ARTICLE IN PRESS

International Journal of Pressure Vessels and Piping 84 (2007) 312

www.elsevier.com/locate/ijpvp

Alloy design of creep resistant 9Cr steel using a dispersion

of nano-sized carbonitrides
F. Abe, M. Taneike1, K. Sawada
National Institute for Materials Science (NIMS), Japan

Abstract

In order to improve creep strength of tempered martensitic 9Cr steel at 650 1C, alloy design for a dispersion of ne and thermally stable
precipitate particles has been investigated for 9Cr3W3CoVNb steel and 9Cr2WVNbTi steel. Creep tests were carried out at 650 1C
for up to about 10 000 h. By reducing carbon concentration below 0.02%, a dispersion of nano-size MX nitrides of vanadium and
niobium along boundaries as well as in the matrix is achieved in 9Cr3W3CoVNb steel with 0.05% nitrogen. This gives rise to
excellent creep strength at 650 1C, as shown by much higher creep rupture strength than conventional 9Cr steels P92 and T91. Excess
addition of nitrogen, 0.07 and 0.1%, promotes the coarsening of MX nitrides and the formation of Z-phase during creep. A dispersion of
nano-size TiC carbides is also achieved in 9Cr2WVNb steel containing 0.05% Ti by high-temperature normalizing at 1300 1C followed
by tempering. This effectively decreases minimum creep rate and improves creep life.
r 2006 Published by Elsevier Ltd.

Keywords: 9cr steel; Creep strength; Minimum creep rate; MX nitride; TiC; Martensitic microstructure

1. Introduction proportional to the volume fraction. Therefore, optimal

Energy security and lower carbon dioxide emissions are
increasingly seen as key factors in protecting the global
environment. Research and development of heat resistant
steels and alloys for high-efcient USC power plants at
650 1C (923 K) and above are being now promoted in
Europe, USA and Japan [14]. Since 1997, National
Institute for Materials Science (NIMS, Japan) has been
conducting the research and development of advanced
ferritic steels for application to large diameter and thick
section boiler components such as main steam pipe and
header of ultra-supercritical (USC) power plant at 650 1C
[3,5]. Critical issues for the development of ferritic steels for
650 1C USC boilers are the improvement of oxidation
resistance as well as long-term creep rupture strength.
Dispersion strengthening of metals and alloys is inversely
proportional to the mean inter-particle distance and
Corresponding author. Tel.: +81 29 859 2115; fax: +81 29 859 2101.
E-mail addresses: ABE.Fujio@nims.go.jp (F. Abe),
masaki_taneike@mhi.co.jp (M. Taneike).
1
Now at Mitsubishi Heavy Industries, Ltd., Japan
creep strength of heat resistant steels can be obtained by a
dispersion of ne and thermally stable precipitate particles
combined with enough solid solution strengthening.
Microstructure of conventional 9 to 12Cr steels such as
P91 (9Cr1MoVNb steel), P92 (9Cr0.5Mo1.8WVNb
steel) and P122 (11Cr0.4Mo2WCuVNb steel) for thick
section boiler components consists of tempered martensite
lath, block and packet, which contain high density of
dislocations and ne precipitates, after appropriate nor-
malizing and tempering. These steels contain about 0.1%
carbon and about 0.05% nitrogen, which precipitate as
M23C6 carbides rich in chromium and MX carbonitrides
rich in vanadium and niobium during tempering. Fig. 1
shows the TEM micrographs of 9Cr steel containing
0.078% carbon and 0.05% nitrogen (0.078C steel in
Table 1, as will be described later) after tempering, which
are also typical for the microstructure of P91, P92 and
P122. The size of M23C6 carbides is usually much larger in
the vicinity of prior austenite grain boundaries than that
inside grain [6,7]. The size of MX carbonitrides is much
smaller than that of M23C6 carbides and they are
distributed mainly in the matrix within lath, while the

0308-0161/$ - see front matter r 2006 Published by Elsevier Ltd.

doi:10.1016/j.ijpvp.2006.09.003
 ARTICLE IN PRESS
4 F. Abe et al. / International Journal of Pressure Vessels and Piping 84 (2007) 312

M23C6 carbides are distributed along lath, block, packet
and prior austenite grain boundaries, as illustrated in Fig.
2(a) and (b). The M23C6 carbides and MX carbonitrides
further grow in size during creep at elevated temperature
by the mechanism of Ostwald ripening, because most of
carbon and nitrogen atoms in the supersaturated solid
solution of the steels precipitate as carbides and nitrides
during tempering before creep tests [8]. We have revealed
that the coarsening rate of M23C6 carbides is much larger
in the vicinity of prior austenite grain boundaries than
within grain [6,7]. Enlarged M23C6 carbides promote
inhomogeneous microstructure recovery such as re-
covery of excess dislocations, lath and block during creep,
which results in a decrease in resistance to creep deforma-
tion [3,4].
As illustrated in Fig. 2(c), in the present work we are
trying to eliminate unstable M23C6 carbides from marten-
sitic microstructure of 9Cr steel and to distribute very ne
and thermally stable MX carbonitrides not only in the
matrix within lath but also along boundaries. Although
vanadium and niobium carbonitrides have been used as
MX precipitates in conventional 9 to 12Cr steels, we are
also trying to use titanium carbides in order to achieve
further improvement of thermal stability of MX precipi-
tates during creep. Creep test was carried out up to about
10 000 h at 650 1C. We report that dispersion strengthening
due to nano-size carbonitrides gives rise to excellent high-
temperature creep strength for 9Cr steel at 650 1C.

