Effect of Carbon Content on Microstructure and Mechanical

Properties of 9 to 12 pct Cr Ferritic/Martensitic Heat-Resistant

Steels
FENG-SHI YIN, LI-QIAN TIAN, BING XUE, XUE-BO JIANG, and LI ZHOU

Two heats of 9 to 12 pct Cr ferritic/martensitic heat-resistant steels were prepared. One has an
ultralow carbon content of 0.01 wt pct, whereas another heat has a normal carbon content of
0.09 wt pct. The eect of carbon content on microstructure and mechanical properties of 9 to
12 pct Cr ferritic/martensitic heat-resistant steels was studied. The results show that the ultra-
low-carbon steel contains bimodal, nanosized MX precipitates with high density in the matrix
but few M23C6 carbide particles in the normalized-and-tempered state. The smaller nanosized
MX precipitates have two kinds of typical morphology: One is cubic and another is rectangular.
The cubic MX precipitate contains Nb, Ti, and V, whereas the rectangular one only contains Nb
and V. The normal carbon steel has abundant M23C6 carbide particles along the grain and lath
boundaries and much less density of nanosized MX precipitates after the same heat treatments.
After long-term aging at 923 K (650 C) for 10,000 hours, the stress rupture properties of the
ultralow carbon content steel degrades more signicantly. The strength degradation mechanism
of the 9 to 12 pct Cr ferritic/martensitic heat-resistant steels is discussed in this article.

DOI: 10.1007/s11661-012-1092-x
The Minerals, Metals & Materials Society and ASM International 2012

I. INTRODUCTION the growth rate of the MX nitride is much lower than

NINE to 12 pct Cr ferritic/martensitic heat-resistant
steels have been used widely in fossil power plants
because those steels have high thermal conductivity and
low thermal expansion coecient, and they possess less
susceptibility to the thermal fatigue than austenitic
stainless steel.[1] To increase the creep strength, these
steels are strengthened by various strengthening mech-
anisms such as solution hardening by Mo and/or W,
particle hardening by MX within subgrains, particle
hardening because of particles (M23C6 and Fe2W) on
sub-boundaries, and dislocation hardening.[1] In partic-
ular, MX-type carbonitrides, which are composed of
vanadium, niobium, and so on, and precipitate nely
and densely in the matrix of the steels, increase creep
strength signicantly.[13] Taneike et al.[2] reported that
extremely low-carbon 9Cr ferritic steel (9Cr-3W-0.2V-
0.06Nb-3Co-0.05N-B) exhibits much higher creep
strength than 9Cr-0.5Mo-1.8W-VNbN (ASME-P92)
steel does. By decreasing the carbon content of the
ferritic steel, not the M23C6 carbides but only ne MX
nitrides precipitate along lath, block, packet, and prior
austenite grain boundaries as well as in the matrix
during tempering. The ne MX nitride can pin the
boundaries during long-term creep deformation because
that of the M23C6 carbide. Fine precipitation of nano-
size TiC carbides is obtained in 9Cr-2WVNbTi steel by
high-temperature normalizing at 1573 K (1300 C) fol-
lowed by tempering.[3] This decreases minimum creep
rate eectively and improves creep life at 923 K
(650 C). In our previous investigation,[4] it was found
also that ultralow-carbon 9Cr ferritic/martensitic steel
has a dense and homogeneous dispersion of nanosized
MX precipitates in the matrix within martensitic lath
after normalizing-and-tempering heat treatment. Short-
term creep test results at 923 K (650 C) show that the
ultralow-carbon ferritic/martensitic steel has much high-
er creep rupture strength than conventional ASME-P92
steel. To verify whether the ultralow-carbon ferritic/
martensitic steel has high long-term creep strength, the
eect of long-term aging at 923 K (650 C) up to
10,000 hours on the microstructure and mechanical
properties of 9-12Cr ferritic/martensitic heat-resistant
steels with dierent carbon contents were studied in this
article. The current study is helpful for the development
of new heat-resistant alloys used in ultrasupercritical
power plants at 923 K (650 C) and above.
II. EXPERIMENTAL

FENG-SHI YIN, Professor, LI-QIAN TIAN, Student, BING

XUE, Senior Engineer, and XUE-BO JIANG, Associate Professor, are
with the School of Mechanical Engineering, Shandong University of
Technology, Zibo 255049, P.R. China. Contact e-mail: fsyin@sdut.
edu.cn LI ZHOU, Senior Engineer, is with the School of Chemical
Engineering, Shandong University of Technology.
Manuscript submitted September 23, 2011.
Article published online February 24, 2012
Two heats were prepared by vacuum-induction melt-
ing. The composition of the two heats is listed in
Table I. One has an ultralow-carbon content whereas
another has a normal carbon content. Hot forging and
rolling were performed to produce 10-mm-thick plates.
The heating temperatures before forging and rolling
were 1373 K (1100 C), respectively. The plates were

