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Modeling and Simulation of Iron-Carbon Phase Transformation During

Tempering of Steel

Article  in  RARE METAL MATERIALS AND ENGINEERING · February 2012

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Rare Metal Materials and Engineering
Volume 41, Suppl.1, February 2012
Cite this article as: Rare Metal Materials and Engineering, 2012, 41(S1): 006-012.

Modeling and Simulation of Iron-Carbon Phase Transfor-

mation During Tempering of Steel
Dong-ying Ju1, Xiao-hu Deng 2
1
Department of Mechanical Engineering, Saitama Institute of Technology, Saitama, Japan
2
Advanced Science Research Laboratory, Saitama Institute of Technology, Saitama, Japan

Abstract: Tempering is final process used in heat treatment of steel components. It is important to improve the toughness and
ductility of the quenched steel without a great loss of the hardness and strength. However, the traditional tempering process is hard to
satisfy requirements of combination mechanical properties with low cost. A quantitative model is developed to simulate the
micro-structural evolution during tempering process of carbon steel by modifying the previous Ju and Inoue’s model. The model
takes into account tempering parameters, carbon content and morphology for iron-carbon phases. Segregation of carbon atoms,
precipitation of transition carbides (ε-carbide), decomposition of retained austenite and precipitation of cementite can be predicted
respectively. The precipitation of carbides is modeled by considering the competitive precipitations of ε-carbide and cementite. The
kinetics of decomposition of retained austenite into ferrite and cementite is depicted by the modified Avrami equation. To validate
the model, it is applied to simulate the tempering process of the as-quenched plain carbon steel. The volume fractions of iron-carbon
phase are calculated at different tempering temperature and time. It is indicated that tempering time has greater effect on the volume
fraction of carbides at high temperature stage. The calculated results are reasonable consistent with the theoretical descriptions.

Key words: tempering; phase transformation kinetics; transition carbide; cementite

The heat treatment process simulation software, COSMAP
(Computer Simulation of Manufacturing Process) have been
developed by the present authors to simulate the quenching,
carburizing, nitriding, local heating/cooling processes.
COSMAP could be employed to predict the temperature dis-
tribution, phase transformation, stress/strain profiles in the
manner of the coupling between each other, and carbon and
nitrogen concentration in the case of carburizing and nitriding.
The software was the analytical software which was based on
the Metallo-thermo-mechanical theory developed by Inoue
and Ju [1-4] in the framework of finite element scheme.
Tempering is a common process of heating martensitic steel
to a temperature below the lower critical temperature. It is re-
garded as the final heat treatment process for steel parts.
As-quenched steels are tempered to achieve optimum combi-
nations of strength and toughness tailored to fit specific appli-
cations[5, 6]. The main variables that affect the microstructure
and the mechanical properties of as-tempered plain carbon
steel include tempering temperature, time at a temperature,
heating/cooling rate from the tempering temperature and car-
bon content of the steel[7, 8]. It is important to design appropri-
ate tempering process for as-quenched steel components. Re-
cently, some novel heat treatment processes have been devel-
oped by Speer [9-11] and Xu[12-14] respectively. Speer et al. pro-
posed a new process, “quenching and partitioning” [9]. The
process was applied to low-carbon TRIP sheet and medi-
um-carbon bar steel and ductile cast iron. A modified process
designated[14] quenching-partitioning-tempering process was
developed based on the quenching and partitioning process[9].
The process was applied to ultrahigh-strength and
high-strength steels for obtaining good ductility. However, the
thermodynamic and kinetic mechanisms have not been devel-
oped perfectly. Therefore, computer simulations are employed
to model the tempering process of steels.
A quantitative model is constructed to simulate the mi-
cro-structural evolution during the tempering process of car-
bon steel by modifying the previous model[2] in COSMAP.
The paper is organized as follows: The review of tempering
kinetic models are presented in section 2, the modified model
is described in section 3, the results of tempering simulations

Received date: May 25, 2011

Foundation item: support by the High-tech Research Center and Open Research Center at the Saitama Institute of Technology.
Corresponding author: Dong-ying Ju, Ph. D., Professor, Department of Mechanical Engineering, Saitama Institute of Technology, Fukaya, 369-0293, Japan, Tel:
+81-048-585-6826, E-mail: dyju@sit.ac.jp.

