Materials Science and Engineering A 527 (2010) 2772–2779

Contents lists available at ScienceDirect

Materials Science and Engineering A

journal homepage: www.elsevier.com/locate/msea

Microstructural evolution in austenitic heat-resistant cast steel

35Cr25Ni12NNbRE during long-term service
Jiangwen Liu ∗ , Dongling Jiao, Chengping Luo
School of Materials Science and Engineering, South China University of Technology, Guangzhou 510640, China

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

Article history: The microstructural evolution of austenitic heat-resistant cast steel 35Cr25Ni12NNbRE during aging and
Received 27 April 2009 long-term service was investigated using optical microscope (OM), X-ray diffraction (XRD), scanning
Received in revised form electron microscope (SEM) and transmission electron microscope (TEM). The microstructure of the as cast
28 December 2009
steel consists of the dendritic austenite, the block-like eutectic carbide M7 C3 spreaded among austenitic
Accepted 5 January 2010
dendrite, and a small quantity of M23 C6 carbide. The microstructure of the steel aged at 600 ◦ C consists
of eutectic carbide M23 C6 transformed from eutectic carbide M7 C3 and dendritic austenite in which
fine secondary carbide particles M23 C6 precipitated. The precipitated carbide M23 C6 kept a cubic–cubic
Keywords:
Austenitic heat-resistant steel
orientation relationship (OR) with austenite matrix. There existed a carbide precipitation free zone (PFZ)
Microstructure around the eutectic carbide. For the long-term serviced samples, the secondary carbide precipitated in the
Carbide austenite strikingly increased and the PFZ disappeared. Part of the M23 C6 transformed into M6 C, which
Orientation relationship always kept a twin OR, [1 1 4]M6 C //[1 1 0]A //[1 1 0]M23 C6 , with the austenite and the M23 C6 secondary
carbide. In addition, a small quantity of ␴ phase FeCr and ␧-Cr2 N were also identified. The effects of alloy
composition and service condition on the microstructural evolution of the steel were discussed.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction investigations of the microstructural evolution of 25Cr-12Ni-type

As a high-temperature material, Cr–Ni austenitic steels are
broadly used to make components for petrochemical, metal
heat treatment and thermal power generating equipment
[1–8]. For instance, a novel austenitic heat-resistant cast steel
35Cr25Ni12NNbRE was recently developed by the group and used
to make the nozzle and transport chamber of pulverized coal burner
for power station boiler. These components usually served in a
severe condition, bearing not only the high temperature oxidation,
but also the abrasive erosion of the pulverized coal. The service life
of the components made from the N, Nb and RE-containing heat-
resistant cast steel was found much longer than those made from
the 316-type austenitic stainless steel and the HK40-type heat-
resistant steel. Long-term service at high temperature of austenitic
stainless or heat-resistant steels can bring about decomposition
of austenite and forming of carbides and intermetallic compounds
such as sigma, chi, Laves, and epsilon phases [1,2,5–13]. The crys-
tallography of the carbides M23 C6 , M6 C, and ␧-Cr2 N with the
austenite or ferrite in the stainless or heat-resistant steels has been
studied [6,7,13–18]. However, there is still a lacking of detailed
∗ Corresponding author at: School of Materials Science and Engineering, South
China University of Technology, Wushan, Guangzhou 510640, Guangdong, China.
Tel.: +86 20 87114234; fax: +86 20 85511617.
E-mail address: mejwliu@scut.edu.cn (J. Liu).
heat-resistant cast steel occurring during both aging and long-
term service. The purpose of the paper is therefore to study the
microstructural evolution behavior of this steel during long-term
service. The morphology of the precipitates and the OR between
the precipitates and the austenite were characterized. The effects
of the alloy composition and the high temperature service condi-
tion on the microstructural evolution behavior are also elucidated
in the paper.
2. Experiments and materials
The chemical composition (wt.%) of the austenitic heat-resistant
steel 35Cr25Ni12NNbRE was 0.33C, 25.03Cr, 12.55Ni, 0.65Mo,
1.89Si, 1.51Mn, 0.15N, 0.32Nb, 0.1RE, <0.036P, <0.014S, and bal-
ance Fe. The steel was molten in a vacuum induction furnace
and sand-cast into a pulverized coal burner assembly consisting
of a nozzle and a transport chamber. The burner assembly was
solution-treated at 1100 ◦ C for 4 h and water quenched, followed
by isothermal aging at 600 ◦ C for 6 h. The service temperature at
the nozzle was estimated to be 800–900◦ C and that at the trans-
port chamber around 600–700 ◦ C. Three groups of test pieces for
the study were cut from the as cast, as aged burner assembly and
the burner serviced for 3.5 years, respectively.
