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Materials Today: Proceedings 2S (2015) S561 – S564

International Conference on Martensitic Transformations, ICOMAT-2014

Modelling of the fraction of martensite in low-alloy steels

F. Huyan*, P. Hedström, A. Borgenstam
Department of Materials Science and Engineering, KTH Royal Institute of Technology, 100 44 Stockholm, Sweden

Abstract

Thermodynamics-based modelling of the fraction of martensite formed upon quenching in low-alloy steels is developed. The
adopted modelling approach has two distinct features: 1) it applies the driving force of the transformation, i.e. the difference of
Gibbs energy between austenite and martensite, from thermodynamic calculations; 2) it predicts the sigmoidal shape of
transformation to capture also the initial 10-20% of martensite formation, which is distinct from some previous modelling using
e. g. the Koistinen-Marburger equation. It is found that the general equation can describe the experimental data of martensite
fraction versus quenching temperature for plain carbon steels and low-alloy steels well. Furthermore, the only model parameter
that is needed is linearly proportional to the martensite start temperature of the steel, which opens the possibility for a
thermodynamics-based simple but yet predictive model if it is coupled with the previously developed thermodynamics-based
model for the Ms temperature.
© 2014 The Authors. Published by Elsevier Ltd.
© 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
Selection and Peer-review under responsibility of the chairs of the International Conference on Martensitic Transformations
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
2014. This
Selection andis Peer-review
an open access article
under under theofCC
responsibility the BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).
chairs of the International Conference on Martensitic Transformations 2014.

Keywords: fraction of martensite; steels; thermodynamics; martensitic transformation

1. Introduction

The athermal martensite starts to form at quenching to the martensite start temperature, Ms. However, further
undercooling is required to form more martensite since the elastic and plastic accommodation of the transformation
strains require an additional driving force [1-3]. The fraction of martensite is critical to the performance of steels
since it influences the mechanical properties such as strength and toughness, directly, and a precise description of the

* F.Huyan. Tel.: +46-764-099-860; fax: +46-820-7681.

E-mail address: huyan@kth.se

2214-7853 © 2015 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Selection and Peer-review under responsibility of the chairs of the International Conference on Martensitic Transformations 2014.
doi:10.1016/j.matpr.2015.07.347
562 F. Huyan et al. / Materials Today: Proceedings 2S (2015) S561 – S564

fraction of martensite with undercooling can be utilized in process design or optimization of the properties. For
instance, such a model is valuable in the design of TRIP steels or dual-phase steels.
The model applied most widely is the Koistinen-Marburger (K-M) equation [1] where the fraction of martensite, f,
is expressed as

f = 1 – exp[(Ms – T)] (1)

where α is a material constant and T is the temperature to which the material is quenched. The drawback of the K-M
equation is that it has a parabolic shape instead of a sigmoidal shape and thus it deviates from experimental data
significantly for the initial 10-20% of martensite formation. Recently Lee and van Tyne [2] modified the K-M
equation and added an index term to (Ms-T).
Plenty of other models can also be found in the literature. For instance, Guimaraes and Rios [3] derived a
theoretical model with a parameter which is the maximum temperature where martensite embryos can propagate.
Lee and Lee [4] utilized a differential equation to describe the transformation rate and obtain the fraction by
integration. Yu [5] expressed the fraction with the martensite start and finish temperature. All these models that have
been found in the literature apply temperature as the variable.
Considering that during the martensitic transformation the Gibbs energy difference between austenite and
martensite drives the transformation, it is natural to use the chemical driving force as the variable instead of the
temperature. Thus the aim of the present study is to derive and use a thermodynamically based model to predict the
fraction of martensite with undercooling in steels.

2. Derivation of the present model

The chemical driving force is defined as the difference of the molar Gibbs energy between the parent phase and
the product phase as

Gm Gm Gm GZ (2)

where Gmγ and Gmα

are the molar Gibbs energies for austenite and ferrite, respectively, and ΔGZ is the energy change
related to the Zener ordering. ΔGZ originates from the order-disorder of carbon atoms [6], and the expression used
here is the same as in Ref. [7].
If it is assumed that the fraction of newly formed martensite, df, is proportional to the change of the driving force,
d(ΔGmγ-α), and considering the self-catalyzed effect from the previously formed martensite, it is suggested that

d Gm
df b f 1 f (3)
Gm

in which b is a proportionality constant.