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 Dong-ying Ju et al. / Rare Metal Materials and Engineering, 2012, 41(S1): 006-012
are discussed in section 4, and the conclusions are given in the
final section.
1 Reviews of Phase Transformation Models in
Tempering
The tempering process involves micro-structural evolution
during heating. The origin microstructure obtain after
quenching from austenite consists of plates or laths martensite,
which is super-saturated with carbon and thin films of retained
austenite. The meta-stable martensite and retained austenite
transform into more stable phases. In the past decades, many
scholars have carried out the experimental and theoretical re-
searches on tempering process of steels[15-23]. It is general ac-
cepted that the tempering can be divided into five distinct but
overlapping stages as follows [5-8].
(1) Tempering stage 0 (273~353 K)
Redistribution of carbon atoms takes place by segregation
to dislocations or diffusion to interlath-retained austenite.
(2) Tempering stage 1 (353~453 K)
Precipitation of transition carbide occurs during this stage.
The ε -carbide precipitates in the martensite. This carbide
has a close-packed hexagonal structure. In the high-carbon
steels, an increase in hardness has been observed on tempering
in the range 323~373 K, which is attributed to precipitation
hardening of the martensite by ε-carbide. At the end of stage 1,
the martensite still possesses tetragonality, and the carbon
content of the matrix lower to around 0.25 wt%.
(3) Tempering stage 2 (473~573 K)
During stage 2, retained austenite is decomposed into a
mixture of ferrite and cementite. In martenstic plain carbon
steels below 0.5 wt% C (carbon), the retained austenite is of-
ten below 2%, rising to around 6% at 0.8 wt% C and over
30% at 1.25 wt% C.
(4) Tempering stage 3 (473~623 K):
During the third stage of tempering, segregated carbon and
transition carbides transform into cementite. The likely sites
for the nucleation of the cementite are the ε-carbide interfaces,
Fig.1 Phase transformation with different temperature in tempering process
the twins in the higher carbon martensites and grain boundary
regions (both the interlath boundaries of the martensite and the
original austenite grain boundaries). The matrix has now lost
its tetragonality and became ferrite (0.001~0.02 wt% C).
(5) Tempering stage 4 (>623 K)
Tempering at even higher temperatures leads to a coarsen-
ing and spheroidization of the cementite particles. The coars-
ening commences around 673K, while spheroidization takes
place increasely up to 973K. At the higher end of this range of
temperature, the martensite lath boundaries are replaced by
more equiaxed ferrite grain boundaries by a process which is
best described as recrystallization.
Phase transformations in tempering involve mainly precipi-
tation of carbides and decomposition of the retained austenite.
Based on the above description, micro-structural evolutions
are outlined in Fig.1 depending on the tempering temperature.
In the past decade, many attempts have been carried out to
predict the phase transformation dynamics during the temper-
ing process. Several typical models exist to simulate
iron-carbon phase compositions are described below.
1.1 Ju and Inoue’s model
Ju and Inoue[2] proposed a metallo-thermo-mechanical
model to predict the kinetics of quenching-tempering process.
In their model, the as-tempered structure was regarded as
low-carbon martensite (consists carbide and low degree
over-saturated α solid solutions). The volume fraction of de-
veloping phase might be expressed by modifying the John-
son-Mehl relation as follows:
( )
t
1 − exp − ∫ f1 (T ) f 2 (σ ij )(t − t )3 dt
x= (1)
0
where, t is time, τ is transformation start time, f1(T) stands
for TTT diagram without stress, f2(σij) stands for TTT diagram
under the applied mean stress σm.
The model was employed to simulate the quench-
ing-tempering process of S45C steel. The results of simulated
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 Dong-ying Ju et al. / Rare Metal Materials and Engineering, 2012, 41(S1): 006-012
distributions of martensite and low-carbon martensite were
depicted after tempering process at different temperature and
time. It is conclude that volume fraction of low-carbon mar-
tensite was shown to be increased owing to ε-carbide precipi-
tates from martensite.
1.2 Liu’s model
Liu et al. [24, 25] developed a model based on tempering pa-
rameter to predict the micro-structural evolution during
quenching and tempering process. In their model, tempering
parameter presented the combined effects of both heating time
and temperature on tempering process. Tempering parameter λ
was defined as logarithm of reaction volume X.
 Q 
=X Aτ exp  − 
 RT 
Q = 
l=logτ − + log A
2.3RT
Transformation fraction of martensite during tempering was
predicted using a modified Avrami equation as following.
λλ
− 0 C
x= 1 − exp[− A( ) ] (4)
λλ
1− 0
where, parameter A and C are related with materials, λ0
corresponds to 1% transformation fraction, and λ1 corresponds
to 99% transformation fraction.
The model was employed to predict micro-structural evolu-
tions during tempering process. The simulated results of the
newly designed tempering process were compared with those
from conventional process. It is proved that the conventional
and newly process had the identical results with the newly
process being operated easily and saving about 50 h or so.
1.3 Denis and Aubry’s model
Aurby and Denis [26,27] have developed the global kinetics of
tempering in low-alloy steels. The tempering kinetics on heat-
ing was calculated by isothermal transformation (IT) temper-
ing diagram additivity. Tempering was described through three
independent kinetics processes: the precipitation of transition
carbide, the decomposition of retained austenite into ferrite
and cementite and the transformation of the transition carbide
into cementite, each modeled by a Johnson-Mehl-Avrami
equation.
( (
yK = yKmax 1 − exp −bK (T )t nK (T ) ))
where, yK is the volume fraction of constituent K, yKmax is the
maximum than can be formed at a given temperature, nK and
bK are coefficients that are determined for each temperature
from IT diagram.
They analyzed the effect of self-tempering on the carbu-
rized and quenched process. The self-tempering rates profiles
were predicted by this model. The simulated results indicated
that the effect of self-tempering on martensite did not seem to
be of great influence on the residual stress.
1.4 Wang and Denis’ model
Wang and Denis [28,29] presented a model for describing the
concomitant precipitation of ε -carbide and cementite during
the tempering of martensite, including the nucleation, growth,
coarsening process of carbides. The nucleation rates were de-
scribed by the classical nucleation theory.
∆G*
( N total N act ) Z β exp(−
J =− ) (6)
KT
where, Ntotal is the total number of nucleation sites pre unit
volume, Nact is the number of nuclei formed, R is the gas con-
stant, Z is the Zeldovich factor, β is the attachment rate of the
atoms surrounding the critical nucleus, ΔG* is the critical nu-
cleation energy, and T is the absolute temperature.
(2) The growth or the dissolution rate
dR D  X − X e exp  2g VP /( RgTR )  
 (7)
(3) dt R  X P − X e exp  2g VP /( RgTR )  
 