2. Precipitate design for dispersion of ne carbonitrides in

9Cr steel

2.1. Design of very fine and thermally stable precipitates in

9Cr steel

The volume diffusion controlled Ostwald ripening of

MaCb carbides has been given by [9]
r3  r30 k3 t, (1)

k3 8a bsVDM uM =9aRTupM  uM 2 , (2)

Fig. 1. TEM micrographs of 9Cr3W base steel with 0.078% carbon and
0.05% nitrogen after tempering; 0.078C steel in Table 1: (a) replica near
prior austenite grain boundary, (b) thin lm.
where r and r0 are the average particle radius at the time t
and t 0, respectively, s is the interfacial energy of the
carbides, V is the molar volume of the carbides, DM is the
volume diffusion coefcient of metal M, uM and upM are
the concentration of M in matrix and carbides, respec-
tively, R is gas constant and T is temperature. The main
factors affecting the coarsening rate of precipitate particles
are diffusion coefcient, solid solubility of participating
elements and interfacial energy. We evaluate diffusion
coefcient and solid solubility of alloying elements in iron.
Impurity diffusion coefcients in iron are not different so
much, less than one order of magnitude, among different
elements, such as W, Mo, V and Nb [10]. On the other

Table 1
Chemical compositions and heat treatment conditions of carbon series of 9Cr3W3CoVNb0.05N steels with different carbon concentration

C Si Mn Cr W V Nb Co N (mass %) B Normalizing Tempering

0.002C 0.002 0.29 0.51 9.19 2.96 0.20 0.060 3.09 0.049 0.0070 1100 1C  0.5 h 800 1C  1 h
0.018C 0.018 0.29 0.50 9.16 2.91 0.20 0.058 2.94 0.050 0.0058 1100 1C  0.5 h 800 1C  1 h
0.047C 0.047 0.30 0.51 9.24 2.90 0.20 0.059 3.07 0.050 0.0063 1100 1C  0.5 h 800 1C  1 h
0.078C 0.078 0.31 0.51 9.26 2.93 0.20 0.061 3.08 0.049 0.0064 1100 1C  0.5 h 800 1C  1 h
0.12C 0.120 0.30 0.50 9.27 2.93 0.20 0.058 3.08 0.048 0.0065 1100 1C  0.5 h 800 1C  1 h
0.16C 0.160 0.30 0.51 9.26 2.94 0.20 0.058 3.08 0.047 0.0061 1100 1C  0.5 h 800 1C  1 h
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F. Abe et al. / International Journal of Pressure Vessels and Piping 84 (2007) 312
(a)
(b)
(c)
Fig. 2. Illustration of martensitic 9Cr steel after tempering: (a) subgrain
structure; (b) distribution of M23C6 and MX in conventional.
hand, the solid solubility of alloying elements, which are
equilibrating with their carbides, nitrides and Fe2(Mo,W)
Laves phase in iron, is evaluated by using thermo-calc. This
is shown in Figs. 3. The solid solubility of V, Nb and Ti
equilibrating with their nitrides is very low in
FeM0.05%N alloys, where M and N are alloying
elements and nitrogen, respectively. It should be noted
that TiN is extremely stable for up to melting temperature,
because of extremely low solid solubility in iron for up to
melting temperature. This indicates that we cannot control
a dispersion of ne TiN by appropriate heat treatment,
such as solution treatment and subsequent aging or
tempering. Thus TiN is excluded from the present
precipitate designing. Carbides and nitrides of V and Nb
5
T (C)
700 600 500
10-2
10-4
10-6
10-8
Mole fraction
10-10
10-12
10-14
10-16
10-18
10-20
10-22
0.001 0.0011 0.0012 0.0013
1/T (K-1)
Fig. 3. Solid solubility of alloying elements, which are equilibrating with
their carbides, nitrides and Fe2(Mo,W) Laves phase in iron.
and carbides of Ti are the most probable precipitates,
which show very low coarsening rate during exposure at
elevated temperature. However, the addition of carbon to a
9Cr steel causes the formation of a large amount of M23C6
carbides rich in Cr. Wey et al. [9] reported that the
coarsening rate of Cr carbides in iron was much larger than
that of V and Nb at elevated temperature. Therefore, it is
crucial for 9Cr steels to reduce carbon concentration to
very low amounts, so as to promote the formation of MX
nitrides, where M is V and Nb, as very ne and thermally
stable particles for prolonged periods of exposure at
elevated temperatures and also to eliminate unstable Cr
carbides [11].
The thermo-calc evaluation of equilibrium phases in a
9Cr3W3Co0.2V0.05Nb0.05N steel during tempering
at 800 1C and during creep at 650 1C is shown in Fig. 4 as a
function of carbon concentration. The amount of M23C6
carbides rich in Cr decreases with decreasing carbon
concentration, while the amount of MX carbonitrides is
approximately constant for a wide range of carbon
concentration from 0% to 0.15%. The amount of MX
carbonitrides is larger than that of M23C6 carbides at low
carbon concentrations below 0.02% during tempering at
800 1C and also during creep at 650 1C. The MX
carbonitrides consist of mainly vanadium nitrides and of
small amount of niobium nitrides, suggesting that the MX
carbonitrides are substantially vanadium and niobium
nitrides. This indicates that we can obtain substantially
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6 F. Abe et al. / International Journal of Pressure Vessels and Piping 84 (2007) 312