The microstructures of three groups alloy were characterized
using OM, XRD, SEM, EDS, and TEM. XRD analysis was carried out

0921-5093/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2010.01.002
 J. Liu et al. / Materials Science and Engineering A 527 (2010) 2772–2779
Fig. 1. X-ray diffraction profiles of austenitic heat-resistant cast steel
35Cr25Ni12NNbRE (a) as cast, (b) serviced for 3.5 years, and (c) solution-treated at
1100 ◦ C for 4 h and aged at 600 ◦ C for 6 h.
on a Philips X’Pert diffractometer using Cu K␣1 radiation. Speci-
mens for the OM and SEM were etched by 75%HCl + 25%HNO3 . An
Olympus PME3 and an FEG LEO-1530VP SEM equipped with an
Inca 300 energy dispersive spectrometer (EDS) were employed for
the OM and SEM, respectively. TEM foils were prepared by twin-
jet electropolishing in a solution composed of 6 vol.% perchloric
acid, 35 vol.% butanol and 59 vol.% methanol at −25 ◦ C and a current
of 0.12 A. TEM characterization was carried out on a JEOL100CXII
transmission electron microscope operated at 120 kV and equipped
with a high angle double-tilt specimen holder.
3. Experimental results
3.1. XRD analysis
Fig. 1 shows the XRD profiles of the three groups of specimens.
Austenite and M23 C6 phases were identified in all the three groups.
The diffraction peaks of M7 C3 carbide were clearly identified only
Fig. 2. Optical micrographs of 35Cr25Ni12NNbRE austenitic heat-resistant cast steel (a) as cast, (b) solution treated at 1100 ◦ C for 4 h and aged at 600 ◦ C for 6 h and (c)
serviced for 3.5 years, and (d) PFZs around the eutectic carbide in the as aged sample.
2773
in the as cast sample but not in the aged and/or in the serviced
sample, suggesting that the M7 C3 carbide formed during the solid-
ification of the steel and transformed into other phase after solution
plus aging treatment. A striking diffraction peak (2 = 40.6◦ ) in the
serviced sample could be indexed as {4 2 2} from M6 C carbide, thus
suggesting that M6 C carbide formed during the long-term service.
And as will be shown later by TEM characterization, both M23 C6 and
M6 C indeed coexisted in subjected to long-term service. Except for
the aforementioned phases, no diffraction peak from other phases
could be detected. It is suggested either the diffraction intensity
from other trace, if any, was too weak to be detected, or no other
phases at all formed in the steel. Further phase identification will
be carried out in the following sections using SEM, TEM, and EDS.
3.2. OM, SEM observations and EDS analysis
Fig. 2a presents a typical optical micrograph showing the
microstructure of the as cast alloy. The microstructure consists of
the dendritic austenite grains and eutectic carbide. Fig. 2b presents
a typical optical micrograph showing the microstructure of the
alloy solution treated at 1100 ◦ C and aged at 600 ◦ C for 6 h. The
microstructure consists of the dendritic austenite grains (the bright
zones in Fig. 2b) and coarse, block- or fishbone-like eutectic car-
bide spread along the boundaries of the austenitic dendrites. Fine
particles (the secondary carbide M23 C6 ) precipitated within the
austenite. The detailed features of the microstructure of the as aged
samples (Fig. 2d) show there exists the secondary carbide PFZ at
the eutectic carbide/austenite boundaries, the carbide high-density
precipitation zone (HPZ) in the areas close to the PFZ, and the car-
bide low-density precipitation zone (LPZ) in the areas further away
from PFZ within the austenite dendrites.
