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Acta Materialia 60 (2012) 61206130

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Thermodynamic analysis of two-stage heat treatment in TRIP steels

S. Li a, R. Zhu a, I. Karaman a,b, R. Arroyave a,b,
b

a
Department of Mechanical Engineering, Texas A&M University, TX 77843, USA
Materials Science and Engineering Program, Texas A&M University, TX 77843, USA

Received 31 May 2012; received in revised form 22 July 2012; accepted 22 July 2012
Available online 4 September 2012

Abstract
In this work, we present a detailed thermodynamic analysis of the two-stage heat treatment (intercritical annealing (IA) and banite
isothermal transformation (BIT)) necessary to stabilize retained austenite in transformation-induced plasticity (TRIP) assisted steels.
Through a set of experiments on alloys with nominal composition Fe0.32C1.42Mn1.56Si (wt.%), we monitored the evolution of
the volume fraction of retained austenite at room temperature as a function of the IA and BIT temperatures. We also investigated
the thermodynamic limit for the bainitic transformation during BIT under the displacive (partitionless) transformation assumption.
The fraction of retained austenite at the end of the two-stage heat treatment was calculated by taking into account the corresponding
start of the martensitic transformation (TMs). Comparisons with experiments suggest good qualitative agreement in the fraction of
retained austenite when considering the eect of the IA temperature. On the other hand, the analysis of the eect of BIT on the amount
of retained austenite showed qualitative disagreement with the observations. To further analyze this discrepancy, we utilize a modied
thermodynamic analysis with empirical observations as input, and conclude that the assumption of thermodynamic equilibrium at IA is
not valid at lower IA temperatures. Moreover, the unexpected high carbon enrichment in retained austenite indicates the importance of
the kinetic eects. We conclude that the thermodynamic limit for the bainitic transformation can be used at least to provide a lower
bound to the expected fraction of retained austenite under specic IA + BIT treatment schedules.
Published by Elsevier Ltd. on behalf of Acta Materialia Inc.
Keywords: Transformation-induced plasticity steels; Thermodynamics; Retained austenite; Bainite; Bainitic transformation

1. Introduction
The quest for improvements in vehicle fuel economy
through weight reduction has motivated the development
of advanced high-strength steels (AHSSs). In transformation-induced plasticity (TRIP)-assisted steels, ductility is
improved through the strain-induced martensitic transformation of retained austenite [13], making them good
AHSS candidates. Although TRIP-assisted steels consist
of complex multiphase microstructures, one of their key
characteristics is the fraction of retained austenite available
for the ductility-enhancing martensitic transformation during plastic deformation. Due to the low alloy content of
Corresponding author at: Department of Mechanical Engineering,
Texas A&M University, TX 77843, USA. Tel.: +1 979 845 5416.
E-mail address: rarroyave@tamu.edu (R. Arroyave).

these steels, the stability of the retained austenite at room

temperature is mostly controlled through its level of carbon
enrichment, which in turn can be manipulated through
judicious design of the steels phase constitution via heat
treatments.
The most common strategy to control the phase constitution of TRIP steels is through a two-stage heat treatment
protocol [46] consisting of four distinct processes: (1) fast
heating and dissolution of pearlite; (2) holding at the temperature in which a two-phase, ferrite + austenite, microstructure is stable (intercritical annealing (IA)); (3) rapid
quenching; and (4) holding at a temperature at which a
bainitic isothermal transformation (BIT) takes place. The
purpose of the IA treatmenttypically temperatures on
the order of 10531153 K [7]is to decompose the original
pearlite and generate a ferriteaustenite microstructure,
with the austenite having a considerable carbon enrichment

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S. Li et al. / Acta Materialia 60 (2012) 61206130