0.04 only vanadium and niobium nitrides after tempering by

reducing carbon concentration to very low amounts below
800C 0.02%. Therefore, in the present work we examine the
0.03 MX microstructure and creep deformation behavior using 9Cr
M C
23 6 steel containing different carbon concentrations of 0.002%
Number of mole

Fe W Laves to 0.16%.
2
0.02 2.2. Utilization of titanium carbides in 9Cr steel

Fig. 3(b) suggests that TiC can be used as ne MX

0.01 precipitates in 9Cr steel, because the solid solubility of TiC
is approximately the same as that of NbC and is much
larger than that of TiN. Therefore, there is a possibility
that we can dissolve TiC particles in 9Cr steel by
0 appropriate normalizing and that we can obtain ne
0 0.05 0.1 0.15
precipitation of TiC during subsequent tempering, similar
(a) Carbon concentration ( wt % )
as NbC. For the utilization of TiC in 9Cr steel, it is crucial
0.04 to reduce nitrogen concentration to very low amounts, so
as to promote the formation of TiC as very ne and
650C thermally stable particles.
0.03
3. Experimental
Number of mole

Three series of 9Cr steel were examined in this work.

0.02 These are designated carbon, nitrogen and Ti series,
according to their chemical compositions. The chemical
compositions and heat treatment conditions of the three
series are given in Tables 13. The carbon series are based
0.01
on 9Cr3W3Co0.2V0.05Nb0.05N (wt%) steel with
different carbon concentrations. The steels are designated
0.002C, 0.018C and so on, according to their carbon
0 concentration. Based on the very low carbon steel of
0 0.05 0.1 0.15
0.002C in the carbon series, the nitrogen series contain
(b) Carbonconcentration ( wt % ) different nitrogen concentrations of 0.050.10%. The Ti
0.5
series are based on 0.13C9Cr2W0.2V0.05Nb steel with
and without 0.05Ti. The steel containing 0.05Ti was
subjected to standard normalizing at 1100 1C and also to
0.4 high temperature normalizing at 1300 1C to enable
650C complete dissolution of TiC particles. The Ti series are
Mole fraction in MX

designated 0Ti (no Ti addition), 0.05TiS (0.05Ti addition

0.3 N
and standard normalizing) and 0.05TiH (0.05Ti addition
C and high temperature normalizing), according to their Ti
Nb concentration and normalizing temperature. It should be
0.2
V noted that the holding time in high temperature normal-
izing at 1300 1C was decreased to 1 min to minimize the
0.1 growth of d-ferrite, because d-ferrite appears at high
temperature above g-loop in phase diagram. The concen-
tration of W was reduced to 2% also to avoid the
0 formation of d-ferrite, because the Ti series did not contain
0.00 0.05 0.10 0.15 austenite forming element Co. The steel plates and rods
(c) Carbon concentration ( wt % ) were prepared by vacuum induction melting to 50 kg
ingots, mainly. Creep tests were carried out at 650 1C for
up to about 10 000 h, using specimens of 10 mm in gauge
diameter and 50 mm in gauge length for the carbon and
Fig. 4. Thermo-calc evaluation of phases appearing in nitrogen series and also using specimens of 8 mm in gauge
9Cr3W3Co0.2V0.05Nb05N steel during tempering at 800 1C and diameter and 40 mm in gauge length for the Ti series. The
during creep at 650 1C, as a function of carbon concentration.
longitudinal cross-section of the specimens were observed
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F. Abe et al. / International Journal of Pressure Vessels and Piping 84 (2007) 312 7

Table 2
Chemical compositions and heat treatment conditions of nitrogen series of 9Cr3W3CoVNb0.002C steels with different nitrogen concentration