Where, VP is the molar volume of precipitate, Rg is the gas con-
stant, XP is the carbon molar fraction in the precipitate, X is the
average carbon molar fraction in the matrix, and Xe is the equi-
librium carbon molar fraction at the precipitate/matrix interface.
The model was applied to simulate isothermal tempering of
Fe-0.8C martensite. The simulated results were presented for
tempering at 300 ℃ and 700 ℃. The volume evolution of
ε-carbide and cementite were predicted during the tempering
time. The model could predict not only the kinetics of precipi-
tations but also the micro-structural evolutions. The calculated
values fit well with the experimental results.
1.5 Lee’s model
The tempering kinetics equation was developed using tem-
pered martensite fractions (calculated by experiment) and the
measured strain changes at each tempering stage[30-31]. The Ki-
netics equation was expressed in an ordinary differential form.
Q
y =k0 ⋅ (TC − T ) n .exp(− ) ⋅ yα (1 − y ) β (8)
RT
Where, y is the fraction of tempered martensite, Q is the acti-
vation energy, k0, α, β and n are optimized constants, TC is the
maximum heating temperature of tempering.
The tempering kinetics for tempering stages 1 and 3 of
S45C steel were calculated by the tempering kinetics equation,
(5)
and the calculated tempering kinetics showed a good agree-
ment with the experimental tempering kinetics.
Through some phase transformation kinetic models have
been developed to simulate the micro-structural evolutions in
tempering process[2, 24-31], there were too many assumptions in
these model. Moreover, these models did not treat the carbon
segregation in martensite. Therefore, a modified model is de-
veloped to predict the micro-structural during tempering pro-
cess of steel.
2 Modeling of Transformation in Tempering
In the present model, the transformation of tempering pro-
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 Dong-ying Ju et al. / Rare Metal Materials and Engineering, 2012, 41(S1): 006-012

