Materials Letters 64 (2010) 1411–1414

Contents lists available at ScienceDirect

Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / m a t l e t

Formation of the reversed austenite during intercritical tempering in a

Fe–13%Cr–4%Ni–Mo martensitic stainless steel
Y.Y. Song a, X.Y. Li a,⁎, L.J. Rong a, D.H. Ping b, F.X. Yin b, Y.Y. Li a
a
Institute of Metal Research, Chinese Academy of Sciences, Shenyang, 110016, China
b
National Institute for Materials Science, Sengen 1-2-1, Tsukuba 305-0047, Japan

a r t i c l e i n f o a b s t r a c t

Article history: Formation of the reversed austenite obtained by intercritical tempering has been studied via transmission
Received 19 January 2010 electron microscopy (TEM) in a Fe–13%Cr–4%Ni–Mo low carbon martensitic stainless steel. It is found that
Accepted 9 March 2010 the precipitation of M23C6 carbides along the martensite lath boundaries will result in Ni-enrichment in the
Available online 15 March 2010
adjacent region. The reversed austenite forms with the Ni-enrichment region as the nucleation sites, keeps a
cube–cube orientation relationship with the M23C6 carbides and bears the Kurdjumov–Sachs (K–S)
Keywords:
Reversed austenite
relationship with the martensite. Moreover, the reversed austenite formed inside the martensite laths is also
Martensite lath confirmed. The mechanism for formation of the reversed austenite is discussed in detail.
M23C6 carbide © 2010 Published by Elsevier B.V.
Microstructure
Metals and alloys
Formation

1. Introduction carbides in these steels is of vital importance for their industrial

applications. Thus, in present work, detailed microstructural char-
In low carbon martensitic steels, the obtained higher strength was acteristics obtained by intercritical tempering were studied by means
usually accompanied with a significant loss of toughness [1]. Thus, the of transmission electron microscopy (TEM) to investigate the
martensitic steels for applications require the adjustment of final formation of the reversed austenite in a Fe–13%Cr–4%Ni–Mo low
strength and toughness. An unusual combination of properties is carbon martensitic stainless steel. The mechanism for formation of the
obtained in these steels by normalizing plus intercritical tempering at reversed austenite was discussed.
temperature slightly higher the As temperature, because fine lath-like
reversed austenite can be formed during subsequent cooling, and
dispersed along the martensite lath boundaries or prior austenite 2. Experimental
grain boundaries [2,3]. It is well-known that the reversed austenite
accounts for the high toughness, especially the low temperature The material used in the study was low carbon martensitic
impact toughness, which has been effectively utilized in many kinds stainless steel with the chemical composition of 0.051C–12.34Cr–
of steels, such as maraging steel, TRIP steel and 9% Ni steel [1–5]. 3.86Ni–0.45Mo–0.5Mn–0.022P–0.004S (wt.%), which was supplied as
However, less attention has been paid so far to the study of the a hot-roll sheet. The transformation temperatures, As, Af, Ms and Mf, of
formation of the reversed austenite as compared with the vast the steel were 580, 807, 252 and 90 °C, respectively, which were
amount of research on its effect on mechanical properties of these measured by Formaster-F thermal dilatometer under a regime of
steels. Uncertainties still exist with respect to the mechanism for the heating to 1000 °C for 15 min at a rate of 6 °C/min and then cooling to
formation of the reversed austenite. In addition, in the low carbon room temperature at a rate of 100 °C/s. Specimens were cut from the
martensitic steels such as Fe–13CrNiMo, the M23C6 carbides also can sheet to prepare for the experiments. All specimens were normalized
precipitate even when the carbon content is very low [6]. Surprisingly, at 1050 °C for 2 h and then water quenched. Then tempering heat
few have been concerned with the formation of coexisting carbides treatments were conducted at temperatures of 570, 590 and 610 °C,
and the reversed austenite in these steels. Understanding the holding for 2 h followed by argon-cooling.
formation of the reversed austenite and its relationship with the Thin foil specimens for TEM observations were prepared by means of
a twin-jet polishing technique using an electrolyte of 6 ml HClO4 and
94 ml ethanol. A JEM2010 TEM instrument equipped with an energy-
⁎ Corresponding author. Tel.: +86 23971499. dispersive spectroscopy (EDS) system was used for selected area
E-mail address: xyli@imr.ac.cn (X.Y. Li). electron diffraction (SAED) analysis to observe the microstructure.

