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]

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

YONG YANG, Assistant Research Scientist, KUMAR elements were measured using inductively coupled
SRIDHARAN, Distinguished Research Professor, and TODD R. plasma mass spectrometry (ICP-MS). As may be
ALLEN, Associate Professor, are with the Engineering Physics expected, the compositions for all three conditions are
Department, University of WisconsinMadison, Madison, WI 53706. very similar and within the range of the T22 specica-
Contact e-mail: [email protected] YIREN CHEN, Sta Scientist, is
with Argonne National Laboratory, Argonne, IL 60439.
tion and accuracy of the measurement techniques. The
Manuscript submitted June 27, 2007. nal heat treatment of the pipes involved annealing for
Article published online March 17, 2010 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 the replica specimen, the samples were rst polished to
for 90 minutes and then air cooling to room temper- 1-lm nish with diamond paste and etched with 5 pct
ature. In the fully annealed condition, this alloy consists nital solution. Following this, 30-nm-thick carbon lms
of about 80 pct proeutectoid ferrite with dispersions of were deposited on the sample surfaces using a sputtering
a high density of acicular carbides, and about 20 pct method, scribed into small squares, stripped by etching
bainite.[1] again with 5 pct nital, and nally rinsed in methanol and
The carbide morphology, spatial distribution, and collected on copper grids.
elemental compositions were characterized mainly using To study the transformation of carbide precipitates
the carbon extraction replica technique, with transmis- during service aging, electrolytically extracted residues
sion electron microscopy (TEM) (PHILIPS** CM 200) 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
**PHILIPS is a trademark of FEI Company, Hillsboro, OR. reagent, at 2 V relative to a platinum cathode. The
extracted carbide precipitates were separated by centri-
and energy dispersive spectroscopy (EDS). To prepare 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 III. RESULTS AND DISCUSSION
Zetasizer Nano-Z (Malvern).
Due to the limited size of the available materials, A. TEM and EDS Studies on Carbide Precipitates
miniature bending small ball punch tests was per- Figure 1 shows the morphologies of the carbides in
formed to determine the mechanical properties from the steel sample in the unexposed condition. The
3-mm TEM disks. In this test, a small loading ball proeutectoid ferritic regions were characterized by a
was driven into a at disk sample mounted on a die dispersion of high density of nanometer-sized acicular
while the load displacement was recorded. The defor- carbides, and these carbides were determined, by EDS
mation mode in the disk was a combination of analysis, to contain chromium, molybdenum, iron, and
bending and membrane stretching, and the stress state a signicant amount of silicon. The prior austenite
at the center of the disk was approximately balanced grain boundaries were decorated with a mixture of
biaxial tension. A tabletop screw-driven test frame was M23C6 and M6C carbides. The bainitic regions con-
used for the ball punch test. The test system included tained carbides with morphologies ranging from glob-
a computer-controlled step motor, a 1000-lb load cell, ular to lathlike, and an g carbide (M6C) was clearly
and two linear variable displacement transducers. indentied, as shown in Figure 1(d). This precipitate
Disk specimens were held down in the die with a has a lattice parameter a = 1.084 nm. The microstruc-
clamping torque of 20 lb-in. A 1-mm tungsten carbide ture of unexposed T22 steel also contained a substantial
ball was used as the loading ball. All ball punch tests amount of brous precipitates, which are generally
were conducted at a constant cross-head speed of considered to be Mo2C,[10] but in this present study,
0.46 mm/min. The ball punch test was terminated these carbides were noted to contain about 50 wt pct of
after a sudden load drop was observed beyond chromium.
maximum load. Vickers hardness measurement was Figure 2 shows the obvious changes in the carbide
also performed to examine the softening eect from microstructure of the T22 steel after service aging
aging during long-term service. for 17 years at 810 K (537 C) in the power plant.