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 43A, JULY 20122203

 Table I. Composition of the Ferritic/Martensitic Heat-Resistant Steels (in weight percent)

Steel C Si Mn Cr Ni Mo W Co V Nb Ti B N
0.01C-9Cr 0.01 0.14 0.08 8.9 0.01 0.45 1.65 4.1 0.21 0.08 0.004 0.009 0.02
0.09C-11Cr 0.09 0.13 0.51 11.1 0.04 0.45 1.66 3.1 0.20 0.09 0.005 0.015 0.02

Fig. 1SEM images of the steels normalized at 1373 K (1100 C) for 1 h, cooled in air, and then tempered at 1023 K (750 C) for 1 h:
(a) 0.01C-9Cr and (b) 0.09C-11Cr.

Fig. 2TEM images of the steels normalized at 1373 K (1100 C) for 1 h, cooled in air, and then tempered at 1023 K (750 C) for 1 h:
(a) 0.01C-9Cr and (b) 0.09C-11Cr.

normalized at 1373 K (1100 C) for 1 hour, cooled in
air, and then tempered at 1023 K (750 C) for 1 hour.
The normalized-and-tempered steels were aged at 923 K
(650 C) for up to 10,000 hours in air. Specimens 4 mm
in gage diameter and 20 mm in gage length were
machined from both the normalized-and-tempered and
aged plates with the specimen axis parallel with the
rolling direction. Tensile and stress rupture tests were
conducted in air at 923 K (650 C). The microstructures
of the specimens were characterized by an FEI Sirion
200 (FEI Co., Eindhoven, the Netherlands) eld-emis-
sion scanning electron microscope (FE-SEM). The
precipitates were observed and identied by an FEI
Techai 20 (FEI Co.) transmission electron microscope