0167-577X/$ – see front matter © 2010 Published by Elsevier B.V.

doi:10.1016/j.matlet.2010.03.021
1412 Y.Y. Song et al. / Materials Letters 64 (2010) 1411–1414

3. Results and discussions was observed. It can be seen clearly from the TEM bright field image
(see Fig. 1a) that only carbides precipitated along the martensite lath
The detail microstructure observed by TEM of the samples after boundaries. Fig. 1b indicates the SAED pattern corresponding to
tempering at 570 °C for 2 h is shown in Fig. 1. As the tempering diffraction from the carbides and martensite. There exists [011]M23C6//
temperature was below the As temperature, no reversed austenite [111]α orientation relationship between the carbides and matrix,
which happened in order to lower the interfacial energy [7]. Those
carbides are indexed as Cr23C6 carbides based on the SAED patterns
and EDS results. The dark field image (see Fig. 1c) shows that the size
of the Cr23C6 carbides is very small and less than 100 nm. The
nucleation of carbides at the martensite lath boundary is to be
expected because the martensite lath boundaries are energetically
favorable sites which also provide paths for relatively rapid diffusion
of solute [6].
When the samples were tempered at 590 °C (slightly above the As
temperature) for 2 h, the TEM results were shown in Fig. 2. It can be
seen from the TEM bright field image (see Fig. 2a) that the reversed
austenite was found to coexist with the carbides and formed along the
martensite boundaries. Their combined SAED pattern, together with
martensite matrix, is shown in Fig. 2b, where the reversed austenite is
in a cube–cube orientation relationship with the M23C6 carbide and
bears the Kurdjumov–Sachs (K–S) relationship with the martensite.
The corresponding dark field image of the carbides is shown in Fig. 2c.
The much brighter particle is the M23C6 carbide, and the adjacent
particles are the reversed austenite. It is well-known that both the
austenite and M23C6 carbides have cubic symmetry and the lattice
parameter of M23C6 carbides is approximately three times that of
austenite, so the electron diffraction patterns are readily identified [8].
Many papers have reported the M23C6 carbides precipitate from the
austenite and are in a cube–cube orientation relationship with the
austenite especially in austenite steels [9,10]. However, to the best of
our knowledge, few are reported to show this relationship on M23C6
and the reversed austenite in these martensitic stainless steels.
Concentration profiles for the Cr and Ni determined using EDS, from
the positions indicated in Fig. 2c, as shown in Fig. 2d. It can be seen
that the concentration of Cr element is pretty high in carbides while it
is lower than that of the nominal alloy composition in the reversed
austenite. The concentration of Ni element is pretty high in the
reversed austenite. The precipitation of Cr rich M23C6 carbide must
lead to Cr depletion from the adjacent surrounding, which is offset by
Ni enhancement. Moreover, the M23C6 carbides have a limited
solubility of Ni [11], which also causes the Ni atoms to diffuse to the
adjacent reversed austenite. In our previous results, no carbon atom
enrichment was found in the reversed austenite using three-
dimensional atom probe (3DAP) because of the precipitation of
carbides [12]. Thus we consider that the carbides situated on the grain
boundaries provide the sites for the austenite nucleation, and the
diffusion of Ni atoms that will control the growth the reversed
austenite. The transformation behavior of the austenite is determined
by its stability. A quantitative measure of the austenite stability is the
critical driving force required to transform the austenite particle,
which can be obtained by the equation as follows [13]:

γ→α′ str
ΔG = −ΔG +E +ϒ

where ΔG is the critical driving force for the transformation. ΔGγ − α is

the chemical Gibbes free energy. Estr is the elastic strain energy, and γ
is the interfacial energy. The formation of the new martensite will
cause an increase in interfacial energy by virtue of the new martensite
and M23C6 carbide interfaces formed. The most important is that
compositional enrichment of the austenite with Ni reduces the
chemical driving force and increases the interfacial energy due to
solution hardening of the austenite by the solute elements. It is
believed that the enrichment of Ni in the reversed austenite is the
main reason for its stability in these steels.
Fig. 1. TEM images in samples tempered at 570 °C for 2 h (a) bright field image; (b) the The microstructural observations of the samples tempered at 610 °C
corresponding SAED pattern; (c) dark field image. were shown in Fig. 3. Further growth of the M23C6 carbides and the
 Y.Y. Song et al. / Materials Letters 64 (2010) 1411–1414 1413