due to carbon partitioning. During the BITwhich typically occurs at temperatures within the 600700 K
rangethe formation of essentially carbon-free bainitic
ferrite results in further carbon enrichment of the remaining austeniteprovided that the presence of carbide phases
and other carbon sinks is inhibitedstabilizing it against
martensitic transformation as the alloy is quenched to
room temperature.
Due to the importance of the BIT treatment in dictating
the carbon enrichment (and stability) of austenite, considerable eort has been dedicated to the understanding of
the thermodynamics and kinetics of the bainitic phase
transformation [810]. Although the actual mechanism
for the transformation is still subject to debate, many of
the descriptions of BIT assume that the transformation
occurs in a partionless manner. Upon transformation, the
bainitic ferrite rejects carbon into austenite, enriching and
stabilizing it against martensitic transformation. Bhadeshia
[11] proposed a limit to the carbon enrichment in retained
austenite during BIT resulting from the exhaustiondue to
carbon enrichment in the retained austeniteof the driving
force for partitionless bainite growth. This limit is usually
denoted as the T0 line (see Section 3) [12].
From the viewpoint of the design of the two-stage heat
treatment for TRIP steels, T0 and related constraints have
been proposed as key parameters to predict the maximum
possible carbon enrichment of austenite as well as the latters volume fraction during BIT [13,14]. However, experiments often show signicantly higher carbon enrichments
[8,15,16] than the ones suggested by thermodynamic constraints, resulting in a more stable austenite at room temperature [14,17,18]. The reasons for this discrepancy are
unclear but it has been proposed that the competition
between the actual rate of the transformation and the diffusion of carbon away from bainitic ferrite into austenite
may be important contributors [9,13,14,17,19].
In this work, we present a detailed thermodynamic analysis of the two-stage heat treatment (IA and BIT) necessary
to stabilize retained austenite in transformation-induced
plasticity (TRIP)-assisted steels with typical composition
Fe0.32C1.42Mn1.56Si (wt.%). Using thermodynamic
analysis we examine the phase transformation criteria
based on the thermodynamic limits (i.e. T0) for the completion of the BIT transformation, which constitute reliable
indicators for the volume fraction of retained austenite.
The results are compared with a set of experiments. The
thermodynamic calculations are performed using
Thermo-Calc [20] with the most recent edition of the thermodynamic database for steels (TCFE6 v.6.2). By combining a limited set of experimental data obtained from
dierent heat treatments we proceed to use thermodynamic
calculations and experiments to determine the carbon
enrichment in austenite after the treatments. To accomplish
this, we include estimates for the martensite start and nish
temperatures (TMs and TMf) for austenite both after IA and
during/after BIT. Finally, we discuss the possible use of
thermodynamic criteria to estimate lower bounds for the

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likely volume fraction of retained austenite after the twostep treatment of TRIP steels.
2. Experimental
2.1. Initial processing
Billets of the model TRIP-assisted steel with a nominal
composition of Fe1.5Mn1.5Si0.3C (wt.%) were cast
with dimensions of 25.4 mm  25.4 mm  177.8 mm and
processed at high temperature using equal-channel angular
pressing (ECAP). Inductively coupled plasma atomic emission spectroscopy (ICP-AES) was conducted on the as-cast
materials to determine the actual composition and the
results are shown in Table 1. The as-cast billets were rst
heated up to 1223 K for 1 h to austenitize the microstructure, then quickly ECAP processed at a rate of 25.4 mm s1
non-isothermally while the billets were at 1223 K and the
ECAP die was at 573 K. After ECAP, the billets were air
cooled to room temperature. Two passes were conducted
using route C (180 rotation between the passes along the
longitudinal axis of the billet) with the same extrusion conditions. The purpose of this processing is to homogenize
the as-cast structure.
2.2. Two-step treatment
Dog-bone shaped samples with gage dimensions of
8 mm  3 mm  1 mm were cut from the ECAP-processed
billets using wire electrodischarge machining along the longitudinal axis of the billets. The samples were intercritical
annealed in the furnace, followed by fast quenching into
a salt bath for BIT, and nally quenching into water.
The parameters used are summarized in Table 2. The selection methodology of these parameters will be explained in
detail in the subsequent sections. Each sample was sealed in
an argon environment to avoid decarburization during the
heat treatments.
2.3. Microstructural characterization
The volume fraction of ferrite was measured through
image analysis. Field emission scanning electron microscopy (FE-SEM) images were obtained using a JEOL
JSM-7500F ultra-high-resolution microscope equipped
with a high-brightness conical FE gun and a low-aberration conical objective lens. Additional samples with only
the IA treatment (IA + quenched in water) were prepared

Table 1
Chemical composition (in wt.%) of the as-cast Fe0.3C1.5Mn1.5Si
TRIP-assisted steel determined through ICP-AES.
Element
wt.%

C
0.32

Mn
1.42

Si
1.56

P
0.012

S
0.008

Element
wt.%

Mo
0.02

Cu
0.07

Ni
0.04

Cr
0.06

Fe
Bal.

Al
0.01

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S. Li et al. / Acta Materialia 60 (2012) 61206130

Table 2
Experimental heat treatment conditions used to validate the thermodynamic analysis; IA and BIT stand for the heat treatment conditions for intercritical
annealing and bainitic isothermal transformationm respectively; Vf is the volume fraction of each phase (austenite (Aus) and ferrite (Fer)); wcMn and wcSi are
the weight percentages of Mn and Si in austenite; wcC;BIT represents the carbon content in retained austenite.
Treatment

