Evolution of Carbide Precipitates in 2.

25Cr-1Mo Steel
during Long-Term Service in a Power Plant
YONG YANG, YIREN CHEN, KUMAR SRIDHARAN, and TODD R. ALLEN

Carbide precipitation from the steel matrix during long-term high-temperature exposure can
adversely aect the fracture toughness and high-temperature creep resistance of materials with
implications on the performance of power plant components. In the present work, carbide
evolution in 2.25Cr-1Mo steel after long-term aging during service was investigated. Boiler pipe
samples of this steel were removed from a supercritical water-cooled coal-red power plant after
service times of 17 and 28 years and a mean operational temperature of 810 K (537 C). The
carbide precipitation and coarsening eects were studied using the carbon extraction replica
technique followed by analysis using transmission electron microscopy and energy dispersive
X-ray spectroscopy. The carbides extracted using an electrolytic technique were also analyzed
using X-ray diraction to evaluate phase transformations of the carbides during long-term
service. Small ball punch and Vickers hardness were used to evaluate the changes in mechanical
performance after long-term aging during service.

DOI: 10.1007/s11661-010-0194-6
 The Minerals, Metals & Materials Society and ASM International 2010

I. INTRODUCTION the temperature range 697 to 977 K (424 to 704 C).[4]

DUE to their excellent mechanical properties, good
formability, weldability, and satisfactory corrosion
resistance, low-alloy ferritic steels are used extensively
in power plants and petrochemical industries. Speci-
cally, 2.25Cr-1Mo steel (T22) is commonly used for
steam pipes and pressure vessels of power plants. In the
nuclear industry, this steel has been considered for use in
sodium-heated steam generators. Although the steel is
heat treated to provide an optimum microstructure with
a high density of nely dispersed acicular carbides, the
instability of the initial carbides during long-term high-
temperature exposure can result in a degradation of
mechanical properties, especially the high-temperature
creep-rupture strength and fracture toughness.
Extensive research has been conducted to examine the
precipitation processes in ferritic steels, as well as on
the associated mechanical performance. Baker and
Nutting studied the precipitation reaction sequence in
2.25Cr-1Mo steel after accelerated thermal aging.[1] The
precipitation of coarse M6C carbides has been studied,
and the kinetics of precipitation modeled in niobium-
alloyed ferritic stainless steel during high-temperature
aging up to 500 hours.[2] Carbide transformations in
Cr-Mo steels with varying contents of chromium and
molybdenum have been studied in order to determine
the carbide reaction sequence.[3] Softening due to aging
was clearly observed in annealed 2.25Cr-1Mo steel in
However, most of these previous studies are based on
simulated aging processes to limit the aging times to
those deemed reasonable for laboratory experi-
ments.[1,59] The goal of the present research is to study
the carbide precipitate evolution in boiler pipe samples
fabricated from 2.25Cr-1Mo steel (T22), which were
removed from a supercritical water-cooled coal-red
power plant after service times of 17 and 28 years at
810 K (537 C).
II. EXPERIMENTAL PROCEDURE
The T22 ferritic steels were procured from the Genoa
Station 3 supercritical water coal-red power plant
operated by the Dairyland Power Cooperative, Genoa,
WI. The samples were in the form of pipe components
that were removed after 17 and 28 years service at
810 K (537 C) during the plants nearly 35 years of
operation. The unexposed pipe has the same origin with
the aged ones, and the bulk chemical compositions of
the unexposed control sample and those of the two
aging conditions are listed in Table I. The carbon was
measured using LECO* CNS-2000; other alloying
*LECO is a trademark of LECO Corporation, St. Joseph, MI.

