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Scripta Materialia 64 (2011) 649–652

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Mn partitioning during the intercritical annealing

of ultrafine-grained 6% Mn transformation-induced plasticity steel
Seok-Jae Lee,⇑ Seawoong Lee and Bruno C. De Cooman
Materials Design Laboratory, Graduate Institute of Ferrous Technology, Pohang University of Science and Technology,
Pohang 790-784, Republic of Korea
Received 12 November 2010; revised 9 December 2010; accepted 11 December 2010
Available online 16 December 2010

The partitioning of Mn to austenite formed during the intercritical annealing of an ultrafine-grained 6% Mn transformation-
induced plasticity steel was investigated by means of transmission electron microscopy–energy-dispersive spectroscopy and dilatom-
etry. The partitioning of Mn to ultrafine austenite grain was observed during annealing of cold-rolled martensite where no prior
partitioning of alloying elements had occurred. The calculated volume contraction related to the austenite formation and the asso-
ciated alloying element partitioning as verified by the Mn partitioning during the intercritical annealing was compared with the mea-
sured result.
Ó 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Keywords: Mn partitioning; Intercritical annealing; Ultrafine grain (UFG); Retained austenite

Transformation-induced plasticity (TRIP) steel
is an advanced high-strength steel with an excellent com-
bination of strength and ductility, due to the high rate of
work hardening that results from the strain-induced
martensitic transformation of retained austenite [1].
Controlling the amount and stability of the retained aus-
tenite at room temperature is essential to achieve a good
combination of mechanical strength and ductility. Three
factors influence the stability of the metastable retained
austenite at room temperature:
(i) Chemical composition: both carbon and manga-
nese are strong austenite stabilizers. The addition
of manganese can result in a stable austenite equi-
librium at room temperature [2].
(ii) Grain size: a small grain size affects the austenite
stability by lowering the martensite start tempera-
ture [3,4].
(iii) Mechanical stabilization: the correct amount of
dislocations in austenite effectively suppresses the
transformation kinetics of martensite [5].
Recently ultrafine-grained (UFG) TRIP steel contain-
ing 5–7 wt.% Mn has attracted considerable attention be-
cause of its enhanced strength and ductility, which result
from the large phase fraction of submicron-size austenite
[6,7]. Previous reports about the mechanical properties of
⇑ Corresponding author. E-mail: seokjaelee@postech.ac.kr
UFG Fe–0.05C–6.15Mn–1.4Si (in mass%) TRIP steel
mentioned anomalous austenite stability [8,9]. The grain
size of the TRIP steel annealed in the narrow temperature
range between 640 and 680 °C was 250 nm on average. It
was also reported that Mn and C seemed to have parti-
tioned to austenite during intercritical annealing despite
the short annealing time of 180 s. The evidence presented
included X-ray diffraction (XRD) of the retained aus-
tenite and energy-dispersive X-ray spectroscopy (EDS)
analysis of transmission electron microscopy (TEM)
foils. The occurrence of the observed Mn partitioning
at these relatively low annealing temperatures for a short
holding time could have been due to prior local Mn
enrichment during the hot rolling of the alloy. The objec-
tive of the present study was therefore to investigate
whether the Mn partitioning actually took place during
the intercritical annealing. This was done by a quantita-
tive analysis of the partitioning of the alloying additions
of C and Mn by means of dilatometry.
An ingot with the chemical composition Fe–0.05C–
6.15Mn–1.4Si–0.04Al (in mass%) was prepared by vac-
uum induction melting, then reheated to 1250 °C and
hot-rolled prior to quenching to 200 °C with a water
spray. The hot-rolled material, which was fully martens-
itic, was cold-rolled to a final thickness of 1 mm. Light
optical microscopy and XRD analysis were carried out
to analyze the microstructure of the cold-rolled sheet,
and heavily deformed martensite was observed.

1359-6462/$ - see front matter Ó 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.scriptamat.2010.12.012
650 S.-J. Lee et al. / Scripta Materialia 64 (2011) 649–652
Dilatometric samples (5  1  10 mm3) from the
cold-rolled sheet were heated up to intercritical temper-
atures of 640, 660, and 680 °C at a heating rate of
3 °C s1 and held for 180 s, then cooled to room temper-
ature at a rate of 30 °C s1. The annealing conditions
were selected on the basis of previous work [8,9]. Speci-
mens for TEM were prepared using the focused ion
beam technique. Nanobeam EDS was used to investi-
gate the content of Mn in both the retained austenite
formed during intercritical annealing and the martensite
matrix. XRD analysis and DICTRA calculations were
also carried out to determine the partitioning of Mn
and C to the austenite during intercritical annealing.