Fig. 2c presents a typical optical micrograph showing the
microstructure of the long-term (3.5 years) serviced sample. The
microstructure has significantly changed during the long-term ser-
vice. The secondary carbide strikingly increased and slightly grew
in the austenite, and all the PFZs, HPZs and LPZs have disap-
peared, with spherical, or equiaxial secondary carbide particles
precipitated within the austenite. The former fishbone-like eutec-
2774 J. Liu et al. / Materials Science and Engineering A 527 (2010) 2772–2779
Fig. 3. SEM micrographs and EDS analysis of 35Cr25Ni12NNbRE austenitic heat-resistant cast steel (a) solution treated at 1100 ◦ C for 4 h and aged at 600 ◦ C for 6 h, (b)
serviced for 3.5 years, (c) EDS spectra of eutectic Cr-rich phase (M23 C6 ), (d) EDS spectra of Nb-rich phase, and (e) secondary carbides (M23 C6 ) and Cr-rich phase (eutectic
carbide around minor RE) marked using arrows c to f in (a) and (b).
tic carbides have transformed into piecemeal ones in which some
“black speckle” particles formed. It was however impossible to con-
firm if any other phases had formed at this stage since only optical
microscopy was employed.
Fig. 3a and b shows the SEM micrographs of both the as aged and
the long-term serviced sample, respectively. The SEM micrographs
were imaged using backscattered electrons, and are basically iden-
tical to the OM ones. However some block-like phases have contrast
different from that shown in the OM images. The dark phase was
identified as chromium-rich (M23 C6 ) marked by arrow c in Fig. 3a
and the EDS shown in Fig. 3c. The bright contrast phase was iden-
tified as niobium-rich phase marked by arrow d in Fig. 3a and the
EDS shown in Fig. 3d. Considering the alloy composition and the
heat treatment history, the Nb-rich particles are likely to be the
NbC (FCC, a = 0.4470 nm). However it could neither be identified
by XRD due to its small amount nor by the TEM possibly due to
their fall-off during electropolishing for preparing TEM foils. Fig. 3e
shows the EDS of the secondary M23 C6 carbide particles marked by
arrow e in Fig. 3a and b also presents the evidence of the break-off
eutectic carbide. Considering the part of break-off eutectic carbide
shows rather dark contrast in Fig. 3b, the eutectic carbide probably
has partly graphitized after long-term service, as marked by arrow
f in Fig. 3b and the EDS shown in Fig. 3f.
3.3. TEM observation
TEM observations and selected area electron diffraction (SAED)
were carried out with both the three groups of samples for fur-
ther characterizing the microstructural evolution of the steel. Fig. 4
presents a set of typical TEM micrographs and selected area elec-
tron diffraction patterns (SADPs) of the as cast alloy. Fig. 4a shows
the austenite and the block-like eutectic carbide which was iden-
tified to be of M7 C3 type (M stands for Cr and Fe), and Fig. 4b
shows the corresponding SADPs of M7 C3 carbide. The M7 C3 eutectic
carbides were found not to keep any unique OR with the austen-
ite. Furthermore a small quantity of M23 C6 carbide was detected
in the as cast sample. Fig. 4c and d show a typical TEM micro-
graph of M23 C6 carbide and austenite and corresponding SADPs
indexed [1 1 0]M23 C6 /[1 1 0]A , respectively (the subscript A stands
for austenite), suggesting the carbides M23 C6 (FCC, a = 1.0621 nm)
kept a cubic–cubic OR with the austenite (FCC, a = 0.3585 nm).
Fig. 5 presents a set of micrographs and SADPs of the steel aged at
600 ◦ C. The block-like eutectic carbide particle on the left in Fig. 5a
and the remaining small secondary carbide particles in the austen-
ite were all identified to be of M23 C6 type (M stands for Cr and Fe).
Fig. 5b and c show the typical TEM morphology of the secondary
carbide M23 C6 in HPZ and the corresponding SADPs, respectively.
This SADP could be indexed as B = [1 0 0]A /[1 0 0]M23 C6 (the sub-
script A stands for austenite), thus suggesting the carbides M23 C6
kept a cubic–cubic OR with the austenite. It is clear from Fig. 5c
that the 1:3 relationship between the magnitudes of the recipro-
cal vectors from the carbide and austenite, respectively resulted
from the nearly 3:1 relationship between the lattice parameters of
the two relevant phases. The M23 C6 particle was in fact a cuboid
in shape with its cubic faces parallel to the {1 0 0}A, M23 C6 and the
{1 1 0}A, M23 C6 facets truncated out. Fig. 5d shows the dark field TEM
image of a block-like eutectic carbide and its corresponding SADP
indexed as B = [1 1 2]M23 C6 . The block-like eutectic carbides were
 J. Liu et al. / Materials Science and Engineering A 527 (2010) 2772–2779 2775

Fig. 4. TEM micrographs of the as cast alloy (a) austenite and eutectic M7 C3 carbide, (b) corresponding SADPs of M7 C3 carbide, (c) TEM image of M23 C6 eutectic carbide and
austenite, and (d) corresponding SADPs of carbide and austenite indexed [1 1 0]M23 C6 /[1 1 0]A .