IA
BIT
Vf(Aus)
Vf(Fer)
wcMn
wcSi
wcC;BIT

1023 K, 2 h
613 K, 12 min
11.73 2.5%

1045 K, 2 h
613 K, 15 min
11.85 3.04%
41.20 0.8%
1.48
1.49
1.12 0.06

643 K, 15 min
18.61 1.54%

693 K, 5 min
20.40 1.84%

1.22 0.06

1.21 0.06

in order to measure the volume fraction of IA-ferrite

assuming that the ferrite from IA is stable and no additional ferrite similar to IA-ferrite is formed during BIT.
Samples were mechanically polished and etched using 2%
Nital before imaging. Typical microstructures of the alloys
after the BIT treatment are shown in Fig. 1.
The volume fraction of retained austenite was calculated
based on the X-ray diraction (XRD) spectrum obtained
with a Bruker-AXS D8 diractometer with Cu Ka radiation (wavelength k = 0.15406 nm). Samples were chemically polished in a solution of 14 ml of 40% HF and 30%
H2O2 diluted in 100 ml distilled water before testing. A
direct comparison method [21] was utilized on (1 1 1),
(2 0 0), (2 2 0) austenite peaks and (1 1 0), (2 0 0), (2 1 1) martensite peaks. The carbon content was calculated using the
empirical equation by Dyson [22].
The Mn and Si content after IA was determined using
Cameca SX50 electron microprobe with wavelength-dispersive spectroscopy (WDS). Samples were mechanically
polished without etching before the microprobe investigation. Two or three comparison samples were heat treated
and analyzed to check the repeatability of the experiments.

1083 K, 2 h
613 K, 15 min
7.37 1.04%
15.10 0.5%
1.5
1.43
1.29

1045 K, 10 min
613 K, 15 min
11.56 3.25%
52.70 3.0%
1.40
1.70
1.09 0.09

Fig. 1. SEM image showing a typical microstructure after 1053 K 2 h

(IA) + 693 K 4 min (BIT) + water quenching. Refer to the text and Table
2 for more details.

3. Thermodynamic analysisforward calculation

3.1. Intercritical annealing
As mentioned in the Introduction, we investigated the
two-step heat treatment for the selected TRIP steel using
thermodynamic calculations. The calculation procedure is
outlined in Fig. 2. As shown in the gure, the thermodynamic analysis starts by estimating the phase constitution
of the steel alloy during IA at arbitrary temperatures.
The predicted (metastable) phase diagram for the present
composition is shown in Fig. 3a. As indicated in the diagram, austenite and ferrite coexist between 985 and
1091 K. This range of temperature of 106 K constitutes
the temperature window for potential IA temperatures
(TIA).
One of the main goals of IA treatment is the stabilization of a dual-phase microstructure with sucient volume
fraction of ferrite to result in adequate ductility of the
TRIP steel as well as an austenite phase suciently
enriched with carbon so it is stable against martensitic

Fig. 2. The owchart of the forward thermodynamic calculation model.

transformation during quenching to BIT temperature.

The selection of TIA must also be suciently above the stability boundary for the formation of cementite to guarantee
that there are no carbon sinks that would deplete the

S. Li et al. / Acta Materialia 60 (2012) 61206130

Fig. 3. The thermodynamic equilibrium analysis for Fe0.32C1.42Mn

1.56Si (wt.%): (a) the predicted metastable phase diagram; (b) the chemical
composition and volume fraction of austenite during IA at dierent
temperatures.

IA-austenite of carbon, making it more susceptible to martensitic transformation after quenching.

Fig. 3b shows the equilibrium partitioning of C, Si and
Mn, as well as the equilibrium volume fraction of austenite
as a function of IA. As can be seen, lower TIA result in high
enrichment of C and Mn, leading to a more stable austenite, although in these cases the equilibrium amount of austenite is rather low, suggesting a compromise between
austenite stability and phase constitution.
3.2. Bainitic isothermal transformation
Since IA-ferrite is stable below Ae1 [16], the thermodynamic analysis of the BIT treatment can be carried out
by considering only IA-austenite, with its chemical compo-

6123

Fig. 4. Schematic diagram of the two-step heat treatment: (a) the volume
fraction of the phases at each step of the treatment; (b) the critical
temperatures in BIT treatment; TBIT: BIT treatment temperature; TMs:
BIT
martensite start temperature; TIA
Ms : TMs of IA austenite; TMs : TMs of the
alloy after heat treatment; T00 : the thermodynamic limit of the carbon
 : the average carbon content in
saturation in retained austenite; w
austenite.

sition corresponding to that at the end of IA (point (1) in

Fig. 4). After the IA treatment, the alloy must be quenched
to BIT in order to promote further C-enrichment of austenite. At this stage, the proper quenching rate and holding
temperature are required to avoid the formation of cementite. At the same time, the isothermal holding temperature
(TBIT) must be higher than the martensitic start temperature (TMs) of the IA-austenite and must be lower than
the bainite start temperature (TBs).
Although there is still some uncertainty regarding the
processes involved in the nucleation and growth of bainite,
the most conventional theories by Bhadeshia and collaborators [23] suggest that the nucleation process occurs
through the partitioning of C and the formation of a bainitic ferrite nucleus with C-content close to that obtained
under para-equilibrium conditions. Once ferrite nucleates,
the growth of bainite subunits occurs in a diusionless