C Si Mn Cr W V Nb Co N (mass %) B Normalizing Tempering

0.05N 0.0020 0.29 0.51 9.19 2.96 0.20 0.060 3.09 0.049 0.0070 1100 1C  0.5 h 800 1C  1 h
0.07N 0.0019 0.30 0.50 8.84 3.02 0.20 0.059 3.02 0.074 0.0066 1200 1C  0.5 h 790 1C  4 h
0.10N 0.0020 0.29 0.53 8.87 2.90 0.19 0.060 3.03 0.103 0.0062 1200 1C  0.5 h 790 1C  4 h

Table 3
Chemical compositions and heat treatment conditions of Ti series of 9Cr2WVNb0.13C steels with and without 0.05Ti

C Si Cr W V Nb Co N (mass %) Normalizing Tempering

0Ti 0.13 0.51 8.49 1.93 0.195 0.045 o0.001 0.006 1100 1C  1 h 760 1C  1 h
0.05Ti-S 0.13 0.50 8.42 1.91 0.192 0.044 0.047 0.006 1100 1C  1 h 760 1C  1 h
0.05Ti-H 0.13 0.50 8.42 1.91 0.192 0.044 0.047 0.006 1300 1C  1 h 770 1C  1 h

metallographically by scanning (Hitachi S4700) and
transmission (JEOL 2010F, 200 kV) electron microscopes.
The compositions of precipitates were analyzed by EDX
attached to the TEM.
4. Results and discussion
4.1. Effect of fine distribution of vanadium and niobium
nitrides and elimination of M23C6 carbides on creep behavior
A large number of ne precipitate particles having a size
less than 10 nm are distributed along prior austenite grain
boundaries as well as along lath, block and packet
boundaries in the 0.002C steel after tempering, as shown
in Fig. 5. This is quite different from the microstructure of
the 0.078C steel shown in Fig. 1, where the large particles
of M23C6 carbides of 100300 nm size are distributed along
prior austenite grain boundaries together with the ne
particles of MX carbonitrides. The ne precipitate particles
in Fig. 5 were identied as MX-type carbonitrides and were
conrmed via energy dispersive microanalysis to be rich in
V and Nb [12]. Any Cr-nitrides were not detected. The
spacing between (1 1 1) planes of the MX was measured
from the photograph of the diffraction pattern to be about
2.398 A which corresponds with that of vanadium nitride,
2.390 A. In Fig. 5, the (1 0 0) plane of MX is parallel to the
(1 0 0) plane of an adjacent ferrite matrix. The orientation
relationship is given by (1 0 0)MX//(1 0 0)ferrite, [0 1 0]MX//
[0 1 1]ferrite, [0 0 1]MX//[0 1 1]ferrite. Consequently, the MX
nitrides shown in Fig. 5 have a BakerNutting relationship
[12]. The dense distribution of ne particles along
boundaries causes a signicant decrease in inter-particle
distance. The ne MX carbonitride particles were also
distributed in the matrix within laths in addition to along
boundaries.
Fig. 6 shows the time to rupture and minimum creep rate
of the carbon series (Table 2) at 650 1C and 140 MPa, as a
function of carbon concentration. The time to rupture is
substantially independent of carbon concentration in the
higher carbon region above 0.047% but it signicantly
increases in the lower carbon region below 0.018%, which
is also typical for applied tensile stresses within the range of
140200 MPa. On the other hand, the minimum creep rate
signicantly decreases in the lower carbon region below
0.018%. The present results indicate that ne distributions
of vanadium and niobium nitrides together with the
elimination of M23C6 carbides are very effective for the
reduction of minimum creep rate and the improvement of
creep life at 650 1C.
Fig. 7 compares the creep rate versus time curves
between the two representative steels; the very low carbon
0.002C steel and the 0.078C steels containing carbon
concentration similar as the conventional 9Cr steels such as
P92 and P91 at 650 1C and 140 MPa. The creep and creep
rate curves consist of the primary or transient creep region,
where the creep rate decreases with time, and of the tertiary
or acceleration creep region, where the creep rate increases
with time after reaching a minimum creep rate. There is
substantially no steady-state region, where the creep rate is
constant. Many researchers have shown for engineering
ferritic heat resistant steels that there is an ever evolving
microstructure and the change in creep rate reects coupled
elementary processes, such as micro grain growth, change
in dislocation density, change in precipitate volume
fraction and size [1317]. These results suggest that in
tempered martensitic steels there is no dynamic micro-
structural equilibrium during creep, which characterizes
steady-state creep of simple metals and alloys. In Fig. 7, the
creep rates in the initial stage are lower in the 0.002C steel
than in the 0.078C steel. The decrease in creep rate with
time in the transient creep region, corresponding to the
slope of the creep rate curves in the transient region, is
substantially the same between the two steels. It should be
noted that the minimum creep rate of the 0.002C steel is
1
about 10 of that of the 0.078C steel, while the time
to rupture of the 0.002C steel is about 10 times of the
0.078C steel. Usually, the time to rupture is inversely
proportional to the minimum creep rate. This is known as
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8 F. Abe et al. / International Journal of Pressure Vessels and Piping 84 (2007) 312

Fig. 5. Nano-size MX precipitates along boundaries in 0.002C steel in Table 1, after tempering.

