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May 2000

Materials Letters 43 Ž2000. 225–229
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An effect of high magnetic field on phase transformation
in Fe–C system
H.D. Joo ) , S.U. Kim, N.S. Shin, Y.M. Koo
Center for Aerospace Materials, Pohang UniÕersity 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 Fe–Fe 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 Fe–Fe 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; Fe–C 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 Fe–Fe 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 Ž 9 9 . 0 0 2 6 3 - 3

1. the current consensus is that the collective electron model is intrinsically closer to reality in most cases. is valid in the whole temper- Fig. respectively. It is known that the . Magnetic moments of phases in Fe–C system There are at least two divergent viewpoints in the ferromagnetic model w3. determination of the magnetization vs.. are susceptibility data. but it does not provide any simple model from which first principle calculations can be made. The paramagnetic susceptibilities of g and a phases have been measured by Arajs and Miller w7x. In order to calculate the Gibbs free energy change induced by the applied magnetic field. Magnetization and inverse susceptibility curves below and above the Curie temperature of ferrite: Ža. One is the Weiss model. Because the paramagnetic susceptibility of ferrite satisfies the Curie–Weiss law only above 1150 K. The other is the collective electron model. is from the Curie–Weiss equation fitted from other data w6x. Fig. 2. it is assumed that the magnetic moment per atom in the ferromagnetic region. Žb. we use the molecular field theory w3x. For the calculation of the magnetic moment in ferrite. Žb. such as reported by Gorodestsky et al.D. m H s 2. The relative magnetization of pure iron calculated from molecular field theory as a function of temperature and applied magnetic field. Theory 2.31 w emu moly1 Oey1 x xg s Ž 2. and Že.1. Their susceptibility data also satisfy the Curie–Weiss law and the susceptibility can be determined by fitting the susceptibility data to the Curie–Weiss equation. Žd.. the paramagnetic m H s 1. Joo et al.4x. temperature diagram is the first consideration. A mapping of the M–H–T surface is calculated and it is shown in Fig 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. is the relative magnetization when applied magnetic field is zero. ature range and all data for pure iron can be applied to the Fe–C system.226 H. Therefore. This curve corresponds to the shape of an experimental curve. 1. between paramagnetic and ferromagnetic regions exists. Because of this drawback. w6x. Žc. are experimental data w5. The Gibbs free energy of the paramagnetic region can be determined by the susceptibility x . which deals with almost free itinerant electrons. Although both theories have merits and demerits for describing the magnetic properties of ferromagnetic materials. T q 3370 where xa and xg are the magnetic susceptibilities for a-Fe and g-Fe. and Že.7x.23 w emu moly1 Oey1 x xa s Ž 1. Although disagreement of the magnetic moment per atom. m H . for the weak ferromagnet YFeO 3 .. interpretations of magnetic properties are still more often made on the basis of the Weiss model w4x. which is the ratio of the induced magnetization to the inducing field and roughly follows the Curie–Weiss law. the theory of ferromagnetism in steel is developed on basis of the Weiss model. Žc.219m B . which is applicable to electrons that are localized within the positive ions forming the lattice. T y 1093 7.r Materials Letters 43 (2000) 225–229 2. Žd.