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S. Li et al. / Acta Materialia 60 (2012) 61206130

(partitionless) fashion. Upon transformation, the bainitic

ferrite rejects carbon into austenite, enriching and stabilizing it against martensitic transformation. According to this
model, the bainitic transformation is only thermodynamically possible when (1) the maximum driving force for
the nucleation of para-equilibrium ferrite (DGMax) overcomes the so-called universal nucleation energy barrier
(DGN); and (2) the diusionless driving force for the continued growth of bainite plates (DGc!a) is greater than the
strain energy (DGSE) that accompanies the austeniteferrite
transformation and that results from elastic incompatibilities between matrix (austenite) and precipitate (bainitic ferrite) phases [11]. These two conditions are illustrated in
Fig. 5.
The universal nucleation energy is essential for the prediction of TBs. However, DGN is at best an empirical quantity which was determined by comparing experimentally
determined TBs with the chemical driving force for the

Fig. 5. The schematic diagram of (a) the driving forces for bainitic
transformation and (b) bainite start temperature (TBs).

bainitic transformation obtained from thermodynamic calculations using specic thermodynamic databases.
Bhadeshia and his collaborators have determined this
quantity to be DGN = 3.637(T  273.18) + 2540 [26,19].
Unfortunately, if one is to use these ideas with dierent
thermodynamic databases, it is necessary to adjust this
function. In this work, we have retted this quantity using
the Thermo-Calc database TCFE6 (Fig. 6a), and obtained
the following functional form:
DGN 4:736T  4769

In order to predict the thermodynamic stability limit for

the formation of bainite, one must also calculate the maximum chemical driving force for the formation of bainite,
which is given by [27]:

Fig. 6. (a) The universal energy for bainitic nucleation formulated based
on the TCFE6 database (the empirical data refers to Refs. [24,25]) and (b)
the eective driving force (DGMax  DGN) of Fe0.32C1.42Mn1.56Si,
both as a function of the BIT temperature.

S. Li et al. / Acta Materialia 60 (2012) 61206130



a waFe
DGMax RT ln
2
awcFe


where a waFe and awcFe are the chemical activities of Fe in
bainitic ferrite under para-equilibrium conditions (assuming partitioning of C) and in austenite with a carbon content corresponding to the instantaneous composition of
the austenite matrix. To verify that our calculations yield
similar quantitative results to those resulting from Bhadeshias analysis, we calculate (see Fig. 6b) the eective driving
force (DGMax  DGN) using the updated universal nucleation energy and the chemical driving forces calculated
using Thermo-Calc and compare it with the results obtained using the MUCG83 code [28].
If one assumes that the growth of bainite plates occurs
in a partitionless fashion, then the available chemical driving force for the transformation is given by the dierence in
Gibbs energies of austenite and ferrite Gc  Ga at the
instantaneous composition of the austenite matrix. As the
bainitic transformation progresses, this driving force starts
to decrease until it vanishes completely. The locus of this
composition as a function of temperature is denoted as
T0. This thermodynamic limit for the transformation is further constrained when considering the energy barriers to
the growth of bainite plates, i.e. DGSE, estimated by
Bhadeshia to be about 400 J mol1 [11]. As the transformation progresses, carbon is rejected into the untransformed
austenite, reducing the driving force for subsequent diusionless growth of bainite. Once this driving force equals
DGSE, the bainitic transformation can no longer be sustained and the reaction stops. This thermodynamic constraint to the bainitic transformation is denoted as T00 .
3.3. Martensite start (TMs) and nish (TMf) temperatures
Depending on the chemical composition and heat treatment, martensite may occupy 15% total volume of TRIP
steels [7]. In the present alloy, we are not interested in the further carbon partitioning from martensite into austenite and
the design of the heat treatments is developed around the
idea of minimizing the formation of martensite. In the current two-step heat treatment, martensite may form after
rapid quenching to BIT or after BIT to room temperature.
In other words, if TBIT is higher than TMs after IA
(T BIT > T IA
Ms : cf. point (2) in Fig. 4) and TMs after BIT is lower
than room temperature (T BIT
Ms < 300 K: cf. point (4) in Fig. 4),
martensitic transformation can be avoided. Although there
are many models built to predict TMs [2932], in this work,
a thermodynamics-based model is implemented: the free
energy barrier (DGMs) to martensitic transformation is in
the range of 11001400 J mol1 while the molar fraction of
carbon is between 0.01 to 0.06 [33] and in this case, we can
estimate TMs by calculating the diusionless driving force:
DGc!a < DGMs

6125

Fig. 7. Martensite start temperature (TMs), as a function of the carbon

content in austenite, calculated using dierent approaches.