12000 10-4 10-1

10-2
Minimum creep rate ( 1 / h )

Creep rate ( 1 / h )

10-3
Time to rupture ( h )

8000 10-5

10-4

10-5
4000 -6
10
10-6

10-7
10-2 10-1 100 101 102 103 104
0 -7
10 Time ( h )
0 0.05 0.1 0.15 0.2
Carbon concentration ( wt % ) Fig. 7. Creep rate versus time curves of 0.002C and 0.078C steels in Table
1 at 650 1C and 140 MPa.
Fig. 6. Time to rupture and minimum creep rate of the carbon series in
Table 1 at 650 1C and 140 MPa, as a function of carbon concentration.

MonkmanGrant relationship. The observed longer creep tion strengthening after tempering. However, the difference
life by reducing carbon concentration results from a in initial creep rates between the two steel is only slightly as
decrease in minimum creep rate. shown by 13 orders of magnitude, which is much smaller
The lower values of the initial creep rates in the 0.002C than the difference in minimum creep rate between the two
steel than in the 0.078C steel results from larger precipita- steels. On the other hand, the onset of acceleration creep is
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F. Abe et al. / International Journal of Pressure Vessels and Piping 84 (2007) 312
retarded up to longer times in the 0.002C steel, which
causes the longer duration of transient creep. Abe et al.
[18,19] have revealed for tempered martensitic 9Cr steels
that the migration of lath or block boundaries, causing the
coarsening of the lath or block, is closely correlated with
the onset of acceleration creep and that the coarsening of
lath or block by the migration of boundaries with
absorbing excess dislocations is the major process in
acceleration creep. The dense distribution of ne vanadium
and niobium nitrides along lath and block boundaries
shown in Fig. 5 exerts a large pinning force for boundary
migration up to long times during creep, which retards the
onset of acceleration creep to long times. This is the
stabilization of lath martensitic microstructure in creep
deformation. In Fig. 7, the time to reach minimum creep
rate, corresponding to the onset time of acceleration creep,
is 3418 h for the 0.002C steel, which is much larger than
that of 492 h for the 0.078C steel. The observed signicant
decrease in minimum creep rate by reducing carbon
concentration is explained mainly by the retardation of
the onset of acceleration creep, resulting from the
stabilization of lath-block microstructure during creep.
Fe2W Laves phase was also observed to have precipi-
tated mainly at prior austenite grain boundaries and also at
block and lath boundaries during creep at 650 1C. The
amount and size of Laves phase precipitated were
approximately the same among the steels with different
carbon contents of 0.0020.16%C. Because the size of
Laves phase particles was quite large of 500700 nm and
the number density was low after creep for several
thousands hours at 650 1C, precipitation strengthening
due to the Laves phase is thought to be negligibly small.
Enough creep ductility is also required for thick section
boiler components in USC plant, because the thermal
cycling capabilities of thick section components would be
severely restricted by fatigue damage. Creep-fatigue life is
shown to be proportional to reduction of area in creep
rupture testing [20]. The reduction of area of the 0.002C
steel in creep rupture testing is substantially the same as
that of P92 [21].
4.2. Effect of nitrogen concentration on stability of fine
vanadium and niobium nitrides
The critical issue for the 0.002C steel is considered to be
the formation of Z-phase [22], which degrades long-term
creep strength. Z-phase is a complex nitride of the form
Cr(Nb,V)N [23]. The precipitation of Z-phase during creep
causes a loss of creep strength at long times, because they
consume existing ne M2X and MX precipitates. Strang et
al. [24] pointed out for 12CrMo(W)VNbN steels that the
coarsening of M23C6 carbides is accompanied by dissolu-
tion of the ne matrix MX carbonitrides due to the
precipitation of coarse M6X and or Z-phase. Vodarek and
Strang [25] reported for 12CrMoV steels with Ni contents
in the range of 0.31.2% that increase in Ni content
resulted in accelerated microstructure degradation with
9
650C
200
Stress (MPa)
100
0.05N
80 0.07N
0.10N
P92
60 T91
101 102 103 104 105
Time to rupture ( h )
Fig. 8. Creep rupture data for the 0.05N, 0.07N and 0.10N steels in Table
2 at 650 1C, comparing with those for conventional steels P92 and T91.
more rapid coarsening of M23C6, dissolution of MX,
precipitation of coarse M6X and Fe2Mo. In the present
work, the effect of nitrogen concentration on microstruc-
ture stability and creep strength has been investigated for
the 0.002C steel. The nitrogen concentration was varied in
the range of 0.050.1% as shown in Table 2, where the
0.05N steel was the same as the 0.002C steel in Table 1.
The increase in nitrogen concentration decreases the
creep rupture strength at 650 1C as shown in Fig. 8,
although the creep rupture strength of the 0.07N and
0.10N steels is still much larger than that of conventional
steels P92 [26] and T91 [27]. The time to rupture of the
0.05N steel, which is identical with the 0.002C steel in
Table 1, is approximately two orders of magnitude higher
than the ASME-P92 steel and approximately three orders
of magnitude higher than the ASME-T91 steel at 923 K
and 140 MPa. After tempering, large Cr2N as well as ne
MX nitrides were distributes along lath, block, packet and
prior austenite grain boundaries in the high nitrogen 0.07N
and 0.10N steels, although the amount of Cr2N was slight
[22]. The Cr2N particles occupied the precipitation sites for
ne MX nitrides, resulting in an increase in mean inter-
particle spacing along boundaries. As shown in Fig. 9, the
mean size of MX is only a little bit smaller in the 0.05N
steel than in the 0.07N and 0.10N steels after tempering
and before creep test. During creep at 650 1C, the
agglomeration and coarsening rate of MX nitrides is larger
in the high nitrogen 0.07N and 0.10N steels than in the
0.05N steel. The formation of Z-phase is observed even in
the 0.05N steel after creep rupture testing for 10285 h at
650 1C, although the amount of Z-phase is only slight. It
should be noted that the formation of Z-phase takes place
at shorter times in the high nitrogen 0.07N and 0.10N steels
than in the 0.05N steel during creep at 650 1C [22].
Recently, Gustafson and Hattestrand [28] reported that
the increase in nitrogen content in P92 from 0.05 to 0.06
mass% decreased the coarsening rate of MX carbonitrides
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10 F. Abe et al. / International Journal of Pressure Vessels and Piping 84 (2007) 312