found not to keep any unique OR with the austenite, possibly due to
its direct precipitation from the molten steel. Based on the detailed
TEM electron diffraction analysis and abovementioned XRD result,
this kind of M23 C6 eutectic carbides was probably transformed
from M7 C3 eutectic carbides. Besides the austenite, eutectic car-
bide M23 C6 and secondary carbides M23 C6 , no other phases were
detected in the present TEM work in the aged samples.
Fig. 6 shows the TEM micrographs of the long-term serviced
specimens. Shown in Fig. 6a is the morphology of the secondary
carbide particles precipitated in the area alongside to the grain
boundary between the austenite and eutectic carbide, in which the
PFZ originally formed in the as aged samples. Fig. 6a shows that
the evenly spread secondary carbide significantly increased, but
with only slight growth of the grain size, some carbide particles
were overlapping (connecting) with each other, and the PFZ near
the eutectic carbide had disappeared. Fig. 6b is a bright field TEM
image of two bordering secondary carbide particles, which were
identified to be M23 C6 and M6 C (FCC, a = 1.1082 nm), respectively.
And Fig. 6c and d shows the corresponding dark field TEM images
photographed using the common reflection (2 2 0)M23 C6 /(2 2 0)M6 C

Fig. 5. TEM micrographs of 35Cr25Ni12NNbRE austenitic heat-resistant cast steel solution treated at 1100 ◦ C for 4 h and aged at 600 ◦ C for 6 h (a) morphology of PFZ; (b)
morphology of HPZ, (c) SADPs of M23 C6 carbide and austenite indexed [1 1 0]M23 C6 /[1 1 0]A corresponding to (b), and (d) TEM dark field image of eutectic carbide and
corresponding SADP indexed [1 1 2]M23 C6 .
2776 J. Liu et al. / Materials Science and Engineering A 527 (2010) 2772–2779

Fig. 6. TEM images of M23 C6 and M6 C formed in the long-term serviced steel (a) morphology, (b) BF image of 2 pseudo-twin related M23 C6 and M6 C grains, (c) DF image
of the pseudo-twin related M23 C6 and M6 C grains, taken using the common g = [2 2 0]M23 C6 /[2 2 0]M6 C , (d) DF image of the pseudo-twin related M23 C6 and M6 C grains,
taken using g = [0 0 2]M23 C6 , (e) A composite SADP of austenite, M23 C6 and M6 C corresponding to (b), b = [1 1 0]a /[1 1 0]m23 c6 /[1 1 4]m6 c , and (f) Another composite SADP of
austenite, M23 C6 and M6 C, obtained by specimen tilt, B = [2 2 1]A /[2 2 1]M23 C6 /[0 0 1]M6 C .

and (0 0 2)M23 C6 reflection, respectively. Fig. 6e presents a compos- Stereographic projection describing the ORs among M6 C, M23 C6
ite SADPs taken from Fig. 6b, which is consist of 3 patterns resulting carbide and austenite.
from austenite, M23 C6 and M6 C, respectively, and could be indexed In the present TEM study, we did not found the ␧-(Cr,Fe)2 N (sim-
as B = [1 1 0]A /[1 1 0]M23 C6 /[1 1 4]M6 C . It indicated that M23 C6 kept ple hcp unit cell with a = 0.2760 nm, c = 0.4460 nm) phase in the
a cubic–cubic OR with austenite, same to be the aged sample, but as cast sample or in the aged sample. However, we occasionally
M6 C kept a twin OR with both austenite and M23 C6 . These ORs detected a small quantity of ␧-Cr2 N, which was bordered by the
have been confirmed using dark field images and SADPs analyses eutectic carbide as special core–shell morphology in the long-term-
of carbides precipitated in many other areas of the samples. The lat-
tice parameter and crystal structure of M23 C6 is similar to those of
M6 C carbide (the lattice parameters of them were 1.08–1.12 nm
[16,18]). It is difficult to distinguish them only by the SADPs in
Fig. 6e, even though the reflection spots from M6 C carbide is mis-
fit to those from M23 C6 slightly. However, the crystal structures of
M23 C6 carbide and M6 C carbide are classed as space group Fm3m
and Fd3m, respectively. The reflections (2 0 0), (4 2 0), etc. are for-
bidden for the Fd3m space group, in contrast, the structure factors
|Fhkl | of these reflections are not zero for the Fm3m space group.