the thermodynamic arguments described in Eq. (3). The

gure shows that the thermodynamic model provides lower
austenite stability than Andrews model [34,35]. The maximum dierence is about 20 K comparing to Ishidas model
[29].
Due to the diusionless nature of martensite, the volume
fraction of martensite (VfMar.) at arbitrary temperatures, T,
below TMs is calculated using the KoistinenMarburger
(KM) relation [36,37]:
VfMar 1  exp0:011T Ms  T 

Compared to bainite or ferrite, martensite possesses

higher carbon content. This means that the formation of
martensite during the two-step treatment can limit the carbon enrichment of austenite and reduce its stability against
martensitic transformation upon quenching from TBIT to
room temperature. Ideally, the formation of martensite
can be avoided by careful selection of the heat-treatment
parameters for certain alloy compositions. As shown in
IA
Fig. 4b, if TBIT is higher than T IA
Ms ; Vf Mar: is zero. If the car300
bon content is higher than w in Fig. 4b, the retained austenite will be stable at room temperature. The red1 triangle
in Fig. 4b is the optimum area in which the formation of
martensite can be suppressed and constitutes the ideal design window for the selection of the heat-treatment temperatures for typical TRIP steels.
4. Putting everything togetherthermodynamic-based
estimation of phase constitution after heat treatment
In the sections above, we have described the dierent
components of the thermodynamic analysis necessary to
predict the phase constitution of any TRIP steel alloy at dif-

Fig. 7 compares the martensite start temperature (TMs)

using dierent approaches, including the calculations using

1
For interpretation of color in Figs. 4, 10, the reader is referred to the
web version of this article.

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S. Li et al. / Acta Materialia 60 (2012) 61206130

ferent stages of the heat-treatment process. In order to verify

this approach, we designed a series of experiments on the
present model alloy where we varied the TIA as well as TBIT
and examined the phase constitutions in the resulting microstructure both after IA as well as after BIT once the alloys
had been quenched to room temperature. Table 2 presents
the dierent experiments as well as the phase constitutions
and composition of the austenite after IA. More details on
the experimental techniques are provided in Section 2.
By using the thermodynamic approach described in Section 3, we assume that the system reaches equilibrium during IA and is under para-equilibrium during BIT. The
equilibrium assumption during IA may be reasonable given
the elevated temperature of the treatment (1050 K). However, our previous work [38] suggests that even at these elevated temperatures the alloy only reaches equilibrium
conditions over prolonged times. In fact, we found that
the IA treatments with short holding times may result in
the volume fraction of IA-austenite being signicantly
lower than what one would expect at equilibrium, with
the subsequent greater carbon enrichment of IA-austenite.
Therefore, in the examined cases listed in Table 2, we
selected the IA time as 2 h; thus, we considered that the
assumption of equilibrium should be reasonable.
The assumption of para-equilibrium during BIT should
also be reasonable considering the much larger diusivity
of carbon in austenite (and ferrite) compared to the substitutional elements at typical BIT temperatures. In the present case, however, the dierence in carbon diusivity
between austenite and ferrite is quite signicant [38] and
it is uncertain how this assumption aects our estimates
for the thermodynamics of bainite transformation.
We start our analysis by examining the equilibrium conditions for the IA treatment at 1023 K, which corresponds
to case A in Table 2. In this case, the total fraction of austenite is about 55.6% of total volume, and the chemical
compositions of both phases (ferrite and austenite) are
listed in Table 3.
Assuming an equilibrium volume fraction of austenite
and equilibrium partitioning of the elements, we use the
IA-austenite phase as the matrix phase that undergoes
the bainitic transformation during BIT. By using the predictions of TMs after IA and BIT as well as the thermodynamic and constrained thermodynamic limits for bainite
transformation (T0 and T 00 , respectively), we predicted the
expected volume fraction of retained austenite, using thermodynamic criteria alone.
In Fig. 8, we present the results of the forward thermodynamic calculation in two distinct cases. In Fig. 8a,
we compare the estimated volume fraction for retained austenite using a xed TBIT of 613 K and dierent TIAs. In this
case, the comparison suggests qualitative agreement with
experiments, provided one takes T0 and not T 00 as the thermodynamic limit for the bainitic transformation. As in the
experiments, the predictions suggest a decrease in the volume fraction of austenite as TIA increases. This is mainly
due to the increase in the equilibrium volume fraction of

Table 3
The thermodynamic equilibrium state at 1023 K (the composition is in
wt.%).