cess is divided into three parts, segregation and clusters of
carbon atoms, precipitation of carbides and decomposition of
retained austenite. In order to simplify model, three basis as-
sumptions are made as following:
Firstly, the super-saturated martensite is a dilute solid solu-
tion, and carbon concentration in martensite matrix is uniform.
Secondly, the effects of alloy elements are not taken into
account.
Thirdly, the heating rate is kept constant during tempering =
process.
2.1 Segregation and clusters of carbon atoms
The dynamics of segregation of carbon atoms can be de-
scribed by JMA-like equation
{ }
Cm =C f + (C0 − C f ) ⋅ exp − β ene + (C − C0 ) ⋅ exp − βCnC{ (9) }
where, Cm is the carbon concentration of martensite during
tempering, Cf is the carbon concentration of ferrite, C0 is the
initial carbon concentration.
For isothermal transformations, β is
where, Cα1′ and Cα are the carbon concentration of marten-
site after first-stage and second-stage tempering respectively,
the value are 0.002 and 0.00021 approximately；Cε and Cθ are
the limit concentration of ε -carbide and cementite respec-
tively, the value are 0.0822 and 0.0667.
For θ phase, the value of active energy Q，the value of
frequency factor K0 and the value of Avrami exponent n can
be calculated by
Qθ 308389.22 − 2.5269403 ⋅ 107 ∗ C + 1.3054721 ⋅ 109 ∗ C 2 (22)
K 0θ = 1024.48536 −1299.775∗C + 6532.9∗C
2
(23)
= nθ 0.21825 + 1.96 ∗ C − 746.1 ∗ C 2 (24)
2.3 Decomposition of retained austenite
Decomposition of retained austenite is similar with the
original austenite transformation in quenching process. The
kinetics of decomposition of austenite can be described by a
modified Avrami equation [2]
 4 t 
 3 0 ∫
x=i x imax 1 − exp(− π f (T )(t − t ) ni dt 

(25)

= β (t ) K 0 exp(−
Q
)t (10) For α and θ phase, nα and nθ is 2.5 and 3 respectively,
RT (t ) xamax and xθmax can be calculated by
For isochronal transformation, β can be calculated by follow- C − Cq
xaa
= x=
max eq
ing equation −C
Caq
(26)
t Q C − Ca
β=
0 ∫
(t ) K 0 − exp(
RT (t )
)dt (11) xqq
= x=
max

−C
Cqa
eq

For non-isothermal analysis with constant heating rate where, C is the current carbon content Cα and Cθ are the limit
Φ=dT/dt, the time integral can be replaced by a temperature concentration of ferrite and cementite respectively, the value
integral are 0.00021 and 0.0667.
K0 T Q
∫
The critical temperature of decomposition of the retained
=β (t ) exp(− )dT ′ (12)
Φ T0 RT ′ austenite is
Integration of equation (3) resulted in [8, 19, 33] =TC 490.50 + 977.65 ∗ C − 417.57 ∗ C 2 (27)
RT 2 Q RT 2.4 The procedures of transformational simulation
=β (T ) K 0 exp(− )(1 − 2 + ⋅⋅⋅) (13) Base on the above equations and theoretical description for
ΦQ RT Q
tempering, a phenomenological model is developed to predict
The value of active energy Q，the value of frequency factor K0
quantitatively the volume fraction of the different stages in
and the value of Avrami exponent n can be calculated by
tempering process. The simulated program consists of the fol-
QC = −5844.312 + 1.86527 ⋅ 107 ∗ C − 7.2987 ⋅ 108 ∗ C 2 (14)
lowing modules: (1) Input module, (2) Computing module,
=
Qε 87674.95 + 6.242382 ⋅ 106 ∗ C − 2.298548 ⋅ 108 ∗ C 2 (15)
and (3) Output module. In the computing module, the precipi-
K 0C = 10−2.96129 − 2839.78∗C +107231.78∗C
2
(16)
tation of carbides and decomposition of retained austenite are
K 0ε = 1013.26042 − 689.186∗C +87296∗C
2
(17)
independent process. The flowchart of transformational pro-
=
nC 1.57222 + 313.455 ∗ C − 19740.26 ∗ C 2 (18)
gram is shown in Fig.2.
= nε 0.13596 + 74.636 ∗ C − 5064.9 ∗ C 2 (19)
2.2 Precipitation of carbides 3 Model Application and Results
The kinetics of the precipitation of carbides can be de-
The model is applied to simulated transformation in tem-
scribed by Johnson-Mehl-Avrami equation for heterogeneous
pering process of the as-quenched carbon steel.
solid-state reactions:
⋅ 1 − exp {− βi n }）
In this model, carbon content in martensite is 1.1%, and
x=i ximax （ (20)
volume fraction of martensite and retained austenite is 0.9 and
xεmax
and xθ max
can be calculated by
0.1 respectively. The tempering process parameters are shown
C − Ca1′
xee = x=
max eq in Fig.3. To validate the tempering model, the simulations are
Cea−C ′ presented at different tempering temperature (473-873 K) and
(21)
C − Ca tempering time (20-60 min).
xqq = x=
max eq
Cqa−C Fig.4 shows the predicted volume fraction of as-tempered