Assuming an isotropic behavior, the fundamental
relationship between the measured strain and the rela-
tive volume change of a solid phase is expressed in Eq.
(1) [10–14]:
 
Dl l  l0 1 V  V 0 1 DV
¼ ¼ ¼ ð1Þ
l0 l0 3 V0 3 V0
where l0 and V 0 are the sample length and volume at a
reference temperature, and l and V are the sample length
and volume at a given temperature.
The longitudinal transformation strain equation for
austenite formation from martensite can be derived by
considering the crystal structure change from body-cen-
tered tetragonal (bct) for martensite to face-centered
cubic for austenite:
     parent phase. If both the Mn concentration in the inter-
Dl 1 ð1=4Þa3A V A þ ð1=2Þa2M cM ðV iM  V A Þ
¼  1
l M!A 3 ð1=2Þa2M cM V iM
where aA is the lattice parameter of austenite, aM is the lat-
tice parameter of martensite on the a-axis, cM is the lattice
parameter of martensite on the c-axis, V iM is the initial vol-
ume fraction of martensite and V A is the volume fraction
of transformed austenite. The volumetric change in Eq.
(2) is for the relative volume change per single iron atom.
The volume of the unit cell consists of lattice parameters,
e.g. a2M cM for martensite and a3A for austenite. Alloying
elements affect the lattice parameters of both martensite
and austenite. Eqs. (3) and (4) are for the a- and c-axis lat-
tice parameters, respectively, of martensite, and Eq. (5)
gives the austenite lattice parameter dependence on the
austenite composition as follows:
!
X creases with increasing intercritical annealing tempera-
aM ¼ aM;Fe þ kM
C1 X C þ kM
i Xi ½1 þ aM ðT  298Þ ðnmÞ
i recrystallization of 75% deformed martensite occurred
! intercritical holding time of less than 5 s. The initial de-
X formed martensite was therefore fully recrystallized to
cM ¼ aM;Fe þ k M
C2 X C þ kM
i X i ½1 þ aM ðT  298Þ ðnmÞ
i
! ment in the body-centered cubic lattice of recrystallized
X ferrite by considering the effect of the small carbon con-
aA ¼ aA;Fe þ kA
i X i ½1 þ aA ðT  298Þ ðnmÞ
i
where aM;Fe is the lattice parameter of ferrite that is an
equal value of the lattice parameter of martensite in
carbon-free iron at room temperature, i.e. 0.28664 nm
[10]. aA;Fe is the lattice parameter of austenite in pure
iron at room temperature, i.e. 0.35729 nm [10]. k M C1 is
the coefficient taking into account the influence of car-
bon on the martensite a-axis lattice parameter, k M C2 is
the coefficient taking into account the influence of car-
bon on the c-axis martensite lattice parameter and k M i
is the coefficient taking into account the effect of alloy-
ing element i on the martensite lattice parameter assum-
ing that this effect is isotropic. k A
i is the coefficient for the
effect of alloying element i on the austenite lattice
parameter, X i is the atomic percent of the alloying ele-
ment i, aM is the thermal expansion coefficient of mar-
tensite, aA is the thermal expansion coefficient of
austenite and T is the temperature in kelvin, respec-
tively. The coefficients k M A
i and k i [10,11,15,16] are listed
in Table 1. The C and Mn concentration-dependent
thermal expansion coefficients of martensite and austen-
ite are as follows [10,11]:
aM ¼ ð14:9  1:9X C  0:1471X Mn Þ  106 ðK1 Þ ð6Þ
aA ¼ ð23:875  0:5X C  0:1784X Mn Þ  106 ðK1 Þ ð7Þ
As alloying elements partition between the ferrite and
the austenite, the lattice parameter and thermal expan-
sion coefficient of these phases will be affected, as sug-
gested by Eqs. (3)–(7). The content of a partitioning
element can therefore be predicted from the mass bal-
ance relation between the transformed phase and the
critical austenite phase and the volume fraction of inter-
critical austenite are known, the amount of Mn
ð2Þ partitioned to the martensite phase can be determined
by means of the following equation:
X 0Mn  X A
Mn V A
XM
Mn ¼ ð8Þ
1VA
where X M Mn is the mass concentration of Mn in martens-
ite, X A
Mn is the mass concentration of Mn in the intercrit-
ical austenite, which can be determined experimentally,
X 0Mn is the total Mn concentration and V A is the volume
fraction of austenite.
