-0.8C alloy.
(Received April 26, 2004; Accepted June 17, 2004)
Keywords: ferrite transformation, pearlite transformation, transformation temperature, iron-carbon alloys, high magnetic eld, molecular
eld theory
1. Introduction
Magnetic eld aects the transformation temperature and
microstructure if a transformed phase has dierent suscepti-
bility with parent phase. Fe-C alloy is an ideal system to show
the magnetic eld eect since in this system, austenite (fcc
structure) is a paramagnetic phase and ferrite (bcc structure)
is a ferromagnetic phase below Curie temperature (T
c
,
770

C). Elongated and aligned microstructures formed by

solid/solid transformations in a high magnetic eld have
been reported by ferrite transformation
15)
and reverse
transformation from martensite.
6,7)
Kakeshita et al.
8)
have
investigated the eects of magnetic eld on martensite
transformation temperature (M
s
) in several Fe-based alloys
and found that M
s
increases in a high magnetic eld.
However, for transformation at high temperature, such as
ferrite transformation and pearlite transformation, no exper-
imental data directly show the eect of magnetic eld on
transformation temperature. Recently, equilibrium phase
diagram of Fe-C binary system has been thermodynamically
calculated based on molecular eld theory (MFT) and it was
proposed that a high magnetic eld increases the
austenite(,)/ferrite(o) equilibrium temperature, carbon sol-
ubility in o phase and eutectoid carbon content.
9,10)
In this
paper, we reported our experimental works on the eect of
magnetic eld on phase transformation temperature and
microstructure in Fe-C alloys and compared with the results
of theoretical calculation.
2. Experiments
The alloys used in the present study were Fe-0.8C alloy
prepared by vacuum induction melting and high purity Fe
(99.99%). After cold rolling specimens were machined to
5 mm5 mm1 mm, and then set in a vacuum furnace,
which was installed in a helium-free type superconducting
magnet with a bore size of 100 mm. A magnetic eld
perpendicular to the 5 mm5 mm specimens surface was
increased to 10 T in 27 min before austenitization and kept
constant during austenitization and subsequent cooling, and
then decreased to 0 T. Specimens were xed at the center of
magnetic eld and the magnetic force to the specimen is
negligible. Specimens were austenitized at 1000

C for
15 min and cooled to 600

C at a cooling rate of 10

C/min.
The specimen temperature was measured by a thermocouple
contacted with the specimen and recorded by a digital
recorder. Since the temperature controller has some delay to
control the sample temperature to programmed set value if
the sample temperature changes suddenly due to trans-
formation heat, it is possible to nd a peak in the cooling
curve. The phase transformation temperature was determined
by this peak. Microstructure observation was performed on
the plane parallel to the direction of magnetic eld by optical
microscope after polishing and 3% Nital etching.
3. Results and Discussions
Figure 1(a) shows the cooling curve segments of pure Fe
during transformation in magnetic elds. Without magnetic
eld, it was found that the transformation temperature of pure
Fe from austenite to ferrite is about 906.2

C, which is about
6

C lower than the equilibrium temperature (912

C). This
dierence was known as supercooling and it provides the
chemical driving force for transformation. With increasing
magnetic eld strength, the transformation temperature also
increases gradually. With a maximum magnetic eld of 10 T,
the transformation temperature is about 914.9

C, which is
8.7

C higher than that without magnetic eld. The increased

temperature (T TH T0), the transformation tem-
perature dierence between with (TH) and without (T0) a
magnetic eld (H) was plotted against magnetic eld strength
in Fig. 1(b). It was shown that the transformation temperature
increases linearly with magnetic eld strength. The trans-
*
This Paper was Presented at the Spring Meeting of the Japan Institute of
Metals, held in Tokyo on March 31, 2004
Materials Transactions, Vol. 45, No. 8 (2004) pp. 2622 to 2625
#2004 The Japan Institute of Metals
formation temperature increases about 0.8