9
 Dong-ying Ju et al. / Rare Metal Materials and Engineering, 2012, 41(S1): 006-012

1.0 0.012
a 500

0.8 0.010

Carbon Concentration
Volume Fraction
Temperature
450 0.008

Temperature/K
0.6
Carbon
0.006
Epsilon 400
0.4 Cementite
Tempered martensite 0.004
Ferrite
0.2 Retained austenite 350 0.002

0.0 0 0.000
10 101 102 103 104
1.0 0.012
b 500

0.8 0.010

Carbon Concentration
Volume Fraction
Temperature
450 0.008

Temperature/K
0.6
Carbon
Epsilon
0.006
400
0.4 Cementite
Tempered martensite 0.004
Ferrite
0.2 Retained austenite 350
0.002
Fig.2 Flowchart of transformational program in tempering
0.0 0 0.000
10 101 102 103 104
1.0 0.012
c 500

0.8 0.010

Carbon Concentration
Volume Fraction

450 0.008
Temperature

Temperature/K
0.6
Carbon
Epsilon
0.006
400
0.4 Cementite
Tempered martensite 0.004
Ferrite
0.2 Retained austenite 350 0.002

0.0 0 0.000
10 101 102 103 104
Time/s

Fig.3 Temperature history of tempering process
microstructure in different tempering time at temperature
473 K.
It can be seen that the carbon concentration in martensite
drop quickly with the raise of temperature. The reason is that
interstitial carbon atoms in the tetragonal martensite lattice
may segregate to dislocations or may diffuse to interlath re-
tained austenite. With the rejection of carbon, the martensite
changes into low carbon martensite. It is presented that
ε-carbide precipitates and reaches a maximum volume fraction
xεmax with the tempering process. The decomposition of re-
tained austenite and precipitation of cementite have not been
occurred at the tempering temperature 473 K. It is indicated
that the volume fraction of ε-carbide is independent on the
tempering time at the relatively low-temperature tempering.
Fig.5 shows the volume evolution of as-tempered micro-
structure during the tempering time at temperature 623 K. It
can be seen that the retained austenite is decomposed
Fig.4 Simulated volume fraction of as-tempered microstructure in
different tempering time at temperature 473 K: (a) 20 min, (b)
40 min, and (c) 60 min
into ferrite and cementite phases. In addition, the simulated
results show that ε-carbide dissolution in the matrix is con-
comitant with the precipitation of cementite. The volume frac-
tion of cementite contains both precipitated and decomposed.
From Fig.5a-Fig.5c, it is indicated that volume fraction of ce-
mentite increase slowly as the tempering time.
Fig.6 and Fig.7 show the simulated volume fraction of
as-tempered microstructure after tempering process at 773K
and 873 K. It can be seen that the precipitation of cementite
with the increase of tempering time (Fig.6). In Fig.7, the vol-
ume fraction of cementite increases and reaches the maximum
value xθmax , ncentration increase, the ε-carbide gradually dis-
appear.
As shown as in Fig.4- Fig.7, the tempering time has smaller
effect under the lower tempering temperature. By contrast, the

10
 Dong-ying Ju et al. / Rare Metal Materials and Engineering, 2012, 41(S1): 006-012

as-quenched steel. The segregation of carbon atoms, decom-

1.0 0.012
a position of the retained austenite and precipitation of carbides
600 0.010 are considered. The model is employed to simulate the tem-
0.8