So we can distinguish M6 C from M23 C6 by their different SADPs of
1 0 0 zone.
The real angles between (1 1 0)/(2 2 1) and between
(1 1 4)/(0 0 1) are 19.28◦ and 19.47◦ , respectively. While TEM foil
was tilted about 19.4◦ around the normal of the common reflection
(2 2 0)M23 C6 /(2 2 0)M6 C from zones [1 1 0]A /[1 1 0]M23 C6 /[1 1 4]M6 C
(equivalent to pole A in the stereographic projection in Fig. 7), the
SADPs indexed zones [2 2 1]A /[2 2 1]M23 C6 /[0 0 1]M6 C (equivalent
to pole B in the stereographic projection in Fig. 7) shown in
Fig. 6f can be achieved. It presents obvious proof of reflections
Fig. 7. Stereographic projection showing the ORs among M6 C, M23 C6 carbide and
(2 0 0) forbidden contributed by M6 C carbide. Fig. 7 presents the austenite.
 J. Liu et al. / Materials Science and Engineering A 527 (2010) 2772–2779
Fig. 8. TEM micrographs of ␧ and ␴ phase in the steel serviced 3.5 years (a) BF micrograph of ␧-Cr2 N, (b) SADP of ␧ phase corresponding to (a), B = [1 1 2 0], (c) BF micrograph
of ␴ phase, and (d) SADP of ␴ phase corresponding to (c), B = [0 0 1].
serviced sample. Fig. 8a shows the detailed morphology of ␧-Cr2 N
surrounded by eutectic carbide. Electron diffraction examination
indicated that the core and shell phases belonged to ␧-Cr2 N and
M23 C6 carbide, respectively. Fig. 8b presents the SADP of ␧-Cr2 N
indexed as B = [1 1 2 0]␧ corresponding to Fig. 8a.
Besides the M23 C6 , M6 C and ␧-(Cr,Fe)2 N, a small quantity of
block-like ␴-(CrFe) phase (tetragonal, a = 0.8799, c = 0.4544 nm)
were observed near the eutectic carbides in the long-term serviced
samples. Fig. 8c shows the morphology of this phase, and Fig. 8d
the corresponding SADP indexed as B = [0 0 1]␴ , which was used to
confirm the ␴ phase. It is well known that ␴ phase is likely to form
in Cr–Ni stainless steels during prolonged aging and embrittles the
steels.
Although the Nb-rich phases, possibly NbC, is detected using
the backscattered electron SEM image(Fig. 3a) and EDS analysis
(Fig. 3d), this NbC phase was not found in TEM observations with
both the aged and the long-term serviced samples. The possible
reason was that the NbC particles had been scratched away during
twin-jet electropolishing for TEM thin foil preparation, or no NbC
existed in the observable areas on the TEM thin foils.
4. Discussion
4.1. Formation and fadeout of PFZ
Some researchers reported that PFZs could form along grain
boundaries in many precipitation strengthened alloys including
aluminum alloys [19–23], superalloy [24,25] and austenitic steels
[26,27]. The PFZ formed by the vacancy depletion and the solute
depletion mechanisms [19–25]. PFZ brought to detrimental effect
on the stress corrosion and mechanical properties [22]. How-
ever, the phenomenon of the carbide PFZ, HPZ and LPZ, jointly
forming in the austenite, has not been reported yet. To the as
aged sample, the depletion of vacancy and solute elements, which
existed in the supersaturated austenite along the boundaries after
quenching and short holding time, caused the PFZ. However, a
long holding time tend to forming a fine dispersion of precip-
itates and narrow PFZ [21]. To the long-term serviced sample,
2777
the carbide could inchmeal precipitate within the PFZ and LPZ
because carbon and chromium could fully diffuse in PFZ and LPZ
during long-term service at high temperature. As the result, the
secondary carbide precipitates evenly distributed in whole austen-
ite, i.e., both the PFZ and LPZ faded out with the prolonging of
service time. Considering that the steel bear the combination of
high temperature oxidation and the abrasive erosion of pulver-
ized coal, the PFZs probably induce inconsistent effects on the
properties and working life of the alloy. The PFZs are helpful
to improving oxidation resistance of the alloy because plenty of
chromium dissolved in austenite. On the other hand, the PFZs
are probably disadvantageous to wear-resistance of the alloy
because PFZs were hardly strengthened by carbide precipitat-
ing.