By integration from Ms to a certain temperature T, one obtains
1
f b
(4)
1 a G

in which a is a parameter from the integration and ΔG is denoted as the normalized driving force as
T Ms
G Gm Gm (5)

Moreover, since

Gm Hm Sm T (6)
 F. Huyan et al. / Materials Today: Proceedings 2S (2015) S561 – S564 563

in which ΔHmγ-α and ΔSmγ-α are the molar enthalpy and the entropy of the martensitic transformation, respectively.
Furthermore, if we assume that both are constant in the transformation temperature interval, equation 4 could be
written as a function of temperature as
1
f b
(7)
1 a Ms T

in which
b
a a S (8)

3. Results and discussion

Fig. 1 shows one result of the fitting. The experimental data are from a Fe-0.8C steel containing small amounts of
alloying elements [8]. The steel was quenched after full austenitization and the fraction of martensite was detected
with dilatometry. Fig. 1(a) shows the fitting using the present model. The normalized driving force ΔG is applied as
the variable, and the thermodynamic quantities were calculated with the Thermo-Calc software [9] and the TCFE6
database according to equation 2 and 5. Fig. 1(b) shows the same experimental data which instead is plotted versus
the temperature. The data are fitted with the present model and the K-M model equation 1. Both models give good
agreement with the experimental data when the fraction of martensite is higher than about 20%, however, the K-M
model deviates from the experimental data significantly before about 20% of martensite.
a) b)
100 100
F raction of martensite (%)
F raction of martensite (%)

experimental
experimental K -M
present present
75 75

50 50

25 25

F e-0.80C
F e-0.80C
0 0

0 400 800 1200 1600 0 50 100 150 200 250

Normalized Driving Force ΔG (J/mol) T emperature (°C )

Fig. 1. Fitting of experimental data of fraction of martensite for a Fe-0.8C steel with a) driving force and b) temperature.

By fitting to various experimental data from literature using chemical driving force as the variable, it was found
that the parameter a is approximately 0.05. Subsequently, the parameter a was fixed to be 0.05, and the fitting results
for parameter b including errors bars are plotted versus Ms in Fig. 2(a). The experimental data selected here were
plain carbon steels and low-alloy steels examined with metallographic method, that is, after quenching to a certain
temperature, the steel is held at, or at a slightly higher temperature for a certain time to form tempered martensite,
which is darkened and could be distinguished from the martensite formed during the subsequent quenching. The
quenching rate used in the metallographic method is much faster than the quenching rate using other methods, e.g.
dilatometry measurement. The fitting results for parameter b show a linear relationship with Ms as
b 0.006 Ms 1.502 (9)
Such linear relationship could possibly be related to the increasing activation energy for dislocation movement
with decreasing temperature.
564 F. Huyan et al. / Materials Today: Proceedings 2S (2015) S561 – S564

Thus, combining equations 4 and 9 and setting a = 0.05, the fraction of martensite could be predicted with the
normalized chemical driving force which could be further transformed into the temperature scale. The prediction for
four steels is shown in Fig. 2(b) in black solid lines and there is a good agreement with experimental data. The red
dashed lines are fitted with equation 4 using a fixed parameter of a as 0.05. It should be mentioned that these four
steels were used for fitting in Fig. 2(a) as well.
a) b)
b (fitting parameter)

F raction of martensite (%)

1946 G &S [10] 100 [10]
4 1949 H &C [11] [10]
1953 M &K [12] [12]
1972 M &K [13] 80 [11]
fitted
prediction
3 60

40

2 y=0.006*x+1.502
20
R 2=0.876

0
1
0 100 200 300 400 0 100 200 300 400
M s (°C ) T emperature (°C )

Fig. 2 a) Fitting parameter b versus Ms, error bars from fitting; b) fitting and prediction results for 4 steels. 1946 G&S [10], 1949 H&C [11], 1953
M&K [12], 1972 M&K [13].

The present model should be applied to the steels which are directly quenched. The validation of the present
model for commercial steels, as well as the effect of cooling rate, will be discussed in future works. In addition, it is
interesting to note that the suggested model could become predictive when it is coupled with a thermodynamics-
based model of Ms such as presented in Ref. [7].

4. Conclusion

Thermodynamics-based modeling was performed to describe the fraction of martensite with undercooling. The
model applies chemical driving force as the variable and the sigmoidal shape of the model enables a satisfactory fit
with experimental data. By fitting to various experimental data from direct quenching experiments in the literature, it
is found that the only model parameter needed is linearly proportional to the martensite start temperature of the steel.
This means that the model could be of predictive nature when coupled with a thermodynamics-based Ms model.

References

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[2] S.J. Lee, C.J. van Tyne, Metall. Mater. Trans. A 43 (2012) 422–427.
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