C with increasing
magnetic eld strength of 1 T.
Figure 2(a) shows the cooling curve segments of Fe-0.8C
alloy during pearlite transformation in magnetic elds. The
measured eutectoid transformation temperature is 704.9

C
without magnetic eld. The equilibrium eutectoid trans-
formation temperature is 727

C. A larger supercooling
(about 22

C) was shown compared with that ferrite trans-

formation in pure Fe. This is possible due to eutectoid
transformation needs alloying elements redistribution in
ferrite and cementite, and to that transformation temperature
is relatively lower. With magnetic eld, the transformation
temperature increases gradually. With a magnetic eld of
10 T, it increases to about 720.1

C, which is about 15

C
higher than that without magnetic eld. Figure 2(b) shows the
relationship between T and magnetic eld strength. Same
as the ferrite transformation, they have a linear relationship.
The T is about 1.5

C with increasing magnetic eld

strength of 1 T. It is surprising that T for pure Fe is more
than half of that for eutectoid transformation, if we remember
that ferrite is in paramagnetic state at ferrite transformation
temperature, whereas it is in ferromagnetic state for eutectoid
transformation.
Generally it was believed that the Gibbs free energy of
ferrite phase decreases in an external magnetic eld and it
induces ferrite transformation temperature rising. If we
assume that the magnetic energy has a similar eect on
phase transformation as that of chemical driving force, it is
possible to measure the magnetic energy from the trans-
formation temperature since that the chemical driving force
changes with temperature can be obtained from well
established thermodynamic data. The magnetic energy can
be measured by the following equation,

M
G
m
G
m
T
0
G
m
T
H
1
where G
m
T
0
and G
m
T
H
are the molar chemical
driving force at transformation temperature without and with
a magnetic eld (H), respectively. Figure 3 shows the
chemical driving force changes with temperature in pure Fe
and Fe-0.8C alloy calculated using Thermo-Calc. In Fig.
3(b), G
m
(equ) is the molar free energy of equilibrium state
(austenite or pearlite at temperature above or below A
1
0 6 8 2 4 10
0
2
4
6
8
10
T(0)=906.2C
Magnetic Field Strength, H/T
890
895
900
905
910
915
920
T
e
m
p
e
r
a
t
u
r
e
,

T
/

C
Time
0T
1T
3T
5T
7T
10T
1 min
Ferrite transformation
T
f
(a) (b)

T
/

C

T
(
H
)

T
(
0
)
,
Fig. 1 Cooling curves (a) of pure Fe in magnetic eld after austenitization at 1000

C for 15 min, and the ferrite transformation

temperature increasing with magnetic eld strength (b).
660
680
700
720
740
0 10 20 30 40
0
200
400
600
800
1000
T
e
m
p
e
r
a
t
u
r
e
,

T
/

C

Time
0T
1T
3T
5T
7T
10T
2 min
H
Fe0.8C 60%CR
0 2 4 6 8 10
0
2
4
6
8
10
12
14
16
Magnetic field, H/T
T(0)=704.9C
(a) (b)
T
/

T
(
H
)

T
(
0
)
,
Fig. 2 Cooling curves (a) of Fe-0.8C alloy in magnetic eld after austenitization at 1000

C for 15 min, and the pearlite transformation

temperature increasing with magnetic eld strength (b).
Eect of High Magnetic Field on Phase Transformation Temperature in Fe-C Alloys 2623
temperature). The chemical driving force of ferrite trans-
formation for pure Fe is 4.8 J/mol at 906.2

C and 2.6 J/mol

at 914.9

C, respectively. So the magnetic eld provides a free

energy of 7.4 J/mol to compensate the chemical driving
force change. Similarly, the magnetic energy for eutectoid
transformation was calculated to be about 71 J/mol by
measuring T.
MFT is widely used to model the magnetization changes
with temperature due to its simplicity. Figure 4 shows the
magnetization of pure Fe (bcc) without or with an external
eld of 10 T calculated by MFT. The calculation method is
same as in Ref. 10), but the quantum number of magnetic
spin j was chosen to be 1 instead of 1/2, because it shows a
better t with experimental data. BelowT
c
, the magnetization
composes of spontaneous magnetization (M
zf
) in zero eld
and eld-induced magnetization (M
fi
). At eutectoid trans-
formation temperature (720