2204VOLUME 43A, JULY 2012 METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 3(a) TEM image of carbon lm replica for the 0.01C-9Cr steel at normalized state. (b) EDS results of the nanosized MX particle marked
with an arrow in (a).
(TEM) using carbon lm replicas. Both SEM and TEM
are equipped with energy-dispersive spectrum analysis
(EDS).
III. RESULTS
Figure 1 shows the SEM images of the steels normal-
ized at 1373 K (1100 C) for 1 hour, cooled in air, and
then tempered at 1023 K (750 C) for 1 hour. M23C6-
type carbides are found rarely in the 0.01C-9Cr steel
because the steel contains ultralow carbon content. In
the 0.09C-11Cr steel, plenty of M23C6-type carbide
particles are distributed along the grain boundaries and
lath boundaries. A TEM observation shows that the
bimodal, nanosized MX precipitates distribute densely
in the matrix in the 0.01C-9Cr steel as shown in
Figure 2(a). Compared with the ultralow carbon steel
(0.01C-9Cr steel), the normal carbon steel (0.09C-11Cr
steel) has a much lower density of nanosized MX
precipitates as shown in Figure 2(b). Figure 3 shows a
TEM image of the carbon lm replica for the 0.01C-9Cr
METALLURGICAL AND MATERIALS TRANSACTIONS A
steel at a normalized state. It can be observed that the
larger nanosized MX precipitates are present already
before tempering, which indicated that they are retained
and do not dissolve during the normalizing heat
treatment adopted in the current study as reported in
elsewhere.[5] Using the high-resolution mode of the FEI
Techai F20 TEM, it is found that the smaller nanosized
MX precipitates shown in Figure 2(a) have two kinds of
typical morphology: One is cubic and another is
rectangular, as shown in Figures 4(a) and (c). The
EDS results show that the cubic MX precipitate
contains Nb, Ti, and V (Figure 4(b)), whereas the
rectangular precipitate contains only Nb and V
(Figure 4(d)). Ti does not exist in the rectangular MX
precipitate.
Figures 5(a) and (b) show SEM images of the steels
after aging at 923 K (650 C) for 10,000 hours in air.
W- and Mo-containing Laves phase precipitates are found
along both the grain and lath boundaries in both steels.
Figures 5(c) and (d) show the EDS results of the Laves
phase particles marked with arrows in Figures 5(a) and
(b), respectively. The TEM observation shows that the
VOLUME 43A, JULY 20122205
Fig. 4The morphology of the smaller nanosized MX particles in 0.01C-9Cr steel normalized at 1373 K (1100 C) for 1 h, cooled in air, and
then tempered at 1023 K (750 C) for 1 h: (a) cubic MX precipitate, (b) energy-dispersive spectrum of the cubic MX precipitate, (c) rectangular
MX precipitate, and (d) energy-dispersive spectrum of the rectangular MX precipitate.
smaller nanosized MX precipitates, which distribute
densely in 0.01C-9Cr steel at the normalized-and-
tempered state, almost disappear after aging at 923 K
(650 C) for 10,000 hours, and the Z-phase [Cr(Nb,V)N]
forms instead of the smaller nanosized MX precipitates
as shown in Figure 6. The precipitation of large Z-phase
particles, Cr(V,Nb)N, which replace ne MX nitrides,
(V,Nb)N, has been identied recently as a major cause
of premature breakdown in long-term creep strength of
several new 9 to 12 pct Cr martensitic steels.[6,7]
Figures 7 and 8 show the tensile and stress rupture
test results at 923 K (650 C), respectively. It is shown
that in normalized-and-tempered state, the tensile
strength of the ultralow-carbon steel (0.01C-9Cr steel)
is higher than that of the normal-carbon-content steel
(0.09C-11Cr steel), and the time to rupture at 923 K
(650 C) for the ultralow-carbon steel (0.01C-9Cr steel)
is also much greater than that for the normal-carbon-
content steel (0.09C-11Cr steel), especially under a high-
stress condition. This is a result of the strengthening
eect caused by the dense and homogeneous nanosized
MX precipitates in the 0.01C-9Cr steel. After aged at
923 K (650 C) for 10,000 hours, both the tensile
strength and stress rupture strength at 923 K (650 C)
for both steels decreases greatly. It is unexpected that
both the tensile strength and stress rupture strength of
the ultralow-carbon steel are all lower than these of the
2206VOLUME 43A, JULY 2012
normal carbon content steel indicating that the strength
degradation of the ultralow-carbon steel during long-
time aging is more signicant than that of the normal-
carbon-content steel even though the ultralow-carbon
steel has dense and homogeneous nanosized MX pre-
cipitates in the matrix at the normalized-and-tempered
state.
IV. DISCUSSION
The mechanisms of strength degradation are a result
of the occurrence of microstructure degradation during
creep exposure and are classied as[8]: (1) dissolution of
ne M2X and MX carbonitrides and precipitation of
new phases, (2) preferential recovery of microstructure
in the vicinity of prior austenite grain boundaries, (3)
loss of creep ductility, and (4) recovery of excess
dislocations. In the normalized-and-tempered state and
under a high-stress condition, the relative longer time to
rupture of the ultralow-carbon steel is attributed mainly
to dispersion strengthening because of the high density
of nanosized MX precipitates and solution strengthen-
ing of W and Mo. The strength degradation is more
signicant for the ultralow-carbon-content steel for the
following reasons: (1) After aging at 923 K (650 C) for
10,000 hours, the precipitation of Laves phase depletes
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 5SEM images of the steels aged at 923 K (650 C) for 10,000 h in air showing that the Laves phase precipitates along both grain and lath
boundaries: (a) 0.01C-9Cr and (b) 0.09C-11Cr. (c and d) EDS results of Laves particles marked with the arrows in (a) and (b), respectively.

W and Mo contents in the matrix causing the decrease in
solid solution strengthening of W and Mo; (2) the
conversion of nanosized MX particles into coarse Z
phase particles decreases the dispersion strengthening
because of the nanosized MX particles.
According to the results mentioned, the rate of
strength degradation is relatively lower for the normal
carbon steel than the ultralow-carbon steel, which
indicates that carbon has an important role in high
temperature strength of this kind of steels after aged at
923 K (650 C) for 10,000 hours. The strengthening
mechanisms of these steels include solution hardening
by Mo and W, particle hardening by MX within
subgrains, particle hardening because of particles of
M23C6 and Fe2W on sub-boundaries, and dislocation
hardening.[1] For the ultralow-carbon steel, the harden-
ing by MX within subgrains loses eectiveness after
aging at 923 K (650 C) for 10,000 hours because of the
conversion of nanosized MX particles into coarse
Z-phase particles. Within this condition, the dispersion

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 43A, JULY 20122207

Fig. 6TEM image of 0.01C-9Cr steel aged at 923 K (650 C) for 10,000 h: (a) morphology of Z phase and (b) EDS results of Z phase marked
with arrows.