Austenite
Ferrite

wC

wMn

wSi

Vf

0.561
0.014

1.960
0.734

1.365
1.808

0.556
0.444

Fig. 8. The volume fraction of retained austenite after dierent heat

treatments (the solid curves are the theoretical predictions) while (a) TBIT
is xed at 613 K, (b) TIA is xed at 1045 K.

austenite with increase in TIA during IA. This increased

volume fraction reduces carbon saturation in the IA-austenite, reducing its stability.
While the comparison between the predictions and the
experiments is satisfactory in Fig. 8a, the discrepancy
between the predictions and the experiments shown in
Fig. 8b, where the volume fraction of retained austenite is
plotted as a function of TBIT for a xed TIA, is rather prob-

S. Li et al. / Acta Materialia 60 (2012) 61206130

lematic. It can be clearly seen in Fig. 8b that the trends are

actually opposite: the thermodynamic-based analysis predicts a decrease in the austenite volume fraction as TBIT
increases for a xed TIA, but experiments suggest that this
is not the case. The theoretical decrease in Vf(Aus) with TBIT
could be explained by simply using the lever rule against the
T0 and/or T 00 curves in Fig. 4b: the closer the IA-austenite
composition is to the T0 line, the smaller the carbon saturation of the retained austenite after BIT. The much larger difference between the predicted and the experimental Vf(Aus)
at higher TBIT can be ascribed to many factors: (1) inaccuracies in the thermodynamic database used; (2) assumption of
equilibrium after IA is invalid; (3) overestimation of TMs; (4)
the carbon enrichment of austenite actually goes beyond the
thermodynamic limit; (5) all of the above. Although there
could be inaccuracies in the thermodynamic database used,
the fact is that this is one of the state-of-the-art thermodynamic databases for steels and it has already been shown
to be reliable in many instances. Likewise, although the calculated TMs is expected to have serious limitations, even systematic errors in TMs are not expected to produce the larger
dierences observed in the experiments. In light of this, we
are inclined to believe that reasons (2) or (4) may be at play,
and in the following section we proceed to investigate the
likelihood of these possibilities.

6127

retained austenite (Vf(Aus,4)), (2) volume fraction of IA-ferrite (Vf(Fer)), weight fraction of (3) manganese wcMn and (4)
silicon wcSi in IA-austenite. The reader is referred back to
Fig. 4a for a description of the terminologies.
1. The rst step in this approach is to guess
 theweight fraction of carbon in retained austenite wcC;2 after BIT.
With this estimate and the inputs from the experiments,
BIT
T BIT
Ms can be predicted by using Eq. (3). If T Ms is higher
than room temperature (300 K), the martensitic transformation is expected to occur upon quenching from
TBIT to room temperature. The amount of martensite
generated at this step is assumed as Vf BIT
Mar and can be
predicted as:
Vf BIT
Mar

Vf BIT
Mar
1  exp0:011 T BIT
Ms  300 
Vf Aus; 4

2. The second step is to guess the weight 

fraction
 of carbon
in austenite before the BIT treatment wcC;1 which is at
stage (2) in Fig. 4a. The calculation is similar to the rst
step, and T IA
Ms can be obtained in phase diagram; accordIA
ingly, if TBIT is lower than T IA
Ms ; Vf Mar can be estimated
using Eq. (4).

5. Resolving the discrepancies: reverse thermodynamic

calculation
5.1. Description of the method
The experiments shown in Fig. 8 suggest that the carbon
enrichment of the retained austenite after BIT is perhaps
higher than what one would predict based on the thermodynamic limit T 0 =T 00 . In this section, we investigate this
possibility, and at the same time we try to validate the thermodynamic model used, by combining thermodynamic
analysis along with the experimental observations. This
approach is termed reverse calculation because we are
trying to solve an inverse problem: given some experimental information about the state of the alloy after BIT and
IA, what is the likely evolution of carbon and other constituent elements in order to be consistent with the experiments? Essentially, we propose to use this approach to
estimate the carbon contents in austenite before and after
BIT which are similar to the numerical function of C-con0
 and wT 0 , in Fig. 4. For a given pair of carbon comtents, w
positions before and after BIT, the Vf(Bai) and Vf(Aus)
can be calculated by the lever rule. In addition, Vf IA
Mar and
Vf BIT
can
be
estimated
using
Eq.
(4).
Comparing
these
Mar
three volume fractions of phases with the experimental
results, the carbon contents can be estimated in an iterative
fashion. Fig. 9 contains the owchart for the reverse calculation and the schematic phase diagram for calculating the
potential carbon contents before and after BIT treatment.
In order to obtain the phase diagram, the following inputs
are adopted from experiments: (1) volume fraction of

Fig. 9. (a) Flowchart of the reverse calculation. (b) Schematic diagram of

paired carbon contents and phase diagram.