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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- fracture mode of the material by promoting cleavage
idization, and a large number of carbides precipitated at and decohesion of grains. The broadening of the
the grain boundaries. Furthermore, the densities of precipitate denuded zone at prior austenite grain
acicular carbides and submicron-sized spheroidal car- boundaries also increased with this prolonged service
bides in ferritic regions decreased dramatically. Another aging. The long-needle-shaped carbide, as indexed in
microstructural eect of service aging was the emergence Figure 3(d), was revealed to contain iron, chromium,
within the ferrite regions of a near prior austenite grain molybdenum, and silicon. While iron was dominating,
boundary zone, which was denuded of carbide precip- the carbide is suspected to be an g carbide; however, the
itates. On average, the width of these denuded zones was diraction pattern could not be indexed, possibly
about 2.8 lm. Additionally, the brous carbides found because the M:C ratio in the g carbide is less than 6
in unexposed T22 steel dissolved and carbides with a with the silicon on the metal lattice.[10]
lathlike morphology evolved in the bainitic regions in Quantitative EDS analysis of carbides permitted
the 17 years aged specimen. ternary plots to be constructed, as shown in Figure 4,
Further changes in carbide size, morphology, and which shows the compositions of iron, chromium, and
distribution developed after exposure for 28 years at molybdenum in the carbides measured over the ferritic
810 K (537 C), as shown in Figure 3. The carbides (Figure 4(a)) and bainitic regions (Figure 4(b)). The
continued to coarsen and large agglomerations of 28 years aging changed the stoichiometries of the
carbides, as well as rod-shaped and spheroidal carbides carbides in ferritic regions dramatically and the content
several microns in size, were observed. Concurrently, the of iron increased from ~20 to ~65 wt pct, while the
nanometer-sized acicular precipitates observed in the 17 years aging resulted in minor alterations in compo-
unexposed and 17 years aged samples were absent in sition. A similar trend was also observed in the bainitic
some ferritic grains. The large agglomerations of parti- regions, but the magnitude of increments of iron content
cles at grain boundaries can have a detrimental eect on is much less since the carbides in the bainitic regions
the mechanical properties, and possibly change the for the unexposed and 17 years conditions already

1444VOLUME 41A, JUNE 2010 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).

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
Fig. 5X-ray diraction patterns of the carbides electrolytically
prediction that the equilibrium carbide will be M6C after
extracted from T22 steels with dierent aging histories. long-term tempering or aging.[1,10]
The coarsening of carbide precipitates at various
aging periods is summarized in Figure 6, where the
contained a fairly high content of iron. Generally, long- volume fraction vs size of carbide was quantied. It can
term aging at 810 K (537 C) altered the stoichiometry be seen that the peaks of carbide size distribution kept
of carbide precipitates toward a higher content of iron. 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
B. Studies on the Electrolytically Extracted Carbides tends to be more convergent, with an average size of
The carbide precipitates extracted using the electro- ~5 lm.
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 C. Mechanical Performance
M23C6, M6C, M2C, and M3X, where the M3X has a high A typical load-central deection curve from the small
content of silicon. For 17 years service aging, the peaks ball punch is shown in Figure 7(a). The load P at initial
from M2C and M3X almost disappeared while the peaks localized plastic straining denoted by Py and load
from M6C (g carbide) became much more pronounced. maximum, Pmax, can be empirically related to the yield
For the samples aged in service for 28 years, the M6C strength ry and the tensile strength rmax, respectively:[12]
eventually became the predominant carbide at the
expense of other carbides. The carbide precipitation ry 360Py =t0 1

METALLURGICAL AND MATERIALS TRANSACTIONS A VOLUME 41A, JUNE 20101445

and temperature from the literature.[13] Figure 7(b) displays
the load-central deection curves of the tests on T22
rtensile 130Pmax =t20 2 steels with dierent service aging histories, and the
results of the yield and tensile strength and strain at
where t0 is the initial thickness of the disk. The strain
fracture are summarized in Figure 8. It can be seen that
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 aging and then slightly recovered at 28 years aging. The
tensile strength remained nearly constant at dierent
where tf is the thickness of the thinnest section at aging times, while the ductility of T22 steel aged for
failure, and it can be further correlated to the central 28 years decreased considerably possibly due the large
deection at fracture (d*): agglomerations of carbide at grain boundaries.

The Vickers microhardness test result, shown in
ef ln t0 =tf bd =t0 2 4 Figure 9, agrees very well with the yield strengths from
small ball punch test. It can seen that after 17 years
where b is a constant determined by experiment, and for
service aging, the hardness of the T22 steel decreased
this study, it was selected as 0.06 by tting our results
about 15 pct, while the aging softening was slightly
with the experimental tensile tests on T22 at room
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

 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.

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3. G.D. Pigrova, V.M. Sedov, and Y.I. Archakov: Met. Sci. Heat
Treatment, 1997, vol. 39, pp. 37175.
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