Fig. 7Tensile test results of the steels at 923 K (650 C): (a) normalized-and-tempered state and (b) aged at 923 K (650 C) for 10,000 h.

strengthening of M23C6-type carbide particles along the
grain and lath boundaries is still valid. This might be the
reason why the strength degradation is relatively lower
for the normal carbon steel than the ultralow-carbon
steel.
It must be pointed out that the current result is
dierent from that reported in References 2 and 3, in
which extremely low-carbon 9Cr ferritic steel (0.002C-
9Cr-3W-0.2V-0.06Nb-3Co-0.05NB) exhibits a much
higher creep strength than conventional 9Cr-0.5Mo-
1.8W-VNbN (ASME-P92) steel does. The main dier-
ence lies in the formation of the Z phase. In the current
study, the Z phase in the ultralow-carbon steel forms
after aging at 923 K (650 C) for 3000 hours much
earlier than that does in conventional ASME-P92 steel
which contains individual particles of the Z phase after
several tens of thousand hours of creep.[9]
It is not clear why the current ultralow-carbon steel
forms Z phase much quicker. Many investigations have
been made on the mechanism and inuencing factors of
Z-phase formation, such as tempering temperature and
alloying elements. Sawada et al.[10] examined the eect
of tempering temperature on Z-phase formation and
creep strength in the 9Cr-1Mo-V-Nb-N steel and
reported that the Z phase was observed after long-term
creep in steel tempered at a higher temperature of
1003 K (730 C) or 1038 K (765 C), whereas in steel
tempered at lower temperature of 953 K (680 C), a VX

2208VOLUME 43A, JULY 2012 METALLURGICAL AND MATERIALS TRANSACTIONS A


Fig. 8Stress and time to rupture relationship for the steels at
923 K (650 C). (a) 0.01C-9Cr and (b) 0.09C-11Cr steels normalized
at 1373 K (1100 C) for 1 h, cooled in air, and then tempered at
1023 K (750 C) for 1 h. (c) 0.01C-9Cr and (d) 0.09C-11Cr steels
after aging at 923 K (650 C) for 10,000 h.
rather than a Z phase formed during creep. However, Z
phase was not found in extremely low-carbon 9Cr
ferritic steel, which had been tempered at 1073 K
(800 C).[2] The conicting reports indicated that the
tempering temperature might not be the main reason
why the current ultralow-carbon steel forms Z phase
much quicker. It is known that when the content of
chromium is decreased from 11 to 9 pct, the driving
force for the formation of Z phase is decreased by
almost a factor of 1.5.[6] This is the main reason why the
rate of the Z-phase formation in P92 steel decreases by
several orders of magnitude. In a Z phase, nitrogen
cannot be substituted by carbon. Therefore, any increase
in the nitrogen content with a simultaneous decrease in
carbon content accelerates the formation of Z phase
because the chemical composition of the MX-type phase
shifts from carbonitride to nitride. Therefore, the
increase in nitrogen content to 0.06 pct and any decrease
in the carbon content stimulates growth in the driving
force for the formation of Z phase.[6] It has been shown
that an increase in nitrogen content above 0.05 wt pct
accelerates considerably the formation of Z phase in
steels with 9 pct Cr.[11] Therefore, the nitrogen content
in normal carbon content martensitic steels with 9 pct
Cr is limited by this value. Therefore, in the current
study, the nitrogen content in the ultralow-carbon-
content martensitic steel should be less than this value.
It is interesting that the distribution of the titanium
element is dierent in the smaller nanosized MX
precipitates. Ti exists in the cubic nanosized MX
precipitates not in the rectangular MX precipitate. Up
to now, it is not found that the harmful Z phase contains
titanium; therefore, the titanium modied nanosized
MX precipitates are relatively more dicult to be
converted into Z phase and keep a strengthening eect
for a longer time. This is conrmed in authors previous
study, in which a small addition of titanium causes an
increase in creep rupture life.[5]
METALLURGICAL AND MATERIALS TRANSACTIONS A
V. CONCLUSIONS
The eect of carbon content on the microstructure
and mechanical properties of 9 to 12 pctCr ferritic/
martensitic heat-resistant steels was studied. The fol-
lowing conclusions can be drawn:
1. The ultralow-carbon steel contains bimodal nano-
sized MX precipitates with high density in the
matrix but few of M23C6 carbide particles in the
normalized-and-tempered state. The smaller nano-
sized MX precipitates have two kinds of typical
morphology: one is cubic and another rectangular.
The cubic MX precipitate contains Nb, Ti, and V,
whereas the rectangular one only contains Nb and
V.
2. The normal carbon steel has abundant M23C6 car-
bide particles along the grain and lath boundaries,
and it has much less density of nanosized MX pre-
cipitates after the same heat treatments.
3. After long-term aging at 923 K (650 C) for
10,000 hours, the stress rupture properties of the
ultralow-carbon content steel degrade more signi-
cantly.
4. During long-term aging at 923 K (650 C) for
10000h, the formation of W and Mo-containing
Laves phase and conversion of nanosized MX pre-
cipitates into coarse Z phase particles cause signi-
cant strength degradation.
ACKNOWLEDGMENTS
Financial support is acknowledged from the Natural
Science Foundation of Shandong province (Grant
Y2008F47), National Natural Science Foundation of
China (Grant 50771059), and National High Technol-
ogy Research and Development Program of China
(863 Program) (Grant 2009AA03Z509).
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