Materials Transactions, Vol. 45, No. 7 (2004) pp.

2245 to 2251
Special Issue on Ultrane Grained Structures
#2004 The Japan Institute of Metals

Eect of Grain Renement on Thermal Stability of Metastable Austenitic Steel*1

Setsuo Takaki1 , Kazuhiro Fukunaga1; *2 , Junaidi Syarif2 and Toshihiro Tsuchiyama1
1
2

Department of Materials Science and Engineering, Faculty of Engineering, Kyushu University, Fukuoka 812-8581, Japan
Venture Business Laboratory, Kyushu University, Fukuoka 812-8581, Japan

In martensitic steels, it is well known that a certain chemical driving force (about 180 MJ/m3 ) is required to start martensitic
transformation (Ms), and additional driving force has to be charged further to complete the transformation (Mf). In the case of metastable
austenitic steels with Ms temperature at around room temperature, however, only the chemical driving force needed to start martensitic
transformation has been stored at room temperature. Hence, the state of austenite is very unstable thermally. It has already been known that such
a metastable austenite undergoes a partial martensitic transformation during isothermal holding at room temperature or cooling to a low
temperature. It is very convenient to investigate the behavior of martensitic transformation of austenite. In this study, the eect of austenite grain
size on martensitic transformation is introduced from the viewpoint of microstructural analysis and thermo-dynamics. The steel used in this
investigation is an Fe-16 mass%Cr-10 mass%Ni ternary alloy, which has Ms temperature at around room temperature. The grain size of this steel
can be controlled from 0.8 mm to 80 mm using the technique of reversion of deformation induced martensite. In the material with coarse grain size
(80 mm), about 18% of martensite was detected at room temperature and the amount of martensite was increased to 50% by the following subzero
treatment to 77 K. However, martensite was hardly detected in the material with ultra ne grains (0.8 mm) even after the subzero treatment. It was
found that such a stabilization occurs in the materials with the grain size below 10 mm and the stabilization was reasonably explained by
considering the relation between austenite grain size and elastic strain energy which is required on the single variant martensitic transformation.
(Received January 21, 2004; Accepted May 7, 2004)
Keywords: thermal stability, metastable austenite, martensitic transformation, grain renement, single variant, multi variant, elastic strain
energy, physical energy

1.

Introduction

14
Fe-Cr-Ni alloy

*1This

Paper was presented at the Second International Symposium

Ultrane Grained Structure (ISUGS), held in Geelong, on November 12,
2003
*2Graduate Student, Kyushu University. Present address: Kimitsu R&D
Laboratories, Nippon Steel Corp., Kimitsu 299-1141, Japan

13
Ni content, (mass%)

It is known that metastable austenitic stainless steels

undergo partial martensitic transformation during isothermal
holding at room temperature or cooling below room temperature (sub-zero treatment) when they have Ms temperature at
around room temperature. The thermal stability of austenite
depends on the chemical composition of the steel. Hirayama
et al.1) reported that Ms temperature can be represented by
the Ni equivalent; (Ni+0.65) and the Ni equivalent should be
20.7 for the steels with Ms temperature at room temperature
in the high purity Fe-Cr-Ni ternary alloy. Fully austenitic
structure can be obtained at room temperature in the case
satisfying the following condition; Ni+0.65Cr>20.7 that
means Ms < room temperature.
On the other hand, Tomimura et al.2) have succeeded in
ultra grain renement to submicron in an austenitic stainless
steel by using the reversion of deformation induced martensite which has been formed by heavy cold-working, and also
reported that the stability of austenite is greatly improved
owing to ultra grain renement to submicron level just as
corresponding to 1 mass%(%) Ni addition. However, the
austenite stabilization mechanism is not cleared yet. In this
study, the behavior of martensitic transformation was investigated in connection with the grain size in a metastable
austenitic steel (Fe-16%-10%Ni alloy), and mechanism of
austenite stabilization by grain renement was proposed on
the basis of the calculation of physical energy required for
martensitic transformation.

Ni+0.65Cr = 20.7
(austenite)

12

Ni+0.65Cr = 19.7

11

10

(austenite +
martensite)
Fe-16%Cr-10%Ni steel

9
12

13

14
15
16
17
Cr content (mass%)

18

19

Fig. 1 Structure diagram at room temperature in the relation between Cr

and Ni concentration for Fe-Cr-Ni ternary alloy. Lines in the gure express
Ni equivalent to obtain fully austenitic structure at room temperature;
broken and solid lines are for the material with the grain size of 80 mm and
1 mm, respectively.2)

2.