YONG YANG, Assistant Research Scientist, KUMAR
SRIDHARAN, Distinguished Research Professor, and TODD R.
ALLEN, Associate Professor, are with the Engineering Physics
Department, University of WisconsinMadison, Madison, WI 53706.
Contact e-mail: yyang@cae.wisc.edu YIREN CHEN, Sta Scientist, is
with Argonne National Laboratory, Argonne, IL 60439.
Manuscript submitted June 27, 2007.
Article published online March 17, 2010
elements were measured using inductively coupled
plasma mass spectrometry (ICP-MS). As may be
expected, the compositions for all three conditions are
very similar and within the range of the T22 specica-
tion and accuracy of the measurement techniques. The
nal heat treatment of the pipes involved annealing for
20 minutes at 1203 K (930 C) for austenitization

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 41A, JUNE 20101441

 Table I. Bulk Chemical Composition of T22 Steel as Measured in Various Aged Conditions (Weight Percent)

Service Exposure/Year Cr Si Mn Mo C S P Fe
Unexposed 2.11 0.48 0.4600 0.97 0.152 0.008 0.020 bal
17 2.41 0.46 0.5800 1.12 0.143 0.016 0.021 bal
28 2.31 0.55 0.6000 1.18 0.136 0.010 0.019 bal

Fig. 1Microstructure of unexposed T22 steel: (a) TEM image at low magnication, (b) carbide precipitates at prior austenite grain boundary,
(c) nanometer-sized acicular precipitates in proeutectoid ferritic grain, and (d) carbides in bainitic region.

followed by cooling to 993 K (720 C) and tempering
for 90 minutes and then air cooling to room temper-
ature. In the fully annealed condition, this alloy consists
of about 80 pct proeutectoid ferrite with dispersions of
a high density of acicular carbides, and about 20 pct
bainite.[1]
The carbide morphology, spatial distribution, and
elemental compositions were characterized mainly using
the carbon extraction replica technique, with transmis-
sion electron microscopy (TEM) (PHILIPS** CM 200)
**PHILIPS is a trademark of FEI Company, Hillsboro, OR.
and energy dispersive spectroscopy (EDS). To prepare
the replica specimen, the samples were rst polished to
1-lm nish with diamond paste and etched with 5 pct
nital solution. Following this, 30-nm-thick carbon lms
were deposited on the sample surfaces using a sputtering
method, scribed into small squares, stripped by etching
again with 5 pct nital, and nally rinsed in methanol and
collected on copper grids.
To study the transformation of carbide precipitates
during service aging, electrolytically extracted residues
were analyzed using X-ray diraction (STOE X-ray
diractometer). Carbides were extracted by anodic
dissolution of the steel in a methanol-10 pct HCl
reagent, at 2 V relative to a platinum cathode. The
extracted carbide precipitates were separated by centri-
fuging and rinsed in methanol. The size distribution