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3. With these calculations, the volume fraction of bainite

can be presented as:
BIT
Vf Bai 1  Vf Fer  Vf IA
Mar  Vf Mar  Vf Aus; 4

6
4. Applying the lever rule with the guessed and predicted
carbon concentrations before and after BIT, the volume
fraction of bainite can also be calculated as [19]:
wcC;2  wcC;1
Vf Bai c
7
wC;2  wpara;a
C
where wpara;a
is the carbon concentration in bainite under
C
para-equilibrium conditions.
5. Using Eqs. (6) and (7), the corresponding set of wcC;1 and
wcC;2 can be found at TBIT.
5.2. Validation
In order to verify this reverse thermodynamic analysis,
we use the conventional forward calculation as control. In
this forward calculation, TIA is 1003 K and TBIT is 528 K. In
the reverse calculation, there are two interdependent austenite carbon compositions, corresponding to the state of the
alloy before and after BIT. For a given guess for the carbon content in austenite at the end of BIT there will be a corresponding carbon concentration of IA-austenite. This
approach is illustrated in Fig. 10. A pair of colored points
which stand for wcC;1 and wcC;2 can always be found. One of
the results of this reverse analysis corresponds to a state with
15.4% bainite, which is close to the prediction by the forward
calculation. Comparing Vf (Mar), wcC;1 and wcC;2 , the relative
error is less than 1%. The results are listed in Table 4.
According to Table 4, wcC;1 under the equilibrium condition at 1003 K is 0.656 wt.% and the Mn and Si contents in
austenite are about 2.18 and 1.32 wt.%. The IA-ferrite occupies 52.9% of the total volume. These three parameters,
wMnwSi and Vf(Fer), are the input of the reverse calculation.
If the maximum carbon content in retained austenite meets
the T 00 curve, at 528 K, wcC;2 should be about 1.227 wt.%.
According to the lever rule and KM relation (Eqs. (7)
and (4)),the martensite and bainite should take 20.1% and
15.3% of the total volume, respectively, while the volume
fraction of the retained austenite is about 11.7%.
6. Application of the reverse thermodynamic analysis to the
experimental heat treatment schedules
6.1. Dierent TIA, constant TBIT
According to Table 2, in treatments A, B and E, three different TIA s, 1023, 1045 and 1083 K, are applied, while TBIT
is xed at 613 K. As mentioned above, the thermodynamic
predictions shown in Fig. 8a agree well with experiments if
one considers that the thermodynamic limit to the bainitic
transformation is actually T0. Now we apply the reverse calculation to examine treatments B and E in Table 2:

Fig. 10. The paired points obtained by reverse calculation (TIA = 1003 K,
TBIT = 528 K) which indicates the levels of wcC;1 and wcC;2 . Multiple solid
colors at each level represent the predictions of the iterative process that
nally converges.

Table 4
The predicted state of the product alloy according to the forward and
reverse calculations (TIA = 1003 K, TBIT = 528 K).
Forward
Reverse

Vf(Mar)

Vf(Bai)

wcC;1

wcC;2

0.201
0.200

0.153
0.154

0.656
0.659

1.227
1.227

1. After treatment B, wcC;2 is in the range of 1.141.22 wt.%

by reverse calculation and 1.12 wt.% according to the
XRD measurements. Correspondingly, wcC;1 should be
between 0.53 and 0.63 wt.% in order to obtain the
observed enrichment. This enrichment of IA-austenite
is only possible if the volume fraction of austenite after
IA were less than the one predicted at equilibrium. As
mentioned above, we have already demonstrated that
this is exactly the case when using IA treatment times
in the order of minutes to hours [38] with TIA of the
order of 1045 K.
2. In the case of treatment E, wcC;2 is determined 1.29 wt.%
by using XRD. Using the reverse calculation, the corresponding wcC;1 is found to be 0.358 wt.%. This predicted
value is close to 0.343 wt.% which corresponds to the
equilibrium state at 1083 K. With this low carbon content, martensite forms in the quenching process after
IA. Therefore, Vf(Mar,1) in treatment E is larger than
in treatment B because of wcC;1 . Although they have
the same TBIT, treatment E results in signicantly more
martensite than treatment B. This is the reason why the
treatment E yields higher carbon enrichment but a lower
volume fraction of retained austenite.
3. From the analysis of these two treatments, it is evident
that the closer the alloy is to equilibrium, the less carbon
is dissolved in austenite. On the other hand, under nonequilibrium conditions signicant further enrichment of
IA-austenite can be achieved. This can be understood in