Experimental Procedures

2.1 Material
Figure 1 shows structure diagram at room temperature in
the relation between Cr and Ni concentration for Fe-Cr-Ni
ternary alloy. Lines in the gure express Ni equivalent to
obtain fully austenitic structure at room temperature; broken
and solid lines are for the material with the grain size of
80 mm and 1 mm, respectively.2) The alloy composition; Fe16%Cr-10%Ni was selected to have Ms temperature at 330 K

2246

S. Takaki, K. Fukunaga, J. Syarif and T. Tsuchiyama

Table 1 Chemical composition of the Fe-16%Cr-10%Ni alloy used.

(mass%)
Cr

Ni

Si

Mn

Al

Fe

16.02 10.08 0.003 0.0017 <0:01 <0:01 <0:005 0.0017 <0:0013 bal.

in the large grain sized material but to be completely

stabilized by the ultra grain renement to 1 mm, as shown in
the gure. Chemical composition of the steel used is shown in
Table 1. The ingot was produced in a vacuum with an
induction furnace, and then hot-forged at 1473 K to cylindrical pieces. After the solution treatment of 1273 K1.8 ks,
these cylindrical pieces were drawn at room temperature by
90% in sectional area reduction. It was conrmed that
deformation induced transformation to martensite had almost
completed after the heavy cold-drawing and the cold-drawn
material has almost fully martensitic structure. Since the
reversion from martensite to austenite took place at around
900 K, the grain size of austenite was controlled by changing
the holding temperature of reversion treatment for 0.6 ks. The
grain size of austenite could be changed in the range of
0.8 mm through 80 mm.
2.2 Experimental procedures
The materials with dierent austenite grain size was
subjected to the examination to evaluate the stability of
austenite phase; isothermal holding at room temperature and
then sub-zero treatment into liquid nitrogen (77 K). Microstructure was observed with an optical microscope (OM) and
a transmission electron microscope (TEM). Specimens for
OM observation were prepared by electrolytic etching with
10 mass% oxalic acid. For TEM observation, lm materials
were prepared with the twin-jet polishing method using a
solution of 10% perchloric acid and 90% acetic acid. Grain
size was determined in OM observation by comparing the
microstructure with the ASTM grain size, and in TEM
observation by direct measurement of dark eld image from
15 photographs. Volume fraction of martensite was obtained
by saturation-magnetization measurement.3)
3.

0.2m
Fig. 3

TEM micrograph of the 923 K-reversed steel.

with dierent austenite grain size. It was conrmed that these

materials have once completed the reversion to austenite after
the reversion treatment shown in the caption, but small
amount of martensite less than 5% was detected in the
material (c). The grain size of austenite was determined to be
10 mm and 80 mm in the material (b) and (c), respectively, but
the grain size evaluation by OM observation was dicult in
the material (a). TEM observation of the material (a) revealed
that the grain size is about 0.8 mm, as shown in Figure 3. In
this study, the material (a), (b) and (c) are referred as ultra
ne grained material (0.8 mm), ne grained material (10 mm)
and coarse grained material (80 mm), respectively.
3.2

Inuence of grain renement on the stability of

austenite
It is known that martensitic transformation can proceed
isothermally during holding at the temperature when the
steels have Ms temperature at just above room temperature.
Such a phenomenon is called as isothermal martensitic
transformation.4) Since the Ms temperature of Fe-16%Cr10%Ni alloy is 330 K, isothermal martensitic transformation
can be expected during holding at room temperature. Figure 4

Results and Discussion

3.1 Microstructures of Fe-16%Cr-10%Ni alloy

Figure 2 represents the OM microstructure of the materials

(a) 923K

(b) 1073K

(c) 1273K

20m

Fig. 2 Optical micrographs of the materials with dierent austenite grain

size. The materials were subjected to reversion at 923 K (a), 1073 K (b)
and 1273 K (c) for 0.6 ks after the 90% cold-drawing.

Volume fraction of martensite (%)

40

30

Coarse grain
(80m)
Fine grain
(10m)
Ultra fine grain (0.8m)

20

10

0
0
500 1000 1500 2000 2500 3000
Holding time at ambient temperature, t/ks
Fig. 4 Changes in volume fraction of martensite as a function of holding
time at room temperature.