1442VOLUME 41A, JUNE 2010 METALLURGICAL AND MATERIALS TRANSACTIONS A

Fig. 2Microstructure of T22 steel after 17 years service aging at 810 K (537 C): (a) TEM image of grain structure, (b) prior austenite grain
boundary, (c) carbides in proeutectoid ferritic grain, and (d) bainitic region.
of the carbide precipitates was evaluated using the
Zetasizer Nano-Z (Malvern).
Due to the limited size of the available materials,
miniature bending small ball punch tests was per-
formed to determine the mechanical properties from
3-mm TEM disks. In this test, a small loading ball
was driven into a at disk sample mounted on a die
while the load displacement was recorded. The defor-
mation mode in the disk was a combination of
bending and membrane stretching, and the stress state
at the center of the disk was approximately balanced
biaxial tension. A tabletop screw-driven test frame was
used for the ball punch test. The test system included
a computer-controlled step motor, a 1000-lb load cell,
and two linear variable displacement transducers.
Disk specimens were held down in the die with a
clamping torque of 20 lb-in. A 1-mm tungsten carbide
ball was used as the loading ball. All ball punch tests
were conducted at a constant cross-head speed of
0.46 mm/min. The ball punch test was terminated
after a sudden load drop was observed beyond
maximum load. Vickers hardness measurement was
also performed to examine the softening eect from
aging during long-term service.
METALLURGICAL AND MATERIALS TRANSACTIONS A
III. RESULTS AND DISCUSSION
A. TEM and EDS Studies on Carbide Precipitates
Figure 1 shows the morphologies of the carbides in
the steel sample in the unexposed condition. The
proeutectoid ferritic regions were characterized by a
dispersion of high density of nanometer-sized acicular
carbides, and these carbides were determined, by EDS
analysis, to contain chromium, molybdenum, iron, and
a signicant amount of silicon. The prior austenite
grain boundaries were decorated with a mixture of
M23C6 and M6C carbides. The bainitic regions con-
tained carbides with morphologies ranging from glob-
ular to lathlike, and an g carbide (M6C) was clearly
indentied, as shown in Figure 1(d). This precipitate
has a lattice parameter a = 1.084 nm. The microstruc-
ture of unexposed T22 steel also contained a substantial
amount of brous precipitates, which are generally
considered to be Mo2C,[10] but in this present study,
these carbides were noted to contain about 50 wt pct of
chromium.
Figure 2 shows the obvious changes in the carbide
microstructure of the T22 steel after service aging
for 17 years at 810 K (537 C) in the power plant.
VOLUME 41A, JUNE 20101443
Fig. 3Microstructure of T22 steel after 28 years service aging at 810 K (537 C): (a) TEM image of grain structure, (b) bainitic region,
(c) carbides in proeutectoid ferritic grain, and (d) long-needle-shaped carbide with multiple metallic elements.
The carbides show considerable coarsening and sphero-
idization, and a large number of carbides precipitated at
the grain boundaries. Furthermore, the densities of
acicular carbides and submicron-sized spheroidal car-
bides in ferritic regions decreased dramatically. Another
microstructural eect of service aging was the emergence
within the ferrite regions of a near prior austenite grain
boundary zone, which was denuded of carbide precip-
itates. On average, the width of these denuded zones was
about 2.8 lm. Additionally, the brous carbides found
in unexposed T22 steel dissolved and carbides with a
lathlike morphology evolved in the bainitic regions in
the 17 years aged specimen.
Further changes in carbide size, morphology, and
distribution developed after exposure for 28 years at
810 K (537 C), as shown in Figure 3. The carbides
continued to coarsen and large agglomerations of
carbides, as well as rod-shaped and spheroidal carbides
several microns in size, were observed. Concurrently, the
nanometer-sized acicular precipitates observed in the
unexposed and 17 years aged samples were absent in
some ferritic grains. The large agglomerations of parti-
cles at grain boundaries can have a detrimental eect on
the mechanical properties, and possibly change the
1444VOLUME 41A, JUNE 2010