60 0.10N steels than in the 0.05N steel. It should be noted that

the onset of acceleration creep takes place at shorter times
650C
in the high nitrogen 0.07N and 0.10N steels than in the
Gauge portion
0.05N steel. This results in higher minimum creep rate and
shorter time to rupture in the high nitrogen 0.07N and
Mean radius of MX (nm)

40 0.10N steels. Enhanced coarsening of MX nitrides and

enhanced formation of Z-phase in the high nitrogen steels
during creep promote the onset of acceleration creep.

4.3. Effect of fine titanium carbides on creep

20
Fig. 11 shows the loglog plots of creep rate versus time
0.05N curves of the Ti series in Table 3 at 650 1C under stress
0.07N conditions of 80 and 60 MPa. The creep life increases in
0.10N
order of the 0.05TiS, 0Ti and 0.05TiH steels, where the
0 creep rupture strength of the 0.05TiH steel has similar
0 4000 8000 12000
strength as T91 at 650 1C and 80 MPa even though TiC
Time to rupture ( h )
particles of the same size as the nitrides in the low carbon
Fig. 9. Mean radius of MX nitrides for the 0.05N, 0.0N and 0.10N steels 9Cr steel described above are formed. It should be noted
in Table 2 during creep at 650 1C. that the 0.05TiH steel contained M23C6 carbides as well as

10-1 10-1

650C, 140MPa 650C, 80 MPa

10-2 10-2
Creep rate (1 / h)

10-3 10-3
Creep rate (1/h)

10-4 10-4

10-5 10-5 0Ti

0.05N 0.05Ti-S
0.07N 0.05Ti-H
10-6 0.10N 10-6
10-1 100 101 102 103 104 105
(a) Time (h)
10-7
10-2 10-1 100 101 102 103 104 105
Time ( h )
10-3 650C, 60 MPa
Fig. 10. Creep rate versus time curves of the 0.05N, 0.07N and 0.10N
steels in Table 2 at 650 1C and 140 MPa.
10-4
Creep rate (1 / h)