C) in Fe-0.8C alloy in a
magnetic eld 10 T, the total magnetization was calculated
to be 0.46M
0
(M
0
1.74 10
6
A/m, saturation magnet-
ization of pure Fe at 0 K), which includes a eld induced
magnetization of 0.1M
0
. Magnetic moment exists even above
Curie temperature and the eld induced magnetization at
ferrite transformation temperature in pure Fe, 915

C, is about
0.11M
0
. The change of Gibbs free energy of one mole pure
Fe in an external eld H is written,

M
G
m

Z
H
0
j
0
V
m
MdH j
0
V
m
M
zf

1
2
M

H
2
Where V
m
is the volume of one mole Fe and j
0
is the
permeability of vacuum. The free energy of ferrite in a
magnetic eld of 10 T decreases about 6.1 J/mol at 915

C
and 50.6 J/mol at 720

C calculated from this equation using

above magnetization data. The free energy change in
magnetic eld at 915

C is about one order smaller than that

at 720

C. Since pearlite consists of ferrite and cementite, in

which cementite is paramagnetic and has the volume fraction
of about 13%, the free energy change of one mole pearlite in
a magnetic eld of 10 T should be slightly smaller than
50.6 J/mol.
The calculated magnetic energy based on MFT is smaller
than the value calculated from transformation temperature.
Two reasons may account for it. First, it is possible that the
magnetization in high magnetic eld calculated by MFT is
lower than the real one. Another possibility is that high
magnetic eld not only changes the thermodynamic proper-
ties of phase transformation, but also aects the kinetic
properties, such as nucleation sites, interfacial migration and
atom diusion.
The spontaneous magnetization curve of pure Fe has been
empirically tted from experimental data to a function:
11)
M,M
0
M
0
1 t
[
1 [t At
3,2
Ct
7,2
3
Where t T,T
c
, [ 0.368, A 0.1098 and C 0.129.
This curve was also plotted as a dash-dot curve in Fig. 4. It
was shown that the spontaneous magnetization near T
c
calcu-
lated by MFT (solid curve) is apparently smaller than exper-
imental data. This may be caused by that MFT doesnt take
into account the short-range order of magnetic spins near T
c
.
The susceptibility of paramagnetic o-Fe in the temperature
680 690 700 710 720 730
210
180
150
120
90
60
30
0
30

M
G
m
=71J/mol
Transformation Temperature, T/ C
Fe0.8C: G
m
=G
m
(equ)G
m
(fcc)
T(0 T)
T(10 T)
(a) (b)
880 890 900 910 920 930
30
20
10
0
10
T(10 T)
D
r
i
v
i
n
g

F
o
r
c
e
,


G
m
/
J
m
o
l

1
Tansformation Temperature, T/C
Pure Fe: G
m
=G
m
(bcc)G
m
(fcc)

M
G
m
=7.4 J/mol
T(0 T)
G
m
/
J
m
o
l

D
r
i
v
i
n
g

F
o
r
c
e
,
Fig. 3 Chemical driving force changes with temperature for ferrite transformation in pure Fe (a) and pearlite transformation in Fe-0.8C
alloy (b). The magnetic energy of the transformed phases in a magnetic eld of 10 T was shown in gure.
0 200 400 600 800 1000
0.0
0.2
0.4
0.6
0.8
1.0
M
a
g
n
e
t
i
z
a
t
i
o
n
,

M
/
M
0
Temperature, T/C
0T (Eq. 3)
0T (MFT)
10T (MFT)
10T (Eq. 4)
10T (This study)
Fig. 4 Variation of magnetization of pure Fe with temperature in an
external magnetic eld calculated from molecular eld theory (MFT). M
0
is the spontaneous magnetization of Fe at 0 K. The square symbols are
calculated from measuring the transformation temperature change
(see text).
2624 X. J. Hao and H. Ohtsuka
range of 827907