fracture mode of the material by promoting cleavage
and decohesion of grains. The broadening of the
precipitate denuded zone at prior austenite grain
boundaries also increased with this prolonged service
aging. The long-needle-shaped carbide, as indexed in
Figure 3(d), was revealed to contain iron, chromium,
molybdenum, and silicon. While iron was dominating,
the carbide is suspected to be an g carbide; however, the
diraction pattern could not be indexed, possibly
because the M:C ratio in the g carbide is less than 6
with the silicon on the metal lattice.[10]
Quantitative EDS analysis of carbides permitted
ternary plots to be constructed, as shown in Figure 4,
which shows the compositions of iron, chromium, and
molybdenum in the carbides measured over the ferritic
(Figure 4(a)) and bainitic regions (Figure 4(b)). The
28 years aging changed the stoichiometries of the
carbides in ferritic regions dramatically and the content
of iron increased from ~20 to ~65 wt pct, while the
17 years aging resulted in minor alterations in compo-
sition. A similar trend was also observed in the bainitic
regions, but the magnitude of increments of iron content
is much less since the carbides in the bainitic regions
for the unexposed and 17 years conditions already
METALLURGICAL AND MATERIALS TRANSACTIONS A
Fig. 4Ternary composition plots for carbides in the T22 steels when unexposed (unaged) and after aging for 17 and 28 years: (a) ferritic
regions and (b) bainitic regions (10 regions were measured for each condition).
Fig. 5X-ray diraction patterns of the carbides electrolytically
extracted from T22 steels with dierent aging histories.
contained a fairly high content of iron. Generally, long-
term aging at 810 K (537 C) altered the stoichiometry
of carbide precipitates toward a higher content of iron.
B. Studies on the Electrolytically Extracted Carbides
The carbide precipitates extracted using the electro-
lytic process were analyzed by X-ray diraction, and the
results are shown in Figure 5. For the unexposed
samples, four types of carbides were detected, including
M23C6, M6C, M2C, and M3X, where the M3X has a high
content of silicon. For 17 years service aging, the peaks
from M2C and M3X almost disappeared while the peaks
from M6C (g carbide) became much more pronounced.
For the samples aged in service for 28 years, the M6C
eventually became the predominant carbide at the
expense of other carbides. The carbide precipitation
METALLURGICAL AND MATERIALS TRANSACTIONS A
sequence during tempering of T22 after normalization
was investigated thoroughly and established by Baker
and Nutting;[1] the sequence of precipitation reactions
during tempering of the normalized steel was summa-
rized as follows:
(1) bainite: e-carbides:
M7 C3 ! M6 C
M3 C ! M2 C
M23 C6 ! M6 C
(2) ferrite: M2 C ! M6 C
In our study, no M7C3 was detected in any of the
samples, and this transition carbide might already have
transformed into M6C during the initial tempering at
993 K (720 C). During service aging, all the M2C and
M3X completely transformed into M6C for the rst
17 years period, while the M23C6 with a much lower
transformation rate partially remained even after
28 years service aging. Our results agree well with the
prediction that the equilibrium carbide will be M6C after
long-term tempering or aging.[1,10]
The coarsening of carbide precipitates at various
aging periods is summarized in Figure 6, where the
volume fraction vs size of carbide was quantied. It can
be seen that the peaks of carbide size distribution kept
progressively shifting toward larger particle size during
service aging. Although all three curves display dual
peaks, for the 28 years aged samples, the size of carbide
tends to be more convergent, with an average size of
~5 lm.
C. Mechanical Performance
A typical load-central deection curve from the small
ball punch is shown in Figure 7(a). The load P at initial
localized plastic straining denoted by Py and load
maximum, Pmax, can be empirically related to the yield
strength ry and the tensile strength rmax, respectively:[12]
ry 360Py =t0 1
VOLUME 41A, JUNE 20101445
and
rtensile 130Pmax =t20
where t0 is the initial thickness of the disk. The strain
at failure in a bulge test can also be estimated by[12]