Fig. 2. TEM images in samples tempered at 580 °C for 2 h (a) bright field image; (b) the corresponding SAED pattern; (c) dark field images and (d) EDS for Cr and Ni on the regions
indicated by arrows in (c).

reversed austenite are both observed. Fig. 3a and b shows that the carbon martensitic stainless steel. The M23C6 carbides precipitated
reversed austenite and carbides coexist along the martensitic lath along the martensite laths, which supplied Ni-enrichment in the
boundary and are in a cube–cube orientation relationship just as what is adjacent region. Then, the reversed austenite formed adjacent to the
shown in Fig. 2. But the size of both the carbides and the reversed carbides with the Ni-enrichment as the nucleation sites at the
austenite grow larger. In addition, the reversed austenite without the tempered temperature slightly above the As temperature. The growth
carbides appears to form inside the martensite lath, following the of the reversed austenite was controlled by Ni diffusion. When the
Nishiyama–Wassermann (N–W) orientation relationship with the samples were tempered at elevated temperature, the reversed
martensite parent phase, as shown in Fig. 3c and d. Concentration austenite could form not only along the martensite laths but also
profiles for the Cr and Ni, from the positions indicated in Fig. 3c, are inside the martensite laths.
shown in Fig. 3e. It can be seen that the concentration of Cr is almost
constant while lower than that of the nominal alloy composition in the Acknowledgements
reversed austenite. The concentration of Ni element is pretty high in the
reversed austenite. Thus, at this higher tempered temperature, Ni atoms This work was supported by the National Natural Science
gradually segregate to the martensite lath boundaries as well as Foundation of China under grant No. 50871110.
localized areas inside the martensite laths, for example, dislocations
[10]. It is believed that the stability of the reversed austenite inside the References
martensite laths is also controlled by Ni-enrichment.
[1] Nakagawa H, Miyazaki T. J Mater Sci 1999;34:3901–8.
[2] Bilmes PD, Solari M, Llorente CL. Mater Charact 2001;46:285–96.
[3] Leem DS, Lee YD, Jun JH, Choi CS. Script Mater 2001;45:767–71.
4. Conclusions [4] Ping DH, Ohnuma M, Hirakawa Y, Hono K. Mater Sci Eng A 2005;394:285–9.
[5] Li XY, Song YY, Li YY. In: Balachandran UB, editor. Adv Cryog Eng, 54; 2008.
p. 145–50. Trans. ICMC.
In summary, the formation of the reversed austenite during the [6] Bhadeshia HKDH, Honeycombe RWK. Steels microstructures and properties 3rd
intercritical tempering was discussed in a Fe–13%Cr–4%Ni–Mo low edn; 2006. London.
1414 Y.Y. Song et al. / Materials Letters 64 (2010) 1411–1414

Fig. 3. TEM images in samples tempered at 610 °C for 2 h (a) and (b) bright field TEM image, SAED pattern and dark-field image of the reversed austenite and the M23C6 along the
martensite laths; (c) bright field image of the reversed austenite formed in the martensite lath; (d) the corresponding SAED pattern; and (e) EDS for Cr and Ni on the regions
indicated by arrows in (c).

[7] Howell PR, Bee JV, Honeycombe RWK. Metall Trans A 1979;10:1213–23. [12] Song YY, Ping DH, Yin FX, Li XY, Li YY. Mater Sci Eng A 2010;527:614–8.
[8] Lee TH, Kim SJ. Script Mater 1998;39:951–6. [13] Haidemenopoulos G, Olson GB, Cohen M. In: Olson GB, editor. Innovations in
[9] He Y, Yang K, Sha W, Clelandl DJ. Mater Trans A 2004;35A:2747–55. ultrahigh strength steel technologySagamore Army Materials Research Conference
[10] He Y, Yang K, Sha W. Metall Mater Trans A 2005;36A:2273–87. Proceedings; 1987. p. 549–64. Lake George.
[11] Raghavant M, Mueller RR, Klein CF. Script Metall 1983;17:1189–94.