Carbon Concentration
pering process of as-quenched steel (1.1%-C).
Volume Fraction

Temperature
0.008

Temperature/K
0.6 Carbon
Epsilon 500
Cementite 0.006 1.0 0.012
a
0.4 Tempered martensite 750
Ferrite 0.004 0.8 0.010

Carbon Concentration
Retained austenite 400

Volume Fraction
0.2 0.008

Temperature/K
0.002 Temperature
0.6 Carbon 600
0.0 0 0.000 Epsilon 0.006
10 101 102 103 104 0.4 Cementite
1.0 0.012 Tempered martensite 0.004
b Ferrite 450
600 0.2 Retained austenite
0.002
0.8 0.010

Carbon Concentration
Volume Fraction

0.008 0.000
Temperature/K

Temperature 0.0 0
0.6 10 101 102 103 104
Carbon 500
0.006 1.0 0.012
Epsilon b
0.4 Cementite 750
Tempered martensite 0.004 0.010
0.8

Carbon Concentration
Ferrite 400
Volume Fraction
0.2 Retained austenite 0.008

Temperature/K
0.002 Temperature
0.6 Carbon 600
0.0 0 0.000 Epsilon 0.006
10 101 102 103 104 0.4 Cementite
Tempered martensite 0.004
1.0 0.012
c Ferrite 450
600 0.2 Retained austenite
0.010 0.002
0.8
Carbon Concentration

0.000
Temperature/K
Volume Fraction

Temperature 0.008 0.0

0.6 500 100 101 102 103 104
Carbon
0.006 1.0 0.012
Epsilon c
0.4 Cementite 750
Tempered martensite
400 0.010
0.004 0.8

Carbon Concentration
Ferrite
Volume Fraction

0.2 Retained austenite 0.008

Temperature/K
0.002 Temperature
300 0.6 Carbon 600
0.0 0.000 Epsilon 0.006
100 101 102 103 104 0.4 Cementite
Tempered martensite 0.004
Time/s Ferrite 450
0.2 Retained austenite
0.002
Fig.5 Simulated volume fraction of as-tempered microstructure in
different tempering time at temperature 623 K: (a) 20 min, (b) 0.0 0 0.000
10 101 102 103 104
40 min, and (c) 60 min
Time/s

volume fraction of cementite increases with the tempering

Fig.6 Simulated volume fraction of as-tempered microstructure in
time under the relatively higher tempering temperature. The
different tempering time at temperature 773 K: (a) 20 min, (b)
simulated results are consistent with the previous theoretical
40 min, and (c) 60 min
summaries.

4 Conclusions The distribution of the carbon and volume fractions of

iron-carbon phases can be predicted quantitatively by this
A number of models to simulate the phase transformation model. It is concluded that tempering temperature and tem-
dynamics during tempering process have been developed. pering time have great effect on the generated phase during
Several typical models are briefly reviewed. The tempering the tempering process. The simulated results are in reasonable
transformation dynamics were predicted successfully by these agreement with the theoretical analysis. This model is also the
models. base for further simulations of the evolutions of mechanical
A phenomenological model has been developed to simulate properties during tempering process.
the as-tempered microstructure after tempering process of

11
 Dong-ying Ju et al. / Rare Metal Materials and Engineering, 2012, 41(S1): 006-012

7 G R Speich, W C Leslie. Metallurgical Transactions[J], 1972,

1.0 0.012
a 3(5): 1043
800 0.010 8 C Liu, C M Barkman, B M Korevaar et al. Metallurgical Trans-
0.8

Carbon Concentration
actions A[J], 1988, 19(10): 2415
Volume Fraction

Temperature 0.008

Temperature/K
0.6 9 J Speer, D K Matlock, B C De Cooman et al. Acta Materialia[J],
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0.4 Cementite 10 J Speer, F C Rizzo, D Matlock et al. Materials Research[J], 2005,
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gineering A[J], 2006, 438-440: 25
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10 10 10 10 10
1.0 0.012 13 Z Y Xu. International Heat Treatment and Surface Engineer-
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14 X D Wang, N Zhong, Y H Rong et al. Journal of Materials Re-

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Temperature 0.008
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