4.2. Secondary carbides precipitation
The remarkable microstructural evolution of the heat-resistant
steel 35Cr25Ni12NNbRE is attributed to its chemical composi-
tion and service condition. As the aging time and/or service time
were prolonged, the precipitated carbide markedly increased, but
their size hardly increased. Besides, a small quantity of M6 C car-
bide formed bordering to M23 C6 . In view of the fact the M6 C
grains always bordered on M23 C6 and kept twin OR with austen-
ite and M23 C6 , the M6 C carbide is likely to be transformed from
M23 C6 one. Peng [15–17] reported that M6 C carbide transformed
from M23 C6 kept twin OR with M23 C6 /austenite, but M6 C car-
bide directly precipitated from the austenite kept a cube–cube OR
with M23 C6 /austenite. It may be rationalized that the 3:1 relation
between M23 C6 and austenite in lattice parameter, and the identity
of their crystal structure have favored the cube–cube OR between
the two phases, while the nearly 1:1 relation between M6 C and
M23 C6, and again the identity of their crystal structure have led to
the twin OR between the two phases. These two types of carbides
present similar morphology with fine particle, and they are not easy
to be distinguished using OM or SEM. However, we can distinguish
M23 C6 from M6 C by their different diffraction patterns under spe-
cific zone, for example, in the SADPs of zone 1 0 0 of M23 C6 and
2778 J. Liu et al. / Materials Science and Engineering A 527 (2010) 2772–2779
M6 C, {2 0 0} reflections are forbidden to M6 C (Fd3m), but {2 0 0}
reflections are allowed to M23 C6 (Fm3m).
The M23 C6 carbide is usually observed in the heat resistant
austenitic steels. M23 C6 has a complex cubic lattice with 92 metal
atoms (of Fe or Cr) and 24 carbon atoms per unit cell [18,28]. The
M23 C6 can precipitate on grain boundaries, noncoherent and coher-
ent twin boundaries, and on dislocation in austenite. The preferred
interface is the {1 1 1} plane of M23 C6 , which is parallel to the {1 1 1}
plane of austenite [28]. TEM thin foil observations have revealed
that the sizes of M23 C6 particle precipitated in austenite, either in
as aged or in long-term serviced sample, are less than 1 ␮m. The
conceivable reason is that the misfit between {1 1 1} of M23 C6 and
{1 1 1} of austenite is less than 1.3% [28] and the growth of M23 C6
particles will increase the volume strain. Another reason is that
the growths of M23 C6 particles need the long-range diffusion of Cr
and C in austenite, in this case, the nucleation of new M23 C6 parti-
cles easily occurs in the place near to the original M23 C6 particles.
The competition of nucleation and the growth of M23 C6 rely on the
diffusion of Cr and C, interface energy, and strain energy.
Besides the effects of time and temperature on microstruc-
tural evolution of the steel, alloy elements Mo in this type steel
probably promoted the carbide evolution. Weiss and Stickler
[1] claimed that the M6 C formation was related to Mo in 316
austenite stainless steel, and the carbide forming sequence was
M23 C6 → (Fe,Cr)21 Mo2 C6 → M6 C while the steel was long-term
exposed at high temperature (650 ◦ C). The Mo content in the stud-
ied alloy (0.6 wt.%) is less than that in the 316 stainless steel, so it is
possible the M6 C has direct transformed from M23 C6 . However, it
was not fully ensured whether the intermediate process occurred
due to the lack of further characterization of the carbide particles
by EDS.
4.3. ␧-Cr2 N phase
Based on the TEM results, we occasionally observed that the
␧-Cr2 N formed in the inner of the eutectic carbide as core–shell
morphology in the long-term serviced samples. Neither specific OR
between the inner ␧-Cr2 N and the outer carbide nor between the
outer carbide and austenite was observed. This special ␧-Cr2 N mor-
phology suggested that the core–shell ␧-Cr2 N and carbide directly
formed during the solidification of the steel, and the ␧-Cr2 N, as het-
erogeneous nucleation site of eutectic carbide, formed earlier than
the eutectic carbide did. Although the particular TEM research was
carried out for all the three groups samples, this type of core–shell
␧-Cr2 N phase was not detected in the as cast or in the isother-
mal aged sample. This may be due to the trace ␧-Cr2 N phase did
not exist in the observable areas on the TEM thin foils. In many
austenitic steels containing N, ␧-Cr2 N phase always precipitated in
the austenite while the isothermal aging was carried out at high
temperature [6,7,14,29–32]. However, we have not found ␧-Cr2 N
particles precipitated within the austenite matrix in all the three
groups samples. The conceivable reason is that the core–shell ␧-
Cr2 N combining the eutectic carbide consumed the majority of
nitrogen and the nitrogen content in the austenite matrix was lower
than its solid solubility limit.