Eect of Grain Renement on Thermal Stability of Metastable Austenitic Steel

shows changes in volume fraction of martensite as a function

of holding time at room temperature. An abrupt increase in
the volume fraction of martensite is found in the coarse
grained material in the early stage of isothermal holding, but
the value levels o at about 18% after 500 ks holding. On the
other hand, isothermal martensitic transformation is hard to
occur in the ne grained material, and no martensite is
formed in the ultra ne grained material during holding at
room temperature. Figure 5 shows the change in the volume
fraction of martensite with the sub-zero treatment of 77 K

2247

300 s after the isothermal holding of 1640 ks. The grain

renement to 10 mm is almost enough to suppress isothermal
transformation but it is not enough to suppress thermal
transformation that is caused by under cooling to 77 K.
However, it should be noted that there is no change in the
volume fraction of martensite in the ultra ne grained
material. This means that the grain renement to 1 mm is
enough to suppress even thermal martensitic transformation
in Fe-16%Cr-10%Ni alloy.
3.3

Volume fraction of martensite (%)

60
50
40
30
sub-zero treatment
20
10
0

20
40
60
80
100
Grain size of austenite, d/m

120

Fig. 5 Change in the volume fraction of martensite with the sub-zero

treatment of 77 K300 s after the isothermal holding of 1640 ks.

(a)

Morphology of martensite in metastable austenitic

steel
To clarify the dierence in thermal stability of austenite
that depends on the grain size, morphologies of martensite
were observed by means of OM and TEM for the sub-zero
treated materials. Figure 6 shows OM micrograph (a),
schematic illustration of OM micrograph (b) and TEM
micrograph (c) in the coarse grained material. The coarse
grained material has a typical lath martensitic structure that is
constructed with lath, block and packet. The laths were
formed in two directions within an austenite grain as shown
in Fig. 6(c). This means that these laths were formed in multi
variant transformation. The group of laths forms a block and
a couple of blocks gather to form a packet. After the
completion of martensitic transformation, a prior austenite
grain has been divided to several packets as shown in (b). In
other words, such a stratied structure is formed as a result of
the multi variant transformation, because it is convenient to
accommodate transformation strain each other. However,

(b)

20m

packet

austenite grain

(c)

lath

block
1 m

Fig. 6 OM micrograph (a), schematic illustration of OM micrograph

(b) and TEM micrograph (c) in the coarse grained material.

2248

S. Takaki, K. Fukunaga, J. Syarif and T. Tsuchiyama

(a)

(b)

austenite

martensite

0.2m
(c)

(d)
martensite

dislocation

0.1m
Fig. 7 TEM micrographs observed in the ne grained material (a) and the ultra ne grained material (c), and their schematic
illustrations (b, d).

there is a large dierence in morphology of martensite

between the materials. Figure 7 shows TEM micrographs
observed in the ne grained material (a) and the ultra ne
grained material (c), and their schematic illustrations (b, d).
Judging from the morphology of lath, it can be thought that
the laths in the ne grained material (Fig. 7(a)) were
transformed from the austenite in single variant or variants
with same habit plane. It can be easily expected that the
stratied structure as shown in Fig. 6 will never be formed
after the completion of the martensitic transformation
although lath structure will remain within the grain. When
austenite grain size becomes small as the thickness of
martensite lath, no lath structure was found within the
martensitic transformed austenite grain as shown in photograph (c). Such kind of transformation mode might be
grouped as single or restricted variant transformation.
Figure 8 schematically shows the relation between the
morphology of martensitic structure and grain size of
austenite. The morphology of martensite changes from the
stratied structure to the simplied structure when the grain
size of austenite is rened. The change from multi variant to
single variant transformation should give a huge inuence on
the stability of austenite.
3.4 Energy required for martensitic transformation
Martensitic transformation is realized by the occurrence of
(1) lattice displacement from fcc to bcc structure, and (2)

Stratified structure
(packet block lath)

Simplified structure

block

packet

Multi variant
transformation

lath structure

no lath
structure

Single or multi
variant trans.