during aging at 600 and 650 1C. The enhanced coarsening

of MX nitrides observed in the present high nitrogen 0.07N 10-5
and 0.10N steels during creep is thought to be mainly due
to an effect of the Z-phase formation, which dissolve the 10-6
small MX particles. Another possibility is the formation of 0Ti
0.05Ti-S
Cr2N as well as MX nitrides in the present high nitrogen
0.05Ti-H
0.07N and 0.010N steels during tempering. The coarsening 10-7
rate of Cr2N during exposure at elevated temperature is
usually larger than that of MX. 10-1 100 101 102 103 104 105
Fig. 10 compares the loglog plots of creep rate versus (b) Time ( h )
time curves among the 0.05N, 0.07N and 0.10N steels at Fig. 11. TEM image of carbon extraction replica of the 0.07N steel,
650 1C and 140 MPa.The creep rates in the transient region showing Z-phase by the arrow. The replica was obtained from the
are only a little bit larger in the high nitrogen 0.07N and specimen crept for 1187 h at 923 K.
 ARTICLE IN PRESS
F. Abe et al. / International Journal of Pressure Vessels and Piping 84 (2007) 312
Fig. 12. SEM images of: (a) 0Ti, (b) 0.05Ti-S and (c) 0.05Ti-H steels in Table 3, and TEM image of (d) 0.05Ti-H steel after tempering.
ne TiC but no MX nitride. At a lower stress of 60 MPa,
the 0.05TiH steel exhibits a signicant decrease in creep
rate in the transient region before reaching a minimum
creep rate. The initial creep rates are lower in the 0.05TiH
steel than in the 0Ti and 0.05TiS steels. This is correlated
with the microstructure of the steels after tempering, as
shown in Fig. 12. While the distributions of M23C6 along
lath, block, packet and prior austenite grain boundaries are
substantially the same among the three steels, the number
density of ne MX in the matrix within lath are much
larger in the 0.05TiH steel than the 0Ti and 0.05TiS
steels, as shown in Fig. 12(a)(c). The ne precipitates in
the matrix were identied as substantially MX carbides
because of extremely low concentration of nitrogen in the
Ti series. The size of MX carbides are 10 nm or less as can
be seen from Fig. 12(d). The constituent elements in the
MX particles were analyzed by EDX with TEM using
replica lms. The MX particles in the 0Ti steel were mainly
composed of niobium; perhaps NbC. The MX particles in
the 0.05TiH and 0.05TiS steels consisted of Ti, Nb, V
and Cr, where those in the 0.05TiH steel contained much
vanadium and chromium but less Ti than in the 0.05TiS
steel [29].
It was conrmed by TEM observations that almost no
MX remained in the 0.5TiH steel after normalizing at
1300 1C. Therefore, ne MX particles seen in Fig. 12 have
precipitated during tempering before creep. On the other
hand, large particles of TiC remained as undissolved large
11
inclusions in the 0.05TiS steel after normalizing at
1100 1C. The large particles of TiC consumed large amount
of dissolved Ti and carbon, and hence resultant micro-
structure of the 0.05TiS steel after tempering contained
low density of ne MX particles. This is a reason why the
initial creep rate of the 0.05TiS steel is higher than that of
the 0Ti steel. The present results indicate that ne
precipitation of TiC can be obtained by high-temperature
normalizing followed by appropriate tempering and that
ne TiC effectively decreases the initial creep rates and also
retards the onset of acceleration creep. This effectively
decreases minimum creep rate and hence improves creep
life. The effect of ne distribution of TiC on the decrease in
minimum creep rate is more signicant at a lower stress of
60 MPa than at a higher stress of 80 MPa.
5. Conclusions
1. The time to rupture of 9Cr3W3CoVNb steel
signicantly increases in the lower carbon region below
0.018%, where the precipitates were mainly nano-size
MX nitrides identied as vanadium and niobium
nitrides. The creep rupture strength of the steel contain-
ing 0.002% carbon is much higher than that of
conventional steels T91 and P92 at 650 1C. Fine
distribution of vanadium and niobium nitrides along
lath and block boundaries after tempering effectively
exerts pinning force for migration of lath and block
 ARTICLE IN PRESS
12 F. Abe et al. / International Journal of Pressure Vessels and Piping 84 (2007) 312
boundaries up to long times during creep. This retards
the onset of acceleration creep, resulting in reduction of
minimum creep rate and extension of creep life.
2. Excess addition of nitrogen promotes the coarsening of
MX nitrides and the formation of Z-phase in the
9Cr3W3CoVNb steel during creep at 650 1C,
although the microstructure after tempering is approxi-
mately the same among the steels containing different
nitrogen concentration. The enhanced coarsening of
MX nitrides is mainly due to an effect of the Z-phase
formation, which dissolve the small MX particles. This
increases inter-particle distance during creep, which
results in a decrease in creep rupture strength.
3. Fine precipitation of nano-size TiC carbides is also
obtained in 9Cr2WVNbTi steel by high-temperature
normalizing at 1300 1C followed by tempering. This
effectively decreases minimum creep rate and improves
creep life at 650 1C. The ne distribution of TiC
effectively stabilizes the tempered martensitic micro-
structure against the recovery of lath and block