sy1200q3. X . T y1045 q227exp y 162 at T )1043 K Ž 11 . Next. The thermal Gibbs free energies of austenite and ferrite are derived on the basis of the KRC model by Shiflet et al.00T G gT Ž T .7 at T )1043 K Ž 10 . and an intensive variable.18 X 1 y X Ž 14 y 12exp yWgrRT figurational entropy of solution in austenite. . M.3exp y 88.. q36. y0. the susceptibility of cementite.00243T 2 at T -1043 K DG aM Ž T . T y 506 where x Fe 3 C is the magnetic susceptibility for Fe 3 C. s11. qX Ž DHcg y TDS X S .12T . Ž 8. X . Integration of Eq. which is given by Eq. H . must be determined.5 DG aM Ž T . H. where X is the mole fraction of carbon. Gtotal Ž T . 1 is carried out at each temperature to yield the magnetic Gibbs free energy of ferrite as a function of applied magnetic field. s 5.. Fig. X . Gibbs free energy change by magnetic field When magnetic field is applied. respectively.50T . 2. Ž2. can be obtained from SGTE DATA w11x. – Ž11. DG M ŽT. qRTX ln 227 at T -1043 K T y1045 . s 39. Joo et al.20T . G aFe ŽT . can be written in terms of an extensive variable. w10x. from the previous M–H curves in Fig. sy890q3.00197T 2 Ž 5. G aFe ŽT . Generally. DG aM Ž T .12T . We take Wg s 5880 J moly1 . sy x H 2.7.1exp y 67. w10x. 2 shows the magnetization and inverse susceptibility curve below and above the Curie temperature drawn from the experimental data of Refs. Ž 4. Cementite satisfies the Curie–Weiss relation.. G aFe Ž T . 1 DG aM Ž T ..1 . sy1200q3.28T 13 y 12exp yWgrRT 1 y X Ž 14 y 12exp yWgrRT 1yX G aT Ž T . and are described by Eqs. Ž3. T y1045 q69. 1. s Ž 1 y X . Cementite is ferromagnetic like a-Fe. RT X ln X q Ž 1 y X . but we assume that the equation holds at high temperatures up to 1400 K. Ž7. the resulting free energy changes are classified into two terms. w9x.3 at T )1043 K . H . the paramagnetic Gibbs free energy change by a magnetic field is given by 1 para DG M ŽT . 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. s Ž 1 y X . This has been measured below 575 K. and the magnetic Gibbs free energy.50T . DG M ŽT. H .95 w emu moly1 Oey1 x x Fe 3 C s Ž 3. and G gFe ŽT . s Hd M Ž 7. 200 and 500 kOe.64T Ž 6. G T ŽT. at T -1043 K DG aM Ž T .g are the partial molar enthalpy and the partial molar noncon- y0.D. Ž 9. RT =ln y0. is appropriate for describing the paramagnetic susceptibility of g-Fe in this temperature region.H . H .g q Ž 1 y X . the thermal Gibbs free energy. respectively. The magnetic Gibbs free energy. G gFe Ž T . 1 and 2. q DG M Ž T .2. X .00173T 2 DG aM Ž T .H. DS X S . are the Gibbs free energies of pure a-Fe and g-Fe at temperature T.8x. s G T Ž T .20T . q X Ž 112 000 y 51. Ž9. but Eq. ln Ž 1 y X . 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. These are fitted as functions of temperature at the magnetic fields of 120. X . and DHcg.r Materials Letters 43 (2000) 225–229 Neel temperature of g-Fe is 44 K w8x. Fe 3 C.4T .2 J moly1 Ky1 from Shiflet et al. dG M Ž T . w5. DHcg s 444 000 J moly1 and DS X S .g s 17.

Fig. Joo et al. The thermal Gibbs free energy of cementite determined in this way is given as follows. Ac m . . eutectoid composition and the gra transformation temperature are determined from Fig. Fe–C phase diagram associated with the gra and grFe 3 C transformation for various applied magnetic fields. The Gibbs free energy difference between g and a phase of pure iron as a function of temperature for various magnetic fields. 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. 3C T G Fe Ž . Ž8. the thermal Gibbs free energy is calculated reversely from the experimental phase diagram of the Fe–C system. Since Ac 1 is equal to Ac 3 in pure iron.H . Also. 3. y ž 1 2 xg H 2 / Ž 13 . Eutectoid temperature. Eq. Thus. Ac 3 increases as magnetic field is applied. Fig. the change of phase transformation temperature can be affected by many factors such as heatingrcooling rates and strain energy per unit volume. 3 shows the Gibbs free energy change of the gra transformation vs. 3. the Ac 3 temperature increases from 1180 to 1187 to 1198 K. In contrast to ferrite and austenite. 4. y G aM Ž T . H .H. s DG gT ™ a Ž T . the magnetic Gibbs free energy of cementite can be evaluated from Eq. s 16 700 y 43. which increases 10 K at 120 kOe. g™ a DGtotal ŽT. As the heating rate is increased from 1 to 20 to 50 Krs. but the Ac m temperature hardly moves so that both the eutectic temperature and composition increase.r Materials Letters 43 (2000) 225–229 228 particular magnetic field in pure iron. 4 shows the phase diagram associated with the gra and grFe 3 C transformations as a function of weight percentage carbon. 4. the thermal Gibbs free energy of cementite is difficult to calculate. This method is quite simple because the cementite austenite equilibrium temperature. Results and discussions Fig. because it is formed at a much higher temperature than its Curie temperature. temperature diagram at a Fig. may also be applied to the magnetic Gibbs free energy change of austenite as the Neel temperature of austenite is very low. H . in the phase diagram is almost a straight line and the composition of cementite is constant.4T T The Gibbs free energy calculated in the previous section is used to determine the change of the gra phase diagram. which is summarized in Table 1. s 0 is simply determined as the transformation temperature.D. the temperature at which g™ a Ž DGtotal T. The Ac 3 temperatures have been measured at various heating rates by Abiko and Sadamori w12x. the strain energy due to dislocation accumulation causes a metastable phase Ž 12 . H . Considering kinetics. Thus. respectively. The Gibbs free energy change of the gra transformation in pure iron is given as follows. Ž8.