Single variant
transformation

Fig. 8 Schematic illustration showing relation between the morphology of

martensitic structure and grain size of austenite.

supplementary deformation such as dislocation slip and

twinning. In special, the lattice displacement from fcc to bcc
causes crystallographic anisotropy in terms of the behavior of
expansion and contraction. Since 24 variants of lattice
displacement are possible in fcc-bcc martensitic transformation (K-S relation),5) multi variant transformation is thought
to be convenient to cancel out the crystallographic anisotropy. In this session, the physical energy required for these

Eect of Grain Renement on Thermal Stability of Metastable Austenitic Steel

bcc

fcc
(i)

2249

E (total) = EV +ED +EB

(110)

Single variant transformation

III [110] bcc

1.4% contraction

(Anisotropic volume change)

1877 [MJ/m3]
(17 times)

Elastic strain energy

II [110] bcc
7.0% contraction

The other
physical energy

I
( ii )

Multi variant transformation

II [110] bcc

fcc

(Isotropic volume change)

bcc

106 [MJ/m3]

I [001] bcc
13.9%expansion

Fig. 9 Schematic illustration of lattice displacement in fcc-bcc martensitic

transformation.

processes will be roughly evaluated to clarify the mechanism

of austenite stabilization caused by grain renement.
3.4.1 Elastic strain energy for lattice displacement
Figure 9 shows schematic illustration of lattice displacement in fcc-bcc martensitic transformation. The lattice
displacement consists of two ways of atomic movement;
(i) shear deformation of 36% to 1
10
direction and (ii)
anisotropic deformation accompanying the volume expansion of about 4.5%. The volume expansion of 4.5% is made
up of 13.9% expansion to [001] direction (I direction), 7.0%
contraction to 1
10
direction (II direction) and 1.4%
contraction to 1
1
0
direction (III direction).
In the case an austenitic grain has transformed to
martensite through single variant mode, the increase in
elastic strain energy can be estimated by the following
equation.
EV 1=2EI "I 2 1=2EII "II 2 1=2EIII "III 2

E and " are Youngs modulus and elastic strain in each lattice
plane. Thus, EI , EII , and EIII are 132.1 GPa, 220.8 GPa, and
220.8 GPa, respectively,6) and "I , "II , and "III are 0.139
(expansion), 0.07 (contraction) and 0.014 (contraction),
respectively. The estimated increment in elastic strain energy
is calculated at about 1839 MJ/m3 from the Eq. (1).
On the other hand, the increment in elastic strain energy
required for multi variant transformation can be estimated by
the following equation.
EV 3=2E"

E is Youngs modulus of polycrystalline iron; 200 GPa, and

" is mean strain; 0.015 calculated from volume change
("V 4:5%). Thus, the increment in elastic strain energy is
calculated at about 68 MJ/m3 . These results show that elastic
strain energy required for martensitic transformation is
extremely higher in single variant than multi variant mode
and the diculty of occurrence of single variant transformation in fcc-bcc martensitic transformation of iron.
3.4.2 The other physical energy required for martensitic
transformation
To accommodate lattice displacement, supplementary
deformation has to be introduced by dislocation slip or

Fig. 10 Comparison of transformation energy required for martensitic

transformation between single variant mode and multi variant mode.

twinning. The strain energy required for shear deformation

can be estimated by the Eq. (3).
ED
y 

y is shear stress of pure iron; 100 MPa, and  is shear strain;

0.36. The estimated strain energy ED is 36 MJ/m3 . Since
the value of
y is changeable up to the strength level of
martensite (about 300 MPa), 36 MJ/m3 should be regarded as
the minimum value for ED .
Moreover, boundary energy will be increased owing to the
formation of stratied martensitic structure such as lath,
block and packet. The increment of boundary energy
produced by the formation of martensite-lath is roughly
estimated by the following equation.
EB 2es =

es is boundary energy per unit area; about 0.2 J/m2 ,7) and  is
the mean width of lath; 0.2 mm.8) Thus, the increment of
boundary energy is calculated at about 2 MJ/m3 . The eect
of block and packet boundary can be ignored in comparison
with the inuence of laths.
Figure 10 shows a comparison of transformation energy
required for martensitic transformation between single
variant mode and multi variant mode. The transformation
energy means the total of elastic strain energy, shear
deformation energy and boundary energy. It is found that
the transformation energy is 17 times higher in the single
variant transformation than multi variant transformation, and
the inuence of elastic strain energy is dominant in the
transformation energy, especially for the single variant
transformation.
3.4.3 Estimation of chemical driving force for martensitic transformation
In the martensitic transformation of iron, it is well known
that under cooling from Ms temperature is indispensable to
complete the transformation. Chemical driving force Ec
obtained by the under cooling (T) is stated by the following
equation.9)
Ec ; 0:8T

Figure 11 schematically shows the change in volume fraction

of martensite and Ec as a function of temperature in multi

2250

S. Takaki, K. Fukunaga, J. Syarif and T. Tsuchiyama

(a)

Mf

Multi variant
transformation

d
thin-plate martensite

Ms

To

T 130K
3

-0.8MJ/m3/K

106MJ/m

0
100

austenite grain

Temperature, T/K
(b)

I [001] bcc
Single variant
transformation
Ms

II [110] bcc

To

0
2300K for 1839MJ/m3
(about 300K)

III [110] bcc

-0.8MJ/m3/K

Fig. 12 Schematic illustration showing nucleation of thin-plate martensite

within austenite grain.