the yield strength decreased about 12 pct after 17 years
ef ln t0 =tf 3
where tf is the thickness of the thinnest section at
failure, and it can be further correlated to the central
deection at fracture (d*):

The Vickers microhardness test result, shown in
ef ln t0 =tf bd =t0 2 4
where b is a constant determined by experiment, and for
this study, it was selected as 0.06 by tting our results
with the experimental tensile tests on T22 at room
temperature from the literature.[13] Figure 7(b) displays
the load-central deection curves of the tests on T22
2 steels with dierent service aging histories, and the
results of the yield and tensile strength and strain at
fracture are summarized in Figure 8. It can be seen that
aging and then slightly recovered at 28 years aging. The
tensile strength remained nearly constant at dierent
aging times, while the ductility of T22 steel aged for
28 years decreased considerably possibly due the large
agglomerations of carbide at grain boundaries.
Figure 9, agrees very well with the yield strengths from
small ball punch test. It can seen that after 17 years
service aging, the hardness of the T22 steel decreased
about 15 pct, while the aging softening was slightly
recovered after 28 years aging. However, the most
important factor in determining the long-term mechan-
ical properties is microstructural stability, and the
growth of metal carbides or phase changes can strongly
aect the service life of the steel.

Fig. 6Size distribution of the extracted carbide precipitates from

T22 steels with dierent service aging histories. Fig. 8Summary of the small ball punch tests on T22 steels.

Fig. 7(a) Typical load vs central deection for a small ball punch test and (b) small ball punch tests on T22 steels with dierent service aging
times.

1446VOLUME 41A, JUNE 2010 METALLURGICAL AND MATERIALS TRANSACTIONS A


Fig. 9Vickers hardness vs service aging time.
IV. CONCLUSIONS
Carbide evolution in T22 steel (2.25Cr-1Mo) after
long-term aging (up to 28 years) during service was
thoroughly investigated, and the associated changes in
mechanical performance were estimated using small ball
punch test and Vickers hardness measurements. The
following conclusions were drawn from this study.
1. Long-term service aging at 810 K (537 C) caused a
signicant growth and coarsening of carbides, and
large agglomeration of carbides evolved at the grain
boundaries. After 28 years service aging, some fer-
ritic grains were free from carbide precipitates, and
a wide carbide denuded zone in the vicinity of grain
boundaries was also developed.
2. The chemical compositions of the carbide precipi-
tates started to change signicantly after 17 years
service aging, and the carbides in 28 years aged
steel had an enhanced iron content for both the
ferritic and bainitic regions.
METALLURGICAL AND MATERIALS TRANSACTIONS A
3. After long-term service aging, the M6C became the
predominant carbide at the expense of other car-
bides, which indicates that M6C is the equilibrium
carbide for this steel at 810 K (537 C).
4. The microstructure evolution during long-term ser-
vice caused a slight decrease in the yield strength
after 17 and 28 years aging, while the tensile
strength remained almost constant. The ductility of
T22 steel after 28 years aging deteriorated signi-
cantly from 35 to 27 pct.
REFERENCES
1. R.G. Baker and J. Nutting: J. Iron Steel Inst., 1959, vol. 192,
pp. 25768.
2. N. Fujita, H.K.D.H. Bhadeshia, and M. Kikuchi: Metall. Mater.
Trans. A, 2002, vol. 33A, pp. 333947.
3. G.D. Pigrova, V.M. Sedov, and Y.I. Archakov: Met. Sci. Heat
Treatment, 1997, vol. 39, pp. 37175.
4. P.P. Pizzo and G.L. Mandurrago: Trans. ASME, 1981, vol. 103,
pp. 6270.
5. A.M. Abdel-Latif, J.M. Corbett, and D.M.R. Taplin: Met. Sci.,
1982, vol. 16, pp. 9096.
6. R.A. Stevens and D. Lonsdale: J. Mater. Sci., 1985, vol. 20,
pp. 363138.
7. R.L. Klueh: Proc. Conf., Environmental Degradation of Engineer-
ing Materials, Virginia Polytechnic Institute, Blacksburg, VA,
1977, pp. 64351.
8. B.J. Wendell and J.A. Van Den Avyle: Metall. Trans. A, 1960,
vol. 11A, pp. 127585.
9. T. Ohba, K. Kimura, F. Abe, K. Yagi, and I. Nonaka: Mater. Sci.
Technol., 2005, vol. 21, pp. 47682.
10. M.L. James, L. Klueh Ronald, and R.L. William: Metall. Trans.
A, 1975, vol. 6A, pp. 194955.
11. J. Orr, F.R. Beckitt, and G.D. Fawkers: Ferritic Steel for Fast
Reactor Steam Generators, Proc. Int. Conf. Held by the British
Nuclear Energy Society, Distributed by Telford, London, UK,
1997, pp. 91109.
12. X. Mao and H. Takahashi: J. Nucl. Mater., 1987, vol. 150,
pp. 4252.
13. D. Gandy: The Grade 22 Low Alloy Steel Handbook, Technical
Report, Electric Power Research Institute, Palo Alto, CA, 2005,
pp. 3031.
VOLUME 41A, JUNE 20101447