S. Li et al. / Acta Materialia 60 (2012) 61206130

6129

terms of cementite being dissolved at the very beginning

of the IA treatment which provides abundant carbon to
austenite. Along with the IA treatment, carbon diuses
out of the austenite and further drives ferrite transformation into austenite. In other words, before the alloy
reaches equilibrium, the carbon content should be
higher than the equilibrium one. This observation is validated by analyzing another experiment, labeled F in
Table 2. In treatment F, the alloy is treated for 15 min
at 1045 K during IA. The predicted wcC;1 is 0.55 wt.%
and Vf IA
Mar is zero. Comparing B and F, the 2 h treatment
at 1045 K does not result in obvious dierences when it
comes to the amount of retained austenite after BIT,
even though wcC;1 s are notably dierent.
6.2. Dierent TBIT, constant TIA
According to Table 2, schedules B, C and D correspond
to treatments with the same TIA at 1045 K and TBIT at 613,
643 and 693 K, respectively. As shown above, the forward predictions shown in Fig. 8b do not agree with the
experimentally determined volume factions of austenite.
For each treatment, the observed amount of retained austenite is higher than the predicted one, with dramatic qualitative dierences with respect to the experimental
observations. This discrepancy suggests that the carbon
content in austenite after IA and BIT must be signicantly
higher than what one would predict using the thermodynamic approach. These three samples are treated by the
same IA treatment, and so the chemical composition is ideally identical and it is very likely that the composition of
austenite after IA is also quite similar.
Using the experimental inputs described above, the most
likely combinations of carbon content in austenite before
and after BIT are shown in Fig. 11. In the case of treatment
B, the most likely composition of IA-austenite wcC;1 is
0.53 wt.%, while in the case of treatment C, this composition is closer to 0.63 wt.%. While there is obviously some
uncertainty in the calculations, it is evident that wcC;1 lies
within the 0.530.63 wt.% range after 2 h at 1045 K. This
is signicantly higher than the expected IA-austenite carbon composition if one were to consider equilibrium conditions, but it is consistent with a reduced volume fraction of
austenite reported in Ref. [38].
More importantly than these results, Fig. 11 shows that
by using either the reverse analysis or XRD measurements, one can conclude that wcC;2 must be larger than
T0. This is perhaps the reason why the forward calculation
underestimates the volume fraction of retained austenite.
From this analysis, wcC;1 is about 0.060.16 wt.% larger than
the thermodynamic limit. This enrichment suppresses the
formation of martensite during the quenching process. This
explains why in treatment B, even though wcC;2 is less than
T0, the volume fraction of retained austenite can be larger
than the prediction based on the thermodynamic approach,
simply because of the dierent bounds for the lever rule.

Fig. 11. The reverse calculation while TIA = 1045 K; the dash and dashdot lines cover the range of wcC;2 and the corresponding wcC;1 .

6.3. Final remarkskinetic eects

Fig. 11 shows that in treatments C and D, the carbon
enrichment in retained austenite is clearly beyond the T0
curve. While the reason for this is at the moment uncertain,
it is possible that this super-enrichment of retained austenite is the result of competition between the bainitic transformation and carbon diusion in austenite [13,17]. If the
carbon diusion is relatively slow, the non-homogeneous
distribution of carbon is more obvious which results in
the higher probability of bainite nucleating and the higher
wcC;2 as a consequence. On the other hand, if the phase transition is much slower than carbon diusion, carbon evenly
distributes in austenite and decreases the driving force
gradually, which stops bainitic transformation at T00 . In
fact, several models have been proposed to predict the
kinetics of the bainitic transformation during BIT
[9,19,17]. It is important to note that due to the non-homogeneous distribution of carbon (i.e. the formation of a socalled C-rich austenite lm), the average carbon content
in retained austenite may be higher than the thermodynamic limit T00 [17,14].
7. Conclusion
In this work, we have presented a detailed thermodynamic analysis of the two-stage heat treatment necessary
to stabilize retained austenite in TRIP steels. The results
have been compared with experiments and it has been
shown that when comparing the eect of TIA on the volume
fraction of retained austenite, there is a qualitative agreement with experiments. In these cases, it has also been
shown that the enrichment of carbon in BIT-austenite is
greater than what one would expect considering the thermodynamic limit to the progression of the bainitic transformation during BIT. On the other hand, the analysis of
the eect of BIT on the amount of retained austenite

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S. Li et al. / Acta Materialia 60 (2012) 61206130

showed qualitative disagreement with the observations, as

the experiments suggest a much greater stability of retained
austenite against martensitic transformation.
To make sense of these discrepancies, a reverse thermodynamic analysis is proposed. Using this methodology it is
concluded that the discrepancy with the experiments could
be the result of the non-equilibrium nature of the austenite
after IA, particularly at relatively low TIA s. Further contribution to the observed discrepancies arises from the
observed carbon super enrichment of BIT-austenite. While
the reason for this is uncertain, this is likely the result of competition between the rate of bainite transformation and the
carbon diusion into austenite as baintic ferrite rejects it.
While this study is not exhaustive, the comparison with
the experiments also suggests that the use of thermodynamics to predict the amount of retained austenite after the
two-stage heat treatment of steels yields eectively a lower
bound for the expected retained austenite. The thermodynamic approach can be used to develop computational
optimization approaches to the design of heat treatments
in TRIP steels.
Acknowledgments
This study is funded by the US National Science Foundation, Division of Civil, Mechanical, and Manufacturing
Innovation, Materials and Surface Engineering Program,
Grant No. 0900187. The authors thank Dr. Pedro Rivera,
University of Cambridge, for discussions during the preparation of this manuscript. Dr. Paul Mason from ThermoCalc is acknowledged for his advice regarding the use of
the computational thermodynamics software.
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