Temperature, T/K

Fig. 11 Schematic illustration showing change in volume fraction of

martensite and chemical driving force (Ec ) as a function of temperature
in multi variant (a) and single variant transformation (b).

variant (a) and single variant transformation (b). For the

completion of martensitic transformation, chemical driving
force has to oset the increment in transformation energy. In
the case of multi variant transformation, the transformation
energy can be oset by the under-cooling of 130 K; Ms-Mf in
the Figure (a). The calculated under cooling is reasonable in
comparison with that obtained experimentally in conventional martensitic steels. On the other hand, under cooling of
2300 K is required for the single variant mode to complete
transformation. It is obviously impossible. This result
suggests that austenite phase can be signicantly stabilized
when the martensitic transformation mode is changed from
multi variant to single variant. Grain renement of austenite
probably contributes to the change in the mode of transformation.
3.5

thickness: x

Estimation of elastic strain energy required for

martensite nucleation
Since the largest displacement takes place to the direction
001
bcc as shown in Fig. 9, it is likely presumed that the
nucleation of thin-plate martensite (thickness: x) takes place
as shown in Fig. 12 to minimize total elastic strain energy. In
this model, lattice strain is elastically accommodated over the
space of austenitic grain (grain size: d). The increase in
elastic strain energy can be obtained by the following
equation by modifying the Eq. (1).

EV 1=2EI "I 2 x=d2 1=2EII "II 2
6

1=2EIII "III 2 x=d

Elastic strain energy, EV/MJm-3

EC (MJ/m3) Vol. of marten. (%)

EC (MJ/m3) Vol. of marten. (%)

100

2500
d

2000

1839[MJm-3]
d

1500
Thickness of
martensite: 0.2m

1000

1 m

500
0
0.1

1
10
100
Austenite grain size, d/m

1000

Fig. 13 Relation between grain size of austenite and the elastic strain
energy required for nucleation of thin plate-martensite.

Putting each Youngs modulus and strain into Eq. (6), the
following equation is obtained.
EV 1276:1x=d2 562:6x=d

When the thickness of lath 0.2 mm is put into the value x in the
Eq. (7), EV can be drawn as shown in Fig. 13 as a function
of austenite grain size. It should be noted that the value of
EV greatly increases when the austenite grain size becomes
smaller than 1 mm. This result demonstrates the diculty of
nucleation of martensite lath in ultra ne grained austenite
with the grain size below 1 mm. As the results, ultra grain
renement of austenite makes the occurrence of multi variant
transformation dicult and this leads to the suppression of
martensitic transformation in metastable austenite.

Eect of Grain Renement on Thermal Stability of Metastable Austenitic Steel

4.

Conclusions

The inuence of grain renement on the behavior of

martensitic transformation was investigated in metastable
austenitic stainless steel (Fe-16%Cr-10%Ni alloy), and
mechanism of austenite stabilization caused by grain renement was claried by calculating physical energy required
for martensitic transformation in single variant and multi
variant mode. The results obtained are as follows:
(1) Grain renement of austenite to 1 mm or less is very
eective for suppressing martensitic transformation
from fcc to bcc structure.
(2) Transformation energy is calculated at 1877 MJ/m3 and
106 MJ/m3 for the single variant transformation and
multi variant transformation, respectively, and it is
cleared that elastic strain energy is dominant in the
transformation energy, especially for single variant
transformation.
(3) In an ultra ne grained austenite with the grain size of
1 mm or less, a huge chemical driving force is required
for the nucleation of single variant martensite within the
grain.
(4) Ultra grain renement of austenite makes the occur-

2251

rence of multi variant transformation dicult and this

leads to the suppression of martensitic transformation in
metastable austenite.
Acknowledgement
The authors are grateful to Nisshin Steel Co., Ltd. for
casting and Nippon Steel Corp. for cold-drawing the specimen.
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