C has been determined from experimental

data to be:
12)
2.1,T 1093 4
At constant temperature magnetization M is proportional to
magnetic eld strength H in low magnetic eld,
M H 5
Combining eq. (4) and eq. (5), magnetization in a magnetic
eld of 10 T near ferrite transformation temperature was
calculated and plotted as a dot curve in Fig. 4. It seems the
magnetization increases too fast when temperature is lower
than 900

C. The magnetic energy determined from trans-

formation temperature can be used to calculate magnetization
using eq. (2). The calculated results were shown as square
symbols in Fig. 4.
The increased ferrite transformation temperature (T)
with magnetic eld was compared between experimental
results of this study and calculated value by MFT and was
shown in Fig. 5. The dot line in this gure was calculated
from the susceptibility data (eq. (4)). MFT predicts that T is
nearly proportional to H
2
, while experiment shows T is
nearly proportional to H. Fig. 4 and Fig. 5 show that
calculated results based on MFT is not in a good agreement
with experimental results. It was also noted that the sus-
ceptibility data measured in low eld is not valid in high
magnetic eld. More complicated theory, such as itinerant
electron theory should be employed during calculation of
phase diagrams under high magnetic eld.
Though the transformation temperature in pure Fe is about
145

C higher than Curie temperature, a high magnetic eld

of 10 T can shift it as much as 8

C. Thermodynamic
calculation results shown in Fig. 3 indicate that the chemical
driving force for ferrite transformation in pure Fe increases
much slower with decreasing transformation temperature
than that of eutectoid transformation, so a weak magnet-
ization and then small magnetic energy can induce large
transformation temperature shifting. It was suggested that in
a system if the slopes of Gibbs free energy curve of two
phases is close, it is possible to control the phase trans-
formation by external magnetic eld even both phases are not
in ferromagnetic state.
An elongated and aligned structure was found in Fe-0.4C
alloy by ferrite transformation during slow cooling or
isothermal transformation in a high magnetic eld and it
was suggested that it was due to demagnetization eld
developed in ferrite.
2,3)
However, this kind of structure was
not found in pure Fe and Fe-0.8C alloy through micro-
structural observation. For pure Fe, the reason can be
attributed to that the magnetization at transformation temper-
ature is small and the demagnetization eld is also weak.
Another possibility is that aligned structure formed during
transformation but disappeared by grain growth after trans-
formation. For eutectoid transformation in Fe-0.8C alloy, the
lamellar morphology and orientation relationship between
pearlite and parent austenite phase possibly inhibit the
formation of elongated and aligned structure.
4. Conclusions
The eects of high magnetic eld (maximum 10 T) on the
phase transformation temperature and microstructure in Fe-C
alloys were investigated. It was found that the transformation
temperature for pure Fe from austenite to ferrite has a linear
relationship with magnetic eld strength, about increasing
0.8

C per unit of magnetic eld of 1 T. For eutectoid

transformation in Fe-0.8C alloy, similar relationship exists,
the transformation temperature increases about 1.5

C per unit
of magnetic eld of 1 T. Experimental results are not in a
good agreement with that calculated by molecular eld
theory. By microstructural observation, an elongated and
aligned microstructure by ferrite transformation in a high
magnetic eld was found in Fe-0.4C alloy, but was not found
in pure Fe and Fe-0.8C alloy.
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0 2 4 6 8 10
0
2
4
6
8
10
Magnetic field strength, H/T
Exp
MFM
eq. 4

T
/

C
T
(
H
)

T
(
0
)
,
Fig. 5 Comparison of the transformation temperature increasing in
magnetic eld between experimental results and calculated by molecular
eld theory (solid line) and susceptibility data (eq. (4), dot line).
Eect of High Magnetic Field on Phase Transformation Temperature in Fe-C Alloys 2625