999. Status Solidi 167Ža. w5x S.P. Gorodestsky. in: Introduction to Magnetism and Magnetic Materials. p.S. w7x S. w11x A. Saburi. Appl. 11 Ž1995. For example.J. p. in: Metal Handbook: Heat Treating 4 ASM. 24. 117. p. Ž1998. the possibility of improving mechanical properties may be realized from the eutectoid composition shift.795 0. w9x H. H. 7083. Springer-Verlag. 35 Ž1964. 97. Jiles. Miller. Kindo.818 0. w2x T. 9. In addition. Berlin. ISIJ Int. J. T. CALPHAD 15 Ž1991. 317. therefore. and the authors wish to express appreciation for the financial support. D. 31 Ž1960. 29 Ž1989. Dynamical applications such as imposing magnetic cycles at a particular temperature gives additional driving force for phase transformation. w13x E. w8x H. Chapman & Hall. Treves. 1991. Miller. w4x D. Phys. Wijn. J. Increased carbon content is associated with strengthening and hardening. Technol. p. Cullity. gra Transformation temperature in pure iron Ž8K. Trans.A. 36 Ž1997. 0. Shiflet.P. the change of transformation temperature by high magnetic field can be applied to microstructural control. Metall. J. w6x G. Phys.T. 147. Dinsdale. too. Endo.J. Similarly.R. Industry and Energy of the Republic of Korea. London. Sadamori. Messeria. S. but hypereutectoid primary cementite decreases ductility. 247. in: Introduction to Magnetic Materials. Acknowledgements This work was supported by Pohang Steel and the Ministry of Commerce.%. Wilson. J.H. Wijn.914 1000 1012 1019 1051 1184 1194 1209 1306 transformation w13x. in: Landolt-Bornstein III-19c. 1972. Since external magnetic field enables us to increase carbon content without hypereutectoid transformation. Mater. eutectoid composition and the gra transformation temperature determined from the calculated phase diagram Applied magnetic field ŽT. w14x V. T. K. Shimizu. it can be applied to microstructural control. D.r Materials Letters 43 (2000) 225–229 229 Table 1 Eutectoid temperature. References w1x K. These factors have been widely used for controlling microstructure. Addison Wesley. Kakeshita. 9A Ž1978. 24. Solid State Commun. Joo et al. w10x G. Springer-Verlag. 275. S. . K. Kakeshita.76 0. 1110. Arajs. p. 1988. Appl. Calculated data 0 12 20 50 Eutectoid composition Žwt. Bradley. Appl.D. Abiko. Berlin. 2424. 1981. 986. it may improve mechanical properties. Arajs. 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.I. 1986.S. Phys. 4 Ž1966. w3x B. Phys.J. Aaronson. in: Landolt-Bornstein III-19a.D. w12x K. Shtrikman. Jpn. Eutectoid temperature Ž8K. accelerated cooling and recrystallization-controlled rolling are applied to grain refinement. D. Sci.