4.4. Eutectic carbide
Comparing the type and morphologies of the eutectic carbides
between in the as cast sample and in the as aged sample, we
found that the M7 C3 type carbide fully transformed into the M23 C6
type carbide even though they both basically presented similar
morphology. This transformation indicated that the M7 C3 carbide
forming during the non-equilibrium solidification of the steel was
unstable and replaced by the stable M23 C6 carbide in the tempera-
ture range of solution and aging treatment.
It is a common phenomenon that the carbide graphitized and
spheroidized in carbon and alloy steels subjected to long time
and high temperature service [33]. Comparing the morphologies
of the eutectic carbides between in the as aged sample and in the
long-term serviced sample, we noticed that the “black speckle”
microstructure formed in or nearby the eutectic carbide, and the
most of fishbone-like or coarse eutectic carbides have broke up
into small pieces (Figs. 2 and 3). Obviously, the eutectic carbide had
partly graphitized or spheroidized in the long-term serviced sam-
ple which endured the duplex affections by the high temperature
oxidation and by abrasive erosion of pulverized coal.
4.5. Formation of  phase
It is well know that the ␴ phase not only decreases the mechan-
ical properties of steels but also reduces the corrosion resistance of
steels by removing chromium and molybdenum from austenite. In
the present study, few ␴ phases were detected only in the long-term
serviced samples, but not in the aged samples. Evidently, the long-
term service of the steel at high temperature promoted forming ␴
phase. The reason is that the formation of ␴ phase needs the long-
range redistribution of elements Fe and Cr. This tardive diffusion of
substitutional atom Cr relied on sufficient vacancy concentration at
high temperature. Schwind et al [8] proposed a model for predict-
ing ␴ phase formation in the stabilized austenitic steels AISI321 and
AISI347 and reported that even the formation of a small quantity
␴ phase needed several thousands hours aging at high tempera-
ture. On the other hand, high carbon and nitrogen content in the
steel can slow down the ␴ phase precipitation, because carbon and
nitrogen have low or no solubility in ␴ phase, and because carbides
and nitrides cause the depletion of chromium which is the main
composition of ␴ phase [1,6].
5. Conclusion
Experimental studies on the microstructural evolution of
austenitic heat-resistant cast steel 35Cr25Ni12NNbRE during a
long-term service are summarized as follows.
1) The microstructure of the as cast steel consists of dendritic
austenite and block-like eutectic carbide M7 C3 spreaded among
austenitic dendrite and a small quantity of M23 C6 carbide. After
solution-treated at 1100 ◦ C for 4 h and aged at 600 ◦ C for 6 h,
all the unstable eutectic carbide M7 C3 transformed into M23 C6
type carbide. The microstructure of the steel as aged consists of
dendritic austenite in which some fine M23 C6 particles precip-
itated and eutectic carbide M23 C6 . There exists the secondary
carbide PFZ around the eutectic carbide, the HPZ, and the LPZ
in the austenite dendrite according as the distance to austenite
boundary.
2) For the long-term serviced sample, secondary carbide M23 C6
obviously increased in austenite, and both the PFZ and LPZ disap-
peared. Some M23 C6 transformed M6 C, and M6 C carbide always
kept [1 1 4]M6 C //[1 1 0]A //[1 1 0]M23 C6 twin OR with austenite
and M23 C6 secondary carbide. Furthermore, few of ␴ phase
formed, and the “black speckle” microstructure formed in the
eutectic carbide due to its partial graphitization.
3) The microstructural evolution of the steel during long-term ser-
vice is related to the duplex affects of the steel composition and
the service condition of it.
Acknowledgment
The authors are grateful to the National Natural Science Foun-
dation of China for its financial support to this study, No. 59971019.