subgrains during creep.
Acknowledgment
The authors are grateful to member of the Creep Group
in NIMS for their sincere efforts in creep test.
References
[1] Blum R, Vanstone RW. Materials development for boilers and steam
turbines operating at 700 1C. In: Proceedings of the sixth interna-
tional Charles Parsons turbine conference, Dublin, Ireland, 1618
September 2003. p. 489510.
[2] Viswanathan R, Henry JF, Tanzosh J, Stanko G, Shingledecker J,
Vitalis B. US program on materials technology for USC power
plants. In: Proceedings of the fourth international conference on
advances in materials technology for fossil power plants, Hilton Head
Island, South Carolina, USA, 2528 October 2004. p. 319.
[3] Abe F, Okada H, Wanikawa S, Tabuchi M, Itagaki T, Kimura K, et
al. Guiding principles for development of advanced ferritic steels for
650 1C USC boilers. In: Proceedings of the seventh Liege conference
on materials for advanced power engineering 2002, Liege, Belgium;
30 September2 October 2002. p. 1397406.
[4] Abe F. Bainitic and martensitic creep-resistant steels. Curr Opin Solid
State Mater Sci 2004;8:30511.
[5] Abe F, Horiuchi T, Taneike M, Sawada K. Improvement of creep
strength by boron and nano-size nitrides for tempered-martensitic
9Cr3W3CoVNb steel at 650 1C. In: Proceedings of the sixth
international Charles Parsons turbine conference, Dublin, Ireland;
1618 September 2003 p. 37996.
[6] Horiuchi T, Igarashi M, Abe F. Improved utilization of added B in
9Cr heat-resistant steels containing W. ISIJ Intl 2002;42:S6771.
[7] Abe F, Horiuchi T, Sawada K. High-temperature annealing for
maximization of dissolved boron in creep-resistant martensitic 9Cr
steel. Mater Sci Forum 2003;426:13938.
[8] Abe F. Coarsening behavior of lath and its effect on creep rates in
tempered martensitic 9CrW steels. Mater Sci Eng A 2004;
387389:5659.
[9] Wey MY, Sakuma T, Nishizawa T. Growth of alloy carbide particles
in austenite. Trans Japan Inst Met 1981;22:73342.
[10] Oikawa H. Review on lattice diffusion of substitutional impurities in
iron. Technology reports, Tohoku University, Sendai, Japan, vol. 47.
1982. p. 21524.
[11] Taneike M, Abe F, Sawada K. Creep-strengthening of steel at high
temperatures using nano-sized carbonitride dispersions. Nature
2003;424:2946.
[12] Taneike M, Sawada K, Abe F. Effect of carbon concentration on
precipitation behavior of M23C6 carbides and MX carbonitrides in
martensitic 9Cr steel during heat treatment. Metall Mater Trans A
2004;35A:125562.
[13] Abe F, Araki H, Noda T. The effect of W on dislocation recovery and
precipitation behavior of low radioactivation martensitic 9Cr steels.
Metall Trans A 1991;22A:222535.
[14] Eggeler G, Nilsvang N, Ilschner B. Microstructural changes in a 12%
chromium steel during creep. Steel Res 1987;58:97103.
[15] Eggeler G. The effect of long-term creep on particle coarsening in
tempered martensite ferritic steels. Acta Metall 1989;37:322534.
[16] Williams KR, Wilshire B. Effect of microstructural instability on the
creep and fracture behaviour of ferritic steels. Mater Sci Eng
1977;28:28996.
[17] Straub S, Meier M, Ostermann J, Blum W. Development of
microstructure and strengthening in ferritic steel X20 CrMoV121 at
823 K. VGB Kraftwerkstechnik 1993;73:64653.
[18] Abe F, Nakazawa S, Araki H, Noda T. The role of microstructural
instability on creep behavior of a low radiaoactivation martensitic
9Cr2W steel. Metall Trans A 1992;23A:46977.
[19] Abe F. Effect of quenching, tempering and cold rolling on creep
deformation behavior of a tempered martensitic 9Cr1W steel. Metall
Mater Trans A 2003;34A:91325.
[20] Kimura M, Kobayashi K, Yamaguchi K. Creep and fatigue
properties of newly developed ferritic heat-resisting steels for ultra
super critical power plants. Mater Sci Res Int 2003;9:504.
[21] Abe F. Ultra-Steel R&D in NIMS for 650 1C USC plant. In:
Proceedings of the eighth ultra-steel workshop, Tsukuba, Japan,
2121 July, 2004. p.18893.
[22] Sawada K, Taneike M, Kimura K, Abe F. Effect of nitrogen content
on microstructural aspects and creep behavior in extremely low
carbon 9Cr heat-resistant steel. ISIJ Intl 2004;44:12439.
[23] Strang A, Vodarek V. Z-phase formation in martensitic 12CrMoVNb
steel. Mater Sci Technol 1996;12:5526.
[24] Strang A, Foldyna V, Lenert J, Vodarek V, Mayer K-H. Prediction
of the long-term creep rupture properties of 912%Cr power plant
steels. In: Proceedings of the sixth international Charles Parsons
turbine conference, Dublin, Ireland, 1618 September 2003.
p. 42741.
[25] Vodarek V, Strang A. Effect of nickel on the precipitation processes
in 12CrMoV steel during creep at 550 1C. Scripta Mater 1998;
38:1016.
[26] National Research Institute for Metals Creep Data Sheet, National
Research Institute for Metals, Tokyo, Japan, vol. 43. 1996.
[27] National Institute for Material Science Creep Data Sheet, National
Institute for Material Science, Tokyo, Japan, vol. 48. 2002.
[28] Gustafsson A, Hattestrand M. Coarsening of precipitates in an
advanced creep resistant 9% chromium steelquantitative micro-
scopy and simulations. Mater Sci Eng A 2002;333:27986.
[29] Taneike M, Fujitsuna N, Abe F. Improvement of creep strength by
ne distribution of TiC in 9Cr ferritic heat resistant steel. Mater Sci
Technol 2004;20:145561.