Figure 1 shows the dilatometric curves for three dif-
ferent intercritical annealing processes. The strain con-
traction in the intercritical range is induced by the
formation of intercritical austenite in the martensitic
matrix. The size of the strain reduction therefore in-
ture (IAT). Tokizane et al. [17] reported that the
ð3Þ around the Ac1 temperature and finished after a short
ferrite containing an excess amount of carbon during
slow heating. Eqs. (3) and (4), which are for bct mar-
ð4Þ tensite (a0 ), can be used to determine the carbon enrich-
ð5Þ
tent in the ferrite on its lattice parameter.
Figure 2 shows the change of the Mn distribution
across an ultrafine austenite grain after the annealing
at 660 °C, as determined by TEM–EDS analysis. The
distribution of alloying elements partitioning in the
 S.-J. Lee et al. / Scripta Materialia 64 (2011) 649–652
Table 1. Coefficients for the influence of alloying elements on the lattice parameter of martensite and austenite [10,11,15,16] (in nm per at.%).
C Mn
Martensite (k M
i ) 2.898  104 (a-axis)
2.5855  103 (c-axis)
Austenite (k A
i ) 7.83  104
Figure 1. Dilatometric strain changes related to austenite formation
and the associated Mn partitioning during an intercritical annealing
for 180 s at different isothermal temperatures.
Figure 2. Variation of the distribution of Mn content across ultrafine
austenite grains before and after annealing at 660 °C. The central
region indicates the location of an austenite grain formed from a single
grain of deformed martensite prior to annealing.
cold-rolled sample before annealing and in the samples
annealed at different temperatures was also analyzed.
The initial microstructure of the cold-rolled material
was heavily deformed martensite and all the alloying ele-
ments, including Mn, were distributed uniformly. The
Mn content of an austenite grain in the sample annealed
at 660 °C was about 9.4 mass%, while the content of Mn
in recrystallized ferrite matrix was 5.13 mass%. Both Mn
contents in the austenite grain and the recrystallized fer-
rite matrix were average values determined experimen-
tally. The equilibrium content of Mn in austenite was
also found to be approximately 9.47 mass% by means
651
Si Al
5.43  105 3.0  105 6.0  104
1.144  104 0.0 2.8  104
of Thermo-Calc analysis. The content of Mn in austen-
ite partitioned during the annealing at 660 °C reaches
the equilibrium concentration. It is assumed that the
presence of UFG austenite, the average size of which
was about 250 nm [9], made the Mn partitioning extre-
mely efficient. The average size of austenite grains
formed in the early stage of transformation is much less
than 250 nm and the ratio of the boundary surface to the
volume in these initial austenite grains is considerable.
Mn atoms can quickly diffuse into the very small austen-
ite grains and achieve an equilibrium concentration. The
holding time of 180 s at relatively low temperatures does
not accelerate the austenite growth, but it is a sufficient
condition for the uniform equilibrium distribution of
Mn in the austenite due to the ultrafine grain size.
The average chemical compositions of retained UFG
austenite transformed at different IATs are listed in Ta-
ble 2. The contents of Si and Al in retained austenite
grains were not significantly different from their initial
uniform distribution in the cold-rolled sample. The C
content was in the range of 0.08–0.09 mass%. This range
of C content was also found by the DICTRA simulation
of the intercritical cycle conditions. The C and Mn con-
tents in the intercritical austenite were found to decrease
with increasing IAT as a result of the increased volume
fraction of austenite. Lis et al. [18] investigated the par-
titioning of Mn and C in austenite in the intercritical
temperature range. They did not observed the partition-
ing of the alloying elements Si, Ni and Cr between the
ferrite matrix and the second phase.
Figure 3 shows the effect of the partitioning of C and
Mn on the strain contraction during the intercritical
austenite formation. The reduced strain corresponds to
the isothermal annealing cycles shown in Figure 1. The
calculated strain reduction was in agreement with the
measured value of C and Mn concentrations, taking into
account their full equilibrium partitioning between aus-
tenite and ferrite. The strain contraction calculated by
considering only the C partitioning para-equilibrium-
like condition shows a larger negative strain. The strain
contraction calculated for the absence of any partition-
ing shows a similarly large negative strain. The calcula-
tion points to two important facts. First, the Mn
partitioning between the ultrafine grains of transformed
Table 2. Chemical composition (in mass%) of retained austenite and
volume fraction of retained austenite [9] for samples annealed at
different IATs.