 J. Liu et al. / Materials Science and Engineering A 527 (2010) 2772–2779
References
[1] B. Weiss, R. Stickler, Metallurgical and Materials Transactions B 3 (1972)
851–866.
[2] L.H. de Almeida, A.F. Ribeiro, I. Le May, Materials Characterization 49 (2002)
219–229.
[3] X.Q. Wu, H.M. Jing, Y.G. Zheng, Z.M. Yao, W. Ke, Z.Q. Hu, Materials Science and
Engineering A 293 (2000) 252–260.
[4] K.J. Stevens, T. Levi, I. Minchington, N. Briggs, V. Keast, S. Bulcock, Materials
Science and Engineering A 385 (2004) 292–299.
[5] Q.Z. Chen, C.W. Thomas, D.M. Knowles, Materials Science and Engineering A
374 (2004) 398–408.
[6] T.-H. Lee, S.-J. Kim, Y.-C. Jung, Metallurgical and Materials Transactions A 31
(2000) 1713–1723.
[7] T.-H. Lee, S.-J. Kim, Scripta Materialia 39 (1998) 951–956.
[8] M. Schwind, J.K. Källqvist, J.O. Nilsson, J. Ågren, H.O. Andrén, Acta Materialia 48
(2000) 2473–2481.
[9] M.H. Lewis, Acta Metallurgica 14 (1966) 1421–1428.
[10] H. Sahlaoui, K. Makhlouf, H. Sidhom, J. Philibert, Materials Science and Engi-
neering A 372 (2004) 98–108.
[11] F.R. Beckitt, B.R. Clark, Acta Metallurgica 15 (1967) 113–129.
[12] H.U. Hong, S.W. Nam, Materials Science and Engineering A 332 (2002) 255–261.
[13] T.-H. Lee, C.-S. Oh, C.G. Lee, S.-J. Kim, S. Takaki, Scripta Materialia 50 (2004)
1325–1328.
[14] J.W. Simmons, Materials Science and Engineering A 207 (1996) 159–169.
[15] S.-W. Peng, C.-P. Chou, Scripta Metallurgica et Materialia 26 (1992) 243–248.
[16] S. Peng, T. Tsai, C. Chou, Metallurgical and Materials Transactions A 24 (1993)
1671–1673.
2779
[17] T. Liu, S. Peng, Y. Lin, C. Wu, Metallurgical and Materials Transactions A 21
(1990) 567–574.
[18] K.H. Kuo, C.L. Jia, Acta Metallurgica 33 (1985) 991–996.
[19] H.S. Rosenbaum, D. Turnbull, Acta Metallurgica 6 (1958) 653–659.
[20] J.D. Embury, R.B. Nicholson, Acta Metallurgica 13 (1965) 403–417.
[21] P.N.T. Unwin, G.W. Lorimer, R.B. Nicholson, Acta Metallurgica 17 (1969)
1363–1377.
[22] M. Raghavan, Metallurgical and Materials Transactions A 11 (1980) 993–999.
[23] S.C. Jha, T.H. Sanders, M.A. Dayananda, Acta Metallurgica 35 (1987) 473–482.
[24] T. Krol, D. Baither, E. Nembach, Acta Materialia 52 (2004) 2095–2108.
[25] K.B. Rao, V. Seetharaman, S.L. Mannan, P. Rodriguez, Journal of Nuclear Mate-
rials 102 (1981) 7–16.
[26] M. Mataya, M. Carr, G. Krauss, Metallurgical and Materials Transactions A 13
(1982) 1263–1274.
[27] A. Strutt, K. Vecchio, Metallurgical and Materials Transactions A 30 (1999)
355–362.
[28] M.H. Lewis, B. Hattersley, Acta Metallurgica 13 (1965) 1159–1168.
[29] D. Sundararaman, P. Shankar, V. Raghunathan, Metallurgical and Materials
Transactions A 27 (1996) 1175–1186.
[30] M. Kikuchi, M. Kajihara, S.-K. Choi, Materials Science and Engineering A 146
(1991) 131–150.
[31] J. Erneman, M. Schwind, P. Liu, J.O. Nilsson, H.O. Andrén, J. Ågren, Acta Materialia
52 (2004) 4337–4350.
[32] P. Shankar, D. Sundararaman, S. Ranganathan, Scripta Metallurgica et Materialia
31 (1994) 589–593.
[33] J.R. Foulds, R. Viswanathan, Journal of Materials Engineering and Performance
10 (2001) 484–492.