C Mn Si Al VA
IAT640 0.093 11.6 1.4 0.04 0.163
IAT660 0.088 9.4 1.4 0.04 0.229
IAT680 0.079 7.3 1.4 0.04 0.335
Alloy composition 0.050 6.15 1.4 0.04 0
No partitioning of Si and Al was observed after the intercritical
annealing.
652 S.-J. Lee et al. / Scripta Materialia 64 (2011) 649–652
Figure 3. Effect of alloy partitioning on the strain reduction related to
austenite formation during intercritical annealing at different temper-
atures. The filled circular symbols with an error bar correspond to the
measured strain change. The open rectangular symbols are for the
calculated strain contraction considering full partitioning. The open
lozenge symbols are for the calculated strain contraction considering C
partitioning only. The open triangles are for the strain contraction
calculated in the absence of C and Mn.
austenite and the recrystallized ferrite is effective during
the intercritical annealing even though the holding time
at the relatively low IAT is short. Second, the effect of
the alloying elements on lattice parameter and thermal
expansion coefficient can be used to analyze the dilation
strain change in the temperature range where a phase
transformation associated with alloying element parti-
tioning occurs. The difference between the calculated
strain contraction considering Mn and C partitioning
and the strain in the absence of partitioning decreases
with increasing IAT because the contents of Mn and C
in both the intercritical austenite and the recrystallized
ferrite move toward the average alloy contents with
increasing volume fraction of austenite.
The occurrence of a very efficient Mn partitioning
into UFG austenite formed during a 180 s intercritical
annealing in the temperature range of 640–680 °C was
shown to occur by means of TEM–EDS analysis and
dilatometry. No significant partitioning of alloying
elements was observed in the cold-rolled martensite
prior to annealing, whereas the enrichment of Mn and
C in the retained austenite formed during the annealing
was clearly observed. The quantitative analysis of dila-
tion strain proved the presence of alloying partitioning
during austenite formation at IAT in the UFG 6% Mn
TRIP steel. The efficient partitioning of a substitutional
solute to austenite during the intercritical annealing of
an initially heavily strained UFG martensitic micro-
structure opens a new path for the design of UFG steels
with superior ductility.
[1] B.C. De Cooman, Curr. Opin. Solid State Mater. Sci. 8
(2004) 259–265.
[2] M. Izumiyama, M. Tsuchiya, Y. Imai, J. Jpn. Inst. Met.
34 (1970) 291–295.
[3] A.S. Sastri, D.R.F. West, J. Iron Steel Inst. 203 (1965)
138–145.
[4] E. Jimenez-Melero, N.H. Van Dijk, L. Zhao, J. Sietsma,
S.E. Offerman, J.P. Wright, S. van der Zwaag, Scr. Mater.
56 (2007) 421–424.
[5] J.F. Breedis, Acta Mater. 13 (1965) 239–250.
[6] M.J. Merwin, Mater. Sci. Forum 539–543 (2007) 4327–
4332.
[7] D.W. Suh, S.J. Park, T.H. Lee, C.S. Oh, S.J. Kim, Mater.
Sci. Technol. 25 (2009) 892–895.
[8] S. Lee, K.Y. Lee, B.C. De Cooman, Mater. Sci. Forum
654–656 (2010) 286–289.
[9] B.C. De Cooman, Paper presented at the MS&T 2010,
Houston, TX, USA, 2010.
[10] C.M. Li, F. Sommer, E.J. Mittemeijer, Mater. Sci. Eng. A
325 (2002) 307–319.
[11] S.J. Lee, M.T. Lusk, Y.K. Lee, Acta Mater. 55 (2007)
875–882.
[12] D. San Martı́n, P.E.J. Rivera-Dı́az-del-Castillo, C. Gar-
cı́a-de-Andrés, Scr. Mater. 58 (2008) 926–929.
[13] S.J. Lee, K.D. Clarke, C.J. Van Tyne, Metall. Mater.
Trans. A 41A (2010) 2224–2235.
[14] S.J. Lee, K.D. Clarke, Metall. Mater. Trans. A 41A
(2010) 3027–3031.
[15] N.N. Lipchin, N.L. Oslon, S.A. Kokovyakina, Metal Sci.
Heat Treat. 14 (1972) 7–8.
[16] S.J. Lee, Y.K. Lee, Scr. Mater. 52 (2005) 973–976.
[17] M. Tokizane, N. Matsumura, K. Tsuzaki, T. Maki, I.
Tamura, Metall. Mater. Trans. A 13A (1982) 1379–
1388.
[18] J. Lis, J. Morgiel, A. Lis, Mater. Chem. Phys. 81 (2003)
466–468.